CN101981131B

CN101981131B - Curable resin composition, cured article thereof, and printed circuit board

Info

Publication number: CN101981131B
Application number: CN200980111199.2A
Authority: CN
Inventors: 加藤贤治; 有马圣夫
Original assignee: Taiyo Holdings Co Ltd
Current assignee: Taiyo Holdings Co Ltd
Priority date: 2008-03-28
Filing date: 2009-03-27
Publication date: 2014-01-01
Anticipated expiration: 2029-03-27
Also published as: KR20100131466A; JP5787516B2; KR101612569B1; WO2009119821A1; JPWO2009119821A1; CN101981131A

Abstract

Disclosed are: a curable resin composition which can improve touch dryness of a finger after drying and coating properties; a cured article of the curable resin composition; and a printed circuit board. The curable resin composition comprises a lactic acid ester, a resin having a carboxyl group, and a photopolymerization initiator. The curable resin composition is diluted with the lactic acid ester so that the viscosity of the curable resin composition becomes 0.1 to 250 dPa s. The curable resin composition is applied on a substrate having fine pores formed on a surface layer thereof, and is dried to form a coating film on the substrate. The coating film is subsequently exposed to light, developed, and cured. In this manner, a cured article having a pattern thereon or a printed circuit board can be produced.

Description

Curable resin composition and its cured article and printed circuit board (PCB)

Technical field

The present invention relates to curable resin composition and the cured article and the printed circuit board (PCB) that use it.

Background technology

The pattern of the soldering-resistance layer of use in printed circuit board normally forms in the following way: be coated with curable resin composition being formed with on the substrate of circuit, make its dry dry coating that forms solder resist, make the optical tool vacuum closely sealed and after carrying out contact exposure, developed (with reference to patent documentation 1).

Now, if the touch dry of dry coating is insufficient, during contact exposure and optical tool closely sealed, after exposure, produce that optical tool can't be peeled off or dry coating from rough sledding such as strippable substrates.

In addition, in recent years, in high-density printed circuit board, adopt and utilize laser to be opened the laminated substrate of the processing in small hole.In such laminated circuit board, there is the small hole (blind hole, laser hole) of countless φ 20 μ m～φ 200 μ m, the degree of depth 20 μ m～100 μ m in top layer, and during to its coating solder resist, solder resist swells in small hole.In addition, dry rear soldering-resistance layer cracking, produce the problem of only porose soldering-resistance layer attenuation on every side.

Like this, practical situation are, in curable resin composition, the insufficient caused problem of dried touch dry of filming, the problem of coating such as swell in small hole still are not resolved.

Patent documentation 1: TOHKEMY 2000-7974 communique (claims)

Summary of the invention

the problem that invention will solve

The object of the invention is to, a kind of cured article, printed circuit board (PCB) that can improve the curable resin composition of dried touch dry and coating and use it is provided.

for the scheme of dealing with problems

In order to solve above-mentioned problem, the curable resin composition of a scheme of the present invention is characterised in that, this resin combination is for printed circuit board (PCB), described printed circuit board (PCB) has small hole on the top layer of substrate, and this curable resin composition contains lactate, contains carboxy resin and Photoepolymerizationinitiater initiater.

By such formation, can obtain and not only can improve on substrate the dried touch dry of coating and coating, particularly in the top layer of substrate has the printed circuit board (PCB) in small hole, can improve anti-depression, also there is the curable resin composition of sufficient deep solidified nature.In addition, lactate is preferably used the Pfansteihl ester in natural goods source,, CO exhausted from fossil oil ₂the environment aspect that output is cut down is considered, can be reduced the impact on environment, human body.By with this lactate, the viscosity of curable resin composition being diluted to 0.1～250dPas, thereby improve coating and coating (anti-depression)., in the present invention, in the situation that the top layer of substrate is formed with small hole, be particularly effective.

In addition, by containing containing carboxy resin, can also give alkali-developable to resin combination of the present invention, carry out the development of fine.

Cured article or the printed circuit board (PCB) of a scheme of the present invention are characterised in that, it possesses the pattern by dry coating is exposed and develops, is solidified to form, this dry coating is on substrate, particularly top layer is formed with the curable resin composition that coating on the substrate in small hole is 0.1～250dPas by the viscosity of lactate dilution, dry and form.In addition, this exposure is preferably contact exposure.

By such formation, can obtain the coating suppressed small hole bad, suppress the inhomogeneous of thickness that depression causes, and possess and fully be cured to cured article or printed circuit board (PCB) deep, insulativity, pattern that thermotolerance is high.

In the present invention, small hole means the hole (blind hole, laser hole) of φ 20 μ m～φ 200 μ m, and depth direction is not particularly limited.That is, about depth direction, applicable in the very wide scope in the hole of the shallow bore hole～degree of depth 100 μ m that are several microns in the degree of depth.

The effect of invention

According to the present invention, can improve dried touch dry and to the coating in small hole.Consequently, even carry out contact exposure, also can suppress pattern from strippable substrate, therefore can form the more pattern of fine.

In addition, can suppress bad to the coating in small hole, suppress the inhomogeneous of thickness that depression causes, can fully be cured to deep.

And then, according to the present invention, can suppress bad to the coating in small hole, suppress the inhomogeneous of thickness that depression causes, can form fully be cured to deep, insulativity, pattern that thermotolerance is high.

The accompanying drawing explanation

Figure 1A means the figure of depressed phenomenon.

Figure 1B means the figure of depressed phenomenon.

Fig. 2 A means the figure of coating state in the past.

Fig. 2 B means the figure of drying regime in the past.

Fig. 3 A means the figure of the coating state in a scheme of the present invention.

Fig. 3 B means the figure of the drying regime in a scheme of the present invention.

Fig. 4 means the figure of the diluted viscosity curve in a scheme of the present invention.

description of reference numerals

11... base material

12... copper circuit

12a... small hole

13... curable resin composition

Embodiment

Below, embodiments of the present invention are described.

The curable resin composition of present embodiment is characterised in that, it contains lactate, containing carboxy resin and Photoepolymerizationinitiater initiater.

Such formation is based on following neodoxy: while using lactate as thinner in the curable resin compositions such as alkali developable solder resist, to the base material that is formed with small hole be coated with, dried depressed phenomenon is few.

Depressed phenomenon refers to, for example, and as shown in Figure 1A, be formed with the copper circuit 12 of small hole 12a on base material 11 after, coating curable resin composition 13, while making it dry, as shown in Figure 1B, the phenomenon of the thickness attenuation on every side of the small hole 12a of copper circuit 12.Think that the reason that this depressed phenomenon tails off when using lactate as thinner is relevant with the solvability of lactate and resin.That is,, for the resinous principle of curable resin composition, the dilution efficiency of lactate is lower than other general solvent.Therefore, when curable resin composition is diluted to the viscosity that can use, with respect to the resin solid composition of solvent, relatively tail off.Therefore, corresponding to few resin solid composition, by such curable resin composition relatively heavy back be coated on small hole and circuit on, can guarantee the suitable dry film thickness on circuit.Think, while using like this lactate as thinner, with other general solvent, compare, the coating thickness on small hole has increased, and result, even dry coating also can suppress depressed phenomenon for film.

Here, as shown in Figure 2 A, even, not containing the curable resin composition of lactate, by increasing the coating thickness of the curable resin composition 13 on small hole 12a, as shown in Fig. 2 B, also can suppress depressed phenomenon.Yet in this case, the thickness of the small hole part in addition after existence is dry and after solidifying is the problem of thickening also.

In this, by using the curable resin composition that contains lactate of present embodiment, even increase the coating thickness of the curable resin composition 13 on small hole 12a as shown in Figure 3A, as shown in Figure 3 B, after the drying of curable resin composition 13 and the thickness of the part beyond the small hole 12a after solidifying also can filming, and can suppress depressed phenomenon.

Now, preferably by lactate, the viscosity of curable resin composition of the present invention is adjusted to 0.1～250dPas.More effective, be adjusted to 0.5～50dPas.In addition, dilution efficiency is poor owing to only diluting by lactate, therefore by being used in combination other general solvent, can, on the basis that suppresses depressed phenomenon, easily adjust coating film thickness, composition.

Therefore, usually, if do not increase the coating thickness of curable resin composition 13, can't suppress depressed phenomenon, but according to present embodiment, by adjust the viscosity of composition with lactate, also can suppress depressed phenomenon even thickness is less, can also keep equably the thickness of small hole periphery.

And obtained unexpectedly following opinion: while using lactate as thinner, drying property is good, can improve the touch dry of dry coating; In image formative after exposure, compare when not using lactate, can form thinner minimum residual wires.Detailed reason unclear, the residual solvent quantitative change while thinking due to curable resin composition dry obtains still less, so the photoreactivity of solder resist bottom improves.

For the lactate that can use like this, the lactate in fossil oil source is not only arranged, the lactate that also has the fermentation of the starch by corn etc. to manufacture.The fermented-milk acid esters (L body) in the lactate (the D body of optical isomer and the mixture of L body) in fossil oil source and natural goods source can obtain almost same effect.Because L body lactate (Pfansteihl ester) has the carbon in natural goods source, so pass through to use L body lactate,, CO exhausted at fossil oil ₂the environment aspect that output is cut down, can reduce the impact on environment, human body.

As the lactate in present embodiment, the just own ester of methyl lactate, ethyl lactate, lactic acid n-propyl ester, isopropyl lactate, n-butyl lactate, isobutyl lactate, amyl lactate, isoamyl lactate, lactic acid, cyclohexyl lactate, benzyl lactate etc. be can list particularly, methyl lactate, ethyl lactate etc. preferably listed.These lactate compounds can be used alone or use as mixture of more than two kinds, all can use any in L body, D body.

And then, in the curable resin composition of present embodiment, except lactate, can contain Thermocurable composition, the photosensitivity various constituents that become to grade.As long as insulativity, thermotolerance etc. can be suitable for printed circuit board (PCB), be not limited to specific constituent, can suitably select.

Basically can consider the various schemes that comprise Thermocurable composition or photosensitivity composition or these two kinds of compositions.In the situation that the solder resist of alkali developable, except lactate, containing carboxy resin, can also contain the Thermocurable composition such as the compound that there are 2 above olefinic unsaturated groups in Photoepolymerizationinitiater initiater, molecule and epoxy compounds and thermal curing catalyst as required, filler, organic solvent etc.Curable resin composition of the present invention is due to the material that also can use the natural goods source, therefore also little to the load of environment.

In addition, the kind by using above-mentioned each composition of suitable selection by the optimized curable resin composition of mixing ratio, can access cured article, the printed circuit board (PCB) of desired characteristic.

In present embodiment, as containing carboxy resin, the various resin compounds with carboxyl can be used in molecule, alkali-developable can be given.As such, containing carboxy resin, from the aspect of light solidified, anti-developability, consider, especially preferably in molecule, have ethylenical unsaturated double bonds containing the carboxyl photoresist.In addition, this unsaturated double-bond preferably derives from acrylic or methacrylic acid or their derivative.

As containing the concrete example of carboxy resin, the compound of enumerating below preferably.In addition, (methyl) acrylate is the term of general name acrylate, methacrylic ester and their mixture, and other is similarly expressed too.

(1) (methyl) vinylformic acid with containing the material copolymerization of unsaturated group, obtain containing carboxy resin.

(2) vulcabond and carboxylic diol compound and diatomic alcohol compounds polyaddition reaction obtain containing the carboxylic acid urethane resin.

(3) photosensitivity that vulcabond and 2 officials energy epoxy group(ing) (methyl) acrylate or the anhydride modified thing of its part and carboxylic diol compound and diatomic alcohol compounds polyaddition reaction obtain is containing the carboxylic acid urethane resin.

(4) in the resin of above-mentioned (2) or (3) synthetic, add in molecule there is 1 hydroxyl and end (methyl) propylene acidylate that more than 1, the compound of (methyl) acryl obtains containing the carboxylic acid urethane resin.

(5) in the resin of above-mentioned (2) or (3) synthetic, add in molecule there is 1 isocyanate group and end (methyl) propylene acidylate that more than 1, the compound of (methyl) acryl obtains containing the carboxylic acid urethane resin.

(6) 2 officials can and multifunctional (solid-state) epoxy resin with (methyl) vinylformic acid, react, contain carboxy resin being present in photosensitivity that on the hydroxyl of side chain, 2 yuan of acid anhydrides of addition obtain.

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

(8) 2 officials can trimethylene oxide (oxetane) resins with dicarboxylic acid, react, the primary hydroxyl of generation and 2 yuan of acid anhydrides additions obtain contains the carboxylic acid polyester resin.

(9) above-mentioned resin further with 1 molecule in there is 1 epoxy group(ing) and more than 1 the compound addition of (methyl) acryl and the photosensitivity that obtains containing carboxy resin.

In addition, thisly containing in carboxy resin synthetic, also use lactate.

By containing these containing carboxy resin, because the side chain of main chain, polymkeric substance has a lot of free carboxyls, therefore can utilize dilute alkaline aqueous solution to be developed.

In addition, the acid number containing carboxy resin is preferably 40～200mgKOH/g.While containing the not enough 40mgKOH/g of acid number of carboxy resin, alkali develops and becomes difficult, on the other hand, while surpassing 200mgKOH/g, the dissolving of developing solution to exposure section occurs, and therefore, it is thinner than needed that line becomes, sometimes be dissolved by the developing and peel off exposure section and unexposed indistinction, be difficult to describe normal corrosion-resisting pattern.45～120mgKOH/g more preferably.

In addition, containing the weight-average molecular weight of carboxy resin according to the difference of resin matrix and difference is preferably 2000～150000 usually, 5000～100000 scope more preferably.During weight-average molecular weight less than 2000, tack-free degradation, the wet fastness of filming after exposure is not good, produce film wearing and tearing, resolving power variation greatly while developing.On the other hand, weight-average molecular weight surpasses at 150000 o'clock, the remarkable variation of developability, package stability variation.

In whole compositions, such mixing ratio containing carboxy resin is preferably 20～60 quality %.While being less than above-mentioned scope, coating strength reduces, therefore not preferred.On the other hand, during more than above-mentioned scope, viscosity uprises, the reductions such as coating.30～50 quality % more preferably.

May be used singly or as a mixture of two or more containing carboxy resin like this.

In addition, as Photoepolymerizationinitiater initiater, can use and be selected from the oxime ester is that Photoepolymerizationinitiater initiater, alpha-aminoacetophenone are that Photoepolymerizationinitiater initiater and acyl group phosphorus oxide are one kind or two or more in the group that forms of Photoepolymerizationinitiater initiater.

As the oxime ester, be Photoepolymerizationinitiater initiater, particularly, commercially available product can list the N-1919 that CGI-325, the IRGACURE OXE01 of the manufacture of specialty goods chemical company, IRGACURE OXE02 etc., the manufacture of ADEKA company are clung in west.These oxime esters are that Photoepolymerizationinitiater initiater can be used alone or combine two or more use.

As alpha-aminoacetophenone, it is Photoepolymerizationinitiater initiater, can list for example 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, N-dimethylamino methyl phenyl ketone etc.As commercially available product, can list west and cling to IRGACURE 907, the IRGACURE 369 of the manufacture of specialty goods chemical company, IRGACURE 379 etc.

Be Photoepolymerizationinitiater initiater as the acyl group phosphorus oxide, can list 2,4; 6-trimethylbenzoyl diphenyl phosphine oxide, two (2,4,6-trimethylbenzoyl) phenyl phosphine oxide, two (2; 6-dimethoxy benzoyl)-2,4,4-tri-methyl-amyl phosphine oxide etc.As commercially available product, can list Lucirin TPO, the IRGACURE 819 that west bar specialty goods chemical company manufactures etc. that BASF AG manufactures.

Above-mentioned containing carboxy resin, as long as the mixing ratio of such Photoepolymerizationinitiater initiater is 0.01～30 mass parts with respect to 100 mass parts.During less than 0.01 mass parts, the light solidified deficiency on the copper for printed circuit board (PCB), film and peel off, and the coating characteristics such as chemical proofing reduce, therefore not preferred.On the other hand, while surpassing 30 mass parts, there is the tendency that Photoepolymerizationinitiater initiater becomes acutely in the photoabsorption of welding resistance film coated surface, the deep solidified nature reduces.0.5～15 mass parts more preferably.

In addition, in the situation that the oxime ester is Photoepolymerizationinitiater initiater, above-mentioned containing carboxy resin with respect to 100 mass parts, its mixing ratio is preferably 0.01～20 mass parts.0.01～5 mass parts more preferably.

And then, can use the Photoepolymerizationinitiater initiater except above-claimed cpd, light-initiated auxiliary agent and sensitizing agent in the curable resin composition of present embodiment.Can list such as bitter almond oil camphor compound, acetophenone compound, anthraquinone compounds, thioxanthone compound, ketal compound, benzophenone cpd, xanthone compound and tertiary amine compound etc.

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

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

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

As the thioxanthone compound, can list particularly 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, CTX, 2,4-di-isopropyl thioxanthone etc.

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

As benzophenone cpd, can list particularly benzophenone, 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, can list ethanolamine compound particularly, compound with dialkyl amido benzene structure, for example 4, 4 '-dimethylamino benzophenone (the NISSOCURE MABP that Japanese Cao Da company manufactures), 4, the dialkyl amido benzophenone such as 4 '-diethylin benzophenone (EAB that Hodogaya Chemical Co.LTD. manufactures), 7-(diethylin)-4-methyl-2H-1-chromen-2-ones (7-(diethylin)-4-methylcoumarin) etc. are containing the coumarin compound of dialkyl amido, ethyl 4-dimethy laminobenzoate (the KAYACURE EPA that Japanese chemical drug company manufactures), 2-dimethylamino ethyl benzoate (the Quantacure DMB that International Bio-Synthetics company manufactures), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (the Quantacure BEA that International Bio-Synthetics company manufactures), to dimethylamino M-nitro benzoic acid isopentyl ethyl ester (the KAYACURE DMBI that Japanese chemical drug company manufactures), 4-dimethylaminobenzoic acid-2-ethylhexyl (Esolol 507 that Van Dyk company manufactures) and 4, 4 '-diethylin benzophenone (EAB that Hodogaya Chemical Co.LTD. manufactures) etc.

In these compounds, particularly preferably thioxanthone compound and tertiary amine compound.Consider from the aspect of deep solidified nature, preferably comprise the thioxanthone compound, wherein, preferably 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthone, CTX, 2, the thioxanthone compounds such as 4-di-isopropyl thioxanthone.

Above-mentioned containing carboxy resin with respect to 100 mass parts, the mixing ratio of such thioxanthone compound is preferably below 20 mass parts.When the mixing ratio of thioxanthone compound is too much, the thick film solidified nature reduces, and the cost of product improves.More preferably below 10 mass parts.

As tertiary amine compound, preferably there is the compound of dialkyl amido benzene structure, wherein, the coumarin compound that contains dialkyl amido that particularly preferably dialkyl amido benzophenone cpd, maximum absorption wavelength are 350nm～410nm.As the dialkyl amido benzophenone cpd, 4,4 '-diethylin benzophenone is low preferably because of toxicity.Due to the maximum absorption wavelength of the maximum absorption wavelength coumarin compound that contains dialkyl amido that is 350nm～410nm in 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 reaction tinting pigment self while having used tinting pigment.From the sensitization effect of the laser display excellence to wavelength 400nm～410nm, consider, especially preferably 7-(diethylin)-4-methyl-2H-1-chromen-2-one.

Aforementioned containing carboxy resin with respect to 100 mass parts, the mixing ratio of such tertiary amine compound is preferably 0.1～20 mass parts.During mixing ratio less than 0.1 mass parts of tertiary amine compound, there is the tendency that can not get sufficient sensitization effect.While surpassing 20 mass parts, exist tertiary amine compound to cause the photoabsorption on the surface of filming in dry welding resistance to become tendency violent, that the deep solidified nature reduces.The ratio of 0.1～10 mass parts more preferably.

These Photoepolymerizationinitiater initiaters, light-initiated auxiliary agent and sensitizing agent may be used singly or as a mixture of two or more.

In addition, the compound that has 2 above olefinic unsaturated groups in molecule is, by active energy beam, irradiate carry out photocuring, make containing carboxy resin insoluble or contribute to thawless material in alkali aqueous solution.As such compound, can list the diacrylate class of the glycol such as ethylene glycol, methoxyl group TEG, polyoxyethylene glycol, propylene glycol; The multicomponent methacrylate class of the polyvalent alcohols such as hexylene glycol, TriMethylolPropane(TMP), tetramethylolmethane, Dipentaerythritol, tris(2-hydroxy ethyl)isocyanurate or their ethylene oxide adduct or propylene oxide adduct etc.; The multicomponent methacrylate class of the ethylene oxide adduct of vinylformic acid phenoxy group ester, bisphenol a diacrylate and these phenols or propylene oxide adduct etc.; The multicomponent methacrylate class of the glycidyl ethers such as glycerol diglycidylether, glycerin triglycidyl ether, trihydroxymethylpropanyltri diglycidyl ether, three-glycidyl isocyanuric acid ester; And trimeric cyanamide acrylate and/or each methyl acrylic ester corresponding with the aforesaid propylene acid esters etc.

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

Aforementioned containing carboxy resin with respect to 100 mass parts, the mixing ratio that has the compound of 2 above olefinic unsaturated groups in such molecule is preferably 5～100 mass parts.During mixing ratio less than 5 mass parts, light solidified reduces, and is difficult to develop to form pattern by the postradiation alkali of active energy beam.On the other hand, while surpassing 100 mass parts, to the solvability reduction of alkali aqueous solution, film and become fragile.More preferably 1～100 mass parts, more preferably 5～100 mass parts.

In addition, the Thermocurable composition such as epoxy compounds is used in order to give thermotolerance.The Thermocurable composition that particularly preferably in molecule, there is 2 above ring-type ethers and/or cyclic thioether base (being designated hereinafter simply as ring-type (sulphur) ether).

About thering is the Thermocurable composition of 2 above ring-types (sulphur) ether in such molecule, 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 molecule, can list such as the compound that has at least 2 above epoxy group(ing) in molecule is that the compound that has at least 2 above oxetanyls in multi-functional epoxy compound, molecule is that the compound that has 2 above thioether groups in multifunctional oxetane compound, molecule is episulfide resin etc.

As aforementioned multi-functional epoxy compound, particularly, can list bisphenol A type epoxy resin, as Japan Epoxy Resins Co., Ltd. the EPICOAT828 manufactured, EPICOAT834, EPICOAT1001, EPICOAT1004, the Epiclon840 that Japanese ink chemical industrial company manufactures greatly, Epiclon850, Epiclon1050, Epiclon2055, Dongdu changes into the EpototeYD-011 that company manufactures, YD-013, YD-127, YD-128, the D.E.R.317 that Dow Chemical manufactures, D.E.R.331, D.E.R.661, D.E.R.664, the Araldite6071 that west bar specialty goods chemical company manufactures, Araldite6084, AralditeGY250, AralditeGY260, the SumiepoxyESA-011 that Sumitomo Chemical Co. Ltd. manufactures, ESA-014, ELA-115, ELA-128, the A.E.R.330 that industrial of Asahi Chemical Industry manufactures, A.E.R.331, A.E.R.661, A.E.R.664 etc. (being trade(brand)name), brominated epoxy resin, as Japan Epoxy Resins Co., Ltd. the EPICOATYL903 manufactured, Japanese ink chemical industrial company manufactures greatly Epiclon152, Epiclon165, Dongdu changes into EpototeYDB-400, the YDB-500 that company manufactures, the D.E.R.542 that Dow Chemical manufactures, the Araldite8011 that west bar specialty goods chemical company manufactures, SumiepoxyESB-400, ESB-700 that Sumitomo Chemical Co. Ltd. manufactures, (being trade(brand)name) such as A.E.R.711, A.E.R.714 that industrial of Asahi Chemical Industry manufactures, phenolic resin varnish type epoxy resin, as Japan Epoxy Resins Co., Ltd. the EPICOAT152 manufactured, EPICOAT154, the D.E.N.431 that Dow Chemical manufactures, D.E.N.438, the EpiclonN-730 that Japanese ink chemical industrial company manufactures greatly, EpiclonN-770, EpiclonN-865, Dongdu changes into the EpototeYDCN-701 that company manufactures, YDCN-704, the AralditeECN1235 that west bar specialty goods chemical company manufactures, AralditeECN1273, AralditeECN1299, AralditeXPY307, the EPPN-201 that Japan chemical drug company manufactures, EOCN-1025, EOCN-1020, EOCN-104S, RE-306, the SumiepoxyESCN-195X that Sumitomo Chemical Co. Ltd. manufactures, ESCN-220, the A.E.R.ECN-235 that industrial of Asahi Chemical Industry manufactures, ECN-299 etc. (being trade(brand)name), bisphenol f type epoxy resin, the Epiclon830 manufactured as large Japanese ink chemical industrial company, Japan Epoxy Resins Co., Ltd. the EPICOAT807 manufactured, Dongdu changes into EpototeYDF-170, YDF-175, the YDF-2004 that company manufactures, (being trade(brand)name) such as AralditeXPY306 that west bar specialty goods chemical company manufactures, bisphenol-A epoxy resin, as Dongdu changes into EpototeST-2004, the ST-2007 that company manufactures, ST-3000 (trade(brand)name) etc., glycidyl amine type epoxy resin, as Japan Epoxy Resins Co., Ltd. the EPICOAT604 manufactured, Dongdu changes into the EpototeYH-434 that company manufactures, the AralditeMY720 that west bar specialty goods chemical company manufactures, (being trade(brand)name) such as SumiepoxyELM-120 that Sumitomo Chemical Co. Ltd. manufactures, the glycolylurea type epoxy resin such as AralditeCY-350 (trade(brand)name) that west bar specialty goods chemical company manufactures, DAICEL CHEMICAL INDUSTRIES, the Celoxide2021 that LTD. manufactures, the AralditeCY175 that west bar specialty goods chemical company manufactures, CY179 etc. (being trade(brand)name) alicyclic epoxy resin, Japan Epoxy Resins Co., the YL-933 that Ltd. manufactures, (being trade(brand)name) trihydroxybenzene methylmethane type epoxy resin such as T.E.N., the EPPN-501 that Dow Chemical manufactures, EPPN-502, Japan Epoxy Resins Co., di-cresylol type or united phenol-type epoxy resin or their mixtures such as YL-6056, the YX-4000 that Ltd. manufactures, YL-6121 (being trade(brand)name), the EBPS-200 that Japan chemical drug company manufactures, the EPX-30 that Asahi Electro-Chemical Co. Ltd manufactures, the bisphenol-s epoxy resins such as EXA-1514 (trade(brand)name) that Japanese ink chemical industrial company manufactures greatly, Japan Epoxy Resins Co., the bisphenol-A phenolic varnish type epoxy resin such as EPICOAT157S (trade(brand)name) that Ltd. manufactures, Japan Epoxy Resins Co., the EPICOAT YL-931 that Ltd. manufactures, four hydroxyphenyl ethane type epoxy resin such as Araldite163 (being trade(brand)name) that west bar specialty goods chemical company manufactures, the AralditePT810 that west bar specialty goods chemical company manufactures, (being trade(brand)name) hetero ring type epoxy resin such as TEPIC that daily output chemical industrial company manufactures, the o-phthalic acid diglycidyl ester resins such as Blemmer DGT that Nof Corp. manufactures, Dongdu changes into four glycidyl group dimethylbenzene acyl group ethane (the tetraglycidyl xylenoyl ethane) resins such as ZX-1063 that company manufactures, ESN-190, ESN-360 that chemical company of Nippon Steel manufactures, HP-4032, the EXA-4750 that Japanese ink chemical industrial company manufactures greatly, EXA-4700 etc. are containing the epoxy resin of naphthyl, HP-7200, the HP-7200H etc. that Japanese ink chemical industrial company manufactures greatly have the epoxy resin of Dicyclopentadiene (DCPD) skeleton, the glycidyl methacrylate copolymerization such as CP-50S, CP-50M that Nof Corp. manufactures are epoxy resin, and the copolymerization epoxy resin of N-cyclohexylmaleimide and glycidyl methacrylate, epoxide modified polybutadiene rubber derivative (DAICEL CHEMICAL INDUSTRIES for example, LTD. the PB-3600 manufactured etc.), CTBN modified epoxy (such as Dongdu, changing into YR-102, the YR-450 etc. that company manufactures) etc., but be not limited to these.These epoxy resin can be used alone or in combination of two or more kinds.Wherein, especially preferred phenolic resin varnish type epoxy resin, hetero ring type epoxy resin, bisphenol A type epoxy resin or their mixture.

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

As the compound that there are 2 above cyclic thioether bases in molecule, for example can list Japan Epoxy Resins Co., the bisphenol A-type episulfide resin YL7000 that Ltd. manufactures etc.In addition, also can use and adopt same synthetic method that the Sauerstoffatom of the epoxy group(ing) of phenolic resin varnish type epoxy resin is replaced to episulfide resin that sulphur atom forms etc.

With respect to the 1 equivalent carboxyl containing carboxy resin, the mixing ratio that has the Thermocurable composition of 2 above ring-types (sulphur) ether in molecule is preferably 0.6～2.5 equivalent.While thering is the mixing ratio less than 0.6 of Thermocurable composition of 2 above ring-types (sulphur) ether in molecule, in soldering-resistance layer, there is carboxyl residual, the reductions such as thermotolerance, alkali resistance, electrical insulating property.On the other hand, while surpassing 2.5 equivalent, low-molecular-weight ring-type (sulphur) ether remains in dry coating, makes the reductions such as intensity of filming.0.8～2.0 equivalent more preferably.

In addition, while using in above-mentioned molecule the thermofixation composition with 2 above ring-types (sulphur) ether, preferably contain in the lump thermal curing catalyst.As such thermal curing catalyst, particularly, can list 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, the amine compound such as N-dimethyl benzyl amine; The hydrazide compound such as adipic dihydrazide, sebacic dihydrazide; The phosphorus compounds such as triphenylphosphine etc., in addition, as commercially available product, can list for example four countries and change into 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, the 2P4MHZ (being the trade(brand)name of imidazole compound) that industrial manufactures, U-CAT3503N, 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. that SAN-APRO company manufactures.

But, 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 epoxy group(ing) and/or oxetanyl to get final product with the material reacted of carboxyl.And, can use separately or mix two or more use.

In addition, also can use the compound also worked as the adaptation imparting agent is guanamines, methyl guanamines, benzoguanamine, trimeric cyanamide, 2,4-diamino-6-methacryloxyethyl-s-triazine, 2-vinyl-4,6-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine isocyanuric acid affixture, 2,4-diamino-6-methacryloxyethyl-s-triazine derivatives such as s-triazine isocyanuric acid affixture.Preferably by they be used in combination except the above-mentioned thermal curing catalyst these.

The mixing ratio of these thermal curing catalysts, so long as the ratio of common amount is just enough, for example, containing having the Thermocurable composition of 2 above ring-types (sulphur) ether in carboxy resin or molecule, is preferably 0.1～20 mass parts with respect to 100 mass parts.0.5～15.0 mass parts more preferably.

Filler is to use as required in order to improve this physical strength of filming etc.As such filler, can use inorganic or organic filler, especially preferably use barium sulfate, preparing spherical SiO 2 and talcum.In addition, during for the interlayer insulating film the Copper Foil as prepreg, insulating trip, resin, can use woven fiber glass, inorganic, organic fibre non-woven fabrics.And then, in order to obtain white outward appearance, flame retardant resistance, also can use the metal hydroxidess such as titanium oxide, metal oxide, aluminium hydroxide as the pigment extender filler.

With respect to 100 mass parts, containing carboxy resin, the mixing ratio of this filler is preferably below 300 mass parts.When the mixing ratio of filler surpasses 300 mass parts, the viscosity of Photocurable resin composition uprises and the printing reduction, and cured article becomes fragile.More preferably 0.1～300 mass parts, be particularly preferably 0.1～150 mass parts.

Organic solvent is here organic solvent except lactate, for the synthesis of contain carboxy resin, modulation group compound or for adjusting viscosity in order to be applied to substrate or carrier film.As such organic solvent, such as listing ketone, aromatic hydrocarbon based, glycol ethers, glycol ether acetate class, ester class, alcohols, aliphatic hydrocarbon, petroleum solvent etc.Particularly, the ketones such as methylethylketone, pimelinketone are arranged; Toluene, dimethylbenzene, durene etc. are aromatic hydrocarbon based; The 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; The ester classes such as ethyl acetate, butylacetate, dipropylene glycol methyl ether acetic ester, propylene glycol methyl ether acetate, propylene-glycol ethyl ether acetic ester, propandiol butyl ether acetic ester; The alcohols such as ethanol, propyl alcohol, ethylene glycol, propylene glycol; The aliphatic hydrocarbon such as octane, decane; The petroleum solvents such as sherwood oil, petroleum naphtha, hydrogenated naphtha, solvent naphtha etc.Such organic solvent can be used separately or use as mixture of more than two kinds.

And then, can use as required the known habitual tinting materials such as phthalocyanine blue, phthalocyanine green, iodine green (iodine green), dual-azo yellow, Viola crystallina, titanium oxide, carbon black, naphthalene be black (pigment, dyestuff, pigment all can).

Below, exemplify these tinting materials.

[blue colorant]

Blue colorant has phthalocyanine system, anthraquinone system, and pigment system is the compound that is classified as pigment (Pigment), particularly, can list with following Colour Index (C.I.; The Society of Dyers and Colourists distribution) material of sequence number.

Pigment Blue 15, pigment Blue 15: 1, pigment Blue 15: 2, pigment Blue 15: 3, pigment Blue 15: 4, pigment Blue 15: 6, pigment blue 16, pigment blue 60

As dyestuff, system can be used solvent blue 35, solvent blue 45, solvent blue 63, solvent blue 68, solvent blue 70, solvent blue 83, solvent blue 87, solvent blue 94, solvent blue 97, solvent blue 19 01, solvent blue 19 04, solvent blue 19 22, solvent blue 19 36, solvent blue 67, solvent blue 70 etc.In addition to these, 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 list that pigment Green 7, pigment green 36, solvent green 3, solvent are green 5, solvent is green 20, solvent green 28 etc.In addition to these, can also use metal replacement or unsubstituted phthalocyanine compound etc.

[yellow colorants]

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

(anthraquinone system)

Solvent yellow 16 3, Pigment Yellow 73 24, Pigment Yellow 73 108, Pigment Yellow 73 193, pigment yellow 147, Pigment Yellow 73 199, Pigment Yellow 73 202.

(isoindolinone system)

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

(condensation azo system)

Pigment Yellow 73 93, Pigment Yellow 73 94, Pigment Yellow 73 95, pigment Yellow 12 8, Pigment Yellow 73 155, Pigment Yellow 73 166, Pigment Yellow 73 180.

(benzimidazolone)

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

(monoazo)

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)

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

[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 list following material.

(monoazo system)

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

(tetrazo system)

Pigment red 37,38,41.

(monoazo color lake)

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)

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

The (perylene)

Solvent of red 135, solvent red 179, pigment red 123, pigment red 149, Pigment red 166, Pigment red 178, pigment red179, 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)

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.

In addition, in order to adjust tone, can add purple, orange, brown, black etc. tinting material.Particularly, can list 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.

In addition, can coordinate such additive kinds such as adaptation imparting agent, silane coupling agent such as the defoamers such as thickening material, silicone-based, fluorine system, the macromoleculars such as the known habitual hot stopper such as quinhydrones, Hydroquinone monomethylether, tert-butyl catechol, pyrogallol, thiodiphenylamine, fine particle silica, organobentonite, montmorillonite and/or flow agent, imidazoles system, thiazole system, triazole system.

In such curable resin composition, the Photocurable composition that contains the photosensitivity composition is applied on base material, by photocuring, forms cured article.The laser that photocuring can be 350～410nm by ultraviolet exposure apparatus according or laser generation light source, particularly wavelength is cured.In addition, the hot curing resin composition that contains the thermofixation composition, the thermofixation by being heated of photocuring heat-curable composition, thus form cured article.By base material being made to the substrate that is formed with circuit, can similarly form printed circuit board (PCB).

Particularly, following operation forms cured article, printed circuit board (PCB).For example, viscosity being adjusted to the curable resin composition that is suitable for coating process with lactate and other organic solvent is applied on the base material that comprises the substrate that is formed with circuit by methods such as dip coating, flow coat method, rolling method, scraper coating method, spraying method, silk screen print method, curtain Tu Fa.

Here, as above-mentioned base material, can list the copper clad laminate of all grades (FR-4 etc.) of the materials such as copper clad laminate and Kapton, PET film, glass substrate, ceramic substrate, wafer board etc. for high frequency circuit, wherein said copper clad laminate is used the material such as paper phenol, Epoxide cellulose paper, epoxy glass fabric, polyimide glass, woven fiber glass/epoxy non-woven fabrics, woven fiber glass/Epoxide cellulose paper, epoxy synthon, fluorine polyethylene PPO cyanate and obtains.

Then, make composition at the about temperature of 60～100 ℃ in contained organic solvent volatile dry (temporary transient dry), can form tack-free filming.Perhaps, also composition can be applied on carrier film, drying forms film, and fits on base material after this film is rolled.

Afterwards, adopt contact (or cordless), utilize active energy beam optionally to expose or utilize the direct exposure machine of laser directly to carry out pattern exposure by forming figuratum photomask, unexposed development that for example, by dilute alkaline aqueous solution (0.3～3% aqueous sodium carbonate) will be uncured by rayed, thus pattern formed.

Here, as exposure machine, can use the direct drawing apparatus of laser (laser direct imaging device), be equipped with the exposure machine of metal halide lamp, the direct drawing apparatus of the UV-lamp such as the exposure machine that is equipped with (surpassing) high voltage mercury lamp, the exposure machine that is equipped with mercury short arc lamp or use (surpassing) high voltage mercury lamp.While being exposed by direct drawing apparatus, as long as use the laser of maximum wavelength in the scope of 350～410nm, can be gas laser, Solid State Laser.As direct drawing apparatus, can use devices such as Japanese Orbotech Ltd. system, ORC company system, so long as the device of the laser that the vibration maximum wavelength is 350～410nm can be used any device.

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

In addition, volatile dry can use heated air circulation type drying oven, IR stove, hot plate, convection oven etc., use the device of the thermal source with air heating mode of utilizing steam to make the method for the hot air convection contact in drying machine, and undertaken by the mode that nozzle blows supporter.

And then, in the situation that the composition that contains the Thermocurable composition, make its thermofixation by for example being heated to the approximately temperature of 140～180 ℃, the aforementioned carboxyl containing carboxy resin is reacted with the Thermocurable composition that has 2 above ring-type ethers and/or cyclic thioether base in molecule, can form the cured coating film of the various characteristics excellences such as thermotolerance, chemical proofing, anti-water absorbability, adaptation, electrical characteristic.

In addition, even in the situation that do not contain the Thermocurable composition, in the time of also can making exposure by thermal treatment, the residual ethylenic unsaturated bond generation hot radical polymerization with unreacted state, improve coating characteristic, therefore, also can heat-treat (thermofixation) according to purpose and purposes.

Embodiment

Below, by embodiment, the present invention is carried out to more specific description, but the present invention is not limited to following embodiment.In example, if not otherwise specified, part and % refer to quality criteria.

[synthesizing of curable resin composition]

In possessing the removable flask of 2 liters of stirrer, thermometer, circulation cooling tube, dropping funnel and nitrogen ingress pipe, import 660g cresols phenolic resin varnish type epoxy resin (Japanese chemical drug company system, EOCN-104S, 92 ℃ of softening temperatures, epoxy equivalent (weight) 220), 421.3g Trivalin SF acetic ester and 180.6g solvent naphtha, be heated to 90 ℃ and stirring, make its dissolving.

Then, temporarily be cooled to 60 ℃, add 216g vinylformic acid, 4.0g triphenylphosphine, 1.3g toluhydroquinone, under 100 ℃, reaction is 12 hours, obtains the reaction product that acid number is 0.2mgKOH/g.Add wherein the 241.7g Tetra Hydro Phthalic Anhydride, be heated to 90 ℃, react 6 hours.

Like this, obtaining acid number is the solution (B-1 varnish) containing carboxy resin that 50mgKOH/g, two key equivalent (gram weight of the resin of every 1 mole of unsaturated group) are 400, weight-average molecular weight is 7000.

With resulting B-1 varnish, carry out pre-mixing according to the diluting solvent for mixing ratio shown in table 1 (lactate and organic solvent) by stirrer with together with the composition of coordinating example shown below, then carry out mixingly with 3 roll-type roller mills, prepare the solder resist photosensitive polymer combination.

(coordinating example)

154 parts, varnish (100 parts of solids components)

12 parts of Irg907 (west bar specialty goods chemical company system)

0.5 part of DETX (Japanese chemical drug company system)

20 parts of dipentaerythritol acrylates (DPHA/ Japan chemical drug company system)

Phenol novolak type epoxy resin (Dow Chemical DEN-431 processed)

15 parts

25 parts of di-toluene phenol-type epoxy resins (Japan Epoxy Resins Co., Ltd. YX-4000 processed)

0.3 part of Dyhard RU 100

5 parts of trimeric cyanamides

100 parts, barium sulfate (the barium sulfate B30 processed of Sakai chemical company)

Pigment 1C.I. pigment Blue 15: 3 0.3 parts

0.8 part of pigment 2C.I. pigment yellow 147

3 parts of silicone-based defoamers

[table 1]

* 1: methyl lactate (2-hydroxymethyl propionic acid)

* the wild chemistry institute society lactic acid-fermenting methyl esters processed (L body containing ratio 99.6%) of 2:L-methyl lactate (2-hydroxymethyl propionic acid) Musashi

* 3: ethyl lactate (2-hydroxyethyl propionic acid)

* 4:PM (propylene glycol monomethyl ether)

* 5:PMA (propylene glycol monomethyl ether)

In addition, about the addition of diluting solvent, diluted viscosity opisometer is as shown in Figure 4 calculated the thinning ratio of IWATA CUP in the time of 30 seconds.In addition,

Thinning ratio (%)=black gross weight/100

The lowering time of the China ink of time (second)=based on IWATA CUP

China ink temperature=21 ℃ ± 2 ℃.

At this, the particle size analyzer (grind meter) of manufacturing with ERICHSEN company is measured granularity, estimates the dispersity of the photosensitive polymer combination of gained, is below 15 μ m.

[performance evaluation]

The evaluation of<viscosity >

With E type rotational viscosimeter, under 25 ℃, the light solidifying/heat solidifying resin composition of each embodiment and comparative example is measured, the value while usining rotating speed 5rpm is as viscosity.

The evaluation of<optimum exposure >

By copper thick be that the circuit pattern substrate of 50 μ m grinds with polishing roll, then washing, after drying, by spraying or silk screen printing according to drying after the light solidifying/heat solidifying resin composition of thickness whole each embodiment of coating of mode that be 25 μ m and comparative example, in the heated air circulation type drying oven of 80 ℃, drying is 30 minutes, naturally cools to room temperature.After naturally cooling, with ORC company exposure apparatus processed (HMW680-GW20), by stage phototimer (KodakNo2), exposed, will develop (30 ℃, 0.2MPa, 1 quality % aqueous sodium carbonate) exposure when after 60 seconds, the pattern of residual stage phototimer is 7 sections is as optimum exposure.

[evaluating characteristics]

The color of the cured article of the alkali developable solder resist by each embodiment of visual judgement and comparative example.

By spraying or silk screen printing whole each embodiment of coating of mode that thickness is 25 μ m after forming on figuratum copper clad laminate according to drying and the composition of comparative example, in the heated air circulation type drying oven of 60 ℃ dry 30 minutes, naturally cool to room temperature.Put PET negative film processed on this substrate, with ORC company exposure apparatus processed (HMW680-GW20) crimping 1 minute under reduced pressure, afterwards, the adherence state of the film while according to following benchmark evaluation, peeling off negative film.

Zero: film is not peeled off resistively.

△: film is stripped from, but on filming, has a little vestige residual.

*: resistance is arranged during stripping film, and filming above obviously has vestige residual.

<(for small hole) filling perforation >

After copper facing, have on the substrate in the small hole that is adjusted to φ 100 μ m, the degree of depth 50 μ m by spraying or silk screen printing according to drying after thickness whole each embodiment of coating of mode that be 25 μ m and the composition of comparative example, in the heated air circulation type drying oven of 80 ℃, drying is 30 minutes, naturally cools to room temperature.After naturally cooling, the depression number of the soldering-resistance layer on portalling by visual number, estimated according to following benchmark.

Fraction defective (%)=depression number/total hole count 1700 holes

Below zero: 3%

△: more than 4% and below 10%

*: more than 10%

By line/space be 300/300 μ m, copper thick be that the circuit pattern substrate of 50 μ m grinds with polishing roll, then washing, after drying, by spraying or silk screen printing according to drying after the composition of thickness whole each embodiment of coating of mode that be 25 μ m and comparative example, in the heated air circulation type drying oven of 80 ℃, drying is 30 minutes, naturally cools to room temperature.After naturally cooling, with ORC company exposure apparatus processed (HMW680-GW20), exposed.Exposing patterns is used the pattern of describing the line of 20/30/40/50/60/70/80/90/100 μ m at space part.Exposure is the exposure obtained by the optimum exposure evaluation.After exposure, utilize the 1 quality % aqueous sodium carbonate of 30 ℃ developed and describe pattern, by the thermofixations of 150 ℃ * 60 minutes, obtain cured coating film.

Calculate the minimum residual wires of the cured coating film of resulting light solidifying/heat solidifying resin composition with the opticmicroscope that is adjusted to 200 times.In addition, the line central part is cut off, after carrying out minute surface precision work, use upper diameter, lower diameter, the thickness of the minimum residual wires of the light microscope determining cured coating film that is adjusted to 1000 times.Metewand is: more hour, and then lower diameter is more close to design load for minimum residual wires, and the deep solidified nature is better.

To the results are shown in table 1.

As mentioned above, the solder resist of known embodiment with photosensitive polymer combination refer to tactile drying property, to the filling perforation in small hole and the composition of deep solidified nature excellence.

Like this, according to a scheme of the present invention, can obtain touch dry excellent and then to the filling perforation in small hole and the curable resin composition of deep solidified nature excellence.In addition, can provide light solidifying/heat solidifying resin composition, its cured article that is especially suitable for use as the solder resist purposes and use it to form the printed circuit board (PCB) of pattern.

In addition, the present invention is not limited to above-mentioned embodiment.Can do various distortion in the scope that does not exceed purport in addition implements.

Claims

1. the application of curable resin composition in printed circuit board (PCB), described printed circuit board (PCB) is formed with the hole of Ф 20 μ m～Ф 200 μ m on the top layer of substrate, described curable resin composition contains lactate and contains carboxy resin, by described lactate, the viscosity of curable resin composition is adjusted to 0.5～50dPas, described viscosity is to use E type rotational viscosimeter to measure under rotating speed 5rpm, 25 ℃.

2. application according to claim 1, is characterized in that, described curable resin composition contains Photoepolymerizationinitiater initiater.

3. application according to claim 1, is characterized in that, described curable resin composition contains tinting material.

4. application according to claim 1, is characterized in that, the Pfansteihl ester that described lactate is the natural goods source.

5. application according to claim 1, is characterized in that, described curable resin composition is for covering the solder resist of printed circuit board (PCB).

6. the application of cured article in base material, it is characterized in that, described cured article is by containing lactate and be applied on base material, make it dryly form dry coating, this dry coating is solidified to form containing the curable resin composition of carboxy resin, described base material is formed with the hole of Ф 20 μ m～Ф 200 μ m on top layer, described curable resin composition is adjusted to 0.5～50dPas by it in the viscosity of using E type rotational viscosimeter and measure under rotating speed 5rpm, 25 ℃ by described lactate.

7. a printed circuit board (PCB), it is characterized in that, it possesses the pattern by dry coating is exposed and develops, is solidified to form, described dry coating be on the substrate of printed circuit board (PCB) coating contain lactate and containing the curable resin composition of carboxy resin, make it dry and form, described printed circuit board (PCB) is formed with the hole of Ф 20 μ m～Ф 200 μ m on the top layer of substrate, described curable resin composition is adjusted to 0.5～50dPas by it in the viscosity of using E type rotational viscosimeter and measure under rotating speed 5rpm, 25 ℃ by described lactate.