CN101846882B - Photocuring thermocuring resin composition, dry membrane, cured product and printed circuit board - Google Patents

Abstract

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

Description

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

Technical field

The present invention relates to the light solidifying/heat solidifying resin composition that can develop through dilute alkaline aqueous solution, relate in particular to carry out photocuring through ultraviolet exposure or laser explosure solder resist with composition, its dry film and solidfied material and printed circuit board (PCB) with the cured film that uses their formation.

Background technology

All the time, the photosensitive polymer combination of alkali developable is used by a large amount of as the use in printed circuit board solder resist.The purpose of using solder resist is the top layer circuit of protection printed circuit board (PCB), demanding solder heat resistance property and electrical insulating property.And then recently, the densification of printed circuit board (PCB) is remarkable, and its circuit minimum is line 10 μ m, space 10 μ m, requires than higher in the past insulating reliability.

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

Yet because the densification of printed base plate in recent years, between the fine pattern circuit, insoluble material (inorganic filler, crystallinity epoxy resin etc.) exists with particle, becomes the reason that causes short circuit between circuit.And then; Make in the operation of tellite to the substrate that is formed with various circuit patterns at the dry film lamination that light solidifying/heat solidifying resin composition is applied on the carrier film and drying obtains; The particle of insoluble substance becomes the bad reason of lamination, also is the reason that the feasible productive rate that need highly control the fine pattern substrate manufacture of thickness reduces.Therefore; When the preparation solder resist, carry out various dispersion treatment; Filter for the big particle of removing insoluble composition; But nearly all crystallinity epoxy resin all has compatibility with organic solvent, other resin, and the temperature variation of dispersion step is partly dissolved it, and then recrystallization and become big particle.In addition, also must reduce temperature during filtration, be difficult to obtain full-bodied composition.

The prior art document

Patent documentation

Patent documentation 1: japanese kokai publication hei 1-141904 communique (claims)

Summary of the invention

The problem that invention will solve

The present invention carries out in view of the prior art of aforementioned that kind; Its purpose is; A kind of light solidifying/heat solidifying resin composition is provided; Excellences such as the thermotolerance of its dry coating, chemical gilding patience, electrical insulating property especially can prevent the broken string of the fine pitch circuit that the big particle of insoluble composition causes, it is used to form cured films such as soldering-resistance layer.

The present invention also aims to the printed circuit board (PCB) that excellent dry film of the various characteristics that uses the above-mentioned that kind that such light solidifying/heat solidifying resin composition obtains and flatness and solidfied material is provided and forms through cured films such as this dry film, solidfied material formation soldering-resistance layers.

The scheme that is used to deal with problems

In order to realize aforementioned purpose; The present invention provides a kind of light solidifying/heat solidifying resin composition of alkali-developable; Said composition contains (A) epoxy resin, (B) and contains carboxy resin and (C) Photoepolymerizationinitiater initiater; It is characterized in that; Above-mentioned epoxy resin (A) is to have the 2 officials ability biphenyl epoxy resin (A-1) of structure shown in the formula (I) and the potpourri of epoxy resin (A-2); Wherein, epoxy resin (A-2) be selected from group that bisphenol A type epoxy resin, bisphenol-A phenolic varnish type epoxy resin and xenol phenolic resin varnish type epoxy resin formed, softening point is that 40～100 ℃ and epoxide equivalent are at least a kind of epoxy resin of 180～300, aforementioned epoxy resins (A-1) is (A-1)＜(A-2) with (A-2) ratio.

[Chemical formula 1]

(in the formula, R representes H or CH ₃)

In suitable scheme; Light solidifying/heat solidifying resin composition is suitable as solder resist and uses, wherein, and in the said light solidifying/heat solidifying resin composition; Aforementionedly contain the acid number that carboxy resin (B) has 40～120mgKOH/g; With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, be 20～60 mass parts (A-1) with (A-2) potpourri, also comprise the photo-sensitive monomer (E) that has 2 above olefinic unsaturated groups in 1 molecule.

In addition; The present invention provides a kind of solidfied material; It is for carrying out the solidfied material that photocuring and/or heat curing obtain to the dry film that aforementioned light solidifying/heat solidifying resin composition is applied on the carrier film and drying obtains; Perhaps; To aforementioned light solidifying/heat solidifying resin composition or to this light solidifying/heat solidifying resin composition being applied on the carrier film and the dry dry film that obtains carries out photocuring and/or heat curing and the solidfied material that obtains, photocuring on copper also is provided especially and the solidfied material that obtains, carries out the pattern-like photocuring and the solidfied material that obtains.

And then the present invention also provides a kind of printed circuit board (PCB), it is characterized in that, it has aforementioned solidfied material, especially has light solidifying/heat solidifying resin composition or dry film are carried out behind the pattern-like photocuring heat curing again and the cured film that obtains.

The invention effect

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

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

Embodiment

As previously mentioned; Light solidifying/heat solidifying resin composition of the present invention contains (A) epoxy resin, (B) and contains carboxy resin and (C) Photoepolymerizationinitiater initiater; Said composition is characterised in that; Above-mentioned epoxy resin (A) is to have the 2 officials ability biphenyl epoxy resin (A-1) of structure shown in the aforementioned formula (I) and the potpourri of epoxy resin (A-2); Said epoxy resin (A-2) be selected from group that bisphenol A type epoxy resin, bisphenol-A phenolic varnish type epoxy resin and xenol phenolic resin varnish type epoxy resin formed, softening point is that 40～100 ℃ and epoxide equivalent are at least a kind of epoxy resin of 180～300, (A-1) of aforementioned epoxy resins is (A-1)＜(A-2) with ratio (A-2).

Research according to inventor etc.; As epoxy resin, (A) excellence, the especially insulating reliabilities between fine pattern such as the thermotolerance of the 2 officials ability biphenyl epoxy resin (A-1) with structure shown in the aforementioned formula (I) in the composition, chemical gilding patience, electrical insulating property are excellent; Therefore be the composition that is even more important; But then, because it has high crystallinity in resinous principle, organic solvent, easily owing to recrystallization takes place factors such as temperature variation; Make and thickization of particle in the potpourri become the reason that causes short circuit between circuit.And then; Will comprise 2 officials can biphenyl epoxy resin the light solidifying/heat solidifying resin composition of (A-1) be applied on the carrier film and dry and dry film lamination that obtain is made in the operation of tellite to the substrate that is formed with various circuit patterns; The big particle that produces becomes the bad reason of lamination, the reason that the especially feasible productive rate that need highly control the fine pattern substrate manufacture of thickness reduces.

Therefore; The inventor etc. further investigate, and the result finds, when epoxy resin (A) is to have the 2 officials ability biphenyl epoxy resin (A-1) of structure shown in the aforementioned formula (I) and the potpourri of epoxy resin (A-2); Wherein, Said epoxy resin (A-2) be selected from group that bisphenol A type epoxy resin, bisphenol-A phenolic varnish type epoxy resin and xenol phenolic resin varnish type epoxy resin formed, softening point is that 40～100 ℃ and epoxide equivalent are at least a kind of epoxy resin of 180～300, its cooperation ratio is (A-1)＜(A-2), and through stir, method such as mixing, heating makes particle microminiaturization that 2 officials can biphenyl epoxy resin (A-1) or when dissolving and resulting mixture; Its thermotolerance, chemical gilding patience excellence; Can prevent that with 2 officials can biphenyl epoxy resin (A-1) be the generation of the big particle of cause, therefore, can prevent short circuit between circuit; Has excellent electrical insulating property; And then, can prevent to light solidifying/heat solidifying resin composition is applied on the carrier film and the lamination of the dry dry film that obtains when carrying out lamination bad, thereby accomplished the present invention.

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

At first; In the epoxy resin (A) of the light solidifying/heat solidifying resin composition that constitutes alkali-developable of the present invention; As 2 officials ability biphenyl epoxy resin (A-1); Can use Japan Epoxy Resins Co., YL-6056, YX4000, YX4000K, YX4000H, YX4000HK, YL6121, YL6121H, YL6640, YL6677 di-cresols types such as (being trade name) or united phenol-type epoxy resin that Ltd. makes or their potpourri.

In addition; In aforementioned epoxy resins (A); As softening point is that 40～100 ℃ and epoxide equivalent are 180～300 bisphenol A type epoxy resin, bisphenol-A phenolic varnish type epoxy resin and/or xenol phenolic resin varnish type epoxy resin (A-2); Can enumerate out for example Japan Epoxy Resins Co., the JER834 that Ltd. makes, the Epiclon860 that big Japanese ink chemical industrial company makes, the EpototeYD-134 that Dongdu changes into manufactured, (being trade name) bisphenol A type epoxy resins such as D.E.R.337 that Dow Chemical Company makes; Japan Epoxy Resins Co., the EpiclonN-865 bisphenol-A phenolic varnish type epoxy resin such as (being trade name) that the JER157S that Ltd. makes, big Japanese ink chemical industrial company make; The NC-3000 of Japan's chemical drug manufactured, NC-3000H, NC-3000L, NC-3100 xenols such as (trade names) phenolic resin varnish type epoxy resin etc., but be not limited to these.These epoxy resin can use separately or make up more than 2 kinds and use.

Aforementioned epoxy resins (A-1) is (A-1)＜(A-2) with the ratio that cooperates of (A-2).When cooperation ratio (A-1) surpassed the cooperation ratio of (A-2), (A-1) dissolubility in composition reduced, and the ageing stability relevant with the crystallization of potpourri reduces.

Contain carboxy resin (B) with respect to 100 mass parts, aforementioned epoxy resins (A-1) and use level (A-2) are 10～100 mass parts for example, and the scope that is preferably 20～60 mass parts is fit to.Compare with above-mentioned scope, when epoxy resin (A-1) and use level (A-2) are too much, the alkali-developable variation, take place easily resolution bad, produce the development residue.On the other hand, during less than 10 mass parts, the solder heat resistance property of the cured coating film that obtains is impaired, so not preferred.

In addition, can also use other epoxy resin and aforementioned epoxy resins (A-1) and (A-2) combination.As other epoxy resin, can use known epoxy resin commonly used, there is not special qualification.As such epoxy resin, for example can enumerate out, the compound that has at least 2 above epoxy radicals in the molecule is the multi-functional epoxy compound.

As aforementioned multi-functional epoxy compound; Can enumerate out for example bisphenol A type epoxy resin; Like Japan Epoxy Resins Co.; Ltd. the jER828, jER1001, the jER1004 that make; Epiclon840, Epiclon850, Epiclon1050, Epiclon2055 that DIC Corporation makes; Dongdu changes into EpototeYD-011, YD-013, YD-127, the YD-128 of manufactured, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 that Dow ChemicalCompany makes, Araldite6071, Araldite6084, AralditeGY250, AralditeGY260 that west crust specialty goods chemical company makes; SumiepoxyESA-011, ESA-014, ELA-115, ELA-128 that Sumitomo Chemical Co. Ltd. makes, (being trade name) such as the A.E.R.330 that industrial group of Asahi Chemical Industry makes, A.E.R.331, A.E.R.661, A.E.R.664; Brominated epoxy resin; Like Japan Epoxy Resins Co.; Ltd. the JERYL903 that makes, Epiclon152, Epiclon165 that DIC Corporation makes, Dongdu changes into EpototeYDB-400, the YDB-500 of manufactured; The D.E.R.542 that Dow Chemical Company makes; The Araldite8011 that west crust specialty goods chemical company makes, SumiepoxyESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. makes, (being trade name) such as the A.E.R.711 that industrial group of Asahi Chemical Industry makes, A.E.R.714; Phenolic resin varnish type epoxy resin; Like Japan Epoxy Resins Co.; Ltd. the jER152, the jER154 that make; D.E.N.431, D.E.N.438 that DowChemical Company makes, EpiclonN-730, EpiclonN-770, EpiclonN-865 that DICCorporation makes, Dongdu changes into EpototeYDCN-701, the YDCN-704 of manufactured; AralditeECN1235, AralditeECN1273, AralditeECN1299, AralditeXPY307 that west crust specialty goods chemical company makes; EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, the RE-306 of Japan's chemical drug manufactured, SumiepoxyESCN-195X, ESCN-220 that Sumitomo Chemical Co. Ltd. makes, (being trade name) such as the A.E.R.ECN-235 that industrial group of Asahi Chemical Industry makes, ECN-299; Bisphenol f type epoxy resin; Epiclon830 like DIC Corporation manufacturing; Japan Epoxy Resins Co.; Ltd. the jER807 that makes, Dongdu changes into EpototeYDF-170, YDF-175, the YDF-2004 of manufactured, (being trade name) such as AralditeXPY306 that west crust specialty goods chemical company makes; Bisphenol-A epoxy resin changes into EpototeST-2004, ST-2007, ST-3000 (trade name) of manufactured etc. like Dongdu; Glycidyl amine type epoxy resin; Like Japan EpoxyResins Co.; Ltd. the jER604 that makes; Dongdu changes into the EpototeYH-434 of manufactured, the AralditeMY720 that west crust specialty goods chemical company makes, (being trade name) such as SumiepoxyELM-120 that Sumitomo Chemical Co. Ltd. makes; The AralditeCY-350 hydantoins type epoxy resin such as (trade names) that west crust specialty goods chemical company makes; Alicyclic epoxy resin, like DAICEL CHEMICALINDUSTRIES, the Celoxide2021 that LTD. makes, (being trade name) such as the AralditeCY175 that west crust specialty goods chemical company makes, CY179; Trihydroxy benzene methylmethane type epoxy resin, like Japan Epoxy Resins Co., the YL-933 that Ltd. makes, (being trade name) such as the T.E.N. that Dow Chemical Company makes, EPPN-501, EPPN-502; Bisphenol-s epoxy resin is like the EPX-30 of Japanese chemical drug manufactured EBPS-200, Asahi Electro-Chemical Co. Ltd's manufacturing, the EXA-1514 (trade name) that DIC Corporation makes etc.; Four hydroxyphenyl ethane type epoxy resin, like Japan Epoxy Resins Co., (being trade name) such as Araldite163 that the jERYL-931 that Ltd. makes, west crust specialty goods chemical company make; The Araldite PT810 that west crust specialty goods chemical company makes, (being trade name) hetero ring type epoxy resin such as TEPIC that daily output chemical industrial company makes; The o-phthalic acid diglycidyl ester resins such as Blemmer DGT that Nof Corp. makes; Dongdu changes into four glycidyl group xylene acyl group ethane (tetraglycidylxylenoyl ethane) resins such as ZX-1063 of manufactured; ESN-190, ESN-360 that chemical company of Nippon Steel makes, the HP-4032 that DIC Corporation makes, EXA-4750, EXA-4700 etc. contain the epoxy resin of naphthyl; The HP-7200 that DIC Corporation makes, HP-7200H etc. have the epoxy resin of bicyclopentadiene skeleton; GMA copolymerization such as the CP-50S that Nof Corp. makes, CP-50M are epoxy resin; And the copolymerization epoxy resin of cyclohexyl maleimide and GMA; Epoxide modified polybutadiene rubber derivant (DAICEL CHEMICAL INDUSTRIES for example, the PB-3600 that LTD. makes etc.), CTBN modified epoxy (for example Dongdu changes into the YR-102, YR-450 of manufactured etc.) etc., but be not limited to these.These epoxy resin can use separately or make up more than 2 kinds and use.In these, preferred phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their potpourri.

When being 100 moles of % with all consumptions of epoxy resin, aforementioned other the use level of epoxy resin is preferably 75 moles below the %.Use when surpassing 75 moles of %, may not obtain being derived from the characteristic of 2 officials ability biphenyl epoxy resin (A-1) fully.The preferred consumption of other epoxy resin is 50 moles below the %.

As the aforementioned carboxy resin (B) that contains, be purpose to give alkali-developable, can use the existing known various carboxy resins that contain that have carboxyl in the molecule.From photo-curable, anti-development property aspect, especially molecule, have ethylenical unsaturated double bonds to contain carboxyl photoresist (B ') be especially preferred.In addition, its unsaturated double-bond preferred source is from acrylic or methacrylic acid or their derivant.In addition, only use do not have ethylenical unsaturated double bonds contain carboxy resin the time, have photo-curable in order to make composition, need with after have 1 above olefinic unsaturated group in the molecule stated photo-sensitive monomer (E) combination use.

As the object lesson that contains carboxy resin (B), the compound of that kind of enumerating below preferred (any of oligomer and polymkeric substance all can).

(1) contains the carboxy resin that contains that the copolymerization of unsaturated group compound obtains through unsaturated carboxylic acids such as (methyl) acrylic acid and styrene, AMS, low alkyl group (methyl) acrylic ester, isobutylene etc.

(2) pass through aliphatic diisocyanate; The side chain aliphatic diisocyanate; The ester ring type diisocyanate; Diisocyanate and dihydromethyl propionic acids such as aromatic diisocyanate; Dimethylolpropionic acids etc. contain carboxylic diol compound and polycarbonate-based polyvalent alcohol; Polyethers is a polyvalent alcohol; Polyester is a polyvalent alcohol; The polyolefin polyvalent alcohol; Acrylic acid series multiple alcohol; Bisphenol-A is the alkylene oxide adducts dibasic alcohol; Have phenol property hydroxyl and alcohol hydroxyl group diatomic alcohol compounds such as compound addition polymerization and obtain contain the carboxyl urethane resin.

(3) through 2 officials such as diisocyanate and bisphenol A type epoxy resin, bisphenol-A epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, di-toluene phenol-type epoxy resin, united phenol-type epoxy resin can epoxy resin the photonasty that obtains of the addition polymerization of (methyl) acrylic ester or the anhydride modified thing of its part, carboxylic diol compound and diatomic alcohol compounds contain the carboxyl urethane resin.

(4) through having 1 hydroxyl in adding (methyl) hydroxyalkyl acrylate equimolecular in the resin of aforementioned (2) or (3) synthetic and the photonasty of end (methyl) the propylene acidylate that the compound of (methyl) acryloyl group obtains more than 1 contains the carboxyl urethane resin.

(5) has 1 NCO in the reaction with same mole thing equimolecular through adding IPDI and pentaerythritol triacrylate in the resin of aforementioned (2) or (3) synthetic and the photonasty of end (methyl) the propylene acidylate that the compound of (methyl) acryloyl group obtains more than 1 contains the carboxyl urethane resin.

(6) through state after making 2 such officials can (solid-state) epoxy resin or 2 officials can be above multifunctional (solid-state) epoxy resin and the reaction of (methyl) acrylic acid, make the hydroxyl that is present in side chain and 2 yuan of acid anhydrides additions and the photonasty that obtains contains carboxy resin.

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

(8) through after state 2 such officials and can react with dicarboxylic acid by oxetane resin, the primary hydroxyl of generation and 2 yuan of acid anhydrides additions and obtain contain carboxyl polyester resin.

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

In addition, (methyl) acrylic ester in this instructions is the term of general designation acrylic ester, methacrylate and their potpourri, below, other similar expression is too.

The carboxy resin (B) that contains of above-mentioned that kind has a plurality of free carboxyls on the side chain of trunk polymer, therefore can utilize dilute alkaline aqueous solution to develop.

In addition, the above-mentioned acid number that contains carboxy resin (B) is the scope of 40～200mgKOH/g, further is preferably the scope of 45～120mgKOH/g.The acid number that contains carboxy resin is lower than 40mgKOH/g, then is difficult to alkali and develops, on the other hand; Surpass 200mgKOH/g, the dissolving of developer solution to exposure portion takes place, therefore; It is thinner than needed that line becomes; Sometimes be developed the liquid dissolving exposure portion and unexposed indistinction and peel off, be difficult to describe normal corrosion-resisting pattern, so not preferred.

In addition, the above-mentioned weight-average molecular weight that contains carboxy resin (B) further is preferably 5000～100000 scope according to resin matrix and difference is generally 2000～150000.During weight-average molecular weight less than 2000, tack-free degradation takes place sometimes, the film wearing and tearing take place, the remarkable variation of resolution in the moisture-proof variation of filming after the exposure during development.On the other hand, weight-average molecular weight surpasses at 150000 o'clock, and the remarkable variation of development property, bin stability variation take place sometimes.

In whole compositions, such use level that contains carboxy resin (B) is 20～80 quality %, and the scope that is preferably 30～60 quality % is fit to.When the use level that contains carboxy resin (B) was less than above-mentioned scope, epithelium intensity reduced, so not preferred.On the other hand, during more than above-mentioned scope, the viscosity of composition uprises, and so reductions such as coating are not preferred.

These contain the material that carboxy resin (B) is not limited to use aforementioned list, can use a kind, also can multiple mixing use.

As Photoepolymerizationinitiater initiater (C); Preferred to use the oxime ester that is selected from the group shown in (II) that has formula be Photoepolymerizationinitiater initiater (C 1), and the alpha-aminoacetophenone with group shown in the formula (III) is a Photoepolymerizationinitiater initiater (C2) or/and to have the acylphosphine oxide of group shown in the following formula (IV) be the Photoepolymerizationinitiater initiater more than a kind in the group formed of Photoepolymerizationinitiater initiater (C3).

[Chemical formula 2]

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

R ²Represent the alkyl (optional choosing wantonly by the replacement of the hydroxyl more than 1, at the alkyl middle-of-chain has the oxygen atom more than 1) of phenyl (optional), carbon number 1～20, the naphthenic base of carbon number 5～8, the alkanoyl or the benzoyl (optional) of carbon number 2～20 by the replacement of the alkyl or phenyl of carbon number 1～6 by the alkyl of carbon number 1～6, phenyl or halogen atom replacement

R ³And R ⁴The alkyl or aryl alkyl of representing carbon number 1～12 independently of one another,

R ⁵And R ⁶Represent the alkyl of hydrogen atom, carbon number 1～6 independently of one another or represent the cyclic alkyl ether that both bondings form,

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

Oxime ester as having group shown in the aforementioned formula (II) is a Photoepolymerizationinitiater initiater, preferably can enumerate out compound shown in the 2-shown in the following formula (V) (acetoxyl group iminomethyl) thioxanthene-9-one, the formula (VI) and the compound shown in the formula (VII).

[chemical formula 3]

[chemical formula 4]

In the formula, R ⁹The alkanoyl of the alkyl of expression hydrogen atom, halogen atom, carbon number 1～12, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl, carbon number 2～12, (carbon number at the alkyl that constitutes alkoxy is under the situation more than 2 to the alkoxy carbonyl group of carbon number 2～12; Alkyl optional by the hydroxyl more than 1 replace, choose wantonly at the alkyl middle-of-chain have the oxygen atom more than 1) or carbobenzoxy

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

R ¹¹Represent the alkyl (optional choosing wantonly by the replacement of the hydroxyl more than 1, at the alkyl middle-of-chain has the oxygen atom more than 1) of hydrogen atom, phenyl (optional), carbon number 1～20, the naphthenic base of carbon number 5～8, the alkanoyl or the benzoyl (optional) of carbon number 2～20 by the replacement of the alkyl or phenyl of carbon number 1～6 by the alkyl of carbon number 1～6, phenyl or halogen atom replacement.

[chemical formula 5]

In the formula, R ¹³, R ¹⁴And R ¹⁹The alkyl of representing carbon number 1～12 independently of one another,

R ¹⁵, R ¹⁶, R ¹⁷And R ¹⁸The alkyl of representing hydrogen atom or carbon number 1～6 independently of one another,

M representes O, S or NH,

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

At aforementioned oxime ester is in the Photoepolymerizationinitiater initiater, and the compound shown in (acetoxyl group iminomethyl) thioxanthene-9-one of the 2-shown in the aforementioned formula (V) and the formula (VI) is preferred.As commercially available article, can enumerate out CGI-325, IRGACURE OXE01, IRGACURE OXE02 that west crust specialty goods chemical company makes, the N-1919 of ADEKA manufactured etc.These oxime esters are that Photoepolymerizationinitiater initiater can use or make up use more than 2 kinds separately.

Alpha-aminoacetophenone as having group shown in the aforementioned formula (III) is a Photoepolymerizationinitiater initiater; Can enumerate out 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino acetophenone etc.As commercially available article, can enumerate out the west and cling to the IRGACURE 907 of specialty goods chemical company manufacturing, IRGACURE 369, IRGACURE379 etc.

Acylphosphine oxide as having group shown in the aforementioned formula (IV) is a Photoepolymerizationinitiater initiater, can enumerate out 2,4; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide, two (2,6-dimethoxy benzoyl)-2; 4,4-tri-methyl-amyl phosphine oxide etc.As commercially available article, can enumerate out the Lucirin TPO that BASF AG makes, the IRGACURE 819 that west crust specialty goods chemical company makes etc.

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the use level of such Photoepolymerizationinitiater initiater (C) is 0.01～30 mass parts, and the scope that is preferably 0.5～15 mass parts is fit to.During use level less than 0.01 mass parts of Photoepolymerizationinitiater initiater (C), the photo-curable on the copper is not enough, films and peels off, and coating characteristics such as chemical proofing reduce, so not preferred.On the other hand, when surpassing 30 mass parts, Photoepolymerizationinitiater initiater (C) becomes violent in the light absorption of resistance weldering film coated surface, and so the tendency that exists the deep curable to reduce is not preferred.

In addition, when being Photoepolymerizationinitiater initiater for the oxime ester with group shown in the aforementioned formula (II), with respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, its use level is preferably 0.01～20 mass parts, further is preferably the scope of 0.01～5 mass parts.

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

If enumerate the object lesson of benzoin compound, for example benzoin, benzoin methylether, benzoin ethyl ether, benzoin iso-propylether then arranged.

If enumerate the object lesson of acetophenone compound, for example acetophenone, 2 then arranged, 2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone.

If enumerate the object lesson of anthraquinone compounds, for example 2-methylanthraquinone, 2-EAQ, 2-tert-butyl group anthraquinone, 1-chloroanthraquinone then arranged.

If enumerate the object lesson of thioxanthones compound, for example then have 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2,4-diisopropyl thioxanthones.

If enumerate the object lesson of ketal compound, for example acetophenone dimethyl ketal, benzil dimethyl ketal then arranged.

If enumerate the object lesson of benzophenone cpd, for example benzophenone, 4-benzoyl diphenyl sulfide, 4-benzoyl-4 '-methyldiphenyl thioether, 4-benzoyl-4 '-ethyl diphenyl sulfide, 4-benzoyl-4 '-propyl group diphenyl sulfide then arranged.

If enumerate the object lesson of tertiary amine compound; The compound that ethanolamine compound is for example then arranged, has dialkyl amido benzene structure; For example 4; 4 '-dimethylamino benzophenone (the NISSOCURE MABP of Japanese Cao Da manufactured), 4; Dialkyl amido benzophenone, 7-(lignocaine)-4-methyl-2H-1-chromen-2-one (7-(lignocaine)-4-methylcoumarin) etc. such as 4 '-lignocaine benzophenone (Hodogaya Chemical Co.LTD. make EAB) contain the coumarin compound, ethyl 4-dimethy laminobenzoate (KAYACUREEPA of Japanese chemical drug manufactured), 2-dimethylamino ethyl benzoate (the Quantacure DMB of International Bio-Synthetics manufactured), 4-dimethylamino benzoic acid (n-butoxy) ethyl ester (the Quantacure BEA of International Bio-Synthetics manufactured) of dialkyl amido, to dimethylamino benzoic acid isopentyl ethyl ester (the KAYACURE DMBI of Japanese chemical drug manufactured), 4-dimethylamino benzoic acid-2-Octyl Nitrite (Esolol 507 of VanDyk manufactured) and 4,4 '-lignocaine benzophenone (EAB of Hodogaya Chemical Co.LTD. manufacturing).

In the aforesaid compound, preferred thioxanthones compound and tertiary amine compound.The curable aspect is considered from the deep, and composition of the present invention preferably comprises the thioxanthones compound, and is wherein preferred 2,4-dimethyl thioxanthones, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthones compounds such as 4-diisopropyl thioxanthones.

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the use level of such thioxanthones compound is preferably below 20 mass parts, and the ratio that further is preferably below 10 mass parts is fit to.When the use level of thioxanthones compound is too much, cause the thick film curable to reduce, the cost of goods increases, so not preferred.

As tertiary amine compound, preferably have the compound of dialkyl amido benzene structure, wherein, especially preferred dialkyl amido benzophenone cpd, maximum absorption wavelength are the coumarin compound that contains dialkyl amido of 350nm～410nm.As the dialkyl amido benzophenone cpd, 4,4 '-lignocaine benzophenone is low preferred because of toxicity.Because maximum absorption wavelength is that the maximum absorption wavelength of the coumarin compound that contains dialkyl amido of 350nm～410nm is in the ultraviolet range; Therefore; Provide painted less, water white photosensitive composite is mathematical, also can be provided in the painted soldering-resistance layer of the color of reflection coloring pigment self when having used coloring pigment.From the excellent sensitization effect of the laser display of wavelength 400nm～410nm being considered preferred especially 7-(lignocaine)-4-methyl-2H-1-chromen-2-one.

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the use level of such tertiary amine compound is preferably 0.1～20 mass parts, further is preferably the ratio of 0.1～10 mass parts.During use level less than 0.1 mass parts of tertiary amine compound, existence can not obtain the tendency of sufficient sensitization effect.On the other hand, when surpassing 20 mass parts, tertiary amine compound causes becoming violent, the tendency that exists the deep curable to reduce in the light absorption on the surface that drying resistance weldering is filmed.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizer can use separately or use as the potpourri more than 2 kinds.

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the total amount of such Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizer is that the scope below 35 mass parts is preferred.When surpassing 35 mass parts, exist because the tendency that their light absorption causes the deep curable to reduce.

In order to give thermotolerance,, can also add heat-curing resin except in light solidifying/heat solidifying resin composition of the present invention, adding the aforementioned epoxy resins.Especially the Thermocurable composition (D) that has 2 above ring-type ethers and/or cyclic thioether base (below, abbreviate ring-type (sulphur) ether as) in the preferred molecule.

The Thermocurable composition (D) that has 2 above ring-types (sulphur) ether in such molecule is the compound that has any or 2 kinds of groups of 2 above three-membered rings, four-membered ring or pentacyclic ring-type ether or cyclic thioether base in the molecule, and can enumerate out the compound that has at least 2 above oxetanyls in the molecule and be the compound that has at least 2 above thioether groups in multifunctional oxetane compound (D-1), the molecule is episulfide resin (D-2) etc.

As aforementioned multifunctional oxetane compound (D-1); Can enumerate out two [(3-methyl-3-oxetanes ylmethoxy) methyl] ethers, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] ether, 1; Two [(3-methyl-3-oxetanes ylmethoxy) methyl] benzene, 1 of 4-, two [(3-ethyl-3-oxetanes ylmethoxy) methyl] benzene of 4-, acrylic acid (3-methyl-3-oxetanyl) methyl esters, acrylic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters, their multifunctional oxetanes classes such as oligomer or multipolymer; And novolac resin, gather (para hydroxybenzene ethene), cardo type bisphenols, calixarene kind, resorcinol calixarenes (calixresorcinarene) type or silsesquioxane (silsesquioxane) and wait the pure etherate of resin with hydroxyl and oxetanes etc.In addition, can enumerate the multipolymer etc. of the unsaturated monomer of providing the oxetanes ring and (methyl) alkyl acrylate.

As the compound (D-2) that has 2 above cyclic thioether bases in the aforementioned molecule, can enumerate out for example Japan Epoxy Resins Co., the bisphenol A-type episulfide resin YL7000 that Ltd. makes etc.In addition, also can use and adopt same synthetic method that the oxygen atom of the epoxy radicals of phenolic resin varnish type epoxy resin is replaced to episulfide resin that sulphur atom forms etc.

Use level about the Thermocurable composition (D) that has 2 above ring-types (sulphur) ether in the aforementioned molecule; With respect to the aforementioned 1 equivalent carboxyl that contains carboxy resin (B); Ring-type (sulphur) ether is preferably 0.6～2.5 equivalent, and the scope that further is preferably 0.8～2.0 equivalent is fit to.When having the use level less than 0.6 of Thermocurable composition (D) of 2 above ring-types (sulphur) ether in the molecule, have carboxyl residual in the soldering-resistance layer, so reductions such as thermotolerance, alkali resistance, electrical insulating property are not preferred.On the other hand, when surpassing 2.5 equivalents, low-molecular-weight ring-type (sulphur) ether remains in the dry coating, makes the reductions such as intensity of filming, so not preferred.

Light solidifying/heat solidifying resin composition of the present invention preferably contains thermal curing catalyst.As such thermal curing catalyst, can enumerate out for example imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole; Dicyandiamide, benzyl dimethylamine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl-N, N-dimethyl benzyl amine, 4-methyl-N, amines such as N-dimethyl benzyl amine; Hydrazide compound such as adipic dihydrazide, sebacic dihydrazide; Phosphorus compounds such as triphenylphosphine etc.In addition; As commercially available article; For example can enumerating out, four countries change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, the 2P4MHZ (being the trade name of imidazole compound) that industrial group makes; The U-CAT of SAN-APRO manufactured (registered trademark) 3503N, U-CAT3502T (being the trade name of the blocked isocyanate compound of dimethyl amine), DB U, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compound and salt thereof) etc.Be not limited in these compounds; So long as the material of the thermal curing catalyst of the thermal curing catalyst of epoxy resin, oxetane compound or promotion epoxy radicals and/or oxetanyl and carboxyl reaction gets final product, can use separately or mix more than 2 kinds and use.In addition; Can also use guanamines, methyl guanamines, benzoguanamine, melamine, 2; 4-diamido-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamido-s-triazine, 2-vinyl-4,6-diamido-s-triazine isocyanuric acid addition product, 2; 4-diamido-6-methacryloxyethyl-Striazine derivatives such as s-triazine isocyanuric acid addition product preferably also uses these as acting compound of adaptation imparting agent and the combination of aforementioned hot curing catalysts.

The use level of these thermal curing catalysts is so long as the ratio of common amount is just enough; For example; Contain the Thermocurable composition (D) that has 2 above ring-types (sulphur) ether in carboxy resin (B) or the molecule with respect to 100 mass parts; Be preferably 0.1～20 mass parts, further be preferably 0.5～15.0 mass parts.

The photo-sensitive monomer (E) that has 2 above olefinic unsaturated groups in the molecule that uses in the light solidifying/heat solidifying resin composition of the present invention is, makes the aforementioned carboxy resin (B) that contains that contains the olefinic unsaturated group in aqueous alkali, not dissolve or help thawless material through active energy beam irradiation carrying out photocuring.As such compound, can enumerate out the diacrylate class of glycol such as monoethylene glycol, methoxyl TEG, polyglycol, propylene glycol; The multicomponent methacrylate class of polyvalent alcohols such as hexanediol, trimethylolpropane, pentaerythrite, dipentaerythritol, three-hydroxyethyl isocyanuric acid ester or their ethylene oxide adduct or propylene oxide adduct etc.; The multicomponent methacrylate class of the ethylene oxide adduct of phenoxy group acrylic ester, bisphenol a diacrylate and their phenols or propylene oxide adduct etc.; The multicomponent methacrylate class of glycidol ethers such as glycerine diglycidyl ether, glycerine triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester; And the melamine acrylic ester and/or with corresponding each methyl acrylic ester of aforesaid propylene acid esters etc.

The hydroxyl that also can enumerate out Epocryl that the reaction of polyfunctional epoxy resin such as cresols phenolic resin varnish type epoxy resin and acrylic acid obtains and this Epocryl and half urethanes that is formed by diisocyanate such as hydroxy acrylate such as pentaerythritol triacrylate and IPDIs react the epoxy polyurethane acrylate compound that obtains etc.Such epoxy acrylate is that resin can not reduce its dry to touch property ground raising photo-curable.

With respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, the use level that has the photo-sensitive monomer (E) of 2 above olefinic unsaturated groups in such molecule is below 100 mass parts, and the ratio that further is preferably 5～70 mass parts is fit to.During aforementioned use level less than 5 mass parts, photo-curable reduces, and is difficult to develop through the postradiation alkali of active energy beam form pattern, so not preferred.On the other hand, when surpassing 100 mass parts, to the dissolubility reduction of aqueous alkali, filming becomes fragile, so not preferred.

Light solidifying/heat solidifying resin composition of the present invention can cooperate colorant (F).As colorant, can use red (F-1), blue (F-2), green (F-3), yellow (F-4) to wait and use known colorant always, can be any one of pigment, dyestuff, pigment.Wherein, from reducing carrying capacity of environment and, preferably not containing halogen to the viewpoint of the influence of human body.

Red stain (F-1):

As red stain, monoazo system, bisdiazo system, monoazo color lake system, benzimidazolone Xi 、 perylene system, diketopyrrolopyrrolecocrystals system, condensation azo system, anthraquinone system, quinacridone etc. are arranged, particularly, can enumerate out following material.

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

Bisdiazo system: pigment red 37,38,41.

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

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

Perylene system: solvent of red 135, solvent red 179, pigment red 123, pigment red 149, paratonere 166, paratonere 178, paratonere 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, solvent red 207.

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

Blue colorant (F-2):

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

As dyestuff system, can use solvent blue 35, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc.Except above-mentioned, can also use metal to replace or unsubstituted phthalocyanine compound.

Green colourant (F-3):

As green colourant, phthalocyanine system, anthraquinone Xi 、 perylene system are arranged equally, particularly, can use that pigment Green 7, pigment green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 etc.Except above-mentioned, can also use metal to replace or unsubstituted phthalocyanine compound.

Yellow colorants (F-4):

As yellow colorants, monoazo system, bisdiazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone system etc. are arranged, particularly, can enumerate out following material.

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

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

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

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

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

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

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

Concrete illustrative words; Pigment violet 19,23,29,32,36,38,42 is arranged, 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 not special restriction of the cooperation ratio of the colorant of aforementioned that kind (F) with respect to the aforementioned carboxy resin (B) that contains of 100 mass parts, is preferably 0～10 mass parts, and the ratio that is preferably 0.1～5 mass parts especially is sufficient.

For physical strength of filming of improving light solidifying/heat solidifying resin composition of the present invention etc., as required, can cooperate filler.As such filler, can use known inorganic or organic filler commonly used, especially preferably use barium sulphate, preparing spherical SiO 2 and talcum.And then, in order to obtain outward appearance, the anti-flammability of white, can also use with the material of metal hydroxides such as titanium dioxide, metal oxide, hydrate of aluminium as the extender pigment filler.The use level of filler is preferably below the 75 quality % of total composition, further is preferably the ratio of 0.1～60 quality %.When the use level of filler surpassed 75 quality % of total composition, the viscosity increase of insulation compsn, coating, formability reduced, solidfied material becomes fragile, so not preferred.

And then, for synthetic above-mentioned carboxy resin (B), the modulation group compound of containing, perhaps to adjust so that be applied on substrate or the carrier film for viscosity, light solidifying/heat solidifying resin composition of the present invention can be with an organic solvent.

As such organic solvent, can enumerate out ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.More specifically, ketones such as MEK, cyclohexanone are arranged; Toluene, xylene, durene etc. are aromatic hydrocarbon based; Glycol ethers such as cellosolve, methyl cellosolve, butyl cellosolve, carbitol, methyl carbitol, BC, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, DPG diethyl ether, Triethylene glycol ethyl ether; Ester classes such as ethyl acetate, butyl acetate, dipropylene glycol methyl ether acetic acid esters, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic acid esters, propylene glycol butyl ether acetic acid esters; Alcohols such as ethanol, propyl alcohol, monoethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, naphtha, hydrogenated naphtha, solvent naphtha etc.Such organic solvent can use separately or use as the potpourri more than 2 kinds.

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

Light solidifying/heat solidifying resin composition of the present invention is adjusted to the viscosity that is fit to coating process with for example aforementioned organic solvent; Be applied on the base material through methods such as dip coating, flow coat method, rolling method, scraper rubbing method, silk screen print method, curtain Tu Fa; Under about 60～100 ℃ temperature, make organic solvent volatile dry contained in the composition (temporary transient dry), can form tack-free film.In addition, above-mentioned composition is applied on the carrier film, drying forms film, this film is rolled the material that forms fit on the base material, can form resin insulating barrier.Afterwards; Adopt contact (or noncontact mode); Utilize active energy beam optionally to make public or utilize the direct exposure machine of laser directly to carry out pattern exposure through forming figuratum photomask; With unexposed development, can form corrosion-resisting pattern through dilute alkaline aqueous solution (for example 0.3～3wt% aqueous sodium carbonate).And then; Make its heat curing through for example under about 140～180 ℃ temperature, heating; Make aforementioned carboxyl that contains carboxy resin (B) and aforementioned epoxy resins (A) reaction or further with in the molecule have Thermocurable composition (D) reaction of 2 above ring-type ethers and/or cyclic thioether base, can form various characteristics excellent in curing such as thermotolerance, chemical proofing, anti-hydroscopicity, adaptation, electrical characteristics and film.

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

Be coated with the volatile dry that carries out behind the light solidifying/heat solidifying resin composition of the present invention and can use heated air circulation type drying oven, IR stove, hot plate, convective oven etc. (use has the device of the thermal source of the air heat mode of utilizing steam, the mode that makes the method for the hot air convection contact in the dryer and blow supporter through nozzle).

Following such to being coated with make public (irradiation of active energy beam) of filming that obtains behind light solidifying/heat solidifying resin composition of the present invention and the volatile dry.The exposure portion of filming (by the part of active energy beam irradiation) is cured.

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

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

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

Dry film has carrier film, solder mask and as required and the structure that the coverlay that can peel off that uses forms according to this order lamination.Solder mask is that the light solidifying/heat solidifying resin composition with alkali-developable is applied on carrier film or the coverlay and dry and layer that obtain.Lamination coverlay above that after forming solder mask on the carrier film perhaps is laminated to this layered product on the carrier film after forming solder mask on the coverlay again, can obtain dry film.

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

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

As coverlay, can use polyethylene film, polypropylene film etc., its with bounding force of solder mask than with carrier film little better.

In order to use dry film on printed circuit board (PCB), to make diaphragm (permanent diaphragm), peel off coverlay, solder mask is overlapping with the base material that is formed with circuit, use laminating machine etc. that it is fitted, form solder mask being formed with on the base material of circuit.With likewise aforementioned, the solder mask that forms is made public, develops, is heating and curing, then can form cured coating film.Carrier film is peeled off before exposure or after the exposure and all can.

Embodiment

Below embodiment is shown and comparative example describes the present invention particularly, certainly, the present invention does not receive the qualification of following embodiment.In addition, following " part " and " % " if do not specify, are meant quality criteria.

Synthetic example 1 (containing the synthetic of carboxy resin)

(Japanese chemical drug (strain) is made in possessing 2 liters removable flask of stirring machine, thermometer, reflux condensing tube, tap funnel and nitrogen ingress pipe, to import 660g cresols phenolic resin varnish type epoxy resin; EOCN-104S; 92 ℃ of softening points; Epoxide equivalent 220), 421.3g carbitol acetic acid esters and 180.6g solvent naphtha, be heated to 90 ℃ and stir and make its dissolving.Then,, add 216g acrylic acid, 4.0g triphenylphosphine and 1.3g methylnaphthohydroquinone immediately, it was reacted 12 hours down at 100 ℃, obtain the reaction product that acid number is 0.2mgKOH/g in case be cooled to 60 ℃.Add the 241.7g tetrabydrophthalic anhydride therein, be heated to 90 ℃, reacted 6 hours.Obtaining acid number thus is that 50mgKOH/g, two key equivalent (unsaturated group is the gram weight of the resin of 1 molar equivalent) are 400, and weight-average molecular weight is that 7000 solid component concentration is the solution that 65% photonasty contains carboxy resin.Below, the solution that this photonasty is contained carboxy resin is called B 1 varnish.

Synthetic example 2 (containing the synthetic of carboxy resin)

With 400 parts of epoxide equivalents be 800, softening point be 79 ℃ Bisphenol F type solid epoxy resin with 925 parts of epichlorokydrin and 462.5 parts of dmso solutions after, under agitation, add 81.2 parts of 98.5%NaOH down at 70 ℃, add and continue 100 minutes.Adding the back further reacted 3 hours down at 70 ℃.Then; Most of superfluous unreacted epichlorokydrin and dimethyl sulfoxide (DMSO) are removed in distillation under reduced pressure; To comprise the salt of by-product and the reaction product of dimethyl sulfoxide (DMSO) and dissolve, add 10 parts of 30%NaOH again, react 1 hour down at 70 ℃ with 750 parts of methyl isobutyl ketones.After reaction finishes, carry out 2 washings with 200 parts of water.After the oil and water separation, methyl isobutyl ketone distillation is reclaimed, obtain 370 parts of epoxide equivalents and be 290, softening point is 62 ℃ epoxy resin (A-0) through oil reservoir.

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

Embodiment 1～5 and comparative example 1～3

Cooperate the ratio (mass parts) shown in the example to cooperate the various compositions shown in the table 1, after the stirring machine premixed, join in the airtight container, heating is 60 minutes in 100 ℃ heated air circulation type dryer according to each.After confirming that the composition that obtains is complete dissolved state, stir, at room temperature placed 2 hours, after confirming to return to room temperature, this mixed liquor is obtained A liquid with the filtration of 5 μ m filtrators through stirring machine.The A liquid that obtains carries out granulometry with ERICHSEN manufactured particle size analyzer, estimates dispersion degree, is below the 5 μ m.This A liquid 5 ℃ of held after 24 hours, is carried out granulometry with the particle size analyzer of ERICHSEN manufactured, estimate dispersion degree.

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

[table 1]

[table 2]

As shown in table 2; According to it is considered herein that; Having used the embodiment 1～5 of (A-1) and epoxy resin (A-2) and not used the dispersion degree of the comparative example 3 of A-1 composition is below the 5 μ m; Therewith relatively, the comparative example 1,2 that does not use (A-1) and (A-2) epoxy resin according to the ratio of the present invention's regulation is all owing to the former of A-1 composition thereby generation big particle, and dispersion degree reduces significantly.

Embodiment 6

Use 20 parts of KAYARAD TMPTA (trimethylolpropane triacrylate, Japanese chemical drug (strain) are made) to replace the DPHA of the routine 1-4 of aforementioned cooperation to prepare A liquid, likewise carry out the evaluation of dispersion degree with embodiment 4, dispersion degree is below the 5 μ m.

Embodiment 7

Use 20 parts of NK EsterA-DCP (dihydroxymethyl tristane diacrylate, Xin Zhong village chemical industry (strain) are made) to replace the DPHA of the routine 1-4 of aforementioned cooperation to prepare A liquid, likewise carry out the evaluation of dispersion degree with embodiment 4, dispersion degree is below the 5 μ m.

Embodiment 8

Use 20 parts of ARONIX M-350 (trimethylolpropane EO modification triacrylate, East Asia synthetic (strain) are made) to replace the DPHA of the routine 1-4 of aforementioned cooperation to prepare A liquid, likewise carry out the evaluation of dispersion degree with embodiment 4, dispersion degree is below the 5 μ m.

Embodiment 9

Use 20 parts of TMPTMA (trimethylol-propane trimethacrylate, Xin Zhong village chemical industry (strain) is made) to replace the DPHA of the routine 1-4 of aforementioned cooperation to prepare A liquid, likewise carry out the evaluation of dispersion degree with embodiment 4, dispersion degree is below the 5 μ m.

Embodiment 10

Use 20 parts of NK EsterBPE-500 (ethoxylation bisphenol a dimethacrylate, Xin Zhong village chemical industry (strain) is made) to replace the DPHA of the routine 1-4 of aforementioned cooperation to prepare A liquid, likewise carry out the evaluation of dispersion degree with embodiment 4, dispersion degree is below the 5 μ m.

Embodiment 11～13 and comparative example 4

That uses aforementioned synthetic example contains carboxy resin solution B 1 varnish, cooperates the various compositions except the barium sulphate slurry shown in the cooperation example 2 of table 3 according to the ratio shown in the table 3 (mass parts), after the stirring machine premixed, carries out mixing with 3 roll-type roller mills.Then, in said composition, add the barium sulphate slurry of ratio (mass parts) shown in the table 3, stir with stirring machine.Filter said composition with 5 μ m filtrators, preparation B liquid.The B liquid that obtains carries out granulometry with the particle size analyzer of ERICHSEN manufactured, estimates dispersion degree, is below the 5 μ m.Then, said composition 5 ℃ of held after 24 hours, being carried out granulometry with the particle size analyzer of ERICHSEN manufactured, estimate dispersion degree, is below the 5 μ m.

[table 3]

Various compositions shown in the cooperation of table 4 example 3 are cooperated according to the ratio shown in the table 4 (mass parts), with the stirring machine premixed after, carry out mixingly with 3 roll-type roller mills, prepare C liquid.The C liquid that obtains carries out granulometry with the particle size analyzer of ERICHSEN manufactured, estimates dispersion degree, is below the 15 μ m.

[table 4]

Big particle on the dry coating

After B liquid that cooperates example 2 and the C liquid that cooperates example 3 mixed respectively, mix, obtain light solidifying/heat solidifying resin composition with stirring machine.This light solidifying/heat solidifying resin composition is suitably diluted with MEK respectively; Fully stir with stirring machine, the particle size analyzer with the ERICHSEN manufactured carries out granulometry then, estimates dispersion degree; The dispersion degree of C liquid is not merely below the 15 μ m, and is below the 5 μ m.Think that reason is, the above big particle of 5 μ m of C liquid dissolves when mixing with B liquid.Then, this solution is applied on the PET film (TORAY INDUS TRIES, INC. make FB-50:16 μ m) with applicator, makes that to film after the drying be 50 μ m, with 80 ℃ heated air circulation type kiln drieds after 30 minutes, 15 ℃ of following natural cooling 24 hours.This plate is used observation by light microscope, estimate having or not of crystalloid big particle.Determinating reference is following.

Zero: do not have the crystalloid big particle

△: the generation of visible small amount of crystal

*: the crystalloid big particle produces in a large number

The plyability of dry coating

To form figuratum copper clad laminate polishing grinds; Then with the dry coating after the above-mentioned observation with vacuum laminator ((strain) name mechanism make manufacturing MVLP-500) heated lamination under pressurization degree: 0.8MPa, 70 ℃, 1 minute, the condition of vacuum tightness: 133.3Pa, obtain having the substrate (unexposed substrate) of unexposed solder mask.

This substrate is used observation by light microscope, and the determinating reference below using is estimated.Evaluation result is as shown in table 5.

Zero: the surface state behind the lamination is level and smooth

△: lamination is bad to cause part generation concavo-convex

*: lamination is bad to cause whole generation concavo-convex

[table 5]

As shown in table 5; According to the present invention, under the situation of the embodiment 11～13 that has used (A-1) and epoxy resin (A-2), B liquid and C liquid are mixed the light solidifying/heat solidifying resin composition that obtains suitably dilute with MEK respectively; When fully stirring with stirring machine; Big particle all dissolves, after the drying through 24 hours after, do not have in the dry coating to produce yet and think the big particle that causes by the A-1 composition.In addition, this is coated with film lamination and can obtains flatness.Therewith relatively, under the situation of comparative example 4, with MEK dilution, after the stirring, big particle all dissolves, but after drying is placed, and thinks the big particle that caused by the A-1 composition, and filming on the lamination metacoxal plate also becomes inhomogeneous.

Embodiment 14

Use 155 parts of B2 varnish to replace cooperating routine 2 B1 varnish, through implementing the making of dry film, the evaluation of surface state with embodiment 11 same methods.The result is identical with embodiment 11.

Embodiment 15

Use 222 parts of Cyclomer P (ACA) Z250 (DAICEL-CYTECCompany LTD. make contain carboxy resin; Solid constituent 45 quality %) replace cooperating the B1 varnish of example 2 to prepare B liquid, through implementing the making of dry film, the evaluation of surface state with embodiment 11 same methods.The result is identical with embodiment 11.

Embodiment 16～20, comparative example 5～7

According to cooperating the ratio (mass parts) shown in the example 4 to cooperate, with the stirring machine premixed after, carry out mixingly with 3 roll-type roller mills the various compositions shown in the cooperation of table 6 example 4, prepare D liquid.The dispersion degree of the composition that obtains carries out the granulometry evaluation with the particle size analyzer of ERICHSEN manufactured, is below the 15 μ m.

[table 6]

Embodiment 21, comparative example 8

Various compositions shown in the cooperation of table 7 example 5 according to cooperating the ratio (mass parts) shown in the example 5 to cooperate, use the stirring machine premixed, carry out mixingly then with 3 roll-type roller mills, prepare E liquid.The dispersion degree of the composition that obtains carries out the granulometry evaluation with the particle size analyzer of ERICHSEN manufactured, is below the 15 μ m.

[table 7]

Then, with aforementioned A liquid, E liquid and D liquid according to combined hybrid shown in the table 8 after, stir with stirring machine, obtain light solidifying/heat solidifying resin composition.In addition, after the preparation, A liquid, E liquid are used after 7 days 15 ℃ of held.

[table 8]

Performance evaluation:

Big particle on the dry coating

The light solidifying/heat solidifying resin composition of previous embodiment 16～21 and comparative example 5～8 is applied on the glass plate with applicator; Make that filming after the drying is 50 μ m; After dry 30 minutes, at room temperature natural cooling is 24 hours in 80 ℃ heated air circulation type drying oven.This plate is used observation by light microscope, estimate having or not of crystalloid big particle.Determinating reference is following.

Zero: no crystalloid big particle

△: visible small amount of crystal produces

*: produce bulk crystallization shape big particle

Optimum exposure

The circuit pattern substrate of the thick 35 μ m of copper is ground with polishing roll; After washing, the drying; Through the light solidifying/heat solidifying resin composition of whole coating of silk screen print method previous embodiment 16～21 and comparative example 5～8, drying is 60 minutes in 80 ℃ heated air circulation type drying oven.After the drying, use the exposure device that is equipped with high-pressure sodium lamp (short-arc lamp) to make public through stage metraster (KodakNo.2), will develop (30 ℃, 0.2MPa, 1wt%Na ₂CO ₃Exposure when the pattern of residual stage metraster is 7 sections after the 60 seconds WS) is as optimum exposure.

Attribute testing:

On the figuratum copper clad laminate of formation,, make that dried thickness is 20 μ m, after under 80 ℃ dry 30 minutes, naturally cool to room temperature through the composition of above-mentioned each embodiment 16～21 of whole coating of serigraphy and comparative example 5～8.The exposure device that use is equipped with high-pressure sodium lamp (short-arc lamp) makes public to the soldering-resistant pattern on this substrate with the optimum exposure exposure, uses 30 ℃ 1wt%Na then ₂CO ₃The WS developed for 60 seconds under the condition of spray pressure 0.2MPa, obtained corrosion-resisting pattern.This substrate is transmitted in the stove at cumulative exposure amount 1000mJ/cm at UV ²Condition under carry out ultraviolet ray irradiation, then 150 ℃ down heating be cured in 60 minutes.Characteristic to the printed base plate (evaluation substrate) of gained is estimated as follows.

Solder heat resistance property

The evaluation substrate that is coated with the rosin series solder flux is impregnated in the solder bath that is redefined for 260 ℃, with modification alcohol washing solder flux, the expansion of visual valuation resist layer and peeling off then.Judgment standard is following.

◎: repeat more than 6 times 10 seconds dippings and also can't see and peel off.

Zero: repeat more than 3 times 10 seconds dippings and also can't see and peel off.

△: repeat that have a little to peel off behind the dipping 10 seconds more than 3 times.

*: repeat 3 times to flood interior 10 seconds, resist layer has expansion, peels off.

Chemical gilding patience

Use commercially available article electroless nickel bath and chemical gilding to bathe, under the condition of nickel 0.5 μ m, golden 0.03 μ m, carry out plating, band is peeled off the back and is had or not the infiltration of peeling off, have or not plating through the visual resist layer of estimating.Judgment standard is following.

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

Zero: can see a little infiltration behind the plating, can't see after band is peeled off and peel off.

△: can see a little infiltration behind the plating, also can see after band is peeled off and peeling off.

*: peel off behind the plating.

Electrical characteristics

Use the comb-type electrode pattern Alloy instead of Copper foil substrate of line/space=20/20 μ m, make under these conditions and estimate substrate, 10 these comb-type electrodes are applied the bias voltage of DC10V, under 130 ℃, the condition of 85%R.H., in groove, measure insulating resistance value.In the mensuration, resistance value becomes 10 ⁴Comb-type electrode below the Ω is judged to be short circuit, calculates the quantity that does not have the comb-type electrode of short circuit after 100 hours.

Embodiment 22

Dry film is made

After the Photosetting and thermosetting oil/fat composition difference suitable dilution of MEK with embodiment 16; Use applicator to be applied to PET film (TORAY INDUSTRIES; INC. make FB-50:16 μ m) on, make that dried thickness is 20 μ m, obtained dry film down in dry 30 minutes at 80 ℃.

Substrate manufacture

To form figuratum copper clad laminate polishing grinds; The dry film that to make according to the method described above then obtains having the substrate (unexposed substrate) of unexposed solder mask with vacuum laminator ((strain) name mechanism make manufacturing MVLP-500) heated lamination under pressurization degree: 0.8MPa, 70 ℃, 1 minute, the condition of vacuum tightness: 133.3Pa.

The test substrate with cured film to obtaining carries out each evaluation test through afore-mentioned test method and evaluation method.

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

[table 9]

Shown in above-mentioned table 9, to compare with comparative example 5～8, embodiments of the invention 16～22 do not produce big particle on dry coating, and solder heat resistance property, chemical gilding patience, electrical characteristics are excellent.

On the other hand, in the situation of the comparative example 5 that does not fully comprise the A-2 composition, the minimizing of visible crystalloid big particle, but do not reach the generation that prevents recrystallization fully.And then, the situation in comparative example 6 and 8, the visible reductions of thinking the electrical characteristics that a large amount of generations of big particle cause.Comparative example 7 does not have big particle to produce, but the reduction of visible solder heat resistance property, electrical characteristics.

Claims (8)

1. the light solidifying/heat solidifying resin composition of an alkali-developable; Said composition contains (A) epoxy resin, (B) and contains carboxy resin and (C) Photoepolymerizationinitiater initiater; It is characterized in that; Said epoxy resin (A) is to have the 2 officials ability biphenyl epoxy resin (A-1) of structure shown in the formula (I) and the potpourri of epoxy resin (A-2); Said epoxy resin (A-2) for the group that is selected from bisphenol A type epoxy resin and bisphenol-A phenolic varnish type epoxy resin and formed, softening point is that 40～100 ℃ and epoxide equivalent are at least a kind of epoxy resin of 180～300, (A-1) of said epoxy resin and ratio (A-2) are (A-1)＜(A-2)

In the formula, R representes H or CH ₃

2. light solidifying/heat solidifying resin composition according to claim 1 is characterized in that, said epoxy resin (A) is in the state of dissolving when mixing.

3. light solidifying/heat solidifying resin composition according to claim 1; It is characterized in that; Saidly contain the acid number that carboxy resin (B) has 40～120mgKOH/g; With respect to the said carboxy resin (B) that contains of 100 mass parts, (A-1) of said epoxy resin is 20～60 mass parts with potpourri (A-2).

4. light solidifying/heat solidifying resin composition according to claim 1 is characterized in that, it further contains the photo-sensitive monomer that has the liquid state of 2 above olefinic unsaturated groups in (E) 1 molecule.

5. according to each described light solidifying/heat solidifying resin composition of claim 1～4, it is characterized in that it is used to form solder resist.

6. dry film, it is applied on the carrier film and dry obtaining through each the described light solidifying/heat solidifying resin composition with said claim 1～4.

7. solidfied material, it is through being applied on the base material and the dry dry coating that obtains carries out photocuring and/or heat curing obtains to each the described light solidifying/heat solidifying resin composition with said claim 1～4; Perhaps, through the dry coating that said light solidifying/heat solidifying resin composition is applied on the carrier film and the dry dry film lamination that forms obtains to the base material being carried out photocuring and/or heat curing obtains.

8. printed circuit board (PCB), it has the described solidfied material of aforementioned claim 7.