CN102636954B - Photocurable thermosetting resin composition, dry film and cured product thereof, and printed wiring board using the same - Google Patents

Abstract

The invention provides a photocuring thermocuring resin composition, dry membrane, cured product and printed circuit board. An alkali developable photocuring thermocuring resin composition contains (A) an epoxy resin, (B) a carboxyl-contained resin and (C) a photopolymerisable initiator, the epoxy resin (A) has a mixture of a bifunctional biphenyl epoxy resin (A-1) with a structure shown as the general formula (I) and an epoxy resin (A-2), the epoxy resin (A-2) is at least one epoxy resin with the softening point of 40 to 100 DEG C and the weight per epoxy equivalent of 180 to 300, selected from a bisphenol A type epoxy resin, a bisphenol A phenolic varnish type epoxy resin and a diphenol phenolic varnish type epoxy resin, The epoxy resin (A-1) is less than the epoxy resin (A-2). In the chemical formula 1, R is H or CH3.

Description

Light solidifying/heat solidifying resin composition, dry film, solidfied material, printed circuit board (PCB)

The divisional application that the application is the applying date is on March 22nd, 2010, application number is 201010139611.6, denomination of invention is the application of " light solidifying/heat solidifying resin composition, dry film, solidfied material, printed circuit board (PCB) ".

Technical field

The present invention relates to the light solidifying/heat solidifying resin composition that can be developed by dilute alkaline aqueous solution, particularly relate to and carry out the solder resist composition of photocuring, its dry film and solidfied material by ultraviolet exposure or laser explosure and there is the printed circuit board (PCB) of the cured film using their to be formed.

Background technology

All the time, the photosensitive polymer combination of alkali developable is widely used as Solder-Resist Inks for Printed Circuit Board.Use the object of solder resist to be protect the surface circuit of printed circuit board (PCB), require high solder heat resistance and electrical insulating property.And then recently, the densification of printed circuit board (PCB) is remarkable, and its circuit is minimum is 10 μm, line, 10 μm, space, requires insulating reliability higher than ever.

Existing alkali developable solder resist is made up of sour modified epoxy acrylic ester and Photoepolymerizationinitiater initiater, reactive diluent, epoxy resin, filler.In these compositions, especially epoxy resin bears the vital role improving thermotolerance, electrical characteristics, adaptation.From the view point of special thermotolerance, light characteristic, in the epoxy, crystalline epoxy resin is the composition (with reference to patent documentation 1) be even more important.

But due to the densification of printed base plate in recent years, between fine pattern circuit, insoluble material (inorganic filler, Cristalline epoxy resin etc.) exists with particle, becomes the reason causing short circuit between circuit.And then, light solidifying/heat solidifying resin composition to be applied in carrier film and the dry dry film lamination obtained makes in the operation of tellite to the substrate being formed with various circuit pattern, the particle of insoluble substance becomes the bad reason of lamination, is also the reason that the productive rate of the fine pattern substrate manufacture making to need Altitude control thickness reduces.Therefore, various dispersion treatment is carried out when preparing solder resist, filter to remove the big particle of insoluble composition, but nearly all Cristalline epoxy resin all has compatibility with organic solvent, other resin, the temperature variation of dispersion step makes it be partly dissolved, and then recrystallization and become big particle.In addition, during filtration, also must reduce temperature, be difficult to obtain full-bodied composition.

prior art document

patent documentation

Patent documentation 1: Japanese Unexamined Patent Publication 1-141904 publication (claims)

Summary of the invention

the problem that invention will solve

The present invention carries out in view of foregoing prior art, its object is to, a kind of light solidifying/heat solidifying resin composition is provided, the excellence such as thermotolerance, chemical gilding patience, electrical insulating property of its dry coating, the broken string of the fine pitch circuitry that especially can prevent the big particle of insoluble composition from causing, it is for the formation of cured films such as soldering-resistance layers.

The present invention also aims to, the dry film and solidfied material that use the as described above various characteristic that obtains of such light solidifying/heat solidifying resin composition and flatness excellence and the printed circuit board (PCB) being formed the cured films such as soldering-resistance layer by this dry film, solidfied material are provided.

for the scheme of dealing with problems

In order to realize aforementioned object, the invention provides a kind of light solidifying/heat solidifying resin composition of alkali-developable, said composition contains (A) epoxy resin, (B) containing carboxy resin and (C) Photoepolymerizationinitiater initiater, it is characterized in that, above-mentioned epoxy resin (A) has 2 officials' energy biphenyl epoxy resin (A-1) of structure shown in following general formula (I) and the potpourri of epoxy resin (A-2), wherein, epoxy resin (A-2) is selected from bisphenol A type epoxy resin, the group that bisphenol A novolac type epoxy resin and xenol phenolic resin varnish type epoxy resin form, softening point be 40 ~ 100 DEG C and epoxide equivalent be 180 ~ 300 at least a kind of epoxy resin, aforementioned epoxy resins (A-1) is (A-1) < (A-2) with the ratio of (A-2).

[chemical formula 1]

(in formula, R represents H or CH ₃.)

In suitable scheme, light solidifying/heat solidifying resin composition is suitable as solder resist and uses, wherein, in described light solidifying/heat solidifying resin composition, the aforementioned acid number containing carboxy resin (B) with 40 ~ 120mgKOH/g, aforementioned relative to 100 mass parts containing carboxy resin (B), (A-1) and the potpourri of (A-2) be 20 ~ 60 mass parts, also comprise the photo-sensitive monomer (E) in 1 molecule with more than 2 olefinic unsaturated groups.

In addition, the invention provides a kind of solidfied material, it is for being applied to by aforementioned light solidifying/heat solidifying resin composition in carrier film and the dry dry film the obtained solidfied material that carries out photocuring and/or heat curing and obtain, or, to aforementioned light solidifying/heat solidifying resin composition or to this light solidifying/heat solidifying resin composition being applied in carrier film and the dry dry film the obtained solidfied material that carries out photocuring and/or heat curing and obtain, also provide especially on copper photocuring and obtain solidfied material, carry out pattern-like photocuring and the solidfied material that obtains.

And then the present invention also provides a kind of printed circuit board (PCB), it is characterized in that, its have said curing thing, especially have pattern-like photocuring is carried out to light solidifying/heat solidifying resin composition or dry film after heat curing and the cured film obtained again.

Invention effect

Light solidifying/heat solidifying resin composition of the present invention contains (A) epoxy resin, (B) containing carboxy resin and (C) Photoepolymerizationinitiater initiater, it is characterized in that, above-mentioned epoxy resin (A) has 2 officials' energy biphenyl epoxy resin (A-1) of structure shown in aforementioned formula (I) and the potpourri of epoxy resin (A-2), described epoxy resin (A-2) is selected from bisphenol A type epoxy resin, the group that bisphenol A novolac type epoxy resin and xenol phenolic resin varnish type epoxy resin form, softening point be 40 ~ 100 DEG C and epoxide equivalent be 180 ~ 300 at least a kind of epoxy resin, the ratio of (A-1) and (A-2) of aforementioned epoxy resins is (A-1) < (A-2), therefore, the ageing stability relevant to the crystallization of epoxy resin composition is excellent, solder heat resistance, chemical gilding patience, the excellences such as electrical insulating property, especially the cured film that insulating reliability between fine pattern is high can be formed.

Therefore, light solidifying/heat solidifying resin composition of the present invention advantageously can be applicable to the cured film such as soldering-resistance layer forming printed circuit board (PCB), flexible print wiring board.

Embodiment

As previously mentioned, light solidifying/heat solidifying resin composition of the present invention contains (A) epoxy resin, (B) containing carboxy resin and (C) Photoepolymerizationinitiater initiater, the feature of said composition is, above-mentioned epoxy resin (A) has 2 officials' energy biphenyl epoxy resin (A-1) of structure shown in aforementioned formula (I) and the potpourri of epoxy resin (A-2), described epoxy resin (A-2) is selected from bisphenol A type epoxy resin, the group that bisphenol A novolac type epoxy resin and xenol phenolic resin varnish type epoxy resin form, softening point be 40 ~ 100 DEG C and epoxide equivalent be 180 ~ 300 at least a kind of epoxy resin, the ratio of (A-1) and (A-2) of aforementioned epoxy resins is (A-1) < (A-2).

According to the research of the present inventor etc., as epoxy resin, (A) excellence such as thermotolerance, chemical gilding patience, electrical insulating property with 2 officials' energy biphenyl epoxy resin (A-1) of structure shown in aforementioned formula (I) in composition, especially the insulating reliability between fine pattern is excellent, therefore be the composition be even more important, but then, because it has high crystallinity in resinous principle, organic solvent, easily there is recrystallization due to factors such as temperature variation, make particle coarsening in potpourri, become the reason causing short circuit between circuit.And then, can the light solidifying/heat solidifying resin composition of biphenyl epoxy resin (A-1) to be applied to comprising 2 officials in carrier film and the dry and dry film lamination that obtains makes in the operation of tellite to the substrate being formed with various circuit pattern, the big particle produced becomes the bad reason of lamination, especially makes the reason that the productive rate of the fine pattern substrate manufacture needing Altitude control thickness reduces.

Therefore, the present inventor etc. conduct in-depth research, found that, when epoxy resin (A) has 2 officials' energy biphenyl epoxy resin (A-1) of structure shown in aforementioned formula (I) and the potpourri of epoxy resin (A-2), wherein, described epoxy resin (A-2) is selected from bisphenol A type epoxy resin, the group that bisphenol A novolac type epoxy resin and xenol phenolic resin varnish type epoxy resin form, softening point be 40 ~ 100 DEG C and epoxide equivalent be 180 ~ 300 at least a kind of epoxy resin, its mixing ratio is (A-1) < (A-2), and by stirring, mixing, the methods such as heating make 2 officials can biphenyl epoxy resin (A-1) particle microminiaturization or dissolving and resulting mixture time, its thermotolerance, chemical gilding patience is excellent, can prevent can the generation of biphenyl epoxy resin (A-1) big particle that is cause with 2 officials, therefore, short circuit between circuit can be prevented, there is excellent electrical insulating property, and then, can prevent to light solidifying/heat solidifying resin composition to be applied in carrier film and the dry dry film obtained carries out lamination time lamination bad, thus complete the present invention.

Below, each constituent of light solidifying/heat solidifying resin composition of the present invention is explained.

First, in the epoxy resin (A) of light solidifying/heat solidifying resin composition forming alkali-developable of the present invention, as 2 officials' energy biphenyl epoxy resin (A-1), the di-toluene phenolic such as YL-6056, YX4000, YX4000K, YX4000H, YX4000HK, YL6121, YL6121H, YL6640, the YL6677 (being trade name) that Japan Epoxy Resins Co., Ltd. can be used to manufacture or united phenol-type epoxy resin or their potpourri.

In addition, in aforementioned epoxy resins (A), be 40 ~ 100 DEG C as softening point and epoxide equivalent is the bisphenol A type epoxy resin of 180 ~ 300, bisphenol A novolac type epoxy resin and/or xenol phenolic resin varnish type epoxy resin (A-2), such as Japan Epoxy Resins Co. can be listed, Ltd. the JER834 manufactured, the Epiclon860 that large Japanese ink chemical industrial company manufactures, Dongdu changes into the Epotote YD-134 that company manufactures, (the being trade name) bisphenol A type epoxy resins such as the D.E.R.337 that Dow Chemical Company manufactures, the bisphenol A novolac type epoxy resin such as the EpiclonN-865 (being trade name) that the JER157S that Japan Epoxy Resins Co., Ltd. manufactures, large Japanese ink chemical industrial company manufacture, the xenol phenolic resin varnish type epoxy resins etc. such as NC-3000, NC-3000H, NC-3000L, NC-3100 (trade name) that chemical drug Inc. of Japan makes, but be not limited to these.These epoxy resin can be used alone or in combination of two or more kinds.

Aforementioned epoxy resins (A-1) is (A-1) < (A-2) with the mixing ratio of (A-2).(A-1), when compounding ratio exceedes the compounding ratio of (A-2), (A-1) dissolubility in the composition reduces, and the ageing stability relevant to the crystallization of potpourri reduces.

Relative to 100 mass parts containing carboxy resin (B), the use level of aforementioned epoxy resins (A-1) and (A-2) is such as 10 ~ 100 mass parts, and the scope being preferably 20 ~ 60 mass parts is applicable.Compared with above-mentioned scope, when the use level of epoxy resin (A-1) and (A-2) is too much, alkali-developable is deteriorated, and easy generation resolution is bad, generation development residue.On the other hand, during less than 10 mass parts, the solder heat resistance of the cured coating film obtained is impaired, therefore not preferred.

In addition, other epoxy resin and aforementioned epoxy resins (A-1) and (A-2) can also be used to combine.As other epoxy resin, can use known conventional epoxy resin, there is no particular limitation.As such epoxy resin, can list such as, there is in molecule compound and the multi-functional epoxy compound of more than at least 2 epoxy radicals.

As aforementioned multi-functional epoxy compound, such as bisphenol A type epoxy resin can be listed, as Japan Epoxy Resins Co., Ltd. the jER828 manufactured, jER1001, jER1004, the Epiclon840 that DIC Corporation manufactures, Epiclon850, Epiclon1050, Epiclon2055, Dongdu changes into the EpototeYD-011 that company manufactures, YD-013, YD-127, YD-128, the D.E.R.317 that Dow ChemicalCompany manufactures, D.E.R.331, D.E.R.661, D.E.R.664, the Araldite6071 that Ciba Specialty product chemical company manufactures, Araldite6084, AralditeGY250, AralditeGY260, the SumiepoxyESA-011 that Sumitomo Chemical Co. Ltd. manufactures, ESA-014, ELA-115, ELA-128, the A.E.R.330 that industrial group of Asahi Chemical Industry manufactures, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name), brominated epoxy resin, as Japan Epoxy Resins Co., Ltd. the JERYL903 manufactured, Epiclon152, Epiclon165 that DIC Corporation manufactures, Dongdu changes into EpototeYDB-400, YDB-500 that company manufactures, the D.E.R.542 that Dow Chemical Company manufactures, the Araldite8011 that Ciba Specialty product chemical company manufactures, SumiepoxyESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. manufactures, A.E.R.711, A.E.R.714 etc. (being trade name) that industrial group of Asahi Chemical Industry manufactures, phenolic resin varnish type epoxy resin, as Japan Epoxy Resins Co., Ltd. the jER152 manufactured, jER154, the D.E.N.431 that DowChemical Company manufactures, D.E.N.438, the EpiclonN-730 that DICCorporation manufactures, EpiclonN-770, EpiclonN-865, Dongdu changes into the EpototeYDCN-701 that company manufactures, YDCN-704, the AralditeECN1235 that Ciba Specialty product chemical company manufactures, AralditeECN1273, AralditeECN1299, AralditeXPY307, the EPPN-201 that chemical drug Inc. of Japan makes, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the SumiepoxyESCN-195X that Sumitomo Chemical Co. Ltd. manufactures, ESCN-220, the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry manufactures, ECN-299 etc. (being trade name), bisphenol f type epoxy resin, as the Epiclon830 that DIC Corporation manufactures, Japan Epoxy Resins Co., Ltd. the jER807 manufactured, Dongdu changes into EpototeYDF-170, YDF-175, YDF-2004 that company manufactures, the AralditeXPY306 that Ciba Specialty product chemical company manufactures etc. (being trade name), bisphenol-A epoxy resin, as Dongdu changes into EpototeST-2004, ST-2007, ST-3000 (trade name) etc. of company's manufacture, glycidyl amine type epoxy resin, as Japan EpoxyResins Co., Ltd. the jER604 manufactured, Dongdu changes into the EpototeYH-434 that company manufactures, the AralditeMY720 that Ciba Specialty product chemical company manufactures, the SumiepoxyELM-120 that Sumitomo Chemical Co. Ltd. manufactures etc. (being trade name), the hydantoins type epoxy resin such as the AralditeCY-350 (trade name) that Ciba Specialty product chemical company manufactures, alicyclic epoxy resin, as the Celoxide2021 that DAICEL CHEMICALINDUSTRIES, LTD. manufacture, AralditeCY175, CY179 etc. (being trade name) that Ciba Specialty product chemical company manufactures, trihydroxy benzene methylmethane type epoxy resin, as T.E.N., EPPN-501, EPPN-502 etc. (being trade name) that the YL-933 that Japan Epoxy Resins Co., Ltd. manufactures, Dow Chemical Company manufacture, bisphenol-s epoxy resin, the EXA-1514 (trade name) etc. that EPX-30, DIC Corporation as Japanese chemical drug Inc. makes EBPS-200, Asahi Electro-Chemical Co. Ltd manufactures manufactures, four hydroxy phenyl ethane type epoxy resin, as the jERYL-931 of Japan Epoxy Resins Co., Ltd. manufacture, the Araldite163 of Ciba Specialty product chemical company manufacture etc. (being trade name), (being trade name) hetero ring type epoxy resin such as the Araldite PT810 that Ciba Specialty product chemical company manufactures, the TEPIC that Nissan Chemical Industries company manufactures, the o-phthalic acid diglycidyl ester resins such as the Blemmer DGT that Nof Corp. manufactures, Dongdu changes into four glycidyl group dimethylbenzene ethane (tetraglycidylxylenoyl ethane) resins such as the ZX-1063 of company's manufacture, ESN-190, ESN-360 that chemical company of Nippon Steel manufactures, HP-4032, EXA-4750, EXA-4700 etc. that DIC Corporation manufactures are containing the epoxy resin of naphthyl, HP-7200, HP-7200H etc. that DIC Corporation manufactures have the epoxy resin of bicyclopentadiene skeleton, the glycidyl methacrylate copolymerization system epoxy resin such as CP-50S, CP-50M that Nof Corp. manufactures, and the copolymerization epoxy resin of N-cyclohexylmaleimide and glycidyl methacrylate, epoxide modified polybutadiene rubber derivant (such as DAICEL CHEMICAL INDUSTRIES, LTD. the PB-3600 etc. manufactured), CTBN modified epoxy (such as Dongdu changes into YR-102, YR-450 etc. that company manufactures) etc., but be not limited to these.These epoxy resin can be used alone or in combination of two or more kinds.In these, preferred phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their potpourri.

When being 100 % by mole with the consumption of epoxy resin entirety, other the use level of epoxy resin aforementioned is preferably less than 75 % by mole.When use is more than 75 % by mole, the characteristic being derived from 2 officials' energy biphenyl epoxy resin (A-1) may not be obtained fully.The preferred consumption of other epoxy resin is less than 50 % by mole.

As aforementioned containing carboxy resin (B), to give for the purpose of alkali-developable, can use in molecule and there are the existing known various containing carboxy resin of carboxyl.From photo-curable, resistance to developability aspect, what especially have ethylenical unsaturated double bonds in molecule is especially preferred containing carboxyl photoresist (B ').In addition, its unsaturated double-bond preferred source is from acrylic or methacrylic acid or their derivant.In addition, only use do not have ethylenical unsaturated double bonds containing carboxy resin time, in order to make composition have photo-curable, need with molecule described later in there is more than 1 olefinic unsaturated group photo-sensitive monomer (E) combinationally use.

As containing the object lesson of carboxy resin (B), the preferably following such compound (oligomer and polymkeric substance any one) enumerated.

(1) what obtained containing the copolymerization of unsaturated group compound by the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methyl styrene, low alkyl group (methyl) acrylate, isobutylene etc. contains carboxy resin.

(2) aliphatic diisocyanate is passed through, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, the diisocyanate such as aromatic diisocyanate and dihydromethyl propionic acid, dimethylolpropionic acids etc. are containing carboxylic diol compound and polycarbonate-based polyvalent alcohol, polyethers system polyvalent alcohol, polyester-based polyols, polyolefin polyvalent alcohol, acrylic acid series multiple alcohol, bisphenol-A system alkylene oxide adducts dibasic alcohol, have the diatomic alcohol compounds such as the compound of phenolic hydroxyl group and alcohol hydroxyl group addition polymerization and obtain containing carboxyl urethane resin.

(3) photonasty obtained by (methyl) acrylate of 2 functional epoxy resins such as diisocyanate and bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, di-toluene phenol-type epoxy resin, united phenol-type epoxy resin or the addition polymerization of the anhydride modified thing of its part, carboxylic diol compound and diatomic alcohol compounds is containing carboxyl urethane resin.

(4) by adding the compound in (methyl) hydroxyalkyl acrylate equimolecular with 1 hydroxyl and more than 1 (methyl) acryloyl group in the synthesis of the resin of aforementioned (2) or (3), the acrylated photonasty of the end (methyl) obtained contains carboxyl urethane resin.

(5) by having the compound of 1 isocyanate group and more than 1 (methyl) acryloyl group in the reaction with same mole thing equimolecular that adds isophorone diisocyanate and pentaerythritol triacrylate in the synthesis of the resin of aforementioned (2) or (3), the acrylated photonasty of the end (methyl) that obtains contains carboxyl urethane resin.

(6) by making aftermentioned 2 officials like that (solid-state) epoxy resin or 2 officials can react with (methyl) acrylic acid by multifunctional (solid-state) epoxy resin above, make to be present in the hydroxyl of side chain and 2 yuan of acid anhydrides additions and the photonasty that obtains contains carboxy resin.

(7) by aftermentioned 2 officials like that can reacts with (methyl) acrylic acid by the polyfunctional epoxy resin that obtains of the further epoxidation of hydroxyl epichlorokydrin of (solid-state) epoxy resin, the hydroxyl of generation and 2 yuan of acid anhydrides additions and the photonasty that obtains contains carboxy resin.

(8) can oxetane resins and dicarboxylic acid be reacted by aftermentioned 2 officials like that, the primary hydroxyl of generation and 2 yuan of acid anhydrides additions and obtain contain carboxyl polyester resin.

(9) by making the resin of above-mentioned (1) ~ (8) have the compound addition of 1 epoxy radicals and more than 1 (methyl) acryloyl group and the photonasty that obtains containing carboxy resin further with in 1 molecule.

In addition, (methyl) acrylate in this instructions is the term being referred to as acrylate, methacrylate and their potpourri, and below, other similar expression too.

As described above have multiple free carboxyl containing carboxy resin (B) on the side chain of trunk polymer, and dilute alkaline aqueous solution therefore can be utilized to develop.

In addition, the above-mentioned acid number containing carboxy resin (B) is the scope of 40 ~ 200mgKOH/g, the more preferably scope of 45 ~ 120mgKOH/g.Containing the acid number of carboxy resin lower than the words of 40mgKOH/g, then be difficult to alkali development, on the other hand, more than 200mgKOH/g, there is developer solution to the dissolving in exposure portion, therefore, line becomes thinner than required, sometimes be dissolved by the developing stripping exposure portion and unexposed portion indistinction, be difficult to describe normal corrosion-resisting pattern, thus not preferred.

In addition, the above-mentioned weight-average molecular weight containing carboxy resin (B) is different according to resin matrix, is generally 2000 ~ 150000, more preferably the scope of 5000 ~ 100000.During Weight-average molecular quantity not sufficient 2000, tack-free degradation occurs sometimes, the moisture-proof of the film after exposure is deteriorated, and film wearing and tearing occur during development, and resolution is significantly deteriorated.On the other hand, when weight-average molecular weight is more than 150000, sometimes occur developability be significantly deteriorated, bin stability be deteriorated.

In whole composition, such use level containing carboxy resin (B) is 20 ~ 80 quality %, and the scope being preferably 30 ~ 60 quality % is applicable.When use level containing carboxy resin (B) is less than above-mentioned scope, epithelium intensity reduces, therefore not preferred.On the other hand, during more than above-mentioned scope, the viscosity of composition uprises, the reductions such as coating, therefore not preferred.

These are not limited to containing carboxy resin (B) material using aforementioned list, can use a kind, also can be multiple used in combination.

As Photoepolymerizationinitiater initiater (C); preferred use is selected from oxime ester system Photoepolymerizationinitiater initiater (C1) with group shown in following general formula (II), has alpha-aminoacetophenone system Photoepolymerizationinitiater initiater (C2) of group shown in following general formula (III) or/and the Photoepolymerizationinitiater initiater of more than a kind in the group that forms of acylphosphine oxide system Photoepolymerizationinitiater initiater (C3) with group shown in following formula (IV).

[chemical formula 2]

In formula, R ¹represent the alkyl (optionally being replaced, optionally have at alkyl middle-of-chain the oxygen atom of more than 1 by the hydroxyl of more than 1) of hydrogen atom, phenyl (optionally being replaced by the alkyl of carbon number 1 ~ 6, phenyl or halogen atom), carbon number 1 ~ 20, the naphthenic base of carbon number 5 ~ 8, the alkanoyl of carbon number 2 ~ 20 or benzoyl (optionally being replaced by the alkyl or phenyl of carbon number 1 ~ 6)

R ²represent the alkyl (optionally being replaced, optionally have at alkyl middle-of-chain the oxygen atom of more than 1 by the hydroxyl of more than 1) of phenyl (optionally being replaced by the alkyl of carbon number 1 ~ 6, phenyl or halogen atom), carbon number 1 ~ 20, the naphthenic base of carbon number 5 ~ 8, the alkanoyl of carbon number 2 ~ 20 or benzoyl (optionally being replaced by the alkyl or phenyl of carbon number 1 ~ 6)

R ³and R ⁴represent the alkyl or aryl alkyl of carbon number 1 ~ 12 independently of one another,

R ⁵and R ⁶represent alkyl or the cyclic alkyl ether of bonding both representing of hydrogen atom, carbon number 1 ~ 6 independently of one another,

R ⁷and R ⁸the aryl representing the alkyl of the straight-chain of carbon number 1 ~ 10 or branched, cyclohexyl, cyclopentyl, aryl independently of one another or replaced by halogen atom, alkyl or alkoxy, wherein, R ⁷and R ⁸one of also can represent R '-C (=O)-Ji (, R ' represents the alkyl of carbon number 1 ~ 20) here.

As the oxime ester system Photoepolymerizationinitiater initiater with group shown in aforementioned formula (II), 2-(Acetyloxyimino methyl) thioxanthene-9-one, the compound shown in the compound shown in following general formula (VI) and following general formula (VII) shown in following formula (V) preferably can be listed.

[chemical formula 3]

[chemical formula 4]

In formula, R ⁹represent that the alkoxy carbonyl group of the alkanoyl of the alkyl of hydrogen atom, halogen atom, carbon number 1 ~ 12, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl, carbon number 2 ~ 12, carbon number 2 ~ 12 is (when the carbon number of the alkyl forming alkoxy is more than 2; alkyl is optionally replaced by the hydroxyl of more than 1, optionally have the oxygen atom of more than 1 at alkyl middle-of-chain) or carbobenzoxy

R ¹⁰, R ¹²represent the alkyl (optionally being replaced, optionally have at alkyl middle-of-chain the oxygen atom of more than 1 by the hydroxyl of more than 1) of phenyl (optionally being replaced by the alkyl of carbon number 1 ~ 6, phenyl or halogen atom), carbon number 1 ~ 20, the naphthenic base of carbon number 5 ~ 8, the alkanoyl of carbon number 2 ~ 20 or benzoyl (optionally being replaced by the alkyl or phenyl of carbon number 1 ~ 6) independently of one another

R ¹¹represent the alkyl (optionally being replaced, optionally have at alkyl middle-of-chain the oxygen atom of more than 1 by the hydroxyl of more than 1) of hydrogen atom, phenyl (optionally being replaced by the alkyl of carbon number 1 ~ 6, phenyl or halogen atom), carbon number 1 ~ 20, the naphthenic base of carbon number 5 ~ 8, the alkanoyl of carbon number 2 ~ 20 or benzoyl (optionally being replaced by the alkyl or phenyl of carbon number 1 ~ 6).

[chemical formula 5]

In formula, R ¹³, R ¹⁴and R ¹⁹represent the alkyl of carbon number 1 ~ 12 independently of one another,

R ¹⁵, R ¹⁶, R ¹⁷and R ¹⁸represent the alkyl of hydrogen atom or carbon number 1 ~ 6 independently of one another,

M represents O, S or NH,

M and p represents the integer of 0 ~ 5 independently of one another.

In aforementioned oxime ester system Photoepolymerizationinitiater initiater, 2-(Acetyloxyimino methyl) thioxanthene-9-one shown in aforementioned formula (V) and the compound shown in formula (VI) are preferred.As commercially available product, CGI-325, IRGACURE OXE01, IRGACURE OXE02 that Ciba Specialty product chemical company manufactures can be listed, the N-1919 etc. that ADEKA company manufactures.These oxime ester system Photoepolymerizationinitiater initiaters can be used alone or in combination of two or more kinds.

As the alpha-aminoacetophenone system Photoepolymerizationinitiater initiater with group shown in aforementioned formula (III), 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino acetophenone etc. can be listed.As commercially available product, the IRGACURE 907 of Ciba Specialty product chemical company manufacture, IRGACURE 369, IRGACURE379 etc. can be listed.

As the acylphosphine oxide system Photoepolymerizationinitiater initiater with group shown in aforementioned formula (IV); can 2 be listed; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide, two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide, two (2,6-Dimethoxybenzoyl)-2; 4,4-trimethylpentylphosphine oxide etc.As commercially available product, the Lucirin TPO that BASF AG manufactures can be listed, the IRGACURE 819 etc. that Ciba Specialty product chemical company manufactures.

Aforementioned relative to 100 mass parts containing carboxy resin (B), the use level of such Photoepolymerizationinitiater initiater (C) is 0.01 ~ 30 mass parts, and the scope being preferably 0.5 ~ 15 mass parts is applicable.When the use level of Photoepolymerizationinitiater initiater (C) is less than 0.01 mass parts, the coating characteristics such as the photo-curable on copper is not enough, and film is peeled off, chemical proofing reduce, therefore not preferred.On the other hand, during more than 30 mass parts, Photoepolymerizationinitiater initiater (C) becomes violent in the light absorption of welding resistance film coated surface, there is the tendency that deep curability reduces, therefore not preferred.

In addition, during for having oxime ester system's Photoepolymerizationinitiater initiater of group shown in previously described formula (II), aforementioned relative to 100 mass parts containing carboxy resin (B), its use level is preferably 0.01 ~ 20 mass parts, more preferably the scope of 0.01 ~ 5 mass parts.

As other Photoepolymerizationinitiater initiater being adapted at using in light solidifying/heat solidifying resin composition of the present invention, light-initiated auxiliary agent and sensitizer, benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthone compounds, ketal compound, benzophenone cpd, xanthone compound and tertiary amine compound etc. can be listed.

If enumerate the object lesson of benzoin compound, then there are such as benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether.

If enumerate the object lesson of acetophenone compound, then there are such as acetophenone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone.

If enumerate the object lesson of anthraquinone compounds, then there are such as 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone.

If enumerate the object lesson of thioxanthone compounds, then there are such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone.

If enumerate the object lesson of ketal compound, then there are such as acetophenone dimethyl ketal, benzil dimethyl ketal.

If enumerate the object lesson of benzophenone cpd, then have such as benzophenone, 4-benzoyl diphenyl thioether, 4-benzoyl-4 '-methyldiphenyl thioether, 4-benzoyl-4 '-ethyl diphenyl sulfide, 4-benzoyl-4 '-propyl group diphenyl sulfide.

If enumerate the object lesson of tertiary amine compound, then there is such as ethanolamine compound, there is the compound of dialkyl amido benzene structure, such as 4, 4 '-dimethylamino benzopheone (the NISSOCURE MABP that Japanese Cao Da company manufactures), 4, the dialkyl amido benzophenone such as 4 '-lignocaine benzophenone (EAB that Hodogaya Chemical Co.LTD. manufactures), 7-(lignocaine)-4-methyl-2H-1-chromen-2-ones (7-(lignocaine)-4-methylcoumarin) etc. are containing the coumarin compound of dialkyl amido, ethyl 4-dimethy laminobenzoate (KAYACUREEPA that Japanese chemical drug Inc. makes), 2-dimethylamino ethyl benzoate (the Quantacure DMB that International Bio-Synthetics company manufactures), 4-dimethylamino benzoic acid (n-butoxy) ethyl ester (the Quantacure BEA that International Bio-Synthetics company manufactures), to dimethylamino benzoic acid isopentyl ethyl ester (the KAYACURE DMBI that Japanese chemical drug Inc. makes), 4-dimethylamino benzoic acid-2-Octyl Nitrite (Esolol 507 that VanDyk company manufactures) and 4, 4 '-lignocaine benzophenone (EAB that Hodogaya Chemical Co.LTD. manufactures).

In aforesaid compound, preferred thioxanthone compounds and tertiary amine compound.From the viewpoint of deep curability, composition of the present invention preferably comprises thioxanthone compounds, wherein, and the preferably thioxanthone compounds such as 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone.

Aforementioned relative to 100 mass parts containing carboxy resin (B), the use level of such thioxanthone compounds is preferably below 20 mass parts, and the ratio more preferably below 10 mass parts is applicable.When the use level of thioxanthone compounds is too much, cause thick film curability to reduce, the cost of goods increases, therefore not preferred.

As tertiary amine compound, preferably have the compound of dialkyl amido benzene structure, wherein, especially preferred dialkyl amido benzophenone cpd, maximum absorption wavelength are the coumarin compound containing dialkyl amido of 350nm ~ 410nm.As dialkyl amido benzophenone cpd, 4,4 '-lignocaine benzophenone is because toxicity is low preferably.Because maximum absorption wavelength is that the maximum absorption wavelength of the coumarin compound containing dialkyl amido of 350nm ~ 410nm is in ultraviolet range, therefore, there is provided painted less, water white photosensitive composite is mathematical, also can be provided in the painted soldering-resistance layer of the color reflecting coloring pigment self when employing coloring pigment.Consider from the sensitization effect of the laser display excellence to wavelength 400nm ~ 410nm, particularly preferably 7-(lignocaine)-4-methyl-2H-1-chromen-2-one.

Aforementioned relative to 100 mass parts containing carboxy resin (B), the use level of such tertiary amine compound is preferably 0.1 ~ 20 mass parts, more preferably the ratio of 0.1 ~ 10 mass parts.When the use level of tertiary amine compound is less than 0.1 mass parts, there is the tendency that can not obtain sufficient sensitization effect.On the other hand, during more than 20 mass parts, tertiary amine compound causes the light absorption on the surface of dry welding resistance film to become violent, there is the tendency that deep curability reduces.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can be used alone or use as potpourri of more than two kinds.

Aforementioned relative to 100 mass parts containing carboxy resin (B), the total amount of such Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer is the scope of below 35 mass parts is preferred.During more than 35 mass parts, there is the tendency because their light absorption causes deep curability to reduce.

In order to give thermotolerance, except adding except aforementioned epoxy resins in light solidifying/heat solidifying resin composition of the present invention, heat-curing resin can also be added.Especially preferably there is in molecule the Thermocurable composition (D) of more than 2 cyclic ether group and/or cyclic thioether base (hreinafter referred to as ring-type (sulphur) ether).

Having 2 in such molecule with the Thermocurable composition (D) of upper annular (sulphur) ether is the compound of any one or 2 kinds of groups in molecule with more than 2 three-membered rings, four-membered ring or pentacyclic cyclic ether group or cyclic thioether base, can list in molecule the compound and episulfide resin (D-2) etc. in the compound with more than at least 2 oxetanyls and multifunctional oxetane compound (D-1), molecule with more than at least 2 thioether groups.

As aforementioned multifunctional oxetane compound (D-1), two [(3-methyl-3-oxetanylmethoxy) methyl] ether can be listed, two [(3-ethyl-3-oxetanylmethoxy) methyl] ether, 1, two [(3-methyl-3-oxetanylmethoxy) methyl] benzene of 4-, 1, two [(3-ethyl-3-oxetanylmethoxy) methyl] benzene of 4-, acrylic acid (3-methyl-3-oxetanyl) methyl esters, acrylic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters, the multifunctional oxetanes classes such as their oligomer or multipolymer, and novolac resin, poly-(4-Vinyl phenol), cardo type bisphenols, calixarene kind, resorcinol calixarenes (calixresorcinarene) class or silsesquioxane (silsesquioxane) etc. have the resin of hydroxyl and the etherate etc. of oxetanes alcohol.In addition, the multipolymer etc. of unsaturated monomer and (methyl) alkyl acrylate with oxetanes ring can be listed.

As the compound (D-2) in previous molecular with more than 2 cyclic thioether bases, the bisphenol A-type episulfide resin YL7000 etc. that such as Japan Epoxy Resins Co., Ltd. manufactures can be listed.In addition, the episulfide resin etc. adopting same synthetic method the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin to be replaced to sulphur atom can also be used.

About there are 2 with the use level of the Thermocurable composition (D) of upper annular (sulphur) ether in previous molecular, relative to the aforementioned 1 equivalent carboxyl containing carboxy resin (B), ring-type (sulphur) ether is preferably 0.6 ~ 2.5 equivalent, and more preferably the scope of 0.8 ~ 2.0 equivalent is applicable.Have in molecule 2 with the use level of the Thermocurable composition (D) of upper annular (sulphur) ether less than 0.6 time, have carboxyl to remain in soldering-resistance layer, reductions such as thermotolerance, alkali resistance, electrical insulating property, therefore not preferred.On the other hand, during more than 2.5 equivalent, low-molecular-weight ring-type (sulphur) ether remains in dry coating, makes the reductions such as painting film strength, therefore not preferred.

Light solidifying/heat solidifying resin composition of the present invention is preferably containing thermal curing catalyst.As such thermal curing catalyst, the imdazole derivatives such as such as imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole can be listed; Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, the amines such as N-dimethyl benzyl amine; The hydrazide compound such as adipic dihydrazide, sebacic dihydrazide; The phosphorus compounds etc. such as triphenylphosphine.In addition, as commercially available product, 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade name of imidazole compound) that such as four countries change into industrial group's manufacture can be listed, U-CAT (registered trademark) 3503N, U-CAT3502T (being the trade name of the blocked isocyanate compound of dimethyl amine) that SAN-APRO company manufactures, DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc.Be not limited in these compounds, as long as the thermal curing catalyst of epoxy resin, the thermal curing catalyst of oxetane compound or promote the material of epoxy radicals and/or oxetanyl and carboxyl reaction, can be used alone or mix two or more use.In addition, guanamines, methyl guanamines, benzoguanamine, melamine, 2 can also be used, 4-diamido-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid adduct, 2, these compounds also worked as adaptation imparting agent and aforementioned hot curing catalysts are preferably combinationally used by the Striazine derivatives such as 4-diamido-6-methacryloxyethyl-s-triazine isocyanuric acid adduct.

As long as the ratio of the common amount of the use level of these thermal curing catalysts is just enough, such as, there are 2 with the Thermocurable composition (D) of upper annular (sulphur) ether relative to 100 mass parts containing in carboxy resin (B) or molecule, be preferably 0.1 ~ 20 mass parts, more preferably 0.5 ~ 15.0 mass parts.

The photo-sensitive monomer (E) in the molecule used in light solidifying/heat solidifying resin composition of the present invention with more than 2 olefinic unsaturated groups is, is irradiated carry out photocuring and make aforementioned insoluble or contribute to thawless material in aqueous alkali containing carboxy resin (B) containing olefinic unsaturated group by active energy beam.As such compound, the diacrylate class of the glycol such as ethylene glycol, methoxyl TEG, polyglycol, propylene glycol can be listed; The multicomponent methacrylate class of the polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, three-hydroxyethylisocyanurate or their ethylene oxide adduct or propylene oxide adduct etc.; The multicomponent methacrylate class of the ethylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and their phenols or propylene oxide adduct etc.; The multicomponent methacrylate class of the glycidol ethers such as glycerin diglycidyl ether, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester; And melamine acrylate and/or each methyl acrylic ester etc. corresponding with aforesaid propylene acid esters.

The epoxy polyurethane acrylate compound etc. that the hydroxyl that also can list Epocryl that the polyfunctional epoxy resins such as cresol novolak type epoxy resin and acrylic acid is obtained by reacting and this Epocryl is obtained by reacting with half urethanes formed by diisocyanate such as hydroxy acrylate and isophorone diisocyanate such as pentaerythritol triacrylates.Such epoxy acrylate system resin improves photo-curable with can not reducing its dry to touch.

Aforementioned relative to 100 mass parts containing carboxy resin (B), the use level in such molecule with the photo-sensitive monomer (E) of more than 2 olefinic unsaturated groups is below 100 mass parts, and more preferably the ratio of 5 ~ 70 mass parts is applicable.During aforementioned cooperation quantity not sufficient 5 mass parts, photo-curable reduces, and is difficult to form pattern by the postradiation alkali development of active energy beam, therefore not preferred.On the other hand, during more than 100 mass parts, reduce the dissolubility of aqueous alkali, film becomes fragile, therefore not preferred.

Light solidifying/heat solidifying resin composition of the present invention can be combined with toner (F).As colorant, the conventional known colorant such as red (F-1), blue (F-2), green (F-3), yellow (F-4) can be used, can be pigment, dyestuff, pigment any one.Wherein, from the view point of reduction carrying capacity of environment and the impact on human body, preferably not containing halogen.

red stain (F-1):

As red stain, there are monoazo system, bisdiazo system, monoazo color lake system, benzimidazolone Xi, perylene system, diketopyrrolopyrrolecocrystals system, condensation azo system, anthraquinone system, quinacridone etc., particularly, following material can be listed.

Monoazo system: paratonere 1,2,3,4,5,6,8,9,12,14,15,16,17,21,22,23,31,32,112,114,146,147,151,170,184,187,188,193,210,245,253,258,266,267,268,269.

Bisdiazo system: pigment red 37,38,41.

Monoazo color lake is: pigment red 4 8:1,48:2,48:3,48:4,49:1,49:2,50:1,52:1,52:2,53:1,53:2,57:1,58:4,63:1,63:2,64:1,68.

Benzimidazolone system: paratonere 171, paratonere 175, paratonere 176, paratonere 185, paratonere 208.

Perylene system: solvent of red 135, solvent red 179, pigment red 123, pigment red 149, paratonere 166, paratonere 178, pigment red179, paratonere 190, paratonere 194, paratonere 224.

Diketopyrrolopyrrolecocrystals system: paratonere 254, paratonere 255, paratonere 264, paratonere 270, paratonere 272.

Condensation azo system: paratonere 220, paratonere 144, paratonere 166, pigment red 21 4, paratonere 220, paratonere 221, paratonere 242.

Anthraquinone system: paratonere 168, paratonere 177, pigment red 21 6, solvent red 149, solvent red 150, solvent red 52, solvent red 207.

Quinacridone: pigment red 122, paratonere 202, paratonere 206, Pigment Red 207, paratonere 209.

blue colorant (F-2):

As blue colorant, have phthalocyanine system, anthraquinone system, pigment system is the compound being classified as pigment (Pigment), particularly, can use with following such color index (C.I.; The Society of Dyers and Colourists issues) material of sequence number: pigment blue 15, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3, pigment blue 15: 4, pigment blue 15: 6, pigment blue 16, pigment blue 60.

As dyestuff system, solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc. can be used.In addition to the foregoing, metal can also be used to replace or unsubstituted phthalocyanine compound.

green colourant (F-3):

As green colourant, have phthalocyanine system, anthraquinone Xi, perylene system equally, particularly, can use that pigment Green 7, pigment green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 etc.In addition to the foregoing, metal can also be used to replace or unsubstituted phthalocyanine compound.

yellow colorants (F-4):

As yellow colorants, there are monoazo system, bisdiazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone system etc., particularly, following material can be listed.

Anthraquinone system: solvent yellow 16 3, pigment yellow 24, pigment yellow 108, pigment yellow 193, pigment yellow 147, pigment yellow 199, pigment yellow 202.

Isoindolinone system: pigment yellow 110, pigment yellow 109, pigment yellow 13 9, pigment yellow 17 9, pigment yellow 185.

Condensation azo system: pigment yellow 93, pigment yellow 94, pigment yellow 95, pigment Yellow 12 8, pigment yellow 155, pigment yellow 166, pigment yellow 180.

Benzimidazolone system: pigment Yellow 12 0, pigment yellow 151, pigment yellow 154, pigment yellow 156, pigment yellow 17 5, pigment yellow 181.

Monoazo system: pigment yellow 1,2,3,4,5,6,9,10,12,61,62,62:1,65,73,74,75,97,100,104,105,111,116,167,168,169,182,183.

Bisdiazo system: pigment Yellow 12,13,14,16,17,55,63,81,83,87,126,127,152,170,172,174,176,188,198.

In addition, in order to adjust tone, purple, orange, brown, black etc. colorant can be added.

The words of particular instantiation, there is pigment violet 19, 23, 29, 32, 36, 38, 42, solvent violet 13, 36, C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73, C.I. pigment brown 23, C.I. pigment brown 25, C.I. pigment black 1, C.I. pigment black 7 etc.

The mixing ratio of foregoing colorant (F) is not particularly limited, and aforementioned relative to 100 mass parts containing carboxy resin (B), be preferably 0 ~ 10 mass parts, the ratio being particularly preferably 0.1 ~ 5 mass parts is sufficient.

In order to improve the physical strength etc. of the film of light solidifying/heat solidifying resin composition of the present invention, as required, filler can be coordinated.As such filler, known conventional inorganic or organic filler can be used, especially preferably use barium sulphate, preparing spherical SiO 2 and talcum.And then, in order to obtain outward appearance, the anti-flammability of white, the material that can also to use with metal hydroxides such as titanium dioxide, metal oxide, aluminium hydroxide be extender pigment filler.The use level of filler is preferably below the 75 quality % of total composition, more preferably the ratio of 0.1 ~ 60 quality %.When the use level of filler exceedes 75 quality % of total composition, the viscosity of insulation composition increases, be coated with, formability reduces, solidfied material becomes fragile, therefore not preferred.

And then, above-mentioned containing carboxy resin (B), modulation group compound in order to synthesize, or in order to viscosity adjustment is to be applied in substrate or carrier film, light solidifying/heat solidifying resin composition of the present invention can be with an organic solvent.

As such organic solvent, ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, petroleum solvent etc. can be listed.More specifically, the ketone such as MEK, cyclohexanone is had; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; The glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; The ester classes such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propandiol butyl ether acetic acid esters; The alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; The aliphatic hydrocarbon such as octane, decane; The petroleum solvents etc. such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha.Such organic solvent can be used alone or uses as potpourri of more than two kinds.

As required, light solidifying/heat solidifying resin composition of the present invention can also coordinate with known conventional additive kind, as quinhydrones, the known conventional hot polymerization inhibitors such as hydroquinone monomethyl ether, tert-butyl catechol, 1,2,3,-thrihydroxy-benzene, phenothiazine, the known conventional tackifier such as fine particle silica, organobentonite, smectite, defoamer and/or the levelling agents such as silicone-based, fluorine system, macromolecular, the silane coupling agents such as imidazoles system, thiazole system, triazole system, antioxidant, rust preventive etc.

With such as aforementioned organic solvents, light solidifying/heat solidifying resin composition of the present invention is adjusted to the viscosity of applicable coating process, be applied on base material by methods such as dip coating, flow coat method, rolling method, scraper rubbing method, silk screen print method, curtain Tu Fa, at the temperature of about 60 ~ 100 DEG C, make organic solvent volatile dry (temporarily dry) contained in composition, tack-free film can be formed.In addition, be applied to by above-mentioned composition in carrier film, drying forms film, fits on base material by the material that this film is rolled, and can form resin insulating barrier.Afterwards, adopt contact (or cordless), utilize active energy beam optionally to expose by forming figuratum photomask or utilize the direct exposure machine of laser directly to carry out pattern exposure, by dilute alkaline aqueous solution (such as 0.3 ~ 3wt% aqueous sodium carbonate), is developed in unexposed portion, can corrosion-resisting pattern be formed.And then, its heat curing is made by such as heating at the temperature of about 140 ~ 180 DEG C, make aforementioned carboxyl containing carboxy resin (B) and aforementioned epoxy resins (A) is reacted or further with molecule in there is more than 2 cyclic ether group and/or cyclic thioether base Thermocurable composition (D) react, the cured coating film of the various excellents such as thermotolerance, chemical proofing, resistance to hydroscopicity, adaptation, electrical characteristics can be formed.

As above-mentioned base material, except being pre-formed with the printed circuit board (PCB) of circuit, flexible printed circuit board, the copper clad laminate, Kapton, PET film, glass substrate, ceramic substrate, wafer board etc. of all grades (FR-4 etc.) employing the compound substances such as paper-phenolics, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimide, glass cloth/nonwoven fabrics-epoxy resin, glass cloth/paper-epoxy resin, synthon-epoxy resin, fluororesin tygon PPO cyanate can also be adopted.

The volatile dry carried out after being coated with light solidifying/heat solidifying resin composition of the present invention can use (use have the device of the thermal source of the air heat mode utilizing steam, the method that the hot air convection in dryer is contacted and the mode of being blown supporter by nozzle) such as heated air circulation type drying oven, IR stove, hot plate, convective oven.

As follows to coating light solidifying/heat solidifying resin composition of the present invention and the film obtained after volatile dry expose (irradiation of active energy beam).The exposure portion (part by active energy beam irradiates) of film is cured.

Irradiating the exposure machine used as above-mentioned active energy beam, direct drawing apparatus (such as by utilizing the laser direct imaging device of the direct rendering image of laser from the cad data of computing machine) can being used, be equipped with the exposure machine of metal halide lamp, be equipped with the exposure machine of (surpassing) high-pressure sodium lamp, be equipped with the exposure machine of mercury short arc lamp or employ the direct drawing apparatus of the UV-lamp such as (surpassing) high-pressure sodium lamp.As active energy beam, as long as use maximum wavelength to be that the laser of the scope of 350 ~ 410nm is just passable, can be used gas laser, Solid State Laser any one.In addition, its exposure is different from thickness etc., is generally 5 ~ 200mJ/cm ², be preferably 5 ~ 100mJ/cm ², be more preferably 5 ~ 50mJ/cm ²scope in.As above-mentioned direct drawing apparatus, the device that such as Japanese Orbotech Ltd., PENTAX company etc. manufactures can be used, as long as vibration maximum wavelength is the device of the laser of 350 ~ 410nm, arbitrary device can be used.

As aforementioned developing method, infusion process, elution method, gunite, spread coating etc. can be used, as developer solution, potassium hydroxide can be used, the aqueous alkali of NaOH, sodium carbonate, sal tartari, sodium phosphate, sodium silicate, ammonia, amine etc.

Except be coated directly onto the method for base material with liquid state except, light solidifying/heat solidifying resin composition of the present invention can also use with the form of dry film, wherein, described dry film has and is coated with solder resist in advance and dry and solder mask that is that formed on the film of polyethylene terephthalate etc.It is as follows when light solidifying/heat solidifying resin composition of the present invention uses as dry film.

Dry film have by carrier film, solder mask and as required and the coverlay that can peel off used according to the structure of this order lamination.Solder mask to be applied to by the light solidifying/heat solidifying resin composition of alkali-developable on carrier film or coverlay and dry and layer that is that obtain.To form after solder mask lamination coverlay thereon on a carrier film, or again this laminate layer is pressed onto in carrier film form solder mask on coverlay after, can dry film be obtained.

As carrier film, thickness can be used to be the thermoplastic films such as the mylar of 2 ~ 150 μm.

Solder mask is uniformly applied to carrier film or coverlay on also dry by knife type coater, lip coating machine (lip coater), comma coater (comma coater), film coater etc. with the thickness of 10 ~ 150 μm by alkali-developable light solidifying/heat solidifying resin composition and is formed.

As coverlay, can polyethylene film, polypropylene film etc. be used, the bounding force of itself and solder mask than with little better of carrier film.

In order to use dry film to make diaphragm (permanent diaphragm) on a printed circuit, peel off coverlay, solder mask is overlapping with the base material being formed with circuit, use laminating machine etc. to make it fit, the base material being formed with circuit forms solder mask.In the same manner as aforementioned, the solder mask formed exposed, develops, is heating and curing, then can form cured coating film.Carrier film before exposure or exposure after stripping.

embodiment

Below illustrate that embodiment and comparative example are described particularly to the present invention, certainly, the present invention is not by the restriction of following embodiment.In addition, " part " and " % " below, if not otherwise specified, all refers to quality criteria.

synthesis example 1 (synthesis containing carboxy resin)

In the removable flask of 2 liters possessing stirring machine, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, importing 660g cresol novolak type epoxy resin, (Japanese chemical drug (strain) manufactures, EOCN-104S, softening point 92 DEG C, epoxide equivalent 220), 421.3g carbitol acetate and 180.6g solvent naphtha, be heated to 90 DEG C and stir and make it dissolve.Then, once be cooled to 60 DEG C, add 216g acrylic acid, 4.0g triphenylphosphine and 1.3g methylnaphthohydroquinone immediately, make it react 12 hours at 100 DEG C, obtain the reaction product that acid number is 0.2mgKOH/g.Add 241.7g tetrabydrophthalic anhydride wherein, be heated to 90 DEG C, react 6 hours.Obtain that acid number is 50mgKOH/g, double bond equivalent (unsaturated group is the gram weight of the resin of 1 molar equivalent) is 400 thus, weight-average molecular weight be 7000 solid component concentration be that the photonasty of 65% is containing the solution of carboxy resin.Below, the solution this photonasty being contained carboxy resin is called B1 varnish.

synthesis example 2 (synthesis containing carboxy resin)

Be 800 by 400 parts of epoxide equivalents, softening point is, after bisphenol-f type solid epoxy resin 925 parts of epichlorokydrin of 79 DEG C and 462.5 parts of dmso solutions, under agitation, at 70 DEG C, add 81.2 parts of 98.5%NaOH, add and continue 100 minutes.React 3 hours further at 70 DEG C after interpolation.Then, the unreacted epichlorokydrin that under reduced pressure distillation removing major part is superfluous and dimethyl sulfoxide (DMSO), the reaction product of the salt and dimethyl sulfoxide (DMSO) that comprise by-product is dissolved with 750 parts of methyl isobutyl ketones, then adds 10 parts of 30%NaOH, react 1 hour at 70 DEG C.After reaction terminates, carry out 2 washings with 200 parts of water.After oil and water separation, by oil reservoir by methyl isobutyl ketone Distillation recovery, obtain the epoxy resin (A-0) that 370 parts of epoxide equivalents are 290, softening point is 62 DEG C.

Then, add the epoxy resin (A-0) that 2900 parts (10 equivalents) obtain, 720 parts of (10 equivalent) acrylic acid, 2.8 parts of methylnaphthohydroquinones, 1950 parts of carbitol acetate, be heated to 90 DEG C, stir and reaction mixture is dissolved.Then, reactant liquor is cooled to 60 DEG C, adds 16.7 parts of triphenylphosphines, be heated to 100 DEG C, react about 32 hours, obtain the reactant that acid number is 1.0mgKOH/g.Then, add 786 parts of (7.86 moles) succinic anhydrides, 423 parts of carbitol acetate wherein, be heated to 95 DEG C, react about 6 hours.The photonasty that the acid number obtaining solid constituent is thus 100mgKOH/g, solid component concentration is 65% contains the solution of carboxy resin.Below, the solution this photonasty being contained carboxy resin is called B2 varnish.

embodiment 1 ~ 5 and comparative example 1 ~ 3

Various compositions shown in table 1 are coordinated according to the ratio (mass parts) shown in each coordinating example, after stirring machine premixed, joins in airtight container, heat 60 minutes in the hot air circulation type drying machine of 100 DEG C.Confirm that the composition obtained is after complete dissolved state, stirred by stirring machine, at room temperature place 2 hours, after confirming to return to room temperature, this mixed liquor 5 μm of metre filter are obtained A liquid.The A liquid ERICHSEN Inc. granulation grade analyzer obtained carries out granulometry, and evaluating dispersion degree, is less than 5 μm.After this A liquid is placed 24 hours at 5 DEG C, carry out granulometry with the particle size analyzer that ERICHSEN company manufactures, evaluate dispersion degree.

The evaluation result of dispersion degree is shown in table 2.

[table 1]

[table 2]

As shown in table 2, according to it is considered herein that, the dispersion degree of the embodiment 1 ~ 5 employing the epoxy resin of (A-1) and (A-2) and the comparative example 3 not using A-1 composition is less than 5 μm, on the other hand, the ratio do not specified according to the present invention uses the comparative example 1,2 of (A-1) and (A-2) epoxy resin all to produce big particle due to the reason of A-1 composition, and dispersion degree significantly reduces.

embodiment 6

20 parts of KAYARAD TMPTA (trimethylolpropane triacrylate, Japanese chemical drug (strain) manufacture) are used to replace the DPHA of aforementioned cooperation example 1-4 to prepare A liquid, carry out the evaluation of dispersion degree similarly to Example 4, dispersion degree is less than 5 μm.

embodiment 7

20 parts of NK EsterA-DCP (dihydroxymethyl tristane diacrylate, Xin Zhong village chemical industry (strain) manufacture) are used to replace the DPHA of aforementioned cooperation example 1-4 to prepare A liquid, carry out the evaluation of dispersion degree similarly to Example 4, dispersion degree is less than 5 μm.

embodiment 8

20 parts of ARONIX M-350 (trimethylolpropane EO modified triacrylate, East Asia synthesis (strain) manufacture) are used to replace the DPHA of aforementioned cooperation example 1-4 to prepare A liquid, carry out the evaluation of dispersion degree similarly to Example 4, dispersion degree is less than 5 μm.

embodiment 9

Use 20 parts of TMPTMA (trimethylol-propane trimethacrylates, Xin Zhong village chemical industry (strain) manufactures) replace the DPHA of aforementioned cooperation example 1-4 to prepare A liquid, carry out the evaluation of dispersion degree similarly to Example 4, dispersion degree is less than 5 μm.

embodiment 10

Use 20 parts of NK EsterBPE-500 (Ethoxylated bisphenol A dimethylacrylates, Xin Zhong village chemical industry (strain) manufactures) replace the DPHA of aforementioned cooperation example 1-4 to prepare A liquid, carry out the evaluation of dispersion degree similarly to Example 4, dispersion degree is less than 5 μm.

embodiment 11 ~ 13 and comparative example 4

What use aforementioned synthesis example contains carboxy resin solution B 1 varnish, the various compositions except barium sulphate slurry shown in coordinating example 2 of table 3 are coordinated according to the ratio (mass parts) shown in table 3, after stirring machine premixed, carry out mixing with 3 roll-type roller mills.Then, in said composition, add the barium sulphate slurry of ratio shown in table 3 (mass parts), stir with stirring machine.By 5 μm of metre filter said compositions, preparation B liquid.The particle size analyzer that the B liquid ERICHSEN company obtained manufactures carries out granulometry, and evaluating dispersion degree, is less than 5 μm.Then, after said composition is placed 24 hours at 5 DEG C, carry out granulometry with the particle size analyzer that ERICHSEN company manufactures, evaluating dispersion degree, is less than 5 μm.

[table 3]

Various compositions shown in the coordinating example 3 of table 4 are coordinated according to the ratio (mass parts) shown in table 4, after stirring machine premixed, carries out mixing with 3 roll-type roller mills, preparation C liquid.The particle size analyzer that the C liquid ERICHSEN company obtained manufactures carries out granulometry, and evaluating dispersion degree, is less than 15 μm.

[table 4]

big particle on dry coating

After the B liquid of coordinating example 2 and the C liquid of coordinating example 3 being mixed respectively, with stirring machine mixing, obtain light solidifying/heat solidifying resin composition.This light solidifying/heat solidifying resin composition is suitably diluted with MEK respectively, fully stir with stirring machine, then carry out granulometry with the particle size analyzer that ERICHSEN company manufactures, evaluate dispersion degree, the dispersion degree of C liquid is not only less than 15 μm, and is less than 5 μm.Think that reason is, the big particle of more than 5 μm of C liquid dissolves when mixing with B liquid.Then, this solution applicator is applied in PET film (TORAY INDUSTRIES, INC. manufacture FB-50:16 μm), makes dry rear film be 50 μm, with the heated air circulation type kiln drieds of 80 DEG C after 30 minutes, at 15 DEG C, naturally cool 24 hours.By this plate observation by light microscope, evaluate the presence or absence of crystalloid big particle.Determinating reference is as follows.

Zero: there is no crystalloid big particle

△: the generation of visible a small amount of crystal

×: crystalloid big particle produces in a large number

the plyability of dry coating

Figuratum copper clad laminate polishing grinding will be formed, then by the dry coating vacuum laminator ((strain) name mechanism do manufactured MVLP-500) after above-mentioned observation in pressurization degree: 0.8MPa, 70 DEG C, 1 minute, heated lamination under the condition of vacuum tightness: 133.3Pa, obtain the substrate (unexposed substrate) with unexposed solder mask.

By this substrate observation by light microscope, following determinating reference is used to evaluate.Evaluation result is as shown in table 5.

Zero: the surface state after lamination is level and smooth

△: lamination is bad causes part generation concavo-convex

×: lamination is bad causes whole generation concavo-convex

[table 5]

As shown in table 5, according to the present invention, when employ (A-1) and (A-2) epoxy resin embodiment 11 ~ 13, the light solidifying/heat solidifying resin composition that B liquid and C liquid are mixed to get suitably is diluted with MEK respectively, when fully stirring with stirring machine, big particle all dissolves, and after the drying after 24 hours, does not also produce the big particle thinking to be caused by A-1 composition in dry coating.In addition, this film lamination can be obtained flatness.On the other hand, when comparative example 4, with MEK dilution, after stirring, big particle all dissolves, but after drying is placed, think the big particle caused by A-1 composition, the film on lamination metacoxal plate also becomes uneven.

embodiment 14

Use 155 parts of B2 varnish to replace the B1 varnish of coordinating example 2, implement the making of dry film, the evaluation of surface state by method similarly to Example 11.Result is identical with embodiment 11.

embodiment 15

Use 222 parts of Cyclomer P (ACA) Z250 (DAICEL-CYTECCompany LTD. manufacture containing carboxy resin, solid constituent 45 quality %) replace the B1 varnish of coordinating example 2 to prepare B liquid, implement the making of dry film, the evaluation of surface state by method similarly to Example 11.Result is identical with embodiment 11.

embodiment 16 ~ 20, comparative example 5 ~ 7

Various compositions shown in the coordinating example 4 of table 6 are coordinated according to the ratio (mass parts) shown in coordinating example 4, after stirring machine premixed, carries out mixing with 3 roll-type roller mills, preparation D liquid.The particle size analyzer that the dispersion degree ERICHSEN company of the composition obtained manufactures carries out granulometry evaluation, is less than 15 μm.

[table 6]

embodiment 21, comparative example 8

Various compositions shown in the coordinating example 5 of table 7 are coordinated according to the ratio (mass parts) shown in coordinating example 5, uses stirring machine premixed, then carry out mixing with 3 roll-type roller mills, preparation E liquid.The particle size analyzer that the dispersion degree ERICHSEN company of the composition obtained manufactures carries out granulometry evaluation, is less than 15 μm.

[table 7]

Then, by aforementioned A liquid, E liquid and D liquid according to after combined hybrid shown in table 8, stir with stirring machine, obtain light solidifying/heat solidifying resin composition.In addition, after preparation, use after A liquid, E liquid are placed 7 days at 15 DEG C.

[table 8]

performance evaluation:

big particle on dry coating

The light solidifying/heat solidifying resin composition applicator of previous embodiment 16 ~ 21 and comparative example 5 ~ 8 is applied on glass plate, dry rear film is made to be 50 μm, in the heated air circulation type drying oven of 80 DEG C after dry 30 minutes, at room temperature naturally cool 24 hours.By this plate observation by light microscope, evaluate the presence or absence of crystalloid big particle.Determinating reference is as follows.

Zero: nodeless mesh shape big particle

△: visible a small amount of crystal produces

×: produce bulk crystallization shape big particle

optimum exposure

The circuit pattern substrate polishing roll of thick for copper 35 μm is ground, after washing, drying, the light solidifying/heat solidifying resin composition of previous embodiment 16 ~ 21 and comparative example 5 ~ 8 is coated with, drying 60 minutes in the heated air circulation type drying oven of 80 DEG C by whole of silk screen print method.After drying, the exposure device being equipped with high-pressure sodium lamp (short-arc lamp) is used to be exposed by stage metraster (KodakNo.2), will develop (30 DEG C, 0.2MPa, 1wt%Na ₂cO ₃aqueous solution) pattern of stage metraster residual after 60 seconds exposure when being 7 sections is as optimum exposure.

attribute testing:

Forming the composition by whole of serigraphy coating the various embodiments described above 16 ~ 21 and comparative example 5 ~ 8 on figuratum copper clad laminate, making dried thickness be 20 μm, at 80 DEG C, naturally cooling to room temperature after dry 30 minutes.The exposure device that use is equipped with high-pressure sodium lamp (short-arc lamp) exposes the soldering-resistant pattern on this substrate with optimum exposure exposure, then uses the 1wt%Na of 30 DEG C ₂cO ₃aqueous solution was developed for 60 seconds under the condition spraying 0.2MPa, obtained corrosion-resisting pattern.This substrate is transmitted in stove at cumulative exposure amount 1000mJ/cm at UV ²condition under carry out Ultraviolet radiation, then heat at 150 DEG C and be cured for 60 minutes.The characteristic of the printed base plate (evaluation substrate) of gained is evaluated as follows.

solder heat resistance

The evaluation substrate being coated with rosin series solder flux is impregnated in the solder bath being redefined for 260 DEG C, with modification alcohol washing solder flux, the then expansion of visual valuation resist layer and stripping.Judgment standard is as follows.

◎: repeat more than 6 times 10 seconds dipping also can't see stripping.

Zero: repeat more than 3 times 10 seconds dipping also can't see stripping.

△: repeating more than 3 times 10 seconds has a little stripping after dipping.

×: within repeating 3 times, 10 seconds flooded, and resist layer has expansion, stripping.

chemical gilding patience

Use commercially available product electroless nickel bath and chemical gilding bath, under 0.5 μm, nickel, the gold condition of 0.03 μm, carry out plating, band peel off after by visual resist layer of evaluating with or without peeling off, with or without the infiltration of plating.Judgment standard is as follows.

◎: can't see infiltration completely, peel off.

Zero: can see a little infiltration after plating, band can't see stripping after peeling off.

△: can see a little infiltration after plating, band also can see stripping after peeling off.

×: there is stripping after plating.

electrical characteristics

Use the comb-type electrode pattern of line/space=20/20 μm to replace copper clad laminate, make under these conditions and evaluate substrate, 10 pieces of these comb-type electrodes are applied to the bias voltage of DC10V, 130 DEG C, in groove, measure insulating resistance value under the condition of 85%R.H..In mensuration, resistance value becomes 10 ⁴the comb-type electrode of below Ω is judged to be short circuit, calculates the quantity not having the comb-type electrode of short circuit after 100 hours.

embodiment 22

dry film makes

After the Photosetting and thermosetting oil/fat composition of embodiment 16 suitably being diluted respectively with MEK, applicator is used to be applied to PET film (TORAY INDUSTRIES, INC. FB-50:16 μm is manufactured) on, make dried thickness be 20 μm, at 80 DEG C, drying obtains dry film in 30 minutes.

substrate manufacture

Figuratum copper clad laminate polishing grinding will be formed, then by the dry film vacuum laminator ((strain) name mechanism do manufactured MVLP-500) that makes according to the method described above in pressurization degree: 0.8MPa, 70 DEG C, 1 minute, heated lamination under the condition of vacuum tightness: 133.3Pa, obtain the substrate (unexposed substrate) with unexposed solder mask.

By aforementioned test methods and evaluation method, each evaluation test is carried out to the test substrate with cured film obtained.

The result of aforementioned each evaluation test is shown in table 9.

[table 9]

As shown in Table 9 above, compared with comparative example 5 ~ 8, embodiments of the invention 16 ~ 22 do not produce big particle on dry coating, and solder heat resistance, chemical gilding patience, electrical characteristics excellence.

On the other hand, fully do not comprising the situation of comparative example 5 of A-2 composition, the minimizing of visible crystalloid big particle, but do not reaching the generation preventing recrystallization completely.And then, in the situation of comparative example 6 and 8, think that big particle produces the reduction of the electrical characteristics caused in a large number as seen.Comparative example 7 does not have big particle to produce, but the reduction of visible solder heat resistance, electrical characteristics.

Claims (7)

1. the light solidifying/heat solidifying resin composition of an alkali-developable, described composition contains (A) epoxy resin, (B) containing carboxy resin, (C) Photoepolymerizationinitiater initiater, and thermal curing catalyst, colorant, there is in molecule the photo-sensitive monomer of more than 2 olefinic unsaturated groups, barium sulphate, silicone-based defoamer and organic solvent, it is characterized in that, described epoxy resin (A) is that 2 officials with structure shown in following general formula (I) biphenyl epoxy resin A-1 and softening point can be 40 ~ 100 DEG C and epoxide equivalent is the potpourri of the xenol phenolic resin varnish type epoxy resin A-2 of 180 ~ 300, the ratio of A-1 and the A-2 of described epoxy resin is A-1 < A-2,

In formula, R represents H or CH ₃,

Described epoxy resin (A) dissolves in dry coating,

Described light solidifying/heat solidifying resin composition, by the liquid containing above-mentioned 2 officials' energy biphenyl epoxy resin A-1, above-mentioned xenol phenolic resin varnish type epoxy resin A-2 and above-mentioned organic solvents, is formed containing the liquid in carboxy resin, above-mentioned (C) Photoepolymerizationinitiater initiater and above-mentioned thermal curing catalyst, above-mentioned colorant, above-mentioned molecule with the photo-sensitive monomer of more than 2 olefinic unsaturated groups, above-mentioned barium sulphate, above-mentioned silicone-based defoamer and above-mentioned organic solvent with containing above-mentioned (B);

Above-mentioned (B) is by making 2 officials above polyfunctional epoxy resin react with (methyl) acrylic acid containing carboxy resin, makes to be present in the hydroxyl of side chain and 2 yuan of acid anhydrides additions and the photonasty that obtains contains carboxy resin,

Above-mentioned (C) Photoepolymerizationinitiater initiater is oxime ester system Photoepolymerizationinitiater initiater (C1) with group shown in following general formula (II), and has alpha-aminoacetophenone system Photoepolymerizationinitiater initiater (C2) of group shown in following general formula (III);

In formula (II), R ¹represent hydrogen atom; optionally by the phenyl of the alkyl of carbon number 1 ~ 6, phenyl or halogen atom replacement; optionally replaced, optionally have at alkyl middle-of-chain the alkyl of the carbon number 1 ~ 20 of the oxygen atom of more than 1 by the hydroxyl of more than 1; the naphthenic base of carbon number 5 ~ 8; optionally by the alkanoyl of the carbon number 2 ~ 20 of the alkyl or phenyl of carbon number 1 ~ 6 replacement or benzoyl

R ²represent optionally by the phenyl of the alkyl of carbon number 1 ~ 6, phenyl or halogen atom replacement; optionally replaced, optionally have at alkyl middle-of-chain the alkyl of the carbon number 1 ~ 20 of the oxygen atom of more than 1 by the hydroxyl of more than 1; the naphthenic base of carbon number 5 ~ 8; optionally by the alkanoyl of the alkyl or phenyl alternate c atoms number 2 ~ 20 of carbon number 1 ~ 6 or benzoyl

In formula (III), R ³and R ⁴represent the alkyl or aryl alkyl of carbon number 1 ~ 12 independently of one another,

R ⁵and R ⁶represent alkyl or the cyclic alkyl ether of bonding both representing of hydrogen atom, carbon number 1 ~ 6 independently of one another.

2. light solidifying/heat solidifying resin composition according to claim 1, it is characterized in that, the described acid number containing carboxy resin (B) with 40 ~ 120mgKOH/g, contain carboxy resin (B) relative to described in 100 mass parts, the potpourri of A-1 and the A-2 of described epoxy resin is 20 ~ 60 mass parts.

3. light solidifying/heat solidifying resin composition according to claim 1, is characterized in that, the photo-sensitive monomer in described molecule with more than 2 olefinic unsaturated groups is liquid.

4. the light solidifying/heat solidifying resin composition according to any one of claims 1 to 3, is characterized in that, it is for the formation of solder resist.

5. a dry film, it obtains by being applied to by the light solidifying/heat solidifying resin composition described in any one of described claims 1 to 3 also dry in carrier film.

6. a solidfied material, it is by to be applied to by the light solidifying/heat solidifying resin composition described in any one of described claims 1 to 3 on base material and dry and dry coating that is that obtain carries out photocuring and/or heat curing and obtains; Or, by described light solidifying/heat solidifying resin composition to be applied in carrier film and the dry coating that dry dry film lamination obtains to base material carries out photocuring and/or heat curing and obtains.

7. a printed circuit board (PCB), it has aforementioned solidfied material according to claim 6.