CN101827876A - Resin composition - Google Patents
Resin composition Download PDFInfo
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- CN101827876A CN101827876A CN200880112087A CN200880112087A CN101827876A CN 101827876 A CN101827876 A CN 101827876A CN 200880112087 A CN200880112087 A CN 200880112087A CN 200880112087 A CN200880112087 A CN 200880112087A CN 101827876 A CN101827876 A CN 101827876A
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/285—Permanent coating compositions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
- C08G18/4045—Mixtures of compounds of group C08G18/58 with other macromolecular compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
- C08G18/44—Polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
- C08G18/581—Reaction products of epoxy resins with less than equivalent amounts of compounds containing active hydrogen added before or during the reaction with the isocyanate component
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/69—Polymers of conjugated dienes
- C08G18/698—Mixtures with compounds of group C08G18/40
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/182—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing using pre-adducts of epoxy compounds with curing agents
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/42—Polycarboxylic acids; Anhydrides, halides or low molecular weight esters thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/688—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing phosphorus
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/03—Use of materials for the substrate
- H05K1/0393—Flexible materials
Abstract
Disclosed is a resin composition which is excellent in solvent resistance, flexibility (bendability), low warping property, and electrical insulation. This resin composition is useful as an overcoating agent for flexible printed wiring boards. Specifically disclosed is a resin composition for overcoats of flexible printed wiring boards, which contains a polyurethane resin (A) having an epoxy group and a urethane structure, and an epoxy curing agent (B).
Description
Technical field
The present invention relates to carry out the flexible printed circuit board of protection and the electronic equipments that is built-in with this flexible printed circuit board with the cured article of this resin combination as the useful resin combination of the protective layer material (オ one バ one コ one ト material) on the electronic circuit surface of protecting flexible printed board, surface.
Background technology
The flexible printed circuit board (FPC) that utilizes among TCP (band year encapsulation, Tape Carrier Package) or the COF (covering brilliant film, Chip OnFlexible or Film) etc. mainly is made of the surface protection film of substrate with the surface of this substrate of protection usually, and this substrate has the conductor layer (conductor circuit layer) that has formed circuit on the one or both sides of the film of polyester phthalate or polyimide.The insulating protective film of using as FPC; the covering layer film that the common known film that will utilize mould that the polyimide film stamping-out is become desired shape and obtain is provided with bond layer pastes the method on the substrate, is printed as required pattern, makes its solidified method by the resin combination (protective layer coating agent) of silk screen printing with the varnish shape.The method of using covering layer film is because unfavorable aspect operation or cost, and the method that is coated with the protective layer coating agent by silk screen printing becomes main flow.Protective layer coating agent as flexible printed circuit board is used for example, discloses the composition that contains Resins, epoxy, imidazolium compounds and long-chain biatomic acid acid anhydride in the special fair 5-75032 communique of Japan.
Summary of the invention
The protective layer coating agent that flexible printed circuit board is used need satisfy the material of performances such as solvent resistance, flexibility (bendability), low warpage properties and electrical insulating property simultaneously.Therefore, the objective of the invention is to, provide these excellents, as the useful resin combination in the protective layer coating agent of flexible printed circuit board.
The inventor furthers investigate in order to solve above-mentioned problem; found that; the above-mentioned excellent that contains the resin combination of urethane resin with epoxy group(ing) and carboxylamine ester structure and epoxy hardener; be resin combination, thereby finish the present invention as the protective layer used excellence of flexible printed circuit board.That is, the present invention includes following content.
[1] protective layer of flexible printed circuit board (overcoat) is used resin combination, contains (A) and has the urethane resin of epoxy group(ing) and carboxylamine ester structure and (B) epoxy hardener.
[2] above-mentioned [1] described resin combination, wherein, urethane resin further has the structure more than a kind that is selected from polycarbonate structure, polydiene structure, polyester construction and the polyether structure.
[3] above-mentioned [1] described resin combination, wherein, urethane resin further has polycarbonate structure and/or polydiene structure.
[4] above-mentioned [1] described resin combination, wherein, urethane resin further has polycarbonate structure.
[5] any described resin combination in above-mentioned [1]～[4], wherein, urethane resin be polyol compound, (b) intramolecularly of making (a) intramolecularly have 2 above hydroxyls have the epoxy compounds of 1 above hydroxyl and 1 above epoxy group(ing) and (c) intramolecularly have the polyisocyanate compound reaction of 2 above isocyanate group and the urethane resin that obtains.
[6] above-mentioned [5] described resin combination, wherein, polyol compound is the polyol compound more than a kind that is selected from polycarbonate polyol, polydiene polyvalent alcohol, the pure and mild polyether glycol of polyester polyols.
[7] above-mentioned [5] described resin combination, wherein, polyol compound is polycarbonate polyol and/or polydiene polyvalent alcohol.
[8] above-mentioned [5] described resin combination, wherein, polyol compound is a polycarbonate polyol.
[9] any described resin combination in above-mentioned [1]～[8], wherein, (B) epoxy hardener is an anhydride compound.
[10] any described resin combination in above-mentioned [1]～[8], wherein, (B) epoxy hardener is the tetraprotic acid dianhydride.
[11] any described resin combination in above-mentioned [1]～[10] wherein, further contains (C) oxazoline compound.
[12] above-mentioned [11] described resin combination, wherein, (C) oxazoline compound Wei bisoxazoline compound.
[13] any described resin combination in above-mentioned [1]～[12], wherein, resin combination is a paste resin composition.
[14] any described resin combination in above-mentioned [1]～[13], it further contains curing catalyst.
[15] flexible printed circuit board, its surface is protected with the cured article of any described resin combination in above-mentioned [1]～[14].
[16] electronic equipments, it is built-in with above-mentioned [15] described flexible printed circuit board.
[17] resin combination contains urethane resin that (A) have epoxy group(ing) and carboxylamine ester structure, (B) epoxy hardener and (C) oxazoline compound.
[18] above-mentioned [17] described resin combination, wherein, urethane resin further has polycarbonate structure and/or polydiene structure.
[19] above-mentioned [17] described resin combination, wherein, urethane resin further has polycarbonate structure.
[20] any described resin combination in above-mentioned [17]～[19], wherein, urethane resin be polyol compound, (b) intramolecularly of making (a) intramolecularly have 2 above hydroxyls have the epoxy compounds of 1 above hydroxyl and 1 above epoxy group(ing) and (c) intramolecularly have the polyisocyanate compound reaction of 2 above isocyanate group and the urethane resin that obtains.
[21] above-mentioned [20] described resin combination, wherein, polyol compound is polycarbonate polyol and/or polydiene polyvalent alcohol.
[22] above-mentioned [20] described resin combination, wherein, polyol compound is a polycarbonate polyol.
[23] any described resin combination in above-mentioned [17]～[22], wherein, epoxy hardener is an anhydride compound.
[24] any described resin combination in above-mentioned [17]～[22], wherein, epoxy hardener is the tetraprotic acid dianhydride.
[25] any described resin combination in above-mentioned [17]～[24], wherein ， oxazoline compound Wei bisoxazoline compound.
[26] any described resin combination in above-mentioned [17]～[25], wherein, resin combination is a paste resin composition.
Resin combination of the present invention is solvent resistance, flexibility (bendability), low warpage properties and electrical insulating property excellence, as the resin combination of the protective layer used excellence of flexible printed circuit board.
Embodiment
" urethane resin with epoxy group(ing) and carboxylamine ester structure " of composition among the present invention (A) considers preferably further have polycarbonate structure, polydiene structure, polyester construction or polyether structure from the viewpoint of giving full play to effect of the present invention.In these structures, be preferably polycarbonate structure, polybutadiene configuration, be preferably polycarbonate structure especially.Can also in 1 molecule of urethane resin, contain said structure more than 2 kinds simultaneously with epoxy group(ing) and carboxylamine ester structure.
" urethane resin " with epoxy group(ing) and carboxylamine ester structure, can preference as polyol compound, (b) intramolecularly that makes (a) intramolecularly have 2 above hydroxyls have the epoxy compounds of 1 above hydroxyl and 1 above epoxy group(ing) and (c) polyisocyanate compound of intramolecularly with 2 above isocyanate group react and obtain.
Have the polyol compound of 2 above hydroxyls as the intramolecularly of raw material (a), can enumerate polycarbonate polyol, polydiene polyvalent alcohol, the pure and mild polyether glycol of polyester polyols etc.
As polyester polyol, can enumerate adipic acid ester class polyvalent alcohols such as polyethylene glycol adipate polyvalent alcohol, poly adipate succinic acid ester polyvalent alcohol, phthalandione class polyvalent alcohol, polycaprolactone polyol etc.Polyol compound also can make up 2 kinds with on use.
As polyether glycol, can enumerate polypropylene glycol, polytetramethylene ether dibasic alcohol, polyvinyl ethoxylated polyhydric alcohol etc.As the polyvinyl ethoxylated polyhydric alcohol, can enumerate TOE-2000H (consonance fermentation ケ ミ カ Le (strain) system) etc.
As the polydiene polyvalent alcohol, can enumerate polybutadiene polyol, polyisoprene polyvalent alcohol etc.The polydiene polyvalent alcohol can use hydrogenation polydiene polyvalent alcohols such as hydrogenated butadiene polymer polyvalent alcohol, hydrogenated polyisoprene polyvalent alcohol.As polybutadiene polyol, can enumerate and mainly have 1, the end of 4-key is the liquid polybutadiene Poly bd R-45HT of hydroxyl, R-15HT (above) by the emerging product of bright dipping (strain) system, end is the polyhutadiene hydride Port リ テ one Le H of hydroxyl, Port リ テ one Le HA (above) by Mitsubishi Chemical's (strain) system, mainly have 1, the terminal hydroxyl polyhutadiene G-1000 of 2-key, G-2000, G-3000 (above) by Japanese Cao Da (strain) system, above-mentioned mainly have 1, the hydride GI-1000 of the terminal hydroxyl polybutadiene of 2-key, GI-2000, GI-3000 (above) etc. by Japanese Cao Da (strain) system.As the polyisoprene polyvalent alcohol, can enumerate terminal the be liquid isoprene Poly ip of hydroxyl, エ Port one Le (above) etc. by the emerging product of bright dipping (strain) system.
As polycarbonate polyol, can enumerate the polycarbonate polyol that contains from the repeating unit of the dibasic alcohol more than a kind or 2 kinds in the polyvalent alcohols such as straight chain shape aliphatic dihydroxy alcohol, ester ring type dibasic alcohol, glycerine.As straight chain shape aliphatic dihydroxy alcohol, can enumerate 1,6-hexylene glycol, 1,5-pentanediol, 1,4-butyleneglycol, 3-methyl isophthalic acid, 5-pentanediol, 1,9-nonanediol, 2-methyl isophthalic acid, 8-ethohexadiol etc.As the ester ring type dibasic alcohol, can enumerate 1,4 cyclohexane dimethanol.
In these polyvalent alcohols, consider, be preferably polybutadiene polyol and polycarbonate polyol, be preferably polycarbonate polyol especially from the viewpoint of water tolerance, thermotolerance and flexibility.As polybutadiene polyol, be preferably the polyhutadiene dibasic alcohol especially, as polycarbonate polyol, be preferably PCDL especially.
The number-average molecular weight of polyvalent alcohol is preferably 400～5000.Number-average molecular weight was less than 400 o'clock, and there is the trend that reduces in the flexibility of the cured article of resin combination, and surpassed at 5000 o'clock, and there is the trend that reduces in the solvability of urethane resin in solvent.
The epoxy compounds that has 1 above hydroxyl and 1 above epoxy group(ing) as the intramolecularly of raw material (b), can enumerate intramolecularly has the hydroxyl more than 1 and is selected from the epoxy compounds of epoxy group(ing) more than a kind in glycidyl ether structure, glycidyl ester structure, glycidyl amine structure, ester ring type epoxy construction, the oxyethane ring structure.As commercially available product, intramolecularly has the epoxy compounds of 1 above hydroxyl and 1 above glycidyl ether structure can enumerate エ ピ コ one ト 1001, エ ピ コ one ト 1004 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system) etc., in addition, the epoxy compounds of intramolecularly with 1 above hydroxyl and 1 above oxyethane ring structure can be enumerated the epoxidised polyhutadiene PB-3600 of C-terminal (ダ イ セ Le chemical industry (strain)).
(b) epoxy compounds of intramolecularly with 1 above hydroxyl and 1 above epoxy group(ing) can have more than 1 compound with the active hydrogen base of epoxy reaction and react and obtain by making (d) intramolecularly have the epoxy compounds of 2 above epoxy group(ing) and (e) intramolecularly.
As the epoxy compounds that the intramolecularly of raw material (d) has 2 above epoxy group(ing), can enumerate bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A epoxy resin, A Hydrogenated Bisphenol A F type Resins, epoxy, novolac-type Resins, epoxy, cresols novolac-type Resins, epoxy, dicyclopentadiene-type epoxy resin, alkyl novolac-type Resins, epoxy, bisphenol-type epoxy resin, naphthalene type Resins, epoxy, the epoxide of condenses of phenol and aromatic aldehyde with phenol hydroxyl, the triglycidyl group isocyanuric acid ester, alicyclic epoxy resin, the glycidyl polyimide resin, the glycidyl esters resin, the diglycidyl ether of aliphatic dihydroxy alcohol, the Resins, epoxy such as diglycidyl ether of ester ring type dibasic alcohol.These epoxy compoundss can make up 2 kinds with on use.
Have more than 1 compound with the active hydrogen base of epoxy reaction as the intramolecularly of raw material (e), can enumerate the compound with 1 above phenol hydroxyl, compound etc. with 1 above carboxyl.Because when having 3 above active hydrogen bases, with the reaction of epoxy compounds in might gelation, compound (e) preferably has 1 or 2 active hydrogen bases.As compound, can enumerate phenolic compound, thiophenol compound, carboxylic acid cpd etc. with 1 active hydrogen base.As compound, can enumerate dihydroxyphenyl propane, Bisphenol F, bisphenol S, bis-phenol, quinhydrones, hexanodioic acid, sebacic acid, dodecanedioic acid, 8,12-eicosadienoic acid, octadecane dicarboxylic acid etc. with 2 active hydrogen bases.These compounds can make up 2 kinds with on use.
Raw material (d) with (e) can be under 80 ℃～180 ℃ of temperature of reaction, reacted 1 hour～8 hours usually.Organic solvent can be added as required during reaction, catalyzer can be added as required in addition.As catalyzer, can enumerate nitrogen compound, Phosphorus compound etc.
The polyisocyanate compound that has 2 above isocyanate group as the intramolecularly of raw material (c), can enumerate 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, diphenylmethanediisocyanate, dicyclohexyl methane diisocyanate, naphthalene diisocyanate, Xylene Diisocyanate, hydrogenated xylene diisocyanate, tetramethylene Xylene Diisocyanate, trimethyl hexamethylene diisocyanate, norbornylene vulcabond etc.These polyisocyanates can make up 2 kinds with on use.
As raw material (a) and (b) and (c) reaction conditions, for example can be in organic solvent, under 15 ℃～120 ℃ of the temperature of reaction, the reaction times is generally 1 hour～react under 8 hours the condition.In addition, can also add catalyzer as required reacts.
If the number of the hydroxyl of raw material (a) is the number of the hydroxyl of Xa, raw material (b) is that the number of the isocyanate group of Xb, raw material (c) is Y, then the value of preferred (the Xa+Xb)/Y of raw material (a) and (b) and (c) reactive ratio is 1～3, more preferably 1.01～2.This ratio was less than 1.0 o'clock, and the state excessive with isocyanate group reacts, and was difficult to control molecular weight, surpassed at 3 o'clock, had the trend that is difficult to improve molecular weight.
In addition, raw material (a) and raw material (b) preferably according to weight ratio with (a): (b)=90: 10～10: 90 scope uses, further preferably use with 90: 10～30: 70 scope.The weight ratio of raw material (a) was greater than 90: 10 o'clock, and there is the trend that reduces in the thermotolerance of filming after the curing, and the weight ratio of raw material (b) was greater than 10: 90 o'clock, and there is inadequate trend in flexibility.
As the organic solvent that uses in the reaction, for example can enumerate, N, dinethylformamide, N, the N-diethylformamide, N, the N-N,N-DIMETHYLACETAMIDE, N, the N-diethyl acetamide, the N-N-methyl-2-2-pyrrolidone N-, nitrogenous compound kind solvents such as tetramethyl-urea, dimethyl sulfoxide (DMSO), sulfocompound kind solvents such as diethyl sulfoxide, cyclic ester compounds solvents such as gamma-butyrolactone, ketones solvents such as pimelinketone, diglyme, ether solvents such as triglyme, the Trivalin SF acetic ester, propylene glycol monomethyl ether, esters solvent isopolarity solvents such as propylene glycol list ethyl ether acetic ester.These solvents can mix 2 kinds with on use.In addition, as required suitably non-polar solvent such as BTX aromatics use.
Reaction can also add catalyzer as required and carry out, as catalyzer, can enumerate tetramethyl butane diamine, benzyl dimethyl amine, trolamine, triethylamine, N, tertiary amines such as N-lupetidine, α-Jia Jibianji dimethyl amine, N-methylmorpholine, triethylenediamine, organo-metallic catalysts such as dibutyl tin laurate, dimethyltin chloride, cobalt naphthenate, zinc naphthenate etc.
The number-average molecular weight of the composition among the present invention (A) is preferably 500～100000, and more preferably 2000～50000.Number-average molecular weight is to measure the value of the polystyrene conversion that obtains with gel permeation chromatography (GPC) among the present invention.Obtain number-average molecular weight specifically by the GPC method, be that determinator uses clear and electrician's (strain) system GPC-101, chromatographic column are used clear and the system ShodexKF-800RH/LF-804 of electrician's (strain) society, moving phase are used tetrahydrofuran (THF), under 40 ℃ of column temperatures, measure, use the typical curve of polystyrene standard to calculate.The number-average molecular weight of composition (A) was less than 500 o'clock, and there is inadequate trend in the flexibility of filming after the curing, if surpass 100000, then the viscosity of composition (A) raises, and has unworkable trend.
The epoxy equivalent (weight) of the composition among the present invention (A) is preferably 500～25000, and more preferably 500～10000.The epoxy equivalent (weight) of composition (A) might damage the flexibility of cured coating film less than 500 o'clock, if surpass 25000, then there is inadequate trend in crosslinking reaction.Among the present invention, epoxy equivalent (weight) is to measure the value that obtains according to JIS K7236.
Composition among the present invention (B) epoxy hardener is so long as the crosslinked or then qualification especially of polymeric compounds with epoxy group(ing).Specifically, can enumerate anionic polymerization catalyst, Dyhard RU 100, guanamines derivative, melamine derivative, polyprotonic acid hydrazide compound, fatty amine compound, aromatic amine compound, poly-thiol compound, anhydride compound, line style phenolic aldehyde such as imidazolium compounds and add cationic polymerisation catalysts such as multifunctional phenolic compound, hexafluoro-antimonic acid triphenyl phosphonium such as resin etc. clearly.
In these epoxy hardeners, consider to be preferably anhydride compound from reactive viewpoint.As anhydride compound, can enumerate anhydride phthalic acid, the tetrahydrochysene anhydride phthalic acid, six hydrogen anhydride phthalic acids, methyl tetrahydrochysene anhydride phthalic acid, methyl six hydrogen anhydride phthalic acids, methyl-4-norbornylene-1, the 2-dicarboxylic anhydride, hydrogenation methyl-4-norbornylene-1, the 2-dicarboxylic anhydride, trialkyl tetrahydrochysene anhydride phthalic acid, dodecenylsuccinic anhydride, 5-(2,5-dioxo tetrahydrochysene-3-furyl)-3-methyl-3-tetrahydrobenzene-1, the 2-dicarboxylic anhydride, trimellitic acid 1,2-anhydride, the pyromellitic acid acid anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, the naphthalene tetracarboxylic acid dianhydride, oxygen di-phthalandione dianhydride, 3,3 '-4,4 '-sulfobenzide tetracarboxylic dianhydride, 1,3,3a, 4,5,9b-six hydrogen-5-(tetrahydrochysene-2,5-dioxo-3-furyl)-and naphtho-[1,2-C]-furans-1, the 3-diketone, ethylene glycol bisthioglycolate (trimellitic acid 1,2-anhydride ester), the acid anhydrides of vinylbenzene and the maleic acid copolymerized polymer-types such as styrene-maleic acid resin that obtain etc.In these acid anhydrides, consider from the easiness of three-dimensional cross-linked reaction and reactive viewpoint, be preferably anhydride group and in 1 molecule be 2 officials can more than acid anhydrides, be preferably the tetraprotic acid dianhydride especially.
As the composition among the present invention (B) epoxy hardener, use to have with the active hydrogen base of epoxy reaction and during usually not with the solidifying agent of hydroxyl reaction, preferably make the number (W of the epoxy group(ing) of composition (A)
EP) and be to use in 1: 0.2～1: 2 with the ratio of the number of the active hydrogen base of epoxy reaction.The ratio of active hydrogen radix order and epoxy group(ing) number is less than 0.2 or surpass at 2.0 o'clock, and there is inadequate trend in crosslinking reaction.Wherein, " usually not with hydroxyl reaction " refers under the temperature below the solidification value (for example 80～200 ℃) when resin combination is solidified and can not react with hydroxyl.As have with the active group of epoxy reaction, usually not with the epoxy hardener of hydroxyl reaction, can enumerate phenolic compounds such as Dyhard RU 100, guanamines derivative, polyprotonic acid hydrazide compound, fatty amine compound, aromatic amine compound and phenolic novolac etc.
" urethane resin " of the present invention with epoxy group(ing) and carboxylamine ester structure as mentioned above, preferably by polyol compound, (b) intramolecularly that makes (a) intramolecularly have 2 above hydroxyls have the epoxy compounds of 1 above hydroxyl and 1 above epoxy group(ing) and (c) polyisocyanate compound of intramolecularly with 2 above isocyanate group react and obtain.
In addition, as mentioned above, the number of establishing the hydroxyl of raw material (a) is that the number of the hydroxyl of Xa, raw material (b) is that the number of the isocyanate group of Xb, raw material (c) is Y, and then the value of (Xa+Xb)/Y is preferably 1～3, and think that this urethane resin has hydroxyl this moment.
If the molecular weight of raw material (a) composition is Ma, hydroxyl equivalent is that the molecular weight of Za, raw material (b) composition is that Mb, hydroxyl equivalent are that the molecular weight of Zb, raw material (c) is that Mc, isocyanate group equivalent are Zc, and then functional group's number of per 1 molecule can be calculated by following formula in each composition.Wherein, functional group's number of per 1 molecule hydroxyl is that functional group's number of per 1 molecule hydroxyl in Na, the raw material (b) is that functional group's number of per 1 molecule isocyanate base in Nb, the raw material (c) is Nc in the raw material (a).
Na＝Ma/Za
Nb＝Mb/Zb
Nc＝Mc/Zc
Further, can calculate the theoretical value of the hydroxyl equivalent that makes the resin that raw material (a), raw material (b) and raw material (c) obtain with the molar ratio reaction of a: b: c by following formula.
(Ma×a+Mb×b+Mc×c)/(Na×a+Nb×b-Nc×c)
" urethane resin with epoxy group(ing) and carboxylamine ester structure " of the present invention is when having the mode of hydroxyl in theory according to the reactive ratio of raw material as mentioned above, consider that from the viewpoint that promotes crosslinking reaction epoxy hardener is the anhydride compound of use and epoxy group(ing) and hydroxyl reaction especially preferably.
The use level of anhydride compound can be adjusted preferred amount by the hydroxyl of being derived by the aforementioned calculation formula, preferably makes the number (W of the number of anhydride group with respect to hydroxyl
OH) with the number (W of epoxy group(ing)
EP) the ratio of total be 0.1～2.0 to use.If less than 0.1 or surpass 2.0, then there is the trend of the effect that can not obtain sufficient crosslinking reaction with respect to the ratio of hydroxyl and the total of the number of epoxy group(ing) in the number of anhydride group.Wherein, anhydride group and hydroxyl be with the reaction of 1: 1 equivalence ratio, similarly anhydride group and epoxy group(ing) and react with 1: 1 equivalence ratio.
So in the present invention, " urethane resin with epoxy group(ing) and carboxylamine ester structure " has in the embodiment of hydroxyl, and epoxy hardener uses the system of anhydride compound (particularly quaternary acid anhydrides) to consider preferred from promoting viewpoints such as crosslinking reaction, raising solvent resistance.At this moment, the hydroxyl equivalent of this urethane resin is preferably 250～50000, and more preferably 1000～25000.There was the trend of damaging the flexibility of filming in hydroxyl equivalent less than 250 o'clock, if surpass 50000, then owing to the reactivity with anhydride compound reduces, had the inadequate trend of effect in the crosslinking reaction.
Resin combination of the present invention can also further contain composition (C) De oxazoline compound in order further to improve insulating reliability.Zuo Wei oxazoline compound, can enumerate the 2-ethyl-2-oxazoline, 2-propyl group-2-oxazoline, 2-butyl-2-oxazoline, 2-octyl group-2-oxazoline, 2-cyclohexyl-2-oxazoline, 2-allyl group-2-oxazoline, 2-phenyl-2-oxazoline, lauryl An base ethyl oxazoline, dilauryl An base ethyl oxazoline, lauryl oxygen base ethyl oxazoline, 2,2 '-two (2-oxazolines), 2,2 '-ethylene (2-oxazoline), 2,2 '-tetramethylene two (2-oxazoline), 2,2 '-(1, the 3-phenylene) two (2-oxazolines), 2,2 '-(1, the 4-phenylene) two (2-oxazoline) etc.Further, can also enumerate and contain Zhe Xie oxazoline compound, compound of Han You oxazoline skeleton etc. in vinylbenzene/2-pseudoallyl-polymkeric substance such as 2-oxazoline multipolymer as monomeric unit De Ju oxazoline compound.In the Zhe Xie oxazoline compound, have 2 Yi Shang oxazoline skeleton De oxazoline compounds, consider to be preferably the bisoxazoline compound from reactive view further from carrying out the viewpoint consideration of crosslinking reaction, being preferably.Wherein be preferably 2,2 '-(1, the 3-phenylene) two (2-oxazoline) especially and (be designated hereinafter simply as 1,3-PBO).The preferred Shi oxazolinyl of the use level of oxazoline compound is 0.05～3.0 with the ratio of anhydride group, more preferably 0.1～2.0.During less than 0.05 molar equivalent, the effect of Tian Jia oxazoline compound is little, if surpass 3.0, then insulating reliability might reduce on the contrary.
Can also and use the curing catalyst of the curing reaction that promotes epoxy hardener in the resin combination of the present invention as required.As curing catalyst, can enumerate triphenylphosphine, Peng Suan phosphonium compounds, tetraphenyl boric acid tetraphenylphosphoniphenolate, tetraphenyl boric acid Zheng Ding Ji Phosphonium, 1, metal-salts such as the 2-ethylhexoate of 8-diazabicyclo-[5.4.0]-7-undecylene (DBU), DBU, zinc octoate, stannous octoate, carbamide compounds such as phenyl dimethyl urea, the two dimethyl ureas of toluene, methylenediphenyl dimethyl urea etc.
In the resin combination of the present invention, in the scope of performance effect of the present invention, can cooperate various resin additives.As resin additive, can enumerate silicon-dioxide, aluminum oxide, barium sulfate, talcum, clay, mica powder, aluminium hydroxide, magnesium hydroxide, lime carbonate, magnesiumcarbonate, magnesium oxide, boron nitride, aluminum borate, barium titanate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanates, titanium oxide, barium zirconate, inorganic filling materials such as calcium zirconate, the acrylic rubber particle, polyamide particles, organic filler materials such as siloxanes particle, silane coupling agent, the phthalate coupling agent, coupling agents such as aluminium class coupling agent, the type siloxane defoamer, the fluorine defoamer, defoamers such as acrylate copolymer defoamer, titanium oxide, mineral dyes such as zinc oxide, phthalocyanine blue, phthalocyanine green, iodine is green, two diazonium Huangs, pigment dyestuffs such as carbon black, tinting materials such as organic dye, hindered phenol compound, Phosphorus compound, the sulphur compounds, antioxidants such as hydrazide kind compound, benzotriazole compound, UV light absorber such as hindered amine compound, Phosphorus compound, aluminium hydroxide, fire retardants such as magnesium hydroxide, even paint, the thixotropy imparting agent, 2,4,6-tri-thiol-s-triazole, 2,5-dimercapto-1,3, adaptation rising agents such as 4-thiadiazoles etc.
Resin combination of the present invention can by use planetary-type mixer, triple-roller mill, ball mill etc. will contain (A) contain the urethane resin of epoxy group(ing) and (B) epoxy hardener the gradation composition dissolving or disperse to prepare.During preparation, can also use the organic solvent that is used to adjust viscosity as required.The organic solvent that is used for adjusting viscosity can use and the identical solvent of the employed organic solvent of above-mentioned reaction.When being used as the protective layer of flexible printed circuit board, be prepared into paste resin composition usually.
Paste resin composition of the present invention is coated on the established part of flexible printed circuit board,, can obtains the flexible printed circuit board that all surfaces or part surface are protected by resin combination of the present invention thus the coated face drying.Those skilled in the art can suitably easily set drying conditions according to the kind of the paste resin composition that uses, but following dry about 1～120 minute at 100～200 ℃ usually.Thickness to formed surface protection film does not limit especially yet, is generally 5～100 μ m.The flexible printed circuit board of protecting the surface with resin combination of the present invention is not limited especially; can use TAB (Tape Automated Bonding) flexible printed circuit board, COF to print various flexible printed circuit boards such as flexible printed circuit board, but resin combination of the present invention can be preferably used as TAB uses flexible printed circuit board with flexible printed circuit board, COF protective layer especially with flexible printed circuit board, multi-layer flexible printed circuit board, conductive paste.
Use in the mode that is built in the various electronic equipments with the flexible printed circuit board that resin combination of the present invention has carried out protection on the surface.For example, be preferably used as the internal wiring of various electronic equipments such as portable phone, digital camera, Kamera, game machine, Personal Computer, printing press, hard disk drive, plasm TV, LCD TV, liquid-crystal display, auto-navigation system, duplicating machine, facsimile recorder, AV apparatus, instrumentation apparatus, medicine equipment.
Below enumerate embodiment the present invention is carried out specific description, but the present invention is not limited by it.Among the embodiment, part refers to mass parts.And, try to achieve the hydroxyl equivalent of the urethane resin that contains epoxy group(ing) of the Resins, epoxy of hydroxyl of synthesis example 1 and synthesis example 2～6 by calculating.Make in the synthesis example 1 produce and with the equimolar hydroxyl of phenol hydroxyl of the dihydroxyphenyl propane of Resins, epoxy (HP-7200) reaction, and make エ ピ コ one ト 1001 that uses in the synthesis example 2～6 that 2 epoxy group(ing) be arranged in 1 molecule, measured value from this prerequisite and epoxy equivalent (weight), think that molecular weight is 2 times of epoxy equivalent (weight), through type:
Number=(molecular weight-57)/(228+58) of the hydroxyl in 1 molecule)-1 try to achieve the number of 1 hydroxyl in the molecule.Wherein, " 57 " are the molecular weight of glycidyl ether, and " 228 " are the molecular weight of dihydroxyphenyl propane, the molecular weight of the compound of the secondary hydroxyl structure that " 58 " produce when reacting for the phenolic group with glycidyl ether structure and dihydroxyphenyl propane.＜synthesis example 1〉Resins, epoxy (E-1) synthetic of hydroxyl
In 500ml flask, add dicyclopentadiene-type epoxy resin HP-7200 (big Japanese イ Application キ chemical industry (strain) system, epoxy equivalent (weight) 260) 291.4g, dihydroxyphenyl propane (Mitsui Chemicals (strain) system) 55.6g with whipping appts, thermometer, condenser, as the ethyl glycol ether acetic ester 150.0g of solvent, under nitrogen gas stream, be heated to 70 ℃, obtain uniform solution.After wherein adding triphenylphosphine 2.9g, be warming up to 120 ℃, under this state, carry out reaction in 5 hours, obtain the Resins, epoxy E-1 of hydroxyl.
The proterties of the Resins, epoxy E-1 of hydroxyl:
Viscosity: 74Pas (25 ℃, E type viscometer)
Solids component: 70%
Number-average molecular weight: 1700 (GPC, polystyrene conversion)
Epoxy equivalent (weight): 538
Hydroxyl equivalent: 711
＜synthesis example 2〉contain urethane resin (EU-1) synthetic of epoxy group(ing)
To having whipping appts, thermometer, add PCDL T-6001 (the ケ ミ カ Le ズ of Asahi Chemical Industry (strain) in the 500ml flask of condenser, hydroxyl value 115mgKOH/g) 185.5g, 188.8g＜synthesis example 1 shown in the Resins, epoxy E-1 of hydroxyl, gamma-butyrolactone 90.0g, under nitrogen gas stream, add 2 when stirring under the room temperature, 4-tolylene diisocyanate 32.3g, the 1% solution 3.5g of dibutyl tin laurate イ プ ゾ one Le #150 (the emerging product of bright dipping (strain) system), temperature of charge (product temperature) (temperature of mixture) is warming up to 80 ℃, reacted 3 hours.Confirm to disappear by infrared spectroscopic analysis, finish reaction, obtain containing the urethane resin EU-1 of epoxy group(ing) based on the absorption of isocyanate group.
The proterties that contains the urethane resin EU-1 of epoxy group(ing):
Viscosity: 107Pas (25 ℃, E type viscometer)
Solids component: 70%
Number-average molecular weight: 4100 (GPC, polystyrene conversion)
Epoxy equivalent (weight): 1411
Hydroxyl equivalent: 1476
＜synthesis example 3〉contain urethane resin (EU-2) synthetic of epoxy group(ing)
To having whipping appts, thermometer, add PCDL T-6001 (the ケ ミ カ Le ズ of Asahi Chemical Industry (strain) in the 500ml flask of condenser, hydroxyl value 115mgKOH/g) 134.5g, エ ピ コ one ト 1001 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system as the Resins, epoxy of hydroxyl, epoxy equivalent (weight) 475) 41.9g, gamma-butyrolactone 88.0g, the 1% solution 2.1g of dibutyl tin laurate イ プ ゾ one Le #150 (the emerging product of bright dipping (strain) system), under nitrogen gas stream, add 4 bit by bit when stirring under the room temperature, 4 '-diphenylmethanediisocyanate 33.7g is so that temperature of charge is no more than 80 ℃.Add 4, after whole amounts of 4 '-diphenylmethanediisocyanate, temperature of charge is warming up to 80 ℃, reacted 1 hour.Confirm to disappear by infrared spectroscopic analysis, finish reaction, obtain containing the urethane resin EU-2 of epoxy group(ing) based on the absorption of isocyanate group.
The proterties that contains the urethane resin EU-2 of epoxy group(ing):
Viscosity: 239Pas (25 ℃, E type viscometer)
Solids component: 70%
Number-average molecular weight: 5326 (GPC, polystyrene conversion)
Epoxy equivalent (weight): 2199
Hydroxyl equivalent: 2085
＜synthesis example 4〉contain urethane resin (EU-3) synthetic of epoxy group(ing)
To having whipping appts, thermometer, add PCDL UM-CARB90 (1/3) (the emerging product of space portion (strain) system in the 500ml flask of condenser, with 1,4-cyclohexanedimethanol/1, the Copolycarbonate dibasic alcohol of glycol component is contained in 6-hexylene glycol=1/3, hydroxyl value 126mgKOH/g) 114.2g, エ ピ コ one ト 1001 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system as the Resins, epoxy of hydroxyl, epoxy equivalent (weight) 475) 58.0g, gamma-butyrolactone 198.0g, under nitrogen gas stream, add 2 when stirring under the room temperature, 4-tolylene diisocyanate 27.8g, the 1% solution 2.0g of dibutyl tin laurate イ プ ゾ one Le #150 (the emerging product of bright dipping (strain) system), temperature of charge is warming up to 80 ℃, reacted 3 hours.Confirm to disappear by infrared spectroscopic analysis, finish reaction, obtain containing the urethane resin EU-3 of epoxy group(ing) based on the absorption of isocyanate group.
The proterties that contains the urethane resin EU-3 of epoxy group(ing):
Viscosity: 65Pas (25 ℃, E type viscometer)
Solids component: 50%
Number-average molecular weight: 8034 (GPC, polystyrene conversion)
Epoxy equivalent (weight): 1443
Hydroxyl equivalent: 2928
＜synthesis example 5〉contain urethane resin (EU-4) synthetic of epoxy group(ing)
To having whipping appts, thermometer, add PCDL UM-CARB90 (1/1) (the emerging product of space portion (strain) system in the 500ml flask of condenser, with 1,4-cyclohexanedimethanol/1, the Copolycarbonate dibasic alcohol of glycol component is contained in 6-hexylene glycol=1/1, hydroxyl value 124mgKOH/g) 170.1g, and polyhutadiene dibasic alcohol G-1000 (Japanese Cao Da (strain) system, hydroxyl value 72mgKOH/g) 15.3g, エ ピ コ one ト 1001 (ジ ヤ パ Application エ Port キ シ レ ジ Application (strain) system as the Resins, epoxy of hydroxyl, epoxy equivalent (weight) 475) 58.0g, ethyl glycol ether acetic ester 117.2g, under nitrogen gas stream, add 2 when stirring under BR＞A room temperature, 4-tolylene diisocyanate 34.5g, the 1% solution 2.8g of dibutyl tin laurate イ プ ゾ one Le #150 (the emerging product of bright dipping (strain) system), temperature of charge is warming up to 80 ℃, reacted 3 hours.Confirm to disappear by infrared spectroscopic analysis, finish reaction, obtain containing the urethane resin EU-4 of epoxy group(ing) based on the absorption of isocyanate group.
The proterties that contains the urethane resin EU-4 of epoxy group(ing):
Viscosity: 267Pas (25 ℃, E type viscometer)
Solids component: 70%
Number-average molecular weight: 7723 (GPC, polystyrene conversion)
Epoxy equivalent (weight): 2028
Hydroxyl equivalent: 2139
＜synthesis example 6〉do not contain urethane resin (U-1) synthetic of epoxy group(ing)
In 500ml flask, add PCDL T-6001 (the ケ ミ カ Le ズ of Asahi Chemical Industry (strain), hydroxyl value 115mgKOH/g) 329.1g, gamma-butyrolactone 121.7g with whipping appts, thermometer, condenser, add 2 when under nitrogen gas stream, under the room temperature, stirring, the 1% solution 3.3g of 4-tolylene diisocyanate 45.9g, dibutyl tin laurate イ プ ゾ one Le #150 (the emerging product of bright dipping (strain) system), temperature of charge is warming up to 80 ℃, reacted 3 hours.By infrared spectroscopic analysis, confirm to disappear based on the absorption of isocyanate group, finish reaction, obtain containing the urethane resin U-1 of epoxy group(ing).
The proterties that does not contain the urethane resin U-1 of epoxy group(ing):
Viscosity: 185Pas (25 ℃, E type viscometer)
Solids component: 75%
Number-average molecular weight: 8600 (GPC, polystyrene conversion)
Hydroxyl equivalent: 2541
Embodiment 1
To be scaled the polyurethane resin solution that contains epoxy group(ing) (EU-1) that obtains in the synthesis example 2 of 40.0g according to solids component, as B-4400 (big Japanese イ Application キ chemical industry (strain) system, anhydride equivalent 132) 2.91g, triphenylphosphine (pure chemistry (strain) system) 0.21g of tetraprotic acid dianhydride, as hydrophilic fumed silica A-380 (Japanese ア エ ロ ジ Le (strain) system) the 0.8g mixing of inorganic filler, with triple-roller mill carry out mixing after, add gamma-butyrolactone viscosity is adjusted to about 20～40Pas, the preparation hot curing resin composition.
Embodiment 2
New adding 1, (three states pharmaceutical industry (strain) Zhi, oxazolinyl equivalent 108) 3.44g is as the bisoxazoline compound for 3-PBO, making B-4400 is that 3.64g, triphenylphosphine are 0.24g, in addition carries out the preparation hot curing resin composition similarly to Example 1.
Embodiment 3
Make the polyurethane resin solution that contains epoxy group(ing) (EU-2) that obtains in the synthesis example 3 be scaled 40.0g, 1 according to solids component, 3-PBO is that 2.22g, B-4400 are that 2.26g, triphenylphosphine are 0.22g, in addition carry out the preparation hot curing resin composition similarly to Example 2.
Embodiment 4
Make the polyurethane resin solution that contains epoxy group(ing) (EU-3) that obtains in the synthesis example 4 be scaled 40.0g, 1 according to solids component, 3-PBO is that 2.07g, B-4400 are that 2.70g, triphenylphosphine are 0.23g, in addition carry out the preparation hot curing resin composition similarly to Example 2.
Embodiment 5
Make the polyurethane resin solution that contains epoxy group(ing) (EU-4) that obtains in the synthesis example 5 be scaled 40.0g, 1 according to solids component, 3-PBO is that 3.24g, B-4400 are that 2.64g, triphenylphosphine are 0.23g, in addition carry out the preparation hot curing resin composition similarly to Example 2.
＜reference example 1 〉
Make the polyurethane resin solution that does not contain epoxy group(ing) (U-1) that obtains in the synthesis example 6 be scaled 45.8g, be that 2.13g, triphenylphosphine are that 0.22g, A-380 are 1.00g for 4.18g, B-4400 as the HP-7200 (big Japanese イ Application キ chemical industry (strain) system, epoxy equivalent (weight) 260) of new Resins, epoxy according to solids component, in addition carry out the preparation hot curing resin composition similarly to Example 1.
＜reference example 2 〉
Making the polyurethane resin solution that does not contain epoxy group(ing) (U-1) that obtains in the synthesis example 6 be scaled 35.0g, HP-7200 according to solids component is that 15.0g, B-4400 are that 7.62g, triphenylphosphine are 0.29g, in addition similarly carry out the preparation hot curing resin composition with reference example 1.
＜reference example 3 〉
New 1 of the 1.99g that adds, 3-PBO as the bisoxazoline compound, to make B-4400 be that 9.24g, triphenylphosphine are 0.31g, in addition similarly carries out the preparation hot curing resin composition with reference example 2.
" as the evaluation of protective layer material on the electronic circuit surface of protection flexible printed board "
The evaluation of＜solvent resistance 〉
Use 200 order versions with the hot curing resin composition silk screen printing for preparing in embodiment and the reference example at the thick polyimide film of 50 μ m (ユ one ピ レ Star Network ス 50S: the emerging product of space portion (strain) system), solidified 1 hour down and then solidified 2 hours down at 150 ℃ at 120 ℃.Use infiltration has acetone cotton rod, solidify face with the power wiping of 400～500g, N/R situation is designated as zero, sees on the printing surface that the situation that scratch, color come off is designated as △, the situation that printing surface dissolves, exposes base material is designated as *.The result is as shown in table 1.
＜bendability evaluation 〉
Use 200 order versions with the hot curing resin composition silk screen printing for preparing in embodiment and the reference example at the thick polyimide film of 50 μ m (ユ one ピ レ Star Network ス 50S: the emerging product of space portion (strain) system), solidified 1 hour down and then solidified 2 hours down at 150 ℃ at 120 ℃.The printing surface that makes polyimide film is the outside, crooked 180 degree.The situation that cured film is not produced albefaction is designated as zero, and the situation that cured film is observed albefaction or be full of cracks is designated as *.The result is as shown in table 1.
The evaluation of＜warpage 〉
The version of using 200 orders, 10cm * 10cm size with the hot curing resin composition silk screen printing for preparing in embodiment and the reference example at the thick polyimide film of 50 μ m (ユ one ピ レ Star Network ス 50S: the emerging product of space portion (strain) system), after solidifying 1 hour under 120 ℃, cut out 4 with 5cm * 5cm size.They are further appended curing 2 hours under 150 ℃, as test film.Owing to solidify, test film produces warpage in the mode of printing surface depression.4 test films are placed on the level and smooth sheet glass to print supine mode, 1 vertex position of warpage maximum in each test film is measured from the size of sheet glass projection, calculate 4 mean value.The result is as shown in table 1.
The evaluation of＜electrical insulation reliability 〉
With the hot curing resin composition for preparing in embodiment and the reference example, use 200 order version silk screen printings on the polyimide base material of the comb-type electrode pattern that is formed with 30 μ m spacings, silk screen printing was solidified 1 hour down and then was solidified 2 hours down at 150 ℃ at 120 ℃ in being formed with on the polyimide film of thickness 37.5 μ m on the polyimide substrate of comb-type electrode pattern that L/S=15/15 μ m, circuit thickness are 8 μ m to cover all surfaces of comb-type electrode pattern.When it is applied the voltage of 60V, in 120 ℃, the atmosphere of relative humidity 85%, place.Be measured to observe ion migration or insulating resistance value reduction (until 10
6Ω is following) till hold-time, with it as HAST (Highly Accelerated temperature and humidity Stress Test) the durable time.The result is as shown in table 1.
As shown in Table 1; in the embodiments of the present invention; contain (A) and have the urethane resin of epoxy group(ing) and carboxylamine ester structure and (B) the protective layer used resin combination of the flexible printed circuit board of epoxy hardener, compare with comparative example 1～3, the warpage of printed circuit board significantly reduces.Contain further that (embodiment 2～5 of C) oxazoline compound further reduces warpage, and simultaneously electrical insulation reliability is also excellent.Therefore, the solvent resistance of hot curing resin composition of the present invention, bendability excellence, and can have warpage properties and electrical insulation reliability concurrently.
The application all comprises its content in this manual based on the Japanese Patent Application 2007-271600 in Japanese publication.
Claims (16)
1. the protective layer used resin combination of a flexible printed circuit board, said composition contain (A) and have the urethane resin of epoxy group(ing) and carboxylamine ester structure and (B) epoxy hardener.
2. resin combination as claimed in claim 1, wherein, urethane resin further has the structure more than a kind that is selected from polycarbonate structure, polydiene structure, polyester construction and the polyether structure.
3. resin combination as claimed in claim 1, wherein, urethane resin further has polycarbonate structure and/or polydiene structure.
4. resin combination as claimed in claim 1, wherein, urethane resin further has polycarbonate structure.
5. as any described resin combination in the claim 1～4, wherein, urethane resin be polyol compound, (b) intramolecularly of making (a) intramolecularly have 2 above hydroxyls have the epoxy compounds of 1 above hydroxyl and 1 above epoxy group(ing) and (c) intramolecularly have the polyisocyanate compound reaction of 2 above isocyanate group and the urethane resin that obtains.
6. resin combination as claimed in claim 5, wherein, polyol compound is the polyol compound more than a kind that is selected from polycarbonate polyol, polydiene polyvalent alcohol, the pure and mild polyether glycol of polyester polyols.
7. resin combination as claimed in claim 5, wherein, polyol compound is polycarbonate polyol and/or polydiene polyvalent alcohol.
8. resin combination as claimed in claim 5, wherein, polyol compound is a polycarbonate polyol.
9. as any described resin combination in the claim 1～8, wherein, (B) epoxy hardener is an anhydride compound.
10. as any described resin combination in the claim 1～8, wherein, (B) epoxy hardener is the tetraprotic acid dianhydride.
11. as any described resin combination in the claim 1～10, it further contains (C) oxazoline compound.
12. resin combination as claimed in claim 11, wherein, (C) oxazoline compound Wei bisoxazoline compound.
13. as any described resin combination in the claim 1～12, wherein, resin combination is a paste resin composition.
14. as any described resin combination in the claim 1～13, it further contains curing catalyst.
15. flexible printed circuit board, its surface is protected with the cured article of any described resin combination in the claim 1～14.
16. electronic equipments, it is built-in with the described flexible printed circuit board of claim 15.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007271600 | 2007-10-18 | ||
| JP2007-271600 | 2007-10-18 | ||
| PCT/JP2008/068820 WO2009051209A1 (en) | 2007-10-18 | 2008-10-17 | Resin composition |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101827876A true CN101827876A (en) | 2010-09-08 |
| CN101827876B CN101827876B (en) | 2012-12-05 |
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| Application Number | Title | Priority Date | Filing Date |
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| CN200880112087.4A Active CN101827876B (en) | 2007-10-18 | 2008-10-17 | Resin composition |
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| Country | Link |
|---|---|
| JP (1) | JP5392088B2 (en) |
| KR (1) | KR101473208B1 (en) |
| CN (1) | CN101827876B (en) |
| TW (1) | TWI453253B (en) |
| WO (1) | WO2009051209A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105683316A (en) * | 2013-05-31 | 2016-06-15 | 塞特工业公司 | Formulated polyurethane resin compositions for flood coating electronic circuit assemblies |
| CN111741993A (en) * | 2018-02-20 | 2020-10-02 | Dic株式会社 | Curable composition and fiber-reinforced composite material |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011004756A1 (en) * | 2009-07-06 | 2011-01-13 | 昭和電工株式会社 | Thermosetting composition for protective film for wiring board |
| JP5547456B2 (en) * | 2009-11-10 | 2014-07-16 | スリーエム イノベイティブ プロパティズ カンパニー | One-pack type epoxy resin composition and bonding method using the same |
| JP5929466B2 (en) * | 2012-04-23 | 2016-06-08 | 味の素株式会社 | Resin composition |
| JP6911286B2 (en) * | 2016-06-20 | 2021-07-28 | Dic株式会社 | Polycarbonate modified epoxy resin and adhesive |
| CN114127152A (en) * | 2019-08-06 | 2022-03-01 | Dic株式会社 | Curable composition, cured product, fiber-reinforced composite material, and molded article |
| JP7466629B2 (en) * | 2019-08-30 | 2024-04-12 | トランジションズ オプティカル リミテッド | Photochromic Compositions Comprising Polyols and Poly(anhydrides) |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3079605B2 (en) * | 1991-02-28 | 2000-08-21 | ジェイエスアール株式会社 | Composition for forming conductive elastomer |
| JPH06100806A (en) * | 1992-09-21 | 1994-04-12 | Kansai Paint Co Ltd | Electrodeposition coating composition |
| CN1087758C (en) * | 1997-05-11 | 2002-07-17 | 化学工业部海洋涂料研究所 | Cavitation erosion preventing paint |
| JPH1161037A (en) * | 1997-08-14 | 1999-03-05 | Ajinomoto Co Inc | Resin composition for flexible circuit overcoat |
| JPH1171551A (en) * | 1997-08-29 | 1999-03-16 | Ajinomoto Co Inc | Resin composition for flexible circuit overcoating |
| JP3962940B2 (en) * | 1998-10-15 | 2007-08-22 | 味の素株式会社 | Resin composition for flexible circuit overcoat |
| US20020061970A1 (en) * | 2000-09-14 | 2002-05-23 | Hidenori Sawada | Resin composition for coating material |
| JP2006137943A (en) * | 2004-10-15 | 2006-06-01 | Ajinomoto Co Inc | Resin composition |
| JP5135698B2 (en) * | 2005-03-28 | 2013-02-06 | 宇部興産株式会社 | Modified polyimide resin containing polycarbonate, composition thereof and cured insulating film |
| WO2007023655A1 (en) * | 2005-08-24 | 2007-03-01 | Daicel Chemical Industries, Ltd. | Polyester polyol and polyurethane resin |
| JP4864399B2 (en) * | 2005-09-21 | 2012-02-01 | 昭和電工株式会社 | Resin composition for overcoat |
-
2008
- 2008-10-14 TW TW097139357A patent/TWI453253B/en active
- 2008-10-17 JP JP2009538155A patent/JP5392088B2/en active Active
- 2008-10-17 KR KR1020107010323A patent/KR101473208B1/en active IP Right Grant
- 2008-10-17 WO PCT/JP2008/068820 patent/WO2009051209A1/en active Application Filing
- 2008-10-17 CN CN200880112087.4A patent/CN101827876B/en active Active
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105683316A (en) * | 2013-05-31 | 2016-06-15 | 塞特工业公司 | Formulated polyurethane resin compositions for flood coating electronic circuit assemblies |
| CN111741993A (en) * | 2018-02-20 | 2020-10-02 | Dic株式会社 | Curable composition and fiber-reinforced composite material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101827876B (en) | 2012-12-05 |
| JPWO2009051209A1 (en) | 2011-03-03 |
| TWI453253B (en) | 2014-09-21 |
| WO2009051209A1 (en) | 2009-04-23 |
| TW200932830A (en) | 2009-08-01 |
| KR101473208B1 (en) | 2014-12-16 |
| JP5392088B2 (en) | 2014-01-22 |
| KR20100076016A (en) | 2010-07-05 |
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