CN101845216A - Curable resin composition, the dry film that uses it and printed circuit board (PCB) - Google Patents

Abstract

Curable resin composition is provided, uses its dry film and printed circuit board (PCB), in detail, curable resin composition is provided, uses its dry film and forms the printed circuit board (PCB) that flame retardant resistance cured film such as soldering-resistance layer forms by them, this curable resin composition contains halogen-free flame retardants, can form the solder mask of flame retardant resistance, low warpage properties, insulating reliability excellence.This curable resin composition contains (A) and contains carboxy resin, (B) P contained compound and (C) the multiple oxyhydroxide of stratiform.Except aforementioned each composition, by also containing the Thermocurable composition that has 2 above ring-type ethers and/or cyclic thioether base in (D) molecule, can become hot curing resin composition, by also containing (F) Photoepolymerizationinitiater initiater and (G) photopolymerization monomer, can become light solidifying/heat solidifying resin composition.Preferably also contain (E) aluminium hydroxide.

Description

Curable resin composition, the dry film that uses it and printed circuit board (PCB)

Technical field

The present invention relates to curable resin composition, relate in particular to the curable resin composition of the solder resist that can form flame retardant resistance, low warpage properties, insulating reliability excellence.The invention still further relates to the dry film of this curable resin composition of use and the printed circuit board (PCB) of flame retardant resistance.

Background technology

All the time, printed circuit board (PCB) and flexible electric circuit board (below, abbreviate FPC as) be owing to be equipped in the e-machine, thereby wish that it has flame retardant resistance, also is required flame retardant resistance as their solder resist of a part.Wherein, FPC is made of polyimide substrate usually, and therefore, its printed circuit board (PCB) with glass epoxy substrate is different, is film.Yet,, therefore, during for the FPC of film, the burden of fire-retardantization of solder resist is become greatly relatively because the solder resist that should be coated with all is identical thickness in printed circuit board (PCB) or in FPC.

Therefore, all the time, various schemes have been proposed for fire-retardantization of solder resist.For example; TOHKEMY 2007-10794 communique (patent documentation 1) has proposed a kind of FPC flame retardant resistance photosensitive polymer combination, the P contained compound that it contains the optical polymerism compound, (c) Photoepolymerizationinitiater initiater, (d) blocked isocyanate compound of polymerisable ethylenic unsaturated bonds such as halogenation aromatic nucleus such as having the bromo phenyl in (a) binder polymer, (b) molecule and (methyl) acryl and (e) has phosphorus atom in the molecule.Yet from the viewpoint of environmental pressure, it is not preferred using the such halogen compounds of compound with halogenation aromatic nucleus and polymerisable unsaturated double-bond.

Therefore, from alleviating the viewpoint of environmental pressure, recently, using the phthalocyanine blue of halogen atom-containing not and yellow colorants to replace in the past green colourant is that the solder resist of chlorination phthalocyanine green is being popularized (for example, with reference to patent documentation 2).In addition, owing to advocate clear and definite in appearance Halogen, therefore, also the someone uses the direct solder resist of using the blueness of phthalocyanine blue.Though the formation of solder resist is the protection that is used for copper circuit, its another effect is that wound, dirt on the heat that makes copper circuit, moisture, electric caused variable color, the copper circuit etc. is difficult for being found (opacifying power).For this point, usually solder resist is added tinting material, make its concentration make that greatly bad being difficult for of outward appearance seen.Yet, compare with the green of phthalocyanine green, the opacifying power of blue welding resistance China ink, the green welding resistance China ink that obtains by blue colorant and yellow colorants a little less than, can not bring into play bad order sometimes fully and be difficult for the function of being seen this tinting material.

It with FPC the printed base plate of the film of representative produces warpage when also existing in the photocuring of solder resist or thermofixation because of cure shrinkage problem.

Use P contained compound as the method that realizes Halogen and fire-retardantization widely known to everybody.Yet under the situation of the solder resist of the printed circuit board (PCB) that must realize secular electrical insulating property, a little less than the hydrolytic resistances such as P contained compound, especially phosphoric acid ester, electrical characteristic, especially resistance to migration are poor, therefore have the shortcoming that can not use in a large number.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2007-10794 communique (claims)

Patent documentation 2: TOHKEMY 2000-7974 communique (claims)

Summary of the invention

The problem that invention will solve

The present invention carries out in order to solve foregoing prior art problems, its main purpose is, a kind of curable resin composition that contains halogen-free flame retardants is provided, and described curable resin composition can form the solder mask of flame retardant resistance, low warpage properties, insulating reliability excellence.

And then, the objective of the invention is to, by using this curable resin composition, provide the dry film of low warpage and flame retardant resistance and insulating reliability excellence and the printed circuit board (PCB) of the flame retardant resistance epithelium of characteristic with such excellence.

The scheme that is used to deal with problems

In order to realize aforementioned purpose, the invention provides a kind of curable resin composition, it is characterized in that it contains (A) and contains carboxy resin, (B) P contained compound and (C) the multiple oxyhydroxide of stratiform.

In a scheme, except aforementioned each composition, also contain the Thermocurable composition that has 2 above ring-type ethers and/or cyclic thioether base in (D) molecule, can become hot curing resin composition thus.In other preferred scheme, also contain (E) aluminium hydroxide.In other scheme, also contain (F) Photoepolymerizationinitiater initiater and (G) photopolymerization monomer, can become light solidifying/heat solidifying resin composition thus.In other preferred scheme, also contain tinting material (H).In preferred scheme, the above-mentioned carboxy resin (A) that contains is the carboxy resin that contains with carboxylamine ester structure, or has a carboxy resin that contains of xenol Novolac structure and olefinic unsaturated group, in addition, the Thermocurable composition (D) that has 2 above ring-type ethers and/or cyclic thioether base in the above-mentioned molecule is the Resins, epoxy with xenol Novolac skeleton, and then the multiple oxyhydroxide (C) of above-mentioned stratiform is hydrotalcite.Such curable resin composition is adapted at using in the formation of solder resist of printed circuit board (PCB).

In addition, the present invention also provides, to aforementioned curable resin composition being applied on the film and the dry dry film that forms carries out thermofixation and/or photocuring and the cured article that obtains; Perhaps, to aforementioned curable resin composition or to this curable resin composition being applied on the carrier film and the dry dry film that obtains carries out thermofixation and/or photocuring and the cured article that obtains.The present invention also provides the printed circuit board (PCB) with aforementioned cured article.

The invention effect

Curable resin composition of the present invention contains (A) and contains carboxy resin and (B) P contained compound and (C) the multiple oxyhydroxide of stratiform, preferably also contain (E) aluminium hydroxide, thus, can form that Halogen is formed and environmental pressure is little, the epithelium of flame retardant resistance, low warpage properties, insulating reliability excellence.Therefore, the curable resin composition of the application of the invention, the printed circuit board (PCB) of welding resistance epithelium of flame retardant resistance that the dry film of low warpage and flame retardant resistance and insulating reliability excellence can be provided and have the characteristic of such excellence.

Embodiment

The invention is characterized in, used simultaneously to contain the multiple oxyhydroxide (C) of carboxy resin (A), stratiform and as P contained compound (B) this point of fire retardant.Think that by being used in combination multiple oxyhydroxide (C) of stratiform and P contained compound (B), to the acid such as hydrolysate phosphoric acid of P contained compound, especially phosphoric acid ester, the multiple oxyhydroxide (C) of stratiform plays the effect of antacid, result, the generation that can suppress to move.In addition, if increase the addition of the multiple oxyhydroxide of stratiform, then also can obtain the result that flame retardant resistance improves, the result can reduce the consumption of P contained compound.Think that this is because the multiple oxyhydroxide self of stratiform is aquo compound, has under the high temperature when burning to produce rare gas element, make the effect that flame is less.As seen, the multiple oxyhydroxide of stratiform has very effective effect as the fire retardant of P contained compound system, is the dramatic effect that is difficult to imagine.

Below, each constituent of curable resin composition of the present invention is described in detail.

As the contained carboxy resin (A) that contains in the curable resin composition of the present invention, can use the resin compound known commonly used that contains carboxyl in the molecule.And then, under the situation of resin combination that is alkali-developable, from light solidified, anti-development aspect, have in the molecule ethylenical unsaturated double bonds to contain carboxyl photoresist (A ') be preferred.And it is preferred that its unsaturated group is derived from the acrylic or methacrylic acid derivative.In addition, do not have under the situation that contains carboxy resin of ethylenical unsaturated double bonds only using, to have light solidified in order to make composition, need with molecule described later in have 2 above olefinic unsaturated groups photopolymerization monomer (G) be used in combination.

As the object lesson that contains carboxy resin (A), such compound of enumerating below suitable use the (any of oligopolymer and polymkeric substance all can).

(1) contains the carboxy resin that contains that the copolymerization of unsaturated group compound obtains by unsaturated carboxylic acids such as (methyl) vinylformic acid and vinylbenzene, alpha-methyl styrene, low alkyl group (methyl) acrylate, iso-butylene etc.

(2) pass through aliphatic diisocyanate, the side chain aliphatic diisocyanate, the ester ring type vulcabond, vulcabond and dimethylol 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, dihydroxyphenyl propane is the alkylene oxide adducts dibasic alcohol, have phenol hydroxyl and alcohol hydroxyl group diatomic alcohol compounds such as compound polyaddition reaction and obtain contain the carboxyl urethane resin.

(3) be that polyvalent alcohol, polyester are that polyvalent alcohol, polyolefin polyvalent alcohol, acrylic acid series multiple alcohol, dihydroxyphenyl propane are the alkylene oxide adducts dibasic alcohol, polyaddition reaction with diatomic alcohol compounds such as compound of phenol hydroxyl and alcohol hydroxyl group obtains urethane resin by diisocyanate cpd such as aliphatic diisocyanate, side chain aliphatic diisocyanate, ester ring type vulcabond, aromatic diisocyanate and polycarbonate-based polyvalent alcohol, polyethers, its terminal end that obtains with anhydride reaction contains the carboxyl urethane resin.

(4) by 2 officials such as vulcabond 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 Resins, epoxy (methyl) acrylate or the photosensitivity that obtains of the polyaddition reaction of the anhydride modified thing of its part, carboxylic diol compound and diatomic alcohol compounds contain the carboxyl urethane resin.

(5) by have 1 hydroxyl in adding (methyl) hydroxyalkyl acrylate equimolecular in the resin of above-mentioned (2) or (4) synthetic and the compound of (methyl) acryl obtains more than 1 end (methyl) propylene acidylate contain the carboxyl urethane resin.

(6) have 1 isocyanate group in the reaction with same mole thing equimolecular by adding isophorone diisocyanate and pentaerythritol triacrylate in the resin of above-mentioned (2) or (4) synthetic and the compound of (methyl) acryl obtains more than 1 end (methyl) propylene acidylate contain the carboxyl urethane resin.

(7) photosensitivity that obtains by making the reaction of such multifunctional (solid-state) Resins, epoxy of aftermentioned and (methyl) vinylformic acid, make 2 yuan of acid anhydrides additions such as the hydroxyl that is present in side chain and Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride contains carboxy resin.

(8) polyfunctional epoxy resin and the reaction of (methyl) vinylformic acid that obtain with the further epoxidation of epoxy chloropropane of the hydroxyl by can (solid-state) Resins, epoxy with 2 officials, the hydroxyl of generation and 2 yuan of acid anhydrides additions and the photosensitivity that obtains contains carboxy resin.

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

(10) resin of above-mentioned by making (1)～(9) further with in (methyl) glycidyl acrylate, (methyl) vinylformic acid Alpha-Methyl glycidyl ester equimolecular has 1 epoxy group(ing) and the compound addition of (methyl) acryl obtains more than 1 photosensitivity contains carboxy resin.

These contain in the carboxy resin, preferably (X) contains the carboxyl urethane resin, especially the isocyanate group of the composition with isocyanate group (comprising vulcabond) of this urethane resin not with the phenyl ring Direct Bonding contain the carboxyl urethane resin, and (Y) in aforementioned resin synthetic used polyfunctional epoxy resin be to have structure of bisphenol A, the Bisphenol F structure, the xenol structure, xenol Novolac structure, bis-xylene phenol structure, especially have the compound of xenol Novolac structure and add hydrogen compound, from low warpage, setting out in crooked patience aspect, is preferred.In addition, from others, aforementioned (2), (3), (4), (5), (6) and their modifier as (10) have amino-formate bond at main chain, are preferred from warpage.In addition, have the photosensitivity group in the molecule of aforementioned (1) (2) (3) (9) resin in addition, therefore, the photoreactivity height is preferred.

In addition, in this manual, (methyl) acrylate is the term of general designation acrylate, methacrylic ester and their mixture, below, other similar expression is too.

The foregoing carboxy resin (A) that contains has a plurality of free carboxyls on the side chain of trunk polymer, the cross-linking set when therefore becoming thermofixation.In addition, under situation, can utilize dilute alkaline aqueous solution to develop as Photocurable resin composition.

In addition, the aforementioned acid number that contains carboxy resin (A) is preferably the scope of 30～200mgKOH/g, 40～200mgKOH/g more preferably, and the scope that is preferably 45～120mgKOH/g especially is an ideal.Viewpoint from alkali-developable, the words that contain the not enough 30mgKOH/g of acid number of carboxy resin, then be difficult to alkali and develop, on the other hand, surpass the words of 200mgKOH/g, the dissolving of developing solution to exposure portion takes place, therefore, it is thinner than needed that line becomes, and is developed the liquid dissolving portion of exposure sometimes and unexposed indistinction and peels off, be difficult to describe normal corrosion-resisting pattern, so not preferred.

In addition, the aforementioned weight-average molecular weight that contains carboxy resin (A) is according to resin matrix and difference is generally 2000～150000, and then is that 5000～100000 scope is preferred.During weight-average molecular weight less than 2000, tack-free poor performance takes place sometimes, the wet fastness of filming after the exposure is poor, produces the film wearing and tearing when developing, the remarkable variation of resolving power.On the other hand, weight-average molecular weight surpasses at 150000 o'clock, the remarkable variation of development takes place sometimes, the storage stability variation.

The foregoing use level that contains carboxy resin (A) be in all compositions 5～60 quality %, be preferably 10～60 quality %, more preferably 20～60 quality %, be preferably 30～50 quality % especially.When being less than above-mentioned scope, coating strength reduces, 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.

Curable resin composition of the present invention preferably comprises P contained compound (B).P contained compound can be the commonly used known material as organic phosphorus flame retardant, and the compound shown in phosphoric acid ester and condensed phosphoric acid esters, cyclic phosphazene compound, phosphonitrile oligopolymer, hypophosphite or the following general formula (I) is arranged.

[Chemical formula 1]

In the formula, R ¹, R ²And R ³Represent halogen atom substituting group in addition independently of one another.

As the commercially available product of the compound shown in the above-mentioned general formula (I), HCA, SANKO-220, M-ESTER, HCA-HQ (being the trade(brand)name of three light (strain)) etc. are arranged

As the used particularly preferred P contained compound (B) of the present invention, can list that (1) has acrylate-based P contained compound as reactive group, (2) have phenol hydroxyl P contained compound, (3) oligopolymer or polymkeric substance, (4) phosphonitrile oligopolymer and (5) hypophosphite as reactive group.

(1) has acrylate-based P contained compound

The phosphorus element-containing acrylate can be to have the compound that comprises (methyl) acrylate more than 2 in phosphoric and the molecule, particularly, can list the R in the aforementioned formula (1) ¹And R ²Be hydrogen atom, R ³Be the compound of acrylate derivative, usually can be by 9, the 10-dihydro-9-oxy is assorted-and 10-phospho hetero phenanthrene-10-oxide compound synthesizes by Michael reaction (michael addition reaction) with known polyfunctional acrylic ester monomer commonly used.

As above-mentioned known acrylate monomer commonly used, can list the diacrylate class of glycol such as ethylene glycol, methoxyl group TEG, polyoxyethylene glycol, propylene glycol; The multicomponent methacrylate class of polyvalent alcohols such as hexylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, three-hydroxyethyl isocyanuric acid ester or their ethylene oxide adduct, propylene oxide adduct or caprolactone affixture etc.; The multicomponent methacrylate class of the ethylene oxide adduct of phenoxy group acrylate, bisphenol a diacrylate and these phenols or propylene oxide adduct etc.; And the urethane acrylate class of above-mentioned polyalcohols; The multicomponent methacrylate class of glycidyl ethers such as glycerol diglycidylether, glycerol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester; And the trimeric cyanamide acrylate and/or with corresponding each methyl acrylic ester of aforesaid propylene acid esters etc.

(2) has the P contained compound of phenol hydroxyl

This has hydrophobicity, the thermotolerance height of the P contained compound of phenol hydroxyl, can not reduce the solder heat resistance height because of hydrolysis causes electrical characteristic.In addition, as suitable combination, the Resins, epoxy, other Resins, epoxy that have biphenyl backbone by use is as (D) composition, itself and Resins, epoxy are reacted and is included in its network, therefore, can not ooze out this advantage after having curing.As commercially available product, the HCA-HQ of three light (strain) manufacturing etc. is arranged.

(3) oligopolymer or polymkeric substance

The P contained compound of oligopolymer or polymkeric substance, to make that bendability reduces less because of the influence of alkyl chain, in addition, because its molecular weight is big, do not ooze out this advantage after can obtaining solidifying.As commercially available product, the M-Ester-HP that has three light (strain) to make, the phosphorous VYLON 337 of (strain) manufacturing etc. spins in Japan.

(4) phosphonitrile oligopolymer

As the phosphonitrile oligopolymer, phenoxy phosphazene compound is effectively, and the ring of replacement or unsubstituted phenoxy phosphonitrile oligopolymer or tripolymer, the tetramer, pentamer is arranged, and liquid, pressed powder all is fit to use.As commercially available product, there is (strain) volt to see FP-100, the FP-300 of pharmacy manufacturing, FP-390 etc.Wherein, the phenoxy phosphazene oligopolymer that is replaced by alkyl or hydroxyl, cyano group isopolarity group is to containing the solvability height of carboxy resin, even heavy addition does not have disadvantageous effects such as recrystallization yet, so preferably.

(5) hypophosphite

By using hypophosphite, can not damage cured coating film flexibility ground and further improve flame retardant resistance.In addition, by using the hypophosphite of excellent heat resistance, can suppress oozing out of fire retardant in the hot pressing when mounted.As commercially available product, can list EXOLI TOP 930, EXOLI TOP 935 etc. that Clariant company makes.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level of these P contained compounds as fire retardant (B) is that the scope of 0～200 mass parts is preferred, is preferably 0～100 mass parts especially.Use level is during more than above-mentioned scope, and so the variation such as curved characteristic of the cured film that obtains are not preferred.

As the multiple oxyhydroxide (layered doublehydroxide) of the stratiform of aforementioned (C) composition, suitable hydrotalcite and the hydrotalcite sample compound of using.Hydrotalcite and hydrotalcite sample compound are a kind of in the clay mineral of natural output, and the basic layer [Mg by positively charged for example arranged _1-XAl _X(OH) ₂] ^X+With electronegative middle layer [(CO ₃) _X/2MH ₂O] ^X-The lamellated mineral compound that constitutes.The metal of most divalent, 3 valencys can obtain identical therewith laminate structure, and general structure is shown in following formula (II).

[Chemical formula 2]

[M _1-X ²⁺M _X ³⁺(OH) ₂][A _X/n ^n-·mH ₂O] (II)

In the formula, M ²⁺The metallic cation of expression divalent, M ³⁺The metallic cation of representing 3 valencys, A ^N-The negatively charged ion of expression n valency, the subscript of each element and each atomic group is represented the ratio of each element and each atomic group, X is 0＜X≤0.33.M 〉=0, but it is owing to dehydration alters a great deal.

Object lesson as the multiple oxyhydroxide (C) of stratiform can list IndigiriteMg ₂Al ₂[(CO ₃) ₄(OH) ₂] 15H ₂O, Fe ²⁺ ₄Al ₂[(OH) ₁₂CO ₃] 3H ₂O, Quintinite Mg ₄Al ₂(OH) ₁₂CO ₃H ₂O, Manasseite Mg ₆Al ₂[(OH) ₁₆CO ₃] 4H ₂O, SjOegrenite Mg ₆Fe ³⁺ ₂[(OH) ₁₆CO ₃] 4H ₂O, Zaccagnaite Zn ₄Al ₂(CO ₃) (OH) ₁₂3H ₂O, Desautelsite Mg ₆Mn ³⁺ ₂[(OH) ₁₆CO ₃] 4H ₂O, Hydrotalcite Mg ₆Al ₂[(OH) ₁₆CO ₃] 4H ₂O, Pyroaurite Mg ₆Fe ³⁺ ₂[(OH) ₁₆CO ₃] 4H ₂O, Reevesite Ni ₆Fe ³⁺ ₂[(OH) ₁₆CO ₃] 4H ₂O, Stichtite Mg ₆Cr ₂[(OH) ₁₆CO ₃] 4H ₂O, Takovite Ni ₆Al ₂[(OH) ₁₆CO ₃] 4H ₂O etc.

In addition, as the commercially available product of synthetic hydrotalcite class, can list ALCAMIZER, DHT-4A, Kyoward 500, Kyoward100 that consonance chemical industry (strain) is made, HT-1, the HT-7 of the STABIACE series that Sakai chemistry (strain) is made, HT-P etc.

Particularly preferably be the synthetic hydrotalcite class, preferred median size is following, the following materials of 1 μ m more preferably of 2 μ m.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level of the multiple oxyhydroxide (C) of aforementioned stratiform is for example 5～100 mass parts, and the scope that is preferably 10～50 mass parts is fit to.Compare with above-mentioned scope, when use level is too much, the viscosity of composition and the thixotropy situation too high, that printing reduces, cured article becomes fragile that becomes takes place sometimes, so not preferred.On the other hand, during less than 5 mass parts, anti-ion migration effect is impaired, so not preferred.

For composition of the present invention is consisted of hot curing resin composition, improve thermotolerance, characteristics such as insulating reliability and the Thermocurable composition (D) that uses, so long as can with carboxyl reaction that contains carboxy resin and molecule in have 2 above ring-type ethers and/or cyclic thioether base (below, abbreviate ring-type (sulphur) ether as) existing known compound, can use, wherein, from thermotolerance, the viewpoint of gold-plated patience is set out, the above Resins, epoxy of 2 functionalities is preferred, Resins, epoxy with xenol Novolac skeleton can improve thermotolerance, gold-plated patience, so flame retardant resistance is preferred especially.As Resins, epoxy, can list NC-3000L, NC-3000, NC-3000H, NC-3100 etc. that for example Japanese chemical drug (strain) is made with xenol Novolac skeleton.In addition, can also use 2 functionality blocked isocyanates of vulcabond, vulcabond.

In addition, in hot curing resin composition of the present invention, can be used as the Thermocurable composition that has 2 above ring-types (sulphur) ether in the molecule that the Thermocurable composition uses, be to have 2 above triatomic rings in the molecule, the compound of any of tetra-atomic ring or pentacyclic ring-type ether or cyclic thioether base or 2 kinds of groups, can list the compound that has 2 above epoxy group(ing) in the molecule for example is multi-functional epoxy compound (D-1), the compound that has 2 above oxetanyls in the molecule is multifunctional oxetane compound (D-2), the compound that contains 2 above thioether groups in the molecule is an episulfide resin (D-3) etc.

As aforementioned multi-functional epoxy compound (D-1), for example can list, bisphenol A type epoxy resin, as Japan Epoxy Resins Co., Ltd. the jER828 of Zhi Zaoing, jER834, jER1001, jER1004, the Epiclon840 that DIC Corporation makes, Epiclon850, Epiclon1050, Epiclon2055, Dongdu changes into the EpototeYD-011 that company makes, YD-013, YD-127, YD-128, the D.E.R.317 that Dow ChemicalCompany makes, D.E.R.331, D.E.R.661, D.E.R.664, the Araldite6071 of west crust specialty goods chemical company, Araldite6084, AralditeGY250, AralditeGY260, the SumiepoxyESA-011 that Sumitomo Chemical Co. Ltd. makes, ESA-014, ELA-115, ELA-128, the A.E.R.330 that industrial of Asahi Chemical Industry makes, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade(brand)name); Brominated epoxy resin, as Japan Epoxy Resins Co., Ltd. the jERYL903 of Zhi Zaoing, Epiclon152, Epiclon165 that DIC Corporation makes, Dongdu changes into EpototeYDB-400, the YDB-500 that company makes, 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(brand)name) such as A.E.R.711, A.E.R.714 that industrial of Asahi Chemical Industry makes; Phenolic resin varnish type epoxy resin, as Japan Epoxy Resins Co., Ltd. the jER152 of Zhi Zaoing, jER154, the D.E.N.431 that DowChemical Company makes, D.E.N.438, the EpiclonN-730 that DICCorporation makes, EpiclonN-770, EpiclonN-865, Dongdu changes into the EpototeYDCN-701 that company makes, YDCN-704, the AralditeECN1235 that west crust specialty goods chemical company makes, AralditeECN1273, AralditeECN1299, AralditeXPY307, the EPPN-201 that Japan's chemical drug corporate system is made, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the SumiepoxyESCN-195X that Sumitomo Chemical Co. Ltd. makes, ESCN-220, the A.E.R.ECN-235 that industrial of Asahi Chemical Industry makes, ECN-299 etc. (being trade(brand)name); Bisphenol f type epoxy resin, Epiclon830 as DIC Corporation manufacturing, Japan Epoxy Resins Co., Ltd. the jER807 of Zhi Zaoing, Dongdu changes into EpototeYDF-170, YDF-175, the YDF-2004 that company makes, (being trade(brand)name) such as AralditeXPY306 that west crust specialty goods chemical company makes; Bisphenol-A epoxy resin, EpototeST-2004, the ST-2007 that makes as Dongdu company that changes into, ST-3000 (trade(brand)name) etc.; Glycidyl amine type epoxy resin, as Japan EpoxyResins Co., Ltd. the jER604 of Zhi Zaoing, Dongdu changes into the EpototeYH-434 that company makes, the AralditeMY720 that west crust specialty goods chemical company makes, (being trade(brand)name) such as SumiepoxyELM-120 that Sumitomo Chemical Co. Ltd. makes; Glycolylurea type Resins, epoxy clings to the AralditeCY-350 (trade(brand)name) of specialty goods chemical company manufacturing etc. as the west; Alicyclic epoxy resin, as DAICELCHEMICAL INDUSTRIES, the Celoxide2021 that LTD. makes, (being trade(brand)name) such as AralditeCY175, CY179 that west crust specialty goods chemical company makes; Trihydroxybenzene methylmethane type Resins, epoxy, as Japan Epoxy Resins Co., the YL-933 that Ltd. makes, (being trade(brand)name) such as T.E.N., the EPPN-501 that Dow Chemical Company makes, EPPN-502; Japan Epoxy Resins Co., YL-6056, YX-4000, YL-6121 di-cresylol type or united phenol-type epoxy resin or their mixtures such as (being trade(brand)name) that Ltd. makes; Japan's chemical drug corporate system is made EBPS-200, the EPX-30 that Asahi Electro-Chemical Co. Ltd makes, the EXA-1514 bisphenol-s epoxy resins such as (trade(brand)names) that DIC Corporation makes; Japan EpoxyResins Co., the jER157S bisphenol-A phenolic varnish type Resins, epoxy such as (trade(brand)names) that Ltd. makes; Japan Epoxy Resins Co., the jERYL-931 that Ltd. makes, four hydroxyphenyl ethane type Resins, epoxy such as Araldite163 (being trade(brand)name) that west crust specialty goods chemical company makes; The AralditePT810 that west crust specialty goods chemical company makes, (being trade(brand)name) hetero ring type Resins, epoxy 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 dimethylbenzene acyl group ethane (the tetraglycidyl xylenoyl ethane) resins such as ZX-1063 that company makes; Chemical company of Nippon Steel makes ESN-190, ESN-360, and DIC Corporation makes the Resins, epoxy that HP-4032, EXA-4750, EXA-4700 etc. contain naphthyl; DIC Corporation makes the Resins, epoxy that HP-7200, HP-7200H etc. have the Dicyclopentadiene (DCPD) skeleton; The glycidyl methacrylate copolymerization such as CP-50S, CP-50M that Nof Corp. makes are Resins, epoxy; And the copolymerization Resins, epoxy of cyclohexyl maleimide and glycidyl methacrylate; Epoxide modified polybutadiene rubber derivative (DAICEL CHEMICAL INDUSTRIES for example, the PB-3600 that LTD. makes etc.), CTBN modified epoxy (for example Dongdu changes into YR-102, the YR-450 etc. that company makes) etc., but be not limited to these.These Resins, epoxy can be used alone or in combination of two or more kinds.

As aforementioned multifunctional oxetane compound (D-2), can list two [(3-methyl-3-trimethylene oxide ylmethoxy) methyl] ethers, two [(3-ethyl-3-trimethylene oxide ylmethoxy) methyl] ether, 1, two [(3-methyl-3-trimethylene oxide ylmethoxy) methyl] benzene of 4-, 1, two [(3-ethyl-3-trimethylene oxide ylmethoxy) methyl] benzene of 4-, vinylformic acid (3-methyl-3-oxetanyl) methyl esters, vinylformic acid (3-ethyl-3-oxetanyl) methyl esters, methacrylic acid (3-methyl-3-oxetanyl) methyl esters, methacrylic acid (3-ethyl-3-oxetanyl) methyl esters, multifunctional trimethylene oxide classes such as their oligopolymer or multipolymer; And novolac resin, poly-(para hydroxybenzene ethene), cardo type bisphenols, calixarene kind, Resorcinol calixarene (calixresorcinarene) class or silsesquioxane (silsesquioxane) etc. have the resin of hydroxyl and the etherate of trimethylene oxide alcohol etc.In addition, can list the multipolymer etc. of unsaturated monomer with trimethylene oxide ring and (methyl) alkyl acrylate.

Episulfide resin (D-3) as having 2 above cyclic thioether bases in the aforementioned molecule for example can list, 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 Sauerstoffatom of the epoxy group(ing) 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, ring-type (sulphur) ether is preferably 0.6～2.5 equivalent, 0.8～2.0 normal scope more preferably.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 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.

In order further to improve thermotolerance, the insulating reliability of cured coating film, in in curable resin composition of the present invention, cooperating aforementioned molecule, have the Thermocurable composition (D) of 2 above ring-types (sulphur) ether, can also cooperate known heat-curing resins commonly used such as polyimide resin, cyclic carbonate compound, bismaleimides, oxazine compound, oxazoline compound, the inferior diamine resin of carbon such as the compound that has 2 above isocyanate group or closure isocyanate group in 1 molecule, melamine resin, melamine derivative, benzoguanamine resin.

As the compound that has 2 above isocyanate group or closure isocyanate group in aforementioned 1 molecule, can list the compound that has 2 above isocyanate group in 1 molecule and be the compound that has 2 above closure isocyanate group in polyisocyanate compound or 1 molecule is blocked isocyanate compound etc.

As aforementioned polyisocyanate compound, can use for example aromatic polyisocyanate, aliphatic polyisocyante or ester ring type polyisocyanates.Object lesson as aromatic polyisocyanate, can list 4,4 '-'-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-vulcabond, o-Xylol vulcabond, m xylene diisocyanate and 2,4 toluene diisocyanate dimer.Object lesson as aliphatic polyisocyante, can list tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, trimethyl hexamethylene diisocyanate, 4,4-methylene-bis (cyclohexyl isocyanate) and isophorone diisocyanate.As the object lesson of ester ring type polyisocyanates, can list the bicycloheptane triisocyanate.And the adducts of the isocyanate compound that lists above, biuret body and isocyanuric acid ester body.

Closure isocyanate group contained in the aforementioned blocked isocyanate compound is, isocyanate group is by protected with the reaction of encapsulant, thereby by the group of temporary transient passivation.When being heated to specified temperature, this encapsulant dissociates, and generates isocyanate group.

As the blocked isocyanate compound, can use the addition reaction product of isocyanate compound and isocyanic ester encapsulant.As can with the isocyanate compound of encapsulant reaction, can list isocyanuric acid ester type, bisacetal type, add mould assembly etc.As this isocyanate compound, can use for example aromatic polyisocyanate, aliphatic polyisocyante or ester ring type polyisocyanates.As the object lesson of aromatic polyisocyanate, aliphatic polyisocyante and ester ring type polyisocyanates, can list the such compound shown in the top example.

As the isocyanic ester encapsulant, for example can listing, phenol such as phenol, cresols, xylenol, chlorophenol and ethylphenol are encapsulant; Lactan such as ε-Ji Neixianan, δ-Valerolactim, butyrolactam and azetidinone are encapsulant; Methyl aceto acetate and methyl ethyl diketone isoreactivity methylene base system encapsulant; Alcohol such as methyl alcohol, ethanol, propyl alcohol, butanols, amylalcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, benzylic ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate and ethyl lactate are encapsulant; Oximes such as formoxime, ethylidenehydroxylamine, acetoxime, methyl ethyl ketoxime, diacetyl monoxime, hexamethylene oxime are encapsulant; Mercaptan such as butyl sulfhydryl, hexylmercaptan, tert-butyl mercaptan, thiophenol, methylbenzene thiophenol, ethyl thiophenol are encapsulant; Acid amides such as ethanamide, benzamide is an encapsulant; Imide series such as succinimide and maleimide encapsulant; Amine such as xylidine, aniline, butylamine, dibutylamine are encapsulant; Imidazoles such as imidazoles, 2-ethyl imidazol(e) are encapsulant; Imines such as methylenimine and propylidene imines are encapsulant etc.

The blocked isocyanate compound can use commercially available material, can list for example SumiduleBL-3175, BL-4165, BL-1100, BL-1265, DesmoduleTPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm2170, Desmotherm2265 (more than, Sumika BayerUrethane Co., Ltd. make, trade(brand)name), coronate2512, coronate2513, coronate2520 (more than, Japanese polyurethane industry society makes trade(brand)name), B-830, B-815, B-846, B-870, B-874, B-882 (Mitsui Takeda Chemical Co., Ltd. make, two names of an article), TPA-B80E, 17B-60PX, E402-B80T (AsahiKasei Chemicals Corporation makes, trade(brand)name) etc.In addition, SumiduleBL-3175, BL-4265 are to use the methylethyl oxime to obtain as encapsulant.

The compound that has 2 above isocyanate group or closure isocyanate group in the 1 above-mentioned molecule can be used singly or in combination of two or more thereof.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level that has the compound of 2 above isocyanate group or closure isocyanate group in the 1 such molecule is 1～100 mass parts, more preferably the ratio of 2～70 mass parts is fit to.During aforementioned use level less than 1 mass parts, so the obdurability that can not be filmed fully is not preferred.On the other hand, when surpassing 100 mass parts, the storage stability of composition reduces, so not preferred.

As other Thermocurable composition, also can list melamine derivative, benzoguanamine derivative etc.For example melamine methylol compound, methylol benzoguanamine compound, methylol glycoluril compounds and hydroxymethyl urea compound etc. are arranged.And then alkoxy methyl melamine compound, alkoxy methyl benzoguanamine compound, alkoxy methyl glycoluril compounds and alkoxy methyl urea compounds are transformed to alkoxy methyl respectively with the methylol of melamine methylol compound, methylol benzoguanamine compound, methylol glycoluril compounds and hydroxymethyl urea compound and obtain.There is no particular limitation to the kind of this alkoxy methyl, can be for example methoxymethyl, ethoxyl methyl, propoxy-methyl, butoxymethyl etc.Especially be that melamine derivative below 0.2% is preferred to human body, eco-friendly formalin concentration.

As these commercially available product, can list for example 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 (more than, Mitsui CyanamidCo.Ltd makes), NIKALAC Mx-750, NIKALAC Mx-032, NIKALACMx-270, NIKALAC Mx-280, NIKALAC Mx-290, NIKALACMx-706, NIKALAC Mx-708, NIKALAC Mx-40, NIKALACMx-31, NIKALAC Ms-11, NIKALAC Mw-30, NIKALACMw-30HM, NIKALAC Mw-390, NIKALAC Mw-100LM, NIKALAC Mw-750LM (more than, Sanwa Chemical Co.Ltd. makes) etc.Above-mentioned Thermocurable composition can be used alone or in combination of two or more kinds.

When using the Thermocurable composition (D) that has 2 above ring-types (sulphur) ether in the aforementioned molecule, preferably contain thermal curing catalyst.As such thermal curing catalyst, can list 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; Dyhard RU 100, benzyldimethylamine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl group-N, N-dimethyl benzyl amine, 4-methyl-N, amine compound 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 product, for example there are four countries to change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade(brand)name of imidazole compound) that industrial makes, U-CAT (registered trademark) 3503N that SAN-APRO company makes, U-CAT3502T (being the trade(brand)name of the blocked isocyanate compound of dimethyl amine), DBU, 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 thermal curing catalyst of the thermal curing catalyst of Resins, epoxy, oxetane compound, or promote the material of the reaction of epoxy group(ing) and/or oxetanyl and carboxyl to get final product, can use separately or mix more than 2 kinds and use.In addition, can also use guanamines, acetylguanamine, benzoguanamine, trimeric cyanamide, 2,4-diamino-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine isocyanuric acid affixture, 2,4-diamino-6-methacryloxyethyl-s-triazine derivatives such as s-triazine isocyanuric acid affixture preferably also is used in combination these as compound and the aforementioned hot curing catalysts that the adaptation imparting agent works.

The use level of these thermal curing catalysts for example with respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, is preferably 0.1～20 mass parts, more preferably 0.5～15.0 mass parts so long as the ratio of common amount is just enough.

As aluminium hydroxide (E), can directly use commercially available material.As commercially available product, HIGILITE series, HW, H21, H31, H32, H42M, H43M etc. for example clear and that electrician's (strain) makes are arranged.In addition, the less aluminium hydroxide of particle diameter is effective aspect folding resistance, therefore, from the flame retardant resistance of the cured film that obtains, the viewpoint of bendability, it is machined to primary particle size with dispersions such as ball mills in advance with solvent, resin, by filtrations such as filtration select more than the 3 μ m, more preferably the aluminium hydroxide more than the 1 μ m is preferred.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level of these aluminium hydroxides (E) is that the scope of 1～300 mass parts is an ideal, is preferably 1～200 mass parts, 10～150 mass parts more preferably.

As the Photoepolymerizationinitiater initiater (F) that constitutes Photocurable resin composition of the present invention, can use and be selected from the oxime ester with oxime ester base is that Photoepolymerizationinitiater initiater, alpha-aminoacetophenone are that Photoepolymerizationinitiater initiater, acylphosphine oxide are the Photoepolymerizationinitiater initiater more than a kind in the group formed of Photoepolymerizationinitiater initiater.

As the oxime ester is Photoepolymerizationinitiater initiater, as commercially available product, can list CGI-325, IRGACURE OXE01, IRGACUREOXE02 that west crust specialty goods chemical company makes, N-1919, ADEKA ARKLSNCI-831 etc. that ADEKA Corporation makes.

In addition, the Photoepolymerizationinitiater initiater that intramolecularly has 2 oxime ester bases also is to be fit to use, and particularly, can list the oxime ester compound with the carbazole structure shown in the following general formula (III).

[chemical formula 3]

(in the formula, X represents hydrogen atom, the alkyl of carbonatoms 1～17, the alkoxyl group of carbonatoms 1～8, phenyl, phenyl is (by the alkyl of carbonatoms 1～17, the alkoxyl group of carbonatoms 1～8, amino, alkylamino or dialkyl amido with alkyl of carbonatoms 1～8 replace), naphthyl is (by the alkyl of carbonatoms 1～17, the alkoxyl group of carbonatoms 1～8, amino, alkylamino or dialkyl amido with alkyl of carbonatoms 1～8 replace), Y, Z represents hydrogen atom respectively, the alkyl of carbonatoms 1～17, the alkoxyl group of carbonatoms 1～8, halogen group, phenyl is (by the alkyl of carbonatoms 1～17, the alkoxyl group of carbonatoms 1～8, amino, alkylamino or dialkyl amido with alkyl of carbonatoms 1～8 replace), naphthyl is (by the alkyl of carbonatoms 1～17, the alkoxyl group of carbonatoms 1～8, amino, alkylamino or dialkyl amido with alkyl of carbonatoms 1～8 replace), anthryl (anthryl), pyridyl, benzofuryl (benzofuryl), benzothienyl (benzothienyl), Ar represents the alkylidene group of carbonatoms 1～10, vinylidene, phenylene, diphenylene, pyridylidene (pyridylene), naphthylidene, thiophene, anthrylene (anthrylene), inferior thienyl (thienylene), furylidene (furylene), 2,5-pyrroles-two base, 4,4 '-toluylene-two base, 4,2 '-vinylbenzene-two base, n represents 0 or 1 integer.

In the aforementioned formula, especially preferredly be, X, Y are respectively methyl or ethyl, and Z is a methyl or phenyl, and n is 0, and Ar is phenylene, naphthylidene, thiophene or inferior thienyl.

As alpha-aminoacetophenone is Photoepolymerizationinitiater initiater, can list 2-methyl isophthalic acid-[4-(methylthio group) phenyl]-2-morpholino acetone-1,2-benzyl-2-dimethylamino-1-(4-morpholino phenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl particularly) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino methyl phenyl ketone etc.As commercially available product, can list the west and cling to IRGACURE 907, the IRGACURE 369 of the manufacturing of specialty goods chemical company, IRGACURE 379 etc.

As acylphosphine oxide is Photoepolymerizationinitiater initiater, can list 2,4 particularly; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4, the 6-trimethylbenzoyl) phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.As commercially available product, can list Lucirin TPO, the IRGACURE 819 that west crust specialty goods chemical company makes etc. that BASF AG makes.

In the aforesaid Photoepolymerizationinitiater initiater, acylphosphine oxide series initiators is preferably considered from the light performance of fading, and its photopermeability preferably and have a flame retardant resistance effect.In addition, the efficiency of initiator of oxime ester series initiators is good, and only with just improving light sensitivity effectively on a small quantity, therefore, the degassing during thermal treatment after epithelium against corrosion forms is few, and is effective to the warpage of reduction epithelium, is preferred.Both being used in combination is particularly preferred.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the scope that the use level of foregoing Photoepolymerizationinitiater initiater (F) is 0.01～30 mass parts, be preferably 0.5～15 mass parts is fit to.During use level less than 0.01 mass parts of Photoepolymerizationinitiater initiater (F), the light solidified deficiency on the copper is filmed and is peeled off, and coating characteristics such as chemical proofing reduce, so not preferred.On the other hand, when surpassing 30 mass parts, Photoepolymerizationinitiater initiater (F) becomes violent in the photoabsorption of welding resistance film coated surface, and so the tendency that exists the deep solidified nature to reduce is not preferred.

In addition, the oxime ester of the group shown in aforementioned for having (III) is the situation of Photoepolymerizationinitiater initiater, with respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, its use level is preferably 0.01～20 mass parts, and more preferably the scope of 0.01～5 mass parts is an ideal.

Other Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizing agent as being adapted at using in the Photocurable resin composition of the present invention can list bitter almond oil camphor compound, acetophenone compound, anthraquinone compounds, thioxanthone compound, ketal compound, benzophenone cpd, xanthone compound and tertiary amine compound etc.

If enumerate the object lesson of bitter almond oil camphor compound, for example bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether then arranged.

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

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

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

If enumerate the object lesson of ketal compound, for example methyl phenyl ketone 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, it then for example is ethanolamine compound, compound with dialkyl amido benzene structure, for example 4,4 '-dimethylamino benzophenone (the NISSOCURE MABP that Japanese Cao Da company makes), 4,4 '-diethylin benzophenone dialkyl amido benzophenone such as (EAB that Hodogaya Chemical Co.LTD. makes), 7-(diethylin)-4-methyl-2H-1-chromen-2-one (7-(diethylin)-4-methylcoumarin) etc. contains the coumarin compound of dialkyl amido, ethyl 4-dimethy laminobenzoate (KAYACUREEPA that Japanese chemical drug corporate system is made), 2-dimethylamino ethyl benzoate (the Quantacure DMB that International Bio-Synthetics company makes), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (the Quantacure BEA that International Bio-Synthetics company makes), to dimethylamino M-nitro benzoic acid isopentyl ethyl ester (the KAYACURE DMBI that Japanese chemical drug corporate system is made), 4-dimethylaminobenzoic acid-2-ethylhexyl (Esolol 507 that VanDyk company makes) and 4,4 '-diethylin benzophenone (EAB that Hodogaya Chemical Co.LTD. makes).

In the aforesaid compound, preferred thioxanthone compound and tertiary amine compound.Consider from solidified nature aspect, deep, preferably comprise the thioxanthone compound in the composition of the present invention, wherein preferred 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthone compounds such as 4-di-isopropyl thioxanthone.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level of such thioxanthone compound is preferably below 20 mass parts, and more preferably the following ratio of 10 mass parts is fit to.When the use level of thioxanthone compound is too much, cause the thick film solidified nature 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 '-diethylin 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 ultra-violet region, 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 tinting pigment self when having used tinting pigment.Consider preferred especially 7-(diethylin)-4-methyl-2H-1-chromen-2-one from sensitization effect to the laser display excellence of wavelength 400nm～410nm.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level of such tertiary amine compound is preferably 0.1～20 mass parts, more preferably the ratio of 0.1～10 mass parts.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 the photoabsorption on the surface that dry welding resistance is filmed to become violent, the tendency that exists the deep solidified nature to reduce.

Can use N-phenylglycine class known commonly used as chain-transfer agent, phenoxy acetic acids, sulfo-phenoxy acetic acids, thyroidan etc. in the Photocurable resin composition of the present invention in order to improve light sensitivity.If enumerate the object lesson of chain-transfer agent, for example then have, mercaptosuccinic acid, Thiovanic acid, thiohydracrylic acid, methionine(Met), halfcystine, thiosalicylic acid and derivative thereof etc. have the chain-transfer agent of carboxyl; Mercaptoethanol, mercaprol, Mercaptobutanol, mercapto-propanediol, sulfydryl butyleneglycol, hydroxybenzene mercaptan and derivative thereof etc. have the chain-transfer agent of hydroxyl; 1-butyl sulfhydryl, butyl-3-mercaptopropionic acid ester, methyl-3-mercaptopropionic acid ester, 2,2-(ethylidene dioxy base) diethyl mercaptan, sulfur alcohol, 4-methylbenzene mercaptan, Dodecyl Mercaptan, propylmercaptan, butyl sulfhydryl, pentan-thiol, 1-spicy thioalcohol, cyclopentyl mercaptan, cyclohexylmercaptan, thioglycerol, 4,4-thiobis benzenethiol etc.

And then, as the heterogeneous ring compound that chain-transfer agent works, can list for example sulfydryl-4-butyrolactone (another name: 2-sulfydryl-4-butyrolactone) with sulfydryl, 2-sulfydryl-4-methyl-4-butyrolactone, 2-sulfydryl-4-ethyl-4-butyrolactone, 2-sulfydryl-4-fourth mercapto lactone, 2-sulfydryl-4-butyrolactam, N-methoxyl group-2-sulfydryl-4-butyrolactam, N-oxyethyl group-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-oxyethyl group) ethyl-2-sulfydryl-4-butyrolactam, 2-sulfydryl-5-valerolactone, 2-sulfydryl-5-Valerolactim, N-methyl-2-sulfydryl-5-Valerolactim, N-ethyl-2-sulfydryl-5-Valerolactim, N-(2-methoxyl group) ethyl-2-sulfydryl-5-Valerolactim, N-(2-oxyethyl group) ethyl-2-sulfydryl-5-Valerolactim and 2-sulfydryl-6-hexanolactam etc.

As the chain-transfer agent of the development that does not damage Photocurable resin composition, promptly have a heterogeneous ring compound of sulfydryl, especially preferred mercaptobenzimidazole, 3-sulfydryl-4-methyl-4H-1,2,4-triazole, 5-methyl isophthalic acid, 3,4-thiadiazoles-2-mercaptan, 1-phenyl-5-sulfydryl-1H-tetrazolium.These chain-transfer agents can be used alone or in combination of two or more kinds.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent, sensitizing agent and chain-transfer agent can use separately or use as the mixture more than 2 kinds.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the total amount of such Photoepolymerizationinitiater initiater, light-initiated auxiliary agent, sensitizing agent and chain-transfer agent is that the following scope of 35 mass parts is preferred.When surpassing 35 mass parts, exist because the tendency that their photoabsorption causes the deep solidified nature to reduce.

The photopolymerization monomer (G) that is used for composition of the present invention is consisted of Photocurable resin composition is, makes Photocurable resin composition of the present invention insoluble or help its thawless material in alkali aqueous solution by active energy beam irradiation carrying out photocuring.As such compound, can list the diacrylate class of glycol such as ethylene glycol, methoxyl group TEG, polyoxyethylene glycol, propylene glycol; The multicomponent methacrylate class of polyvalent alcohols such as hexylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, 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 acrylate, bisphenol a diacrylate and these phenols or propylene oxide adduct etc.; The glycerol diglycidylether, glycerol triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, the multicomponent methacrylate class of glycidyl ethers such as three-glycidyl isocyanuric acid ester; And the trimeric cyanamide acrylate and/or with corresponding each methyl acrylic ester of aforesaid propylene acid esters etc.

And then the hydroxyl that can list Epocryl that the reaction of polyfunctional epoxy resin such as cresols phenolic resin varnish type epoxy resin and vinylformic acid obtains and this Epocryl and half urethanes that is formed by vulcabond such as hydroxy acrylate such as pentaerythritol triacrylate and isophorone diisocyanates react the epoxy polyurethane acrylic compound that obtains etc.Such epoxy acrylate is that resin can not reduce its touch dry ground raising light solidified.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level that has the photopolymerization monomer (G) of 2 above olefinic unsaturated groups in such molecule is below 100 mass parts, more preferably the ratio of 5～70 mass parts.During aforementioned use level less than 5 mass parts, light solidified reduces, and is difficult to develop by the postradiation alkali of active energy beam form pattern, so not preferred.On the other hand, when surpassing 100 mass parts, to the solvability reduction of alkali aqueous solution, filming becomes fragile, so not preferred.

Curable resin composition of the present invention can cooperate tinting material (H).As tinting material (H), can use known tinting materials commonly used such as red, blue, green, Huang, can be any one of pigment, dyestuff, pigment.Particularly, can list and have following color index (C.I.; The Society of Dyers and Colourists distribution) material of sequence number.Wherein, from reducing carrying capacity of environment and to the viewpoint of the influence of human body, preferably not conforming to has halogen.

Red stain:

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

Monoazo system: Pigment red 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.

Tetrazo 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: Pigment red 171, Pigment red 175, Pigment red 176, Pigment red 185, Pigment red 208.

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

Diketopyrrolopyrrolecocrystals system: Pigment red 254, Pigment red 255, Pigment red 264, Pigment red 270, Pigment red 272.

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

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

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

Blue colorant:

As blue colorant, phthalocyanine system, anthraquinone system are arranged, pigment system is the compound that is classified as pigment (Pigment), and concrete has: 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:

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:

As yellow colorants, monoazo system, tetrazo system, condensation azo system, benzimidazolone system, isoindolinone system, anthraquinone system etc. are arranged, particularly, can list following material.

Anthraquinone system: solvent yellow 16 3, Pigment Yellow 73 24, Pigment Yellow 73 108, Pigment Yellow 73 193, pigment yellow 147, Pigment Yellow 73 199, Pigment Yellow 73 202.

Isoindolinone system: Pigment Yellow 73 110, Pigment Yellow 73 109, pigment yellow 13 9, pigment yellow 17 9, Pigment Yellow 73 185.

Condensation azo system: Pigment Yellow 73 93, Pigment Yellow 73 94, Pigment Yellow 73 95, pigment Yellow 12 8, Pigment Yellow 73 155, Pigment Yellow 73 166, Pigment Yellow 73 180.

Benzimidazolone system: pigment Yellow 12 0, Pigment Yellow 73 151, pigment yellow 154, Pigment Yellow 73 156, pigment yellow 17 5, Pigment Yellow 73 181.

Monoazo system: Pigment Yellow 73 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.

Tetrazo 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. tinting material.

The words of particular instantiation, pigment violet 19 is arranged, 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.

There is no particular limitation to the cooperation ratio of foregoing tinting material (H), with respect to the aforementioned carboxy resin (A) 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 curable resin composition of the present invention etc., as required, can cooperate filler.As such filler, can use known inorganic or organic filler commonly used, except above-named aluminium hydroxide, hydrotalcite, can also use preparing spherical SiO 2, barium sulfate, silicon-dioxide, talcum, magnesium hydroxide, boehmite, aluminum oxide, titanium oxide etc., they can use separately or cooperate more than 2 kinds and use.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level of these fillers is preferably below 300 mass parts, and more preferably 0.1～300 mass parts is preferably 0.1～150 mass parts especially.When the use level of filler surpassed 300 mass parts, the viscosity that curable resin composition can take place increased, and printing reduces, and cured article becomes fragile, so not preferred.

, touch dry flexible in order to improve can use known binder polymer commonly used in the curable resin composition of the present invention.As binder polymer, the polymkeric substance of optimum fiber prime system, polyester system, phenoxy resin system.As cellulose-based polymkeric substance, can list N-BUTYL ACETATE Mierocrystalline cellulose (CAB), propyl acetate Mierocrystalline cellulose (CAP) series that Eastman company makes, as the polyester based polymer, the VYLON series that company makes is spun by preferred Japan, as the phenoxy resin based polymer, preferred dihydroxyphenyl propane, Bisphenol F and their phenoxy resin that adds hydrogen compound.With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the addition of these binder polymers is preferably below 50 mass parts, and more preferably 1～30 mass parts is preferably 5～30 mass parts especially.When the use level of binder polymer surpassed 50 mass parts, the alkali-developable of curable resin composition was poor, and shorten the working life that can develop, so not preferred.

In order to improve the adaptation of interlayer, perhaps improve the adaptation of photo-sensitive resin and base material, can use driving fit promotor in the curable resin composition of the present invention.If enumerate concrete example, benzoglyoxaline, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole, morpholinyl methyl isophthalic acid-phenyl-triazole-2-thioketones, 5-amino-morpholinyl methylthiazol-2-thioketones, 2-sulfydryl-5-methylthio group-thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole are for example then arranged, contain amino benzotriazole, silane coupling agent etc.

Usually, the oxidation Once you begin of most of macromolecular materials, oxidative degradation then constantly takes place continuously, cause the function of macromolecular material to reduce, therefore, can add (1) that is used for anti-oxidation in the curable resin composition of the present invention makes the radical scavenger of free radical ineffective treatment of generation or/and (2) are harmless material and the antioxidants such as peroxide decomposer that do not produce new free radical with the peroxide breakdown that produces.

The particular compound of the antioxidant that works as radical scavenger, can enumerate Resorcinol, the 4-tert-butyl catechol, the 2-Tert. Butyl Hydroquinone, the hydroquinone monomethyl ether, 2,6-di-t-butyl-p-cresol, 2,2-methylene radical-two (4-methyl-6-tert butyl phenol), 1,1,3-three (2-methyl-4-hydroxyl-5-tert-butyl-phenyl) butane, 1,3,5-trimethylammonium-2,4,6-three (3, the 5-di-tert-butyl-4-hydroxyl benzyl) benzene, 1,3,5-three (3 ', 5 '-di-tert-butyl-4-hydroxyl benzyl)-guanamine, 4,6-(1H, 3H, 5H) phenol such as triketone system; Quinone based compounds such as methyl naphthoquinone (menaquinone), benzoquinones; Amine compounds such as two (2,2,6,6-tetramethyl--4-piperidyl)-sebacates, thiodiphenylamine etc.

Radical scavenger can use commercially available material, can list for example ADKSTAB AO-30, ADK STAB AO-330, ADK STAB AO-20, ADKSTAB LA-77, ADK STAB LA-57, ADK STAB LA-67, ADK STABLA-68, ADK STAB LA-87 (more than, rising sun electrification company makes, trade(brand)name), IRGANOX 1010, IRGANOX 1035, IRGANOX 1076, IRGANOX1135, TINUVIN 111FDL, TINUVIN 123, TINUVIN 144, TINUVIN 152, TINUVIN 292, TINUVIN 5100 (more than, west crust specialty goods chemical company makes trade(brand)name) etc.

The particular compound of the antioxidant that works as peroxide decomposer, can list chalcogenide compounds such as phosphorus series compound, tetramethylolmethane four lauryl thiopropionates, dilauryl thiodipropionate, distearyl 3,3 '-thiodipropionate such as triphenylphosphate etc.

Peroxide decomposer can use commercially available material, can list for example ADKSTAB TPP (rising sun electrification company makes trade(brand)name), MARKAO-412S (ADEKAARGUS CHEMICAL CO., LTD manufacturing, trade(brand)name), SumilizerTPS (sumitomo chemical company manufacturing, trade(brand)name) etc.

Above-mentioned antioxidant can be used singly or in combination of two or more thereof.

In addition, therefore macromolecular material, makes it to ultraviolet stabilization in order to take measures owing to absorb light takes place to decompose and deterioration usually, except use above-mentioned antioxidant in curable resin composition of the present invention, can also use UV light absorber.

As UV light absorber, can list benzophenone derivates, benzoate derivatives, benzotriazole derivatives, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate derivative, cinnamyl o-aminobenzoate derivative, dibenzoylmethane derivative etc.As the object lesson of benzophenone derivates, can list 2-hydroxyl-4-methoxy benzophenone, Octabenzone, 2,2 '-dihydroxyl-4-methoxy benzophenone and 2,4 dihydroxyl benzophenone etc.Object lesson as benzoate derivatives, can list 2-Ethylhexyl salicylate, phenyl salicylic acid esters, to tert-butyl-phenyl salicylate, 2,4-di-tert-butyl-phenyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoic acid ester etc.Object lesson as benzotriazole derivatives, can list 2-(2 '-hydroxyl-5 '-tert-butyl-phenyl) benzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole, 2-(2 '-hydroxyl-the 3 '-tertiary butyl-5 '-aminomethyl phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-3 ', 5 '-di-tert-butyl-phenyl)-5-chlorobenzotriazole, 2-(2 '-hydroxyl-5 '-aminomethyl phenyl) benzotriazole and 2-(2 '-hydroxyl-3 ', 5 '-di-tert-pentyl-phenyl) benzotriazole etc.As the object lesson of pyrrolotriazine derivatives, can list hydroxyphenyltriazinuv, two ethyl hexyl oxy phenol p-methoxy-phenyl triazines etc.

As UV light absorber, can use commercially available material, for example can list TINUVIN PS, TINUVIN 99-2, TINUVIN 109, TINUVIN 384-2, TINUVIN 900, TINUVIN 928, TINUVIN 1130, TINUVIN 400, TINUVIN 405, TINUVIN 460, TINUVIN 479 (more than, west crust specialty goods chemical company makes trade(brand)name) etc.

Above-mentioned UV light absorber can be used a kind or make up more than 2 kinds and to use separately, by using with aforementioned antioxidant combination, can realize the stabilization of the shaping thing that obtained by curable resin composition of the present invention.

And then, for synthetic above-mentioned carboxy resin (A), the modulation group compound of containing, perhaps for the viscosity adjustment in case be applied to substrate or carrier film on, curable resin composition of the present invention can be with an organic solvent.

As such organic solvent, can list ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.More specifically, ketones such as methylethylketone, pimelinketone are arranged; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; Cellosolve, methylcyclohexane, ethylene glycol butyl ether; Glycol ethers such as Trivalin SF, methyl carbitol, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol diethyl ether, Triethylene glycol ethyl ether; Ester classes such as ethyl acetate, butylacetate, dipropylene glycol methyl ether acetic ester, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic ester, propylene glycol butyl ether acetic ester; Alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; Aliphatic hydrocarbon such as octane, decane; Oil series solvents such as sherwood oil, petroleum naphtha, hydrogenated naphtha, solvent naphtha etc.Such organic solvent can use separately or use as the mixture more than 2 kinds.

As required, curable resin composition of the present invention can further cooperate known tackifier commonly used such as known hot stopper commonly used, fine particle silica, organobentonite, polynite, defoamer and/or flow agents such as silicone-based, fluorine system, macromolecular, silane coupling agents such as imidazoles system, thiazole system, triazole system, antioxidant, the additive kind known commonly used that rust-preventive agent etc. are such.

The aforementioned hot stopper can be used to prevent aforementioned polymerizable compound thermopolymerization or through the time polymerization.As hot stopper, can list for example 4-methoxyphenol, quinhydrones, the quinhydrones that alkyl or aryl replaces, tert-butyl catechol, pyrogallol, the 2-dihydroxy benaophenonel, 4-methoxyl group-2-dihydroxy benaophenonel, protochloride ketone, thiodiphenylamine, chloranil, naphthylamines, 2-Naphthol, 2,6-di-t-butyl-4-cresols, 2,2 '-methylene-bis (4-methyl-6-tert butyl phenol), pyridine, oil of mirbane, dinitrobenzene, picric acid, the 4-Tolylamine, methylene blue, the reactant of copper and organic sequestering agent, wintergreen oil and thiodiphenylamine, nitroso compound, the inner complex of nitroso compound and Al etc.

Curable resin composition of the present invention can be the form of dry film, wherein dry film possess carrier film (supporter) and be formed on this carrier film by above-mentioned curable resin composition form the layer.

During dry film, with curable resin composition of the present invention with aforementioned organic solvent diluting to adjust to suitable viscosity, by comma coating machine (comma coater), knife coater, lip coating machine (lip coater), rod is coated with machine (rod coater), extrusion coating machine (squeeze coater), contrary formula coating machine (reverse caoter), transmit roller coating machine (transfer roll cater), photogravure coating machine (gravure coater), spraying machines etc. are coated with into homogeneous thickness on carrier film, usually, drying can obtain film in 1～30 minute under 50～130 ℃ temperature.There is no particular limitation to coating film thickness, and usually, dried thickness is at 10～150 μ m, preferably suitably select in the scope of 20～60 μ m.

As carrier film, can use plastics film, preferably use the plastics film such as polyester film, Kapton, polyamidoimide film, polypropylene film, polystyrene film of polyethylene terephthalate etc.There is no particular limitation to the thickness of carrier film, suitably selects in the scope of 10～150 μ m usually.

After film forming on the carrier film, further,, it is desirable at the strippable mulch film of the surface laminated of film for the surface attachment dust that prevents film etc.

As strippable mulch film, can use polyethylene film for example, polytetrafluoroethylene film, polypropylene film, surface-treated paper etc., as long as film is littler than the bounding force of film and mulch film with the bounding force of carrier film when peeling off mulch film.

Curable resin composition use-case of the present invention organic solvent is as described above adjusted to the viscosity that is fit to coating process, utilize methods such as dip coating, flow coat method, rolling method, scraper coating method, silk screen print method, curtain Tu Fa to be applied on the base material, 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, and this film rolled when forming dry film, fit on the base material making under cured resin composition layer and the mode that base material contacts by laminating machine etc., peel off carrier film then, can form resin insulating barrier.

In the situation that is Photocurable resin composition, adopt contact (or noncontact mode) to make active energy beam by forming figuratum photomask and optionally expose or utilizing the direct exposure machine of laser directly to carry out pattern exposure thereafter, with unexposed development, can form corrosion-resisting pattern by dilute alkaline aqueous solution (for example 0.3～3wt% aqueous sodium carbonate).And then, under for the situation of composition that contains Thermocurable composition (D), make its thermofixation by for example being heated to about 140～180 ℃ temperature, Thermocurable composition (D) reaction that has 2 above ring-type ethers and/or cyclic thioether base in aforementioned carboxyl that contains carboxy resin (A) and the molecule can form the cured coating film of each excellent such as thermotolerance, chemical proofing, anti-water absorbability, adaptation, electrical characteristic.In addition, even under the situation that does not contain Thermocurable composition (D), also can make when exposing with the residual ethylenic unsaturated bond generation hot radical polymerization of unreacted state by thermal treatment, coating characteristic improves, and therefore also can heat-treat (thermofixation) according to purpose and purposes.

As above-mentioned base material, except the printed circuit board (PCB) that is pre-formed circuit, flexible printed circuit board, can adopt high frequency circuit with the copper clad laminate of all grades (FR-4 etc.) of copper clad laminate etc., other Kapton, PET film, glass substrate, ceramic substrate, wafer board etc., wherein aforementioned copper clad laminate uses phenol paper, epoxy paper, epoxy glass fabric, glass polyimide, material such as woven fiber glass/epoxy non-woven fabrics, woven fiber glass/epoxy paper, synthon epoxy, fluorine polyethylene PPO cyanate and obtaining.

Be coated with the volatile dry that carries out behind the curable resin composition of the present invention and can use heated air circulation type drying oven, IR stove, hot plate, convection oven etc. (use has the device of the thermal source of the air heating mode of utilizing steam, makes the method for the hot air convection contact in the drying machine and the mode of blowing supporter by nozzle).

Under the situation that is Photocurable resin composition, will and make expose (irradiation of active energy beam) of filming that obtains after the solvent evaporates drying by coating, make exposure portion (part of being shone by active energy beam) solidify.

As the used exposure machine of above-mentioned active energy beam irradiation, so long as the ultraviolet device that is equipped with high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, mercury short arc lamp etc. and shines 350～450nm scope gets final product, and then, also can be to use direct drawing apparatus (for example utilizing the laser direct imaging device of the direct rendering image of laser) by cad data from computer.As the laser source of directly retouching machine, be the laser of the scope of 350～410nm as long as use maximum wavelength, can be any of gas laser, Solid State Laser.Be used for exposure that image forms according to thickness etc. and different, be generally 20～800mJ/cm ², be preferably 20～600mJ/cm ²Scope in.

As aforementioned developing method, can use pickling process, drip-rinsing process, gunite, spread coating etc., as developing solution, can use the alkali aqueous solution of potassium hydroxide, sodium hydroxide, yellow soda ash, salt of wormwood, sodium phosphate, water glass, ammonia, amine etc.

Embodiment

Below, embodiment is shown and comparative example describes particularly to the present invention, but the present invention is not subjected to the qualification of following embodiment.In addition, following " part " and " % " if there is no particular limitation, are meant quality criteria.

Synthesis example 1

(A-1) be equivalent to the synthetic of the aforementioned resin that contains carboxy resin (2):

In the reaction vessel that possesses whipping appts, thermometer, condenser, drop into 3600g (4.5 moles) as have 2 above alcohol hydroxyl groups compound by 1,5-pentanediol and 1,6-hexylene glycol deutero-PCDL (Asahi KaseiChemicals Corporation makes, TJ5650J, number-average molecular weight 800), 814g (5.5 moles) dimethylolpropionic acid and 118g (1.6 moles) adjust the propyl carbinol of agent (reaction terminating agent) as molecular weight.Then, drop into 2009g (10.8 moles) as the trimethyl hexamethylene diisocyanate that does not have the isocyanate compound of aromatic nucleus, stop after being heated to 60 ℃ while stirring, when beginning to reduce, the temperature in reaction vessel heats once more, continue to stir at 80 ℃, confirm the absorption spectrum (2280cm of isocyanate group by infrared absorption spectrum ^-1) after the disappearance, finish reaction.Then, adding the Trivalin SF acetic ester, to make solids component be 60wt%, obtain containing thinner thick liquid contain carboxy resin.The acid number of the solids component that contains carboxyl urethane that obtains is 49.8mgKOH/g.

Synthesis example 2

(A-2) be equivalent to the synthetic of the aforementioned resin that contains carboxy resin (5):

In the reaction vessel that possesses whipping appts, thermometer, condenser, drop into 2400g (3 moles) by 1,5-pentanediol and 1,6-hexylene glycol deutero-PCDL (Asahi Kasei Chemicals Corporation makes, TJ5650J, number-average molecular weight 800), 603g (4.5 moles) dimethylol propionic acid and 238g (2.6 moles) are as the vinylformic acid 2-hydroxyl ethyl ester of monohydroxy compound.Then, drop into the isophorone diisocyanate of 1887g (8.5 moles) as polyisocyanates, stop after being heated to 60 ℃ while stirring, when beginning to reduce, the temperature in reaction vessel heats once more, continue to stir at 80 ℃, confirm the absorption spectrum (2280cm of isocyanate group by infrared absorption spectrum ^-1) after the disappearance, finish reaction.Then, add the Trivalin SF acetic ester and make that solids component is 50 quality %.The acid number of the solids component that contains carboxy resin that obtains is 50mgKOH/g.

Synthesis example 3

(A-3) be equivalent to the synthetic of the aforementioned resin that contains carboxy resin (4):

In removable flask, add RE310S (the 2 officials energy bisphenol A type epoxy resin that 368.0g Japan's chemical drug (strain) is made, 72.06), 2.94g is as 2 of hot stopper epoxy equivalent (weight): the 184g/ equivalent) as bisphenol type epoxy compound, 142.7g vinylformic acid (molecular weight:, 6-di-t-butyl-p-cresol and 1.53g react as the triphenylphosphine of catalysts, acid number until reaction solution under 98 ℃ temperature is below the 0.5mgKOH/g, obtains epoxy carbonate (a) (theoretical molecular: 510.7).Then, in this reaction solution, add the Trivalin SF acetic ester of 588.2g, add 105.5g dimethylol propionic acid (b) (molecular weight: 134.16), be warmed up to 45 ℃ as reaction solvent.In this solution, slowly splash into 264.7g isophorone diisocyanate (c) (molecular weight: 222.28), make temperature of reaction be no more than 65 ℃.After dripping end, temperature is increased to 80 ℃, makes its reaction 6 hours, until recording 2250cm by the infrared absorption spectrum assay method ^-1Near absorption disappears, and then reaction is 2 hours under 98 ℃ temperature, obtains comprising the resin solution of 60 weight % aqueous alkaline solution-soluble urethane resins.Measure acid number, be 28.9mgKOH/g (solids component acid number: 48.1mgKOH/g).

(A-4) be equivalent to the aforementioned resin that contains carboxy resin (7):

Use with aforementioned contain carboxy resin (7) suitable, contain the photosensitivity group and used the multi-functional epoxy's of xenol Novolac structure photosensitivity to contain carboxy resin [Japanese chemical drug (strain) is made ZCR-1601H (solids component 65%, the acid number of resin are 98mgKOH/g)].

The preparation of aluminium hydroxide slurry:

700g aluminium hydroxide (clear make with electrician's (strain) HIGILITE42M) and 280g are mixed stirring as Trivalin SF acetic ester, the 20g BYK-110 of solvent, use the zirconium oxide bead of 0.5 μ m to carry out dispersion treatment by ball mill.After repeating this operation 3 times,, make aluminium hydroxide slurry (E-1) by the strainer of 3 μ m.

The preparation of silica slurry:

700g preparing spherical SiO 2 (Admatechs company make SO-E2), 295g mixed as the vinyl silicane coupling agent of silane coupling agent as the Trivalin SF acetic ester of solvent, 5g stir, the material that obtains and above-mentionedly similarly carry out dispersion treatment with ball mill.After repeating this operation 3 times, the strainer by 3 μ m filters then, makes silica slurry.

Embodiment 1～9, comparative example 1,2

The resin solution that uses above-mentioned synthesis example cooperates according to the ratio (mass parts) shown in various compositions shown in the table 1 and the table 1, carries out pre-mixing by stirrer, carries out mixingly then with 3 roll-type roller mills, prepares curable resin composition.At this, measure granularity with the particle size analyzer (grind meter) that ERICHSEN company makes, estimate the dispersity of the curable resin composition of gained, be below the 15 μ m.

[table 1]

Performance evaluation:

Optimum exposure

With copper thick be that the circuit pattern substrate of 35 μ m grinds with polishing roll, then after washing, the drying, by the light solidifying/heat solidifying resin composition of silk screen print method whole coating previous embodiment 2～9 and comparative example 1,2, drying is 30 minutes in 80 ℃ heated air circulation type drying oven.After the drying, use the exposure apparatus (HMW-680-GW20 that ORC MANUFACTURING Co.Ltd makes) that is equipped with metal halide lamp to expose by stage phototimer (KodakNo.2), will develop (30 ℃, 0.2MPa, 1wt%Na ₂CO ₃Exposure when the aqueous solution) pattern of residual stage phototimer is 6 sections during 90 seconds is as optimum exposure.

Testing of characteristic:

At the composition that forms on the figuratum Kapton substrate whole coating the various embodiments described above 1～9 and comparative example 1,2,, naturally cool to room temperature by silk screen printing 80 ℃ of dryings 30 minutes.For the hot curing resin composition of embodiment 1, the substrate heating under 150 ℃ that obtains was made its curing in 60 minutes.Light solidifying/heat solidifying resin composition for embodiment 2～9 and comparative example 1,2, the exposure apparatus (HMW-680-GW20) that use is equipped with metal halide lamp exposes to the soldering-resistant pattern on the substrate that obtains with optimum exposure, with 30 ℃ 1wt%Na ₂CO ₃The aqueous solution developed for 90 seconds under the condition of spray pressure 0.2MPa, obtained corrosion-resisting pattern.The heating under 150 ℃ of this substrate was cured in 60 minutes.The printed base plate (evaluation substrate) that obtains is carried out following evaluating characteristics.

Solder heat resistance

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 as follows.

Zero: carry out flooding 1 time 10 second, can't see and peel off.

△: carry out flooding 1 time 5 second, can't see and peel off.

*: carry out flooding 1 time 5 second, resist layer has expansion, peels off.

Chemical gilding patience

Use commercially available product electroless nickel bath and chemical gilding to bathe, carry out plating under the condition of nickel 3 μ m, golden 0.03 μ m, band is peeled off the back and is had or not the infiltration of peeling off and having or not plating by the visual valuation resist layer.Judgment standard is as follows.

Zero: can't see infiltration, 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.

Low warpage properties

Will be with Kapton200H (DU PONT-TORAY CO., LTD. the Kapton of Zhi Zaoing, thickness 25 μ m) the curing tunicle that replaces above-mentioned Kapton substrate to make is cut to 50 * 50mm size, measures the warpage at 4 angles, obtain its mean value, estimate according to following benchmark.

Zero: the not enough 1mm of warpage

△: warpage is the above and not enough 4mm of 1mm

*: warpage is more than the 4mm

Electrical characteristic

Use the comb-type electrode pattern of the line/space=50/50 μ m of circuit pattern, under above-mentioned condition, make and estimate substrate, under 110 ℃, the heating and moistening condition of 85%R.H., this comb-type electrode is applied the bias voltage of DC50V, confirm having or not of migration after 200 hours.Determinating reference is as follows.

Zero: can't see any variation

△: slight variations is arranged

*: move

Flame retardant resistance

The Kapton (Kapton50H) thick with the thick Kapton of 50 μ m (Kapton 200H), Kapton (Kapton 100H) that 25 μ m are thick and 12.5 μ m replaces above-mentioned Kapton substrate, by the composition of silk screen printing each embodiment of whole coating and comparative example, after under 80 ℃ dry 20 minutes, naturally cool to room temperature thereon.And then, similarly whole coating carried out at its back side by silk screen printing, after under 80 ℃ dry 20 minutes, naturally cool to room temperature, obtain the two sided coatings substrate.For the hot curing resin composition of embodiment 1, the two sided coatings substrate heating under 150 ℃ that obtains was cured in 60 minutes.Light solidifying/heat solidifying resin composition for embodiment 2～9 and comparative example 1,2, the exposure apparatus (HMW-680-GW20) that use is equipped with metal halide lamp carries out whole exposure with optimum exposure to the solder resist of the two sided coatings substrate that obtains, with 30 ℃ 1wt%Na ₂CO ₃The aqueous solution developed for 90 seconds under the condition of spray pressure 0.2MPa, 150 ℃ of following thermofixations 60 minutes, as assess sample.For this flame retardant resistance evaluation sample, carry out the thin material testing vertical flammability according to the UL94 specification.Be shown VTM-0 or VTM-1 based on the UL94 specification table during evaluation.

The result of aforementioned each evaluation test gathers at table 2 and illustrates.

[table 2]

Embodiment 10～15

Mismatch the silicone-based defoamer, other uses the preparation of compositions flame retardant photocurable resin composition shown in the embodiment 2,3,6～9 shown in the table 1, with methylethylketone it is diluted, be applied on the carrier film then, heat drying, forming thickness is the photosensitive polymer combination layer of 20 μ m, and the mulch film of fitting thereon obtains dry film.Afterwards, peel off mulch film, use laminating machine will form figuratum copper clad laminate and film adhered.The exposure apparatus (HMW-680-GW20) that use is equipped with metal halide lamp exposes with the soldering-resistant pattern of optimum exposure to this substrate, peels off carrier film then, with 30 ℃ 1%Na ₂CO ₃The aqueous solution carried out for 90 seconds and develops under the condition of spray pressure 0.2MPa, obtain corrosion-resisting pattern.Afterwards, heating was cured in 60 minutes in 150 ℃ hot-air drier, made the test substrate.For the test substrate that obtains, carry out the evaluation test of each characteristic by as hereinbefore test method and evaluation method with cured film.

The result of aforementioned each evaluation test gathers in table 3 and illustrates.

[table 3]

Claims (12)

1. a curable resin composition is characterized in that, it contains (A) and contains carboxy resin, (B) P contained compound and (C) the multiple oxyhydroxide of stratiform.

2. curable resin composition according to claim 1 is characterized in that, it further contains the Thermocurable composition that has 2 above ring-type ethers and/or cyclic thioether base in (D) molecule.

3. curable resin composition according to claim 1 is characterized in that, it further contains (E) aluminium hydroxide.

4. curable resin composition according to claim 1 is characterized in that, it further contains (F) Photoepolymerizationinitiater initiater and (G) photopolymerization monomer.

5. curable resin composition according to claim 1 is characterized in that, the described carboxy resin (A) that contains is the carboxy resin that contains with carboxylamine ester structure.

6. curable resin composition according to claim 1 is characterized in that, the described carboxy resin (A) that contains has xenol Novolac structure and olefinic unsaturated group.

7. curable resin composition according to claim 1 is characterized in that, layered multiple oxyhydroxide (C) is the represented compound of following general structural formula (II),

[M _1-X ²⁺M _X ³⁺(OH) ₂][A _X/n ^n-·mH ₂O] (II)

In the formula, M ²⁺The metallic cation of expression divalent, M ³⁺The metallic cation of representing 3 valencys, A ^N-The negatively charged ion of expression n valency, the subscript of each element and each atomic group is represented the ratio of each element and each atomic group, X is 0＜X≤0.33, m 〉=0.

8. curable resin composition according to claim 2 is characterized in that, the Thermocurable composition (D) that has 2 above ring-type ethers and/or cyclic thioether base in the described molecule is the Resins, epoxy with xenol Novolac skeleton.

9. according to each described curable resin composition of claim 1～8, it is characterized in that it is used to form solder resist.

10. dry film, it is applied on the film by each the described curable resin composition with claim 1～8 and drying forms.

11. a cured article, it carries out thermofixation by the dry coating that each the described curable resin composition with claim 1～8 is applied on the base material and drying obtains and/or photocuring obtains; Perhaps, by the dry coating that described curable resin composition is applied on the film and the dry dry film lamination that forms obtains to the base material being carried out thermofixation and/or photocuring obtains.

12. a printed circuit board (PCB), it has the described cured article of aforementioned claim 11.