CN105462306A - Curable resin composition, dry film, cured product and printed wiring board - Google Patents
Curable resin composition, dry film, cured product and printed wiring board Download PDFInfo
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- CN105462306A CN105462306A CN201510580494.XA CN201510580494A CN105462306A CN 105462306 A CN105462306 A CN 105462306A CN 201510580494 A CN201510580494 A CN 201510580494A CN 105462306 A CN105462306 A CN 105462306A
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Abstract
The invention provides a curable resin composition, a dry film, a cured product and a printed wiring board with excellent heat resistance; the curable resin composition comprises curable resin and a colorant of the following formula (1); in the formula (1), R 1 and R 2 respectively represent alkyl; m and n respectively represent a random integer between 0 and 6.
Description
Technical field
The present invention relates to curable resin composition, dry film, cured article and printed circuit board (PCB).
Background technology
Such as, as the solder mask composition of printed circuit board material in order to improve outward appearance, hide circuit and being colored.Usually the solder mask composition be colored, for green, is mixed with blue colorant and yellow colorants.The wavelength region may of the photoabsorption of yellow colorants is overlapping with the patterning wavelength (350 ~ 450nm) of photo-corrosion-resisting agent composition in recent years.Therefore, the photo-corrosion-resisting agent composition comprising yellow colorants is in the past restricted to the addition of yellow colorants in the formation of trickle pattern plotter.Therefore, there is the present situation that blue comparatively strong or that green is lighter photo-corrosion-resisting agent composition becomes main flow.The shielding of green lighter photo-resist not only circuit is poor, and seems outward appearance because thermal conductance causes substrate variable color and there occurs change, therefore not preferred.
On the other hand, the photosensitive polymer combination (patent documentation 1) of the low Huang Se perylene system tinting material of the absorbancy of the wavelength region comprising 350 ~ 450nm is proposed.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2009-258613 publication
Summary of the invention
the problem that invention will solve
But perylene system tinting material recorded by patent documentation 1 is dyestuff system tinting material, thermotolerance is insufficient compared with pigment system tinting material.Therefore, the curable resin composition obtaining excellent heat resistance is difficult to.
The present invention advantageously solves the problem, and its object is to, and provides the curable resin composition of excellent heat resistance, dry film, cured article and possesses the printed circuit board (PCB) of this cured article.
for the scheme of dealing with problems
The feature of curable resin composition that solve the problem, one embodiment of the present invention is, it contains the tinting material shown in curable resin and following formula (1).
(in formula (1), R1 and R2 is respectively alkyl, m and n is respectively the arbitrary integer in 0 ~ 6.)
At this, the tinting material shown in formula (1) is preferably the tinting material shown in following formula (2).
The feature of other embodiments of curable resin composition of the present invention is, it is also containing the tinting material beyond the tinting material shown in above-mentioned formula (1).
In addition, the feature of the dry film of other embodiments of the present invention is, above-mentioned curable resin composition is coated with also dry and obtains by it on film.
In addition, the feature of the cured article of other embodiments of the present invention is, it makes above-mentioned curable resin composition or the solidification of above-mentioned dry film form.
In addition, the feature of the printed circuit board (PCB) of other embodiments of the present invention is, it possesses above-mentioned cured article.
the effect of invention
According to the present invention, the curable resin composition of excellent heat resistance, dry film, cured article can be provided and possess the printed circuit board (PCB) of this cured article.
Accompanying drawing explanation
Fig. 1 is the wavelength-absorbance curve figure of tinting material of the present invention.
Fig. 2 is the explanatory view of dam (Dam) shape of cured article.
Embodiment
Below, the present invention is described in detail.
The feature of curable resin composition of the present invention is, it contains the tinting material shown in curable resin and following formula (1).
In formula (1), R1 and R2 is respectively alkyl, m and n is respectively the arbitrary integer in 0 ~ 6.At this, alkyl is such as the alkyl of carbonatoms 1 ~ 6, specifically, is methyl, ethyl, propyl group etc.
Tinting material > shown in < formula (1)
Tinting material shown in above-mentioned formula is low in the absorbancy of the wavelength region may of 350 ~ 450nm, and colour developing is good, and compared with dyestuff system tinting material in the past excellent heat resistance.Such as, by the tinting material shown in above-mentioned formula being used as the yellow colorants of alkali developable curable resin composition, even the curable resin composition comprising yellow colorants also can obtain high resolving power, in addition, thermotolerance, dispersion stabilization are excellent.
Characteristic is described in detail, under comprising the condition of the thickness 10 ± 5 μm of the dry coating of curable resin composition when being 10% in the content of this tinting material of solids component benchmark in this curable resin composition of tinting material shown in above-mentioned (1), absorbancy can become less than 2.0 at 350 ~ 450nm place.Therefore, the good curable resin composition of resolving power can be obtained.
In addition, Fig. 1 illustrates the wavelength-absorbance curve figure of tinting material shown in above-mentioned (2).It should be noted that, be convenient to compare, the wavelength-absorbance curve of green 5 (SG5) of colorant Solvent that the colour developing of the dyestuff system shown in patent documentation 1 is orange is shown in the lump.The absorbancy of solvent green 5 is also less than 2.0 under 350 ~ 450nm, but solvent green 5 can clearly not have thermotolerance, dispersion stabilization in embodiment described later.This due to tinting material be that the such feature of dyestuff causes, if solvability is dissolved completely by the dyestuff about solvent, then can develop the color with molecular level (numeratorlevel), on the other hand, water tolerance, thermotolerance etc. die down.In addition, for the mixing of undissolved solvent, may occur the generation of dyestuff grain, painted inequality and through time dyestuff the worry to appear in one's mind etc.
In addition, under comprising the condition of the thickness 10 ± 5 μm of the dry coating of curable resin composition when being 10% in the content of this tinting material of solids component benchmark in this curable resin composition of tinting material shown in above-mentioned (1), in using the colour examining of colourimeter to measure, can by b
*value is set to more than 60.The colour developing of the tinting material shown in this expression above-mentioned (1) is good.The colour developing of the tinting material shown in above-mentioned (1) is good, by using this tinting material, can obtain the good curable resin composition that develops the color.
And then-5% weightlessness, in TG/DTA measures, can be set to more than 300 DEG C by the tinting material shown in above-mentioned (1).Therefore, the excellent heat resistance of the tinting material shown in above-mentioned (1).Use the excellent heat resistance of the curable resin composition of this tinting material.
Coloring agents shown in above-mentioned (1) is if any the LumogenYellowS0795 etc. of BASFJAPANLTD..Tinting material shown in formula (1) is preferably the tinting material shown in following formula (2).
The compounding amount be applicable to of tinting material shown in above-mentioned (1) counts 0.01 ~ 60%, more preferably 0.01 ~ 50% with the solids component benchmark except solvent in curable resin composition.It should be noted that, the tinting material shown in above-mentioned (1) can also can without surface treatment through surface treatment.
< curable resin >
As curable resin, can be applicable to using heat-curing resin and light-cured resin.
(heat-curing resin)
Curable resin composition of the present invention is owing to comprising heat-curing resin, and thermotolerance improves, and in addition, improves with the adaptation of substrate.When comprising heat-curing resin, can alkali soluble resins be combinationally used, in addition, can for not comprising the composition of alkali soluble resins yet.
Heat-curing resin is at least any one the heat-curing resin had in preferred molecule in cyclic ether group and cyclic thioether base (hereinafter referred to as ring-type (sulphur) ether).
The heat-curing resin in this molecule with ring-type (sulphur) ether is the compound of the one or both had in molecule in the cyclic ether group of 3,4 or 5 rings or cyclic thioether base, such as, can enumerate: epoxy compounds, oxetane compound, episulfide resin etc.
As epoxy compounds, can enumerate: the bisphenol-type epoxy resins such as bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol E-type epoxy resin, bis-phenol M type epoxy resin, bis-phenol P type epoxy resin, bisphenol Z type epoxy resin, the phenolic resin varnish type epoxy resins such as bisphenol A novolac type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, biphenyl type epoxy resin, biphenyl aralkyl-type epoxy resin, aryl alkene fundamental mode epoxy resin, four hydroxy phenyl ethane type epoxy resin, naphthalene type epoxy resin, anthracene type epoxy resin, phenoxy group type epoxy resin, dicyclopentadiene type epoxy resin, norbornene-type epoxy resin, diamantane type epoxy resin, fluorenes type epoxy resin, glycidyl methacrylate copolymerization system epoxy resin, the copolymerization epoxy resin of N-cyclohexylmaleimide and glycidyl methacrylate, epoxide modified polybutadiene rubber derivative, CTBN modified epoxy, TriMethylolPropane(TMP) polyglycidyl ether, phenyl-1, 3-diglycidylether, xenyl-4, 4 '-diglycidylether, 1, 6-hexanediol diglycidyl ether, the diglycidylether of ethylene glycol or propylene glycol, sorbyl alcohol polyglycidyl ether, three (2, 3-epoxypropyl) isocyanuric acid ester, three-glycidyl three (2-hydroxyethyl) isocyanuric acid ester etc.
As multifunctional oxetane compound, can enumerate: two [(3-methyl-3-oxetanylmethoxy) methyl] ether, two [(3-ethyl-3-oxetanylmethoxy) methyl] ether, Isosorbide-5-Nitrae-bis-[(3-methyl-3-oxetanylmethoxy) methyl] benzene, Isosorbide-5-Nitrae-bis-[(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 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 trimethylene oxide alcohol and novolac resin, poly-(4-Vinyl phenol), cardo type bisphenols, calixarene kind class, Resorcinol calixarene (calixresorcinarene) class or silsesquioxane (silsesquioxane) etc. have the etherate etc. of the resin of hydroxyl.In addition, also can enumerate: there is the unsaturated monomer of trimethylene oxide ring and the multipolymer etc. of (methyl) alkyl acrylate.
As the compound in molecule with more than 2 cyclic thioether bases, such as, can enumerate: the bisphenol A-type episulfide resin YL7000 etc. that JapanEpoxyResinsCo., Ltd. manufacture.In addition, also can use and by same synthetic method, the Sauerstoffatom of the epoxy group(ing) of phenolic resin varnish type epoxy resin is replaced with sulphur atom and the episulfide resin etc. obtained.
As other heat-curing resins, can enumerate: phenoxy resin, urea (urea) resin, melamine resin etc. resin, unsaturated polyester resin, bimaleimide resin, diallyl phthalate ester resin, silicone resin, the resin with benzimidazole dihydrochloride ring, norbornene resin, cyanate ester resin, isocyanate resin, urethane resin, benzocyclobutane olefine resin, maleimide resin, bismaleimide-triazine resin, poly methylene imine resin, Thermocurable polyimide resin etc. containing triazine ring.
(light-cured resin (radical polymerization))
As light-cured resin, particularly preferably use the compound in molecule with more than 1 ethylenic unsaturated bond.As the compound with ethylenic unsaturated bond, known usual optical polymerism oligopolymer and optical polymerism vinyl monomer etc. can be used.
As optical polymerism oligopolymer, can enumerate: unsaturated polyester system oligopolymer, (methyl) acrylic acid or the like oligopolymer etc.As (methyl) acrylic acid or the like oligopolymer, can enumerate: epoxy (methyl) acrylate such as phenol Novolac epoxy (methyl) acrylate, cresol novolak epoxy (methyl) acrylate, biphenol type epoxy (methyl) acrylate, carbamate (methyl) acrylate, epoxy amino manthanoate (methyl) acrylate, polyester (methyl) acrylate, polyethers (methyl) acrylate, polybutadiene-modified (methyl) acrylate etc.It should be noted that, in this manual, (methyl) acrylate refers to the term being referred to as acrylate, methacrylic ester and their mixture, is also same for other similar statements.
As optical polymerism vinyl monomer, known usual material can be enumerated, such as, can enumerate: the styrene derivativess such as vinylbenzene, chloro-styrene, alpha-methyl styrene; The vinyl esters such as vinyl-acetic ester, vinyl butyrate or vinyl benzoate; The vinyl ethers such as vinyl isobutyl ether, vinyl n-butyl ether, vinyl tertbutyl ether, vinyl n-pentyl ether, vinyl isoamyl ether, vinyl Octadecane base ether, vinyl cyclohexyl ether, ethylene glycol monobutyl vinyl ether, triethylene glycol monomethyl vinyl ether; (methyl) acrylic amides such as acrylamide, Methacrylamide, N hydroxymethyl acrylamide, N-methylol methacrylamide, N-methoxymethyl acrylamide, N-ethoxymethyl acrylamide, N-butoxy methyl acrylamide; The allylic cpds such as isocyanuric acid triallyl ester, Phthalic acid, diallyl ester, diallyl isophthalate; (methyl) acrylic acid ester classes such as (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) vinylformic acid tetrahydro furfuryl ester, (methyl) isobornyl acrylate, (methyl) phenyl acrylate, (methyl) phenoxy ethyl acrylate; (methyl) hydroxyalkyl acrylates classes such as (methyl) Hydroxyethyl acrylate, (methyl) Propylene glycol monoacrylate, tetramethylolmethane three (methyl) acrylate; Alkoxyalkylene glycol list (methyl) esters of acrylic acids such as (methyl) methoxyethyl ethyl ester, (methyl) ethioxy ethyl ester; The alkylidene polyol such as ethylene glycol bisthioglycolate (methyl) acrylate, butyleneglycol two (methyl) esters of acrylic acid, neopentyl glycol two (methyl) acrylate, 1,6-hexylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, tetramethylolmethane four (methyl) acrylate, Dipentaerythritol six (methyl) acrylate gathers (methyl) acrylate; The polyether polyols such as Diethylene Glycol two (methyl) acrylate, triethylene glycol two (methyl) acrylate, ethoxylated trimethylolpropane triacrylate, propoxylation trimethylolpropane tris (methyl) acrylate gather (methyl) esters of acrylic acid; Hydroxypivalic acid DOPCP two (methyl) acrylate etc. gather (methyl) esters of acrylic acid; Poly-(methyl) esters of acrylic acid of the isocyanuric acid ester type such as three [(methyl) acrylyl oxy-ethyl] isocyanuric acid ester etc.
When curable resin composition of the present invention is used for the printing of ink-jetting style, curable resin composition of the present invention preferably comprise 2 officials can (methyl) acrylate, 3 officials can above multifunctional (methyl) acrylate and have in (methyl) acrylate of hydroxyl at least any one.
As the concrete example of 2 officials' energy (methyl) acrylate, can enumerate: 1,4 butanediol diacrylate, 1,6 hexanediol diacrylate, 1,9-nonanediol diacrylate, the diacrylate of the dibasic alcohol such as decamethylene-glycol diacrylate, glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, polyethyleneglycol diacrylate, propylene glycol diacrylate, tripropylene glycol diacrylate, polypropyleneglycol diacrylate, neopentylglycol diacrylate, to at least any one and the diacrylate of the dibasic alcohol obtained in neopentyl glycol addition of ethylene oxide and propylene oxide, the diacrylate of the glycol such as caprolactone modification 3-hydroxypivalic acid neopentylglycol diacrylate, dihydroxyphenyl propane EO affixture diacrylate, bisphenol-ap O affixture diacrylate, Tricyclodecane Dimethanol diacrylate, hydrogenation Dicyclopentadiene (DCPD) diacrylate, cyclohexyl diacrylate etc. has the diacrylate of ring texture, or the methacrylate monomer etc. corresponding with them.
Can (methyl) acrylate as commercially available 2 officials, can enumerate: LIGHTACRYLATE1,6HX-A, 1,9ND-A, 3EG-A, 4EG-A (trade(brand)name that KYOEISHACHEMICALCo., LTD. manufacture); HDDA, 1,9-NDA, DPGDA, TPGDA (Daicel-CytecCompanyLtd. manufacture trade(brand)name); VISCOAT#195, #230, #230D, #260, #310HP, #335HP, #700HV, #540 (trade(brand)name that OSAKAORGANICCHEMICALINDUSTRYLTD. manufactures); ARONIXM-208, M-211B, M-215, M-220, M-225, M-240, M-270 (trade(brand)name that TOAGOSEICO., LTD. manufacture) etc.
Can the concrete example of above multifunctional (methyl) acrylate as 3 officials, can enumerate: pentaerythritol triacrylate, Viscoat 295, Pehanorm triacrylate, ethylene-oxide-modified Viscoat 295, epoxy pronane modification Viscoat 295, Epicholorohydrin modification Viscoat 295, tetramethylol methane tetraacrylate, pentaerythritol tetramethylacrylate, tetramethylol methane tetraacrylate, ethylene-oxide-modified tricresyl phosphate acrylate, Epicholorohydrin modification glycerol triacrylate, dipentaerythritol acrylate, Dipentaerythritol monohydroxypentaacrylate, or with the polyfunctional acrylic ester that their silsesquioxane modifier etc. is representative, or the methacrylate monomer corresponding with them, 3 officials' energy methacrylic esters, 6-caprolactone modification three (acryloyl-oxyethyl) isocyanuric acid ester etc.
As the concrete example of (methyl) acrylate with hydroxyl, can enumerate: (methyl) vinylformic acid 2-hydroxyl-3-acryloxypropyl ester, (methyl) vinylformic acid 2-hydroxyl-3-phenoxyethyl acrylate, single (methyl) vinylformic acid 1, 4-cyclohexanedimethanoester ester, (methyl) vinylformic acid 2-hydroxyl ethyl ester, (methyl) vinylformic acid 2-hydroxypropyl acrylate, (methyl) vinylformic acid 4-hydroxybutyl ester, tetramethylolmethane three (methyl) acrylate, Dipentaerythritol monohydroxy five (methyl) acrylate, (methyl) vinylformic acid 2-hydroxypropyl acrylate etc.
As the commercially available product of (methyl) acrylate with hydroxyl, can enumerate: ARONIXM-5700 (TOAGOSEICO., LTD. the trade(brand)name manufactured), 4HBA, 2HEA, CHDMMA (more than, NipponKaseiChemicalCo., Ltd manufacture trade(brand)name), BHEA, HPA, HEMA, HPMA (more than, NipponShokubaiCo., Ltd. the trade(brand)name manufactured), LightEsterHO, LightEsterHOP, LightEsterHOA (more than, KYOEISHACHEMICALCo., the trade(brand)name of LTD. manufacture) etc.
(light-cured resin (cationoid polymerisation))
As light-cured resin, can be applicable to using alicyclic ring epoxy compound and vinyl ether compound etc.Wherein, as alicyclic ring epoxy compound, can enumerate: 3, 4, 3 ', 4 '-diepoxy bis cyclohexane (diepoxybicyclohexyl), 2, 2-two (3, 4-epoxycyclohexyl) propane, 2, 2-two (3, 4-epoxycyclohexyl)-1, 3-HFC-236fa, two (3, 4-epoxycyclohexyl) methane, 1-[1, 1-two (3, 4-epoxycyclohexyl)] ethylbenzene, two (3, 4-epoxycyclohexyl) adipic acid ester, 3, 4-epoxycyclohexyl-methyl (3, 4-epoxy) cyclohexane carboxylate, (3, 4-epoxy-6-methylcyclohexyl) methyl-3 ', 4 '-epoxy-6-methylcyclohexanecarboxylic acid ester, ethene-1, 2-two (3, 4-epoxy cyclohexane carboxylic acid) ester, epoxy cyclohexane, 3, 4-epoxycyclohexyl methyl alcohol, 3, 4-epoxycyclohexylethyl Trimethoxy silane etc. has the alicyclic ring epoxy compound etc. of epoxy group(ing).As commercially available product, such as, can enumerate: CELLOXIDE2000, CELLOXIDE2021, CELLOXIDE3000, EHPE3150 that DAICELCHEMICALINDUSTRIES, LTD. manufacture; The EPOMIKVG-3101 that MitsuiChemicals, Inc. manufacture; The E-1031S that YUKASHELLEPOXYKABUSHIKIKAISHA manufactures; TETRAD-X, TETRAD-C that MITSUBISHIGASCHEMICALCOMPANY, INC. manufacture; NIPPONSODACO., EPB-13, EPB-27 etc. of LTD. manufacture.
As vinyl ether compound, can enumerate: the ring-type ether type vinyl ether such as Isosorbide divinyl ether, oxanorbornene divinyl ether (oxyethane ring, trimethylene oxide ring, butyl oxide link etc. have the vinyl ether of cyclic ether group); The vinyl aryl ethers such as Vinyl phenyl ether; The alkyl vinyl ether such as n-butyl vinyl ether, octyl vinyl ether; The cycloalkyl vinyl ethers such as cyclohexyl vinyl ether; The polyfunctional vinyl ethers such as quinhydrones divinyl ether, BDO divinyl ether, hexanaphthene divinyl ether, cyclohexanedimethanol divinyl base ether; α position and/or β position have the substituent vinyl ether compound such as alkyl, allyl group etc.As commercially available product, such as, can enumerate: 2-hydroxyethyl vinyl ether (HEVE), diethylene glycol monovinyl base ether (DEGV), 2-hydroxy butyl vinyl ether (HBVE), triethyleneglycol divinylether etc. that Maruzen Petrochemical Co., Ltd. manufactures.
(alkali soluble resins)
Curable resin composition of the present invention can contain alkali soluble resins.As alkali soluble resins, preferably use containing carboxy resin or resol.Not only can improve the adaptation with substrate, and particularly when using containing carboxy resin, from developability aspect more preferably.Containing carboxy resin also can for have ethylenical unsaturated double bonds containing carboxyl photoresist.
(1) epoxy resin and (methyl) vinylformic acid is made react, the dibasic acid anhydride such as addition Tetra hydro Phthalic anhydride, Tetra Hydro Phthalic Anhydride, hexahydrophthalic anhydride on the hydroxyl being present in side chain and obtain contain carboxyl photoresist.
(2) make the further epoxidation of the hydroxyl of epoxy resin with epoxy chloropropane and the polyfunctional epoxy resin that obtains and (methyl) vinylformic acid reacts, and make the hydroxyl of generation and dibasic acid anhydride addition and obtain contain carboxyl photoresist.
(3) by make at least to have in epoxy compounds and 1 molecule 1 alcohol hydroxyl group and 1 phenolic hydroxyl group compound, react with the monocarboxylic acid containing unsaturated group such as (methyl) vinylformic acid, and the multi-anhydride 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 is reacted and obtains contain carboxyl photoresist.
(4) make to have in 1 molecules such as the condenses of the condenses of dihydroxyphenyl propane, Bisphenol F, bisphenol S, novolak phenolics, poly(4-hydroxystyrene), naphthols and aldehydes, dihydroxy naphthlene and aldehydes reaction product that the compound of more than 2 phenolic hydroxyl group and the oxirane such as oxyethane, propylene oxide react and obtain, react with the monocarboxylic acid containing unsaturated group such as (methyl) vinylformic acid, and the reaction product of gained and multi-anhydride are reacted and are obtained contain carboxyl photoresist.
(5) reaction product obtained by making to have in 1 molecule the compound of more than 2 phenolic hydroxyl group and the reaction of the cyclic carbonate compound such as ethylene carbonate, Texacar PC, react with the monocarboxylic acid containing unsaturated group, and the reaction product of gained and multi-anhydride are reacted and are obtained contain carboxyl photoresist.
(6) by the diisocyanate cpds such as aliphatic diisocyanate, Branched fatty (cyclo) aliphatic diisocyanates, ester ring type vulcabond, aromatic diisocyanate and polycarbonate-based polyvalent alcohol, polyethers system polyvalent alcohol, polyester-based polyols, polyolefin polyvalent alcohol, acrylic polyol, dihydroxyphenyl propane system oxirane affixture dibasic alcohol, have the diatomic alcohol compounds such as compound of phenolic hydroxyl group and alcohol hydroxyl group polyaddition reaction and obtain urethane resin, make the end of urethane resin and anhydride reaction and the end that obtains containing carboxyl urethane resin.
(7) obtain in the polyaddition reaction by vulcabond and the carboxylic diol compound such as dimethylol propionic acid, dimethylolpropionic acid, diatomic alcohol compounds containing in the synthesis of carboxyl urethane resin, add the compound in (methyl) hydroxyalkyl acrylates equimolecular with 1 hydroxyl and more than 1 (methyl) acryl and carry out the acrylated and carboxylic photosensitivity urethane resin that obtains of end (methyl).
(8) obtain in the polyaddition reaction by vulcabond and carboxylic diol compound, diatomic alcohol compounds containing in the synthesis of carboxyl urethane resin, add the compound in the reaction with same mole thing equimolecular of isophorone diisocyanate and pentaerythritol triacrylate with 1 isocyanate group and more than 1 (methyl) acryl and carry out the acrylated and carboxylic photosensitivity urethane resin that obtains of end (methyl).
(9) what obtained containing the compound copolymerization of unsaturated group by the unsaturated carboxylic acids such as (methyl) vinylformic acid and vinylbenzene, alpha-methyl styrene, (methyl) lower alkyl acrylate, iso-butylene etc. contains carboxy resin.
(10) make the dicarboxylic acid such as oxetane resin and hexanodioic acid, phthalic acid, hexahydrophthalic acid react, and make the primary hydroxyl of generation and dibasic acid anhydride addition and obtain containing carboxyl polyester resin.
(11) above-mentioned (1) ~ (10) containing addition 1 molecule on carboxy resin in have cyclic ether group and (methyl) acryl compound and obtain containing carboxyl photoresist.
Above-mentioned have multiple carboxyl, therefore, it is possible to utilize dilute alkaline aqueous solution to develop containing carboxy resin on the side chain of trunk polymer.
In addition, the acid number containing carboxy resin is the scope of 40 ~ 200mgKOH/g is suitable, is more preferably the scope of 45 ~ 120mgKOH/g.If be more than 40mgKOH/g containing the acid number of carboxy resin, then alkali development becomes easy, on the other hand, during for below 200mgKOH/g, easily describes normal corrosion-resisting pattern, therefore preferably.
In addition, the above-mentioned weight-average molecular weight containing carboxy resin is different according to resin matrix, is generally the scope of 2000 ~ 150000, more preferably 5000 ~ 100000.When weight-average molecular weight is more than 2000, resistance to developability, the resolving power of the film after non-adhesion behavior, exposure become good.On the other hand, when weight-average molecular weight is less than 150000, developability is excellent.
Also resin other than the above can be used containing carboxy resin, a kind can be individually used, also can be used in combination multiple.
As resol, the compound with phenolic hydroxyl group can be used, such as, there is the compound of biphenyl backbone or phenylene skeleton or the skeleton both them; Or can use containing phenolic hydroxyl group compound, such as use phenol, ortho-cresol, p-cresol, alkali cresols, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenols, 3,4-xylenols, 3,5-xylenol, pyrocatechol, Resorcinol, quinhydrones, toluhydroquinone, 2,6-dimethyl hydroquinones, Trimethylhydroquinone, pyrogallol, Phloroglucinol etc. and synthesis, the resol with various skeleton.
Such as can use the known usual resol such as the condenses of the condenses of phenol resol resins, alkylphenol novolac resin, bisphenol A novolac resin, dicyclopentadiene type resol, Xylok type resol, terpene modified resol, polystyrene phenols, Bisphenol F, bisphenol S type resol, poly-4-Vinyl phenol, naphthols and aldehydes, dihydroxy naphthlene and aldehydes.
They can be used alone or in combination of two or more kinds.
As the commercially available product of above-mentioned resol, can enumerate: CST70, CST90, S-1P, S-2P (manufacture of Wan Shan oil Co., Ltd.) etc. of HF1H60 (MEIWAPLASTICINDUSTRIES, LTD. manufacture), PHENOLITETD-2090, PHENOLITETD-2131 (Dainippon Ink Chemicals's manufacture), BESMOLCZ-256-A (Dainippon Ink Chemicals's manufacture), SHONOLBRG-555, SHONOLBRG-556 (ShowaDenkoK.K. manufacture), CGR-951 (manufacture of Wan Shan oil Co., Ltd.) or polyvinyl phenol.These resol can be used alone or two or more use of proper combination.
In the present invention, as alkali soluble resins, can use containing any one in carboxy resin and resol or their mixture.
It should be noted that, in curable resin composition of the present invention, use containing the material of ethylenically unsaturated group as alkali soluble resins time, above-mentioned light-cured resin can be combinationally used.Light-cured resin is irradiated by active energy beam and promotes photocuring and promote the dissolving of alkali soluble resins in alkali aqueous solution.In any case, one or more light-cured resins can be used.
The total compounding amount of curable resin and alkali soluble resins counts 10 ~ 90 quality % with the solids component benchmark except solvent in curable resin composition, and preferably, the scope of 20 ~ 90 quality % is suitable.When the compounding amount of curable resin is more than 10 quality %, overlay film intensity improves.On the other hand, when the compounding amount of curable resin is below 90 quality %, the viscosity of curable resin composition becomes appropriateness, to raisings such as the coatings of carrier film.
Other tinting materials of < >
Except the tinting material shown in above-mentioned formula (1) of the present invention, tinting material can also be contained.Such as by adding blue colorant, green curable resin composition can be obtained by the tinting material shown in this blue colorant and above-mentioned formula (1).Mixing yellow colorants in the past and blue colorant can become bluish green when forming green, when mixing the tinting material shown in above-mentioned formula (1) and blue colorant, can form bright-coloured green.
In addition, by adding violet colorant in curable resin composition of the present invention, the curable resin composition of black can be obtained by the tinting material shown in this violet colorant and above-mentioned formula (1).It should be noted that, by adding violet colorant and blue colorant in curable resin composition of the present invention, also can obtain the curable resin composition of black.Such as, on the substrate with copper circuit, when use comprises the black curable resin composition of the tinting material shown in above-mentioned formula (1) and forms cured film, cured coating film black compared with the black cured film that the substrate of copper circuit formed with having in the past can be formed.
(blue colorant)
As blue colorant, that there is phthalocyanine system, anthraquinone system, dioxazine system, cobalt system etc., that pigment system is categorized as pigment (Pigment), dyestuff system is categorized as solvent (Solvent) compound etc., specifically, the following compound with Colour Index (colorindex) number like this can be enumerated.In addition, aside from them, the substituted or unsubstituted phthalocyanine compound of metal can also be used.
Pigment system: pigment Blue 15,15:1,15:2,15:3,15:4,15:6,16,60;
Dyestuff system: solvent blue 35,45,63,67,68,70,83,87,94,97,104,122,136
(violet colorant)
As violet colorant, specifically, can enumerate: pigment violet 19,29,32,36,37,38,42; Solvent violet 13,36; Pigment black 1, Pigment black 7, pigment brown 25 etc.
Curable resin composition of the present invention, except above-mentioned blue colorant, violet colorant, in order to adjust tone etc. further, can also use the tinting material of other colors.Specifically, such as can enumerate: black colorant, red stain, green colourant, orange colorant, dark brown tinting material, white color agents, yellow colorants etc.
(black colorant)
As black colorant, can list: the carbon black series pigments such as C.I. Pigment black 6,7,9,18; C.I. the graphite series pigments such as Pigment black 8,10; C.I. Pigment black 11,12,27, the iron oxide pigment such as pigment brown 35; Such as, the titanium of the ferric oxide of the KN-370 of Toda Kogyo Corp.'s manufacture, the 13M-T of MitsubishiMaterialsCorporation manufacture is black; C.I. anthraquione pigmentss such as Pigment black 20 grade; C.I. the cobalt oxide series pigments such as Pigment black 13,25,29; C.I. the cupric oxide series pigments such as Pigment black 15,28; C.I. the manganese series pigments such as Pigment black 14,26; C.I. series pigments such as weisspiessglanz such as Pigment black 23 grade; C.I. pigment such as magnesium oxide-nickel series such as Pigment black 30 grade; C.I. Pigment black 31,32, LumogenBlackFK4280 perylene pigments that BASFJAPANLTD. manufactures, the aniline series pigments of Pigment black 1 and moly-sulfide, bismuth sulfide is also as illustrated in applicable pigment.These pigment can be used alone or proper combination uses.Particularly preferably be that titanium is black, cobalt oxide, they can maintain insulativity, light solidified, and improve thermotolerance by carrying out interpolation in the scope not affecting precipitation, tone.
(red stain)
As red stain, have: monoazo system, tetrazo system, azo lake system, benzimidazolone Xi, perylene system, diketopyrrolopyrrolecocrystals system, condensation azo system, anthraquinone system, quinacridone etc., specifically, the following tinting material with Colour index number like this can be enumerated.
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 is: 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 171,175,176,185,208;
Perylene system: solvent of red 135,179; Pigment red 123,149,166,178,179,190,194,224;
Diketopyrrolopyrrolecocrystals system: Pigment red 254,255,264,270,272;
Condensation azo system: Pigment red 144,166,214,220,221,242;
Anthraquinone system: Pigment red 168,177,216, solvent red 149,150,52,207;
Quinacridone: pigment red 122,202,206,207,209.
(green colourant)
As green colourant, have phthalocyanine system, anthraquinone system, specifically, can use pigment Green 7,36, solvent green 3,5,20,28 etc.In addition to the foregoing, the substituted or unsubstituted phthalocyanine compound of metal can also be used.
(orange colorant)
As orange colorant, specifically, can enumerate: pigment orange 1,5,13,14,16,17,24,34,36,38,40,43,46,49,51,61,63,64,71,73 etc.
(dark brown tinting material)
As dark brown tinting material, specifically, can enumerate: pigment brown 23,25 etc.
(white color agents)
As white color agents, can enumerate: the zinc oxide shown in Pigment white 4, titanium oxide shown in Pigment white 6, zinc sulphide shown in Pigment white 7, from tinting strength and avirulent viewpoint, particularly preferably titanium oxide, such as can enumerate: FujiTitaniumIndustryCo., Ltd. the TR-600 manufactured, TR-700, TR-750, TR-840, IshiharaSangyoKaisha, Ltd. the R-550 manufactured, R-580, R-630, R-820, CR-50, CR-60, CR-90, TitanKogyo, Ltd. the KR-270 manufactured, KR-310, the Titanium Dioxide (Rutile) Top grades such as KR-380, FujiTitaniumIndustryCo., Ltd. TA-100, TA-200, TA-300, TA-500, IshiharaSangyoKaisha of manufacturing, Ltd. A100, A220, TitanKogyo of manufacturing, the anatase-type titanium oxides such as KA-15, KA-20, KA-35, KA-90 that Ltd. manufactures.For white color agents, if such as added on a small quantity in the mode becoming 0.1 ~ 3 quality % in the composition, then sometimes can expect the effect improving shielding.
(yellow colorants)
As yellow colorants, have: monoazo system, tetrazo system, condensation azo system, benzimidazolone system, isoindolinone, anthraquinone system etc., specifically can enumerate following tinting material.
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;
Condensation azo system: Pigment Yellow 73 93,94,95,128,155,166,180;
Benzimidazolone system: pigment Yellow 12 0,151,154,156,175,181;
Isoindolinone system: Pigment Yellow 73 109,110,139,179,185;
Anthraquinone system: solvent yellow 16 3, Pigment Yellow 73 24,108,193,147,199,202;
< photoreaction initiator >
Photoreaction initiator can be contained in composition of the present invention.As photoreaction initiator, as long as utilize rayed produce free radical, alkali, acid etc. and curable resin can be made to solidify, then can be any person.As photoreaction initiator, can enumerate: the known usual compounds such as aminoacetophenone system, benzoin ether system, benzil ketals system, acylphosphine oxide system, oxime ether system, oxime ester system, luxuriant titanium system.
As photoreaction initiator, preferably one kind or two or more containing what be selected from the group that is made up of the luxuriant titanium system shown in oxime ester system that is shown below, that comprise structure division shown in general formula (I), the alpha-aminoacetophenone system comprising structure division shown in general formula (II), the acylphosphine oxide system comprising structure division shown in general formula (III) and general formula (IV).
In general formula (I), R
1represent hydrogen atom, phenyl, alkyl, cycloalkyl, alkyloyl or benzoyl.R
2represent phenyl, alkyl, cycloalkyl, alkyloyl or benzoyl.
R
1and R
2shown phenyl can have substituting group, as this substituting group, such as, can enumerate: the alkyl, phenyl, halogen atom etc. of carbonatoms 1 ~ 6.
As R
1and R
2shown alkyl, the alkyl of preferred carbonatoms 1 ~ 20, can comprise more than 1 Sauerstoffatom in alkyl chain.In addition, also can replace with more than 1 hydroxyl.
As R
1and R
2shown cycloalkyl, the cycloalkyl of preferred carbonatoms 5 ~ 8.
As R
1and R
2shown alkyloyl, the alkyloyl of preferred carbonatoms 2 ~ 20.
As R
1and R
2shown benzoyl, can have substituting group, as this substituting group, such as, can enumerate: carbonatoms is the alkyl, phenyl etc. of 1 ~ 6.
In general formula (II), R
3and R
4represent the alkyl or aryl alkyl of carbonatoms 1 ~ 12 independently of one another, R
5and R
6represent the alkyl of hydrogen atom or carbonatoms 1 ~ 6 independently of one another, or also can both bondings and form cyclic alkyl ether.
In general formula (III), R
7and R
8represent that (wherein, both are except the situation of the carbonyl of carbonatoms 1 ~ 20 for the carbonyl of the aryl that the alkyl of carbonatoms 1 ~ 10, cyclohexyl, cyclopentyl, aryl or halogen atom, alkyl or alkoxyl group replace or carbonatoms 1 ~ 20 independently of one another.)。
In general formula (IV), R
9and R
10represent halogen atom, aryl, halogenated aryl independently of one another, containing heterocycle halogenated aryl.
As the oxime ester system photoreaction initiator comprising structure division shown in general formula (I); can enumerate: { 1-[4-(thiophenyl)-2-(O-benzoyl oxime)] } 1,2-acetyl caproyl, 1-[9-ethyl-6-(2-methyl benzoyl)-9H-carbazole-3-base]-1-(O-acetyl oxime) ethyl ketone, the compound shown in following formula (I-1), 2-(Acetyloxyimino methyl) thioxanthene-9-one and the compound etc. shown in following general formula (I-2).
In general formula (I-2), R
11with the R in general formula (I)
1synonym, R
12and R
14separately with the R in general formula (I)
2synonym.R
13represent that the alkoxy carbonyl of the alkyloyl of the alkyl of hydrogen atom, halogen atom, carbonatoms 1 ~ 12, cyclopentyl, cyclohexyl, phenyl, benzyl, benzoyl, carbonatoms 2 ~ 12, carbonatoms 2 ~ 12 is (when the carbonatoms of the alkyl of formation alkoxyl group is more than 2; alkyl can replace with more than 1 hydroxyl, also can have more than 1 Sauerstoffatom at alkyl middle-of-chain) or phenoxy group carboxyl.
In the middle of these, the compound shown in preferred above-mentioned formula (I-2).
This oxime ester system photoreaction initiator also can for having the compound of multiple oxime ester base.
When using this oxime ester system's photoreaction initiator, in order to improve the sensitivity for exposure, preferably combination uses the alpha-aminoacetophenone system photoreaction initiator etc. comprising structure division shown in general formula (II).
As the alpha-aminoacetophenone system photoreaction initiator comprising structure division shown in general formula (II), can enumerate: 2-methyl isophthalic acid-[4-(methyl sulphur) phenyl]-2-morpholinopropanone-1,2-benzyl-2-dimethylamino-1-(4-morphlinophenyl)-butane-1-ketone, 2-(dimethylamino)-2-[(4-aminomethyl phenyl) methyl]-1-[4-(4-morpholinyl) phenyl]-1-butanone, N, N-dimethylamino benzoylformaldoxime etc.
As the acylphosphine oxide system photoreaction initiator comprising structure division shown in general formula (III); can enumerate: 2; 4; 6-trimethyl benzoyl diphenyl base phosphine oxide, two (2; 4,6-trimethylbenzoyl)-phenyl phosphine oxide, two (2,6-Dimethoxybenzoyl)-2; 4,4-trimethyl-pentyl phosphine oxide etc.
As the luxuriant titanium system photoreaction initiator shown in general formula (IV), can enumerate: two (η 5-2,4-cyclopentadiene-1-base)-bis-(the fluoro-3-of 2,6-bis-(1H-pyrroles-1-base)-phenyl) titanium.
The compounding rate of this photoreaction initiator, relative to curable resin 100 mass parts, is preferably 0.01 ~ 100 mass parts, is more preferably the ratio of 0.5 ~ 80 mass parts.Relative to curable resin 100 mass parts, when the compounding rate of photoreaction initiator is more than 0.01 mass parts, light solidified becomes good and the coating characteristics such as film separability, chemical proofing become good, therefore preferably.On the other hand, relative to curable resin 100 mass parts, when the compounding rate of photoreaction initiator is below 100 mass parts, deep solidified nature is excellent, therefore preferably.
And then, in curable resin composition of the present invention, the photoreaction initiator beyond above-claimed cpd, light-initiated auxiliary agent and sensitizing agent can be used, such as, can enumerate: bitter almond oil camphor compound, anthraquinone compounds, thioxanthone compounds, ketal compound, benzophenone cpd, acetophenone compound, xanthone compound and tertiary amine compound etc.
Enumerating the concrete example of bitter almond oil camphor compound, such as, is bitter almond oil camphor, benzoin methyl ether, benzoin ethyl ether, benzoin iso-propylether.Enumerating the concrete example of acetophenone compound, such as, is methyl phenyl ketone, 2,2-dimethoxy-2-phenyl acetophenone, 2,2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone.Enumerating the concrete example of anthraquinone compounds, such as, is 2-methylanthraquinone, 2-ethyl-anthraquinone, 2-tertiary butyl anthraquinone, 1-chloroanthraquinone.Enumerating the concrete example of thioxanthone compounds, such as, is 2,4-dimethyl thioxanthone, 2,4-diethyl thioxanthones, CTX, 2,4-diisopropylthioxanthone.Enumerating the concrete example of ketal compound, such as, is methyl phenyl ketone dimethyl ketal, benzil dimethyl ketal.Enumerating the concrete example of benzophenone cpd, such as, is benzophenone, 4-benzoyl diphenyl thioether, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4-benzoyl-4 '-ethyl diphenyl thioether, 4-benzoyl-4 '-propyl group diphenylsulfide.
Enumerate the concrete example of tertiary amine compound, it is such as ethanolamine compound, there is the compound of dialkyl amido benzene structure, be such as 4, 4 '-dimethylamino benzophenone (NIPPONSODACO., LTD. the NISSOCUREMABP manufactured), 4, 4 '-diethylamino benzophenone (HODOGAYACHEMICALCO., LTD. the EAB manufactured) etc. dialkyl amido benzophenone, 7-(diethylamino)-4-methyl-2H-1-chromen-2-ones (7-(diethylamino)-4-methylcoumarin) etc. are containing the coumarin compound of dialkyl amido, EDMAB (NipponKayakuCo., Ltd. the KAYACUREEPA manufactured), 2-dimethyl amino benzoate (QuantacureDMB that InternationalBio-SyntheticsCorporation manufactures), 4-dimethylaminobenzoic acid (n-butoxy) ethyl ester (QuantacureBEA that InternationalBio-SyntheticsCorporation manufactures), ESCAROL 507 isopentyl ethyl ester (NipponKayakuCo., Ltd. the KAYACUREDMBI manufactured), 4-dimethylaminobenzoic acid 2-ethylhexyl (Esolol507 that VanDykCorporation manufactures), 4, 4 '-diethylamino benzophenone (HODOGAYACHEMICALCO., LTD. the EAB manufactured).
As tertiary amine compound, preferably have the compound of dialkyl amido benzene structure, wherein, particularly preferably dialkyl amido benzophenone cpd, maximum absorption wavelength are in the coumarin compound containing dialkyl amido of 350 ~ 410nm.As dialkyl amido benzophenone cpd, 4, the toxicity of 4 '-diethylamino benzophenone is also low and preferred.The coumarin compound containing dialkyl amido that maximum absorption wavelength is in 350 ~ 410nm is in ultra-violet region due to maximum absorption wavelength, therefore, uses tinting material, can provide the coloring film of reflection tinting material self color.Particularly, 7-(diethylamino)-4-methyl-2H-1-chromen-2-one because going out excellent sensitization effect relative to the laser display of wavelength 400 ~ 410nm preferably.
< thermal curing catalyst >
In curable resin composition of the present invention, thermal curing catalyst can also be contained.As thermal curing catalyst, such as, can enumerate: the imdazole derivatives such as imidazoles, glyoxal ethyline, 2-ethyl imidazol(e), 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyano ethyl-2-phenylimidazole, 1-(2-cyano ethyl)-2-ethyl-4-methylimidazole; Dyhard RU 100, benzyl dimethyl amine, 4-(dimethylamino)-N, N-dimethyl benzyl amine, 4-methoxyl group-N, N-dimethyl benzyl amine, 4-methyl-N, the hydrazine compounds such as the amine compound such as N-dimethyl benzyl amine, adipic dihydrazide, sebacic dihydrazide; The phosphorus compounds etc. such as triphenylphosphine.In addition, as commercially available catalyzer, such as, can enumerate: U-CAT3503N, U-CAT3502T (being the trade(brand)name of the blocked isocyanate compounds of dimethyl amine) that 2MZ-A, 2MZ-OK, 2PHZ, 2P4BHZ, 2P4MHZ (being the trade(brand)name of imidazole compound) that Shikoku Chem manufactures, San-AproLtd. manufacture, DBU, DBN, U-CATSA102, U-CAT5002 (being two ring type amidine compounds and its salt) etc.And then, be not limited to these, as long as the material of the thermal curing catalyst of epoxy resin, oxetane compound or promotion epoxy group(ing) and/or oxetanyl and carboxyl reaction just can use, they can be used alone or mix two or more and use.In addition, also guanamines, methyl guanamines, benzoguanamine, trimeric cyanamide, 2 can be used, 4-diamino-6-methacryloxyethyl-s-triazine, 2-vinyl-2,4-diamino-s-triazine, 2-vinyl-4,6-diamino-s-triazine tricarbimide affixture, 2, these compounds also worked as adaptation imparting agent and thermal curing catalyst are preferably combinationally used by the s-triazine derivatives such as 4-diamino-6-methacryloxyethyl-s-triazine tricarbimide affixture.
The compounding amount of thermal curing catalyst is namely enough with normally used ratio, such as, relative to curable resin 100 mass parts, is preferably 0.1 ~ 20 mass parts, is more preferably 0.5 ~ 15.0 mass parts.
Other compounding ingredients of < >
In composition of the present invention, in order to improve the characteristic such as adaptation, physical strength, linear expansivity of cured article, can compounding inorganic filling material.As this inorganic filling material, such as, can use: the known usual inorganic filling materials such as barium sulfate, barium titanate, silica powder, micro mist shape silicon oxide, soft silica, talcum, clay, magnesiumcarbonate, calcium carbonate, aluminum oxide, aluminium hydroxide, mica powder.
In composition of the present invention, and then as required, can be compounding: in the defoamers such as known usual thickening material, silicon-type, fluorine system, macromolecular such as the known usual stopper such as quinhydrones, Hydroquinone monomethylether, tert-butyl catechol, pyrogallol, thiodiphenylamine, fine particle silica, organobentonite, montmorillonite and flow agent at least any one, the such known usual additive kind of imidazoles system, thiazole system, silane coupling agent, antioxidant, photostabilizer, dispersion agent, curing catalyst, fire retardant, the flame retardant etc. such as triazole.
Composition of the present invention can containing the organic solvent for modulation group compound, adjustment viscosity.As organic solvent, such as, can use: the ketone such as methylethylketone, pimelinketone; Toluene, dimethylbenzene, tetramethyl-benzene 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 (DPM), dipropylene glycol diethyl ether, Tripropylene glycol monomethyl Ether; The ester classes such as ethyl acetate, butylacetate, n-Butyl lactate, cellosolve acetate, butyl cellosolve acetate, carbitol acetate, acetate of butyl carbitol, propylene glycol methyl ether acetate, dipropylene glycol monomethyl ether acetic ester, Texacar PC; The aliphatic hydrocarbon such as octane, decane; The petroleum solvents etc. such as sherwood oil, petroleum naphtha, solvent naphtha.These organic solvents can be used alone or in combination of two or more kinds.
Curable resin composition of the present invention can be used as the material that insulating film is formed.In addition, the curable resin composition of the application of the invention, can obtain the indicating meter component of high-quality.Curable resin composition of the present invention can also be used for printing ink, mark ink, ink-jet, photomask make that material, printing pull (proof) make material, etch resist, the making of the occlusion image such as wiring pattern, conductive paste, conducting film, black matrix of the partition of solder resist, tectum, Xi Di (SolderDam), interlayer dielectic, plasma display panel (PDP), dielectric pattern, electrode (conductor circuit) pattern, electronic unit etc.
Curable resin composition of the present invention is particularly suitable for the formation of the insulativity curing overlay film of printed circuit board (PCB), is further adapted for the formation of the permanent cured overlay film of insulativity, is particularly suitable for solder resist and tectal formation.
Composition of the present invention can become in the upper coating of carrier film (supporter), dry and obtain the form of dry film.During dry film, by composition of the present invention with above-mentioned organic solvent diluting to adjust to suitable viscosity, by comma coater (commacoater), knife coater, lip coating machine (lipcoater), bar coater (rodcoater), extrusion coating machine (squeezecoater), inverse formula coating machine (reversecoater), delivery roll coating machine (transferrollcater), gravure coater (gravurecoater), spraying machines etc. are coated into uniform thickness on a carrier film, usually at the temperature of 50 ~ 130 DEG C dry 1 ~ 30 minute, thus can dry coating be formed.Coating film thickness is not particularly limited, usually, with dried film thickness gauge, 0.1 ~ 100 μm, preferably suitably select in the scope of 0.5 ~ 50 μm.
As carrier film, can plastics film be used, preferably use the plastics films such as polyester film, Kapton, polyamidoimide film, polypropylene film, polystyrene film such as polyethylene terephthalate.Thickness for carrier film is not particularly limited, and usually suitably selects in the scope of 0.1 ~ 150 μm.
Now, after carrier film forms film, in order to prevent the surface attachment dust etc. of film, the stacked strippable mulch film in the preferred surface at film further.As strippable mulch film, such as can use polyethylene film, polytetrafluoroethylene film, polypropylene film, surface treated paper etc., as long as the cohesive force of film and mulch film is less than the mulch film of the cohesive force of film and carrier film when peeling off mulch film.
In addition, after using above-mentioned organic solvent composition of the present invention to be adjusted to the viscosity being suitable for coating process, utilize dip coating, flow coat method, rolling method, stick coating method, silk screen print method, curtain to be coated with method, method such as mould painting method, ink jet printing etc. is applied on base material, the organic solvent volatile dry contained by composition (temporarily dry) is made at the temperature of about 50 DEG C ~ 90 DEG C, thus the dry coating that can cannot do not formed stickyly.In addition, composition of the present invention is applied in carrier film, dry formation film, when being batched and obtained dry film, laminating machine etc. is utilized to fit on base material in the mode of the film of composition and substrate contact, then peel off carrier film, the layer of curable resin composition can be formed thus on base material.
Such as these films irradiated by active energy beam and make its photocuring or be heated to the temperature of 100 DEG C ~ 250 DEG C and make its thermofixation, can cured article be obtained thus.
As above-mentioned base material, except being pre-formed with the printed circuit board (PCB) of circuit, beyond flexible printed circuit board, can also enumerate: adopt and employ paper resol, paper epoxy resin, woven fiber glass epoxy resin, glass polyimide resin, woven fiber glass/non-woven fabrics epoxy resin, woven fiber glass/paper epoxy resin, synthon epoxy resin, the copper-clad laminated board of all grades (FR-4 etc.) of the materials such as the high frequency circuit copper-clad laminated board of fluoro-resin polyethylene polyphenylene oxide cyanate ester resin etc., and Kapton, PET film, glass substrate, ceramic substrate, wafer board etc.
Carrying out volatile dry after being coated with composition of the present invention can use heated air circulation type drying oven, IR stove, hot plate, convection oven etc. to carry out, namely, use and there is the device of the thermal source of the air heating mode utilizing steam, the method that the hot air convection in drying machine is contacted and blow the method to supporter by nozzle.
As the exposure machine irradiated for active energy beam, as long as being equipped with high voltage mercury lamp, ultrahigh pressure mercury lamp, metal halide lamp, mercury short arc lamp etc. and irradiating the ultraviolet device of 350 ~ 450nm scope, in addition, direct drawing apparatus (such as by utilizing the laser direct imaging device of direct irradiation active energy beam and rendering image from the cad data of computer) can also be used.As the light source directly retouching machine, as long as use maximum wavelength to be in the light source of the light in the scope of 350 ~ 410nm.Different according to thickness etc. for the formation of the exposure of image, usually can be 20 ~ 1000mJ/cm
2, be preferably 20 ~ 800mJ/cm
2scope in.
In addition, as developing method, pickling process, drip-rinsing process, spray method, spread coating etc. can be used, as developing solution, the alkali aqueous solution of potassium hydroxide, sodium hydroxide, sodium carbonate, salt of wormwood, sodium phosphate, water glass, ammonia, amine etc. can be used.
Embodiment
Below, illustrate that embodiment and comparative example are specifically described the present invention, but the present invention is not limited to following content.It should be noted that, below, " part ", " % " represent " mass parts ", " quality % " in case of no particular description.
(synthesis example 1)
In TC acetic ester 600g, dropping into o-cresol phenolic epoxy varnish, (Dainippon Ink Chemicals manufactures, trade(brand)name; EPICLON (registered trademark) N-695, softening temperature 95 DEG C, epoxy equivalent (weight) 214, average functional group number 7.6) 1070g (Racemic glycidol radix (aromatic nucleus sum): 5.0 moles), vinylformic acid 360g (5.0 moles) and quinhydrones 1.5g, be heated to 100 DEG C stir, uniform dissolution.Then, drop into triphenylphosphine 4.3g, be heated to 110 DEG C of reactions after 2 hours, be warming up to 120 DEG C and carry out reaction in 12 hours again.In the reaction solution of gained, drop into fragrant family hydrocarbon (Solvesso150) 415g, Tetra Hydro Phthalic Anhydride 456.0g (3.0 moles), at 110 DEG C, carry out reaction in 4 hours, cool.Obtain the alkali soluble resins solution of solids component acid number 89mgKOH/g, solids component 65% thus.
[preparation of curable resin composition]
For each composition shown in table 1 ~ 4, be suitable for adding organic solvent and make it disperse, carry out mixing with triple-roller mill, obtain curable resin composition.It should be noted that, in table 1 ~ 4, the content of each composition is the solids component removing solvent.In addition, the curable resin composition of yellow, green curable resin composition are suitable for the addition of stopper.Wherein, in same hue, equal parts is set to.
[table 1]
[table 2]
[table 3]
[table 4]
< alkali soluble resins >
Synthesis example 1 (what have epoxy acrylic ester structure contains carboxy resin)
< heat-curing resin >
N870: bisphenol A novolac type epoxy resin (Dainippon Ink Chemicals's manufacture)
828: bisphenol A type epoxy resin (Mitsubishi chemical Co., Ltd's manufacture)
< photoreaction initiator >
TPO: acylphosphine oxide system photoreaction initiator (BASFJAPANLTD. manufacture)
Irg784: luxuriant titanium sub-group compound (BASFJAPANLTD. manufacture)
OXE02: oxime ester based compound (BASFJAPANLTD. manufacture)
Irg907: methyl phenyl ketone based compound (BASFJAPANLTD. manufacture)
< light-cured resin >
DPHA:6 functional acrylate monomers (NipponKayakuCo., Ltd. manufacture)
TMPTA: Viscoat 295 (NipponKayakuCo., Ltd. manufacture)
A-NOD-N:1,9-nonanediol diacrylate (manufacture of chemical industry Co., Ltd. of Xin Zhong village)
LAROMERLR8863:EO modification Viscoat 295 (BASFJAPANLTD. manufacture)
< thermal curing catalyst >
Trimeric cyanamide
DICY: Dyhard RU 100
2PHZ: imidazoles (Shikoku Chem's manufacture)
< tinting material >
Blue: pigment Blue 15: 3 (FARSTOGENBULEFA5380, Dainippon Ink Chemicals manufactures)
Purple: pigment violet 37 (CROMOPHTALVIOLETB, BASFJAPANLTD. manufacture)
Yellow: the compound shown in formula (2)
It should be noted that, be convenient to compare, prepared green 5 (SG5) of solvent (PLASTYELLOW8025 has this KCC to manufacture) separately.
< defoamer >
Silicon-type defoamer
< other: inorganic filling material >
Silicon-dioxide
[evaluation method of embodiment 1 ~ 25, comparative example 1 ~ 4]
The evaluation result of embodiment 1 ~ 25, comparative example 1 ~ 4 is shown in table 5 ~ 8.It should be noted that, each evaluation method evaluated is as follows.
[table 5]
[table 6]
[table 7]
[table 8]
< tone >
Judged by visual.
The making > of < evaluate cure film
(light-cured type)
Utilize silk screen printing to coat on cleaned glass by the curable resin composition of embodiment 1 ~ 3,5 ~ 13 and comparative example 1 ~ 3 with the whole face of the mode becoming 20 μm after drying, in heated air circulation type drying oven, make its dry 10 minutes with 80 DEG C.The DXP-3580 using ORCMANUFACTURINGCO., LTD. to manufacture is irradiated this dry coating with the exposure becoming 8 sections by stage phototimer (Stuffer41 section).Then, utilize heated air circulation type drying oven at 150 DEG C, make curable resin composition solidify 60 minutes and obtain cured coating film.
(thermohardening type)
Utilize silk screen printing to be coated on cleaned glass with the whole face of the mode becoming 20 μm after drying by the curable resin composition of embodiment 4,14 ~ 18 and comparative example 4, utilize heated air circulation type drying oven at 150 DEG C, make it solidify 60 minutes and obtain cured coating film.
(inkjet type)
The curable resin composition of embodiment 19 ~ 25 is filled in FUJIFILMGlobalGraphicSystemsCo., ink-jet printer DMP-2831,10pL box that Ltd. manufactures, and carries out ink jet printing on cleaned glass, result injectivity is good.As condition of cure, use the transmission stove with high voltage mercury lamp with exposure 1000mJ/cm
2carry out rayed, make curable resin composition solidify and obtain cured coating film.
< colourity >
The cured coating film utilizing above-mentioned making method to make is utilized determination of colority device KonicaMinolta, the CM-2600d that Inc. manufactures passes through CIEL with SCI pattern
*a
*b
*mode measures.The preferred L of resin combination of black
*be worth low and a
*, b
*close to 0 time closer to black.The green preferred a of resin combination
*closer to green when being worth low.The yellow preferred b of resin combination
*yellow grow when being worth high.
< cured article outward appearance >
The cured coating film utilizing above-mentioned making method to make surface is observed with about 25 times by opticmicroscope.Be considered as zero when being even by colored state, by confirm the situation of painted uneven pattern be considered as ×.
< 150 DEG C add pressure ooze out >
On the cured article utilizing above-mentioned making method to make, whether check on film when to fit PET film at 150 DEG C transferred with curable resin composition.Evaluate as described below.
Zero: not painted to PET
×: PET variable color is yellow
< sensitivity >
The curable resin composition of embodiment 1 ~ 3,5 ~ 13 and comparative example 1 ~ 3 is coated with the whole face of the mode becoming 20 μm after drying and utilizes MECCo., the single-clad board of thick 15 μm of the copper that the CZ8100 Ltd. manufactured carries out pre-treatment and obtains, makes its dry 30 minutes with 80 DEG C in heated air circulation type drying oven.Use the DXP-3580 of ORCMANUFACTURINGCO., LTD. manufacture by stage phototimer (Stuffer41 section) with 150mJ/cm
2dry coating is exposed, and utilizes 1 quality % sodium carbonate solution of development 30 DEG C under the condition spraying 0.2MPa, carry out development in 60 seconds, now read the pattern of residual stage phototimer.Residual hop count is more, and sensitivity is better and preferred.
The making > of < resolving power sample for evaluation
The curable resin composition of embodiment 1 ~ 3,5 ~ 13 and comparative example 1 ~ 3 is coated with the whole face of the mode becoming 20 μm after drying and utilizes MECCo., the single-clad board of thick 15 μm of the copper that the CZ8100 Ltd. manufactured carries out pre-treatment and obtains, makes its dry 30 minutes at heated air circulation type drying oven clock with 80 DEG C.This dry coating uses ORCMANUFACTURINGCO., and the DXP-3580 that LTD. manufactures describes the dam pattern of line width 100 μm with the exposure becoming 8 sections by stage phototimer (Stuffer41 section).Then, after carrying out development in 60 seconds by the 1 quality % sodium carbonate solutions of 30 DEG C under the condition spraying 0.2MPa, the dam shape of 100 μm of cured article is observed.The evaluation of dam shape as shown in Figure 2.
< dispersion stabilization >
Sealed by the curable resin composition of each embodiment and each comparative example, under 15 DEG C of atmosphere, keeping is after 1 month, confirms the separation of tinting material when breaking a seal.Changing conditions is not had to be evaluated as zero state, by the average evaluation confirming tinting material separation be ×.
Based on table 5 ~ 8, the compound of use formula (2) is as tinting material, for the tone of the resin combination as light-cured type be yellow embodiment 1,5,12,13, the embodiment of black 2,6, any person in green embodiment 3,7 ~ 11, there is suitable tone and sensitivity, excellent in resolution and thermotolerance, dispersion stabilization, excellent appearance.In addition, embodiment 4,14 ~ 18 as thermohardening type is the example of alkali-free soluble resin, the excellent heat resistance of yellow hot curing resin composition (embodiment 4,14), the hot curing resin composition (embodiment 15) of black, green hot curing resin composition (embodiment 16 ~ 18).And then the embodiment 19 ~ 25 as inkjet type has suitable tone and thermotolerance, dispersion stabilization, excellent appearance.
In contrast, for the comparative example 1 ~ 4 using solvent green 5 as tinting material, thermotolerance, outward appearance, dispersion stabilization are poor.
Claims (5)
1. a curable resin composition, is characterized in that, it contains the tinting material shown in curable resin and following formula (1),
In formula (1), R1 and R2 is respectively alkyl, m and n is respectively the arbitrary integer in 0 ~ 6.
2. curable resin composition according to claim 1, it is also containing the tinting material beyond the tinting material shown in described formula (1).
3. a dry film, is characterized in that, it is coated with on film by curable resin composition described in claim 1 or 2 and drying obtains.
4. a cured article, is characterized in that, it is that the curable resin composition described in claim 1 or 2 or dry film according to claim 3 are solidified.
5. a printed circuit board (PCB), is characterized in that, it possesses cured article according to claim 4.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014201321 | 2014-09-30 | ||
| JP2014-201321 | 2014-09-30 | ||
| JP2015-124764 | 2015-06-22 | ||
| JP2015124764A JP6626275B2 (en) | 2014-09-30 | 2015-06-22 | Curable resin composition, dry film, cured product and printed wiring board |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105462306A true CN105462306A (en) | 2016-04-06 |
Family
ID=55600488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510580494.XA Pending CN105462306A (en) | 2014-09-30 | 2015-09-11 | Curable resin composition, dry film, cured product and printed wiring board |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105462306A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111886293A (en) * | 2018-03-28 | 2020-11-03 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, and electronic component |
| CN111918933A (en) * | 2018-03-30 | 2020-11-10 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, laminated structure, and electronic component |
| CN116790094A (en) * | 2023-06-15 | 2023-09-22 | 广东宝士电气有限公司 | Flame-retardant waterproof bus duct and preparation method thereof |
-
2015
- 2015-09-11 CN CN201510580494.XA patent/CN105462306A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111886293A (en) * | 2018-03-28 | 2020-11-03 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, and electronic component |
| CN111886293B (en) * | 2018-03-28 | 2023-08-01 | 太阳控股株式会社 | Curable resin composition, dry film, cured product, and electronic component |
| CN111918933A (en) * | 2018-03-30 | 2020-11-10 | 太阳油墨制造株式会社 | Curable resin composition, dry film, cured product, laminated structure, and electronic component |
| CN116790094A (en) * | 2023-06-15 | 2023-09-22 | 广东宝士电气有限公司 | Flame-retardant waterproof bus duct and preparation method thereof |
| CN116790094B (en) * | 2023-06-15 | 2024-01-12 | 广东宝士电气有限公司 | Flame-retardant waterproof bus duct and preparation method thereof |
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