CN103543608A - Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same - Google Patents
Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same Download PDFInfo
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- CN103543608A CN103543608A CN201310470387.2A CN201310470387A CN103543608A CN 103543608 A CN103543608 A CN 103543608A CN 201310470387 A CN201310470387 A CN 201310470387A CN 103543608 A CN103543608 A CN 103543608A
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- 238000000034 method Methods 0.000 title claims 8
- 238000004519 manufacturing process Methods 0.000 title claims 2
- 239000011342 resin composition Substances 0.000 title abstract 2
- 230000007261 regionalization Effects 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract 26
- 150000001875 compounds Chemical class 0.000 claims abstract 13
- 239000011230 binding agent Substances 0.000 claims abstract 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical group CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims abstract 5
- 125000003545 alkoxy group Chemical group 0.000 claims abstract 4
- 125000000217 alkyl group Chemical group 0.000 claims abstract 4
- 125000005907 alkyl ester group Chemical group 0.000 claims abstract 2
- 125000002541 furyl group Chemical group 0.000 claims abstract 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract 2
- 125000001544 thienyl group Chemical group 0.000 claims abstract 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 7
- 229910052799 carbon Inorganic materials 0.000 claims 7
- 230000003287 optical effect Effects 0.000 claims 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 5
- 229910052760 oxygen Inorganic materials 0.000 claims 4
- 239000001301 oxygen Substances 0.000 claims 4
- 239000000758 substrate Substances 0.000 claims 4
- -1 (methyl) benzyl Chemical group 0.000 claims 3
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical class COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims 3
- 206010070834 Sensitisation Diseases 0.000 claims 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- 230000015572 biosynthetic process Effects 0.000 claims 2
- 125000005843 halogen group Chemical group 0.000 claims 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 2
- 239000000049 pigment Substances 0.000 claims 2
- 230000008313 sensitization Effects 0.000 claims 2
- 241001597008 Nomeidae Species 0.000 claims 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 claims 1
- 239000007983 Tris buffer Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 125000005250 alkyl acrylate group Chemical group 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 claims 1
- 238000005530 etching Methods 0.000 claims 1
- 238000003475 lamination Methods 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 229920001515 polyalkylene glycol Polymers 0.000 claims 1
- 150000003440 styrenes Chemical class 0.000 claims 1
- 125000004432 carbon atom Chemical group C* 0.000 abstract 3
- 239000000470 constituent Substances 0.000 abstract 2
- 230000001235 sensitizing effect Effects 0.000 abstract 2
- 239000003999 initiator Substances 0.000 abstract 1
- 0 C*(*)C(c1ccccc1C(O**)=O)=O Chemical compound C*(*)C(c1ccccc1C(O**)=O)=O 0.000 description 1
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- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
- C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/04—Acids; Metal salts or ammonium salts thereof
- C08F220/06—Acrylic acid; Methacrylic acid; Metal salts or ammonium salts thereof
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F257/00—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00
- C08F257/02—Macromolecular compounds obtained by polymerising monomers on to polymers of aromatic monomers as defined in group C08F12/00 on to polymers of styrene or alkyl-substituted styrenes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
- C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
- C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D4/00—Coating compositions, e.g. paints, varnishes or lacquers, based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; Coating compositions, based on monomers of macromolecular compounds of groups C09D183/00 - C09D183/16
- C09D4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09D159/00 - C09D187/00
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
- G03F7/028—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
- G03F7/09—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
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- 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
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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- General Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Architecture (AREA)
- Structural Engineering (AREA)
- Materials For Photolithography (AREA)
- Polymerisation Methods In General (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
Disclosed is a photosensitive resin composition comprising (A) a binder polymer, (B) a photopolymerizable compound, (C) a photopolymerization initiator and (D) a sensitizing dye, wherein the binder polymer (A) has a constituent unit derived from (meth)acrylic acid and a constituent unit derived from (meth)acrylic acid benzyl ester or a (meth)acrylic acid benzyl ester derivative, the photopolymerizable compound (B) comprises a compound having one ethylenically unsaturated bond, and the sensitizing dye (D) comprises a compound represented by general formula (1). In formula (1), R1 and R2 independently represent a substituted or unsubstituted phenyl, thienyl or furyl group; R3 represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or an alkylester group having 1 to 10 carbon atoms; a and b independently represent an integer of 0 to 2; and m represents an integer of 0 to 5.
Description
The application is to be dividing an application of February 3, application number in 2010 are 201080007574.1, denomination of invention is < < photosensitive polymer combination and the photosensitive element that has used said composition, the formation method of resist pattern and the manufacture method > > of printed-wiring board (PWB) Chinese patent application the applying date of original application.
Technical field
The present invention relates to photosensitive polymer combination and used the photosensitive element of said composition, the formation method of resist pattern and the manufacture method of printed-wiring board (PWB).
Background technology
In the manufacture field of printed-wiring board (PWB), the anticorrosive additive material using as etching, plating etc., is widely used photosensitive polymer combination, photosensitive element (laminated body).
Printed-wiring board (PWB) example is manufactured as described below.First, the photosensitive polymer combination layer laminate (lamination) of photosensitive element is formed with on substrate at circuit.Next, the established part irradiation active ray to photosensitive polymer combination layer makes this established part exposure, solidifies.Then, after peeling off and removing supporting film, by the part except this established part (unexposed uncured portion) is removed to (development) from substrate, thereby on substrate, form the resist pattern that the solidfied material by photosensitive polymer combination forms.The resist pattern of gained is implemented to etch processes or plating is processed and on substrate, forms circuit, then finally peel off and remove resist and manufacture printed-wiring board (PWB).
Here etch processes refers to not formed and remove with the conductor layer etching of substrate by the circuit of resist pattern coating, then peels off the method for resist.On the other hand, plating is processed and to be referred to and process not formed by the circuit of resist pattern coating the plating that conductor layer with substrate carries out copper and scolder etc., then removes resist, to being carried out soft etching method by the metal covering of this resist coating.
As the method for above-mentioned exposure, in the past, used and take the method that mercury vapor lamp exposes across photomask as light source.In addition, proposed to be in recent years called as DLP (digital light processing, Digital Light Processing), LDI (laser direct imaging, Laser Direct Imaging), the numerical data of pattern is directly depicted in to photosensitive polymer combination layer directly describe exposure method (for example,, with reference to non-patent literature 1).This is directly described exposure method and compares with the exposure method across photomask, and position alignment precision is good, and can obtain the pattern of fine, therefore imports in the making of high-density packages substrate.
In exposure process, in order to enhance productivity, need to shorten the time shutter as far as possible.Yet, the above-mentioned exposure method of directly describing, owing to using the monochromatic light such as laser as light source, on one side scanning substrate irradiation light on one side, therefore compare with the exposure method across photomask in the past, have need to the longer time shutter tendency.Therefore, compared with the past, need further to improve the sensitivity of photosensitive polymer combination.
On the other hand, the densification along with printed-wiring board (PWB) in recent years, has also improved the requirement of the high resolving power of photosensitive polymer combination and high adhesion.Particularly, in the making of base plate for packaging, it is 10/10 (unit: the μ m) photosensitive polymer combination of following resist pattern that requirement can form live width/spacing (L/S).
In addition, high-density packages substrate is because the width between circuit is narrow, so resist shape excellence is also important.If the cross sectional shape of resist is trapezoidal or the hangover of the bottom of inverted trapezoidal or resist, the etch processes by subsequently or plating are processed the circuit forming and may be short-circuited, open circuit, therefore not preferred, preferably resist is shaped as rectangle and trails without bottom.
In addition,, for photosensitive polymer combination, require the peel property after solidifying excellent.That is, by shortening the splitting time of resist, improve the production efficiency of stripping process, in addition, by reducing the stripping film size of resist, prevent that stripping film from adhering to again, improving the rate of manufacturing a finished product on circuit substrate.
Here, in patent documentation 1, as thering is the photosensitive polymer combination that can tackle the excellent sensitivity of directly describing exposure method, the photosensitive polymer combination that uses specific binder polymer, sensitization pigment etc. is disclosed.
In patent documentation 2, disclose, in order to make adaptation (resistance to development fluidity) to substrate good, and imported the photosensitive polymer combination that polyfunctional acrylic ester compound has increased crosslinking points.
In patent documentation 3, disclose, in order to make the contrast (imaging) between exposed portion and unexposed portion good, and used the photosensitive polymer combination of the polymerization inhibitors such as catechol, quinhydrones.
Patent documentation 1: TOHKEMY 2005-122123 communique
Patent documentation 2: TOHKEMY 2003-215799 communique
Patent documentation 3: TOHKEMY 2000-162767 communique
Non-patent literature 1: " エ レ Network ト ロ ニ Network ス real dress skill Intraoperative ", in June, 2002 number, p.74～79
Summary of the invention
Invent problem to be solved
For photosensitive polymer combination, require to make sensitivity, resolution, adaptation, resist shape and solidify after each balance of properties such as peel property improve well.
Yet, the photosensitive polymer combination of patent documentation 1, although sensitivity, peel property aspect are good, resolution and adaptation aspect are not necessarily abundant.
The photosensitive polymer combination of patent documentation 2, has good adaptation, but then, insufficient aspect peel property, has the tendency that is difficult to solidfied material to be removed from strippable substrate.
The photosensitive polymer combination of patent documentation 3, although good aspect resolution, adaptation and imaging, insufficient aspect sensitivity, in the situation that directly describing exposure method, use needs to grow the time shutter.
Photosensitive polymer combination like this, in the past all cannot meet desired each characteristic of the photosensitive polymer combination making after resist pattern forms balance well fully.
Therefore, the object of this invention is to provide sensitivity, resolution, adaptation, resist shape and solidify after peel property good photosensitive polymer combination all, and used the photosensitive element of said composition, the formation method of resist pattern and the manufacture method of printed-wiring board (PWB).
For solving the method for problem
To achieve these goals, the invention provides a kind of photosensitive polymer combination, to contain (A) binder polymer, (B) optical polymerism compound, (C) Photoepolymerizationinitiater initiater and (D) photosensitive polymer combination of sensitization pigment, wherein, (A) binder polymer has based on (methyl) acrylic acid structural unit, structural unit based on (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant, (B) optical polymerism compound comprises the compound with 1 ethylenic unsaturated bond, and (D) sensitization pigment comprises the compound shown in following general formula (1).
[changing 1]
[in formula (1), R
1and R
2represent independently of one another to replace or unsubstituted phenyl, thienyl or furyl R
3the alkyl ester group that represents the alkyl of carbon number 1～10, the alkoxy of carbon number 1～10 or carbon number 1～10, a and b represent 0～2 integer independently of one another, m represents 0～5 integer, in the situation that m is 2～5, a plurality of R of existence
3both can be the same or different separately.]
That is, photosensitive polymer combination of the present invention, owing to thering is above-mentioned formation, thus sensitivity, resolution, adaptation, resist shape and solidify after peel property all good.The inventor infers, (A) binder polymer by use with specific structure unit, fissility after can improving resolution and solidifying, (B) optical polymerism compound that comprises the compound with 1 ethylenic unsaturated bond by use, can make resolution, adaptation, resist shape and solidify after peel property balance improve well, (D) sensitization pigment that comprises compound shown in above-mentioned general formula by use, can improve sensitivity, by by they combinations, can obtain the photosensitive polymer combination that meets above-mentioned complete characteristic.
In photosensitive polymer combination of the present invention, (B) optical polymerism compound can comprise the compound representing with following general formula (2) or following general formula (3) respectively.
[changing 2]
[in formula (2), R
4represent hydrogen atom or methyl, R
5represent hydrogen atom, methyl or halogenated methyl, R
6represent the alkyl of carbon number 1～6, alkoxy, hydroxyl or the halogen atom of carbon number 1～6, n represents 0～4 integer, and p represents 1～4 integer, in the situation that n is 2～4, and a plurality of R of existence
6both can be the same or different.]
[changing 3]
[in formula (3), R
7represent hydrogen atom or methyl, R
8represent the alkyl of carbon number 1～12, alkoxy, hydroxyl or the halogen atom of carbon number 1～12, r represents 1～12 integer, and k represents 0～5 integer, in the situation that k is 2～5, and a plurality of R of existence
8both can be the same or different.]
Thus, the resolution of photosensitive polymer combination, adaptation, resist shape and solidify after the further balance of peel property improve well.
In addition, (B) optical polymerism compound can also to comprise bisphenol-A be two (methyl) acrylate compounds.Thus, further improve alkali development, resolution and solidify after peel property.
In addition, (B) optical polymerism compound can also comprise trimethylolpropane tris (methyl) acrylate compounds with (gathering) oxygen ethylidene chain or (gathering) oxygen propylidene chain.Thus, further improve the alkali development, resolution, adaptation of photosensitive polymer combination and solidify after peel property.
In addition, (B) optical polymerism compound can also comprise poly alkylene glycol two (methyl) acrylate with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.Thus, the flexible raising of the solidfied material of photosensitive polymer combination (cured film).
In photosensitive polymer combination of the present invention, if (A) binder polymer also has the structural unit based on (methyl) alkyl acrylate, the peel property after can further improving alkali development and solidifying.In addition, (A) binder polymer can also have the structural unit of styrene-based or styrene derivative, and thus, resolution and the adaptation of photosensitive polymer combination further improve.
In addition, (A) acid number of binder polymer is preferably 100～250mgKOH/g.Thus, the alkali development of photosensitive polymer combination further improves.
In addition, (A) weight-average molecular weight of binder polymer is preferably 10000～100000.Thus, can make the alkali development of photosensitive polymer combination and the further balance of adaptation improve well.
From the viewpoint of the sensitivity of further raising photosensitive polymer combination, photosensitive polymer combination of the present invention can also contain (E) amine compound.
The present invention also provides photosensitive element, possesses: supporting film and the photosensitive polymer combination layer being formed by above-mentioned photosensitive polymer combination forming on this supporting film.The photosensitive element of the application of the invention, can sensitivity effectively form well resolution, adaptation, resist shape and solidify after peel property good resist pattern all.
The present invention also provides a kind of formation method of resist pattern, comprises following operation: lamination procedure, by the photosensitive polymer combination layer laminate being formed by above-mentioned photosensitive polymer combination on substrate; Exposure process, irradiates active ray to the established part of photosensitive polymer combination layer and makes this established part exposure, solidifies; Developing procedure by the part except established part of photosensitive polymer combination layer is removed from substrate, thereby forms the resist pattern that the solidfied material by photosensitive polymer combination forms on substrate.Thus, can sensitivity effectively form well resolution, adaptation, resist shape and solidify after peel property good resist pattern all.
The wavelength of above-mentioned active ray is preferably 390～420nm.Thus, can sensitivity effectively form well the better resist pattern of resolution, adaptation and resist shape.
In addition, the invention provides a kind of manufacture method of printed-wiring board (PWB), comprise following operation: the substrate that the formation method by above-mentioned resist pattern has been formed to resist pattern carries out etching or plating.According to this manufacture method, can precision effectively manufacture well high-density packages substrate, there is the printed-wiring board (PWB) of the densification circuit that silicon chip connects up such again.
The effect of invention
According to the present invention, sensitivity, resolution, adaptation, resist shape can be provided and solidify after peel property good photosensitive polymer combination all, and used the photosensitive element of said composition, the formation method of resist pattern and the manufacture method of printed-wiring board (PWB).
Accompanying drawing explanation
Fig. 1 is the diagrammatic cross-section that shows a preferred implementation of photosensitive element of the present invention.
Fig. 2 is for illustrating the diagrammatic cross-section of resist pattern " bottom hangover ".
Fig. 3 is for illustrating the diagrammatic cross-section of resist pattern " development residue ".
Embodiment
Below, to being elaborated for implementing best mode of the present invention.Yet, the invention is not restricted to following embodiment.In addition, in this manual, (methyl) acrylic acid refers to acrylic or methacrylic acid, and (methyl) acrylate refers to acrylate or methacrylate, and (methyl) acryloyl group refers to acryloyl group or methacryl.In addition, (gathering) oxygen ethylidene chain refers to oxygen ethylidene or polyoxyethylene chain, and (gathering) oxygen propylidene chain refers to oxygen propylidene or polyoxy propylidene chain.
< photosensitive polymer combination >
The photosensitive polymer combination of present embodiment contains (A) binder polymer (below also referred to as " (A) composition "), (B) optical polymerism compound (below also referred to as " (B) composition "), (C) Photoepolymerizationinitiater initiater (below also referred to as " (C) composition ") and (D) sensitization pigment (below also referred to as " (D) composition ").
Below, to forming each composition of photosensitive polymer combination of the present invention, describe in more detail.
[(A) composition: binder polymer]
Binder polymer as (A) composition has based on (methyl) acrylic acid structural unit and the structural unit based on (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant.Such binder polymer can be by for example making (methyl) acrylic acid and, (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant carry out the incompatible manufacture of radical polymerization.In addition, as required can also other polymerizable monomer of copolymerization.
As (methyl) benzyl acrylate derivant, for example can enumerate, on the benzyl position of (methyl) benzyl acrylate and/or phenyl, there is substituent material.
(A) content of the structural unit based on (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant in composition, the viewpoint of the fissility from resolution and solidifying, preferably take (A) composition gross mass as benchmark be 5～65 quality %, more preferably 10～55 quality %, more preferably 20～45 quality %.If this content is less than 5 quality %, there is the tendency that is not easy to obtain sufficient resolution, if this content is greater than 65 quality %, stripping film becomes large, has the elongated tendency of splitting time.
As other polymerizable monomer except (methyl) acrylic acid, (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant, for example can enumerate substituted polymerizable styrene derivative on the α positions such as styrene, vinyltoluene, α-methyl styrene or aromatic ring; The acrylamides such as diacetone acrylamide; The ester class of the vinyl alcohols such as vinyl n-butyl ether; (methyl) alkyl acrylate, (methyl) acrylic acid cycloalkyl ester, (methyl) acrylic acid furfuryl group ester, (methyl) acrylic acid tetrahydro furfuryl ester, (methyl) isobornyl acrylate, (methyl) acrylic acid adamantane esters, (methyl) acrylic acid two cyclopentyl esters, (methyl) acrylic acid dimethyl aminoethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, (methyl) acrylic acid 2,2,2-trifluoroethyl ester, (methyl) acrylic acid 2,2, (methyl) acrylate such as 3,3-tetrafluoro propyl diester; (methyl) acrylic acid derivatives such as α-bromine (methyl) acrylic acid, α-chlorine (methyl) acrylic acid, β-furyl (methyl) acrylic acid, β-styryl (methyl) acrylic acid; The maleic acid derivatives such as maleic acid, maleic anhydride, monomethyl maleate, ethyl maleate, maleic acid list isopropyl ester; Organic acid derivatives and the vinyl cyanide such as fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid, propiolic acid.These monomers can be used separately or two or more combination in any is used.
From improving the viewpoint of alkali development and peel property, (A) binder polymer preferably comprises the structural unit based on (methyl) alkyl acrylate.In the situation that (A) binder polymer has the structural unit based on (methyl) alkyl acrylate, from the viewpoint of alkali development and peel property, its content be take the gross mass of (A) composition and is preferably 1～50 quality % as benchmark.In addition, from further raising fissility aspect, more than above-mentioned content is preferably 1 quality %, more preferably more than 2 quality %, more preferably more than 3 quality %.In addition, the resolution from further raising alkaline development and the aspect of adaptation, above-mentioned content is preferably below 50 quality %, more preferably below 30 quality %, more preferably below 20 quality %.
As (methyl) alkyl acrylate, can enumerate the compound shown in following general formula (4).In formula (4), R
9represent hydrogen atom or methyl, R
10the alkyl that represents carbon number 1～12.
[changing 4]
As the R in formula (4)
10the alkyl of shown carbon number 1～12, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl, heptyl, octyl group, nonyl, decyl, undecyl, dodecyl and their constitutional isomer.From the viewpoint of further raising peel property, abovementioned alkyl is preferably the alkyl of carbon number below 4.
As the compound shown in above-mentioned general formula (4), for example can enumerate (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) butyl acrylate, (methyl) acrylic acid pentyl ester, (methyl) Hexyl 2-propenoate, (methyl) acrylic acid heptyl ester, (methyl) 2-ethyl hexyl acrylate, (methyl) 2-EHA, (methyl) acrylic acid ester in the ninth of the ten Heavenly Stems, (methyl) decyl acrylate, (methyl) acrylic acid undecyl ester, (methyl) dodecylacrylate.These compounds can be used separately or two or more combination in any is used.
From the viewpoint that resolution, adaptation and peel property balance are improved well, (A) binder polymer can also comprise the structural unit of styrene-based or derivatives thereof.In the situation that (A) binder polymer has the structural unit of styrene-based or derivatives thereof, from the viewpoint of resolution, adaptation and peel property, its content be take the gross mass of (A) composition and is preferably 5～65 quality % as benchmark.In addition, from the viewpoint of further raising resolution and adaptation, more than above-mentioned content is preferably 5 quality %, more preferably more than 10 quality %, more preferably more than 15 quality %, more than being particularly preferably 20 quality %, more than being extremely preferably 30 quality %.In addition, from the viewpoint of further raising fissility, above-mentioned content is preferably below 65 quality %, more preferably, below 60 quality %, more preferably, below 55 quality %, is particularly preferably below 50 quality %.
(A) acid number of binder polymer is preferably 100～250mgKOH/g.In addition, from improving the viewpoint of alkali development, more than the acid number of binder polymer is preferably 100mgKOH/g, more preferably more than 120mgKOH/g, more preferably more than 140gKOH/g, more than being particularly preferably 150mgKOH/g.In addition, from making the viewpoint that resistance to development fluidity (adaptation) is excellent, the acid number of binder polymer is preferably below 250mgKOH/g, more preferably below 230mgKOH/g, more preferably, below 220mgKOH/g, be particularly preferably below 210mgKOH/g.In addition, in the situation that carrying out solvent develop, preferably marginally modulate the polymerizable monomer (monomer, monomer) that (methyl) acrylic acid etc. has carboxyl.
As for the weight-average molecular weight (Mw) of (A) binder polymer, in the situation that measure (by having used the typical curve of polystyrene standard to convert) by gel permeation chromatography (GPC), be preferably 10000～100000.In addition,, from making the good aspect of resistance to development fluidity (adaptation) of the solidfied material of photosensitive polymer combination, the Mw of binder polymer is preferably more than 10000, more preferably more than 20000, more preferably more than 25000.In addition,, from the excellent aspect of alkali development, the Mw of binder polymer is preferably below 100000, more preferably below 80000, more preferably below 70000.
(A) dispersion degree of binder polymer (Mw/Mn) is preferably 1.0～3.0, and more preferably 1.0～2.0.From adaptation and excellent in resolution aspect, be preferably below 3.0, more preferably below 2.0.
(A) binder polymer, can contain the light in the scope of wavelength 350～440nm is had to photosensitive characteristic base at its molecule as required.
(A) binder polymer, can be used separately a kind of binder polymer, also can combination in any use two or more binder polymer.Binder polymer in situation about being used in combination as two or more, for example can enumerate two or more binder polymer of two or more that comprises different copolymer composition (comprising different monomers unit as copolymer composition) binder polymer, two or more binder polymer of different weight-average molecular weight, different dispersion degree.In addition, can use the polymkeric substance with multi-mode molecular weight distribution of recording in Japanese kokai publication hei 11-327137 communique.
(A) content of composition (binder polymer) preferably with respect to (A) composition and (B) total amount 100 mass parts of composition be 30～70 mass parts.From giving the aspect of film, more than being preferably 30 mass parts, more preferably more than 35 mass parts, more preferably more than 40 mass parts.In addition, from sensitivity and excellent in resolution aspect, be preferably below 70 mass parts, more preferably below 65 mass parts, more preferably below 60 mass parts.
[(B) composition: optical polymerism compound]
Optical polymerism compound as (B) composition comprises the compound in molecule with 1 ethylenic unsaturated bond.The viewpoint that peel property balance from making resolution, adaptation, resist shape and solidifying improves well, its content preferably comprises 1～30 mass parts with respect to gross mass 100 mass parts of (B) composition integral body, more preferably comprise 3～25 mass parts, further preferably comprise 5～20 mass parts.
As the optical polymerism compound in molecule with 1 ethylenic unsaturated bond, for example can enumerate, compound shown in following general formula (2), following general formula (3), above-mentioned (methyl) alkyl acrylate, from obtaining better the viewpoint of effect of the present invention, preferably comprise the compound shown in following general formula (2) or following general formula (3).
[changing 5]
[changing 6]
In formula (2), R
4represent hydrogen atom or methyl.R
5represent hydrogen atom, methyl or halogenated methyl, be preferably methyl or halogenated methyl, more preferably halogenated methyl.As halogenated methyl, can enumerate the methyl after being replaced by fluorine atom, chlorine atom, bromine atoms, iodine atom, astatine atom etc.R
6represent the alkyl of carbon number 1～6, alkoxy, hydroxyl or the halogen atom of carbon number 1～6, the alkoxy of the alkyl of above-mentioned carbon number 1～6 or carbon number 1～6 can be both also side chain shape for straight chain shape.In addition, p represents 1～4 integer, is preferably 1～3 integer.N represents 0～4 integer, in the situation that n is 2～4, and a plurality of R of existence
6both can be the same or different.
As the compound shown in above-mentioned general formula (2), for example can enumerate, γ-chloro-beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl phthalic ester, beta-hydroxy ethyl-β '-(methyl) acryloxy ethyl phthalic ester and beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl phthalic ester, wherein, preferred γ-chloro-beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl phthalic ester.γ-chloro-beta-hydroxy propyl group-β '-methacryloxyethyl phthalic ester can be used as FA-MECH (Hitachi Chemical Co., Ltd.'s system, trade name) and is purchased.These compounds can use separately or two or more is used in combination.
In above-mentioned general formula (3), R
7represent hydrogen atom or methyl.R
8represent the alkyl of carbon number 1～12, alkoxy, hydroxyl or the halogen atom of carbon number 1～12, the preferably alkyl of carbon number 1～12, the more preferably alkyl of carbon number 6～12.R represents 1～12 integer, preferably 3～10 integer, more preferably 4～8 integer.K represents 0～5 integer, in the situation that k is 2～5, and a plurality of R of existence
8both can be the same or different.
As the compound shown in above-mentioned general formula (3), for example can enumerate Nonylphenoxy triethylene oxygen base acrylate, Nonylphenoxy four ethyleneoxy group acrylate, Nonylphenoxy five ethyleneoxy group acrylate, Nonylphenoxy six ethyleneoxy group acrylate, Nonylphenoxy seven ethyleneoxy group acrylate, Nonylphenoxy eight ethyleneoxy group acrylate, Nonylphenoxy nine ethyleneoxy group acrylate, Nonylphenoxy ten ethyleneoxy group acrylate, Nonylphenoxy 11 ethyleneoxy group acrylate.These compounds can use separately or two or more is at random used in combination.
In addition,, from the viewpoint that sensitivity, resolution and adaptation are improved, (B) composition preferably also comprises the optical polymerism compound in molecule with 2 above ethylenic unsaturated bonds.As the optical polymerism compound in molecule with 2 above ethylenic unsaturated bonds, for example can enumerate, bisphenol-A is two (methyl) acrylate compounds, makes polyvalent alcohol and α, in beta-unsaturated carboxylic acid reaction and the compound that obtains, molecule, have amino-formate bond the carbamate monomers such as (methyl) acrylate compounds, make the compound and the α that contain glycidyl, the compound of beta-unsaturated carboxylic acid reaction gained.These compounds can use separately or two or more is used in combination.
The viewpoint of the peel property from improving resolution and solidifying, (B) preferably to comprise bisphenol-A be two (methyl) acrylate compounds to optical polymerism compound.
As bisphenol-A, it is two (methyl) acrylate compounds, for example can enumerate, 2, two (4-((methyl) acryloxy polyethoxy) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy the gathers propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy the gathers butoxy) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy polyethoxy the gathers propoxyl group) phenyl) propane of 2-.Wherein, from the viewpoint of further raising resolution and peel property, preferably 2, two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2-.
As two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2,2-, for example can enumerate two (4-((methyl) acryloxy diethoxy) phenyl) propane of 2,2-, two (4-((methyl) acryloxy triethoxy) phenyl) propane of 2,2-, two (4-((methyl) acryloxy tetraethoxy) phenyl) propane of 2,2-, two (4-((methyl) acryloxy five ethoxys) phenyl) propane of 2,2-, two (4-((methyl) acryloxy six ethoxys) phenyl) propane of 2,2-, two (4-((methyl) acryloxy seven ethoxys) phenyl) propane of 2,2-, two (4-((methyl) acryloxy eight ethoxys) phenyl) propane of 2,2-, two (4-((methyl) acryloxy nine ethoxys) phenyl) propane of 2,2-, two (4-((methyl) acryloxy ten ethoxys) phenyl) propane of 2,2-, two (4-((methyl) acryloxy 11 ethoxys) phenyl) propane of 2,2-, two (4-((methyl) acryloxy ten diethoxies) phenyl) propane of 2,2-, two (4-((methyl) acryloxy ten triethoxies) phenyl) propane of 2,2-, two (4-((methyl) acryloxy ten tetraethoxies) phenyl) propane of 2,2-, two (4-((methyl) acryloxy 15 ethoxys) phenyl) propane of 2,2-, two (4-((methyl) acryloxy 16 ethoxys) phenyl) propane of 2,2-.Wherein, the 1 intramolecular oxygen ethylidene number of two (4-((methyl) acryloxy polyethoxy) phenyl) propane of 2,2-is preferably 4～20, and more preferably 8～15.
Wherein, 2, two (4-(the methacryloxy five ethoxys) phenyl) propane of 2-can be used as BPE-500 (Xin Zhong village chemical industry Co., Ltd. system, trade name) or FA-321M (Hitachi Chemical Co., Ltd.'s system, trade name) is purchased.Two (4-(the methacryloxy 15 ethoxys) phenyl) propane of 2,2-can be used as BPE-1300 (Xin Zhong village chemical industry Co., Ltd. system, trade name) and is purchased.They can use separately or two or more combination in any is used.
As two (4-((methyl) acryloxy the gathers propoxyl group) phenyl) propane of 2,2-, for example can enumerate two (4-((methyl) acryloxy dipropoxy) phenyl) propane of 2,2-, two (4-((methyl) acryloxy tripropoxy) phenyl) propane of 2,2-, two (4-((methyl) acryloxy four propoxyl group) phenyl) propane of 2,2-, two (4-((methyl) acryloxy five propoxyl group) phenyl) propane of 2,2-, two (4-((methyl) acryloxy six propoxyl group) phenyl) propane of 2,2-, two (4-((methyl) acryloxy seven propoxyl group) phenyl) propane of 2,2-, two (4-((methyl) acryloxy eight propoxyl group) phenyl) propane of 2,2-, two (4-((methyl) acryloxy nine propoxyl group) phenyl) propane of 2,2-, two (4-((methyl) acryloxy ten propoxyl group) phenyl) propane of 2,2-, two (4-((methyl) acryloxy 11 propoxyl group) phenyl) propane of 2,2-, two (4-((methyl) acryloxy ten dipropoxies) phenyl) propane of 2,2-, two (4-((methyl) acryloxy ten tripropoxies) phenyl) propane of 2,2-, two (4-((methyl) acryloxy 14 propoxyl group) phenyl) propane of 2,2-, two (4-((methyl) acryloxy 15 propoxyl group) phenyl) propane of 2,2-, two (4-((methyl) acryloxy 16 propoxyl group) phenyl) propane of 2,2-.
As 2, two (4-((methyl) acryloxy polyethoxy the gathers propoxyl group) phenyl) propane of 2-, for example can enumerate, 2, two (4-((methyl) acryloxy diethoxy eight propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy tetraethoxy four propoxyl group) phenyl) propane, 2 of 2-, two (4-((methyl) acryloxy six ethoxy six propoxyl group) phenyl) propane of 2-.
Content in the situation that (B) composition comprises bisphenol-A system (methyl) acrylate compounds, preferably take (B) composition gross mass as benchmark be 20～80 quality %, more preferably 30～70 quality %.
As making polyvalent alcohol and α, beta-unsaturated carboxylic acid reacts and the compound of acquisition, for example can enumerate, ethylidene number is 2～14 polyglycol two (methyl) acrylate, propylidene number is 2～14 polypropylene glycol two (methyl) acrylate, trimethylolpropane two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, EO modification trimethylolpropane tris (methyl) acrylate (the repeating to add up to 1～5 of oxygen ethylidene), PO modification trimethylolpropane tris (methyl) acrylate, EO, PO modification trimethylolpropane tris (methyl) acrylate, tetramethylol methane three (methyl) acrylate, tetramethylol methane four (methyl) acrylate, dipentaerythritol five (methyl) acrylate, dipentaerythritol six (methyl) acrylate.These compounds can use separately or two or more is used in combination.Here, " EO modification " refers to the compound (by the compound after polyoxyethylene) of the block structure with (gathering) oxygen ethylidene chain, " PO modification " refers to the compound (by the compound after polyoxy propylidene) of the block structure with (gathering) oxygen propylidene chain, and " EOPO modification " refers to the compound (by the compound after polyoxyethylene and polyoxy propylidene) of the block structure with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.
Wherein, tetramethylol methane triacrylate can be used as A-TMM-3 (Xin Zhong village chemical industry Co., Ltd. system, trade name) be purchased, EO modification trimethylol-propane trimethacrylate can be used as TMPT21E, TMPT30E (Hitachi Chemical Co., Ltd.'s system, trade name) and is purchased.
In addition, the viewpoint that the further balance of peel property from making alkali development, resolution, adaptation and solidifying improves well, (B) composition can comprise in molecule trimethylolpropane tris (methyl) acrylate compounds with (gathering) oxygen ethylidene chain or (gathering) oxygen propylidene chain, wherein, preferably comprise in molecule trimethylolpropane tris (methyl) acrylate compounds with (gathering) oxygen ethylidene chain.In the situation that (B) composition comprises these compounds, its content be take the gross mass of (B) optical polymerism compound and is preferably 5～50 quality % as benchmark, more preferably 10～40 quality %.
In addition, from improving the flexible viewpoint of the solidfied material (cured film) of photosensitive polymer combination, (B) composition can comprise in molecule poly alkylene glycol two (methyl) acrylate with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.In the situation that (B) composition comprises these compounds, its content be take the gross mass of (B) optical polymerism compound and is preferably 5～50 quality % as benchmark, more preferably 10～40 quality %.
As poly alkylene glycol two (methyl) acrylate, preferably as intramolecular (gathering) oxyalkylene chain, there is (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain (the sub-n-pro-pyl of (gathering) oxygen) chain or (gathering) oxygen isopropylidene chain).In addition, poly alkylene glycol two (methyl) acrylate can also there is the sub-normal-butyl chain of (gathering) oxygen, (gather) oxygen isobutylidene chain, (gathering) oxygen Asia n-pentyl chain, (gathering) oxygen hexylidene chain, as their (gathering) oxyalkylene chain of carbon number 4～6 left and right of constitutional isomer etc.
In the molecule of poly alkylene glycol two (methyl) acrylate, (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain can be distinguished continuous block and exist, and also can randomly exist.In addition, in (gathering) oxygen isopropylidene chain, can be that the secondary carbon of propylidene is combined with oxygen atom, can be also primary carbon is combined with oxygen atom.
As poly alkylene glycol two (methyl) acrylate, the compound shown in following general formula (5), (6) or (7) particularly preferably.They can use separately or two or more is used in combination.
[changing 7]
In above-mentioned formula (5), (6) and (7), R represents hydrogen atom or methyl independently of one another, and EO represents oxygen ethylidene, and PO represents oxygen propylidene.M
1, m
2, m
3and m
4the repetition number of the structural unit that expression is formed by oxygen ethylidene, n
1, n
2, n
3and n
4the repetition number of the structural unit that expression is formed by oxygen propylidene, the repetition sum m of oxygen ethylidene
1+ m
2, m
3and m
4(mean value) represents 1～30 integer independently of one another, the repetition sum n of oxygen propylidene
1, n
2+ n
3and n
4(mean value) represents 1～30 integer independently of one another.
In the compound shown in above-mentioned general formula (5), (6) or (7), the repetition of oxygen ethylidene sum m
1+ m
2, m
3and m
4be 1～30 integer, be wherein preferably 1～10 integer, more preferably 4～9 integer, more preferably 5～8 integer.From the excellent aspect of resolution, adaptation and resist shape, the sum of the repetition number of oxygen ethylidene is preferably below 30, more preferably, below 10, more preferably, below 9, is particularly preferably below 8.
In addition the repetition of oxygen propylidene sum n,
1, n
2+ n
3and n
4be 1～30 integer, be wherein preferably 5～20 integer, more preferably 8～16 integer, more preferably 10～14 integer.From the raising of resolution and the excellent aspect of the minimizing of sludge, the repetition sum of oxygen propylidene is preferably below 30, more preferably, below 20, more preferably, below 16, is particularly preferably below 14.
As the compound shown in general formula (5), can enumerate R=methyl, m
1+ m
2=6 (mean values), n
1the vinyl compound of=12 (mean values) (Hitachi Chemical Co., Ltd.'s system, trade name " FA-023M ") etc.As the compound shown in general formula (6), can enumerate R=methyl, m
3=6 (mean values), n
2+ n
3the vinyl compound of=12 (mean values) (Hitachi Chemical Co., Ltd.'s system, trade name " FA-024M ") etc.As the compound shown in general formula (7), can enumerate R=hydrogen atom, m
4=1 (mean value), n
4the vinyl compound of=9 (mean values) (Xin Zhong village chemical industry Co., Ltd. system, trade name " NK エ ス テ Le HEMA-9P ") etc.They can use separately or two or more is used in combination.
As (methyl) acrylate compounds in molecule with amino-formate bond, for example can enumerate, (methyl) acrylic monomer and the diisocyanate cpd (isophorone diisocyanate, 2 on β position with OH base, 6-toluene diisocyanate, 2,4-toluene diisocyanate, 1, hexamethylene-diisocyanate etc.) addition reaction, three ((methyl) acryloxy tetraethylene glycol isocyanates) hexa-methylene isocyanuric acid ester, EO modified amido formic ether two (methyl) acrylate, EOPO modified amido formic ether two (methyl) acrylate.As EO modified amido formic ether two (methyl) acrylate, can enumerate UA-11 (Xin Zhong village chemical industry Co., Ltd. system, trade name).In addition,, as EOPO modified amido formic ether two (methyl) acrylate, can enumerate UA-13 (Xin Zhong village chemical industry Co., Ltd. system, trade name).They can use separately or two or more is used in combination.
(B) content of composition (optical polymerism compound), preferably with respect to (A) composition and (B) total amount 100 mass parts of composition be 30～70 mass parts.From improving sensitivity and resolution aspect, (B) more than the content of composition is preferably 30 mass parts, more preferably more than 35 mass parts, more preferably more than 40 mass parts.From giving film aspect and the resist shape from solidifying excellent aspect, (B) content of composition is preferably below 70 mass parts, more preferably below 65 mass parts, more preferably below 60 mass parts.
[(C) composition: Photoepolymerizationinitiater initiater]
As (C) Photoepolymerizationinitiater initiater, as long as select to make the optical wavelength and the initiating agent that the needed wavelength of (C) Photoepolymerizationinitiater initiater performance function conforms to of used exposure machine, can use without particular limitation known initiating agent in the past.As (C) Photoepolymerizationinitiater initiater, for example can enumerate benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butanone-1,2-methyl isophthalic acid-aromatic ketones such as [4-(methyl mercapto) phenyl]-2-morpholino-1-acetone; The quinones such as alkyl-anthraquinone; The benzoin ether compounds such as benzoin alkylether; The benzoin compounds such as benzoin, alkyl benzene acyloin; The dibenzoyl derivants such as dibenzoyl dimethyl acetal; 2-(Chloro-O-Phenyl)-4,5-diphenyl-imidazole dimer, 2-(adjacent fluorophenyl)-4,5-diphenyl-imidazole dimer etc. 2,4,5-triarylimidazoles dimer; 9-phenylacridine, 1, the acridine derivatives such as 7-(9,9 '-acridinyl) heptane.They can use separately or two or more is used in combination.
(C) content of composition (Photoepolymerizationinitiater initiater) preferably with respect to (A) composition and (B) total amount 100 mass parts of composition be 0.1～10 mass parts.From the excellent aspect of sensitivity, resolution or adaptation, (C) more than the content of composition is preferably 0.1 mass parts, more preferably more than 1 mass parts, more preferably more than 2 mass parts, more than being particularly preferably 3 mass parts.In addition, the excellent aspect of resist shape from solidifying, (C) content of composition is preferably below 10 mass parts, more preferably, below 7 mass parts, more preferably, below 6 mass parts, is particularly preferably below 5 mass parts.
[(D) composition: sensitization pigment]
Sensitization pigment as (D) composition comprises the compound shown in following general formula (1).
[changing 8]
In formula (1), R
1and R
2represent independently of one another to replace or unsubstituted phenyl, thienyl or furyl, from further putting forward high-resolution viewpoint, preferably replace or unsubstituted phenyl.As its substituting group, can enumerate the alkyl ester group of the alkyl of carbon number 1～10, the alkoxy of carbon number 1～10 or carbon number 1～10, the preferred alkyl of carbon number 1～10 or the alkoxy of carbon number 1～10, the more preferably alkoxy of the alkyl of carbon number 3～8 or carbon number 1～5.A and b represent 0～2 integer independently of one another.
R
3the alkyl ester group that represents the alkyl of carbon number 1～10, the alkoxy of carbon number 1～10 or carbon number 1～10.Wherein, the preferred alkyl of carbon number 1～10 or the alkoxy of carbon number 1～10, the more preferably alkoxy of the alkyl of carbon number 3～8 or carbon number 1～5.M represents 0～5 integer.When m is 2～5, a plurality of R
3both can be the same or different each other.
From further raising sensitivity and the deliquescent viewpoint solvent, R
1～R
3the alkyl of the preferred carbon number 1～3 of substituting group or the alkoxy of carbon number 1～10.
The alkoxy of the alkyl of above-mentioned carbon number 1～10 or carbon number 1～10 can be both also side chain shape for straight chain shape.As the alkyl of carbon number 1～10, for example can enumerate, methyl, ethyl, isopropyl, normal-butyl, the tert-butyl group, isopentyl, tertiary octyl group, but be not limited to this.In addition, a in general formula (1) and the summation of b are preferably 1～6, and more preferably 1～4, more preferably 1～3.
As the compound shown in above-mentioned general formula (1), for example can enumerate, 1-(4-methoxyphenyl)-3-styryl-5-phenyl-pyrazole quinoline, 1-phenyl-3-(4-methoxyl-styrene)-5-(4-methoxyphenyl)-pyrazoline, 1, 5-pair-(4-methoxyphenyl)-3-(4-methoxyl-styrene)-pyrazoline, 1-(4-isopropyl phenyl)-3-styryl-5-phenyl-pyrazole quinoline, 1-phenyl-3-(4-cumene vinyl)-5-(4-isopropyl phenyl)-pyrazoline, 1, 5-pair-(4-isopropyl phenyl)-3-(4-cumene vinyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(the 4-tert-butyl group-styryl)-5-(the 4-tert-butyl group-phenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-(4-methoxyl-styrene)-5-(4-methoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(the 4-tert-butyl group-styryl)-5-(the 4-tert-butyl group-phenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-(4-isopropyl-styryl)-5-(4-isopropyl-phenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(4-cumene vinyl)-5-(4-isopropyl phenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(4-methoxyl-styrene)-5-(4-methoxyphenyl)-pyrazoline, 1-phenyl-3-(3, 5-dimethoxy-styryl)-5-(3, 5-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(3, 4-dimethoxy-styryl)-5-(3, 4-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, 6-dimethoxy-styryl)-5-(2, 6-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, 5-dimethoxy-styryl)-5-(2, 5-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, 3-dimethoxy-styryl)-5-(2, 3-Dimethoxyphenyl)-pyrazoline, 1-phenyl-3-(2, 4-dimethoxy-styryl)-5-(2, 4-Dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(3, 5-dimethoxy-styryl)-5-(3, 5-Dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(3, 4-dimethoxy-styryl)-5-(3, 4-Dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2, 6-dimethoxy-styryl)-5-(2, 6-Dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2, 5-dimethoxy-styryl)-5-(2, 5-Dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2, 3-dimethoxy-styryl)-5-(2, 3-Dimethoxyphenyl)-pyrazoline, 1-(4-methoxyphenyl)-3-(2, 4-dimethoxy-styryl)-5-(2, 4-Dimethoxyphenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-(3, 5-dimethoxy-styryl)-5-(3, 5-Dimethoxyphenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-(3, 4-dimethoxy-styryl)-5-(3, 4-Dimethoxyphenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-(2, 6-dimethoxy-styryl)-5-(2, 6-Dimethoxyphenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-(2, 5-dimethoxy-styryl)-5-(2, 5-Dimethoxyphenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-(2, 3-dimethoxy-styryl)-5-(2, 3-Dimethoxyphenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-(2, 4-dimethoxy-styryl)-5-(2, 4-Dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(3, 5-dimethoxy-styryl)-5-(3, 5-Dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(3, 4-dimethoxy-styryl)-5-(3, 4-Dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2, 6-dimethoxy-styryl)-5-(2, 6-Dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2, 5-dimethoxy-styryl)-5-(2, 5-Dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2, 3-dimethoxy-styryl)-5-(2, 3-Dimethoxyphenyl)-pyrazoline, 1-(4-isopropyl-phenyl)-3-(2, 4-dimethoxy-styryl)-5-(2, 4-Dimethoxyphenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-styryl-5-phenyl-pyrazole quinoline, 1-phenyl-3-(the 4-tert-butyl group-styryl)-5-(the 4-tert-butyl group-phenyl)-pyrazoline, 1, 5-pair-(the 4-tert-butyl group-phenyl)-3-(the 4-tert-butyl group-styryl)-pyrazoline, 1-(the tertiary octyl group-phenyl of 4-)-3-styryl-5-phenyl-pyrazole quinoline, 1-phenyl-3-(the tertiary octyl group-styryl of 4-)-5-(the tertiary octyl group-phenyl of 4-)-pyrazoline, 1, 5-pair-(the tertiary octyl group-phenyl of 4-)-3-(the tertiary octyl group-styryl of 4-)-pyrazoline, 1-(4-dodecyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline, 1-phenyl-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(the tertiary octyl group-phenyl of 4-)-3-(the 4-tert-butyl group-styryl)-5-(the 4-tert-butyl group-phenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-(the tertiary octyl group-styryl of 4-)-5-(the tertiary octyl group-phenyl of 4-)-pyrazoline, 1-(4-dodecyl-phenyl)-3-(the 4-tert-butyl group-styryl)-5-(the 4-tert-butyl group-phenyl)-pyrazoline, 1-(the 4-tert-butyl group-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(4-dodecyl-phenyl)-3-(the tertiary octyl group-styryl of 4-)-5-(the tertiary octyl group-phenyl of 4-)-pyrazoline, 1-(the tertiary octyl group-phenyl of 4-)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-(2, 4-dibutyl-phenyl)-3-(4-dodecyl-styryl)-5-(4-dodecyl-phenyl)-pyrazoline, 1-phenyl-3-(3, 5-di-t-butyl-styryl)-5-(3, 5-di-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(2, 6-di-t-butyl-styryl)-5-(2, 6-di-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(2, 5-di-t-butyl-styryl)-5-(2, 5-di-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(2, 6-di-n-butyl-styryl)-5-(2, 6-di-n-butyl-phenyl)-pyrazoline, 1-(3, 4-di-t-butyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline, 1-(3, 5-di-t-butyl-phenyl)-3-styryl-5-phenyl-pyrazole quinoline, 1-(the 4-tert-butyl group-phenyl)-3-(3, 5-di-t-butyl-phenyl)-pyrazoline, 1-(3, 5-di-t-butyl-phenyl)-3-(3, 5-di-t-butyl-styryl)-5-(3, 5-di-t-butyl-phenyl)-pyrazoline, 1-phenyl-3-(2-thienyl)-5-(4-tert-butyl-phenyl)-pyrazoline, 1-phenyl-3-(2-thienyl) vinyl-5-(2-thienyl)-pyrazoline, 1-phenyl-3-(2-thienyl)-5-(2-thienyl)-pyrazoline, 1-phenyl-3-(2-thienyl)-5-styryl pyrazoline etc.These compounds can use separately or two or more is used in combination.
In above-claimed cpd, from the synthetic viewpoint of easily carrying out and sensitivity being improved, particularly preferably 1-phenyl-3-(4-methoxyl-styrene)-5-(4-methoxyphenyl)-pyrazoline.In addition, from the synthetic viewpoint of easily carrying out and the dissolubility solvent being improved, particularly preferably 1-phenyl-3-(4-cumene vinyl)-5-(4-isopropyl phenyl)-pyrazoline.
From sensitivity and excellent in resolution aspect, (D) content of the compound shown in the above-mentioned general formula (1) in composition be take the gross mass of (D) composition and is preferably 10～100 quality % as benchmark, more preferably 30～100 quality %, more preferably 50～100 quality %.
In addition,, in photosensitive polymer combination of the present invention, in the degree of not destroying effect of the present invention, can coordinate in the lump the sensitization pigment except the compound shown in above-mentioned general formula (1).Specifically for example can enumerate dialkyl amido benzophenone, anthracene class, Coumarins, xanthene ketone, oxazole class, Benzooxazole kind, thiazoles, benzothiazoles, triazole type, Stilbene class, triazines, thiophene-based, naphthalimide class, triaryl amine.They can use separately or two or more is used in combination.
(D) content of composition preferably with respect to (A) composition and (B) total amount 100 mass parts of composition be 0.01～10 mass parts.From sensitivity and excellent in resolution aspect, (D) more than the content of composition is preferably 0.01 mass parts, more preferably more than 0.05 mass parts, more preferably more than 0.1 mass parts.The excellent aspect of resist shape from solidifying, (D) content of composition is preferably below 10 mass parts, more preferably below 5 mass parts, more preferably below 3 mass parts.
[(E) composition: amine compound]
The photosensitive polymer combination of present embodiment, from further putting forward highly sensitive viewpoint, can contain amine compound as (E) composition.As (E) amine compound, can enumerate two [4-(dimethylamino) phenyl] methane, two [4-(diethylamino) phenyl] methane, leuco crystal violet etc.They can use separately or two or more is used in combination.
The in the situation that of containing (E) composition (amine compound) at photosensitive polymer combination, its content preferably with respect to (A) composition and (B) total amount 100 mass parts of composition be 0.01～10 mass parts.From the excellent aspect of sensitivity, (E) more than the content of composition is preferably 0.01 mass parts, more preferably more than 0.05 mass parts, more preferably more than 0.1 mass parts.In order to prevent that excessive (E) amine compound is separated out as foreign matter after film forms, (D) content of composition is preferably below 10 mass parts, more preferably below 5 mass parts, more preferably below 2 mass parts.
[other composition]
The photosensitive polymer combination of present embodiment can also contain the optical polymerism compound (oxetane compound etc.) of the ring-type ether in molecule with at least 1 cationically polymerizable as required, cationic polymerization initiators, malachite green and other dyes, tribromo phenylsulfone, the light display toners such as leuco crystal violet, heat colour developing preventing agent, the plastifier such as para toluene sulfonamide, pigment, filling agent, defoamer, fire retardant, stabilizing agent, adaptation imparting agent, levelling agent, peel off promoter, antioxidant, spices, preparation, thermal cross-linking agent.They can use separately or two or more is used in combination.Their content preferably with respect to (A) composition and (B) total amount 100 mass parts of composition be respectively 0.01～20 about mass parts.
The solution > of < photosensitive polymer combination
The photosensitive polymer combination of present embodiment can be dissolved in the solution (coating fluid) as solid constituent 30～60 quality % left and right in organic solvent and use.As organic solvent, for example can enumerate methyl alcohol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, DMF, propylene glycol monomethyl ether or their mixed solvent.
By above-mentioned coating fluid being coated on the surface of sheet metal etc., making it dry, thereby can form the photosensitive polymer combination layer that the photosensitive polymer combination by present embodiment forms.As sheet metal, can enumerate the iron-based alloys such as copper, copper series alloy, nickel, chromium, iron, stainless steel, be preferably copper, copper series alloy, iron-based alloy.
The thickness of photosensitive polymer combination layer is different and different according to its purposes, and preferred dried thickness is 1～100 μ m left and right.Can with diaphragm coating photosensitive polymer combination layer with surface sheet metal opposition side.As diaphragm, can enumerate the polymer film of tygon, polypropylene etc.
< photosensitive element >
Photosensitive element 1 of the present invention, as shown in Figure 1, the photosensitive polymer combination layer 3 that possesses supporting film 2 and form on supporting film 2 also possesses diaphragm 4 as required on photosensitive polymer combination layer 3.
By by the solution coat of above-mentioned photosensitive polymer combination on supporting film 2, make it dry, thereby can on supporting film 2, form the photosensitive polymer combination layer 3 being formed by above-mentioned photosensitive polymer combination.Like this, can obtain the photosensitive element 1 of the present embodiment of the photosensitive polymer combination layer 3 that possesses supporting film 2 and form on this supporting film 2.
As supporting film, can use the polymer film with thermotolerance and solvent resistance of the polyester such as polyethylene terephthalate, polypropylene, tygon etc.The thickness of supporting film (polymer film), considers the impact on its intensity and resolution, is preferably 1～100 μ m, more preferably 5～50 μ m, more preferably 5～30 μ m.If this thickness is less than 1 μ m, while peeling off supporting film, supporting film has crackly tendency.In addition, in order not bring impact to resolution, be preferably below 100 μ m, more preferably below 50 μ m, more preferably below 30 μ m.
Photosensitive element 1 can also possess coating photosensitive polymer combination layer 3 and surperficial diaphragms 4 supporting film 2 opposition sides as required.
As diaphragm, preferably the cohesive force of photosensitive polymer combination layer is less than to the diaphragm of supporting film to the cohesive force of photosensitive polymer combination layer, in addition, be preferably the film of low flake.Here, " flake " refer to by material by heat fusing, mixing, extrude, biaxial stretch-formed, the tape casting etc. is while manufacturing film, the foreign matter of material, dissolved matter, oxidative degradation thing etc. do not enter and form in film.That is, " low flake " means that above-mentioned foreign matter in film etc. is few.
As diaphragm, specifically can use the polymer film with thermotolerance and solvent resistance of the polyester such as polyethylene terephthalate, polypropylene, tygon etc., polyester etc.As commercially available product, can enumerate the ALPHAN MA-410 processed of Oji Paper, E-200C, the polypropylene screen of Shin Etsu Film Co., Ltd.'s system etc., the polyethylene terephthalate film of the PS series such as the PS-25 processed of Teijin Ltd etc.In addition, diaphragm can be identical with supporting film.
The thickness of diaphragm is preferably 1～100 μ m, 5～50 μ m more preferably, and more preferably 5～30 μ m, are particularly preferably 15～30 μ m.If this thickness is less than 1 μ m, when photosensitive polymer combination layer and diaphragm lamination (lamination) are on substrate, diaphragm has crackly tendency, if be greater than 100 μ m, aspect cheapness, has inadequate tendency.
The solution of photosensitive polymer combination can be coated with the known methods such as machine, rod coater by roll coater, comma coating machine, intaglio plate formula coating machine, air-blade type coating machine, mould to the coating on supporting film to carry out.
The dry of above-mentioned solution preferably carries out about 5～30 minutes at 70～150 ℃.After dry, the remaining organic solvent amount in photosensitive polymer combination layer, from preventing the viewpoint of the organic solvent diffusion subsequent handling, is preferably below 2 mass parts.
The thickness of the photosensitive polymer combination layer in photosensitive element is different and different according to purposes, and preferred dried thickness is 1～100 μ m, more preferably 1～50 μ m, more preferably 5～40 μ m.If this thickness is less than 1 μ m, have and be difficult for the tendency that industry applies, if be greater than 100 μ m, there are adaptation and resolution to be difficult for the tendency fully obtaining.
It is 5～75% that above-mentioned photosensitive polymer combination layer is preferably the ultraviolet ray of wavelength 405nm to transmission of ultraviolet rays.From the excellent aspect of adaptation, this transmissivity is preferably more than 5%, more preferably more than 10%, more preferably more than 15%.From excellent in resolution aspect, be preferably below 75%, more preferably below 65%, more preferably below 55%.
Above-mentioned transmissivity can be measured by UV spectrometer.As UV spectrometer, can enumerate the 228A type processed W of Hitachi Co., Ltd light beam spectrophotometer.
Photosensitive element can also have the middle layers such as cushion, tack coat, light absorbing zone, gas barrier layer etc.
The photosensitive element of gained can or be wound into web-like with sheet and preserve on volume core.In the situation that being wound into web-like, preferably take supporting film as outside mode reel.As volume core, can enumerate the plastics of polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin (acrylonitrile-butadiene-styrene copolymer) etc. etc.From the viewpoint of protection end face, the end face of preferably rolling up at the photosensitive element of the web-like obtaining like this arranges end face spacer, from the viewpoint on refractory limit, damp proof end face spacer is preferably set.As bundling method, preferably wrap in the black sheet that moisture-penetrability is little and pack.
The formation method > of < resist pattern
Can form resist pattern with photosensitive polymer combination of the present invention.The formation method of the resist pattern that present embodiment relates to comprises following operation: (i) lamination procedure, by the photosensitive polymer combination layer laminate being formed by above-mentioned photosensitive polymer combination on substrate, (ii) exposure process, established part irradiation active ray to photosensitive polymer combination layer makes this established part exposure, solidifies, (iii) developing procedure, the part except established part of photosensitive polymer combination layer is removed from substrate, thereby on substrate, form the resist pattern that the solidfied material by photosensitive polymer combination forms.
(i) lamination procedure
First, by the photosensitive polymer combination layer laminate being formed by photosensitive polymer combination on substrate.As substrate, can use the substrate (circuit formation substrate) of the conductor layer that possesses insulation course and form on this insulation course.
Photosensitive polymer combination layer to the lamination on substrate by for example after removing the diaphragm of above-mentioned photosensitive element, on one side the photosensitive polymer combination layer heating of photosensitive element carried out with aforesaid substrate crimping on one side.Thus, can obtain and comprise substrate, photosensitive polymer combination layer and supporting film and by they lamination forms successively laminated body.
From the viewpoint of adaptation and tracing ability, this lamination operation is preferably under reduced pressure carried out.Photosensitive polymer combination layer during crimping and/or the heating of substrate are preferably carried out at the temperature of 70～130 ℃, preferably at 0.1～1.0MPa left and right (1～10kgf/cm
2left and right) under pressure, carry out crimping, but be not particularly limited in above-mentioned condition.In addition, if photosensitive polymer combination layer is heated to 70～130 ℃, do not need in advance substrate to be carried out to thermal pretreatment, but in order further to improve lamination, can carry out the thermal pretreatment of substrate yet.
(ii) exposure process
Next, to the established part of the photosensitive polymer combination layer on substrate, irradiating active ray makes this established part exposure, solidifies.Now, in the situation that the supporting film being present on photosensitive polymer combination layer is permeability to active ray, can irradiate active ray through supporting film, in the situation that supporting film is light-proofness, after removing supporting film, to photosensitive polymer combination layer, irradiate active ray.
As exposure method, can enumerate through the minus or the eurymeric mask pattern that are called as former figure (artwork) active ray is irradiated to the method (mask exposure method) on image.In addition, can adopt (the laser direct imaging by LDI, Laser Direct Imaging) exposure method, DLP (digital light processing, Digital Light Processing) exposure method etc. are directly described the method that exposure method is image shape irradiation active ray.
Light source as active ray, can use known light source, for example can use, solid state laser, the semiconductor lasers etc. such as the gas lasers such as carbon arc lamp, mercury vapor arc lamp, high-pressure mercury-vapor lamp, xenon lamp, argon laser, YAG laser instrument radiate the light source of ultraviolet ray, visible ray etc. effectively.
As the wavelength (exposure wavelength) of active ray, from obtaining more effectively the viewpoint of effect of the present invention, preferably in the scope of 350～420nm, more preferably in the scope of 390～420nm.
(iii) developing procedure
Then, by the part except established part of photosensitive polymer combination layer is removed from substrate, thereby on substrate, form the resist pattern that the solidfied material by photosensitive polymer combination forms.The in the situation that of there is supporting film on photosensitive polymer combination layer, after removing supporting film, then remove (development) part (unexposed portion) except afore mentioned rules part (exposed portion).Developing method has wet development and dry development, but is widely used wet development.
In the situation that adopting wet development, use the developer solution corresponding with photosensitive polymer combination, by known developing method, develop.As developing method, can enumerate the method for having used impregnation method, alr mode, spray pattern, brushing, beating, having swiped, shake impregnating, from putting forward high-resolution viewpoint, most preferably high-pressure fog mode.Also two or more Combination of Methods in them can be developed.
As developer solution, can enumerate alkaline aqueous solution, water system developer solution, organic solvent is developer solution etc.
In the situation that using alkaline aqueous solution as developer solution, safety and stable, operability is good.As the alkali of alkaline aqueous solution, can use the alkali metal hydroxides such as oxyhydroxide of lithium, sodium or potassium; The carbonic acid alkaline metal such as the carbonate of lithium, sodium, potassium or ammonium or supercarbonate; The alkali metal phosphate such as potassium phosphate, sodium phosphate; The alkali metal pyrophosphate such as sodium pyrophosphate, potassium pyrophosphate.
As alkaline aqueous solution, preferably the thin solution of the thin solution of 0.1～5 quality % sodium carbonate, 0.1～5 quality % sal tartari is, the thin solution of the thin solution of 0.1～5 quality % NaOH, 0.1～5 quality % sodium tetraborate.The pH value of alkaline aqueous solution is preferably 9～11 scope, and its temperature regulates according to the alkali development of photosensitive polymer combination layer.Can also in alkaline aqueous solution, sneak into surfactant, defoamer, for a small amount of organic solvent of promoting to develop etc.
Water system developer solution is for example the developer solution that comprises water or alkaline aqueous solution and more than one organic solvents.Here, as the alkali of alkaline aqueous solution, except above-mentioned material, for example can enumerate, borax or sodium metasilicate, Tetramethylammonium hydroxide, monoethanolamine, ethylenediamine, diethylene triamine, TRIS, DAP, morpholine.About the pH value of water system developer solution, preferably as far as possible little in the scope of fully carrying out of developing, preferred pH8～12, more preferably pH9～10.
As the organic solvent using in water system developer solution, can enumerate acetone, ethyl acetate, there is alkoxyethanol, ethanol, isopropyl alcohol, butanols, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, the diethylene glycol monobutyl ether of the alkoxy of carbon number 1～4.These organic solvents can use separately or two or more is used in combination.The concentration of the organic solvent in water system developer solution is preferably 2～90 quality % conventionally, and its temperature can be adjusted according to alkali development.Can in water system developer solution, sneak on a small quantity surfactant, defoamer etc.
As organic solvent, be developer solution, can enumerate the organic solvents such as 1,1,1-trichloroethanes, 1-METHYLPYRROLIDONE, DMF, cyclohexanone, methyl isobutyl ketone, gamma-butyrolacton.In order to prevent catching fire, preferably in these organic solvents, add the water of the scope of 1～20 quality %.
Can also, after removing unexposed portion, carry out as required heating or the 0.2～10J/cm of 60～250 ℃ of left and right
2the exposure of left and right, thus resist pattern is further solidified.
The manufacture method > of < printed-wiring board (PWB)
To formed the substrate of resist pattern by said method, carry out etching or plating, thereby can manufacture printed-wiring board (PWB).The etching of substrate or plating are to using formed resist pattern as mask, conductor layer of substrate etc. to be carried out.
As the etching solution carrying out in etched situation, can enumerate copper chloride solution, ferric chloride solution, alkaline etch solution, hydrogen peroxide etching solution, wherein, from the good aspect of etching factor, preferably use ferric chloride solution.
As the method for plating carrying out in the situation of plating, can enumerate that the scolder platings such as copper facing, high homogeneity (Ha イ ス ロ ー) scolder plating, the watts such as plating copper sulphate, plating cupric pyrophosphate are bathed the nickel plating such as (nickelous sulfate-nickel chloride) plating, nickel sulfamic acid, the hard gold of plating, to plate soft gold etc. gold-plated.
After etching or plating finish, resist pattern for example can be by peeling off than the stronger aqueous solution of alkaline aqueous solution alkalescence of using of developing.As this alkaline aqueous solution, for example can use 1～10 quality % sodium hydrate aqueous solution, 1～10 quality % potassium hydroxide aqueous solution.Wherein, preferably use 1～10 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solution, more preferably use 1～5 quality % sodium hydrate aqueous solution or potassium hydroxide aqueous solution.
As the mode of peeling off of resist pattern, can enumerate impregnation method, spray pattern etc., they can use separately also can merge use.In addition, about having formed the printed-wiring board (PWB) of resist pattern, can be multilayer printed circuit board, also can there is path through hole, can be also high-density packages substrate and the printed-wiring board (PWB) with the densification circuit as connected up again in silicon chip.
Embodiment
Below, more specifically the present invention will be described to enumerate embodiment.Yet, the invention is not restricted to following embodiment.
(A) binder polymer
(A-1)
The solution that will be obtained by mixing by the methacrylic acid 150g as polymerizable monomer (monomer, monomer), benzyl methacrylate 125g, methyl methacrylate 25g and styrene 200g (mass ratio 30/25/5/40), azoisobutyronitrile 9.0g is as " solution a ".
The solution obtaining dissolving azoisobutyronitrile 1.2g in the mixed liquor at methyl cellosolve 60g and toluene 40g (mass ratio 3:2) 100g is as " solution b ".
In the flask that possesses stirring machine, reflux condenser, thermometer, tap funnel and nitrogen ingress pipe, add mixed liquor (mass ratio 3:2) 450g of methyl cellosolve 270g and toluene 180g, to being blown into nitrogen in flask, stir on one side on one side, heat to 80 ℃.
Through 4 hours, in the mixed liquor in flask, drip above-mentioned solution a, while then stir 80 ℃ of insulations 2 hours.Then, drip above-mentioned solution b in the solution in 10 minutes clockwise flasks, then the solution in the stirred flask of one side is on one side 80 ℃ of insulations 3 hours.Then, make the solution in flask be warmed up to 90 ℃ through 30 minutes, at 90 ℃, be incubated 2 hours, then cooling, obtained the solution of binder polymer (A-1).
The nonvolatile component (solid constituent) of binder polymer (A-1) is 47.8 quality %, and weight-average molecular weight is 30000, and acid number is 196mgKOH/g.In addition, weight-average molecular weight is to measure by gel permeation chromatography (GPC), and the typical curve of use polystyrene standard converts and derives.The condition of GPC is as follows.
(GPC condition)
Pump: the L-6000 of Hitachi type (Hitachi Co., Ltd's system)
Post: amount to 3 below
Gelpack?GL-R420
Gelpack?GL-R430
Gelpack GL-R440 (more than, Hitachi Chemical Co., Ltd.'s system, trade name)
Eluent: tetrahydrofuran
Measure temperature: 40 ℃
Flow: 2.05mL/ minute
Detecting device: the L-3300 of Hitachi type RI (Hitachi Co., Ltd's system, trade name)
(A-2) and (A-3)
As polymerizable monomer (monomer, monomer), with the mass ratio shown in table 1, use the material shown in table 1, in addition, similarly operate with the solution that obtains binder polymer (A-1), obtained binder polymer (A-2) and solution (A-3).
Table 1
[modulation of the solution of photosensitive polymer combination]
By by the composition shown in following table 2 and table 3 according to mixing with use level shown in table, thereby modulate the solution of the photosensitive polymer combination of embodiment 1～13 and comparative example 1～3.Wherein, the quality (solid constituent amount) that the use level of (A) composition shown in table 2 and table 3 is nonvolatile component.
Table 2
Table 3
About the detailed content of each composition shown in above-mentioned table, as described below.
(B) optical polymerism compound
TMPT21 (Hitachi Chemical Co., Ltd.'s system, trade name): EO modification trimethylolpropane triacrylate (in general formula (1), R
1=R
2=R
3=methyl, the compound of a+b+c=21 (mean value))
Two (4-(the methacryloxy five ethoxys) phenyl) propane of FA-321M (Hitachi Chemical Co., Ltd.'s system, trade name): 2,2-
FA-024M (Hitachi Chemical Co., Ltd.'s system, trade name): in general formula (6), R=methyl, m
3=6 (mean values), n
2+ n
3the compound of=12 (mean values)
M-114 (Toagosei Co., Ltd's system, trade name): 4-n-nonyl phenoxy group eight EDIAs
BPE-100 (Xin Zhong village chemical industry Co., Ltd. system, trade name): EO modified bisphenol A is dimethylacrylate (the repeating to add up to 2.6 of oxygen ethylidene)
FA-MECH (Hitachi Chemical Co., Ltd.'s system, trade name): (2-hydroxyl-3-chlorine) propyl group-2-methacryloxyethyl phthalic ester
(C) Photoepolymerizationinitiater initiater
B-CIM (Hampford company system, trade name): 2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline
(D) sensitization pigment
(D-1): 1-phenyl-3-(4-t-butyl styrene base)-5-(4-tert-butyl-phenyl) pyrazoline
(D-2): 1-phenyl-3-(4-methoxyl-styrene)-5-(4-methoxyphenyl) pyrazoline
(D-3): 1-phenyl-3-(4-cumene vinyl)-5-(4-isopropyl phenyl) pyrazoline
(D-4): 1,3-diphenyl-5-(4-isopropyl phenyl) pyrazoline
(D-5): 1-phenyl-3-(4-methoxyphenyl)-5-(4-tert-butyl-phenyl) pyrazoline
(D-6): 1-phenyl-3-(2-thienyl)-5-(4-tert-butyl-phenyl) pyrazoline
(D-7): 1-phenyl-3-(2-thienyl) vinyl-5-(2-thienyl) pyrazoline
(D-8): 1-phenyl-3-(2-thienyl)-5-(2-thienyl) pyrazoline
(D-9): 1-phenyl-3-(2-thienyl)-5-styryl pyrazoline (more than, Nippon Chemical Works Co. Ltd.'s system)
(E) amine compound
LCV (hillside plot KCC system, trade name): leuco crystal violet
(dyestuff)
MKG (Osaka Organic Chemical Industry Co., Ltd.'s system, trade name): malachite green
[photosensitive element]
The solution of the photosensitive polymer combination of above-described embodiment and comparative example is coated on respectively equably to polyethylene terephthalate film (Teijin Ltd's system of thickness 16 μ m, trade name " HTF-01 ") on, with the hot wind convection type exsiccator of 70 ℃ and 110 ℃, be dried, having formed dried thickness is the photosensitive polymer combination layer of 25 μ m.Diaphragm (the Tamapoly Co., Ltd. system of fitting on this photosensitive polymer combination layer; trade name " NF-15 "), obtained by polyethylene terephthalate film (supporting film), photosensitive polymer combination layer and the diaphragm photosensitive element that lamination forms successively.
[laminated base plate]
The muller (system opens in Co., Ltd. three) that use has a hairbrush that #600 is suitable is to copper-coated laminated board (the Hitachi Chemical Co., Ltd.'s system consisting of glass epoxide material and the Copper Foil (thickness 35 μ m) that forms on its two sides, trade name " MCL-E-67 ") grind on copper surface, washing, then makes it dry with air stream.Make it be warmed up to 80 ℃ this copper-coated laminated board (hereinafter referred to as " substrate ") heating, the photosensitive element lamination (lamination) then embodiment 1～14 and comparative example 1～3 being related to is on the copper surface of substrate.About lamination, while make the lip-deep mode of the closely sealed copper at substrate of photosensitive polymer combination layer of each photosensitive element at 120 ℃ of temperature, stack pressure 4kgf/cm according to removing diaphragm
2condition under carry out.Like this, obtained the laminated base plate that has photosensitive polymer combination layer and polyethylene terephthalate film at the copper surface of substrate superimposed layer.
[evaluation of sensitivity]
The laminated base plate of gained is naturally cooling, in the moment that becomes 23 ℃, closely sealed following optical tool on the polyethylene terephthalate film of laminated base plate, the 41 rank exposure guide rules that described optical tool has the big or small 20mm * 187mm of concentration range 0.00～2.00, concentration rank 0.05, exposure guide rule, the size on each rank is 3mm * 12mm.Use take that the bluish-violet color laser diode of wavelength 405nm is light source directly retouches exposure machine (sub-mechanical Co., Ltd. of dimension of Hitachi system, trade name " DE-1AH "), with 70mJ/cm
2energy (exposure) across optical tool and polyethylene terephthalate film, photosensitive polymer combination layer is exposed.In addition, the mensuration of illumination is used the ultraviolet illuminometer (Ushio Electric Inc's system, trade name " UIT-150 ") of having applied corresponding to the probe of 405nm to carry out.
After exposure, from laminated base plate, peel off polyethylene terephthalate film, photosensitive polymer combination layer is exposed, 1 quality % aqueous sodium carbonate is sprayed 24 seconds at 30 ℃, thereby removed unexposed portion.Like this, on the copper surface of substrate, formed the cured film that the solidfied material by photosensitive polymer combination forms.By measuring the remaining exponent number of the exposure guide rule obtaining as cured film, evaluate the sensitivity of photosensitive polymer combination.Sensitivity represents with the exponent number of exposure guide rule, and this exponent number is higher, means that sensitivity is better.The results are shown in table 5 and table 6.
[evaluation of resolution and adaptation]
Use live width (L)/spacing (S) (being designated as below " L/S ") be 5/5～30/30 (unit: μ m) describe pattern, the energy that becomes 11 rank with the remaining exponent number of 41 rank exposure guide rules is to the photosensitive polymer combination layer of above-mentioned laminated base plate expose (describing).After exposure, carry out the development treatment same with the evaluation of above-mentioned sensitivity.
After development, does not occur, in complications or damaged the resist pattern forming, by the value of minimum live width/spacing, to evaluate resolution adaptation thoroughly removing gap portion (unexposed portion) and line part (exposed portion).This numerical value is less, means that resolution and adaptation are all better.The results are shown in table 5 and table 6.
[evaluation of resist shape]
In the evaluation of above-mentioned resolution and adaptation, use the scanning electron microscope S-500A of Hitachi to observe the resist shape of gained (cross sectional shape of resist pattern).The results are shown in table 5 and table 6.
In the situation that resist is be shaped as trapezoidal or inverted trapezoidal in the situation that or have a bottom hangover of resist, the etch processes by subsequently or plating are processed the circuit forming easily the tendency that is short-circuited, opens circuit.Therefore, preferably resist is shaped as rectangle (rectangle), and there is no the bottom hangover of resist, does not also have development residue.Therefore, the situation that resist shape is good is designated as " rectangle ", and the situation of observing bottom hangover in resist pattern is designated as to " bottom hangover ", the situation of observing development residue is designated as " development residue ".
Here, Fig. 2 is for illustrating the diagrammatic cross-section of resist pattern " bottom hangover ".As shown in Figure 2, " bottom hangover " refers to, in the situation that observe the section shape of resist pattern, the resist pattern 14 on the surface of the Copper Foil 13 of substrate 12 after formed development is not rectangle but in the such shape of gap portion (unexposed portion) bottom hangover.In addition, Fig. 3 is for illustrating the diagrammatic cross-section of resist pattern " development residue "." development residue " refer to, in the situation that observe the section shape of resist pattern, the resist pattern 14 after development be not rectangle but bottom hangover significantly, at gap portion, remain development residue 15 and the state that is landfilled between line.
[evaluation of peel property]
Upper by each photosensitive element being stacked in to above-mentioned copper-coated laminated board (substrate), expose under the conditions shown in Table 4 and develop, thereby being produced on the test film (40mm * 50mm) that has formed cured film on substrate.This test film, at the lower diel of placing of room temperature (25 ℃), is then peeled off under the conditions shown in Table 4.To from substrate, be stripped from time till removing completely as splitting time from starting to be stirred to cured film.In addition, the size of the stripping film after visualization is peeled off, evaluates according to following benchmark.Splitting time is shorter, stripping film size is less, means that peel property is better.In addition, the situation that stripping film is of a size of to sheet is designated as " L ", and the situation that 30-40mm is square is designated as " M ", by being less than the square situation of 30mm, is designated as " S ".The results are shown in table 5 and table 6.
Table 4
Table 5
Table 6
* 1 exposure 70mJ/cm
2under exponent number
Clear and definite by table 5 and table 6, the sensitivity of the photosensitive polymer combination of embodiment 1～14, resolution, adaptation, resist shape and solidify after peel property all good.On the other hand, about binder polymer do not use (methyl) benzyl acrylate comparative example 1, do not use and in molecule, there is the optical polymerism compound of 1 ethylenic unsaturated bond as the comparative example 2,3 of optical polymerism compound, compare with embodiment, resolution, adaptation, resist shape, stripping film size are all poor.
Industry utilizability
Photosensitive polymer combination of the present invention can be used as the materials'use of the resist pattern that is formed for manufacturing printed-wiring board (PWB).Particularly, peel property due to the sensitivity of above-mentioned photosensitive polymer combination, resolution, adaptation, resist shape and after solidifying is all good, is therefore also applicable to be formed for to manufacture the resist pattern that high-density packages substrate etc. has the printed-wiring board (PWB) of graph thinning densification circuit.
Description of reference numerals
1 is photosensitive element;
2 is supporting film;
3 is photosensitive polymer combination layer;
4 is diaphragm;
12 is substrate;
13 is Copper Foil;
14 is resist pattern;
15 is development residue.
Claims (14)
1. a photosensitive polymer combination, is to contain (A) binder polymer, (B) optical polymerism compound, (C) Photoepolymerizationinitiater initiater and (D) photosensitive polymer combination of sensitization pigment,
Described (A) binder polymer has based on (methyl) acrylic acid structural unit and the structural unit based on (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant,
Described (B) optical polymerism compound comprises the compound with 1 ethylenic unsaturated bond,
Described (D) sensitization pigment comprises the compound shown in following general formula (1),
In formula (1), R
1and R
2represent independently of one another to replace or unsubstituted phenyl, thienyl or furyl R
3the alkyl ester group that represents the alkyl of carbon number 1～10, the alkoxy of carbon number 1～10 or carbon number 1～10, a and b represent 0～2 integer independently of one another, m represents 0～5 integer, in the situation that m is 2～5, a plurality of R of existence
3both can be the same or different each other.
2. photosensitive polymer combination according to claim 1, described (B) optical polymerism compound comprises the compound representing with following general formula (2) or following general formula (3) respectively,
In formula (2), R
4represent hydrogen atom or methyl, R
5represent hydrogen atom, methyl or halogenated methyl, R
6represent the alkyl of carbon number 1～6, alkoxy, hydroxyl or the halogen atom of carbon number 1～6, p represents 1～4 integer, and n represents 0～4 integer, in the situation that n is 2～4, and a plurality of R of existence
6both can be the same or different,
In formula (3), R
7represent hydrogen atom or methyl, R
8represent the alkyl of carbon number 1～12, alkoxy, hydroxyl or the halogen atom of carbon number 1～12, r represents 1～12 integer, and k represents 0～5 integer, in the situation that k is 2～5, and a plurality of R of existence
8both can be the same or different.
3. photosensitive polymer combination according to claim 1 and 2, it is two (methyl) acrylate compounds that described (B) optical polymerism compound also comprises bisphenol-A.
4. according to the photosensitive polymer combination described in any one in claim 1～3, described (B) optical polymerism compound also comprises trimethylolpropane tris (methyl) acrylate compounds with (gathering) oxygen ethylidene chain or (gathering) oxygen propylidene chain.
5. according to the photosensitive polymer combination described in any one in claim 1～4, described (B) optical polymerism compound also comprises poly alkylene glycol two (methyl) acrylate with (gathering) oxygen ethylidene chain and (gathering) oxygen propylidene chain.
6. according to the photosensitive polymer combination described in any one in claim 1～5, described (A) binder polymer also has the structural unit based on (methyl) alkyl acrylate.
7. according to the photosensitive polymer combination described in any one in claim 1～6, described (A) binder polymer also has the structural unit of styrene-based or styrene derivative.
8. according to the photosensitive polymer combination described in any one in claim 1～7, the acid number of described (A) binder polymer is 100～250mgKOH/g.
9. according to the photosensitive polymer combination described in any one in claim 1～8, the weight-average molecular weight of described (A) binder polymer is 10000～100000.
10. according to the photosensitive polymer combination described in any one in claim 1～9, also contain (E) amine compound.
11. 1 kinds of photosensitive elements, possess: the photosensitive polymer combination layer that supporting film and the photosensitive polymer combination by described in any one of claim 1～10 forming on this supporting film form.
The formation method of 12. 1 kinds of resist patterns, comprises following operation:
Lamination procedure, the photosensitive polymer combination layer laminate that the photosensitive polymer combination described in any one by claim 1～10 is formed on substrate,
Exposure process, irradiates active ray to the established part of described photosensitive polymer combination layer afore mentioned rules is partly exposed, is cured,
Developing procedure by the part except described established part of described photosensitive polymer combination layer is removed from described substrate, thereby forms the resist pattern that the solidfied material by photosensitive polymer combination forms on described substrate.
The formation method of 13. resist patterns according to claim 12, the wavelength of described active ray is in the scope of 390～420nm.
The manufacture method of 14. 1 kinds of printed-wiring board (PWB)s, comprises following operation: the substrate that the method by described in claim 12 or 13 has been formed to resist pattern carries out etching or plating.
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| JP2009044087 | 2009-02-26 | ||
| JP2009-044087 | 2009-02-26 |
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| CN201510212089.2A Pending CN104808444A (en) | 2009-02-26 | 2010-02-03 | Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same |
| CN2010800075741A Pending CN102317864A (en) | 2009-02-26 | 2010-02-03 | Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same |
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| CN2010800075741A Pending CN102317864A (en) | 2009-02-26 | 2010-02-03 | Photosensitive resin composition, and photosensitive element, resist pattern formation method and printed circuit board production method each utilizing same |
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| KR (1) | KR101339530B1 (en) |
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Cited By (2)
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| CN107111231A (en) * | 2014-12-22 | 2017-08-29 | 日产化学工业株式会社 | Photosensitive polymer combination and adhesive composite |
| CN108165095A (en) * | 2017-12-28 | 2018-06-15 | 深圳市容大感光科技股份有限公司 | A kind of ink and its localization method of quick positioning base material reverse side reference position |
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| WO2012081680A1 (en) * | 2010-12-16 | 2012-06-21 | 日立化成工業株式会社 | Photosensitive element, method for forming resist pattern, and method for producing printed circuit board |
| JP5935462B2 (en) * | 2011-05-10 | 2016-06-15 | 日立化成株式会社 | Photosensitive element, resist pattern forming method, printed wiring board manufacturing method |
| JP6358094B2 (en) * | 2012-11-20 | 2018-07-18 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method |
| JP6136414B2 (en) * | 2013-03-19 | 2017-05-31 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for manufacturing substrate with resist pattern, and method for manufacturing printed wiring board |
| KR20160101931A (en) | 2013-12-27 | 2016-08-26 | 히타치가세이가부시끼가이샤 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed circuit board |
| JPWO2016043162A1 (en) | 2014-09-18 | 2017-07-06 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for manufacturing substrate with resist pattern, and method for manufacturing printed wiring board |
| JP6642809B2 (en) * | 2015-03-31 | 2020-02-12 | 日産化学株式会社 | Coating solution for resist pattern coating and pattern forming method |
| KR102372527B1 (en) | 2016-03-17 | 2022-03-08 | 쇼와덴코머티리얼즈가부시끼가이샤 | The photosensitive resin composition, the photosensitive element, the manufacturing method of the board|substrate with a resist pattern, and the manufacturing method of a printed wiring board |
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Also Published As
| Publication number | Publication date |
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| CN102317864A (en) | 2012-01-11 |
| KR20110106912A (en) | 2011-09-29 |
| KR101339530B1 (en) | 2013-12-10 |
| JPWO2010098183A1 (en) | 2012-08-30 |
| TWI479261B (en) | 2015-04-01 |
| TW201042389A (en) | 2010-12-01 |
| CN104808444A (en) | 2015-07-29 |
| WO2010098183A1 (en) | 2010-09-02 |
| JP5327310B2 (en) | 2013-10-30 |
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