CN102393605B

CN102393605B - Photosensitive resin composition, photosensitive element, method for resist pattern formation, and method for manufacturing printed wiring board

Info

Publication number: CN102393605B
Application number: CN201110391729.2A
Authority: CN
Inventors: 宫坂昌宏; 村松有纪子; 南川华子
Original assignee: Hitachi Chemical Co Ltd
Current assignee: Lishennoco Co ltd
Priority date: 2006-12-27
Filing date: 2007-11-22
Publication date: 2014-06-11
Anticipated expiration: 2027-11-22
Also published as: KR101168828B1; CN102385253B; TWI644175B; JP5679080B2; KR101141909B1; JP2014134815A; TW200848929A; JP2012137768A; CN102393605A; TWI412887B; CN101568883A; CN102385253A; KR20090084944A; WO2008078483A1; KR20110112473A; CN101568883B; JP2012198573A; JP5029617B2; TW201224656A; JPWO2008078483A1

Abstract

This invention provides a photosensitive resin composition comprising (A) a binder polymer containing a divalent group represented by general formulae (I) to (IV), (B) a photopolymerizable compound, and (C) a photopolymerization initiator. Formulaes (I) (II) (III) (IV) are shown in the description, wherein R<1>, R<3>, R<5>, and R<6> each independently represent a hydrogen atom or a methyl group; R<2> and R<4> each independently represent an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an OH group, or a halogen atom; and R<7> represents an alkyl group having 1 to 6 carbon atoms.

Description

The formation method of photosensitive polymer combination, photosensitive element, corrosion-resisting pattern and the manufacture method of printed circuit board (PCB)

The application is to be on November 22nd, 2007 applying date of original application, application number is 200780048173.9, and denomination of invention is the divisional application of the Chinese patent application of " the formation method of photosensitive polymer combination, photosensitive element, corrosion-resisting pattern and the manufacture method of printed circuit board (PCB) ".

Technical field

The present invention relates to the formation method of photosensitive polymer combination, photosensitive element, corrosion-resisting pattern and the manufacture method of printed circuit board (PCB).

Background technology

In the manufacture field of printed circuit board (PCB); as the erosion resistant for etching or plating etc.; be widely used photosensitive element (duplexer); described photosensitive element has following structure: supporting after the layer (hereinafter referred to as " photosensitive polymer combination layer ") that forms photosensitive polymer combination or contain this photosensitive polymer combination on film the structure of configuration protection film on photosensitive polymer combination layer.

In the past, use above-mentioned photosensitive element, for example, manufactured printed circuit board (PCB) according to following order., first, form the photosensitive polymer combination layer with stacked photosensitive element on substrate at circuit such as copper facing thin layer laminations.Now, (following with the face of support film that is contacted with photosensitive polymer combination layer, being called " below " of photosensitive polymer combination layer) face of opposition side is (following, be called " above " of photosensitive polymer combination layer), be sealed at formation circuit and form the face with the circuit of substrate.Therefore, on photosensitive polymer combination layer when configuration protection film, peel off diaphragm while carry out this stacked operation.In addition, carry out stacked (normal pressure layered manner) by the circuit formation substrate that the heating of photosensitive polymer combination layer is crimped on to bottom.

Then, by mask etc., photosensitive polymer combination layer is carried out to pattern exposure.Now, the arbitrary time before exposure or after exposure is peeled off support film.,, dissolve or disperse to remove the unexposed portion of photosensitive polymer combination layer by developer solution thereafter.Then, implement etch processes or plating and form pattern, finally peel off and remove cured portion.

So-called etch processes here, is to remove after the circuit formation use metal covering of substrate of the curing resist coating that is not developed rear formation by etching, peels off the method for solidifying resist.On the other hand, so-called plating, be to be undertaken after the plating of copper and scolder etc. by the circuit formation metal covering of substrate to the curing resist coating that is not developed rear formation, remove and solidify resist and the metal covering by this resist coating is carried out to etching method.

As the gimmick of above-mentioned pattern exposure, in the past, utilized the method that uses mercury vapor lamp to expose by photomask as light source.In addition, proposed to be called in recent years the scheme of DLP (digit optical processing) as new exposure technique, that is, that directly the numerical data of pattern is drawn at photosensitive polymer combination layer directly draws exposure method.This directly draws exposure method compared with exposure method by photomask, and position quality of fit is good and can obtain good pattern, therefore importing for high-density packages substrate manufacture.

In order to improve productive capacity, in pattern exposure, the time shutter must be shortened as far as possible.Above-mentioned directly drawing in exposure method, if the composition of the sensitivity of the photosensitive polymer combination same degree using in use and the in the past exposure method by photomask needs the more time shutter conventionally.Therefore, must improve the illumination of exposure device side or the sensitivity of photosensitive polymer combination.

In addition,, except above-mentioned sensitivity, the peel property of resolution and resist is also excellent, for photosensitive polymer combination, is also very important.If photosensitive polymer combination can provide the corrosion-resisting pattern of excellent in resolution, can fully reduce the short circuit between circuit or open circuit.In addition, if photosensitive polymer combination can form the resist of peel property excellence, shorten the splitting time of resist, thereby improve the formation efficiency of corrosion-resisting pattern, and, also reduced the size of resist stripping film, thereby the residue of peeling off of resist tails off, the yield rate that circuit forms improves.For this requirement, propose to use the photosensitive polymer combination (for example,, referring to patent documentation 1,2) of specific binder polymer, Photoepolymerizationinitiater initiater etc. and sensitivity, resolution and resist peel property excellence.

Patent documentation 1: TOHKEMY 2006-234995 communique

Patent documentation 2: TOHKEMY 2005-122123 communique

Summary of the invention

The problem that invention will solve

But, the photosensitive polymer combination that above-mentioned

patent documentation

1 and 2 is recorded, 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 manufacture method of printed circuit board (PCB) with abundant raising resolution and resist peel property effect.

The method of dealing with problems

The inventor etc., in order to address the above problem, are conceived to binder polymer, have carried out active research.Found that, by using the binder polymer of ad hoc structure, can obtain having the photosensitive polymer combination of abundant raising resolution and resist peel property effect, complete thus the present invention.

That is to say, the present invention is a kind of photosensitive polymer combination, and it contains:

(A) there is the divalent group of following general formula (I) expression and the divalent group of the divalent group of following general formula (II) expression and following general formula (III) expression and the binder polymer of the divalent group that following general formula (IV) represents;

(B) optical polymerism compound; And

(C) Photoepolymerizationinitiater initiater,

Herein, in formula (I), formula (II), formula (III) and formula (IV), R ¹, R ³, R ⁵and R ⁶represent independently respectively hydrogen atom or methyl, R ²and R ⁴represent independently respectively the alkyl of carbon number 1～3, alkoxy, hydroxyl or the halogen atom of carbon number 1～3, R ⁷the alkyl that represents carbon number 1～6, m or n represent respectively 0～5 integer independently, m or n are 2～5 o'clock, multiple R ²or R ⁴mutually can be identical or different.

Present inventor thinks, photosensitive polymer combination of the present invention, and the binder polymer of this ad hoc structure of (A) composition above-mentioned by 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 by containing (A)～(C) composition, thus there is excellent sensitivity.

In addition, photosensitive polymer combination of the present invention, wherein (A) binder polymer, with respect to its total amount 100 mass parts, there is divalent group that 10～60 mass parts general formulas (I) represent, divalent group that 10～60 mass parts general formulas (II) represent, divalent group, 1 mass parts that 20～50 mass parts general formulas (III) represent above and be less than the divalent group that the general formula (IV) of 15 mass parts represents.Thus, 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, in the time using the light in specific wavelength coverage with peak to expose, can near this specific wavelength coverage, keep absorption 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 forms on this supporting film.By this supporting film, owing to thering is the photosensitive polymer combination layer that contains above-mentioned photosensitive polymer combination, even therefore forming when corrosion-resisting pattern by directly describing exposure method, also can carry out with enough resolution.In addition, also has the effect that fully improves resist peel property.

In addition, the present invention is a kind of formation method of corrosion-resisting pattern, and it has: form with on substrate the stacked operation of the stacked photosensitive polymer combination layer that contains above-mentioned photosensitive polymer combination at circuit; The established part irradiation active ray of described photosensitive polymer combination layer is made to the exposure process of exposure portion photocuring; And form the developing procedure of removing the part beyond the described exposure portion of described photosensitive polymer combination layer with substrate from the circuit of stacked described photosensitive polymer combination layer.According to the formation method of this corrosion-resisting pattern, the photosensitive polymer combination layer that contains above-mentioned photosensitive polymer combination due to use has formed corrosion-resisting pattern, therefore, though by the time shutter short directly describe exposure method, also can form the corrosion-resisting pattern with enough resolution.In addition, also has the effect that fully improves resist peel property.

In addition, the present invention is a kind of manufacture method of printed circuit board (PCB), and it has: the circuit that the formation method of the corrosion-resisting pattern by above-mentioned is formed with to corrosion-resisting pattern forms the operation of carrying out etching or plating and form conductive pattern with substrate.According to the manufacture method of this printed circuit board (PCB), owing to having used the circuit formation substrate that is formed with corrosion-resisting pattern by the formation method of above-mentioned corrosion-resisting pattern, therefore, can manufacture and can form highdensity circuit, and abundant inhibition is simultaneously opened circuit or the printed board circuit plate of short circuit.

Invention effect

According to the present invention, can provide a kind of photosensitive polymer combination, photosensitive element, the formation method of corrosion-resisting pattern and manufacture method of printed circuit board (PCB) with abundant raising resolution and resist peel property effect.

The simple declaration of accompanying drawing

[Fig. 1] is the pattern sectional view that represents a preferred implementation of photosensitive element of the present invention.

The explanation of symbol

1... the best mode that photosensitive element, 2... supporting film, 3... photosensitive polymer combination layer, 4... diaphragm carry out an invention

Below, the preferred embodiment of the present invention is elaborated.In addition; in the present invention; (methyl) acrylic acid represents acrylic or methacrylic acid, and (methyl) acrylate represents acrylate or the methacrylate corresponding with it, and (methyl) acryloyl group represents acryloyl group or methacryl.

Photosensitive polymer combination of the present invention, it contains (A) and has the divalent group (below also referred to as " structural unit ") of above-mentioned general formula (I) expression and the divalent group of the divalent group of above-mentioned general formula (II) expression and above-mentioned general formula (III) expression and the binder polymer of the divalent group that above-mentioned general formula (IV) represents; (B) optical polymerism compound; And (C) Photoepolymerizationinitiater initiater.

First, to describing as the binder polymer of (A) composition.

(A) binder polymer, in above-mentioned general formula (I), R ¹represent hydrogen atom or methyl, R ²represent the alkyl of carbon number 1～3, alkoxy, hydroxyl or the halogen atom of carbon number 1～3, m represents 0～5 integer.As the polymerizable monomer of structural unit that gives general formula (I) and represent, can enumerate styrene or styrene derivative.In addition, in the present invention, " styrene derivative " refers to that the hydrogen atom in styrene is substituted the material that base organic group or halogen atoms etc. such as () alkyl replaces.As styrene derivative, for example, can enumerate α-methyl styrene etc.

In addition, in above-mentioned general formula (II), R ³represent hydrogen atom or methyl, R ⁴represent the alkyl of carbon number 1～3, alkoxy, hydroxyl or the halogen atom of carbon number 1～3, m represents 0～5 integer.As the polymerizable monomer of structural unit that gives general formula (II) and represent, 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 ⁵represent hydrogen atom or methyl.As the polymerizable monomer of structural unit that gives general formula (III) and represent, can enumerate (methyl) acrylic acid.

In addition, in above-mentioned general formula (IV), R ⁶represent independently respectively hydrogen atom or methyl, R ⁷the alkyl that represents carbon number 1～6, m or n represent respectively 0～5 integer independently.From shortening splitting time and can put forward high-resolution viewpoint and consider, 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 structural unit that gives general formula (IV) and represent, can enumerate (methyl) alkyl acrylate.

As (methyl) alkyl acrylate, for example, can enumerate the compound of following general formula (V) expression etc.

CH ₂＝C(R ⁸)-COOR ⁹(Ⅴ)

Herein, in above-mentioned general formula (V), R ⁸represent hydrogen atom or methyl, R ⁹represent the alkyl of carbon number 1～6.In addition, as R ⁹the alkyl of represented carbon number 1～6, for example, can enumerate methyl, ethyl, propyl group, butyl, amyl group, hexyl and their constitutional isomer.The polymerizable monomer representing as above-mentioned general formula (V), 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 two or more is used in combination.

In the binder polymer as (A) composition, containing of the structural unit that above-mentioned general formula (I) represents is proportional, with respect to (A) composition total amount 100 mass parts, be preferably 10～60 mass parts, more preferably 15～55 mass parts, more preferably 20～50 mass parts, and be particularly preferably 20～40 mass parts.Adaptation and the resist peel property that thus, can make the photosensitive polymer combination layer that contains photosensitive polymer combination form use substrate for circuit are all good.

In addition, containing of the structural unit that above-mentioned general formula (II) represents is proportional, with respect to (A) composition total amount 100 mass parts, be preferably 10～60 mass parts, more preferably 15～55 mass parts, more preferably 20～50 mass parts, are particularly preferably 25～45 mass parts.Adaptation and the resist peel property that thus, can make the photosensitive polymer combination layer that contains photosensitive polymer combination form use substrate for circuit are all good.

In addition, containing of the structural unit that above-mentioned general formula (III) represents is proportional, with respect to (A) composition total amount 100 mass parts, be preferably 10～60 mass parts, more preferably 15～50 mass parts, more preferably 20～40 mass parts, and be particularly preferably 25～35 mass parts.Thus, can make resist peel property and developability all good.

In addition, containing of the structural unit that above-mentioned general formula (IV) represents is proportional, with respect to (A) composition total amount 100 mass parts, be preferably 1 mass parts above and be less than 15 mass parts, more preferably 2～13 mass parts, more preferably 4～12 mass parts, and be particularly preferably 5～10 mass parts.Adaptation and the resist peel property that thus, can make the photosensitive polymer combination layer that contains photosensitive polymer combination form use substrate for circuit are all good.

In addition, in the binder polymer as (A) composition, proportional when containing of the structural unit of above-mentioned general formula (I) expression and the structural unit of above-mentioned general formula (II) expression, while being less than 10 mass parts separately, have the tendency of resolution variation, in the time that it exceedes 60 mass parts separately, have stripping film and become large, the tendency that splitting time is elongated.In addition the structural unit representing when above-mentioned general formula (III), while being less than 10 mass parts, have alkali dissolubility variation containing proportional, stripping film becomes large simultaneously, the tendency that splitting time is elongated, in the time that it exceedes 60 mass parts, has the tendency of resolution variation.In addition, the structural unit representing when above-mentioned general formula (IV) while being less than 1 mass parts, have the tendency that fissility declines containing proportional, when it is 15 mass parts when above, have the tendency of resolution decline.

In the time using this binder polymer to prepare photosensitive polymer combination, can use separately a kind of binder polymer, also binder polymer combination in any of more than two kinds can be used.Binder polymer while being used in combination as two or more, for example, can enumerate (containing different repetitives as constituent) the of more than two kinds binder polymer being formed by different copolymer component, binder polymer of more than two kinds, the binder polymer of more than two kinds of different dispersion degree etc. of different weight-average molecular weight.In addition, can also use the polymkeric substance with multimode molecular weight distribution of recording in Japanese kokai publication hei 11-327137 communique.

(A) weight-average molecular weight of binder polymer (Mw) and number-average molecular weight (Mn), can measure by gel permeation chromatography (GPC) (converting by the typical curve that uses polystyrene standard).According to this determination method, the Mw of binder polymer is preferably 5000～150000, and more preferably 10000～100000, and be particularly preferably 20000～50000.In the time that Mw is less than 5000, have the tendency that resistance to development fluidity declines, in the time that it exceedes 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 exceedes 3.0, have the tendency that adaptation and resolution decline.

In addition, (A) binder polymer, for example, can be used together styrene resin, epikote, amide-type resin, acid amides epikote, alkyd based resin, phenolic resin etc.In addition, these resins can use separately, or two or more is used in combination.

Binder polymer of the present invention, for example, can make polymerizable monomer carry out free radical polymerization by conventional method and manufacture.

Above-mentioned (A) binder polymer, also can contain above-mentioned general formula (I)～(IV) represent structural unit beyond structural unit.Above-mentioned (A) binder polymer, most preferably only there is the structural unit that above-mentioned general formula (I)～(IV) represents, but also can be not damaging in the degree of the object of the invention, contain the total amount with respect to (A) composition, be 1～10 about mass parts except the structural unit them.At this moment,, as the polymerizable monomer of the structural unit the structural unit representing except above-mentioned general formula (I)～(IV), for example, can enumerate (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, the acrylamides such as diacetone acrylamide, vinyl cyanide, the ester class of the vinyl alcohol such as vinyl-n-butyl ether, (methyl) tetrahydrofurfuryl acrylate, (methyl) acrylic acid dimethylamino ethyl ester, (methyl) acrylic acid diethylamino ethyl ester, (methyl) glycidyl acrylate, 2,2,2-trifluoroethyl (methyl) acrylate, 2,2,3,3-tetrafluoro propyl group (methyl) acrylate, (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, the maleic acid monoesters such as maleic acid list isopropyl ester, fumaric acid, cinnamic acid, alpha-cyano cinnamic acid, itaconic acid, crotonic acid, propiolic acid etc.These monomers can use separately, or two or more is used in combination.

(A) binder polymer in the present invention, the developability viewpoint while carrying out alkali development from use aqueous slkali is considered, is preferably formed by the one kind or two or more polymkeric substance with carboxyl.This (A) binder polymer, for example, can make by conventional method carrying out free radical polymerization containing carboxyl polymerizable monomer and polymerizable monomer in addition and manufacture beyond (methyl) acrylic acid.

(A) acid number of binder polymer, is preferably 80～250mgKOH/g, more preferably 100～220mgKOH/g, and be particularly preferably 150～210mgKOH/g.In the time that this acid number is less than 80mgKOH/g, have the elongated tendency of development time, in the time that it exceedes 250mgKOH/g, have the tendency of the resistance to development fluidity decline of the resist of photocuring.In addition,, in the time carrying out solvent develop as developing procedure, preferably a small amount of preparation has the polymerizable monomer of carboxyl.

In addition, (A) binder polymer can also contain and have photosensitive characteristic group at its molecule as required.

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 particularly preferably 40～60 mass parts.In the time that this use level is less than 30 mass parts, have the tendency that cannot obtain excellent in shape, in the time that it exceedes 70 mass parts, have the tendency that cannot obtain good sensitivity and resolution.As the binder polymer of (A) composition, can use separately a kind, or two or more is used in combination.

Then, to describing as the optical polymerism compound of (B) composition.

As the optical polymerism compound of (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 react with the compound that contains glycidyl and compound, in molecule, there is the ammonia ester carbamate monomers such as (methyl) acrylate compounds of ammonia ester bond, Nonylphenoxy gathers ethyleneoxy group acrylate (also referred to as " Nonylphenoxy polyethylene glycol acrylate "), O-phthalic acid compounds, (methyl) alkyl acrylate etc.These compounds can use separately, or two or more is used in combination.

As the above-mentioned α that makes, beta-unsaturated carboxylic acid and polyol reaction and compound, for example, can enumerate ethylidene number and be 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, 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 etc.These compounds can use separately, or two or more is used in combination.Herein, " EO " representative ring oxidative ethane, the compound of EO modification represents the material of the block structure with ethylene oxide group.In addition, " PO " representative ring Ethylene Oxide, the compound of PO modification represents the material of the block structure with propylene oxide group.

As above-mentioned bisphenol-A class two (methyl) acrylate compounds, for example, can enumerate 2,2-bis-(4-((methyl) acryloxy polyethoxy) phenyl) propane, 2,2-bis-(4-((methyl) acryloxy gathers propoxyl group) phenyl) propane, 2,2-bis-(4-((methyl) acryloxy gathers butoxy) phenyl) propane, 2,2-bis-(4-((methyl) acryloxy polyethoxy gathers propoxyl group) phenyl) propane etc.As above-mentioned 2, 2-bis-(4-((methyl) acryloxy polyethoxy) phenyl) propane, for example, can enumerate 2, 2-bis-(4-((methyl) acryloxy diethoxy) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy triethoxy) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy tetraethoxy) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy five ethoxys) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy six ethoxys) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy seven ethoxys) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy eight ethoxys) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy nine ethoxys) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy ten ethoxys) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy 11 ethoxys) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy ten diethoxies) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy ten triethoxies) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy ten tetraethoxies) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy 15 ethoxys) phenyl) propane, 2, 2-bis-(4-((methyl) acryloxy 16 ethoxys) phenyl) propane etc.

2,2-bis-(4-(methacryloxy five ethoxys) phenyl) propane, (Xin Zhong village chemical industry (strain) is manufactured to can be used as BPE-500, trade name) or FA-321M (Hitachi change into industry (strain) manufacture, trade name) commercially obtain, 2,2-bis-(4-(methacryloxy 15 ethoxys) phenyl) propane, can be used as BPE-1300 (Xin Zhong village chemical industry (strain) is manufactured, trade name) commercially obtains.2,2-bis-(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 two or more is used in combination.

As (methyl) acrylate compounds in molecule with ammonia ester bond, for example, can be set forth in (methyl) acrylic monomers and the diisocyanate cpd (isophorone diisocyanate on β position with OH base, 2, 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) acrylate, EO, PO modification ammonia ester two (methyl) acrylate etc.As EO modification ammonia ester two (methyl) acrylate, for example, can enumerate UA-11 (Xin Zhong village chemical industry (strain) is manufactured, trade name).In addition,, as above-mentioned EO, PO modification ammonia ester two (methyl) acrylate, for example, can enumerate UA-13 (Xin Zhong village chemical industry (strain) is manufactured, trade name).These compounds can use separately, or two or more is used in combination.

As the poly-ethyleneoxy group acrylate of Nonylphenoxy, for example, can enumerate 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.As Nonylphenoxy eight ethyleneoxy group acrylate, for example, can enumerate M-114 (East Asia synthetic (strain) manufactures, trade name).These compounds can use separately, or two or more is used in combination.

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 two or more is used in combination.

Further, (B) of the present invention composition, considers from the flexible viewpoint that can mention cured film, preferably contains and in molecule, has the two poly alkylene glycol two (methyl) acrylate of glycol chain and propylene glycol chain.Should (methyl) acrylate, as long as have glycol chain and propylene glycol chain (positive propylene glycol chain or Isopropanediol chain), the two,, as intramolecular alkylene glycol chain, is just not particularly limited.In addition, should (methyl) acrylate, can also further contain positive butylene glycol chain, isobutyl glycol chains, positive pentanediol chain, hexanediol chain, their alkylene glycol chain of carbon number 4～6 left and right such as constitutional isomer.

When above-mentioned glycol chain and propylene glycol chain are while being multiple, multiple glycol chains and propylene glycol chain can respectively be done for oneself and exist with block continuously, also can randomly exist.In addition, in above-mentioned Isopropanediol chain, propylidene can be that secondary carbon is combined with oxygen atom, can be also that primary carbon is combined with oxygen atom.

In these (B) compositions, there is the ethene unsaturated link that at least one can polymerization, and in molecule, there is the two poly alkylene glycol two (methyl) acrylate of glycol chain and propylene glycol chain, for example, can enumerate following general formula (VI):

The compound, the following general formula (VII) that represent:

The compound, the following general formula (VIII) that represent:

The compound representing etc., herein, in formula (VI), formula (VII) and formula (VIII), R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴and R ¹⁵the alkyl that represents independently respectively hydrogen atom or carbon number 1～3, EO represents glycol chain, PO represents propylene glycol chain, m ¹～m ⁴and n ¹～n ⁴represent independently respectively 1～30 integer.These compounds can use separately, or two or more is used in combination.

As the alkyl of carbon number 1～3 in above-mentioned general formula (VI)～(VIII), for example, can enumerate methyl, ethyl, n-pro-pyl, isopropyl.

In addition sum (the m of the repeat number of glycol chain in 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 particularly preferably 5～8 integer.If this repeat number exceedes 30, have the tendency of sheltering (tent) reliability and the deterioration of resist shape.

In addition sum (the n of the repeat number of propylene glycol chain in 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 particularly preferably 10～14 integer.If this repeat number exceedes 30, have resolution and worsen, and produce the tendency of mud.

The object lesson of the compound representing as above-mentioned general formula (VI), for example, can enumerate R ¹⁰=R ¹¹=methyl, m ¹+ m ²=4 (mean values), n ¹the vinyl compound (Hitachi changes into industry (strain) manufacture, trade name: FA-023M) of=12 (mean values) etc.In addition, the object lesson of the compound representing as above-mentioned general formula (VII), for example, can enumerate R ¹²=R ¹³=methyl, m ³=6 (mean values), n ²+ n ³the vinyl compound (Hitachi changes into industry (strain) manufacture, trade name: FA-024M) of=12 (mean values) etc.Further, the object lesson of the compound representing as above-mentioned general formula (VIII), for example, can enumerate R ¹⁴=R ¹⁵=hydrogen atom, m ⁴=1 (mean value), n ⁴the vinyl compound (Xin Zhong village chemical industry (strain) is manufactured, sample name: NK ester HEMA-9P) of=9 (mean values) etc.These compounds can use separately, or two or more is used in combination.

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 particularly preferably 40～60 mass parts.In the time that this use level is less than 30 mass parts, has the tendency that cannot obtain good sensitivity and resolution, and in the time that it exceedes 70 mass parts, have the tendency that cannot obtain excellent in shape.

As the optical polymerism compound of (B) composition, can use separately a kind, or two or more is used in combination.This optical polymerism compound, considers from the viewpoint that improves resistance to plating and adaptation, preferably contains (methyl) acrylate compounds in bisphenol-A class (methyl) acrylate compounds or molecule with ammonia ester bond.In addition, consider from the viewpoint that improves sensitivity and resolution, preferably contain bisphenol-A class (methyl) acrylate compounds.

In addition, as the optical polymerism compound of (B) composition, from reducing the size of resist stripping film, shortening the viewpoint of splitting time considers, preferably contain in molecule, have one can polymerization the optical polymerism unsaturated compound of ethene unsaturated link, more preferably by molecule, have one can polymerization the optical polymerism unsaturated compound of ethene unsaturated link and molecule in there are two above ethene unsaturated links that can polymerization optical polymerism unsaturated compound be used in combination.At this moment, for example, as in molecule, have one can polymerization the optical polymerism unsaturated compound of ethene unsaturated link, can enumerate poly-ethyleneoxy group (methyl) acrylate of phenoxy group, phenoxy group gathers ethyleneoxy group-polytrimethylene oxygen base (methyl) acrylate, Octylphenoxy six ethyleneoxy group (methyl) acrylate, Octylphenoxy seven ethyleneoxy group (methyl) acrylate, Octylphenoxy eight ethyleneoxy group (methyl) acrylate, Octylphenoxy nine ethyleneoxy group (methyl) acrylate, Octylphenoxy ten ethyleneoxy group (methyl) acrylate, Nonylphenoxy gathers ethyleneoxy group (methyl) acrylate, Nonylphenoxy gathers ethyleneoxy group-polytrimethylene oxygen base (methyl) acrylate, there is the phthalic acid derivatives of (methyl) acrylic etc.In addition, as the optical polymerism unsaturated compound in molecule with two above ethene unsaturated links that can polymerization, can enumerate 1, 6-hexanediol two (methyl) acrylate, 1, 4-cyclohexanediol two (methyl) acrylate, ethylidene number is 2～14 polyglycol two (methyl) acrylate, propylidene number is 2～14 polypropylene glycol two (methyl) acrylate, poly-ethylidene polytrimethylene glycol two (methyl) acrylate of above-mentioned general formula (VI)～(VIII), bisphenol-A class two (methyl) acrylate, in molecule, there is two (methyl) acrylate of ammonia ester bond, two (acryloxy ethyl) hydroxyethyl isocyanuric acid ester, bisphenol A diglycidyl ether two (methyl) acrylate, (methyl) acrylic acid addition product of O-phthalic acid glycidyl ester etc.

In addition, improve the viewpoint of resolution, splitting time and exposure tolerance considers from equilibrium, particularly preferably by a kind of molecule, have one can polymerization the optical polymerism unsaturated compound of ethene unsaturated link, and the optical polymerism unsaturated compound in 2 kinds of molecules with two above ethene unsaturated links that can polymerization is used in combination.At this moment, as in molecule, have one can polymerization the optical polymerism unsaturated compound of ethene unsaturated link, for example, can use phenoxy group to gather poly-ethyleneoxy group (methyl) acrylate of ethyleneoxy group (methyl) acrylate, Nonylphenoxy, there is any in the phthalic acid derivatives of (methyl) acrylic.In addition, as the optical polymerism unsaturated compound in molecule with two above ethene unsaturated links that can polymerization, for example, can be by least one compound being selected from poly-ethylidene polytrimethylene glycol two (methyl) acrylate, EO modification ammonia ester two (methyl) acrylate and EO, PO modification ammonia ester two (methyl) acrylate of above-mentioned general formula (VI)～(VIII), and bisphenol-A class two (methyl) acrylate compounds is used in combination.

Then, to describing as the Photoepolymerizationinitiater initiater of (C) composition.

As the Photoepolymerizationinitiater initiater of (C) composition, for example, can enumerate 4, 4 '-bis-(diethylamino) benzophenone, benzophenone, 2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-1-butanone, 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 benzil derivants such as benzil dimethyl acetal, 2-(Chloro-O-Phenyl)-4, 5-diphenyl-imidazole dipolymer, 2-(Chloro-O-Phenyl)-4, 5-bis-(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, 7-bis-(9, 9 '-acridinyl) acridine derivatives such as heptane etc.

In addition, above-mentioned 2,4, in 5-triarylimidazoles dipolymer, two 2,4, the substituting group of the aryl of 5-triarylimidazoles dipolymer can be identical and become symmetrical compound, also can be different and become asymmetrical compound.In addition, Photoepolymerizationinitiater initiater, considers from the viewpoint of adaptation and sensitivity, is preferably used as six aryl united imidazoles of 2,4,5-triarylimidazoles dipolymer.These Photoepolymerizationinitiater initiaters, can use separately, or two or more are used in combination.

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 particularly preferably 3.5～5 mass parts.In the time that this use level is less than 0.1 mass parts, have the tendency that is difficult to obtain good sensitivity or resolution, in the time that it exceedes 10 mass parts, have the tendency that is difficult to obtain desirable excellent in shape.As the Photoepolymerizationinitiater initiater of (C) composition, can use separately a kind, or two or more is used in combination.

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 in the present invention, be the material that can effectively utilize the absorbing wavelength of active ray used while exposure, the compound that preferably greatly absorbing wavelength is 370～420nm.In the present invention, by using this sensitizing coloring matter, for the exposure light of directly describing exposure method, can there is sufficiently high sensitivity.If the very big absorbing wavelength of sensitizing coloring matter is less than 370nm, even if have under gold-tinted environment the tendency that stability also declines.

As sensitizing coloring matter, for example, can enumerate pyrazolines, anthracene class, Coumarins, xanthene ketone,

azole, benzo

azole, thiazoles, benzothiazoles, triazole type, Stilbene class, triazines, thiophene-based, naphthalimide class etc.Sensitizing coloring matter, considers from the viewpoint that can improve resolution, adaptation and sensitivity, preferably contains 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 particularly preferably 0.1～2 mass parts.In the time that this use level is less than 0.01 mass parts, have the tendency that cannot obtain good sensitivity or resolution, in the time that it exceedes 10 mass parts, have the tendency that is difficult to the corrosion-resisting pattern that obtains desirable excellent in shape.As the sensitizing coloring matter of (D) composition, can use separately a kind, or two or more is used in combination.

As the amine compound of (E) composition, as long as can improving the sensitivity of photosensitive polymer combination and there is amino material in molecule, be just not particularly limited.As its object lesson, for example, can enumerate two [4-(dimethylamino) phenyl] methane, two [4-(diethylamino) phenyl] methane, leuco crystal violet 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, more preferably 0.05～5 mass parts, and be particularly preferably 0.1～2 mass parts.In the time that this use level is less than 0.01 mass parts, has the tendency that cannot obtain good sensitivity, and in the time that it exceedes 10 mass parts, have after film forming the tendency that (E) composition is easily separated out as foreign matter.As the amine compound of (E) composition, can use separately a kind, or two or more is used in combination.

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, contain respectively the optical polymerism compound (oxetane compound etc.) in the molecule about 0.01～20 mass parts with the ring-type ether of at least one cationically polymerizable, cationic polymerization initiators, the dyestuffs such as peacock green, tribromo-benzene sulfone, 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 etc.They can use separately, or two or more is used in combination.

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 of 30～60 quality % left and right.This solution can be as the coating fluid of the photosensitive polymer combination layer of formation photosensitive element.

In addition, above-mentioned coating fluid, except being used to form the photosensitive polymer combination layer of photosensitive element, for example, can also serve as aqueous resist-coating on the surface of sheet metal and after dry, and coating diaphragm uses.As the material of sheet metal, for example, 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 etc.

Then, photosensitive element of the present invention is described.Fig. 1 is the pattern sectional view that represents a preferred implementation of photosensitive element of the present invention.Photosensitive element 1 shown in Fig. 1, the photosensitive polymer combination layer 3 that contains above-mentioned photosensitive polymer combination forming by supporting film 2, on supporting film 2 and the diaphragm 4 being layered on photosensitive polymer combination layer 3 form.

Supporting film 2, can use, and such as polyethylene terephthalate, polypropylene, tygon, polyester etc. have the polymer film of thermotolerance and solvent resistance.As commercial goods, can enumerate, for example Oji Paper (strain) A Lufan processed (ア Le Off ア Application) MA-410, E-200C (more than, for trade name), the polypropylene screen of SHIN-ETSU HANTOTAI's film (strain) system etc., Supreme Being people's (strain) PS series processed (for example, trade name: PS-25) etc. polyethylene terephthalate film etc., but be not limited to this.

In addition, the thickness of supporting film 2 is preferably 1～100 μ m, more preferably 5～25 μ m.In the time that this thickness is less than 1 μ m, have peel off supporting film before development time, the crackly tendency of supporting film, and in the time that it exceedes 100 μ m, have the tendency that resolution declines.In addition, supporting film 2 can be also, and 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 photosensitive polymer combination layer is used.

Photosensitive polymer combination layer 3, preferably by above-mentioned photosensitive polymer combination is dissolved in above-mentioned solvent, after forming solid constituent and being the solution (coating fluid) of 30～60 about quality %, by this solution coat on supporting film 2 and dry and form.Coating, can pass through, and the known method that for example uses roll coater, comma coating machine, intaglio plate coating machine, Kohler coater, mould to be coated with machine, excellent painting machine etc. carries out.Dry, can carry out about 5～30 minutes at 70～150 ℃.In addition, the remaining organic solvent amount in photosensitive polymer combination, from prevent after the viewpoint of organic solvent diffusion operation consider, be preferably below 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.In the time that this thickness is less than 1 μ m, have the tendency that is difficult to coating industrial, and when it exceedes 100 μ m, have effect of the present invention and reduce, and the tendency of bounding force, resolution decline.

In addition, photosensitive polymer combination layer 3, the transmitance of the light that is 405nm with respect to wavelength is preferably 5～75%, and more preferably 7～60%, be particularly preferably 10～40%.In the time that this transmitance is less than 5%, has the tendency of adaptation variation, and in the time that it exceedes 75%, have the tendency of resolution variation.Above-mentioned transmitance, can measure by UV spectrometer, as above-mentioned UV spectrometer, can enumerate (strain) Hitachi 228A type processed W light beam spectrophotometer (trade name) etc.

Diaphragm 4, preferably the bounding force between photosensitive polymer combination layer 3 and diaphragm 4 is than the little film of bounding force between photosensitive polymer combination layer 3 and supporting film 2, and, be preferably the film of low flake.In addition, " flake " refer to by material is carried out heat fusing, mixing, extrude, biaxial stretch-formed, casting method etc. is while manufacturing film, the foreign matter of material, dissolved matter, oxidative degradation thing etc. do not enter the situation in film.

As diaphragm 4, can use such as polyethylene terephthalate, polypropylene, tygon, polyester etc. to there is the polymer film of thermotolerance and solvent resistance.As commercial goods, can enumerate, the all MA-410 of for example Oji Paper (strain) A Lu processed, E-200C (more than, for trade name), the polypropylene screen of SHIN-ETSU HANTOTAI's film (strain) system etc., Supreme Being people's (strain) PS series processed (for example, trade name: PS-25) etc. polyethylene terephthalate film etc., but be not limited to this.

The thickness of diaphragm 4 is preferably 1～100 μ m, more preferably 5～50 μ m, more preferably 5～30 μ m.In the time that this thickness is less than 1 μ m, while having lamination, the tendency that diaphragm breaks, and in the time that it exceedes 100 μ m, have less economical tendency.

In addition, photosensitive element 1 of the present invention, can further have the middle layers such as cushion, adhesive linkage, light absorbing zone, barrier layer for gases etc.In addition, the photosensitive element 1 of gained, can preserve with sheet, or preserves with the drum being wound on core.In addition, at this moment supporting film 1 is preferably 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, end face dividing plate is set, and consider from the viewpoint of resistance to edge fusing, damp proof end face dividing plate is preferably set.In addition,, as bundling method, be preferably coated to pack with the little black sheet material of moisture-penetrability.As above-mentioned volume core, for example, can enumerate the plastics such as polyvinyl resin, acrylic resin, polystyrene resin, Corvic, ABS resin (acrylonitrile-butadiene-styrene copolymer) etc.

Then, the formation method of corrosion-resisting pattern of the present invention is described.

The formation method of corrosion-resisting pattern of the present invention, at least has: form with on substrate the stacked operation of the stacked photosensitive polymer combination layer that contains above-mentioned photosensitive polymer combination at circuit; The established part irradiation active ray of described photosensitive polymer combination layer is made to the exposure process of exposure portion photocuring; And form from circuit the developing procedure of removing the photosensitive polymer combination of the part beyond described exposure portion with substrate.In addition, " circuit formation substrate " refers to the substrate of the conductor layer that has insulation course and form on insulation course.In addition, circuit formation substrate, can multiple stratification and form circuit in inside, also can have minor diameter through hole.

Form with the laminating method on substrate at circuit as photosensitive polymer combination layer in stacked operation, can enumerate following methods.First, diaphragm is slowly peeled off from photosensitive polymer combination layer, meanwhile, by closely sealed the surperficial part of the photosensitive polymer combination layer slowly the exposing surface that forms the formation circuit of using substrate at circuit.Then, heat photosensitive polymer combination layer on one side, photosensitive polymer combination lamination is connected on to circuit on one side and forms with on substrate, carry out thus stacked.Should operate, consider from the viewpoint of adaptation and traceability, preferably under reduced pressure carry out stacked.Photosensitive element stacked preferably heated photosensitive polymer combination layer and/or circuit formation substrate at 70～130 ℃, and crimping pressure is preferably 0.1～1.0MPa left and right (1～10kgf/cm ²left and right), but be not limited to these conditions.In addition,, as long as mentioned above at 70～130 ℃ of heating photosensitive polymer combination layers, without in advance circuit being formed and carries out thermal pretreatment with substrate, but in order further to improve stackability, also can carry out circuit and form the thermal pretreatment with substrate.

As the method that forms exposure portion in exposure process, can enumerate negative film or positive mask pattern by being called as former figure, active ray is radiated to the method (mask exposure method) on image.At this moment, in the time that the supporting film existing on photosensitive polymer combination layer can see through active ray, can irradiate active ray by supporting film, and in the time that supporting film has light-proofness, remove after supporting film, on photosensitive polymer combination layer, irradiate active ray.In addition, also can adopt by the direct picture of laser or DLP (Digital Light Processing) exposure method etc. and directly describe the method for exposure method with image shape irradiation active ray.

As the light source of active ray, can use known light source, solid state laser, the semiconductor lasers etc. such as gas laser, YAG laser instrument such as such as carbon arc lamp, mercury vapor arc lamp, high-pressure mercury-vapor lamp, xenon lamp, argon gas laser can effectively be launched the light source of ultraviolet ray, visible ray etc.

As the method for removing the part beyond exposure portion in developing procedure, can enumerate, first, in the time there is supporting film on photosensitive polymer combination layer, remove supporting film, then, remove the part beyond exposure portion by wet developing, dry process development etc., and the method for developing.Thus, form corrosion-resisting pattern.

For example, in the time of 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 by for example, the known methods such as impregnation method, alr mode, spray pattern, shake dipping, brushing, blade coating develop.In order to improve resolution, visualization way is suitably for high-pressure fog mode most.In addition, can be used together as required two or more developing methods.

As developer solution, can use safety stable, and the good alkaline aqueous solution of operability etc.As the alkali of above-mentioned alkaline aqueous solution, can use the alkali hydroxides such as the such as oxyhydroxide of lithium, sodium or potassium; The carbonic acid such as carbonate or the supercarbonate alkali of lithium, sodium, potassium or ammonium; The alkali metal phosphate such as potassium phosphate, sodium phosphate; The alkali metal pyrophosphate such as sodium pyrophosphate, potassium pyrophosphate; Borax etc.

In addition, as above-mentioned alkaline aqueous solution used in developing, be preferably the lean solution of 0.1～5 quality % sodium carbonate, the lean solution of 0.1～5 quality % sal tartari, lean solution, the lean solution of 0.1～5 quality % sodium tetraborate (borax) etc. of 0.1～5 quality % NaOH.In addition, the pH of this alkaline aqueous solution is preferably 9～11 scope, and the developability that its temperature can adapt sense photosensitive resin composition layer is adjusted.In addition,, in alkaline aqueous solution, can also add surfactant, defoamer, for a small amount of organic solvent of promoting to develop etc.

As above-mentioned water system developer solution, can enumerate the developer solution that water or aqueous alkali and more than one organic solvent form.Herein, as the alkali of alkaline aqueous solution, except aforementioned substances, can also enumerate, such as sodium metasilicate, tetramethyl ammonium hydroxide, monoethanolamine, ethylenediamine, Diethylenetriamine, TRIS, DAP, morpholine etc.The pH of developer solution, in the scope that can fully develop at resist, preferably as far as possible little, it is preferably pH8～12, more preferably pH9～10.

As above-mentioned organic solvent, can enumerate such as acetone, ethyl acetate, the alkoxyethanol with the alkoxy of carbon number 1～4, ethanol, isopropyl alcohol, butanols, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether etc.They can use separately, or two or more is used in combination.The concentration of organic solvent, is preferably 2～90 quality % conventionally, and its temperature can be adjusted according to developability.In addition,, in aqueous developer solution, can also add on a small quantity surfactant, defoamer etc.

In addition, be developer solution as independent organic solvent with an organic solvent, can enumerate, for example 1,1,1-trichloroethanes, 1-METHYLPYRROLIDONE, DMF, cyclohexanone, methylisobutylketone, gamma-butyrolacton etc.In order to prevent catching fire, these organic solvents are developer solution, preferably in the scope of 1～20 quality %, add water.

As the processing after developing, can be as required, carry out heating or the 0.2～10J/cm of 60～250 ℃ of left and right ²the exposure of left and right, and further solidify corrosion-resisting pattern.

Then, the manufacture method of printed circuit board (PCB) of the present invention is described.

The manufacture method of printed circuit board (PCB) of the present invention is that circuit that the formation method of the corrosion-resisting pattern by the invention described above is formed with to corrosion-resisting pattern forms the method for carrying out etching or plating and form conductive pattern with substrate.

Circuit forms with etching or the plating of substrate, be the corrosion-resisting pattern that forms as mask, and circuit is formed and is carried out with the conductor layer of substrate etc.Etching solution when carrying out etching, can enumerate 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, such as the scolding tin plating such as the copper such as copper sulphate plating, cupric pyrophosphate plating plating, high homogeneous scolding tin plating, watt are bathed the 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 finish, for example can use, peel off corrosion-resisting pattern than the stronger aqueous solution of alkaline aqueous solution alkalescence used in developing.As this alkaline aqueous solution, 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 such as impregnation method, spray pattern etc., can use separately impregnation method, spray pattern, also can be combined with.Obtain thus printed circuit board (PCB).

Above, the preferred embodiment 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 to more detailed explanation, but the present invention is not limited to these embodiment.

(synthesizing of binder polymer ((A) composition))

Having in the flask of stirring machine, reflux condenser, thermometer, tap funnel and nitrogen ingress pipe, adding 450g mass ratio is the methyl cellosolve of 3: 2 and the complex of toluene, is blown into nitrogen while stirs, and 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 9.0g azoisobutyronitrile is (following, be called " solution a ") as comonomer, with 4 hours, solution a is splashed into the complex of the pre-prepd mass ratio methyl cellosolve that is 3: 2 and toluene, then in 80 ℃ of stirrings, be incubated 2 hours.Further, with 10 minutes, the solution that is dissolved with 1.2g azoisobutyronitrile is splashed in the complex that 100g mass ratio is the methyl cellosolve of 3: 2 and toluene.Stir solution after splashing into while 80 ℃ of insulations 3 hours, be then heated to 90 ℃ with 30 minutes.After 2 hours, cooling 90 ℃ of insulations, obtain binder polymer (A-1).

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 by gel permeation chromatography, and uses the typical curve of polystyrene standard convert and derive.The condition of GPC is as follows.

Pump: the L-6000 of Hitachi type ((strain) Hitachi manufactures, trade name)

Post: Gelpack GL-R420+Gelpack GL-R430+Gelpack GL-R440 (totally 3) (more than, Hitachi changes into industry (post) manufacture, trade name)

Eluent: tetrahydrofuran

Measure temperature: 40 ℃

Flow: 2.05mL/ minute

Detecting device: the L-3300 of Hitachi type RI ((post) Hitachi manufactures, trade name)

In addition, use and the identical method of synthetic method of above-mentioned binder polymer (A-1), synthesize the binder polymer (A-2) of composition as shown in table 1 below～(A-10).

[table 1]

(preparation of photosensitive polymer combination)

With the mass ratio shown in table 2, above-mentioned binder polymer (A-1)～(A-10) and following material are coordinated to the solution of the photosensitive polymer combination of Preparation Example 1～6 and comparative example 1～5.

< optical polymerism compound ((B) composition) >

B-1:2,2-bis-(4-(methacryloxy five ethoxys) phenyl) propane (Hitachi changes into industry (strain) manufacture, trade name: FA-321M)

B-2: the compound being represented by above-mentioned general formula (VII), and R ¹²and R ¹³be respectively methyl, m ³=6 (mean values), n ²+ n ³the vinyl compound (Hitachi changes into industry (strain) manufacture, trade name: FA-024M) of=12 (mean values)

B-3:4-n-nonyl phenoxy group eight ethyleneoxy group acrylate (East Asia synthetic (strain) manufactures, trade name: M-114)

< Photoepolymerizationinitiater initiater ((C) composition) >

C-1:2,2 '-bis-(2-chlorphenyl)-4,4 ', 5,5 '-tetraphenyl bisglyoxaline (Hampford society manufactures, trade name: BCIM)

< sensitizing coloring matter ((D) composition) >

D-1:9,10-dibutoxy anthracene (Kawasaki changes into industry (strain) manufacture, and trade name: DBA shows wavelength [λ n]=368nm, the 388nm, the 410nm that greatly absorb)

< (E) developer (amines) >

E-1: leuco crystal violet (hillside plot chemistry (strain) manufacture)

< dyestuff >

Peacock green (Osaka organic chemistry industry (strain) manufacture)

< solvent >

Acetone

Toluene

Methyl alcohol

[table 2]

(making of photosensitive element)

By the solution of each photosensitive polymer combination of gained, the thickness that is uniformly coated on formation supporting film is on the polyethylene terephthalate film of 16 μ m.Then, use the hot wind convection type dryer of 70 ℃ and 110 ℃ to be dried, forming dried thickness is the photosensitive polymer combination layer of 25 μ m.Then, pressurize protective film is stacked on photosensitive polymer combination layer by roller, obtain the photosensitive element of each embodiment 1～6 and comparative example 1～5.

(making of test film)

Then, to the subsides copper-surfaced plywood as Copper Foil (thickness is 35mm) being layered in to the glass epoxide material on two sides, (Hitachi changes into industry (strain) manufacture to the muller (three Kei (strain) manufacture) that use has a brush that is equivalent to #600, trade name: MLC-E-67) copper surface grind, washing, then make it dry by air stream, obtain copper-surfaced plywood (substrate).Then, copper-surfaced plywood is heated to after 80 ℃, on copper-surfaced plywood, removes on one side the diaphragm of above-mentioned each photosensitive element, on one side by closely sealed each photosensitive polymer combination layer on the surface of copper-surfaced plywood, at 120 ℃, 4kgf/cm ²pressure under carry out lamination (stacked), make test film.

(evaluating characteristics)

< photo sensitivity >

In the time that the copper-surfaced plywood that is laminated with each photosensitive element is cooled to 23 ℃, the optical tool (phototool) of 41 sections of stage metraster that will have concentration range and be 0.00～2.00, concentration gradient are 0.05, lattice chip size is 20mm × 187mm, each section is of a size of 3mm × 12mm is closely sealed on supporting film.Use the machine of directly the retouching DE-1AH (trade name) manufacturing as the sub-machinery of dimension (Hitachi Via Mechanics) company of Hitachi of light source using the bluish-violet color laser diode of 405nm, with 50mJ/cm ²exposure by optical tool and supporting film to photosensitive polymer combination layer expose (describing).In addition, the mensuration of illumination is used the ultraviolet illuminometer (USHIO motor (strain) is manufactured, trade name: UIT-150) of having applied corresponding to the probe of 405nm to carry out.

Then, peel off supporting film, at 30 ℃, 1 quality % aqueous sodium carbonate was sprayed for 24 seconds, remove the unexposed portion of photosensitive polymer combination layer, and develop.Then,, by being determined at the hop count of stage metraster of the photocuring film forming on copper-surfaced plywood, evaluate the photo sensitivity of photosensitive polymer combination.The evaluation of photo sensitivity, represents, the hop count of this stage metraster is higher, represents that photo sensitivity is higher with the hop count of stage metraster.Acquired results is shown in table 4.

< resolution >

Resolution, is used that to have live width/interval width be that the Wiring pattern of 6/6～30/30 (unit: mm) exposes as the optical tool of resolution evaluation negative film.Herein, with regard to resolution, be in the corrosion-resisting pattern that will form by the development after exposure, (unit: μ is m) as the index of resolution for minimum value in the interval width between the live width in the part that unexposed portion is completely removed.The numerical value that resolution is evaluated is the smaller the better.Acquired results is shown in table 4.

< resist shape >

Resist shape after development, is used scanning electron microscope (trade name: the scanning electron microscope S-500A of Hitachi) to observe.Resist shape is wished for approaching rectangle.

< fissility >

Fissility uses following methods to evaluate.First, form the photosensitive polymer combination layer of each embodiment and comparative example on copper-surfaced plywood, expose each photosensitive polymer combination layer development, make the photocuring film of 40mm × 50mm size.Then, use 3% sodium hydrate aqueous solution to peel off.The evaluation of fissility, the time peel off end during using photocuring film from copper-surfaced plywood is as splitting time.In addition peel off, the size of the stripping film after end by visualization.The size index of the condition of strip step and stripping film is shown in table 3.Acquired results is shown in table 4.

[table 3]

< 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, 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, although fissility is good, resolution is low.In addition, in comparative example 3,4, although be high resolving power, splitting time is long, and stripping film size is large.As mentioned above, confirmed the effect of photosensitive polymer combination of the present invention.

Industrial applicibility

Claims

1. a photosensitive polymer combination, it contains:

(A) there is divalent group and the divalent group of following general formula (II) expression and divalent group and the divalent group of following general formula (IV) expression and the binder polymer that weight-average molecular weight is 20000～50000 that following general formula (III) represents that following general formula (I) represents

(B) optical polymerism compound, and

(C) Photoepolymerizationinitiater initiater,

In formula (I), formula (II), formula (III) and formula (IV), R ¹, R ³, R ⁵and R ⁶represent independently respectively hydrogen atom or methyl, R ²and R ⁴represent independently respectively the alkyl of carbon number 1～3, alkoxy, hydroxyl or the halogen atom of carbon number 1～3, R ⁷the alkyl that represents carbon number 1～6, m or n represent respectively 0～5 integer independently, m or n are 2～5 o'clock, multiple R ²or R ⁴mutually can be identical or different,

Wherein, described (B) optical polymerism compound contains and in molecule, has the two poly alkylene glycol two (methyl) acrylate of glycol chain and propylene glycol chain.

2. photosensitive polymer combination according to claim 1, wherein, described (A) binder polymer, with respect to its total amount 100 mass parts, contains the divalent group that general formula (I) represents described in 10～60 mass parts.

3. a photosensitive polymer combination, it contains:

(A) have and come from the structural unit of styrene or styrene derivative and come from the structural unit of (methyl) benzyl acrylate or (methyl) benzyl acrylate derivant and come from (methyl) acrylic acid structural unit and come from the structural unit of (methyl) alkyl acrylate and the binder polymer that weight-average molecular weight is 20000～50000

(B) optical polymerism compound, and

(C) Photoepolymerizationinitiater initiater,

4. photosensitive polymer combination according to claim 3, wherein, described (A) binder polymer, with respect to its total amount 100 mass parts, contains the structural unit that comes from styrene or styrene derivative described in 10～60 mass parts.

5. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, described general formula (I) represent structural unit or come from styrene or the structural unit of styrene derivative containing proportional be 15～55 mass parts.

6. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, described general formula (I) represent structural unit or come from styrene or the structural unit of styrene derivative containing proportional be 20～50 mass parts.

7. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, described general formula (I) represent structural unit or come from styrene or the structural unit of styrene derivative containing proportional be 20～40 mass parts.

8. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, described general formula (II) represent structural unit or come from (methyl) benzyl acrylate or the structural unit of (methyl) benzyl acrylate derivant containing proportional be 15～55 mass parts.

9. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, described general formula (II) represent structural unit or come from (methyl) benzyl acrylate or the structural unit of (methyl) benzyl acrylate derivant containing proportional be 20～50 mass parts.

10. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, described general formula (II) represent structural unit or come from (methyl) benzyl acrylate or the structural unit of (methyl) benzyl acrylate derivant containing proportional be 25～45 mass parts.

11. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, the structural unit that the described general formula (III) of described (A) binder polymer represents or come from (methyl) acrylic acid structural unit containing proportional be 10～60 mass parts.

12. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, the structural unit that the described general formula (III) of described (A) binder polymer represents or come from (methyl) acrylic acid structural unit containing proportional be 15～50 mass parts.

13. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, the structural unit that the described general formula (III) of described (A) binder polymer represents or come from (methyl) acrylic acid structural unit containing proportional be 20～40 mass parts.

14. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, the structural unit that the described general formula (III) of described (A) binder polymer represents or come from (methyl) acrylic acid structural unit containing proportional be 25～35 mass parts.

15. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, the structural unit that the described general formula (IV) of described (A) binder polymer represents or come from (methyl) alkyl acrylate structural unit containing proportional be that 1 mass parts is above and be less than 15 mass parts.

16. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, the structural unit that the described general formula (IV) of described (A) binder polymer represents or come from (methyl) alkyl acrylate structural unit containing proportional be 2～13 mass parts.

17. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, the structural unit that the described general formula (IV) of described (A) binder polymer represents or come from (methyl) alkyl acrylate structural unit containing proportional be 4～12 mass parts.

18. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to total amount 100 mass parts of (A) binder polymer composition, the structural unit that the described general formula (IV) of described (A) binder polymer represents or come from (methyl) alkyl acrylate structural unit containing proportional be 5～10 mass parts.

19. according to the photosensitive polymer combination described in any one in claim 1～4, and wherein, described poly alkylene glycol two (methyl) acrylate is at least one compound of selecting the compound representing from general formula (VI)～(VIII),

In formula (VI), formula (VII) and formula (VIII), R ¹⁰, R ¹¹, R ¹², R ¹³, R ¹⁴and R ¹⁵the alkyl that represents independently respectively hydrogen atom or carbon number 1～3, EO represents glycol chain, PO represents propylene glycol chain, m ¹～m ⁴and n ¹～n ⁴represent independently respectively 1～30 integer.

20. according to the photosensitive polymer combination described in any one in claim 1～4, and wherein, described (B) optical polymerism compound contains bisphenol-A class (methyl) acrylate compounds.

21. according to the photosensitive polymer combination described in any one in claim 1～4, and wherein, described (C) Photoepolymerizationinitiater initiater contains six aryl united imidazoles.

22. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain (A) binder polymer composition 30～70 mass parts, (B) optical polymerism compound composition 30～70 mass parts and (C) Photoepolymerizationinitiater initiater composition 0.1～10 mass parts.

23. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain (A) binder polymer composition 30～70 mass parts, (B) optical polymerism compound composition 30～70 mass parts and (C) Photoepolymerizationinitiater initiater composition 2～6 mass parts.

24. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain (A) binder polymer composition 30～70 mass parts, (B) optical polymerism compound composition 30～70 mass parts and (C) Photoepolymerizationinitiater initiater composition 3.5～5 mass parts.

25. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain (A) binder polymer composition 35～65 mass parts, (B) optical polymerism compound composition 35～65 mass parts and (C) Photoepolymerizationinitiater initiater composition 2～6 mass parts.

26. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain (A) binder polymer composition 40～60 mass parts, (B) optical polymerism compound composition 40～60 mass parts and (C) Photoepolymerizationinitiater initiater composition 3.5～5 mass parts.

27. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, further contains (D) sensitizing coloring matter.

28. photosensitive polymer combinations according to claim 27, wherein, described (D) sensitizing coloring matter contain from pyrazolines, anthracene class, Coumarins, xanthene ketone,

azole, benzo

at least one compound of selecting in azole, thiazoles, benzothiazoles, triazole type, Stilbene class, triazines, thiophene-based and naphthalimide class.

29. photosensitive polymer combinations according to claim 27, wherein, described (D) sensitizing coloring matter contains anthracene class.

30. photosensitive polymer combinations according to claim 27, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain described (D) sensitizing coloring matter 0.01～10 mass parts.

31. photosensitive polymer combinations according to claim 27, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain described (D) sensitizing coloring matter 0.05～5 mass parts.

32. photosensitive polymer combinations according to claim 27, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain described (D) sensitizing coloring matter 0.1～2 mass parts.

33. according to the photosensitive polymer combination described in any one in claim 1～4, wherein, further contains (E) amine compound.

34. photosensitive polymer combinations according to claim 33, wherein, described (E) amine compound is to have amino compound.

35. photosensitive polymer combinations according to claim 33, wherein, described (E) amine compound is two [4-(dimethylamino) phenyl] methane, two [4-(diethylamino) phenyl] methane or leuco crystal violet.

36. photosensitive polymer combinations according to claim 33, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain described (E) amine compound 0.01～10 mass parts.

37. photosensitive polymer combinations according to claim 33, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain described (E) amine compound 0.05～5 mass parts.

38. photosensitive polymer combinations according to claim 33, wherein, with respect to (A) binder polymer composition and (B) total amount 100 mass parts of optical polymerism compound composition, contain described (E) amine compound 0.1～2 mass parts.

39. 1 kinds of photosensitive elements, its there is supporting film and on this supporting film, form contain claim 1～38 in the photosensitive polymer combination layer of photosensitive polymer combination described in any one.

The formation method of 40. 1 kinds of corrosion-resisting patterns, it has: form with on substrate the stacked operation of the stacked photosensitive polymer combination layer that contains the photosensitive polymer combination described in any one in claim 1～38 at circuit; The established part irradiation active ray of described photosensitive polymer combination layer is made to the exposure process of exposure portion photocuring; And form the developing procedure of removing the part beyond the described exposure portion of described photosensitive polymer combination layer with substrate from the circuit of stacked described photosensitive polymer combination layer.

The manufacture method of 41. 1 kinds of printed circuit board (PCB)s, it has: the circuit that the formation method of the corrosion-resisting pattern by described in claim 40 is formed with to corrosion-resisting pattern forms the operation of carrying out etching or plating and form conductive pattern with substrate.