CN102770495A - Resin composition for polyester base material and dry film and printed circuit boards using same - Google Patents

Abstract

In order to form a film coating that is able to achieve halogen-free flame resistance and that, also, has superior, low warping characteristics, even on printed circuit boards that use a polyester base, the resin composition for the polyester base material contains a resin that contains a carboxyl group, titanium oxide and a phosphorous compound. A thermosetting resin composition can be obtained by further including a thermosetting component that has a plurality of cyclic ether groups and/or cyclic thioether groups in a molecule, in addition to each of the aforementioned components. Furthermore, a photocurable, thermosetting resin can be obtained by including photopolymerisation initiators or photopolymerising monomers. A printed circuit board, which is formed of flame-resistant hard-setting film formed by said components, is provided by using the kind of resin composition described or a dry film thereof.

Description

Polyester base material is with resin combination, the dry film that uses it and printed substrate

Technical field

The present invention relates to resin combination that polyester base material uses, particularly can form the curable resin composition of filming of low warpage and excellent in flame retardance.The invention still further relates to dry film that uses this resin combination and printed substrate with its cured coating film.

Background technology

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

Therefore, all the time, various schemes have been proposed fire-retardantization of filming.For example; TOHKEMY 2007-10794 communique (patent documentation 1) has proposed the photosensitive polymer combination of a kind of FPC with flame retardant resistance, and it contains the photopolymerizable compound, (c) Photoepolymerizationinitiater initiater, (d) blocked isocyanate compounds 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 phosphorus 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.

On the other hand, the base material that uses among the FPC uses Kapton usually, but along with the variation that requires performance, also begin part use liquid crystalline polymers, with PEN, polyethylene terephthalate polyester as representative.In addition, from the viewpoint of environment protection, require filming of Halogen equally.Yet, with respect to polyimide from flame retardant resistance, the employed polyester base material of flexible electric circuit board does not have flame retardant resistance, in the practical situation, uses the flame retardant resistance FPC of polyester film can't obtain the effect of Halogen.

And then, with FPC the printed base plate of the film of representative produces warpage when also existing in the photocuring of filming or thermofixation because of cure shrinkage problem.

The prior art document

Patent documentation

Patent documentation 1: TOHKEMY 2007-10794 communique

Summary of the invention

The problem that invention will solve

The present invention carries out in order to solve like aforesaid prior art problems; Its main purpose does; Even a kind of printed substrate that uses polyester base material is provided, also can form the resin combination that to realize that the excellent polyester base material that is coated with rete of Halogen, flame retardant resistance and low warpage properties is used.

And then the object of the invention does, provides a kind of through using this resin combination, thus the printed substrate that has the dry film of low warpage and excellent in flame retardance and have the flame retardant resistance epithelium of this excellent specific property.

The scheme that is used to deal with problems

In order to realize aforementioned purpose, according to the present invention, the resin combination that provides a kind of polyester base material to use is characterized in that, contains carboxy resin, titanium oxide and phosphorus compound.

According to the present invention, provide a kind of polyester base material to use compsn, it is characterized in that, also comprise heat-curing resin.

In addition, according to the present invention, provide a kind of polyester base material to use compsn, it is characterized in that, the aforementioned carboxy resin that contains is the carboxy resin that contains with carboxylamine ester structure.

And, according to the present invention, provide a kind of polyester base material to use compsn, it is characterized in that the aforementioned hot curable resin comprises the epoxy resin with xenol Novolac skeleton.

In addition, according to the present invention, a kind of dry film is provided, it is coated with drying with above-mentioned resin combination and forms on film.

And then, a kind of cured coating film being provided according to the present invention, it carries out photocuring and/or thermofixation and obtains to above-mentioned resin combination or to above-mentioned resin combination is coated with the dry dry film that forms on film.

In addition, according to the present invention, a kind of printed substrate is provided also, it has cured coating film, and the dry dry film that forms carries out photocuring to said cured coating film and/or thermofixation obtains to above-mentioned resin combination or to above-mentioned resin combination is coated with on film.

The effect of invention

According to the present invention; The resin combination that contains carboxy resin, titanium oxide and phosphorus compound through use; Even use not have under the situation of the polyester base material of flame retardant resistance, also can provide halogen to form, environmental pressure is few, excellent in flame retardance and excellent the filming of low warpage properties.

Embodiment

The inventor etc. further investigate in order to realize aforementioned problems; The result finds; The compsn that contains carboxy resin, titanium oxide and phosphorus compound on the polyester base material of poor heat resistance with lower temperature, contain carboxy resin and solidify; Can form with the adaptation excellent in curing of base material and film, and titanium oxide helps flame retardant resistance and low warpage properties, phosphorus compound to help flame retardant resistance, thus; Can give flame retardant resistance to the independent polyester base material that does not have flame retardant resistance of substrate, so can form in the flexible substrate must obligato low warpage properties, anti-bending property excellent in curing films.This is the surprising effect of not expecting when only being worked as fire retardant by phosphorus compound.

Below, polyester base material of the present invention each constituent with resin combination is elaborated.

As the aforementioned carboxy resin that contains, be purpose to give crosslinking reaction, adaptation and alkali-developable, can use the known in the past various carboxy resins that contain that have carboxyl in the molecule.Especially, from the aspect of light solidified, anti-development property, the carboxyl photoresist that contains that has ethylenical unsaturated double bonds in the molecule is preferred as the photosensitive composite that carries out the alkali development.And its unsaturated double-bond preferably derives from acrylic or methacrylic acid or their verivate.In addition, only use do not have ethylenical unsaturated double bonds contain carboxy resin the time, be light solidified in order to make compsn, the photosensitive compounds (photopolymerization monomer) that has a plurality of olefinic unsaturated groups in the molecule that combination is stated after using is necessary.

As the concrete example that contains carboxy resin, preferably as below the compound (any of oligopolymer and polymkeric substance all can) enumerated.

(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, (methyl) lower alkyl acrylate, iso-butylene etc.

(2) pass through aliphatic diisocyanate; The side chain aliphatic diisocyanate; The ester ring type vulcabond; Vulcabond and dimethylol propionic acids such as aromatic diisocyanate; Dimethylolpropionic acids etc. contain carboxylic diol compound and polycarbonate-based polyvalent alcohol; Polyethers is a polyvalent alcohol; Polyester is a polyvalent alcohol; The polyolefin polyvalent alcohol; Acrylic acid series multiple alcohol; Dihydroxyphenyl propane is an oxirane affixture divalent alcohol; Have phenol property hydroxyl and alcohol hydroxyl group diatomic alcohol compounds such as compound and compound as required with an alcohol hydroxyl group polyaddition reaction and obtain contain the carboxyl urethane resin.

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

(4) through have 1 hydroxyl in adding (methyl) hydroxyalkyl acrylate equimolecular in the resin of aforementioned (2) or (3) synthetic and the compound of (methyl) acryl obtains more than 1 end (methyl) propylene acidylate contain carboxyl photosensitivity urethane resin.

(5) 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 (3) synthetic and the compound of (methyl) acryl obtains more than 1 end (methyl) propylene acidylate contain carboxyl photosensitivity urethane resin.

(6) through make as after 2 officials that state can or 2 officials can be above multifunctional (solid-state) epoxy resin and the reaction of (methyl) vinylformic acid, make the hydroxyl that is present in side chain and 2 yuan of acid anhydrides additions and obtain contain the carboxyl photoresist.

(7) through make with as after 2 officials that state can (solid-state) epoxy resin the hydroxyl polyfunctional epoxy resin and the reaction of (methyl) vinylformic acid that obtain with the further epoxidation of epoxy chloropropane, the hydroxyl of generation and 2 yuan of acid anhydrides additions and obtain contain the carboxyl photoresist.

(8) through make as after 2 officials stating can react by oxetane resin 2 yuan of acid anhydrides additions such as the primary hydroxyl of generation and Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride and obtain contain carboxyl polyester resin with dicarboxylicacid such as hexanodioic acid, phthalic acid, hexahydrophthalic acids.

(9) through making oxirane reactions such as the compound that has a plurality of phenol property hydroxyls in 1 molecule and oxyethane, propylene oxide; The reaction product that makes gained with contain the reaction of unsaturated group monocarboxylic acid, the reaction product that makes gained react with multi-anhydride and obtain contain the carboxyl photoresist.

(10) reaction product through making cyclic carbonate compound reaction gained such as the compound that has a plurality of phenol property hydroxyls in 1 molecule and ethylene carbonate, Texacar PC with contain the reaction of unsaturated group monocarboxylic acid, the reaction product that makes gained react with multi-anhydride and obtain contain the carboxyl photoresist.

(11) through making the compound that has 1 alcohol hydroxyl group and 1 phenol property hydroxyl in 1 molecules such as the epoxy compounds that has a plurality of epoxy group(ing) in 1 molecule and p-hydroxyphenylethanol at least, contain the reaction of unsaturated group monocarboxylic acid with (methyl) vinylformic acid etc., multi-anhydrides such as the alcohol hydroxyl group of the reaction product of gained and maleic anhydride, Tetra Hydro Phthalic Anhydride, trimellitic acid 1,2-anhydride, pyromellitic acid dianhydride, adipic anhydride react and obtain contain the carboxyl photoresist.

(12) resin of above-mentioned through making (1) ~ (11) further with in 1 molecules such as (methyl) glycidyl acrylate, (methyl) vinylformic acid Alpha-Methyl glycidyl ester has 1 epoxy group(ing) and the compound addition of (methyl) acryl forms more than 1 contains the carboxyl photoresist.

In addition, in this specification sheets, (methyl) propenoate is the term of general designation propenoate, methacrylic ester and their mixture, and is also identical to other similar expression.

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

In addition, the scope that the above-mentioned acid number that contains carboxy resin is 20 ~ 120mgKOH/g is an ideal, more preferably the scope of 40 ~ 100mgKOH/g.When containing the not enough 20mgKOH/g of the acid number of carboxy resin, the adaptation that can not get sometimes filming, under the situation of Photocurable resin composition, be difficult to alkali sometimes and develop.On the other hand, when acid number surpassed 120mgKOH/g, it is very big that the warpage of cured coating film becomes, and is unsuitable for the polyester film as target with the coating agent.In addition, under the situation of Photocurable resin composition, be developed the liquid dissolving portion of exposure sometimes and unexposed indistinction and peel off, be difficult to describe normal corrosion-resisting pattern, so not preferred.

As preferably containing carboxy resin; Acid number is 20 ~ 60mgKOH/g under the situation of hot curing resin composition; From the viewpoint of adaptation and low warpage is preferred, and then gives under the situation of development property, and it is preferred that the resin combination of these resins and acid number 60 ~ 120mgKOH/g is used.

In addition; Resin as low acid number; The carboxyl urethane that contains with carboxylamine ester structure is preferred from the viewpoint of adaptation, low warpage, as the resin of high acid value, have aromatic nucleus to contain carboxy resin preferred from the viewpoint of flame retardant resistance, thermotolerance, development property.

If this relation is put upside down, then under the situation of the Photocurable resin composition that must develop, poor visualization takes place in the time of can having, the result of low sometimes warpage, bending property difference.

As preferred especially urethane resin, be the material of raw material gained preferably with polyester polyol, polycarbonate diol, polyethers and aliphatics and ester ring type isocyanic ester.In addition, as the carboxy resin that contains with aromatic ring, the carboxy resin that contains with xenol Novolac structure is preferred from flame retardant resistance, stable on heating viewpoint.

In addition, the aforementioned weight-average molecular weight that contains carboxy resin is according to resin matrix and difference, usually 2000 ~ 150000 and then be that 5000 ~ 100000 scope is preferred.During weight-average molecular weight less than 2000, not sticking sometimes poor performance, the wet fastness of filming after the exposure worsens, the film decrement takes place when developing sometimes, and resolving power is variation significantly.On the other hand, weight-average molecular weight surpasses at 150000 o'clock, and development property significantly worsens sometimes, sometimes the storage stability variation.

The scope that this compounding amount that contains carboxy resin is 20 ~ 60 quality % in whole compsns, be preferably 30 ~ 50 quality % is suitable.The compounding amount that contains carboxy resin than above-mentioned scope after a little while, epithelium intensity reduces sometimes, so not preferred.On the other hand, than above-mentioned scope for a long time, sometimes the viscosity of compsn uprise, reduction such as coating, so not preferred.

These contain the carboxy resin ground that contains that carboxy resin can be not limited to aforementioned list and use, and can use a kind or mix multiple use.

As titanium oxide used in the resin combination of the present invention, can use titanium oxide, rutile-type, anatase-type titanium oxide, implement surface treatment, implemented surface-treated titanium oxide etc. with organic cpds with moisture MOX through sulfuric acid process, chlorine manufactured.In these titanium oxide, Titanium Dioxide (Rutile) Top grade is further preferred.Anatase-type titanium oxide is because compare whiteness with rutile-type higher and often used.Yet,, can cause the resin variable color in the Photocurable resin composition because anatase-type titanium oxide has photocatalytic activity.Therewith relatively, it is slightly poor that the whiteness of Titanium Dioxide (Rutile) Top grade is compared with Detitanium-ore-type, but because it does not have photolytic activity basically, can obtain stable filming.

As Titanium Dioxide (Rutile) Top grade, can use known Titanium Dioxide (Rutile) Top grade.Particularly; Can use FUJI TITANIUM INDUSTRY Co.; Ltd. the TR-600, TR-700, TR-750, the TR-840 that make; R-550, R-580, R-630, R-820, CR-50, CR-60, CR-90, CR-97 that the former industry of stone (strain) is made, FUJI TITANIUM INDUSTRY Co., the KR-270 that Ltd. makes, KR-310, KR-380 etc.In these Titanium Dioxide (Rutile) Top grades, the titanium oxide that can use the surface to handle with aqueous alumina or white lake, this viewpoint from dispersiveness, storage stability, flame retardant resistance is preferred especially.

Aforementioned to contain carboxy resin be 1 ~ 500 mass parts to the compounding amount of this titanium oxide, be preferably 5 ~ 300 mass parts with respect to 100 mass parts.During aforementioned compounding quantity not sufficient 1 mass parts, can't fully obtain low warpage properties, the flame retardant resistance of cured coating film, so not preferred.On the other hand, when surpassing 500 mass parts, be difficult to obtain the sufficient flexibility of cured coating film, so not preferred.

Resin combination of the present invention comprises phosphorus compound.As phosphorus compound, can use commonly used known material as organic phosphorus flame retardant, 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 phosphorus compound of the present invention, can enumerate out that (1) has acrylate-based phosphorus compound as reactive group, (2) have phenol property hydroxyl phosphorus compound, (3) oligopolymer or polymkeric substance and (4) phenoxy phosphazene oligopolymer as reactive group.

(1) has acrylate-based phosphorus compound

The phosphorus element-containing propenoate can be to have the compound that comprises a plurality of (methyl) propenoate 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 phosphorus compound of phenol property hydroxyl

This hydrophobicity, thermotolerance with phosphorus compound of phenol property hydroxyl is high, can not reduce because of hydrolysis causes electrical characteristic, and anti-welding heat performance is high.In addition,,, itself and epoxy resin reaction and quilt are included in the network, therefore, can not oozed out this advantage after having curing through using as the epoxy resin with biphenyl backbone of Thermocurable composition, other epoxy resin as suitable combination.As commercially available article, the HCA-HQ of three light (strain) manufacturing etc. is arranged.

(3) oligopolymer or polymkeric substance

The phosphorus compound of oligopolymer or polymkeric substance is less because of the influence toughness reduction of alkyl chain, in addition, because its molecular weight is big, can obtains solidifying the back nothing and ooze out this advantage.As commercially available article, the M-Ester-HP that has three light (strain) to make, the VYLON 337 of (strain) manufacturing etc. spins in Japan.

(4) phosphonitrile oligopolymer

As the phosphonitrile oligopolymer, phenoxy phosphazene compound is effectively, and the ring of replacement or unsubstituted phenoxy phosphonitrile oligopolymer or tripolymer, the tetramer, pentamer is arranged, and liquid, pressed powder all is fit to use.As commercially available article, there is (strain) volt to see the FP-100 of pharmacy manufacturing, FP-300, FP-390 etc.

In addition, through using hypophosphite, can further improve flame retardant resistance and do not damage the flexibility of cured coating film.In addition, through using the hypophosphite of this 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.

These phosphorus compounds can use a kind or mix to use multiple.

The compounding amount of these phosphorus compounds is that 1 ~ 200 mass parts is suitable with respect to the aforementioned carboxy resin that contains of 100 mass parts, is preferably 5 ~ 100 mass parts especially.During compounding quantity not sufficient 1 mass parts of phosphorus compound, can't obtain sufficient flame retardant resistance, so not preferred.On the other hand, when surpassing 200 mass parts, so the deteriorations such as bending characteristic of the oozing out of fire retardant, cured coating film are not preferred.

In the aforementioned phosphorus compound; The phosphorus compound, phosphorus element-containing polymkeric substance, phosphonitrile oligopolymer, the hypophosphite that preferably have reactive group; When particularly consisting of Photocurable resin composition; The phosphorus element-containing acryliccompound is preferred from the viewpoint of oozing out, and the phosphorus element-containing polyester polymers is preferred from the viewpoint of adaptation.In addition, the phenoxy phosphazene of phosphonitrile oligopolymer, hypophosphite are preferred from stable on heating viewpoint, and then to have substituent substituent phenoxy phosphonitriles such as cyanic acid, alkyl be preferred from deliquescent viewpoint.

When resin combination of the present invention consists of hot curing resin composition, when perhaps consisting of light solidifying/heat solidifying resin composition; From the purpose of characteristics such as the thermotolerance that improves cured coating film, insulating reliability, but compounding can with the aforementioned known in the past Thermocurable composition that contains the carboxyl reaction that carboxy resin has.As the Thermocurable composition, especially preferably have the epoxy resin of xenol Novolac skeleton, for example can enumerate out NC-3000L that Japanese chemical drug (strain) makes, NC-3000, NC-3000H, NC-3100 etc.

In addition, preferred especially Thermocurable composition is the Thermocurable composition that has a plurality of ring-type ethers and/or cyclic thioether base (below, abbreviate ring-type (sulphur) ether as) in the molecule in the resin combination of the present invention.Wherein, can be the epoxy resin of 2 functionalities, can use vulcabond, its 2 functionality blocked isocyanate in addition.

This Thermocurable composition that in molecule, has a plurality of ring-types (sulphur) ether is the compound that has any or 2 kinds of groups of a plurality of triatomic rings, tetra-atomic ring or pentacyclic ring-type ether or cyclic thioether base in the molecule, and for example can enumerate out the compound that has a plurality of epoxy group(ing) in the molecule at least and be the compound that has a plurality of oxetanyls in multi-functional epoxy compound, the molecule at least and be the compound that has a plurality of thioether groups in multifunctional oxetane compound, the molecule is episulfide resin etc.

As aforementioned multi-functional epoxy compound; For example can enumerate out Japan Epoxy Resins Co.; Ltd. the jER (registered trademark) 828, jER834, jER1001, the jER1004 that make; Epiclon (registered trademark) 840, Epiclon850, Epiclon1050, Epiclon2055 that DIC Corporation makes; Dongdu changes into Epotote (registered trademark) YD-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 Chemical Company makes; Araldite6071, Araldite6084, AralditeGY250, AralditeGY260 that Ciba Japan Corporation makes, SumiepoxyESA-011, ESA-014, ELA-115, ELA-128 that Sumitomo Chemical Co. Ltd. makes, (being trade(brand)name) bisphenol A type epoxy resins 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; Japan Epoxy Resins Co.; Ltd. the jER YL903 that makes; Epiclon 152, Epiclon 165 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 Araldite 8011 that Ciba Japan Corporation makes; SumiepoxyESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. makes, (being trade(brand)name) brominated epoxy resins such as the A.E.R.711 that industrial of Asahi Chemical Industry makes, A.E.R.714; Japan Epoxy Resins Co.; Ltd. the j ER 152, the j ER 154 that make; D.E.N.431, D.E.N.438 that Dow Chemical Company makes; EpiclonN-730, EpiclonN-770, EpiclonN-865 that DIC Corporation makes; Dongdu changes into EpototeYDCN-701, the YDCN-704 of manufactured; AralditeECN1235, AralditeECN1273, AralditeECN1299, AralditeXPY307 that Ciba Japan Corporation makes; EPPN (registered trademark)-201, EOCN (registered trademark)-1025, EOCN-1020, EOCN-104S, the RE-306 of Japan's chemical drug manufactured, SumiepoxyES CN-195X, ES CN-220 that Sumitomo Chemical Co. Ltd. makes, (being trade(brand)name) phenolic resin varnish type epoxy resins such as the A.E.R.ECN-235 that industrial of Asahi Chemical Industry makes, ECN-299; The Epiclon830 that DIC Corporation makes; Japan Epoxy Resins Co.; Ltd. the j ER807 that makes; Dongdu changes into EpototeYDF-170, YDF-175, the YDF-2004 of manufactured, (being trade(brand)name) bisphenol f type epoxy resins such as AralditeXPY306 that Ciba Japan Corporation makes; Dongdu changes into EpototeST-2004, ST-2007, the ST-3000 bisphenol-A epoxy resins such as (trade(brand)names) of manufactured; Japan Epoxy Resins Co.; Ltd. the jER604 that makes; Dongdu changes into the EpototeYH-434 of manufactured; The AralditeMY720 that Ciba Japan Corporation makes, (being trade(brand)name) glycidyl amine type epoxy resins such as SumiepoxyELM-120 that Sumitomo Chemical Co. Ltd. makes; The AralditeCY-350 NSC 9226 type epoxy resin such as (trade(brand)names) that Ciba Japan Corporation makes; DAICEL CHEMICAL INDUSTRIES, the Celoxide (registered trademark) 2021 that Ltd. makes, (being trade(brand)name) alicyclic epoxy resins such as the AralditeCY175 that Ciba Japan Corporation makes, CY 179; Japan Epoxy Resins Co., the YL-933 that Ltd. makes, (being trade(brand)name) trihydroxybenzene methylmethane type epoxy resin 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; The EBPS-200 of Japan's chemical drug manufactured, the EPX-30 that ADEKA Corporation makes, the EXA-1514 bisphenol-s epoxy resins such as (trade(brand)names) that DIC Corporation makes; Japan Epoxy Resins Co., the jER157S bisphenol-A phenolic varnish type epoxy resin such as (trade(brand)names) that Ltd. makes; Japan Epoxy Resins Co., four phenylor ethane type epoxy resin such as Araldite163 (being trade(brand)name) that the jERYL-931 that Ltd. makes, Ciba Japan Corporation make; The AralditePT810 (trade(brand)name) that Ciba Japan Corporation makes, the TEPIC hetero ring type epoxy resin such as (registered trademarks) that daily output chemical industrial company makes; The o-phthalic acid diglycidyl ester resins such as Blemmer (registered trademark) 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; The HP-4032 that the ESN-190 that chemical company of Nippon Steel makes, ESN-360, DIC Corporation make, EXA-4750, EXA-4700 etc. contain naphthyl epoxy resin; The HP-7200 that DIC Corporation 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 then 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.Wherein, preferred especially phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their mixture.

As aforementioned multifunctional oxetane compound; 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) etc. and have the resin of hydroxyl and the etherate of oxa-cyclobutanol etc.In addition, can enumerate the multipolymer etc. of the unsaturated monomer of providing the trimethylene oxide ring and (methyl) alkyl acrylate.

As the compound that has a plurality of 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.

The compounding amount of Thermocurable composition of compound etc. that has a plurality of ring-types (sulphur) ether in aforementioned epoxy resin with xenol Novolac skeleton, the molecule is with respect to aforementioned carboxyl 1 equivalent that contains carboxy resin, is preferably 0.3 ~ 2.5 equivalent, 0.5 ~ 2 normal scope more preferably.When having the compounding quantity not sufficient 0.3 of Thermocurable composition of a plurality of ring-types (sulphur) ether in the molecule, tail off with the aforementioned crosslinking reaction that contains carboxy resin, so reduction such as thermotolerance, alkali resistance, electrical insulating property, so not preferred.On the other hand, when surpassing 2.5 equivalents, low-molecular-weight ring-type (sulphur) ether is remaining in dry coating, causes the reductions such as intensity of filming, so not preferred.

Use when having the Thermocurable compositions such as compound of a plurality of ring-types (sulphur) ether in above-mentioned epoxy resin with biphenyl backbone, the molecule, preferably contain thermal curing catalyst.As such thermal curing catalyst, for example can enumerate out 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; For example can enumerate out four countries and change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, the 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 compounds 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 epoxy group(ing) and/or oxetanyl and carboxyl reaction to get final product, can use separately or mix more than 2 kinds and use.In addition; Also can use guanamines, methyl guanamines, 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 also uses these as compound and the combination of aforementioned hot curing catalysts that the adaptation imparting agent plays a role.

The compounding amount of these thermal curing catalysts is that the ratio of common amount is promptly enough, for example with respect to the aforementioned carboxy resin that contains of 100 mass parts, is preferably 0.1 ~ 20 mass parts, 0.5 ~ 15 mass parts more preferably.

Can also add white lake in the resin combination of the present invention.Use the purpose of white lake to be, approaching when particularly forming Photocurable resin composition with affinity, the specific refractory power of photoresist, can carry out photocuring effectively.The whiteness of aforementioned titanium oxide, opacifying power are excellent, but specific refractory power is high, and be also strong to ultraviolet reflection, and therefore, when using in a large number, thick film (10 μ m ~ 50 μ m) has sensitivity and the problem of resolving power reduction of the Photocurable resin composition of requirement resolving power.Therefore, white lake and titanium oxide are used simultaneously, make light see through fully along the depth direction of photoresist.Through this method, can when keeping opacifying power, improve the resolving power of alkali-developable Photocurable resin composition.

Be used for white lake of the present invention and can use known white lake commonly used,, can enumerate out the HIGILITE series of for example clear and electrician's manufactured etc. as commercially available article.

Aforementioned to contain carboxy resin be 10 ~ 300 mass parts to the compounding amount of this white lake, be preferably 20 ~ 200 mass parts with respect to 100 mass parts.During aforementioned compounding quantity not sufficient 10 mass parts, can't fully obtain resolving power, the flame retardant resistance of cured coating film, so not preferred.On the other hand, when surpassing 300 mass parts, so the deterioration of bending property is not preferred.

When resin combination of the present invention consists of Photocurable resin composition or light solidifying/heat solidifying resin composition, but the compounding Photoepolymerizationinitiater initiater.As preferred initiator, can use that to be selected from by the oxime ester with oxime ester base be that Photoepolymerizationinitiater initiater, alpha-aminoacetophenone are that Photoepolymerizationinitiater initiater, acylphosphine oxide are the Photoepolymerizationinitiater initiater more than a kind in the group formed of Photoepolymerizationinitiater initiater.

As the oxime ester is the commercially available article of Photoepolymerizationinitiater initiater, can enumerate out CGI-325, IRGACURE (registered trademark) OXE01, IRGACURE OXE02 that Ciba Japan Corporation makes, the N-1919 that ADEKA Corporation makes, NCI-831 etc.In addition, the Photoepolymerizationinitiater initiater that has 2 oxime ester bases in the molecule also is to be fit to use, and particularly, can enumerate out the oxime ester compound with carbazole structure shown in the formula.

[Chemical formula 2]

(in the formula; X representes the alkoxyl group, phenyl, phenyl (being replaced by alkoxyl group, the amino of the alkyl of carbonatoms 1 ~ 17, carbonatoms 1 ~ 8, alkylamino or dialkylamino 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 dialkylamino with alkyl of carbonatoms 1 ~ 8; Y, Z represent the alkoxyl group, halogen group, phenyl, phenyl (being replaced by alkoxyl group, the amino of the alkyl of carbonatoms 1 ~ 17, carbonatoms 1 ~ 8, alkylamino or dialkylamino with alkyl of carbonatoms 1 ~ 8) of alkyl, the carbonatoms 1 ~ 8 of Wasserstoffatoms, carbonatoms 1 ~ 17 respectively; Naphthyl (being replaced), anthryl, pyridyl, benzofuryl (benzofuryl), benzothienyl (benzothienyl) by alkoxyl group, the amino of the alkyl of carbonatoms 1 ~ 17, carbonatoms 1 ~ 8, alkylamino or dialkylamino with alkyl of carbonatoms 1 ~ 8; Ar representes alkylidene group, vinylidene, phenylene, biphenylene, pyridylidene (pyridylene), naphthylidene, thiophene, anthrylene (anthrylene), inferior thienyl (thienylene), the furylidene (furylene), 2 of singly-bound or carbonatoms 1 ~ 10; 5-pyrroles-two base, 4; 4 '-stilbene-two base, 4; 2 '-vinylbenzene-two base, n are 0 or 1 integer.)

In the aforementioned formula, preferably, X, Y are respectively methyl or ethyl, and Z is a methyl or phenyl, and n is 0, and Ar is singly-bound or phenylene, naphthylidene, thiophene or inferior thienyl.

The compounding amount that this oxime ester is a Photoepolymerizationinitiater initiater is preferably 0.01 ~ 5 mass parts with respect to the aforementioned carboxy resin that contains of 100 mass parts.During less than 0.01 mass parts, light solidified is insufficient, films to peel off and coating characteristic such as chemical proofing reduces.On the other hand, when surpassing 5 mass parts, there is the photoabsorption of film coated surface to become violent, the tendency that the deep solidified nature reduces.0.5 ~ 3 mass parts more preferably.

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 IRGACURE 907 that Ciba Japan Corporation makes, 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 Ciba Japan Corporation makes etc.

These alpha-aminoacetophenones be Photoepolymerizationinitiater initiater, acylphosphine oxide be the compounding amount of Photoepolymerizationinitiater initiater with respect to the aforementioned carboxy resin that contains of 100 mass parts, be preferably 0.01 ~ 15 mass parts.During less than 0.01 mass parts, likewise the light solidified on copper is insufficient, films to peel off and coating characteristic such as chemical proofing reduces.On the other hand, when surpassing 15 mass parts, the reduction effect that can't obtain outgasing, and then have the photoabsorption of film coated surface to become violent, the tendency that the deep solidified nature reduces.0.5 ~ 10 mass parts more preferably.

As other Photoepolymerizationinitiater initiater that suits in resin combination of the present invention, to use, light-initiated auxiliary agent and sensitizing agent, can enumerate out bitter almond oil camphor compound, acetophenone compound, anthraquinone compounds, thioxanthone compound, ketal compound, benzophenone cpd, tertiary amine compound and xanthone compound etc.

As the bitter almond oil camphor compound, particularly can enumerate out bitter almond oil camphor, benzoin methylether, ethoxybenzoin, benzoin iso-propylether etc.

As acetophenone compound, particularly can enumerate out methyl phenyl ketone, 2,2-dimethoxy-2-phenyl methyl phenyl ketone, 2,2-diethoxy-2-phenyl methyl phenyl ketone, 1,1-dichloroacetophenone etc.

As anthraquinone compounds, particularly can enumerate out 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone etc.

As the thioxanthone compound, particularly can enumerate out 2,4-dimethyl-thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2,4-di-isopropyl thioxanthone etc.

As ketal compound, particularly can enumerate out methyl phenyl ketone dimethyl ketal, benzil dimethyl ketal etc.

As benzophenone cpd, particularly can enumerate out 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 etc.

As tertiary amine compound; Particularly; The compound that for example can enumerate out ethanolamine compound, have dialkylamino benzene structure; For example 4 of commercially available article; 4 '-dimethylamino UVNUL MS-40 (the NISSOCURE MABP of Japanese Cao Da manufactured), 4; 4 '-diethylin UVNUL MS-40 (Hodogaya Chemical Co.; The EAB that makes) etc. Ltd. dialkylamino UVNUL MS-40,7-(diethylin)-4-methyl-2H-1-chromen-2-one (7-(diethylin)-4-methylcoumarin) etc. contain coumarin compound, 4-dimethyl ethyl aminobenzoate (KAYACURE of Japanese chemical drug manufactured (registered trademark) EPA), 2-dimethyl ethyl aminobenzoate (the Quantacure DMB of International Bio-Synthetics manufactured), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (the Quantacure BEA of International Bio-Synthetics manufactured), p-(dimethylamino)-benzoic acid isopentyl ethyl ester (the KAYACURE DMBI of Japanese chemical drug manufactured), the 4-dimethylaminobenzoic acid-2-ethylhexyl (Esolol 507 of VanDyk manufactured), 4 of dialkylamino; 4 '-diethylin UVNUL MS-40 (Hodogaya Chemical Co., the EAB that Ltd. makes) etc.

Among these, preferred thioxanthone compound and tertiary amine compound.The solidified nature aspect from the deep especially preferably comprises the thioxanthone compound.Wherein, preferably comprise 2,4-dimethyl-thioxanthone, 2,4-diethyl thioxanthone, 2-clopenthixal ketone, 2, thioxanthone compounds such as 4-di-isopropyl thioxanthone.

As the compounding amount of this thioxanthone compound,, be preferably below 20 mass parts with respect to the aforementioned carboxy resin that contains of 100 mass parts.When the compounding amount of thioxanthone compound surpasses 20 mass parts, cause the cost of reduction of thick film solidified nature and goods to rise.More preferably below 10 mass parts.

In addition; As tertiary amine compound; The compound that preferably has dialkylamino benzene structure, wherein, preferred especially dialkylamino benzophenone cpd, maximum absorption wavelength are coumarin compound that contains dialkylamino and coumarin ketone (ketocoumarin) class of 350nm ~ 450nm.

As the dialkylamino benzophenone cpd, 4,4 '-diethylin UVNUL MS-40 is low preferred because of toxicity.Because containing the maximum absorption wavelength of the coumarin compound of dialkylamino is 350nm ~ 410nm; In the ultra-violet region; Therefore; Can provide painted less, water white photosensitive composite is mathematical, also can be provided at the coloring film of the color of reflection tinting pigment self when having used tinting pigment.Preferred especially 7-(diethylin)-4-methyl-2H-1-chromen-2-one.

As the compounding amount of this tertiary amine compound,, be preferably 0.1 ~ 20 mass parts with respect to the aforementioned carboxy resin that contains of 100 mass parts.During compounding quantity not sufficient 0.1 mass parts of tertiary amine compound, the tendency that can't obtain sufficient sensitization effect is arranged.When surpassing 20 mass parts, the tendency that has the deep solidified nature to reduce.0.1 ~ 10 mass parts more preferably.

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

The total amount of this Photoepolymerizationinitiater initiater, light-initiated auxiliary agent and sensitizing agent is preferably below 35 mass parts with respect to the aforementioned carboxy resin that contains of 100 mass parts.When surpassing 35 mass parts, the tendency that causes deep solidified nature reduction because of their photoabsorption is arranged.

In addition, these Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizing agent are owing to absorb certain wavelengths, and therefore according to circumstances, the sensitivity step-down plays a role as UV light absorber sometimes.They are not only to use from the purpose of the sensitivity that improves compsn.Can make its light that absorbs specific wavelength as required, improve the photoreactivity on surface, make that the thread shape and the opening of filming are changed to vertically, cone-shaped, back taper shape, and can improve the working accuracy of live width, opening diameter.

Particularly preferably be the acylphosphine oxide series initiators in the aforementioned lights polymerization starter; Can know from the photobleaching performance and consider; Its photopermeability is best; And make except having phosphoric radical polymerization carries out effectively, end is the structure of phosphorus element-containing because it is grown up, so also has the effect of giving material as fire-retardantization.In addition, the efficiency of initiation of oxime ester series initiators is good, and only with just improving sensitivity effectively on a small quantity, therefore, the volume change that the degassing when forming epithelium post-heat-treated against corrosion causes is few, and is effective to the warpage of reduction epithelium, is preferred.Particularly preferably be both and make up use.

Resin combination of the present invention is that the photosensitive compounds that has a plurality of ethylenically unsaturated groups in the molecule that uses under the situation of light solidified is photocuring through the active energy beam irradiation, can make or helps to make the aforementioned material that carboxy resin is insoluble to alkali aqueous solution that contains.As this photosensitive compounds; Can use known polyester (methyl) propenoate commonly used, polyethers (methyl) propenoate, carbamate (methyl) propenoate, carbonic ether (methyl) propenoate, epoxy (methyl) propenoate; Particularly, can enumerate out hydroxy alkyl acrylate classes such as vinylformic acid 2-hydroxyl ethyl ester, vinylformic acid 2-hydroxypropyl acrylate; The diacrylate class of glycol such as terepthaloyl moietie, methoxyl group TEG, polyoxyethylene glycol, Ucar 35; N, N-DMAA, N hydroxymethyl acrylamide, N, acrylic amides such as N-dimethylaminopropyl acrylic amide; N, N-dimethyl amino ethyl acrylate, N, amino alkyl acrylates classes such as N-dimethylaminopropyl propenoate; The multicomponent methacrylate class of polyvalent alcohols such as pinakon, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their ethylene oxide adduct, propylene oxide adduct or 6-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.; The multicomponent methacrylate class of glycidyl ethers such as glycerin diglycidyl ether, T 55, trihydroxymethylpropanyltri diglycidyl ether, triglycidyl group isocyanuric acid ester; Be not limited to above-mentionedly in addition, also can enumerate out polyvalent alcohols such as polyether glycol, PCDL, C-terminal polyhutadiene, polyester polyol are directly carried out acroleic acid esterification or be situated between carrying out esters of acrylic acid and the trimeric cyanamide propenoate of urethane acrylateization and/or each methyl acrylic ester corresponding with the aforesaid propylene acid esters etc. by vulcabond.

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 then this Epocryl and half carbamate compounds that is formed by vulcabond such as hydroxy acrylate such as pentaerythritol triacrylate and isophorone diisocyanates react the epoxy urethane acrylate compound that obtains etc.Such epoxy acrylate is that resin can not reduce its touch dry property ground raising light solidified.

The compounding amount that has the photosensitive compounds of a plurality of ethylenically unsaturated groups in this molecule is 5 ~ 100 mass parts, the ratio of 10 ~ 70 mass parts more preferably with respect to the aforementioned carboxy resin that contains of 100 mass parts.During aforementioned compounding quantity not sufficient 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.Particularly preferably be polyvalent alcohols such as tetramethylolmethane, Dipentaerythritol, TriMethylolPropane(TMP) in the multi-functional propenoate carry out material, 2 functionality polyethers, polyester and polycarbonate that molecule prolongs with oxyethane, propylene oxide and caprolactone urethane acrylate among these.

But resin combination compounding tinting material of the present invention.As tinting material, can use known tinting materials commonly used such as red, blue, green, Huang, any one of pigment, dyestuff, pigment all can.Particularly, can enumerate out and have following Colour 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, azo 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), 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, also can 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 also add purple, orange, brown, black etc. tinting material.

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

Compounding ratio like aforesaid tinting material has no particular limits, and with respect to the aforementioned carboxy resin that contains of 100 mass parts, is preferably the ratio that is preferably 0.1 ~ 5 mass parts below 10 mass parts, especially and is enough.

Resin combination of the present invention is in order to improve its physical strength of filming etc., compounding filler as required.As such filler, can use known inorganic or organic filler commonly used, especially preferably use permanent white, spherical silicon dioxide, hydrotalcite and talcum.And then also can use metal hydroxidess such as MOX, Marinco H as the pigment extender filler.

The compounding amount of these fillers with respect to 100 mass parts aforementioned contain carboxy resin be preferably below 500 mass parts, more preferably 0.1 ~ 300 mass parts, be preferably 0.1 ~ 150 mass parts especially.When the compounding amount of filler surpassed 500 mass parts, the viscosity of resin combination uprised sometimes, and printing reduction sometimes, cured article become fragile, so not preferred.

And then, resin combination of the present invention for synthetic aforementioned contain carboxy resin, preparation compsn or in order to adjust viscosity so that be coated on substrate, the carrier film, 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; Glycol ethers such as cellosolve, methylcyclohexane, ethylene glycol butyl ether, 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.

Usually; The oxidation Once you begin of most of macromolecular materials; Oxidative degradation then constantly takes place continuously, causes the raw-material function of polymer to reduce, therefore; For anti-oxidation, can add the radical scavenger of the radical ineffective treatment that makes generation in the resin combination of the present invention or/and be harmless material, the inhibitors such as peroxide decomposer that do not produce new radical with the peroxide breakdown that produces.

The particular compound of the inhibitor that plays a role as radical scavenger can be enumerated out quinhydrones, 4-tert-butyl catechol, 2-tertiary butylated 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 p methoxy phenol, benzoquinones, two (2; 2,6,6-tetramethyl-4-piperidyl)-amine compound such as sebate, thiodiphenylamine or the like.

Radical scavenger can be commercially available material; For example can enumerate out ADKSTAB (registered trademark) AO-30, ADK STAB AO-330, ADK STABAO-20, ADK STAB LA-77, ADK STAB LA-57, ADK STABLA-67, ADK STAB LA-68, ADK STAB LA-87 (more than; ADEKA Corporation makes; Trade(brand)name); IRGANOX (registered trademark) 1010, IRGANOX1035, IRGANOX1076, IRGANOX1135, TINUVIN (registered trademark) 111FDL, TINUVIN123, TINUVIN144, TINUVIN152, TINUVIN292, TINUVIN5100 (more than; Ciba Japan Corporation makes, trade(brand)name) etc.

The particular compound of the inhibitor that plays a role as 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 be commercially available material; (ADEKA Corporation makes for example can to enumerate out ADKSTAB TPP; Trade(brand)name), MARKAO-412S (ADEKA ARGUS CHEMICAL Co.; Ltd. make trade(brand)name), SumilizerTPS (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, therefore macromolecular material, in resin combination of the present invention, in order to carry out the measure to ultraviolet stabilization, except using above-mentioned inhibitor, can also use UV light absorber owing to absorb light is decomposed, deterioration usually.

As UV light absorber, can enumerate out benzophenone derivates, benzoate derivatives, OR 10154, pyrrolotriazine derivatives, benzothiazole derivant, cinnamate derivates, 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 Whitfield's ointment 2-ethylhexyl, salol, TBS, 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 be 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; Ciba Japan Corporation 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, can realize the stabilization by the cured film of resin combination gained of the present invention.

Resin combination of the present invention consists of under the situation of Photocurable resin composition or light solidifying/heat solidifying resin composition; In order to improve sensitivity, can use N-phenylglycine class known commonly used as chain-transfer agent, phenoxy acetic acids, sulfo-phenoxy acetic acids, thyroidan etc.If enumerate the object lesson of chain-transfer agent, then there are for example mercaptosuccinic acid, Thiovanic acid, thiohydracrylic acid, methionine(Met), halfcystine, thiosalicylic acid and verivate thereof etc. to 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.

In addition, can use multi-functional mercaptan based compound, have no particular limits, for example can use 1,6-ethanthiol, 1, analiphatic sulphur alcohols such as 10-mercaptan in the last of the ten Heavenly stems two, dimercapto Anaesthetie Ether, dimercapto diethylammonium thioether; Xylylene two mercaptan, 4,4 '-dimercapto diphenylsulfide, 1, aromatic mercaptans classes such as 4-phenylene dimercaptan; Ethylene glycol bis (mercaptoacetate), polyoxyethylene glycol two (mercaptoacetate), Ucar 35 two (mercaptoacetate), glycerine three (mercaptoacetate), trimethylolethane trimethacrylate (mercaptoacetate), trimethylolpropane tris (mercaptoacetate), tetramethylolmethane four (mercaptoacetate), Dipentaerythritol six (mercaptoacetate) polyvalent alcohol of etc.ing gather (mercaptoacetate) class; Ethylene glycol bis (3-mercaptopropionic acid ester), polyoxyethylene glycol two (3-mercaptopropionic acid ester), Ucar 35 two (3-mercaptopropionic acid ester), glycerine three (3-mercaptopropionic acid ester), trimethylolethane trimethacrylate (mercaptopropionic acid ester), trimethylolpropane tris (3-mercaptopropionic acid ester), tetramethylolmethane four (3-mercaptopropionic acid ester), Dipentaerythritol six (3-mercaptopropionic acid ester) polyvalent alcohol of etc.ing gather (3-mercaptopropionic acid ester) class; 1, two (the 3-sulfydryl butyryl acyloxy) butane, 1,3 of 4-, 5-three (3-sulfydryl fourth oxygen ethyl)-1,3,5-triazines-2,4,6 (1H, 3H, 5H)-triketone, tetramethylolmethane four (3-sulfydryl butyric ester) wait and gather (sulfydryl butyric ester) class.

As these commercially available article; For example can enumerate out BMPA, MPM, EHMP, NOMP, MBMP, STMP, TMMP, PEMP, DPMP and TEMPIC (more than; Sakai chemical industry (strain) is made), KARENZ (registered trademark) MT-PE1, KARENZ MT-BD1 and KARENZ-NR1 (more than, clear with electrician's (strain) manufacturing) 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, 2-mercaptobenzothiazole, 2-sulfydryl-5-methylthio group-thiadiazoles, 2-sulfydryl-6-hexanolactam, 2 for example can enumerate out sulfydryl-4-GBL (another name:; 4; Trade(brand)name ZISNET F), 2-dibutylamino-4 (three associations change into (strain) and make 6-tri-thiol-s-triazine:; Trade(brand)name ZISNET DB) and 2-anilino-4 (three associations change into (strain) and make:, (three associations change into (strain) and make 6-dimercapto-s-triazine 6-dimercapto-s-triazine: trade(brand)name ZISNET AF) etc.

As the chain-transfer agent of the development property of not damaging Photocurable resin composition or light solidifying/heat solidifying resin composition, promptly have a heterogeneous ring compound of sulfydryl; Preferred especially mercaptobenzothiazole, 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.

In order to improve the adaptation of interlayer, or be coated with the adaptation of rete and base material, can use driving fit promotor in the resin combination of the present invention.If enumerate concrete example; The Accel M that Kawaguchi's chemical industry (strain) is made), morpholinyl methyl isophthalic acid-phenyl-triazole-2-thioketones benzoglyoxaline for example, benzoxazole, benzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercaptobenzothiazole (trade(brand)name:, 5-amino-morpholinyl methylthiazol-2-thioketones, 2-sulfydryl-5-methylthio group-thiadiazoles, triazole, tetrazolium, benzotriazole, carboxyl benzotriazole, contain amino benzotriazole, silane coupling agent etc. is then arranged.

Resin combination of the present invention also can be as required further known thickening materials commonly used such as the known hot stopper commonly used of compounding, fine particle silica, organobentonite, polynite; The skimmer and/or the flow agent of silicon system, fluorine system, macromolecular etc.; The silane coupling agent of imidazoles system, thiazole system, triazole system etc.; Inhibitor, the additive kind known commonly used that rust-preventive agent etc. are such.

Hot stopper can be used for preventing polymerizable compound thermopolymerization or through the time polymerization.As hot stopper; For example can enumerate out 4-methoxyphenol, quinhydrones, the substituted quinhydrones of alkyl or aryl, tert-butyl catechol, pyrogallol, 2-dihydroxy benaophenonel, 4-methoxyl group-2-dihydroxy benaophenonel, cuprous chloride, 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.

Resin combination of the present invention is adjusted to the viscosity that is fit to coating process with for example aforementioned organic solvent; Utilizing dip coating, flow coat method, rolling method, rod to be coated with methods such as method, silk screen print method, curtain Tu Fa is applied on the base material; Under about 60 ~ 100 ℃ temperature, make organic solvent volatile dry contained in the compsn (temporary transient dry), what can cannot not form stickingly films.In addition, above-mentioned compsn is applied on the carrier film and makes it be dried to film, this film is rolled and is attached on the base material, can form resin insulating barrier thus.Afterwards, under the situation that is Photocurable resin composition or light solidifying/heat solidifying resin composition, can carry out whole exposure with the conveyer belt type light curring unit of irradiation active energy beam.And then through contact or noncontact mode; Make active energy beam carry out the selectivity exposure or utilize the direct exposure machine of laser directly to carry out pattern exposure through forming figuratum photomask; With unexposed development, form corrosion-resisting pattern through dilute alkaline aqueous solution (for example 0.3 ~ 3wt% aqueous sodium carbonate).And then; Under the situation that is hot curing resin composition or light solidifying/heat solidifying resin composition; For example make its thermofixation through being heated to about 140 ~ 180 ℃ temperature; Thereby the Thermocurable composition reaction that has a plurality of ring-type ethers and/or cyclic thioether base in aforementioned carboxyl that contains carboxy resin 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 of the Photocurable resin composition that does not contain the Thermocurable composition; Also can be through thermal treatment; With the ethylenic unsaturated bond generation hot radical polymerization of the residual light solidified composition of unreacted state, coating characteristic improves when making exposure, therefore also can heat-treat (thermofixation) according to purpose and purposes.

Resin combination of the present invention can use nothing from polyester base materials such as the polyethylene terephthalate of flame retardant resistance, PENs, especially for the polyester base material of flexible electric circuit board and give its flame retardant resistance aptly, also can use other base materials certainly.As other base material, can enumerate out thermoplastic films such as the polyester film that has been pre-formed circuit, Kapton, polycarbonate film, TAC film.Be not limited to this in addition, also can use Thermocurable film etc.

Be coated with the volatile dry that carries out behind the resin combination 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).

Be coated with resin combination of the present invention as stated, and with after the solvent evaporates drying, to filming of gained make public (irradiation of active energy beam).The exposure portion of filming (by the part of active energy beam irradiation) solidifies.

As the exposure machine that is used for above-mentioned irradiation active energy beam; So long as the ultraviolet device that is equipped with high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, mercury short arc lamp etc. and shines 350 ~ 450nm scope gets final product, can also 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.

The exposure that is used to form image can be 20 ~ 2000mJ/cm usually according to thickness etc. and different ², be preferably 20 ~ 1500mJ/cm ²Scope in.

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

Except being coated directly onto with liquid state the method for base material; Resin combination of the present invention can also use with the form of dry film; Wherein, said dry film have in advance coating dry resin compsn on the film of polyethylene terephthalate etc. and form be coated with rete.Resin combination of the present invention is as follows as the situation that dry film uses.

Dry film has carrier film, is coated with rete and structure that the mulch film that can peel off that uses as required forms according to this sequential cascade.Being coated with rete is on carrier film or mulch film, to be coated with also dry aforementioned resin and layer that obtain.Form on the carrier film be coated with rete after laminated cover film above that, perhaps on mulch film, form and be coated with rete, and this duplexer is layered on the carrier film, can obtain dry film.

As carrier film, can use the thermoplastic films such as polyester film of 2 ~ 150 μ m thickness.

Being coated with rete is that resin combination is coated with on carrier film or mulch film and dry formation through the thickness with 10 ~ 150 μ m such as knife coater, lip coating machine (lip coater), comma coating machine (comma coater), film coated machine equably.

As mulch film, can use polyvinylidene film, PP SHEET FOR OPP TAPE etc., its with the bonding force that is coated with rete than carrier film be coated with the bonding force of rete little better.

When using dry film on printed substrate, to make protective membrane (permanent protective membrane), peel off mulch film, overlapping with being coated with rete with the base material that is formed with circuit, use laminating machine etc. that it is fitted, be coated with rete being formed with to form on the base material of circuit.Be coated with rete and aforementionedly likewise make public, develop, be heating and curing what form, then can form cured coating film.Carrier film is peeled off before exposure or after the exposure and all can.

Embodiment

Below, embodiment is shown and comparative example describes the present invention particularly, but the present invention does not receive the restriction of following embodiment.

Synthetic example 1

In the reaction vessel that possesses whipping appts, TM, condensing surface, drop into 3600g (4.5 moles) as have 2 above alcohol hydroxyl groups compound by 1; 5-pentanediol and 1; 6-pinakon deutero-PCDL (Asahi Kasei Chemicals Corporation makes, TJ5650J, number-average molecular weight 800), 814g (5.5 moles) dimethylolpropionic acid and 118g (1.6 moles) are as the propyl carbinol of molecular weight regulator (reaction terminating agent).Then; Drop into 2009g (10.8 moles) as the trimethyl hexamethylene diisocyanate that does not have the isocyanate compound of aromatic nucleus; Stop after being heated to 60 ℃ while stirring; Heat once more when the temperature in reaction vessel begins to reduce, continue to stir, confirm the absorption spectrum (2280cm of NCO through FTIR at 80 ℃ ^-1) after the disappearance, finish reaction.Then, adding the Trivalin SF acetic ester, to make solids component be 60 quality %, obtain containing thinner thick liquid contain carboxy resin.The acid number of the solids component that contains carboxyl urethane of gained is 49.8mgKOH/g.Below, this reaction product is called resin solution (A-1).

Synthetic example 2

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, add the Trivalin SF acetic ester and make that solids component is 50 quality %.The acid number of the solids component that contains carboxy resin that obtains is 50mgKOH/g.Below, this reaction product is called resin solution (A-2).

Synthetic example 3

In removable flask, add RE310S (the 2 officials ability bisphenol A type epoxy resin that 368.0g makes as the Japanese chemical drug (strain) of bisphenol type epoxy compound; The 184g/ equivalent), 142.7g vinylformic acid (molecular weight: 72.06), 2.94g is as 2 of hot stopper epoxy equivalent (weight):; 6-di-t-butyl-p-cresol and 1.53g are as the triphenylphosphine of catalysts; The acid number that reacts until reaction solution under 98 ℃ temperature is below the 0.5mgKOH/g, obtains epoxy carbonate (a) (theoretical molecular: 510.7).Then, in this reaction solution, add 588.2g as Trivalin SF acetic ester, 105.5g dimethylol propionic acid (the b) (molecular weight: 134.16), make it be warmed up to 45 ℃ of reaction with solvent.In this solution, slowly splash into 264.7g isophorone diisocyanate (c) (molecular weight: 222.28), make temperature of reaction be no more than 65 ℃.After dripping end, temperature is increased to 80 ℃, makes its reaction 6 hours, until recording 2250cm through the FTIR assay method ^-1Near absorption disappears, and then reaction is 2 hours under 98 ℃ temperature, obtains comprising the resin solution of 60 quality % aqueous alkaline solution-soluble urethane resins.Measure acid number, be 28.9mgKOH/g (solids component acid number: 48.1mgKOH/g).Below, this reaction product is called resin solution (A-3).

Use contains the photosensitivity group and has used the solution that contains carboxyl photoresist (ZCR-1601 that Japanese chemical drug (strain) is made: solids component 65%, the acid number of resin are 98mgKOH/g) of the multi-functional epoxyization thing of xenol phenolic varnish structures.Below, this resin solution is called (A-4).

The preparation of white lake slurry:

700g white lake (HIGILITE42M that clear and electrician's (strain) makes), 280g mixed as Trivalin SF acetic ester, the 20gBYK-110 (Ricinate that BYK-Chemie.Japan.K.K makes) of solvent stir, use the zirconium oxide bead of 0.5 μ m to carry out dispersion treatment through ball mill.After repeating this operation 3 times,, make the white lake slurry through the strainer of 3 μ m.

Embodiment 1 ~ 8, comparative example 1 ~ 4

Use the resin solution of above-mentioned synthetic example,, carry out pre-mixing with stirrer according to ratio (mass parts) compounding shown in various compositions shown in the table 1 and the table 1, carry out with 3 roll-type roller mills then mixing, the preparation curable resin composition., measuring granularity with the particle size analyzer that ERICH Sen corp. makes here, estimate the dispersity of each curable resin composition that obtains, is 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 light solidifying/heat solidifying resin composition of whole coating of silk screen print method the foregoing description 2 ~ 8 and comparative example 3,4, drying is 30 minutes in 80 ℃ heated air circulation type drying oven.After the drying, use the exposure apparatus (HMW-680-GW20) that is equipped with metal halide lamp to make public through stage phototimer (KodakNo.2), will develop (30 ℃, 0.2MPa, 1wt%Na ₂CO ₃Exposure when the aqueous solution) pattern of residual stage phototimer is 6 sections during 60 seconds is as optimum exposure.

< electrical characteristic >

The compsn of above-mentioned each embodiment 1 ~ 8 and comparative example 1 ~ 4 is applied on the figuratum Kapton substrate of formation (ESPANEX MGrade, Nippon Steel's (strain) make) through the whole face of silk screen printing, after under 80 ℃ dry 30 minutes, naturally cools to room temperature.For the hot curing resin composition of embodiment 1 and comparative example 1,2, the substrate that obtains heating under 130 ℃ was made its curing in 60 minutes.For the light solidifying/heat solidifying resin composition of embodiment 2 ~ 8 and comparative example 3,4, use the exposure apparatus (HMW-680-GW20) that is equipped with metal halide lamp the soldering-resistant pattern on the substrate of gained to be made public, with 30 ℃ 1wt%Na with optimum exposure ₂CO ₃The aqueous solution developed for 60 seconds under the condition of spray pressure 0.2MPa, obtained corrosion-resisting pattern.The heating under 130 ℃ of this substrate was made its curing in 60 minutes.Printed base plate (evaluation substrate) to obtaining carries out following evaluating characteristics.

Under above-mentioned condition, make to estimate substrate, this comb-type electrode is applied the bias voltage of DC100V, in 85 ℃, the constant temperature and humidity cabinet of 85%R.H., confirm having or not of migration after 1000 hours.Determinating reference is following.

Zero: can't see any variation.

△: slight variations is arranged.

*: move.

< flexible (folding resistance) >

Be applied on the thick PET film (polyethylene terephthalate) of 25 μ m through the whole face of compsn of silk screen printing above-mentioned each embodiment 1 ~ 8 and comparative example 1 ~ 4; After under 80 ℃ dry 30 minutes, naturally cool to room temperature; For the hot curing resin composition of embodiment 1 and comparative example 1,2, with the substrate of gained 130 ℃ down heating made its curing in 60 minutes.For the light solidifying/heat solidifying resin composition of embodiment 2 ~ 8 and comparative example 3,4, use the exposure apparatus (HMW-680-GW20) that is equipped with metal halide lamp the corrosion-resisting pattern on the gained substrate to be made public, with 30 ℃ 1wt%Na with optimum exposure ₂CO ₃The aqueous solution developed for 60 seconds under the condition of spray pressure 0.2MPa, obtained corrosion-resisting pattern, this substrate was heated down at 130 ℃ made its curing in 60 minutes.

Evaluation substrate to gained repeats the 180 ° bendings of several based on the curling joint machine, through the crackle production that observation by light microscope visual and multiplying power 200 is filmed at this moment, estimates the number of times that does not crack.

< low warpage properties >

Will with the evaluation of flexible (folding resistance) with sample likewise manufactured samples be cut into 50 * 50mm size, measure the warpage at 4 angles, obtain its MV, estimate according to following benchmark.

Zero: the not enough 1mm of warpage

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

*: warpage is more than the 4mm

< flame retardant resistance >

Be applied on thick PET of 25 μ m or the PEN (PEN) through the whole face of each curable resin composition of silk screen printing, after under 80 ℃ dry 30 minutes, naturally cool to room temperature the foregoing description 1 ~ 8 and comparative example 1 ~ 4.Print similarly at the back side, obtains the double spread dry substrate.For the hot curing resin composition of embodiment 1 and comparative example 1,2, with the double spread dry substrate of gained 130 ℃ down heating made its curing in 60 minutes.Light solidifying/heat solidifying resin composition for embodiment 2 ~ 8 and comparative example 3,4; The exposure apparatus (HMW-680-GW20) that use is equipped with metal halide lamp carries out whole exposure with optimum exposure to the two sides of the double spread dry substrate of gained, with 30 ℃ 1wt%Na ₂CO ₃The aqueous solution developed for 60 seconds under the condition of spray pressure 0.2MPa, heated down at 130 ℃ to make its curing in 60 minutes.

Use the evaluation substrate of gained, carry out thin material testing vertical flammability, carry out its flame retardant resistance evaluation according to the UL94 standard.

The result of aforementioned each evaluation test is shown in table 2 in the lump.

[table 2]

By the result shown in the above-mentioned table 2, can know under the situation of resin combination of embodiment 1 ~ 8 to have sufficient low warpage properties, flexible, and also have excellent flame concurrently.On the other hand, can know the comparative example 1,3 of oxygen-free titanium and not under the situation of the resin combination of the comparative example 2,4 of P contained compound, realize that low warpage properties, balance flexible and flame retardant resistance are unusual difficulties.

Embodiment 9 ~ 15

With each not compounding of light solidifying/heat solidifying resin composition silicon of the embodiment shown in the table 12 ~ 8 is that skimmer and each curable resin composition of preparing dilute with methylethylketone; Be coated on the carrier film and heat drying; Form the photosensitive polymer combination layer of thickness 20 μ m, the mulch film of fitting above that obtains dry film.Utilize laminating machine this dry film to be fitted on the test substrate that uses in the afore-mentioned test method, make the test substrate.For the test substrate of gained, likewise operate with aforementioned evaluation method, carry out the evaluation test of each characteristic.The result is shown in table 3.

[table 3]

Utilizability on the industry

Even polyester base material of the present invention has used the printed substrate of polyester base material with resin combination, also can form can realize Halogen, flame retardant resistance and low warpage properties excellent be coated with rete.Therefore, this resin combination, its dry film can be used to form the cured films such as soldering-resistance layer of the flame retardant resistance of printed substrate, flexible electric circuit board etc. aptly.

Claims (4)

1. the resin combination that polyester base material is used is characterized in that, contain carboxy resin,

Titanium oxide and

Phosphorus compound.

2. dry film, it is coated with drying with the described resin combination of claim 1 and forms on film.

3. cured coating film, it carries out photocuring and/or thermofixation and obtains to the described resin combination of claim 1 or to said resin combination is coated with the dry dry film that forms on film.

4. printed substrate, it has cured coating film, and the dry dry film that forms carries out photocuring to said cured coating film and/or thermofixation obtains to the described resin combination of claim 1 or to said resin combination is coated with on film.