CN105527793A - Photosensitive resin composition and hardening substance thereof - Google Patents
Photosensitive resin composition and hardening substance thereof Download PDFInfo
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- CN105527793A CN105527793A CN201510672400.1A CN201510672400A CN105527793A CN 105527793 A CN105527793 A CN 105527793A CN 201510672400 A CN201510672400 A CN 201510672400A CN 105527793 A CN105527793 A CN 105527793A
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Abstract
The invention provides a photosensitive resin composition and a hardening substance thereof. The photosensitive resin composition is high in sensitivity, bendability, adhesiveness, pencil hardness, solvent resistance, acid resistance, heat resistance and gold plating resistance. The invention also provides a hardening substance of the photosensitive resin composition. The photosensitive resin composition comprises aqueous alkali soluble resin (A), cross-linking agent (B), polymerization initiator (C) and epoxy resin (D) represented by the following formula (1). In the formula, rate of (i) to (ii) =1 to 3, wherein G represents glycidyl; and n is an average value of repetitions and n= 0 to 5.
Description
Technical field
The present invention relates to the photosensitive polymer combination containing epoxy resin etc. and hardening thing thereof.
Background technology
Use and there is the photosensitive polymer combination of photosensitive epoxy carboxylic acids's ester compounds, environmentally, hot, mechanical property or excellent to the harmony of the various characteristics such as the adherence of base material.Therefore, be used in coating/field such as coating, solid for a long time all always.Also be used in the industrial circle that electrically/electronic component manufactures the wide scopes such as purposes or printed base plate manufacture purposes recently, its range of application expands gradually.With the expansion of this range of application, for the high function using the photosensitive polymer combination of epoxy carboxylic acids's ester compounds to require additional flexibility, low warpage properties, low water absorbable etc., manufacture by electrically/electronic component the photosensitive polymer combination that centered by purposes or printed base plate manufacture purposes, active development is various.One example, record in patent documentation 1: be applicable to hard (rigid) substrate, the solder resist (solderresist) being also applicable to flexible base plate uses photonasty thermosetting resin composition.
Again, recorded the photosensitive polymer combination using united phenol-type epoxy resin (such as Japanese chemical drug NC-3000 etc.) as rigidizer in patent documentation 2, but sufficient developability, thermotolerance and cohesive cannot have been obtained.
Again, used in the present invention epoxy resin (a) has been recorded in patent documentation 3.
[patent documentation 1] Japanese Unexamined Patent Publication 2000-109541 publication
[patent documentation 2] Japanese Unexamined Patent Publication 2004-155916 publication
[patent documentation 3] Japanese Unexamined Patent Publication 2013-043958 publication.
Summary of the invention
(problem of invention for solving)
Problem of the present invention is to provide a kind of resin combination and hardening thing thereof, this resin combination is excellent for the photonasty of active energy ray, and to be undertaken developing and forming figure (pattern) by dilute alkaline aqueous solution be fine image, simultaneously make the cured film of its thermmohardening gained have sufficient pliability in after-hardening (Postcure) step, be therefore applicable to high-insulativity and cohesive, developability, thermotolerance, solder resist ink without the gold-plated patience excellence of electric-type.
(solving the means of problem)
The present invention about:
(1) photosensitive polymer combination, it contains aqueous alkaline solution-soluble resin (A), crosslinking chemical (B), Photoepolymerizationinitiater initiater (C) and the epoxy resin (D) shown in following general formula (1);
In formula, (i) is that (i)/(ii)=1 to 3, G represents glycidyl with the ratio of (ii), and n is the mean value of repeat number, and is 0 to 5.
(2) softening point of the epoxy resin (D) as the photosensitive polymer combination of (1), wherein, shown in general formula (1) is 50 to 150 DEG C.
(3) a kind of described photosensitive polymer combination, wherein, aqueous alkaline solution-soluble resin (A) is: the monocarboxylic acid (b) making the epoxy compound (a) of the epoxy radicals in molecule with more than 2 and have an ethene unsaturated group in molecule reacts epoxy carboxylic acids's ester compounds of gained, the resultant of reaction (A1) with multi-anhydride (c).
(4) a kind of described photosensitive polymer combination, wherein, aqueous alkaline solution-soluble resin (A) for: the monocarboxylic acid (b) making the epoxy resin (a) shown in following general formula (1) and there is ethene unsaturated group in molecule react gained epoxy carboxylic acids's ester compounds, with the resultant of reaction of multi-anhydride (c) (A1 ').
In formula, (i) is that (i)/(ii)=1 to 3, G represents glycidyl with the ratio of (ii), and n is the mean value of repeat number, and is 0 to 5.
(5) a kind of described photosensitive polymer combination, wherein, aqueous alkaline solution-soluble resin (A) is: the epoxy compound (d) making to have 2 epoxy radicals in molecule and the monocarboxylic acid (b) in molecule with ethene unsaturated group react gained epoxy carboxylic acids's ester compounds, with diisocyanate cpd (e), there is in molecule the carboxylic acid (f) of 2 hydroxyls and the resultant of reaction (A2) of arbitrary diatomic alcohol compounds (g).
(6) hardening thing, the hardening thing of photosensitive polymer combination described in it.
(7) base material, has the layer of described hardening thing.
(8) article, have described base material.
(effect of invention)
Use aqueous alkaline solution-soluble resin, crosslinking chemical, Photoepolymerizationinitiater initiater and epoxy resin for having the photosensitive polymer combination of the compound gained of the structure of general formula (1), it is carrying out light sensitivity excellence in light stiffening formation film with ultraviolet, and the hardening thing of gained is fully met bendability, cohesive, pencil hardness, solvent resistance, acid resistance, thermotolerance, resistance to gold-plated property etc., especially, printed base plate photosensitive polymer combination and optical waveguide formation photosensitive polymer combination is applicable to.
Such as, be also suitable for being used in the purposes of the printing distributing board solder resist, multi-layer printed circuit board interlayer dielectic, pliability printing distributing board solder resist, plating resist, photonasty optical waveguide etc. that require high reliability.
Embodiment
The present invention makes the epoxy resin (D) being used as rigidizer for [in formula, (i) is (i)/(ii)=1 to 3 with the ratio of (ii) with described general formula (1).G represents glycidyl.N is for repeat number and be 0 to 5] shown in the epoxy resin with polycycle alkyl.
The method for making that the epoxy resin (D) that the present invention uses can be recorded by patent documentation 1 obtains.But the method for making with the epoxy resin (D) of the structure of described general formula (1) is not limited to the method for making of patent documentation 1 record.
More preferably described general formula (i) is used to be (i)/(ii)=1 to 3 person with the ratio of described general formula (ii) in the present invention.That is, the glycidyl ethers body for resorcinol structure over half of A in general formula (1) is characterised in that.This ratio is important for being promoted to of developability, pigment-dispersing and thermotolerance.Again, be less than 3 amounts limiting the glycidyl ethers body of resorcinol structure by (i)/(ii), water-intake rate and obdurability can be improved.In described general formula (1), n is repetitive, is the positive number of mean value 0 to 5.By making n be no more than 5, control developability when forming photosensitive polymer combination or coating.When n is more than 5, not only developability, also has problems to the dissolubility of solvent, therefore not preferred.In the market, epoxy resin (D) is desirable derives from NC-3500 series (Japanese chemical drug (stock) system; (i)/(ii)=1 to 3, n (mean value)=0 to 5).
The softening point (ball and ring method) of epoxy resin (D) is 50 to 150 DEG C, preferably 52 to 100 DEG C, especially preferably 52 to 95 DEG C.Time below 50 DEG C, sticking property is serious, is difficult to operation, can has problems in productivity.Again, when more than 150 DEG C, be the temperature close to forming temperature, mobility when cannot guarantee shaping, thus not preferred.
Epoxide equivalent preferably 180 to the 350g/eq. of epoxy resin (D).More preferably 190 to 300g/eq..When epoxide equivalent is lower than 180g/eq., functional group is too many, therefore the hardening thing after sclerosis, water-intake rate is high, easily becomes fragile again.When epoxide equivalent is more than 350g/eq., fully do not carry out outside epoxidation, softening point becomes very large, or chlorine dose becomes very many, and not preferred.
Again, the chlorine dose of epoxy resin (D) counts 200 to 1500ppm with perchloro-(Hydrolyze method), preferably 200 to 900ppm.Even if be also preferred to be no more than 900ppm from the specification epoxy monomer of JPCN.And, if chlorine dose is many, electric reliability can be affected, thus not preferred.During lower than 200ppm, excessive purification step must be had, have problems in productivity, thus not preferred.
Epoxy resin (D) is 0.05 to 5Pas the viscosity that dissolves of 150 DEG C.Be preferred with 0.05 to 2.0Pas.If viscosity is more than 2.0Pas, have problems in mobility, the mobility when punching press (press) or imbedibility have problems.During lower than 0.05Pas, molecular weight is too little, therefore thermotolerance is low.
Aqueous alkaline solution-soluble resin (A) is that the monocarboxylic acid (b) such as making the epoxy compound (a) of the epoxy radicals in molecule with more than 2 and have an ethene unsaturated group in molecule reacts epoxy carboxylic acids's ester compounds of gained, the resultant of reaction (A1) with multi-anhydride (c).Again, aqueous alkaline solution-soluble resin (A) be the epoxy compound (d) such as making to have 2 epoxy radicals in molecule and the monocarboxylic acid (b) in molecule with ethene unsaturated group react gained epoxy carboxylic acids's ester compounds, with diisocyanate cpd (e), there is in molecule the carboxylic acid (f) of 2 hydroxyls and the resultant of reaction (A2) of arbitrary diatomic alcohol compounds (g).
In the present invention in order to manufacture the epoxy compound (a) in molecule with the epoxy radicals of more than 2 that aqueous alkaline solution-soluble resin (A) uses or the epoxy compound (d) in molecule with 2 epoxy radicals, the epoxy compound being 100 to 900g/ equivalent with epoxide equivalent is preferred.When epoxide equivalent does not reach 100g/ equivalent, the molecular weight of the aqueous alkaline solution-soluble resin (A) of gained is little, there is the anxiety being difficult to film forming maybe cannot obtain abundant flexual situation, again, when epoxide equivalent is more than 900g/ equivalent, there is the Drug delivery rate step-down of the monocarboxylic acid (b) of ethene unsaturated group, have the anxiety of photonasty reduction.
The epoxy compound (a) in molecule with the epoxy radicals of more than 2 can be illustrated as phenol phenolic resin varnish type epoxy resin, cresol novolak type epoxy resin, trihydroxy benzene methylmethane type epoxy resin, bicyclopentadiene phenol-type epoxy resin, bisphenol-type epoxy resin, united phenol-type epoxy resin, di-first phenol-type epoxy resin, bisphenol-A phenolic resin varnish type epoxy resin, the epoxy resin with naphthalene skeleton, hetero ring type epoxy resin etc.
Phenol phenolic resin varnish type epoxy resin can be illustrated as EpiclonN-770 (large Japanese ink chemical industry (stock) system), D.E.N438 (Dow Chemical's system), Epikote154 (japan epoxy resin (stock) system), RE-306 (Japanese chemical drug (stock) system) etc.
Cresol novolak type epoxy resin can be illustrated as EpiclonN-695 (large Japanese ink chemical industry (stock) system), EOCN-102S, EOCN-103S, EOCN-104S (Japanese chemical drug (stock) system), UVR-6650 (UnionCarbide Inc.), ESCN-195 (Sumitomo Chemical (stock) system) etc.
Trihydroxy benzene methylmethane type epoxy resin can be illustrated as EPPN-503, EPPN-502H, EPPN-501H (Japanese chemical drug (stock) system), TACTIX-742 (Dow Chemical's system), EpikoteE1032H60 (japan epoxy resin (stock) system) etc.
Bicyclopentadiene phenol-type epoxy resin can be illustrated as EpiclonEXA-7200 (large Japanese ink chemical industry (stock) system), TACTIX-556 (Dow Chemical's system) etc.
Bisphenol-type epoxy resin can be illustrated as bisphenol-A-type epoxy resin, bisphenol-Ftype epoxy resin etc.Bisphenol-A-type epoxy resin can be illustrated as Epikote828, Epikote1001 (japan epoxy resin system), UVR-6410 (UnionCarbide Inc.), D.E.R-331 (Dow Chemical's system), YD-8125 (Dongdu changes into Inc.) etc.Again, bisphenol-Ftype epoxy resin can be illustrated as UVR-6490 (UnionCarbide Inc.), YDF-8170 (Dongdu changes into Inc.) etc.
United phenol-type epoxy resin can be illustrated as NC-3000, NC-3000L, NC-3500 (Japanese chemical drug (stock) system), YL-6121H (japan epoxy resin (stock) system) etc.
Di-first phenol-type epoxy resin can be illustrated as YX-4000 (japan epoxy resin (stock) system) etc.
Bisphenol A novolac type epoxy resin can be illustrated as EpiclonN-880 (large Japanese ink chemical industry (stock) system), EpikoteE157S75 (japan epoxy resin (stock) system) etc.
The epoxy resin with naphthalene skeleton can be illustrated as NC-7000 (Japanese chemical drug (stock) system), EXA-4750 (large Japanese ink chemical industry (stock) system) etc.
Alicyclic epoxy resin can be illustrated as EHPE-3150 (Daicel chemical industry (stock) system) etc.
Hetero ring type epoxy resin can be illustrated as TEPIC-L, TEPIC-H, TEPIC-S (any one is Nissan Chemical Industries (stock) system) etc.
In the present invention, the epoxy compound (a) in molecule with the epoxy radicals of more than 2 is preferably with united phenol-type epoxy resin, wherein, is preferred with the epoxy resin shown in general formula (1).
As long as the epoxy compound (d) in molecule with 2 epoxy radicals, for having 2 epoxy radicals persons, has in the epoxy compound (a) of the epoxy radicals of more than 2, also can be and have 2 epoxy radicals persons in molecule.Concrete example can be illustrated as phenyl bisglycidyl ethers such as quinhydrones bisglycidyl ethers, catechol bisglycidyl ethers, resorcinol bisglycidyl ethers; Bisphenol-A-type epoxy resin, 2 officials' energy bisphenol-A-type epoxy resins (Japanese chemical drug (stock) RE-310S processed that such as aftermentioned Production Example is recorded), bisphenol-Ftype epoxy resin, bis-phenol-S type epoxy resin, 2,2-pair-(4-hydroxy phenyl)-1,1,1,3, the biphenol type epoxy compounds such as the epoxy compound of 3,3-HFC-236fa; The A Hydrogenated Bisphenol A type epoxy compounds such as the epoxy compound of A Hydrogenated Bisphenol A-A type epoxy resin, A Hydrogenated Bisphenol A-F type epoxy resin, A Hydrogenated Bisphenol A-S type epoxy resin, hydrogenation 2,2-pairs-(4-hydroxy phenyl)-1,1,1,3,3,3-HFC-236fa; The halogenated bisphenols type epoxy compounds such as brominated bisphenol-A type epoxy resin, brominated bisphenol-F type epoxy resin; The ester ring type bisglycidyl ethers compounds such as cyclohexanedimethanol bisglycidyl ethers compound; The aliphatics bisglycidyl ethers compounds such as 1,6-hexanediol bisglycidyl ethers, BDO bisglycidyl ethers, diethylene glycol bisglycidyl ethers; The polythiaether type bisglycidyl ethers compounds such as polythiaether bisglycidyl ethers; United phenol-type epoxy resin etc.
The commercially available product of these epoxy compounds can be illustrated as Epikote828, Epikote1001, Epikote1002, Epikote1003, Epikote1004 (any one is japan epoxy resin system), EPOMIKR-140, EPOMIKR-301, EPOMIKR-304 (any one is Mitsui Chemicals system), DER-331, DER-332, DER-324 (any one is Dow Chemical's system), Epiclon840, Epiclon850 (any one is large Japanese ink system) UVR-6410 (UnionCarbide Inc.), the bisphenol-A-type epoxy resin of YD-8125 (Dongdu changes into Inc.) etc., the bisphenol-Ftype epoxy resin of UVR-6490 (UnionCarbide Inc.), YDF-2001, YDF-2004, YDF-8170 (any one is Dongdu and changes into Inc.), Epiclon830, Epiclon835 (any one is large Japanese ink system) etc., A Hydrogenated Bisphenol A-A type the epoxy resin of HBPA-DGE (ball is apt to petrochemistry system), RikaresinHBE-100 (new Japan Chemical system) etc., brominated bisphenol-A type the epoxy resin of DER-513, DER-514, DER-542 (any one is Dow Chemical's system) etc., the alicyclic epoxy resin of Celloxide2021 (Daicel system), RikaresinDME-100 (new Japan Chemical system), EX-216 (Nagase changes into system) etc., the aliphatics bisglycidyl ethers compound of ED-503 (rising sun electrification system), RikaresinW-100 (new Japan Chemical system), EX-212, EX-214, EX-850 (any one is Nagase and changes into system) etc., the polythiaether type bisglycidyl ethers compound of FLEP-50, FLEP-60 (any one is Toraythiokol system) etc., the biphenyl phenolic epoxy compound of YX-4000 (japan epoxy resin system) etc.
The monocarboxylic acid (b) in molecule with ethene unsaturated group used to manufacture aqueous alkaline solution-soluble resin (A) in the present invention can use with no particular limitation, can illustrate as acrylic compounds or crotonic acid, α-cyanogen cinnamic acid, cinnamic acid or monounsaturated dicarboxylic acid or unsaturated dibasic acid and the reactant etc. of single glycidyl compounds with unsaturated group.
Acrylic compounds can be illustrated as (methyl) acrylic acid, β-styrene acrylic, beta-tetrahydro furfuryl acrylic acid, monounsaturated dicarboxylic acid acid anhydride or unsaturated dicarboxylic acid anhydride and the half ester class etc. of reaction with same mole thing in 1 molecule with the half ester class of (methyl) acrylate derivative of 1 hydroxyl and reaction with same mole thing, monounsaturated dicarboxylic acid or unsaturated dibasic acid and monocycle oxygen (methyl) acrylate derivative class.
The concrete example of monounsaturated dicarboxylic acid acid anhydride can be illustrated as succinic anhydride, six hydrogen anhydride phthalic acids etc.Again, the concrete example of unsaturated dicarboxylic acid anhydride can be illustrated as maleic anhydride, anhydride phthalic acid, tetrahydrochysene anhydride phthalic acid etc.The concrete example in 1 molecule with (methyl) acrylate derivative of 1 hydroxyl can be illustrated as (methyl) Hydroxyethyl Acrylate, (methyl) hydroxypropyl acrylate, new penta tetrol triacrylate, two new penta tetrol five acrylate etc.Half ester the class such as described monounsaturated dicarboxylic acid acid anhydride or unsaturated dicarboxylic acid anhydride of reaction with same mole thing and there is the resultant of reaction etc. of (methyl) acrylate derivative of 1 hydroxyl in 1 molecule.The concrete example of monocycle oxygen (methyl) acrylate derivative class can be illustrated as phenyl glycidyl ether and (methyl) acrylic acid resultant of reaction, cresyl glycidyl ether and (methyl) acrylic acid resultant of reaction, naphthyl list glycidyl ethers and (methyl) acrylic acid resultant of reaction etc.
The concrete example of monounsaturated dicarboxylic acid can be illustrated as succinic acid, glutaric acid, hexane diacid, six hydrogen phthalandiones etc.
The concrete example of unsaturated dibasic acid can be illustrated as maleic acid, phthalandione, tetrahydrochysene phthalandione etc.
The concrete example with single glycidyl compounds of unsaturated group can be illustrated as the reactant etc. of the reactant of (methyl) Glycidyl Acrylate, (methyl) Hydroxyethyl Acrylate and epihalohydrins, (methyl) hydroxypropyl acrylate and epihalohydrins.
In there is the monocarboxylic acid (b) of ethene unsaturated group with regard to regard to susceptibility during photosensitive polymer combination in molecule, the resultant of reaction of outstanding preferably (methyl) acrylic acid, (methyl) acrylic acid and 6-caprolactone or cinnamic acid.
The multi-anhydride (c) used to manufacture aqueous alkaline solution-soluble resin (A) in the present invention can use with no particular limitation, as long as but namely all can use for the acid anhydride structure person in molecule with more than 1.Specifically above especially preferably be selected from succinic anhydride, acetic anhydride, anhydride phthalic acid, pyromellitic dianhydride, maleic anhydride, tetrahydrochysene anhydride phthalic acid, six hydrogen anhydride phthalic acids, ethylene glycol-bis--(trimellitic anhydride), glycerine-bis--(trimellitic anhydride) monoacetate, 1, 2, 3, 4,-butane tetracarboxylic acid dianhydride, 3, 3 ', 4, 4 '-diphenyl sulfone tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-benzophenone tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-biphenyl tetracarboxylic dianhydride, 3, 3 ', 4, 4 '-diphenyl ether tetracarboxylic dianhydride, 2, 2-two-(3, 4-dicarboxyphenyi acid anhydride) propane, 2, 2-two-(3, 4-dicarboxyphenyi acid anhydride) HFC-236fa, 5-(2, 5-dioxotetrahydro-3-furyl)-3-methylcyclohexene-1, 2-dicarboxylic anhydride, 3a, 4, 5, 9b-tetrahydrochysene-5-(tetrahydrochysene-2, 5-dioxo-3-furyl)-naphtho-[1, 2-c] furans-1, multi-anhydride among 3-diketone.
In the present invention in order to manufacture aqueous alkaline solution-soluble resin (A2) as long as and use diisocyanate cpd (e) for have 2 isocyanate group persons in molecule, can use with no particular limitation.Again, a plurality of diisocyanate cpd also can be made to react simultaneously.Wherein, the diisocyanate cpd (e) that flexibility etc. are special excellent, preferred phenylene diisocyanate, toluene diisocyanate, Xylene Diisocyanate, tetramethylxylene diisocyanate, methyl diphenylene diisocyanate, naphthalene diisocyanate, dimethyl diphenyl diisocyanate (tolidinediisocyanate), hexamethylene diisocyanate, dicyclohexyl methyl hydride diisocyanate, different Buddhist ketone diisocyanate, acrol (allylene) sulfone ether diisocyanate, allyl cyanide diisocyanate, N-acyl group diisocyanate, trimethyl hexamethylene diisocyanate, 1, two (isocyanatomethyl) cyclohexane of 3-or norborneol-diisocyanate methyl.
In the present invention in order to manufacture the carboxylic acid (f) in molecule with 2 hydroxyls that aqueous alkaline solution-soluble resin (A2) uses, as long as be the diatomic alcohol compounds simultaneously in molecule with alcohol hydroxyl group or phenolic hydroxyl group and carboxyl, can use with no particular limitation.The carboxylic acid (f) in molecule with 2 hydroxyls preferably has the carboxylic acid of 2 alcohol hydroxyl groups of aqueous alkali developability excellence, more preferably the dihydroxymethyl carboxylic acid such as dihydromethyl propionic acid (such as 2,2-two (dihydroxymethyl)-propionic acid), dimethylolpropionic acid.
In the present invention in order to manufacture the arbitrary diatomic alcohol compounds (g) that aqueous alkaline solution-soluble resin (A2) uses, as long as be aliphatics or the ester ring type compound that 2 hydroxyls are binding on 2 different carbon atoms, can use with no particular limitation.Can illustrate as ethylene glycol on concrete, propylene glycol, trimethylene, Isosorbide-5-Nitrae-butanediol, 1,5-pentane diol, 1,6-hexane diol, 1,7-heptane glycol, 1,8-heptane glycol, 1,9-nonane glycol, 1,10-decane glycol, hydrogen styrax, benzopinacol, cyclopentane-1,2-glycol, cyclohexane-1,2-glycol, cyclohexane-Isosorbide-5-Nitrae-glycol, cyclohexane-1,2-dimethanol, cyclohexane-Isosorbide-5-Nitrae-dimethanol, there is in end the hycar (emerging AT × 013 produced, such as space portion) of hydroxyl, there is in end the spiral shell glycerine (such as 3,9-two (2-hydroxyl-1,1-dimethyl ethyl)-2,4,8,10-tetra-oxaspiro [5,5] hendecane) of hydroxyl, in end, there is hydroxyl diox glycol (such as 2-(2-hydroxyl-1,1-dimethyl ethyl)-5-ethyl-5-hydroxyl-1,3-diox), there is in end the tristane-dimethanol of hydroxyl, in end, there is hydroxyl and have in side chain polystyrene huge monomer (such as East Asia synthesis system HS-6), in end, there is hydroxyl and there is in side chain the diatomic alcohol compounds such as the huge monomer (such as the HN-6 of East Asia synthesis system) of Styrene-Acrylnitrile Copolymer, or these diatomic alcohol compounds and oxirane, the reactant that epoxypropane etc. are oxide-based.
The manufacture of aqueous alkaline solution-soluble resin (A1) be in the present invention by make by the epoxy compound (a) of the epoxy radicals in be set forth in molecule with more than 2 and have in molecule ethene unsaturated group monocarboxylic acid (b) reaction (hereinafter referred to as the first reaction) and generate and have epoxy carboxylic acids's ester compounds of alcohol hydroxyl group, react (reacting hereinafter referred to as second) to carry out with multi-anhydride (c).
Again, the manufacture of aqueous alkaline solution-soluble resin (A2) is in the present invention by making there is epoxy carboxylic acids's ester compounds of alcohol hydroxyl group by the epoxy compound (d) in be set forth in molecule with 2 epoxy radicals and the reaction (first reaction) and generating of monocarboxylic acid (b) in molecule with ethene unsaturated group, carries out amine formic ether (urethane) change and react (reacting hereinafter referred to as the 4th) to carry out with diisocyanate cpd (e) and the carboxylic acid (f) in molecule with 2 hydroxyls.Now, the diatomic alcohol compounds (g) of any composition also can be made to react.
First reaction is solvent-free or do not have the solvent of alcohol hydroxyl group, the ketone such as such as acetone, ethyl methyl ketone, cyclohexanone on concrete; Benzene,toluene,xylene, tetramethylbenzene etc. are aromatic hydrocarbon based; The glycol ethers such as ethylene glycol dimethyl ether, ethylene glycol bisthioglycolate ethylether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol Anaesthetie Ether; The ester classes such as ethyl acetate, butyl acetate, methylcellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate (CA), propylene glycol monomethyl ether, glutaric acid dialkyl, succinic acid dialkyl, hexane diacid dialkyl; The cyclic ester classes such as gamma-butyrolacton; The petroleum solvents such as sherwood oil, naphtha, non-hydrogenated petroleum brain, solvent naphtha, further can carrying out separately or in mixed organic solvents in described crosslinking chemical (B) etc.
The feed-in ratio of the raw material in this reaction is the monocarboxylic acid (b) in molecule with ethene unsaturated group, relative to epoxy compound (a) or epoxy compound (d) 1 equivalent, is 80 to 120 equivalent %.When exceeding this scope, in the second reaction, there is the anxiety of the thermostability step-down of the aqueous alkaline solution-soluble resin (A) of the anxiety causing gelation or final gained.
In first reaction, in order to promote that reaction is to use catalyst to be preferred, the use amount of this catalyst is 0.1 to 10 quality % relative to the weight of reactant.Temperature of reaction is now 60 to 150 DEG C, and again, the reaction time is 5 to 60 hours.The concrete example of spendable catalyst can be illustrated as triethylamine, benzyl dimethyl amine, chlorination triethyl ammonium, benzyl bromide trimethyl ammonium, benzene iodide methyl trimethoxy base ammonium, triphenylphosphine, antimony triphenyl, methyl triphenyl antimony, sad chromium, zirconium caprylate etc.Again, thermal polymerization inhibitor preferably uses Hydroquinone monomethylether, 2-methylnaphthohydroquinone, quinhydrones, diphenyl picryl diamine, diphenylamine, 3,5-bis--tertiary butyl-4-hydroxy toluene etc.First reaction is suitably sampling on one side, makes the acid value of sample be below 1mgKOH/g, preferably makes the time point of below 0.5mgKOH/g as terminal.
Second reaction is after the first reaction terminating, makes the esterification that reactant liquor and described multi-anhydride (c) are reacted.Even if without catalyst, also can react, but in order to promote reaction, also can use alkaline catalyst, the use amount of this catalyst is be below 10 quality % relative to the weight of reactant.Temperature of reaction is now 40 to 120 DEG C, and again, the reaction time is 5 to 60 hours.
The addition of multi-anhydride (c) is that interpolation makes the solid acid value of aqueous alkaline solution-soluble resin (A1) become the calculated amount of 50 to 150mgKOH/g.When solid acid value does not reach 50mgKOH/g, insufficient to the dissolubility of aqueous alkali, when carrying out patterning, likely produce residue, or cannot be patterning.Again, when solid acid value is more than 150mgKOH/g, too high to the dissolubility of aqueous alkali, likely the figure of photo-hardening can be peeled off, and not preferred.
4th reaction is after the first reaction terminating, the carboxylic acid (f) and arbitrary diatomic alcohol compounds (g) in be set forth in molecule with 2 hydroxyls is added in reactant liquor, after becoming dispersion liquid or solution, and then, low add described diisocyanate cpd (e) and the amidocarbonic acid esterification making it react reaction.Even if also can react without catalyst, but in order to promote that reaction also can use alkaline catalyst, the use amount of this catalyst is be below 10 quality % relative to the weight of reactant.Temperature of reaction is now 40 to 120 DEG C, and the reaction time is 5 to 60 hours again.Again, now, also can use as described in solvent or thermal polymerization inhibitor.4th reaction is while suitable sampling, makes sample at the 2250cm of infrared absorption spectrum
?1the time point that neighbouring absorption disappears is set to terminal.
The feed-in amount in molecule with the carboxylic acid (f) of 2 hydroxyls is that interpolation makes the solid acid value of aqueous alkaline solution-soluble resin (A2) become the calculated amount of 50 to 150mgKOH/g.The feed-in amount of diisocyanate cpd (e) is that the mode making the ratio of molal quantity/(molal quantity of compound (e)) of (molal quantity of the molal quantity+compound (f) of the epoxy carboxylic acids's ester compounds generated by the first reaction)+arbitrary diatomic alcohol compounds (g) in the 4th reaction become the scope of 1 to 5 is added.When this value does not reach 1, in the end residual isocyanate of aqueous alkaline solution-soluble resin (A2), there is thermostability low, and the anxiety of gelation in preserving.Again, when this value is more than 5, there is the molecular weight step-down of aqueous alkaline solution-soluble resin (A2), the anxiety of sticky (tack) property or sensitivity variation.Again, when solid acid value does not reach 50mgKOH/g, not enough to the dissolubility of aqueous alkali, when carrying out patterning, likely produce residue, or cannot be patterning.Again, when solid acid value is more than 150mgKOH/g, too high to the dissolubility of aqueous alkali, the anxiety having the figure of photo-hardening to peel off etc., and not preferred.
When aqueous alkaline solution-soluble resin (A) uses solvent, in a suitable approach except desolventizing, can be separated whereby.In the present invention, the usual alkaline soluble aqueous solution of aqueous alkaline solution-soluble resin (A), but also dissolve in described solvent, when being used in solder resist, plating resist etc., also can develop by solvent.
In the photosensitive polymer combination of the described aqueous alkaline solution-soluble resin (A) used in photosensitive polymer combination of the present invention containing ratio, when being 100 quality % with the solid of photosensitive polymer combination, be generally 15 to 70 quality %, preferably 20 to 60 quality %.
The crosslinking chemical (B) used in photosensitive polymer combination of the present invention can be illustrated as (methyl) acrylic acid 2-hydroxy methacrylate, (methyl) acrylic acid 2-hydroxy propyl ester, Isosorbide-5-Nitrae-butanediol list (methyl) acrylate, carbitol (methyl) acrylate, acryloyl morpholine, there is (methyl) acrylate (such as (methyl) acrylic acid 2-hydroxy methacrylate of hydroxyl, (methyl) acrylic acid 2-hydroxy propyl ester, Isosorbide-5-Nitrae-butanediol list (methyl) acrylate etc.) and polycarboxylic acid anhydrides (such as succinic anhydride, maleic anhydride, anhydride phthalic acid, tetrahydrochysene anhydride phthalic acid, six hydrogen anhydride phthalic acids etc.) the half ester of reactant, polyglycol two (methyl) acrylate, tripropylene glycol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, trimethylolpropane polyethoxy three (methyl) acrylate, glycerine gathers propoxyl group three (methyl) acrylate, two (methyl) acrylate (such as Japanese chemical drug (stock) system of the 6-caprolactone addition product of hydroxyl trimethylace tonitric DOPCP, KAYARADHX-220, HX-620 etc.), new penta tetrol four (methyl) acrylate, poly-(methyl) acrylate (DPCA that such as aftermentioned embodiment is recorded) of the reactant of two new penta tetrols and 6-caprolactone, two new penta tetrols gather (methyl) acrylate, single or poly-glycidyl compounds (such as, butyl glycidyl ethers, phenyl glycidyl ether, polyglycol bisglycidyl ethers, polypropylene glycol bisglycidyl ethers, 1,6-hexane diol bisglycidyl ethers, six hydrogen phthalandione diepoxy propyl diesters, glycerine gathers glycidyl ethers, glycerine polyethoxy glycidyl ethers, trimethylolpropane gathers glycidyl ethers, trimethylolpropane polyethoxy gathers epoxy (methyl) acrylate etc. of glycidyl ethers etc. and (methyl) acrylic acid reactant.Crosslinking chemical (B) can be used alone, and again, also can mix two or more and use.These in photosensitive polymer combination containing ratio using the solid of photosensitive polymer combination as 100 quality % time, be generally 2 to 40 quality %, preferably 3 to 30 quality %.
The Photoepolymerizationinitiater initiater (C) used in photosensitive polymer combination of the present invention can use with no particular limitation, but concrete on can illustrate as styrax classes such as styrax, styrax methyl ether, styrax ethylether, styrax propyl ether, benzoin isobutyl butyl ethers; Acetophenone, 2, the acetophenones such as 2-diethoxy-2-phenyl acetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenyl-propane-1-ketone, diethoxy acetophenone, 1-hydroxycyclohexylphenylketone, 2-methyl isophthalic acid-(4-(methyl sulphur) phenyl)-2-morpholinopropane-1-ketone (Irgacure-907 that such as aftermentioned embodiment is recorded); The Anthraquinones such as 2-EAQ, 2-tert-butyl group anthraquinone, 2-chloroanthraquinone, 2-amyl anthraquinone; The thioxanthones such as 2,4-diethyl thioxanthone (DETX-S that such as aftermentioned embodiment is recorded), 2-isopropyl thioxanthone, 2-chlorothiaxanthenone; The acetalses such as acetophenone dimethylacetal, benzyl dimethyl acetal; Benzophenone, 4-benzoyl-4 '-dimethyl diphenyl sulfide, 4, the benzophenones such as 4 '-bis-methyl aminobenzophenones; The phosphinoxidess etc. such as TMDPO, two (2,4,6-trimethylbenzoyl)-phenyl phosphine oxide.Photoepolymerizationinitiater initiater (C) can be used alone, and again, also can mix two or more and use.In these photosensitive polymer combinations containing ratio be using the solid of photosensitive polymer combination as 100 quality % time, be generally 1 to 30 quality %, preferably 2 to 25 quality %.
These Photoepolymerizationinitiater initiaters (C) can use separately or as potpourri of more than two kinds, further can with 3 grades of amine such as triethanolamine, methyldiethanolamine; The promoter such as benzoic acid derivative such as N, N-dimethyl amido ethyl benzoate, N, N-dimethyl amido isoamyl benzoate etc. are combined and use.The addition of these promoter is relative to Photoepolymerizationinitiater initiater (C), is preferred with the addition of below 100 quality %.
The equivalent preferably calculated from the solid acid value of aqueous alkaline solution-soluble resin (A) and use amount containing ratio of the epoxy resin (D) shown in general formula (1) less than 200% amount.If this amount, more than 200%, has the anxiety that the developability of photosensitive polymer combination of the present invention obviously reduces, and not preferred.
Epoxy resin (D) shown in general formula (1) can be pre-mixed in described resin combination, but carries out being mixed into preferably before coating printed base plate.Namely, preferably allocate in using described (A) composition as main body, and in wherein allotment have hardenable epoxy promoter etc. host solution, with using the epoxy resin (D) shown in general formula (1) as in the two-liquid type of the epoxy resin solution of main body, mix these in use and use.
When obtaining photosensitive polymer combination of the present invention, can just improve the object of each performance of composition and add the filling agents such as various adjuvant such as talcum, barium sulphate, calcium carbonate, magnesium carbonate, barium titanate, aluminium hydroxide, aluminium oxide, silicon dioxide, clay according to need; AEROSIL etc. give thixotropy agent; The colorants such as phthalocyanine blue, phthalocyanine green, titanium dioxide; Poly-silica system levelling agent (KS-66 that such as aftermentioned embodiment is recorded), fluorine system levelling agent or defoamer (BYK-354 that such as aftermentioned embodiment is recorded); The polymerization inhibitor such as quinhydrones, Hydroquinone monomethylether; Thermmohardening catalyst (melamine that such as aftermentioned embodiment is recorded) etc.
Photosensitive polymer combination of the present invention is such as by mixed cross-linker (B) in the described aqueous alkaline solution-soluble resin (A), Photoepolymerizationinitiater initiater (C), epoxy resin (D) and obtaining.
Photosensitive polymer combination of the present invention also can be used as the dry film resist that resin combination is formed with the structure that support membrane and diaphragm form sandwich.Photosensitive polymer combination of the present invention is preferably processed into aqueous or membranaceous.
Photosensitive polymer combination of the present invention except the layer insulation material that can be used as such as electronic component, connect optical waveguide between light part or printed base plate the resist material of solder resist, coating (coverlay) etc. except, also can make to be used as optical filter, printing ink, sealant, coating, smears, solid etc.
Hardening thing of the present invention makes described photosensitive polymer combination sclerosis of the present invention by the irradiation of ultraviolet Isoenergetical line and obtains.Irradiate sclerosis by ultraviolet Isoenergetical line to be implemented by conventional method.Such as, during irradiation ultraviolet radiation, as long as use the ultraviolet generation devices such as Cooper-Hewitt lamp, high-pressure mercury-vapor lamp, extra-high-pressure mercury vapour lamp, xenon lamp, luminescence-utraviolet laser (excimer laser etc.).
Hardening thing of the present invention be used in as the layer insulation material of such as resist film, accumulation (build-up) engineering method or optical waveguide as printed base plate, optoelectronic substrate or photopolymer substrate electrical/base material such as electronics/light base material.These concrete examples can be illustrated as article such as computer, family's electrical article, action machines.The thickness of this sclerosis nitride layer is generally about 0.5 to 160 μm, is preferred with about 1 to 100 μm.
Described printed base plate such as can be obtained by following way.Namely, during by using aqueous resin combination, photosensitive polymer combination of the present invention is coated with by methods such as screen printing method, spraying process, roller rubbing method, electrostatic coating processes, curtain Tu Fa with the thickness of 5 to 160 μm on printed wiring substrate, by film with usual 50 to 110 DEG C, preferably 60 to 100 DEG C of dryings, and form film.Thereafter, the light shield of exposure figure is formed with by negative film etc. and directly or indirectly usual with 10 to 2000mJ/cm to film
2the contour energy line of intensity illumination ultraviolet of left and right, makes unexposed portion utilize developer solution described later to be developed by the dynamic dipping of such as Pen Tu, Oscillating, brushing (brushing), washing (scrubbing) etc.Thereafter; further irradiation ultraviolet radiation according to need; then; usually heat with the temperature of 100 to 200 DEG C, preferably 140 to 180 DEG C; whereby, can obtain that to have gold-plated property excellent and meet the printed base plate of the permanent diaphragm of each characteristics such as thermotolerance, solvent resistance, acid resistance, cohesive, bendability.
The aqueous alkali being used in development can use the inorganic base aqueous solutions such as potassium hydroxide, NaOH, sodium carbonate, sal tartari, sodium bicarbonate, saleratus, sodium phosphate, potassium phosphate; Or the organic base aqueous solution such as tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrabutylammonium, monoethanolamine, diethanolamine, triethanolamine.
(embodiment)
Below, further illustrate the present invention by embodiment, but the present invention is not limited to following embodiment.
Synthesis example 1
In being provided with stirring apparatus, in the 3L flask of recirculatory pipe, add Japanese chemical drug (stock) EOCN-103S (multifunctional cresol novolak type epoxy resin, epoxide equivalent: 215.0g/ equivalent) 860.0g is as the epoxy compound (a) of epoxy radicals in molecule with more than 2, acrylic acid (molecular weight: 72.06) 288.3g is as the monocarboxylic acid (b) in molecule with ethene unsaturated group, carbitol acetate 492.1g is as anti-solvent-applied, 2, 6-bis--tert-butyl-para-cresol 4.921g is as polymerization inhibitor, and triphenylphosphine 4.921g is as reaction catalyst, with 98 DEG C of reactions to making the acid value of reactant liquor become below 0.5mgKOH/g, obtained epoxy carboxylic acids's ester compounds.Then, the carbitol acetate 169.8g as anti-solvent-applied, tetrahydrochysene anhydride phthalic acid 201.6g as multi-anhydride (c) is added in this reactant liquor, with 95 DEG C of reactions 4 hours, obtain the resin solution (this solution is set to A1-1) containing aqueous alkaline solution-soluble resin (A1) 65 quality %.Measure acid value, be 67.3mgKOH/g (solid acid value: 103.6mgKOH/g).The epoxide equivalent of compound measures (even if in following synthesis example, the epoxide equivalent of compound measures with same way) according to JISK7236.Again, almost according to JISK0070, (solution of titration is not potassium hydroxide-ethanol solution to the acid value of resin, but carry out with sodium hydrate aqueous solution) and measure (even if in following synthesis example, the acid value of resin measures with same way).
Synthesis example 2
In being provided with stirring apparatus, in the 1L flask of recirculatory pipe, add Japanese chemical drug (stock) NC-3500 (united phenol-type epoxy resin processed, epoxide equivalent: 209.0g/ equivalent) 209.0g is as the epoxy compound (a) of epoxy radicals in molecule with more than 2, acrylic acid (molecular weight: 72.06) 72.06g is as the monocarboxylic acid (b) in molecule with ethene unsaturated group, carbitol acetate 121.39g is as anti-solvent-applied, 2, 6-bis--tert-butyl-para-cresol 0.850g is as polymerization inhibitor, and triphenylphosphine 0.850g is as reaction catalyst, with 98 DEG C of reactions to making the acid value of reactant liquor become below 0.5mgKOH/g, obtained epoxy carboxylic acids's ester compounds.Then, the carbitol acetate 86.32g as anti-solvent-applied, tetrahydrochysene anhydride phthalic acid 102.51g as multi-anhydride (c) is added in this reactant liquor, with 95 DEG C of reactions 4 hours, obtain the resin solution (this solution is set to A1 '-2) containing aqueous alkaline solution-soluble resin (A1 ') 65 quality %.Measure acid value, be 66.8mgKOH/g (solid acid value: 102.7mgKOH/g).
Synthesis example 3
In being provided with stirring apparatus, in the 3L flask of recirculatory pipe, add Japanese chemical drug (stock) RE-310S processed (2 officials' energy bisphenol-A-type epoxy resins, epoxide equivalent: 184.0g/ equivalent) 368.0g is as the epoxy compound (d) of epoxy radicals in molecule with more than 2, acrylic acid (molecular weight: 72.06) 141.2g is as the monocarboxylic acid (b) in molecule with ethene unsaturated group, Hydroquinone monomethylether 1.02g is as polymerization inhibitor, and triphenylphosphine 1.53g is as reaction catalyst, with 98 DEG C of reactions to making the acid value of reactant liquor become below 0.5mgKOH/g, obtained epoxy carboxylic acids's ester compounds (molecular weight: 509.2).Then, the carbitol acetate 755.5g, 2 as anti-solvent-applied is added in this reactant liquor, two (the dihydroxymethyl)-propionic acid of 2-(molecular weight: 134.16) 268.3g as have in molecule 2 hydroxyls carboxylic acid (f), the 2-methylnaphthohydroquinone 1.08g as thermal polymerization inhibitor, (molecular weight: 304.38) 140.3g, is warming up to 45 DEG C to the spiral shell glycol as any diatomic alcohol compounds (g).Trimethyl hexamethylene diisocyanate (the molecular weight: 210.27) 485.2g as diisocyanate cpd (e) low is instilled in the mode making temperature of reaction be no more than 65 DEG C in this solution.After instillation stops, temperature is made to rise to 80 DEG C, by infrared absorption spectrum determination method, react 6 hours until the absorption near 2250cm-1 disappears, obtain the resin solution (this solution is set to A2-3) containing aqueous alkaline solution-soluble resin (A2) 65 quality %.Measure acid value, be 52.0mgKOH/g (solid acid value: 80.0mgKOH/g).
Embodiment 1,2,3, comparative example 1
Use the NC-3500 that described synthesis example 1,2 and (A1-1), (A1 '-2), (A2-3) of synthesis example 3 gained and the Japanese chemical drug (stock) as the epoxy resin (D) shown in general formula (1) are made, after being set to the allotment ratio shown in table 1, mix with 3 roller mills, obtain photosensitive polymer combination of the present invention.By this photosensitive polymer combination by screen printing method, the mode becoming the thickness of 15 to 25 μm with dry film thickness coats printed base plate, by film with the hot-air drier of 80 DEG C drying 30 minutes.Then, use ultraviolet exposure apparatus according (ORC makes institute's (stock), pattern HMW-680GW), by describing to have the shade of circuitous pattern and irradiation ultraviolet radiation.Thereafter, carry out spray development with 1% aqueous sodium carbonate, the resin of removing ultraviolet non-irradiation unit.After washing and drying, printed base plate is reacted 60 minutes with the hot-air drier heat hardening of 150 DEG C, obtain cured film.For the hardening thing of gained, as aftermentioned, carry out the test of viscosity, developability, resolution, light sensitivity, surface gloss, substrate warp, bendability, cohesive, pencil hardness, solvent resistance, acid resistance, thermotolerance, resistance to gold-plated property, resistance to PCT (PressureCookerTest) property, resistance to sudden heating.These results are shown in table 2.Again, test method and appraisal procedure as follows.
Continuous for degreasing friction has been coated the dried film of substrate by (stickiness), the viscosity of assessment film.
Zero degreasing silk floss does not adhere to.
The flocking of × degreasing silk floss adheres to film.
(developability) uses following assessment benchmark.
During zero development, ink is removed completely, can develop.
During × development, there is the part be not developed.
(resolution), in dried film, makes the minus figure of 50 μm bond, and irradiates exposure accumulated light 200mJ/cm
2ultraviolet.Then, with 1% aqueous sodium carbonate, with 2.0kg/cm
2spray pressure developed for 60 seconds, with microscopic examination transfer graphic.Use following benchmark.
Zero pattern edge is differentiated with straight line.
× stripping or pattern edge are zigzag.
(light sensitivity), in dried film, makes density step tablet (steptablet) 21 sections (Kodak's system) bond, and irradiates exposure accumulated light 500mJ/cm
2ultraviolet.Then, with 1% aqueous sodium carbonate, with 2.0kg/cm
2spray pressure developed for 60 seconds, confirm not develop and the hop count of residual film.
(surface gloss) irradiates exposure 500mJ/cm in dried film
2ultraviolet.Then, with 1% aqueous sodium carbonate, with 2.0kg/cm
2spray pressure developed for 60 seconds, the cured film after seeing drying.Use following benchmark.
Zero can't see dim atomization completely
× a little dim atomization can be seen
(substrate warp) uses following benchmark.
Zero can't see warpage in substrate
△ substrate is few warpage only
× warpage of substrate can be seen
Cured film is bent 180 DEG C and observes by (bendability).Use following benchmark.
Zero can't see face breaks
× face breaks
(cohesive), according to JISK5400, makes the chessboard eye of 100 1mm in test film, undertaken peeling off (peeling) test by Cellotape (registered trademark).Observe the stripping state of chessboard eye, with following benchmarking exercise.
〇 is without stripping
× there is stripping
(pencil hardness) is assessed according to JISK5400.
Test film at room temperature be impregnated in isopropyl alcohol 30 minutes by (solvent resistance).After confirming that whether outward appearance is without exception, carry out the disbonded test by Cellotape (registered trademark), with following benchmarking exercise.
Zero appearance of film is without exception, without swelling or peeling off
× film swells or peels off
Test film at room temperature be impregnated in 10% aqueous hydrochloric acid solution 30 minutes by (acid resistance).After confirming that whether outward appearance is without exception, carry out the disbonded test by Cellotape (registered trademark), with following benchmarking exercise.
Zero appearance of film is without exception, without swelling or peeling off
× film swells or peels off
(thermotolerance), in test film coating rosin system scaling powder, impregnated in solder bath 30 second of 270 DEG C.In this, as 1 circulation, repeat 3 circulations.Let cool to room temperature, carry out the disbonded test by Cellotape (registered trademark), with following benchmarking exercise.
〇 appearance of film is without exception, without swelling or peeling off
× film swells or peels off
(resistance to PCT) by test substrate 121 DEG C, place 96 hours in the water of 2 air pressure after, after confirming that whether outward appearance without exception, carry out the disbonded test by Cellotape (registered trademark), with following benchmarking exercise.
Zero appearance of film is without exception, without swelling or peeling off
× film swells or peels off
Test film circulates using-55 DEG C/30 minutes, 125 DEG C/30 minutes as 1 and applies thermal history by (resistance to sudden heating), and after 1000 circulations, microscopic examination test film, with following benchmarking exercise.
Zero film does not produce be full of cracks (crack)
× film produces be full of cracks
[table 1]
Note
* 1 Japanese chemical drug (stock) system: 6-caprolactone modified hydroxyl front three machine acetic acid neopentylglycol diacrylate
* 2BASF system: 2-methyl-(4-(methyl sulphur) phenyl)-2-morpholine propane-1-ketone
* 3 Japanese chemical drug (stock) systems: 2,4-diethyl thioxanthone
* 4 Japanese chemical drug (stock) systems: xenol aralkyl-type epoxy resin
* 5 Japanese chemical drug (stock) systems: an xenol-phenol/diformazan phenol-type epoxy resin
* 6BYKCHEMIE system: levelling agent
* 7 SHIN-ETSU HANTOTAI's chemical industry (stock) systems: defoamer
* 8 Osaka Organic Chemical Industry systems: carbitol acetate
[table 2]
From described result obviously, use photosensitive polymer combination of the present invention that aqueous alkaline solution-soluble resin, crosslinking chemical, Photoepolymerizationinitiater initiater and epoxy resin (D) are the compound gained with the structure of general formula (1) inviscid and light sensitivity is high.Hardening thing of the present invention is the excellences such as solder heat resistance, resistance to chemical reagents, resistance to gold-plated property, and hardening thing surface does not produce be full of cracks again, even if using the situation through the substrate of filming, the warpage of substrate is also few.
[utilizing possibility in industry]
The photosensitive polymer combination that aqueous alkaline solution-soluble resin of the present invention, crosslinking chemical, Photoepolymerizationinitiater initiater and epoxy resin are the compound gained with the structure of general formula (1) is used to be suitable for printed base plate photosensitive polymer combination and optical waveguide formation photosensitive polymer combination.
Claims (5)
1. a photosensitive polymer combination, it contains aqueous alkaline solution-soluble resin, crosslinking chemical, Photoepolymerizationinitiater initiater and the epoxy resin shown in following general formula (1);
In formula, (i) is that (i)/(ii)=1 to 3, G represents glycidyl with the ratio of (ii), and n is the mean value of repeat number, and is 0 to 5.
2. photosensitive polymer combination as claimed in claim 1, it is characterized in that, described aqueous alkaline solution-soluble resin is: make the epoxy compound of the epoxy radicals in molecule with more than 2 and have in molecule ethene unsaturated group monocarboxylic acid reaction gained epoxy carboxylic acids's ester compounds, with the resultant of reaction of multi-anhydride.
3. photosensitive polymer combination as claimed in claim 1, it is characterized in that, described aqueous alkaline solution-soluble resin for: make the epoxy resin shown in following general formula (1) and have in molecule ethene unsaturated group monocarboxylic acid reaction gained epoxy carboxylic acids's ester compounds, with the resultant of reaction of multi-anhydride;
In formula, (i) is that (i)/(ii)=1 to 3, G represents glycidyl with the ratio of (ii), and n is the mean value of repeat number, and is 0 to 5.
4. photosensitive polymer combination as claimed in claim 1, it is characterized in that, described aqueous alkaline solution-soluble resin is: epoxy carboxylic acids's ester compounds of the epoxy compound making to have 2 epoxy radicals in molecule and the reaction of the monocarboxylic acid in molecule with ethene unsaturated group gained, with diisocyanate cpd, in molecule, have the carboxylic acid of 2 hydroxyls and the resultant of reaction of arbitrary diatomic alcohol compounds.
5. a hardening thing is the hardening thing of photosensitive polymer combination according to claim 1.
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| CN110120180A (en) * | 2018-02-05 | 2019-08-13 | Jsr株式会社 | Wiring construction element |
| CN111032754A (en) * | 2017-08-29 | 2020-04-17 | 东亚合成株式会社 | Resin sheet and curable composition for producing the same |
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| TWI809257B (en) * | 2019-03-12 | 2023-07-21 | 日商日本化藥股份有限公司 | Unsaturated group-containing polycarboxylate resin, photosensitive resin composition, cured product, substrate, and article |
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| JP6972943B2 (en) * | 2016-11-21 | 2021-11-24 | 三菱ケミカル株式会社 | Epoxy resin, epoxy resin composition, cured product and electrical / electronic parts |
| KR102383697B1 (en) * | 2018-03-26 | 2022-04-05 | 동우 화인켐 주식회사 | Negative-type photosensitive resin comopsition |
| JP7302262B2 (en) * | 2019-04-26 | 2023-07-04 | 三菱ケミカル株式会社 | Photosensitive colored resin composition, cured product, and image display device |
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| CN111032754A (en) * | 2017-08-29 | 2020-04-17 | 东亚合成株式会社 | Resin sheet and curable composition for producing the same |
| CN110120180A (en) * | 2018-02-05 | 2019-08-13 | Jsr株式会社 | Wiring construction element |
| TWI809257B (en) * | 2019-03-12 | 2023-07-21 | 日商日本化藥股份有限公司 | Unsaturated group-containing polycarboxylate resin, photosensitive resin composition, cured product, substrate, and article |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105527793B (en) | 2020-07-28 |
| JP2016080871A (en) | 2016-05-16 |
| KR20160045590A (en) | 2016-04-27 |
| TWI666516B (en) | 2019-07-21 |
| TW201616231A (en) | 2016-05-01 |
| JP6275620B2 (en) | 2018-02-07 |
| KR102365882B1 (en) | 2022-02-21 |
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