CN102472970B - Light solidifying/heat solidifying resin composition - Google Patents

Abstract

The present invention provides to be formed to be had PCT patience, HAST patience, the gold-plated property of chemically-resistant, the light solidifying/heat solidifying resin composition of curing overlay film, its dry film and the solidfied material of cold-hot impact important for semiconductor-sealing-purpose solder resist and is formed the printed circuit board (PCB) of the curing overlay film of solder resist etc. by them.The light solidifying/heat solidifying resin composition of available alkaline aqueous solution development contain containing carboxy resin, Photoepolymerizationinitiater initiater, containing based elastomers and sulfhydryl compound.Above-mentioned is not the most the resin derived by epoxy resin containing carboxy resin.

Description

Light solidifying/heat solidifying resin composition

Technical field

The present invention relates to the light solidifying/heat solidifying resin composition that can be developed by alkaline aqueous solution, particularly relate to By ultraviolet exposure or laser explosure come the solder resist compositions of photocuring, its dry film and solidfied material and have use it The printed circuit board (PCB) of curing overlay film that formed.

Background technology

Now, from the viewpoint of high accuracy, high density, a part of civilian printed circuit board (PCB) and major part industry are used The solder resist of printed circuit board (PCB), uses and forms image by developing after uv irradiation and utilize heat and/or illumination to inject The final liquid developable solder flux solidifying (being fully cured) of row, from the misgivings to environmental problem, uses alkaline aqueous solution Photic solder resist as the alkali developable of developer solution becomes main flow, and is made in a large number in the manufacture of actual printed circuit board (PCB) With.It addition, the densification of the printed circuit board (PCB) corresponding to compactization along with electronic equipment in recent years, for solder resist Also require operability, high performance.

But, the photic solder resist of existing alkali developable there is a problem from the viewpoint of durability.I.e. with in the past Thermohardening type, the material of solvent development type compare alkali resistance, resistance to water, thermostability equal difference.This is considered as because alkali develops The photic solder resist of type in order to alkali development and with there is hydrophilic radical material as main component, chemical reagent, water, water steam Gas etc. are easily impregnated with so that chemical proofing reduces, overlay film against corrosion reduces with the adaptation of copper.Its result, as chemically-resistant The alkali resistance of medicine is weak, particularly at BGA (BGA, Ball Grid Array), CSP (chip size packages body) etc. In semiconductor package body, it is especially desirable to PCT patience (pressure cooker testing (the pressure cooker of humidity resistance should be referred to as Test) patience), but this harsh under conditions of, can only tolerate several hours～about tens hours, this is present situation.It addition, Execute in HAST test (Highly Accelerated Life Test) under alive state under humidified condition, in almost all cases, A few hours are it is confirmed that produce to generation based on migration (migration) is bad.

It addition, in recent years, exist and transformation, the use of the unleaded solder adjoint to the misgivings of environmental problem are installed to surface The highest tendency is become Deng the temperature involved by, encapsulation.Thereupon, the arrival temperature of encapsulation inside and outside significantly increases, In existing liquid photosensitive resist, exist and on film, produce cracking because of thermal shock or from substrate, encapsulant The problem peeled off, needs to improve this.

On the other hand, the carboxylic resin that existing solder resist is used generally use the modification by epoxy resin and The derivative ester modified resin of epoxy acrylic.Such as, Japanese Laid-Open Patent Publication 61-243869 publication (patent documentation 1) reports By the photoresist that addition anhydride in novolak type epoxy compounds and the monacid product of unsaturation is obtained, The solder mask composition that Photoepolymerizationinitiater initiater, diluent and epoxide are formed.It addition, Japanese Unexamined Patent Publication 3-250012 public affairs Report (patent documentation 2) discloses the solder mask composition formed by photoresist, Photoepolymerizationinitiater initiater, organic solvent etc., This photoresist is addition on epoxy resin (methyl) acrylic acid, and then obtains with polybasic carboxylic acid or its anhydride reaction , described epoxy resin is to make chloropropylene oxide and salicylide and the reaction of monohydric phenol obtain.

But, the electrical characteristics containing carboxy resin used in existing solder mask composition are poor.

Prior art literature

Patent documentation

Patent documentation 1: Japanese Laid-Open Patent Publication 61-243869 publication (claims)

Patent documentation 2: Japanese Unexamined Patent Publication 3-250012 publication (claims)

Summary of the invention

The problem that invention is to be solved

The present invention makes in view of above-mentioned problem of the prior art, its main purpose is, provide photo-curable heat Hardening resin composition, it can be formed, and to have PCT patience important for semiconductor-sealing-purpose solder resist, HAST resistance to Property, the gold-plated property of chemically-resistant, the curing overlay film of cold-hot impact.

And then, it is an object of the invention to, it is provided that by using this light solidifying/heat solidifying resin composition to obtain The dry film of above-mentioned various excellents and solidfied material and formed the curing overlay films such as soldering-resistance layer by this dry film, solidfied material and The printed circuit board (PCB) become.

For solving the scheme of problem

In order to reach above-mentioned purpose, according to the present invention, it is provided that the photo-curable heat cure can developed by alkaline aqueous solution Property resin combination, it is characterised in that containing containing carboxy resin, Photoepolymerizationinitiater initiater, containing based elastomers and sulfydryl chemical combination Thing.

This contain carboxy resin to be preferably is not the resin derived by epoxy resin.In a preferred embodiment, the present invention Light solidifying/heat solidifying resin composition be to contain Thermocurable composition, the resistance preferably further containing coloring agent further Solder flux light solidifying/heat solidifying resin composition.

And then, according to the present invention, it is provided that described light solidifying/heat solidifying resin composition is coated carrier film and does Dry and the dry film of Photosetting and thermosetting that obtains and by solid to described light solidifying/heat solidifying resin composition or dry film light The solidfied material change, preferably obtained with pattern-like photocuring with the light source of wavelength 350nm～410nm.

And then, according to the present invention, also providing for printed circuit board (PCB), it has by irradiating active energy beam, preferably passing through Directly draw ultraviolet make described light solidifying/heat solidifying resin composition or dry film with pattern-like photocuring, then heat cure And the curing overlay film obtained.

The effect of invention

The light solidifying/heat solidifying resin composition of the present invention with as the composition that can be developed by alkaline aqueous solution Combine containing carboxy resin, containing containing based elastomers and sulfhydryl compound.Not only there is raising gained containing based elastomers The cured coating film effect to the crack resistance of cold cycling, but also there is the raising adaptation of solder resist, particularly PCT patience Effect.On the other hand, sulfhydryl compound is with photonasty composition and the described additive reaction containing based elastomers and crosslinking For the purpose of and add, be possible to prevent the coating characteristic that caused by the oxidation of vinyl to reduce, and then the friendship of softness can be obtained Connection, therefore, is favorably improved the characteristic such as PCT patience, HAST patience.It addition, sulfhydryl compound is also as chain-transferring agent and/or close Conjunction property imparting agent works, and therefore, it can obtain the sensitivity raising of compositions, the raising of adaptation simultaneously.Its result, not only The flexibility raising of the cured coating film obtained, the crack resistance raising to cold cycling, and then the close of solder resist can also be improved Conjunction property, particularly PCT patience.Therefore, the light solidifying/heat solidifying resin composition of the application of the invention, tool can be formed There are PCT patience important for semiconductor-sealing-purpose solder resist, HAST patience, the gold-plated property of chemically-resistant, cold-hot impact Curing overlay film.

It should be noted that in this manual, (methyl) acrylate be acrylate, methacrylate and they The general designation of mixture, other similar statement is too.

Detailed description of the invention

As it has been described above, the light solidifying/heat solidifying resin composition of the present invention is characterised by, containing containing carboxy resin, Photoepolymerizationinitiater initiater, containing based elastomers and sulfhydryl compound.

As above-mentioned containing carboxy resin, it is possible to use known conventional carboxyl.Preferably, as being considered will not make absolutely Edge less reliable (halide ion content is considerably less) containing carboxy resin, it is generally desirable to use do not use epoxy resin conduct Initiation material containing carboxy resin.In the middle of them, molecule has ethylenical unsaturated double bonds containing carboxyl photoresist from It is preferred from the standpoint of photo-curable, resistance to developability.And, its unsaturated double-bond preferably originates from acrylic acid or metering system Acid or their derivant.It should be noted that only use do not have ethylenical unsaturated double bonds containing carboxy resin time, in order to make Compositions has photo-curable, needs to be applied in combination the compound in molecule described later with more than 1 ethylenically unsaturated group (photo-sensitive monomer).

As the concrete example containing carboxy resin that can use in the present invention.The compound being exemplified below can be listed (oligomer and polymer).

(1) multifunctional (solid-state) epoxy resin making more than two senses described later or two senses is anti-with (methyl) acrylic acid Should, addition phthalic anhydride, tetrabydrophthalic anhydride, hexahydrophthalic anhydride etc. two on the hydroxyl be present in side chain Unit anhydride and obtain containing carboxyl photoresist.

(2) make to be carried out obtained by epoxidation by the hydroxyl of two senses (solid-state) epoxy resin described later with chloropropylene oxide further Polyfunctional epoxy resin reacts with (methyl) acrylic acid, generate hydroxyl on addition dibasic acid anhydride and obtain photosensitive containing carboxyl Property resin.

(3) epoxide in a part with multiple epoxy radicals is made to have at least one alcohol hydroxyl group in a part With the product of the monocarboxylic acid reaction gained containing unsaturated group such as the compound of a phenolic hydroxyl group, (methyl) acrylic acid The multi-anhydrides such as alcohol hydroxyl group and maleic anhydride, tetrabydrophthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, adipic acid Reaction and obtain containing carboxyl photoresist.

(4) bisphenol-A, Bisphenol F, bisphenol S, novolak phenolics, poly(4-hydroxystyrene), naphthols and aldehydes are made The a part such as the condensation substance of condensation substance, dihydroxy naphthlene and aldehydes have compound and oxirane, the ring of multiple phenolic hydroxyl group The monocarboxylic acid containing unsaturated group such as the product of the alkylene oxide such as Ethylene Oxide reaction gained and (methyl) acrylic acid reacts, and makes Gained product react with multi-anhydride and obtain containing carboxyl photoresist.

(5) compound in a part with multiple phenolic hydroxyl group and the ring-type carbon such as ethylene carbonate, propylene carbonate are made The product of ester compound reaction gained is reacted with the monocarboxylic acid containing unsaturated group, makes gained product with polynary Anhydride reaction and obtain containing carboxyl photoresist.

(6) make by aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type diisocyanate, fragrance The diisocyanate cpds such as (cyclo) aliphatic diisocyanates and polycarbonate-based polyhydric alcohol, polyethers system polyhydric alcohol, polyester-based polyols, poly- Olefin-based polyhydric alcohol, acrylic acid series multiple alcohol, bisphenol-A system alkylene oxide addition product dihydroxylic alcohols, there is phenolic hydroxyl group and alcohol hydroxyl group The sudden reaction of the diatomic alcohol compounds such as compound and the end of polyurethane resin that obtains and anhydride reaction and containing of obtaining Terminal carboxyl group polyurethane resin.

(7) by carboxylic diol compound such as diisocyanate and dihydromethyl propionic acid, dimethylolpropionic acid etc., With in the sudden reaction of diatomic alcohol compounds and the synthesis containing carboxyl polyurethane resin that carries out, add (methyl) acrylic acid hydroxyl alkane Ester equimolecular has the compound of 1 hydroxyl and more than 1 (methyl) acryloyl group carry out end (methyl) acrylated and Obtain containing carboxyl polyurethane resin.

(8) entered by diisocyanate and carboxylic diol compound and the sudden reaction of diatomic alcohol compounds In the synthesis containing carboxyl polyurethane resin of row, add isophorone diisocyanate and pentaerythritol triacrylate etc. rub The compound in your reactant equimolecular with 1 NCO and more than 1 (methyl) acryloyl group carries out end (first Base) acrylated and obtain containing carboxyl polyurethane resin.

(9) by the unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, α-methyl styrene, (methyl) acrylic acid lower The compound copolymerization containing unsaturated group such as Arrcostab, isobutene. and obtain containing carboxy resin.

(10) aftermentioned such multifunctional oxetane resin and adipic acid, phthalic acid, hexahydro O-phthalic are made The dicarboxylic acids reactions such as acid, 2 yuan of anhydride of addition on the primary hydroxyl generated and addition (first further in obtaining containing carboxyl polyester resin Base) 1 molecule such as glycidyl acrylate, (methyl) acrylic acid Alpha-Methyl ethylene oxidic ester has 1 epoxy radicals and 1 with The compound of upper (methyl) acryloyl group and obtain containing carboxyl photoresist.

(11) above-mentioned (1)～(10) containing carboxy resin in addition a part has cyclic ether group and (methyl) propylene The compound of acyl group and obtain containing carboxyl photoresist.

Above-mentioned containing in carboxy resin, do not use epoxy resin as initiation material as it has been described above, especially can suitably use Containing carboxy resin.Such containing carboxy resin because not using epoxy resin as initiation material, therefore there is chloride ion impurities Considerably less feature.In the present invention, the suitable chloride ion impurities content containing carboxy resin used is 0～100ppm, is preferably 0 ～50ppm, more preferably 0～30ppm.Therefore, can particularly suitable use above-mentioned enumerate containing carboxy resin (4)～(8).

It addition, do not use epoxy resin as the tree that can be readily available not hydroxyl containing carboxy resin of initiation material Fat.It is known that generally, the existence of hydroxyl also has the feature being improved the excellences such as adaptation by hydrogen bond, but moisture-proof can be made notable Reduce.What following description resin-phase ester modified with the epoxy acrylic that common solder resist is used compared does not uses epoxy resin The advantage containing carboxy resin as initiation material.

The phenol resol resins not having chlorine component can be readily available.Obtain by making it carry out alkylene oxide modification The part propylene acidifying of phenolic resin and the importing of anhydride, can with double bond equivalent 300～550, acid number 40～ The scope of 120mgKOH/g obtains the resin without hydroxyl.

On the other hand, by the complete acrylic acid of epoxy radicals of the epoxy resin by similar phenol resol resins synthesis Change, and when importing anhydride on all hydroxyls, double bond equivalent becomes 400～500, acid number becomes very large, it is impossible to even if obtaining The most also there is the film of resistance to developability.And then, owing to acid number is high, thus poor water resistance, insulating reliability, PCT patience Significantly reduce.I.e. so that the epoxy acrylate system resin derivative by the phenol novolak type epoxy resin being similar to does not has completely It is extremely difficult for having hydroxyl.

It addition, polyurethane resin can also be easily synthesized without hydroxyl by blending hydroxyl and the equivalent of NCO The resin of base.Preferably resin is by not using the phosgene isocyanate compound as initiation material, not using epihalohydrin Material synthesis chloride ion impurities amount 0～30ppm containing carboxy resin, more preferably with the side of the most not hydroxyl The resin of formula synthesis.

From the viewpoint, it is possible to use before as concrete example illustrate containing carboxy resin (1)～(3), in order to Obtain and have as the more excellent PCT patience of semiconductor-sealing-purpose solder resist, HAST patience, the solder resist group of cold-hot impact Compound, can suitably use above-mentioned containing carboxy resin (4)～(8).

It addition, about formerly illustrate by obtain with the copolymerization containing unsaturated group compound containing carboxy resin (9), by (methyl) acrylic acid 3,4-epoxycyclohexanecarboxylate is as having cyclic ether group and (methyl) acryloyl group in 1 molecule What compound reacted and obtained also uses alicyclic epoxy thing containing carboxyl photoresist, and therefore chloride ion impurities is few, permissible Use aptly.

On the other hand, make containing carboxy resin (9) and as 1 molecule has cyclic ether group and the change of (methyl) acryloyl group The glycidyl methacrylate reaction of compound and obtain material, make containing carboxy resin (9) with as containing unsaturated group The glycidyl methacrylate copolymerization of compound and the material that obtains, have the anxiety that chloride ion impurities quantitative change is many.It addition, synthesis During polyurethane resin, it is also possible to use epoxy acrylate modified feedstock as diatomic alcohol compounds.Although introducing chloride ion Impurity, but can use from the viewpoint of can controlling chloride ion impurities amount.

Above-mentioned this containing carboxy resin owing to having multiple free carboxy on the side chain of trunk polymer, the most permissible Developed by alkaline aqueous solution.

It addition, the above-mentioned acid number containing carboxy resin is preferably the scope of 40～150mgKOH/g, more preferably 40～ The scope of 130mgKOH/g.When acid number containing carboxy resin is less than 40mgKOH/g, alkali development becomes difficulty, on the other hand, exceedes During 150mgKOH/g, the dissolving of the exposure portion caused due to developer solution is accelerated, and line becomes thinner than required, exposure portion sometimes With unexposed portion indistinction be dissolved by the developing stripping, it is difficult to describe normal corrosion-resisting pattern.

Additionally, the aforementioned weight average molecular weight containing carboxy resin is different according to resin matrix, it is usually preferred to 2000～ The scope of 150000, further preferably 5000～100000 scope.When weight average molecular weight is less than 2000, non-stick sometimes Difference, the moisture-proof of the film after exposure is poor, and film thickness loss occurs during development, and image resolution ratio significantly deteriorates sometimes.The opposing party Face, when weight average molecular weight is more than 150000, developability is significantly deteriorated, and storage-stable is poor.

Such compounding amount containing carboxy resin is 20～60 mass % in all compositions, preferably 30～50 matter Amount %.When this compounding amount is less than above-mentioned scope, coating strength reduces, therefore the most preferred.On the other hand, this compounding amount is more than above-mentioned model When enclosing, viscosity uprises or coating etc. reduces, therefore the most preferred.

As Photoepolymerizationinitiater initiater, it is possible to use choosing freely has the oxime ester system Photoepolymerizationinitiater initiater of oxime ester base, alpha-amido More than a kind Photoepolymerizationinitiater initiater in the group that 1-Phenylethanone. system Photoepolymerizationinitiater initiater, acylphosphine oxide system Photoepolymerizationinitiater initiater form.

As the commercially available product of oxime ester system Photoepolymerizationinitiater initiater, the CGI-that Xiba Special Chemical Product Co., Ltd manufactures can be listed 325, N-1919, ADEKA ARKLS that IRGACURE OXE01, IRGACURE OXE02, Adeka Corporation manufacture NCI-831 etc..It addition, the Photoepolymerizationinitiater initiater that intramolecular has 2 oxime ester bases also can be suitable for, specifically, can arrange Enumerate the oxime ester compound with carbazole structure shown in following formula:

(in formula, X represents that hydrogen atom, the alkyl of carbon number 1～17, the alkoxyl of carbon number 1～8, phenyl, phenyl are (by carbon number 1 ～the alkyl of 17, the alkoxyl of carbon number 1～8, amino, the alkyl amino with the alkyl of carbon number 1～8 or dialkyl amido take Generation), naphthyl (by the alkyl of carbon number 1～17, the alkoxyl of carbon number 1～8, amino, there is the alkyl amino of the alkyl of carbon number 1～8 Or dialkyl amido replaces), Y, Z represent hydrogen atom, the alkyl of carbon number 1～17, the alkoxyl of carbon number 1～8, halogen radical respectively Group, phenyl, phenyl (by the alkyl of carbon number 1～17, the alkoxyl of carbon number 1～8, amino, have the alkyl of the alkyl of carbon number 1～8 Amino or dialkyl amido replace), naphthyl (by the alkyl of carbon number 1～17, alkoxyl, the amino of carbon number 1～8, there is carbon number 1 ～the alkyl amino of alkyl of 8 or dialkyl amido replace), anthryl, pyridine radicals, benzofuranyl (benzofuryl), benzo Thienyl (benzothienyl), Ar represents the alkylidene of carbon number 1～10, ethenylidene, phenylene, diphenylene, sub-pyridine Base (pyridylene), naphthylene, thiophene, anthrylene (anthrylene), sub-thienyl (thienylene), furylidene (furylene), 2,5-pyrroles-diyl, 4,4 '-stilbene-diyl, 4,2 '-styrene diyl).N represents the integer of 0 or 1. In particular it is preferred that in formula, X, Y are methyl or ethyl respectively, Z is methyl or phenyl, and n is 0, and Ar is phenylene, naphthylene, thiophene Fen or sub-thienyl.)

Relative to 100 mass parts containing carboxy resin, the compounding amount of this oxime ester system Photoepolymerizationinitiater initiater is preferably 0.01～5 Mass parts.During less than 0.01 mass parts, photo-curable on copper is not enough, and film can be peeled off and the film such as chemical proofing is special Property reduce.On the other hand, during more than 5 mass parts, the light of welding resistance film coated surface absorbs and becomes strong, there is deep curable and reduces Tendency.More preferably 0.5～3 mass parts.

As alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, specifically, 2-methyl isophthalic acid-[4-(methyl mercapto) can be listed Phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone, 2-(diformazan ammonia Base)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino 1-Phenylethanone. etc..Make For commercially available product, IRGACURE 907, IRGACURE 369, IRGACURE that Xiba Special Chemical Product Co., Ltd manufactures can be listed 379 etc..

As acylphosphine oxide system Photoepolymerizationinitiater initiater, specifically, 2,4,6-trimethylbenzoyls two can be listed Phenyl phosphine oxide, double (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide, double (2,6-Dimethoxybenzoyl)-2,4, 4-trimethyl-pentyl phosphine oxide etc..As commercially available product, Lucirin TPO, Ciba Specialty that BASF AG manufactures can be listed The IRGACURE819 etc. that Xue Pin company manufactures.

Relative to 100 mass parts containing carboxy resin, these alpha-aminoacetophenone system Photoepolymerizationinitiater initiater, acylphosphine oxide systems The compounding amount of Photoepolymerizationinitiater initiater is preferably 0.01～15 mass parts.During less than 0.01 mass parts, similarly, the photocuring on copper Property not enough, film can be peeled off and the coating characteristic such as chemical proofing reduces.On the other hand, time more than 15 mass parts, it is impossible to fill Ground is divided to obtain the reducing effect of aerofluxus, and then, the light of welding resistance film coated surface absorbs and becomes strong, has what deep curable reduced Tendency.More preferably 0.5～10 mass parts.

Additionally, as the Photoepolymerizationinitiater initiater, light-initiated of the Photocurable resin composition being applicable to present embodiment Auxiliary agent and sensitizer, can list benzoin compound, acetophenone compound, anthraquinone compounds, thioxanthone compounds, ketalization Compound, benzophenone cpd, tertiary amine compound and ton ketone etc..

As benzoin compound, specifically, such as benzoin, benzoin methylether, benzoin ethyl ether, benzene can be listed Anisoin isopropyl ether etc..

As acetophenone compound, specifically, include, for example out 1-Phenylethanone., 2,2-dimethoxy-2-phenyl benzene second Ketone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone etc..

As anthraquinone compounds, specifically, include, for example out 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tert-butyl anthracene Quinone, 1-chloroanthraquinone etc..

As thioxanthone compounds, specifically, include, for example out 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthene Ketone, CTX, 2,4-diisopropylthioxanthone etc..

As ketal compound, specifically, include, for example out 1-Phenylethanone. dimethyl ketal, benzil dimethyl ketal Deng.

As benzophenone cpd, specifically, include, for example out benzophenone, 4-benzoyl diphenyl thioether, 4-benzoyl-4 '-methyldiphenyl thioether, 4-benzoyl-4 '-ethyl diphenyl sulfide, 4-benzoyl-4 '-propyl group hexichol Thioether etc..

As tertiary amine compound, specifically, include, for example out ethanolamine compound, there is dialkyl amido benzene structure Compound, such as in commercially available product, 4 can be listed, (Tso Tat Co., Ltd., Japan manufactures 4 '-dimethylamino benzopheone NISSOCUREMABP), 4,4 '-lignocaine benzophenone (Hodogaya Chemical Co.LTD. manufacture EAB) etc. two (7-(lignocaine)-4-methyl is fragrant for alkyl amino benzophenone, 7-(lignocaine)-4-methyl-2H-1-chromen-2-one Legumin) etc. coumarin compound containing dialkyl amido, ethyl 4-dimethy laminobenzoate (chemical medicine company of Japan manufactures KAYACURE EPA), (International Bio-Synthetics company manufactures 2-dimethylamino ethyl benzoate Quantacure DMB), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (International Bio-Synthetics Company manufacture Quantacure BEA), to dimethylamino benzoic acid isopentyl ethyl ester (Japan chemical medicine company manufacture KAYACURE DMBI), 4-dimethylaminobenzoic acid-2-Octyl Nitrite (Esolol 507 that Van Dyk company manufactures), 4, 4 '-lignocaine benzophenone (EAB that Hodogaya Chemical Co.LTD. manufactures) etc..

In the middle of them, thioxanthone compounds and tertiary amine compound are preferred.From the standpoint of the curable of deep especially It preferably comprises thioxanthone compounds.Wherein, particularly preferably contain 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2- Clopenthixal ketone, 2, the thioxanthone compounds such as 4-diisopropylthioxanthone.

Relative to 100 mass parts containing carboxy resin, the compounding amount of this thioxanthone compounds is preferably below 20 mass parts. When the compounding amount of thioxanthone compounds is more than 20 mass parts, thick film curable reduces, and can cause the cost up of goods.More Below preferably 10 mass parts.

It addition, as tertiary amine compound, preferably there is the compound of dialkyl amido benzene structure, wherein, particularly preferred two Alkyl amino benzophenone cpd, the maximum absorption wavelength coumarin chemical combination containing dialkyl amido between 350～450nm Thing and coumarin ketone (ketocoumarin) class.

As dialkyl amido benzophenone cpd, 4,4 '-lignocaine benzophenone toxicity is the lowest, thus preferably. Owing to the maximum absorption wavelength of the coumarin compound containing dialkyl amido is in the ultraviolet range of 350～410nm, therefore, Be possible not only to obtain coloring less, water white photosensitive composite, it is also possible to obtain use coloring pigment, reflection coloring pigment The coloring soldering-resistance layer of the color of self.From the viewpoint of the sensitization effect that the laser display to wavelength 400～410nm is excellent, Particularly preferably 7-(lignocaine)-4-methyl-2H-1-chromen-2-one.

Relative to 100 mass parts polyurethane resin Han carboxyl, the compounding amount of this tertiary amine compound is preferably 0.1～20 matter Amount part.When the compounding amount of tertiary amine is less than 0.1 mass parts, there is the tendency that can not obtain sufficient sensitization effect.More than 20 mass During part, the light absorption in dry welding resistance film coated surface caused because of tertiary amine compound becomes strong, there is deep curable and reduces Tendency.More preferably 0.1～10 mass parts.

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

Above-mentioned relative to 100 mass parts containing carboxy resin, this Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer total Amount is preferably below 35 mass parts.During more than 35 mass parts, exist and cause deep curable to reduce owing to their light absorbs Tendency.

Additionally, these Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer are owing to absorbing specific wavelength, so according to feelings Condition light sensitivitys meeting step-down, works as UV absorbent sometimes.But, they are the most only merely for the sense improving compositions The purpose of luminosity and use.It can be made as required to absorb the light of specific wavelength, improve the photoreactivity on surface, make etchant resist Wire shaped and opening is changed to vertically, cone-shaped, reverse tapered shape, and the machining accuracy of live width, opening diameter can be improved.

For the present invention photo-hardening thermosetting resin composition containing based elastomers be possible not only to improve institute Obtain the cured coating film crack resistance to cold cycling, and be improved the adaptation of solder resist, the effect of especially PCT patience. As such compound, as long as skeleton has the elastomer of vinyl, so that it may use without particular limitation, wherein, for The above-mentioned characteristic of imparting, can suitably use butadiene derivatives.It addition, the butadiene derivatives that can suitably use has epoxy During the functional groups such as base, hydroxyl, acryloyl group, and the compatibility of other material improves, and has the feature of excellent storage stability.

As the concrete example containing based elastomers, can list Epolead PB3600, Epofriend CT310, Epofriend AT501 (be above DAICEL CHEMICAL INDUSTRIES, LTD. manufacture trade name), Ricon130, Ricon131、Ricon134、Ricon142、Ricon150、Ricon152、Ricon153、Ricon154、Ricon156、 Ricon157、RiconP30D、Ricon657、Ricon100、Ricon181、Ricon184、Ricon130MA8、 Ricon130MA13、Ricon130MA20、Ricon131MA5、Ricon131MA10、Ricon131MA17、Ricon131MA20、 Ricon184MA6, Ricon156MA17, CN301, CN307 (being above the trade name that Sartomer Company manufactures), Denalex R-45EPT (trade name that Nagase ChemteX Corporation manufactures), BAC-45 (Osaka Organic Chemical Industry (strain) system The trade name made), Poly bd, Poly ip, Epol (being above out the trade name that the emerging product of light (strain) manufactures), Polytail H (trade name that Mitsubishi Chemical's (strain) manufactures) etc..

Above-mentioned relative to 100 mass parts containing carboxy resin, such compounding amount containing based elastomers be 5 mass parts with Upper, 60 mass parts the following is suitable, more than more preferably 10 mass parts, below 50 mass parts.During less than 5 mass parts, it is impossible to Confirm the effect containing based elastomers, on the other hand, during more than 60 mass parts, have the viscosity causing film to deteriorate, develop not The worry of good grade, thus the most preferred.

The light solidifying/heat solidifying resin composition of the present invention with to the above-mentioned additive reaction containing based elastomers and For the purpose of crosslinking, containing sulfhydryl compound.By adding sulfhydryl compound, the coating characteristic that ethylene oxide is caused can be prevented Reduce, and then, it is possible to obtain soft cross-linking agent, therefore, the characteristic such as PCT patience, HAST patience improves.It addition, sulfydryl chemical combination Thing also works as chain-transferring agent and/or adaptation imparting agent, therefore, can obtain the raising of compositions light sensitivitys, close simultaneously The raising of conjunction property.

As sulfhydryl compound, include, for example out mercaptoethanol, mercaprol, Mercaptobutanol., mercapto-propanediol, sulfydryl Butanediol, oxybenzene mercaptan and derivant thereof；1-butyl mercaptan, butyl-3-thiopropionate, methyl-3-thiopropionate, 2,2- (ethylene epoxide) diethyl mercaptan, ethyl mercaptan, 4-methylbenzenethiol, lauryl mercaptan, propanethiol, butyl mercaptan, amyl hydrosulfide, 1-are pungent Mercaptan, cyclopentanethiol, cyclohexylmercaptan, thioglycerol, 4,4-thiobisbenzenethiol etc..As their commercially available product, such as, can arrange Enumerate BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC and (be above chemical industry (strain) Manufacture), Karenz MT-PE1, Karenz MT-BD1, Karenz-NR1 (being above what Showa electrician (strain) manufactured) etc..

And then, as having the sulfhydryl compound of heterocycle, include, for example out sulfydryl-4-butyrolactone (other title: 2-mercapto Base-4-butyrolactone (butanolide)), 2-sulfydryl-4-methyl-4-butyrolactone, 2-sulfydryl-4-ethyl-4-butyrolactone, 2-mercapto Base-4-fourth thiolactone, 2-sulfydryl-4-butyrolactam, N-methoxyl group-2-sulfydryl-4-butyrolactam, N-ethyoxyl-2-sulfydryl-4- Butyrolactam, N-methyl-2-sulfydryl-4-butyrolactam, N-ethyl-2-sulfydryl-4-butyrolactam, N-(2-methoxyl group) ethyl- 2-sulfydryl-4-butyrolactam, N-(2-ethyoxyl) ethyl-2-sulfydryl-4-butyrolactam, 2-sulfydryl-5-valerolactone, 2-sulfydryl- 5-valerolactam, N-methyl-2-sulfydryl-5-valerolactam, N-ethyl-2-sulfydryl-5-valerolactam, N-(2-methoxyl group) second Base-2-sulfydryl-5-valerolactam, N-(2-ethyoxyl) ethyl-2-sulfydryl-5-valerolactam, 2-mercaptobenzothiazole, 2-mercapto Base-5-methyl mercapto-thiadiazoles, 2-sulfydryl-6-caprolactam, 2,4,6-tri-thiols-s-triazine (three association chemical conversion (strain) manufacture: business Name of an article Zisnet F), 2-dibutylamino-4,6-dimercapto-s-triazine (three association chemical conversion (strain) manufacture: trade name Zisnet DB), 2-anilino--4, (three chemical conversion (strain) formula commercial firms of association manufacture 6-dimercapto-s-triazine: trade name Zisnet AF) etc..It addition, can Suitably use 2-mercaptobenzimidazole, 2-mercaptobenzooxazole, 2-mercaptobenzothiazole (chemical industry Co., Ltd. of Kawaguchi system Make: trade name Accel M), 3-sulfydryl-4-methyl-4H-1,2,4-triazoles, 5-methyl isophthalic acid, 3,4-thiadiazoles-2-mercaptan, 1-benzene Base-5-sulfydryl-1H-TETRAZOLE etc..It is two or more that these sulfhydryl compounds may be used alone or in combination use.

Above-mentioned relative to 100 mass parts containing carboxy resin, the compounding amount of such sulfhydryl compound be 0.01 mass parts with Upper, 10 mass parts the following is suitable, more preferably more than 0.05 mass parts, below 5 mass parts.Less than 0.01 mass parts Time, it is impossible to confirm the additive effect of sulfhydryl compound.On the other hand, during more than 10 mass parts, have and cause photo-curable heat cure Property resin combination poor visualization, be dried the worry of management retractility reduction etc., therefore the most preferred.

And then, in the light solidifying/heat solidifying resin composition of the present invention, in order to give thermostability, heat can be added Curable composition.As the Thermocurable composition used in the present invention, it is possible to use blocked isocyanate compounds, amino tree Fat, maleimide compound, benzoxazine resins, carbodiimide resin, cyclic carbonate compound, multi-functional epoxy's chemical combination The known conventional heat-curing resin such as thing, multifunctional oxetane compound, episulfide resin.In the middle of them, excellent The Thermocurable composition of choosing is to have multiple cyclic ether group and/or cyclic thioether base (the most ring-type (sulfur) ether in 1 molecule Base) Thermocurable composition.These have commercially available of a great variety, according to its structure of the Thermocurable composition of ring-type (sulfur) ether Difference can give various characteristic.

The Thermocurable composition in such molecule with multiple ring-type (sulfur) ether is to have 3,4 or 5 rings in molecule Cyclic ether group or cyclic thioether base in any one or there is the compound of 2 both the above groups, include, for example out: Molecule has the compound of the most multiple epoxy radicals, i.e. multi-functional epoxy compound；Molecule has the most multiple oxa-ring The compound of butane group, the most multifunctional oxetane compound；Molecule has the compound of multiple thioether group, i.e. epithio Resin etc..

As above-mentioned multi-functional epoxy compound, include, for example out Japan Epoxy Resins Co., Ltd. and manufacture JER828, jER834, jER1001, jER1004；The Epiclon 840 of DIC company manufacture, Epiclon 850, Epiclon 1050、Epiclon 2055；Epo Tohto YD-011, YD-013, YD-127, YD-128 that Dongdu chemical conversion company manufactures；Dow D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 that Chemical Company manufactures；Ciba Specialty chemicals The araldite 6071 of company's manufacture, araldite 6084, araldite GY250, araldite GY260；Sumitomo Chemical Sumi-epoxy ESA-011, ESA-014, ELA-115, ELA-128 that industrial group manufactures；Industrial group of Asahi Chemical Industry manufactures A.E.R.330, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade name) bisphenol A type epoxy resin；Japan The jERYL903 that Epoxy Resins Co., Ltd. manufactures；Epiclon 152, the Epiclon 165 that DIC company manufactures；Dongdu Epo Tohto YDB-400, YDB-500 that chemical conversion company manufactures；The D.E.R.542 that Dow Chemical Company manufactures； The Araldite 8011 that Xiba Special Chemical Product Co., Ltd manufactures；The Sumi-epoxy ESB-that Sumitomo Chemical Co. Ltd. manufactures 400、ESB-700；The brominated oxygen tree of A.E.R.711, A.E.R.714 etc. (being trade name) that industrial group of Asahi Chemical Industry manufactures Fat；JER152, jER154 that Japan Epoxy Resins Co., Ltd. manufactures；Dow Chemical Company manufactures D.E.N.431、D.E.N.438；The Epiclon N-730 of DIC company manufacture, Epiclon N-770, Epiclon N-865；East All it is melted into Epo Tohto YDCN-701, YDCN-704 that company manufactures；The araldite that Xiba Special Chemical Product Co., Ltd manufactures ECN1235、araldite ECN1273、araldite ECN1299、araldite XPY307；Nippon Kayaku Co., Ltd. EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the NC-3000 manufactured；Sumitomo Chemical Sumi-epoxy ESCN-195X, ESCN-220 that company manufactures；Industrial group of Asahi Chemical Industry manufacture A.E.R.ECN-235, The phenolic resin varnish type epoxy resin of ECN-299 etc. (being trade name)；The Epiclon 830 that DIC company manufactures；Japan The jER807 that Epoxy Resins Co., Ltd. manufactures；Epo Tohto YDF-170, YDF-that Dongdu chemical conversion company manufactures 175、YDF-2004；(the being trade name) bisphenol F type epoxy such as the araldite XPY306 that Xiba Special Chemical Product Co., Ltd manufactures Resin；The hydrogenated bisphenol A type such as Epo Tohto ST-2004, ST-2007, ST-3000 (trade name) that Dongdu chemical conversion company manufactures Epoxy resin；The jER604 that Japan Epoxy Resins Co., Ltd. manufactures；The Epo Tohto that Dongdu chemical conversion company manufactures YH-434；The araldite MY720 that Xiba Special Chemical Product Co., Ltd manufactures；The Sumi-that Sumitomo Chemical Co. Ltd. manufactures (the being trade name) glycidyl amine type epoxy resins such as epoxy ELM-120；Xiba Special Chemical Product Co., Ltd manufactures The hydantoin type epoxy resin such as araldite CY-350 (trade name)；DAICEL CHEMICAL INDUSTRIES, LTD. system The Celloside 2021 made；Araldite CY175, CY179 that Xiba Special Chemical Product Co., Ltd manufactures etc. (being trade name) Alicyclic epoxy resin；The YL-933 that Japan Epoxy Resins Co., Ltd. manufactures；Dow Chemical Company system T.E.N., EPPN-501, EPPN-502 etc. (being trade name) the three hydroxyphenyl methane type epoxy resin made；Japan Epoxy Di-cresol type or the xenols such as YL-6056, YX-4000, YL-6121 (being trade name) that Resins Co., Ltd. manufactures Type epoxy resin or their mixture；The EBPS-200 that Nippon Kayaku Co., Ltd. manufactures；Asahi Electro-Chemical Co. Ltd The EPX-30 manufactured；The bisphenol-s epoxy resins such as the EXA-1514 (trade name) that DIC company manufactures；Japan Epoxy The bisphenol A novolac type epoxy resin such as the jER157S (trade name) that Resins Co., Ltd. manufactures；Japan Epoxy The jERYL-931 that Resins Co., Ltd. manufactures；Araldite 163 grade that Xiba Special Chemical Product Co., Ltd manufactures (is business The name of an article) four hydroxy phenyl ethane type epoxy resin；The araldite PT810 that Xiba Special Chemical Product Co., Ltd manufactures；Nissan Chemical work The hetero ring type epoxy resin of the TEPIC that industry company manufactures etc. (being trade name)；The Bremmer DGT that Nof Corp. manufactures Deng o-phthalic acid diglycidyl ester resin；The four glycidyl group xyloyls such as the ZX-1063 that Dongdu chemical conversion company manufactures Base ethane (tetraglycidyl xylenoyl ethane) resin；ESN-190, ESN-that chemical company of Nippon Steel manufactures 360, HP-4032, EXA-4750, the EXA-4700 etc. that DIC company the manufactures epoxy resin containing naphthyl；The HP-that DIC company manufactures 7200, HP-7200H etc. have the epoxy resin of bicyclopentadiene skeleton；CP-50S, CP-50M etc. that Nof Corp. manufactures Glycidyl methacrylate copolymerization system epoxy resin；And N-cyclohexylmaleimide and glycidyl methacrylate Copolymerization epoxy resin；CTBN modified epoxy (YR-102, YR-450 etc. that such as chemical conversion company in Dongdu manufactures) etc., but also It is not limited to them.These epoxy resin may be used alone or in combination two or more use.

As above-mentioned multifunctional oxetane compound, double [(3-methyl-3-oxetanyl methoxy can be listed Base) methyl] ether, double [(3-ethyl-3-oxetanylmethoxy) methyl] ether, Isosorbide-5-Nitrae-bis-[(3-methyl-3-oxa-ring fourth Alkyl methoxyl group) methyl] benzene, Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanylmethoxy) methyl] benzene, acrylic acid (3-methyl- 3-oxetanyl) methyl ester, acrylic acid (3-ethyl-3-oxetanyl) methyl ester, methacrylic acid (3-methyl-3-oxygen Azetidinyl) methyl ester, methacrylic acid (3-ethyl-3-oxetanyl) methyl ester, their oligomer or copolymer etc. Multifunctional oxetanes class；And oxa-cyclobutanol and novolac resin, poly-(4-Vinyl phenol), cardo type bis-phenol Class, calixarene kind, resorcinol calixarenes (calix resorcin arene) class or silsesquioxane Etc. (silsesquioxane) there is the etherate etc. of the resin of hydroxyl.It addition, also can list, there is oxetanes ring Unsaturated monomer and the copolymer etc. of (methyl) alkyl acrylate.

As above-mentioned molecule has the episulfide resin of multiple cyclic thioether base, include, for example out Japan YL7000 (bisphenol A-type episulfide resin), Dongdu chemical conversion (strain) that Epoxy Resins Co., Ltd. manufactures manufacture YSLV-120TE etc..Use same synthetic method by the epoxy radicals of phenolic resin varnish type epoxy resin alternatively, it is also possible to use The episulfide resin etc. that oxygen atom replaces to sulphur atom and obtains.

Relative to above-mentioned carboxyl 1 equivalent containing carboxy resin, above-mentioned molecule has the thermosetting of multiple ring-type (sulfur) ether The compounding amount of the property changed composition is preferably 0.6～2.5 equivalents, more preferably in the range of 0.8～2.0 equivalents.Molecule have many When the compounding amount of the Thermocurable composition of individual ring-type (sulfur) ether is less than 0.6 equivalent, carboxyl residues in soldering-resistance layer, thermostability, resistance to Alkalescence, electrical insulating property etc. reduce, therefore the most preferred.On the other hand, during more than 2.5 equivalent, ring-type (sulfur) ether of low-molecular-weight is residual Stay in dry coating, thus be coated with film strength etc. and reduce, thus the most preferred.

It addition, as the Thermocurable composition that can be suitable for, melamine derivative, benzoguanamine derivant can be listed In amino resins.Such as have melamine methylol compound, methylolbenzoguanamine compound, methylol glycoluril compound and Hydroxymethyl urea compound etc..And then, alkoxymethylated melamine compound, aikoxymethytated benzoguanamine chemical combination Thing, aikoxymethytated glycolurils compound and aikoxymethytated urea compounds can be by by melamine methylol chemical combination The methylol of thing, methylolbenzoguanamine compound, methylol glycoluril compound and hydroxymethyl urea compound is transformed to respectively Alkoxy methyl and obtain.To the kind of this alkoxy methyl, there is no particular limitation, such as, can be methoxy, ethoxy Ylmethyl, propoxy methyl, butoxymethyl etc..To human body, eco-friendly formalin concentration be particularly preferably 0.2% with Under melamine derivative.

As their commercially available product, include, for example out Cymel 300, Cymel 301, Cymel 303, Cymel 370, Cymel 325、Cymel 327、Cymel 701、Cymel 266、Cymel 267、Cymel 238、Cymel 1141、Cymel 272、Cymel 202、Cymel 1156、Cymel 1158、Cymel 1123、Cymel 1170、Cymel 1174、Cymel UFR65, Cymel 300 (above by Mitsui-Cyanamid, Ltd. manufactures), NIKALAC Mx-750, NIKALAC Mx- 032、NIKALAC Mx-270、NIKALAC Mx-280、NIKALAC Mx-290、NIKALAC Mx-706、NIKALAC Mx- 708、NIKALAC Mx-40、NIKALAC Mx-31、NIKALAC Ms-11、NIKALAC Mw-30、NIKALAC Mw-30HM、 NIKALAC Mw-390, NIKALAC Mw-100LM, NIKALAC Mw-750LM (above by SANWA Chemical Co., Ltd. manufacture) etc..

These Thermocurable compositions may be used singly or in combination of two or more.

It addition, in the light solidifying/heat solidifying resin composition of the present invention, in order to improve compositions curable and The obdurability of gained cured film, can add and have multiple NCO or the compound of blocked isocyanate base in 1 molecule. This 1 molecule has the compound of multiple NCO or blocked isocyanate base can list 1 molecule has multiple The compound of NCO, i.e. polyisocyanate compound, or 1 molecule have the chemical combination of multiple blocked isocyanate base Thing, i.e. blocked isocyanate compounds etc..

As above-mentioned polyisocyanate compound, it is possible to use such as aromatic polyisocyanate, aliphatic polyisocyanic acid Ester or ester ring type polyisocyanates.As the object lesson of aromatic polyisocyanate, can list 4,4 '-diphenyl-methane two is different Cyanate, 2,4 toluene diisocyanate, 2,6-toluene di-isocyanate(TDI), naphthalene-1,5-diisocyanate, o-Dimethylbenzene two isocyanide Acid esters, m xylene diisocyanate and 2,4 toluene diisocyanate dimer.Tool as aliphatic polyisocyante Style, can list tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl Hexamethylene diisocyanate, 4,4-di-2-ethylhexylphosphine oxide (cyclohexyl isocyanate) and isophorone diisocyanate.As fat The object lesson of ring type polyisocyanates, can list bicycloheptane triisocyanate.Also can list the isocyanide of previous enumeration The addition product of ester compound, biuret body and isocyanuric acid ester body.

Blocked isocyanate base contained in blocked isocyanate compounds is that NCO is by anti-with sealer Should and protected, temporarily by the group of deactivation.When being heated to the temperature of regulation, this sealer dissociates, and generates Carbimide. Ester group.

As blocked isocyanate compounds, it is possible to use isocyanate compound is anti-with the addition of isocyanate-terminated dose Answer product.As the isocyanate compound that can react with end-capping reagent, isocyanurate type, biuret form, adduction can be listed Thing type etc..As this isocyanate compound, it is possible to use such as aromatic polyisocyanate, aliphatic polyisocyante or fat Ring type polyisocyanates.As aromatic polyisocyanate, aliphatic polyisocyante, the concrete example of alicyclic polyisocyanates Son, can list the compound of above illustration.

As isocyanate-terminated dose, include, for example out the phenol systems such as phenol, cresol, xylenol, chlorophenol and ethyl-phenol End-capping reagent；The lactams system end-capping reagents such as epsilon-caprolactams, δ-valerolactam, butyrolactam, azetidinone；Acetoacetic acid Ethyl ester and acetylacetone,2,4-pentanedione isoreactivity methylene base system end-capping reagent；Methanol, ethanol, propanol, butanol, amylalcohol, glycol monoethyl ether, second two Alcohol list ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzylic ether, methyl glycollate, glycolic fourth The alcohol system end-capping reagents such as ester, DAA, methyl lactate and ethyl lactate；Formaldoxime, aldoxime, acetone oxime (acetoxime), first The oxime system end-capping reagents such as acetophenone oxime, diacetyl monoxime, hexamethylene oxime；Butyl mercaptan, hexyl mercaptan, tert-butyl mercaptan, phenylmercaptan., methylbenzene The mercaptan such as thiophenol, ethyl thiophenol system end-capping reagent；The amide such as acetamide, benzamide system end-capping reagent；Butanimide and maleoyl The imide series end-capping reagents such as imines；The amine system end-capping reagents such as dimethylaniline, aniline, butylamine, dibutyl amine；Imidazoles, 2-ethyl imidazol(e) Deng imidazoles system end-capping reagent；The imines system end-capping reagents etc. such as methylene imine and propylidene imines.

Blocked isocyanate compounds can be commercially available product, include, for example out Sumidule BL-3175, BL-4165, BL-1100, BL-1265, Desmodur TPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm 2170, Desmotherm 2265 (being manufactured by Sumika Bayer Urethane Co., Ltd. above, trade name), CORONATE 2512, CORONATE 2513, CORONATE 2520 (are manufactured by Japanese polyurethane industrial group, commodity above Name), B-830, B-815, B-846, B-870, B-874, B-882 are (above by MITSUI TAKEDA CHEMICALS, INC. system Make, trade name), TPA-B80E, 17B-60PX, E402-B80T are (above by Asahi Kasei Chemicals Corporation manufactures, trade name) etc..Additionally, Smudule BL-3175, BL-4265 are to use Methylethyl oxime as envelope End agent and the material that obtains.

The compound in above-mentioned 1 molecule with multiple NCO or blocked isocyanate base can be used alone a kind Or combine two or more to use.

Above-mentioned relative to 100 mass parts containing carboxy resin, such 1 molecule has multiple NCO or blocks different The compounding amount of the compound of cyanic acid ester group be 1～100 mass parts, more preferably 2～70 the ratio of mass parts be applicable.Above-mentioned join When mixed amount is less than 1 mass parts, it is impossible to obtain sufficient film obdurability, the most preferably.On the other hand, during more than 100 mass parts, protect Deposit stability to reduce, thus the most preferred.

In the light solidifying/heat solidifying resin composition of the present invention, in order to promote hydroxyl, carboxyl and NCO Curing reaction, ammonia esterification catalyst can be added.As ammonia esterification catalyst, choosing free stannum series catalysts, gold are preferably used Belong to chloride, acetyl acetone salt, metal sulfate, amines or/and amine salt composition group in the urethane of more than a kind Change catalyst.

As stannum series catalysts, include, for example out the organo-tin compound such as stannous octoate, dibutyl tin laurate, nothing Machine tin compound etc..

As metal chloride, the chloride of the metal being made up of Cr, Mn, Co, Ni, Fe, Cu or Al can be listed, such as Cobaltic chloride, Nickel Chloride, iron chloride etc..

As acetyl acetone salt, the levulinic of the metal being made up of Cr, Mn, Co, Ni, Fe, Cu or Al can be listed Ketone salt, such as acetylacetone cobalt, nickel acetylacetonate, ferric acetyl acetonade etc..

As metal sulfate, the sulfate of the metal being made up of Cr, Mn, Co, Ni, Fe, Cu or Al can be listed, such as Copper sulfate etc..

As amines, include, for example and have known triethylenediamine, N, N, N ', N '-tetramethyl-1,6- Hexamethylene diamine, double (2-dimethyl aminoethyl) ether, N, N, N ', N ", N "-five methyl diethylentriamine, N-methylmorpholine, N-second Base morpholine, N, N-dimethylethanolamine, dimorpholine base diethyl ether, N-Methylimidazole., dimethyl aminopyridine, triazine, N '-(2- Ethoxy)-N, N, N '-trimethyl-bis-(2-amino-ethyl) ether, N, N-Exxal8 amine, N, N-dimethylamino ethoxy Ethanol, N, N, N '-trimethyl-N '-(2-ethoxy) ethylenediamine, N-(2-ethoxy)-N, N ', N ", N "-tetramethyl diethylidene Triamine, N-(2-hydroxypropyl)-N, N ', N ", N "-tetramethyl diethylenetriamines, N, N, N '-trimethyl-N '-(2-ethoxy) third Diamidogen, N-methyl-N '-(2-ethoxy) piperazine, double (N, N-dimethylaminopropyl) amine, double (N, N-dimethylaminopropyl) Isopropanolamine, 2-amino quinine ring, 3-amino quinine ring, 4-amino quinine ring, 2-quinuclidinol, 3-quinuclidinol, 4-quinuclidinol, 1- (2 '-hydroxypropyl) imidazoles, 1-(2 '-hydroxypropyl)-2-methylimidazole, 1-(2 '-ethoxy) imidazoles, 1-(2 '-ethoxy)-2-first Base imidazoles, 1-(2 '-hydroxypropyl)-2-methylimidazole, 1-(3 '-aminopropyl) imidazoles, 1-(3 '-aminopropyl)-2-methyl miaow Azoles, 1-(3 '-hydroxypropyl) imidazoles, 1-(3 '-hydroxypropyl)-2-methylimidazole, N, N-dimethylaminopropyl-N '-(2-hydroxyl second Base) amine, N, N-dimethylaminopropyl-N ', N '-bis-(2-ethoxy) amine, N, N-dimethylaminopropyl-N ', N '-bis-(2- Hydroxypropyl) amine, N, N-dimethyl aminoethyl-N ', N '-bis-(2-ethoxy) amine, N, N-dimethyl aminoethyl-N ', N '-bis- (2-hydroxypropyl) amine, tripolycyanamide and/or benzoguanamine etc..

As above-mentioned amine salt, include, for example out the organic of DBU (1,8-diaza-dicyclo [5.4.0] endecatylene-7) The amine salt etc. of phosphate-gallate series.

The compounding amount of these ammonia esterification catalysts is i.e. enough in the ratio of common amount, such as, relative to 100 mass Part is containing carboxy resin, preferably 0.1～20 mass parts, more preferably 0.5～10 mass parts.

When using the Thermocurable composition in above-mentioned molecule with multiple ring-type (sulfur) ether, preferably comprise heat cure catalyst Agent.As this thermal curing catalyst, such as, imidazoles, 2-methylimidazole, 2-ethyl imidazol(e), 2-ethyl-4-methyl can be listed Imidazoles, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methyl The imdazole derivatives such as imidazoles；Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzylamine, 4-methoxyl group-N, N-dimethyl benzylamine, 4-methyl-N, the amines such as N-dimethyl benzylamine；The hydrazine such as adipic dihydrazide, sebacic dihydrazide Compound；The phosphorus compounds etc. such as triphenylphosphine.It addition, as commercially available product, include, for example out what chemical conversion industrial group of four countries manufactured 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (are the trade name of imidazole compound), and SAN-APRO Ltd. manufactures U-CAT (registered trade mark) 3503N, U-CAT3502T (are the trade name of the blocked isocyanate compounds of dimethylamine), DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc..Particularly it is not limited to these chemical combination Thing, as long as the thermal curing catalyst of epoxy resin thermosetting catalyst, oxetane compound or promote epoxy radicals and/ Or the material of the reaction of oxetanylmethoxy and carboxyl, can be used alone or two or more is used in mixed way.It addition, also may be used With use guanamines, acetylguanamine, benzoguanamine, tripolycyanamide, 2,4-diaminourea-6-methylacryoyloxyethyl-s-triazine, 2- Vinyl-2,4-diaminourea-s-triazine, 2-vinyl-4,6-diaminourea-s-triazine isocyanuric acid adduct, 2,4-diamino The Striazine derivatives such as base-6-methylacryoyloxyethyl-s-triazine isocyanuric acid adduct, preferably using these also as close The compound that conjunction property imparting agent works is applied in combination with above-mentioned thermal curing catalyst.

The ratio that compounding amount is common amount of these thermal curing catalysts is i.e. enough, such as, relative to 100 mass Part containing carboxy resin or 1 molecule have the Thermocurable composition of multiple ring-type (sulfur) ether, preferably 0.1～20 mass parts, More preferably 0.5～15 mass parts.

The Photocurable resin composition of the present invention can be compounded coloring agent.As coloring agent, it is possible to use red, blue, green, The known conventional coloring agent such as Huang, can be any one of pigment, dyestuff, pigment.But, from reducing carrying capacity of environment and right From the viewpoint of the impact of human body, preferably without halogen.

Red stain:

As red stain, have monoazo system, bisazo (disazo) be, azo lake system, benzimidazolone (benzimidazolon) be, be, diketopyrrolopyrrolecocrystals system, condensation azo system, anthraquinone system, quinacridone etc., tool Body ground, can list following such with Colour Index (C.I.；The Society of Dyers and Colourists Distribution) material numbered.

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。

Bisazo system: pigment red 37,38,41.

Monoazo color lake be: 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.

System: solvent of red 135, solvent red 179, pigment red 123, pigment red 149, paratonere 166, paratonere 178, pigment Red 179, 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, molten Agent red 207.

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

Blue colorant:

As blue colorant, having phthalocyanine system, anthraquinone system, pigment system is classified as the compound of pigment (pigment), Specifically, material as described below can be listed: pigment blue 15, pigment blue 15: 1, pigment blue 15: 2, pigment blue 15: 3, face Material blue 15:4, pigment blue 15: 6, pigment blue 16, pigment blue 60.

As dyestuff system, it is possible to use solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent Indigo plant 87, solvent blue 94, solvent blue 97, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc..In addition to the foregoing, The substituted or unsubstituted phthalocyanine compound of metal can also be used.

Green colourant:

As green colourant, similarly there are phthalocyanine system, anthraquinone system, are, specifically, it is possible to use pigment Green 7, face Expecting green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 etc..In addition to the foregoing, it is also possible to use metal replace or Unsubstituted phthalocyanine compound.

Yellow colorants:

As yellow colorants, there are monoazo system, bisazo system, condensation azo system, benzimidazole system, isoindolinone System, anthraquinone system etc., specifically, can list following material.

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

Indolinone 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。

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

Additionally, in order to adjust tone, purple, orange, the coloring agent of brown, black etc. can be added.

As particular instantiation, have 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 compounding ratio of above-mentioned coloring agent is not particularly limited, above-mentioned relative to 100 mass parts containing carboxy resin, preferably Be 0～10 mass parts, particularly preferred 0.1～5 mass parts ratio i.e. enough.

The molecule used in the light solidifying/heat solidifying resin composition of the present invention has multiple olefinic unsaturated group Group compound be by active energy beam irradiate occur photocuring, make above-mentioned containing carboxy resin insoluble in alkaline aqueous solution, Or contribute to making containing the carboxy resin material insoluble in alkaline aqueous solution.As this compound, it is possible to use known conventional Polyester (methyl) acrylate, polyethers (methyl) acrylate, carbamate (methyl) acrylate, carbonic ester (methyl) third Olefin(e) acid ester, epoxy (methyl) acrylate etc., specifically, can list acrylic acid 2-hydroxyl ethyl ester, acrylic acid 2-hydroxypropyl acrylate etc. Hydroxyalkyl acrylates class；The diacrylate esters of the glycol such as ethylene glycol, methoxyl group TEG, Polyethylene Glycol, propylene glycol； N,N-DMAA, N hydroxymethyl acrylamide, N, the acrylic amide such as N-dimethylaminopropylacryl amide；Third Olefin(e) acid N, N-dimethylamino ethyl ester, acrylic acid N, the acrylate class such as N-dimethylamino propyl ester；Hexanediol, three Polyhydric alcohol or their ethyleneoxide additions such as hydroxymethyl-propane, tetramethylolmethane, dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate The multicomponent methacrylate class of thing, propylene oxide adduct or 6-caprolactone addition product etc.；Benzene oxypropylene acid esters, bisphenol-A two propylene Acid esters and the multicomponent methacrylate class of the ethylene oxide adduct of these phenols or propylene oxide adduct etc.；Glycerol two contracts Water glycerin ether, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester etc. The multicomponent methacrylate class of glycidyl ether；It is not limited to above-claimed cpd, also can list polyether polyol, Merlon two Unit's direct acroleic acid esterification of polyhydric alcohol such as alcohol, C-terminal polybutadiene, PEPA or carry out ammonia via diisocyanate Urethane acrylate and the esters of acrylic acid that obtains and melamine acrylate, and/or with aforesaid propylene acid esters pair The various methyl acrylic esters etc. answered.

And then, the polyfunctional epoxy resins such as cresol novolak type epoxy resin of sening as an envoy to can be enumerated and react with acrylic acid and obtain Epocryl, this Epocryl hydroxyl further with the hydroxyl such as pentaerythritol triacrylate The epoxy that half carbamate compounds of the diisocyanate such as acrylate and isophorone diisocyanate reacts and obtains Urethane acrylate compound etc..This epoxy acrylate system resin can improve photo-curable without making finger touch Drying property reduces.

Above-mentioned relative to 100 mass parts containing carboxy resin, such molecule has the change of multiple ethylenically unsaturated group The compounding amount of compound is the ratio of 5～100 mass parts, the ratio of more preferably 1～70 mass parts.Above-mentioned compounding amount is less than 5 matter During amount part, photo-curable reduces, it is difficult to the alkali development after being irradiated by active energy beam forms pattern, therefore the most preferred.Separately On the one hand, during more than 100 mass parts, the dissolubility in alkaline aqueous solution reduces, and film becomes fragile, therefore the most preferred.

In order to improve the physical strength etc. of the film of the light solidifying/heat solidifying resin composition of the present invention, according to need Want, filler can be compounded.As this filler, known conventional inorganic filler or organic filler can be used, particularly preferably use Barium sulfate, spherical silica and Talcum.And then, in order to obtain the outward appearance of white, anti-flammability, it is also possible to use titanium oxide, metal oxygen The metal hydroxides such as compound, aluminium hydroxide is as extender pigment filler.Above-mentioned relative to 100 mass parts containing carboxy resin, this The compounding amount of a little fillers is preferably below 200 mass parts, more preferably 0.1～150 mass parts, particularly preferably 1～100 mass Part.When the compounding amount of filler is more than 200 mass parts, the viscosity of compositions increases, printing reduces, or solidfied material becomes fragile, therefore not Preferably.

And then, in order to improve dry to touch, improve treatability etc., the Photosetting and thermosetting resin combination of the present invention Thing can also use binder polymer.It is, for example possible to use Polyester polymer, polyurethane series polymer, Amino-Polyester Formic acid esters based polymer, polyamide-based polymer, polyesteramide based polymer, acrylic acid series polymeric compounds, cellulose-based polymer, Polymer in poly lactic acid series, phenoxy group based polymer etc..These binder polymers can be used alone or can be as two or more Mixture use.

And then, in order to give flexibility, improve the fragility etc. of solidfied material, the Photosetting and thermosetting resin group of the present invention Compound can also use elastomer.It is, for example possible to use polyester-based elastomer, polyurethane series elastomer, polyester urethane Based elastomers, polyamide-based elastomer, polyesteramide based elastomers, acrylic elastomer etc..These elastomers can be independent Use or use as mixture of more than two kinds.

And then, above-mentioned containing carboxy resin, regulation compositions in order to synthesize, or in order to adjust viscosity to be applied to base On plate, carrier thin film, the light solidifying/heat solidifying resin composition of the present invention can use organic solvent.

As this organic solvent, ketone, aromatic hydrocarbon, glycol ethers, glycol ethers acetate esters, ester can be listed Class, alcohols, aliphatic hydrocarbon, petroleum solvent etc..More specifically, for the ketone such as butanone, Ketohexamethylene；Toluene, dimethylbenzene, four Toluene etc. are aromatic hydrocarbon；Cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, butyl carbitol, third The glycol ethers such as glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, triethylene glycol monomethyl ether；Ethyl acetate, vinegar Acid butyl ester, dipropylene glycol methyl ether acetas, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetas, propandiol butyl ether acetas Deng esters；The alcohols such as ethanol, propanol, ethylene glycol, propylene glycol；The aliphatic hydrocarbon such as octane, decane；Petroleum ether, Petroleum, hydrogenation stone The petroleum solvent such as cerebrol, solvent naphtha etc..Such organic solvent can be used alone or as mixture of more than two kinds Use.

Generally, most of macromolecular materials, once oxidation, will occur oxidative degradation the most continuously, cause high score The function of sub-raw material reduces, therefore, in the light solidifying/heat solidifying resin composition of the present invention, for anti-oxidation, and can It is decomposed into innocuous substance and not adding the peroxide making radical scavenger that the free radical of generation lost efficacy and/or make generation The antioxidants such as the peroxide decomposer that can produce new free radical.Especially at the use butadiene-based elastomer of the present invention Compositions in when using antioxidant, PCT patience improves, and stripping, variable color during HAST tail off, and is effective.

As playing the antioxidant of radical scavenger effect, specifically, include, for example out hydroquinone, the 4-tert-butyl group Catechol, TBHQ, p methoxy phenol, 2,6-di-t-butyl-paracresol, 2,2-methylene-bis-(4-methyl- 6-tert-butyl phenol), 1,1,3-tri-(2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethyl-2,4,6-tri- (3,5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-tri-(3 ', 5 '-di-tert-butyl-4-hydroxyl benzyl)-guanamines, 4,6- Quinone based compound, double (2,2,6,6-tetramethyl-4-piperidines such as phenol system, p methoxy phenol, benzoquinone such as (1H, 3H, 5H) triketone Base)-the amine compound such as sebacate, phenothiazine etc..

Radical scavenger can be commercially available product, include, for example out ADK STAB AO-30, ADK STAB AO-330, ADK STAB AO-20、ADK STAB LA-77、ADK STAB LA-57、ADK STAB LA-67、ADK STAB LA-68、 ADK STAB LA-87 (being rising sun electrification company above to manufacture, trade name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076、IRGANOX 1135、TINUVIN 111FDL、TINUVIN 123、TINUVIN 144、TINUVIN 152、 TINUVIN 292, TINUVIN 5100 (being Xiba Special Chemical Product Co., Ltd above to manufacture, trade name) etc..

As playing the antioxidant of peroxide decomposer effect, as concrete compound, include, for example out Asia The phosphorus series compounds such as triphenyl phosphate, tetramethylolmethane four lauryl thioacrylic acid ester, dilauryl thiodipropionate, two hard Aliphatic radical-3, the chalcogenide compound etc. such as 3 '-thiodipropionate.

Peroxide decomposer can be commercially available product, and (rising sun electrification company manufactures, business to include, for example out ADK STAB TPP The name of an article), MARK AO-412S (ADEKA ARGUS CHEMICALCO., LTD. manufacture, trade name), Sumilizer TPS (firmly Friend KCC manufactures, trade name) etc..

These antioxidants may be used singly or in combination of two or more.

The deterioration it addition, usual macromolecular material is decomposed due to absorbing light, therefore, in order to take for ultraviolet Stabilisation countermeasure, in the light solidifying/heat solidifying resin composition of the present invention, in addition to above-mentioned antioxidant, permissible Use UV absorbent.

As UV absorbent, can enumerate benzophenone derivates, benzoate derivatives, benzotriazole derivatives, Pyrrolotriazine derivatives, benzothiazole derivant, cinnamic acid ester (cinnamate) derivant, o-aminobenzoa (anthraxnilate) derivant, dibenzoylmethane derivatives etc..As the concrete example of benzophenone derivates, can arrange Enumerate ESCALOL 567, Octabenzone, 2,2 '-dihydroxy-4-methoxybenzene And benzophenone and 2,4-DihydroxyBenzophenone etc..As the concrete example of benzoate derivatives, salicylic acid 2-ethyl can be listed Own ester, phenyl salicylate, TBS., 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid Ester and palmityl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester etc..As the concrete example of benzotriazole derivatives, can list 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl- 3 '-tert-butyl group-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzene three Azoles, 2-(2 '-hydroxyl-5 '-tolyl) benzotriazole and 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole etc..Make For the concrete example of pyrrolotriazine derivatives, hydroxyphenyl-triazine, double ethylhexyloxyphenol anisyl triazines etc. can be listed.

As UV absorbent, can be commercially available product, can enumerate such as TINUVINPS, TINUVIN 99-2, TINUVIN 109、TINUVIN 384-2、TINUVIN 900、TINUVIN 928、TINUVIN 1130、TINUVIN 400、 TINUVIN 405, TINUVIN 460, TINUVIN 479 (being above Xiba Special Chemical Product Co., Ltd to manufacture, trade name) etc..

Above-mentioned UV absorbent can be used alone one or be used in combination of two or more, by with above-mentioned antioxidant group Close and use, it is possible to achieve the stabilisation of the molding obtained by the light solidifying/heat solidifying resin composition of the present invention.

In the light solidifying/heat solidifying resin composition of the present invention, in order to improve interlayer adaptation or photonasty tree Lipid layer and the adaptation of base material, can use closely sealed accelerator.When enumerating concrete example, for instance that benzimidazole, benzothiazole, benzene And thiazole, 2-mercaptobenzimidazole, 2-mercaptobenzooxazole, 2-mercaptobenzothiazole (trade name: chemical industrial company of Kawaguchi system The Accel M made), 3-morpholinomethyl-1-phenyl-triazole-2-thioketone, 5-amino-3-morpholinomethyl-thiazole-2-thioketone, 2-sulfydryl-5-methyl mercapto-thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole, even containing amino benzotriazole, silane Connection agent etc..

The light solidifying/heat solidifying resin composition of the present invention can add micropowder Silicon stone, organic as required further The thixotropic agent such as bentonite, montmorillonite, brucite.From the point of view of as the ageing stability of thixotropic agent, preferably organobentonite, neatly Stone.Particularly brucite has the electrical characteristics of excellence.Furthermore it is possible to be compounded hot polymerization inhibitor, silicon-type, fluorine system, macromolecular Deng silane coupler, antirust agent and bis-phenol system, triazine sulfur such as defoamer and/or levelling agent, imidazoles system, thiazole system, triazole systems The known conventional additive kind such as the copper inhibitors such as alcohol system.

Above-mentioned hot polymerization inhibitor may be used for preventing the thermal polymerization of above-mentioned polymerizable compound or through time polymerization.Gather as thermal resistance Agent, include, for example out 4-methoxyphenol, hydroquinone, the substituted hydroquinone of alkyl or aryl, tert-butyl catechol, even benzene three Phenol, 2-dihydroxy benaophenonel, 4-methoxyl group-2-dihydroxy benaophenonel, Cu-lyt., phenothiazine, chloranil, naphthylamines, betanaphthol, BHT, 2,2 '-di-2-ethylhexylphosphine oxide (4-methyl-6-tert-butylphenol), pyridine, Nitrobenzol, dinitro benzene, Picric acid (Picric acid), 4-toluidines, methylene blue, copper and the reactant of organic sequestering agent, methyl salicylate and phenol Thiazine, nitroso compound, nitroso compound and the chelate etc. of Al.

The light solidifying/heat solidifying resin composition of the present invention such as regulates to being suitable to coating side with above-mentioned organic solvent The viscosity of method, is applied to base by methods such as dip coating, flow coat method, rolling method, scraper rubbing method, silk screen print method, curtain coatings On material, by making the organic solvent volatile dry (being temporarily dried) contained in compositions at a temperature of about 60～100 DEG C, permissible Form not snearing film.Then, use contact (or cordless) to make active energy beam pass through the figuratum light of formation to cover Mould carries out selectivity exposure or directly carries out pattern exposure by the direct exposure machine of laser, utilizes alkaline aqueous solution (such as 0.3～3% aqueous sodium carbonate) is developed in unexposed portion, thus form corrosion-resisting pattern.And then, for containing Thermocurable composition Compositions in the case of, the such as temperature by being heated to about 140～180 DEG C makes its heat cure, obtains above-mentioned containing carboxy resin Carboxyl and molecule in there is the Thermocurable composition of multiple cyclic ether group and/or cyclic thioether base react, can be formed heat-resisting The cured coating film of the various excellents such as property, chemical proofing, resistance to hygroscopicity, adaptation, electrical characteristics.Wherein, even if not In the case of Thermocurable composition, by heat treatment, the alkene of the photo-curable composition remained with unreacted state during exposure Belonging to unsaturated bond and be also carried out hot radical polymerization, coating characteristic improves, therefore, it can carry out heat treatment according to purpose purposes (heat cure).

As above-mentioned base material, in addition to being pre-formed with the printed circuit board (PCB) in loop, flexible printed circuit board, also can make Paper using-phenolic resin, paper-epoxy resin, glass cloth-epoxy resin, glass-polyimides, glass cloth/non-woven fabrics-asphalt mixtures modified by epoxy resin The composites such as fat, glass cloth/paper-epoxy resin, synthetic fibers-epoxy resin, fluororesin polyethylene PPO cyanate The copper-clad laminated board of all grades (FR-4 etc.) made, Kapton, PET film, glass substrate, ceramic substrate, crystalline substance Plectane etc..

The volatile dry carried out after the light solidifying/heat solidifying resin composition of the coating present invention can use hot blast (use has the thermal source of the air mode of heating utilizing steam for circulating drying oven, IR stove, hot plate, Convective Heating furnace box etc. Equipment, makes the method that the hot air convection in drying machine contacts and the mode being blown on supporter by nozzle) carry out.

To obtain after being coated with the light solidifying/heat solidifying resin composition of the present invention volatile dry as described below Film is exposed (irradiation active energy beam).Exposure portion (part irradiated by the active energy beam) solidification of film.

The exposure machine used is irradiated, it is possible to use directly describing device (such as utilizes as above-mentioned active energy beam From the cad data of computer, directly use the laser direct imaging device of laser scanning picture picture), be equipped with metal halide The exposure machine of lamp, it is equipped with the exposure machine of (surpassing) high voltage mercury lamp, is equipped with the exposure machine of hydrargyrum short-arc lamp or uses (surpassing) high-pressure mercury The direct describing device of the Burdick lamps such as lamp.As active energy beam, as long as using maximum wavelength in 350～410nm scopes Interior laser, then can be any one of gas laser, Solid State Laser.It addition, its light exposure is different according to thickness etc., logical It is often 5～200mJ/cm²Scope, preferably 5～100mJ/cm²Scope, more preferably 5～50mJ/cm²In the range of.Make For above-mentioned direct describing device, such as, can use the dress that the company such as Orbotech Ltd., PENTAX CORPORATION manufactures Put, produce maximum wavelength at the device of laser of 350～410nm as long as can vibrate, then can use any device.

As above-mentioned developing method, it is possible to use infusion process, shower method, nebulization, spread coating etc., as developer solution, can To use the alkaline aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium phosphate, sodium silicate, ammonia, amine etc..

In addition to the method being coated directly onto on base material with liquid, the Photosetting and thermosetting resin combination of the present invention Thing can also use to have the form of the dry film of solder mask, and this solder mask is to be pre-coated with solder resist at poly terephthalic acid On the thin film such as glycol ester and be dried and formed.The light solidifying/heat solidifying resin composition of the use present invention described below Situation as dry film.

Dry film has and carrier thin film, solder mask and the strippable cover film used as required is stacked gradually and shape The structure become.Solder mask is the light solidifying/heat solidifying resin composition of alkali-developable to be coated on carrier thin film or covers thin On film and be dried and the layer that obtains.Dry film can be obtained as follows: on carrier thin film after formation solder mask thereon Stacking cover film or on cover film formed solder mask, this laminate layers is stacked on carrier thin film.

As carrier thin film, the thermoplastic film such as mylar that can use 2～150 μ m-thick.

Solder mask is to utilize knife type coater, lip coating machine, comma coater, film coater etc. that alkali-developable light is solid The property changed hot curing resin composition with the thickness of 10～150 μm homogeneous be coated on carrier thin film or cover film and dry and Formed.

As cover film, it is possible to use polyethylene film, polypropylene film etc., preferably cover film and solder mask is viscous Relay is less with the bonding force of solder mask than carrier thin film.

In order to use dry film to make protecting film (permanent protecting film) on a printed circuit, peel off cover film, by welding resistance Layer is overlapping with the base material being formed with circuit, uses laminating machine etc. to fit, and forms solder mask on the base material be formed with circuit. As described above to formed solder mask be exposed, develop, be heating and curing time, cured coating film can be formed.Carrier thin film Before exposure or peel off after exposure and all may be used.

Embodiment

Embodiment given below and comparative example illustrate the present invention, but the invention is not restricted to following embodiment.Wherein, Following " part " and " % " all refers to quality criteria if not otherwise specified.

Synthesis example 1

1070g ((+)-2,3-Epoxy-1-propanol radix (aromatic rings sum): 5.0 rub is added in 600g diethylene glycol monoethyl ether acetas You) o-cresol phenolic epoxy varnish (manufacture of DIC company, EPICLON N-695, softening point 95 DEG C, epoxide equivalent 214, Average functional group number 7.6), 360g (5.0 moles) acrylic acid and 1.5g hydroquinone, be heated to 100 DEG C and stir so that it is be the most molten Solve.Then, add 4.3g triphenylphosphine, be heated to 110 DEG C, after reacting 2 hours, be warming up to 120 DEG C, then react 12 hours.In The reactant liquor of gained adds 415g fragrance family hydrocarbon (Solvesso 150), 456.0g (3.0 moles) tetrahydrophthalic acid Acid anhydride, 110 DEG C carry out 4 hours reaction, after cooling, it is thus achieved that solid constituent acid number 89mgKOH/g, solid constituent 65% resin molten Liquid.Hereinafter, varnish A-1 it is referred to as.

Synthesis example 2

(Nippon Kayaku Co., Ltd. manufactures, EOCN-to add 2200 parts of cresol novolak type epoxy resins 104S, softening point 92 DEG C, epoxide equivalent 220), 134 parts of dihydromethyl propionic acids, 648.5 parts of acrylic acid, 4.6 parts of methylnaphthohydroquinones, 1131 parts of carbitol acetate and 484.9 parts of solvent naphthas, be heated to 90 DEG C and stir, making reactant mixture dissolve.Then, Make reactant liquor be cooled to 60 DEG C, add 13.8 parts of triphenylphosphines, be heated to 100 DEG C, react about 32 hours, it is thus achieved that acid number The reactant of 0.5mgKOH/g.Afterwards, 364.7 parts of tetrabydrophthalic anhydrides, 137.5 parts of carbitol acetate are added wherein And 58.8 parts of solvent naphthas, it is heated to 95 DEG C, reacts about 6 hours, cooling, it is thus achieved that solid constituent acid number 40mgKOH/g, do not wave Send out the resin solution containing carboxyl photoresist of composition 65%.Hereinafter, varnish A-2 it is referred to as.

Synthesis example 3

Make 400 parts of epoxide equivalents 800, the bisphenol-f type solid epoxy resin of softening point 79 DEG C and 925 portions of chloropropylene oxides, 462.5 After part dmso solution, under agitation added 81.2 parts of 98.5%NaOH in 70 DEG C through 100 minutes.Exist further after interpolation 70 DEG C are reacted 3 hours.Afterwards, the unreacted chloropropylene oxide of surplus and the major part of dimethyl sulfoxide are under reduced pressure distilled and remove Go, make the reaction product containing by-product salt Yu dimethyl sulfoxide be dissolved in 750 parts of methylisobutylketones, and then add 10 parts 30%NaOH, reacts 1 hour at 70 DEG C.After having reacted, carry out twice washing with 200 parts of water.After oil-water separation, from oil Layer Distillation recovery methylisobutylketone, it is thus achieved that 370 parts of epoxide equivalents 290, epoxy resin (a-1) of softening point 62 DEG C.Add 2900 Part epoxy resin (a-1) of (10 equivalent) gained, 720 parts of (10 equivalent) acrylic acid, 2.8 parts of methylnaphthohydroquinones, 1950 parts of carbitols Acetas, is heated to 90 DEG C, stirring, makes reactant mixture dissolve.Then, make reactant liquor be cooled to 60 DEG C, add 16.7 part three Phenylphosphine, is heated to 100 DEG C, carries out reaction in about 32 hours, it is thus achieved that the reactant of acid number 1.0mgKOH/g.Then, add wherein Enter 786 parts of (7.86 moles) succinic anhydrides, 423 parts of carbitol acetate, be heated to 95 DEG C, carry out reaction in about 6 hours, it is thus achieved that Gu Body composition acid number 100mgKOH/g, the resin solution of solid constituent 65%.Hereinafter, varnish A-3 it is referred to as.

Synthesis example 4

Being provided with thermometer, nitrogen gatherer hold concurrently alkylene oxide gatherer and agitating device autoclave in, add 119.4g phenolic varnish type cresol novolac resin (Showa macromolecule (strain) manufactures, trade name " Shonol CRG951 ", OH equivalent: 119.4), 1.19g potassium hydroxide and 119.4g toluene, while stirring to carrying out nitrogen displacement, heat temperature raising in system.Then, It is slowly added dropwise 63.8g expoxy propane, at 125～132 DEG C, 0～4.8kg/cm²Lower reaction 16 hours.It is then cooled to room temperature, In this reaction solution, add mixing 1.56g 89% phosphoric acid neutralize potassium hydroxide, it is thus achieved that nonvolatile component 62.1%, hydroxyl The propylene oxide reaction solution of the phenolic varnish type cresol novolac resin of value 182.2g/eq..This is that every 1 equivalent phenolic hydroxyl group is put down All materials of addition 1.08 mol of alkylene oxide.

Then, be provided with blender, thermometer and air be blown in the reactor of pipe interpolation 293.0g gained novolaks The alkylene oxide reaction solution of type cresol resin, 43.2g acrylic acid, 11.53g methanesulfonic acid, 0.18g methylnaphthohydroquinone and 252.9g first Benzene, is blown into air with the speed of 10ml/ minute, and limit is stirred, while react 12 hours at 110 DEG C.Reaction generate water with first The form of the azeotropic mixture of benzene distillates, and has distillated the water of 12.6g.It is then cooled to room temperature, by 15% hydroxide of 35.35g With gained reaction solution in sodium water solution, then wash.Then, by vaporizer, with 118.1g diethylene glycol monomethyl ether acetic acid Displacement limit, toluene limit is evaporated by ester, it is thus achieved that phenolic varnish type acrylic ester resin solution.Then, it is being provided with agitator, thermometer Addition 332.5g gained phenolic varnish type acrylic ester resin solution and 1.22g triphenyl it is blown in the reactor of pipe with air Phosphine, is blown into air with the speed of 10ml/ minute, and limit is stirred, while be slowly added 60.8g tetrabydrophthalic anhydride, 95～101 React 6 hours at DEG C.Obtain solid matter acid number be 88mg KOH/g, nonvolatile component 71% containing carboxyl photoresist Resin solution.Hereinafter referred to as varnish A-4.

Synthesis example 5

In the 5 liters of detachable flasks being provided with thermometer, blender and reflux condenser, put into 1245g as polymerization (DAICEL CHEMICAL INDUSTRIES, LTD. manufacture Placcel 208, molecular weight to the polycaprolactone glycol of thing polyhydric alcohol 830), 201g as the dihydromethyl propionic acid of the dihydroxy compounds with carboxyl, 777g as the different Fo Er of polyisocyanates Ketone diisocyanate and 119g, as the acrylic acid 2-hydroxyl ethyl ester of (methyl) acrylate with hydroxyl, put into each further The p methoxy phenol of 0.5g and di-tert-butyl hydroxy toluene.It is heated to 60 DEG C while stirring, stops, adding 0.8g tin dilaurate Dibutyl tin.If the temperature in reaction vessel starts to reduce, again heat, continuously stirred at 80 DEG C, confirm infrared ray Absorption spectrum (the 2280cm of NCO in absorption spectrum^-1) disappear then stopped reaction, it is thus achieved that the carbamic acid of thick liquid Ester acrylate compounds.Carbitol acetate is used to regulate to nonvolatile component=50 mass %.Obtain the acid of solid matter Value 47mg KOH/g, nonvolatile component 50% the resin of carbamate (methyl) acrylate compounds with carboxyl molten Liquid.Hereinafter referred to as varnish A-5.

Synthesis example 6

It is being provided with 2 liters of detachable flasks of blender, thermometer, reflux condenser, Dropping funnel and nitrogen ingress pipe In, add 900g as the diethylene glycol dimethyl ether of solvent and 21.4g as the peroxidating 2 ethyl hexanoic acid uncle of polymerization initiator (Nof Corp. manufactures butyl ester, trade name；Perbutyl O), it is heated to 90 DEG C.After heating, dripped wherein through 3 hours 309.9g methacrylic acid, 116.4g methyl methacrylate and the lactone-modified HEMA of 109.8g (Placcel FM1:DAICEL CHEMICAL INDUSTRIES, LTD. manufacture) and 21.4g are as double (4-of polymerization initiator Tert-butylcyclohexyl) (Nof Corp. manufactures peroxy dicarbonate, trade name；Peroyl TCP), further ripening 6 is little Time, it is thus achieved that containing carboxyl copolymer resins.It addition, reaction is carried out in a nitrogen atmosphere.

Then, in gained is containing carboxyl copolymer resins, 363.9g acrylic acid 3,4-epoxycyclohexanecarboxylate (DAICEL are added CHEMICAL INDUSTRIES, LTD. manufacture, trade name；Cyclomer A200), 3.6g is as the dimethyl of ring opening catalyst Benzylamine, 1.80g, as the p methoxy phenol of polymerization inhibitor, are heated to 100 DEG C and are stirred, and thus carry out epoxy radicals Opening.After 16 hours, it is thus achieved that solid constituent acid number is 108.9mgKOH/g, weight average molecular weight is 25000, solid The resin solution of composition 54%.Hereinafter referred to as varnish A-6.

Reference example

Use the resin solution obtained in above-mentioned each synthesis example, with the various compositions shown in table 1 below together, with table 1 institute Show that ratio (mass parts) mixes, after blender ready-mixed, use triple-roller mill to carry out mixing, prepare Photosetting and thermosetting Resin combination.Use the flask burn processing chromatography of ions based on JPCA specification, to gained Photosetting and thermosetting tree The halide content (chloride and the total of bromide) of oil/fat composition carries out quantitative.Its result is together shown in table 1.

[table 1]

From result shown in above-mentioned table 1, use not using epoxy resin as initiation material containing carboxylic acid resin, containing ethylene Based elastomeric, light solidifying/heat solidifying resin composition (reference data 4, reference data 5, the reference data of sulfhydryl compound 6), light solidifying/heat solidifying resin composition (reference data 1, the reference data of carboxylic acid photoresist are contained with using other 2, reference data 3) compare, halide content is substantially few.

Embodiment 1～14 and comparative example 1～3

Use the resin solution of above-mentioned synthesis example, with the various compositions shown in table 2 below together, with the ratio shown in table 2 (mass parts) coordinates, and after blender ready-mixed, carries out mixing with triple-roller mill, prepares solder resist photosensitive resin composition Thing.Here, by utilizing the granulometry of Hegman fineness grind instrument (grindmeter) that ERICHSEN company manufactures to come gained sense The dispersion of photosensitive resin composition is evaluated, and result is below 15 μm.

[table 2]

Remarks:

^*1:2-methyl isophthalic acid-(4-methyl mercapto phenyl)-2-morpholino propane-1-ketone (Irgacure 907: Ciba Specialty Xue Pin company manufactures)

^*2:2,4-diethyl thioxanthone (KAYACURE DETX-S Nippon Kayaku Co., Ltd. manufacture)

^*3:1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1,1-(O-acetyl oxime) ethyl ketone (manufacture of Irgacure OXE 02: Xiba Special Chemical Product Co., Ltd)

^*4:ADEKA ARKLS NCI-831 (manufacture of ADEKA company)

^*5: phenolic resin varnish type epoxy resin (RE306CA90: chemical medicine company of Japan manufactures)

^*6: di-first phenol-type epoxy resin (YX-4000: epoxy resin company of Japan manufactures)

^*7: C-terminal liquid polybutadiene (manufacture of Chu Guangxingchan company)

^*8: epoxidized polybutadiene (DAICEL CHEMICAL INDUSTRIES, LTD. manufacture)

^*9:2-mercaptobenzothiazoler (manufacture of chemical industrial company of Kawaguchi)

^*Double (3-sulfydryl butyryl acyloxy) butane of 10:1,4-(Showa electrician company manufacture)

^*11:2-dibutylamino-4,6-dimercapto-s-triazine (three chemical conversion companies of association manufacture)

^*12:1,3,5-tri-(3-sulfydryl butoxyethyl group)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketones (Showa electricity Work company manufactures)

^*13:2,4,6-tri-thiols-s-triazine (three chemical conversion companies of association manufacture)

^*14: tetramethylolmethane four (3-mercaptobutylate) (Showa electrician company manufacture)

^*15:C.I. pigment blue 15: 3

^*16:C.I. pigment yellow 147

^*17: antioxidant (Xiba Special Chemical Product Co., Ltd's manufacture)

^*18:B-30 (chemical company's manufacture)

^*19: brucite (consonance chemical industrial company manufactures)

^*20: diethylene glycol monoethyl ether acetas

^*21: Dipentaerythritol Pentaacrylate

^*22: blocked isocyanate (Asahi Kasei Chemicals Corporation manufacture)

^*23: methylated melamine resins (SANWA Chemical Co., Ltd. manufacture)

Performance evaluation:

<optimum exposure>

The circuit pattern substrate of 18 μm thick to copper carries out the roughened copper surface process (Mec that MecCorporation manufactures Etch Bond CZ-8100) after, carry out washing, be dried, then, by silk screen print method whole topcoating cloth above-described embodiment and The light solidifying/heat solidifying resin composition of comparative example, is dried 60 minutes in the heated air circulation type drying oven of 80 DEG C.It is dried Afterwards, use the exposure device carrying high voltage mercury lamp, be exposed by stage actinometer (Kodak No.2), will development Time (30 DEG C, 0.2MPa, 1% aqueous sodium carbonate) 90 seconds, the pattern of the stage actinometer of residual is light exposure when 7 sections As optimum exposure.

<developability>

By silk screen print method, pure Cu substrate is coated with above-described embodiment and the Photosetting and thermosetting tree of comparative example Oil/fat composition so that dried thickness is about 25 μm, is dried 30 minutes in the heated air circulation type drying oven of 80 DEG C.It is dried After, developed by 1wt% aqueous sodium carbonate, measured to by stopwatch (stopwatch) removing dry coating Time.

<maximum development life-span>

By silk screen printing, the whole face of compositions of above-described embodiment and comparative example is coated on the figuratum Copper Foil base of formation On plate, it is dried at 80 DEG C, every 10 minutes taking-up substrates from 20 minutes to 80 minutes, naturally cools to room temperature.In spray Under conditions of mist pressure is 0.2MPa, with the 1wt% aqueous sodium carbonates of 30 DEG C, this substrate is carried out development in 90 seconds, will not have The maximum allowable drying time of residue residual develops the life-span as maximum.

<viscosity>

By silk screen printing, the whole face of compositions of above-described embodiment and comparative example is coated on the figuratum Copper Foil base of formation On plate, it is dried 30 minutes in the heated air circulation type drying oven of 80 DEG C, lets cool to room temperature.By PET negativity thin film and this substrate Contact, the HMW-GW20 manufactured by ORC A.B. is crimped under 1 minute reduced pressure, then, peels off according to following standard evaluation The attaching state of thin film during negative film.

Zero: during stripping film, entirely without resistance, film there is no remaining trace.

△: during stripping film, has a little resistance, with a small amount of vestige on film.

×: during stripping film, there is resistance, with obvious vestige on film.

Attribute testing:

By silk screen printing, the whole face of compositions of above-described embodiment and comparative example is coated on the figuratum Copper Foil base of formation On plate, it is dried 30 minutes at 80 DEG C, lets cool to room temperature.Use the exposure device carrying high voltage mercury lamp with optimum exposure to this Substrate carries out solder resist pattern exposure, under conditions of atomisation pressure 0.2MPa, carries out with the 1wt% aqueous sodium carbonate of 30 DEG C Development in 90 seconds, it is thus achieved that corrosion-resisting pattern.By UV belt conveyor furnace, in accumulated exposure amount 1000mJ/cm²Under conditions of to this base After plate irradiation ultraviolet radiation, heat at 160 DEG C and solidify for 60 minutes.Evaluation gained printed base plate as described below (evaluates base Plate) characteristic.

<acid resistance>

Substrate will be evaluated at 10vol%H₂SO₄Aqueous solution at room temperature impregnates 30 minutes, be visually confirmed to be infiltration, film Dissolution, and then utilize adhesive tape to peel off confirmation stripping.

Zero: do not find change.

△: the least change.

×: film has expansion or swelling comes off.

<alkali resistance>

Evaluation substrate at room temperature impregnated 30 minutes in 10vol%NaOH aqueous solution, is visually confirmed to be infiltration, film Dissolution, and then utilize adhesive tape to peel off confirmation stripping.

Zero: do not find change.

△: the least change.

×: film has expansion or swelling comes off.

<resistance to soldering heat performance>

Be coated with rosin series solder flux evaluates substrate in being redefined for the weld groove of 260 DEG C, with modified alcohol washing weldering After agent, the expansion of visual valuation resist layer is peeled off.Criterion is as follows.

Zero: even if being repeated 3 times above 10 seconds dippings, the most do not find to peel off.

△: when being repeated 3 times above 10 seconds dippings, has a little stripping.

×: within 10 seconds are immersed in 3 times, resist layer i.e. has expansion, stripping.

<the gold-plated property of chemically-resistant>

Use electroless nickel bath and the chemical gilding bath of commercially available product, under conditions of nickel 5 μm, golden 0.05 μm, carry out plating, Peeled off by adhesive tape evaluate resist layer with or without peel off, be plated with without penetrate into, then, by adhesive tape peel off evaluate resist layer with or without Peel off.Criterion is as follows.

◎: do not find to penetrate into, peel off.

Zero: confirm there is slight infiltration after plating, after adhesive tape is peeled off, nothing is peeled off.

△: confirm there is slight infiltration after plating, adhesive tape also shows stripping after peeling off.

×: there is stripping after plating.

<PCT patience>

Use PC T device (ESPEC Corp. manufacture HAST SYSTEM TPC-412MD), 121 DEG C, saturated, Will be formed with the evaluation processing substrate 240 hours of welding resistance cured coating film under conditions of 0.2MPa, evaluate the state of film, then, The evaluation carrying out peeling off is peeled off by adhesive tape.Criterion is as follows.

◎: without expansion, stripping, variable color, dissolution, also entirely without confirming stripping in adhesive tape stripping.

Zero: without expansion, stripping, variable color, dissolution, adhesive tape confirms few stripping in peeling off.

△: have a small amount of expansion, stripping, variable color, dissolution, adhesive tape confirms occur peeling off in peeling off.

×: finding a large amount of expansion, stripping, variable color, dissolution, adhesive tape also confirms a large amount of stripping occur in peeling off.

<cold-hot impact>

Make the evaluation substrate with the welding resistance cured coating film defining hollow pattern, hollow zero pattern.In cold and hot punching Hit in exerciser (manufacture of Etac company), be 1 cycle with-55 DEG C/30 minutes～150 DEG C/30 minutes, gained is evaluated substrate Carry out the resistance test in 1000 cycles.After test, the cured film after being processed by visualization, judge to split according to following standard The situation occurred of stricture of vagina.

Zero: cracking frequency is less than 30%

△: cracking frequency is 30～50%

×: cracking frequency is more than 50%

<HAST characteristic>

The BT substrate being formed with comb-type electrode (line/spacing=30 micron/30 micron) is formed welding resistance cured coating film, system Become to evaluate substrate.This evaluation substrate is put into 130 DEG C, in hot and humid groove under the atmosphere of humidity 85%, applies 5V voltage, enter HAST test in the little time slot of row 168.According to following criterion evaluation insulating resistance value in 168 little grooves constantly.

◎: 10⁸More than Ω

Zero: 10⁷～10⁸Ω

△: 10⁶～10⁷Ω

×: 10⁶Below Ω

[table 3]

Embodiment 15～27 and comparative example 4～6

With butanone by the embodiment 2 prepared in the compounding ratio shown in table 2～13 and each compositions of comparative example 1,2,3 Dilution, is coated in PET film, is dried 30 minutes at 80 DEG C, forms the photosensitive polymer combination layer of thickness 20 μm.Enter And, fit over thin film thereon to make dry film, respectively as embodiment 15～27 and comparative example 4～6.

<dry film evaluation>

From dry film obtained as above, peel off cover film, film hot-pressing is connected on the figuratum copper clad laminate of formation On, then, as the substrate used with the coating characteristic evaluation of above-described embodiment under conditions of expose.After exposure, stripping From carrier thin film, under conditions of atomisation pressure 0.2MPa, carry out development in 90 seconds with the 1wt% aqueous sodium carbonate of 30 DEG C, Obtain corrosion-resisting pattern.By UV belt conveyor furnace, in accumulated exposure amount 1000mJ/cm²Under conditions of to this substrate irradiate ultraviolet After line, heat 60 minutes at 160 DEG C, solidify.By above-mentioned test method and evaluation methodology, gained had solidification The test substrate of overlay film carries out the evaluation test of each characteristic.Result is shown in table 4.

[table 4]

From the result shown in above-mentioned table 3 and table 4 it can be seen that the light solidifying/heat solidifying resin composition of the present invention is made For the gold-plated property of chemically-resistant required for having semiconductor-sealing-purpose solder resist concurrently, PCT patience, cold-hot impact, HAST characteristic (electricity Characteristic) light solidifying/heat solidifying resin composition be useful.

Claims (4)

1. the permanent protecting film photo-curable heat cure of making on a printed circuit can developed by alkaline aqueous solution Property resin combination, it is characterised in that containing containing carboxy resin, Photoepolymerizationinitiater initiater, containing based elastomers and sulfydryl chemical combination Thing, above-mentioned is selected from following (1)～the one of (6) containing carboxy resin,

(1) end of the polyurethane resin obtained by diisocyanate cpd and the sudden reaction of diatomic alcohol compounds is made Obtain with anhydride reaction containing terminal carboxyl group polyurethane resin；

(2) carried out by diisocyanate and carboxylic diol compound and the sudden reaction of diatomic alcohol compounds In synthesis containing carboxyl polyurethane resin, add in molecule and there is 1 hydroxyl and the compound of more than 1 (methyl) acryloyl group Carry out end (methyl) acrylated and obtain containing carboxyl polyurethane resin；

(3) carried out by diisocyanate and carboxylic diol compound and the sudden reaction of diatomic alcohol compounds In synthesis containing carboxyl polyurethane resin, add in molecule and there is 1 NCO and more than 1 (methyl) acryloyl group Compound carry out end (methyl) acrylated and obtain containing carboxyl polyurethane resin；

(4) compound in a part with multiple phenolic hydroxyl group is made to react gained with alkylene oxide or cyclic carbonate compound Product and reacting containing the monocarboxylic acid of unsaturated group, make gained product react with multi-anhydride and obtain containing carboxylic Base photoresist；

(5) multifunctional oxetane resin reacts with dicarboxylic acids, generate primary hydroxyl on 2 yuan of anhydride of addition and obtain containing carboxylic Base polyester resin has 1 epoxy radicals and the compound of more than 1 (methyl) acryloyl group in further addition 1 molecule and obtains Arrive containing carboxyl photoresist；

(6) above-mentioned (1)～(5) any one containing carboxy resin in addition a part has cyclic ether group and (methyl) third The compound of enoyl-and obtain containing carboxyl photoresist, wherein,

Described sulfhydryl compound is 2-mercaptobenzothiazole, 1,4-double (3-sulfydryl butyryl acyloxy) butane, 2-dibutylamino-4,6- Dimercapto-s-triazine, 1,3,5-tri-(3-sulfydryl butoxyethyl group)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-triketone, 2,4, Any one in 6-tri-thiol-s-triazine, tetramethylolmethane four (3-mercaptobutylate),

Relative to containing carboxy resin described in 100 mass parts, the compounding amount of described sulfhydryl compound is 0.01～10 mass parts.

2. a dry film for Photosetting and thermosetting, it is by the Photosetting and thermosetting resin group described in claim 1 Compound is coated on thin film and is dried and obtains.

3. a solidfied material, it is obtained as below: be coated with by the light solidifying/heat solidifying resin composition described in claim 1 Cloth is on base material and photocatalytic coating film that is dry and that obtain solidifies；Or make the dry coating light obtained on base material by dry film lamination solid Changing, described light solidifying/heat solidifying resin composition is coated on thin film and is dried and obtains by described dry film.

4. having a printed circuit board (PCB) for curing overlay film, described curing overlay film is obtained as below: by irradiating active-energy Ray, makes to be coated on base material by the light solidifying/heat solidifying resin composition described in claim 1 and be dried and obtain Film with pattern-like photocuring, then heat cure；Or by irradiating active energy beam, make on base material, obtain dry film lamination The dry coating obtained is with pattern-like photocuring, and then heat cure, described dry film is by described Photosetting and thermosetting resin group Compound is coated on thin film and is dried and obtains.