CN101343345A - Polyurethane resin, heat solidifying resin composition containing the same and its solidifying article - Google Patents
Polyurethane resin, heat solidifying resin composition containing the same and its solidifying article Download PDFInfo
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- CN101343345A CN101343345A CNA200810130575XA CN200810130575A CN101343345A CN 101343345 A CN101343345 A CN 101343345A CN A200810130575X A CNA200810130575X A CN A200810130575XA CN 200810130575 A CN200810130575 A CN 200810130575A CN 101343345 A CN101343345 A CN 101343345A
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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
- C08G18/54—Polycondensates of aldehydes
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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
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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
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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
- C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
- C08G18/72—Polyisocyanates or polyisothiocyanates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
- C08J3/247—Heating methods
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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
- C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
- C08L75/04—Polyurethanes
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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
Abstract
Provided is a polyurethane resin, a thermosetting resin composition including the same and a condensate thereof, forming into a flexible overlay film with excellent sealing performance, flexibility resistance, low warping performance, solder thermal endurance, chemigold plating endurance, electric insulativity and the like, providing a peotective film made of condensate in low cost, a flexible printed plate board of an insulation layer and the like. The polyurethane resin has a phenolic hydroxyl group, preferably has one phenolic hydroxyl group through reacting (a) polyisocyanate, (b) the compound with more than two alcoholic hydroxyl groups and (c) the compound with one alcoholic hydroxyl group and more than one phenolic hydroxyl group to be guided to a terminal. The thermosetting resin composition includes polyurethane resin with the phenolic hydroxyl group and thermoset compound, preferably epoxy resin. Preferably a curing accelerant is included.
Description
Technical field
The present invention relates to be suitable for to form adaptation with base material; folding resistance; low warpage properties; the scolding tin thermotolerance; the gold-plated property of chemically-resistant; the flexible overlay film that electrical insulating property etc. are excellent; have the urethane resin of phenolic hydroxyl group and contain its compositions of thermosetting resin; and the protective membrane of making by its cured article; insulating material; manufacturing at printed-wiring board (PWB); particularly in the manufacturing of flexible print circuit board; band carries the solder resist that uses in the manufacturing of encapsulation; protective membranes such as interlayer dielectric; insulation layer, or backlight liquid crystal display; the backplate protective membrane of the electroluminescence panel that uses in the indicating meter that demonstration information is used etc.; mobile phone; clock and watch; the protective membrane of the display panel of automobile audio etc.; IC; in the super LSI sealing materials etc. is useful.
Background technology
Carry at flexible print circuit board, band that employed solder resist has following type in the manufacturing of encapsulation: the type of using the mould consistent to be called as to paste with caking agent again behind the Kapton stamping-out of coverlay film with pattern, by silk screen printing be coated with the welding resistance printing ink that can form ultraviolet hardening with flexible overlay film, thermohardening type type, form the type of liquid photoresist printing ink with flexible overlay film.
But, coverlay film since with the tracing ability of Copper Foil on have problems, therefore can not form pattern with high precision.On the other hand, ultraviolet hardening welding resistance printing ink and liquid photoresist printing ink, with base material be that the adaptation of polyimide is poor, can't obtain flexible fully.In addition, because the cooling contraction after the cure shrinkage of welding resistance printing ink and the curing is big, thereby warpage takes place, this becomes problem.
In addition, existing thermohardening type welding resistance printing ink, having disclosed in Japanese special fair 5-75032 number (patent documentation 1) is the epoxy resin etching resisting ink composition of necessary composition with Resins, epoxy and dibasic acid anhydride, but be adjusted into and giving under the flexible situation formed overlay film, with base material be the adaptation variation of polyimide, the problem that exists anti-plating, PCT patience and scolding tin thermotolerance to reduce.
Therefore, TOHKEMY 2006-117922 number (patent documentation 2) proposed following compositions of thermosetting resin, it contains (A) urethane, has 2 above carboxyls in its 1 molecule and has ammonia ester bond that the reaction by polycarbonate diol (a) and polyisocyanates (b) forms and (B) thermoset composition.By such carboxyl urethane resin that contains is used in combination with Resins, epoxy as the thermoset composition, can solve the problem of aforesaid existing welding resistance printing ink, but also exist needs to improve part aspect the characteristics such as scolding tin thermotolerance.
Patent documentation 1: Japan's special fair 5-75032 communique (claims)
Patent documentation 2: TOHKEMY 2006-117922 communique (claims)
Summary of the invention
The problem that invention will solve
Therefore; the objective of the invention is to solve aforementioned such prior art problems; provide a kind of and be suitable for forming with the urethane resin of the flexible overlay film of excellences such as the gold-plated property of adaptation, folding resistance, low warpage properties, scolding tin thermotolerance, chemically-resistant of base material, electrical insulating property and contain its compositions of thermosetting resin, provide at lower cost thus to be formed with protective membrane, printed-wiring board (PWB), the particularly flexible print circuit board of insulation layer, the band made by its cured article and to carry parts or goods such as encapsulation.
The means that are used to deal with problems
In order to realize aforementioned purpose, according to the present invention, can provide a kind of urethane resin, it is characterized in that having phenolic hydroxyl group.Can provide a kind of in addition and have the urethane resin of carboxyl and phenolic hydroxyl group, more preferably provide a kind of urethane resin that has phenolic hydroxyl group endways.
Further, in the ideal mode, can provide a kind of making (a) polyisocyanates, (b) to have the compound of 2 above alcoholic extract hydroxyl groups and (c) have the compound reaction of 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in 1 molecule and the urethane resin that obtains.
In addition,, can provide a kind of compositions of thermosetting resin, it is characterized in that, contain that (A) is aforementioned to have the urethane resin of phenolic hydroxyl group and (B) heat-curable compounds according to the present invention.
In the ideal mode, above-mentioned heat-curable compounds (B) is a Resins, epoxy, in addition, also preferably contains (C) curing catalyst.Mineral filler and/or organic filler can also be contained, as required, organic solvent can also be contained.
Further, according to the present invention, can provide a kind of aforementioned compositions of thermosetting resin is solidified and the cured article that obtains, part or all printed-wiring board (PWB) that is covered by this cured article on surface.
The invention effect
Urethane resin of the present invention is characterized in that, has phenolic hydroxyl group or has carboxyl and phenolic hydroxyl group.Its result, therefore the functional group of this carboxyl, phenolic hydroxyl group and the heat-curable compounds epoxy group(ing) generation crosslinking reaction of Resins, epoxy for example during thermofixation can improve characteristics such as scolding tin thermotolerance.
Urethane resin of the present invention is characterized in that, further preferably has phenolic hydroxyl group endways.Thus, be present in terminal phenolic hydroxyl group and compare with the phenolic hydroxyl group in being present in main chain, itself and the reactivity raising of epoxy group(ing) etc. can further improve characteristics such as scolding tin thermotolerance.
In addition, urethane resin of the present invention, the ideal mode obtains for the compound reaction that makes (a) polyisocyanates, (b) and have the compound of 2 above alcoholic extract hydroxyl groups and (c) have 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in 1 molecule.The urethane resin of Huo Deing can improve characteristics such as scolding tin thermotolerance as described above owing to have phenolic hydroxyl group endways like this.
Therefore, excellent flexible overlay films such as the gold-plated property of adaptation, folding resistance, low warpage properties, scolding tin thermotolerance, chemically-resistant of suitable formation of urethane resin of the present invention and base material, electrical insulating property.
Among the present invention; contain this simultaneously and have phenolic hydroxyl group or also have the urethane resin of carboxyl and the compositions of thermosetting resin of heat-curable compounds, it is useful that its flexible print circuit board as flexible excellence, band carry in the manufacturing of encapsulation protective membrane, dielectric resin material such as employed solder resist.In addition, the overlay film that is obtained by such compositions of thermosetting resin is because therefore warpage not after the thermofixation carries an encapsulation installation parts or a chip to flexible print circuit board, band easily.Therefore, compositions of thermosetting resin of the present invention can form the flexible protective membrane of various characteristics excellences such as adaptation, folding resistance, low warpage properties, the gold-plated property of chemically-resistant, scolding tin thermotolerance, electrical insulating property with low-cost high productivity ground.
Description of drawings
Fig. 1 is the chart that the IR of the urethane resin with phenolic hydroxyl group of manufacturing in the expression synthesis example 1 composes.
Embodiment
The inventor is in order to solve foregoing problems, further investigate, found that urethane resin, more preferably make (a) polyisocyanates, (b) have the compound of 2 above alcoholic extract hydroxyl groups and (c) have the compound reaction of 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in 1 molecule and the urethane resin that obtains, have phenolic hydroxyl group with phenolic hydroxyl group, it is when thermofixation, the epoxy group(ing) generation crosslinking reaction of the functional group of this phenolic hydroxyl group and heat-curable compounds, for example Resins, epoxy can improve characteristics such as scolding tin thermotolerance.Usually, it is low more that the cross-linking density of resin becomes, and that formed overlay film flexible becomes is big more, the warpage of the overlay film after the thermofixation will tail off.But cross-linking density reduces, and characteristics such as the scolding tin thermotolerance of the overlay film that is obtained, anti-plating, chemical proofing also reduce easily.The present invention is by importing phenolic hydroxyl group to urethane resin, particularly by using the compound (c) that has 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in 1 molecule to import phenolic hydroxyl group endways as one of moiety of urethane resin, can these conflicting characteristics of balance, improve the characteristics such as scolding tin thermotolerance of gained overlay film.
Below, each composition that has the urethane resin of phenolic hydroxyl group and contain its compositions of thermosetting resin of the present invention is elaborated.
At first, urethane resin of the present invention (A) is preferably and makes polyisocyanates (a), have the compound (b) of 2 above alcoholic extract hydroxyl groups and also play to react the compound (c) that has 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in aforementioned 1 molecule that stops the agent effect thereby react and have the urethane resin that is directed to terminal phenolic hydroxyl group, comprise following urethane resin in addition, that is, make polyisocyanates (a) and have compound (b) reaction of 2 above alcoholic extract hydroxyl groups and obtain, imported the urethane resin of phenolic hydroxyl group at molecular side chain as this compound (b) with compound with phenolic hydroxyl group and 2 above alcoholic extract hydroxyl groups; Perhaps use the urethane resin etc. have the compound of carboxyl and 2 above alcoholic extract hydroxyl groups and to have imported carboxyl at molecular side chain.In the latter's urethane resin, as terminal sealing agent (reaction stops agent), in can using above-mentioned 1 molecule, have the compound (c) of 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group, can also use monohydroxy compounds such as fatty alcohol, monohydroxy list (methyl) acrylic compound, having alcoholic extract hydroxyl group, amino, sulfydryl etc. can stop agent with the existing known various reactions such as monocarboxylic acid that isocyanate group is carried out the functional group of addition reaction or condensation reaction.
Aforementioned urethane resin (A) for example is under the situation of aforementioned ideal urethane resin, can once the compound (c) that has 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in polyisocyanates (a), the compound (b) with 2 above alcoholic extract hydroxyl groups and 1 molecule be mixed and make its reaction, also can make above-mentioned polyisocyanates (a) and polyvalent alcohol (b) reaction, then make also to play and react compound (c) reaction that has 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in above-mentioned 1 molecule that stops the agent effect.In addition, under the situation of aforesaid other urethane resin, also can once polyisocyanates (a), the compound (b) with phenolic hydroxyl group and/or carboxyl and 2 above alcoholic extract hydroxyl groups and reaction be stopped the agent mixing and make its reaction, but viewpoint from the molecular weight adjustment, preferably make the reaction of above-mentioned polyisocyanates (a) and polyvalent alcohol (b), then stop the agent reaction with reaction again.
Previous reaction is carried out under catalyst-free, but in order to improve speed of response, preferably is heated to 70～100 ℃ by mixing under room temperature～100 ℃.In addition, the reaction ratio (mol ratio) of above-mentioned (a)～(c) composition is suitably for (a): (b)=1: 1～2: 1, preferred 1: 1～1.5: 1, (a+b): (c)=1: 0.01～0.5, preferred 0.02～0.3 ratio.
Aforementioned polyisocyanates (a) can use existing known various polyisocyanates, is not limited to specific compound.The object lesson of polyisocyanates (a) for example can enumerate 2, the 4-tolylene diisocyanate, 2, the 6-tolylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, MDI, the o-Xylol vulcabond, m xylene diisocyanate, the p-Xylol vulcabond, hydrogenation o-Xylol vulcabond, the hydrogenation m xylene diisocyanate, hydrogenation p-Xylol vulcabond, the vulcabond dicyclohexyl methyl hydride, trimethyl hexamethylene diisocyanate, hexanaphthene-1, the 3-dimethylene diisocyanate, hexanaphthene-1, the 4-dimethylene diisocyanate, 1, vulcabond such as 5-naphthalene diisocyanate.Particularly, preferred tolylene diisocyanate, trimethyl hexamethylene diisocyanate.Use under the situation of these vulcabond, can obtain the cured article of scolding tin excellent heat resistance.
Then, compound (b) with 2 above alcoholic extract hydroxyl groups can use existing known various polyvalent alcohols, be not limited to specific compound, be fit to use polycarbonate-based polyvalent alcohol, polyethers such as polycarbonate diol be polyvalent alcohol, polyester be polyvalent alcohol, polyolefin polyvalent alcohol, acrylic acid series multiple alcohol, dihydroxyphenyl propane be the alkylene oxide adducts glycol, have carboxyl and alcoholic extract hydroxyl group compound, have the compound of phenolic hydroxyl group and alcoholic extract hydroxyl group etc.Polycarbonate diol can list: comprise from the repeating unit of straight chain shape aliphatic diol more than a kind or 2 kinds as the polycarbonate diol (b-1) of structural unit, comprise from the repeating unit of ester ring type glycol more than a kind or 2 kinds as the polycarbonate diol (b-2) of structural unit or comprise from the repeating unit of straight chain shape aliphatic diol and ester ring type glycol two sides' glycol polycarbonate diol (b-3) as structural unit.In addition, use compound (b-4) and use under the situation of compound (b-5) with phenolic hydroxyl group and 2 above alcoholic extract hydroxyl groups etc., can make molecular side chain have functional group's (phenolic hydroxyl group, carboxyl) with carboxyl and 2 above alcoholic extract hydroxyl groups.These compounds (b-1)～(b-5) can use separately or mix more than 2 kinds and use.
Can enumerate for example by 1 as the object lesson of the polycarbonate diol (b-1) of structural unit aforementioned comprising from the repeating unit of straight chain shape aliphatic diol more than a kind or 2 kinds, 6-hexylene glycol deutero-polycarbonate diol, by 1,5-pentanediol and 1,6-hexylene glycol deutero-polycarbonate diol, by 1,4-butyleneglycol and 1,6-hexylene glycol deutero-polycarbonate diol, by the 3-methyl isophthalic acid, 5-pentanediol and 1,6-hexylene glycol deutero-polycarbonate diol etc.
Aforementioned containing from the repeating unit of ester ring type glycol more than a kind or 2 kinds can enumerate for example by 1,4 cyclohexane dimethanol deutero-polycarbonate diol etc. as the object lesson of the polycarbonate diol (b-2) of structural unit.
Can enumerate for example by 1 as the object lesson of the polycarbonate diol (b-3) of structural unit aforementioned comprising from the repeating unit of straight chain shape aliphatic diol and ester ring type glycol two sides' glycol, 6-hexylene glycol and 1,4 cyclohexane dimethanol deutero-polycarbonate diol etc.
Aforementioned object lesson with compound (b-4) of carboxyl and 2 above alcoholic extract hydroxyl groups can be enumerated dimethylol propionic acid, dimethylolpropionic acid etc.By using these compounds, can easily in urethane resin, import carboxyl with carboxyl and 2 above alcoholic extract hydroxyl groups.
Aforementioned object lesson with compound (b-5) of phenolic hydroxyl group and 2 above alcoholic extract hydroxyl groups can be enumerated 6-hydroxy-5-methyl base-1, the 3-xylyl alcohol, 2,4-two (methylol)-6-cyclohexylphenol, 3,3 '-methylene-bis (2-hydroxy-5-methyl base-phenylcarbinol), 4,4 '-(1-methyl ethylidene) two [2-methyl-6-methylolphenol], 4,4 '-[1,4-phenylene two (1-methyl ethylidene)] two [2-methyl-6-methylolphenol], 2-hydroxyl-5-fluoro-1, the 3-xylyl alcohol, 4,4 '-methylene-bis (2-methyl-6-methylolphenol), 4,4 '-methylene-bis (2,5-dimethyl-3-methylolphenol), 4,4 '-cyclohexylidene two (2-methyl-6-methylolphenol), 4,4 '-cyclohexylidene two (2-cyclohexyl-6-methylolphenol), 2, two [(2-hydroxyl-3-methylol-5-aminomethyl phenyl) the methyl]-4-methylphenols of 6-, 2-hydroxyl-5-ethyl-1, the 3-xylyl alcohol, 2-hydroxyl-4,5-dimethyl-1, the 3-xylyl alcohol, 2-hydroxyl-5-(1-methyl-propyl)-1, the 3-xylyl alcohol, 4-(1, the 1-dimethyl ethyl)-2-hydroxyl-1, the 3-xylyl alcohol, 2-hydroxyl-5-cyclohexyl-1, the 3-xylyl alcohol, 2-hydroxyl-5-(1,1,3, the 3-tetramethyl butyl)-1, the 3-xylyl alcohol, 2, two [(the 4-hydroxyls-3-methylol-2 of 6-, the 5-3,5-dimethylphenyl) methyl]-3, the 4-xylenol, 2, two [(the 4-hydroxyls-3-methylol-2 of 6-, the 5-3,5-dimethylphenyl) methyl]-the 4-cyclohexylphenol, 2-hydroxyl-1,3,5-benzene three methyl alcohol, 3,5-dimethyl-2,4, the 6-tri hydroxy methyl phenol, 4,4 ', 4 "-and ethylidine three (2-methyl-6-methylolphenol); 2; 3; 5,6-four (methylol)-1,4-Benzenediol; 4; 4 '-methylene-bis [2, two (methylol) phenol of 6-] etc.By using these compounds, can easily in urethane resin, import phenolic hydroxyl group with phenolic hydroxyl group and 2 above alcoholic extract hydroxyl groups.
The aforementioned trend that has low warpage properties, flexible excellence from the repeating unit of straight chain shape aliphatic diol as the polycarbonate diol of structural unit that contains.In addition, contain the trend that has crystallinity raising, anti-zinc-plated property, scolding tin excellent heat resistance from the repeating unit of ester ring type glycol as the polycarbonate diol of structural unit.From above viewpoint, these polycarbonate diols can make up 2 kinds with on use, or use and to contain from the repeating unit of straight chain shape aliphatic diol and ester ring type glycol two sides' glycol polycarbonate diol as structural unit.In order to show the balance of low warpage properties, flexible and scolding tin thermotolerance, anti-zinc-plated property better, the copolymerization ratio of preferably using straight chain shape aliphatic diol and ester ring type glycol is 3: 7～7: 3 polycarbonate diol by quality ratio.
Aforementioned polycarbonate diol preferred number average molecular weight is 200～5000, but it is that preferred number average molecular weight is 400～2000 under 3: 7～7: 3 the situation by quality ratio as the copolymerization ratio of structural unit, straight chain shape aliphatic diol and ester ring type glycol that polycarbonate diol contains from the repeating unit of straight chain shape aliphatic diol and ester ring type glycol.
Aforementioned dihydroxyphenyl propane is the alkylene oxide adducts ethylene oxide adduct that can enumerate dihydroxyphenyl propane, propylene oxide adduct, butylene oxide ring affixture etc., propylene oxide adducts of preferred dihydroxyphenyl propanes in the middle of these.
The compound (c) that has 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in aforementioned 1 molecule uses in order to import phenolic hydroxyl group in urethane, also play effect, particularly so long as have in the molecule and can just can play the effect that reaction stops agent with 1 alcoholic extract hydroxyl group of isocyanate reaction and the compound of phenolic hydroxyl group as the terminal sealing agent of urethane.The object lesson of such compound (c) can list for example methylolphenol, methylol cresols, methylol-DI-tert-butylphenol compounds, p-hydroxybenzene-2-methyl alcohol, p-hydroxybenzene-3-propyl alcohol, p-hydroxybenzene-4-butanols, hydroxyethyl cresols, 2,6-dimethyl-4-methylolphenol, 2,4-dimethyl-6-methylolphenol, 2,3,6-trimethylammonium-4-methylolphenol, 2-cyclohexyl-4-methylol-5-methylphenol, 4-methyl-6-methylol benzene-1, the 2-glycol, 4-(1, the 1-dimethyl ethyl)-and 6-methylol benzene-1, hydroxyalkyl phenol or hydroxyalkyl cresols such as 2-glycol; Para Hydroxy Benzoic Acid, hydroxy phenyl M-nitro benzoic acid or hydroxyphenoxy phenylformic acid etc. have the carboxylate of the phenol that contains carboxyl substituent and ethylene glycol, propylene glycol, Diethylene Glycol, triethylene glycol, dipropylene glycol, tripropylene glycol etc.; The monocycle oxidative ethane affixture of bis-phenol, the monocycle Ethylene Oxide affixture of bis-phenol, p-hydroxyphenylethanol etc., but be not limited to these.These compounds (c) can use separately or mix more than 2 kinds and use.
Aforementioned weight-average molecular weight with urethane resin (A) of phenolic hydroxyl group is preferably 500～100000, and further preferred 8000～50000.Here, weight-average molecular weight is the value in polystyrene by gel permeation chromatography.Have the weight-average molecular weight less than 500 of the urethane resin (A) of phenolic hydroxyl group, damage the stretchiness of cured film, flexible and intensity sometimes, on the other hand, surpass 100000 words, solvability to solvent reduces, even dissolving viscosity is also too high, so the restriction of use aspect is bigger.
In the compositions of thermosetting resin of the present invention, the heat-curable compounds (B) that cooperates with aforementioned urethane resin (A) with phenolic hydroxyl group is fit to use that to have in 1 molecule more than 2 to be Resins, epoxy, the oxetane compound of the epoxy group(ing), oxetanyl etc. of phenolic hydroxyl group (or the also and carboxyl) reaction of urethane resin with aforementioned (A) composition, special preferred epoxy.
The object lesson of Resins, epoxy can list for example bisphenol A type epoxy resin, bisphenol-A epoxy resin, brominated bisphenol a type epoxy resin, bisphenol f type epoxy resin, bisphenol-s epoxy resin, phenolic resin varnish type epoxy resin, phenol novolak type epoxy resin, the cresols phenolic resin varnish type epoxy resin, N-Racemic glycidol type Resins, epoxy, the phenolic resin varnish type epoxy resin of dihydroxyphenyl propane, di-cresols type Resins, epoxy, bisphenol-type epoxy resin, chelating type Resins, epoxy, oxalic dialdehyde type Resins, epoxy, contain aminoepoxy resin, rubber modified epoxy resin, the Dicyclopentadiene (DCPD) phenol aldehyde type epoxy resin, the 2-glycidyl phthalide resin, the heterocyclic ring epoxy resins, four Racemic glycidol xylyl ethane resin, the silicone modified epoxy, 6-caprolactone modified epoxy etc.In addition, can also use in order to give flame retardant resistance in its structure to import halogen, the equiatomic Resins, epoxy of phosphorus such as chlorine, bromine are arranged.
In the compositions of thermosetting resin of the present invention, aforementioned heat-curable compounds (B) can use separately or use with the form of the mixture more than 2 kinds.Promptly have the urethane resin of phenolic hydroxyl group with respect to 100 mass parts aforementioned (A) composition, the use level of heat-curable compounds (B) is expected for the ratio of 5～150 mass parts, preferred 10～80 mass parts.The words of less than 5 mass parts; the inadequate situation of scolding tin thermotolerance that has the curing overlay film of compositions of thermosetting resin; on the other hand, surpass 150 mass parts, each characteristic, the particularly electrical insulating property during as the insulating protective film of flexible print circuit board (FPC) has the trend of deterioration.
The curing catalyst that uses among the present invention (C) is the material that is used to promote the thermofixation reaction, uses in order further to improve characteristic such as adaptation, chemical proofing, thermotolerance.The object lesson of such curing catalyst can be enumerated imidazoles and derivative thereof (for example, four countries change into 2MZ, 2E4MZ, C 11Z, C17Z, 2PZ, 1B2MZ, 2MZ-CN, 2E4MZ-CN, C11Z-CN, 2PZ-CN, 2PHZ-CN, 2MZ-CNS, 2E4MZ-CNS, 2PZ-CNS, 2MZ-AZINE, 2E4MZ-AZINE, C11Z-AZINE, 2MA-OK, 2P4MHZ, 2PHZ, the 2P4BHZ of industry (strain) system etc.); Guanamines such as acetoguanamine, benzoguanamine class; Polyamines classes such as diaminodiphenyl-methane, m-phenylenediamine, m-xylene diamine, diamino diphenyl sulfone, Dyhard RU 100, urea, urea derivative, melamine, polynary hydrazides; These organic acid salt and/or epoxy adduct; The amine complex of boron trifluoride; Ethyl diamino-s-triazine, 2,4-diamino-s-triazine, 2,4-diamino-pyrrolotriazine derivatives classes such as 6-xylyl-s-triazine; Trimethylamine, trolamine, N, N-dimethyl octylame, N-benzyl dimethyl amine, pyridine, N-methylmorpholine, six (N-methyl) melamine, 2,4, amines such as 6-three (dimethylamino phenol), tetramethyl guanidine, Metha Amino Phenon; Polyphenols such as polyvinylphenol, poly-ethylene bromide base phenol, phenolic varnish, alkyl phenolic varnish; Organic phosphine classes such as tributylphosphine, triphenylphosphine, three-2-cyano ethyl phosphine; Three normal-butyls (2, phosphonium salt classes such as 5-dihydroxy phenyl) phosphonium bromide, phosphonium hexadecanyl-3-butyl chloride; Quaternary ammonium salts such as phenmethyl trimethyl ammonium chloride, phenyl tributyl ammonium chloride; Multi-anhydride; Phenylbenzene iodine a tetrafluoro borate, triphenylsulfonium hexafluoro antimonate, 2,4, the light cationic polymerisation catalysts such as OPTOMER SP-170 of the Irgacure 261 of 6-triphenyl thiapyran inner salt (Thiopyrylium) hexafluorophosphate, Ciba Geigy corporate system, rising sun electrification (strain) system; The phenylethylene-maleic anhydride resin; The known curing catalyst commonly used or the solidifying agent classes such as reaction with same mole thing of organic multiple isocyanates such as the reaction with same mole thing of phenyl isocyanate and dimethyl amine, tolylene diisocyanate, isophorone diisocyanate and dimethyl amine.
These curing catalysts (C) can use separately or mix more than 2 kinds and use.Curing catalyst (C) and nonessential use are wanted to promote can preferably use in the scope of 0.1～25 mass parts with respect to the aforementioned heat-curable compounds of 100 mass parts (B) under the solidified situation especially.Surpass 25 mass parts, the sublimability composition of its cured article increases, so not preferred.
Compositions of thermosetting resin of the present invention can for example dispersion mill (dispersion mill), kneader, three roller roller mills, ball mill etc. dissolve or disperse and make with mixing machine with aforementioned urethane resin (A), heat-curable compounds (B) and curing catalyst as required (C) with phenolic hydroxyl group.At this moment, can use epoxy group(ing), phenolic hydroxyl group are the inert solvent.The preferred organic solvent of such inert solvent.
Organic solvent is in order to make aforementioned urethane resin (A), heat-curable compounds (B) with phenolic hydroxyl group and to dissolve easily or disperse or using in order to be adjusted to the viscosity that is suitable for being coated with.Organic solvent can be enumerated for example toluene, dimethylbenzene, ethylbenzene, oil of mirbane, hexanaphthene, isophorone, diethylene glycol dimethyl ether, ethylene glycol diethyl ether, carbitol acetate, 1-Methoxy-2-propyl acetate, the propylene-glycol ethyl ether acetic ester, dipropylene glycol methyl ether acetate, the diethylene glycol ether acetic ester, the methoxypropionic acid methyl esters, the methoxy propyl acetoacetic ester, the ethoxy-propionic acid methyl esters, ethoxyl ethyl propionate, vinyl acetic monomer, n-butyl acetate, isoamyl acetate, ethyl lactate, acetone, methylethylketone, pimelinketone, N, dinethylformamide, N,N-dimethylacetamide, N-Methyl pyrrolidone, gamma-butyrolactone, dimethyl sulfoxide (DMSO), chloroform and methylene dichloride etc.The use level of organic solvent can suitably be set according to the viscosity of expecting.
In order to improve the adaptation with base materials such as polyimide, in case of necessity, can also contain known sulfhydryl compound commonly used in the compositions of thermosetting resin of the present invention.Sulfhydryl compound can be enumerated 2 mercaptopropionic acid, trimethylolpropane tris (2-sulfo-propyl ester), 2 mercapto ethanol, 2-aminothiophenol, 3-sulfydryl-1,2, and 4-triazole, 3-sulfydryl-propyl trimethoxy silicane etc. contains mercaptosilane coupling agents etc.These both can use separately separately also can make up more than 2 kinds and use.It is the following scopes of 10 mass parts that its use level is suitably for the aforementioned urethane resin (A) with phenolic hydroxyl group of per 100 mass parts.The use level of sulfhydryl compound exceeds under the situation of above-mentioned scope, epoxy group(ing) (with epoxy reaction), the cross-linking density that consumes the necessary aforementioned epoxy resins of crosslinking reaction is descended, so not preferred.
In order to improve characteristics such as adaptation, hardness, thermotolerance, in case of necessity, can also contain inorganic and/or organic filler in the compositions of thermosetting resin of the present invention.Mineral filler can list barium sulfate, lime carbonate, barium titanate, silicon-dioxide, soft silica, talcum, clay, mica powder etc., and organic filler can list silica flour, nylon powder, fluorine powder (Fluorine Powder) etc.In the above-mentioned filler, what agent of low hygroscopicity, low volumetric expansion were excellent especially is silicon-dioxide.Though silicon-dioxide its dissolve, crystallinity, even these mixture is also no problem, but undertaken under the situation of surface-treated silicon-dioxide by coupling agent etc., can improve electrical insulating property, so preferred especially.The median size of filler be preferably 25 μ m following, more preferably 10 μ m following, further below the preferred 3 μ m.It is below 300 mass parts that the use level of these mineral fillers and/or organic filler is suitably for the aforementioned urethane resin (A) with phenolic hydroxyl group of per 100 mass parts, the ratio of preferred 5～150 mass parts.The use level of filler surpasses aforementioned proportion, and the folding resistance of curing overlay film will reduce and not preferred.
Further, in the compositions of thermosetting resin of the present invention, only otherwise damage effect of the present invention, can also add other additive, tinting material beyond the aforementioned composition.Additive can be enumerated thickening materials such as asbestos, ORBEN, wilkinite, and silicone-based, fluorine are defoamer, flow agent, fiber-reinforced materials such as glass fibre, charcoal fiber, boron nitride fibre etc.; Tinting material can enumerate that phthalocyanine blue, phthalocyanine green, iodine are green, dual-azo yellow, titanium oxide, carbon black etc.Further, can add known hot stopper commonly used, UV light absorber, silane coupling agent, softening agent, whipping agent, fire retardant, static inhibitor, anti-aging agent, antibacterial mildew inhibitor etc. as required.
Compositions of thermosetting resin with above such composition can also be used for various forms, purposes such as dry film or prepreg except being coated with existing known the whole bag of tricks such as method, rolling method, spraying method and dip coating is applied on the printed-wiring board (PWB) by curtain.Can use all kinds of SOLVENTS according to its using method, purposes, but according to circumstances not only can use good solvent but also can use poor solvent.
In addition; compositions of thermosetting resin of the present invention is applied to the flexible print circuit board, the band that are formed with circuit by silk screen print method and carries on encapsulation or the electroluminescence panel; the temperature that for example is heated to 120～180 ℃ to be to carry out thermofixation, can form no cure shrinkage and cooling thus and shrink excellent solder resist film, protective membranes such as the gold-plated property of warpage, the adaptation to base material, folding resistance, low warpage properties, chemically-resistant that caused, scolding tin thermotolerance, electrical insulating property.
Embodiment
Below embodiment is shown and comparative example is specifically described the present invention.In addition, be quality criteria during the no special declaration of following " part " and " % ".
Synthesis example 1
In the reaction vessel that possesses whipping appts, thermometer, condenser, add as the compound with 2 above alcoholic extract hydroxyl groups by 1,5-pentanediol and 1,6-hexylene glycol deutero-polycarbonate diol (the emerging product of space portion (strain) system, PCDL800, number-average molecular weight 800) 360g (0.45mol), dimethylolpropionic acid 81.4g (0.55mol) and as the hydroxylphenylethyl alcohol 22.1g (0.16mol) of the compound that has 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in 1 molecule.Then, adding is as the tolylene diisocyanate 187.9g (1.08mol) of polyisocyanates, be heated to 60 ℃ while stirring, stop heating, the moment that temperature in reaction vessel begins to reduce heats once more, continue down to stir at 80 ℃, confirm the absorption spectrum (2280cm of isocyanate group by infrared absorption spectrum
-1) disappear termination reaction.Then, add carbitol acetate so that solids component reaches 50wt%, acquisition contains the urethane resin with phenolic hydroxyl group (varnish A) of the thick liquid nano of thinner.The acid number of the solids component of the urethane resin of gained is 50.1mgKOH/g.The IR spectrogram of the urethane resin with phenolic hydroxyl group of gained is shown in Figure 1.
Synthesis example 2
In the reaction vessel that possesses whipping appts, thermometer, condenser, add as the compound with 2 above alcoholic extract hydroxyl groups by 1,5-pentanediol and 1,6-hexylene glycol deutero-polycarbonate diol (the emerging product of space portion (strain) system, PCDL800, number-average molecular weight 800) 360g (0.45mol), dimethylolpropionic acid 81.4g (0.55mol) and as the hydroxylphenylethyl alcohol 22.1g (0.16mol) of the compound that has 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in 1 molecule.Then, adding is as the tolylene diisocyanate 83.5g (0.48mol) and the trimethyl hexamethylene diisocyanate 111.6g (0.60mol) of polyisocyanates, be heated to 60 ℃ while stirring, stop heating, the moment that temperature in reaction vessel begins to reduce heats once more, continue down to stir at 80 ℃, confirm the absorption spectrum (2280cm of isocyanate group by infrared absorption spectrum
-1) disappear termination reaction.Then, add carbitol acetate so that solids component reaches 50wt%, acquisition contains the urethane resin with phenolic hydroxyl group (varnish B) of the thick liquid nano of thinner.The acid number of the solids component of the urethane resin that obtains is 49.2mgKOH/g.
Synthesis example 3
In the reaction vessel that possesses whipping appts, thermometer, condenser, add as the compound with 2 above alcoholic extract hydroxyl groups by 1,5-pentanediol and 1,6-hexylene glycol deutero-polycarbonate diol (the emerging product of space portion (strain) system, PCDL800, number-average molecular weight 800) 800g (1.00mol) and as the hydroxylphenylethyl alcohol 22.1g (0.16mol) of the compound that has 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in 1 molecule.Then, adding is as the tolylene diisocyanate 187.9g (1.08mol) of polyisocyanates, be heated to 60 ℃ while stirring, stop heating, the moment that temperature in reaction vessel begins to reduce heats once more, continue down to stir at 80 ℃, confirm the absorption spectrum (2280cm of isocyanate group by infrared absorption spectrum
-1) disappear termination reaction.Then, add carbitol acetate so that solids component reaches 50wt%, acquisition contains the urethane resin with phenolic hydroxyl group (varnish C) of the thick liquid nano of thinner.
Varnish D:
With Daicel Chemical Industries, Ltd., the acrylic copolymeric resin CyclomerACA Z250 of system (solids component acid number 70.0mgKOH/g) uses as varnish D.
Embodiment 1～4 and comparative example 1
Each composition shown in the table 1 is at room temperature mixed the modulation compositions of thermosetting resin with three roller roller mills according to the cooperation ratio shown in the table 1.The compositions of thermosetting resin that obtained by the thick about 15 μ m of silk screen printing coating film forming on substrate, is carried out thermofixation in 60 minutes under 150 ℃.
[table 1]
Curing overlay film to aforementioned each compositions of thermosetting resin is estimated following various characteristics according to following method.The results are shown in table 2.
(1) adaptation
Each compositions of thermosetting resin of the foregoing description 1～4 and comparative example 1 is printed onto KAPTON 200H (DU PONT-TORAY CO. by the whole face of silk screen printing respectively, the Kapton of LTD system, thickness 50 μ m) on, under 150 ℃, carry out thermofixation in 60 minutes (dry film thickness 15 μ m).The adaptation of its curing overlay film is estimated according to following benchmark based on JIS D 0202.
Zero: when tessellated number keeps fully
△: tessellated number is residual less than 100,60 when above
*: tessellated number is only residual during less than 60
(2) folding resistance
Each compositions of thermosetting resin of the foregoing description 1～4 and comparative example 1 is printed onto KAPTON 200H (DU PONT-TORAY CO. by the whole face of silk screen printing respectively, the Kapton of LTD system, thickness 50 μ m) on, under 150 ℃, carry out thermofixation in 60 minutes (dry film thickness 15 μ m).With crooked 180 ° of the curing overlay film that obtained, estimate according to following benchmark.
Zero: flawless on the curing overlay film
△: some crackles are arranged on the curing overlay film
*: crackle is arranged on the curing overlay film
(3) low warpage properties
Each compositions of thermosetting resin of the foregoing description 1～4 and comparative example 1 is printed onto KAPTON 200H (DU PONT-TORAY CO. by the whole face of silk screen printing respectively, the Kapton of LTD system, thickness 50 μ m) on, under 150 ℃, carry out thermofixation in 60 minutes (dry film thickness 15 μ m).After the cooling, the curing overlay film that is obtained is cut into 50 * 50mm, warpage is estimated according to following benchmark.
Zero: do not have warpage
△: some warpages are arranged
*: warpage is arranged
(4) the gold-plated property of chemically-resistant
With each compositions of thermosetting resin of the foregoing description 1～4 and comparative example 1 respectively pattern be printed onto on the printed-wiring board (PWB) (thickness 1.6mm), under 150 ℃, carry out thermofixation in 60 minutes and obtain test film (dry film thickness 15 μ m).Use the test film that is obtained, carry out chemical gilding, the gold-plated property of chemically-resistant is estimated according to following benchmark by the aftermentioned operation.
Zero: curing overlay film do not expand, peels off, variable color
△: curing overlay film has some expansions, peels off, variable color
*: curing overlay film expands, peels off, variable color
The chemical gilding operation:
1. degreasing: test film was flooded 3 minutes in 30 ℃ acid degreasing fluid (Nippon MacDermid Co., Inc., the 20vol% aqueous solution of Ltd. system, Metex L-5B).
2. washing: test film was flooded in flowing water 3 minutes.
3. soft etching: at room temperature test film was flooded 1 minute in the ammonium persulfate aqueous solution of 14.3wt%.
4. washing: test film was flooded in flowing water 3 minutes.
5. acid dipping: at room temperature test film was flooded 1 minute in the aqueous sulfuric acid of 10vol%.
6. washing: test film was flooded in flowing water 30 seconds～1 minute.
7. catalyzer is given: test film was flooded 3 minutes in 30 ℃ catalyzer liquid (the 10vol% aqueous solution of Meltex Inc. system, Melplate Activator 350).
8. washing: test film was flooded in flowing water 3 minutes.
9. chemical nickel plating: with test film dipping 30 minutes in 85 ℃, the nickel plating bath (MeltexInc. system, Melplate Ni-865M, the 20vol% aqueous solution) of pH=4.6.
10. acid dipping: at room temperature, test film was flooded 1 minute in the aqueous sulfuric acid of 10vol%.
11. washing: test film was flooded in flowing water 30 seconds～1 minute.
12. chemical gilding: with test film dipping 30 minutes in 85 ℃, the golden plating bath (MeltexInc. system, Aurolectroless UP 15vol%, the potassium auric cyanide 3wt% aqueous solution) of pH=6.
13. washing: test film was flooded in flowing water 3 minutes.
14. Warm Wash: test film is immersed in 60 ℃ the warm water, fully wash 3 minutes after, finish-drying removes water.
(5) scolding tin thermotolerance
With each compositions of thermosetting resin of the foregoing description 1～4 and comparative example 1 respectively pattern be printed onto on the printed-wiring board (PWB) (thickness 1.6mm), under 150 ℃, carry out thermofixation in 60 minutes (dry film thickness 15 μ m).Coating rosin is solder flux (flux) on the curing overlay film that is obtained, and floods in 10 seconds in 260 ℃ weld groove, according to following benchmark the state of curing overlay film is estimated.
Zero: curing overlay film do not expand, peels off, variable color
△: curing overlay film has some expansions, peels off, variable color
*: curing overlay film expands, peels off, variable color
(6) electrical insulating property
Each compositions of thermosetting resin of the foregoing description 1～4 and comparative example 1 is gone up to make and filmed at the polyimide substrate (Nippon Steel's chemistry (strain) system ESPANEX) of L/S=20/20 μ m respectively, under 150 ℃, carry out thermofixation in 60 minutes (dry film thickness 15 μ m).According to following benchmark the electrical insulating property of the curing overlay film that obtained is estimated.
Humidified condition: 120 ℃ of temperature, humidity 85%RH, 0.17MPa, apply voltage 60V, 100 hours
Condition determination: minute 60 seconds, apply voltage 60V
Zero: the insulating resistance value 10 behind the humidification
9The migration that Ω is above, do not have copper
△: the insulating resistance value 10 behind the humidification
9The migration that Ω is above, have copper
*: the insulating resistance value 10 behind the humidification
8The migration that Ω is following, have copper
[table 2]
By the result shown in the above-mentioned table 2 as can be known, the curing overlay film that is formed by compositions of thermosetting resin of the present invention is to the gold-plated property of adaptation, folding resistance, low warpage properties, the chemically-resistant of base material, scolding tin excellent heat resistance.In addition, insulating reliability also is good result.In contrast, use under the situation of the comparative example 1 that contains carboxy resin (varnish D) of acrylic acid copolymer system, no problem to the gold-plated property of adaptation, the chemically-resistant of base material, electrical insulating property aspect, but folding resistance and low warpage properties are poor.
Claims (12)
1. urethane resin is characterized in that, has phenolic hydroxyl group.
2. urethane resin is characterized in that, has carboxyl and phenolic hydroxyl group.
3. urethane resin according to claim 1 and 2 is characterized in that, has phenolic hydroxyl group endways.
4. urethane resin, it makes (a) polyisocyanates, (b) have the compound of 2 above alcoholic extract hydroxyl groups and (c) has the compound reaction of 1 alcoholic extract hydroxyl group and 1 above phenolic hydroxyl group in 1 molecule and obtain.
5. urethane resin according to claim 4, the reaction ratio (mol ratio) of described (a)～(c) composition is (a): (b)=and 1: 1～2: 1, (a+b): ratio (c)=1: 0.01～0.5.
6. compositions of thermosetting resin is characterized in that, contains any described urethane resin of (A) claim 1～5 and (B) heat-curable compounds.
7. compositions of thermosetting resin according to claim 6, with respect to 100 mass parts described (A) composition, the use level of described heat-curable compounds (B) is 5～150 mass parts.
8. compositions of thermosetting resin according to claim 6 is characterized in that, described heat-curable compounds (B) is a Resins, epoxy.
9. compositions of thermosetting resin according to claim 6 is characterized in that, also contains (C) curing catalyst.
10. compositions of thermosetting resin according to claim 6 is characterized in that, also contains mineral filler and/or organic filler.
11. cured article, it forms any described compositions of thermosetting resin curing of described claim 6～10.
12. printed-wiring board (PWB), part or all of its surface covered by the cured article of any described compositions of thermosetting resin of described claim 6～10.
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| JP2007181398A JP4709188B2 (en) | 2007-07-10 | 2007-07-10 | Urethane resin, thermosetting resin composition containing the same, and cured product thereof |
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| JP2007-181398 | 2007-07-10 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102352154A (en) * | 2011-10-25 | 2012-02-15 | 珠海光纬金电科技有限公司 | Antistatic insulating black ink |
| CN104559285A (en) * | 2013-10-16 | 2015-04-29 | 台湾太阳油墨股份有限公司 | Thermosetting resin composition, cured product thereof and display member using the same |
| CN109923622A (en) * | 2016-12-01 | 2019-06-21 | 昭和电工株式会社 | Transparent conductive substrate and its manufacturing method |
| TWI830430B (en) * | 2021-10-15 | 2024-01-21 | 日商信越化學工業股份有限公司 | The method for producing the polyurethane, a method for preparing a polyurethane conductive paste composition, a conductive wiring and a conductive wiring |
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| JP5552749B2 (en) * | 2009-02-25 | 2014-07-16 | 宇部興産株式会社 | Curable resin composition |
| JP5901141B2 (en) * | 2010-05-17 | 2016-04-06 | 昭和電工株式会社 | Light-emitting element mounting substrate, light-emitting element mounting substrate manufacturing method, light-emitting device, light-emitting device manufacturing method, and white resin composition |
| JP5398754B2 (en) * | 2011-02-04 | 2014-01-29 | 太陽ホールディングス株式会社 | Urethane resin, thermosetting resin composition containing the same, and cured product thereof |
| CN102675588B (en) * | 2012-05-23 | 2013-09-04 | 福建越特新材料科技有限公司 | Preparation method of antibacterial and mildew-proof TDI (toluene diisocyanate) memory polyurethane foam |
| CN104004344B (en) * | 2014-06-09 | 2016-05-18 | 天津信赛科贸有限公司 | A kind of preparation method of waterproof Embedding Material |
| JP6948196B2 (en) * | 2017-09-14 | 2021-10-13 | 株式会社クラレ | Polyurethane, polyurethane moldings for polishing layers and polishing pads |
| JP2022078861A (en) * | 2020-11-13 | 2022-05-25 | 信越化学工業株式会社 | Polyurethane, polyurethane production method, conductive paste composition, conductive wire, and method for producing conductive wire |
| EP4249461A1 (en) * | 2020-11-20 | 2023-09-27 | Shin-Etsu Chemical Co., Ltd. | Phenol compound, electroconductive paste composition, method for producing electroconductive paste composition, and electroconductive wiring line and production method therefor |
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| JPS63287947A (en) * | 1987-05-21 | 1988-11-25 | Fuji Photo Film Co Ltd | Photosensitive composition |
| EP0307666A1 (en) * | 1987-08-26 | 1989-03-22 | Ciba-Geigy Ag | Phenol-terminated polyurethanes or polyurea, and epoxy resins containing these compounds |
| JP3656771B2 (en) * | 1995-11-29 | 2005-06-08 | 日立化成工業株式会社 | Process for producing modified polyamide resin, modified polyamide resin obtained by the process, adhesive and film using the same |
| JP2003221496A (en) * | 2002-01-31 | 2003-08-05 | Toyobo Co Ltd | Viscoelastic resin composition and complex vibration- suppression material using the same |
| US8524838B2 (en) * | 2004-09-21 | 2013-09-03 | Showa Denko K.K. | Heat-curable urethane resin composition |
| JP5190976B2 (en) | 2004-09-21 | 2013-04-24 | 昭和電工株式会社 | Thermosetting resin composition using urethane resin |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102352154A (en) * | 2011-10-25 | 2012-02-15 | 珠海光纬金电科技有限公司 | Antistatic insulating black ink |
| CN102352154B (en) * | 2011-10-25 | 2014-01-15 | 珠海光纬金电科技有限公司 | Antistatic insulating black ink |
| CN104559285A (en) * | 2013-10-16 | 2015-04-29 | 台湾太阳油墨股份有限公司 | Thermosetting resin composition, cured product thereof and display member using the same |
| CN104559285B (en) * | 2013-10-16 | 2019-10-29 | 台湾太阳油墨股份有限公司 | Thermosetting resin constituent, its hardening thing and the display component using it |
| CN109923622A (en) * | 2016-12-01 | 2019-06-21 | 昭和电工株式会社 | Transparent conductive substrate and its manufacturing method |
| CN109923622B (en) * | 2016-12-01 | 2020-06-19 | 昭和电工株式会社 | Transparent conductive substrate and method for manufacturing same |
| TWI830430B (en) * | 2021-10-15 | 2024-01-21 | 日商信越化學工業股份有限公司 | The method for producing the polyurethane, a method for preparing a polyurethane conductive paste composition, a conductive wiring and a conductive wiring |
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| TW200911867A (en) | 2009-03-16 |
| JP2009019081A (en) | 2009-01-29 |
| CN101343345B (en) | 2011-11-02 |
| JP4709188B2 (en) | 2011-06-22 |
| KR100981814B1 (en) | 2010-09-13 |
| TWI392694B (en) | 2013-04-11 |
| KR20090006011A (en) | 2009-01-14 |
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