CN101568883B - Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board - Google Patents
Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board Download PDFInfo
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- CN101568883B CN101568883B CN2007800481739A CN200780048173A CN101568883B CN 101568883 B CN101568883 B CN 101568883B CN 2007800481739 A CN2007800481739 A CN 2007800481739A CN 200780048173 A CN200780048173 A CN 200780048173A CN 101568883 B CN101568883 B CN 101568883B
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- photosensitive polymer
- polymer combination
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- mass parts
- expression
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- 238000000034 method Methods 0.000 title claims description 61
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000011342 resin composition Substances 0.000 title abstract description 3
- 230000007261 regionalization Effects 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 155
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 65
- 150000001875 compounds Chemical class 0.000 claims abstract description 46
- 239000011230 binding agent Substances 0.000 claims abstract description 40
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 10
- 125000003545 alkoxy group Chemical group 0.000 claims abstract description 6
- 125000005843 halogen group Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- -1 amine compound Chemical class 0.000 claims description 138
- 230000014509 gene expression Effects 0.000 claims description 47
- 239000000758 substrate Substances 0.000 claims description 31
- 230000003287 optical effect Effects 0.000 claims description 24
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 22
- 229910052799 carbon Inorganic materials 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 21
- 238000007747 plating Methods 0.000 claims description 21
- 238000005530 etching Methods 0.000 claims description 13
- 238000004040 coloring Methods 0.000 claims description 11
- 230000001235 sensitizing effect Effects 0.000 claims description 11
- 238000013459 approach Methods 0.000 claims description 10
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- 125000003118 aryl group Chemical group 0.000 claims description 4
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- 125000004432 carbon atom Chemical group C* 0.000 abstract 3
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- 239000000203 mixture Substances 0.000 description 48
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- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 25
- 239000001294 propane Substances 0.000 description 24
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
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- 238000000576 coating method Methods 0.000 description 8
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- BAPJBEWLBFYGME-UHFFFAOYSA-N acrylic acid methyl ester Natural products COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 7
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
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- 229910052802 copper Inorganic materials 0.000 description 6
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 206010034972 Photosensitivity reaction Diseases 0.000 description 5
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
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- 230000036211 photosensitivity Effects 0.000 description 5
- 229920000139 polyethylene terephthalate Polymers 0.000 description 5
- 239000005020 polyethylene terephthalate Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000004793 Polystyrene Substances 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
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- 239000002585 base Substances 0.000 description 4
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical class C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 4
- 239000000470 constituent Substances 0.000 description 4
- 125000000219 ethylidene group Chemical group [H]C(=[*])C([H])([H])[H] 0.000 description 4
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- 238000005227 gel permeation chromatography Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
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- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 4
- 239000010695 polyglycol Substances 0.000 description 4
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- 229920005989 resin Polymers 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 241001597008 Nomeidae Species 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 3
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 3
- 125000005250 alkyl acrylate group Chemical group 0.000 description 3
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- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
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- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical class OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 3
- OSFBJERFMQCEQY-UHFFFAOYSA-N propylidene Chemical group [CH]CC OSFBJERFMQCEQY-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
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- 239000004328 sodium tetraborate Substances 0.000 description 3
- 235000010339 sodium tetraborate Nutrition 0.000 description 3
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- 150000003440 styrenes Chemical class 0.000 description 3
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 2
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
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Images
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- G03F7/033—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with binders the binders being polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
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- 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
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
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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
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- Chemical Kinetics & Catalysis (AREA)
- Materials For Photolithography (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Polymerisation Methods In General (AREA)
- Non-Metallic Protective Coatings For Printed Circuits (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
Abstract
本发明的感光性树脂组合物，其含有：(A)具有下述通式(I)～(IV)表示的二价基团的粘合剂聚合物；(B)光聚合性化合物；以及(C)光聚合引发剂，
The photosensitive resin composition of the present invention contains: (A) a binder polymer having a divalent group represented by the following general formulas (I) to (IV); (B) a photopolymerizable compound; and ( C) photopolymerization initiator,
Description
Technical field
The present invention relates to the formation method of photosensitive polymer combination, photosensitive element, corrosion-resisting pattern and the manufacturing approach of printed circuit board (PCB).
Background technology
In the manufacturing field of printed circuit board (PCB); As the erosion resistant that is used for etching or plating etc.; Photosensitive element (duplexer) is widely used; Said photosensitive element has following structure: behind the layer of supporting to form photosensitive polymer combination on the film or to contain this photosensitive polymer combination (below be called " photosensitive polymer combination layer "), and the structure of configuration protection film on the photosensitive polymer combination layer.
In the past, used above-mentioned photosensitive element, for example made printed circuit board (PCB) according to following order.That is, at first, form photosensitive polymer combination layer with substrate laminated photosensitive element at circuit such as copper facing thin layer laminations.At this moment; With the face of the support film that is contacted with the photosensitive polymer combination layer (below; " following " that is called the photosensitive polymer combination layer) face of opposition side (below, be called " top " of photosensitive polymer combination layer), driving fit forms the face with the circuit of substrate in forming circuit.Therefore, on the photosensitive polymer combination layer, during the configuration protection film, carry out this range upon range of operation while peel off diaphragm.In addition, carry out range upon range of (normal pressure layered manner) through the circuit formation that the heating of photosensitive polymer combination layer is crimped on bottom with substrate.
Then, through mask etc. the photosensitive polymer combination layer is carried out pattern exposure.At this moment, before exposure or the exposure after arbitrary time peel off the support film.Through developer solution dissolve or disperse remove the unexposed portion of photosensitive polymer combination layer thereafter.Then, enforcement etch processes or plating are handled and are formed pattern, peel off at last and remove cured portion.
So-called here etch processes is after removing the metal covering of circuit formation with substrate of the curing resist lining that is not developed back formation through etching, to peel off the method for solidifying resist.On the other hand; So-called plating is handled; Be through after the circuit that is not developed the curing resist lining that the back forms being formed plating that metal covering with substrate carries out copper and scolder etc. and handling, remove and solidify resist and the metal covering that is covered through this resist is carried out etching method.
As the gimmick of above-mentioned pattern exposure, in the past, utilized the method for using mercury vapor lamp to make public through photomask as light source.In addition, proposed to be called the scheme of DLP (digit optical processings) in recent years as new exposure technique, that is, direct numerical data with pattern is directly drawn exposure method what the photosensitive polymer combination layer was drawn.This is directly drawn exposure method and compares with the exposure method through photomask, and the position quality of fit is good and can obtain good pattern, therefore importing for the high-density packages substrate manufacture.
In order to improve productive capacity, must shorten the time shutter as far as possible in the pattern exposure.Above-mentioned directly drawing in the exposure method, if use with the exposure method through photomask in the past in the composition of sensitivity of the photosensitive polymer combination same degree used, then need the more time shutter usually.Therefore, must improve the illumination of exposure device side or the sensitivity of photosensitive polymer combination.
In addition, except that above-mentioned sensitivity, the peel property of resolution and resist is also excellent, for photosensitive polymer combination, also is very important.If photosensitive polymer combination can provide the corrosion-resisting pattern of excellent in resolution, then can fully reduce the short circuit between circuit or open circuit.In addition; If photosensitive polymer combination can form the excellent resist of peel property, then shortened the splitting time of resist, thereby improved the formation efficient of corrosion-resisting pattern; And; Also reduced the size of resist stripping film, thereby the residue of peeling off of resist tails off, circuit-formed yield rate improves.For this requirement, specific binder polymer, Photoepolymerizationinitiater initiater etc. and the excellent photosensitive polymer combination (for example, referring to patent documentation 1,2) of sensitivity, resolution and resist peel property have been proposed to use.
Patent documentation 1: TOHKEMY 2006-234995 communique
Patent documentation 2: TOHKEMY 2005-122123 communique
Summary of the invention
The problem that invention will solve
Yet the photosensitive polymer combination that above-mentioned patent documentation 1 and 2 is put down in writing, its resolution and resist peel property are still not enough.
Therefore, the object of the invention is to provide a kind of photosensitive polymer combination, photosensitive element, the formation method of corrosion-resisting pattern and manufacturing approach of printed circuit board (PCB) with abundant raising resolution and resist peel property effect.
The method of dealing with problems
The inventor etc. are conceived to binder polymer in order to address the above problem, and have carried out active research.The result finds that through using the binder polymer of ad hoc structure, the photosensitive polymer combination that can obtain having abundant raising resolution and resist peel property effect is accomplished the present invention thus.
That is to say that the present invention is a kind of photosensitive polymer combination, it contains:
(A) have the divalent group of formula (I) expression and divalent group and the divalent group of formula (III) expression and the binder polymer of the divalent group that formula (IV) is represented of formula (II) expression;
(B) optical polymerism compound; And
(C) Photoepolymerizationinitiater initiater,
[changing 1]
[changing 2]
[changing 3]
[changing 4]
Here, in formula (I), formula (II), formula (III) and the formula (IV), R
1, R
3, R
5And R
6Represent hydrogen atom or methyl, R respectively independently
2And R
4Represent the alkyl of carbon number 1～3, alkoxy, hydroxyl or the halogen atom of carbon number 1～3 respectively independently, R
7The alkyl of expression carbon number 1～6, m or n represent 0～5 integer respectively independently, m or n are 2～5 o'clock, a plurality of R
2Or R
4Each other can be identical or different.
The present inventor thinks, photosensitive polymer combination of the present invention, and the binder polymer of this ad hoc structure of above-mentioned (A) composition through using can obtain the effect of above-mentioned abundant raising resolution and resist peel property.In addition, photosensitive polymer combination of the present invention, above-mentioned through containing (A)～(C) composition, thus have excellent sensitivity.
In addition; Photosensitive polymer combination of the present invention; (A) binder polymer wherein; With respect to its total amount 100 mass parts, have divalent group, the expression of 10～60 mass parts general formulas (II) of 10～60 mass parts general formulas (I) expressions divalent group, the divalent group of 20～50 mass parts general formulas (III) expression, 1 mass parts is above and less than the divalent group of general formula (IV) expression of 15 mass parts.Thus, the resolution and the resist peel property of photosensitive polymer combination have further been improved.
In addition, photosensitive polymer combination of the present invention, wherein (C) Photoepolymerizationinitiater initiater preferably contains six aryl united imidazoles.Thus, the sensitivity of photosensitive polymer combination and the adaptation of resist have been improved.
In addition, photosensitive polymer combination of the present invention preferably further contains (D) sensitizing coloring matter.Thus, when using the light that in the certain wavelengths scope, has the peak to make public, can near this certain wavelengths scope, keep absorbing greatly, and improve the sensitivity of photosensitive polymer combination.
In addition, photosensitive polymer combination of the present invention preferably further contains (E) amine compound.Thus, can further improve the sensitivity of photosensitive polymer combination.
In addition, the present invention is a kind of photosensitive element, the photosensitive polymer combination layer that contains above-mentioned photosensitive polymer combination that it has supporting film and on this supporting film, forms.Through this supporting film, owing to have a photosensitive polymer combination layer that contains above-mentioned photosensitive polymer combination, even, also can carry out with enough resolution therefore when directly describing exposure method and form corrosion-resisting pattern.In addition, also has the effect that fully improves the resist peel property.
In addition, the present invention is a kind of formation method of corrosion-resisting pattern, and it has: on circuit forms with substrate, and the range upon range of range upon range of operation that contains the photosensitive polymer combination layer of above-mentioned photosensitive polymer combination; The established part irradiation active ray of said photosensitive polymer combination layer is made the exposure process of exposure portion photocuring; And form the developing procedure of removing the part beyond the said exposure portion of said photosensitive polymer combination layer with substrate from the circuit of range upon range of said photosensitive polymer combination layer.Formation method according to this corrosion-resisting pattern; Owing to use the photosensitive polymer combination layer that contains above-mentioned photosensitive polymer combination to form corrosion-resisting pattern; Therefore, though through the time shutter short directly describe exposure method, also can form corrosion-resisting pattern with enough resolution.In addition, also has the effect that fully improves the resist peel property.
In addition, the present invention is a kind of manufacturing approach of printed circuit board (PCB), and it has: the circuit that the formation method through above-mentioned corrosion-resisting pattern is formed with corrosion-resisting pattern forms with substrate and carries out the operation that etching or plating form conductive pattern.Manufacturing approach according to this printed circuit board (PCB); Because forming, the circuit that has used formation method through above-mentioned corrosion-resisting pattern to be formed with corrosion-resisting pattern uses substrate; Therefore, can make and to form highdensity circuit, and abundant simultaneously inhibition is opened circuit or the printed board circuit plate of short circuit.
The invention effect
According to the present invention, a kind of photosensitive polymer combination, photosensitive element, the formation method of corrosion-resisting pattern and manufacturing approach of printed circuit board (PCB) with abundant raising resolution and resist peel property effect can be provided.
The simple declaration of accompanying drawing
[Fig. 1] is the pattern sectional view of a preferred implementation of expression photosensitive element of the present invention.
The explanation of symbol
1... photosensitive element, 2... supporting film, 3... photosensitive polymer combination layer, 4... diaphragm
The best mode that carries out an invention
Below, preferred implementation of the present invention is elaborated.In addition, in the present invention, (methyl) acrylic acid is represented acrylic or methacrylic acid, and (methyl) acrylic ester is represented acrylic ester or the methacrylate corresponding with it, and (methyl) acryloyl group is represented acryloyl group or methacryl.
Photosensitive polymer combination of the present invention, it contains divalent group and the divalent group of above-mentioned general formula (III) expression and the binder polymer of the divalent group that above-mentioned general formula (IV) is represented of divalent group that (A) have above-mentioned general formula (I) expression (below be also referred to as " structural unit ") and above-mentioned general formula (II) expression; (B) optical polymerism compound; And (C) Photoepolymerizationinitiater initiater.
At first, the binder polymer as (A) composition is described.
(A) binder polymer, in above-mentioned general formula (I), R
1Expression hydrogen atom or methyl, R
2The alkyl of expression carbon number 1～3, alkoxy, hydroxyl or the halogen atom of carbon number 1～3, m representes 0～5 integer.As the polymerizable monomer of the structural unit that gives general formula (I) expression, can enumerate styrene or styrene derivative.In addition, in the present invention, " styrene derivative " is meant that the hydrogen atom in the styrene is substituted the substituted material of base (organic group such as alkyl or halogen atom etc.).As styrene derivative, for example, can enumerate AMS etc.
In addition, in above-mentioned general formula (II), R
3Expression hydrogen atom or methyl, R
4The alkyl of expression carbon number 1～3, alkoxy, hydroxyl or the halogen atom of carbon number 1～3, m representes 0～5 integer.As the polymerizable monomer of the structural unit that gives general formula (II) expression, can enumerate (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant.As (methyl) benzyl acrylate derivant, for example, can enumerate (methyl) acrylic acid 4-methyl benzyl ester etc.
In addition, in above-mentioned general formula (III), R
5Expression hydrogen atom or methyl.As the polymerizable monomer of the structural unit that gives general formula (III) expression, can enumerate (methyl) acrylic acid.
In addition, in above-mentioned general formula (IV), R
6Represent hydrogen atom or methyl, R respectively independently
7The alkyl of expression carbon number 1～6, m or n represent 0～5 integer respectively independently.From the viewpoint consideration that can shorten splitting time and can improve resolution, R
7Be preferably the alkyl of carbon number 1～4, and the alkyl of carbon number 1 (methyl) more preferably.As the polymerizable monomer of the structural unit that gives general formula (IV) expression, can enumerate (methyl) alkyl acrylate.
As (methyl) alkyl acrylate, for example, can enumerate the compound of formula (V) expression etc.
CH
2＝C(R
8)-COOR
9 (V)
Here, in above-mentioned general formula (V), R
8Expression hydrogen atom or methyl, R
9The alkyl of expression carbon number 1～6.In addition, as R
9The alkyl of represented carbon number 1～6 for example, can be enumerated methyl, ethyl, propyl group, butyl, amyl group, hexyl and their constitutional isomer.As the polymerizable monomer of above-mentioned general formula (V) expression, 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 etc.These polymerizable monomers can use separately or combination use more than 2 kinds.
In the conduct binder polymer of (A) composition; Containing of the structural unit of above-mentioned general formula (I) expression is proportional; With respect to (A) composition total amount 100 mass parts, be preferably 10～60 mass parts, more preferably 15～55 mass parts; Further be preferably 20～50 mass parts, and be preferably 20～40 mass parts especially.Thus, can make the photosensitive polymer combination layer that contains photosensitive polymer combination form all good with the adaptation and the resist peel property of substrate for circuit.
In addition, containing of the structural unit of above-mentioned general formula (II) expression is proportional, with respect to (A) composition total amount 100 mass parts, is preferably 10～60 mass parts, and more preferably 15～55 mass parts further are preferably 20～50 mass parts, are preferably 25～45 mass parts especially.Thus, can make the photosensitive polymer combination layer that contains photosensitive polymer combination form all good with the adaptation and the resist peel property of substrate for circuit.
In addition, containing of the structural unit of above-mentioned general formula (III) expression is proportional, with respect to (A) composition total amount 100 mass parts; Be preferably 10～60 mass parts; More preferably 15～50 mass parts further are preferably 20～40 mass parts, and are preferably 25～35 mass parts especially.Thus, can make resist peel property and development property all good.
In addition, containing of the structural unit of above-mentioned general formula (IV) expression is proportional, with respect to (A) composition total amount 100 mass parts; Be preferably more than 1 mass parts and less than 15 mass parts; More preferably 2～13 mass parts further are preferably 4～12 mass parts, and are preferably 5～10 mass parts especially.Thus, can make the photosensitive polymer combination layer that contains photosensitive polymer combination form all good with the adaptation and the resist peel property of substrate for circuit.
In addition; As in the binder polymer of (A) composition, proportional when containing of the structural unit of the structural unit of above-mentioned general formula (I) expression and above-mentioned general formula (II) expression, during separately less than 10 mass parts; Have the tendency of resolution variation; When it surpasses 60 mass parts separately, have stripping film and become big, the tendency that splitting time is elongated.In addition, proportional during when containing of the structural unit of above-mentioned general formula (III) expression less than 10 mass parts, have alkali dissolution property variation, stripping film becomes big simultaneously, and the tendency that splitting time is elongated when it surpasses 60 mass parts, has the tendency of resolution variation.In addition, proportional during when containing of the structural unit of above-mentioned general formula (IV) expression less than 1 mass parts, have the tendency that fissility descends, when it is 15 mass parts when above, have the tendency that resolution descends.
When using this binder polymer to prepare photosensitive polymer combination, can use a kind of binder polymer separately, also can the binder polymer combination in any more than 2 kinds be used.Binder polymer when using as combination more than 2 kinds; For example, can enumerate by formed (containing different repetitives) binder polymer, the binder polymer more than 2 kinds of different weight-average molecular weight, binder polymer more than 2 kinds of different dispersion degree more than 2 kinds of different copolymer component etc. as constituent.In addition, can also use the polymkeric substance of being put down in writing in the japanese kokai publication hei 11-327137 communique with multimode molecular weight distribution.
(A) weight-average molecular weight of binder polymer (Mw) and number-average molecular weight (Mn) can be measured (typical curve through using polystyrene standard converts) through gel permeation chromatography (GPC).According to this determination method, the Mw of binder polymer is preferably 5000～150000, and more preferably 10000～100000, and be preferably 20000～50000 especially.When Mw less than 5000 the time, have the tendency that anti-development fluidity descends, when it surpasses 150000, have the elongated tendency of development time.
In addition, (A) dispersion degree of binder polymer (Mw/Mn) is preferably 1.0～3.0, and more preferably 1.0～2.0.If dispersion degree surpasses 3.0, then have the tendency that adaptation and resolution descend.
In addition, (A) binder polymer, for example, can and with styrene resin, epikote, amide-type resin, acid amides epikote, alkyd based resin, phenolic resin etc.In addition, these resins can use separately, or combination is used more than 2 kinds.
Binder polymer of the present invention for example, can make polymerizable monomer carry out free radical polymerization through conventional method and make.
Above-mentioned (A) binder polymer also can contain the structural unit structural unit in addition that above-mentioned general formula (I)～(IV) is represented.Above-mentioned (A) binder polymer; The structural unit that most preferably only has above-mentioned general formula (I)～(IV) expression; But also can in the degree of not damaging the object of the invention, contain total amount with respect to (A) composition, be about 1～10 mass parts except that the structural unit them.At this moment; Polymerizable monomer as the structural unit except that the structural unit of above-mentioned general formula (I)～(IV) expression; For example; Can enumerate ester class, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, 2 of vinyl alcohol such as acrylic amide, vinyl cyanide, vinyl-n-butyl ether such as (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 undecane ester, (methyl) acrylic acid dodecane ester, 2-hydroxyethyl, 2-hydroxypropyl, 3-hydroxypropyl, 4-hydroxyl butyl, diacetone acrylamide; 2; 2-trifluoroethyl (methyl) acrylic ester, 2; 2; 3, maleic acid monoesters, fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid, propiolic acids etc. such as 3-tetrafluoro propyl group (methyl) acrylic ester, (methyl) acrylic acid, α-bromine (methyl) acrylic acid, α-chlorine (methyl) acrylic acid, β-furyl (methyl) acrylic acid, β-styryl (methyl) acrylic acid, maleic acid, maleic anhydride, monomethyl maleate, ethyl maleate, maleic acid list isopropyl ester.These monomers can use separately, or combination is used more than 2 kinds.
(A) binder polymer among the present invention is considered from using aqueous slkali to carry out the development property viewpoint of alkali when developing, and is preferably formed by the polymkeric substance that has carboxyl more than a kind or 2 kinds.This (A) binder polymer for example, can make contain carboxyl polymerizable monomer and polymerizable monomer in addition beyond (methyl) acrylic acid carry out free radical polymerization and make through conventional method.
(A) acid number of binder polymer is preferably 80～250mgKOH/g, 100～220mgKOH/g more preferably, and be preferably 150～210mgKOH/g especially.When this acid number during less than 80mgKOH/g, have the elongated tendency of development time, when it surpasses 250mgKOH/g, have the tendency that the anti-development fluidity of the resist of photocuring descends.In addition, when carrying out solvent develop as developing procedure, preferred a small amount of preparation has the polymerizable monomer of carboxyl.
In addition, (A) binder polymer can also contain at its molecule as required and has photosensitive characteristic group.
As the use level of the binder polymer of (A) composition, with respect to (A) composition and (B) total amount 100 mass parts of composition, be preferably 30～70 mass parts, more preferably 35～65 mass parts are preferably 40～60 mass parts especially.When this use level during less than 30 mass parts, have the tendency that can't obtain excellent in shape, when it surpasses 70 mass parts, have the tendency that can't obtain good sensitivity and resolution.As the binder polymer of (A) composition, can use a kind separately, perhaps combination is used more than 2 kinds.
Then, the optical polymerism compound as (B) composition is described.
Optical polymerism compound as (B) composition; For example; Can enumerate and make α; Beta-unsaturated carboxylic acid and polyol reaction and compound, bisphenol-A class two (methyl) acrylate compounds, make α, beta-unsaturated carboxylic acid with the compound reaction that contains glycidyl compound, ammonia ester carbamate monomer, the Nonylphenoxies such as (methyl) acrylate compounds that in molecule, has an ammonia ester bond gather ethyleneoxy group acrylic ester (being also referred to as " Nonylphenoxy polyethylene glycol acrylate "), O-phthalic acid compounds, (methyl) alkyl acrylate etc.These compounds can use separately, or combination is used more than 2 kinds.
As the above-mentioned α that makes; Beta-unsaturated carboxylic acid and polyol reaction and compound; For example, can enumerate the ethylidene number is that 2～14 polyglycol two (methyl) acrylic ester, propylidene number are 2～14 polypropylene glycol two (methyl) acrylic ester, trimethylolpropane two (methyl) acrylic ester, trimethylolpropane tris (methyl) acrylic ester, EO modification trimethylolpropane tris (methyl) acrylic ester, PO modification trimethylolpropane tris (methyl) acrylic ester, EO, PO modification trimethylolpropane tris (methyl) acrylic ester, tetramethylol methane three (methyl) acrylic ester, tetramethylol methane four (methyl) acrylic ester, dipentaerythritol five (methyl) acrylic ester, dipentaerythritol six (methyl) acrylic ester etc.These compounds can use separately, or combination is used more than 2 kinds.Here, " EO " representative ring oxidative ethane, the compound of EO modification represent to have the material of the block structure of ethylene oxide group.In addition, " PO " representative ring Ethylene Oxide, the compound of PO modification represent to have the material of the block structure of propylene oxide group.
As above-mentioned bisphenol-A class two (methyl) acrylate compounds; For example; Can enumerate 2,2-two (4-((methyl) acryloxy polyethoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy gathers propoxyl group) phenyl) propane, 2; 2-two (4-((methyl) acryloxy gathers butoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy polyethoxy gathers propoxyl group) phenyl) propane etc.As above-mentioned 2,2-two (4-((methyl) acryloxy polyethoxy) phenyl) propane, for example; Can enumerate 2; 2-two (4-((methyl) acryloxy diethoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy triethoxy) phenyl) propane, 2,2-two (4-((methyl) acryloxy tetraethoxy) phenyl) propane, 2; 2-two (4-((methyl) acryloxy five ethoxys) phenyl) propane, 2; 2-two (4-((methyl) acryloxy six ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy seven ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy eight ethoxys) phenyl) propane, 2; 2-two (4-((methyl) acryloxy nine ethoxys) phenyl) propane, 2; 2-two (4-((methyl) acryloxy ten ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy 11 ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy ten diethoxies) phenyl) propane, 2; 2-two (4-((methyl) acryloxy ten triethoxies) phenyl) propane, 2; 2-two (4-((methyl) acryloxy ten tetraethoxies) phenyl) propane, 2,2-two (4-((methyl) acryloxy 15 ethoxys) phenyl) propane, 2,2-two (4-((methyl) acryloxy 16 ethoxys) phenyl) propane etc.
2,2-two (4-(methacryloxy five ethoxys) phenyl) propane, (Xin Zhong village chemical industry (strain) is made to can be used as BPE-500; Trade name) or FA-321M (Hitachi changes into industry (strain) and makes; Trade name) in commercial acquisition, 2,2-two (4-(methacryloxy 15 ethoxys) phenyl) propane; Can be used as BPE-1300 (Xin Zhong village chemical industry (strain) is made, trade name) in commercial acquisition.2,2-two (4-((methyl) acryloxy polyethoxy) phenyl) propane, its 1 intramolecular ethylene oxide group number is preferably 4～20, and more preferably 8～15.These compounds can use separately, or combination is used more than 2 kinds.
As (methyl) acrylate compounds that has ammonia ester bond in the molecule; For example; Can be set forth in (methyl) acrylic monomers and the diisocyanate cpd (IPDI, 2 that have the OH base on the β position; 6-toluene diisocyanate, 2; 4-toluene diisocyanate, 1,6-hexamethylene diisocyanate etc.) addition reaction, three ((methyl) acryloxy TEG isocyanates) hexa-methylene isocyanuric acid ester, EO modification ammonia ester two (methyl) acrylic ester, EO, PO modification ammonia ester two (methyl) acrylic ester etc.As EO modification ammonia ester two (methyl) acrylic ester, for example, can enumerate UA-11 (Xin Zhong village chemical industry (strain) is made, trade name).In addition, as above-mentioned EO, PO modification ammonia ester two (methyl) acrylic ester, for example, can enumerate UA-13 (Xin Zhong village chemical industry (strain) is made, trade name).These compounds can use separately, or combination is used more than 2 kinds.
Gather the ethyleneoxy group acrylic ester as Nonylphenoxy; For example, can enumerate Nonylphenoxy four ethyleneoxy group acrylic ester, Nonylphenoxy five ethyleneoxy group acrylic ester, Nonylphenoxy six ethyleneoxy group acrylic ester, Nonylphenoxy seven ethyleneoxy group acrylic ester, Nonylphenoxy eight ethyleneoxy group acrylic ester, Nonylphenoxy nine ethyleneoxy group acrylic ester, Nonylphenoxy ten ethyleneoxy group acrylic ester, Nonylphenoxy 11 ethyleneoxy group acrylic ester.As Nonylphenoxy eight ethyleneoxy group acrylic ester, for example, can enumerate M-114 (East Asia synthetic (strain) made trade name).These compounds can use separately, or combination is used more than 2 kinds.
As above-mentioned O-phthalic acid compounds, for example, can enumerate γ-chloro-beta-hydroxy propyl group-β '-(methyl) acryloxy ethyl-phthalic ester, beta-hydroxy alkyl-β '-(methyl) acryloxyalkyl-phthalic ester etc.These compounds can use separately, or combination is used more than 2 kinds.
Further, (B) of the present invention composition is considered from the flexible viewpoint that can mention cured film, preferably contains in molecule, to have the two PAG two (methyl) acrylic ester of glycol chain and propylene glycol chain.Should (methyl) acrylic ester, the two does not just limit as intramolecular alkylene glycol chain especially as long as have glycol chain and propylene glycol chain (positive propylene glycol chain or Isopropanediol chain).In addition, should (methyl) acrylic ester, can also further contain positive butylene glycol chain, isobutyl glycol chains, positive pentanediol chain, hexanediol chain, their alkylene glycol chain of carbon numbers such as constitutional isomer about 4～6.
When above-mentioned glycol chain and propylene glycol chain when being a plurality of, a plurality of glycol chains and propylene glycol chain can respectively be done for oneself and existed with block continuously, also can randomly exist.In addition, in above-mentioned Isopropanediol chain, propylidene can be that secondary carbon combines with oxygen atom, also can be that primary carbon combines with oxygen atom.
In these (B) compositions, have the ethene property unsaturated link that at least one can polymerization, and have the two PAG two (methyl) acrylic ester of glycol chain and propylene glycol chain in the molecule, for example, can enumerate formula (VI):
[changing 5]
Compound, the formula (VII) of expression:
[changing 6]
Compound, the formula (VIII) of expression:
[changing 7]
The compound of expression etc., here, in formula (VI), formula (VII) and the formula (VIII), R
10, R
11, R
12, R
13, R
14And R
15Represent the alkyl of hydrogen atom or carbon number 1～3 respectively independently, EO representes glycol chain, and PO representes propylene glycol chain, m
1～m
4And n
1～n
4Represent 1～30 integer respectively independently.These compounds can use separately, or combination is used more than 2 kinds.
As the alkyl of carbon number 1～3 in the above-mentioned general formula (VI)～(VIII), for example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl.
In addition, the sum (m of the repeat number of glycol chain in the above-mentioned general formula (VI)～(VIII)
1+ m
2, m
3And m
4) be 1～30 integer, be preferably 1～10 integer, more preferably 4～9 integer is preferably 5～8 integer especially.If this repeat number surpasses 30, then have the tendency of sheltering (tent) reliability and the deterioration of resist shape.
In addition, the sum (n of the repeat number of propylene glycol chain in the above-mentioned general formula (VI)～(VIII)
1, n
2+ n
3And n
4) be 1～30 integer, be preferably 5～20 integer, more preferably 8～16 integer is preferably 10～14 integer especially.If this repeat number surpasses 30, then have resolution and worsen, and produce the tendency of mud.
As the object lesson of the compound of above-mentioned general formula (VI) expression, for example, can enumerate R
10=R
11=methyl, m
1+ m
2=4 (mean values), n
1(Hitachi changes into industry (strain) manufacturing, trade name: FA-023M) etc. to the vinyl compound of=12 (mean values).In addition, as the object lesson of the compound of above-mentioned general formula (VII) expression, for example, can enumerate R
12=R
13=methyl, m
3=6 (mean values), n
2+ n
3(Hitachi changes into industry (strain) manufacturing, trade name: FA-024M) etc. to the vinyl compound of=12 (mean values).Further, as the object lesson of the compound of above-mentioned general formula (VIII) expression, for example, can enumerate R
14=R
15=hydrogen atom, m
4=1 (mean value), n
4The vinyl compound of=9 (mean values) (make, sample name: NK ester HEMA-9P) etc. by Xin Zhong village chemical industry (strain).These compounds can use separately, or combination is used more than 2 kinds.
As the use level of the optical polymerism compound of (B) composition, with respect to (A) composition and (B) total amount 100 mass parts of composition, be preferably 30～70 mass parts, more preferably 35～65 mass parts are preferably 40～60 mass parts especially.When this use level during, have the tendency that can't obtain good sensitivity and resolution, and when it surpasses 70 mass parts, have the tendency that can't obtain excellent in shape less than 30 mass parts.
As the optical polymerism compound of (B) composition, can use a kind separately, perhaps combination is used more than 2 kinds.This optical polymerism compound is considered from the viewpoint that improves anti-plating property and adaptation, preferably contains (methyl) acrylate compounds that has ammonia ester bond in bisphenol-A class (methyl) acrylate compounds or the molecule.In addition, consider, preferably contain bisphenol-A class (methyl) acrylate compounds from the viewpoint that improves sensitivity and resolution.
In addition; Optical polymerism compound as (B) composition; From reducing the size of resist stripping film; Shorten the viewpoint of splitting time and consider, preferably contain have in the molecule one can polymerization the optical polymerism unsaturated compound of ethene property unsaturated link, more preferably with have in the molecule one can polymerization optical polymerism unsaturated compound and the molecule of ethene property unsaturated link in have more than two the optical polymerism unsaturated compound combination use of ethene property unsaturated link that can polymerization.At this moment; For example; As have in the molecule one can polymerization the optical polymerism unsaturated compound of ethene property unsaturated link, can enumerate phenoxy group and gather ethyleneoxy group (methyl) acrylic ester, phenoxy group and gather that ethyleneoxy group-polytrimethylene oxygen base (methyl) acrylic ester, Octylphenoxy six ethyleneoxy group (methyl) acrylic ester, Octylphenoxy seven ethyleneoxy group (methyl) acrylic ester, Octylphenoxy eight ethyleneoxy group (methyl) acrylic ester, Octylphenoxy nine ethyleneoxy group (methyl) acrylic ester, Octylphenoxy ten ethyleneoxy group (methyl) acrylic ester, Nonylphenoxy gather ethyleneoxy group (methyl) acrylic ester, Nonylphenoxy gathers ethyleneoxy group-polytrimethylene oxygen base (methyl) acrylic ester, has the phthalic acid derivatives of (methyl) acrylic etc.In addition; As the optical polymerism unsaturated compound that has more than two ethene property unsaturated link that can polymerization in the molecule; Can enumerate 1; 6-hexanediol two (methyl) acrylic ester, 1,4-cyclohexanediol two (methyl) acrylic ester, ethylidene number are that 2～14 polyglycol two (methyl) acrylic ester, propylidene number are (methyl) acrylic acid addition product of two (methyl) acrylic ester of gathering of 2～14 polypropylene glycol two (methyl) acrylic ester, above-mentioned general formula (VI)～(VIII) having ammonia ester bond in ethylidene polytrimethylene glycol two (methyl) acrylic ester, bisphenol-A class two (methyl) acrylic ester, the molecule, two (acryloxy ethyl) hydroxyethyl isocyanuric acid ester, bisphenol A diglycidyl ether two (methyl) acrylic ester, O-phthalic acid glycidyl ester etc.
In addition; Improve the viewpoint of resolution, splitting time and exposure tolerance considers from equilibrium; Especially preferably with have in a kind of molecule one can polymerization optical polymerism unsaturated compound and 2 kinds of molecules of ethene property unsaturated link in have more than two an ethene property unsaturated link that can polymerization the combination of optical polymerism unsaturated compound use.At this moment; As have in the molecule one can polymerization the optical polymerism unsaturated compound of ethene property unsaturated link; For example, can use phenoxy group to gather ethyleneoxy group (methyl) acrylic ester, Nonylphenoxy gathers ethyleneoxy group (methyl) acrylic ester, has in the phthalic acid derivatives of (methyl) acrylic any.In addition; As the optical polymerism unsaturated compound that has more than two ethene property unsaturated link that can polymerization in the molecule; For example; Can at least a compound and the combination of bisphenol-A class two (methyl) acrylate compounds that gather in ethylidene polytrimethylene glycol two (methyl) acrylic ester, EO modification ammonia ester two (methyl) acrylic ester and EO, PO modification ammonia ester two (methyl) acrylic ester that be selected from above-mentioned general formula (VI)～(VIII) be used.
Then, the Photoepolymerizationinitiater initiater as (C) composition is described.
Photoepolymerizationinitiater initiater as (C) composition; For example; Can enumerate benzil derivant, 2-(Chloro-O-Phenyl)-4 such as benzoin ether compounds such as quinones, benzoin alkylether, benzil dimethyl acetal such as 4,4 '-two (diethylamino) benzophenone, benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino-aromatic ketones such as 1-acetone, alkyl-anthraquinone, 5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4; 5-two (methoxyphenyl) imidazole dimer, 2-(adjacent fluorophenyl)-4; 5-diphenyl-imidazole dipolymer, 2-(o-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer, 2-(p-methoxyphenyl)-4,5-diphenyl-imidazole dipolymer etc. 2; 4; 5-triarylimidazoles dipolymer, 9-phenylacridine, 1, acridine derivatives such as 7-two (9,9 '-acridinyl) heptane etc.
In addition, above-mentioned 2,4, in the 5-triarylimidazoles dipolymer, two 2,4, the substituting group of the aryl of 5-triarylimidazoles dipolymer can be identical and become the compound of symmetry, also can be different and become asymmetrical compound.In addition, Photoepolymerizationinitiater initiater is considered from the viewpoint of adaptation and sensitivity, preferably uses as 2,4 six aryl united imidazoles of 5-triarylimidazoles dipolymer.These Photoepolymerizationinitiater initiaters can use separately, or combination is used more than 2 kinds.
In addition, as the use level of the Photoepolymerizationinitiater initiater of (C) composition, with respect to (A) composition and (B) total amount 100 mass parts of composition, be preferably 0.1～10 mass parts, more preferably 2～6 mass parts are preferably 3.5～5 mass parts especially.When this use level during less than 0.1 mass parts, have the tendency that is difficult to obtain good sensitivity or resolution, when it surpasses 10 mass parts, have the tendency that is difficult to obtain desirable excellent in shape.As the Photoepolymerizationinitiater initiater of (C) composition, can use a kind separately, perhaps combination is used more than 2 kinds.
Photosensitive polymer combination of the present invention preferably except above-mentioned (A)～(C) composition, also contains (D) sensitizing coloring matter and/or (E) amine compound.
As the sensitizing coloring matter of (D) composition among the present invention, be the material that can effectively utilize the absorbing wavelength of active ray used when making public, preferably greatly absorbing wavelength is the compound of 370～420nm.Among the present invention,,, can have sufficiently high sensitivity for the exposure light of directly describing exposure method through using this sensitizing coloring matter.If the very big absorbing wavelength of sensitizing coloring matter is less than 370nm, even then have under the gold-tinted environment, stability is the tendency of decline also.
As sensitizing coloring matter, for example, can enumerate pyrazolines, anthracene class, Coumarins, xanthene ketone, oxazole class, Benzooxazole kind, thiazoles, benzothiazoles, triazole type, Stilbene class, triazines, thiophene-based, naphthalimide class etc.Sensitizing coloring matter is considered from the viewpoint that can improve resolution, adaptation and sensitivity, preferably contains the anthracene class.In addition, the use level of sensitizing coloring matter with respect to (A) composition and (B) total amount 100 mass parts of composition, is preferably 0.01～10 mass parts, and more preferably 0.05～5 mass parts is preferably 0.1～2 mass parts especially.When this use level during less than 0.01 mass parts, have the tendency that can't obtain good sensitivity or resolution, when it surpasses 10 mass parts, have the tendency of the corrosion-resisting pattern that is difficult to obtain desirable excellent in shape.As the sensitizing coloring matter of (D) composition, can use a kind separately, perhaps combination is used more than 2 kinds.
As the amine compound of (E) composition, so long as can improve the sensitivity of photosensitive polymer combination and in molecule, have amino material, just not special the qualification.As its object lesson, for example, can enumerate two [4-(dimethylamino) phenyl] methane, two [4-(diethylamino) phenyl] methane, LCV etc.The use level of amine compound with respect to (A) composition and (B) total amount 100 mass parts of composition, is preferably 0.01～10 mass parts, 0.05～5 mass parts more preferably, and be preferably 0.1～2 mass parts especially.When this use level during less than 0.01 mass parts, have the tendency that can't obtain good sensitivity, and when it surpasses 10 mass parts, then have film forming after, (E) tendency separated out as foreign matter easily of composition.As the amine compound of (E) composition, can use a kind separately, perhaps combination is used more than 2 kinds.
In photosensitive polymer combination of the present invention; As required; Can be with respect to (A) composition and (B) total amount 100 mass parts of composition, light developers such as dyestuff, tribromo-benzene sulfone, LCV, the heat colour developings such as optical polymerism compound (oxetane compound etc.), cationic polymerization initiators, peacock green that contain the ring-type ether that has at least one cationically polymerizable in the molecule about 0.01～20 mass parts respectively prevent plastifier such as agent, para toluene sulfonamide, pigment, filling agent, foam-breaking agent, fire retardant, stabilizing agent, adaptation imparting agent, levelling agent, peel off promoter, anti-oxidant, spices, preparation, thermal cross-linking agent etc.They can use separately, or combination is used more than 2 kinds.
In addition; Photosensitive polymer combination of the present invention; Can also be dissolved in methyl alcohol, ethanol, acetone, methyl ethyl ketone, methyl cellosolve, ethyl cellosolve, toluene, N; Dinethylformamide, propylene glycol monomethyl ether equal solvent or their mixed solvent, forming solid constituent is the solution about 30～60 quality %.This solution can be as the coating fluid of the photosensitive polymer combination layer that forms photosensitive element.
In addition, above-mentioned coating fluid, except the photosensitive polymer combination layer that is used to form photosensitive element, for example, and can also be as aqueous resist-coated on the surface of sheet metal and after the drying, the lining diaphragm uses.As the material of sheet metal, for example, can enumerate iron-based alloys such as copper, copper series alloy, nickel, chromium, iron, stainless steel, be preferably copper, copper series alloy, iron-based alloy etc.
Then, photosensitive element of the present invention is described.Fig. 1 is the pattern sectional view of a preferred implementation of expression photosensitive element of the present invention.Photosensitive element 1 shown in Figure 1 is by supporting film 2, constitute at photosensitive polymer combination layer 3 that contains above-mentioned photosensitive polymer combination that forms on the supporting film 2 and the diaphragm 4 that is layered on the photosensitive polymer combination layer 3.
Supporting film 2 can use, and for example polyethylene terephthalate, polypropylene, tygon, polyester etc. have the polymer film of thermotolerance and solvent resistance.As the commercial goods; Can enumerate; For example Oji Paper (strain) system A Lufan (ア Le Off ア Application) MA-410, E-200C (more than; Be trade name), polypropylene screen, Supreme Being people's (strain) system PS series (for example, trade name: PS-25) wait polyethylene terephthalate film etc., but be not limited to this of SHIN-ETSU HANTOTAI's film (strain) system etc.
In addition, the thickness of supporting film 2 is preferably 1～100 μ m, more preferably 5～25 μ m.When this thickness during less than 1 μ m, have when before development, peeling off supporting film, the crackly tendency of supporting film, and when it surpasses 100 μ m, have the tendency that resolution descends.In addition, supporting film 2 also can be, one deck is as the holder of photosensitive polymer combination layer, and one deck is as the diaphragm of photosensitive polymer combination in addition, and the enterprising enforcement in two sides that is layered in the photosensitive polymer combination layer is used.
Photosensitive polymer combination layer 3, preferably through above-mentioned photosensitive polymer combination is dissolved in the above-mentioned solvent, after forming solid constituent and being the solution (coating fluid) about 30～60 quality %, with this solution coat on supporting film 2 and dry and form.Coating can be passed through, and for example uses roll coater, comma coating machine, intaglio plate coating machine, Kohler coater, mould to be coated with the known method that machine, rod be coated with machine etc. and carries out.Drying can be carried out about 5～30 minutes at 70～150 ℃.In addition, the remaining organic solvent amount in the photosensitive polymer combination, from prevent after the viewpoint of organic solvent diffusion the operation consider, be preferably below the 2 quality %.
In addition, the thickness of photosensitive polymer combination layer 3, according to the purposes of photosensitive element and difference, dried thickness is preferably 1～100 μ m, more preferably 1～50 μ m.When this thickness during less than 1 μ m, have and in industry, be difficult to the tendency that is coated with, and when it surpassed 100 μ m, having effect of the present invention reduced, and the tendency that descends of bounding force, resolution.
In addition, photosensitive polymer combination layer 3 is that the transmitance of the light of 405nm is preferably 5～75% with respect to wavelength, more preferably 7～60%, be preferably 10～40% especially.When this transmitance less than 5% the time, have the tendency of adaptation variation, and when it surpasses 75%, have the tendency of resolution variation.Above-mentioned transmitance can be measured through the UV spectrometer, as above-mentioned UV spectrometer, can enumerate (strain) Hitachi system 228A type W light beam spectrophotometer (trade name) etc.
As diaphragm 4, the polymer film that can use for example polyethylene terephthalate, polypropylene, tygon, polyester etc. to have thermotolerance and solvent resistance.As the commercial goods; Can enumerate; For example all MA-410 of Oji Paper (strain) system A Lu, E-200C (more than; Be trade name), polypropylene screen, Supreme Being people's (strain) system PS series (for example, trade name: PS-25) wait polyethylene terephthalate film etc., but be not limited to this of SHIN-ETSU HANTOTAI's film (strain) system etc.
The thickness of diaphragm 4 is preferably 1～100 μ m, and more preferably 5～50 μ m further are preferably 5～30 μ m.When this thickness during less than 1 μ m, when having lamination, the tendency that diaphragm breaks, and when it surpasses 100 μ m, have less economical tendency.
In addition, photosensitive element 1 of the present invention can further have middle layers such as cushion, adhesive linkage, light absorbing zone, barrier layer for gases etc.In addition, the photosensitive element 1 of gained can be preserved with sheet, or preserves with the drum that is wound on the core.In addition, at this moment supporting film 1 preferably is wound on outermost.Consider from the viewpoint of protection end face, on the end face of the photosensitive element roller of preferred above-mentioned drum the end face dividing plate is set, and consider, damp proof end face dividing plate preferably is set from the viewpoint of anti-edge fusing.In addition, as bundling method, preferably coat and pack with the little black sheet material of moisture-penetrability.As above-mentioned volume core, for example, can enumerate polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin plastics such as (acrylonitrile-butadiene-styrene copolymers) etc.
Then, the formation method to corrosion-resisting pattern of the present invention describes.
The formation method of corrosion-resisting pattern of the present invention has at least: on circuit forms with substrate, and the range upon range of range upon range of operation that contains the photosensitive polymer combination layer of above-mentioned photosensitive polymer combination; The established part irradiation active ray of said photosensitive polymer combination layer is made the exposure process of exposure portion photocuring; And form the developing procedure of removing the photosensitive polymer combination of the part beyond the said exposure portion with substrate from circuit.In addition, " circuit form use substrate " is meant and has insulation course and the substrate of formed conductor layer on insulation course.In addition, circuit forms use substrate, can multiple stratification and in inside the formation circuit, also can have the minor diameter through hole.
Form with the laminating method on the substrate at circuit as photosensitive polymer combination layer in the range upon range of operation, can enumerate following method.At first, diaphragm is slowly peeled off from the photosensitive polymer combination layer, meanwhile, the surface portion driving fit of the photosensitive polymer combination layer that slowly exposes is formed on the surface with the formation circuit of substrate at circuit.Then,, form with on the substrate, carry out range upon range of thus Yi Bian the photosensitive polymer combination lamination is connected on circuit Yi Bian heat the photosensitive polymer combination layer.Should operate, consider, preferably under reduced pressure carry out range upon range of from the viewpoint of adaptation and tracking property.Photosensitive element range upon range of, preferably 70～130 ℃ down heating photosensitive polymer combination layers and/or circuit form and use substrate, and crimping pressure is preferably (1～10kgf/cm about 0.1～1.0MPa
2About), but be not limited to these conditions.In addition, as long as, then need not in advance circuit to be formed to carry out thermal pretreatment, but, also can carry out circuit and form thermal pretreatment with substrate in order further to improve stackability with substrate as stated at 70～130 ℃ of heating photosensitive polymer combination layers.
As the method that forms exposure portion in the exposure process, can enumerate negative film or positive mask pattern through being called as former figure, active ray is radiated at the method (mask exposure method) on the image.At this moment, when the supporting film that exists on the photosensitive polymer combination layer can see through active ray, can be through supporting film irradiation active ray, and when supporting film has light-proofness, remove supporting film after, on the photosensitive polymer combination layer, shine active ray.In addition, also can adopt through direct picture of laser or DLP (Digital LightProcessing) exposure method etc. and directly describe the method for exposure method with image shape irradiation active ray.
Light source as active ray; Can use known light source, for example the effective light source of emitted in ultraviolet line, visible light etc. of solid state laser, semiconductor lasers etc. such as gas lasers such as carbon arc lamp, mercury vapor arc lamp, high-pressure mercury-vapor lamp, xenon lamp, argon gas laser, YAG laser instrument.
As the method for removing the part beyond the exposure portion in the developing procedure, can enumerate, at first; When having supporting film on the photosensitive polymer combination layer, remove supporting film, then; Remove the part beyond the exposure portion through wet developing, dry process development etc., and the method for developing.Thus, form corrosion-resisting pattern.
For example; When wet developing; Using alkaline aqueous solution, water system developer solution, organic solvent is the developer solution corresponding to photosensitive polymer combination such as developer solution, and through for example, impregnation method, alr mode, spray pattern, shakes known methods such as dipping, brushing, blade coating and develops.In order to improve resolution, visualization way is suitably for the high-pressure fog mode most.In addition, as required can be also with two or more developing methods.
As developer solution, can be safe in utilization and stable, and the good alkaline aqueous solution of operability etc.As the alkali of above-mentioned alkaline aqueous solution, can use, for example the alkali hydroxides such as oxyhydroxide of lithium, sodium or potassium; Carbonic acid alkali such as the carbonate of lithium, sodium, potassium or ammonium or supercarbonate; Alkali metal phosphate such as potassium phosphate, sodium phosphate; Alkali metal pyrophosphate such as sodium pyrophosphate, potassium pyrophosphate; Borax etc.
In addition; As used above-mentioned alkaline aqueous solution in developing, be preferably the lean solution of 0.1～5 quality % sodium carbonate, the lean solution of 0.1～5 quality % sal tartari, the lean solution of 0.1～5 quality % NaOH, the lean solution of 0.1～5 quality % sodium tetraborate (borax) etc.In addition, the pH of this alkaline aqueous solution is preferably 9～11 scope, and the development property that its temperature can adapt sense photosensitive resin composition layer is adjusted.In addition, in alkaline aqueous solution, can also add surfactant, foam-breaking agent, be used to promote a small amount of organic solvent that develops etc.
As above-mentioned water system developer solution, can enumerate water or aqueous alkali and more than one the formed developer solution of organic solvent.Here, as the alkali of alkaline aqueous solution, except aforementioned substances; Can also enumerate; For example sodium metasilicate, tetramethyl ammonium hydroxide, monoethanolamine, ethylenediamine, Diethylenetriamine, 2-amino-2-hydroxymethyl-1, ammediol, 1,3-diamido-2-propyl alcohol, morpholine etc.The pH of developer solution, preferably as far as possible little in the scope that resist can fully develop, it is preferably pH8～12, more preferably pH9～10.
As above-mentioned organic solvent, can enumerate for example acetone, ethyl acetate, alkoxyethanol, ethanol, isopropyl alcohol, butanols, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether etc. with alkoxy of carbon number 1～4.They can use separately, or combination is used more than 2 kinds.The concentration of organic solvent is preferably 2～90 quality % usually, and its temperature can be adjusted according to development property.In addition, in aqueous developer solution, can also add surfactant, foam-breaking agent etc. on a small quantity.
In addition, be developer solution as independent with an organic solvent organic solvent, can enumerate, for example 1,1,1-trichloroethanes, N-Methyl pyrrolidone, N, dinethylformamide, cyclohexanone, methylisobutylketone, gamma-butyrolacton etc.In order to prevent to catch fire, these organic solvents are developer solution, preferably in the scope of 1～20 quality %, add water.
As the processing after developing, can carry out heating or 0.2～10J/cm about 60～250 ℃ as required
2About exposure, and further solidify corrosion-resisting pattern.
Then, the manufacturing approach to printed circuit board (PCB) of the present invention describes.
The manufacturing approach of printed circuit board (PCB) of the present invention is that circuit that formation method to the corrosion-resisting pattern through the invention described above is formed with corrosion-resisting pattern forms with substrate and carries out the method that etching or plating form conductive pattern.
Circuit forms etching or the plating with substrate, be with the corrosion-resisting pattern that forms as mask, and circuit formation carried out with the conductor layer of substrate etc.Etching solution when carrying out etching can be enumerated copper chloride solution, ferric chloride solution, alkaline etching liquid, hydrogen peroxide etching solution, wherein, considers from the viewpoint that etching factor is good, preferably uses ferric chloride solution.In addition; Coating method when carrying out plating; Can enumerate, for example scolding tin plating such as copper such as copper sulphate plating, cupric pyrophosphate plating plating, high homogeneous scolding tin plating, watt are bathed golden plating such as nickel plating, hard golden plating, soft golden plating such as (nickelous sulfate-nickel chloride) plating, nickel sulfamic acid etc.
After etching or plating end, for example can use, peel off corrosion-resisting pattern than the used stronger WS of alkaline aqueous solution alkalescence in developing.As this alkaline WS, can use for example 1～10 quality % sodium hydrate aqueous solution, 1～10 quality % potassium hydroxide aqueous solution etc.As peeling off mode, can enumerate for example impregnation method, spray pattern etc., can use impregnation method, spray pattern separately, also can be used in combination.Obtain printed circuit board (PCB) thus.
More than, preferred implementation of the present invention is described, but the present invention is not limited to above-mentioned embodiment.
Embodiment
Below, the preferred embodiments of the present invention are done more detailed explanation, but the present invention is not limited to these embodiment.
(synthesizing of binder polymer ((A) composition))
In the flask with stirring machine, reflux condenser, thermometer, tap funnel and nitrogen ingress pipe, adding the 450g mass ratio is 3: 2 the methyl cellosolve and the complex of toluene, stirs while be blown into nitrogen, is heated to 80 ℃.On the other hand; The solution that preparation 150g methacrylic acid, 25g methyl methacrylate, 125g benzyl methacrylate and 200g styrene mix with the 9.0g azoisobutyronitrile (below; Be called " solution a ") as comonomer; Use solution a to be splashed in 4 hours to be 3: 2 the complex of methyl cellosolve and toluene insulation 2 hours in 80 ℃ of stirrings then to pre-prepd mass ratio.Further, using the solution will be dissolved with the 1.2g azoisobutyronitrile in 10 minutes to splash into the 100g mass ratio is in 3: 2 the complex of methyl cellosolve and toluene.Solution while stirring after splashing into is incubated 3 hours at 80 ℃, is heated to 90 ℃ with 30 minutes then.After 2 hours, cooling obtains binder polymer (A-1) 90 ℃ of insulations.
The nonvolatile component (solid constituent) of binder polymer (A-1) is 47.8 quality %, and weight-average molecular weight is 30,000.In addition, weight-average molecular weight is through gel permeation chromatography, and uses the typical curve of polystyrene standard to convert and derive.The condition of GPC is as follows.
Pump: the L-6000 of Hitachi type ((strain) Hitachi makes, trade name)
Post: Gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R440 (totally 3) (more than, Hitachi changes into industry (post) manufacturing, trade name)
Eluent: tetrahydrofuran
Measure temperature: 40 ℃
Flow: 2.05mL/ minute
Detecting device: the L-3300 of Hitachi type RI ((post) Hitachi makes, trade name)
In addition, the identical method of synthetic method of use and above-mentioned binder polymer (A-1), the binder polymer (A-2)～(A-10) of synthetic composition as shown in table 1 below.
[table 1]
(preparation of photosensitive polymer combination)
Above-mentioned binder polymer (A-1)～(A-10) and following material are cooperated the solution of the photosensitive polymer combination of preparation embodiment 1～6 and comparative example 1～5 with the mass ratio shown in the table 2.
< optical polymerism compound ((B) composition) >
B-1:2, (Hitachi changes into industry (strain) manufacturing, trade name: FA-321M) to 2-two (4-(methacryloxy five ethoxys) phenyl) propane
B-2: by the compound of above-mentioned general formula (VII) expression, and R
12And R
13Be respectively methyl, m
3=6 (mean values), n
2+ n
3(Hitachi changes into industry (strain) manufacturing, trade name: FA-024M) to the vinyl compound of=12 (mean values)
(East Asia synthetic (strain) made trade name: M-114) to B-3:4-n-nonyl phenoxy group eight ethyleneoxy group acrylic ester
< Photoepolymerizationinitiater initiater ((C) composition) >
C-1:2,2 '-two (2-chlorphenyl)-4,4 ', 5, (Hampford society makes 5 '-tetraphenyl bisglyoxaline, trade name: BCIM)
< sensitizing coloring matter ((D) composition) >
D-1:9,10-dibutoxy anthracene (Kawasaki changes into industry (strain) manufacturing, and trade name: DBA shows wavelength [λ the n]=368nm, 388nm, the 410nm that greatly absorb)
< (E) developer (amines) >
E-1: LCV (hillside plot chemistry (strain) is made)
< dyestuff >
Peacock green (Osaka organic chemistry industry (strain) is made)
< solvent >
Acetone
Toluene
Methyl alcohol
[table 2]
(making of photosensitive element)
With the solution of each photosensitive polymer combination of gained, being uniformly coated on the thickness that forms supporting film is on the polyethylene terephthalate film of 16 μ m.Then, use the hot air convection formula dryer of 70 ℃ and 110 ℃ to carry out drying, forming dried thickness is the photosensitive polymer combination layer of 25 μ m.Then, protective film is stacked on the photosensitive polymer combination layer, obtains the photosensitive element of each embodiment 1～6 and comparative example 1～5 through the roller pressurization.
(making of test film)
Then; Use muller (three Kei (strain) manufacturing) to (Hitachi changes into industry (strain) manufacturing as the subsides copper-surfaced plywood that Copper Foil (thickness is 35mm) is layered in the glass epoxide material on two sides with the brush that is equivalent to #600; Trade name: grind on copper surface MLC-E-67); Washing makes its drying through airflow then, obtains copper-surfaced plywood (substrate).Then, the copper-surfaced plywood is heated to 80 ℃ after, on one side on the copper-surfaced plywood, remove the diaphragm of above-mentioned each photosensitive element, on one side with each photosensitive polymer combination layer driving fit on the surface of copper-surfaced plywood, at 120 ℃, 4kgf/cm
2Pressure under carry out lamination (range upon range of), make test film.
(evaluating characteristics)
< photo sensitivity >
When the range upon range of copper-surfaced plywood that each photosensitive element arranged was cooled to 23 ℃, optical tool (phototool) driving fit that will have concentration range and be 0.00～2.00, concentration gradient is 0.05, the lattice chip size is 20mm * 187mm, each section 41 sections stage metraster being of a size of 3mm * 12mm was on supporting film.Use is with the bluish-violet color laser diode of the 405nm machine of directly the retouching DE-1AH (trade name) as the inferior machinery of Hitachi's dimension (Hitachi Via Mechanics) manufactured of light source, with 50mJ/cm
2Exposure through optical tool and supporting film to photosensitive polymer combination layer make public (describing).In addition, the mensuration of illumination is used ultraviolet illuminometer (USHIO motor (strain) manufacturing, the trade name of having used corresponding to the probe of 405nm: UIT-150) carry out.
Then, peel off supporting film, 1 quality % aqueous sodium carbonate was sprayed for 24 seconds, remove the unexposed portion of photosensitive polymer combination layer, and develop at 30 ℃.Then, through being determined at the hop count of the stage metraster of formed photocuring film on the copper-surfaced plywood, estimate the photo sensitivity of photosensitive polymer combination.The evaluation of photo sensitivity representes that with the hop count of stage metraster the hop count of this stage metraster is high more, representes that then photo sensitivity is high more.The gained result is shown in table 4.
< resolution >
Resolution uses that to have live width/interval width be that 6/6～30/30 (unit: Wiring pattern mm) makes public as the optical tool of resolution evaluation with negative film.Here, with regard to resolution, be with in the corrosion-resisting pattern that forms through the development after the exposure, (the unit: of the minimum value in the interval width between the live width in unexposed part of being removed fully μ m) as the index of resolution.The numerical value that resolution is estimated is more little good more.The gained result is shown in table 4.
< resist shape >
Resist shape after the development is used scanning electron microscope (trade name: the scanning electron microscope S-500A of Hitachi) observe.The resist shape is hoped near rectangle.
< fissility >
Fissility uses following method to estimate.At first, on the copper-surfaced plywood, form the photosensitive polymer combination layer of each embodiment and comparative example, the photocuring film of 40mm * 50mm size is made in make public each photosensitive polymer combination layer and development.Then, use 3% sodium hydrate aqueous solution to peel off.The evaluation of fissility is peeled off time when finishing as splitting time with the photocuring film from the copper-surfaced plywood.In addition, peel off the size of the stripping film after the end through visualization.The size index of the condition of strip step and stripping film is shown in table 3.The gained result is shown in table 4.
[table 3]
| Step etc. | Condition etc. |
| Exposure | Exposure: 60mJ/cm 2, size: 40mm * 50mm |
| Develop | Developer solution: 1%Na 2CO 3, the liquid temperature: 30 ℃, atomizing |
| Peel off | Stripper: 3%NaOH, the liquid temperature: 50 ℃, dipping stirs |
| The size of stripping film | L: sheet, M:30～40mm is below S:30mm is square |
Table 4
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|
|
Embodiment 5 | Embodiment 6 | Comparative example 1 | Comparative example 2 | Comparative example 3 | Comparative example 4 | Comparative example 5 | |
| Photo sensitivity * | 11 | 11 | 11 | 11 | 11 | 11 | 11 | 11 | 11 | 11 | 11 |
| Resolution (μ m) | 10 | 10 | 10 | 10 | 10 | 10 | 12 | 15 | 10 | 10 | 12 |
| Splitting time (s) | 80 | 95 | 68 | 82 | 90 | 50 | 65 | 45 | 220 | 100 | 75 |
| The size of stripping film | S | S | S | S | S | S | S | S | L | M | S |
| The resist shape | Rectangle | Rectangle | Rectangle | Rectangle | Rectangle | Rectangle | Rectangle | Rectangle | Rectangle | Rectangle | Rectangle |
* exposure is 50mJ/cm
2The stage hop count
< evaluation result >
As shown in table 4, each embodiment 1～6, its resolution is the high resolving power of 10 μ m, and splitting time is suitably short, in addition, the stripping film size is also little, and has obtained the equilibrium of resolution and fissility.On the other hand, in comparative example 1,2,5, though fissility is good, resolution is low.In addition, in comparative example 3,4, though be high resolving power, splitting time is long, and the stripping film size is big.As stated, confirmed the effect of photosensitive polymer combination of the present invention.
Industrial applicibility
According to the present invention, a kind of photosensitive polymer combination, photosensitive element, the formation method of corrosion-resisting pattern and manufacturing approach of printed circuit board (PCB) with abundant raising resolution and resist peel property effect can be provided.
Claims (8)
1. photosensitive polymer combination, it contains:
(A) having divalent group that divalent group that divalent group and the formula (III) of divalent group and formula (II) expression of formula (I) expression represent and formula (IV) represent and dispersion degree is 1.0～2.0 binder polymer;
(B) optical polymerism compound; And
(C) Photoepolymerizationinitiater initiater,
[changing 1]
[changing 2]
[changing 3]
[changing 4]
In formula (I), formula (II), formula (III) and the formula (IV), R
1, R
3, R
5And R
6Represent hydrogen atom or methyl, R respectively independently
2And R
4Represent the alkyl of carbon number 1～3, alkoxy, hydroxyl or the halogen atom of carbon number 1～3 respectively independently, R
7The alkyl of expression carbon number 1～6, m or n represent 0～5 integer respectively independently, m or n are 2～5 o'clock, a plurality of R
2Or R
4Each other can be identical or different.
2. photosensitive polymer combination according to claim 1; Wherein, Said (A) binder polymer; With respect to its total amount 100 mass parts, have divalent group, the said general formula of 10～60 mass parts (II) expression of the said general formula of 10～60 mass parts (I) expression divalent group, the divalent group of the said general formula of 20～50 mass parts (III) expression, 1 mass parts is above and less than the divalent group of said general formula (IV) expression of 15 mass parts.
3. photosensitive polymer combination according to claim 1 and 2, wherein, said (C) Photoepolymerizationinitiater initiater contains six aryl united imidazoles.
4. photosensitive polymer combination according to claim 1 and 2 wherein, further contains (D) sensitizing coloring matter.
5. photosensitive polymer combination according to claim 1 and 2 wherein, further contains (E) amine compound.
6. photosensitive element, it has supporting film and the photosensitive polymer combination layer of each the described photosensitive polymer combination that contains claim 1～5 that on this supporting film, forms.
7. the formation method of a corrosion-resisting pattern, it has: on circuit forms with substrate, the range upon range of operation of the photosensitive polymer combination layer of range upon range of each the described photosensitive polymer combination that contains claim 1～5; The established part irradiation active ray of said photosensitive polymer combination layer is made the exposure process of exposure portion photocuring; And form the developing procedure of removing the part beyond the said exposure portion of said photosensitive polymer combination layer with substrate from the circuit of range upon range of said photosensitive polymer combination layer.
8. the manufacturing approach of a printed circuit board (PCB), it has: the circuit that the formation method through the described corrosion-resisting pattern of claim 7 is formed with corrosion-resisting pattern forms with substrate and carries out the operation that etching or plating form conductive pattern.
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| JP352734/2006 | 2006-12-27 | ||
| PCT/JP2007/072622 WO2008078483A1 (en) | 2006-12-27 | 2007-11-22 | Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board |
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| CN201110391729.2A Division CN102393605B (en) | 2006-12-27 | 2007-11-22 | Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board |
| CN201110253925.3A Division CN102385253B (en) | 2006-12-27 | 2007-11-22 | Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board |
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| CN201110391729.2A Active CN102393605B (en) | 2006-12-27 | 2007-11-22 | Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board |
| CN2007800481739A Active CN101568883B (en) | 2006-12-27 | 2007-11-22 | Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board |
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| CN201110391729.2A Active CN102393605B (en) | 2006-12-27 | 2007-11-22 | Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board |
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| WO2008078483A1 (en) * | 2006-12-27 | 2008-07-03 | Hitachi Chemical Company, Ltd. | Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board |
| JP5327310B2 (en) * | 2009-02-26 | 2013-10-30 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern forming method, and printed wiring board manufacturing method |
| JP4849197B1 (en) * | 2010-07-30 | 2012-01-11 | 日立化成工業株式会社 | Photosensitive resin composition, photosensitive element using the same, resist pattern manufacturing method, lead frame manufacturing method, printed wiring board, and printed wiring board manufacturing method |
| US20130298398A1 (en) * | 2010-11-17 | 2013-11-14 | Masahiro Miyasaka | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring 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 |
| JP5853588B2 (en) * | 2011-10-26 | 2016-02-09 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method |
| CN103076717A (en) * | 2011-10-26 | 2013-05-01 | 日立化成工业株式会社 | Photosensitive resin composition, photosensitive component, forming method of corrosion-resistant pattern and manufacturing method of printed wiring board |
| CN103076719B (en) * | 2011-10-26 | 2019-08-09 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, method for forming resist pattern, and method for manufacturing printed wiring board |
| TWI521016B (en) | 2012-07-18 | 2016-02-11 | 財團法人工業技術研究院 | Method for etching a polyimide-containing layer |
| JP6318484B2 (en) * | 2013-07-09 | 2018-05-09 | 日立化成株式会社 | Photosensitive resin composition, photosensitive element, resist pattern forming method and printed wiring board manufacturing method |
| 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 |
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| 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 |
| MY186932A (en) * | 2015-09-11 | 2021-08-26 | Asahi Chemical Ind | Photosensitive resin composition |
| CN106909026B (en) * | 2017-03-31 | 2019-11-22 | 苏州福斯特光伏材料有限公司 | A kind of anti-corrosion agent composition that can directly describe exposure image and resist layer laminate |
| CN109856912A (en) * | 2019-03-11 | 2019-06-07 | 浙江福斯特新材料研究院有限公司 | A kind of high adhesion force photosensitive polymer combination |
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| WO2021192058A1 (en) * | 2020-03-24 | 2021-09-30 | 昭和電工マテリアルズ株式会社 | Photosensitive resin composition, photosensitive element, and method for producing wiring board |
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| KR101141909B1 (en) | 2012-05-03 |
| CN102393605B (en) | 2014-06-11 |
| TWI412887B (en) | 2013-10-21 |
| JPWO2008078483A1 (en) | 2010-04-15 |
| TWI644175B (en) | 2018-12-11 |
| KR20090084944A (en) | 2009-08-05 |
| CN101568883A (en) | 2009-10-28 |
| JP2014134815A (en) | 2014-07-24 |
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| KR20110112473A (en) | 2011-10-12 |
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| JP5679080B2 (en) | 2015-03-04 |
| KR101168828B1 (en) | 2012-07-25 |
| JP2012198573A (en) | 2012-10-18 |
| JP5029617B2 (en) | 2012-09-19 |
| TW201224656A (en) | 2012-06-16 |
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| WO2008078483A1 (en) | 2008-07-03 |
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