CN101845219B - Curable resin composition, dry membrane and printed circuit board using same - Google Patents

Abstract

The invention provides a curable resin composition, dry membrane and printed circuit board using the same, more particularly, the invention provide a curable resin composition and a dry membrane, as well as a printed circuit board formed by a flame-resistant curable membrane such as a solder resisting membrane and the like formed by using the same, wherein, the curable resin composition has a halogen-free flame retardant, and can form a solder resisting layer with low warpage and excellent flame resistance and bending. The curable resin composition contains (A) carboxyl-contained resin, (B) aluminium hydroxide and (C) spherical silica a thermocuring resin composition comprises the above (A), (B) and (C), and (D) a thermocuring component with more than two ring-shaped ether group and/or ring-shaped sulfide group, and a photocuring thermocuring resin composition comprises the above (A), (B), (C) and (D), and (F) a photopolymerisable initiator and (G) a photopolymerisable monomer, preferably contains (E) a phosphorus-containing compound.

Description

Curable resin composition, the dry film that uses it and printed substrate

Technical field

The present invention relates to curable resin composition, relate in particular to the curable resin composition that can form the excellent solder resist of low warpage and flame retardant resistance and toughness.The invention still further relates to the dry film of use curable resin composition and the printed substrate of flame retardant resistance.

Background technology

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

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 and has used the flame retardant resistance photosensitive polymer combination, and it contains the photopolymerizable 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 the P contained compound of 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, the solder resist that the phthalocyanine blue of using halogen atom-containing not and yellow colorants replace green colourant chlorination phthalocyanine green in the past is universal (for example, with reference to patent documentation 2).In addition, owing to advocate clear and definite in appearance Halogen, therefore, also the someone adopts the solder resist of the blueness of direct use phthalocyanine blue.But though the formation of solder resist is the protection that is used for copper circuit, its another effect is be difficult for coming to light (opacifying powers) such as the wounds, dirt on the heat that makes copper circuit, moisture, electric caused variable color, the copper circuit.For this point, usually solder resist is added tinting material, make its concentration make the bad difficult quilt of outward appearance see greatly.Yet, compare with the green of phthalocyanine green, the opacifying power of blue resistance weldering China ink, the green resistance weldering 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 photocuring or the thermofixation of solder resist because of cure shrinkage problem.

Known white lake is flame retardant filler, if join in the resin combination, adds manyly more, and its compsn has flame retardant resistance more.Yet being shaped as of white lake is unsetting, and it is the crackle of starting point that there is the interface that produces with white lake and resin in excessive interpolation, has the crooked patience of cured film to reduce such problem.Therefore, in requiring the use in printed circuit board solder resist of toughness, especially the FPC substrate with solder resist in, its addition is restricted.

In addition, as the method for the crackle that prevents organism and inorganics interface, the known method that the inorganic particle of raising as filler arranged organic affinity all the time, is carried out silane coupling agent processing, titanic acid ester and aluminum chelate processing etc.Yet present situation is that these methods that improve affinity do not have effect basically to white lake, the effect of the cured film bending that can not improve basically.

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 for the prior art problems that solves aforementioned that kind; Its main purpose is; A kind of curable resin composition that contains halogen-free flame retardants is provided, and said curable resin composition can form the solder mask with low warpage, resistance to bend(ing).

And then, the objective of the invention is to, through using said curable resin composition, excellent dry film of low warpage and flame retardant resistance and toughness and the printed substrate with flame retardant resistance epithelium of such excellent specific property are provided.

The scheme that is used to deal with problems

In order to realize aforementioned purpose, the present invention provides a kind of curable resin composition, it is characterized in that, it contains (A) and contains carboxy resin, (B) white lake and (C) preparing spherical SiO 2.

In a scheme, except aforementioned each the 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 version, also contain (E) P contained compound.In other scheme, also contain (F) Photoepolymerizationinitiater initiater and (G) photopolymerization monomer, can become light solidifying/heat solidifying resin composition thus.In other preferred version, 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 epoxy resin with xenol Novolac skeleton.Such curable resin composition is adapted at using in the formation of solder resist of printed substrate.

In addition, the present invention also provides 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 substrate with aforementioned cured article.

The invention effect

Curable resin composition of the present invention contains (A) and contains carboxy resin and (B) white lake and (C) preparing spherical SiO 2; Preferably also contain (E) P contained compound, can form thus that Halogen is formed and environmental pressure is little, flame retardant resistance and low warpage, the excellent epithelium of toughness.Therefore, the curable resin composition of the application of the invention, the printed substrate that the excellent dry film of low warpage and flame retardant resistance and toughness can be provided and have the flame retardant resistance resistance weldering epithelium of such excellent specific property.

Embodiment

In order to solve aforementioned problems; The inventor etc. further investigate; The result finds; Cooperate with white lake (B) through containing carboxy resin (A) and preparing spherical SiO 2 (C), can keep the flame retardant resistance of curable resin composition, and can improve crooked patience as flame retardant filler.Especially, because therefore the face that preparing spherical SiO 2 does not have the starting point of the crackle that becomes cured film, itself just has the surprising effect that improves crooked patience.And then, very effective with the surface treatment of silane coupling agent etc. to silicon-dioxide, can significantly improve crooked patience.Such effect is complete unexpected surprising effect.

Below, each constituent of curable resin composition of the present invention is carried out detailed explanation.

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 property 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 compsn, need with after have 2 above olefinic unsaturated groups in the molecule stated photopolymerization monomer (G) combination use.

As the object lesson that contains carboxy resin (A), the compound of that kind 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 through unsaturated carboxylic acids such as (methyl) vinylformic acid and vinylbenzene, alpha-methyl styrene, low alkyl group (methyl) propenoate, 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 divalent alcohol; Have phenol property 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 divalent alcohol, polyaddition reaction with diatomic alcohol compounds such as compound of phenol property hydroxyl and alcohol hydroxyl group obtains urethane resin through diisocyanate cpd such as aliphatic diisocyanate, side chain aliphatic diisocyanate, ester ring type vulcabond, aromatic diisocyanate and polycarbonate-based polyvalent alcohol, polyethers, it is terminal obtain with anhydride reaction contain the terminal carboxyl(group) urethane resin.

(4) through 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 epoxy resin the photosensitivity that obtains of the polyaddition reaction of (methyl) propenoate or the anhydride modified thing of its part, carboxylic diol compound and diatomic alcohol compounds contain the carboxyl urethane resin.

(5) through 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 NCO in the reaction with same mole thing equimolecular through 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 through stating such multifunctional (solid-state) epoxy resin and the reaction of (methyl) vinylformic acid after making, 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 through can (solid-state) epoxy resin with 2 officials, the hydroxyl of generation and 2 yuan of acid anhydrides additions and the photosensitivity that obtains contains carboxy resin.

(9) can react by oxetane resin the primary hydroxyl of generation and 2 yuan of acid anhydrides additions and obtain contain carboxyl polyester resin with dicarboxylicacid through stating 2 such officials after making.

(10) resin of above-mentioned through 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 NCO of the composition with NCO (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, Bisphenol F structure, xenol structure, xenol Novolac structure, bis-xylene phenol structure, especially have the compound and the hydrogenated compound thereof of xenol Novolac structure, be preferred from low warpage, crooked patience aspect.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) (9) resin in addition, therefore, photoreactivity is high, is preferred.

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

The carboxy resin (A) that contains of aforementioned that kind 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, further is preferably 40～200mgKOH/g, and the scope that is preferably 45～120mgKOH/g especially is an ideal.From the viewpoint of alkali-developable, contain the not enough 30mgKOH/g of acid number of carboxy resin, then be difficult to alkali and develop; On the other hand, surpass 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, when developing, produces the film wearing and tearing, the remarkable variation of resolving power.On the other hand, weight-average molecular weight surpasses at 150000 o'clock, the remarkable variation of development property takes place sometimes, the package stability variation.

The use level that contains carboxy resin (A) of aforementioned that kind be in all compsns 5～60 quality %, be preferably 10～60 quality %, further be 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 compsn uprises, and so reductions such as coating are not preferred.

As white lake (B), can directly use commercially available material.As commercially available article, the HIGILITE series, HW, H21, H31, H32, H42M, H43M of for example clear and electrician's manufactured etc. are arranged.In addition; The less white lake of particle diameter is effective aspect folding resistance; Therefore; From the flame retardant resistance of the cured film that obtains, the viewpoint of toughness, reinstate dispersion such as ball mill in advance with solvent, resin one and be machined to primary particle size, through filtrations such as filtration select more than the 3 μ m, the white lake that further is preferably 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 white lakes (B) is that the scope of 1～200 mass parts is an ideal, is preferably 1～150 mass parts, further is preferably 10～100 mass parts.

It is the commercially available preparing spherical SiO 2 of 0.25 μ m, 0.5 μ m, 1 μ m, 1.5 μ m, 2 μ m, 3 μ m, 5 μ m etc. that preparing spherical SiO 2 (C) can directly use median size.As commercially available article, the SO series that has Admatech company to make.In addition; Also can in being combined with the compsn of this preparing spherical SiO 2, directly cooperate silane coupling agent etc.; From the viewpoint of toughness, it is preferred using following particle: at first, with ball mill etc. solvent, silane coupling agent and preparing spherical SiO 2 are carried out surface treatment; Make silane coupling agent disperse equably, remove by filter the particle more than the 5 μ m through filtering to wait again at silica sphere.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level of these preparing spherical SiO 2s (C) is that the scope of 1～200 mass parts is an ideal, is preferably 1～150 mass parts, further is preferably 5～100 mass parts.

In order compsn of the present invention to be consisted of the Thermocurable composition (D) that hot curing resin composition uses to improve characteristic such as thermotolerance, insulating reliability; 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; Viewpoint from thermotolerance, gold-plated patience; The above epoxy resin of 2 functionalities is preferred, and the epoxy resin with xenol Novolac skeleton can improve thermotolerance, gold-plated patience, flame retardant resistance, so preferred especially.As epoxy resin, can enumerate out NC-3000L that for example Japanese chemical drug (strain) makes, NC-3000, NC-3000H, NC-3100 etc. with xenol Novolac skeleton.

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 the compound that has any or 2 kinds of groups of 2 above triatomic rings, tetra-atomic ring or pentacyclic ring-type ether or cyclic thioether base in the molecule, can enumerate out the compound that has 2 above epoxy group(ing) in the molecule for example and be the compound that has 2 above oxetanyls in multi-functional epoxy compound (D-1), the molecule and be the compound that has 2 above thioether groups in multifunctional oxetane compound (D-2), the molecule is episulfide resin (D-3) etc.

As aforementioned multi-functional epoxy compound (D-1); For example can enumerate out; Bisphenol A type epoxy resin; Like Japan Epoxy Resins Co.; Ltd. Epiclon840, Epiclon850, Epiclon1050, Epiclon2055 that the jER828 that makes, jER834, jER1001, jER1004, DIC Corporation make; Dongdu changes into EpototeYD-011, YD-013, YD-127, the YD-128 of manufactured, D.E.R.317, D.E.R.331, D.E.R.661, D.E.R.664 that Dow ChemicalCompany makes, Araldite6071, Araldite6084, AralditeGY250, AralditeGY260 that west crust specialty goods chemical company makes; SumiepoxyESA-011, ESA-014, ELA-115, ELA-128 that Sumitomo Chemical Co. Ltd. makes, (being trade(brand)name) such as the A.E.R.330 that industrial of Asahi Chemical Industry makes, A.E.R.331, A.E.R.661, A.E.R.664; Brominated epoxy resin; Like Japan Epoxy Resins Co.; Ltd. the jER YL903 that makes, Epiclon152, Epiclon165 that DIC Corporation makes, Dongdu changes into EpototeYDB-400, the YDB-500 of manufactured; The D.E.R.542 that Dow Chemical Company makes; The Araldite8011 that west crust specialty goods chemical company makes, SumiepoxyESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. makes, (being trade(brand)name) such as the A.E.R.711 that industrial of Asahi Chemical Industry makes, A.E.R.714; Phenolic resin varnish type epoxy resin; Like Japan Epoxy Resins Co.; Ltd. the jER152, the jER154 that make; D.E.N.431, D.E.N.438 that DowChemical Company makes, EpiclonN-730, EpiclonN-770, EpiclonN-865 that DICCorporation makes, Dongdu changes into EpototeYDCN-701, the YDCN-704 of manufactured; AralditeECN1235, AralditeECN1273, AralditeECN1299, AralditeXPY307 that west crust specialty goods chemical company makes; EPPN-201, EOCN-1025, EOCN-1020, EOCN-104S, the RE-306 of Japan's chemical drug manufactured, SumiepoxyESCN-195X, ESCN-220 that Sumitomo Chemical Co. Ltd. makes, (being trade(brand)name) such as the A.E.R.ECN-235 that industrial of Asahi Chemical Industry makes, ECN-299; Bisphenol f type epoxy resin; Epiclon830 like DIC Corporation manufacturing; Japan Epoxy Resins Co.; Ltd. the jER807 that makes, Dongdu changes into EpototeYDF-170, YDF-175, the YDF-2004 of manufactured, (being trade(brand)name) such as AralditeXPY306 that west crust specialty goods chemical company makes; Bisphenol-A epoxy resin changes into Epotote ST-2004, ST-2007, ST-3000 (trade(brand)name) of manufactured etc. like Dongdu; Glycidyl amine type epoxy resin; Like Japan EpoxyResins Co.; Ltd. the j ER604 that makes; Dongdu changes into the EpototeYH-434 of manufactured, the AralditeMY720 that west crust specialty goods chemical company makes, (being trade(brand)name) such as SumiepoxyELM-120 that Sumitomo Chemical Co. Ltd. makes; NSC 9226 type epoxy resin clings to the AralditeCY-350 (trade(brand)name) of specialty goods chemical company manufacturing etc. like the west; Alicyclic epoxy resin, like DAICELCHEMICAL INDUSTRIES, the Celoxide2021 that LTD. makes, (being trade(brand)name) such as the AralditeCY175 that west crust specialty goods chemical company makes, CY179; Trihydroxybenzene methylmethane type epoxy resin, like Japan Epoxy Resins Co., the YL-933 that Ltd. makes, (being trade(brand)name) such as the T.E.N. that Dow Chemical Company makes, EPPN-501, EPPN-502; Japan Epoxy Resins Co., YL-6056, YX-4000, YL-6121 di-cresylol types such as (being trade(brand)name) or united phenol-type epoxy resin that Ltd. makes or their mixture; Japan chemical drug manufactured 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 big Japanese ink chemical industrial company makes; JapanEpoxy Resins Co., the jER157S bisphenol-A phenolic varnish type epoxy resin such as (trade(brand)names) that Ltd. makes; Japan Epoxy Resins Co., the jERYL-931 that Ltd. makes, four phenylor ethane type epoxy resin 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 epoxy resin such as TEPIC that daily output chemical industrial company makes; The o-phthalic acid diglycidyl ester resins such as Blemmer DGT that Nof Corp. makes; Dongdu changes into four glycidyl group YLENE acyl group ethane (the tetraglycidyl xylenoyl ethane) resins such as ZX-1063 of manufactured; ESN-190, ESN-360 that chemical company of Nippon Steel makes, the HP-4032 that DIC Corporation makes, EXA-4750, EXA-4700 etc. contain the epoxy resin of naphthyl; The HP-7200 that DICCorporation makes, HP-7200H etc. have the epoxy resin of Dicyclopentadiene (DCPD) skeleton; SY-Monomer G copolymerization such as the CP-50S that Nof Corp. makes, CP-50M are epoxy resin; And the copolymerization epoxy resin of cyclohexyl maleimide and SY-Monomer G; Epoxide modified polybutadiene rubber verivate (DAICEL CHEMICAL INDUSTRIES for example, the PB-3600 that LTD. makes etc.), CTBN modified epoxy (for example Dongdu changes into the YR-102, YR-450 of manufactured etc.) etc., but be not limited to these.These epoxy resin can use separately or make up more than 2 kinds and use.

As aforementioned multifunctional oxetane compound (D-2); Can enumerate out 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, 1 of 4-, 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, methylacrylic acid (3-methyl-3-oxetanyl) methyl esters, methylacrylic acid (3-ethyl-3-oxetanyl) methyl esters, their multifunctional trimethylene oxide classes such as oligopolymer or multipolymer; And novolac resin, gather (para hydroxybenzene ethene), cardo type bisphenols, calixarene kind, Resorcinol calixarene (calixresorcinarene) type or silsesquioxane (silsesquioxane) and wait the pure etherate of resin with hydroxyl and trimethylene oxide etc.In addition, can enumerate the multipolymer etc. of the unsaturated monomer of providing the trimethylene oxide ring and (methyl) alkyl acrylate.

As the episulfide resin (D-3) that has 2 above cyclic thioether bases in the aforementioned molecule, for example can enumerate out Japan Epoxy Resins Co., the bisphenol A-type episulfide resin YL7000 that Ltd. makes etc.In addition, also can use and adopt same compound 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.

About the use level of 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, further is preferably 0.8～2.0 normal scope.When having the use level less than 0.6 of Thermocurable composition (D) of 2 above ring-types (sulphur) ether in the molecule, in soldering-resistance layer, have carboxyl residual, 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 NCOs or closure NCO in 1 molecule, melamine resin, melamine derivative, benzoguanamine resin.

As the compound that has 2 above NCOs or closure NCO in aforementioned 1 molecule; Can enumerate out the compound that has 2 above NCOs in 1 molecule is polyisocyanate compound, or the compound that has 2 above closure NCOs in 1 molecule is a blocked isocyanate compound etc.

As aforementioned polyisocyanate compound, can use for example aromatic polyisocyanate, aliphatic polyisocyante or ester ring type POLYMETHYLENE POLYPHENYLISOCYANATE.Object lesson as aromatic polyisocyanate; Can enumerate out 4; 4 '-'-diphenylmethane diisocyanate, 2,4 toluene 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 enumerate out 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 POLYMETHYLENE POLYPHENYLISOCYANATE, can enumerate out the bicycloheptane triisocyanate.And above adducts, biuret body and the isocyanuric acid ester body of the isocyanate compound enumerated out.

Closure NCO contained in the aforementioned blocked isocyanate compound is, NCO is through being 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 NCO.

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 enumerate out 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 POLYMETHYLENE POLYPHENYLISOCYANATE.As the object lesson of aromatic polyisocyanate, aliphatic polyisocyante and ester ring type POLYMETHYLENE POLYPHENYLISOCYANATE, can enumerate out the compound of that kind that top illustration goes out.

As the isocyanic ester encapsulant, for example can enumerate out, 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, NSC 27786, 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.

Such blocked isocyanate compound can use commercially available material, for example can enumerate out SumiduleBL-3175, BL-4165, BL-1100, BL-1265; DesmoduleTPLS-2957, TPLS-2062, TPLS-2078, TPLS-2117, Desmotherm2170, Desmotherm2265 (more than, Sumika BayerUrethane Co., Ltd. makes; Trade(brand)name), coronate2512, coronate2513, coronate2520 (more than, Japanese polyurethane industrial makes; Trade(brand)name); B-830, B-815, B-846, B-870, B-874, B-882 (Mitsui Takeda Chemical Co., Ltd. makes, trade(brand)name); 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 NCOs or closure NCO in the 1 above-mentioned molecule can use a kind perhaps to make up use more than 2 kinds separately.

With respect to the aforementioned carboxy resin (A) that contains of 100 mass parts, the use level that has the compound of 2 above NCOs or closure NCO in the 1 such molecule is 1～100 mass parts, and the ratio that further is preferably 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 compsn reduces, so not preferred.

As other Thermocurable composition, also can enumerate out melamine derivative, benzoguanamine verivate 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.Kind to this alkoxy methyl does not have special qualification, 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 Superlysoform concentration.

As these commercially available article; For example can enumerate out Cymel 300, Cymel 301, Cymel 303, Cymel 370, Cymel 325, Cymel 327, Cymel 701, Cymel 266, Cymel 267, Cymel 238, Cymel 1141, Cymel 272, Cymel 202, Cymel 1156, Cymel 1158, Cymel 1123, Cymel 1170, Cymel 1174, Cymel UFR65, Cymel 300 (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 use separately or make up more than 2 kinds and use.

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 enumerate out for example imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-imdazole derivatives such as 2-ethyl-4-methylimidazole; 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 article; Can enumerate out for example has four countries to change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade(brand)name of imidazole compound) that industrial makes, the U-CAT of SAN-APRO manufactured (registered trademark) 3503N, 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 epoxy resin, 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-cyanidin(e)s such as s-triazine isocyanuric acid affixture preferably uses these as acting compound of adaptation imparting agent and the combination of aforementioned hot curing catalysts.

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

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

[Chemical formula 1]

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

As the commercially available article 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 preferred especially P contained compound (E) of the present invention, can enumerate out that (1) has acrylate-based P contained compound as reactive group, (2) have phenol property 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 propenoate can be to have the compound that comprises (methyl) propenoate more than 2 in phosphoric and the molecule, particularly, can enumerate out the R in the aforementioned formula (1) ¹And R ²Be Wasserstoffatoms, 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 through Michael reaction (michael addition reaction) with known polyfunctional acrylic ester monomer commonly used.

As above-mentioned known acrylate monomer commonly used, can enumerate out the diacrylate class of glycol such as terepthaloyl moietie, methoxyl group TEG, polyoxyethylene glycol, Ucar 35; The multicomponent methacrylate class of polyvalent alcohols such as pinakon, 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 propenoate, 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 USP Kosher diglycidylether, USP Kosher triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester; And the trimeric cyanamide propenoate and/or with corresponding each methyl acrylic ester of aforesaid propylene acid esters etc.

(2) has the P contained compound of phenol property hydroxyl

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

(3) oligopolymer or polymkeric substance

As the P contained compound of oligopolymer or polymkeric substance, to make that toughness 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 article, 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 that replaces or do not have substituted phenoxy phosphazene oligopolymer or tripolymer, the tetramer, pentamer is arranged, and liquid, pressed powder all is fit to use.As commercially available article, there is (strain) volt to see the FP-100 of pharmacy manufacturing, FP-300, FP-390 etc.Wherein, high by alkyl or hydroxyl, the substituted phenoxy phosphazene oligopolymer of cyanic acid isopolarity group to the solvability that contains carboxy resin, even heavy addition does not have disadvantageous effects such as recrystallization yet, so preferably.

(5) hypophosphite

Through using hypophosphite, can not damage cured coating film flexibility ground and further improve flame retardant resistance.In addition, through using the hypophosphite of excellent heat resistance, can suppress oozing out of fire retardant in the hot pressing when mounted.As commercially available article, can enumerate out EXOLIT OP 930, EXOLIT OP 935 of Clariant manufactured etc.

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 (E) is that the scope of 0～200 mass parts is preferred, especially is preferably 0～100 mass parts.Use level is during more than above scope, and so the variation such as curved characteristic of the cured film that obtains are not preferred.

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.

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

In addition, the Photoepolymerizationinitiater initiater that intramolecularly has 2 oxime ester bases also is to be fit to use, and particularly, can enumerate out the oxime ester compound with the carbazole structure shown in the formula.

[Chemical formula 2]

(in the formula; X representes the alkoxyl group, phenyl (being replaced by alkoxyl group, the amino of the alkyl of carbonatoms 1～17, carbonatoms 1～8, alkylamino or dialkyl amido with alkyl of carbonatoms 1～8) of alkyl, the carbonatoms 1～8 of Wasserstoffatoms, carbonatoms 1～17; Naphthyl (being replaced) by alkoxyl group, the amino of the alkyl of carbonatoms 1～17, carbonatoms 1～8, alkylamino or dialkyl amido with alkyl of carbonatoms 1～8; Y, Z represent the alkoxyl group, halogen group, phenyl (being replaced by alkoxyl group, the amino of the alkyl of carbonatoms 1～17, carbonatoms 1～8, alkylamino or dialkyl amido with alkyl of carbonatoms 1～8) of alkyl, the carbonatoms 1～8 of Wasserstoffatoms, carbonatoms 1～17 respectively; Naphthyl (being replaced) by alkoxyl group, the amino of the alkyl of carbonatoms 1～17, carbonatoms 1～8, alkylamino or dialkyl amido with alkyl of carbonatoms 1～8; Anthryl, pyridyl, benzofuryl (benzofuryl), benzothienyl (benzothienyl); Ar representes alkylidene group, vinylidene, phenylene, diphenylene, pyridylidene (pyridylene), naphthylidene, thiophene, anthrylene (anthrylene), inferior thienyl (thienylene), the furylidene (furylene), 2 of carbonatoms 1～10; 5-pyrroles-two base, 4; 4 '-toluylene-two base, 4; 2 '-vinylbenzene-two base, n representes 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 enumerate out 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) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N particularly, N-dimethylamino methyl phenyl ketone etc.As commercially available article, can enumerate out the west and cling to the IRGACURE907 of specialty goods chemical company manufacturing, IRGACURE 369, IRGACURE 379 etc.

As acylphosphine oxide is Photoepolymerizationinitiater initiater, can enumerate out 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 article, can enumerate out the Lucirin TPO of BASF AG's manufacturing, the IRGACURE 819 that west crust specialty goods chemical company makes etc.

In the aforesaid Photoepolymerizationinitiater initiater, especially preferred is the acylphosphine oxide series initiators, considers from the light performance of fading, and its photopermeability preferably and have an effect of flame retardant resistance.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, so preferably.Both make up and use is preferred especially.

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

In addition; For the oxime ester with the group shown in the aforementioned formula (II) 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 the scope that further is preferably 0.01～5 mass parts is an ideal.

As other Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and the sensitizing agent that is adapted at using in the Photocurable resin composition of the present invention; Can enumerate out 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 UVNUL MS-40,4-benzoyl-diphenyl sulfide, 4-benzoyl--4 '-methyldiphenyl thioether, 4-benzoyl--4 '-ethyl diphenyl sulfide, 4-benzoyl--4 '-propyl group diphenyl sulfide then arranged.

If enumerate the object lesson of tertiary amine compound; The compound that for example is ethanolamine compound then, has dialkyl amido benzene structure; For example 4; 4 '-dimethylamino UVNUL MS-40 (the NISSOCURE MABP of Japanese Cao Da manufactured), 4; Dialkyl amido UVNUL MS-40,7-(diethylin)-4-methyl-2H-1-chromen-2-one (7-(diethylin)-4-methylcoumarin) etc. such as 4 '-diethylin UVNUL MS-40 (Hodogaya Chemical Co.LTD. make EAB) contain the coumarin compound, ethyl 4-dimethy laminobenzoate (KAYACUREEPA of Japanese chemical drug manufactured), 2-dimethylamino ethyl benzoate (the Quantacure DMB of International Bio-Synthetics manufactured), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (the Quantacure BEA of International Bio-Synthetics manufactured) of dialkyl amido, to dimethylamino TRIMETHOXY BENZOIC ACID (FOR MANUFACTURING OF T.M. isopentyl ethyl ester (the KAYACURE DMBI of Japanese chemical drug manufactured), 4-dimethylaminobenzoic acid-2-ethylhexyl (Esolol 507 of VanDyk manufactured) and 4,4 '-diethylin UVNUL MS-40 (EAB of Hodogaya Chemical Co.LTD. manufacturing).

In the aforesaid compound, preferred thioxanthone compound and tertiary amine compound.The solidified nature aspect is considered from the deep, and compsn of the present invention preferably comprises the thioxanthone compound, and is 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 the ratio that further is preferably below 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 UVNUL MS-40 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.From the excellent sensitization effect of the laser display of wavelength 400nm～410nm being considered preferred especially 7-(diethylin)-4-methyl-2H-1-chromen-2-one.

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, further is preferably the ratio of 0.1～10 mass parts.During use level less than 0.1 mass parts of tertiary amine compound, existence can not obtain the tendency of sufficient sensitization effect.On the other hand, when surpassing 20 mass parts, tertiary amine compound causes becoming violent, the tendency that exists the deep solidified nature to reduce in the photoabsorption on the surface that drying resistance weldering is filmed.

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 verivate thereof etc. have the chain-transfer agent of carboxyl; Mercaptoethanol, mercaprol, Mercaptobutanol, mercapto-propanediol, sulfydryl butyleneglycol, hydroxybenzene mercaptan and verivate 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 acting heterogeneous ring compound of chain-transfer agent with sulfydryl; 2-sulfydryl-4-GBL), 2-sulfydryl-4-methyl-4-GBL, 2-sulfydryl-4-ethyl-4-GBL, 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. for example can enumerate out sulfydryl-4-GBL (another name:.

Heterogeneous ring compound as the chain-transfer agent of the development property of not damaging Photocurable resin composition with 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 use separately or make up more than 2 kinds and use.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizing 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 and sensitizing agent is that the scope below 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 compsn of the present invention is consisted of Photocurable resin composition is, makes Photocurable resin composition of the present invention in alkali aqueous solution, not dissolve or helps its thawless material through active energy beam irradiation carrying out photocuring.As such compound, can enumerate out the diacrylate class of glycol such as terepthaloyl moietie, methoxyl group TEG, polyoxyethylene glycol, Ucar 35; The multicomponent methacrylate class of polyvalent alcohols such as pinakon, 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 propenoate, bisphenol a diacrylate and these phenols or propylene oxide adduct etc.; The multicomponent methacrylate class of glycidyl ethers such as USP Kosher diglycidylether, USP Kosher triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester; And the trimeric cyanamide propenoate and/or with corresponding each methyl acrylic ester of aforesaid propylene acid esters etc.

And then the hydroxyl that can enumerate out 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 CALCIUM ACRYLATE compound that obtains etc.Such epoxy acrylate is that resin can not reduce its touch dry property 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, further is 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 through 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 enumerate out 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, preferably not containing halogen to the viewpoint of the influence of human body.

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 enumerate out 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), has particularly: 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 enumerate out 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.

Concrete illustrative words have pigment violet 19,23,29,32,36,38,42, solvent violet 13,36, C.I. pigment orange 1, C.I. pigment orange 5, C.I. pigment Orange 13, C.I. pigment orange 14, C.I. pigment orange 16, C.I. pigment orange 17, C.I. pigment orange 24, C.I. pigment orange 34, C.I. pigment orange 36, C.I. pigment orange 38, C.I. pigment orange 40, C.I. pigment orange 43, C.I. pigment orange 46, C.I. pigment orange 49, C.I. pigment orange 51, C.I. pigment orange 61, C.I. pigment orange 63, C.I. pigment orange 64, C.I. pigment orange 71, C.I. pigment orange 73, C.I. pigment brown 23, C.I. pigment brown 25, C.I. Pigment black 1, C.I. Pigment black 7 etc.

Cooperation ratio to the tinting material (H) of aforementioned that kind does not have special qualification, 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 the top white lake of enumerating out, the preparing spherical SiO 2; Can also use permanent white, silicon-dioxide, talcum, hydrotalcite, Marinco H, 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, further is 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 property flexible in order to improve can be used 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 enumerate out N-BUTYL ACETATE Mierocrystalline cellulose (CAB), propyl acetate Mierocrystalline cellulose (CAP) series of Eastman manufactured; As the polyester based polymer; The VYLON series of manufactured is spun by preferred Japan, as the phenoxy resin based polymer, and the phenoxy resin of preferred dihydroxyphenyl propane, Bisphenol F and their hydrogenated 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, further is 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.

For the adaptation that improves interlayer or 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 the radical scavenger of radical ineffective treatment that (1) that is used for anti-oxidation make generation in the curable resin composition of the present invention or/and (2) are harmless material and the inhibitors such as peroxide decomposer that do not produce new radical with the peroxide breakdown that produces.

As the particular compound of the acting inhibitor of radical scavenger, can enumerate Resorcinol, 4-tert-butyl catechol, 2-Tert. Butyl Hydroquinone, 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, two (2; 2,6,6-tetramethyl--4-piperidyl)-amine compound such as sebacate, thiodiphenylamine etc.

Radical scavenger can use commercially available material; For example can enumerate out 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 manufactured; 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.

Particular compound as the acting inhibitor of peroxide decomposer; Can enumerate out 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, for example can enumerate out ADK STAB TPP (rising sun electrification manufactured; Trade(brand)name), MARKAO-412S (ADEKA ARGUS CHEMICAL CO.; LTD makes, the face name of an article), SumilizerTP S (sumitomo chemical company manufacturing, trade(brand)name) etc.

Above-mentioned inhibitor can use a kind perhaps to make up use more than 2 kinds separately.

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

As UV light absorber, can enumerate out benzophenone derivates, benzoate derivatives, OR 10154, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate verivate, cinnamyl o-aminobenzoate verivate, dibenzoylmethane derivative etc.As the object lesson of benzophenone derivates, can enumerate out 2-hydroxyl-4-methoxy benzophenone, UV-531,2,2 '-dihydroxyl-4-methoxy benzophenone and 2,4 dihydroxyl benzophenone etc.Object lesson as benzoate derivatives; Can enumerate out 2-WMO, 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 OR 10154; Can enumerate out 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 enumerate out hydroxyphenyltriazinuv, two ethyl hexyl oxy phenol p-methoxy-phenyl triazines etc.

As UV light absorber; Can use commercially available material; For example can enumerate out 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 use a kind or make up more than 2 kinds and to use separately, through using with aforementioned antioxidant combination, and the stabilization of the shaping thing that can realize obtaining by curable resin composition of the present invention.

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

As such organic solvent, can enumerate out ketone, aromatic hydrocarbon based, glycol ethers, glycol ethers acetate esters, ester class, alcohols, aliphatic hydrocarbon, oil series solvent etc.More specifically, can enumerate out ketones such as methylethylketone, pimelinketone; Toluene, YLENE, 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 ETHYLE ACETATE, butylacetate, dipropylene glycol methyl ether acetic ester, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic ester, Ucar 35 butyl ether acetic ester; Alcohols such as ethanol, propyl alcohol, terepthaloyl moietie, Ucar 35; 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 hot stopper commonly used; Known tackifier commonly used such as fine particle silica, organobentonite, smectite, skimmer and/or flow agents such as silicone-based, fluorine system, macromolecular, silane coupling agents such as imidazoles system, thiazole system, triazole system; Inhibitor, 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; For example can enumerating out, 4-methoxyphenol, quinhydrones, alkyl or aryl replace quinhydrones, tert-butyl catechol, pyrogallol, 2-dihydroxy benaophenonel, 4-methoxyl group-2-dihydroxy benaophenonel, protochloride ketone, thiodiphenylamine, chloranil, naphthylamines, β-Nai Fen, 2; 6-di-t-butyl-4-cresols, 2, the inner complex of reactant, wintergreen oil and thiodiphenylamine, nitroso compound, nitroso compound and the Al of 2 '-methylene-bis (4-methyl-6-tert butyl phenol), pyridine, oil of mirbane, dinitrobenzene, TNP, 4-Tolylamine, methylene blue, copper and organic sequestering agent etc.

Curable resin composition of the present invention can be processed the form of dry film, this dry film possess carrier film (supporter) and on this carrier film, form 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; Be coated with machine (rod coater), extrusion coating machine (sq ueeze coater), contrary formula coating machine (reverse caoter), transmission roller coating machine (transfer roll cater), photogravure coating machine (gravure coater), spraying machine etc. through comma coating machine (comma coater), knife coater, lip coating machine (lip coater), rod and on carrier film, be coated with into homogeneous thickness; Usually, drying can obtain film in 1～30 minute under 50～130 ℃ temperature.Coating film thickness is not had special qualification, 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 of the polyester film, Kapton, polyamidoimide film, PP SHEET FOR OPP TAPE, polystyrene film etc. of polyethylene terephthalate etc.Thickness to carrier film does not have special qualification, 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 polyvinylidene film for example, polytetrafluoroethylene film, PP SHEET FOR OPP TAPE, 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 of the present invention is adjusted to the viscosity that is fit to coating process with for example aforementioned organic solvent; 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 compsn (temporary transient dry), can form tack-free film.In addition, above-mentioned compsn is applied on the carrier film, drying forms film; And this film rolled when forming dry film; The mode that contacts with base material with cured resin composition layer through laminating machine etc. fits on the base material, peels off carrier film then, can form resin insulating barrier thus.

Under the situation that is Photocurable resin composition; Afterwards; Utilize the exposure of active energy beam selectivity or utilize the direct exposure machine of laser directly to carry out pattern exposure through forming figuratum photomask by contact (or noncontact mode); With unexposed development, can form corrosion-resisting pattern through dilute alkaline aqueous solution (for example 0.3～3wt% aqueous sodium carbonate).And then; Under for the situation of compsn that contains Thermocurable composition (D); Make its thermofixation through 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 making public with the residual ethylenic unsaturated bond generation hot radical polymerization of unreacted state through 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 substrate that is pre-formed circuit, the flexible printed circuit board; Use phenol paper, epoxy paper, epoxy glass fabric, glass polyimide in addition, the copper clad laminate of woven fiber glass/epoxy non-woven fabrics, woven fiber glass/epoxy paper, synthon epoxy, fluorine Vilaterm PPO cyanate etc. and all grades (FR-4 etc.) of obtaining, other Kapton, PET film, glass substrate, ceramic substrate, wafer board etc.

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, the mode that makes the method for the hot air convection contact in the drying machine and blow supporter through nozzle).

Under the situation that is Photocurable resin composition,, make exposure portion (by the part of active energy beam irradiation) solidify through to being coated with and making make public (irradiation of active energy beam) of filming that obtains after the solvent evaporates drying.

As the used exposure machine of above-mentioned active energy beam irradiation; Get final product so long as be equipped with the ultraviolet device of irradiation 350～450nm scopes such as high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, mercury short arc lamp; 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) through cad data from computingmachine.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 Pottasium 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 the present invention particularly, but the present invention does not receive the qualification of following embodiment.In addition, following " part " and " % " if there is not special qualification, are meant quality criteria.

Synthetic example

(A-1) be equivalent to the synthetic of the aforementioned resin that contains carboxy resin (5):

In the reaction vessel that possesses whipping appts, TM, condensing surface, drop into 2400g (3 moles) by 1; 5-pentanediol and 1; 6-pinakon 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 2-hydroxy ethyl methacrylate of monohydroxy compound.Then; Drop into the isophorone diisocyanate of 1887g (8.5 moles), stop after being heated to 60 ℃ while stirring, heat once more when the temperature in reaction vessel begins to reduce as POLYMETHYLENE POLYPHENYLISOCYANATE; Continue to stir at 80 ℃, confirm the absorption spectrum (2280cm of NCO through FTIR ^-1) after the disappearance, finish reaction.Then, adding the Trivalin SF acetic ester, to make solids component be 50 quality %.The acid number of the solids component that contains carboxy resin that obtains is 50mgKOH/g.

(A-2) be equivalent to the aforementioned photosensitivity that contains carboxy resin (7) and contain carboxy resin:

The Japanese chemical drug (strain) that will have the photosensitivity group and use the multi-functional epoxy's of xenol Novolac structure photosensitivity to contain carboxy resin is made the resin solution of ZCR-1601H (solids component 65% is 98mgKOH/g as the acid number of resin) as A-2.

The preparation of white lake slurry:

700g white lake (clear make with electrician's (strain) HIGILITE42M) and 280g are mixed stirring as Trivalin SF acetic ester, the 20gBYK-110 of solvent, use the zirconium oxide bead of 0.5 μ m to carry out dispersion treatment through ball mill.Repeat this operation 3 times,, make white lake slurry (B-1) through the strainer of 3 μ m.

The preparation of silica slurry:

700g preparing spherical SiO 2 (Admatech GmbH 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 likewise carry out dispersion treatment with ball mill.After repeating this operation 3 times, the strainer through 3 μ m filters, and makes silica slurry (C-1).

700g preparing spherical SiO 2 (Admatech GmbH makes SO-C5) and above-mentioned silica slurry are likewise disperseed,, make silica slurry (C-2) through the strainer of 5 μ m.

Embodiment 1～9, comparative example 1～4

Use the resin solution of above-mentioned synthetic example, cooperate according to the ratio (mass parts) shown in various compositions shown in the table 1 and the table 1, carry out pre-mixing through stirrer, carry out mixingly then with 3 roll-type roller mills, preparation hinders solid welding voltinism resin combination.At this, measure granularity with the particle size analyzer of ERICHSEN manufactured, estimate the dispersity of the curable resin composition that obtains, 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; Through the Thermocurable Photocurable resin composition of whole coating of silk screen print method previous embodiment 2～9 and comparative example 1～4, drying is 30 minutes in 80 ℃ heated air circulation type drying oven.After the drying, use the exposure apparatus (MW-680-GW20 that ORC MANUFACTURING Co.Ltd makes) that is equipped with metal halide lamp to make public through stage phototimer (KodakNo.2), will develop (90 ℃, 0.2MPa, 1wt%Na ₂CO ₃Exposure when the pattern of remaining stage phototimer is 6 sections in the time of the aqueous solution) 90 seconds is as optimum exposure.

Testing of characteristic:

Solder heat resistance property

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

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.

Flame retardant resistance

The compsn of each embodiment and comparative example is applied to 12.5 μ m or thick Kapton (the DU PONT-TORAY CO. of 25 μ m through the whole face of silk screen printing; LTD. the Kapton 100H, the 50H that make) on, after under 80 ℃ dry 20 minutes, naturally cool to room temperature.And then, likewise, whole coating carried out at its back side through silk screen printing, after under 80 ℃ dry 20 minutes, naturally cool to room temperature, obtain the two sided coatings substrate.For the substrate of embodiment 1, under 150 ℃, carry out thermofixation in 60 minutes, with it as assess sample.For the substrate of embodiment 2～9 and comparative example 1～4, use the exposure apparatus (HMW-680-GW20) that is equipped with metal halide lamp solder resist to be carried out whole exposure, with 30 ℃ 1wt%Na with optimum exposure ₂CO ₃The aqueous solution is pressed in spray under the condition of 0.2MPa and was developed for 90 seconds, under 150 ℃, carries out thermofixation in 60 minutes, with it as assess sample.Use sample for this flame retardant resistance evaluation, carry out the thin material testing vertical flammability according to the UL94 specification.Be shown VTM-0 or NG (not reaching the sample of VTM-0) based on the UL94 specification table during evaluation.

Flexible (folding resistance)

The compsn of each embodiment and comparative example is applied on the thick Kapton of 25 μ m (DU PONT-TORAY CO., the Kapton 100H that LTD. makes) through the whole face of silk screen printing, after under 80 ℃ dry 30 minutes, naturally cools to room temperature.For the substrate of embodiment 1, under 150 ℃, carry out thermofixation in 60 minutes, with it as assess sample.For the substrate of embodiment 2～9 and comparative example 1～4, use the exposure apparatus (HMW-680-GW20) that is equipped with metal halide lamp solder resist to be carried out whole exposure, with 30 ℃ 1wt%Na with optimum exposure ₂CO ₃The aqueous solution is pressed in spray under the condition of 0.2MPa and was developed for 90 seconds, under 150 ℃, carries out thermofixation in 60 minutes, with it as assess sample.

For the assess sample that obtains, carry out repeatedly 180 ° of bendings through the curling joint machine, a situation arises to observe crackle in the tectum (coverlayer) at this moment through visual and opticmicroscope (multiplying power * 200), estimates the number of times that crackle does not take place.

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

[table 2]

Embodiment 10～17

Mismatch the silicone-based skimmer; Other uses the preparation of compositions flame retardant photocurable resin composition shown in the embodiment 2～9 shown in the table 1, with the methylethylketone dilution, is applied on the carrier film; Heat drying; Forming thickness is the photosensitive polymer combination layer of 20 μ m, and the mulch film of fitting above that 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 makes public with the soldering-resistant pattern of optimum exposure to this substrate, peels off carrier film, uses 30 ℃ 1wt%Na then ₂CO ₃The aqueous solution developed for 90 seconds under the condition of spray pressure 0.2MPa, obtained corrosion-resisting pattern.Afterwards, carry out being heating and curing in 60 minutes, make the test substrate with 150 ℃ hot-air driers.For the test substrate that obtains with cured film, through with aforementioned identical TP and evaluation method, carry out the evaluation test of each characteristic.

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

[table 3]

Claims (10)

1. a curable resin composition is characterized in that, it contains (A) and contains the Thermocurable composition that has 2 above ring-type ethers and/or cyclic thioether base in carboxy resin, (B) white lake, (C) preparing spherical SiO 2 and (D) molecule;

The said carboxy resin (A) that contains, acid number is the scope of 30～200mgKOH/g, and weight-average molecular weight is 2000～150000 scope, and use level is the scope of 5～60 quality % in all compsns;

With respect to the said carboxy resin (A) that contains of 100 mass parts, the use level of said white lake (B) and said preparing spherical SiO 2 (C) is respectively the scope of 1～200 mass parts;

With respect to the said 1 equivalent carboxyl that contains carboxy resin (A), the use level that has the Thermocurable composition (D) of 2 above ring-type ethers and/or cyclic thioether base in the said molecule is 0.6～2.5 normal scope.

2. a curable resin composition is characterized in that, it contains (A) and contains the photopolymerization monomer that has 2 above olefinic unsaturated groups in carboxy resin, (B) white lake, (C) preparing spherical SiO 2, (F) Photoepolymerizationinitiater initiater and (G) molecule;

The said carboxy resin (A) that contains, acid number is the scope of 30～200mgKOH/g, and weight-average molecular weight is 2000～150000 scope, and use level is the scope of 5～60 quality % in all compsns;

With respect to the said carboxy resin (A) that contains of 100 mass parts, the use level of said white lake (B) and said preparing spherical SiO 2 (C) is respectively the scope of 1～200 mass parts;

With respect to the said carboxy resin (A) that contains of 100 mass parts, the use level of said Photoepolymerizationinitiater initiater (F) is the scope of 0.01～30 mass parts;

With respect to the said 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 the said molecule is the scope of 5～100 mass parts.

3. curable resin composition according to claim 1 and 2 is characterized in that, it further contains (E) P contained compound, and with respect to the said carboxy resin (A) that contains of 100 mass parts, the use level of said P contained compound (E) is the scope of 0～200 mass parts.

4. curable resin composition according to claim 1 and 2 is characterized in that, the said carboxy resin (A) that contains is the carboxy resin that contains with carboxylamine ester structure.

5. curable resin composition according to claim 1 and 2 is characterized in that, the said carboxy resin (A) that contains has xenol Novolac structure and olefinic unsaturated group.

6. curable resin composition according to claim 1 is characterized in that, the Thermocurable composition (D) that has 2 above ring-type ethers and/or cyclic thioether base in the said molecule is the epoxy resin with xenol Novolac skeleton.

7. curable resin composition according to claim 1 and 2 is characterized in that, it is a solder resist.

8. dry film, it is through with claim 1 or 2 described curable resin compositions are applied on the film and drying forms.

9. cured article, it is through to claim 1 or 2 described curable resin compositions are applied on the base material and the dry dry coating that obtains carries out thermofixation and/or photocuring obtains; Perhaps, through the dry coating that said curable resin composition is applied on the carrier film and the dry dry film lamination that forms obtains to the base material being carried out thermofixation and/or photocuring obtains.

10. printed substrate, it has the described cured article of aforementioned claim 9.