CN101682999A - Insulating resin composition - Google Patents
Insulating resin composition Download PDFInfo
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- CN101682999A CN101682999A CN200880018017A CN200880018017A CN101682999A CN 101682999 A CN101682999 A CN 101682999A CN 200880018017 A CN200880018017 A CN 200880018017A CN 200880018017 A CN200880018017 A CN 200880018017A CN 101682999 A CN101682999 A CN 101682999A
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- resin composition
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- polyurethane
- insulating resin
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Classifications
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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
- C08G18/08—Processes
- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
- C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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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
- C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
- C08G18/6541—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/34
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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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
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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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/02—Fillers; Particles; Fibers; Reinforcement materials
- H05K2201/0203—Fillers and particles
- H05K2201/0206—Materials
- H05K2201/0212—Resin particles
Abstract
Disclosed is an insulating resin composition to be arranged on a base of a flexible printed wiring board, which contains a urethane (X), an epoxy resin (B) and a filler (C). This insulating resin composition is characterized in that the urethane (X) is a polyurethane-polyurea resin (A), a hydroxy group-containing urethane prepolymer (f), or a mixture of the polyurethane-polyurea resin (A) and thehydroxy group-containing urethane prepolymer (f). The polyurethane-polyurea resin (A) is obtained by reacting a polyamino compound (e) with an isocyanate group-containing urethane prepolymer (d) whichis prepared by reacting a polyol compound (a),anorganic diisocyanate (b) and a carboxyl group-containing diol compound (c). The hydroxy group-containing urethane prepolymer (f) is obtained by reacting an polyol compound (a), an organic diisocyanate (b) and a carboxyl group-containing diol compound (c). The insulating resin composition is further characterized in that the filler (C) is an organicresin filler and the base is a thermoplastic resin base. This insulating resin composition exhibits good adhesion to the base as well as low warping property, flexural property, blocking resistance and flame retardancy.
Description
Technical field
The present invention relates to insulating resin composition as the insulating barrier use of printed wiring board.And then specifically, relate to thermoplastic resin as insulating resin composition that uses in the flexible printed wiring board of base material etc. and the flexible printed wiring board that uses this resin combination to constitute.
Background technology
In recent years, printed circuit board is according to desired final finished, environment, cost, and uses various forms of printed circuit boards, and its characteristic is the demanding level along with multifunction also.Wherein, the purposes of utilizing flexible substrate is having the tendency of increase in recent years, in be contained in printed circuit board in the various diversified goods according to its purposes, performance etc., to divide into the polyimides be the substrate of base material, be substrate of base material etc. with the polyester.
Generally speaking, the formation of flexible circuit board can be enumerated the formation that the order lamination with substrate layer, conductor layer, insulating barrier forms, because the densification of wiring in recent years, also have on above-mentioned insulating barrier and then the so multilayer structured formation of conductor layer is set.Under this situation, the insulating barrier of coated conductor layer can will insulate between conductor, or protection conductor self avoids from all-environment infringement etc., thereby undertakes important function as one of inscape of printed circuit board.In addition, the angle on the safety of above-mentioned insulating barrier when end article burns is considered, in most cases requires to have the function of anti-flammability.As other characteristics, flexible, insulation reliability, the thermal endurance etc. of also having relatively high expectations.
For example, in the used in flexible substrate insulating material of polyethylene terephthalate, use the insulating material (patent documentation 1) that contains halogen as base material.The insulating material that contains halogen is the good especially material of anti-flammability, and is also excellent as the characteristic of insulating material, thereby is preferred for requiring the insulating material purposes of anti-flammability.But, in recent years, consider that from the angle of environmental issue flame-retardant materials just develops towards the direction of not using halogen, yet present incapability still can satisfy anti-flammability under the situation of not using halogen, and can take into account the insulating material of other rerum naturas.
[patent documentation 1] Japanese kokai publication sho 60-158273 communique
Summary of the invention
The object of the present invention is to provide under the situation of not using the halogen based material, can show high flame retardant, and flexible, use insulating resin composition and used the flexible printed wiring board of said composition for excellent flexible printed wiring board such as the adaptation of base material, resistance to blocking.
The present invention relates to above-mentioned insulating resin composition, it contains polyurethane (X), epoxy resin (B) and filler (C), and is used to be arranged on the base material of flexible printed wiring board, it is characterized in that,
Above-mentioned polyurethane (X) is
Make the polyurethane prepolymer (d) that contains NCO and polyamino compound (e) react the polyurethanes carbamide resin (A) that modulation forms, the described polyurethane prepolymer (d) that contains NCO is that the diol compound (c) that makes polyol compound (a), organic diisocyanate (b) and contain carboxyl reacts to modulate and forms; Or
The diol compound (c) that makes polyol compound (a), organic diisocyanate (b) and contain carboxyl reacts the polyurethane prepolymer that contains hydroxyl (f) that modulation forms; Or
Above-mentioned polyurethanes carbamide resin (A) and the above-mentioned mixture that contains the polyurethane prepolymer (f) of hydroxyl,
Above-mentioned filler (C) is the organic resin filler;
Above-mentioned base material is the thermoplastic resin base material.
In addition, the present invention relates to above-mentioned insulating resin composition, it is characterized in that, the total weight 100 weight % with respect to above-mentioned polyurethane (X) contain epoxy resin (B) 3～200 weight %.
In addition, the present invention relates to above-mentioned insulating resin composition, it is characterized in that, the total weight 100 weight % with respect to above-mentioned polyurethane (X) and epoxy resin (B) contain organic resin filler (C) 0.1～200 weight %.
In addition, the present invention relates to above-mentioned insulating resin composition, it is characterized in that, organic resin filler (C) is at least a kind the filler that is selected from urea resin system, melmac system, polyurethane resin system and benzoguanamine resin system.In addition, the present invention relates to above-mentioned insulating resin composition, it is characterized in that, polyol compound (a) is to react as sour composition and glycol with terephthalic acid (TPA) and/or M-phthalic acid at least and the PEPA modulated.
In addition, relate to above-mentioned insulating resin composition, it is characterized in that, and then to contain fusing point be more than 40 ℃ and the wax below 180 ℃ (D).
In addition, relate to above-mentioned insulating resin composition, it is characterized in that, wax (D) is N, N '-ethylidene-bis-stearamides.
In addition, the present invention relates to flexible printed wiring board, it is characterized in that, the insulating barrier that is arranged on the conductor layer is formed by above-mentioned insulating resin composition, and described conductor layer is arranged at least one surface of thermoplastic resin base material of flexible printed wiring board.
According to the present invention, it is the flexible printed wiring board insulating resin composition of thermoplastic resin that base material can be provided, maybe can provide the flexible printed wiring board that has used above-mentioned insulating resin composition, under the situation of not using the Halogen material, can give high flame retardant, and with flexible, for the adaptation of no surface-treated base material.
Embodiment
At first, describe for insulating resin composition of the present invention.Insulating resin composition of the present invention contains particular polyurethane (X), epoxy resin (B) and organic resin filler (C) as mentioned above.
Above-mentioned polyurethane (X) is the mixture of polyurethanes carbamide resin (A), polyurethane prepolymer (f) or polyurethanes carbamide resin (A) and polyurethane prepolymer (f).
The polyurethanes carbamide resin (A) that contains as above-mentioned polyurethane (X) in the insulating resin composition reacts polyurethane prepolymer (d), polyamino compound (e) and reaction terminating agent as required with NCO and obtains.The above-mentioned polyurethane prepolymer (d) that contains NCO is that the diol compound (c) that makes polyol compound (a), organic diisocyanate (b) and contain carboxyl reacts and modulates.
In addition, in insulating resin composition, the polyurethane prepolymer (f) that contains as above-mentioned polyurethane (X) is that the diol compound (c) that makes polyol compound (a), organic diisocyanate (b) and contain carboxyl reacts, and obtain with the state that has hydroxyl endways.
As polyol compound (a), can use general known as the polyol component that constitutes polyurethane resin, various PPG classes, polyester polyols alcohols, polycarbonate polyol class, polybutadiene diol class or their mixture etc.
The PPG class can be enumerated the polymer of for example oxirane, expoxy propane, oxolane or the like or copolymer etc.
The polyester polyols alcohols can be enumerated for example ethylene glycol, 1,2-propylene glycol, 1, ammediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, pentanediol, 3-methyl isophthalic acid, 5-pentanediol, hexylene glycol, ethohexadiol, 1, saturated and undersaturated low-molecular-weight diol classes such as 4-butanediol, diethylene glycol (DEG), triethylene glycol, dipropylene glycol or dimer diol; And make n-butyl glycidyl ether, the alkyl glycidyl ether class of 2-ethylhexyl glycidol ethers, or the monocarboxylic acid ethylene oxidic ester class of tertiary carbonic acid glycidyl ester etc., and adipic acid, phthalic acid, M-phthalic acid, terephthalic acid (TPA), maleic acid, fumaric acid, butanedioic acid, oxalic acid, malonic acid, glutaric acid, pimelic acid (pimelic acid), suberic acid (suberic acid), the omega-dicarboxylic acids of azelaic acid or decanedioic acid etc., or their acid anhydride class, the polyester polyols alcohols that carries out dehydrating condensation and obtain carries out ring-opening polymerisation with the cyclic ester compound and the polyester polyols alcohols that obtains.
The polycarbonate polyol class can use 1) reactant of glycol or bis-phenol and carbonic ester; With 2) glycol or bis-phenol in the presence of alkali with the reactant of phosgene.Carbonic ester can be enumerated for example dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate or propylene carbonate etc.In addition, glycol can be enumerated for example ethylene glycol, propylene glycol, dipropylene glycol, diethylene glycol (DEG), triethylene glycol, butanediol, the 3-methyl isophthalic acid, the 5-pentanediol, the 2-methyl isophthalic acid, the 8-ethohexadiol, 3,3 '-the dihydroxymethyl heptane, polyethylene glycol, polyoxypropylene glycol, propylene glycol, 1, the 3-butanediol, 1, the 4-butanediol, 1, the 5-pentanediol, 1, the 6-hexylene glycol, 1, the 4-hydroxymethyl-cyclohexane, 1, the 9-nonanediol, neopentyl glycol, ethohexadiol, the butyl ethyl pentanediol, 2-ethyl-1, the 3-hexylene glycol, cyclohexanediol, 3,9-pair (1,1-dimethyl-2-ethoxy or 2,2,8,10-four oxygen volution [5.5] hendecanes etc.In addition, bis-phenol can be enumerated for example bisphenol-A, Bisphenol F, or on bisphenols the bisphenols etc. of alkylene oxide such as addition of ethylene oxide or expoxy propane.
Number-average molecular weight (Mn) for above-mentioned polyol compound (a), be that thermal endurance, mechanical property and/or the dissolubility etc. of considering gained polyurethanes carbamide resin (A) and/or polyurethane prepolymer (f) afterwards and suitably determine, usually preferably in 500～8000 scope, and then be preferably 1000～5000.If Mn is less than 500, then the urethane bonds in polyurethanes carbamide resin (A) and/or the polyurethane prepolymer (f) is too much, there is the flexibility of polymer backbone to reduce, the tendency that descends for the cementability of base material, if Mn surpasses 8000 in addition, then there is between crosslinking points the molecule quantitative change big, the tendency that thermal endurance reduces.
Above-mentioned polyol compound (a) can use separately, also can will share more than 2 kinds.And then, in the scope of the performance of not losing polyurethanes carbamide resin (A) and/or polyurethane prepolymer (f), the part of above-mentioned polyol compound (a) also can be used the low-molecular-weight diol class, for example employed various low-molecular-weight diols in the manufacturing of above-mentioned polyol compound (as the polyalcohol of the parent material of above-mentioned PEPA, PCDL).
Especially, when using PEPA as above-mentioned polyol compound (a), as with the dicarboxylic acids composition of glycol reaction, in molecular structure, have the terephthalic acid (TPA) of aromatic rings and/or the many PEPAs of content of M-phthalic acid by use, can improve the toughness and the viscosity of polyurethanes carbamide resin (A) and/or polyurethane prepolymer (f), and increase and to contain the hardness that is coated with rete and the viscosity of insulating resin composition, thereby be particularly preferred.
And then, only use terephthalic acid (TPA) and/or M-phthalic acid as the dicarboxylic acids composition, and itself and glycol are reacted, modulate PEPA thus, by using this PEPA, can significantly improve the bending of filming, thereby be particularly preferred.
Organic diisocyanate compound (b) can use aromatic diisocyanate, aliphatic diisocyanate, alicyclic isocyanate or their mixture, preferred especially IPDI.
Aromatic diisocyanate can enumerate 1,5-naphthalene diisocyanate, 4,4 '-methyl diphenylene diisocyanate, 4,4 '-diphenyl dimethylmethane vulcabond, 4,4 '-benzyl isocyanate ester, dialkyl group methyl diphenylene diisocyanate, tetraalkyl methyl diphenylene diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, toluene di-isocyanate(TDI) or XDI etc.
Aliphatic diisocyanate can be enumerated butane-1,4-vulcabond, hexamethylene diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate or LDI etc.
Alicyclic diisocyanate can be enumerated cyclohexane-1,4-vulcabond, IPDI, norbornane two methyl isocyanates, two (4-isocyanates cyclohexyl) methane, 1, two (isocyanates methyl) cyclohexanes of 3-or methylcyclohexane diisocyanate etc.
The diol compound (c) that contains carboxyl can be enumerated for example dimethylolalkanoic acids such as dihydroxymethyl acetic acid, dihydromethyl propionic acid, dimethylolpropionic acid or dihydroxymethyl valeric acid; Or dihydroxysuccinic acid, dihydroxy-benzoic acid.Consider preferred dihydromethyl propionic acid or dimethylolpropionic acid especially from reactive, deliquescent angle.
React for the diol compound (c) that makes polyol compound (a), organic diisocyanate (b) and contain carboxyl, and the condition when obtaining having the polyurethane prepolymer (d) of NCO, except making the NCO surplus, other do not limit especially, and the equivalent proportion that preferably makes NCO/hydroxyl is in 1.05/1～3/1 scope.And then preferred 1.2/1～2/1.In addition, reaction is carried out between normal temperature～150 ℃ usually, considers from the angle of manufacturing time, side reaction control, preferably carries out between 60～120 ℃.
Condition when reacting the polyurethane prepolymer (f) that obtains having hydroxyl for the diol compound (c) that makes polyol compound (a), organic diisocyanate (b) and contain carboxyl, except making the hydroxyl surplus, other do not limit especially, and the equivalent proportion of preferred isocyanate base/hydroxyl is in 0.8/1～0.99/1 scope.In addition, reaction is carried out between normal temperature～150 ℃ usually, and then considers from the angle of manufacturing time, side reaction control, preferably carries out between 60～120 ℃.
Polyurethanes carbamide resin (A) reacts polyurethane prepolymer (d) with NCO and polyamino compound (e) and obtains as mentioned above.
Polyamino compound (e) plays a role as the chain elongation agent, except ethylenediamine, propane diamine, hexamethylene diamine, diethylenetriamines, trien, IPD, dicyclohexyl methyl hydride-4,4 '-diamines or norbornane diamines outside, can also use 2-(2-aminoethylamino) ethanol, 2-AEEA, 2-ethoxy propane diamine, two-2-AEEA or two-2-hydroxypropyl ethylenediamine etc. to have the amine of hydroxyl.Wherein, preferably use IPD.
When synthesizing polyurethanes carbamide resin (A) when the polyurethane prepolymer (d) with NCO is reacted with polyamino compound (e), in order to regulate the molecular weight of gained polyurethanes carbamide resin (A), can and use reaction terminating agent.Reaction terminating agent can use the dialkyl amine of di-n-butylamine etc.; The dialkanol amine of diethanol amine etc.; The alcohols of ethanol or isopropyl alcohol etc.
Condition when polyurethane prepolymer (d), polyamino compound (e) and reaction terminating agent as required with NCO are reacted, do not limit especially, preferably when the free isocyanate groups that will be present in polyurethane prepolymer (d) two ends was decided to be 1 equivalent, the total equivalent that makes the amino in polyamino compound (e) and the reaction terminating agent was in 0.5～1.3 scope.And then it is preferred in 0.8～0.995 scope.When the total equivalent of amino less than 0.5 the time, can't fully increase the molecular weight of polyurethanes carbamide resin (A).If surpass 1.3, then polyamino compound (e) and reaction terminating agent are residual in a large number with unreacted state, epoxy resin in the insulating resin composition (B) directly reacts with unreacted amino, or unreacted amino presents catalytic activity in insulating resin composition, and the up time of insulating resin composition is reduced.
The weight average molecular weight (Mw) of polyurethanes carbamide resin (A) is preferably 5000～200000 scope.
The weight average molecular weight (Mw) that contains the polyurethane prepolymer (f) of hydroxyl is preferably 5000～100000 scope.
In addition, the acid number of polyurethanes carbamide resin (A) and/or polyurethane prepolymer (f) is preferably the scope of 1～80mgKOH/g.And acid number is meant the acid number that obtains according to carboxyl, is the numerical value for the solid formation branch of polyurethanes carbamide resin (A) and/or polyurethane prepolymer (f).When the acid number of polyurethanes carbamide resin (A) and/or polyurethane prepolymer (f) during less than 1mgKOH/g, become not enough with the crosslinked of epoxy resin (B) contained in the insulating resin composition, curable reduces, and viscosity increases simultaneously, can not present solvent resistance.In addition, when acid number during, following situation is arranged greater than 80mgKOH/g, promptly, excessively crosslinked with epoxy resin (B) contained in the insulating resin composition, reduce for dhering strength, and form the reason that causes adherend generation warpage by cure shrinkage as the base material of adherend.In addition, the anti-flammability during for the insulating barrier that forms flexible circuit board, excessive when crosslinked when above-mentioned insulating material, the vertical stream (dripping) that has because of hindering substrate prolongs combustion, the situation that causes anti-flammability to reduce, because of rather than preferably.
When synthetic polyurethanes carbamide resin (A) and/or polyurethane prepolymer (f), can be with a kind of independent use that is selected from ester series solvent, ketone series solvent, glycol ethers series solvent, aliphat series solvent, aromatic series series solvent, pure series solvent, carbonic ester series solvent or the water etc., or will be used in combination more than two kinds.
The ester series solvent can be enumerated for example ethyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, amyl acetate or ethyl lactate etc.
The ketone series solvent can be enumerated for example acetone, methylethylketone, methylisobutylketone benzene, diisobutyl ketone, diacetone alcohol, isophorone or cyclohexanone etc.
The glycol ethers series solvent can be enumerated for example acetate of ethylene glycol monoethyl ether, glycol monomethyl isopropyl ether, ethylene glycol monobutyl ether or these monoether classes; The acetate of diethylene glycol dimethyl ether, diethyl carbitol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, dihydroxypropane single-ether or these monoether classes etc.
The aliphat series solvent can be enumerated for example normal heptane, n-hexane, cyclohexane, hexahydrotoluene or ethyl cyclohexane etc.
The aromatic series series solvent can be enumerated for example toluene or dimethylbenzene etc.
The alcohol series solvent can be enumerated for example methyl alcohol, ethanol, 1-propyl alcohol, 2-propyl alcohol, 1-butanols or cyclohexanol etc.
The carbonic ester series solvent can be enumerated for example dimethyl carbonate, carbonic acid ethyl methyl esters or n-butyl carbonate etc.
In addition, the epoxy resin that contains in the insulating resin composition of the present invention (B) is the compound with epoxy radicals, can also can be solid, shaped for liquid, and epoxy resin (B) does not limit especially, can use the epoxy resin that on average has 2 above epoxy radicals in 1 molecule.
Epoxy resin (B) can use the epoxy resin of glycidol ether type epoxy, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin or annular aliphatic (alicyclic ring type) epoxy resin etc.
The glycidol ether type epoxy can be enumerated for example bisphenol A type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, bisphenol-A D type epoxy resin, the cresols phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, the polyglycidyl ether of biphenyl cascophen (Japanese chemical drug corporate system: NC-3000 etc.), the polyglycidyl ether of bicyclopentadiene cascophen (Japanese chemical drug corporate system: XD-1000 etc.), the alpha-Naphthol phenolic resin varnish type epoxy resin, the bisphenol A-type phenolic resin varnish type epoxy resin, dicyclopentadiene-type epoxy resin, biphenyl type epoxy resin, three (glycidyl oxygen base phenyl) methane, four (glycidyl oxygen base phenyl) ethane etc.
Glycidyl amine type epoxy resin can be enumerated four glycidyl group diaminodiphenyl-methane, triglycidyl group para-aminophenol, triglycidyl group m-aminophenol or four glycidyl group m-xylene diamine etc.
Glycidyl ester type epoxy resin can be enumerated o-phthalic acid diglycidyl ester, hexahydrophthalic acid 2-glycidyl ester or tetrahydrophthalic acid 2-glycidyl ester etc.
Annular aliphatic (alicyclic ring type) epoxy resin can be enumerated epoxycyclohexyl methyl-epoxycyclohexane carboxylate or two (epoxycyclohexyl) own diester etc.
Epoxy resin can be used alone or will be used in combination more than two kinds.
Epoxy resin (B) is considered from high adhesiveness and/or stable on heating angle, is preferably used bisphenol A type epoxy resin, cresols phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, three (glycidyl oxygen base phenyl) methane or four (glycidyl oxygen base phenyl) ethane.
In insulating resin composition of the present invention, for the cooperate ratio of above-mentioned polyurethane (X) with epoxy resin (B), preferably above-mentioned relatively polyurethane (X) 100 weight portions, epoxy resin (B) is 3～200 weight portions, more preferably 5～100 weight portions.If the amount of epoxy resin (B) is less than 5 weight portions, then there is curable to reduce, the situation of viscosity takes place.If epoxy resin (B), then has the tendency for the cementability reduction of base material more than 200 weight portions.
By in insulating resin composition of the present invention, containing organic resin filler (C), can increase anti-flammability not adding under the situation of at present known fire retardant.And then, make its be applicable to simultaneously require mobile, viscosity and/or and base material between the purposes of adaptation, can improve anti-flammability, the level of requirement also can be kept or be increased to these rerum naturas simultaneously.In addition, for these organic resin fillers (C), by above-mentioned polyurethane (X) and epoxy resin (B) are made up, inorganic with silicon dioxide, talcum or the filler pigment etc. that generally use in known insulating properties composition is that filler is compared, and discovery can significantly improve anti-flammability.For this mechanism of action, though in theory still do not have discovery, think since inorganic when burning be filler and unburned and residual, thereby inorganic be between the filler flammable thing be easy to by and the cause of burning etc.
Organic resin filler (C) is the particulate filler that contains organic resin etc.For example can enumerating, urea resin is that filler, melmac are that filler, polyurethane resin are that filler or benzoguanamine resin are filler.These organic resin fillers (C) have commercially available thing, and for example urea resin is filler " the PERGOPAK series " that can enumerate the ALBEMARLE corporate system etc.In addition, melmac is filler " Epostar M30 " that can enumerate Nippon Catalytic Chem Ind's system for example etc.Polyurethane resin is the filler cross-linked polyurethane pearls such as " ARTPEARLC-200, C-300, C-400, C-800 " that can enumerate Industries, Inc's system on the root for example etc.In addition, benzoguanamine resin is filler " Epostar M05, MS " that can enumerate Nippon Catalytic Chem Ind's system for example etc.Phenolic resins be filler for example can enumerate Sumitomo Bakelite corporate system " PR-RES-5 ", clear and macromolecule corporate system "
PMB-1010 " etc.The acrylic resin filler can enumerate ponding for example change into product Industries, Inc system "
MBX series " etc.Styrene resin be filler can enumerate ponding for example change into product Industries, Inc system "
SBX series " etc.These organic resin fillers (C) are the shot-like particles that contains the organic resin that monomer is polymerized, in the main chain of this resin and/or between main chain, even be crosslinked or noncrosslinking arbitrary structure, can find the increase effect of anti-flammability, but for crosslinked structure, owing to can improve solvent resistance, thereby be preferred.These organic resin fillers (C) can use or mix use separately.
The average grain diameter of organic resin filler (C) does not limit especially, can be according to the formation of final use, require characteristic to select, consider from the angle that can significantly improve anti-flammability, preferably use the organic resin filler that in molecular structure, has nitrogen-atoms.Specifically, the urea resin that especially preferably contains the urea key is that filler, the polyurethane resin that contains urethane bonds are filler, are that filler or benzoguanamine resin are filler as the melmac of amino-compound.
Above-mentioned relatively polyurethane of the use level of organic resin filler (C) (X) and epoxy resin (B) 100 weight portions are preferably 0.1～200 weight portion.If below 0.1 weight portion, the situation of the effect that can not find anti-flammability is arranged, because of rather than preferred.In addition,, then have the flowability control of insulating properties composition to be tending towards situation of difficult, or the situation of mechanical properties variation such as flexibility if surpass 200 weight portions, because of rather than preferably.Improve anti-flammability effect and mechanical properties, more preferably 3～30 weight portions in order to take into account.
In insulating resin composition of the present invention, in order to promote polyurethanes carbamide resin (A) and/or polyurethane prepolymer (f), and the reaction of epoxy resin (B) and the reaction between epoxy resin (B), can contain curing accelerator and/or curing agent.The curing accelerator of epoxy resin (B) can use tertiary amine compound, phosphine compound or imidazolium compounds etc., and curing agent can use dicyandiamide, carboxylic acid hydrazides, acid anhydrides etc., perhaps the dialkyl group ureas of aliphat or aromatic series dimethyl urea etc.In addition, polyurethane prepolymer (f) is owing to have hydroxyl, thereby can utilize at present that known isocyanates or blocked isocyanate carries out crosslinked.
Can enumerate triethylamine, benzyl dimethylamine, 1 as the tertiary amine compound of curing accelerator, 8-diazabicyclo (5.4.0) endecatylene-7 or 1,5-diazabicyclo (4.3.0) nonene-5 grade and their salt.In addition, phosphine compound can be enumerated for example triphenylphosphine or tributylphosphine etc.The preferred glyoxal ethyline of imidazolium compounds, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2, imidazolium compoundss such as 4-methylimidazole or 2-phenylimidazole and these imidazolium compoundss and epoxy resin are reacted and be thawless form for solvent, or imidazolium compounds is enclosed form in the microcapsules etc. improvement the latent property curing accelerator of storage stability.
Can enumerate butanedioic acid hydrazides or adipic acid hydrazides etc. as the carboxylic acid hydrazides of curing agent.In addition, acid anhydrides can be enumerated for example hexahydrophthalic anhydride or trimellitic anhydride etc.
These curing accelerators, curing agent can will share more than 2 kinds, and its addition is preferably the scope of 0.1～30 weight portion with respect to epoxy resin (B) 100 weight portions.
In insulating resin composition of the present invention, under the scope that does not make for the cementability variation of base material, can cooperate resin, silane coupling agent, heat-resisting stabilizing agent, coloring pigment, dyestuff, bonding resin, plasticizer, ultra-violet absorber, defoamer and/or the levelling conditioning agent etc. given.
By also using heat-resisting stabilizing agent, can give more excellent soldering resistance.Heat-resisting stabilizing agent can use that hindered phenol system, phosphorus (phosphate) are, lactone system, hydroxylamine system or sulphur system etc., and the heat-resisting stabilizing agent of hindered phenol system is effective especially.
The purpose of insulating resin composition of the present invention is, and then by containing wax (D), can keep the rerum natura against corrosion of bending property, adaptation and/or anti-flammability etc., significantly improve the resistance to blocking (purpose is to reduce surface viscosity) when applying high temperature and high the heavy burden simultaneously.
The fusing point of wax (D) is more than 40 ℃ and below 180 ℃, and this considers it is particularly preferred from the angle that improves the resistance to blocking under the temperature conditions more than 40 degree.This wax (D) can be enumerated N-hydroxyethyl-12-hydroxyl stearmide, below, N, N '-ethylidene-two-oleamide, N, N '-ethylidene-two-castor oil acid amides, N, N '-ethylidene-two-octadecane diene amide, N, N '-ethylidene-two-12-hydroxyl stearmide, N, N '-ethylidene-two-stearmide, N, N '-hexa-methylene-two-castor oil acid amides, N, N '-hexa-methylene-two-12-hydroxyl stearmide or N, N '-xylylene-two-acid amides such as 12-hydroxyl stearmide are wax, particularly owing to apply 10kg/cm under the temperature conditions more than 80 degree
2Resistance to blocking excellence during above heavy burden, thereby preferably use N, N '-ethylidene-two-stearmide.The addition of wax (D) is with respect to the solid formation branch of insulating resin composition, is preferably more than 0.1% and below 10%.If less than 0.1%, then have and to find that resistance to blocking increases the situation of effect, if surpass 10%, then has the situation of infringement as the balancing performance of insulating resin composition.
Because insulating resin composition of the present invention contains organic resin filler (C), thereby can find the anti-flammability that significantly improves, but according to so that the flame retardancy level that requires, also can add known fire retardant at present.The kind of fire retardant, particularly phosphorus system, can enumerate for example polyphosphoric acid salt, phosphine class or phosphonitrile (phosphazene) class etc.Material with the polyphosphate surface utilizes melamine to apply to form because water absorption is low, thereby is preferred for insulating material purposes of the present invention.In addition, owing to phosphine class, phosphonitrile class are difficult to be subjected to hydrolysis, thereby are preferred for the insulating material purposes.The phosphine class can be used known material, especially, 1, two (diphenyl phosphine) ethane, 1 of 2-, two (diphenyl phosphine) propane, 1 of 3-, two (diphenyl phosphine) butane or 1 of 4-, two (diphenyl phosphine) pentanes of 5-etc. are owing to phosphorus atoms ratio height shared in structure, more phosphorus atoms can be added in the insulating resin composition by a small amount of interpolation, thereby be particularly preferred.
Consider from the angle that increases resistance to blocking, preferably in insulating resin composition of the present invention and then contain the modification organopolysiloxane as antiblocking agent.The modification organopolysiloxane is for example a part of methyl of dimethyl silicone polymer to be replaced the material that forms with polyether-based, polyester-based, alkyl, aralkyl and/or other organic groups, for example can enumerate BYK-Chemie corporate system " BYK-306, BYK-310 ", the sharp health corporate system " KF-410, X-22-4039 " of SHIN-ETSU HANTOTAI's silicon, CHISSO corporate system "
FM-4411, FM-0411 ", TORAYDow Corning corporate system " 54ADDITIVE, 8503ADDITIVE " etc., limit especially.Wherein, particularly having the modification organopolysiloxane of hydroxyl, carboxyl or epoxy radicals isoreactivity functional group and the composition in the insulating resin composition reacts, mode with chemistry is fixed on the film coated surface, have the continuation of excellent resistance to blocking and the non-polluting of manufacturing line thus, thus more preferred.Modification organopolysiloxane with this reactive functional groups for example can enumerate BYK-Chemie corporate system " BYK-370, BYK-375, BYK-377 ", the sharp health corporate system " KF-101, KF-6001, X-22-4741, X-22-3701E, X-22-4039, X-22-162C, X-22-163C, X-22-4952, X-22-170BX, X-22-173DX " of SHIN-ETSU HANTOTAI's silicon, CHISSO corporate system "
FM-4411, FM-0411 " etc.
The insulating barrier that contains insulating resin composition of the present invention, can be by on the single face at least of various base materials, utilize present known method, for example screen painting, airblade coating, die head coating, scraper coating, roller coat, curtain coating, rod are coated with, intaglio printing, hectographic printing, dip-coating, spraying or spin coating etc., after above-mentioned insulating resin composition was coated with, drying formed under common 40～160 ℃ temperature.In addition, consider that from the angle that can bring into play sufficient various performance and processing ease the dry film thickness of insulating barrier is preferably 5 μ m～500 μ m, nearly and preferred 10 μ m～100 μ m.
Secondly, describe for the flexible printed wiring board that has used insulating resin composition of the present invention.Flexible printed wiring board is for the flexible printed wiring board that has formed conductive pattern on the thermoplastic resin base material with flexible and insulating properties by printing technology, apply insulating resin composition of the present invention as insulating barrier, and carry out drying, curing, the substrate that it is fixedly formed.Therefore, in the flexible printed wiring board of simple structure, at least one surface of thermoplastic resin base material, have conductor layer, and on this conductor layer, have insulating resin composition of the present invention as insulating barrier.In addition, flexible printed wiring board also can have following structures,, has conductor layer at least one surface of thermoplastic resin base material that is, on this conductor layer, have insulating resin composition of the present invention as insulating barrier, and at this insulating barrier superimposed layer conductor layer.
The thermoplastic resin base material can use following such known materials, that is, it reaches more than the VTM-2 grade in the burning test of having utilized UL94 vertical combustion method, can drip from base material.This base material can be enumerated polyethylene terephthalate or Merlon etc.
Embodiment
Below, utilize embodiment and then explain the present invention, but following embodiment does not carry out any restriction to interest field of the present invention.And, " part " among the embodiment and " % " expression " weight portion " and " weight % ".
[synthesis example 1]
In reaction vessel with mixer, thermometer, reflux cooler, Dropping feeder and nitrogen ingress pipe, adding is by terephthalic acid (TPA), adipic acid and 3-methyl isophthalic acid, [KURARAY (thigh) makes " Kuraray Polyol P-2011 " to the PEPA that the 5-pentanediol obtains, Mn=2011] 140 parts of 454.6 parts, 16.5 parts of dimethylolpropionic acids, 105.0 parts of IPDIs and toluene, under the nitrogen atmosphere, reacted 3 hours in 90 ℃, add 360 parts of toluene therein, obtain having the polyurethane prepolymer solution of NCO.Then, in the mixture of 335.5 parts of 19.3 parts of IPDs, 2.20 parts of di-n-butylamines, 294.5 parts of 2-propyl alcohol and toluene, 968.5 parts of the polyurethane prepolymer solution that interpolation is obtained with NCO, under 50 ℃, carry out 3 hours reaction, then under 70 ℃, carry out 2 hours reaction, dilute for 54 parts with 126 parts of toluene and 2-propyl alcohol, obtain Mw=57,000, the polyurethanes carbamide resin solution A-1 of acid number=10mgKOH/g (solid form minute: 30%).
[synthesis example 2]
Has mixer, thermometer, reflux cooler, in the reaction vessel of Dropping feeder and nitrogen ingress pipe, adding is by terephthalic acid (TPA), adipic acid and 3-methyl isophthalic acid, [KURARAY (thigh) makes " Kuraray Polyol P-2011 " to the PEPA that the 5-pentanediol obtains, Mn=2011] 345.3 parts, 10.7 parts of dimethylolpropionic acids, 94.5 parts of 51.1 parts of IPDIs and carbitol acetates, under the nitrogen atmosphere, reacted 3 hours in 90 ℃, in reaction product, add 310.5 parts of carbitol acetates, obtain Mw=30,000, the polyurethane prepolymer solution f-1 with hydroxyl of acid number=10mgKOH/g (divides Gu form: 50.1%).
[synthesis example 3]
Has mixer, thermometer, reflux cooler, in the reaction vessel of Dropping feeder and nitrogen ingress pipe, adding is by M-phthalic acid and 3-methyl isophthalic acid, [KURARAY (thigh) makes " Kuraray Polyol P-2030 " to the PEPA that the 5-pentanediol obtains, Mn=2033] 637.1 parts, 20.8 parts of dimethylolpropionic acids, 162.5 parts of 95.9 parts of IPDIs and carbitol acetates, under the nitrogen atmosphere, reacted 3 hours in 90 ℃, in reaction product, add 575 parts of carbitol acetates, obtain Mw=30,000, the polyurethane prepolymer solution f-2 with hydroxyl of acid number=10.5mgKOH/g (divides Gu form: 50.5%).
[synthesis example 4]
Has mixer, thermometer, reflux cooler, in the reaction vessel of Dropping feeder and nitrogen ingress pipe, adding is by adipic acid and 3-methyl isophthalic acid, 637.1 parts of the PEPAs that the 5-pentanediol obtains [KURARAY (thigh) makes " Kuraray Polyol P-2010 "], 20.8 parts of dimethylolpropionic acids, 162.5 parts of 95.9 parts of IPDIs and carbitol acetates, under the nitrogen atmosphere, reacted 3 hours in 90 ℃, in reaction product, add 575 parts of carbitol acetates, obtain Mw=30,000, the polyurethane prepolymer solution f-3 with hydroxyl of acid number=10.5mgKOH/g (divides Gu form: 50.5%).
In addition, the polyurethanes carbamide resin is to utilize GPC to measure the weight average molecular weight through polystyrene conversion of trying to achieve with the weight average molecular weight (Mw) that contains the polyurethane prepolymer of hydroxyl, and the GPC condition determination is as follows:
Device: clear and electrician's (thigh) system of Shodex GPC System-21[]
Chromatographic column: with Shodex KF-802, KF-803L, KF-805L[is clear and electrician's (thigh) system] add up to 3 and be connected use.
Solvent: oxolane
Flow velocity: 1.0mL/min
Temperature: 40 ℃
Sample solution concentration: 0.2 weight %
Sample injection rate: 100 μ L
[embodiment]
According to the prescription shown in table 1 and the table 2, modulate the insulating resin composition of embodiment 1～12 and comparative example 1～5 respectively.(corporate system is spun to untreated polyethylene terephthalate thin film by Japan: E5100 on the surface, thickness 75 μ m) on, above-mentioned composition is coated with at single face, so that dried thickness is 10 μ m, drying is 30 minutes in 80 ℃ baking oven, and then it was solidified 1 hour, form and estimate sample.
* 1:JER1031S: four (glycidyl oxygen base phenyl) ethane (Japan Epoxy Resins (thigh) system, epoxide equivalent=180～220g/eq)
* 2: urea resin is a filler: ALBEMARLE corporate system, PERGOPAK M5, average grain diameter (d50)=3.5～6.0 μ m
* 3: crosslinking polyurethane resin filler: Industries, Inc's system on the root, ARTPEARLP-800T, average grain diameter=7 μ m
* 4: the condensed type melmac is a filler: Nippon Catalytic Chem Ind's system, EpostarM30, average grain diameter=2.5～4.0 μ m
* 5: the condensed type benzoguanamine resin is a filler: Japanese catalyst chemical company system, EpostarM05, average grain diameter=4～6 μ m
* 6: crosslinked acrylic resin is a filler: ponding changes into product Industries, Inc system,
MBX-8, average grain diameter=8 μ m
* 7: cross-linked styrene resin system filler: ponding changes into product Industries, Inc system,
SBX-6, average grain diameter=6 μ m
* 8: phenolic resins is filler: Sumitomo Bakelite corporate system PR-RES-5
* 9: inorganic filler (silicon dioxide): NIPSIL SS-50F:TOSOH SILICA limited company system, average grain diameter=1.2 μ m
* 10: inorganic filler (silicon dioxide): DEGUSSA corporate system, AEROSIL R812, average grain diameter=7nm
* 11: thermal curing agents: DICY-7:Japan Epoxy Resins (thigh) system, the broken dicyandiamide of micro mist
* 12: thermal curing agents: U-CAT SA102:SAN-APRO corporate system, the caprylate of diazabicyclo endecatylene
* 13: blocked isocyanate: MF-K60X: chemistry limited company of Asahi Chemical Industry system
* 14: wax: N, N '-ethylidene-two-stearmide
[assessment item]
Adaptation is estimated: according to JIS K5600, carrying out the gridiron pattern number is the gridiron pattern belt stripping test of 100 (10 * 10).Represent adaptation with gridiron pattern number residual behind the tape stripping (maximum 100)/100.
Warpage is estimated: will estimate sample and cut into 5cm * 5cm, and place 24 hours under 40% constant-temperature constant-humidity environment under 25 ℃.Sample is rested on the level and smooth table top, and the distance (mm) between mensuration end face and table top.
Resistance to blocking 1: will estimate between the coated face of sample and fit, and under 60 ℃, apply 200g/cm
2Heavy burden after 24 hours, estimate with 3 stages and to be coated with intermembranous extent of exfoliation.
Zero: do not have sticking carbuncle sense (inviscid) fully
△: experience sticking carbuncle sense (microviscosity) a little
*: the sticking carbuncle sense (viscosity is big) of strong impression
Resistance to blocking 2: will estimate between the coated face of sample and fit, and under 80 ℃, apply 12kg/cm
2Heavy burden after 24 hours, estimate with 2 stages and to be coated with intermembranous extent of exfoliation.
Zero: be coated with intermembranous nothing cohesion and destroy
*: be coated with intermembranous appearance cohesion and destroy
Bending property 1: the coated surface that will estimate sample inwards, 1 double flat, the crackle that the range estimation affirmation is filmed etc.
Bending property 2: for the same place that estimates sample, coated surface is inwards carried out 1 time 180 spend bending, again coated surface is carried out 1 time 180 degree bending towards the outside, and, add up to 10 circulations repeatedly, the crackle that the range estimation affirmation is filmed etc. as 1 circulation.
Anti-flammability: carry out burning test according to UL94 vertical combustion method.Test is implemented for 5 samples.In addition, in this evaluation, measure light for the 1st time after, the mean value of required time till extinguishing, and comparing.Under this situation, the time is short more, and then anti-flammability is high more.In addition, after lighting for the 1st time, do not extinguish and prolong the sample that fires to graticule, in table 1 and table 2, " anti-flammability evaluation " is designated as " not meeting ", and then mensuration flame prolongs and fires to time of graticule and compare.Under this situation, it is long to prolong the combustion time, and then burning rate is slow, and anti-flammability is comparatively good.
According to the evaluation result shown in table 1 and the table 2 as can be known, the cited insulating resin composition of embodiment has excellent adaptation, warpage, resistance to blocking, bending, even for the prescription that does not add fire retardant, also show excellent flame, can satisfy as the big event of flexible circuit board with insulating material.And, according to the occupation mode of flexible circuit board, irrelevant resistance to blocking, flexible purposes (for example connector part) are arranged also, even but also will satisfy necessary anti-flammability under this situation.Therefore, the cited insulating resin composition of embodiment also can be preferred for this purposes.On the other hand, the cited composition of comparative example shows the tendency of obvious variation aspect anti-flammability, be difficult to use as the insulating material that flexible circuit board is used.
Industrial applicability
Insulating resin composition of the present invention can be used for being formed on the insulating barrier that arranges on the conductor layer, Described conductor layer is arranged at least one table of the thermoplastic resin base material of flexible printed wiring board On the face. Above-mentioned insulating resin composition has cementability, low warpage properties, the bending for base material concurrently Property, resistance to blocking and anti-flammability.
More than, continue to use specific mode the present invention is described, but for those skilled in the art aobvious and easy The distortion of seeing and improvement all are covered by in the scope of the present invention.
Claims (8)
1. insulating resin composition, it contains polyurethane (X), epoxy resin (B) and filler (C), and is used to be arranged on the base material of flexible printed wiring board, it is characterized in that,
Above-mentioned polyurethane (X) is
Make the polyurethane prepolymer (d) that contains NCO and polyamino compound (e) react the polyurethanes carbamide resin (A) that is modulated into, the described polyurethane prepolymer (d) that contains NCO is that the diol compound (c) that makes polyol compound (a), organic diisocyanate (b) and contain carboxyl reacts to modulate and forms; Or
The diol compound (c) that makes polyol compound (a), organic diisocyanate (b) and contain carboxyl reacts the polyurethane prepolymer that contains hydroxyl (f) that is modulated into; Or
Above-mentioned polyurethanes carbamide resin (A) and the above-mentioned mixture that contains the polyurethane prepolymer (f) of hydroxyl,
Above-mentioned filler (C) is the organic resin filler,
Above-mentioned base material is the thermoplastic resin base material.
2. insulating resin composition according to claim 1 is characterized in that, the total weight 100 weight % with respect to above-mentioned polyurethane (X) contain epoxy resin (B) 3～200 weight %.
3. insulating resin composition according to claim 1 and 2 is characterized in that, the total weight 100 weight % with respect to above-mentioned polyurethane (X) and epoxy resin (B) contain organic resin filler (C) 0.1～200 weight %.
4. according to each described insulating resin composition in the claim 1～3, it is characterized in that organic resin filler (C) is at least a kind the filler that is selected from urea resin system, melmac system, polyurethane resin system and benzoguanamine resin system.
5. according to each described insulating resin composition in the claim 1～4, it is characterized in that polyol compound (a) is to react the PEPA that is modulated into terephthalic acid (TPA) and/or M-phthalic acid as sour composition and glycol at least.
6. according to each described insulating resin composition in the claim 1～5, it is characterized in that, and then to contain fusing point be more than 40 ℃ and the wax below 180 ℃ (D).
7. insulating resin composition according to claim 6 is characterized in that, wax (D) is N, N '-ethylidene-bis-stearamides.
8. flexible printed wiring board, it is characterized in that, the insulating barrier that is arranged on the conductor layer is formed by each described insulating resin composition in the claim 1～7, and described conductor layer is arranged at least one surface of thermoplastic resin base material of flexible printed wiring board.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007142813A JP2008202019A (en) | 2007-01-25 | 2007-05-30 | Insulating resin composition |
| JP142813/2007 | 2007-05-30 | ||
| PCT/JP2008/059998 WO2008146908A1 (en) | 2007-05-30 | 2008-05-30 | Insulating resin composition |
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| CN101682999A true CN101682999A (en) | 2010-03-24 |
| CN101682999B CN101682999B (en) | 2011-05-18 |
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| CN (1) | CN101682999B (en) |
| TW (1) | TWI433891B (en) |
| WO (1) | WO2008146908A1 (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370389A (en) * | 2011-01-21 | 2013-10-23 | 东洋油墨Sc控股株式会社 | Adhesive agent composition and laminated body |
| CN105492534A (en) * | 2013-09-26 | 2016-04-13 | 东洋纺株式会社 | Polyurethane resin composition and adhesive composition, laminate, and printed wiring board using same |
| CN110819100A (en) * | 2019-11-15 | 2020-02-21 | 安徽德科科技有限公司 | High-thermal-stability circuit board material and preparation method thereof |
| CN112740837A (en) * | 2018-10-31 | 2021-04-30 | 三井化学株式会社 | Bendable wiring substrate, stretchable wiring substrate, and electronic device obtained from the same |
| CN114716777A (en) * | 2020-12-22 | 2022-07-08 | 广东生益科技股份有限公司 | Transparent resin composition, flexible copper clad laminate containing same and application thereof |
| CN114901758A (en) * | 2019-12-25 | 2022-08-12 | 京瓷株式会社 | Insulating resin |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6619757B2 (en) * | 2015-02-09 | 2019-12-11 | 株式会社有沢製作所 | Low dielectric resin composition |
| JP6815750B2 (en) * | 2016-05-17 | 2021-01-20 | 株式会社カネカ | Manufacturing method of thermosetting resin composition and its use |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001179111A (en) * | 1999-10-14 | 2001-07-03 | Nippon Steel Corp | Metallic carrier for automobile exhaust gas cleaning catalyst and its manufacturing method |
| JP2003133701A (en) * | 2001-10-24 | 2003-05-09 | Sekisui Chem Co Ltd | Resin-covered circuit board and protecting method thereof |
| WO2007032463A1 (en) * | 2005-09-16 | 2007-03-22 | Toyo Ink Manufacturing Co., Ltd. | Adhesive composition, adhesive sheet using same, and use of those |
| JP2007119599A (en) * | 2005-10-28 | 2007-05-17 | Toyo Ink Mfg Co Ltd | Urethane adhesive |
-
2008
- 2008-05-30 WO PCT/JP2008/059998 patent/WO2008146908A1/en active Application Filing
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103370389A (en) * | 2011-01-21 | 2013-10-23 | 东洋油墨Sc控股株式会社 | Adhesive agent composition and laminated body |
| CN103370389B (en) * | 2011-01-21 | 2014-12-03 | 东洋油墨Sc控股株式会社 | Adhesive agent composition and laminated body |
| CN105492534A (en) * | 2013-09-26 | 2016-04-13 | 东洋纺株式会社 | Polyurethane resin composition and adhesive composition, laminate, and printed wiring board using same |
| CN105492534B (en) * | 2013-09-26 | 2018-09-21 | 东洋纺株式会社 | Polyurethane resin composition and the adhesive composite, laminated body, printed wiring board for using it |
| CN112740837A (en) * | 2018-10-31 | 2021-04-30 | 三井化学株式会社 | Bendable wiring substrate, stretchable wiring substrate, and electronic device obtained from the same |
| CN110819100A (en) * | 2019-11-15 | 2020-02-21 | 安徽德科科技有限公司 | High-thermal-stability circuit board material and preparation method thereof |
| CN114901758A (en) * | 2019-12-25 | 2022-08-12 | 京瓷株式会社 | Insulating resin |
| CN114716777A (en) * | 2020-12-22 | 2022-07-08 | 广东生益科技股份有限公司 | Transparent resin composition, flexible copper clad laminate containing same and application thereof |
| CN114716777B (en) * | 2020-12-22 | 2023-07-11 | 广东生益科技股份有限公司 | Transparent resin composition, flexible copper-clad plate containing same and application of transparent resin composition |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI433891B (en) | 2014-04-11 |
| CN101682999B (en) | 2011-05-18 |
| WO2008146908A1 (en) | 2008-12-04 |
| TW200909518A (en) | 2009-03-01 |
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