CN111316164B - Photosensitive resin laminate and method for producing resist pattern - Google Patents
Photosensitive resin laminate and method for producing resist pattern Download PDFInfo
- Publication number
- CN111316164B CN111316164B CN201880072368.5A CN201880072368A CN111316164B CN 111316164 B CN111316164 B CN 111316164B CN 201880072368 A CN201880072368 A CN 201880072368A CN 111316164 B CN111316164 B CN 111316164B
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- photosensitive resin
- resin composition
- composition layer
- mass
- resin laminate
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- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 48
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- 239000003999 initiator Substances 0.000 claims description 31
- 239000000203 mixture Substances 0.000 claims description 26
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
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- NWVVVBRKAWDGAB-UHFFFAOYSA-N p-methoxyphenol Chemical compound COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- IEQIEDJGQAUEQZ-UHFFFAOYSA-N phthalocyanine Chemical compound N1C(N=C2C3=CC=CC=C3C(N=C3C4=CC=CC=C4C(=N4)N3)=N2)=C(C=CC=C2)C2=C1N=C1C2=CC=CC=C2C4=N1 IEQIEDJGQAUEQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920001748 polybutylene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 239000005033 polyvinylidene chloride Substances 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
- JEVGKYBUANQAKG-UHFFFAOYSA-N victoria blue R Chemical compound [Cl-].C12=CC=CC=C2C(=[NH+]CC)C=CC1=C(C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 JEVGKYBUANQAKG-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
-
- 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
- G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
- G03F7/031—Organic compounds not covered by group G03F7/029
-
- 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
-
- 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
-
- 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
- G03F7/105—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers having substances, e.g. indicators, for forming visible images
-
- 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
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
-
- 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
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
- H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/18—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using precipitation techniques to apply the conductive material
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Chemical & Material Sciences (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Inorganic Chemistry (AREA)
- Materials For Photolithography (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Laminated Bodies (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition, wherein the photosensitive resin composition contains (A) an alkali-soluble polymer, and wherein the support film is peelable from the photosensitive resin composition layer, and wherein the moisture content in the photosensitive resin composition layer is 0.1 mass% or more, based on 100 mass% of the total mass of the photosensitive resin composition layer.
Description
Technical Field
The present invention relates to a photosensitive resin laminate and a method for producing a resist pattern.
Background
In the fields of manufacturing a circuit board, precision machining of metal, and the like, a method of forming a desired circuit or machining metal by forming a predetermined resist pattern on a substrate, and then performing etching, plating, and the like is known.
In this case, in order to form a resist pattern on a substrate, a photosensitive resin laminate having a photosensitive resin composition layer on a support film is widely used. The photosensitive resin laminate is often provided in a state in which a cover film is laminated on a photosensitive resin composition layer.
The circuit board is manufactured by, for example, the following method.
The cover film of the photosensitive resin laminate is peeled off, and the photosensitive resin laminate is laminated on the conductive layer of the circuit board so as to be in contact with the photosensitive resin composition layer. Next, the photosensitive resin composition layer of the photosensitive resin laminate is exposed in a pattern, and then the unexposed portion is developed and removed, thereby forming a resist pattern. Then, patterning of the conductive film is performed by an appropriate means such as etching, whereby a circuit board can be obtained.
Patent document 1, for example, discloses a method of forming a circuit board using a photosensitive resin laminate.
The exposure of the photosensitive resin composition layer is usually performed through a support film.
In this case, if the support film of the photosensitive resin laminate contains foreign matter, light scattering occurs during exposure, and the resolution inherent in the photosensitive resin laminate may be impaired.
Patent document 2 relates to a technique for limiting the amount of particles and aggregates having a diameter of 5 μm or more contained in a support film in order to avoid a reduction in resolution caused by foreign matter in the support film.
Prior art literature
Patent literature
Patent document 1 Japanese patent application laid-open No. 2013-054363
Patent document 2 International publication No. 2008/093643
Disclosure of Invention
Problems to be solved by the invention
When a circuit board is formed using a photosensitive resin laminate, there are cases where the sensitivity is insufficient or the original sensitivity cannot be sufficiently exhibited.
In addition, inorganic particles or organic particles may be intentionally blended with the support film to improve the winding property at the time of film production, to improve the storage property at the time of storage by winding into a roll, and the like. In order to avoid a decrease in resolution caused by foreign matter contained in the support film, if the technique of patent document 2 is adopted, there is a concern that the compounding of the particles as described above is limited, and productivity, preservability, and the like of the support film are impaired.
As another method for avoiding the degradation of resolution due to foreign matter contained in the support film, exposure may be performed after laminating a photosensitive resin laminate on a substrate and then peeling the support film.
However, when the support film is peeled off, the photosensitive resin composition layer is exposed. Therefore, according to this method, the exposed photosensitive resin composition layer is brought into contact with various parts of the processing apparatus in the step until the resist pattern is formed.
Since the photosensitive resin composition layer generally has high adhesive force, a part of the photosensitive resin composition layer may adhere when it is contacted with an apparatus for forming wiring such as an exposure machine. If a part of the photosensitive resin composition layer adheres to the device, the following problems may occur: in the next and subsequent exposure, the attached matter becomes a foreign matter, causing light scattering, and impairing the resolution; the foreign matter blocks the exposure light, and the exposure light cannot be irradiated to a portion where the exposure light is intended to be irradiated, and thus a desired resist pattern shape or the like cannot be obtained.
The present invention has been made to improve the above-described situation.
Accordingly, an object of the present invention is to provide a photosensitive resin laminate which can stably exhibit high sensitivity and can obtain a resist pattern of a desired shape, and a method for forming a resist pattern using the same.
Solution for solving the problem
The above object of the present invention is achieved by the present invention described below.
Scheme 1
A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition,
the photosensitive resin composition contains (A) an alkali-soluble polymer,
the support film is releasable from the photosensitive resin composition layer,
When the total mass of the photosensitive resin composition layer is 100 mass%, the moisture content in the photosensitive resin composition layer is 0.1 mass% or more.
Scheme 2
The photosensitive resin laminate according to claim 1, wherein the amount of moisture contained in the photosensitive resin composition layer is 0.2 mass% or more, based on 100 mass% of the total mass of the photosensitive resin composition layer.
Scheme 3
The photosensitive resin laminate according to claim 1 or 2, wherein the amount of moisture contained in the photosensitive resin composition layer is 2.0 mass% or less, based on 100 mass% of the total mass of the photosensitive resin composition layer.
Scheme 4
The photosensitive resin laminate according to claim 3, wherein the amount of moisture contained in the photosensitive resin composition layer is 1.5 mass% or less, based on 100 mass% of the total mass of the photosensitive resin composition layer.
Scheme 5
The photosensitive resin laminate according to any one of claims 1 to 4, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 20gf/inch or less.
Scheme 6
The photosensitive resin laminate according to claim 5, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 15gf/inch or less.
Scheme 7
The photosensitive resin laminate according to claim 5, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 10gf/inch or less.
Scheme 8
The photosensitive resin laminate according to claim 5, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 5gf/inch or less.
Scheme 9
The photosensitive resin laminate according to claim 5, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 3gf/inch or less.
Scheme 10
The photosensitive resin laminate according to claim 5, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 1gf/inch or less.
Scheme 11
The photosensitive resin laminate according to any one of claims 1 to 10, wherein the photosensitive resin composition layer contains 0.01 to 1 mass% of an organic solvent having a boiling point of 55 ℃ or higher, based on 100 mass% of the total mass of the photosensitive resin composition layer.
Scheme 12
The photosensitive resin laminate according to claim 11, wherein the organic solvent is at least 1 selected from the group consisting of toluene, acetone, methyl ethyl ketone, methanol, ethanol, and isopropanol.
Scheme 13
The photosensitive resin laminate according to any one of the aspects 1 to 12, wherein the photosensitive resin composition optionally contains (C) a compound having an olefinic double bond,
when the photosensitive resin composition contains (C) a compound having an olefinic double bond, the mass W of the compound having an olefinic double bond in the photosensitive resin composition C Mass W relative to the alkali-soluble polymer (A) A Ratio (ratio W) C /W A ) Is 0.30 or less.
Scheme 14
The photosensitive resin laminate according to any one of claims 1 to 13, wherein the photosensitive resin composition contains (B) a photopolymerization initiator and (C) a compound having an olefinic double bond.
Scheme 15
The photosensitive resin laminate according to claim 13 or 14, wherein the (C) compound having an olefinic double bond comprises a compound having a (meth) acrylate group at a terminal.
Scheme 16
The photosensitive resin laminate according to any one of the aspects 1 to 12, wherein the photosensitive resin composition contains (B) a photopolymerization initiator and does not contain (C) a compound having an olefinic double bond,
And the alkali-soluble polymer (A) has an olefinic double bond group at the end of a side chain.
Scheme 17
The photosensitive resin laminate according to claim 14 or 16, wherein the (B) photopolymerization initiator contains a 2,4, 5-triarylimidazole dimer.
Scheme 18
The photosensitive resin laminate according to any one of claims 1 to 17, wherein the alkali-soluble polymer (a) has an aromatic hydrocarbon group.
Scheme 19
The photosensitive resin laminate according to any one of claims 1 to 18, wherein the photosensitive resin composition contains diamond green (green) or leuco crystal violet.
Scheme 20
The photosensitive resin laminate according to any one of claims 1 to 19, wherein the support film comprises the following regions: when square small pieces having a side length of 5mm are cut out at arbitrary 10 positions different from each other of the support film, the number of fine particles having a diameter of 1.5 μm or more contained in each small piece is 1 or more on the average of the 10 positions.
Scheme 21
The photosensitive resin laminate according to any one of claims 1 to 20, wherein exposure is performed in a state where the support film is peeled off.
Scheme 22
The photosensitive resin laminate according to any one of claims 1 to 21, wherein a cover film is provided on a surface side of the photosensitive resin composition layer opposite to the support film.
Scheme 23
The photosensitive resin laminate according to any one of claims 1 to 22, wherein the photosensitive resin laminate is wound into a roll.
Scheme 24
A method of manufacturing a resist pattern, comprising:
a lamination step of adhering the photosensitive resin composition layer of the photosensitive resin laminate according to any one of claims 1 to 23 to a substrate;
a support film peeling step of peeling the support film of the photosensitive resin laminate;
an exposure step of exposing the photosensitive resin laminate; and
and a developing step of developing the photosensitive resin laminate subjected to the exposure.
Scheme 25
The method for producing a resist pattern according to claim 24, wherein the exposure step includes a step of exposing the photosensitive resin laminate from a side on which the support film is provided.
Scheme 26
A method of manufacturing a circuit substrate, comprising: a circuit forming step of manufacturing a substrate having a resist pattern by the method according to claim 24 or 25, and then forming a circuit on the substrate by etching or plating the substrate having the resist pattern.
Scheme 27
The method for manufacturing a circuit board according to claim 26, comprising a resist pattern peeling step of: the resist pattern is stripped.
Scheme 28
A method for producing a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition,
the photosensitive resin composition contains (A) an alkali-soluble polymer,
and the support film is releasable from the photosensitive resin composition layer,
the manufacturing method comprises the following steps:
a step 1 of producing a 1 st photosensitive resin laminate in which the moisture content contained in the photosensitive resin composition layer is lower than the lower limit value of a predetermined range; and
a step 2 of storing the 1 st photosensitive resin laminate in an environment having a predetermined humidity for a predetermined time to produce a 2 nd photosensitive resin laminate having a moisture content in the photosensitive resin composition layer within a predetermined range,
the predetermined range is 0.1 mass% or more, based on 100 mass% of the total mass of the photosensitive resin composition layer.
Scheme 29
The method for producing a photosensitive resin laminate according to claim 28, wherein the predetermined range is 2.0 mass% or less, based on 100 mass% of the total mass of the photosensitive resin composition layer.
Scheme 30
The method for producing a photosensitive resin laminate according to claim 28 or 29, wherein the step 2 comprises storing the 1 st photosensitive resin laminate in an environment having a temperature of 20 ℃ or higher and a humidity of 40% rh or higher for 12 hours or longer.
Scheme 31
A method for producing a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film, the method comprising the steps of:
a photosensitive resin composition blend solution containing (A) an alkali-soluble polymer, (D) an organic solvent, and (E) water is applied to the support film, and then (D) the organic solvent is removed to form a photosensitive resin composition layer, thereby forming a photosensitive resin laminate,
when the total mass of the photosensitive resin composition layer is set to 100 mass%, the moisture content in the photosensitive resin composition layer is 0.1 mass% or more.
Scheme 32
The method for producing a photosensitive resin laminate according to any one of claims 28 to 31, wherein the photosensitive resin laminate is wound into a roll.
ADVANTAGEOUS EFFECTS OF INVENTION
According to the present invention, a photosensitive resin laminate which can stably exhibit high sensitivity and can obtain a resist pattern of a desired shape, and a method for forming a resist pattern using the same can be provided.
Detailed Description
< photosensitive resin laminate >)
The photosensitive resin laminate of the present invention is characterized in that,
which is a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition,
the photosensitive resin composition contains (A) an alkali-soluble polymer,
the support film can be peeled from the photosensitive resin composition layer,
when the total mass of the photosensitive resin composition layer is set to 100 mass%, the moisture content in the photosensitive resin composition layer is 0.1 mass% or more.
The photosensitive resin laminate of the present invention may further comprise a cover film on the surface of the photosensitive resin composition layer opposite to the support film.
The photosensitive resin laminate of the present invention is prepared by laminating a photosensitive resin composition layer on a substrate, then peeling the support film to expose the photosensitive resin composition layer, and then exposing the substrate.
The photosensitive resin laminate of the present invention can stably exhibit high sensitivity by setting the total mass of the photosensitive resin composition layer to 100 mass%, and the moisture content in the photosensitive resin composition layer is 0.1 mass% or more.
In the photosensitive resin laminate of the present invention, it is preferable that the adhesive force of the surface of the photosensitive resin composition layer in contact with the support film is limited to 20gf/inch or less, so that adhesion of a part of the photosensitive resin composition layer can be avoided even if the exposed photosensitive resin composition layer is in contact with the processing device during exposure treatment or the like. In the International unit System (SI), 20gf/inch corresponds to 7.72mN/mm (1 gf/inch=0.386 mN/mm).
Hereinafter, each element constituting the photosensitive resin laminate of the present invention will be described by way of a non-limiting example of a specific embodiment (this embodiment).
[ support film ]
As the support film in the photosensitive resin laminate of the present embodiment, a transparent film is preferable.
Examples of such a support film include a film composed of a polyethylene terephthalate film, a polyvinyl alcohol film, a polyvinyl chloride film, a vinyl chloride copolymer film, a polyvinylidene chloride film, a vinylidene chloride copolymer film, a polymethyl methacrylate copolymer film, a polystyrene film, a polyacrylonitrile film, a styrene copolymer film, a polyamide film, a cellulose derivative film, and the like. These films may also be stretched films as needed.
(supporting particles in film)
The support film in this embodiment preferably includes the following regions: when square chips having a side length of 5mm are cut at 10 points different from each other, the number of particles having a diameter of 1.5 μm or more contained in each chip is 1 or more (1/25 mm based on the average value at 10 points 2 The above). The size of the "region" is arbitrary and can be appropriately set according to the area of the support film. The film containing fine particles in this ratio is preferable because it is less likely to cause wrinkles when wound into a roll for storage and is less likely to adhere to the film even when stored in a roll.
From the viewpoints of wrinkle resistance, blocking resistance, etc. at the time of winding and coiling, the number of fine particles of 1.5 μm or more in the support film is preferably 5/25 mm in terms of the average value at square-shaped chips 10 having a side length of 5mm of the support film 2 Above, 10 pieces/25 mm 2 Above, 50 pieces/25 mm 2 Above, 100 pieces/25 mm 2 Above or 150/25 mm 2 The above. On the other hand, from the viewpoint of ensuring transparency as a film, the number of fine particles having a diameter of 1.5 μm or more in the support film is preferably 1,000/25 mm, as an average value at square-shaped chips 10 having a side length of 5mm of the support film 2 Hereinafter, more preferably 500 pieces/25 mm 2 The following is given.
The diameter of the fine particles in the support film is preferably 100 μm or less, more preferably 50 μm or less, and still more preferably 30 μm or less.
The fine particles having a diameter of 1.5 μm or more in the support film may be inorganic particles or organic particles. Examples of the inorganic particles include fine particles composed of silica, calcium carbonate, calcium silicate, kaolin, talc, mica, zeolite, aluminosilicate, aluminum hydroxide, alumina, barium sulfate, titanium oxide, zinc oxide, calcium phosphate, glass, and the like; examples of the organic particles include fine particles composed of polystyrene, poly (meth) acrylate, silicone, and the like.
(thickness and haze of support film)
The thickness of the support film is not particularly limited. However, the thinner the support film is, the more advantageous from the viewpoint of image formability and economy, and the thicker the support film is, the more advantageous from the viewpoint of functions such as maintaining strength. In consideration of these requirements, the thickness of the support film is preferably 5 μm or more and 50 μm or less, more preferably 10 μm or more and 30 μm or less.
The haze of the support film is preferably 5% or less.
[ photosensitive resin composition layer ]
The photosensitive resin composition layer contains a photosensitive resin composition.
The photosensitive resin composition in the photosensitive resin composition layer contains (a) an alkali-soluble polymer.
The photosensitive resin composition may contain 1 or more components selected from the group consisting of (B) a photopolymerization initiator and (C) a compound having an olefinic double bond, in addition to the alkali-soluble polymer (a), and may contain 1 or more components selected from the group consisting of a colorant, an inhibitor and other additives.
(photosensitive resin composition)
Alkali-soluble polymer (A)
The alkali-soluble polymer (a) in this embodiment is a polymer soluble in an alkali aqueous solution.
(A) The alkali-soluble polymer may be made soluble in an aqueous alkali solution by containing a carboxyl group or an acid anhydride group or both. (A) The alkali-soluble polymer preferably contains a carboxyl group and has an acid equivalent weight of 100 to 600. The acid equivalent means the mass in gram units of the alkali-soluble polymer having 1 equivalent of carboxyl group therein. The acid equivalent is preferably set to 100 or more from the viewpoint of improving development resistance, resolution and adhesion, and is preferably set to 600 or less from the viewpoint of improving development and releasability. The acid equivalent amount can be measured by a potentiometric titration method using a sodium hydroxide aqueous solution of 0.1mol/L using a titration apparatus (for example, automatic biogas-flat titration apparatus (COM-555) manufactured by Pingzhou Kogyo Co., ltd.). (A) The acid equivalent of the alkali-soluble polymer is more preferably 250 to 450.
The alkali-soluble polymer (a) preferably has a weight average molecular weight of 5,000 to 500,000 in terms of polystyrene as measured by Gas Permeation Chromatography (GPC). From the viewpoint of the properties of the developed aggregate and the properties of the unexposed film such as the chipping property in the photosensitive resin laminate, the weight average molecular weight is preferably 5,000 or more. On the other hand, from the viewpoint of improving the solubility in the developer, the weight average molecular weight is preferably 500,000 or less. The chipability is a property of suppressing the phenomenon of flying out of chips when the unexposed film is cut by a cutter. If the chipping property is poor, scattered chips may adhere to, for example, the upper surface of the photosensitive resin laminate, and the chips may be transferred to the mask in a subsequent exposure step, resulting in defects such as defects.
In order to improve the edge-fusion property when the photosensitive resin laminate of the present invention is produced and stored in a roll form wound in a roll form, the weight average molecular weight of the alkali-soluble polymer (a) is preferably adjusted to the above range. The edge fusion property is a property of suppressing a phenomenon that the photosensitive resin layer overflows from the end surface of the roll when the photosensitive resin laminate is wound into a roll.
(A) The weight average molecular weight of the alkali-soluble polymer is more preferably 5,000 to 300,000, still more preferably 10,000 to 200,000.
(A) The alkali-soluble polymer preferably has an aromatic hydrocarbon group.
By having an aromatic hydrocarbon group in the alkali-soluble polymer (a), the following benefits can be obtained: resolution and adhesion are improved, the amount of aggregates generated during development is reduced, and etching resistance is improved.
The alkali-soluble polymer (a) preferred in the present embodiment can be obtained by copolymerizing 1 or 2 or more monomers selected from the following 1 st monomer and 2 nd monomer. One or more selected from the group consisting of the 3 rd monomer and the 4 th monomer may be copolymerized with the 1 st monomer and the 2 nd monomer.
The 1 st monomer is a carboxylic acid or an acid anhydride having one polymerizable double bond in the molecule. Examples of the 1 st monomer include (meth) acrylic acid, fumaric acid, cinnamic acid, crotonic acid, itaconic acid, maleic anhydride, and maleic acid half ester. (meth) acrylic acid is particularly preferred. Here, (meth) acrylic refers to acrylic or methacrylic.
(A) The copolymerization ratio of the 1 st monomer in the alkali-soluble polymer can be easily calculated from the value of the desired acid equivalent in the alkali-soluble polymer. (A) The copolymerization ratio of the 1 st monomer in the alkali-soluble polymer is preferably 10 mass% or more and 50 mass% or less based on the total mass of all the monomers. The copolymerization ratio is preferably 10 mass% or more from the viewpoint of exhibiting good developability, etc., and the copolymerization ratio of the 1 st monomer is more preferably 15 mass% or more from the viewpoint of exhibiting good developability. The copolymerization ratio is preferably 50% by mass or less from the viewpoint of improving resolution, suppressing occurrence of resist runout, and the like, more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less from the viewpoint of these.
The 2 nd monomer is an aromatic group-containing monomer, and is a monomer having an aromatic group and a polymerizable double bond in the molecule.
Examples of the 2 nd monomer include aromatic vinyl compounds such as styrene, α -alkylstyrene, hydroxystyrene, acetoxystyrene, halogenated styrene, halogenated alkylstyrene, vinyltoluene, and vinylnaphthalene; benzyl (meth) acrylate, naphthalene (meth) acrylate, and other aromatic group-containing esters of (meth) acrylic acid. Among these, benzyl (meth) acrylate is particularly preferable.
(A) The copolymerization ratio of the 2 nd monomer in the alkali-soluble polymer is preferably 20 mass% or more and 90 mass% or less based on the total mass of all the monomers. The copolymerization ratio is preferably 20 mass% or more from the viewpoints of improving resolution and adhesion, suppressing the occurrence of aggregates during development, improving etching resistance, and the like. From this viewpoint, the copolymerization ratio of the 2 nd monomer is more preferably 25% by mass or more, still more preferably 30% by mass or more, and particularly preferably 40% by mass or more. On the other hand, from the viewpoint of exhibiting suitable developability, the copolymerization ratio of the 2 nd monomer is preferably 90 mass% or less.
In view of cost, it is preferable to use an aromatic vinyl compound as at least a part of the 2 nd monomer, preferably as all of the 2 nd monomer. (A) The copolymerization ratio of the aromatic vinyl compound in the alkali-soluble polymer is preferably 20 mass% or more and 90 mass% or less based on the total mass of the monomers. The copolymerization ratio is preferably 20 mass% or more from the viewpoints of improving resolution, improving adhesion, exhibiting good development aggregation property, etching resistance, and the like. From this viewpoint, the copolymerization ratio of the aromatic vinyl compound is more preferably 25% by mass or more, still more preferably 30% by mass or more, and particularly preferably 40% by mass or more. From the viewpoint of exhibiting proper developability and cured film flexibility, the copolymerization ratio is preferably 90 mass% or less, more preferably 85 mass% or less.
The 3 rd monomer is a monomer other than the 1 st monomer and the 2 nd monomer and contains one polymerizable double bond in the molecule, and may be used as a comonomer of the alkali-soluble polymer (A) if necessary.
Examples of the 3 rd monomer include (meth) acrylic esters such as methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-ethylhexyl (meth) acrylate; ester compounds of carboxylic acids such as vinyl acetate and vinyl propionate with vinyl alcohol; (meth) acrylonitrile, and the like.
(A) The copolymerization ratio of the 3 rd monomer in the alkali-soluble polymer is preferably 50 mass% or less, more preferably 20 mass% or less based on the total mass of all the monomers.
The 4 th monomer is a monomer other than the 1 st monomer, the 2 nd monomer and the 3 rd monomer and contains 2 or more polymerizable double bonds in the molecule, and may be used as a comonomer of the alkali-soluble polymer (A) if necessary.
The alkali-soluble polymer (a) obtained by copolymerizing the 4 th monomer is preferably a polymer having a double bond group in a side chain, and preferably a polymer having a double bond group at a terminal of a side chain.
The 4 th monomer is preferably a monomer having 2 polymerizable double bonds in the molecule, and examples thereof include di (meth) acrylate compounds such as polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 2-hydroxy-3- (meth) acryloxypropyl (meth) acrylate, tricyclodecane dimethanol di (meth) acrylate, and α, ω -alkanediol di (meth) acrylate.
The length of the polyethylene chain, polypropylene chain or polytetramethylene chain in these compounds is preferably 100 or more and 2,000 or less, more preferably 200 or more and 1,000 or less, based on the molecular weight of these chain blocks. The length of the alkane in the α, ω -alkanediol di (meth) acrylate is preferably 4 or more and 20 or less, more preferably 6 or more and 10 or less in terms of the number of carbon atoms linked in one direction.
(A) The copolymerization ratio of the 4 th monomer in the alkali-soluble polymer is preferably 30 mass% or less, more preferably 10 mass% or less, based on the total mass of all the monomers.
In one embodiment, the glass transition temperature Tg of the alkali-soluble polymer (A) may be in the range of 30℃to 125℃inclusive, preferably 50℃to 110℃inclusive, more preferably 50℃to 105℃inclusive, and still more preferably 50℃to 90℃inclusive. From the viewpoint of controlling the adhesive force, it is preferable to set Tg to 30℃or higher. On the other hand, from the viewpoint of controlling the cross-sectional shape of the resist to be a good rectangle, it is preferable to set the Tg to 110 ℃ or lower.
(A) The alkali-soluble polymer can be obtained by copolymerizing a monomer mixture containing the above monomers in respective predetermined amounts, preferably in an appropriate solvent by a known method. The copolymerization can be carried out, for example, by known radical polymerization.
When the total mass of the photosensitive resin composition is 100 mass%, the proportion of the alkali-soluble polymer (a) in the photosensitive resin composition of the present embodiment is preferably in the range of 40 mass% or more and 85 mass% or less, and more preferably in the range of 50 mass% or more and 75 mass% or less. From the viewpoint of controlling the adhesive force, it is advantageous to make the ratio 40 mass% or more. On the other hand, from the viewpoint of controlling the development time, it is advantageous to make it 85 mass% or less.
Photopolymerization initiator (B)
The photosensitive resin composition in the photosensitive resin composition layer of the photosensitive resin laminate of the present embodiment optionally contains (B) a photopolymerization initiator.
The photopolymerization initiator (B) optionally contained in the photosensitive resin composition includes, for example, triarylimidazole dimer, aromatic ketone, acridine compound, N-aryl- α -amino acid compound, quinone compound, anthracene compound, pyrazoline derivative, and the like, and 1 or more selected from them can be used.
The triarylimidazole dimer is preferably a 2,4, 5-triarylimidazole dimer, and examples thereof include a 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-chlorophenyl) -4, 5-di (methoxyphenyl) imidazole dimer, a 2- (o-fluorophenyl) -4, 5-diphenylimidazole dimer, a 2- (o-methoxyphenyl) -4, 5-diphenylimidazole dimer, and a 2- (p-methoxyphenyl) -4, 5-diphenylimidazole dimer.
Examples of the aromatic ketone include benzophenone, 4' -bis (dimethylamino) benzophenone (milbetone), 4' -bis (diethylamino) benzophenone, N ' -tetraethyl-4, 4' -diaminobenzophenone, 4-methoxy-4 ' -dimethylaminobenzophenone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl ] -2-morpholino-acetone-1, and the like.
Examples of the acridine compound include 1, 7-bis (9, 9' -acridinyl) heptane, 9-phenylacridine, 9-methylacridine, 9-ethylacridine, 9-chloroethylacridine, 9-methoxyacridine, 9-ethoxyacridine, 9- (4-methylphenyl) acridine, 9- (4-ethylphenyl) acridine, 9- (4-methoxyphenyl) acridine, 9- (4-dimethylaminophenyl) acridine, 9- (4-chlorophenyl) acridine, 9- (3-methylphenyl) acridine, 9- (3-chlorophenyl) acridine, and 9- (3-bromophenyl) acridine.
Examples of the N-aryl- α -amino acid compound include N-phenylglycine, N-methyl-N-phenylglycine, and N-ethyl-N-phenylglycine.
Examples of the quinone compound include 2-ethylanthraquinone, phenanthrenequinone, 2-t-butylanthraquinone, octamethylanthraquinone, 1, 2-benzanthraquinone, 2, 3-benzanthraquinone, 2-phenylanthraquinone, 2, 3-diphenylanthraquinone, 1-chloroanthraquinone, 2-methylanthraquinone, 1, 4-naphthoquinone, 9, 10-phenanthrenequinone, 2-methyl-1, 4-naphthoquinone, and 2, 3-dimethylanthraquinone.
Examples of the anthracene compound include 9, 10-dibutoxyanthracene, 9, 10-diethoxyanthracene, and 9, 10-diphenylanthracene.
Examples of the pyrazoline derivative include 1-phenyl-3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-biphenyl) -5- (4-tert-octyl-phenyl) -pyrazoline, 1- (4- (benzoxazol-2-yl) phenyl) -3- (4-tert-butyl-styryl) -5- (4-tert-butyl-phenyl) -pyrazoline, 1-phenyl-3- (4-isopropylstyryl) -5- (4-isopropylstyryl) -pyrazoline, 1-phenyl-3- (4-methoxystyryl) -5- (4-methoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 5-dimethoxystyryl) -5- (3, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (3, 4-dimethoxystyryl) -5- (3, 4-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 6-dimethoxystyryl) -5- (2, 6-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 5-dimethoxystyryl) -5- (2, 5-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 3-dimethoxystyryl) -5- (2, 3-dimethoxyphenyl) -pyrazoline, 1-phenyl-3- (2, 4-dimethoxystyryl) -5- (2, 4-dimethoxyphenyl) -pyrazoline, and the like.
When the photosensitive resin composition in the present embodiment contains the photopolymerization initiator (B), the ratio is preferably in the range of 0.1 mass% to 20 mass% when the total mass of the photosensitive resin composition is 100 mass%. The proportion of the photopolymerization initiator (B) being 0.1 mass% or more is from the viewpoint of obtaining an exposure pattern having a sufficient film residue ratio after development. On the other hand, the blending amount of 20 mass% or less is based on the viewpoint of obtaining high resolution by allowing light to sufficiently pass through the entire thickness of the photosensitive resin composition layer at the time of exposure and the viewpoint of suppressing development aggregation in the developer. (B) The more preferable range of the ratio of the photopolymerization initiator is 0.3 mass% or more and 10 mass% or less.
Among the above, the photopolymerization initiator (B) in the present embodiment preferably contains a 2,4, 5-triarylimidazole dimer, and more preferably contains a 2,4, 5-triarylimidazole dimer and an aromatic ketone.
In these cases, the proportion of the 2,4, 5-triarylimidazole dimer is preferably in the range of 0.1 mass% or more and 15 mass% or less, more preferably 1 mass% or more and 10 mass% or less, based on 100 mass% of the total mass of the photosensitive resin composition.
The proportion of the aromatic ketone is preferably 5 mass% or less, more preferably 0.05 mass% or more and 3 mass% or less, and still more preferably 0.1 mass% or more and 1 mass% or less, based on 100 mass% of the total mass of the photosensitive resin composition.
Compounds having olefinic double bonds
The photosensitive resin composition in the photosensitive resin laminate of the present embodiment optionally contains (C) a compound having an olefinic double bond.
The compound (C) having an olefinic double bond optionally contained in the photosensitive resin composition preferably contains a compound having a (meth) acrylate group at the end.
(C) The number of terminal (meth) acrylate groups in the compound having an olefinic double bond may be 1 or more, and is preferably 2 or more, more preferably 3 or more, and still more preferably 4 or more from the viewpoints of improving the crosslinking density, improving the resolution and the adhesion, and the like. On the other hand, from the viewpoint of the peeling property, it is preferably 10 or less functions, more preferably 6 or less functions, further preferably 5 or less functions, and particularly preferably 4 or less functions.
(C) The molecular weight of the compound having an olefinic double bond is preferably 500g/mol or more and 5,000g/mol or less, more preferably 600g/mol or more and 4,000g/mol or less, and still more preferably 700g/mol or more and 3,000g/mol or less.
The compound having an olefinic double bond in (C) having a terminal (meth) acrylate group in the photosensitive resin composition of the photosensitive resin laminate may be, for example, the following compound depending on the number of terminal (meth) acrylate groups contained in the molecule.
Examples of the compound having 1 terminal (meth) acrylate group include:
4-n-nonylphenoxy octaethylene glycol acrylate,
4-n-nonylphenoxy tetraethylene glycol acrylate,
Gamma-chloro-beta-hydroxypropyl-beta' -methacryloyloxyethyl-phthalate, and the like.
Examples of the compound having 2 terminal (meth) acrylate groups include:
polypropylene glycol di (meth) acrylate,
A di (meth) acrylate of ethylene glycol obtained by adding an average of 2 moles of ethylene oxide to each of both ends of bisphenol A,
A di (meth) acrylate of ethylene glycol obtained by adding an average of 5 moles of ethylene oxide to each of both ends of bisphenol A,
A di (meth) acrylate of an alkylene glycol obtained by adding an average of 6 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A,
And di (meth) acrylic acid esters of alkylene glycols obtained by adding an average of 15 moles of ethylene oxide and an average of 2 moles of propylene oxide to both ends of bisphenol A.
Examples of the compound having 3 terminal (meth) acrylate groups include:
glycerol tri (meth) acrylate,
Trimethylol tri (meth) acrylate,
Polyoxypropyltrimethylolpropane tri (meth) acrylate,
Polyoxyethyltrimethylolpropane tri (meth) acrylate,
Trimethylpropane triglycidyl ether tri (meth) acrylate,
A tri (meth) acrylate obtained by adding an average of 3 moles of ethylene oxide to the terminals of 3 hydroxyl groups of trimethylolpropane, respectively,
A tri (meth) acrylate obtained by adding an average of 9 moles of ethylene oxide to the terminal end of the hydroxyl group of trimethylolpropane,
A tri (meth) acrylate obtained by adding an average of 15 moles of ethylene oxide to the terminal ends of 3 hydroxyl groups of trimethylolpropane, respectively,
And tri (meth) acrylic acid esters obtained by adding 30 moles of ethylene oxide to the terminals of 3 hydroxyl groups of trimethylolpropane, respectively.
Examples of the compound having 4 terminal (meth) acrylate groups include:
pentaerythritol tetra (meth) acrylate,
Tetra (meth) acrylate obtained by adding 9 moles of ethylene oxide to the terminal end of 4 hydroxyl groups of pentaerythritol,
A tetra (meth) acrylate obtained by adding an average of 12 moles of ethylene oxide to the terminal end of 4 hydroxyl groups of pentaerythritol,
A tetra (meth) acrylate obtained by adding an average of 15 moles of ethylene oxide to the terminal end of each of 4 hydroxyl groups of pentaerythritol,
A tetra (meth) acrylate obtained by adding an average of 20 moles of ethylene oxide to the terminal end of 4 hydroxyl groups of pentaerythritol,
A tetra (meth) acrylate obtained by adding an average of 28 moles of ethylene oxide to the terminal end of each of 4 hydroxyl groups of pentaerythritol,
And tetra (meth) acrylic acid esters obtained by adding an average of 35 moles of ethylene oxide to the terminal ends of 4 hydroxyl groups of pentaerythritol.
Examples of the compound having 5 terminal (meth) acrylate groups include:
dipentaerythritol penta (meth) acrylate, and the like.
Examples of the compound having 6 terminal (meth) acrylate groups include:
dipentaerythritol hexa (meth) acrylate,
A hexa (meth) acrylate obtained by adding an average of 6 moles of ethylene oxide to the terminal end of 6 hydroxyl groups of dipentaerythritol,
A hexa (meth) acrylate obtained by adding an average of 12 moles of ethylene oxide to the terminal end of 6 hydroxyl groups of dipentaerythritol,
A hexa (meth) acrylate obtained by adding an average of 13 moles of ethylene oxide to the terminal end of 6 hydroxyl groups of dipentaerythritol,
And hexa (meth) acrylic acid esters obtained by adding an average of 24 moles of ethylene oxide to the terminal end of 6 hydroxyl groups of dipentaerythritol.
(C) The compound having an olefinic double bond may be composed of only a compound having a (meth) acrylate group at the terminal, or may be a mixture of a compound having a (meth) acrylate group at the terminal and a compound having an olefinic double bond other than the compound.
The proportion of the compound having a terminal (meth) acrylate group in the compound having an olefinic double bond is preferably 50 mass% or more, 60 mass% or more, 70 mass% or more, 80 mass% or more, 90 mass% or more, or 95 mass% or more, or 100 mass% or more, based on 100 mass% of the total mass of the compound having an olefinic double bond.
When the photosensitive resin composition in the present embodiment contains (C) a compound having an olefinic double bond, the ratio is preferably in the range of 5 mass% to 50 mass% when the total mass of the photosensitive resin composition is 100 mass%. The proportion of the compound having an olefinic double bond in (C) is 5 mass% or more, from the viewpoint of improving the exposure sensitivity and resolution of the photosensitive resin composition layer and the adhesion between the cured resist and the substrate. On the other hand, the proportion of 50 mass% or less is based on the viewpoint of suppressing adhesion and the viewpoint of suppressing peeling delay of the cured resist. (C) The proportion of the compound having an olefinic double bond is more preferably 10 to 45% by mass.
Coloring agent-
The photosensitive resin composition of the present embodiment may contain a colorant.
Examples of the colorant include leuco dyes and coloring materials other than leuco dyes.
When the photosensitive resin composition contains a colorant, it is preferable in view of visibility. The present invention is also advantageous in terms of recognition when an alignment mark for exposure is read by an inspection machine or the like.
Examples of leuco dyes include tris (4-dimethylaminophenyl) methane [ leuco crystal violet ], bis (4-dimethylaminophenyl) phenyl methane [ leuco malachite green ], and the like. In particular, leuco crystal violet is preferably used as the leuco dye from the viewpoint of good contrast.
Examples of coloring substances other than leuco dyes include magenta, phthalocyanine GREEN, gold amine base, accessory red, crystal violet, methyl orange, nile blue 2B, victoria blue, malachite GREEN (manufactured by baogu chemical corporation, aizen (registered trademark) MALACHITE GREEN), basic blue 20, adamant GREEN (manufactured by baogu chemical corporation, aizen (registered trademark) DIAMOND GREEN GH), and the like.
The photosensitive resin composition of the present embodiment preferably contains adamantine green or leuco crystal violet as a colorant.
When the photosensitive resin composition of the present embodiment contains a colorant, the ratio is preferably 0.001 mass% or more and 10 mass% or less, assuming that the total mass of the photosensitive resin composition is 100 mass%. From the viewpoint of improving the handleability, the ratio is preferably 0.001 mass% or more. On the other hand, from the viewpoint of maintaining the storage stability of the photosensitive resin laminate of the present embodiment, the ratio is preferably 10 mass% or less. The proportion of the colorant in the photosensitive resin composition is more preferably 0.01% by mass or more and 5% by mass or less, and still more preferably 0.05% by mass or more and 3% by mass or less.
Inhibitors-
The photosensitive resin composition of the present embodiment may contain an inhibitor.
Examples of the inhibitor include aluminum nitrosophenyl hydroxylamine salts, p-methoxyphenol, 4-t-butylcatechol, and 4-ethyl-6-t-butylphenol. These inhibitors may function, for example, as polymerization inhibitors.
Other additives-
The photosensitive resin composition of the present embodiment may further contain additives other than the additives described above.
Examples of the other additives include 2-mercaptobenzimidazole, 1H-tetrazole, 1-methyl-5-mercapto-1H-tetrazole, 2-amino-5-mercapto-1, 3, 4-thiadiazole, 3-amino-5-mercapto-1, 2, 4-triazole, 3-mercapto-triazole, 4, 5-diphenyl-1, 3-diazole-2-yl, and 5-amino-1H-tetrazole. These other additives may, for example, function as antioxidants.
(scheme of photosensitive resin composition)
The photosensitive resin composition of the present embodiment contains (a) an alkali-soluble polymer, and may contain 1 or more components selected from (B) a photopolymerization initiator and (C) a compound having an olefinic double bond. The photosensitive resin composition of the present embodiment may contain, for example, (B) a photopolymerization initiator in addition to (a) an alkali-soluble polymer, and (C) a compound having an olefinic double bond in addition to (a) an alkali-soluble polymer.
(moisture content of photosensitive resin composition layer)
The present inventors have studied the exposure behavior and sensitivity of a photosensitive resin composition layer of a photosensitive resin laminate in detail, and as a result, have found that the sensitivity is improved when a certain amount of moisture is contained in the photosensitive resin composition layer.
The inventors speculate that the reason is as follows. The present invention is not limited by a particular theory.
When the negative-type photosensitive resin composition layer is exposed to light, the curing reaction proceeds due to crosslinking, and the glass transition temperature (Tg) of the photosensitive resin composition layer increases. It is considered that if Tg of the photosensitive resin composition layer increases, components such as a monomer and an initiator contained in the layer are difficult to move, and further progress of the curing reaction is hindered, and a predetermined sensitivity is not exhibited.
However, when the photosensitive resin composition layer contains a certain amount of moisture, the Tg increases relatively slowly even if the curing reaction proceeds at the time of exposure. Therefore, it is considered that the movement of the components in the layer is not hindered, and the curing reaction can proceed further, so that the decrease in sensitivity is suppressed. According to a preferred embodiment of the present invention, the support film may be peeled off for exposure at the time of exposure. In this case, the sensitivity tends to be lowered because free gene air oxygen generated in the photosensitive resin composition layer is deactivated during exposure, but the sensitivity can be improved when the moisture content is appropriate. In addition, in the photosensitive resin composition layer in the photosensitive resin laminate having low adhesion, the fluidity of the photosensitive resin composition is also low with a decrease in adhesion. If the fluidity is low, the movement of the components in the photosensitive resin composition is restricted, and thus the sensitivity at the time of exposure may be insufficient. Therefore, having an appropriate amount of moisture is also effective for sensitivity reduction in the case where the adhesive force is limited.
When the total mass of the photosensitive resin composition layer is 100% by mass from the viewpoint of improving sensitivity, the moisture content of the photosensitive resin composition layer of the present embodiment is 0.1% by mass or more, preferably 0.15% by mass or more, 0.20% by mass or more, 0.25% by mass or more, 0.30% by mass or more, 0.35% by mass or more, 0.40% by mass or more, 0.45% by mass or more, 0.50% by mass or more, 0.55% by mass or more, 0.60% by mass or more, 0.65% by mass or more, 0.70% by mass or more, 0.75% by mass or more, 0.80% by mass or more, 0.85% by mass or more, 0.90% by mass or more, 0.95% by mass or more, and 1.0% by mass or more.
The amount of water in the photosensitive resin composition layer is not particularly limited from the viewpoint of improving sensitivity. However, if the moisture content in the photosensitive resin composition layer is too high, the reactivity may be lowered. From the viewpoint of avoiding such a situation, the moisture content of the photosensitive resin composition layer is preferably 2.0 mass% or less, more preferably 1.8 mass% or less, still more preferably 1.5 mass% or less, still more preferably 1.2 mass% or less, particularly preferably 1.0 mass% or less, and may be 0.90 mass% or less, 0.80 mass% or less, 0.75 mass% or less, 0.70 mass% or less, 0.65 mass% or less, 0.60 mass% or less, 0.55 mass% or less, 0.50 mass% or less, 0.45 mass% or less, 0.40 mass% or 0.35 mass% or less, when the total mass of the photosensitive resin composition layer is 100 mass%.
When the moisture content of the photosensitive resin composition layer is distributed in the surface by winding the photosensitive resin laminate into a roll, for example, the desired effect can be exhibited if the moisture content of the partial region in the surface of the photosensitive resin composition layer is within the above-described range. However, in the present invention, the moisture content in the photosensitive resin composition layer may satisfy the above numerical range on the whole roll.
(adhesive force of photosensitive resin composition layer)
As described above, the photosensitive resin laminate of the present embodiment is based on the premise that the photosensitive resin composition layer is laminated on the substrate, and then the support film is peeled off to expose the photosensitive resin composition layer, and then the exposure is performed. In this case, the photosensitive resin composition layer in the present embodiment preferably has a limited adhesive force, since adhesion of a part of the photosensitive resin composition layer can be avoided even if the exposed photosensitive resin composition layer contacts the device.
From this viewpoint, in the photosensitive resin laminate of the present embodiment, the adhesive force of the surface of the photosensitive resin composition layer in contact with the support film is preferably 20gf/inch or less. The adhesive force is more preferably 15gf/inch or less, 10gf/inch or less, 8gf/inch or less, 6gf/inch or less, 5gf/inch or less, 4gf/inch or less, 3gf/inch or less, 2gf/inch or 1gf/inch or less. The lower limit of the adhesive force is not particularly limited, and may be 0.1gf/inch or more, 0.2gf/inch or more, 0.5gf/inch or more, 1gf/inch or more, 2gf/inch or more, 3gf/inch or more, or 5gf/inch or more.
The adhesive force of the surface of the photosensitive resin composition layer in contact with the support film can be measured as a force when 180 ° peeling is performed in the longitudinal direction from the support film having a width of 25mm and a length of 80mm of the photosensitive resin composition layer using a commercially available tensile tester. As the adhesive force, the maximum value of the force measured from the start of peeling to the end of peeling was used. Specifically, the measurement can be performed by the method described in examples described below.
The adhesive force of the photosensitive resin composition layer in this embodiment is limited to a certain range. The photosensitive resin composition layer having the adhesive force may contain, for example, a photosensitive resin composition whose types and amounts of constituent components are adjusted so as to exhibit the desired adhesive force.
It is considered that the expression of the adhesive force of the photosensitive resin composition layer containing the photosensitive resin composition is related to the double bonds, particularly terminal double bonds, of the components contained in the photosensitive resin composition. That is, if the photosensitive resin composition contained in the photosensitive resin composition layer contains a large number of terminal double bonds, the adhesive force is high, and if the terminal double bonds are small, the adhesive force is weakened.
Further, it is considered that since the compound (C) having an olefinic double bond contains a large number of terminal double bonds in its molecule in a preferred embodiment, the amount of terminal double bonds contained in the photosensitive resin composition layer can be limited by limiting the proportion of the compound (C) having an olefinic double bond in the photosensitive resin composition or not using the compound, whereby the adhesive force of the photosensitive resin composition layer can be suppressed.
Specifically, the adhesive force of the surface of the photosensitive resin composition layer containing the photosensitive resin composition, which is in contact with the support film, can be set to 20gf/inch or less, preferably 15gf/inch or less, 10gf/inch or less, 8gf/inch or less, 6gf/inch or less, 5gf/inch or less, 4gf/inch or less, 3gf/inch or less, 2gf/inch or less, or 1gf/inch or less, for example, by the following 2 methods.
The 1 st method is as follows: when the photosensitive resin composition contains (C) a compound having an olefinic double bond, the mass W of the compound having an olefinic double bond in (C) the photosensitive resin composition is determined C Mass W relative to the alkali-soluble polymer (A) A Ratio (ratio W) C /W A ) Limited to below 0.30. The ratio W C /W A It may be 0.25 or less, 0.20 or less, or 0.15 or less.
The method is based on the following considerations: the adhesive force of the photosensitive resin composition layer is directly suppressed by limiting the proportion of the compound (C) having an olefinic double bond in the photosensitive resin composition.
Method 2: the photosensitive resin composition does not contain (C) a compound having an olefinic double bond, and the alkali-soluble polymer (A) is made to have an olefinic double bond group at the end of a side chain.
In the method 1, the proportion of the compound having an olefinic double bond in the photosensitive resin composition can be reduced within the above-mentioned range, but if the proportion is set to zero, the compound having an olefinic double bond in the photosensitive resin composition is completely absent, and there is a possibility that there is no problem that the terminal double bond derived from the compound is completely absent and there is no double bond to be crosslinked upon exposure.
Thus, method 2 is based on the following considerations: instead of using (C) a compound having an olefinic double bond, the alkali-soluble polymer (A) is provided with a double bond which facilitates crosslinking upon exposure to light.
The alkali-soluble polymer (a) having an olefinic double bond group at the terminal of the side chain can be obtained by copolymerizing a monomer mixture containing a 4 th monomer having 2 or more polymerizable double bonds in the molecule. The alkali-soluble polymer (A) may be a copolymer of the 1 st monomer, the 2 nd monomer and the 4 th monomer, or may be a copolymer of the 1 st monomer, the 2 nd monomer, the 3 rd monomer and the 4 th monomer.
As described above, the 1 st monomer is a carboxylic acid or an acid anhydride having 1 polymerizable double bond in the molecule; the 2 nd monomer is a monomer with aromatic groups and polymerizable double bonds in the molecule; the 3 rd monomer is a monomer other than the 1 st monomer and the 2 nd monomer and has 1 polymerizable double bond in the molecule.
In both the method 1 and the method 2, the photosensitive resin composition may contain (B) a photopolymerization initiator. That is, the photosensitive resin composition in method 1 contains (A) an alkali-soluble polymer, (B) a photopolymerization initiator, and (C) a compound having an olefinic double bond, and the mass W of the compound C Mass W relative to the alkali-soluble polymer (A) A Ratio (ratio W) C /W A ) Is 0.30 or less; the photosensitive resin composition in method 2 may contain (a) an alkali-soluble polymer having an olefinic double bond group at the terminal of the side chain and (B) a photopolymerization initiator, but not (C) a compound having an olefinic double bond.
The thickness of the photosensitive resin composition layer in the photosensitive resin laminate varies depending on the application, but is preferably 5 to 100. Mu.m, more preferably 7 to 60. Mu.m, still more preferably 10 to 50. Mu.m, particularly preferably 15 to 30. Mu.m. The thinner the photosensitive resin composition layer, the higher the resolution and the thicker the thickness, the higher the film strength.
(flexibility of photosensitive resin composition layer)
For example, when the photosensitive resin laminate of the present invention is produced and stored in the form of a roll wound in a roll shape, the photosensitive resin composition layer in the photosensitive resin laminate is preferably moderately soft.
The flexibility of the photosensitive resin composition layer can be evaluated by using the melt viscosity.
The melt viscosity of the photosensitive resin composition layer having moderate flexibility is preferably 1×10 5 cps～1×10 10 cps, more preferably 1X 10 5 cps～1×10 9 cps, further preferably 1X 10 5 cps～1×10 8 A range of cps. The term "melt viscosity" as used herein refers to a value at 60℃measured by, for example, the following method or a method considered equivalent thereto by those skilled in the art.
[ melt viscosity of photosensitive resin composition layer ]
The photosensitive resin laminate was subjected to moisture control at 23 ℃ and 50% rh overnight in a state where the photosensitive resin composition layer was exposed. The viscosity of the photosensitive resin composition layer after humidity control was measured using a flowability tester (product name "Flow tester cf-500D") manufactured by shimadzu corporation under the following conditions, and the measured value at 60 ℃ was used as the melt viscosity of the photosensitive resin composition layer.
Rate of temperature increase (Rate): 2 ℃/min
Start temperature (StartT): 40 DEG C
End temperature (EndT): 110 DEG C
Preheating temperature (PreH): 120 seconds
Measurement interval (intvl.): 2 DEG C
Measurement of movable range (Strk): max20mm
Load (Load):
20kg/cm 2 (weight 1.5 kg)
CylinderPressure 1.961×10 06 Pa
Die diameter (Die d): 1.0mm
Die length (Die l): 1.0mm
(organic solvent in photosensitive resin composition layer)
The photosensitive resin composition layer having flexibility as described above can be realized, for example, by containing an organic solvent in the photosensitive resin composition layer.
The boiling point of the organic solvent contained in the photosensitive resin composition layer is preferably 55 ℃ or higher, 60 ℃ or higher, 65 ℃ or higher, or 70 ℃ or higher, from the viewpoint of remaining even after heating at the time of producing the photosensitive resin laminate, and from the viewpoint of evaporation after forming the resist pattern, for example, 120 ℃ or lower, 110 ℃ or lower, 100 ℃ or lower, or 90 ℃ or lower.
Examples of such an organic solvent include:
aromatic hydrocarbons such as benzene and toluene;
ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, etc.;
alcohols such as methanol, ethanol, isopropanol, and 1-butanol;
Halogenated hydrocarbons such as chloroform, carbon tetrachloride, 1, 2-dichloroethane, and 1, 1-trichloroethane;
esters such as methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, and isobutyl acetate;
ethers such as tetrahydrofuran and 1, 4-dioxane.
Among these organic solvents, at least 1 selected from the group consisting of aromatic hydrocarbons, ketones and alcohols is preferable, and at least 1 selected from the group consisting of toluene, acetone, methyl ethyl ketone, methanol, ethanol and isopropanol is particularly preferable.
From the viewpoint of imparting flexibility to the photosensitive resin composition layer, the content of the organic solvent in the photosensitive resin composition layer is preferably 0.01 mass% or more, 0.03 mass% or more, or 0.05 mass% or more, assuming that the total mass of the photosensitive resin composition layer is 100 mass%. On the other hand, from the viewpoint of maintaining the shape of the photosensitive resin composition layer and ensuring an appropriate adhesive force, it is preferably 1 mass% or less, 0.9 mass% or less, or 0.8 mass% or less.
[ cover film ]
The photosensitive resin laminate of the present embodiment may include a cover film on a surface of the photosensitive resin composition layer opposite to the support film.
An important characteristic of the cover film used in the photosensitive resin laminate is to have an appropriate adhesion force. That is, the adhesion force of the cover film to the photosensitive resin composition layer is preferably sufficiently smaller than the adhesion force of the support film to the photosensitive resin composition layer, and the cover film can be easily peeled from the photosensitive resin laminate. Examples of the cover film include a polyethylene film, a polypropylene film, a polystyrene film, a polyvinyl chloride film, an ABS (acrylonitrile-butadiene-styrene copolymer) film, and a film having excellent peelability as shown in japanese unexamined patent publication No. 59-202457.
The thickness of the cover film is preferably 10 to 100. Mu.m, more preferably 10 to 50. Mu.m.
[ photosensitive resin laminate roll ]
The photosensitive resin laminate of the present embodiment may be in the form of a roll of the photosensitive resin laminate wound into a roll.
The photosensitive resin laminate roll may include, for example, a roll core, a cover film, an end face separator, and the like in addition to the support film and the photosensitive resin laminate.
Method for producing photosensitive resin laminate
The photosensitive resin laminate of the present embodiment can be produced, for example, by laminating a photosensitive resin composition layer on a support film and further covering the support film as necessary. As the lamination method, a known method can be used.
For example, each component of the photosensitive resin composition constituting the photosensitive resin composition layer is dissolved in an appropriate solvent to prepare a coating liquid. Then, the coating liquid is applied onto a support film, and then the solvent is removed by drying, thereby forming a photosensitive resin composition layer on the support film, whereby a photosensitive resin laminate having a support film and a photosensitive resin composition layer composed of the photosensitive resin composition can be produced.
The photosensitive resin composition layer of the obtained photosensitive resin laminate may be further laminated with a cover sheet to prepare a photosensitive resin laminate having a cover sheet.
Examples of the solvent used in preparing the coating liquid include aromatic hydrocarbons typified by benzene and toluene; ketones typified by acetone and Methyl Ethyl Ketone (MEK); alcohols typified by methanol, ethanol and isopropanol. Among these solvents, at least 1 selected from toluene, acetone, methyl ethyl ketone, methanol, ethanol and isopropyl alcohol is preferably used because an appropriate amount of these organic solvents can be left in the obtained photosensitive resin composition layer.
The amount of the solvent to be used is preferably increased or decreased appropriately, and the viscosity of the coating liquid at 25℃is adjusted to a range of 500 to 4,000 mPas, and the coating liquid is then used for coating.
As described above, the photosensitive resin composition layer in the photosensitive resin laminate of the present embodiment preferably contains an appropriate amount of moisture.
The method for adjusting the moisture content of the photosensitive resin composition layer is not particularly limited. However, the following production methods 1 and 2 are exemplified.
[ 1 st manufacturing method ]
The 1 st production method for obtaining the photosensitive resin laminate of the present embodiment is a production method of a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film,
The photosensitive resin composition contains (A) an alkali-soluble polymer, and the support film is releasable from the photosensitive resin composition layer,
the manufacturing method comprises the following steps:
step 1, manufacturing a 1 st photosensitive resin laminate in which the moisture content in the photosensitive resin composition layer is lower than the lower limit value of the prescribed range;
a step 2 of storing the 1 st photosensitive resin laminate in an environment having a predetermined humidity for a predetermined time to produce a 2 nd photosensitive resin laminate having a moisture content in a predetermined range in the photosensitive resin composition layer,
the predetermined range is 0.1 mass% or more, where the total mass of the photosensitive resin composition layer is 100 mass%.
The lower limit value of the predetermined range of the moisture content in the 1 st production method may be the same as the lower limit value described above as the moisture content to be preferably contained in the photosensitive resin composition layer of the present embodiment from the viewpoint of improving sensitivity. In addition, from the viewpoint of suppressing the decrease in reactivity, the upper limit value of the predetermined range of the moisture content in the production method 1 may be the same as the upper limit value described above as the moisture content to be preferably contained in the photosensitive resin composition layer.
(step 1)
In step 1 of the 1 st production method, a 1 st photosensitive resin laminate is obtained, which comprises a support film and a photosensitive resin composition layer containing a predetermined photosensitive resin composition on the support film, wherein the moisture content in the photosensitive resin composition layer is lower than the lower limit value of the predetermined range.
For forming a photosensitive resin composition layer containing a photosensitive resin composition on a support film, the following method can be used, for example.
First, each component constituting the predetermined photosensitive resin composition (that is, (a) an alkali-soluble polymer, preferably at least one selected from the group consisting of (B) a photopolymerization initiator and (C) a compound having an olefinic double bond, and optional components used as needed) is dissolved or dispersed in an appropriate organic solvent to prepare a photosensitive resin composition blend. Then, the supporting film is coated with the seasoning liquid, and then the organic solvent is removed, whereby a photosensitive resin laminate comprising the supporting film and a photosensitive resin composition layer containing the photosensitive resin composition can be produced.
As the organic solvent used in the preparation of the blend liquid, aromatic hydrocarbons typified by benzene and toluene are mentioned above; ketones typified by acetone and Methyl Ethyl Ketone (MEK); alcohols typified by methanol, ethanol and isopropanol.
The amount of the solvent to be used is preferably increased or decreased as appropriate, and the solid content concentration of the blend (the ratio of the total mass of the components other than the organic solvent in the blend to the total mass of the blend) is adjusted to be in the range of preferably 10 mass% or more and 80 mass% or less, more preferably 20 mass% or more and 70 mass% or less, still more preferably 30 mass% or more and 60 mass% or less, and then the blend is applied.
Examples of suitable means for applying the blending liquid to the support film include roll coaters, comma coaters, gravure coaters, air knife coaters, die coaters, and bar coaters.
The removal of the organic solvent after the application of the mixed solution can be performed by heating at a temperature of, for example, 50 ℃ to 120 ℃, preferably 60 ℃ to 100 ℃, for a time of, for example, 30 seconds to 1 hour, preferably 1 minute to 30 minutes.
Thus, a photosensitive resin composition layer containing a photosensitive resin composition can be formed on the support film, thereby obtaining a photosensitive resin laminate. If necessary, a protective film may be laminated on the surface of the photosensitive resin composition layer opposite to the support film.
Thus, the 1 st photosensitive resin laminate in which the moisture content contained in the photosensitive resin composition layer is lower than the lower limit value of the predetermined range can be obtained.
The photosensitive resin laminate may be wound into a roll. The photosensitive resin laminate may be wound around an appropriate winding core, or an end face separator may be disposed on the wound end face.
(step 2)
The water content in the photosensitive resin composition layer of the 1 st photosensitive resin laminate obtained as described above is lower than the lower limit value of the predetermined range in which the desired effect of the present invention is exhibited. Therefore, the photosensitive resin laminate of item 1 is stored for a predetermined time in an environment having a predetermined humidity, and the 2 nd photosensitive resin laminate (that is, the photosensitive resin laminate of the present embodiment) in which the moisture content in the photosensitive resin composition layer is within a predetermined range is produced.
The predetermined humidity in step 2 may be, for example, 40% RH or more, preferably 50% RH or more, 60% RH or more, 70% RH or more, 80% RH or more, or 90% RH or more.
The predetermined time may be, for example, 0.5 days (12 hours) or more, preferably 1 day (24 hours) or more, 1.5 days (36 hours) or more, 2 days (48 hours) or more, 3 days (72 hours) or more, 5 days (120 hours) or more, or 7 days (168 hours) or more.
The temperature during storage may be 0 ℃ or higher and 40 ℃ or lower, preferably 10 ℃ or higher and 35 ℃ or lower, more preferably 20 ℃ or higher and 30 ℃ or lower, and typically may be room temperature.
[ method for producing 2 ]
The 2 nd production method for obtaining the photosensitive resin laminate of the present embodiment is a production method of a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film,
the method comprises the following steps: a photosensitive resin composition blend containing components constituting a predetermined photosensitive resin composition, an organic solvent and water is applied onto a support film, and then the organic solvent is removed to form a photosensitive resin composition layer, thereby forming a photosensitive resin laminate,
when the total mass of the photosensitive resin composition layer is set to 100 mass%, the moisture content in the photosensitive resin composition layer is 0.1 mass% or more.
In the production method 2, a photosensitive resin composition layer containing a photosensitive resin composition containing a predetermined amount of moisture is formed on a support film, and the photosensitive resin laminate of the present embodiment is directly obtained.
Specifically, first, each component constituting the desired photosensitive resin composition (that is, (a) an alkali-soluble polymer, preferably at least one selected from the group consisting of (B) a photopolymerization initiator and (C) a compound having an olefinic double bond, and optional components used as needed) and water are dissolved or dispersed in an organic solvent to prepare a photosensitive resin composition blend. Then, the supporting film is coated with the seasoning liquid, and then the organic solvent is removed, whereby a photosensitive resin laminate comprising the supporting film and a photosensitive resin composition layer containing a photosensitive resin composition containing a predetermined amount of moisture can be produced.
The amount of water added to the photosensitive resin composition blend is preferably set so that the amount of water in the photosensitive resin composition layer in the obtained photosensitive resin laminate is a desired value. That is, since each component of the photosensitive resin composition and the organic solvent added to the blend liquid sometimes contain moisture as impurities, the amount of moisture in the photosensitive resin composition layer is considered to be larger than the amount of added moisture. On the other hand, when the organic solvent is removed after the application of the blend liquid, part of the water may evaporate together with the organic solvent, and therefore, the amount of water in the photosensitive resin composition layer may be considered to be smaller than the amount of water added.
Therefore, it is preferable to set the amount of water to be added to the photosensitive resin composition blended solution so that the amount of water in the obtained photosensitive resin composition layer becomes a desired value in consideration of the increase or decrease in the amount of water caused by these phenomena.
The 2 nd production method may be performed in the same manner as the 1 st step in the 1 st production method, except that the above-mentioned blended solution added with water is used as the blended solution of the photosensitive resin composition.
In the production method 2, the amount of moisture contained in the photosensitive resin composition layer is also set from the viewpoints of sensitivity improvement and reactivity.
Therefore, from the viewpoint of improving sensitivity, the lower limit value of the moisture content in the photosensitive resin composition layer obtained by the production method of the 2 nd may be the same as the lower limit value described above as the moisture content to be preferably contained in the photosensitive resin composition layer of the present embodiment. In addition, from the viewpoint of suppressing the decrease in reactivity, the upper limit value of the predetermined range of the moisture content in the 2 nd production method may be the same as the upper limit value described above as the moisture content to be preferably contained in the photosensitive resin composition layer.
In the production method 2, the photosensitive resin laminate may be wound into a roll. The photosensitive resin laminate may be wound around an appropriate winding core, or an end face separator may be disposed on the wound end face.
Method for producing resist pattern
With the photosensitive resin laminate of the present embodiment, a resist pattern can be formed on a desired substrate.
The method for producing a resist pattern includes, for example: a lamination step of adhering the photosensitive resin composition layer of the photosensitive resin laminate of the present embodiment to a substrate;
a peeling step of peeling the support film of the photosensitive resin laminate;
An exposure step of exposing the photosensitive resin laminate;
and a developing step of developing the exposed photosensitive resin laminate. After these steps, a heating step may be further included, as the case may be.
[ laminating step ]
The lamination step is a step of adhering the photosensitive resin composition layer of the photosensitive resin laminate to the substrate.
As the base material, for example, a silicon wafer, a copper-clad laminate, a flexible substrate, or the like can be used. When the photosensitive resin composition layer is adhered to the substrate, it can be carried out using a suitable apparatus such as a thermal laminator.
[ support film peeling Process ]
In the support film peeling step, the support film of the photosensitive resin laminate is peeled off. By this operation, the photosensitive resin composition layer of the photosensitive resin laminate is exposed, and exposure in the next step is performed in this state. Therefore, even if the support film contains a plurality of fine particles having a diameter of 1.5 μm or more, light at the time of exposure is not scattered by the fine particles, and therefore the photosensitive resin laminate can exhibit a predetermined resolution.
[ Exposure procedure ]
Next, in the exposure step, the photosensitive resin laminate is exposed. Exposure is performed from the side of the photosensitive resin laminate on which the support film is provided.
In this step, a pattern-like exposure is performed. The pattern exposure can be performed, for example, by the following method:
a method of exposing the photosensitive resin composition layer with a mask having a desired wiring pattern in contact with the mask,
method of exposing desired wiring pattern by direct image-wise exposure method, or
A method of exposing an image of a photomask by an exposure method in which the image is projected through a lens.
The light used for exposure preferably includes light of a bright line in the ultraviolet region, and light from a light source such as a semiconductor laser, a metal halide lamp, a high-pressure mercury lamp, or an excimer laser can be used. The exposure amount can be appropriately set according to the composition of the photosensitive resin composition contained in the photosensitive resin composition layer, the desired line width, and the like.
[ developing Process ]
The development step performed after the exposure step is a step of developing and removing the unexposed portion with a developer made of an aqueous alkali solution to form a resist pattern on the substrate.
As the aqueous alkali solution, na is preferably used 2 CO 3 Or K 2 CO 3 Is a solution of (a) and (b). The aqueous alkali solution may be appropriately selected depending on the properties of the photosensitive resin composition, and Na having a concentration of about 0.2 mass% or more and 2 mass% or less and a temperature of 20 ℃ or more and 40 ℃ or less is preferably used 2 CO 3 An aqueous solution.
The resist pattern can be obtained through the above steps. The surface of the substrate (for example, the copper surface of the copper-clad laminate) is exposed at the portion removed in the developing step.
[ heating Process ]
In the heating step optionally performed, the resist pattern to be formed may be heated at a temperature of, for example, 100 ℃ to 300 ℃ for 1 minute to 5 hours. By performing this heating step, the adhesion, chemical resistance, and the like of the obtained resist pattern can be further improved. For example, a hot air type heating furnace, an infrared type heating furnace, or a far infrared type heating furnace can be used for heating.
Method for manufacturing circuit board
The circuit board can be manufactured by using a substrate having a resist pattern obtained by the above-described < method for manufacturing a resist pattern >.
The method of manufacturing a circuit board according to the present embodiment includes a circuit forming step:
according to the above-described method for producing a resist pattern, a substrate having a resist pattern is produced, and then a circuit is formed on the substrate by etching or plating the substrate having a resist pattern.
After the circuit forming step, a resist pattern stripping step of stripping the resist pattern may be further included.
[ Circuit Forming Process ]
In the circuit forming step, a circuit is formed on a substrate having a resist pattern by etching or plating the substrate.
In etching, an etching solution is sprayed from above to the substrate having the resist pattern, and the surface of the substrate not covered with the resist pattern is etched to form a desired circuit pattern. The etching method includes acid etching, alkaline etching, and the like, and may be performed by selecting a method suitable for the photosensitive resin laminate to be used.
[ resist Pattern stripping Process ]
In the resist pattern stripping step, the resist pattern is stripped from the substrate after the circuit formation. The resist pattern is peeled off, for example, by treating the substrate after the circuit formation with an alkaline aqueous solution (peeling liquid) stronger than the developer.
The aqueous alkali for resist pattern stripping is not particularly limited. Generally, an aqueous solution of NaOH or KOH having a concentration of 2 mass% or more and 5 mass% or less and a temperature of 40 ℃ or more and 70 ℃ or less is used. A small amount of water-soluble organic solvent may be added to the stripping liquid.
Examples
Preparation of photosensitive resin composition
Preparation example 1
The following components were dissolved in acetone as a solvent to prepare a photosensitive resin composition 1.
(A) Alkali-soluble polymer: 47 parts by mass of methacrylic acid/benzyl methacrylate copolymer (polymerization ratio 20/80 (mass ratio), acid equivalent weight 430, weight average molecular weight 5 ten thousand),
(B) Photopolymerization initiator: 0.1 part by mass of 4,4' -bis (diethylamino) benzophenone and 3 parts by mass of 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer,
(C) Compounds having an olefinic double bond: 14 parts by mass of tetraacrylate obtained by adding an average of 15 moles of ethylene oxide to the 4 terminals of pentaerythritol,
Dye: 0.05 part by mass of adamantine green and 0.3 part by mass of leuco crystal violet
Preparation examples 2 to 5
Fixing the amount of alkali-soluble polymer (A) to 47 parts by mass, changing the amount of compound (C) having an olefinic double bond, and changing the mass W of compound (C) having an olefinic double bond C Mass W relative to the alkali-soluble polymer (A) A Ratio (ratio W) C /W A ) Photosensitive resin compositions 2 to 5 were prepared in the same manner as in preparation example 1 except that the proportions shown in table 1 were changed.
The photosensitive resin compositions 1 to 5 obtained in preparation examples 1 to 5 had solution viscosities ranging from 500 mPas to 4,000 mPas both inclusive, as measured at 25 ℃.
Preparation example 6
161.75g of the photosensitive resin composition 6 was prepared by mixing the following components.
(A) Alkali-soluble polymer: 73g (29.9 g based on the copolymer) of MEK solution (copolymer concentration: 41.0 mass%) of methacrylic acid/styrene/benzyl methacrylate polymer (polymerization ratio: 30/20/50 (mass ratio, acid equivalent: 290, weight average molecular weight: 55,000), 50g (copolymer concentration: 40.0% based on the copolymer) of MEK solution (polymerization ratio: 30/20/40/10 (mass ratio), acid equivalent: 290, weight average molecular weight: 50,000),
(B) Compounds having an olefinic double bond: pentaerythritol triacrylate and pentaerythritol tetraacrylate 7: 20g of a mixture of 3 (product name "M-306" manufactured by Toyama Synthesis Co., ltd.) and 15g of a dimethacrylate of a polyalkylene glycol obtained by further adding an average of 3 moles of ethylene oxide to each of both ends of a polypropylene glycol to which an average of 12 moles of propylene oxide was added,
(C) Photopolymerization initiator: 3g of 2- (o-chlorophenyl) -4, 5-diphenyl imidazole dimer, 0.2g of 4,4' -bis (diethylamino) benzophenone,
Organic solvent: 15g of MEK,
Optional ingredients: leuco crystal violet 0.5g and adamantine green 0.05g as colorants
Preparation example 7
141.75g of the photosensitive resin composition 7 was prepared by mixing the following components.
(A) Alkali-soluble polymer: 101g (50.0 g based on the copolymer) of a Methyl Ethyl Ketone (MEK) solution (copolymer concentration 49.5 mass%) of a methacrylic acid/benzyl methacrylate copolymer (polymerization ratio 20/80 (mass ratio), acid equivalent weight 430, weight average molecular weight 55,000),
(B) Compounds having an olefinic double bond: 20g of a dimethacrylate of polyethylene glycol obtained by adding an average of 5 moles of ethylene oxide to both ends of bisphenol A (product name "BPE-500" manufactured by Xinzhou chemical Co., ltd.), 15g of a tetramethyl acrylate obtained by adding an average of 9 moles of ethylene oxide to the ends of 4 hydroxyl groups of pentaerythritol,
(C) Photopolymerization initiator: 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer 5g and 1-phenyl-3- (4-biphenyl) -5- (4-tert-butyl-phenyl) -pyrazoline 0.2g,
Organic solvent: 15g of MEK,
Optional ingredients: leuco crystal violet 0.5g and adamantine green 0.05g as colorants
Preparation example 8
The following components were dissolved in acetone as a solvent to prepare a photosensitive resin composition 8.
(A) Alkali-soluble polymer: 50 parts by mass of methacrylic acid/methyl methacrylate/styrene/butyl acrylate (polymerization ratio 25/10/60/5 (mass ratio), acid equivalent 344, weight average molecular weight 2 ten thousand),
(B) Photopolymerization initiator: 0.1 part by mass of 4,4' -bis (diethylamino) benzophenone and 3 parts by mass of 2- (o-chlorophenyl) -4, 5-diphenylimidazole dimer,
(C) Compounds having an olefinic double bond: 20 parts by mass of a tetramethyl acrylate obtained by adding an average of 15 moles of ethylene oxide to the 4 terminals of pentaerythritol, and 20 parts by mass of a dimethyl acrylate obtained by adding an average of 2 moles of ethylene oxide to the two terminals of bisphenol A,
Dye: 0.05 part by mass of adamantine green and 0.3 part by mass of leuco crystal violet
Experimental examples 1 to 5
In experimental examples 1 to 5, photosensitive resin laminates were produced using the photosensitive resin compositions 1 to 5 obtained in preparation examples 1 to 5, respectively, as a photosensitive resin composition blend, and adhesion of the photosensitive resin composition layers and contamination resistance to silicon wafers were evaluated.
Experimental example 1
1. Production of photosensitive resin laminate
The photosensitive resin composition 1 prepared as described above was applied to one surface of a support film made of polyethylene terephthalate (PET), and dried to form a photosensitive resin composition layer, thereby obtaining a photosensitive resin laminate comprising a support and a photosensitive resin composition layer composed of the photosensitive resin composition layer. The thickness of the support film used here was 12. Mu.m.
2. Evaluation
(1) Evaluation of adhesive force of photosensitive resin composition layer
A copper-clad laminate of 200mm X85 mm and 1.6mm thickness was laminated so as to be in contact with the photosensitive resin composition layer side of the photosensitive resin laminate obtained in the "production of photosensitive resin laminate" described above. Rectangular slits having a width of 25mm and a length of 80mm were formed in the support film of the laminated photosensitive resin laminate using a cutter.
A Tensilon tensile tester (model name "RTM500" manufactured by ORIENTEC CORPORATION) was used for the test. The copper-clad laminate having the photosensitive resin laminate laminated thereon was fixed so that the slit in the longitudinal direction of the support film was perpendicular to the slit, and the lower distal end portion of the support film having the slit formed thereon was peeled off and clamped by the chuck of the Tensilon tensile tester.
Then, the chuck of the Tensilon tensile tester was moved upward at a tensile speed of 100 mm/min, and the force (adhesive force) when 180℃peeling was performed in the longitudinal direction from the photosensitive resin composition layer to the support film was measured. As the adhesive force, the maximum value of the force measured from the start of peeling to the end of peeling was used.
(2) Evaluation of contamination resistance of SUS plate
The support film was peeled off from the photosensitive resin laminate obtained in the above "1. Production of photosensitive resin laminate", and the support film was peeled off and placed on the surface of the photosensitive resin laminate with a dimension of 25cm 2 Is a SUS plate of (c). A plastic container to which 500mL of water was added was placed thereon, and after standing for 10 seconds, the plastic container was removed, and the SUS plate was peeled off.
Then, the surface of the peeled SUS plate was visually observed, and the adhesion easiness of the photosensitive resin composition layer to the surface of the SUS plate was determined based on the following criteria.
A: no fouling was observed at all, and it was judged that there was no problem in practical use
B: the dirt was slightly observed, but the degree of blurring was slightly determined to be practically no problem
C: significant fouling was observed, and it was judged that there was a practical problem due to fouling accumulation
Experimental examples 2 to 5
A photosensitive resin laminate was produced and evaluated in the same manner as in experimental example 1, except that the photosensitive resin composition described in table 1 was used as a photosensitive resin composition blend.
The evaluation results of experimental examples 1 to 5 are shown in table 1.
TABLE 1
Table 1.
According to table 1, in the photosensitive resin laminate of experimental example 5 in which the adhesive force of the photosensitive resin composition layer exceeded the predetermined range of the present invention, as a result, contamination with SUS plate was "C", which was not suitable for practical use. In contrast, in the photosensitive resin laminates of examples 1 to 4 in which the adhesive force of the photosensitive resin composition layer was 20gf/inch or less, which was defined in the present invention, contamination resistance to SUS plates was "a" or "B", and it was confirmed that the laminate was suitable for practical use.
Experimental examples 6 to 16
In examples 6 to 16, a photosensitive resin laminate was produced in which a support film and a photosensitive resin composition layer and a protective film were laminated in this order. The obtained laminated body was stored under predetermined conditions in the form of a laminated film in examples 6 to 10 and in the form of a roll in examples 11 to 16, respectively, and the moisture content in the photosensitive resin composition layer was adjusted. Then, the relationship between the moisture content in the photosensitive resin composition layer and the sensitivity of the photosensitive resin laminate was examined.
Experimental example 6
As the photosensitive resin composition blend, photosensitive resin composition 4 was used.
A photosensitive resin composition 4 was applied to one surface of a 16 μm thick polyethylene terephthalate film (product name "FB-40" manufactured by Toli Co., ltd.) as a support film, and heated in a drying oven at 95℃for 3 minutes to remove the solvent, thereby forming a photosensitive resin composition layer having a film thickness of 25 μm after the solvent removal.
A 19 μm thick polyethylene film (tamopo co., ltd. Product name "GF-818") was adhered as a protective film to the photosensitive resin composition layer, to obtain a photosensitive resin laminate in which a support film, a photosensitive resin composition layer, and a protective film were laminated in this order.
After the obtained photosensitive resin laminate was stored at a temperature of 23℃and a humidity of 5% RH for 5 hours, the moisture content of the photosensitive resin composition layer and the sensitivity of the photosensitive resin laminate were evaluated by the following methods, respectively. The evaluation results are shown in table 2.
[ measurement of moisture content ]
The water content of the photosensitive resin composition layer was measured by karl fischer electric quantity titration using a micro water content measuring device under the following conditions using the photosensitive resin composition layer cut from the photosensitive resin laminate as a sample. The obtained moisture content was evaluated as a value in mass% when the total mass of the photosensitive resin composition layer was set to 100 mass%.
(1) Measuring device and related equipment
Trace moisture measuring device: product name (AQ-2200 AF) manufactured by Pingshu Industrial Co Ltd "
Single-chamber electrolytic cell unit: p/n C310109-A
Moisture gasification device: EV-2000
(2) Reagents and the like
Anode liquid: aqualyteRS-A
Dehydrating solution: general moisture measuring solvent S
Carrier gas: dehydrated air
(3) Measurement conditions
Gasification chamber temperature: 150 DEG C
And (3) idle firing time: 3 minutes
Sample amount: 0.1g
(4) Measuring environment
Ambient temperature: 20 DEG C
Humidity: 30% RH
[ measurement of sensitivity ]
(1) The whole surface of the substrate
A copper-clad laminate sheet of 0.4mm thickness, on which 35 μm rolled copper foil was laminated, was used as a substrate, and a grinding material (Japan Carlit co., ltd. Product name "banku ram (registered trademark) R") was sprayed onto the laminated surface of the rolled copper foil at a spray pressure of 0.2MPa, whereby the surface was polished.
(2) Lamination
While the polyethylene film of the photosensitive resin laminate was peeled off, the photosensitive resin composition of the laminate was laminated on the polished surface of the copper-clad laminate preheated to 60℃at a roll temperature of 105℃using a hot roll laminator (product name "AL-700" manufactured by Asahi Kabushiki Kaisha Co., ltd.) to obtain an evaluation substrate. The air pressure during lamination was 0.35MPa, and the lamination speed was 1.5m/min.
(3) Exposure to light
For an evaluation substrate after 15 minutes from the lamination of the photosensitive resin composition layer on the substrate, exposure was performed from the polyethylene terephthalate film side of the support film through a mask of a Stouffer 41Step table (Stouffer 41Step table).
As an exposure machine, a parallel light exposure machine (ORC MANUFACTURING CO., LTD. Product name "HMW-801") was used to give an exposure of 200mJ/cm 2 Exposure is performed.
(4) Development process
And developing the exposed evaluation substrate to prepare a resist pattern. The development was performed by the following method: an alkali developing machine (FUJIKIKO co., ltd., developing machine for dry film) was used, and 1 mass% Na at 30 ℃ 2 CO 3 The aqueous solution is sprayed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin composition layer. The development time is 2 times the minimum development time.
Herein, the minimum development time refers to the minimum time required for the photosensitive resin composition layer of the unexposed portion to be completely dissolved.
(5) Sensitivity evaluation method
The highest number of residual film steps in the resist pattern obtained after development was read and used as an index of sensitivity. The larger the value, the higher the sensitivity.
Experimental examples 7 to 10
After a photosensitive resin laminate was obtained in the same manner as in example 6, the laminate was stored under the storage conditions described in table 2.
Using the photosensitive resin laminate after storage, evaluation was performed in the same manner as in experimental example 6.
The evaluation results are shown in Table 2.
Experimental examples 11 to 13
A photosensitive resin laminate was obtained in the same manner as in experimental example 6, except that the photosensitive resin composition 6 obtained in preparation example 6 was used as a photosensitive resin composition blend. The obtained photosensitive resin laminate was wound around a winding core, thereby producing a photosensitive resin laminate roll.
The resulting rolls were stored under the conditions described in table 2, and then evaluated in the same manner as in experimental example 6. In the (3) exposure step, the exposure amount was set to 160mJ/cm with respect to the sensitivity of the photosensitive resin laminate 2 Except for the exposure, the evaluation was performed in the same manner as in experimental example 6.
The evaluation results are shown in Table 2.
Experimental examples 14 to 16
A photosensitive resin laminate was produced in the same manner as in experimental example 6 except that the photosensitive resin composition 7 obtained in preparation example 7 was used as a photosensitive resin composition blend, and the obtained photosensitive resin laminate was wound around a winding core, thereby producing a photosensitive resin laminate roll.
The obtained rolls were stored under the conditions described in table 2, and then evaluated in the same manner as in experimental example 6. In the (3) exposure step, a direct drawing exposure machine (product name "DE-1DH", manufactured by Weiya machinery Co., ltd., light source: gaN blue-violet diode, dominant wavelength 405.+ -. 5 nm) was used as an exposure machine to expose the photosensitive resin laminate to light of 85mW/cm 2 Exposure of 60mJ/cm 2 The evaluation was performed in the same manner as in experimental example 6 except that the exposure was performed.
The evaluation results are shown in Table 2.
TABLE 2
As is clear from Table 2, in the case of using a parallel light exposure machine, in the case of example 6 in which the moisture content of the photosensitive resin composition layer was less than 0.1 mass%, the highest number of residual films was 16, and in the cases of examples 7 to 13 in which the moisture content was 0.1 mass% or more, the number of residual films was increased to 17 to 20.
In addition, when the direct drawing exposure machine was used, the highest number of residual film stages in examples 14 to 16, in which the moisture content of the photosensitive resin composition layer was 0.1 mass% or more, was 14 to 16.
Experimental examples 17 to 22
In experimental examples 17 to 22, the photosensitive resin composition 4 obtained in the above preparation example 4 was used as a photosensitive resin composition blend liquid, and the relationship between the content of the organic solvent in the photosensitive resin composition layer and the chipping properties of the photosensitive resin laminate was examined.
A photosensitive resin composition 4 was applied to one surface of a 16 μm thick polyethylene terephthalate (PET) film (product name "FB-40" manufactured by Toli Co., ltd.) as a support film, and heated in a drying oven at 95℃to remove the solvent, thereby forming a photosensitive resin composition layer having a film thickness of 25 μm after the solvent removal, and a photosensitive resin laminate was obtained. At this time, the content of the organic solvent (acetone) in the photosensitive resin composition layer was adjusted by changing the heating time in the drying oven.
The obtained photosensitive resin laminate was evaluated for the adhesive force of the surface of the photosensitive resin composition layer in contact with the support film, the peeling trace at the time of peeling the support film, the melt viscosity of the photosensitive resin composition layer, and the chipping properties of the photosensitive resin laminate, respectively, by the following methods.
The evaluation results are shown in Table 3.
[ peeling trace at peeling of support film ]
The support film was peeled from the photosensitive resin laminate at a peeling speed of 300 mm/min. The presence or absence of peeling marks on the surface of the photosensitive resin composition layer after peeling the support was visually observed, and evaluated based on the following criteria.
A: the peeling trace was not observed at all (peeling trace "good")
B: the peeling trace was rarely observed (peeling trace "can")
C: the case where a significant peeling trace was observed or the case where a large number of peeling traces were observed (peeling trace "poor")
[ chip Property of photosensitive resin laminate ]
A10 cm X10 cm sample was cut out of the obtained photosensitive resin laminate, and was pierced 5 times by a NT Cutter (trade name, manufactured by NT Incorporated, new test cutting blade) from the surface on the photosensitive resin composition layer side. Then, the pierced portion of the cutting blade and the surface of the cutting blade were visually observed, and evaluated according to the following criteria.
A: no chipping of the photosensitive resin layer is generated at the pierced portion, and no chipping of the photosensitive resin layer is adhered to the dicing blade (good chipping property)
B: although the dicing blade is free from chipping of the photosensitive resin layer, the punctured portion generates a very small amount of chipping of the photosensitive resin layer (chipping property "can")
C: when a small amount of chipping of the photosensitive resin layer is generated in the pierced portion and a small amount of chipping of the photosensitive resin layer is adhered to the dicing blade (chipping "bad")
D: the chipping of the photosensitive resin layer is generated remarkably at the pierced portion, and the chipping of the photosensitive resin layer is adhered remarkably to the dicing blade (chipping property "remarkable bad')
TABLE 3
Table 3.
According to table 3, in the photosensitive resin laminate of experimental example 7 in which the photosensitive resin composition layer did not contain an organic solvent (acetone), the result was "D" for the chipping property and "significantly poor for the chipping property". In contrast, in the photosensitive resin laminates of examples 18 to 22 in which the photosensitive resin composition layer contained an organic solvent, improvement in chipping was observed.
The above results relate to the case where acetone was used as the solvent of the mixture of the photosensitive resin composition, but the same results were confirmed when toluene, methyl ethyl ketone, methanol, ethanol or isopropanol was used as the solvent instead of acetone.
Experimental example 23
As the photosensitive resin composition blend, photosensitive resin composition 8 was used.
A16 μm thick polyethylene terephthalate film (product name "FB-40" manufactured by Toli Co., ltd.) was coated with the photosensitive resin composition 8 on one side thereof as a support film, and the resultant was heated in a drying oven at 95℃for 3 minutes to remove the solvent, thereby forming a photosensitive resin composition layer having a film thickness of 15. Mu.m after the solvent removal.
A 19 μm thick polyethylene film (tamopo co., ltd. Product name "GF-818") was adhered as a protective film to the photosensitive resin composition layer, to obtain a photosensitive resin laminate in which a support film, a photosensitive resin composition layer, and a protective film were laminated in this order.
Using the obtained photosensitive resin laminate, sensitivity and resolution were measured by the following methods.
[ measurement of sensitivity 2]
(1) The whole surface of the substrate
A copper-clad laminate sheet of 0.4mm thickness, on which 35 μm rolled copper foil was laminated, was used as a substrate, and a grinding material (Japan Carlit co., ltd. Product name "banku ram (registered trademark) R") was sprayed onto the laminated surface of the rolled copper foil at a spray pressure of 0.2MPa, whereby the surface was polished.
(2) Lamination
While the polyethylene film of the photosensitive resin laminate was peeled off, the photosensitive resin composition of the laminate was laminated on the polished surface of the copper-clad laminate preheated to 60℃at a roll temperature of 105℃using a hot roll laminator (product name "AL-700" manufactured by Asahi Kabushiki Kaisha Co., ltd.) to obtain an evaluation substrate. The air pressure during lamination was 0.35MPa, and the lamination speed was 1.5m/min.
(3) Exposure to light
After 15 minutes from the lamination of the photosensitive resin composition layer on the substrate, exposure was performed from the photosensitive resin composition layer side through a mask of a step exposure meter of step 41.
As an exposure machine, a parallel light exposure machine (ORC MANUFACTURING CO., LTD. Product name "HMW-801") was used to give an exposure of 200mJ/cm 2 Exposure is performed.
In addition, exposure was performed with a quartz glass chrome mask having a pattern in which 7 striped negative patterns were collected, with a line/space interval of 3 μm/7 μm after patterning. At this time, the portion corresponding to 3 μm as a line was exposed to light, and the photosensitive resin composition layer was cured. .
In experimental example 23, exposure was performed in a state where the support film was laminated on the photosensitive resin layer at the time of exposure, and in experimental examples 24 to 25, the polyethylene terephthalate film of the support film was peeled off from the evaluation substrate, and exposure was performed in a state where the photosensitive resin composition layer on the substrate was exposed.
(4) Development process
And developing the exposed evaluation substrate to prepare a resist pattern. The development was performed by the following method: an alkali developing machine (FUJIKIKO co., ltd., developing machine for dry film) was used, and 1 mass% Na at 30 ℃ 2 CO 3 The aqueous solution is sprayed for a predetermined time to dissolve and remove the unexposed portion of the photosensitive resin composition layer. The development time is 2 times the minimum development time.
Herein, the minimum development time refers to the minimum time required for the photosensitive resin composition layer of the unexposed portion to be completely dissolved.
(5) Sensitivity evaluation method
The highest number of residual film steps in the resist pattern obtained after development was read and used as an index of sensitivity. The larger the value, the higher the sensitivity.
(6) Method for evaluating resolution
The 7 resist patterns arranged at intervals of 3 μm/7 μm were observed with an optical microscope, and whether or not 7 resist patterns were formed without offset or adhesion failure was confirmed, and evaluated according to the following criteria.
A: all 7 strips can be formed without offset and poor adhesion
B: the pattern formed without offset and poor adhesion is 5 or 6
C: the pattern formed without offset and poor adhesion is below 4 strips
(7) Sidewall looseness
The number of recesses (concave portions) of 1 μm or more was confirmed in all of the 7 resist patterns arranged at intervals of 3 μm/7 μm from the top to 40 μm in the side walls, and evaluated according to the following criteria.
A: no recess
B: the concave is 1 to 4 parts
C: the dent is more than 5
(8) Method for measuring moisture content
The moisture of the photosensitive resin composition layer was measured by the method described in [ moisture measurement ].
TABLE 4
Table 4.
As is clear from table 4, in experimental examples 23 to 25 in which the moisture content was within the range of the present invention, any one of the resolution and the sidewall looseness was good, and in the case where the moisture content was 1.05 mass%, even without the support film, an extremely good pattern in which the sidewall looseness was not present while maintaining high sensitivity was obtained. In the photosensitive resin composition layer of the present invention, an initiating radical is generated by an initiator by exposure to light, and is added to a compound having an olefinic double bond to start polymerization, whereby the exposed portion is cured. In the case where the support film is not provided, oxygen in the free gene air generated in the photosensitive resin composition layer at the time of exposure is deactivated, and thus sensitivity tends to be lowered, but in the case where an appropriate amount of moisture is provided, sensitivity can be improved. In addition, by performing exposure without interposing a support film, a pattern excellent in shape can be obtained.
Claims (31)
1. A photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition, wherein the adhesive force of the surface of the photosensitive resin composition layer in contact with the support film is 20gf/inch or less,
The photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a photopolymerization initiator and (C) a compound having an olefinic double bond,
the photopolymerization initiator (B) is a compound that generates an initiating radical by exposure to light,
the support film is releasable from the photosensitive resin composition layer,
when the total mass of the photosensitive resin composition layer is 100 mass%, the moisture content in the photosensitive resin composition layer is 0.1 mass% or more.
2. The photosensitive resin laminate according to claim 1, wherein the amount of moisture contained in the photosensitive resin composition layer is 0.2 mass% or more, based on 100 mass% of the total mass of the photosensitive resin composition layer.
3. The photosensitive resin laminate according to claim 1 or 2, wherein the moisture content in the photosensitive resin composition layer is 2.0 mass% or less, based on 100 mass% of the total mass of the photosensitive resin composition layer.
4. The photosensitive resin laminate according to claim 3, wherein the amount of moisture contained in the photosensitive resin composition layer is 1.5 mass% or less, based on 100 mass% of the total mass of the photosensitive resin composition layer.
5. The photosensitive resin laminate according to claim 1, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 15gf/inch or less.
6. The photosensitive resin laminate according to claim 1, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 10gf/inch or less.
7. The photosensitive resin laminate according to claim 1, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 5gf/inch or less.
8. The photosensitive resin laminate according to claim 1, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 3gf/inch or less.
9. The photosensitive resin laminate according to claim 1, wherein an adhesive force of a surface of the photosensitive resin composition layer in contact with the support film is 1gf/inch or less.
10. The photosensitive resin laminate according to claim 1 or 2, wherein the photosensitive resin composition layer contains 0.01 to 1 mass% of an organic solvent having a boiling point of 55 ℃ or higher, based on 100 mass% of the total mass of the photosensitive resin composition layer.
11. The photosensitive resin laminate according to claim 10, wherein the organic solvent is at least 1 selected from toluene, acetone, methyl ethyl ketone, methanol, ethanol, and isopropanol.
12. The photosensitive resin laminate according to claim 1 or 2,
the mass W of the compound (C) having an olefinic double bond in the photosensitive resin composition C Mass W relative to the alkali-soluble polymer (A) A Ratio W of (2) C /W A Is 0.30 or less.
13. The photosensitive resin laminate according to claim 12, wherein the (C) compound having an olefinic double bond comprises a compound having a (meth) acrylate group at a terminal.
14. The photosensitive resin laminate according to claim 1 or 2, wherein,
the alkali-soluble polymer (A) has an olefinic double bond group at the end of a side chain.
15. The photosensitive resin laminate according to claim 14, wherein the (B) photopolymerization initiator contains a 2,4, 5-triarylimidazole dimer.
16. The photosensitive resin laminate according to claim 1 or 2, wherein the alkali-soluble polymer (a) has an aromatic hydrocarbon group.
17. The photosensitive resin laminate according to claim 1 or 2, wherein the photosensitive resin composition contains adamant green or leuco crystal violet.
18. The photosensitive resin laminate according to claim 1 or 2, wherein the support film comprises the following regions: when square small pieces having a side length of 5mm are cut out at arbitrary 10 positions different from each other of the support film, the number of fine particles having a diameter of 1.5 μm or more contained in each small piece is 1 region or more in terms of the average value at the 10 positions.
19. The photosensitive resin laminate according to claim 1 or 2, wherein exposure is performed in a state where the support film is peeled off.
20. The photosensitive resin laminate according to claim 1 or 2, wherein a cover film is provided on a surface side of the photosensitive resin composition layer opposite to the support film.
21. The photosensitive resin laminate according to claim 1 or 2, wherein the photosensitive resin laminate is wound into a roll.
22. A method of manufacturing a resist pattern, comprising:
a lamination step of adhering the photosensitive resin composition layer of the photosensitive resin laminate according to any one of claims 1 to 21 to a substrate;
a support film peeling step of peeling the support film of the photosensitive resin laminate;
an exposure step of exposing the photosensitive resin laminate; and
And a developing step of developing the photosensitive resin laminate subjected to the exposure.
23. The method for producing a resist pattern according to claim 22, wherein the exposure step includes a step of exposing the photosensitive resin laminate from a side on which the support film is provided.
24. A method of manufacturing a circuit substrate, comprising: a circuit forming step of manufacturing a substrate having a resist pattern by the method according to claim 22 or 23, and then forming a circuit on the substrate by etching or plating the substrate having the resist pattern.
25. The method for manufacturing a circuit board according to claim 24, comprising a resist pattern peeling step of: the resist pattern is stripped.
26. A method for producing a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer formed on the support film and containing a photosensitive resin composition, wherein the adhesive force of the surface of the photosensitive resin composition layer in contact with the support film is 20gf/inch or less,
the photosensitive resin composition contains (A) an alkali-soluble polymer, (B) a photopolymerization initiator and (C) a compound having an olefinic double bond,
The photopolymerization initiator (B) is a compound that generates an initiating radical by exposure to light,
and the support film is releasable from the photosensitive resin composition layer,
the manufacturing method comprises the following steps:
a step 1 of producing a 1 st photosensitive resin laminate in which the moisture content contained in the photosensitive resin composition layer is lower than the lower limit value of a predetermined range; and
a step 2 of storing the 1 st photosensitive resin laminate in an environment having a predetermined humidity for a predetermined time to produce a 2 nd photosensitive resin laminate having a moisture content in the photosensitive resin composition layer within a predetermined range,
the predetermined range is 0.1 mass% or more, based on 100 mass% of the total mass of the photosensitive resin composition layer.
27. The method according to claim 26, wherein the predetermined range is 2.0 mass% or less, based on 100 mass% of the total mass of the photosensitive resin composition layer.
28. The method according to claim 26 or 27, wherein the step 2 comprises storing the 1 st photosensitive resin laminate in an atmosphere having a temperature of 20 ℃ or higher and a humidity of 40% rh or higher for 12 hours or longer.
29. A method for producing a photosensitive resin laminate comprising a support film and a photosensitive resin composition layer containing a photosensitive resin composition formed on the support film, the method comprising the steps of:
a photosensitive resin composition blend solution containing (A) an alkali-soluble polymer, (B) a photopolymerization initiator, (C) a compound having an olefinic double bond, (D) an organic solvent, and (E) water is applied onto the support film, and then the (D) organic solvent is removed to form a photosensitive resin composition layer, thereby forming a photosensitive resin laminate,
the photopolymerization initiator (B) is a compound that generates an initiating radical by exposure to light,
when the total mass of the photosensitive resin composition layer is set to 100 mass%, the water content in the photosensitive resin composition layer is 0.1 mass% or more,
the adhesive force of the surface of the photosensitive resin composition layer, which is in contact with the support film, is 20gf/inch or less.
30. The method for producing a photosensitive resin laminate according to any one of claims 26 to 27 and 29, wherein the photosensitive resin laminate is wound into a roll.
31. The method for producing a photosensitive resin laminate according to claim 28, wherein the photosensitive resin laminate is wound into a roll.
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| JP2018101022 | 2018-05-25 | ||
| JP2018-101022 | 2018-05-25 | ||
| PCT/JP2018/040908 WO2019088268A1 (en) | 2017-11-06 | 2018-11-02 | Photosensitive resin laminate and method for producing resist pattern |
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| JP2022000683A (en) * | 2019-12-13 | 2022-01-04 | 旭化成株式会社 | Photosensitive resin composition, transfer film using photosensitive resin composition |
| CN116348294A (en) * | 2020-10-23 | 2023-06-27 | 旭化成株式会社 | Photosensitive resin laminate |
| TW202448973A (en) * | 2023-04-14 | 2024-12-16 | 日商旭化成股份有限公司 | Photosensitive resin laminate and method for forming photoresist pattern |
| WO2025018412A1 (en) * | 2023-07-20 | 2025-01-23 | 旭化成株式会社 | Photosensitive element, photosensitive element roll, method for forming resist pattern, and method for forming conductor pattern |
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| Publication number | Publication date |
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| KR102522749B1 (en) | 2023-04-17 |
| KR20200054313A (en) | 2020-05-19 |
| JP2022188113A (en) | 2022-12-20 |
| TWI689524B (en) | 2020-04-01 |
| JPWO2019088268A1 (en) | 2020-11-26 |
| MY197618A (en) | 2023-06-28 |
| KR20220164618A (en) | 2022-12-13 |
| JP7190439B2 (en) | 2022-12-15 |
| KR102570709B1 (en) | 2023-08-24 |
| WO2019088268A1 (en) | 2019-05-09 |
| TW201925250A (en) | 2019-07-01 |
| CN111316164A (en) | 2020-06-19 |
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