[go: up one dir, main page]

CN115667404B - Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device - Google Patents

Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device Download PDF

Info

Publication number
CN115667404B
CN115667404B CN202180039172.8A CN202180039172A CN115667404B CN 115667404 B CN115667404 B CN 115667404B CN 202180039172 A CN202180039172 A CN 202180039172A CN 115667404 B CN115667404 B CN 115667404B
Authority
CN
China
Prior art keywords
group
compound
formula
carbon atoms
polymerizable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202180039172.8A
Other languages
Chinese (zh)
Other versions
CN115667404A (en
Inventor
野崎敦靖
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Corp
Original Assignee
Fujifilm Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Fujifilm Corp filed Critical Fujifilm Corp
Publication of CN115667404A publication Critical patent/CN115667404A/en
Application granted granted Critical
Publication of CN115667404B publication Critical patent/CN115667404B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B32B15/088—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/16—Layered products comprising a layer of synthetic resin specially treated, e.g. irradiated
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • B32B27/26—Layered products comprising a layer of synthetic resin characterised by the use of special additives using curing agents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • C08G73/22—Polybenzoxazoles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3472—Five-membered rings
    • C08K5/3475—Five-membered rings condensed with carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L101/00—Compositions of unspecified macromolecular compounds
    • C08L101/02—Compositions of unspecified macromolecular compounds characterised by the presence of specified groups, e.g. terminal or pendant functional groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen or carbon only, not provided for in groups C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/032—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders
    • G03F7/037—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polyamides or polyimides
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/075—Silicon-containing compounds
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
    • G03F7/11—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having cover layers or intermediate layers, e.g. subbing layers
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/20—Exposure; Apparatus therefor

Landscapes

  • Chemical & Material Sciences (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Structural Engineering (AREA)
  • Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
  • Materials For Photolithography (AREA)

Abstract

The present invention provides a curable resin composition, a cured film obtained by curing the curable resin composition, a laminate including the cured film, a method for producing the cured film, and a semiconductor device including the cured film or the laminate, wherein the curable resin composition includes: at least 1 resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides, and polybenzoxazoles; and a compound B as a compound having a polymerizable group and an azole group.

Description

Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
Technical Field
The invention relates to a curable resin composition, a cured film, a laminate, a method for producing the cured film, and a semiconductor device.
Background
Polyimide and polybenzoxazole are excellent in heat resistance, insulation, and the like, and therefore are suitable for various applications. The use is not particularly limited, and examples of the semiconductor device for packaging include use of a material as an insulating film or a sealing material, or use of a protective film. And also used as a base film (base film) or a cover film (coverlay film) of a flexible substrate.
For example, in the above-mentioned applications, polyimide or polybenzoxazole is used in the form of a curable resin composition containing at least one resin selected from polyimide, polyimide precursor, polybenzoxazole, and polybenzoxazole precursor.
Such a curable resin composition is applied to a substrate, for example, by coating, etc., to form a resin film, and then, if necessary, exposure, development, heating, etc., to form a cured film on the substrate.
The polyimide precursor and the polybenzoxazole precursor are cyclized, for example, by heating, and become polyimide and polybenzoxazole, respectively, in the cured film.
Since the curable resin composition can be applied by a known coating method or the like, it can be said that the applied curable resin composition has excellent flexibility in manufacturing such as high design freedom in terms of shape, size, application position and the like when applied. In addition to the high performance of polyimide, polybenzoxazole, and the like, the expansion of the industrial application of the curable resin composition is expected from the viewpoint of excellent suitability for such production.
For example, patent document 1 describes (a) a polyimide precursor, (B) a compound having a heterocyclic structure with a nitrogen atom having a pka of 8.30 to 8.80, and (C) a resin composition containing 5-amino-1H-tetrazole.
Technical literature of the prior art
Patent literature
Patent document 1: japanese patent application laid-open No. 2012-002281
Disclosure of Invention
Technical problem to be solved by the invention
In the production of a cured film that is made of a curable resin composition and is in contact with a metal, the cured film is required to have improved adhesion to the metal.
Examples of the metal include metals included in a metal layer such as a conductive layer, and examples thereof include copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten, preferably copper, aluminum, and an alloy containing these metals, more preferably copper or an alloy containing copper, and even more preferably copper.
For example, in a laminate including a metal layer and a cured film in contact with the metal layer, improvement in adhesion between the metal layer and the cured film is required.
The purpose of the present invention is to provide a curable resin composition that can provide a cured film that has excellent adhesion to metal, a cured film obtained by curing the curable resin composition, a laminate that includes the cured film, a method for producing the cured film, and a semiconductor device that includes the cured film or the laminate.
Means for solving the technical problems
Examples of representative embodiments of the present invention are shown below.
A curable resin composition comprising:
At least 1 resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides, and polybenzoxazoles; and
A compound B which is a compound having a polymerizable group and an azole group.
<2> The curable resin composition according to <1>, wherein,
The compound B has at least 1 group selected from an amine group, a carbamate group and a urea group.
<3> The curable resin composition according to <1> or <2>, wherein,
The compound B contains at least 1 group selected from radical polymerizable groups and alkoxysilyl groups as the polymerizable groups.
<4> The curable resin composition according to any one of <1> to <3>, wherein,
The oxazolyl group in the above-mentioned compound B is a group represented by the following formula (B-1) or the following formula (B-2);
[ chemical formula 1]
In the formula (B-1), R B1 represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, Z B1～ZB4 each independently represents =cr B7 -or a nitrogen atom, R B7 represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, and at least 1 of R B1 and R B7 included in the formula (B-1) represents a bonding position to a structure having a polymerizable group;
In the formula (B-2), R B2～RB3 each independently represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, Z B5 and Z B3 each independently represent =cr B8 —or a nitrogen atom, R B8 represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, and at least 1 of R B2～RB6 and R B8 included in the formula (B-2) represents a bonding position to a structure having a polymerizable group.
<5> The curable resin composition according to any one of <1> to <4>, comprising a compound B having a molecular weight of less than 2,000 as the above compound B.
<6> The curable resin composition according to any one of <1> to <5>, which comprises the compound B as a resin as the above-mentioned compound B.
<7> The curable resin composition according to any one of <1> to <6>, further comprising a compound C which is a compound having an azole group without a polymerizable group.
<8> The curable resin composition according to <7>, wherein,
The compound C is a compound represented by the following formula (C-1) or the following formula (C-2);
[ chemical formula 2]
In the formula (C-1), Z 1～Z4 each independently represents a group consisting of CR 7 -or a nitrogen atom, R 1 represents a hydrogen atom or a 1-valent organic group, R 7 represents a hydrogen atom or a 1-valent organic group, and the structure represented by the formula (C-1) does not include a polymerizable group;
In the formula (C-2), Z 5～Z6 each independently represents a=CR 8 -or a nitrogen atom, R 2～R6 each independently represents a hydrogen atom or a 1-valent organic group, R 8 represents a hydrogen atom or a 1-valent organic group, and the structure represented by the formula (C-2) does not include a polymerizable group.
<9> The curable resin composition according to any one of <1> to <8>, wherein,
At least 1 resin selected from the group consisting of a polyimide precursor, a polybenzoxazole precursor, a polyimide and a polybenzoxazole has a polymerizable group polymerizable with the polymerizable group in the compound B.
<10> The curable resin composition according to any one of <1> to <9>, further comprising a compound D as a silane coupling agent having a polymerizable group different from an alkoxysilyl group and having no azole group.
<11> The curable resin composition according to <10>, wherein,
At least 1 resin selected from the group consisting of polyimide precursor, polybenzoxazole precursor, polyimide and polybenzoxazole has a polymerizable group polymerizable with the polymerizable group in the compound D.
<12> The curable resin composition according to any one of <1> to <11>, further comprising a compound E as a silane coupling agent having no any one of a polymerizable group and an azole group different from an alkoxysilyl group.
<13> The curable resin composition according to any one of <1> to <12>, which is used for forming an interlayer insulating film for a rewiring layer.
<14> A cured film obtained by curing the curable resin composition according to any one of <1> to <13 >.
<15> A laminate comprising 2 or more layers of the cured film of <14> and a metal layer between any of the cured films.
<16> A method for producing a cured film, comprising:
a film forming step of applying the curable resin composition according to any one of <1> to <13> to a substrate to form a film.
<17> The method for producing a cured film according to <16>, comprising:
An exposure step of exposing the film; and a developing step of developing the film.
<18> The method for producing a cured film according to <16> or <17>, comprising:
and a heating step of heating the film at 50 to 450 ℃.
<19> A semiconductor device comprising the cured film of <14> or the laminate of <15 >.
Effects of the invention
According to the present invention, there are provided a curable resin composition capable of providing a cured film excellent in adhesion to a metal, a cured film obtained by curing the curable resin composition, a laminate comprising the cured film, a method for producing the cured film, and a semiconductor device comprising the cured film or the laminate.
Detailed Description
Hereinafter, a main embodiment of the present invention will be described. However, the present invention is not limited to the specific embodiments.
In the present specification, a numerical range indicated by a symbol such as "to" refers to a range in which numerical values before and after "to" are included as a lower limit value and an upper limit value, respectively.
In the present specification, the term "process" includes not only an independent process but also a process which cannot be clearly distinguished from other processes as long as the intended function of the process can be achieved.
In the labeling of groups (radicals) in the present specification, the label which is not labeled with a substituted and unsubstituted includes a group (radical) having no substituent, and also includes a group (radical) having a substituent. For example, "alkyl" includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also exposure using a particle beam such as an electron beam or an ion beam. Examples of the light used for exposure include an open spectrum of a mercury lamp, an extreme ultraviolet ray typified by an excimer laser, an extreme ultraviolet ray (EUV light), an active ray such as an X-ray or an electron beam, and radiation.
In the present specification, "(meth) acrylate" means either or both of "acrylate" and "methacrylate", "(meth) acrylic acid" means either or both of "acrylic acid" and "methacrylic acid", and "(meth) acryl" means either or both of "acryl" and "methacryl".
In the present specification, me in the structural formula represents methyl, et represents ethyl, bu represents butyl, and Ph represents phenyl.
In the present specification, the total solid component means the total mass of the components after the solvent is removed from all the components of the composition. In the present specification, the solid content concentration refers to the mass percentage of the other components than the solvent with respect to the total mass of the composition.
In the present specification, unless otherwise specified, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are defined as polystyrene equivalent values measured by Gel Permeation Chromatography (GPC). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) can be obtained by using HLC-8230 GPC (manufactured by TOSOH CORPORATION) and using a protection column HZ-L、TSKgel Super HZM-M、TSKgel Super HZ4000、TSKgel Super HZ3000、TSKgel Super HZ2000(TOSOH CORPORATION as a column, for example. These molecular weights were measured using THF (tetrahydrofuran) as an eluent unless otherwise specified. Unless otherwise specified, a 254nm wavelength detector of UV (ultraviolet) light is used for detection in GPC measurement.
In the present specification, when the positional relationship of each layer constituting the laminate is described as "up" or "down", another layer may be provided above or below the layer that is the standard among the layers of interest. That is, the 3 rd layer or element may be interposed between the standard layer and the other layer, and the standard layer and the other layer may not be in contact. The direction of stacking the layers on the substrate is referred to as "up", or the direction from the substrate toward the photosensitive layer is referred to as "up", and the opposite direction is referred to as "down", unless otherwise specified. In addition, the vertical direction is set for convenience in the present specification, and in a practical embodiment, the "upward" direction in the present specification may be different from the vertical direction.
In the present specification, unless otherwise specified, the composition may contain 2 or more compounds corresponding to each component contained in the composition. Unless otherwise specified, the content of each component in the composition refers to the total content of all compounds corresponding to the component.
In the present specification, unless otherwise specified, the temperature was 23℃and the air pressure was 101,325Pa (1 air pressure), and the relative humidity was 50% RH.
In this specification, a combination of preferred embodiments is a more preferred embodiment.
(Curable resin composition)
The curable resin composition of the present invention comprises: at least 1 resin (hereinafter also referred to as "specific resin") selected from the group consisting of polyimide precursor, polybenzoxazole precursor, polyimide and polybenzoxazole; and a compound B as a compound having a polymerizable group and an azole group.
The curable resin composition of the present invention may be a negative type curable resin composition or a positive type curable resin composition, but is preferably a negative type curable resin composition.
The negative-type curable resin composition is a composition in which, when a layer formed of the curable resin composition is exposed, an unexposed portion (non-exposed portion) is removed by a developer.
The positive-type curable resin composition is a composition in which, when a layer formed of the curable resin composition is exposed, the exposed portion (exposed portion) is removed by a developer.
According to the curable resin composition of the present invention, a cured film excellent in adhesion to a metal can be obtained.
The mechanism by which the above-described effects can be obtained is not clear, but it is assumed that the following is possible.
The curable composition of the present invention comprises the compound B having a polymerizable group and an azole group, and the cured film obtained has excellent adhesion to a metal.
It is considered that the azole group in the compound B coordinates to the surface of the metal, and the polymerizable group in the compound B is polymerized in the cured film, so that the polymer of the compound B exists on the surface of the metal side in the cured film.
It is considered that the presence of the polymer exerts an anchor effect on a cured resin such as polyimide and improves adhesion.
When a specific resin such as polyimide has a polymerizable group or when the curable resin composition contains a silane coupling agent, the effect of improving the adhesion is remarkable.
This is presumably because polymerization is also formed between the specific resin and the compound B or between the silane coupling agent and the compound B in the cured film.
In the production of a laminate including a film made of a curable resin composition, for example, a metal layer may be formed on a cured film made of a curable resin composition, and another cured film made of a curable resin composition may be formed on the metal layer, for example, the metal layer and the cured film may be laminated.
According to the curable resin composition of the present invention, it is considered that delamination between resin layers and between metal layers and resin layers is suppressed even in such a laminate.
This is also assumed to be because a relatively soft polymer of the compound B exists between a resin such as a hard polyimide and a hard metal.
In the present invention, suppressing delamination between resin layers and between metal layers and resin layers in a laminate is also referred to as "excellent adhesion in multilayer lamination".
Here, patent document 1 does not describe nor suggest a curable resin composition containing a compound B having a polymerizable group and an azole group.
The components contained in the curable resin composition of the present invention will be described in detail below.
< Specific resin >
The curable resin composition of the present invention contains at least 1 resin (specific resin) selected from the group consisting of polyimide, polyimide precursor, polybenzoxazole and polybenzoxazole precursor.
The curable resin composition of the present invention preferably contains polyimide or a polyimide precursor, more preferably contains a polyimide precursor, as the specific resin.
Further, it is preferable that the specific resin has a polymerizable group.
Examples of the polymerizable group in the specific resin include a known polymerizable group such as a radical polymerizable group, an epoxy group, an oxetane group, a hydroxymethyl group, and an alkoxymethyl group.
The radical polymerizable group is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group, or a vinylphenyl group, (meth) acrylamido group, and (meth) acryloyloxy group is preferable.
The specific resin is preferably a polymerizable group having a polymerizable group polymerizable with a polymerizable group in the compound B described later.
Examples of the combination of polymerizable groups include a combination in which a specific resin has a radical polymerizable group and a compound B has a radical polymerizable group, a combination in which a specific resin has an epoxy group and a compound B has an epoxy group, and the like.
According to the above aspect, it is considered that the polymerizable group in the specific resin and the polymerizable group in the compound B are combined in the cured film, and the bonding between the specific resin and the compound B becomes firm, and the adhesion between the obtained cured film and the metal is further improved.
When the curable resin composition contains a compound D described later, the specific resin preferably has a polymerizable group capable of polymerizing with a polymerizable group in the compound D.
Examples of the combination of polymerizable groups include a combination in which a specific resin has a radical polymerizable group and compound D has a radical polymerizable group, a combination in which a specific resin has an epoxy group and compound D has an epoxy group, and the like.
According to the above aspect, it is considered that the polymerizable group in the specific resin and the polymerizable group in the compound D are combined in the cured film, and the bonding between the specific resin and the compound D becomes firm, so that the adhesion between the obtained cured film and the metal is further improved.
In the above embodiment, it is preferable that the compound B has an alkoxysilyl group.
According to the above aspect, in the cured film, the polymerizable group in the specific resin is polymerized with the polymerizable group in the compound D, and the alkoxysilyl group in the compound B is condensed with the compound D as the silane coupling agent, so that it is considered that the bonding between the respective compounds becomes firm, and the adhesion of the obtained cured film to the metal is further improved.
Further, it is preferable that the specific resin contains a radical polymerizable group.
When the specific resin has a radical polymerizable group, the curable resin composition preferably contains a photo radical polymerization initiator described later as a sensitizer, more preferably contains a photo radical polymerization initiator described later and contains a radical crosslinking agent described later as a sensitizer, and even more preferably contains a photo radical polymerization initiator described later and contains a radical crosslinking agent described later and contains a sensitizer described later as a sensitizer. For example, a negative photosensitive layer is formed from such a curable resin composition.
The specific resin may have a polar conversion group such as an acid-decomposable group.
When the specific resin has an acid-decomposable group, the curable resin composition preferably contains a photoacid generator described later as a photosensitive agent. Such a curable resin composition forms, for example, a chemically amplified positive photosensitive layer or negative photosensitive layer.
[ Polyimide precursor ]
The type of polyimide precursor used in the present invention is not particularly limited, but is preferably one containing a repeating unit represented by the following formula (2).
(2)
[ Chemical formula 3]
In the formula (2), a 1 and a 2 each independently represent an oxygen atom or NH, R 111 represents a 2-valent organic group, R 115 represents a 4-valent organic group, and R 113 and R 114 each independently represent a hydrogen atom or a 1-valent organic group.
Each of a 1 and a 2 in formula (2) independently represents an oxygen atom or NH, and is preferably an oxygen atom.
R 111 in the formula (2) represents a 2-valent organic group. Examples of the 2-valent organic group include a group containing a linear or branched aliphatic group, a cyclic aliphatic group, and an aromatic group, preferably a group composed of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination of these groups, and more preferably a group containing an aromatic group having 6 to 20 carbon atoms. As a particularly preferred embodiment of the present invention, a group represented by-Ar-L-Ar-can be exemplified. Wherein Ar is an aromatic group, L is a group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -or-NHCO-, or a combination of 2 or more of the foregoing. The preferred ranges of these are as described above.
R 111 is preferably derived from diamines. The diamine used for the production of the polyimide precursor includes linear or branched aliphatic, cyclic aliphatic or aromatic diamines, and the like. The diamine may be used in an amount of 1 or 2 or more.
Specifically, a diamine containing a group composed of a linear or branched aliphatic group having 2 to 20 carbon atoms, a cyclic aliphatic group having 6 to 20 carbon atoms, an aromatic group having 6 to 20 carbon atoms, or a combination of these groups is preferable, and a diamine containing a group composed of an aromatic group having 6 to 20 carbon atoms is more preferable. Examples of the aromatic group include the following.
[ Chemical formula 4]
In the formula, A is preferably a single bond or a group selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-, -SO 2 -, -NHCO-, or a combination of these, more preferably a single bond, a group selected from alkylene groups having 1 to 3 carbon atoms which may be substituted with a fluorine atom, -O-, -C (=O) -, -S-, or-SO 2 -, and still more preferably-CH 2-、-O-、-S-、-SO2-、-C(CF3)2 -or-C (CH 3)2 -.
Wherein, represents the bonding position with other structures.
Specific examples of the diamine include at least 1 diamine selected from the following: 1, 2-diaminoethane, 1, 2-diaminopropane, 1, 3-diaminopropane, 1, 4-diaminobutane and 1, 6-diaminohexane; 1, 2-or 1, 3-diaminocyclopentane, 1,2-, 1, 3-or 1, 4-diaminocyclohexane, 1,2-, 1, 3-or 1, 4-bis (aminomethyl) cyclohexane, bis- (4-aminocyclohexyl) methane, bis- (3-aminocyclohexyl) methane, 4 '-diamino-3, 3' -dimethylcyclohexylmethane, and isophorone diamine; m-p-phenylenediamine, diaminotoluene, 4' -or 3,3' -diaminobiphenyl, 4' -diaminodiphenyl ether, 3-diaminodiphenyl ether, 4' -and 3,3' -diaminodiphenylmethane, 4' -and 3,3' -diaminodiphenylsulfone, and 4,4' -and 3,3' -diaminodiphenyl sulfide, 4' -or 3,3' -diaminobenzophenone, 3' -dimethyl-4, 4' -diaminobiphenyl, 2' -dimethyl-4, 4' -diaminobiphenyl, 3' -dimethoxy-4, 4' -diaminobiphenyl, and 2, 2-bis (4-aminophenyl) propane, 2-bis (4-aminophenyl) hexafluoropropane, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane 2, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, bis (3-amino-4-hydroxyphenyl) sulfone, bis (4-amino-3-hydroxyphenyl) sulfone, 4' -diamino p-diphenyl, 4' -bis (4-aminophenoxy) biphenyl, bis [4- (4-aminophenoxy) phenyl ] sulfone, bis [4- (3-aminophenoxy) phenyl ] sulfone, bis [4- (2-aminophenoxy) phenyl ] sulfone, 1, 4-bis (4-aminophenoxy) benzene, 9, 10-bis (4-aminophenyl) anthracene, 3' -dimethyl-4, 4' -diaminodiphenyl sulfone, 1, 3-bis (4-aminophenoxy) benzene, 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenyl) benzene, 3' -diethyl-4, 4' -diaminodiphenyl methane 3,3' -dimethyl-4, 4' -diaminodiphenylmethane, 4' -diaminooctafluorobiphenyl, 2-bis [4- (4-aminophenoxy) phenyl ] propane, 2-bis [4- (4-aminophenoxy) phenyl ] hexafluoropropane, 9-bis (4-aminophenyl) -10-hydroanthracene, 3',4,4' -tetraminobiphenyl, 3', 4' -tetraminodiphenyl ether, 1, 4-diaminoanthraquinone, 1, 5-diaminoanthraquinone, 3-dihydroxy-4, 4' -diaminobiphenyl, 9' -bis (4-aminophenyl) fluorene, 4' -dimethyl-3, 3' -diaminodiphenyl sulfone, and, 3,3', 5' -tetramethyl-4, 4' -diaminodiphenylmethane, 2, 4-and 2, 5-diaminocumene, 2, 5-dimethyl-p-phenylenediamine, ethylguanazine, 2,3,5, 6-tetramethyl-p-phenylenediamine, 2,4, 6-trimethyl-m-phenylenediamine, bis (3-aminopropyl) tetramethyldisiloxane, 2, 7-diaminofluorene, 2, 5-diaminopyridine, 1, 2-bis (4-aminophenyl) ethane, diaminobenzanilide, esters of diaminobenzoic acid, 1, 5-diaminonaphthalene, diaminobenzole, 1, 3-bis (4-aminophenyl) hexafluoropropane, 1, 4-bis (4-aminophenyl) octafluorobutane, 1, 5-bis (4-aminophenyl) decafluoropentane, 1, 7-bis (4-aminophenyl) tetradecapetan, 2-bis [4- (3-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [4- (2-aminophenoxy) phenyl ] hexafluoropropane, 2-bis [ 2-aminophenoxy ] hexafluoropropane, 2, 4-bis [ 2, 5-diaminophenoxy ] hexafluoropropane, 2, 4-bis [ 2, 5-aminophenoxy ] hexafluoropropane, 2-bis [ 2, 4-aminophenoxy ] hexafluoropropane 4,4' -bis (4-amino-2-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-3-trifluoromethylphenoxy) biphenyl, 4' -bis (4-amino-2-trifluoromethylphenoxy) diphenylsulfone, 4' -bis (3-amino-5-trifluoromethylphenoxy) diphenylsulfone, 2-bis [4- (4-amino-3-trifluoromethylphenoxy) phenyl ] hexafluoropropane, 3',5,5' -tetramethyl-4, 4' -diaminobiphenyl, 4' -diamino-2, 2' -bis (trifluoromethyl) biphenyl, 2', 5', 6' -hexafluorotriazine, and 4,4' -diamino-p-tetracene.
Further, diamines (DA-1) to (DA-18) described in paragraphs 0030 to 0031 of International publication No. 2017/038598 are also preferable.
In addition, the following diamines can also be preferably used.
[ Chemical formula 5]
Further, diamines having 2 or more alkylene glycol units in the main chain as described in paragraphs 0032 to 0034 of International publication No. 2017/038598 may be preferably used.
From the viewpoint of flexibility of the obtained organic film, R 111 is preferably represented by-Ar-L-Ar-. Wherein Ar is an aromatic group, L is a group consisting of an aliphatic hydrocarbon group having 1 to 10 carbon atoms which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -or-NHCO-, or a combination of 2 or more of the foregoing. Ar is preferably a phenylene group which is preferably a phenylene group, L is preferably an aliphatic hydrocarbon group having 1 or 2 carbon atoms which may be substituted with a fluorine atom-O-, -CO-, -S-or-SO 2 -. The aliphatic hydrocarbon group herein is preferably an alkylene group.
From the viewpoint of the i-ray transmittance, R 111 is preferably a 2-valent organic group represented by the following formula (51) or formula (61). In particular, from the viewpoint of i-ray transmittance and availability, the organic group having a valence of 2 represented by formula (61) is more preferable.
(51)
[ Chemical formula 6]
In the formula (51), R 50～R57 is each independently a hydrogen atom, a fluorine atom or a 1-valent organic group, and at least 1 of R 50～R57 is a fluorine atom, a methyl group or a trifluoromethyl group.
Examples of the 1-valent organic group of R 50～R57 include an unsubstituted alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), a fluorinated alkyl group having 1 to 10 carbon atoms (preferably 1 to 6 carbon atoms), and the like.
[ Chemical formula 7]
In formula (61), R 58 and R 59 are each independently a fluorine atom or a trifluoromethyl group.
Examples of the diamine compound having the structure represented by the formula (51) or (61) include 2,2 '-dimethylbenzidine, 2' -bis (trifluoromethyl) -4,4 '-diaminobiphenyl, 2' -bis (fluoro) -4,4 '-diaminobiphenyl, and 4,4' -diaminooctafluorobiphenyl. These may be used in 1 kind or in combination of 2 or more kinds.
R 111 may have a structure containing a polymerizable group.
For example, R 111 may be a structure derived from a diamine compound having a polymerizable group.
The diamine compound having a polymerizable group is not particularly limited, and is preferably a compound having an aromatic ring structure, and more preferably a compound having a structure in which an amino group and a polymerizable group are directly bonded to the aromatic ring structure.
The polymerizable group is preferably a group containing an ethylenically unsaturated group, a cyclic ether group, a hydroxymethyl group, or an alkoxymethyl group, more preferably a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloyloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a hydroxymethyl group, or an alkoxymethyl group, and still more preferably a (meth) acryloyloxy group, a (meth) acrylamide group, an epoxy group, a hydroxymethyl group, or an alkoxymethyl group.
When R 111 is a structure containing a polymerizable group, R 111 is preferably a structure represented by the following formula (1-1).
[ Chemical formula 8]
In the formula (1-1), Y 1 represents an n+2-valent group containing an aromatic hydrocarbon group, P 1 represents a group containing a polymerizable group, n represents an integer of 1 or more, and each represents a bonding position to a nitrogen atom to which R 111 in the formula (2) is bonded.
-Y1-
In the formula (1-1), Y 1 represents an n+2-valent group containing an aromatic hydrocarbon group.
The aromatic hydrocarbon group in Y 1 is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, still more preferably a group in which 2 or more hydrogen atoms are removed from the benzene ring, and particularly preferably a group in which 3 or more hydrogen atoms are removed from the benzene ring.
In formula (1-1), the bonding positions of Y 1 to 2 of the bonding positions described in formula (1-1) are preferably aromatic hydrocarbon groups. That is, 2 of the groups described in formula (1-1) are preferably directly bonded to the aromatic hydrocarbon ring structure included in Y 1.
In formula (1-1), the bonding positions with P 1 in Y 1 are preferably aromatic hydrocarbon groups. That is, P 1 is preferably directly bonded to the aromatic hydrocarbon ring structure contained in Y 1.
Y 1 is preferably at least 1 structure selected from the structures represented by the following formulas (A2-1) to (A2-5), more preferably at least 1 structure selected from the structures represented by the above formulas (A2-1) to (A2-5).
[ Chemical formula 9]
In the formulas (A2-1) to (A2-5), R A211～RA214、RA221～RA224、RA231～RA238、RA241～RA248 and R A251～RA258 each independently represent a hydrogen atom, an alkyl group, a cyclic alkyl group, an alkoxy group, a hydroxyl group, a cyano group, a halogenated alkyl group, or a halogen atom, L A231 and L A241 each independently represent a single bond, a carbonyl group, a sulfonyl group, a saturated hydrocarbon group of valence 2, an unsaturated hydrocarbon group of valence 2, a heteroatom, a heterocyclic group, or a halogenated alkylene group, at least 1 of R A211～RA214, at least 1 of R A221～RA224, at least 1 of R A231～RA238, at least 1 of R A241～RA248, and at least 1 of R A251～RA258 may be a bonding position to P 1 in the formula (1-1), and each independently represent a bonding position to other structures.
Among these, from the viewpoint of solvent solubility, Y 1 preferably includes a structure represented by any of the formulae (A2-1) to (A2-4), and more preferably includes a structure represented by any of the formulae (A2-2) or (A2-4).
In the formulae (A2-1) to (A2-5), R A211～RA214、RA221～RA224、RA231～RA238、RA241～RA248 and R A251～RA258 do not include a bonding position to the carbonyl group in the formula (1-1), and at least 1 of R A211～RA214, at least 1 of R A221～RA224, at least 1 of R A231～RA238, at least 1 of R A241～RA248, and at least 1 of R A251～RA258 may be a bonding position to P 1 in the formula (1-1).
In the formula (A2-1), when R A211～RA214 is not a bond to P 1, R A211～RA214 is preferably independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms or a halogen atom, and more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a halogenated alkyl group having 1 to 3 carbon atoms, and even more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, from the viewpoint of solvent solubility.
Examples of the halogen atom or the halogen atom in the halogenated alkyl group in R A211～RA214 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and preferably a chlorine atom or a bromine atom.
In the formula (A2-2), R A221～RA224 has the same meaning as R A211～RA214 in the formula (A2-1), and the preferable mode is the same.
In the formula (A2-3), R A231～RA238 is preferably independently a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, a cyclic alkyl group having 3 to 12 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a hydroxyl group, a cyano group, a halogenated alkyl group having 1 to 3 carbon atoms or a halogen atom, and from the viewpoint of solvent solubility, it is more preferably a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms or a halogenated alkyl group having 1 to 3 carbon atoms, and it is more preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Examples of the halogen atom or the halogen atom in the halogenated alkyl group in R A231～RA238 include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like, and preferably a chlorine atom or a bromine atom.
In the formula (A2-3), L A231 is preferably a saturated hydrocarbon group having 2 carbon atoms and 1 to 6 carbon atoms, an unsaturated hydrocarbon group having 2 carbon atoms and 5 to 24 carbon atoms, -O-, -S-, -NR N, a heterocyclic group or a halogenated alkylene group having 1 to 6 carbon atoms, more preferably a saturated hydrocarbon group having 1 to 6 carbon atoms, -O-or heterocyclic group, and still more preferably a single bond or-O-.
R N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, further preferably an alkyl group or an aryl group, and particularly preferably a hydrogen atom.
The 2-valent unsaturated hydrocarbon group may be a 2-valent aliphatic unsaturated hydrocarbon group, or may be a 2-valent aromatic hydrocarbon group, and is preferably a 2-valent aromatic hydrocarbon group.
The heterocyclic group is preferably a group in which 2 hydrogen atoms are removed from an aliphatic or aromatic heterocyclic ring, more preferably a group in which 2 hydrogen atoms are removed from a ring structure such as a pyrrolidine ring, tetrahydrofuran ring, tetrahydrothiophene ring, pyrrole ring, furan ring, thiophene ring, piperidine ring, tetrahydropyran, pyridine ring, morpholine ring, or the like. These heterocycles may in turn form fused rings with other heterocycles or hydrocarbon rings.
The number of ring members of the above-mentioned heterocycle is preferably 5 to 10, more preferably 5 or 6.
The hetero atom in the heterocyclic group is preferably an oxygen atom, a nitrogen atom or a sulfur atom.
Examples of the halogen atom in the halogenated alkylene group include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom or a bromine atom is preferable.
In the formula (A2-4), R A241～RA248、LA241 has the same meaning as R A231～RA238、LA231 in the formula (A2-3), and the preferable mode is the same.
In the formula (A2-5), R A251～RA258 has the same meaning as R A211～RA214 in the formula (A2-1), and the preferable mode is the same.
In the formula (A2-1), at least 1 of R A211～RA214 is preferably a bond site to P 1 in the formula (1-1), more preferably 1 of R A211～RA214 is a bond site to P 1, and still more preferably R A213 is a bond site to P 1.
In the formula (A2-2), at least 1 of R A221～RA224 is preferably a bond site to P 1 in the formula (1-1), more preferably 1 of R A221～RA224 is a bond site to P 1, and still more preferably R A223 is a bond site to P 1.
In the formula (A2-3), at least 1 of R A231～RA238 is preferably a bond site to P 1 in the formula (1-1), more preferably 2 of R A231～RA238 is a bond site to P 1, still more preferably a total of 2 of 1 of R A231～RA234 and 1 of R A235～RA238 is a bond site to P 1, and particularly preferably 2 of R A231 and R A238 are bond sites to P 1.
In the formula (A2-4), at least 1 of R A241～RA248 is preferably a bond site to P 1 in the formula (1-1), more preferably 2 of R A241～RA248 is a bond site to P 1, still more preferably a total of 2 of 1 of R A241～RA244 and 1 of R A245～RA248 is a bond site to P 1, and particularly preferably 2 of R A241 and R A248 are bond sites to P 1.
In the formula (A2-5), at least 1 of R A251～RA258 is preferably a bond site to P 1 in the formula (1-1), more preferably 2 of R A251～RA258 is a bond site to P 1, still more preferably a total of 2 of 1 of R A251～RA254 and 1 of R A255～RA258 is a bond site to P 1, and particularly preferably 2 of R A253 and R A257 are bond sites to P 1.
In the formulae (A2-1) to (A2-5), preferably 2 are each in the formula (1-1). That is, the 2 nitrogen atoms to which R 111 in formula (2) are bonded are preferably directly bonded to the positions represented by 2 x in formulae (A2-1) to (A2-5).
Among these, Y 1 is preferably a group represented by the following formula (Y-1) or (Y-2).
[ Chemical formula 10]
In the formula (Y-1), R Y11、RY12、RY13 has the same meaning as R A211、RA212 and R A214 in the formula (A2-1), and the preferable mode is the same.
In the formula (Y-2), R Y21～RY26 has the same meaning as R A2A2～RA247 in the formula (A2-4), and the preferable mode is the same.
In the formula (Y-1) or the formula (Y-2), each represents a bonding position to 2 nitrogen atoms bonded to R 111 in the formula (2), and each# represents a bonding position to P 1 in the formula (1-1).
-P1-
In the formula (1-1), P 1 represents a group containing a polymerizable group.
The polymerizable group is preferably a group containing an ethylenically unsaturated group, a cyclic ether group, a hydroxymethyl group, or an alkoxymethyl group, more preferably a vinyl group, a (meth) allyl group, a (meth) acrylamide group, a (meth) acryloyloxy group, a maleimide group, a vinylphenyl group, an epoxy group, an oxetanyl group, a hydroxymethyl group, or an alkoxymethyl group, and still more preferably a (meth) acryloyloxy group, a (meth) acrylamide group, an epoxy group, a hydroxymethyl group, or an alkoxymethyl group.
The number of polymerizable groups contained in P 1 is 1 or more, preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 5, particularly preferably 1 or 2, and most preferably 1.
Further, P 1 is preferably a group represented by the following formula (P-1).
[ Chemical formula 11]
In the formula (P-1), L 1 represents a single bond or a linking group with a valence of m+1, A 2 represents a polymerizable group, m represents an integer of 1 or more, and represents a bonding position with Y 1.
In the formula (P-1), L 1 is preferably a single bond or a hydrocarbon group, an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N -, or these groups bonded to 2 or more, more preferably a single bond or a hydrocarbon group, an ether bond, a carbonyl group, -NR N, or these groups bonded to 2 or more.
R N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, further preferably an alkyl group or an aryl group, and particularly preferably a hydrogen atom.
The hydrocarbon group in the above-mentioned L 1 is preferably a saturated aliphatic hydrocarbon group having 1 to 30 carbon atoms, an aromatic hydrocarbon group having 6 to 30 carbon atoms, or a group represented by a combination of these, more preferably a saturated aliphatic hydrocarbon group having 1 to 10 carbon atoms, a group in which 2 or more hydrogen atoms are removed from the benzene ring, or a group represented by a bond of these.
In the formula (P-1), A 2 is preferably vinyl, (meth) allyl, (meth) acrylamido, (meth) acryloyloxy, maleimido, vinylphenyl, epoxy, oxetanyl, hydroxymethyl or alkoxymethyl, more preferably (meth) acryloyloxy, (meth) acrylamido, epoxy, hydroxymethyl or alkoxymethyl.
In the formula (P-1), m is preferably an integer of 1 to 15, more preferably an integer of 1 to 10, further preferably an integer of 1 to 5, particularly preferably 1 or 2, and most preferably 1.
Further, P 1 is preferably a group represented by the following formula (P-2) or formula (P-3).
[ Chemical formula 12]
*—A2(P-2)*—Z1—L2—A2(P-3)
In the formula (P-2), a 2 represents a polymerizable group, and represents a bonding position to Y 1.
In the formula (P-2), A 2 has the same meaning as A 2 in the formula (P-1), and the preferable mode is the same.
In the formula (P-3), A 2 represents a polymerizable group, L 2 represents a hydrocarbon group or a hydrocarbon group and an ether bond, a carbonyl group, a thioether bond, a sulfonyl group, -NR N, or a combination of these groups, Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond or a carbonate bond, and represents a bond position to Y 1. R N is as described above.
In the formula (P-3), A 2 has the same meaning as A 2 in the formula (P-1), and the preferable mode is the same.
In the formula (P-3), L 2 is preferably a hydrocarbon group, (poly) alkyleneoxy group or a group represented by these combinations. The hydrocarbon group is preferably an alkylene group, a 2-valent aromatic hydrocarbon group, or a group represented by a combination of these, and more preferably an alkylene group.
In the present specification, (poly) alkyleneoxy means alkyleneoxy or polyalkyleneoxy. In the present invention, the polyalkoxylene group means a group in which an alkyleneoxy group is directly bonded to 2 or more groups. The alkylene groups in the plurality of alkylene groups included in the polyalkylene oxide group may be the same or different. When the polyalkylene oxide group contains a plurality of alkylene oxide groups having different alkylene groups, the alkylene oxide groups in the polyalkylene oxide group may be arranged randomly, may have a block or may have an alternating pattern.
The alkylene group is preferably an alkylene group having 1 to 30 carbon atoms, more preferably an alkylene group having 1 to 20 carbon atoms, and still more preferably an alkylene group having 1 to 10 carbon atoms.
The aromatic hydrocarbon group is preferably an aromatic hydrocarbon group having 6 to 30 carbon atoms, more preferably an aromatic hydrocarbon group having 6 to 20 carbon atoms, still more preferably a phenylene group or a naphthylene group, and particularly preferably a phenylene group.
The alkylene group in the (poly) alkyleneoxy group is preferably an alkylene group having 2 to 10 carbon atoms, more preferably an alkylene group having 2 to 4 carbon atoms, still more preferably an ethylene group or a propylene group, and still more preferably an ethylene group.
The number of alkyleneoxy groups contained in the polyalkyleneoxy group (the number of repeating polyalkyleneoxy groups) is preferably 2 to 20, more preferably 2 to 10, still more preferably 2 to 5, and particularly preferably 2 to 4.
In the formula (P-3), Z 1 represents an ether bond, an ester bond, a urethane bond, a urea bond, an amide bond or a carbonate bond, more preferably an ester bond, a urethane bond, a urea bond or an amide bond.
In the present invention, when simply described as "ester bond", "urethane bond", "amide bond" or the like, the direction of these bonds is not limited. For example, when Z 1 is an ester bond, the bonding position to L 2 in Z 1 may be a carbon atom or an oxygen atom in the ester bond.
R 115 in the formula (2) represents a 4-valent organic group. The organic group having a valence of 4 is preferably an organic group having a valence of 4 including an aromatic ring, and more preferably a group represented by the following formula (5) or formula (6).
In the formula (5) or the formula (6), each independently represents a bonding position to another structure.
[ Chemical formula 13]
In the formula (5), R 112 is preferably a single bond or a group selected from aliphatic hydrocarbon groups having 1 to 10 carbon atoms, which may be substituted with a fluorine atom, -O-, -CO-, -S-, -SO 2 -and-NHCO-, and combinations thereof, more preferably a single bond, a group selected from alkylene groups having 1 to 3 carbon atoms, which may be substituted with a fluorine atom, -O-, -CO-, -S-and-SO 2 -, and still more preferably a group having a valence of 2 selected from-CH 2-、-C(CF3)2-、-C(CH3)2 -, -O-, -CO-, -S-and-SO 2 -.
Specifically, R 115 is a tetracarboxylic acid residue remaining after the acid anhydride group is removed from the tetracarboxylic dianhydride. The tetracarboxylic dianhydride may be used in an amount of 1 or 2 or more.
The tetracarboxylic dianhydride is preferably represented by the following formula (O).
[ Chemical formula 14]
In the formula (O), R 115 represents a 4-valent organic group. The preferable range of R 115 is the same as that of R 115 in the formula (2), and the preferable range is also the same.
Specific examples of the tetracarboxylic dianhydride include pyromellitic dianhydride (PMDA), 3',4' -biphenyl tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfide tetracarboxylic dianhydride, 3',4,4' -diphenyl sulfone tetracarboxylic dianhydride, 3',4' -benzophenone tetracarboxylic dianhydride, 4' -oxydiphthalic dianhydride, 2,3,6, 7-naphthalene tetracarboxylic dianhydride, 1,4,5, 7-naphthalene tetracarboxylic dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, and 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) hexafluoropropane dianhydride, 1, 3-diphenylhexafluoropropane-3, 4-tetracarboxylic dianhydride, 1,4,5, 6-naphthalene tetracarboxylic dianhydride, 2',3,3' -diphenyltetracarboxylic dianhydride, 3,4,9, 10-perylene tetracarboxylic dianhydride, 1,2,4, 5-naphthalene tetracarboxylic dianhydride, 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 1,8,9, 10-phenanthrene tetracarboxylic dianhydride, 1-bis (2, 3-dicarboxyphenyl) ethane dianhydride, 1-bis (3, 4-dicarboxyphenyl) ethane dianhydride, 1,2,3, 4-benzene tetracarboxylic dianhydride, and alkyl groups having 1 to 6 carbon atoms and alkyl derivatives having 1 to 6 carbon atoms.
Further, as preferable examples, tetracarboxylic dianhydrides (DAA-1) to (DAA-5) described in paragraph 0038 of International publication No. 2017/038598 can be cited.
It is also preferred that at least one of R 111 and R 115 has an OH group. More specifically, R 111 is a residue of a bisaminophenol derivative.
R 113 and R 114 each independently represent a hydrogen atom or a 1-valent organic group, and preferably at least one of R 113 and R 114 contains a polymerizable group, and more preferably both contain a polymerizable group. The polymerizable group is a group that can undergo a crosslinking reaction by the action of heat, radicals, or the like, and is preferably a radical polymerizable group. Specific examples of the polymerizable group in the specific resin include a group having an ethylenically unsaturated bond, an alkoxymethyl group, a hydroxymethyl group, an acyloxymethyl group, an epoxy group, an oxetanyl group, a benzoxazolyl group, a blocked isocyanate group, a hydroxymethyl group, and an amino group. The radical polymerizable group of the polyimide precursor or the like is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a vinyl group, (meth) allyl group, a group represented by the following formula (III), and the like, and the group represented by the following formula (III) is preferable.
[ Chemical formula 15]
In the formula (III), R 200 preferably represents a hydrogen atom or a methyl group, a hydrogen atom.
In formula (III), the bonding position to other structures is represented.
In the formula (III), R 201 represents an alkylene group having 2 to 12 carbon atoms, -CH 2CH(OH)CH2 -, or a polyalkoxy group.
Examples of preferred R 201 groups include ethylene, propylene, trimethylene, tetramethylene, 1, 2-butanediyl, 1, 3-butanediyl, pentamethylene, hexamethylene, octamethylene, dodecamethylene, -CH 2CH(OH)CH2 -, and polyalkoxy groups, more preferably ethylene, propylene, trimethylene, -CH 2CH(OH)CH2 -, and still more preferably polyalkoxy groups.
In the present invention, the polyalkoxylene group means a group to which 2 or more alkyleneoxy groups are directly bonded. The alkylene groups in the plurality of alkylene groups included in the polyalkylene oxide group may be the same or different.
When the polyalkylene oxide group contains a plurality of alkylene oxide groups having different alkylene groups, the alkylene oxide groups in the polyalkylene oxide group may be arranged randomly, may have a block or may have an alternating pattern.
The number of carbon atoms of the alkylene group (including the number of carbon atoms of the substituent in the case where the alkylene group has a substituent) is preferably 2 or more, more preferably 2 to 10, still more preferably 2 to 6, still more preferably 2 to 5, still more preferably 2 to 4, particularly preferably 2 or 3, and most preferably 2.
The alkylene group may have a substituent. Preferred substituents include alkyl groups, aryl groups, halogen atoms, and the like.
The number of alkyleneoxy groups (the number of repeating polyalkyleneoxy groups) contained in the polyalkyleneoxy group is preferably 2 to 20, more preferably 2 to 10, and still more preferably 2 to 6.
The polyalkylene group is preferably a polyethylene oxide group, a polypropylene oxide group, a polytrimethylene oxide group, a polytetramethylene oxide group, or a group formed by bonding a plurality of ethylene oxide groups and a plurality of propylene oxide groups, more preferably a polyethylene oxide group or a polypropylene oxide group, and still more preferably a polyethylene oxide group, from the viewpoints of solvent solubility and solvent resistance. The ethyleneoxy groups and propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. The preferable mode of repeating the number of ethyleneoxy groups and the like in these groups is as described above.
R 113 and R 114 are each independently a hydrogen atom or a 1-valent organic group. Examples of the 1-valent organic group include an aromatic group having an acidic group bonded to 1, 2 or 3 carbons constituting an aryl group, and an aralkyl group. Specifically, examples thereof include an aromatic group having 6 to 20 carbon atoms and an aralkyl group having 7 to 25 carbon atoms. More specifically, a phenyl group having an acidic group and a benzyl group having an acidic group are exemplified. The acidic groups are preferably OH groups.
R 113 or R 114 is also more preferably a hydrogen atom, a 2-hydroxybenzyl group, a 3-hydroxybenzyl group or a 4-hydroxybenzyl group.
From the viewpoint of solubility to an organic solvent, R 113 or R 114 is preferably a 1-valent organic group. The organic group having a valence of 1 is preferably an alkyl group containing a linear or branched alkyl group, a cyclic alkyl group, or an aromatic group, and more preferably an alkyl group substituted with an aromatic group.
The number of carbon atoms of the alkyl group is preferably 1 to 30. The alkyl group may be any of linear, branched, and cyclic. As the straight-chain or branched-chain alkyl group, examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, tetradecyl, octadecyl, isopropyl, isobutyl, sec-butyl, tert-butyl, 1-ethylpentyl, 2-ethylhexyl, 2- (2- (2-methoxyethoxy) ethoxy, 2- (2-ethoxyethoxy) ethoxy, 2- (2- (2-methoxyethoxy) ethoxy and 2- (2- (2- (2-ethoxyethoxy) ethoxy. The cyclic alkyl group may be a monocyclic cyclic alkyl group or a polycyclic cyclic alkyl group. Examples of the monocyclic cyclic alkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Examples of the polycyclic cyclic alkyl group include adamantyl, norbornyl, bornyl, camphene, decalin, tricyclodecyl, tetracyclodecyl, camphoric acyl, dicyclohexyl and apple alkenyl groups. Among them, cyclohexyl is most preferable from the viewpoint of both high sensitivity and high sensitivity. The alkyl group substituted with an aromatic group is preferably a linear alkyl group substituted with an aromatic group described later.
As the aromatic group, specifically, a substituted or unsubstituted benzene ring, naphthalene ring, pentalene ring, indene ring, azulene ring, heptene ring, indene ring, perylene ring, fused pentacene ring, acenaphthylene ring, phenanthrene ring, anthracene ring, fused tetracene ring,A ring, a polytrimethylene ring, a fluorene ring, a biphenyl ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, an indolizine ring, an indole ring, a benzofuran ring, a benzothiophene ring, an isobenzofuran ring, a quinolizine ring, a quinoline ring, a phthalazine ring, a naphthyridine ring, a quinoxaline ring, an isoquinoline ring, a carbazole ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromene ring, a xanthene ring, a phenoxathiazine ring, a phenothiazine ring, or a phenazine ring. Most preferably a benzene ring.
In the formula (2), when R 113 is a hydrogen atom or when R 114 is a hydrogen atom, the polyimide precursor may form a counter salt with a tertiary amine compound having an ethylenically unsaturated bond. Examples of such tertiary amine compounds having an ethylenically unsaturated bond include N, N-dimethylaminopropyl methacrylate.
At least one of R 113 and R 114 may be a polar group such as an acid-decomposable group. The acid-decomposable group is not particularly limited as long as it is a group that decomposes under the action of an acid to generate an alkali-soluble group such as a phenolic hydroxyl group or a carboxyl group, but is preferably an acetal group, a ketal group, a silyl ether group, a tertiary alkyl ester group, or the like, and more preferably an acetal group from the viewpoint of exposure sensitivity.
Specific examples of the acid-decomposable group include t-butoxycarbonyl, isopropoxycarbonyl, tetrahydropyranyl, tetrahydrofuranyl, ethoxyethyl, methoxyethyl, ethoxymethyl, trimethylsilyl, t-butoxycarbonylmethyl, and trimethylsilylether groups. From the viewpoint of exposure sensitivity, ethoxyethyl or tetrahydrofuranyl is preferable.
The polyimide precursor preferably has a fluorine atom in a structural unit. The fluorine atom content in the polyimide precursor is preferably 10 mass% or more, and preferably 20 mass% or less.
In order to improve adhesion to the substrate, the polyimide precursor may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.
The repeating unit represented by the formula (2) is preferably a repeating unit represented by the formula (2-A). That is, at least 1 of the polyimide precursor and the like used in the present invention is preferably a precursor having a repeating unit represented by the formula (2-a). With such a configuration, the width of the exposure latitude can be further increased.
(2-A)
[ Chemical formula 16]
In the formula (2-A), it is preferable that A 1 and A 2 represent an oxygen atom, R 111 and R 112 each independently represent a 2-valent organic group, R 113 and R 114 each independently represent a hydrogen atom or a 1-valent organic group, at least one of R 113 and R 114 is a group containing a polymerizable group, and both are polymerizable groups.
A 1、A2、R111、R113 and R 114 are each independently the same as those of A 1、A2、R111、R113 and R 114 in the formula (2), and the preferable ranges are also the same.
R 112 has the same meaning as R 112 in formula (5), and the preferable range is also the same.
The polyimide precursor may contain 1 type of the repeating structural unit represented by the formula (2), or may contain 2 or more types. The structural isomer of the repeating unit represented by formula (2) may be contained. The polyimide precursor may contain a repeating structural unit of another kind in addition to the repeating unit of the above formula (2).
As an embodiment of the polyimide precursor in the present invention, a polyimide precursor in which 50 mol% or more, further 70 mol% or more, and particularly 90 mol% or more of all the repeating units are the repeating units represented by the formula (2) can be exemplified.
The weight average molecular weight (Mw) of the polyimide precursor is preferably 18,000 ～ 30,000, more preferably 20,000 ～ 27,000, and further preferably 22,000 ～ 25,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The molecular weight of the polyimide precursor is preferably 2.5 or more, more preferably 2.7 or more, and even more preferably 2.8 or more. The upper limit of the molecular weight dispersity of the polyimide precursor is not particularly limited, and is, for example, preferably 4.5 or less, more preferably 4.0 or less, further preferably 3.8 or less, further preferably 3.2 or less, further preferably 3.1 or less, further preferably 3.0 or less, and particularly preferably 2.95 or less.
In the present specification, the dispersity of the molecular weight is a value calculated using the weight average molecular weight/number average molecular weight.
[ Polyimide ]
The polyimide used in the present invention may be an alkali-soluble polyimide or a polyimide which is soluble in a developer mainly composed of an organic solvent.
In the present specification, the alkali-soluble polyimide means a polyimide in which 0.1g or more, preferably 0.5g or more, more preferably 1.0g or more, of the polyimide is dissolved in 100g of a 2.38 mass% aqueous tetramethylammonium solution at 23 ℃. The upper limit of the amount of dissolution is not particularly limited, but is preferably 100g or less.
Further, from the viewpoints of film strength and insulation properties of the obtained organic film, the polyimide is preferably a polyimide having a plurality of imide structures in the main chain.
In the present specification, "main chain" means a relatively longest bonding chain among molecules of a polymer compound constituting a resin, and "side chain" means other bonding chains.
Fluorine atom-
From the viewpoint of film strength of the obtained organic film, the polyimide preferably has fluorine atoms.
The fluorine atom is preferably R 132 in the repeating unit represented by the formula (4) described below or R 131 in the repeating unit represented by the formula (4) described below, and more preferably R 132 in the repeating unit represented by the formula (4) described below or R 131 in the repeating unit represented by the formula (4) described below as a fluorinated alkyl group.
The amount of fluorine atoms is preferably 1 to 50mol/g, more preferably 5 to 30mol/g, relative to the total mass of the polyimide.
Silicon atom-
From the viewpoint of film strength of the obtained organic film, the polyimide preferably has a silicon atom.
The silicon atom is preferably contained in R 131 in the repeating unit represented by the following formula (4), and more preferably contained in R 131 in the repeating unit represented by the following formula (4) as an organic modified (poly) siloxane structure described below.
The silicon atom or the organic modified (poly) siloxane structure may be contained in a side chain of the polyimide, but is preferably contained in a main chain of the polyimide.
The amount of silicon atoms is preferably 0.01 to 5mol/g, more preferably 0.05 to 1mol/g, relative to the total mass of the polyimide.
Ethylenic unsaturation
From the viewpoint of the film strength of the obtained organic film, polyimide is preferably one having an ethylenically unsaturated bond.
The polyimide may have an ethylenically unsaturated bond at the terminal of the main chain or may have an ethylenically unsaturated bond in the side chain, but preferably has an ethylenically unsaturated bond in the side chain.
The ethylenically unsaturated bond is preferably a radical polymerizable group.
The ethylenically unsaturated bond is preferably R 132 in the repeating unit represented by the following formula (4) or R 131 in the repeating unit represented by the following formula (4), and more preferably R 132 in the repeating unit represented by the following formula (4) or R 131 in the repeating unit represented by the following formula (4) is contained as a group having an ethylenically unsaturated bond.
Among these, the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by the following formula (4), and more preferably contained in R 131 in the repeating unit represented by the following formula (4) as a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted by direct bonding to an aromatic ring, such as a vinyl group, an allyl group, and a vinylphenyl group, (meth) acryl, (meth) acryloyloxy, and a group represented by the following formula (IV).
[ Chemical formula 17]
In the formula (IV), R 20 represents a hydrogen atom or a methyl group, preferably a methyl group.
In the formula (IV), R 21 represents an alkylene group having 2 to 12 carbon atoms, -O-CH 2CH(OH)CH2 -, -C (=O) O-, -O (C=O) NH-, a (poly) alkyleneoxy group having 2 to 30 carbon atoms (the alkylene group has preferably 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, particularly preferably 2 or 3 carbon atoms, and the repetition number is preferably 1 to 12, more preferably 1 to 6 carbon atoms, particularly preferably 1 to 3 carbon atoms) or a group obtained by combining 2 or more of these carbon atoms.
Among these, R 21 is preferably a group represented by any one of the following formulas (R1) to (R3), more preferably a group represented by formula (R1).
[ Chemical formula 18]
In the formulae (R1) to (R3), L represents a single bond, an alkylene group having 2 to 12 carbon atoms, a (poly) alkyleneoxy group having 2 to 30 carbon atoms, or a group obtained by bonding 2 or more of these groups, X represents an oxygen atom or a sulfur atom, X represents a bonding position to another structure, and ∈ is a bonding position to an oxygen atom bonded to R 201 in the formula (III).
In the formulae (R1) to (R3), the preferred mode of the alkylene group having 2 to 12 carbon atoms or the (poly) alkylene group having 2 to 30 carbon atoms in L is the same as the preferred mode of the alkylene group having 2 to 12 carbon atoms or the (poly) alkylene group having 2 to 30 carbon atoms in R 21 described above.
In the formula (R1), X is preferably an oxygen atom.
In the formulae (R1) to (R3), the meanings are the same as those in the formula (IV), and the preferable modes are also the same.
The structure represented by the formula (R1) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having an isocyanate group and an ethylenically unsaturated bond (for example, 2-isocyanatoethyl methacrylate or the like).
The structure represented by the formula (R2) is obtained, for example, by reacting a polyimide having a carboxyl group with a compound having a hydroxyl group and an ethylenically unsaturated bond (for example, 2-hydroxyethyl methacrylate or the like).
The structure represented by the formula (R3) is obtained, for example, by reacting a polyimide having a hydroxyl group such as a phenolic hydroxyl group with a compound having a glycidyl group and an ethylenically unsaturated bond (for example, glycidyl methacrylate or the like).
The polyalkylene group is preferably a polyethylene oxide group, a polypropylene oxide group, a polytrimethylene oxide group, a polytetramethylene oxide group, or a group formed by bonding a plurality of ethylene oxide groups and a plurality of propylene oxide groups, more preferably a polyethylene oxide group or a polypropylene oxide group, and still more preferably a polyethylene oxide group, from the viewpoints of solvent solubility and solvent resistance. The ethyleneoxy groups and propyleneoxy groups may be arranged randomly, may be arranged in blocks, or may be arranged in an alternating pattern. The preferable mode of repeating the number of ethyleneoxy groups and the like in these groups is as described above.
In formula (IV), the bonding position to other structure is preferably a bonding position to the main chain of polyimide.
The amount of the ethylenic unsaturated bond is preferably 0.05 to 10mol/g, more preferably 0.1 to 5mol/g, relative to the total mass of the polyimide.
Further, from the viewpoint of the productivity, the amount of the ethylenic unsaturated bond is preferably 0.0001 to 0.1mol/g, more preferably 0.0005 to 0.05mol/g, relative to the total mass of the polyimide.
Crosslinkable groups other than ethylenically unsaturated bonds
The polyimide may have a crosslinkable group other than an ethylenically unsaturated bond.
Examples of the crosslinkable group other than the ethylenically unsaturated bond include a cyclic ether group such as an epoxy group and an oxetanyl group, an alkoxymethyl group such as a methoxymethyl group, and a hydroxymethyl group.
The crosslinkable group other than the ethylenically unsaturated bond is preferably contained in R 131 in the repeating unit represented by formula (4) described later, for example.
The amount of the crosslinkable group other than the ethylenic unsaturated bond is preferably 0.05 to 10mol/g, more preferably 0.1 to 5mol/g, relative to the total mass of the polyimide.
The amount of the crosslinkable group other than the ethylenic unsaturated bond is preferably 0.0001 to 0.1mol/g, more preferably 0.001 to 0.05mol/g, based on the total mass of the polyimide, from the viewpoint of the productivity.
Polarity-switching group-
The polyimide may have a polar conversion group such as an acid-decomposable group. The acid-decomposable groups in the polyimide are the same as those described for R 113 and R 114 in the above formula (2), and the preferable modes are also the same.
Acid number-
When the polyimide is subjected to alkali development, the acid value of the polyimide is preferably 30mgKOH/g or more, more preferably 50mgKOH/g or more, and still more preferably 70mgKOH/g or more, from the viewpoint of improving the developability.
The acid value is preferably 500mgKOH/g or less, more preferably 400mgKOH/g or less, and still more preferably 200mgKOH/g or less.
When the polyimide is subjected to development using a developer containing an organic solvent as a main component (for example, the "solvent development" described later), the acid value of the polyimide is preferably 2 to 35mgKOH/g, more preferably 3 to 30mgKOH/g, and still more preferably 5 to 20mgKOH/g.
The acid value is measured by a known method, for example, by JIS K0070: the measurement was performed by the method described in 1992.
Further, as the acid group contained in the polyimide, an acid group having a pKa of 0 to 10 is preferable, and an acid group having a pKa of 3 to 8 is more preferable, from the viewpoint of both storage stability and developability.
PKa refers to the equilibrium constant Ka expressed as its negative common logarithmic pKa, taking into account the dissociation reaction of hydrogen ions released from the acid. In the present specification, unless otherwise specified, pKa is a calculated value based on ACD/ChemSketch (registered trademark). Alternatively, reference may be made to the values described in "change 5 th edition of the chemical handbook" by the Japanese chemical society.
In the case where the acid group is a polybasic acid such as phosphoric acid, the pKa is a first dissociation constant.
As such an acid group, the polyimide preferably contains at least 1 selected from a carboxyl group and a phenolic hydroxyl group, and more preferably contains a phenolic hydroxyl group.
Phenolic hydroxyl radical-
From the viewpoint of making the development rate of the alkali developer appropriate, the polyimide preferably has a phenolic hydroxyl group.
The polyimide may have a phenolic hydroxyl group at a terminal of the main chain or may have a phenolic hydroxyl group in a side chain.
The phenolic hydroxyl group is preferably contained in R 132 in the repeating unit represented by the formula (4) described below or R 131 in the repeating unit represented by the formula (4) described below, for example.
The amount of the phenolic hydroxyl groups is preferably 0.1 to 30mol/g, more preferably 1 to 20mol/g, relative to the total mass of the polyimide.
The polyimide used in the present invention is not particularly limited as long as it is a polymer compound having an imide ring, but is preferably a compound containing a repeating unit represented by the following formula (4), more preferably a compound containing a repeating unit represented by the formula (4) and having a polymerizable group.
(4)
[ Chemical formula 19]
In formula (4), R 131 represents a 2-valent organic group, and R 132 represents a 4-valent organic group.
When the polymerizable group is present, the polymerizable group may be located at least one of R 131 and R 132, as shown in the following formula (4-1) or formula (4-2), or may be located at the terminal of the polyimide.
(4-1)
[ Chemical formula 20]
In the formula (4-1), R 133 is a polymerizable group, and the other groups have the same meaning as in the formula (4).
(4-2)
[ Chemical formula 21]
At least one of R 134 and R 135 is a polymerizable group, and when not a polymerizable group, it is an organic group, and the other groups have the same meaning as in formula (4).
The polymerizable group is the same as the polymerizable group described for the polymerizable group contained in the polyimide precursor and the like.
R 131 represents a 2-valent organic group. The organic group having a valence of 2 may be exemplified by the same group as R 111 in the formula (2), and the preferable range is also the same.
R 131 is a diamine residue remaining after removal of the amino group of the diamine. Examples of the diamine include aliphatic, cyclic aliphatic and aromatic diamines. Specific examples thereof include R 111 in formula (2) of the polyimide precursor.
From the viewpoint of more effectively suppressing warpage upon calcination, R 131 is preferably a diamine residue having at least 2 alkylene glycol units in the main chain. More preferably, the diamine residues containing 2 or more ethylene glycol chains, propylene glycol chains, or both in total in 1 molecule, and still more preferably, the diamine residues containing no aromatic ring are used.
Examples of diamines containing 2 or more ethylene glycol chains, propylene glycol chains, or both in total in 1 molecule include JEFFAMINE (registered trademark) KH-511, ED-600, ED-900, ED-2003, EDR-148, EDR-176, D-200, D-400, D-2000, D-4000 (trade name is given above, manufactured by HUNTSMAN Co., ltd.), 1- (2- (2-aminopropoxy) ethoxy) propoxy) propan-2-amine, 1- (1- (1- (2-aminopropoxy) propan-2-yl) oxy) propan-2-amine, and the like, but are not limited thereto.
R 132 represents a 4-valent organic group. As the organic group having a valence of 4, the same organic group as R 115 in the formula (2) can be exemplified, and the preferable range is also the same.
For example, 4 linkers of 4-valent organic groups exemplified as R 115 are bonded to 4-C (=o) -moieties in the above formula (4) to form a condensed ring.
R 132 is a tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride. Specific examples thereof include R 115 in formula (2) of the polyimide precursor. From the viewpoint of the strength of the organic film, R 132 is preferably an aromatic diamine residue having 1 to 4 aromatic rings.
It is also preferable to have an OH group in at least one of R 131 and R 132. More specifically, preferable examples of R 131 include 2, 2-bis (3-hydroxy-4-aminophenyl) propane, 2-bis (3-hydroxy-4-aminophenyl) hexafluoropropane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, and the above-mentioned (DA-1) to (DA-18), and more preferable examples of R 132 include the above-mentioned (DAA-1) to (DAA-5).
The polyimide also preferably has a fluorine atom in a structural unit. The content of fluorine atoms in the polyimide is preferably 10 mass% or more, and preferably 20 mass% or less.
In order to improve adhesion to a substrate, polyimide may be copolymerized with an aliphatic group having a siloxane structure. Specifically, examples of the diamine component include bis (3-aminopropyl) tetramethyldisiloxane, bis (p-aminophenyl) octamethylpentasiloxane, and the like.
In order to improve the storage stability of the composition, it is preferable to seal the main chain end of the polyimide with a blocking agent such as monoamine, acid anhydride, monocarboxylic acid, monoacylchloride compound, or monoacylester compound. Among these, monoamines are more preferably used, and preferable examples of monoamines include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-hydroxy-5-aminophenol, 3-aminophenol, and thiophenol. These may be used in an amount of 2 or more, or a plurality of different terminal groups may be introduced by reacting a plurality of kinds of terminal groups.
Imidization ratio (ring closure ratio)
The imidization ratio (also referred to as "ring closure ratio") of the polyimide is preferably 70% or more, more preferably 80% or more, and still more preferably 90% or more, from the viewpoints of film strength, insulation, and the like of the obtained organic film.
The upper limit of the imidization ratio is not particularly limited as long as it is 100% or less.
The imidization ratio is measured, for example, by the following method.
The infrared absorption spectrum of polyimide was measured to obtain peak intensity P1 around 1377cm -1 as an absorption peak derived from the imide structure. Then, after heat-treating the polyimide at 350℃for 1 hour, the infrared absorption spectrum was measured again to obtain the peak intensity P2 in the vicinity of 1377cm -1. Using the obtained peak intensities P1 and P2, the imidization ratio of polyimide can be obtained according to the following formula.
Imidization ratio (%) = (peak intensity P1/peak intensity P2) x100
The polyimide may contain all of the repeating structural units of the above formula (4) including one kind of R 131 or R 132, or may contain 2 or more kinds of repeating units of the above formula (4) including R 131 or R 132 of different kinds. The polyimide may contain a repeating structural unit of another kind in addition to the repeating unit of the above formula (4).
Polyimide can be synthesized by, for example, the following method: a method of reacting a tetracarboxylic dianhydride with a diamine compound (a part of which is replaced with a monoamine capping agent) at a low temperature; a method of reacting a tetracarboxylic dianhydride (a part of which is replaced with an acid anhydride or a monoacyl chloride compound or a monoacyl ester compound capping agent) with a diamine compound at a low temperature; a method in which a diester is obtained by using a tetracarboxylic dianhydride and an alcohol, and then the diester is reacted in the presence of a diamine (a part of which is replaced with a monoamine capping agent) and a thickener; a method in which a diamine (a part of which is replaced with a monoamine capping agent) is reacted with a residual dicarboxylic acid after obtaining a diester by using a tetracarboxylic dianhydride and an alcohol, to obtain a polyimide precursor, and the polyimide precursor is fully imidized by a known imidization reaction method; or stopping imidization in the middle of the reaction, and introducing a part of imide structure; and a method of introducing a part of imide structure by mixing a completely imidized polymer and the polyimide precursor.
Commercially available polyimide products include Durimide 284 (registered trademark) (FUJIFILM co., ltd.) and MATRIMIDE5218 (manufactured by HUNTSMAN corporation).
The weight average molecular weight (Mw) of the polyimide is 4,000 ～ 100,000, preferably 5,000 to 70,000, more preferably 8,000 to 50,000, and still more preferably 10,000 ～ 30,000. By setting the weight average molecular weight to 5,000 or more, the folding endurance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. In the case where two or more kinds of polyimide are contained, it is preferable that the weight average molecular weight of at least 1 kind of polyimide is within the above range.
[ Polybenzoxazole precursors ]
The polybenzoxazole precursor used in the present invention is not particularly limited in its structure and the like, but preferably contains a repeating unit represented by the following formula (3).
(3)
[ Chemical formula 22]
In the formula (3), R 121 represents a 2-valent organic group, R 122 represents a 4-valent organic group, and R 123 and R 124 each independently represent a hydrogen atom or a 1-valent organic group.
In the formula (3), R 123 and R 124 have the same meaning as R 113 in the formula (2), and the preferable ranges are also the same. That is, at least one is preferably a polymerizable group.
In formula (3), R 121 represents a 2-valent organic group. The organic group having a valence of 2 is preferably a group containing at least one of an aliphatic group and an aromatic group. The aliphatic group is preferably a straight chain aliphatic group. R 121 is preferably a dicarboxylic acid residue. The dicarboxylic acid residues may be used in an amount of 1 or 2 or more.
The dicarboxylic acid residue is preferably a dicarboxylic acid residue containing an aliphatic group or a dicarboxylic acid residue containing an aromatic group, and more preferably a dicarboxylic acid residue containing an aromatic group.
The dicarboxylic acid having an aliphatic group is preferably a dicarboxylic acid having a linear or branched (preferably linear) aliphatic group, and more preferably a dicarboxylic acid comprising a linear or branched (preferably linear) aliphatic group and 2-COOH. The number of carbon atoms of the linear or branched (preferably linear) aliphatic group is preferably 2 to 30, more preferably 2 to 25, still more preferably 3 to 20, still more preferably 4 to 15, and particularly preferably 5 to 10. The straight chain aliphatic group is preferably an alkylene group.
As the dicarboxylic acid comprising a straight chain aliphatic group, examples thereof include malonic acid, dimethylmalonic acid, ethylmalonic acid, isopropylmalonic acid, di-n-butylmalonic acid, succinic acid, tetrafluorosuccinic acid, methylsuccinic acid, 2-dimethylsuccinic acid, 2, 3-dimethylsuccinic acid, dimethylmethylsuccinic acid, glutaric acid, hexafluoroglutaric acid, and 2-methylglutaric acid, 3-methylglutaric acid, 2-dimethylglutaric acid, 3-dimethylglutaric acid, 3-ethyl-3-methylglutaric acid, adipic acid, octafluoro-adipic acid, 3-methyladipic acid, pimelic acid, 2, 6-tetramethylpimelic acid, suberic acid, dodecafluoro-suberic acid, azelaic acid, sebacic acid hexadecane diacid, 1, 9-azelaic acid, dodecanedioic acid, tridecane diacid, tetradecane diacid, pentadecanedioic acid, hexadecane diacid, heptadecanedioic acid, octadecane diacid, nonadecanedioic acid, eicosane diacid, heneicosane diacid, docosane diacid, ditridecane diacid, tetracosane diacid, cyclopentadecanedioic acid, hexacosane diacid, heptadecanedioic acid, octacosane diacid, nonadecanedioic acid, triacontane diacid, tricosane diacid, triacontane diacid, diglycolic acid (diglycolic acid), and dicarboxylic acids represented by the following.
[ Chemical formula 23]
(Wherein Z is a hydrocarbon group having 1 to 6 carbon atoms and n is an integer of 1 to 6.)
The dicarboxylic acid containing an aromatic group is preferably a dicarboxylic acid having an aromatic group as follows, more preferably a dicarboxylic acid having only an aromatic group and 2-COOH as follows.
[ Chemical formula 24]
Wherein A represents a group of valence 2 selected from-CH 2-、-O-、-S-、-SO2-、-CO-、-NHCO-、-C(CF3)2 -and-C (CH 3)2 -and each independently represents a bonding position to another structure.
Specific examples of the dicarboxylic acid containing an aromatic group include 4,4 '-carbonyldibenzoic acid, 4' -dicarboxydiphenyl ether, and terephthalic acid.
In formula (3), R 122 represents a 4-valent organic group. The organic group having a valence of 4 has the same meaning as R 115 in the above formula (2), and the preferable range is also the same.
R 122 is also preferably a group derived from a bisaminophenol derivative, as a group derived from a bisaminophenol derivative, examples thereof include 3,3 '-diamino-4, 4' -dihydroxybiphenyl, 4 '-diamino-3, 3' -dihydroxybiphenyl, 3 '-diamino-4, 4' -dihydroxydiphenyl sulfone, 4 '-diamino-3, 3' -dihydroxydiphenyl sulfone bis- (3-amino-4-hydroxyphenyl) methane, 2-bis (3-amino-4-hydroxyphenyl) propane, 2-bis- (3-amino-4-hydroxyphenyl) hexafluoropropane, 2-bis- (4-amino-3-hydroxyphenyl) hexafluoropropane bis- (4-amino-3-hydroxyphenyl) methane, 2-bis- (4-amino-3-hydroxyphenyl) propane, 4 '-diamino-3, 3' -dihydroxybenzophenone, 3 '-diamino-4, 4' -dihydroxybenzophenone, 4 '-diamino-3, 3' -dihydroxydiphenyl ether, 3 '-diamino-4, 4' -dihydroxydiphenyl ether, 1, 4-diamino-2, 5-dihydroxybenzene, 1, 3-diamino-2, 4-dihydroxybenzene, 1, 3-diamino-4, 6-dihydroxybenzene, and the like. These bisaminophenols may be used alone or in combination.
Among the bisaminophenol derivatives, the following bisaminophenol derivatives having an aromatic group are preferable.
[ Chemical formula 25]
Wherein X 1 represents-O-, -S-, -C (CF 3)2-、-CH2-、-SO2 -, -NHCO-, and # each represents a bonding position to other structures, R represents a hydrogen atom or a substituent having a valence of 1, preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, and, R 122 is also preferably a structure represented by the above formula, when R 122 is a structure represented by the above formula, it is preferable that, of the total of 4, any 2 are bonding positions to the nitrogen atom bonded to R 122 in formula (3) and the other 2 are bonding positions to the oxygen atom bonded to R 122 in formula (3), more preferably, 2 are bonding positions to an oxygen atom bonded to R 122 in formula (3), and 2 # are bonding positions to a nitrogen atom bonded to R 122 in formula (3), or 2 are bonding positions to a nitrogen atom bonded to R 122 in formula (3), and 2 # are bonding positions to an oxygen atom bonded to R 122 in formula (3), further preferably 2 are bonding positions to an oxygen atom bonded to R 122 in formula (3), and 2 # are bonding positions to a nitrogen atom bonded to R 122 in formula (3).
[ Chemical formula 26]
In the formula (A-S), R 1 is a hydrogen atom, an alkylene group, a substituted alkylene group, -O-, -S-, -SO 2 -, -CO-, -NHCO-, a single bond, or an organic group selected from the group of the following formula (A-sc). R 2 is any one of a hydrogen atom, an alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different. R 3 is any one of a hydrogen atom, a linear or branched alkyl group, an alkoxy group, an acyloxy group, and a cyclic alkyl group, and may be the same or different.
[ Chemical formula 27]
(In the formula (A-sc): represents an aromatic ring bonded to an aminophenol group of the bisaminophenol derivative represented by the formula (A-s))
In the above formula (a-s), it is considered that the presence of a substituent also in the ortho position to the phenolic hydroxyl group, i.e., R 3, brings the carbonyl carbon of the amide bond closer to the hydroxyl group, and the effect of attaining a high cyclization ratio upon curing at a low temperature is particularly preferable.
In the above formula (a-s), it is preferable that R 2 be an alkyl group and R 3 be an alkyl group because the effect of high transparency to i-rays and high cyclization ratio when cured at low temperature can be maintained.
In the above formula (A-s), R 1 is more preferably an alkylene group or a substituted alkylene group. Specific examples of the alkylene group and the substituted alkylene group of R 1 include a linear or branched alkyl group having 1 to 8 carbon atoms, and among them, from the viewpoint of obtaining a polybenzoxazole precursor having a sufficient solubility in a solvent and excellent balance of high transparency to i-rays and a high cyclization ratio when cured at a low temperature, more preferably-CH 2-、-CH(CH3)-、-C(CH3)2 -.
Examples of the production method of the bisaminophenol derivative represented by the formula (A-s) include paragraphs 0085 to 0094 and example 1 (paragraphs 0189 to 0190) of Japanese unexamined patent publication No. 2013-256506, which are incorporated herein by reference.
Specific examples of the structure of the bisaminophenol derivative represented by the formula (A-s) include those described in paragraphs 0070 to 0080 of Japanese patent application laid-open No. 2013-256506, which are incorporated herein by reference. Of course, these are not limiting.
The polybenzoxazole precursor may contain other kinds of repeating structural units in addition to the repeating unit of the above formula (3).
From the viewpoint of suppressing warpage associated with the generation of closed loops, it is preferable to include a diamine residue represented by the following formula (SL) as another type of repeating structural unit.
[ Chemical formula 28]
In the formula (SL), Z has a structure of a and a structure of b, R 1s is a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, R 2s is a hydrocarbon group having 1 to 10 carbon atoms, at least 1 of R 3s、R4s、R5s、R6s is an aromatic group, and the rest is a hydrogen atom or an organic group having 1 to 30 carbon atoms, which may be the same or different. The polymerization of the a structure and the b structure may be block polymerization or random polymerization. Regarding the mole% of the Z moiety, the a structure is 5 to 95 mole%, the b structure is 95 to 5 mole%, and a+b is 100 mole%.
In the formula (SL), preferable Z is that R 5s and R 6s in the b structure are phenyl groups. The molecular weight of the structure represented by the formula (SL) is preferably 400 to 4,000, more preferably 500 to 3,000. By setting the molecular weight in the above range, the elastic modulus of the polybenzoxazole precursor after dehydration and ring closure can be reduced more effectively, and the effect of suppressing warpage and the effect of improving solvent solubility can be achieved at the same time.
When the diamine residue represented by the formula (SL) is contained as another type of repeating structural unit, it is preferable that the tetracarboxylic acid residue remaining after the removal of the anhydride group from the tetracarboxylic dianhydride is further contained as a repeating structural unit. Examples of such tetracarboxylic acid residues include R 115 in formula (2).
For example, when the polybenzoxazole precursor is used in a composition described later, the weight average molecular weight (Mw) of the polybenzoxazole precursor is preferably 18,000 ～ 30,000, more preferably 20,000 ～ 29,000, and further preferably 22,000 ～ 28,000. The number average molecular weight (Mn) is preferably 7,200 to 14,000, more preferably 8,000 to 12,000, and still more preferably 9,200 to 11,200.
The dispersion degree of the molecular weight of the polybenzoxazole precursor is preferably 1.4 or more, more preferably 1.5 or more, and further preferably 1.6 or more. The upper limit of the molecular weight dispersity of the polybenzoxazole precursor is not particularly limited, and is preferably 2.6 or less, more preferably 2.5 or less, further preferably 2.4 or less, further preferably 2.3 or less, and further preferably 2.2 or less, for example.
[ Polybenzoxazole ]
The polybenzoxazole is not particularly limited as long as it is a polymer compound having a benzoxazole ring, but is preferably a compound represented by the following formula (X), more preferably a compound represented by the following formula (X) and having a polymerizable group. The polymerizable group is preferably a radical polymerizable group. The compound may be a compound represented by the following formula (X) and having a polar conversion group such as an acid-decomposable group.
[ Chemical formula 29]
In the formula (X), R 133 represents a 2-valent organic group, and R 134 represents a 4-valent organic group.
When the polymerizable group or the acid-decomposable group has a polar conversion group, the polymerizable group or the acid-decomposable group may be located at least one of R 133 and R 134, or may be located at the terminal of the polybenzoxazole as shown in the following formula (X-1) or formula (X-2).
(X-1)
[ Chemical formula 30]
In the formula (X-1), at least one of R 135 and R 136 is a polar conversion group such as a polymerizable group or an acid-decomposable group, and if it is not a polar conversion group such as a polymerizable group or an acid-decomposable group, it is an organic group, and the other groups have the same meaning as in the formula (X).
(X-2)
[ Chemical formula 31]
In the formula (X-2), R 137 is a polar conversion group such as a polymerizable group or an acid-decomposable group, the other is a substituent, and the other groups have the same meaning as in the formula (X).
The polar conversion group such as a polymerizable group or an acid-decomposable group is the same as the polymerizable group described in the polymerizable group contained in the polyimide precursor or the like.
R 133 represents a 2-valent organic group. Examples of the 2-valent organic group include aliphatic and aromatic groups. Specific examples thereof include R 121 in formula (3) of the polybenzoxazole precursor. Further, the preferable examples are the same as R 121.
R 134 represents a 4-valent organic group. Examples of the 4-valent organic group include R 122 in formula (3) of the polybenzoxazole precursor. Further, the preferable examples are the same as R 122.
For example, 4 linkers of 4-valent organic groups exemplified as R 122 are bonded to the nitrogen atom or oxygen atom in the above formula (X) to form a condensed ring. For example, when R 134 is an organic group as described below, the following structure is formed.
[ Chemical formula 32]
The oxazolization ratio of the polybenzoxazole is preferably 85% or more, more preferably 90% or more. When the rate of the oxazolization is 85% or more, the film shrinkage due to the closed loop generated when the oxazolization is performed by heating is reduced, and the occurrence of warpage can be more effectively suppressed.
The polybenzoxazole may contain all of the repeating structural units of the above formula (X) including one kind of R 131 or R 132, or may contain 2 or more different kinds of repeating units of the above formula (X) including R 131 or R 132. The polybenzoxazole may contain a repeating structural unit of another kind in addition to the repeating unit of the above formula (X).
The polybenzoxazole is obtained, for example, by reacting a bisaminophenol derivative with a compound selected from the group consisting of a dicarboxylic acid containing R 133 or a dicarboxylic acid dichloride (dicarboxylic acid dichloride) of the above dicarboxylic acid, a dicarboxylic acid derivative, and the like to obtain a polybenzoxazole precursor, and then subjecting the polybenzoxazole precursor to an oxazolization reaction by a known method.
In the case of dicarboxylic acid, an active ester-type dicarboxylic acid derivative obtained by reacting 1-hydroxy-1, 2, 3-benzotriazole or the like in advance may be used in order to improve the reaction yield or the like.
The weight average molecular weight (Mw) of the polybenzoxazole is preferably 5,000 to 70,000, more preferably 8,000 to 50,000, still more preferably 10,000 ～ 30,000. By setting the weight average molecular weight to 5,000 or more, the folding endurance of the cured film can be improved. In order to obtain an organic film excellent in mechanical properties, the weight average molecular weight is particularly preferably 20,000 or more. When two or more polybenzoxazoles are contained, it is preferable that the weight average molecular weight of at least 1 polybenzoxazole is within the above range.
[ Method for producing polyimide precursor and the like ]
Polyimide precursors and the like are obtained by reacting a dicarboxylic acid or a dicarboxylic acid derivative with a diamine. Preferably by halogenating a dicarboxylic acid or dicarboxylic acid derivative using a halogenating agent and then reacting with a diamine.
In the method for producing a polyimide precursor or the like, an organic solvent is preferably used in the reaction. The organic solvent may be 1 or 2 or more.
The organic solvent may be appropriately defined according to the raw material, and pyridine, diethylene glycol dimethyl ether (diglyme), N-methylpyrrolidone and N-ethylpyrrolidone may be exemplified.
Polyimide may be produced by cyclizing a polyimide precursor by a method such as thermal imidization or chemical imidization (for example, by allowing a catalyst to act to promote a cyclization reaction) after synthesizing the polyimide precursor, or may be synthesized directly.
It is also preferable to synthesize the catalyst using a non-halogen catalyst without using the halogenating agent. The non-halogen-based catalyst may be any known amidation catalyst containing no halogen atom, and examples thereof include a boroxine trimer (boroxine) compound, an N-hydroxy compound, a tertiary amine, a phosphate, an amine salt, a urea compound, and a carbodiimide compound. Examples of the carbodiimide compound include N, N '-diisopropylcarbodiimide and N, N' -dicyclohexylcarbodiimide.
Blocking agent-
In order to further improve the storage stability of the composition in the production of a polyimide precursor or the like, it is preferable to seal the end of the polyimide precursor or the like with a capping agent such as an acid anhydride, a monocarboxylic acid, a monoacyl chloride compound, a monoacid ester compound, or the like. As the blocking agent, monoamine is more preferably used, and preferable examples of monoamine include aniline, 2-ethynylaniline, 3-ethynylaniline, 4-ethynylaniline, 5-amino-8-hydroxyquinoline, 1-hydroxy-7-aminonaphthalene, 1-hydroxy-6-aminonaphthalene, 1-hydroxy-5-aminonaphthalene, 1-hydroxy-4-aminonaphthalene, 2-hydroxy-7-aminonaphthalene, 2-hydroxy-6-aminonaphthalene, 2-hydroxy-5-aminonaphthalene, 1-carboxy-7-aminonaphthalene, 1-carboxy-6-aminonaphthalene, 1-carboxy-5-aminonaphthalene, 2-carboxy-7-aminonaphthalene, 2-carboxy-6-aminonaphthalene, 2-carboxy-5-aminonaphthalene, 2-aminobenzoic acid, 3-aminobenzoic acid, 4-aminosalicylic acid, 5-aminosalicylic acid, 6-aminosalicylic acid, 2-aminobenzenesulfonic acid, 3-aminobenzenesulfonic acid, 4-aminobenzenesulfonic acid, 3-amino-4, 6-dihydroxypyrimidine, 2-hydroxy-5-aminophenol, 3-aminophenol, 4-aminophenol, and thiophenol. These may be used in an amount of 2 or more, or a plurality of different terminal groups may be introduced by reacting a plurality of kinds of terminal groups.
Solid precipitation-
The polyimide precursor or the like may be produced by a process of precipitating a solid. Specifically, the polyimide precursor or the like in the reaction liquid is precipitated in water, and dissolved in a solvent in which the polyimide precursor or the like such as tetrahydrofuran is soluble, whereby a solid can be precipitated.
Then, the polyimide precursor or the like is dried, and a powdery polyimide precursor or the like can be obtained.
[ Content ]
The content of the specific resin in the composition of the present invention is preferably 20 mass% or more, more preferably 30 mass% or more, further preferably 40 mass% or more, further preferably 50 mass% or more, based on the total solid content of the composition. The content of the resin in the composition of the present invention is preferably 99.5% by mass or less, more preferably 99% by mass or less, further preferably 98% by mass or less, further preferably 97% by mass or less, further preferably 95% by mass or less, based on the total solid content of the composition.
The composition of the present invention may contain only 1 specific resin or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
The curable resin composition of the present invention preferably contains at least two resins.
Specifically, the curable resin composition of the present invention may contain two or more specific resins and other resins described later in total, or may contain two or more specific resins, but preferably contains two or more specific resins.
When the curable resin composition of the present invention contains two or more specific resins, for example, two or more polyimide precursors containing polyimide precursors and having a structure derived from dianhydride (R 115 described by the above formula (2)) are preferably used.
< Other resins >
The composition of the present invention may contain the above specific resin and another resin (hereinafter, also simply referred to as "other resin") different from the specific resin.
Examples of the other resin include polyamideimide, polyamideimide precursor, phenol resin, polyamide, epoxy resin, polysiloxane, resin containing a siloxane structure, and acrylic resin.
For example, by further adding an acrylic resin, a composition excellent in coatability can be obtained, and an organic film excellent in solvent resistance can be obtained.
For example, by adding an acrylic resin having a high polymerizable group valence and having a weight average molecular weight of 20,000 or less to the composition in place of or in addition to a crosslinking agent (also referred to as a polymerizable compound) described later, the coatability of the composition, the solvent resistance of an organic film, and the like can be improved.
When the composition of the present invention contains another resin, the content of the other resin is preferably 0.01 mass% or more, more preferably 0.05 mass% or more, further preferably 1 mass% or more, further preferably 2 mass% or more, further preferably 5 mass% or more, and further preferably 10 mass% or more, based on the total solid content of the composition.
The content of the other resin in the composition of the present invention is preferably 80% by mass or less, more preferably 75% by mass or less, further preferably 70% by mass or less, further preferably 60% by mass or less, further preferably 50% by mass or less, based on the total solid content of the composition.
In addition, as a preferable embodiment of the composition of the present invention, the content of the other resin may be low. In the above aspect, the content of the other resin is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, further preferably 5% by mass or less, further preferably 1% by mass or less, relative to the total solid content of the composition. The lower limit of the content is not particularly limited, and is not less than 0 mass%.
The composition of the present invention may contain only 1 kind of other resin or may contain 2 or more kinds. When the content is 2 or more, the total amount is preferably within the above range.
< Compound B >
The curable resin composition of the present invention contains a compound B as a compound having a polymerizable group and an azole group.
[ Polymerizable group ]
Examples of the polymerizable group in the compound B include a known polymerizable group such as a radical polymerizable group, an alkoxysilyl group, an epoxy group, an oxetanyl group, a hydroxymethyl group, an alkoxymethyl group, and a (block) isocyanate group.
Among these, from the viewpoint of adhesion of the cured film to a metal, it is preferable that the compound B contains at least 1 group selected from a radical polymerizable group and an alkoxysilyl group as a polymerizable group.
The alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group, but is preferably a trialkoxysilyl group from the viewpoint of adhesion of the cured film to a metal.
The alkoxy group in the alkoxysilyl group is preferably an alkoxy group having 1 to 4 carbon atoms, more preferably a methoxy group or an ethoxy group, and still more preferably an ethoxy group.
The radical polymerizable group is preferably a group having an ethylenically unsaturated bond.
Examples of the group having an ethylenically unsaturated bond include a group having a vinyl group which may be substituted and directly bonded to an aromatic ring such as a vinyl group, an allyl group, or a vinylphenyl group, (meth) acrylamido group, and (meth) acryloyloxy group is preferable.
The compound B may have only 1 polymerizable group, or may have 2 or more polymerizable groups.
The compound B may have only 1 polymerizable group or may have 2 or more polymerizable groups. For example, a radical polymerizable group and an alkoxysilyl group may be contained.
[ Azolyl ]
The oxazolyl group in the compound B may be a group having a structure in which 1 or more hydrogen atoms are removed from a heterocyclic 5-membered ring compound which may have a substituent or a condensed ring structure, and is preferably a group having a structure in which 1 or more hydrogen atoms are removed from a heterocyclic 5-membered ring compound which may have a substituent, and a heterocyclic 5-membered ring compound which may have only 1 or more nitrogen atoms and 1 or more carbon atoms as a ring member.
From the viewpoint of adhesion of the cured film to a metal, the azole group is preferably a group having a structure in which 1 or more hydrogen atoms are removed from an azole ring, a pyrazole ring, an indazole ring, an imidazole ring, a benzimidazole ring, a1, 2, 3-triazole ring, a1, 2, 4-triazole ring, a benzotriazole ring, or a tetrazole ring, and more preferably a group having a structure in which 1 or more hydrogen atoms are removed from an imidazole ring, a benzimidazole ring, a1, 2, 4-triazole ring, or a benzotriazole ring.
The azole group in the compound B is preferably a group represented by the following formula (B-1) or the following formula (B-2).
[ Chemical formula 33]
In the formula (B-1), R B1 represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, Z B1～ZB4 each independently represents =cr B7 -or a nitrogen atom, R B7 represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, and at least 1 of R B1 and R B7 included in the formula (B-1) represents a bonding position to a structure having a polymerizable group;
In the formula (B-2), R B2～RB6 each independently represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, Z B5 and Z B6 each independently represent =cr B8 —or a nitrogen atom, R B8 represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, and at least 1 of R B2～RB6 and R B8 included in the formula (B-2) represents a bonding position to a structure having a polymerizable group.
In the formula (B-1), R B1 represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, and more preferably a bonding position to a structure having a polymerizable group.
The 1-valent organic group in R B1 is not particularly limited, and any known organic group can be used as long as the effect of the present invention can be obtained, but is preferably a hydrocarbon group or an amino group, and more preferably an alkyl group or an amino group. The number of carbon atoms of the hydrocarbon group or the alkyl group is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4.
The amino group may be a substituted amino group or an unsubstituted amino group.
In the formula (B-1), Z B1～ZB4 each independently represents=CR B7 -or a nitrogen atom.
Among them, a mode in which 2 of Z B1～ZB4 are nitrogen atoms and 2 are=cr B7 -, a mode in which 1 of Z B1～ZB4 is a nitrogen atom and 3 are=cr B7 -, or a mode in which 3 of Z B1～ZB4 are nitrogen atoms and 1 is=cr B7 -, is preferable.
Among these, the method in which Z B1 and Z B3 are nitrogen atoms and Z B2 and Z B4 are=cr B7 -, the method in which Z B1 and Z B2 are nitrogen atoms and Z B3 and Z B4 are=cr B7 -, the method in which Z B2 is a nitrogen atom and Z B1、ZB3 and Z B4 are=cr B7 -, or the method in which Z B1、ZB2 and Z B3 are nitrogen atoms and Z B4 are=cr B7 -, and the method in which Z B1 and Z B3 are nitrogen atoms and Z B2 and Z B4 are=cr B7 -, are preferable.
R B7 is preferably a hydrogen atom or a 1-valent organic group.
When Z B1、ZB2 and Z B3 are nitrogen atoms and Z B4 is =cr B7 -, R B7 is preferably a bonding position to a structure having a polymerizable group.
The preferred manner of the organic group of valence 1 in R B7 is the same as the preferred manner of the organic group of valence 1 in R B1 described above.
At least 1 of R B1 and R B7 contained in the formula (B-1) represents a bonding position to a structure having a polymerizable group, and preferably at least R B1 represents a bonding position to a structure having a polymerizable group. In the formula (B-1), only R B1 represents a bonding position to a structure having a polymerizable group, and R B7 each independently represents a hydrogen atom or a 1-valent organic group is also one of preferred embodiments of the present invention.
In the formula (B-2), Z B5 and Z B6 each independently represent a group consisting of CR B8 and a nitrogen atom.
Among them, it is preferable that Z B5 and Z B6 each represent a nitrogen atom, or that Z B5 represents a nitrogen atom and Z B5 represents =cr B8 -.
In the formula (B-2), when Z B5 and Z B6 each preferably represent a nitrogen atom, R B6 represents a bonding position to a structure having a polymerizable group. In the formula (B-2), Z B5 and Z B6 each represent a nitrogen atom, and only R B6 represents a bonding position to a structure having a polymerizable group is also one of preferred embodiments of the present invention.
In the formula (B-2), when Z B5 represents a nitrogen atom and Z B6 represents =cr B8 -, R B8 preferably represents a bonding position to a structure having a polymerizable group. In the formula (B-2), when Z B5 represents a nitrogen atom, Z B6 represents =cr B8 -, and only R B8 represents a bonding position to a structure having a polymerizable group, it is also one of preferred embodiments of the present invention.
In the formula (B-2), R B2～RB5 is preferably a hydrogen atom or a 1-valent organic group having no polymerizable group. The preferred manner of the organic group of valence 1 in R B2～RB5 is the same as the preferred manner of the organic group of valence 1 in R B1 described above.
In the formula (B-2), when Z B5 represents a nitrogen atom and Z B6 represents =cr B8 -, R B6 preferably represents a hydrogen atom or a 1-valent organic group having no polymerizable group. The preferred manner of the organic group of valence 1 in R B6 is the same as the preferred manner of the organic group of valence 1 in R B1 described above.
In other cases, R B6 is preferably a bond to a structure having a polymerizable group. In particular, when Z B5 represents a nitrogen atom and Z B6 represents =cr B8 -, R B8 preferably represents a bonding position to a structure having a polymerizable group.
In the formula (B-2), R B8 preferably represents a bonding position to a structure having a polymerizable group.
When Z B5 and Z B6 each represent =cr B8 -, one of R B8 preferably represents a bonding position to a structure having a polymerizable group, and the other represents a hydrogen atom or a 1-valent organic group. The preferred manner of the organic group of valence 1 in R B8 is the same as the preferred manner of the organic group of valence 1 in R B1 described above.
At least 1 of R B2～RB6 and R B8 contained in the formula (B-2) represents a bonding position to a structure having a polymerizable group, and preferably at least R B6 or R B8 represents a bonding position to a structure having a polymerizable group. In the formula (B-2), a preferred embodiment of the present invention is a mode in which only one of R B6 and R B8 represents a bonding position to a structure having a polymerizable group, and the other of R B6 and R B8 and R B2～RB5 independently represent a hydrogen atom or a 1-valent organic group.
Among these, the azole group is preferably a group represented by any one of the following formulas (B-3) to (B-6).
[ Chemical formula 34]
In the formulae (B-3) to (B-6), R B9～RB20 each independently represents a hydrogen atom or a 1-valent organic group having no polymerizable group, and represents a bonding position to a structure having a polymerizable group.
In the formulae (B-3) to (B-6), the preferable mode of the 1-valent organic group in R B9～RB20 is the same as the preferable mode of the 1-valent organic group in R B1 described above.
From the viewpoint of adhesion of the obtained cured film to a metal, the compound B preferably has at least 1 group selected from an amide group, a urethane group and a urea group.
It is presumed that the interaction between the compound B and the specific resin is promoted by the compound B having at least 1 group selected from the group consisting of an amide group, a urethane group and a urea group, and the adhesion between the cured film and the metal is improved.
The amide group, the carbamate group, and the urea group may be directly bonded to the azole group or may be bonded to the azole group via a linking group.
As the above-mentioned linking group, preferably a hydrocarbon group or a hydrocarbon group and a compound selected from the group consisting of-O-, -S-, -C (=O) -, -S (=o) 2 -and-NR N -a group represented by a bond of at least 1 group, more preferably a hydrocarbon group.
R N represents a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom, further preferably an alkyl group or an aryl group, and particularly preferably a hydrogen atom.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and more preferably an alkylene group.
The number of carbon atoms of the hydrocarbon group or alkylene group is preferably 2 to 20, more preferably 2 to 10.
When the compound B has an amide group, a carbamate group or a urea group, the compound B preferably has a structure represented by the following formula (B-7), (B-8) or (B-9) as a structure containing the above-mentioned azole group and amide group, carbamate group or urea group.
[ Chemical formula 35]
In the formula (B-7), X 1 represents an azole group, L 1 represents a single bond or a 2-valent linking group, R B21 represents a hydrogen atom or a 1-valent organic group, and represents a bonding position to a structure having a polymerizable group.
In the formula (B-8), X 2 represents an azole group, L 2 represents a single bond or a 2-valent linking group, R B22 represents a hydrogen atom or a 1-valent organic group, and represents a bonding position to a structure having a polymerizable group.
In the formula (B-9), X 3 represents an azole group, L 3 represents a single bond or a 2-valent linking group, R B23 and R B24 each independently represent a hydrogen atom or a 1-valent organic group, and represent a bonding position to a structure having a polymerizable group.
In formula (B-7), the preferred mode of the azole group in X 1 is as described above. The bonding position to the structure having the polymerizable group in the above azole group corresponds to the bonding position to L 1 in the formula (B-7).
In the formula (B-7), as the 2-valent linking group in L 1, preferably a hydrocarbon group or a group represented by a bond of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -S-, -C (=o) -, -S (=o) 2 -, and-NR N -, more preferably a hydrocarbon group.
R N is as described above.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and more preferably an alkylene group.
The number of carbon atoms of the hydrocarbon group or alkylene group is preferably 2 to 20, more preferably 2 to 10.
In the formula (B-7), R B21 represents a hydrogen atom or a 1-valent organic group, preferably a hydrogen atom. The preferred manner of the 1-valent organic group in R B21 is the same as R B1 described above.
In the formula (B-8), X 2 has the same meaning as X 1 in the formula (B-7), L 2 has the same meaning as L 1 in the formula (B-7), and R B22 has the same meaning as R B21 in the formula (B-7), preferably in the same manner.
In the formula (B-9), X 3 has the same meaning as X 1 in the formula (B-7), L 3 has the same meaning as L 1 in the formula (B-7), and R B23 and R B24 have the same meaning as R B21 in the formula (B-7) independently, and preferably have the same meaning.
The compound B may be a compound having a molecular weight of less than 2,000 (hereinafter, also referred to as "low-molecular compound B"), or may be a resin (hereinafter, also referred to as "resin B").
In addition, from the viewpoint of adhesion of the cured film to a metal, the curable resin composition preferably contains both the low-molecular compound B and the resin B.
[ Low molecular weight Compound B ]
The molecular weight of the low-molecular compound B is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.
The number of polymerizable groups in the low-molecular compound B is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 or 2.
The number of azole groups in the low-molecular compound B is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, further preferably 1 or 2, further preferably 1.
The low molecular compound B is preferably a compound represented by the following formula (BL-1).
[ Chemical formula 36]
In the formula (BL-1), X LA represents an azole group, L LA represents a single bond or a linking group having a valence of m+1, X LB represents a polymerizable group, n represents an integer of 1 or more, and m represents an integer of 1 or more.
In the formula (BL-1), preferred modes of the azole group in X LA are as described above.
In the formula (BL-1), the amino acid sequence, L LA is preferably a single bond, a hydrocarbon group or a mixture of hydrocarbon groups and a member selected from the group consisting of-O-; -S-, -C (=o) -, -S (=o) 2 -and-NR N -is a group represented by bonding at least 1 group.
R N is as described above.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and more preferably an alkylene group.
The number of carbon atoms of the hydrocarbon group or alkylene group is preferably 2 to 20, more preferably 2 to 10.
In the formula (BL-1), a mode in which L LA is a group represented by the following formula (L-1) or formula (L-2) is also one of preferred modes of the present invention.
[ Chemical formula 37]
In the formula (L-1), L 1 represents a single bond or a 2-valent linking group, R B21 represents a hydrogen atom or a 1-valent organic group, L 3 represents a n1+1-valent linking group, n1 represents an integer of 1 or more, and# represents a bonding position with an azole group and represents a bonding position with a polymerizable group.
In the formula (L-2), L 2 represents a single bond or a 2-valent linking group, R B22 and R B23 each independently represent a hydrogen atom or a 1-valent organic group, L 4 represents an n2+1-valent linking group, n2 represents an integer of 1 or more, and # represents a bonding position to an azole group.
In the formula (L-1), L 1 and R B21 have the same meanings as L 1 and R B21 in the formula (B-7), respectively, and the preferable modes are the same.
In the formula (L-1), the amino acid sequence of the formula (I), L 3 is preferably a hydrocarbon group or is selected from the group consisting of hydrocarbon groups and groups selected from-O-, -S-, -C (=O) -, -S (=o) 2 -and-NR N -is a group represented by bonding at least 1 group.
R N is as described above.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and more preferably an alkylene group.
The number of carbon atoms of the hydrocarbon group or alkylene group is preferably 2 to 20, more preferably 2 to 10.
In the formula (L-1), n1 is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.
In the formula (L-2), L 2、RB22 and R B23 have the same meanings as L 2、RB22 and R B23 in the formula (B-8), respectively, and the preferable modes are the same.
In the formula (L-2), L 4 has the same meaning as L 3 in the formula (L-1), and the preferable mode is the same.
In the formula (L-2), n2 is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.
In the formula (BL-1), preferable modes of the polymerizable group in X LB are as described above.
In the formula (BL-1), n is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.
When n is 2 or more, a plurality of L LA and X LB contained in the formula (BL-1) may be the same or different.
In the formula (BL-1), m is preferably an integer of 1 to 10, more preferably an integer of 1 to 4, further preferably 1 or 2, and particularly preferably 1.
When m is 2 or more, the plural xs LB included in the formula (BL-1) may be the same or different.
[ Resin B ]
The resin B is preferably a resin having a repeating unit including an azole group and a repeating unit including a polymerizable group, or a resin having a repeating unit including an azole group and a polymerizable group, more preferably a resin having a repeating unit including an azole group and a repeating unit including a polymerizable group.
The weight average molecular weight of the resin B is preferably 2,000 ～ 100,000, more preferably 3,000 to 70,000, and still more preferably 5,000 to 50,000.
The resin B is preferably an acrylic resin.
The resin B preferably contains a repeating unit represented by the following formula (RA-1) as the repeating unit containing an azole group.
[ Chemical formula 38]
In the formula (RA-1), L 3 represents a single bond or a 2-valent linking group, X 3 represents an azole group, and R represents a hydrogen atom or a methyl group.
In the formula (RA-1), L 3 represents a single bond or a 2-valent linking group.
As the above-mentioned 2-valent linking group, preferably a hydrocarbon group or a group represented by a bond of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -S-, -C (=o) -, -S (=o) 2 -, and-NR N -, more preferably a hydrocarbon group.
R N is as described above.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and more preferably an alkylene group.
The number of carbon atoms of the hydrocarbon group or alkylene group is preferably 2 to 20, more preferably 2 to 10.
Of these, L 3 is preferably a single bond, a group represented by the following formula (RA-1-1) or a group represented by the following formula (BA-1-2).
[ Chemical formula 39]
In formula (BA-1-1) or formula (BA-1-2), L 4 represents a 2-valent linking group, L 5 represents a single bond or a 2-valent linking group, L 6 represents a 2-valent linking group, L 7 represents a single bond or a 2-valent linking group, A 1 and A 2 represent bonding positions with carbonyl groups in formula (BA-1), and-O-or-NR N -, -represents bonding positions with X 3 in formula (BA-1).
In the formula (BA-1-1), L 4 is preferably a hydrocarbon group or is selected from the group consisting of hydrocarbon groups and groups selected from-O-, -S-, -C (=O) -, -S (=o) 2 -and-NR N -a group represented by bonding of at least 1 group, more preferably a hydrocarbon group.
R N is as described above.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and more preferably an alkylene group.
The number of carbon atoms of the hydrocarbon group or alkylene group is preferably 2 to 20, more preferably 2 to 10.
In the formula (BA-1-1), L 5 is preferably a single bond. In the case where L 5 is a 2-valent linking group, the preferable mode of L 5 is the same as the preferable mode when L 1 in the above formula (B-7) is a 2-valent linking group.
In the formula (BA-1-2), L 6 has the same meaning as L 4 in the formula (BA-1-1), and the preferable mode is also the same.
In the formula (BA-1-2), L 7 is preferably a 2-valent linking group. In the case where L 7 is a 2-valent linking group, the preferable mode of L 7 is the same as the preferable mode when L 2 in the above formula (B-8) is a 2-valent linking group.
In the formula (BA-1-1) or the formula (BA-1-2), A 1 and A 2 represent-O-or-NR N -, preferably-0-. R N is as described above.
In formula (BA-1), the preferred mode of oxazolyl in X 3 is as described above. The bonding position to the structure having the polymerizable group in the above-mentioned azole group corresponds to the bonding position to L 3 in the formula (BA-1).
The resin B may contain only 1 type of repeating unit represented by the formula (BA-1), or may contain 2 or more types of repeating units represented by the formula (BA-1).
The resin B preferably contains a repeating unit represented by the following formula (BA-2) as a repeating unit containing a polymerizable group.
[ Chemical formula 40]
In the formula (BA-2), A 3 represents-O-or-NR N-,LP1 represents a 2-valent linking group, R P1 represents a polymerizable group, and R represents a hydrogen atom or a methyl group.
In the formula (BA-2), A 3 represents-O-or-NR N -, preferably-O-. R N is as described above.
In the formula (BA-2), L P1 represents a 2-valent linking group, preferably a hydrocarbon group or a group represented by a bond of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -S-, -C (=0) -, -S (=0) 2 -, and-NR N -, more preferably a hydrocarbon group.
R N is as described above.
The hydrocarbon group is preferably a saturated aliphatic hydrocarbon group, and more preferably an alkylene group.
The number of carbon atoms of the hydrocarbon group or alkylene group is preferably 2 to 20, more preferably 2 to 10.
X P1 represents a polymerizable group, preferably an alkoxysilyl group, an epoxy group, an oxetanyl group or a radical polymerizable group, more preferably an alkoxysilyl group. Preferable modes of the alkoxysilyl group and the radical polymerizable group are as described above.
The resin B may contain only 1 type of repeating unit represented by the formula (RA-2) or 2 or more types of repeating units represented by the formula (RA-2).
In particular, it is also one of the preferred embodiments of the present invention that the resin B contains a plurality of repeating units represented by the formula (RA-2) having different polymerizable groups. In the above embodiment, the resin B preferably includes a repeating unit represented by the formula (RA-2) containing an alkoxysilyl group as a polymerizable group and a repeating unit represented by the formula (RA-2) containing a group different from the alkoxysilyl group as a polymerizable group.
The resin B may have a repeating unit different from the repeating unit represented by the above formula (RA-1) or formula (RA-2).
[ Specific example ]
Specific examples of the compound B include, but are not limited to, the compounds used in the examples.
[ Content ]
The content of the compound B is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass, based on the total solid content of the curable resin composition of the present invention.
The curable resin composition of the present invention may contain only 1 compound B or may contain 2 or more compounds B. When 2 or more compounds B are contained, the total amount is preferably within the above range.
< Compound C >
From the viewpoint of adhesion of the obtained cured film to metal, the curable resin composition of the present invention preferably further comprises a compound C which is a compound having an azole group without a polymerizable group.
The preferred mode of the azole group in the compound C is the same as that of the azole group in the above-mentioned compound B.
The compound C is a compound having no polymerizable group, and the details of the polymerizable group are the same as those of the polymerizable group in the above-described compound B.
The compound C is preferably a compound represented by the following formula (C-1) or the following formula (C-2).
[ Chemical formula 41]
In the formula (C-1), Z 1～Z4 each independently represents a group consisting of CR 7 -or a nitrogen atom, R 1 represents a hydrogen atom or a 1-valent organic group, R 7 represents a hydrogen atom or a 1-valent organic group, and the structure represented by the formula (C-1) does not include a polymerizable group;
In the formula (C-2), Z 5～Z6 each independently represents a=CR 8 -or a nitrogen atom, R 2～R6 each independently represents a hydrogen atom or a 1-valent organic group, R 8 represents a hydrogen atom or a 1-valent organic group, and the structure represented by the formula (C-2) does not include a polymerizable group.
In the formula (C-1), Z 1～Z4 each independently represents=CR 7 -or a nitrogen atom.
Among them, a mode in which 1 of Z 1～Z4 is a nitrogen atom and 3 are=cr 7 -, a mode in which 2 of Z 1～Z4 is a nitrogen atom and 2 are=cr 7 -, or a mode in which 3 of Z 1～Z4 are a nitrogen atom and 1 are=cr 7 -, is preferable.
Among these, the method in which Z 1 and Z 3 are nitrogen atoms and Z 2 and Z 4 are=cr 7 -, the method in which Z 1 and Z 2 are nitrogen atoms and Z 3 and Z 4 are=cr 7 -, or the method in which Z 1、Z2 and Z 3 are nitrogen atoms and Z 4 are=cr 7 -, more preferably the method in which Z 1 and Z 3 are nitrogen atoms and Z 2 and Z 5 are=crb 7 -, or the method in which Z 1、Z2 and Z 3 are nitrogen atoms and Z 4 are=cr 7 -, is preferable.
In the formula (C-1), R 1 is preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom.
The number of carbon atoms of the hydrocarbon group or alkyl group is preferably 1 to 20, more preferably 1 to 10, and still more preferably 1 to 4.
In the formula (C-1), R 7 is preferably the same as R 1.
In the formula (C-2), Z 5 and Z 6 each independently represent a group consisting of CR 8 and a nitrogen atom.
Among them, it is preferable that Z 5 and Z 6 each represent a nitrogen atom, or Z 5 represents a nitrogen atom, and Z 6 represents=cr 8 -.
In the formula (C-2), R 2～R6、R8 is each independently preferably a hydrogen atom or a hydrocarbon group, more preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom.
[ Molecular weight ]
The molecular weight of the compound C is preferably 67 to 500, more preferably 68 to 300.
[ Specific example ]
Specific examples of the compound C include, but are not limited to, the compounds used in the examples.
[ Content ]
The content of the compound C is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass, based on the total solid content of the curable resin composition of the present invention.
The curable resin composition may contain only 1 compound C, or may contain 2 or more compounds C. When 2 or more compounds C are contained, the total amount is preferably within the above range.
< Compound D >
The curable resin composition of the present invention preferably further comprises a compound D as a silane coupling agent having a polymerizable group different from an alkoxysilyl group and having no azole group.
The compound D is preferably a compound containing an alkoxysilyl group and a polymerizable group different from the alkoxysilyl group.
The preferable mode of the alkoxysilyl group in the compound D is the same as that of the alkoxysilyl group in the above-described compound B.
The compound D is a compound having no azole group, and the detailed content of the azole group is the same as that of the azole group in the compound B described above.
Examples of the polymerizable group other than the alkoxysilyl group in the compound D include a known polymerizable group such as a radical polymerizable group, an epoxy group, an oxetanyl group, a hydroxymethyl group, an alkoxymethyl group, a (block) isocyanate group, and the like, and a radical polymerizable group or an epoxy group is preferable.
The preferable mode of the radical polymerizable group in the compound D is the same as the preferable mode of the radical polymerizable group in the above-described compound B.
As the compound D, a compound having a structure represented by the following formula (DA-1) is preferable.
[ Chemical formula 42]
In the formula (DA-1), R D1～RD3 is an alkyl group, L D1 is a 2-valent linking group, and X D1 is a polymerizable group.
In the formula (DA-L), R D1～RD3 is independently an alkyl group having 1 to 4 carbon atoms, more preferably a methyl group or an ethyl group, and still more preferably an ethyl group.
In the formula (DA-1), L D1 represents a 2-valent linking group, preferably a hydrocarbon group or a group represented by a bond of a hydrocarbon group and at least 1 group selected from the group consisting of-O-, -S-, -C (=o) -, -S (=o) 2 -, and-NR N -, more preferably a hydrocarbon group.
R N is as described above.
The form of L D1 having at least 1 group selected from the group consisting of an amide group and a urea group is also one of preferred forms of the present invention.
In the formula (DA-1), X D1 represents a polymerizable group, and preferable modes of the polymerizable group are as described above.
The compound D may be a compound having a molecular weight of less than 2,000 (hereinafter, also referred to as "low-molecular compound D"), or may be a resin (hereinafter, also referred to as "resin D").
In addition, from the viewpoint of adhesion of the cured film to a metal, the curable resin composition preferably contains both the low-molecular compound D and the resin D.
[ Low molecular weight Compound D ]
The molecular weight of the low-molecular compound D is less than 2,000, preferably 1,500 or less, and more preferably 1,000 or less.
The number of polymerizable groups different from the alkoxysilyl groups in the low-molecular compound D is not particularly limited, but is preferably 1 to 10, more preferably 1 to 4, and further preferably 1 or 2.
The low-molecular compound D is a compound represented by the above formula (DA-1), and preferably has a molecular weight within the above range.
[ Resin D ]
The resin D is preferably a resin having a repeating unit including an alkoxysilyl group and a repeating unit including a polymerizable group different from the alkoxysilyl group, or a resin having a repeating unit including an alkoxysilyl group and a polymerizable group different from the alkoxysilyl group, and more preferably a resin having a repeating unit including an alkoxysilyl group and a repeating unit including a polymerizable group different from the alkoxysilyl group.
The weight average molecular weight of the resin D is preferably 2,000 ～ 100,000, more preferably 3,000 to 70,000, and still more preferably 5,000 to 50,000.
The resin D is preferably an acrylic resin.
The repeating unit containing an alkoxysilyl group and the repeating unit containing a polymerizable group different from the alkoxysilyl group in the resin D may preferably be a repeating unit represented by the above formula (BA-2).
The resin D may have a repeating unit different from the repeating unit represented by the above formula (BA-2).
[ Specific example ]
Specific examples of the compound D include, but are not limited to, the compounds used in the examples.
[ Content ]
The content of the compound D is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass, based on the total solid content of the curable resin composition of the present invention.
The curable resin composition may contain only 1 kind of compound D, or may contain 2 or more kinds of compounds D. When 2 or more compounds D are contained, the total amount is preferably within the above range.
< Compound E >
The curable resin composition of the present invention preferably further comprises a compound E as a silane coupling agent having no polymerizable group other than an alkoxysilyl group or an azole group.
The compound E is preferably a compound having an alkoxysilyl group and having no polymerizable group and no azole group different from the alkoxysilyl group.
The compound E is a compound having no polymerizable group other than an alkoxysilyl group, but the details of the polymerizable group other than an alkoxysilyl group are the same as those of the polymerizable group other than an alkoxysilyl group in the above-described compound D.
The compound E is a compound having no azole group, and the detailed content of the azole group is the same as that of the azole group in the above-mentioned compound B.
Examples of the compound E include a compound described in paragraph 0167 of Japanese patent application laid-open No. 2015/199219, a compound described in paragraphs 0062 to 0073 of Japanese patent application laid-open No. 2014-191002, a compound described in paragraphs 0063 to 0071 of International patent application laid-open No. 2011/080992, a compound described in paragraphs 0060 to 0061 of Japanese patent application laid-open No. 2014-191252, a compound described in paragraphs 0045 to 0052 of Japanese patent application laid-open No. 2014-04264, and a compound having no polymerizable group other than an alkoxysilyl group or an azole group in the compound described in paragraph 0055 of International patent application laid-open No. 2014/097594. It is also preferable to use two or more different silane coupling agents as described in paragraphs 0050 to 0058 of Japanese patent application laid-open No. 2011-128358.
The following compounds are also preferably used as the compound E. In the following formula, et represents ethyl.
[ Chemical formula 43]
[ Content ]
The content of the compound E is preferably 0.05 to 10% by mass, more preferably 0.10 to 5% by mass, and even more preferably 0.15 to 2% by mass, based on the total solid content of the curable resin composition of the present invention.
The curable resin composition may contain only 1 compound E, or may contain 2 or more compounds E. When 2 or more compounds E are contained, the total amount is preferably within the above range.
< Solvent >
The curable resin composition of the present invention preferably contains a solvent. The solvent may be any known solvent. The solvent is preferably an organic solvent. Examples of the organic solvent include esters, ethers, ketones, cyclic hydrocarbons, sulfoxides, amides, ureas, alcohols, and the like.
Examples of the esters include ethyl acetate, n-butyl acetate, isobutyl acetate, hexyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, alkyl alkoxyacetate (e.g., methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, 2-alkoxy-2-methyl-2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-alkoxy-methyl-2-ethoxypropionate, ethyl 2-methyl-ethoxypropionate, etc.), ethyl 2-alkoxypropionate, etc.), and the like (e.g., methyl 2-ethoxypropionate, ethyl 2-methyl-ethoxypropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl caproate, ethyl heptanoate, dimethyl malonate, diethyl malonate, and the like.
Examples of the ethers include diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol ethyl methyl ether, and propylene glycol monopropyl ether acetate.
Examples of the ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-methylcyclohexanone, l-glucosone, and dihydro l-glucosone.
Examples of the cyclic hydrocarbon include aromatic hydrocarbons such as toluene, xylene and anisole, and cyclic terpenes such as limonene.
Examples of the sulfoxide include dimethyl sulfoxide.
As the amides, preferred examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-dimethylacetamide, N-dimethylformamide, N-dimethylisobutyramide, 3-methoxy-N, N-dimethylpropionamide, 3-butoxy-N, N-dimethylpropionamide, N-formylmorpholine, N-acetylmorpholine and the like.
Preferred urea compounds include N, N' -tetramethylurea, 1, 3-dimethyl-2-imidazolidinone, and the like.
Examples of the alcohols include methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 1-pentanol, 1-hexanol, benzyl alcohol, ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 2-ethoxyethanol, diethylene glycol monoethyl ether, diethylene glycol monohexyl ether, triethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monomethyl ether, polyethylene glycol monomethyl ether, polypropylene glycol, tetraethylene glycol, ethylene glycol monobutyl ether, ethylene glycol monobenzyl ether, ethylene glycol monophenyl ether, methyl phenyl methanol, n-amyl alcohol, methyl amyl alcohol, diacetone alcohol, and the like.
From the viewpoint of improvement of the coating surface properties, the solvent is preferably mixed with 2 or more types.
In the present invention, one solvent or a mixed solvent of two or more solvents selected from methyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, cyclohexanone, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, ethyl carbitol acetate, butyl carbitol acetate, N-methyl-2-pyrrolidone, propylene glycol methyl ether, and propylene glycol methyl ether acetate are preferable. It is particularly preferred to use dimethyl sulfoxide and gamma-butyrolactone simultaneously. Also, a combination of N-methyl-2-pyrrolidone and ethyl lactate, diacetone alcohol and ethyl lactate, cyclopentanone and gamma-butyrolactone is preferable.
Among these, the curable resin composition of the present invention preferably contains an ester, more preferably contains a lactone-based solvent.
The lactone-based solvent is a solvent containing a lactone structure, and examples thereof include gamma-butyrolactone, epsilon-caprolactone, delta-valerolactone, and the like.
The content of the lactone-based solvent is not particularly limited, but is preferably 30 to 100% by mass, more preferably 40 to 95% by mass, and even more preferably 50 to 90% by mass, based on the total mass of the solvent.
The content of the solvent is preferably an amount to achieve a total solid content concentration of 5 to 80 mass% of the curable resin composition of the present invention, more preferably an amount to achieve a total solid content concentration of 5 to 75 mass% of the curable resin composition of the present invention, still more preferably an amount to achieve a total solid content concentration of 10 to 70 mass% of the curable resin composition of the present invention, and still more preferably an amount to achieve a total solid content concentration of 40 to 70 mass% of the curable resin composition of the present invention from the viewpoint of coatability. The solvent content is adjusted according to the required thickness of the coating film and the coating method.
The solvent may be contained in 1 or 2 or more types. When the solvent is contained in an amount of 2 or more, the total amount is preferably within the above range.
< Sensitizer >
The composition of the present invention preferably comprises a sensitizer.
As the photosensitizer, a photopolymerization initiator is preferable.
[ Photopolymerization initiator ]
In the composition of the present invention, as the photosensitizer, a photopolymerization initiator is preferably contained.
The photopolymerization initiator is preferably a photo radical polymerization initiator. The photo radical polymerization initiator is not particularly limited, and may be appropriately selected from known photo radical polymerization initiators. For example, a photoradical polymerization initiator having photosensitivity to light rays ranging from the ultraviolet region to the visible region is preferable. The active agent may be an active agent that generates an active radical by reacting with a sensitizer excited by light.
The photo radical polymerization initiator is preferably an oxime compound described below.
The photo radical polymerization initiator preferably contains at least 1 compound having a molar absorptivity of at least about 50 L.mol -1·cm-1 in the range of about 300 to 800nm (preferably 330 to 50 Onm). The molar absorptivity of the compound can be measured by a known method. For example, it is preferable to measure it by an ultraviolet-visible spectrophotometer (Cary-5 spectrophotometer (spectrophotometer) manufactured by Varian Co.) using an ethyl acetate solvent at a concentration of 0.01 g/L.
As the photo radical polymerization initiator, a known compound can be arbitrarily used. Examples thereof include halogenated hydrocarbon derivatives (for example, compounds having a triazine skeleton, compounds having an oxadiazole skeleton, compounds having a trihalomethyl group, and the like), acylphosphine compounds such as acylphosphine oxides, oxime compounds such as hexaarylbiimidazole and oxime derivatives, organic peroxides, sulfur compounds, ketone compounds, aromatic onium salts, ketoxime ethers, aminoacetophenones, hydroxyacetophenones, azo compounds, azide compounds, metallocene compounds, organoboron compounds, and iron arene complexes. For details of these, reference is made to paragraphs 0165 to 0182 of Japanese unexamined patent publication (Kokai) No. 2016-027357 and paragraphs 0138 to 0151 of International publication (Kokai) No. 2015/199219, which are incorporated herein by reference.
Examples of the ketone compound include compounds described in paragraph 0087 of Japanese patent application laid-open No. 2015-087611, incorporated herein by reference. Of the commercial products, KAYACURE DETX (manufactured by Nippon Kayaku co., ltd.) may also be preferably used.
In one embodiment of the present invention, as the photo radical polymerization initiator, a hydroxyacetophenone compound, an aminoacetophenone compound, and an acylphosphine compound can be preferably used. More specifically, for example, an aminoacetophenone initiator described in JP-A-10-291969 or an acylphosphine oxide initiator described in JP-A-4225898 can be used.
As the hydroxyacetophenone initiator, IRGACURE 184 (IRGACURE is a registered trademark), DAROCUR 1173, IRGACURE 500, IRGACURE 2959, IRGACURE 127 (trade names: all manufactured by BASF corporation) can be used.
As the aminoacetophenone initiator, IRGACURE 907, IRGACU RE and 369 and IRGACURE 379 (trade names: all manufactured by BASF corporation) which are commercially available products can be used.
As the aminoacetophenone initiator, a compound described in japanese patent application laid-open No. 2009-191179 having an absorption maximum wavelength matching a light source having a wavelength of 365nm or 405nm or the like can be used.
Examples of the acylphosphine initiator include 2,4, 6-trimethylbenzoyl-diphenyl-phosphine oxide and the like. Further, IRGACURE 819 or IRGACURE TPO (trade name: all manufactured by BASF corporation) can be used as a commercial product.
Examples of the metallocene compound include IRGACURE 784 and IRGACURE 784EG (both manufactured by BASF corporation).
As the photo radical polymerization initiator, an oxime compound can be more preferably exemplified. By using an oxime compound, exposure latitude can be more effectively improved. The oxime compound is particularly preferable because it has a wide exposure latitude (exposure margin) and also functions as a photocuring accelerator.
Specific examples of the oxime compound include a compound described in JP-A-2001-233836, a compound described in JP-A-2000-080068, and a compound described in JP-A-2006-342166.
Preferable oxime compounds include, for example, 3-benzoyloxy iminobutane-2-one, 3-acetoxyiminobutane-2-one, 3-propionyloxy iminobutane-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino1-phenylpropane-1-one, 2-benzoyloxy imino1-phenylpropane-1-one, 3- (4-toluenesulfonyloxy) iminobutane-2-one, 2-ethoxycarbonyloxy imino1-phenylpropane-1-one, and the like having the following structures. In the composition of the present invention, it is particularly preferable to use an oxime compound (oxime-based photopolymerization initiator) as a photo radical polymerization initiator. The oxime-based photopolymerization initiator has a linking group of > c=n—o—c (=o) -in the molecule.
[ Chemical formula 44]
Among commercially available products, IRGACURE OXE 01, IRGACURE OXE 02, IRGACURE OXE 03, IRGACURE OXE 04 (manufactured by BASF corporation, above), adeka OptomerN-1919 (manufactured by ADEKA CORPORATION, japanese patent application laid-open No. 2012-014052) can also be preferably used. Also, TR-PBG-304 (Changzhou Tronly New Electronic Materials CO., LTD. Manufactured), ADEKA ARKLS NCI-831, and ADEKA ARKLS NCI-930 (manufactured by ADEKA CORPORATION) can be used. And, DFI-091 (Daito Chemix Corporation manufactured) can be used. Furthermore, an oxime compound having the following structure can also be used.
[ Chemical formula 45]
As the photopolymerization initiator, an oxime compound having a fluorene ring can also be used. Specific examples of the oxime compound having a fluorene ring include a compound described in japanese patent application laid-open No. 2014-137466 and a compound described in japanese patent 6636081.
As the photopolymerization initiator, an oxime compound having a skeleton in which at least 1 benzene ring in the carbazole ring becomes a naphthalene ring can also be used. Specific examples of such oxime compounds include those described in international publication No. 2013/083505.
Furthermore, an oxime compound having a fluorine atom can also be used. Specific examples of such oxime compounds include a compound described in JP 2010-26261028A, compounds 24, 36 to 40 described in section 0345 of JP 2014-500852A, and compound (C-3) described in section 0101 of JP 2013-164471A.
The most preferable oxime compound includes an oxime compound having a specific substituent shown in JP-A2007-269779, an oxime compound having a thioaryl group shown in JP-A2009-191061, and the like.
From the viewpoint of exposure sensitivity, the photo radical polymerization initiator is preferably a compound selected from the group consisting of trihalomethyltriazine compounds, benzyldimethyl ketal compounds, α -hydroxyketone compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzothiazole compounds, benzophenone compounds, acetophenone compounds and derivatives thereof, cyclopentadiene-present-iron complexes and salts thereof, halomethyl oxadiazole compounds, 3-aryl-substituted coumarin compounds.
Further preferred photo-radical polymerization initiators are trihalomethyltriazine compounds, α -aminoketone compounds, acylphosphine compounds, phosphine oxide compounds, metallocene compounds, oxime compounds, triarylimidazole dimers, onium salt compounds, benzophenone compounds, acetophenone compounds, further preferred are at least 1 compound selected from trihalomethyltriazine compounds, α -aminoketone compounds, oxime compounds, triarylimidazole dimers, benzophenone compounds, further preferred are metallocene compounds or oxime compounds, and still further preferred are oxime compounds.
The photo radical polymerization initiator may be an aromatic ketone such as benzophenone, N '-tetramethyl-4, 4' -diaminobenzophenone (miklineketone), N '-tetraalkyl-4, 4' -diaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholinophenone-1, an aromatic ketone such as alkylanthraquinone, benzoin ether compounds such as benzoin alkyl ether, benzoin compounds such as benzoin and alkylbenzoin, benzyl derivatives such as benzyl dimethyl ketal, or the like. In addition, a compound represented by the following formula (I) can be used.
[ Chemical formula 46]
In the formula (I), R I00 is an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms interrupted by 1 or more oxygen atoms, an alkoxy group having 1 to 12 carbon atoms, a phenyl group, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, a halogen atom, a cyclopentyl group, a cyclohexyl group, an alkenyl group having 2 to 12 carbon atoms, an alkyl group having 2 to 18 carbon atoms interrupted by 1 or more oxygen atoms, and a phenyl or biphenyl group substituted by at least 1 of an alkyl group having 1 to 4 carbon atoms, R I01 is a group represented by the formula (II) or the same group as R I00, and R I02～RI04 is each independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, or a halogen atom.
[ Chemical formula 47]
Wherein R I05～RI07 is the same as R I02～RI04 of formula (I) above.
The photo radical polymerization initiator may be any of those described in paragraphs 0048 to 0055 of International publication No. 2015/125469.
When the photopolymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and still more preferably 1.0 to 10% by mass, relative to the total solid content of the composition of the present invention. The photopolymerization initiator may be contained in an amount of 1 or 2 or more. When two or more photopolymerization initiators are contained, the total amount thereof is preferably within the above range.
[ Photo acid generator ]
In the composition of the present invention, it is preferable that the photoacid generator be contained as a photosensitizer.
By containing a photoacid generator, for example, acid is generated in an exposed portion of the composition layer, and the solubility of the exposed portion in a developer (for example, an aqueous alkali solution) is increased, a positive pattern in which the exposed portion is removed by the developer can be obtained.
Further, the composition may contain a polymerizable compound other than the photoacid generator and the radical polymerizable compound described later, and for example, the crosslinking reaction of the polymerizable compound is promoted by an acid generated in the exposed portion, so that the exposed portion is less likely to be removed by the developer than the non-exposed portion. In this way, a negative pattern can be obtained.
The photoacid generator is not particularly limited as long as it generates an acid by exposure, and examples thereof include onium salt compounds such as quinone diazide compounds, diazonium salts, phosphonium salts, sulfonium salts, iodonium salts, imide sulfonate, oxime sulfonate, diazonium disulfonate, disulfone, and sulfonic acid salt compounds such as o-nitrobenzyl sulfonate.
Examples of the quinone diazide compound include a compound in which quinone diazide sulfonic acid is bonded to a polyhydroxy compound via an ester, a compound in which quinone diazide sulfonic acid is bonded to a polyamino compound via a sulfonamide, a compound in which quinone diazide sulfonic acid is bonded to a polyhydroxy polyamino compound via at least one of an ester bond and a sulfonamide bond, and the like. In the present invention, for example, it is preferable that 50 mol% or more of the entire functional groups of these polyhydroxy compounds or polyamino compounds are substituted with quinone diazide groups.
In the present invention, quinone diazide may preferably use any one of 5-naphthoquinone diazide sulfonyl, 4-naphthoquinone diazide sulfonyl. The 4-naphthoquinone diazide sulfonyl ester compound has absorption in the i-ray region of the mercury lamp, and is suitable for i-ray exposure. The absorption of the 5-naphthoquinone diazide sulfonyl ester compound extends to the g-ray region of the mercury lamp, and is suitable for g-ray exposure. In the present invention, it is preferable to select a 4-naphthoquinone diazide sulfonyl ester compound and a 5-naphthoquinone diazide sulfonyl ester compound according to the exposure wavelength. The same molecule may contain a naphthoquinone diazide sulfonyl compound having a 4-naphthoquinone diazide sulfonyl group or a 5-naphthoquinone diazide sulfonyl group, or may contain a 4-naphthoquinone diazide sulfonyl compound and a 5-naphthoquinone diazide sulfonyl compound.
The naphthoquinone diazide compound can be synthesized by an esterification reaction between a compound having a phenolic hydroxyl group and a quinone diazide sulfonic acid compound, and can be synthesized by a known method. By using these naphthoquinone diazide compounds, resolution, sensitivity, and film residue ratio are further improved.
Examples of the naphthoquinone diazide compound include 1, 2-naphthoquinone-2-diazide-5-sulfonic acid and 1, 2-naphthoquinone-2-diazide-4-sulfonic acid, and salts and ester compounds of these compounds.
Examples of the onium salt compound or the sulfonate compound include those described in paragraphs 0064 to 0122 of JP-A2008-013686.
The photoacid generator is also preferably a compound containing an oxime sulfonate group (hereinafter, also simply referred to as "oxime sulfonate compound").
The oxime sulfonate compound is not particularly limited as long as it has an oxime sulfonate group, but is preferably an oxime sulfonate compound represented by the following formula (OS-1), the following formula (OS-103), the following formula (OS-104) or the following formula (OS-105).
[ Chemical formula 48]
In the formula (OS-1), X 3 represents an alkyl group, an alkoxy group or a halogen atom. When a plurality of X 3 are present, they may be the same or different. The alkyl group and the alkoxy group in X 3 may have a substituent. The alkyl group in X 3 is preferably a linear or branched alkyl group having 1 to 4 carbon atoms. The alkoxy group in X 3 is preferably a linear or branched alkoxy group having 1 to 4 carbon atoms. The halogen atom in X 3 is preferably a chlorine atom or a fluorine atom.
In the formula (OS-1), m3 represents an integer of 0 to 3, preferably 0 or 1. When m3 is 2 or 3, a plurality of X 3 may be the same or different.
In the formula (OS-1), R 34 represents an alkyl group or an aryl group, preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, a phenyl group which may be substituted with W, a naphthyl group which may be substituted with W, or an anthryl group which may be substituted with W. W represents a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, a halogenated alkyl group having 1 to 5 carbon atoms, a halogenated alkoxy group having 1 to 5 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogenated aryl group having 6 to 20 carbon atoms.
In the formula (OS-1), a compound in which m3 is 3, X 3 is methyl, the substitution position of X 3 is ortho, R 34 is a linear alkyl group having 1 to 10 carbon atoms, 7-dimethyl-2-oxonorbornylmethyl group or p-tolyl group is particularly preferable.
Specific examples of the oxime sulfonate compound represented by the formula (OS-1) include the following compounds described in paragraphs 0064 to 0068 of Japanese patent application laid-open No. 2011-209692 and paragraphs 0158 to 0167 of Japanese patent application laid-open No. 2015-194674, which are incorporated herein by reference.
[ Chemical formula 49]
In the formulae (OS-103) to (OS-105), R s1 may be an alkyl group, an aryl group or a heteroaryl group, a plurality of R s2 may be each independently a hydrogen atom, an alkyl group, an aryl group or a halogen atom, a plurality of R s6 may be each independently a halogen atom, an alkyl group, an alkoxy group, a sulfonic group, an sulfamoyl group or an alkoxysulfonyl group, xs may be O or S, ns may be 1 or 2, and ms may be an integer of 0 to 6.
In the formulae (OS-L03) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms), the aryl group (preferably having 6 to 30 carbon atoms), or the heteroaryl group (preferably having 4 to 30 carbon atoms) represented by R s1 may have a substituent T.
In the formulae (OS-103) to (OS-105), R s2 is preferably a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms), or an aryl group (preferably having 6 to 30 carbon atoms), and more preferably a hydrogen atom or an alkyl group. Of the R s2 groups which are sometimes present in the compound, preferably 1 or 2 are alkyl groups, aryl groups or halogen atoms, more preferably 1 is an alkyl group, aryl group or halogen atom, particularly preferably 1 is an alkyl group and the remainder are hydrogen atoms. The alkyl or aryl group represented by R s2 may have a substituent T.
In the formula (OS-103), the formula (OS-104) or the formula (OS-105), xs represents O or S, preferably O. In the above formulae (OS-103) to (OS-105), the ring containing Xs as a ring member is a 5-membered ring or a 6-membered ring.
In the formulae (OS-103) to (OS-105), ns represents 1 or 2, and when Xs is O, ns is preferably 1, and when Xs is S, ns is preferably 2.
In the formulae (OS-103) to (OS-105), the alkyl group (preferably having 1 to 30 carbon atoms) and the alkoxy group (preferably having 1 to 30 carbon atoms) represented by R s6 may have a substituent.
In the formulae (OS-103) to (OS-105), ms represents an integer of 0 to 6, preferably an integer of 0 to 2, preferably 0 or 1, and more preferably 0.
The compound represented by the formula (OS-103) is particularly preferably a compound represented by the following formula (OS-106), formula (OS-110) or formula (OS-111), the compound represented by the formula (OS-104) is particularly preferably a compound represented by the following formula (OS-107), and the compound represented by the formula (OS-105) is particularly preferably a compound represented by the following formula (OS-108) or formula (OS-109).
[ Chemical formula 50]
In the formulae (OS-106) to (OS-111), R t1 represents an alkyl group, an aryl group or a heteroaryl group, R t7 represents a hydrogen atom or a bromine atom, R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, and R t2 represents a hydrogen atom or a methyl group.
In the formulae (OS-106) to (OS-111), R t7 represents a hydrogen atom or a bromine atom, preferably a hydrogen atom.
In the formulae (OS-106) to (OS-111), R t8 represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, a halogen atom, a chloromethyl group, a bromomethyl group, a bromoethyl group, a methoxymethyl group, a phenyl group or a chlorophenyl group, preferably an alkyl group having 1 to 8 carbon atoms, a halogen atom or a phenyl group, more preferably an alkyl group having 1 to 8 carbon atoms, further preferably an alkyl group having 1 to 6 carbon atoms, particularly preferably a methyl group.
In the formulae (OS-106) to (OS-111), R t9 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group, preferably a hydrogen atom.
R t2 represents a hydrogen atom or a methyl group, preferably a hydrogen atom.
In the oxime sulfonate compound, the steric structure (E, Z) of the oxime may be either one or a mixture thereof.
Specific examples of the oxime sulfonate compounds represented by the above formulas (OS-103) to (OS-105) include compounds described in paragraphs 0088 to 0095 of Japanese patent application laid-open No. 2011-209792 and paragraphs 0168 to 0194 of Japanese patent application laid-open No. 2015-194674, which are incorporated herein by reference.
As a preferred embodiment of the oxime sulfonate compound containing at least 1 oxime sulfonate group, there may be mentioned compounds represented by the following formulas (OS-101) and (OS-102).
[ Chemical formula 51]
In the formula (OS-L01) or the formula (OS-102), R u9 represents a hydrogen atom, an alkyl group, an alkenyl group, an alkoxy group, an alkoxycarbonyl group, an acyl group, a carbamoyl group, a sulfamoyl group, a sulfo group, a cyano group, an aryl group or a heteroaryl group. More preferably, R u9 is cyano or aryl, and still more preferably, R u9 is cyano, phenyl or naphthyl.
In the formula (OS-101) or the formula (OS-102), R u2a represents an alkyl group or an aryl group.
In the formula (OS-101) or the formula (OS-102), xu represents-O-, -S-, -NH-; -NR u5-、-CH2-、-CRu6 H-or CR u6Ru7-,Ru5～Ru7 each independently represents an alkyl or aryl group.
In the formula (OS-101) or the formula (OS-102), R u1～Ru4 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkenyl group, an alkoxy group, an amino group, an alkoxycarbonyl group, an alkylcarbonyl group, an arylcarbonyl group, an amide group, a sulfo group, a cyano group or an aryl group. 2 of R u1～Ru4 may be bonded to each other to form a ring. In this case, the ring may be condensed to form a condensed ring together with the benzene ring. R u1～Ru4 is preferably a hydrogen atom, a halogen atom or an alkyl group, and is also preferably a mode in which at least 2 of R u1～Ru4 are bonded to each other to form an aryl group. Among them, R u1～Ru4 is preferably a hydrogen atom. The above substituents may each further have a substituent.
The compound represented by the above formula (OS-101) is more preferably a compound represented by the formula (OS-102).
In the oxime sulfonate compound, the steric structure (E, Z, etc.) of the oxime or benzothiazole ring may be either one or a mixture thereof.
Specific examples of the compound represented by the formula (OS-101) include compounds described in paragraphs 0102 to 0106 of Japanese patent application laid-open No. 2011-209692 and paragraphs 0195 to 0207 of Japanese patent application laid-open No. 2015-194674, which are incorporated herein by reference.
Among the above compounds, b-9, b-16, b-31, b-33 are preferable.
In addition, a commercially available product can be used as the photoacid generator. Commercially available products include WPAG-145, WPAG-149, WPAG-170, WPAG-199, WPAG-336, WPAG-367, WPAG-370, WPAG-443, WPAG-469, WPAG-638, WPAG-699 (all manufactured by FUJIFILM Wako Pure Chemical Corporation), omnicat 250, omnicat 270 (all manufactured by IGM RESINS b.v. company), irgacure 250, irgacure 270, irgacure 290 (all manufactured by BASF company), MBZ-101 (manufactured by midri Kagaku co., ltd.) and the like.
Further, as preferable examples, compounds represented by the following structural formulae are also given.
[ Chemical formula 52]
As the photoacid generator, an organic halogenated compound can also be applied. Specific examples of the organic halogenated compound include compounds described in "Bull chem. Soc Japan"42, 2924 (1969), U.S. Pat. No.3,905,815, japanese Kokoku publication No. 46-4605, japanese Kokai publication No. 48-36281, japanese Kokai publication No. 55-32070, japanese Kokai publication No. 60-239736, japanese Kokai publication No. 61-169835, japanese Kokai publication No. 61-169837, japanese Kokai publication No. 62-58241, japanese Kokai publication No. 62-212401, japanese Kokai publication No. 63-70243, japanese Kokai publication No. 63-298339, M.P.Hutt "Jurnal of Heterocyclic Chemistry"1 (No. 3), (1970) and the like, and particularly, the oxazole compound substituted with a trihalomethyl group: s-triazine compounds.
More preferably, can be cited at least 1 single, two or three halogen substituted methyl bonded to the s-three triazine ring s-three triazine derivatives, specifically, for example, can be cited in 2,4, 6-three (single chloromethyl) -s-three triazine, 2,4, 6-three (two chloromethyl) -s-three triazine, 2,4, 6-three (three chloromethyl) -s-three triazine, 2-methyl-4, 6-two (three chloromethyl) -s-three triazine, 2-propyl-4, 6-two (three chloromethyl) -s-three triazine, 2- (alpha, beta-trichloroethyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-phenyl-4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (3, 4-epoxyphenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-chlorophenyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- [ 1- (p-methoxyphenyl) -2, 4-butadienyl ] -4, 6-bis (trichloromethyl) -s-triazine, 2-styryl-4, 6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-isopropoxystyryl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4, 6-bis (trichloromethyl) -s-triazine, 2- (4-naphthyloxy-naphthyl) -4, 6-bis (trichloromethyl) -s-triazine, 2-phenylthio-4, 6-bis (trichloromethyl) -s-triazine, 2-benzylthio-4, 6-bis (trichloromethyl) -s-triazine, 2,4, 6-tris (dibromomethyl) -s-triazine, 2,4, 6-tris (tribromomethyl) -s-triazine, 2-methyl-4, 6-bis (tribromomethyl) -s-triazine, 2-methoxy-4, 6-bis (tribromomethyl) -s-triazine, and the like.
As the photoacid generator, an organoborate compound can also be applied. Specific examples of the organic borate compound include an organic borate described in Japanese patent application laid-open No. 62-143044, japanese patent application laid-open No. 62-150242, japanese patent application laid-open No. 9-188685, japanese patent application laid-open No. 9-188686, japanese patent application laid-open No. 9-188710, japanese patent application laid-open No. 2000-131837, japanese patent application laid-open No. 2002-107916, japanese patent application No. 2764769, japanese patent application laid-open No. 2000-310808 and the like, and Kunz, martin "Rad Tech'98.Proceeding April 19-22, 1998, chicago" and the like, an organic boron sulfonium complex described in Japanese patent application laid-open No. 6-157623, japanese patent application laid-open No. 6-175564, japanese patent application laid-open No. 6-175561, an organic boron oxosulfonium complex described in Japanese patent application laid-open No. 6-175554, japanese patent application laid-open No. 6-175553, a complex described in Japanese patent application laid-open No. 9-31074, japanese patent application laid-open No. 35, japanese patent application laid-open No. 6-128785, and the like.
As the photoacid generator, a disulfone compound can also be used. Examples of the disulfone compound include those described in Japanese patent application laid-open No. Sho 61-166544, japanese patent application laid-open No. 2001-132318, and the like.
Examples of the onium salt compound include diazonium salts described in S.I.Schlesinger, photogr.Sci.Eng.,18, 387 (1974), t.s.bal et al, polymer,21,423 (1980), ammonium salts described in U.S. Pat. No. 4,069,055, japanese patent application publication No. 4-365049, etc., phosphonium salts described in U.S. Pat. No. 4,069,055, U.S. Pat. No. 4,069,056, european patent application publication No. 104,143, U.S. Pat. No. 339,049, U.S. Pat. No. 410,201, iodonium salts described in japanese patent application publication No. 2-150848, japanese patent application publication No. 2-296514, european patent application publication No. 370,693, european patent application publication No. 390,214, european patent application No. 233,567, european patent application No. 297,443, european patent application publication No. 297,442, U.S. 4,933,377, U.S. Pat. 161,811, U.S. Pat. No. 410,201, U.S. Pat. No. 339,049, U.S. Pat. 4,760,013, U.S. Pat. No. 2,2,833,827, german patent application publication No. 2, and selenium salt described in German patent application publication No. 2,833,827, 2,833,827, onium salts such as arsonium salts and pyridinium salts described in Teh, proc.conf.rad.cutting ASIA, p478 Tokyo, oct (1988).
As the onium salts, there may be mentioned onium salts represented by the following general formulae (RI-I) to (RI-III).
[ Chemical formula 53]
In the formula (RI-I), ar 11 represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferable substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamido group having 1 to 12 carbon atoms or an arylamido group, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z 11 - represents a 1-valent anion, which is a halide ion, perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, sulfinate ion, thiosulfate ion, or sulfate ion, and is preferably a perchlorate ion, hexafluorophosphate ion, tetrafluoroborate ion, sulfonate ion, or sulfinate ion in terms of stability. In the formula (RI-II), ar 21、Ar22 each independently represents an aryl group having 20 or less carbon atoms which may have 1 to 6 substituents, and preferable substituents include an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 1 to 12 carbon atoms, an alkynyl group having 1 to 12 carbon atoms, an aryl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an aryloxy group having 1 to 12 carbon atoms, a halogen atom, an alkylamino group having 1 to 12 carbon atoms, a dialkylamino group having 1 to 12 carbon atoms, an alkylamido group or arylamido group having 1 to 12 carbon atoms, a carbonyl group, a carboxyl group, a cyano group, a sulfonyl group, a thioalkyl group having 1 to 12 carbon atoms, and a thioaryl group having 1 to 12 carbon atoms. Z 21 - represents a 1-valent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfate ion, or a sulfate ion, and is preferably a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion in terms of stability or reactivity. In the formula (RI-III), R 31、R32、R33 each independently represents an aryl group having 20 or less carbon atoms, an alkyl group, an alkenyl group, or an alkynyl group, which may have 1 to 6 substituents, and an aryl group is preferable in terms of reactivity and stability. Preferred substituents include alkyl groups having 1 to 12 carbon atoms, alkenyl groups having 1 to 12 carbon atoms, alkynyl groups having 1 to 12 carbon atoms, aryl groups having 1 to 12 carbon atoms, alkoxy groups having 1 to 12 carbon atoms, aryloxy groups having 1 to 12 carbon atoms, halogen atoms, alkylamino groups having 1 to 12 carbon atoms, dialkylamino groups having 1 to 12 carbon atoms, alkylamido or arylamido groups having 1 to 12 carbon atoms, carbonyl groups, carboxyl groups, cyano groups, sulfonyl groups, thioalkyl groups having 1 to 12 carbon atoms, and thioaryl groups having 1 to 12 carbon atoms. Z 31 - represents a 1-valent anion, which is a halogen ion, a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, a thiosulfate ion, or a sulfate ion, and is preferably a perchlorate ion, a hexafluorophosphate ion, a tetrafluoroborate ion, a sulfonate ion, a sulfinate ion, or a carboxylate ion in terms of stability or reactivity.
Specific examples thereof include the following.
[ Chemical formula 54]
[ Chemical formula 55]
[ Chemical formula 56]
[ Chemical formula 57]
When the photoacid generator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and still more preferably 2 to 15% by mass, relative to the total solid content of the composition of the present invention. The photoacid generator may contain only 1 species, or may contain 2 or more species. When two or more photoacid generators are contained, the total amount is preferably within the above range.
[ Photo-alkaline agent ]
The curable resin composition of the present invention may contain a photobase generator as a sensitizer.
The curable resin composition contains a photobase generator and a crosslinking agent described later, and for example, the exposed portion is less likely to be removed by a developer than the non-exposed portion by the action of an alkali generated in the exposed portion to promote cyclization of a specific resin, a crosslinking reaction of the crosslinking agent, and the like. In this way, a negative pattern can be obtained.
The photobase generator is not particularly limited as long as it generates a base by exposure, and a known photobase generator can be used.
For example, as in M.Shirai and M.Tsunooka, prog.Polym.Sci.,21,1 (1996); examples of the polymer processing ,46,2(1997);C.Kutal,Coord.Chem.Rev.,211,353(2001);Y.Kaneko,A.Sarker,and D.Neckers,Chem.Mater.,11,170(1999);H.Tachi,M.Shirai,and M.Tsunooka,J.Photopolym.Sci.Technol.,13,153(2000);M.Winkle,and K.Graziano,J.Photopolym.Sci.Technol.,3,419(1990);M.Tsunooka,H.Tachi,and S.Yoshitaka,J.Photopolym.Sci.Technol.,9,13(1996);K.Suyama,H.Araki,M.Shirai,J.Photopolym.Sci.Technol.,19,81(2006) include transition metal compound complexes, substances having a structure such as ammonium salts, and nonionic compounds in which an alkali component such as an amidine moiety is neutralized by formation of a salt with a carboxylic acid, and an alkali component such as a carbamate derivative, oxime ester derivative, or acyl compound is rendered latent by a carbamate bond or oxime bond.
In the present invention, as the photobase generator, carbamate derivatives, amide derivatives, imide derivatives, α cobalt complexes, imidazole derivatives, cinnamamide derivatives, oxime derivatives, and the like are exemplified as more preferable examples.
The basic substance generated from the photobase generator is not particularly limited, and examples thereof include compounds having an amino group, in particular, polyamines such as monoamines and diamines, and amidines.
From the viewpoint of the imidization rate, the basic substance is preferably one having a relatively large pKa in DMSO (dimethyl sulfoxide) of the conjugate acid. The pKa is preferably 1 or more, more preferably 3 or more. The upper limit of the pKa is not particularly limited, but is preferably 20 or less.
Here, the above pKa represents the logarithm of the reciprocal of the first dissociation constant of the acid, and reference can be made to the values described in Determination of Organic Structures by Physical Methods (authors: brown, H.C., mcDaniel, D.H., hafliger, O., nachod, F.C., compiler: braude, E.A., nachod, F.C., ACADEMIC PRESS, new York, 1955) or Data for Rioehemical Research (authors: dawson, R.M.C.et al; oxford, clarendon Press, 1959). Regarding the compounds not described in these documents, the value calculated from the structural formula using software of ACD/pKa (manufactured by ACD/Labs) was used as pKa.
From the viewpoint of storage stability of the curable resin composition, the photobase generator is preferably a photobase generator that does not contain a salt in the structure, and preferably has no charge on the nitrogen atom of the base moiety generated in the photobase generator. The photobase generator is preferably configured such that the generated base is potentially formed by covalent bonds, and the base generation mechanism is preferably configured such that covalent bonds between the nitrogen atom of the generated base moiety and adjacent atoms are cleaved to generate the base. In the case of a photobase generator that does not contain a salt in the structure, the photobase generator can be made neutral, so that the solvent solubility is better and the service life is prolonged. For these reasons, the amine produced from the photobase generator used in the present invention is preferably a primary amine or a secondary amine.
Also, from the viewpoint of chemical resistance of the pattern, as the photobase generator, a photobase generator containing a salt in the structure is preferable.
For the reasons described above, as the photobase generator, it is preferable that the generated base is rendered latent by a covalent bond, and it is preferable that the generated base is rendered latent by an amide bond, a urethane bond, or an oxime bond.
Examples of the photobase generator of the present invention include photobase generators having a cinnamamide structure as disclosed in japanese patent application laid-open publication No. 2009-080452 and international publication No. 2009/123122, photobase generators having a carbamate structure as disclosed in japanese patent application laid-open publication No. 2006-189591 and japanese patent application laid-open publication No. 2008-247747, photobase generators having an oxime structure and a carbamoyl oxime structure as disclosed in japanese patent application laid-open publication No. 2007-249013 and japanese patent application laid-open publication No. 2008-003581, but the present invention is not limited to these, and other known photobase generators can be used.
In addition, examples of the photobase generator include compounds described in paragraphs 0185 to 0188, 0199 to 0200 and 0202 of Japanese patent application laid-open No. 2012-093746, compounds described in paragraphs 0022 to 0069 of Japanese patent application laid-open No. 2013-194205, compounds described in paragraphs 0026 to 0074 of Japanese patent application laid-open No. 2013-204019, and compounds described in paragraph 0052 of International publication No. 2010/064631.
In addition, as the photobase generator, commercially available ones can be used. Commercially available products include WPBG-266、WPBG-300、WPGB-345、WPGB-140、WPBG-165、WPBG-027、WPBG-018、WPGB-015、WPBG-041、WPGB-172、WPGB-174、WPBG-166、WPGB-158、WPGB-025、WPGB-168、WPGB-167、WPBG-082(, manufactured by FUJIFILM Wako Pure Chemical Corporation, a2502, B5085, N0528, N1052, O0396, O0447, O0448 (Tokyo Chemical Industry co., manufactured by ltd.) and the like.
When the photobase generator is included, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, and even more preferably 2 to 15% by mass, relative to the total solid content of the curable resin composition of the present invention. The photobase generator may contain only one kind or two or more kinds. When the photobase generator is contained in an amount of 2 or more, the total amount is preferably within the above range.
< Thermal polymerization initiator >
The composition of the present invention may contain a thermal polymerization initiator, and in particular, may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or promote polymerization of a compound having polymerizability. By adding the thermal radical polymerization initiator, polymerization reaction of the resin and the polymerizable compound can be performed even in a heating step described later, and therefore solvent resistance can be further improved.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063254.
When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 5 to 15% by mass, relative to the total solid content of the composition of the present invention. The thermal polymerization initiator may be contained in an amount of 1 or2 or more. When two or more thermal polymerization initiators are contained, the total amount thereof is preferably within the above range.
< Thermal acid generator >
The compositions of the present invention may comprise a thermal acid generator.
The thermal acid generator has the following effects: the crosslinking reaction of at least 1 compound selected from the group consisting of a compound having a hydroxymethyl group, an alkoxymethyl group or an acyloxymethyl group, an epoxy compound, an oxetane compound and a benzoxazine compound is promoted by heating to generate an acid.
The thermal decomposition initiation temperature of the thermal acid generator is preferably 50 to 270 ℃, more preferably 50 to 250 ℃. Further, it is preferable to select a material that does not generate an acid when dried (prebaked: about 70 to 140 ℃) after the composition is applied to a substrate, but generates an acid when finally heated (cured: about 100 to 400 ℃) after patterning in subsequent exposure and development, as a thermal acid generator, because it is possible to suppress a decrease in sensitivity at the time of development.
The thermal decomposition initiation temperature was determined as the peak temperature of the lowest temperature exothermic peak when the thermal acid generator was heated to 500 ℃ at 5 ℃/min in a pressure-resistant capsule.
Examples of the equipment used for measuring the thermal decomposition initiation temperature include Q2000 (manufactured by TA Instruments Co., ltd.).
The acid generated from the thermal acid generator is preferably a strong acid, and for example, arylsulfonic acid such as p-toluenesulfonic acid and benzenesulfonic acid, alkylsulfonic acid such as methanesulfonic acid, ethanesulfonic acid and butanesulfonic acid, haloalkylsulfonic acid such as trifluoromethanesulfonic acid, and the like are preferable. Examples of such a thermal acid generator include particles described in paragraph 0055 of JP-A2013-072935.
Among them, from the viewpoint of less residue in the organic film and less tendency to deteriorate the physical properties of the organic film, it is more preferable that the organic film is formed of a sulfonic acid having 1 to 4 carbon atoms in alkyl group or a sulfonic acid having 1 to 4 carbon atoms in haloalkyl group, methyl sulfonic acid (4-hydroxyphenyl) dimethyl sulfonium, methyl sulfonic acid (4- ((methoxycarbonyl) oxy) phenyl) dimethyl sulfonium, benzyl (4-hydroxyphenyl) methyl sulfonium, benzyl (4- ((methoxycarbonyl) oxy) phenyl) methyl sulfonium, methyl sulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, trifluoro methane sulfonic acid (4-hydroxyphenyl) dimethyl sulfonium, trifluoro methane sulfonic acid (4-hydroxyphenyl) methyl sulfonium, trifluoro methane sulfonic acid benzyl (4- ((methoxycarbonyl) oxy) phenyl) methyl sulfonium, trifluoro methane sulfonic acid (4-hydroxyphenyl) methyl ((2-methylphenyl) methyl) sulfonium, 3- (5- (((propylsulfonyl) oxy) phenyl) -imino) -2- (o-thio) phenyl) -2H-thio-2- (o-thio) phenyl) -2- (o-thio) phenyl group, 2-bis (3- (methanesulfonylamino) -4-hydroxyphenyl) hexafluoropropane is preferred as the thermal acid generator.
Further, the compound described in paragraph 0059 of JP-A2013-167742 is also preferable as a thermal acid generator.
The content of the thermal acid generator is preferably 0.01 parts by mass or more, more preferably 0.1 parts by mass or more, relative to 100 parts by mass of the specific resin. Since the crosslinking reaction is promoted by containing 0.01 parts by mass or more, the mechanical properties and solvent resistance of the organic film can be further improved. Further, from the viewpoint of electrical insulation of the organic film, it is preferably 20 parts by mass or less, more preferably 15 parts by mass or less, and further preferably 10 parts by mass or less.
< Onium salt >
The curable resin composition of the present invention may further contain an onium salt.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain an onium salt.
The kind of the onium salt is not particularly limited, and ammonium salts, ammonium (Iminium) salts, sulfonium salts, iodonium salts, or phosphonium salts are preferably mentioned.
Among these, ammonium salts or iminium salts are preferable from the viewpoint of high thermal stability, and sulfonium salts, iodonium salts, or phosphonium salts are preferable from the viewpoint of compatibility with polymers.
The onium salt is a salt of a cation and an anion having an onium structure, and the cation and the anion may be bonded via a covalent bond or may not be bonded via a covalent bond.
That is, the onium salt may be an intramolecular salt having a cationic moiety and an anionic moiety in the same molecular structure, or may be an intermolecular salt in which a cationic molecule and an anionic molecule of different molecules are bonded to each other, but is preferably an intermolecular salt. In the curable resin composition of the present invention, the cationic moiety or cationic molecule and the anionic moiety or anionic molecule may be bonded or dissociated by ionic bonding.
The cation in the onium salt is preferably an ammonium cation, a pyridinium cation, a sulfonium cation, an iodonium cation or a phosphonium cation, and more preferably at least 1 cation selected from the group consisting of a tetraalkylammonium cation, a sulfonium cation and an iodonium cation.
The onium salt used in the present invention may be a thermoalcifer described later.
The thermal alkaline generator is a compound that generates a base by heating, and examples thereof include a compound that generates a base when heated to 40 ℃ or higher.
Examples of the onium salts include those described in paragraphs 0122 to 0138 of International publication No. 2018/043262. In addition, onium salts used in the field of polyimide precursors can be used without particular limitation.
When the curable resin composition of the present invention contains an onium salt, the content of the onium salt is preferably 0.1 to 50% by mass relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5 mass% or more, still more preferably 0.85 mass% or more, still more preferably 1 mass% or more. The upper limit is more preferably 30 mass% or less, still more preferably 20 mass% or less, still more preferably 10 mass% or less, and may be 5 mass% or less, or may be 4 mass% or less.
The onium salt can be used in an amount of 1 or 2 or more. When two or more types are used, the total amount is preferably within the above range.
< Thermal alkaline Agents >
The curable resin composition of the present invention may further contain a thermal alkaline generator.
In particular, when the curable resin composition of the present invention contains a polyimide precursor or a polybenzoxazole precursor as a specific resin, it is preferable to contain a thermal alkaline generator.
The other thermal alkaline generator may be a compound corresponding to the onium salt, or may be a thermal alkaline generator other than the onium salt.
Examples of the thermal alkaline generator other than the onium salts include nonionic thermal alkaline generators.
The nonionic thermal alkaline generator may be a compound represented by the formula (B1) or the formula (B2).
[ Chemical formula 58]
In the formula (B1) and the formula (B2), rb 1、Rb2 and Rb 3 are each independently an organic group having no tertiary amine structure, a halogen atom, or a hydrogen atom. However, rb 1 and Rb 2 do not simultaneously become hydrogen atoms. Further, rb 1、Rb2 and Rb 3 do not both have a carboxyl group. In the present specification, the tertiary amine structure means a structure in which all of 3 links of a nitrogen atom having a valence of 3 are covalently bonded to a carbon atom of a hydrocarbon system. Therefore, the present invention is not limited to the case where the bonded carbon atom is a carbon atom constituting a carbonyl group, that is, the case where an amide group is formed together with a nitrogen atom.
In the formulae (B1) and (B2), rb 1、Rb2 and Rb 3 preferably contain at least 1 cyclic structure, more preferably at least 2 cyclic structures. The cyclic structure may be any of a single ring and a condensed ring, and is preferably a single ring or a condensed ring formed by condensing 2 single rings. The monocyclic ring is preferably a 5-membered ring or a 6-membered ring, more preferably a 6-membered ring. The monocyclic ring is preferably a cyclohexane ring and a benzene ring, and more preferably a cyclohexane ring.
More specifically, rb 1 and Rb 2 are preferably a hydrogen atom, an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), or an arylalkyl group (preferably having 7 to 25 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms). These groups may have a substituent within a range that exerts the effect of the present invention. Rb 1 and Rb 2 may be bonded to each other to form a ring. The ring to be formed is preferably a 4-to 7-membered nitrogen-containing heterocycle. Rb 1 and Rb 2 are particularly preferably a linear, branched or cyclic alkyl group which may have a substituent (preferably a carbon number of 1 to 24, more preferably 2 to 18, still more preferably 3 to 12), more preferably a cycloalkyl group which may have a substituent (a carbon number of 3 to 24 is preferably 3 to 18, more preferably 3 to 12, still more preferably) and further preferably a cyclohexyl group which may have a substituent.
Examples of Rb 3 include an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 12 carbon atoms, still more preferably 2 to 6 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), an arylalkenyl group (preferably having 8 to 24 carbon atoms, more preferably 8 to 20 carbon atoms, still more preferably 8 to 16 carbon atoms), an alkoxy group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryloxy group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), or an arylalkoxy group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19, still more preferably 7 to 12). Among them, cycloalkyl groups (preferably having 3 to 24 carbon atoms, more preferably 3 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), arylalkenyl groups, and arylalkoxy groups are preferable. Rb 2 may further have a substituent within the range where the effect of the present invention is exerted.
The compound represented by the formula (B1) is preferably a compound represented by the following formula (B1-1) or the following formula (B1-2).
[ Chemical formula 59]
Wherein Rb 11 and Rb 12 and Rb 31 and Rb 32 are the same as Rb 1 and Rb 2 in formula (B1), respectively.
Rb 13 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an alkenyl group (preferably having 2 to 24 carbon atoms, more preferably 2 to 18 carbon atoms, still more preferably 3 to 12 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), and may have a substituent within a range that exerts the effects of the present invention. Among them, rb 13 is preferably arylalkyl.
Rb 33 and Rb 34 are each independently a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), or a hydrogen atom.
Rb 35 is an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), or an aryl group.
The compound represented by the formula (B1-1) is also preferably a compound represented by the formula (B1-1 a).
[ Chemical formula 60]
Rb 11 and Rb 12 have the same meaning as Rb 11 and Rb 12 in formula (B1-1).
Rb 15 and Rb 16 are a hydrogen atom, an alkyl group (preferably having 1 to 12 carbon atoms, more preferably 1 to 6 carbon atoms, still more preferably 1 to 3 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 6 carbon atoms, still more preferably 2 to 3 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 10 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 11 carbon atoms), a hydrogen atom or a methyl group.
Rb 17 is preferably an alkyl group (preferably having 1 to 24 carbon atoms, more preferably 1 to 12 carbon atoms, still more preferably 3 to 8 carbon atoms), an alkenyl group (preferably having 2 to 12 carbon atoms, more preferably 2 to 10 carbon atoms, still more preferably 3 to 8 carbon atoms), an aryl group (preferably having 6 to 22 carbon atoms, more preferably 6 to 18 carbon atoms, still more preferably 6 to 12 carbon atoms), an arylalkyl group (preferably having 7 to 23 carbon atoms, more preferably 7 to 19 carbon atoms, still more preferably 7 to 12 carbon atoms), or an aryl group.
The molecular weight of the nonionic thermal alkaline generator is preferably 800 or less, more preferably 600 or less, and further preferably 500 or less. The lower limit is preferably 100 or more, more preferably 200 or more, and still more preferably 300 or more.
Specific examples of the compounds as the thermal alkaline generator among the onium salts or other thermal alkaline generators other than the onium salts are as follows.
[ Chemical formula 61]
[ Chemical formula 62]
[ Chemical formula 63]
The content of the other thermal alkaline generator is preferably 0.1 to 50% by mass based on the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 0.5 mass% or more, and still more preferably 1 mass% or more. The upper limit is more preferably 30 mass% or less, and still more preferably 20 mass% or less. The thermal alkaline generator can be used in 1 or 2 or more. When two or more types are used, the total amount is preferably within the above range.
< Crosslinking agent >
The curable resin composition of the present invention preferably contains a crosslinking agent.
The crosslinking agent may be a radical crosslinking agent or other crosslinking agents.
< Radical crosslinking agent >
The curable resin composition of the present invention preferably further comprises a radical crosslinking agent.
The radical crosslinking agent is a compound having a radical polymerizable group. The radical polymerizable group is preferably a group containing an ethylenically unsaturated bond. Examples of the group containing an ethylenically unsaturated bond include a group having an ethylenically unsaturated bond such as a vinyl group, an allyl group, a vinylphenyl group, and a (meth) acryloyl group.
Among these, the group containing an ethylenically unsaturated bond is preferably a (meth) acryloyl group, and more preferably a (meth) acryloyl group from the viewpoint of reactivity.
The radical crosslinking agent may be any compound having 1 or more ethylenically unsaturated bonds, and more preferably 2 or more compounds.
The compound having 2 ethylenically unsaturated bonds is preferably a compound having 2 groups containing ethylenically unsaturated bonds as described above.
Further, from the viewpoint of film strength of the obtained pattern (cured film), the curable resin composition of the present invention preferably contains a compound having 3 or more ethylenically unsaturated bonds as a radical crosslinking agent. The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 to 15 ethylenically unsaturated bonds, more preferably a compound having 3 to 10 ethylenically unsaturated bonds, and still more preferably a compound having 3 to 6 ethylenically unsaturated bonds.
The compound having 3 or more ethylenically unsaturated bonds is preferably a compound having 3 or more groups containing ethylenically unsaturated bonds, more preferably a compound having 3 to 15, still more preferably a compound having 3 to 10, and particularly preferably a compound having 3 to 6.
The curable resin composition of the present invention preferably contains a compound having 2 ethylenically unsaturated bonds and 3 or more ethylenically unsaturated bonds from the viewpoint of film strength of the obtained pattern (cured film).
The molecular weight of the radical crosslinking agent is preferably 2,000 or less, more preferably 1,500 or less, and further preferably 900 or less. The lower limit of the molecular weight of the radical crosslinking agent is preferably 100 or more.
Specific examples of the radical crosslinking agent include unsaturated carboxylic acids (for example, acrylic acid, methacrylic acid, itaconic acid, crotonic acid, isocrotonic acid, maleic acid, etc.) or esters and amides thereof, and preferably esters of unsaturated carboxylic acids and polyhydric alcohol compounds and amides of unsaturated carboxylic acids and polyhydric amine compounds. In addition, an unsaturated carboxylic acid ester or amide having a nucleophilic substituent such as a hydroxyl group, an amino group, or a sulfanyl group, an addition reaction product with a monofunctional or polyfunctional isocyanate or epoxy, or a dehydration condensation reaction product with a monofunctional or polyfunctional carboxylic acid may be preferably used. It is also preferable to use a substituent of an unsaturated carboxylic acid ester or amide having an electrophilic substituent such as an isocyanate group or an epoxy group, and a monofunctional or polyfunctional alcohol, amide, or thiol, or an unsaturated carboxylic acid ester or amide having a leaving substituent such as a halogeno group (halogeno group) or a p-toluenesulfonyloxy group (tosyloxy group), and a monofunctional or polyfunctional alcohol, amine, or thiol. As another example, a compound group substituted with an unsaturated phosphonic acid, a vinylbenzene derivative such as styrene, a vinyl ether, an allyl ether, or the like may be used instead of the unsaturated carboxylic acid. For a specific example, reference may be made to the descriptions in paragraphs 0113 to 0122 of Japanese patent application laid-open No. 2016-027357, which are incorporated herein by reference.
The radical crosslinking agent is preferably a compound having a boiling point of 100 ℃ or higher at normal pressure. Examples thereof include compounds obtained by adding ethylene oxide or propylene oxide to a polyfunctional alcohol such as polyethylene glycol di (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, hexanediol (meth) acrylate, trimethylolpropane tri (acryloxypropyl) ether, tris (acryloxyethyl) isocyanurate, glycerol or trimethylolethane, and then (meth) acrylated, and urethane (meth) acrylates such as those described in each of Japanese patent application publication No. 48-041708, japanese patent application publication No. 50-006034, japanese patent application publication No. 51-037193, polyester acrylates described in each of Japanese patent application publication No. 48-064183, japanese patent application publication No. 49-043191, and epoxy acrylates as reaction products of epoxy resins and (meth) acrylic acid, and mixtures thereof. Further, the compounds described in paragraphs 0254 to 0257 of JP-A2008-292970 are also preferable. Further, a polyfunctional (meth) acrylate obtained by reacting a compound having a cyclic ether group and an ethylenically unsaturated bond such as glycidyl (meth) acrylate with a polyfunctional carboxylic acid can also be mentioned.
Further, as a preferable radical crosslinking agent other than the above, a compound having a fluorene ring and having 2 or more groups containing an ethylenically unsaturated bond or a cardo (cardo) resin described in japanese unexamined patent publication No. 2010-160418, japanese unexamined patent publication No. 2010-129825, japanese patent publication No. 4364216, and the like can be used.
Further, examples of the compounds include specific unsaturated compounds described in Japanese patent publication No. 46-043946, japanese patent publication No. 01-040337, japanese patent publication No. 01-040336, and vinyl phosphonic acid compounds described in Japanese patent publication No. 02-025493. Furthermore, a perfluoroalkyl group-containing compound described in JP-A-61-022048 can also be used. Furthermore, those described as photopolymerizable monomers and oligomers in Japanese society, shifting, no. 20, no.7, pages 300 to 308 (1984) can also be used.
In addition to the above, the compounds described in paragraphs 0048 to 0051 of Japanese patent application laid-open No. 2015-034964 and the compounds described in paragraphs 0087 to 0131 of International publication No. 2015/199219, which are incorporated herein by reference, can be used.
Further, a compound obtained by (meth) acrylating ethylene oxide or propylene oxide after addition to a polyfunctional alcohol, which is described in JP-A-10-062986 as the specific examples of the compounds represented by the formulas (1) and (2), can also be used as a radical crosslinking agent.
The compounds described in paragraphs 0104 to 0131 of JP-A2015-187211 can also be used as a radical crosslinking agent, and these are incorporated herein.
The radical crosslinking agent is preferably dipentaerythritol triacrylate (commercially available as KAYARAD D-330;Nippon Kayaku Co, manufactured by ltd., manufactured as commercially available as KAYARAD D-320;Nippon Kayaku Co, manufactured by ltd., a-TMMT: shin-Nakamura Chemical co., manufactured by ltd., manufactured as commercially available as KAYARAD D-310;Nippon Kayaku Co, manufactured by ltd., or dipentaerythritol hexa (meth) acrylate (commercially available as KAYARAD DPHA; nippon Kayaku co., manufactured by ltd., manufactured by a-DPH; shin-Nakamura Chemical co., manufactured by ltd.,) or the structure in which these (meth) acryl groups are bonded via a ethylene glycol residue or a propylene glycol residue. These oligomeric forms can also be used.
Examples of the commercial products of the radical crosslinking agent include SR-494 which is a 4-functional acrylate having 4 ethyleneoxy chains, SR-209, 231, 239, nippon Kayaku Co., ltd, DPCA-60 which is a 6-functional acrylate having 6 pentenoxy chains, TPA-330 which is a 3-functional acrylate having 3 isobutyleneoxy chains, urethane oligomer UAS-10, UAB-140 (Nippon Paper Industries Co., ltd., )、NK Ester M-40G、NK Ester 4G、NK Ester M-9300、NK Ester A-9300、UA-7200(Shin-Nakamura Chemical Co.,Ltd.), DPHA-40H (Nippon Kayaku Co., ltd., UA), UA-306H, UA-306T, UA-I, AH-600, T-600, MMP-600 (Kyoeisha chemical, ltd., manufacturing), and BLER 400 (NOF CORPORATlON).
As the radical crosslinking agent, urethane acrylate compounds having an ethylene oxide skeleton as described in Japanese patent application laid-open No. 48-041708, japanese patent application laid-open No. 51-037193, japanese patent application laid-open No. 02-032293, japanese patent application laid-open No. 02-016765, japanese patent application laid-open No. 58-049860, japanese patent application laid-open No. 56-017654, japanese patent application laid-open No. 62-039417, and Japanese patent application laid-open No. 62-039418 are also preferred. As the radical crosslinking agent, a compound having an amino structure or a sulfide structure in the molecule as described in JP-A-63-277653, JP-A-63-260909, and JP-A-01-105238 can also be used.
The radical crosslinking agent may be a radical crosslinking agent having an acid group such as a carboxyl group or a phosphate group. The radical crosslinking agent having an acid group is preferably an ester of an aliphatic polyhydroxy compound and an unsaturated carboxylic acid, and more preferably a radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic acid anhydride with unreacted hydroxyl groups of an aliphatic polyhydroxy compound. Particularly preferred is a radical crosslinking agent having an acid group by reacting a non-aromatic carboxylic anhydride with an unreacted hydroxyl group of an aliphatic polyhydroxy compound, wherein the aliphatic polyhydroxy compound is a pentaerythritol or dipentaerythritol compound. As commercial products, for example, polyacid-modified acrylic oligomers produced by TOAGOSEI CO., LTD. Include M-510 and M-520.
The radical crosslinking agent having an acid group preferably has an acid value of 0.1 to 40mgKOH/g, particularly preferably 5 to 30mgKOH/g. When the acid value of the radical crosslinking agent is within the above range, the workability in production is excellent, and further, the developability is excellent. And, the polymerizability is good. On the other hand, from the viewpoint of the development speed at the time of alkali development, the acid value of the radical crosslinking agent having an acid group is preferably 0.1 to 300mgKOH/g, and particularly preferably 1 to 100mgKOH/g. The acid value is according to JIS K0070: 1992.
From the viewpoints of resolution of the pattern and stretchability of the film, the curable resin composition of the present invention preferably uses 2-functional methacrylate or acrylate. As specific compounds, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, PEG200 dimethacrylate, PEG600 diacrylate, PEG600 dimethacrylate, polytetraethylene glycol diacrylate, polytetraethylene glycol dimethacrylate, neopentyl glycol diacrylate, neopentyl glycol dimethacrylate, 3-methyl-1, 5-pentanediol diacrylate, 1, 6-hexanediol dimethacrylate, dimethylol-tricyclodecane diacrylate, dimethylol-tricyclodecane dimethacrylate, EO adduct diacrylate of bisphenol a, PO adduct dimethacrylate of bisphenol a, 2-hydroxy-3-acryloxypropyl methacrylate, isocyanuric acid modified diacrylate, isocyanuric acid modified dimethacrylate, 2-functional acrylate having a urethane bond, 2-functional methacrylate having a urethane bond can be used. These may be used in combination of 2 or more kinds as required.
Further, from the viewpoint of suppressing warpage associated with the elastic modulus control of the pattern (cured film), a monofunctional radical crosslinking agent can be preferably used as the radical crosslinking agent. As the monofunctional radical crosslinking agent, N-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, carbitol (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, N-methylol (meth) acrylamide, (meth) acrylic acid glycidyl ester, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate and other (meth) acrylic acid derivatives, N-vinyl compounds such as N-vinyl pyrrolidone and N-vinyl caprolactam, allyl glycidyl ether, diallyl phthalate, triallyl trimellitate and other allyl compounds can be preferably used. The monofunctional radical crosslinking agent is preferably a compound having a boiling point of 100℃or higher at normal pressure in order to suppress volatilization before exposure.
When the radical crosslinking agent is contained, the content thereof is preferably more than 0% by mass and 60% by mass or less relative to the total solid content of the curable resin composition of the present invention. The lower limit is more preferably 5 mass% or more. The upper limit is more preferably 50 mass% or less, and still more preferably 30 mass% or less.
The radical crosslinking agent may be used alone, but two or more kinds may be used in combination. When two or more of the above-mentioned components are used at the same time, the total amount thereof is preferably within the above-mentioned range.
< Other Cross-linking agent >
The curable resin composition of the present invention preferably also contains a crosslinking agent other than the radical crosslinking agent.
In the present invention, the other crosslinking agent means a crosslinking agent other than the radical crosslinking agent, preferably a compound having a plurality of groups in the molecule which promote a reaction for forming covalent bonds between other compounds in the composition or reaction products thereof by the sensitization of the sensitizer, and preferably a compound having a plurality of groups in the molecule which promote a reaction for forming covalent bonds between other compounds in the composition or reaction products thereof by the action of an acid or a base.
The acid or base is preferably an acid or base generated from a photoacid generator or photobase generator as a sensitizer in the exposure step.
The other crosslinking agent is preferably a compound having at least 1 group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, and more preferably a compound having a structure in which at least 1 group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group is directly bonded to a nitrogen atom.
Examples of the other crosslinking agent include compounds having a structure in which formaldehyde or formaldehyde and an alcohol are reacted with an amino group-containing compound such as melamine, acetylene urea, alkylene urea, benzoguanamine, or the like to replace a hydrogen atom of the amino group with a hydroxymethyl group or an alkoxymethyl group. The method for producing these compounds is not particularly limited as long as they have the same structure as the compounds produced by the above method. The oligomer may be one in which methylol groups of these compounds are self-condensed with each other.
The crosslinking agent using melamine as the amino group-containing compound is referred to as a melamine-based crosslinking agent, the crosslinking agent using glycoluril, urea or alkylene urea is referred to as a urea-based crosslinking agent, the crosslinking agent using alkylene urea is referred to as an alkylene urea-based crosslinking agent, and the crosslinking agent using benzoguanamine is referred to as a benzoguanamine-based crosslinking agent.
Among these, the curable resin composition of the present invention preferably contains at least 1 compound selected from urea-based crosslinking agents and melamine-based crosslinking agents, more preferably contains at least 1 compound selected from glycoluril-based crosslinking agents and melamine-based crosslinking agents described later.
Specific examples of the melamine-based crosslinking agent include hexamethoxymethyl melamine, hexaethoxymethyl melamine, hexapropoxymethyl melamine, hexabutoxybutyl melamine, and the like.
Specific examples of the urea-based crosslinking agent include: acetylene urea-based cross-linking agents such as monohydroxy-methylated acetylene urea, dihydroxy-methylated acetylene urea, trihydroxy-methylated acetylene urea, tetrahydroxy-methylated acetylene urea, monomethoxy-methylated acetylene urea, dimethoxy-methylated acetylene urea, trimethoxy-methylated acetylene urea, tetraethoxy-methylated acetylene urea, monopropoxy-methylated acetylene urea, dipropoxy-methylated acetylene urea, tripropoxy-methylated acetylene urea, tetrapropoxy-methylated acetylene urea, monobutyl-methylated acetylene urea, dibutoxy-methylated acetylene urea, tributoxy-methylated acetylene urea or tetrabutoxy-methylated acetylene urea,
Urea-based crosslinking agents such as dimethoxymethyl urea, diethoxymethyl urea, dipropoxymethyl urea and dibutoxymethyl urea,
Ethylene urea-based crosslinking agents such as monohydroxymethyl ethylene urea or dihydroxymethyl ethylene urea, monomethoxy methyl ethylene urea, dimethoxy methyl ethylene urea, monoethoxy methyl ethylene urea, diethoxy methyl ethylene urea, monopropoxy methyl ethylene urea, dipropoxy methyl ethylene urea, monobutyl methyl ethylene urea or dibutoxy methyl ethylene urea,
Acryl urea-based crosslinking agents such as monohydroxymethyl acryl urea, dihydroxymethyl acryl urea, monomethoxy methyl acryl urea, dimethoxy methyl acryl urea, monomethoxy methyl acryl urea, diethoxy methyl acryl urea, monopropoxy methyl acryl urea, dipropoxy methyl acryl urea, monobutyl oxy methyl acryl urea or dibutoxy methyl acryl urea,
1, 3-Bis (methoxymethyl) -4, 5-dihydroxy-2-imidazolidinone, 1, 3-bis (methoxymethyl) -4, 5-dimethoxy-2-imidazolidinone, and the like.
Specific examples of the benzoguanamine-based crosslinking agent include monohydroxymethyl benzoguanamine, dihydroxymethyl benzoguanamine, trihydroxymethyl benzoguanamine, tetrahydroxymethyl benzoguanamine, monomethoxy-methyl benzoguanamine, dimethoxy-methyl benzoguanamine, trimethoxy-methyl benzoguanamine, tetramethoxy-methyl benzoguanamine, tetraethoxy-methyl benzoguanamine, monopropoxy-methyl benzoguanamine, dipropoxy-methyl benzoguanamine, tripropoxy-methyl benzoguanamine, tetrapropoxy-methyl benzoguanamine, monobutyloxy-methyl benzoguanamine, dibutoxy-methyl benzoguanamine, tributoxy-methyl benzoguanamine, tetrabutoxy-methyl benzoguanamine, etc.
As the compound having at least 1 group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group, a compound in which at least 1 group selected from the group consisting of a hydroxymethyl group and an alkoxymethyl group is directly bonded to an aromatic ring (preferably a benzene ring) can be preferably used.
Specific examples of such a compound include xylylene glycol, bis (hydroxymethyl) cresol, bis (hydroxymethyl) dimethoxybenzene, bis (hydroxymethyl) diphenyl ether, bis (hydroxymethyl) benzophenone, hydroxymethyl benzyl hydroxy benzoate, bis (hydroxymethyl) biphenyl, dimethyl bis (hydroxymethyl) biphenyl, bis (methoxymethyl) benzene, bis (methoxymethyl) cresol, bis (methoxymethyl) dimethoxybenzene, bis (methoxymethyl) diphenyl ether, bis (methoxymethyl) benzophenone, methoxymethyl phenyl methoxymethylbenzoate, bis (methoxymethyl) biphenyl, dimethyl bis (methoxymethyl) biphenyl, 4',4 "-ethylenetris [2, 6-bis (methoxymethyl) phenol ], 5' - [2, 2-trifluoro-1- (trifluoromethyl) ethylene ] bis [ 2-hydroxy-1, 3-benzenedimethanol ], 3', 5' -tetrakis (methoxymethyl) -1,1 '-biphenyl-4, 4' -diol, and the like.
As other crosslinking agents, commercially available products may be used, and preferable commercially available products include 46DMOC, 46DMOEP (manufactured )、DML-PC、DML-PEP、DML-OC、DML-OEP、DML-34X、DML-PTRP、DML-PCHP、DML-OCHP、DML-PFP、DML-PSBP、DML-POP、DML-MBOC、DML-MBPC、DML-MTrisPC、DML-BisOC-Z、DML-BisOCHP-Z、DML-BPC、DMLBisOC-P、DMOM-PC、DMOM-PTBP、DMOM-MBPC、TriML-P、TriML-35XL、TML-HQ、TML-BP、TML-pp-BPF、TML-BPE、TML-BPA、TML-BPAF、TML-BPAP、TMOM-BP、TMOM-BPE、TMOM-BPA、TMOM-BPAF、TMOM-BPAP、HML-TPPHBA、HML-TPHAP、HMOM-TPPHBA、HMOM-TPHAP( or more by ASAHI YUKIZAI CORPORATION and manufactured Honshu Chemical Industry co., ltd. Above), NIKARAC (registered trademark, the same shall apply hereinafter) MX-290, NIKARAC MX-280, NIKARAC MX-270, NIKARAC MX-279, NIKARAC MW-100LM, NIKARAC MX-750LM (manufactured SANWA CHEMICAL co., ltd. Above), and the like.
The curable resin composition of the present invention preferably further contains at least 1 compound selected from the group consisting of an epoxy compound, an oxetane compound and a benzoxazine compound as another crosslinking agent.
[ Epoxy Compound (Compound having an epoxy group) ]
The epoxy compound is preferably a compound having 2 or more epoxy groups in 1 molecule. The epoxy group undergoes a crosslinking reaction at 200 ℃ or less and does not undergo a dehydration reaction derived from crosslinking, and thus film shrinkage is less likely to occur. Therefore, the epoxy compound is effective for low-temperature curing of the curable resin composition and suppression of warpage.
The epoxy compound preferably contains a polyethylene oxide group. Thereby, the elastic modulus is further reduced, and warpage can be suppressed. The polyethylene oxide group is a group having a repeating unit number of 2 or more, preferably 2 to 15.
Examples of the epoxy compound include bisphenol a type epoxy resins; bisphenol F type epoxy resin; alkylene glycol type epoxy resins such as propylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, ethylene glycol diglycidyl ether, butylene glycol diglycidyl ether, hexamethylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, and the like, or polyhydric alcohol hydrocarbon type epoxy resins; polyalkylene glycol type epoxy resins such as polypropylene glycol diglycidyl ether; and epoxy group-containing silicones such as polymethyl (glycidoxypropyl) siloxane, but the present invention is not limited thereto. Specifically, EPICLON (registered trademark) HP-4032, EPICLON (registered trademark) HP-7200, EPICLON (registered trademark) HP-820, EPICLON (registered trademark) HP-4700, EPICLON (registered trademark) EXA-4710, EPICLON (registered trademark) HP-4770, EPICLON (registered trademark) EXA-859CRP, EPICLON (registered trademark) EXA-1514, EPICLON (registered trademark) EXA-4880, EPICLON (registered trademark) EXA-4850-150, EPICLON (registered trademark) EXA-4850-1000, EPICLON (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-4822, EPICLON (registered trademark) EXA-83OLVP, EPICLON (registered trademark) EXA-8183, EPICLON (registered trademark) EXA-69, EPICLON (registered trademark) N-8157 (registered trademark) EXA-4815-150, EPICLON (registered trademark) EXA-4815 (registered trademark) EXA-4816, EPICLON (registered trademark) EXA-83OLVP (registered trademark) are given as BE-35 (registered trademark) of BE20, DIC Corporation), RIKA RESIN (registered trademark) BEO-60E, RIKA RESIN (registered trademark) HBE-100, RIKA RESIN (registered trademark) DME-100, RIKA RESIN (registered trademark) L-200 (trade name, RIKA RESIN Co., manufactured by Ltd.), EP-4003 RIKA RESIN-4000 RIKA RESIN-4088S, EP-3950S (trade name, manufactured above, ADEKA CORPORATION), CELLOXIDE (registered trademark) 2021P, 2081, 2000, 3000, EHPE3150, EPOLEAD (registered trademark) GT400, CELVENUS (registered trademark) B0134, B0177 (trade name, manufactured above, daicel Corporation manufactured above, )、NC-3000、NC-3000-L、NC-3000-H、NC-3000-FH-75M、NC-3100、CER-3000-L、NC-2000-L、XD-1000、NC-7000L、NC-7300L、EPPN-501H、EPPN-501HY、EPPN-502H、EOCN-1020、EOCN-102S、EOCN-103S、EOCN-104S、CER-1020、EPPN-201、BREN-S、BREN-10S(, manufactured by Nippon Kayaku co., ltd.) and the like.
[ Oxetane Compound (oxetane Compound) ]
Examples of oxetane compounds include compounds having 2 or more oxetane rings in 1 molecule, 3-ethyl-3-hydroxymethyloxetane, 1, 4-bis { [ (3-ethyl-3-oxetanyl) methoxy ] methyl } benzene, 3-ethyl-3- (2-ethylhexyl methyl) oxetane, and 1, 4-benzenedicarboxylic acid-bis [ (3-ethyl-3-oxetanyl) methyl ] ester. As specific examples, the ARON OXETANE series (e.g., next-121, next-221, next-191, next-223) manufactured by TOAGOSEI co., ltd. Can be preferably used, and these can be used alone or in combination of 2 or more.
[ Benzoxazine Compound (Compound having benzoxazolyl group) ]
The benzoxazine compound is preferable because it does not generate outgas at the time of curing due to a crosslinking reaction derived from a ring-opening addition reaction, and further reduces heat shrinkage to suppress generation of warpage.
Preferable examples of the benzoxazine compound include B-a type benzoxazine, B-m type benzoxazine, P-d type benzoxazine, F-a type benzoxazine (trade name, SHIKOKU CHEMICALS CORPORATION manufactured above), benzoxazine adducts of polyhydroxystyrene resins, and phenol novolac type dihydrobenzoxazine compounds. These may be used singly or in combination of two or more.
The content of the other crosslinking agent is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, and particularly preferably 1.0 to 10% by mass, based on the total solid content of the curable resin composition of the present invention. The other crosslinking agent may be contained only in 1 kind, or may be contained in 2 or more kinds. When two or more other crosslinking agents are contained, the total thereof is preferably within the above range.
< Compound having sulfonamide Structure, compound having thiourea Structure >
The curable resin composition of the present invention preferably further contains at least 1 compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, from the viewpoint of improving adhesion to a substrate of the obtained pattern (cured film).
[ Compounds having sulfonamide Structure ]
The sulfonamide structure is represented by the following formula (S-1).
[ Chemical formula 64]
In the formula (S-1), R represents a hydrogen atom or an organic group, and R may be bonded to other structures to form a ring structure, and each independently represents a bonding position to other structures.
R is preferably the same as R 2 in the following formula (S-2).
The compound having a sulfonamide structure may be a compound having 2 or more sulfonamide structures, and preferably a compound having 1 or more sulfonamide structures.
The compound having a sulfonamide structure is preferably a compound represented by the following formula (S-2).
[ Chemical formula 65]
In the formula (S-2), R 1、R2 and R 3 each independently represent a hydrogen atom or a 1-valent organic group, and 2 or more of R 1、R2 and R 3 may be bonded to each other to form a ring structure.
Preferably, R 1、R2 and R 3 each independently represent a 1-valent organic group.
Examples of R 1、R2 and R 3 include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and combinations of 2 or more of these groups.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl.
The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups.
The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl.
Examples of the heterocyclic group include a group having 1 hydrogen atom removed from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a triazine ring.
Among these, compounds in which R 1 is an aryl group and R 2 and R 3 are each independently a hydrogen atom or an alkyl group are preferable.
Examples of the compound having a sulfonamide structure include benzenesulfonamide, dimethylbenzenesulfonamide, N-butylbenzenesulfonamide, sulfonamide, o-toluenesulfonamide, p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthyl-1-sulfonamide, naphthyl-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide, methanesulfonamide, N-dimethylformamide, N-dimethylethanesulfonamide, N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N-dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.
[ Compounds having thiourea Structure ]
The thiourea structure is represented by the following formula (T-1).
[ Chemical formula 66]
In formula (T-1), R 4 and R 5 each independently represent a hydrogen atom or a 1-valent organic group, R 4 and R 5 may be bonded to form a ring structure, R 4 may be bonded to other structures bonded to form a ring structure, and R 5 may be bonded to other structures bonded to form a ring structure, each independently represent a bonding position with other structures.
Preferably, R 4 and R 5 are each independently a hydrogen atom.
Examples of R 4 and R 5 include a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, an alkyl ether group, an alkylsilyl group, an alkoxysilyl group, an aryl ether group, a carboxyl group, a carbonyl group, an allyl group, a vinyl group, a heterocyclic group, and combinations of 2 or more of these groups.
The alkyl group is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms. Examples of the alkyl group include methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, and 2-ethylhexyl.
The cycloalkyl group is preferably a cycloalkyl group having 5 to 10 carbon atoms, and more preferably a cycloalkyl group having 6 to 10 carbon atoms. Examples of the cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
The alkoxy group is preferably an alkoxy group having 1 to 10 carbon atoms, and more preferably an alkoxy group having 1 to 5 carbon atoms. Examples of the alkoxy group include methoxy, ethoxy, propoxy, butoxy, and pentoxy groups.
The alkoxysilyl group is preferably an alkoxysilyl group having 1 to 10 carbon atoms, and more preferably an alkoxysilyl group having 1 to 4 carbon atoms. Examples of the alkoxysilyl group include a methoxysilyl group, an ethoxysilyl group, a propoxysilyl group, and a butoxysilyl group.
The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms. The aryl group may have a substituent such as an alkyl group. Examples of the aryl group include phenyl, tolyl, xylyl, and naphthyl.
Examples of the heterocyclic group include a group having 1 hydrogen atom removed from a heterocyclic structure such as a triazole ring, a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, an oxazole ring, a thiazole ring, a pyrazole ring, an isoxazole ring, an isothiazole ring, a tetrazole ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperidine, a piperazine ring, a morpholine ring, a dihydropyran ring, a tetrahydropyran ring, and a triazine ring.
The compound having a thiourea structure may be a compound having 2 or more thiourea structures, but is preferably a compound having 1 thiourea structure.
The compound having a thiourea structure is preferably a compound represented by the following formula (T-2).
[ Chemical formula 67]
In the formula (T-2), R 4～R7 each independently represents a hydrogen atom or a 1-valent organic group, and at least 2 of R 4～R7 may be bonded to each other to form a ring structure.
In the formula (T-2), R 4 and R 5 have the same meaning as R 4 and R 5 in the formula (T-1), and the preferable mode is the same.
In the formula (T-2), R 6 and R 7 are preferably each independently a 1-valent organic group.
In the formula (T-2), the preferable mode of the 1-valent organic groups in R 6 and R 7 is the same as the preferable mode of the 1-valent organic groups in R 4 and R 5 in the formula (T-1).
Examples of the compound having a thiourea structure include N-acetylthiourea, N-allylthiourea, N-allyl-N '- (2-hydroxyethyl) thiourea, 1-adamantylthiourea, N-benzoylthiourea, N' -diphenylthiourea, 1-benzyl-phenylthiourea, 1, 3-dibutylthiourea, 1, 3-diisopropylthiourea, 1, 3-dicyclohexylthiourea, 1- (3- (trimethoxysilyl) propyl) -3-methylthiourea, trimethylthiourea, tetramethylthiourea, N-diphenylthiourea, ethylenethiourea (2-imidazolinethione), carbimorph (Carbimazole), and 1, 3-dimethyl-2-thiohydantoin.
[ Content ]
The total content of the compound having a sulfonamide structure and the compound having a thiourea structure is preferably 0.05 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.2 to 3 mass%, based on the total mass of the curable resin composition of the present invention.
The curable resin composition of the present invention may contain only one compound selected from the group consisting of a compound having a sulfonamide structure and a compound having a thiourea structure, or may contain two or more compounds. When only one kind of the compound is contained, the content of the compound is preferably within the above range, and when two or more kinds of the compound are contained, the total amount thereof is preferably within the above range.
< Polymerization inhibitor >
The curable resin composition of the present invention preferably contains a polymerization inhibitor.
As polymerization inhibitors, use may preferably be made, for example, of hydroquinone, o-methoxyphenol, methoxyhydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, gallphenol, p-tert-butylcatechol (tert-butylcatechol), 1, 4-benzoquinone, diphenyl-p-benzoquinone, 4 '-thiobis (3-methyl-6-tert-butylphenol), 2' -methylenebis (4-methyl-6-tert-butylphenol), aluminum N-nitroso-N-phenylhydroxylamine salts, phenothiazine, N-nitrosodiphenylamine, N-phenylnaphthylamine, ethylenediamine tetraacetic acid, 1, 2-cyclohexanediamine tetraacetic acid, glycol ether diamine tetraacetic acid, 2, 6-di-tert-butyl-4-methylphenol, 5-nitroso-8-hydroxyquinoline, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 2-nitroso-5- (N-ethyl-sulfopropylamino) phenol, cerium N-nitrosophenyl hydroxylamine salts, N-nitroso-N- (1-naphthylamine salts, bis (4-hydroxy-phenyl-quinone), 4, 3, 2-cyclohexanediol, 4-tert-butylphenol, 4-diphenyl-4-tert-butylphenol, 5-tris (4-tert-butyl-3-hydroxy-2, 6-dimethylbenzyl) -1,3, 5-triazine-2, 4,6- (1H, 3H, 5H) -trione, 4-hydroxy-2, 6-tetramethylpiperidine 1-oxyl radical, phenothiazine, 1-diphenyl-2-pyrrolyl hydrazine, copper (II) dibutyldithiocarbamate, nitrobenzene, N-nitroso-N-phenylhydroxylamine aluminum salt, N-nitroso-N-phenylhydroxylamine ammonium salt, and the like. Further, a polymerization inhibitor described in paragraph 0060 of Japanese patent application laid-open No. 2015-127817 and compounds described in paragraphs 0031 to 0046 of International publication No. 2015/125469 can also be used.
The following compounds (Me is methyl) can be used.
[ Chemical formula 68]
When the curable resin composition of the present invention has a polymerization inhibitor, the content of the polymerization inhibitor is preferably 0.01 to 20.0 mass%, more preferably 0.01 to 5 mass%, still more preferably 0.02 to 3 mass%, and still more preferably 0.05 to 2.5 mass% relative to the total solid content of the curable resin composition of the present invention.
The polymerization inhibitor may be one kind or two or more kinds. When the polymerization inhibitor is two or more, the total thereof is preferably within the above range.
< Metal adhesion improver >
The curable resin composition of the present invention preferably contains a metal adhesion improver for improving adhesion to a metal material used for an electrode, wiring, or the like. Examples of the metal adhesion improver include an aluminum-based adhesion improver, a titanium-based adhesion improver, a compound having a sulfonamide structure, a compound having a thiourea structure, a phosphoric acid derivative compound, a β -ketoester (β -ketoester) compound, an amino compound, and the like.
[ Aluminum-based adhesion auxiliary agent ]
Examples of the aluminum-based adhesion auxiliary agent include aluminum tris (ethylacetoacetate), aluminum tris (acetylacetonate), aluminum ethylacetoacetate diisopropoxide, and the like.
As the metal adhesion improver, compounds described in paragraphs 0046 to 0049 of jp 2014-186186 a and sulfide-based compounds described in paragraphs 0032 to 0043 of jp 2013-072935 can also be used.
The content of the metal adhesion improver is preferably in the range of 0.1 to 30 parts by mass, more preferably in the range of 0.5 to 15 parts by mass, and even more preferably in the range of 0.5 to 5 parts by mass, per 100 parts by mass of the specific resin. When the lower limit value is not less than the upper limit value, the adhesiveness between the pattern and the metal layer is good, and when the upper limit value is not more than the upper limit value, the heat resistance and mechanical properties of the pattern are good. The metal adhesion improver may be one kind or two or more kinds. When two or more kinds are used, the total thereof is preferably within the above range.
< Other additives >
The curable resin composition of the present invention may contain various additives such as a sensitizer, a chain transfer agent, a surfactant, a higher fatty acid derivative, inorganic particles, a curing agent, a curing catalyst, a filler, an antioxidant, an ultraviolet absorber, an anticoagulant, and the like, as required, within a range in which the effects of the present invention can be obtained. When these additives are blended, the total blending amount is preferably 3 mass% or less of the solid content of the curable resin composition.
[ Sensitizer ]
The curable resin composition of the present invention may contain a sensitizer. The sensitizer absorbs a specific active radiation to be in an electron excited state. The sensitizer in an electron excited state is brought into contact with a heat curing accelerator, a thermal radical polymerization initiator, a photo radical polymerization initiator, or the like to cause an effect such as electron transfer, energy transfer, heat generation, or the like. Thus, the thermal curing accelerator, the thermal radical polymerization initiator, and the photo radical polymerization initiator are chemically changed and decomposed to generate radicals, acids, or bases.
As a sensitizer which is used for the preparation of the dye, examples thereof include michaelines, 4 '-bis (diethylamino) benzophenone, 2, 5-bis (4' -diethylaminobenzylidene) cyclopentane, 2, 6-bis (4 '-diethylaminobenzylidene) cyclohexanone, 2, 6-bis (4' -diethylaminobenzylidene) -4-methylcyclohexanone, 4 '-bis (dimethylamino) chalcone, 4' -bis (diethylamino) chalcone, p-dimethylaminobenzylidene indanone, 2- (p-dimethylaminophenyl-biphenylene) -benzothiazole, 2- (p-dimethylaminophenyl-vinylene) benzothiazole 2- (p-dimethylaminophenylvinylene) isonaphthylthiazole, 1, 3-bis (4 '-dimethylaminobenzylidene) acetone, 1, 3-bis (4' -diethylaminobenzylidene) acetone, 3 '-carbonyl-bis (7-diethylaminocoumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N' -ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholinylbenzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2- (p-dimethylaminostyrene) benzoxazole, 2- (p-dimethylaminostyrene) benzothiazole, 2- (p-dimethylaminostyryl) naphtho (1, 2-d) thiazole, 2- (p-dimethylaminobenzoyl) styrene, diphenylacetamide, benzanilide, N-methylacetanilide, 3',4' -dimethylacetoanilide, and the like.
As the sensitizer, a sensitizing dye may be used.
For details of the sensitizing dye, reference is made to paragraphs 0161 to 0163 of Japanese patent application laid-open No. 2016-027357, which is incorporated herein by reference.
When the curable resin composition of the present invention contains a sensitizer, the content of the sensitizer is preferably 0.01 to 20% by mass, more preferably 0.1 to 15% by mass, and even more preferably 0.5 to 10% by mass, relative to the total solid content of the curable resin composition of the present invention. The sensitizer may be used alone or in combination of two or more.
[ Chain transfer agent ]
The curable resin composition of the present invention may contain a chain transfer agent. Chain transfer agents are defined, for example, in the third edition of the Polymer dictionary, edition 2005, pages 683-684. As the chain transfer agent, for example, a compound group having SH, PH, siH and GeH in the molecule can be used. These can supply hydrogen to the low-activity radicals to generate radicals, or generate radicals by deprotonation after oxidation. In particular, a thiol compound can be preferably used.
The chain transfer agent may be any of the compounds described in paragraphs 0152 to 0153 of International publication No. 2015/199219.
When the curable resin composition of the present invention has a chain transfer agent, the content of the chain transfer agent is preferably 0.01 to 20 parts by mass, more preferably 1 to 10 parts by mass, and even more preferably 1 to 5 parts by mass, relative to 100 parts by mass of the total solid content of the curable resin composition of the present invention. The chain transfer agent may be one kind or two or more kinds. When the chain transfer agent is 2 or more, the total amount thereof is preferably within the above range.
[ Surfactant ]
From the viewpoint of further improving coatability, a surfactant may be added to the curable resin composition of the present invention. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone surfactant can be used. The following surfactants are also preferable. In the following formula, brackets indicating the repeating units of the main chain indicate the content (mol%) of each repeating unit, and brackets indicating the repeating units of the side chain indicate the number of repeating units of each repeating unit.
[ Chemical formula 69]
The surfactant may be any of those described in paragraphs 0159 to 0165 of International publication No. 2015/199219.
As the fluorine-based surfactant, a fluorine-containing polymer having an ethylenically unsaturated group in a side chain can also be used. Specific examples thereof include compounds described in paragraphs 0050 to 0090 and 0289 to 0295 of JP-A2010-164965, such as MEGAFACE RS-101, RS-102, and RS-718K manufactured by DIC Corporation.
The fluorine content of the fluorine-based surfactant is preferably 3 to 40% by mass, more preferably 5 to 30% by mass, and particularly preferably 7 to 25% by mass. From the viewpoints of uniformity of the thickness of the coating film and liquid saving, a fluorine-based surfactant having a fluorine content within this range is effective, and the solubility in the composition is also good.
Examples of silicone surfactants include Toray Silicone DC3PA、Toray Silicone SH7PA、Toray Silicone DC11PA、Toray Silicone SH21PA、Toray Silicone SH28PA、Toray Silicone SH29PA、Toray Silicone SH30PA、Toray Silicone SH8400( or more from Dow Corning Toray co., ltd., ltd.), TSF-4440, TSF-4300, TSF-4445, TSF-4460, TSF-4452 (manufactured by Momentive Performance Materials Inc., above), KP341, KF6001, KF6002 (manufactured by Shin-Etsu Chemical Co., ltd., above), BYK307, BYK323, BYK330 (manufactured by BYK Chemie GmbH, above), and the like.
Examples of the hydrocarbon surfactant include those manufactured by Takemoto Oil & Fat Co., ltd.) and the like, which are PIONIN A-76、New Kalgen FS-3PG、PIONIN B-709、PIONIN B-811-N、PIONIN D-1004、PIONIN D-3104、PIONIN D-3605、PIONIN D-6112、PIONIN D-2104-D、PIONIN D-212、PIONIN D-931、PIONIN D-941、PIONIN D-951、PIONIN E-5310、PIONIN P-1050-B、PIONIN P-1028-P、PIONIN P-4050-T( or more.
Examples of the nonionic surfactant include glycerin, trimethylol propane, trimethylol ethane, and ethoxylates and propoxylates thereof (for example, glycerin propoxylate, glycerin ethoxylate, and the like), polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octylphenyl ether, polyoxyethylene nonylphenyl ether, polyethylene glycol dilaurate, polyethylene glycol distearate, sorbitan fatty acid ester, pluronic L10, L31, L61, L62, 10R5, 17R2, 25R2 (manufactured by BASF corporation), tetronic 304, 701, 704, 901, 904, 150R1 (manufactured by BASF corporation), solsperse 20000 (manufactured by Lubrizol Japan Limited), NCW-101, NCW-1001, NCW-1002 (manufactured by FUJIFILM Wako Pure Chemical Corporation), PIONIN D-6112, D-6112-W, D-6315 (TamoOil & Fat, manufactured by Lkeol), ofine 1010, 400, and the like (manufactured by LtCo. NISSIN CHEMICAL).
Specific examples of the cationic surfactant include organosiloxane polymer KP341 (Shin-Etsu Chemical co., ltd., (meth) acrylic (co) polymer Polyflow No.75, no.77, no.90, no.95 (Kyoeisha Chemical co., ltd.,) and W001 (Yusho co., ltd.)) and the like.
Specific examples of the anionic surfactant include W004, W005, W017 (Yusho co., ltd.) and SANDET BL (SANYO KASEI co., ltd.).
When the curable resin composition of the present invention has a surfactant, the content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the curable resin composition of the present invention. The surfactant may be one kind or two or more kinds. When the number of the surfactants is two or more, the total amount thereof is preferably within the above range.
[ Higher fatty acid derivative ]
In order to prevent polymerization inhibition by oxygen, the curable resin composition of the present invention may contain a higher fatty acid derivative such as behenic acid or behenamide so as to be unevenly distributed on the surface of the curable resin composition during drying after application.
Further, the higher fatty acid derivative may be a compound described in paragraph 0155 of International publication No. 2015/199219.
When the curable resin composition of the present invention has a higher fatty acid derivative, the content of the higher fatty acid derivative is preferably 0.1 to 10% by mass relative to the total solid content of the curable resin composition of the present invention. The higher fatty acid derivative may be one kind or two or more kinds. When the number of higher fatty acid derivatives is 2 or more, the total of the higher fatty acid derivatives is preferably within the above range.
[ Thermal polymerization initiator ]
The resin composition of the present invention may also contain a thermal polymerization initiator, and in particular, may contain a thermal radical polymerization initiator. The thermal radical polymerization initiator is a compound that generates radicals by thermal energy to initiate or promote polymerization of a compound having polymerizability. The addition of the thermal radical polymerization initiator can further cause polymerization of the resin and the polymerizable compound, and thus can further improve solvent resistance.
Specific examples of the thermal radical polymerization initiator include compounds described in paragraphs 0074 to 0118 of JP-A-2008-063254.
When the thermal polymerization initiator is contained, the content thereof is preferably 0.1 to 30% by mass, more preferably 0.1 to 20% by mass, still more preferably 0.5 to 15% by mass, relative to the total solid content of the resin composition of the present invention. The thermal polymerization initiator may be contained in an amount of 1 or 2 or more. When two or more thermal polymerization initiators are contained, the total amount thereof is preferably within the above range.
[ Inorganic particles ]
The resin composition of the present invention may contain inorganic particles. Specifically, the inorganic particles may include calcium carbonate, calcium phosphate, silica, kaolin, talc, titanium dioxide, alumina, barium sulfate, calcium fluoride, lithium fluoride, zeolite, molybdenum sulfide, glass, and the like.
The average particle diameter of the inorganic particles is preferably 0.01 to 2.0. Mu.m, more preferably 0.02 to 1.5. Mu.m, still more preferably 0.03 to 1.0. Mu.m, particularly preferably 0.04 to 0.5. Mu.m.
By containing the inorganic particles having the average particle diameter, both the mechanical properties of the cured film and the suppression of scattering of exposure light can be achieved.
[ Ultraviolet absorber ]
The compositions of the present invention may comprise an ultraviolet absorber. As the ultraviolet absorber, salicylate-based, benzophenone-based, benzotriazole-based, substituted acrylonitrile-based, triazine-based, and other ultraviolet absorbers can be used.
Examples of the salicylate-based ultraviolet light absorber include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate, and examples of the benzophenone-based ultraviolet light absorber include 2,2' -dihydroxy-4-methoxybenzophenone, 2' -dihydroxy-4, 4' -dimethoxybenzophenone, 2', 4' -tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2, 4-dihydroxybenzophenone, and 2-hydroxy-4-octoxybenzophenone. Examples of the benzotriazole-based ultraviolet absorber include 2- (2 '-hydroxy-3', 5 '-di-t-butylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-t-butyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -t-amyl-5 '-isobutylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 '-isobutyl-5' -methylphenyl) -5-chlorobenzotriazole, 2- (2 '-hydroxy-3' -isobutyl-5 '-propylphenyl) -5-chlorobenzotriazole, 2- (2' -hydroxy-3 ',5' -di-t-butylphenyl) benzotriazole, 2- (2 '-hydroxy-5' -methylphenyl) benzotriazole, and 2- [2 '-hydroxy-5' - (1, 3-tetramethyl) phenyl ] benzotriazole.
Examples of the substituted acrylonitrile ultraviolet absorber include ethyl 2-cyano-3, 3-diphenylacrylate and 2-ethylhexyl 2-cyano-3, 3-diphenylacrylate. Examples of the triazine ultraviolet light absorber include mono (hydroxyphenyl) triazine compounds such as 2- [4- [ (2-hydroxy-3-dodecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, 2- [4- [ (2-hydroxy-3-tridecyloxypropyl) oxy ] -2-hydroxyphenyl ] -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine, and 2- (2, 4-dihydroxyphenyl) -4, 6-bis (2, 4-dimethylphenyl) -1,3, 5-triazine; bis (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-propoxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine, 2, 4-bis (2-hydroxy-3-methyl-4-propoxyphenyl) -6- (4-methylphenyl) -1,3, 5-triazine, and 2, 4-bis (2-hydroxy-3-methyl-4-hexyloxyphenyl) -6- (2, 4-dimethylphenyl) -1,3, 5-triazine; tris (hydroxyphenyl) triazine compounds such as 2, 4-bis (2-hydroxy-4-butoxyphenyl) -6- (2, 4-dibutoxyphenyl) -1,3, 5-triazine, 2,4, 6-tris (2-hydroxy-4-octyloxyphenyl) -1,3, 5-triazine, and 2,4, 6-tris [ 2-hydroxy-4- (3-butoxy-2-hydroxypropoxy) phenyl ] -1,3, 5-triazine.
In the present invention, one kind of the above-mentioned various ultraviolet absorbers may be used alone, or two or more kinds may be used in combination.
The composition of the present invention may or may not contain an ultraviolet absorber, but when the ultraviolet absorber is contained, the content of the ultraviolet absorber is preferably 0.001 mass% or more and 1 mass% or less, more preferably 0.01 mass% or more and 0.1 mass% or less, relative to the total solid content mass of the composition of the present invention.
[ Organic titanium Compound ]
The resin composition of the present embodiment may contain an organic titanium compound. By containing the organic titanium compound in the resin composition, a resin layer excellent in chemical resistance can be formed even when cured at a low temperature.
As the organic titanium compound that can be used, a compound in which an organic group is bonded to a titanium atom via a covalent bond or an ionic bond can be used.
Specific examples of the organic titanium compound are shown in the following I) to VII):
I) Titanium chelate compound: among them, titanium chelate compounds having 2 or more alkoxy groups are more preferable from the viewpoint of good storage stability of the negative photosensitive resin composition and good cured patterns. Specific examples are titanium bis (triethanolamine) diisopropoxide, titanium bis (2, 4-glutarate) di (n-butoxy) di (2, 4-glutarate), titanium di (isopropoxide) di (tetramethylpimelate), titanium di (ethylacetate) di (isopropoxide), and the like.
II) a titanium tetraalkoxide compound: examples of the titanium include tetra (n-butoxy) titanium, tetraethoxy titanium, tetra (2-ethylhexyl) titanium, tetraisobutoxy titanium, tetraisopropoxy titanium, tetramethylol titanium, tetramethoxypropoxy titanium, tetramethylphenoxy titanium, tetra (n-nonoxy) titanium, tetra (n-propoxy) titanium, tetrastearyl titanium, and tetra [ bis {2,2- (allyloxymethyl) butoxy } titanium.
III) titanocene compound: examples of the compound include pentamethylcyclopentadienyl titanium trimethate, bis (. Eta.5-2, 4-cyclopenta-n-1-yl) bis (2, 6-difluorophenyl) titanium, bis (. Eta.5-2, 4-cyclopenta-n-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium, and the like.
IV) monoalkoxytitanium compounds: for example, titanium isopropoxide, titanium tris (dioctyl phosphate), titanium isopropoxide, etc.
V) titanium oxide compound: examples of the compound include titanium oxide bis (glutarate), titanium oxide bis (tetramethylpimelate), and titanium oxide phthalocyanine.
VI) titanium tetra acetylacetonate compound: for example, titanium tetraacetylacetonate.
VII) titanate coupling agent: for example, isopropyl tridecyl benzene sulfonyl titanate, etc.
Among them, the organic titanium compound is preferably at least 1 compound selected from the group consisting of the above-mentioned I) titanium chelate compound, II) tetraalkoxy titanium compound and III) titanocene compound from the viewpoint of exhibiting more excellent chemical resistance. In particular, bis (ethylacetoacetate) diisopropoxytitanium, tetra (n-butoxy) titanium and bis (. Eta.5-2, 4-cyclopenta-n-1-yl) bis (2, 6-difluoro-3- (1H-pyrrol-1-yl) phenyl) titanium are preferred.
When the organic titanium compound is blended, the blending amount is preferably 0.05 to 10 parts by mass, more preferably 0.1 to 2 parts by mass, relative to 100 parts by mass of the precursor of the cyclized resin. When the amount is 0.05 parts by mass or more, good heat resistance and chemical resistance are exhibited in the resulting cured pattern, whereas when 10 parts by mass or less, the composition is excellent in storage stability.
[ Antioxidant ]
The composition of the present invention may comprise an antioxidant. By containing an antioxidant as an additive, the ductility of the cured film or the adhesion to a metal material can be improved. Examples of the antioxidant include phenol compounds, phosphite compounds, and thioether compounds. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferred examples of the phenol compound include hindered phenol compounds. The compound having a substituent at a position adjacent to the phenolic hydroxyl group (ortho position) is preferable. The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is also preferably a compound having a phenol group and a phosphite group in the same molecule. In addition, a phosphorus antioxidant can be preferably used as the antioxidant. Examples of the phosphorus antioxidant include tris [2- [ [2,4,8, 10-tetrakis (1, 1-dimethylethyl) dibenzo [ d, f ] [1,3,2] dioxaphosphepin (dioxaphosphepin) -6-yl ] oxy ] ethyl ] amine, tris [2- [ (4, 6,9, 11-tetra-t-butyldibenzo [ d, f ] [1,3,2] dioxaphosphepin-2-yl) oxy ] ethyl ] amine, and ethyl bis (2, 4-di-t-butyl-6-methylphenol) phosphite. Commercially available antioxidants include ADKSTAB AO-20、ADKSTAB A0-30、ADKSTAB AO-40、ADKSTAB AO-50、ADKSTAB AO-50F、ADKSTAB AO-60、ADKSTAB AO-60G、ADKSTAB AO-80、ADKSTAB AO-330( and ADEKA CORPORATION). The antioxidant may be any of those described in paragraphs 0023 to 0048 of Japanese patent No. 6268967. Further, the composition of the present invention may contain a latent antioxidant as needed. Examples of the latent antioxidant include a compound which functions as an antioxidant by protecting a site functioning as an antioxidant with a protecting group and by removing the protecting group by heating at 100 to 250 ℃ or heating at 80 to 200 ℃ in the presence of an acid/base catalyst. Examples of the latent antioxidant include compounds described in Japanese patent laid-open publication Nos. 2014/021023 and 2017/030005, and Japanese patent laid-open publication No. 2017-008219. Commercially available antioxidants include ADEKA ARKLS GPA-5001 (manufactured by ADEKA CORPORATION). Examples of the preferable antioxidant include 2, 2-thiobis (4-methyl-6-t-butylphenol), 2, 6-di-t-butylphenol and a compound represented by the general formula (3).
[ Chemical formula 70]
In the general formula (3), R 5 represents a hydrogen atom or an alkyl group having 2 or more carbon atoms, and R 6 represents an alkylene group having 2 or more carbon atoms. R 7 is an alkylene group having 2 or more carbon atoms, or a 1-to 4-valent organic group containing at least 1 of an O atom and an N atom. k represents an integer of 1 to 4.
The compound represented by the general formula (3) inhibits oxidative deterioration of an aliphatic group or a phenolic hydroxyl group of the resin. In addition, by the rust prevention effect on the metal material, oxidation of the metal can be suppressed.
Since the resin and the metal material can be simultaneously acted, k is more preferably an integer of 2 to 4. R 7 is an alkyl group, cycloalkyl group, alkoxy group, alkyl ether group, alkylsilyl group, alkoxysilyl group, aryl ether group, carboxyl group, carbonyl group, allyl group, vinyl group, heterocyclic group, -O-, -NH-, -NHNH-, or a combination of these, and may further have a substituent. Among them, alkyl ether and-NH-are preferable from the viewpoint of solubility in a developer and metal adhesion, and-NH-is more preferable from the viewpoint of interaction with a resin and metal adhesion due to formation of a metal complex.
The compounds represented by the following general formula (3) are exemplified by the following compounds, but are not limited to the following structures.
[ Chemical formula 71]
[ Chemical formula 72]
[ Chemical formula 73]
[ Chemical formula 74]
The amount of the antioxidant to be added is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass, based on the resin. When the amount is less than 0.1 part by mass, it is difficult to obtain an effect of improving the ductility characteristics after reliability or the adhesion to a metal material, and when it is more than 10 parts by mass, there is a possibility that the sensitivity of the resin composition may be lowered by the interaction with the photosensitive agent. The antioxidant may be used in an amount of 1 or 2 or more. When 2 or more kinds are used, the total amount of these is preferably within the above range.
< Restriction on other substances contained >
From the viewpoint of the coating surface properties, the moisture content of the curable resin composition of the present invention is preferably less than 5 mass%, more preferably less than 1 mass%, and even more preferably less than 0.6 mass%. Examples of the method for maintaining the moisture content include adjusting the humidity under the storage condition and reducing the porosity of the storage container.
From the viewpoint of insulation properties, the metal content of the curable resin composition of the present invention is preferably less than 5 mass ppm (parts per million: parts per million), more preferably less than 1 mass ppm, and even more preferably less than 0.5 mass ppm. Examples of the metal include sodium, potassium, magnesium, calcium, iron, chromium, and nickel. When a plurality of metals are contained, the total of these metals is preferably within the above range.
Further, as a method for reducing metal impurities unintentionally contained in the curable resin composition of the present invention, the following methods can be mentioned: selecting a raw material having a small metal content as a raw material constituting the curable resin composition of the present invention; filtering the raw materials constituting the curable resin composition of the present invention by a filter; lining (lining) with polytetrafluoroethylene or the like is performed in the apparatus, and distillation or the like is performed under a condition that contamination is suppressed as much as possible.
In the curable resin composition of the present invention, the halogen atom content is preferably less than 500 mass ppm, more preferably less than 300 mass ppm, and even more preferably less than 200 mass ppm, from the viewpoint of wiring corrosiveness, when the use as a semiconductor material is considered. Among them, the halogen ion is preferably present in an amount of less than 5 mass ppm, more preferably less than 1 mass ppm, and still more preferably less than 0.5 mass ppm. Examples of the halogen atom include a chlorine atom and a bromine atom. Preferably, the total of chlorine atoms and bromine atoms, or chlorine ions and bromine ions is within the above range.
As a method for adjusting the halogen atom content, ion exchange treatment and the like are preferable.
As the container for the curable resin composition of the present invention, a conventionally known container can be used. In addition, as the storage container, a multilayer bottle having 6 types of 6-layer resins on the inner wall of the container or a bottle having 7 layers of 6 types of resins is preferably used in order to prevent impurities from being mixed into the raw material or the curable resin composition. Examples of such a container include a container described in Japanese patent application laid-open No. 2015-123351.
< Use of curable resin composition >
The curable resin composition of the present invention is preferably used for forming an interlayer insulating film for a rewiring layer.
In addition, the present invention can be used for forming an insulating film, a stress buffer film, and the like of a semiconductor device.
< Preparation of curable resin composition >
The curable resin composition of the present invention can be prepared by mixing the above components. The mixing method is not particularly limited, and can be performed by a conventionally known method.
Further, filtration using a filter is preferable for the purpose of removing foreign matters such as dust and particles in the curable resin composition. The filter pore diameter is preferably 1 μm or less, more preferably 0.5 μm or less, and even more preferably 0.1 μm or less. On the other hand, from the viewpoint of productivity, it is preferably 5 μm or less, more preferably 3 μm or less, and still more preferably 1 μm or less. The material of the filter is preferably polytetrafluoroethylene, polyethylene or nylon. The filter may be a filter which has been previously washed with an organic solvent. In the filter filtration step, a plurality of filters may be used in series or in parallel. When a plurality of filters are used, filters having different pore diameters or different materials may be used in combination. And, various materials may be filtered multiple times. In the case of multiple filtration, cyclic filtration may be used. Further, filtration may be performed by pressurization. When filtration is performed by pressurization, the pressurization pressure is preferably 0.05MPa or more and 0.3MPa or less. On the other hand, from the viewpoint of productivity, it is preferably 0.01MPa or more and 1.OMPa or less, more preferably 0.03MPa or more and 0.9MPa or less, and still more preferably 0.05MPa or more and 0.7MPa or less.
In addition to filtration using a filter, a removal treatment of impurities using an adsorbent may be performed. It is also possible to combine filter filtration and impurity removal treatment using an adsorbent. As the adsorbent, a known adsorbent can be used. Examples thereof include inorganic adsorbents such as silica gel and zeolite, and organic adsorbents such as activated carbon.
(Resin film, cured film, laminate, semiconductor device, and method for producing the same)
Next, a resin film, a cured film, a laminate, a semiconductor device, and a method for manufacturing these will be described.
The cured film of the present invention is obtained by curing the curable resin composition of the present invention or the resin film of the present invention. The film thickness of the cured film of the present invention may be, for example, 0.5 μm or more, or 1 μm or more. The upper limit value may be 100 μm or less or 30 μm or less.
The cured film of the present invention may be laminated in two or more layers, and further in 3 to 7 layers, to form a laminate. The laminate of the present invention preferably includes two or more cured films, and any of the cured films includes a metal layer between them. For example, a preferable laminate includes a laminate having a layer structure in which at least 3 layers of a first cured film, a metal layer, and a second cured film are laminated in this order. The first cured film and the second cured film are both cured films of the present invention, and preferable examples thereof include a film obtained by curing the curable resin composition of the present invention. The curable resin composition of the present invention for forming the first cured film and the curable resin composition of the present invention for forming the second cured film may have the same composition or may have different compositions. The metal layer in the laminate of the present invention can be preferably used as a metal wiring of a rewiring layer or the like.
Examples of the field to which the cured film of the present invention can be applied include an insulating film of a semiconductor device, an interlayer insulating film for a rewiring layer, a stress buffer film, and the like. In addition, there may be mentioned patterning of a sealing film, a substrate material (a base film or a cover film of a flexible printed board, an interlayer insulating film) or an insulating film for packaging as described above by etching. For these applications, for example, reference may be made to SCIENCE AND techenology co., ltd, "high functionalization and application TECHNOLOGY of polyimide" 4 th year, basic and development of polyimide materials of persimmon benyanming/main division, CMC TECHNICAL library "release 11 th year 2011", and "new polyimide basic and application" NTS inc.,2010, 8 th year, etc.
The cured film of the present invention can be used for the production of printing plates such as offset printing plates and screen printing plates, the use of the cured film in etching of molded components, the production of protective paints and dielectric layers in electronics, and particularly microelectronics.
The method for producing a cured film of the present invention (hereinafter, also simply referred to as "the method for producing the present invention") preferably includes a film forming step of forming a film (resin film) by applying the curable resin composition of the present invention to a substrate.
The method for producing a cured film of the present invention preferably includes the film formation step, an exposure step of exposing the film, and a development step of developing the film.
The method for producing a cured film of the present invention further preferably includes the film formation step and the development step as needed, and further includes a heating step of heating the film at 50 to 450 ℃.
Specifically, the method preferably includes the following steps (a) to (d).
(A) Film formation step of forming film (curable resin composition layer) by applying curable resin composition to substrate
(B) An exposure step of exposing the film after the film formation step
(C) A developing step of developing the exposed film
(D) A heating step of heating the developed film at 50-450 DEG C
By heating in the heating step, the resin layer cured by exposure can be further cured. In this heating step, for example, the thermal alkaline generator is decomposed to obtain sufficient curability.
The method for producing a laminate according to a preferred embodiment of the present invention includes the method for producing a cured film according to the present invention. The method for producing a laminate according to the present embodiment further includes the step of (a) or the steps of (a) to (c) or the steps of (a) to (d) after forming the cured film according to the method for producing a cured film. In particular, the above steps are sequentially performed a plurality of times, for example, preferably 2 to 5 times (i.e., 3 to 6 times in total). By laminating the cured films in this manner, a laminate can be produced. In the present invention, it is preferable that a metal layer is provided especially on or between the cured films or on and between the cured films. In addition, when the laminate is produced, it is not necessary to repeat all the steps (a) to (d), and as described above, the steps (a), preferably (a) to (c) or (a) to (d), are performed at least a plurality of times, whereby a laminate of cured films can be obtained.
< Film Forming Process (layer Forming Process) >)
The method of producing a preferred embodiment of the present invention includes a film forming step (layer forming step) of forming a film (layer) by applying the curable resin composition to a substrate.
The type of the substrate may be appropriately determined according to the application, and may be a semiconductor fabrication substrate such as silicon, silicon nitride, polysilicon, silicon oxide, amorphous silicon, etc., a metal substrate such as quartz, glass, an optical film, a ceramic material, a vapor deposition film, a magnetic film, a reflective film, ni, cu, cr, fe, etc., paper, SOG (Spin On Glass), TFT (thin film transistor) array substrate, an electrode plate of a Plasma Display Panel (PDP), etc., without being particularly limited. The substrate may be provided with a layer such as an adhesion layer or an oxide layer on the surface. In the present invention, a semiconductor production substrate is particularly preferable, and a silicon substrate, a Cu substrate, and a mold (mold) substrate are more preferable.
The surface of these substrates may be provided with a layer such as an adhesion layer or an oxide layer formed of Hexamethyldisilazane (HMDS) or the like.
As the base material, for example, a plate-shaped base material (substrate) can be used.
The shape of the base material is not particularly limited, and may be circular or rectangular, but is preferably rectangular.
The size of the base material is, for example, 100 to 450mm, preferably 200 to 450mm in diameter when it is circular. In the case of rectangular, for example, the length of the short side is 100 to 1000mm, preferably 200 to 700mm.
When the curable resin composition layer is formed on the surface of the resin layer or the surface of the metal layer, the resin layer or the metal layer serves as a base material.
As a method for applying the curable resin composition to a substrate, coating is preferable.
Specifically, examples of the method to be applied include dip coating, air knife coating, curtain coating, bar coating, gravure coating, extrusion coating, spray coating, spin coating, slit coating, and ink jet coating. From the viewpoint of uniformity of thickness of the curable resin composition layer, spin coating, slit coating, spray coating, and inkjet methods are more preferable. By appropriately adjusting the solid content concentration and the coating conditions according to the method, a resin layer having a desired thickness can be obtained. The coating method may be appropriately selected according to the shape of the substrate, and in the case of a circular substrate such as a wafer, spin coating, spray coating, or ink jet method is preferable, and in the case of a rectangular substrate, slit coating, spray coating, or ink jet method is preferable. In the case of spin coating, for example, a spin speed of 500 to 2,000rpm can be applied for about 10 seconds to 1 minute.
Further, the rotation speed of 300 to 3,500rpm is preferably applied for 10 to 180 seconds depending on the viscosity of the photosensitive resin composition or the film thickness to be set. In order to obtain uniformity of film thickness, a plurality of rotation speeds may be combined and applied.
Further, a method of transferring a coating film previously applied to the temporary support by the application method described above to a substrate can also be applied.
As the transfer method, the production method described in paragraphs 0023, 0036 to 0051 or 0096 to 0108 of japanese patent application laid-open publication No. 2006-023696 or japanese patent application laid-open publication No. 2006-047592 can be preferably used in the present invention.
Further, a step of removing an excess film at the end of the base material may be performed. Examples of such a process include edge bead residue rinse (EBR), air knife (air knife), back rinse (back rinse), and the like.
The following pre-wetting step may be employed: before the resin composition is applied to the substrate, various solvents are applied to the substrate to improve the wettability of the substrate, and then the resin composition is applied.
< Drying Process >
The production method of the present invention may include a step of drying after the film formation step (layer formation step) to remove the solvent. The drying temperature is preferably 50 to 150 ℃, more preferably 70 to 130 ℃, and even more preferably 90 to 110 ℃. The drying time may be exemplified by 30 seconds to 20 minutes, preferably 1 minute to 10 minutes, and more preferably 3 minutes to 7 minutes.
< Exposure procedure >
The production method of the present invention may include an exposure step of exposing the film (curable resin composition layer) to light. The exposure amount is not particularly limited as long as the curable resin composition can be cured, and for example, the exposure amount is preferably 100 to 10,000mJ/cm 2, more preferably 200 to 8,000mJ/cm 2 in terms of exposure energy at 365 nm.
The exposure wavelength can be appropriately defined within a range of 190 to 1,000nm, and is preferably 240 to 550nm.
When the exposure wavelength is described in relation to the light source, examples thereof include (1) a semiconductor laser (wavelength 830nm, 532nm, 488nm, 405nm, etc.), (2) a metal halide lamp, (3) a high-pressure mercury lamp, g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), i-rays (wavelength 365 nm), wide (3 wavelengths of g, h, i-rays), (4) an excimer laser, a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), an F 2 excimer laser (wavelength 157 nm), and (5) extreme ultraviolet rays; EUV (wavelength 13.6 nm), (6) electron beam, (7) second harmonic 532nm, third harmonic 355nm of YAG laser, etc. The curable resin composition of the present invention is particularly preferably exposed by a high-pressure mercury lamp, and among these, exposure by i-rays is preferable. Thus, particularly, high exposure sensitivity can be obtained.
Also, from the viewpoint of operation and productivity, a wide (3 wavelengths of g, h, i rays) light source of a high-pressure mercury lamp or a semiconductor laser 405nm is preferable.
< Developing Process >
The production method of the present invention may include a developing step of developing the exposed film (curable resin composition layer) (developing the film). The unexposed portions (non-exposed portions) are removed by development. The developing method is not particularly limited as long as a desired pattern can be formed, and examples thereof include ejection of a developer from a nozzle, jet spraying, impregnation of a developer of a substrate, and the like, and ejection from a nozzle is preferably used. In the development step, a step of continuously supplying the developer to the substrate, a step of holding the developer in a substantially stationary state on the substrate, a step of vibrating the developer with ultrasonic waves or the like, a step of combining these, and the like can be employed.
The development is performed using a developer.
The developer is not particularly limited, and a known developer may be used, and a developer containing an organic solvent or an aqueous alkali solution may be used.
In the present invention, the developer preferably contains an organic solvent having a ClogP value of-1 to 5, more preferably contains an organic solvent having a ClogP value of 0 to 3. The ClogP value can be obtained as a calculated value by inputting a structural formula in chembiosraw.
When the developer is a developer containing an organic solvent, examples of the organic solvent include preferably ethyl acetate, n-butyl acetate, pentyl formate, isopentyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, epsilon-caprolactone, delta-valerolactone, and alkyl alkoxyacetate (for example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate, and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate), 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and, as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., and, as ketones, for example, methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, N-methyl-2-pyrrolidone, etc., and, as cyclic hydrocarbons, for example, toluene, xylene, anisole, limonene, etc., and, as sulfoxides, for example, dimethyl sulfoxide, and, also, a mixture of these organic solvents, may be preferable.
In the case where the developer is an organic solvent-containing developer, cyclopentanone and γ -butyrolactone are particularly preferable, and cyclopentanone is more preferable in the present invention. In addition, when the developer contains an organic solvent, one or two or more organic solvents may be used in combination.
When the developer is a developer containing an organic solvent, the organic solvent is preferably 50% by mass or more, more preferably 70% by mass or more, and still more preferably 90% by mass or more of the developer. In addition, the developer may be an organic solvent in an amount of 100 mass%.
The developer may also contain other components.
Examples of the other component include a known surfactant and a known antifoaming agent.
When the developer is an aqueous alkali solution, examples of the alkali compound that can be contained in the aqueous alkali solution include TMAH (tetramethylammonium hydroxide), KOH (potassium hydroxide), and sodium carbonate, and TMAH is preferable. For example, when TMAH is used, the content of the alkaline compound in the developer is preferably 0.01 to 10 mass%, more preferably 0.1 to 5 mass%, and even more preferably 0.3 to 3 mass% based on the total mass of the developer.
[ Method for supplying developer ]
The method of supplying the developer is not particularly limited as long as a desired pattern can be formed, and there are a method of immersing the substrate in the developer, spin-on immersion development in which the developer is supplied onto the substrate using a nozzle, and a method of continuously supplying the developer. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, and the like.
The method of supplying the developer with a straight nozzle or the method of continuously supplying the developer with a spray nozzle is preferable from the viewpoints of the permeability of the developer, the removability of the non-image portion, and the efficiency in production, and the method of supplying the developer with a spray nozzle is more preferable from the viewpoints of the permeability of the developer to the image portion.
Further, a process of continuously supplying the developer to the substrate by the straight nozzle, then rotating the substrate to remove the developer from the substrate, and then performing spin drying, then continuously supplying the developer to the substrate again by the straight nozzle, and then rotating the substrate to remove the developer from the substrate may be employed, and this process may be repeated a plurality of times.
As a method for supplying the developer in the developing step, a step of continuously supplying the developer to the substrate, a step of holding the developer in a substantially stationary state on the substrate, a step of vibrating the developer on the substrate by ultrasonic waves or the like, a step of combining these, and the like can be employed.
The development time is preferably 5 seconds to 10 minutes, more preferably 10 seconds to 5 minutes. The temperature of the developing solution at the time of development is not particularly limited, and can be usually 10 to 45 ℃, preferably 20 to 40 ℃.
After the treatment with the developer, further rinsing may be performed. Further, a method of supplying a rinse solution or the like during a period in which the developer in contact with the pattern is not completely dried may be employed. The rinsing is preferably performed in a solvent different from the developer. For example, the curable resin composition may be rinsed with a solvent contained therein.
When the developer is an organic solvent-containing developer, PGMEA (propylene glycol monoethyl ether acetate), IPA (isopropyl alcohol) and the like are exemplified as the rinse liquid, and PGMEA is preferable. The rinse liquid for development based on the developer containing an aqueous alkali solution is preferably water.
The rinsing time is preferably 10 seconds to 10 minutes, more preferably 20 seconds to 5 minutes, and still more preferably 5 seconds to 1 minute. The temperature of the rinse liquid at the time of rinsing is not particularly limited, but is preferably 10 to 45 ℃, more preferably 18 to 30 ℃.
Examples of the organic solvent in the case where the rinse liquid contains an organic solvent include esters, preferably include ethyl acetate, n-butyl acetate, amyl formate, isoamyl acetate, isobutyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl lactate, ethyl lactate, γ -butyrolactone, ε -caprolactone, δ -valerolactone, and alkyl alkoxyacetate (for example: methyl alkoxyacetate, ethyl alkoxyacetate, butyl alkoxyacetate (e.g., methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, etc.), alkyl 3-alkoxypropionate (e.g., methyl 3-alkoxypropionate, ethyl 3-alkoxypropionate, etc. (e.g., methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, etc.), alkyl 2-alkoxypropionate (e.g., methyl 2-alkoxypropionate, ethyl 2-alkoxypropionate, propyl 2-alkoxypropionate, etc. (e.g., methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate)), methyl 2-alkoxy-2-methylpropionate, and ethyl 2-alkoxy-2-methylpropionate (e.g., methyl 2-methoxy-2-methylpropionate), ethyl 2-ethoxy-2-methylpropionate, etc.), methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, methyl 2-oxobutyrate, ethyl 2-oxobutyrate, etc., and as ethers, for example, diethylene glycol dimethyl ether, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene Glycol Monomethyl Ether (PGME), propylene Glycol Monomethyl Ether Acetate (PGMEA), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, etc., may be preferably mentioned, and, examples of ketones include methyl ethyl ketone, cyclohexanone, cyclopentanone, 2-heptanone, 3-heptanone, and N-methyl-2-pyrrolidone, and examples of aromatic hydrocarbons include toluene, xylene, anisole, and limonene, examples of sulfoxides include dimethyl sulfoxide, and examples of alcohols include methanol, ethanol, propanol, isopropanol, butanol, pentanol, octanol, diethylene glycol, propylene glycol, methyl isobutyl carbitol, and triethylene glycol, and examples of amides include N-methyl pyrrolidone, N-ethyl pyrrolidone, and dimethylformamide.
In the case where the rinse liquid contains an organic solvent, the organic solvent can be used singly or in combination of two or more. In the present invention, particularly, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, N-methylpyrrolidone, cyclohexanone, PGMEA, PGME are preferable, cyclopentanone, γ -butyrolactone, dimethyl sulfoxide, PGMEA, PGME are more preferable, and cyclohexanone and PGMEA are further preferable.
When the rinse liquid contains an organic solvent, it is preferable that 50 mass% or more of the rinse liquid is an organic solvent, more preferably 70 mass% or more is an organic solvent, and still more preferably 90 mass% or more is an organic solvent. In addition, the rinse solution may be 100% by mass of an organic solvent.
The rinse solution may further comprise other ingredients.
Examples of the other component include a known surfactant and a known antifoaming agent.
[ Method for supplying rinse solution ]
The method of supplying the rinse liquid is not particularly limited as long as the desired pattern can be formed, and there are a method of immersing the substrate in the rinse liquid, a method of supplying the rinse liquid onto the substrate by holding the liquid, a method of supplying the rinse liquid onto the substrate by a shower, and a method of continuously supplying the rinse liquid onto the substrate by a mechanism such as a straight nozzle.
The method of supplying the rinse liquid using a spray nozzle, a straight nozzle, a spray nozzle, or the like is preferable from the viewpoints of the permeability of the rinse liquid, the removability of the non-image portion, and the efficiency in production, and the method of continuously supplying the rinse liquid using a spray nozzle is more preferable from the viewpoints of the permeability of the rinse liquid to the image portion. The type of the nozzle is not particularly limited, and examples thereof include a straight nozzle, a shower nozzle, a spray nozzle, and the like.
That is, the rinsing step is preferably a step of supplying or continuously supplying a rinsing liquid to the exposed film by a straight nozzle, and more preferably a step of supplying a rinsing liquid by a spray nozzle.
As a method for supplying the developer in the rinsing step, a step of continuously supplying the rinse liquid to the substrate, a step of holding the rinse liquid in a substantially stationary state on the substrate, a step of vibrating the rinse liquid on the substrate by ultrasonic waves or the like, a step of combining these, and the like can be employed.
< Heating Process >
The production method of the present invention preferably includes a step of heating the developed film at 50 to 450 ℃.
The film forming step (layer forming step), the drying step, and the developing step are preferably followed by a heating step. In the heating step, for example, the thermal alkaline generator is decomposed to generate an alkali, and the cyclization reaction as a precursor of the specific resin is performed. The curable resin composition of the present invention may contain a radical polymerizable compound other than the precursor of the specific resin, and curing of a radical polymerizable compound other than the precursor of the unreacted specific resin may be performed in this step. The heating temperature (maximum heating temperature) of the layer in the heating step is preferably 50 ℃ or higher, more preferably 80 ℃ or higher, further preferably 140 ℃ or higher, further preferably 150 ℃ or higher, further preferably 160 ℃ or higher, and further preferably 170 ℃ or higher. The upper limit is preferably 500℃or less, more preferably 450℃or less, further preferably 350℃or less, further preferably 250℃or less, further preferably 220℃or less.
The heating is preferably performed at a heating rate of 1 to 12 ℃/min, more preferably 2 to 10 ℃/min, still more preferably 3 to 10 ℃/min, from the temperature at the start of heating to the maximum heating temperature. The productivity can be ensured while preventing excessive volatilization of the amine by setting the temperature rise rate to 1 ℃/min or more, and the residual stress of the cured film can be reduced by setting the temperature rise rate to 12 ℃/min or less. In the case of an oven capable of rapid heating, the heating is preferably performed at a heating rate of 1 to 8 ℃/sec, more preferably 2 to 7 ℃/sec, still more preferably 3 to 6 ℃/sec, from the temperature at the start of heating to the highest heating temperature.
The temperature at the start of heating is preferably 20 to 150 ℃, more preferably 20 to 130 ℃, still more preferably 25 to 120 ℃. The temperature at the start of heating is the temperature at which the step of heating to the highest heating temperature is started. For example, when the curable resin composition is applied to a substrate and then dried, the temperature of the film (layer) after drying is preferably gradually increased from a temperature lower by 30 to 200 ℃ than the boiling point of the solvent contained in the curable resin composition.
The heating time (heating time at the highest heating temperature) is preferably 10 to 360 minutes, more preferably 20 to 300 minutes, still more preferably 30 to 240 minutes.
In particular, when a multilayer laminate is formed, the heating temperature is preferably 180 to 320 ℃, more preferably 180 to 260 ℃, from the viewpoint of adhesion between layers of the cured film. The reason for this is not clear, but it is considered that the acetylene groups of the specific resin between the layers undergo a crosslinking reaction by setting the temperature to this value.
The heating may be performed stepwise. As an example, the following pretreatment process may be performed: raising the temperature from 25 ℃ to 180 ℃ at 3 ℃/min, maintaining the temperature at 180 ℃ for 60 min, raising the temperature from 180 ℃ to 200 ℃ at 2 ℃/min, and maintaining the temperature at 200 ℃ for 120 min. The heating temperature in the pretreatment step is preferably 100 to 200 ℃, more preferably 110 to 190 ℃, and still more preferably 120 to 185 ℃. In this pretreatment step, it is also preferable to perform the treatment while irradiating ultraviolet rays, as described in U.S. Pat. No. 9159547. By such a pretreatment step, the film characteristics can be improved. The pretreatment step may be performed in a short time of about 10 seconds to 2 hours, and more preferably 15 seconds to 30 minutes. The pretreatment may be performed in 2 stages or more, and for example, the pretreatment step 1 may be performed at 100 to 150 ℃ and the pretreatment step 2 may be performed at 150 to 200 ℃.
The cooling may be further performed after heating, and the cooling rate at this time is preferably 1 to 5 ℃/min.
In view of preventing decomposition of the specific resin, it is preferable to perform the heating step in an atmosphere of low oxygen concentration by flowing inert gas such as nitrogen, helium, argon, or the like. The oxygen concentration is preferably 50ppm (volume ratio) or less, more preferably 20ppm (volume ratio) or less.
The heating means is not particularly limited, and examples thereof include a heating plate, an infrared oven, an electrothermal oven, a hot air oven, and the like.
< Metal layer Forming Process >
The production method of the present invention preferably includes a metal layer forming step of forming a metal layer on the surface of the film (curable resin composition layer) after development.
The metal layer is not particularly limited, and conventional metal species can be used, and copper, aluminum, nickel, vanadium, titanium, chromium, cobalt, gold, and tungsten are exemplified, and copper, aluminum, and an alloy containing these metals are more preferable, and copper is further preferable.
The method for forming the metal layer is not particularly limited, and a conventional method can be applied. For example, the methods described in JP-A2007-157879, JP-A2001-521288, JP-A2004-214501, and JP-A2004-101850 can be applied. For example, photolithography, lift off (lift off), electrolytic plating, electroless plating, etching, printing, a method of combining these, and the like can be considered. More specifically, a patterning method in which sputtering, photolithography, and etching are combined, and a patterning method in which photolithography and electrolytic plating are combined can be given.
The thickness of the metal layer is preferably 0.01 to 100 μm, more preferably 0.1 to 50 μm, and even more preferably 1 to 10 μm in the thickest wall portion.
< Lamination Process >
The production method of the present invention preferably further includes a lamination step.
The lamination step is a series of steps including (a) a film formation step (layer formation step), (b) an exposure step, (c) a development step, and (d) a heating step, which are performed again in this order on the surface of the cured film (resin layer) or the metal layer. However, the film formation step (a) may be repeated. The heating step (d) may be performed at the end or middle of the lamination. That is, the following modes can be adopted: repeating the steps (a) to (c) a predetermined number of times, and then heating the laminated curable resin composition layers to cure the layers in total. In addition, the developing step (c) may be followed by a metal layer forming step (e), and in this case, the heating step (d) may be performed each time, or the heating step (d) may be performed all together after being laminated a predetermined number of times. Of course, the lamination step may further include the drying step, the heating step, and the like as appropriate.
When the lamination step is further performed after the lamination step, the surface activation treatment step may be further performed after the heating step, after the exposure step, or after the metal layer formation step. As the surface activation treatment, a plasma treatment can be exemplified.
The lamination step is preferably performed 2 to 20 times, more preferably 2 to 5 times, and still more preferably 3 to 5 times.
The layers in the lamination step may be the same layer in composition, shape, film thickness, or the like, or may be different layers.
For example, the resin layer is preferably 3 or more and 7 or less layers, more preferably 3 or more and 5 or less layers, as in the resin layer/metal layer/resin layer/metal layer.
In the present invention, in particular, it is preferable that a cured film (resin layer) of the curable resin composition is formed so as to cover the metal layer after the metal layer is provided. Specifically, the film formation step (a), the exposure step (b), the development step (c), the metal layer formation step (e), and the heating step (d) are repeated in this order, or the film formation step (a), the exposure step (b), the development step (c), and the metal layer formation step (e) are repeated in this order, and the heating step (d) is provided at the end or the middle of the repetition. By alternately performing the lamination step of laminating the curable resin composition layers (resin layers) and the metal layer formation step, the curable resin composition layers (resin layers) and the metal layers can be alternately laminated.
(Surface-activating treatment step)
The method for producing a laminate of the present invention may include a surface activation treatment step of surface-activating at least a part of the metal layer and the photosensitive resin composition layer.
The surface activation treatment step is usually performed after the metal layer formation step, but the metal layer formation step may be performed after the surface activation treatment step is performed on the photosensitive resin composition layer after the exposure and development step.
The surface activation treatment may be performed only on at least a part of the metal layer, may be performed only on at least a part of the exposed photosensitive resin composition layer, or may be performed on at least a part of both the metal layer and the exposed photosensitive resin composition layer. It is preferable that at least a part of the metal layer is subjected to a surface activation treatment, and it is preferable that a part or the whole of the region of the metal layer where the photosensitive resin composition layer is formed on the surface is subjected to a surface activation treatment. In this way, by performing the surface activation treatment on the surface of the metal layer, the adhesion with the resin layer provided on the surface can be improved.
It is also preferable that a part or the whole of the photosensitive resin composition layer (resin layer) after exposure is also subjected to a surface activation treatment. In this way, by performing the surface activation treatment on the surface of the photosensitive resin composition layer, adhesion with the metal layer or the resin layer provided on the surface subjected to the surface activation treatment can be improved.
Specifically, the surface activation treatment is selected from plasma treatment of various source gases (oxygen, hydrogen, argon, nitrogen/hydrogen mixed gas, argon/oxygen mixed gas, etc.), corona discharge treatment, etching treatment by CF 4/O2、NF3/O2、SF6、NF3、NF3/O2, surface treatment by Ultraviolet (UV) ozone method, treatment of immersing in an organic surface treating agent containing a compound having at least 1 of amino group and thiol group after removing an oxide film in an aqueous hydrochloric acid solution, and mechanical roughening treatment using a brush, and is preferably plasma treatment, and particularly preferably oxygen plasma treatment using oxygen in the source gases. In the case of corona discharge treatment, the energy is preferably 500 to 200,000J/m 2, more preferably 1000 to 100,000J/m 2, most preferably 10,000 to 50,000J/m 2.
The invention also discloses a semiconductor device comprising the cured film or laminate of the invention. As specific examples of the use of the curable resin composition of the present invention for the formation of an interlayer insulating film for a re-wiring layer, reference may be made to the descriptions of paragraphs 0213 to 0218 and the description of fig. 1 of japanese patent application laid-open publication 2016-027357, which are incorporated herein by reference.
Examples
The present invention will be described in more detail with reference to the following examples. The materials, amounts used, ratios, treatment contents, treatment steps and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, "parts" and "%" are mass standards.
< Synthesis example B-1: synthesis of Compound B-1
In a flask equipped with a stirrer and a condenser, 7.25g (105 mmol) of 1,2, 4-triazole (Tokyo Chemical Industry CO., ltd. Manufacturing.) and 15.52g (100 mmol) of Karenz MOI (SHOWA DENKO k. Manufacturing.) were dissolved in 70mL of tetrahydrofuran (Tokyo Chemical Industry CO., ltd. Manufacturing.) and 0.01g of NITTO KASEI CO., ltd.) and stirred at 25 ℃ for 1 hour. Then, after stirring at 45℃for 2 hours, it was dissolved in 600mL of ethyl acetate and transferred to a separating funnel. Then, the mixture was washed with 100mL of water 2 times, with 150mL of saturated brine 2 times, and dried over sodium sulfate. While this was filtered through a filter paper, it was transferred to a one-necked flask, and the solvent was removed by an evaporator to obtain 18g of B-1. The structure of B-1 is presumed to be represented by the following formula (B-1). B-1 was confirmed by 1 H-NMR spectrum.
1 H-NMR data are shown below.
1 H-NMR data: (heavy dimethyl sulfoxide, 400MHz, internal Standard: tetramethylsilane) )δ(ppm)＝1.85(s、3H)、3.54～3.58(q、2H)、4.24～4.26(t、2H)、5.66(s、1H)、6.03(s、1H)、8.27(s、1H)、8.86～8.90(t、1H)、9.16(s、1H)
[ Chemical formula 75]
< Synthesis example B-2: synthesis of Compound B-2
In a flask equipped with a stirrer and a condenser, 15.2g (0.22 mol) of 1,2, 4-triazole was mixed with 150mL of methylene chloride, and cooled to 10℃or lower. Next, 10.5g (0.1 mol) of methacryloyl chloride was added dropwise over 1 hour, and the temperature was raised to 20 to 25 ℃. After stirring at 20 to 25℃for 3 hours, 200mL of methylene chloride was added, the resulting salt was filtered with filter paper, and the filtrate was recovered. The filtrate was transferred to a separating funnel, washed 2 times with 50mL of water, 2 times with 150mL of saturated brine, and dried over sodium sulfate. While this was filtered through a filter paper, the mixture was transferred to a one-necked flask, and the solvent was removed by a distiller to obtain 12g of B-2. The structure of B-2 is presumed to be represented by the following formula (B-2). B-2 was confirmed by 1 H-NMR spectrum.
1 H-NMR data are shown below.
1 H-NMR data: (deuterated chloroform, 400MHz, internal standard: tetramethylsilane)
δ(ppm)＝2.17(s、3H)、6.09(s、1H)、6.44(s、1H)、8.06(s、1H)、8.95(s、1H)
[ Chemical formula 76]
< Synthesis example B-3: synthesis of Compound B-3
In a flask equipped with a stirrer and a condenser, 7.25g (105 mmol) of 1,2, 4-triazole (Tokyo Chemical Industry CO., ltd. Manufacturing) and 24.7g (100 mmol) of 3- (triethoxysilyl) propyl isocyanate (Tokyo Chemical Industry CO., ltd. Manufacturing) were dissolved in 100mL of tetrahydrofuran (Tokyo Chemical Industry CO., ltd. Manufacturing), and stirred at 25 ℃ for 1 hour. Then, after stirring at 45℃for 2 hours, it was dissolved in 800mL of ethyl acetate and transferred to a separating funnel. Then, the mixture was washed with 100mL of water 2 times, with 150mL of saturated brine 2 times, and dried over sodium sulfate. While this was filtered through a filter paper, it was transferred to a one-necked flask, and the solvent was removed by an evaporator to obtain 26g of B-3. The structure of B-3 is presumed to be represented by the following formula (B-3). B-3 was confirmed by 1 H-NMR spectrum.
1 H-NMR data are shown below.
1 H-NMR data: (deuterated chloroform, 400MHz, internal standard: tetramethylsilane)
δ(ppm)＝0.67～0.72(t、2H)、1.21～1.25(t、9H)、1.74～1.82(M、2H)、3.43～3.48(q、2H)、3.81～3.86(q、6H)、7.19(s、1H)、7.97(s、1H)、8.86(s、1H)
[ Chemical formula 77]
< Synthesis examples B-4 to B-10: synthesis of Compounds B-4 to B-10-
The following B-4 to B-10 were synthesized in the same manner as in Synthesis examples B-1 to B-3.
The estimated structures of the formulae B-4 to B-10 are shown in the following formulae (B-4) to (B-10), respectively.
[ Chemical formula 78]
< Synthesis example AP-1: synthesis of Compound AP-1 ]
15G of propylene glycol monomethyl ether was added to the flask, and the temperature was raised to 80℃while introducing nitrogen gas, and the mixture was stirred.
Subsequently, 14.52g (50 mmol) of 3- (triethoxysilyl) propyl methacrylate (Tokyo Chemical Industry co., ltd.) was added to the Erlenmeyer flask, 50g of the above-described B-46.16g (50 mmol), 50g of propylene glycol monomethyl ether, and 0.46g of a polymerization initiator V-601 (FUJIFILM Wako Pure Chemical Corporation) were dissolved and added dropwise to the flask over 3 hours. Then, after heating to 85℃and stirring for 3 hours, the mixture was cooled to room temperature to obtain an AP-1 solution. The solid content concentration (solid content amount/total mass of solution. Times.100) of the AP-1 solution was 24.1 mass%, and the weight average molecular weight (Mw) of AP-1 was 12,500.
[ Chemical formula 79]
< Synthesis examples AP-2 to AP-4: synthesis of Compounds AP-2 to AP-4
Compounds AP-2 to AP-4 were synthesized in the same manner as in Synthesis example AP-1.
The estimated structures of AP-2 to AP-4 are shown in the following formulas (AP-2) to (AP-4), respectively. In each structure, the subscript between brackets indicates the molar ratio of each repeating unit.
The Mw of AP-2 was 15,800, the Mw of AP-3 was 25,000, and the Mw of AP-4 was 8,500.
[ Chemical formula 80]
< Synthesis examples BP-1 to BP-2: synthesis of Compounds BP-1 to BP-2-
Compounds BP-1 to BP-2 were synthesized in the same manner as in Synthesis example AP-1.
The estimated structures of BP-1 to BP-2 are shown in the following formulas (BP-1) to (BP-2), respectively. In each structure, the subscript between brackets indicates the molar ratio of each repeating unit.
BP-1 had a Mw of 19,100 and BP-2 had a Mw of 32,800.
[ Chemical formula 81]
< Synthesis examples CP-1 to CP-3: synthesis of Compounds CP-1 to CP-3
Compounds CP-1 to CP-3 were synthesized in the same manner as in Synthesis example AP-1.
The estimated structures of CP-1 to CP-3 are shown in the following formulas (CP-1) to (CP-3), respectively. In each structure, the subscript between brackets indicates the molar ratio of each repeating unit.
The Mw of CP-1 was 15,300, the Mw of CP-2 was 20,600, and the Mw of CP-3 was 28,700.
[ Chemical formula 82]
< Synthesis example a-1: synthesis of polybenzoxazole precursor A-1 from 2,2 '-bis (3-amino-4-hydroxyphenyl) hexafluoropropane, 4' -oxo-dibenzoyl chloride
28.0G (76.4 mmol) of 2,2' -bis (3-amino-4-hydroxyphenyl) hexafluoropropane was dissolved in 200g of N-methylpyrrolidone. Then, 12.1g (153 mmol) of pyridine was added thereto, and a solution of 20.7g (70.1 mmol) of 4,4' -oxybenzoyl chloride dissolved in 75g of N-methylpyrrolidone was added dropwise over 1 hour while maintaining the temperature at-10 to 0 ℃. After stirring 30, 1.00g (12.7 mmol) of acetyl chloride was added and stirred for 60 minutes. Next, the polybenzoxazole precursor resin was precipitated in 6 liters of water and the water-polybenzoxazole precursor resin mixture was stirred at 500rpm for 15 minutes. The polybenzoxazole precursor resin was filtered and removed, stirred in 6 liters of water for another 30 minutes and filtered again. Next, the obtained polybenzoxazole precursor resin was dried at 45 ℃ for 3 days under reduced pressure to obtain a polybenzoxazole precursor a-1. The polybenzoxazole precursor a-1 has mw=21500 and mn=9500.
The structure of the polybenzoxazole precursor a-1 is presumed to be represented by the following formula (a-1).
[ Chemical formula 83]
< Synthesis example a-2: synthesis of polyimide precursor (A-2: polyimide precursor having radical polymerizable group) from pyromellitic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate
14.06G (64.5 mmol) of pyromellitic dianhydride (dried at 140℃for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g (258 mmol) of pyridine, 100g of diglyme (diglyme) were mixed and stirred at 60℃for 18 hours to produce a diester of pyromellitic acid and 2-hydroxyethyl methacrylate. Next, after the obtained diester was chlorinated by SOCl 2, the 4,4' -diaminodiphenyl ether was converted into a polyimide precursor in accordance with the same method as in Synthesis example A-5, and a polyimide precursor A-2 was obtained in accordance with the same method as in Synthesis example A-5. The polyimide precursor A-2 had a weight average molecular weight of 21,000.
The structure of the polyimide precursor A-2 is presumed to be represented by the following formula (A-2).
[ Chemical formula 84]
< Synthesis example a-3: synthesis of polyimide precursor (A-3: polyimide precursor having radical polymerizable group) from 4,4 '-oxydiphthalic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate
20.0G (64.5 mmol) of 4,4 '-oxydiphthalic dianhydride (dried at 140℃for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g (258 mmol) of pyridine, 100g of diglyme were mixed and stirred at 60℃for 18 hours to produce a diester of 4,4' -oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, after the obtained diester was chlorinated by SOCl 2, the 4,4' -diaminodiphenyl ether was converted into a polyimide precursor in the same manner as in Synthesis example A-5, and a polyimide precursor A-3 was obtained in the same manner as in Synthesis example A-5. The polyimide precursor A-3 had a weight average molecular weight of 19,600.
The structure of the polyimide precursor A-3 is presumed to be represented by the following formula (A-3).
[ Chemical formula 85]
< Synthesis example a-4: synthesis of polyimide precursor (A-4: polyimide precursor having radical polymerizable group) from 4,4' -oxydiphthalic dianhydride, 4' -diamino-2, 2' -dimethylbiphenyl (diphthaline) and 2-hydroxyethyl methacrylate)
20.0G (64.5 mmol) of 4,4 '-oxydiphthalic dianhydride (dried at 140℃for 12 hours), 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 20.4g (258 mmol) of pyridine, 100g of diglyme were mixed and stirred at 60℃for 18 hours to produce a diester of 4,4' -oxydiphthalic acid and 2-hydroxyethyl methacrylate. Next, after the obtained diester was chlorinated by SOCl 2, 4 '-diamino-2, 2' -dimethylbiphenyl was converted into a polyimide precursor by the same method as in Synthesis example A-5, and a polyimide precursor A-4 was obtained by the same method as in Synthesis example A-5. The polyimide precursor A-4 had a weight average molecular weight of 23,500.
The structure of the polyimide precursor A-4 is presumed to be represented by the following formula (A-4).
[ Chemical formula 86]
[ Synthesis example A-5: synthesis of polyimide precursor A-5 from oxydiphthalic dianhydride, 4 '-biphthalic anhydride, 2-hydroxyethyl methacrylate and 4,4' -diaminodiphenyl ether
9.49G (32.25 mmol) of 4,4' -biphthalic anhydride and 10.0g (32.25 mmol) of oxydiphthalic dianhydride were suspended in 140mL of diglyme while removing water in a drying reactor equipped with a flat bottom joint equipped with a stirrer, a condenser and an internal thermometer. Then, 16.8g (129 mmol) of 2-hydroxyethyl methacrylate, 0.05g of hydroquinone, 0.05g of pure water and 10.7g (135 mmol) of pyridine were added, and stirred at 60℃for 18 hours. Next, after cooling the mixture to-20 ℃, 16.1g (135.5 mmol) of thionyl chloride was added dropwise over 90 minutes. A white precipitate of pyridinium hydrochloride was obtained. Subsequently, the mixture was warmed to room temperature and stirred for 2 hours, and then 9.7g (123 mmol) of pyridine and 25mL of N-methylpyrrolidone (NMP) were added thereto to obtain a transparent solution. Then, a solution in which 11.8g (58.7 mmol) of 4,4' -diaminodiphenyl ether was dissolved in 100mL of NMP was added to the obtained transparent liquid by dropwise addition over 1 hour. Next, 5.6g (17.5 mmol) of methanol and 0.05g of 3, 5-di-t-butyl-4-hydroxytoluene were added, and the mixture was stirred for 2 hours. Next, the polyimide precursor resin was precipitated in 4 liters of water, and the water-polyimide precursor resin mixture was stirred at 500rpm for 15 minutes. The polyimide precursor resin was filtered and obtained, stirred in 4 liters of water for 30 minutes again, and filtered again. Next, the obtained polyimide precursor resin was dried at 45 ℃ under reduced pressure for 3 days to obtain polyimide precursor a-5. The polyimide precursor A-5 thus obtained had a weight average molecular weight of 23,800 and a number average molecular weight of 10,400.
The structure of the polyimide precursor A-5 is presumed to be represented by the following formula (A-5).
[ Chemical formula 87]
< Synthesis example a-6: synthesis of polyimide precursor A-6 from 4,4 '-oxydiphthalic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate
155.1G of 4,4' -Oxydiphthalic Dianhydride (ODPA) was placed in a separate flask, and 134.0g of 2-hydroxyethyl methacrylate (HEMA) and 400ml of gamma-butyrolactone were added. 79.1g of pyridine was added while stirring at room temperature, whereby a reaction mixture was obtained. After the completion of the heat generation by the reaction, the reaction mixture was naturally cooled to room temperature and left to stand for a further 16 hours.
Then, 206.3g of Dicyclohexylcarbodiimide (DCC) was added to the reaction mixture over 40 minutes while stirring a solution of 180mL of gamma-butyrolactone with ice cooling. Subsequently, a suspension of 93.0g of 4,4' -diaminodiphenyl ether in 350mL of gamma-butyrolactone was added over 60 minutes while stirring. After stirring for 2 hours at room temperature, 30mL of ethanol was added and stirred for 1 hour. Then, 400mL of gamma-butyrolactone was added. The precipitate generated in the reaction mixture was removed by filtration to obtain a reaction solution.
The resulting reaction solution was added to 3 liters of ethanol, and a precipitate composed of a crude polymer was formed. The crude polymer thus produced was collected by filtration and dissolved in 1.5 liters of tetrahydrofuran to obtain a crude polymer solution. The obtained crude polymer solution was dropped into 28 liters of water, and the polymer was precipitated, and after filtering the obtained precipitate, vacuum drying was performed, whereby polyimide precursor a-6 was obtained in the form of powder. As a result of measuring the weight average molecular weight (Mw) of the polyimide precursor A-6, it was 24,000.
< Synthesis example a-7: synthesis of polyimide precursor A-7 from 3,3', 4' -biphenyltetracarboxylic dianhydride, 4' -diaminodiphenyl ether and 2-hydroxyethyl methacrylate
In Synthesis example 6, a reaction was carried out in the same manner as described in Synthesis example 6 except that 147.1g of 3,3', 4' -biphenyltetracarboxylic dianhydride was used in place of 155.1g of 4,4' -oxydiphthalic dianhydride, to obtain a polymer A-7. As a result of measurement of the weight average molecular weight (Mw) of this polymer A-7, 22,900 was found.
< Synthesis example PBI-1: synthesis of polyimide PBI-1
In a flask equipped with a condenser and a stirrer, 22.2g (50 mmol) of 4,4' - (hexafluoroisopropylidene) diphthalic anhydride (Tokyo Chemical Industry co., manufactured by ltd.) and 0.02g of 2, 6-tetramethylpiperidine 1-oxyl radical (Tokyo Chemical Industry co., manufactured by ltd.) were dissolved in 100.0g of N-methylpyrrolidone (NMP) while removing water. Subsequently, 11.9g (45 mmol) of diamine (AA-1) described later was added thereto, and the mixture was stirred at 25℃for 3 hours and at 45℃for 3 more hours. Subsequently, 15.8g (200 mmol) of pyridine, 12.8g (125 mmol) of acetic anhydride and 50g of N-methylpyrrolidone (NMP) were added, and the mixture was stirred at 80℃for 3 hours, and 50g of N-methylpyrrolidone (NMP) was added and diluted.
The reaction solution was precipitated in 1 liter of methanol and stirred at 3000rpm for 15 minutes. The resin was filtered and removed, stirred in 1 liter of methanol for another 30 minutes, and filtered again. The resulting resin was dried under reduced pressure at 40℃for 1 day to give polyimide PRI-1.PRI-1 has a molecular weight of mw=19,000, mn= 8,100.
The structure of polyimide PBI-1 is presumed to be a structure represented by the following formula (PBI-1).
[ Chemical formula 88]
< Synthesis example AA-1: synthesis of diamine AA-1
In a flask equipped with a condenser and a stirrer, 26.0g (0.2 mol) of 2-hydroxyethyl methacrylate (FUJIFILM Wako Pure Chemical Corporation manufactured) and 17.4g (0.22 mol) of dehydrated pyridine (FUJIFILM Wako Pure Chemical Corporation manufactured) were dissolved in 78g of ethyl acetate, and the mixture was cooled to 5℃or lower. Next, 48.4g (0.21 mol) of 3, 5-nitrobenzoyl chloride (Tokyo Chemical Industry co., manufactured by ltd.) was dissolved in 145g of ethyl acetate, and the solution was added dropwise to the flask over 1 hour using a dropping funnel. After the completion of the dropwise addition, the mixture was stirred at 10℃or lower for 30 minutes, warmed to 25℃and stirred for 3 hours. Then, the reaction solution was diluted with 600mL of ethyl acetate (CH 3 COOEt), transferred to a separating funnel, and washed successively with 300mL of water, 300mL of saturated sodium bicarbonate (sodium bicarbonate), 300mL of diluted hydrochloric acid, and 300mL of saturated brine. After washing in separate liquid, 30g of magnesium sulfate was dried, concentrated by a distiller and dried in vacuum to obtain 61.0g of dinitro (A-1).
27.9G (500 mmol) of still iron (FUJIFILM Wako Pure Chemical Corporation manufactured) and 5.9g (110 mmol) of ammonium chloride (FUJIFILM Wako Pure Chemical Corporation manufactured) and 3.0g (50 mmol) of acetic acid (FUJIFILM Wako Pure Chemical Corporation manufactured) were weighed into a flask equipped with a condenser and a stirrer, 0.03g of 2, 6-tetramethylpiperidine 1-oxyl (Tokyo Chemical Industry co., ltd.) was added to 200mL of isopropyl alcohol (IPA) and 30mL of pure water, and the mixture was stirred.
Then, 16.2g of the dinitro (A-1) was added thereto over 1 hour and stirred for 30 minutes. Then, the mixture was stirred for 2 hours after the external temperature was raised to 85 ℃, cooled to 25 ℃ or lower, and then filtered using diatomaceous earth (registered trademark). The filtrate was concentrated using a rotary distiller and dissolved in 800mL of ethyl acetate. This was transferred to a separating funnel, washed 2 times with 300mL of saturated sodium bicarbonate, and washed successively with 300mL of water and 300mL of saturated brine. After washing with a liquid, 30g of magnesium sulfate was dried, concentrated by a distiller and dried in vacuo to obtain 11.0g of diamine (AA-1).
[ Chemical formula 89]
< Examples and comparative examples >
In each example, the components described in the following table were mixed to obtain each curable resin composition. In each comparative example, the ingredients described in the following table were mixed, and each comparative composition was obtained.
Specifically, the content of the components other than the solvent described in the table is set as the amount (parts by mass) described in each column of "addition amount" of the table.
Further, the amounts (parts by mass) of the solid components in the solutions were added to the respective AP-1 to AP-4, BP-1 to BP-2, and CP-1 to CP-3 described in the columns of the "addition amounts" of the tables.
The obtained curable resin composition was subjected to pressure filtration through a polytetrafluoroethylene filter having a pore width of 0.8 μm.
In the table, "-" indicates that the composition does not contain a corresponding component.
The details of the components described in the table are as follows.
[ Resin ]
A-1 to A-7, PBI-1: the polybenzoxazole precursors A-1, polyimide precursors A-2 to A-7 and polyimide PBI-1 synthesized in the above synthesis examples
[ Compound B ]
B-1 to B-10: b-1 to B-10 synthesized in the above synthesis examples
AP-1 to AP-4: AP-1 to AP-4 synthesized in the above Synthesis example
CP-1 to CP-3: CP-1 to CP-3 synthesized in the above-mentioned Synthesis example
B-1 to B-10 are compounds corresponding to the low molecular compound B described above.
AP-1 to AP-4 and CP-1 to CP-3 are compounds corresponding to the above-mentioned resin B.
[ Compound C ]
C-1 to C-7: compounds represented by the following formulas (C-1) to (C-7)
[ Chemical formula 90]
[ Compound D ]
D-1 to D-6: compounds represented by the following formulas (D-1) to (D-6)
BP-1 to BP-2: BP-1 to BP-2 synthesized in the above-mentioned Synthesis example
D-1 to D-6 are compounds corresponding to the low molecular compound D described above.
BP-1 to BP-2 are compounds corresponding to the above-mentioned resin D.
[ Chemical formula 91]
[ Compound E ]
E-1 to E-3: compounds represented by the following formulas (E-1) to (E-3)
[ Chemical formula 92]
[ Photopolymerization initiators (all trade names) ]
OXE-01: IRGACURE OXE 01 (manufactured by BASF corporation)
OXE-02: IRGACURE OXE 02 (manufactured by BASF corporation)
[ Polymerizable Compound (trade name in each case) ]
SR-209: SR-209 (manufactured by Sartomer Company, inc)
SR-231: SR-231 (manufactured by Sartomer Company, inc)
SR-239: SR-239 (manufactured by Sartomer Company, inc)
A-DPH: dipentaerythritol hexaacrylate (Shin-Nakamura Chemical co., ltd.)
[ Polymerization inhibitor ]
F-1:1, 4-benzoquinone
F-2: 4-methoxyphenol
F-3:1, 4-dihydroxybenzene
F-4: compounds of the structure
[ Chemical formula 93]
[ Alkali-generating agent ]
I-1 to I-3: compounds of the structure
·I-4：WPBG-27(FUJIFILM Wako Pure Chamical Corporation)
[ Chemical formula 94]
[ Additives ]
J-1: n-phenyl diethanolamine (Tokyo Chemical Industry Co., ltd.)
[ Solvent ]
DMSO: dimethyl sulfoxide
GBL: gamma-butyrolactone
NMP: n-methylpyrrolidone
In the table, "DMSO/GBL" means that a mixture of DMSO and GBL in a mixing ratio (mass ratio) of 80:20 was used.
< Evaluation >
[ Evaluation of copper adhesion ]
Each of the above-described curable resin compositions or comparative compositions was applied to a copper substrate in a layer form by spin coating to form a curable resin composition layer. The copper substrate to which the obtained curable resin composition layer was applied was dried at 100℃for 5 minutes on a hot plate to prepare a curable resin composition layer having a uniform thickness of 20. Mu.m. The curable resin composition layer on the copper substrate was exposed to light using a photomask having a square non-mask portion of 100 μm square formed thereon at an exposure energy of 500mJ/cm 2 using a stepper (Nikon NSR 2005 i9C), and then developed with cyclopentanone for 60 seconds, to obtain a 100 μm square resin layer. Further, the temperature was raised at a temperature raising rate of 10 ℃/min under a nitrogen atmosphere, and after the temperature described in the column of "curing temperature (°c)" in the table was reached, the temperature was maintained for 3 hours, to obtain a resin film 2.
In the case of using I-4 as the alkali generator, after the temperature described in the column of the "curing temperature (. Degree. C.)" was reached, the entire surface of the pattern was subjected to I-ray exposure at an exposure dose of 500mJ/cm 2 while maintaining the temperature for 3 hours.
Shear force was measured on a 100 μm square resin film 2 on a copper substrate in an atmosphere of 65% Relative Humidity (RH) at 25℃by a bond strength tester (CondorSigma, manufactured by XYZTEC). The larger the shearing force is, the larger the adhesion force is, so that the adhesion between the metal and the cured film is excellent, and the preferable result is.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column of "copper adhesion" in the table.
Evaluation criteria-
A: shear force exceeding 40gf
B: the shearing force exceeds 35gf and is less than 40gf
C: the shearing force exceeds 30gf and is less than 35gf
D: the shearing force exceeds 25gf and is less than 30gf
E: a shear force of 25gf or less
1Gf is 9.80665X 10 -3 N.
[ Evaluation of adhesion at the time of multilayer lamination ]
Manufacturing of laminate
Each curable resin composition or comparative composition was applied to a silicon wafer in a layer form by spin coating, and dried at 100 ℃ for 5 minutes using a heating plate, to form a curable resin composition layer. Next, the curable resin composition layer was exposed to light with an exposure energy of 500mJ/cm 2 through a photomask having a circular non-exposed portion having a diameter of 10 μm formed thereon using a stepper (Nikon NSR 2005 i9 c). Next, the cured resin composition layer after exposure was developed with cyclopentanone for 60 seconds, and pores having a diameter of 10 μm were formed. Next, the resin layer (pattern) was formed by heating for 3 hours under a nitrogen atmosphere at the temperature described in the column of "curing temperature (°c)" in the table. In the case of using [ -4 ] as the alkali generator, after the temperature described in the column of "curing temperature (. Degree. C.)" was reached, the entire surface of the pattern was subjected to i-ray exposure at an exposure of 500mJ/cm 2 while maintaining the temperature for 3 hours. Next, the heated resin layer (pattern) was cooled to room temperature, copper plating was performed, and a copper thin film having a thickness of 5 μm was formed on the resin layer, thereby forming a laminate 1.
Next, after the application, exposure, development, and heating of the curable resin composition were performed again after the oxygen plasma was irradiated to the copper thin film of the laminate 1, copper plating treatment was performed to form a copper thin film having a thickness of 5 μm on the resin layer, and a laminate 2 was obtained.
Next, after the application of oxygen plasma to the copper thin film of the laminate 2, the curable resin composition was subjected to application, exposure, development, and heating again, and then copper plating treatment was performed to form a copper thin film having a thickness of 5 μm on the resin layer, thereby obtaining a laminate 3.
Evaluation of peeling defects
The laminate 3 was cut in the vertical direction and a cross section having a width of 5mm was observed, and the presence or absence and number of peeling between the resin layers and between the copper layers and the resin layers were confirmed. The less the occurrence of peeling, the more excellent the adhesion is exhibited when the layers are laminated, and the preferable result is obtained.
The evaluation was performed according to the following evaluation criteria, and the evaluation results are shown in the column of "adhesion at the time of multilayer lamination" in the table.
Evaluation criteria-
A: no peeling was generated
B: peeling off to generate 1-2
C: peeling off to generate 3-5
D: peeling off to generate more than 6
< Example 101>
The curable resin composition used in example 1 was applied to the surface of a copper thin layer of a resin substrate having a copper thin layer formed on the surface thereof in a layer form by spin coating, and dried at 100 ℃ for 4 minutes to form a layer of the curable resin composition having a film thickness of 20 μm, and then exposed to light using a stepper (manufactured by Nikon co., ltd., NSR1505 i 6). Exposure was performed at a wavelength of 365nm through a mask (binary mask with a pattern of 1:1 lines and spaces, line width of 10 μm). After exposure, the mixture was heated at 100℃for 4 minutes. After the above heating, the layer was patterned by developing with cyclohexanone for 2 minutes and rinsing with PGMEA for 30 seconds.
Then, the temperature was raised at a temperature raising rate of 10 ℃/min under a nitrogen atmosphere, and after reaching 230 ℃, the temperature was maintained at 230 ℃ for 3 hours, thereby forming an interlayer insulating film for a rewiring layer. The interlayer insulating film for a rewiring layer is excellent in insulation properties.
Further, as a result of manufacturing a semiconductor device using these interlayer insulating films for a rewiring layer, it was confirmed that there was no problem in operation.

Claims (18)

1. A curable resin composition comprising:
At least 1 resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides, and polybenzoxazoles; and
As the compound B which is a compound having a polymerizable group and an azole group,
The compound B is a resin, and the resin is a compound B,
The polymerizable group is selected from the group consisting of radical polymerizable groups, alkoxysilyl groups, epoxy groups, oxetanyl groups, hydroxymethyl groups, alkoxymethyl groups, isocyanate groups, blocked isocyanate groups.
2. The curable resin composition according to claim 1, wherein,
The compound B has at least 1 group selected from an amide group, a carbamate group, and a urea group.
3. The curable resin composition according to claim 1 or 2, wherein,
The compound B contains at least 1 group selected from radical polymerizable groups and alkoxysilyl groups as the polymerizable groups.
4. The curable resin composition according to claim 1 or 2, wherein,
The oxazolyl group in the compound B is a group represented by the following formula (B-1) or the following formula (B-2);
In the formula (B-1), R B1 represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, Z B1～ZB4 each independently represents =cr B7 -or a nitrogen atom, R B7 represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, and at least 1 of R B1 and R B7 included in the formula (B-1) represents a bonding position to a structure having a polymerizable group;
In the formula (B-2), R B2～RB6 each independently represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, Z B5 and Z B6 each independently represent =cr B8 —or a nitrogen atom, R B8 represents a bonding position to a structure having a polymerizable group, a hydrogen atom, or a 1-valent organic group having no polymerizable group, and at least 1 of R B2～RB6 and R B8 included in the formula (B-2) represents a bonding position to a structure having a polymerizable group.
5. The curable resin composition according to claim 1 or 2, further comprising a compound C which is a compound having an azole group without a polymerizable group.
6. The curable resin composition according to claim 5, wherein,
The compound C is a compound represented by the following formula (C-1) or the following formula (C-2);
In the formula (C-1), Z 1～Z4 each independently represents a group consisting of CR 7 -or a nitrogen atom, R 1 represents a hydrogen atom or a 1-valent organic group, R 7 represents a hydrogen atom or a 1-valent organic group, and the structure represented by the formula (C-1) does not include a polymerizable group;
In the formula (C-2), Z 5～Z6 each independently represents a=CR 8 -or a nitrogen atom, R 2～R6 each independently represents a hydrogen atom or a 1-valent organic group, R 8 represents a hydrogen atom or a 1-valent organic group, and the structure represented by the formula (C-2) does not include a polymerizable group.
7. The curable resin composition according to claim 1 or 2, wherein,
At least 1 resin selected from the group consisting of polyimide precursor, polybenzoxazole precursor, polyimide and polybenzoxazole has a polymerizable group capable of polymerizing with the polymerizable group in the compound B.
8. The curable resin composition according to claim 1 or 2, further comprising a compound D as a silane coupling agent having a polymerizable group different from an alkoxysilyl group and having no azole group.
9. The curable resin composition according to claim 8, wherein,
At least 1 resin selected from the group consisting of polyimide precursor, polybenzoxazole precursor, polyimide and polybenzoxazole has a polymerizable group capable of polymerizing with the polymerizable group in the compound D.
10. The curable resin composition according to claim 1 or 2, further comprising a compound E as a silane coupling agent having no one of a polymerizable group different from an alkoxysilyl group and an azole group.
11. The curable resin composition according to claim 1 or 2, which is used for forming an interlayer insulating film for a rewiring layer.
12. A curable resin composition comprising:
At least 1 resin selected from the group consisting of polyimide precursors, polybenzoxazole precursors, polyimides, and polybenzoxazoles; and
As the compound B which is a compound having a polymerizable group and an azole group,
The polymerizable group is a radical polymerizable group selected from the group consisting of vinyl, allyl, vinylphenyl, (meth) acrylamide, and acryloyloxy.
13. A cured film obtained by curing the curable resin composition according to any one of claims 1 to 12.
14. A laminate comprising 2 or more layers of the cured film of claim 13, comprising a metal layer between any of the cured films.
15. A method of manufacturing a cured film, comprising:
a film forming step of forming a film by applying the curable resin composition according to any one of claims 1 to 12 to a substrate.
16. The method for producing a cured film according to claim 15, comprising:
an exposure step of exposing the film; and a developing step of developing the film.
17. The method for producing a cured film according to claim 15, comprising:
And a heating step of heating the film at 50-450 ℃.
18. A semiconductor device comprising the cured film of claim 13.
CN202180039172.8A 2020-06-03 2021-06-02 Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device Active CN115667404B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2020097007 2020-06-03
JP2020-097007 2020-06-03
PCT/JP2021/021067 WO2021246457A1 (en) 2020-06-03 2021-06-02 Curable resin composition, cured film, laminate, method for manufacturing cured film, and semiconductor device

Publications (2)

Publication Number Publication Date
CN115667404A CN115667404A (en) 2023-01-31
CN115667404B true CN115667404B (en) 2024-05-03

Family

ID=78831198

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202180039172.8A Active CN115667404B (en) 2020-06-03 2021-06-02 Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device

Country Status (5)

Country Link
JP (1) JP7576617B2 (en)
KR (1) KR20230005356A (en)
CN (1) CN115667404B (en)
TW (1) TW202215154A (en)
WO (1) WO2021246457A1 (en)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2023189126A1 (en) * 2022-03-29 2023-10-05
WO2024070963A1 (en) * 2022-09-30 2024-04-04 富士フイルム株式会社 Film production method, photosensitive resin composition, cured product production method, cured product, and laminate
CN116063343B (en) * 2023-01-09 2024-11-08 东莞东阳光科研发有限公司 Compounds and their use as binders in carbon-coated copper foil

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2018016865A (en) * 2016-07-29 2018-02-01 四国化成工業株式会社 Surface treatment agent, resin composition, and utilization of them
CN108137803A (en) * 2015-12-25 2018-06-08 富士胶片株式会社 Resin, composition, cured film, the manufacturing method of cured film and semiconductor devices
CN113994258A (en) * 2019-06-26 2022-01-28 富士胶片株式会社 Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3280949B2 (en) 2000-02-24 2002-05-13 大塚化学株式会社 Modified silicone-based room temperature curable composition
JP2008158421A (en) 2006-12-26 2008-07-10 Asahi Kasei Corp Photosensitive resin composition and photosensitive dry film using the same
JP5402332B2 (en) 2009-07-09 2014-01-29 東レ株式会社 Photosensitive resin composition, photosensitive resin composition film and multilayer wiring board using the same
JP5354609B2 (en) 2010-06-16 2013-11-27 プラス・テク株式会社 Luminous hose
MX355006B (en) 2012-12-19 2018-03-28 Nippon Steel & Sumitomo Metal Corp Press-forming mold and method for manufacturing press-formed product.
JP6523942B2 (en) * 2014-12-19 2019-06-05 四国化成工業株式会社 Surface treatment liquid of inorganic material or resin material, surface treatment method and use thereof
KR102134263B1 (en) 2016-06-24 2020-07-15 도레이 카부시키가이샤 Polyimide resin, polyimide resin composition, touch panel using same, and manufacturing method thereof, color filter and manufacturing method thereof, liquid crystal device and manufacturing method thereof, organic EL device and manufacturing method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108137803A (en) * 2015-12-25 2018-06-08 富士胶片株式会社 Resin, composition, cured film, the manufacturing method of cured film and semiconductor devices
JP2018016865A (en) * 2016-07-29 2018-02-01 四国化成工業株式会社 Surface treatment agent, resin composition, and utilization of them
CN113994258A (en) * 2019-06-26 2022-01-28 富士胶片株式会社 Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device

Also Published As

Publication number Publication date
JPWO2021246457A1 (en) 2021-12-09
CN115667404A (en) 2023-01-31
TW202215154A (en) 2022-04-16
WO2021246457A1 (en) 2021-12-09
JP7576617B2 (en) 2024-10-31
KR20230005356A (en) 2023-01-09

Similar Documents

Publication Publication Date Title
CN115667404B (en) Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
KR102737898B1 (en) Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
TWI870556B (en) Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
CN115190891B (en) Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
CN116234845A (en) Method for producing cured product, method for producing laminate, and method for producing semiconductor device
CN114981360B (en) Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
TW202235490A (en) Resin composition, cured product, laminate, method for producing cured product, and semiconductor device
KR20230004846A (en) Photosensitive resin composition, cured film, laminate, method for producing cured film, and semiconductor device
KR102740154B1 (en) Curable resin composition, cured product, laminate, method for producing cured product, and semiconductor device
KR102766259B1 (en) Resin composition, cured film, laminate, method for producing cured film, and semiconductor device
TW202219119A (en) Curable resin composition, cured article, laminated body, method for producing cured article, semiconductor device, polyimide precursor, and method for producing same
TW202222912A (en) Resin composition, cured object, layered product, method for producing cured object, and semiconductor device
CN115038755A (en) Curable resin composition, resin film, cured film, laminate, method for producing cured film, and semiconductor device
KR20230054708A (en) Resin composition, cured product, laminate, method for producing cured product, and semiconductor device
KR20230057444A (en) Resin composition, cured product, laminate, method for producing cured product, and semiconductor device
TW202208510A (en) Curable resin composition, cured film, laminate, method for producing cured film, semiconductor device, and thermosetting resin
KR102727376B1 (en) Curable resin composition, cured film, laminate, method for producing cured film, and semiconductor device
TWI875941B (en) Resin composition, cured film, laminate, method for producing cured film, and semiconductor element
TWI875930B (en) Resin composition, cured film, laminate, method for producing cured film, and semiconductor element
TW202140621A (en) Photosensitive resin composition, cured film, layered product, method for producing cured film, and semiconductor device
TW202146527A (en) Photosensitive resin composition, method for producing pattern, photosensitive film, cured product, laminate, and device
CN117043273A (en) Resin composition, cured product, laminate, method for producing cured product, and semiconductor device
TW202244639A (en) Method for producing permanent film, method for producing multilayer body, and method for producing semiconductor device
TW202219080A (en) Curable resin composition, cured object, layered product, method for producing cured object, semiconductor device, and polyimide precursor and production method therefor
CN116635453A (en) Method for producing cured product, method for producing laminate, method for producing semiconductor device, and treatment liquid

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant