Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
  • C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
  • C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
  • C08L71/12—Polyphenylene oxides
  • C08L71/126—Polyphenylene oxides modified by chemical after-treatment
• • 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
  • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
  • C08G65/34—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from hydroxy compounds or their metallic derivatives
  • C08G65/48—Polymers modified by chemical after-treatment

Definitions

• the present invention relates to a novolac resin, an epoxy resin composition, and a cured product thereof suitable for use in electrical and electronic materials that require heat resistance and electrical properties (dielectric properties, etc.).
• Epoxy resin compositions are widely used in the fields of electrical and electronic parts, structural materials, adhesives, paints, etc. due to their workability and excellent electrical properties, heat resistance, adhesion, moisture resistance (water resistance), etc. It has been.
• poly (phenylene ether) resins are often used, and various studies have been made.
• Poly (phenylene ether) resin is characterized by its very excellent dielectric properties, but in order to embody the dielectric properties, there are very few functional groups and its low heat resistance is a problem.
• studies such as adding a functional group (a) and bifunctional (b) have been made to deal with these problems.
• (b) there is a slight improvement, but it is still insufficient.
• the present invention provides a polyvalent phenylene ether novolak resin capable of giving a cured product having excellent heat resistance while maintaining excellent dielectric properties, an epoxy resin composition containing the same, and a cured product thereof. With the goal.
• the poly (phenylene ether) resin described in (1) or (2) is an oxidized polymer of biphenols or bisphenols and phenol compounds, (1) or a polyvalent phenylene ether novolak resin described in (2),
• the cured product of the epoxy resin composition using the polyphenylene ether novolak resin of the present invention has not only high dielectric properties but also excellent heat resistance, and an insulating material for electrical and electronic parts and a laminate (print Wiring board, build-up board, etc.) and various composite materials including CFRP, adhesives, paints, etc. In particular, it is extremely useful for a semiconductor sealing material for protecting a semiconductor element.
• the polyvalent phenylene ether novolak resin of the present invention has a structure in which a resin having a poly (phenylene ether) structure is bonded via an organic group such as an alkylene group (hereinafter also referred to as a linking group or a linking group). That is, the polyvalent phenylene ether novolak resin of the present invention is a resin having a poly (phenylene ether) structure resin and a novolac resin structure.
• the resin having a poly (phenylene ether) structure is a resin described in Patent Document 1 or Patent Document 2 described above, and an oxidized polymer of xylenol or trimethylphenol is generally used.
• examples thereof include biphenols and oxidized polymers of phenol compounds such as bisphenols and 2,6-xylenol.
• the bisphenols for example, bisphenols such as bisphenol A, bisphenol F, bisphenol S, and bisphenol I can be used.
• Examples of commercially available products include PPO (registered trademark) manufactured by SABIC, and SA120, SA90-100 and the like are particularly preferable from the range of molecular weight.
• the biphenols include compounds represented by the following formula.
• each R 1 represents an independent substituent, which is a hydrogen atom, a halogen atom, an alkyl group having 1 to 3 carbon atoms, an aralkyl group, an aryl group, or an alkoxy group, and t represents an integer of 1 to 4) .
• Phenol compounds include o-cresol, 2,6-dimethylphenol, 2,3,6-trimethylphenol, 2-ethylphenol, 2-methyl-6-ethylphenol, 2,6-diethylphenol, 2-n -Propylphenol, 2-ethyl-6-n-propylphenol, 2-methyl-6-chlorophenol, 2-methyl-6-bromophenol, 2-methyl-6-isopropylphenol, 2-methyl-6-n- Propylphenol, 2-ethyl-6-bromophenol, 2-methyl-6-n-butylphenol, 2,6-di-n-propylphenol, 2-ethyl-6-chlorophenol, 2-methyl-6-phenylphenol 2-phenylphenol, 2,6-diphenylphenol, 2,6-bis- (4-fluoro Phenyl) phenol, 2-methyl-6-tolyl phenols, monohydric phenolic compounds such as 2,6-di-tolyl phenols.
• the molecular weight of the poly (phenylene ether) resin used is 400 to 8000 (weight average molecular weight gel permeation chromatography in terms of polystyrene), preferably 500 to 4000. If the molecular weight of the resin used is too high, it may cause problems with compatibility with solvents and compatibility with other resins, and may be separated when incorporated into a cured product, resulting in poor curing and uneven distribution of characteristics. Absent. Further, when the molecular weight is small, particularly about 200, it is not preferable because a large difference in dielectric characteristics cannot be obtained as compared with a general novolac resin. Examples of the control of these molecular weights include not only simply connecting molecules but also examples in which molecular weight control is possible by depolymerization with radicals.
• the polyvalent phenylene ether novolak resin of the present invention becomes a novolak or a similar form (all expressed as a novolak for convenience) by connecting the phenylene structure with a bonding group.
• the linking group is preferably a hydrocarbon group having 1 to 20 carbon atoms. Specific examples include methylene, ethylene, propylene, cyclohexane-diyl, phenylmethylene, phenylene bismethylene, bienylene bismethylene, phenylene bisethylene, phenylene bispropylene, and the like.
• a structure represented by the following formula (1) is particularly preferable.
• a raw material poly (phenylene ether) resin and various aldehydes, ketones, benzylmethylene compounds, bond-forming compounds such as compounds having a vinylbenzene structure, etc. are used in the presence of a solvent. It can be synthesized by heating under basic conditions.
• aldehydes such as formaldehyde, acetaldehyde, glyoxal, propyl aldehyde, isovaleraldehyde, octyl aldehyde, furfural, benzaldehyde, pyridinecarbaldehyde, acetone, methyl ethyl ketone, cyclopentanone, Ketones such as cyclohexanone, xylylene glycol, xylylene dihalide (halogen: chlorine, bromine, etc.), bisalkoxymethylbenzene (xylylene bisalkyl ether, specifically bismethoxymethylbenzene, bisethoxymethylbenzene) , Bispropoxymethylbenzene, bisbutoxymethylbenzene, bisphenoxymethylbenzene, bisallyloxymethylbenzene, etc.
• aldehydes such as formaldehyde, acetaldehyde, glyoxal, propyl alde
• xylylene glycol, xylylene dichloride, and bismethoxymethylbenzene are particularly preferred, and the arrangement of substituents may be any of ortho, meta, and para, but there is a balance between heat resistance and mechanical properties.
• xylylene compounds such as biphenyldimethanol, bishalogenomethylbiphenyl (halogen: chlorine, bromine, etc.), bisalkoxymethylbiphenyl (specifically bismethoxymethylbiphenyl, bis Biphenyl bis-methyleneation such as ethoxymethyl biphenyl, bispropoxymethyl biphenyl, bisbutoxymethyl biphenyl, bisphenoxymethyl biphenyl, bisallyloxymethyl biphenyl, etc.
• Benzyl methylene compounds of goods, and the like compounds having a vinyl benzene structure such as divinylbenzene.
• biphenyldimethanol, bischloromethylbiphenyl, and bismethoxymethylbiphenyl are particularly preferable.
• the polyvalent phenylene ether novolak resin of the present invention can be obtained by heating a raw material poly (phenylene ether) resin and a bond-forming compound with a catalyst added to a solvent mixture as necessary. Further, the bond-forming compound may be gradually added to a solution in which a raw material poly (phenylene ether) resin and a catalyst are dissolved as necessary.
• the reaction time is usually 3 to 150 hours, and the reaction temperature is usually 40 to 150 ° C.
• the polyvalent phenylene ether novolak resin thus obtained can be used without being purified depending on the use. Usually, after completion of the reaction, the reaction mixture is neutralized as necessary, and then the crystal It is refined by removing solvents under precipitation or heating under reduced pressure and used for various applications.
• A A method obtained by reprecipitation by diluting with a water-soluble solvent and then mixing with water.
• B A method obtained by diluting with an alcohol having 1 to 4 carbon atoms (methanol, ethanol, propanol, butanol, etc.) and reprecipitation.
• C A method of removing only water contained in the solvent after completion of the reaction / purification (heating under reduced pressure, etc.) and then removing it from the reaction vessel as a solvent-cut varnish.
• the resin concentration is preferably 10 to 90% by weight, more preferably 10 to 80% by weight, and particularly preferably 30 to 80% by weight.
• viscosity is often regarded as important, and its fluidity The viscosity at 25 ° C.
• the solvent which can be used is mentioned later (it is a solvent as described in the term of the curable resin composition varnish).
• D A method of mixing with other resin (the resin described in the section of curing agent for curable resin composition described later) and taking it out from the reaction vessel as a curing agent composition. (The mixing ratio is preferably 90:10 to 30:70, more preferably 80:20 to 30:70, by weight ratio of the other resin and the resin of the present invention. When the blending amount of the resin of the present invention is small, There is no significant improvement in characteristics.)
• the reaction molar ratio (hydroxyl equivalent ratio) between the raw poly (phenylene ether) resin and the bond-forming compound is preferably 1.2: 1 to 20: 1, more preferably 1.5: 1 to 15: 1, particularly Preferably it is 1.5: 1 to 10: 1.
• the reaction molar ratio is less than 1.2: 1, that is, when the raw material poly (phenylene ether) resin is less than 1.2 with respect to the bond-forming compound 1, the molecular weight of the polyvalent phenylene ether novolak resin to be formed becomes too large. Therefore, the solubility in a solvent and the compatibility with other resins may deteriorate.
• heat resistance may be poor.
• Solvents that can be used in the synthesis of the polyvalent phenylene ether novolak resin of the present invention include toluene, xylene, methyl isobutyl ketone, anone, cyclopentanone, methyl ethyl ketone, and the like. Two or more species may be used in combination.
• Solvents that can be used in combination, in addition to the above, alcohols such as methanol, ethanol, isopropanol, butanol, ketones such as acetone, esters such as ethyl acetate, butyl acetate, carbitol acetate, propylene glycol monomethyl ether acetate, tetrahydrofuran, Examples thereof include ethers such as dioxane, nitrogen-containing solvents such as N-methylpyrrolidone, N, N-dimethylformamide, and N, N-dimethylacetamide.
• the amount of the solvent used is usually in the range of 5 to 500 parts by weight, preferably 10 to 400 parts by weight with respect to 100 parts by weight of the total amount of the raw material poly (phenylene ether) resin and the bond-forming compound.
• the catalyst it is basically preferable to use an acidic catalyst.
• the bond-forming compound is benzyl halide
• the reaction can proceed smoothly without the addition of a catalyst. From the viewpoint of ease of subsequent purification, it is preferable to use no catalyst or hardly use it.
• the acidic catalyst When using the catalyst, specific examples of the acidic catalyst include mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid; organic acids such as oxalic acid, toluenesulfonic acid and acetic acid; heteropolyacids such as tungstic acid, activated clay, inorganic acids, Examples include stannic chloride, zinc chloride, ferric chloride, and other acidic catalysts usually used for the production of novolak resins such as organic and inorganic acid salts showing acidity. These catalysts are not limited to those mentioned above, and may be used alone or in combination of two or more.
• the amount of the catalyst used is usually in the range of 0.005 to 2.0 moles, preferably 0.01 to 1.1 moles, or 100 g of the raw poly (phenylene ether) resin relative to the raw material poly (phenylene ether) resin.
• the amount is preferably 0.1 to 50 g, more preferably 0.3 to 20 parts. If the amount of catalyst is small, the progress of the reaction is slow. Moreover, problems such as the need for a reaction at a high temperature and the reaction not proceeding to the end are not preferable. Moreover, when there is too much catalyst amount, a great amount of labor may be applied in post-treatments such as neutralization and purification. In addition, when corrosive gas produces
• the polyvalent phenylene ether novolak resin thus obtained is represented by a structural formula represented by the following formula (A), and specific examples of this representative structural formula will be described below.
• the resulting polyvalent phenylene ether novolak resin is such that the benzene skeleton of the poly (phenylene ether) resin described in B below is connected by the connecting group described in A below, The groups connect the benzene skeletons in the same molecule of the poly (phenylene ether) resin or the benzene skeletons of two or more poly (phenylene ether) resin molecules. And the partial structure around a coupling group becomes a structure like following formula (A), for example.
• the following benzene skeleton represents a benzene skeleton in a poly (phenylene ether) resin molecule.
• P is a residue of a poly (phenylene ether) resin
• X is a linking group represented by the following formula (1)
• R is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
• * is Represents a hydrogen atom or the above X
• n represents an integer of 1 to 2.
• the residue of the above poly (phenylene ether) resin can be further linked to the benzene skeleton in the poly (phenylene ether) resin molecule via X in another benzene skeleton.
• the polyphenylene ether novolak resin of the present invention thus obtained is a brown resin (or powder), is soluble in an organic solvent, and can be handled as a varnish.
• the thus obtained polyvalent phenylene ether novolak resin of the present invention preferably has a hydroxyl group equivalent of 400 to 6000, particularly preferably 500 to 5000.
• the weight average molecular weight is preferably 600 to 50000, and particularly preferably 700 to 25000.
• the polyvalent phenylene ether novolak resin of the present invention can be used as it is as a thermoplastic (or its raw material), mixed with a thermoplastic to improve its properties, or used as a raw material for an epoxy resin and its curing agent. You can also.
• the epoxy resin composition of the present invention containing the polyvalent phenylene ether novolak resin of the present invention (hereinafter also referred to as curable resin composition) will be described.
• an epoxy resin is used as an essential component.
• the curable resin composition of the present invention is a composition containing an epoxy resin-curing agent as an essential component, and always contains a polyvalent phenylene ether novolak resin as a curing agent for the epoxy resin. Moreover, a hardening accelerator is contained as needed.
• bisphenol A bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetofu Non, o-hydroxy
• the curing agent contained in the curable resin composition of the present invention can be used in combination in addition to the above-described polyphenylene ether novolak resin of the present invention.
• it can be used as a curing agent composition of the above-described polyphenylene ether novolak resin of the present invention and another curing agent.
• the proportion of the polyvalent polyphenylene ether novolak resin of the present invention in the total epoxy resin composition is preferably 30% by weight or more, particularly preferably 40% by weight or more.
• Examples of the curing agent that can be used in combination include a phenol resin, a phenol compound, an amine compound, an acid anhydride compound, an amide compound, and a carboxylic acid compound. Specific examples of the curing agent that can be used are as follows.
• Phenolic resins phenolic compounds; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hy Loxyace
• Preferred phenol resins include phenol aralkyl resins (resins having an aromatic alkylene structure) in terms of dielectric constant, and particularly preferred is a structure having at least one selected from phenol, naphthol, and cresol, and serves as the linker.
• a resin characterized in that the alkylene part is at least one selected from a benzene structure, a biphenyl structure, and a naphthalene structure (specifically, zylock, naphthol zylock, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene) And novolak resin.).
• Acid anhydride compounds carboxylic acid compounds; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydro Phthalic anhydride, methylhexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2, Acid anhydrides such as 3-dicarboxylic acid anhydride, cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, etc .; by addition reaction of various alcohols, carbinol-modified silicone, and the above-mentioned acid anhydrides Although the obtained carboxylic acid resin is mentioned, it
• curing agent examples include, but are not limited to, imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, and the like. These may be used alone or in combination of two or more.
• the amount of the curing agent used is preferably 0.7 to 1.2 equivalents in terms of its functional group (hydroxyl group) equivalent to 1 equivalent of the epoxy group of all epoxy resins.
• the amount of the curing agent used is preferably 0.7 to 1.2 equivalents in terms of its functional group (hydroxyl group) equivalent to 1 equivalent of the epoxy group of all epoxy resins.
• a curing accelerator may be used in combination with a curing agent.
• curing accelerators include imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2- (dimethylaminomethyl) phenol, 1,8-diaza.
• -Tertiary amines such as bicyclo (5,4,0) undecene-7
• phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc.
• quaternary ammonium salts triphenylbenzylphosphonium salts, triphenylethylphosphonium salts, tetrabutylphosphonium salts, and the like.
• the counter ion of the quaternary salt is not particularly specified, such as halogen, organic acid ion, hydroxide ion, etc., but organic acid ion and hydroxide ion are particularly preferable), metal compounds such as tin octylate, etc. It is done.
• 0.01 to 5.0 parts by weight is used as necessary with respect to 100 parts by weight of the epoxy resin.
• the curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component.
• the phosphorus-containing compound may be a reactive type or an additive type.
• Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-pho
• Phosphate esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred.
• antioxidant to the curable resin composition of this invention as needed.
• Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more.
• the amount of the antioxidant used is usually 0.008 to 1 part by weight, preferably 0.01 to 0.5 part by weight, per 100 parts by weight of the resin component in the curable resin composition of the present invention.
• phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl- ⁇ - (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2,2 '-Methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis (4-ethyl-6-t-butylphenol), 4,4'-thiobis (3- Til-6-tert-butyl
• sulfur antioxidant examples include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like.
• phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetraylbis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Phosphites such as -di-t-butyl-4-methylphenyl) phosphite, bis [2-tert-butyl-6-methyl
• antioxidants can be used alone, but two or more kinds may be used in combination.
• a phosphorus-based antioxidant is particularly preferable.
• HALS hindered amine-based light stabilizers
• HALS is not particularly limited, but typical examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [ ⁇ 6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl ⁇ ⁇ (2,2,6,6-tetramethyl-4-piperidyl) imino ⁇ hexamethylene ⁇ (2,2,6,6-tetramethyl
• a binder resin can be blended with the curable resin composition of the present invention as required.
• the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins.
• the blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts per 100 parts by weight of the resin component. Part by weight is used as needed.
• An inorganic filler can be added to the curable resin composition of the present invention as necessary.
• inorganic fillers include crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconia, fosterite, steatite, spinel, titania, talc, and the like.
• the present invention is not limited to these. These may be used alone or in combination of two or more.
• the content of these inorganic fillers is used in an amount of 0 to 95% by weight in the curable resin composition of the present invention.
• the curable resin composition of the present invention includes various agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers.
• agents such as silane coupling agents, mold release agents such as stearic acid, palmitic acid, zinc stearate, and calcium stearate, surfactants, dyes, pigments, and ultraviolet absorbers.
• a compounding agent and various thermosetting resins can be added.
• the curable resin composition of the present invention can be obtained by uniformly mixing each component.
• the curable resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method.
• the polyphenylene ether novolak resin and epoxy resin of the present invention and, if necessary, the curing accelerator, phosphorus-containing compound, binder resin, inorganic filler and compounding agent are made uniform using an extruder, kneader, roll or the like as necessary.
• the cured product of the present invention can be obtained by heating at 200 ° C. for 2 to 10 hours.
• the curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone as necessary to obtain a curable resin composition varnish.
• a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone as necessary to obtain a curable resin composition varnish.
• a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper and drying by heating is subjected to hot press molding, whereby the curable resin composition A of the present invention is prepared. It can be a cured product.
• the solvent is used in an amount usually accounting for 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent.
• cured material containing a carbon fiber can also be obtained as it is, for example with a RTM system.
• the curable resin composition of the present invention can also be used as a modifier for a film-type composition. Specifically, it can be used to improve the flexibility of the B-stage.
• a film-type resin composition is formed by applying the curable resin composition of the present invention on the release film as the curable resin composition varnish, removing the solvent under heating, and then performing B-stage. To obtain a sheet-like adhesive.
• This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.
• the curable resin composition of the present invention includes general uses in which an epoxy resin is used.
• adhesives for example, adhesives, paints, coating agents, molding materials (including sheets, films, FRP, etc.), insulating materials (prints)
• a sealing agent for example, an additive to other resins and the like
• the adhesive include civil engineering, architectural, automotive, general office, and medical adhesives, and electronic material adhesives.
• adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, BGA reinforcing underfills, anisotropic conductive films ( ACF) and an adhesive for mounting such as anisotropic conductive paste (ACP).
• sealing agent and substrate potting sealing for capacitors, transistors, diodes, light emitting diodes, ICs, LSIs, etc., dipping, transfer mold sealing, ICs, LSIs for COB, COF, TAB, etc.
• substrate use as which a functionality, such as a network board
• Epoxy equivalent Conforms to JIS K 7236 (ISO 3001) ICI melt viscosity: compliant with JIS K 7117-2 (ISO 3219) Softening point: compliant with JIS K 7234 Total chlorine: compliant with JIS K 7243-3 (ISO 21672-3)
• GPC Column (Shodex KF-603, KF-602.5, KF-602, KF-601x2) The coupled eluent is tetrahydrofuran. The flow rate is 0.5 ml / min. Column temperature is 40 ° C Detection: RI (differential refraction detector)
• MX90-100 polyphenylene ether resin
• Example 2 A flask equipped with a stirrer, reflux condenser, and stirrer is purged with nitrogen, while 75 parts of polyphenylene ether resin (MX90-100 made by Subic), 5 parts of p-xylylene glycol (reagent made by Tokyo Chemical Industry), toluene (genuine) 130 parts of chemical reagent) and 1 part of p-toluenesulfonic acid monohydrate (reagent made by Tokyo Kasei) were reacted at 100 ° C for 2 hours, and then refluxed at 110-120 ° C for 10 hours. It was.
• polyphenylene ether resin MX90-100 made by Subic
• Example 3 A flask equipped with a stirrer, a reflux condenser, and a stirrer is purged with nitrogen while 87.5 parts of a polyphenylene ether resin (MX90-100, manufactured by Savic) and 4.8 parts of p-xylylene glycol (a reagent manufactured by Tokyo Chemical Industry). , 138 parts of methyl isobutyl ketone (reagent manufactured by Junsei Kagaku), 1 part of paratoluenesulfonic acid monohydrate (reagent manufactured by Tokyo Chemical Industry), reacted at 100 ° C. for 2 hours, and then brought to reflux at 110-120 ° C. The reaction was carried out for 7 hours.
• MX90-100 polyphenylene ether resin
• a p-xylylene glycol a reagent manufactured by Tokyo Chemical Industry
• Example 4 In Example 3, the same operation was performed except that 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) was changed to 30 parts, to obtain a curing agent composition (H-2) of the present invention. (Example 5) In Example 3, the same operation was performed except that 70 parts of phenol biphenylene novolak (KAYAHARD GPH-65 manufactured by Nippon Kayaku Co., Ltd.) was changed to 20 parts, and 60% of the polyvalent phenylene ether novolac resin of the present invention was contained. A curing agent composition (H-3) was obtained. The softening point was 130 ° C.
• p- Add 10 parts of xylylene glycol (reagent made by Tokyo Kasei)
• Comparative Example 2 Add 30 parts of polyphenylene ether resin (MX90-100 from Savic) and 20 parts of phenol biphenylene novolak (KAYAHARD GPH-65 from Nippon Kayaku), dissolve in methyl isobutyl ketone, and then remove the solvents under reduced pressure using a rotary evaporator. Then, a comparative curing agent composition (H′-2) was obtained.
• Examples 7 to 8 and Comparative Example 3 ⁇ Dielectric constant and dielectric loss tangent test>
• the curing agent composition and epoxy resin obtained above were blended in the proportions (parts by weight) shown in Table 1, and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing.
• This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
• the tableted epoxy resin composition was transfer-molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation.
• cured material was measured in the following ways.
• ⁇ Dielectric constant / dielectric loss tangent Cavity resonator method Equipment used Kanto Electric Application Development Cavity resonator 1 GHz Reference Teflon (registered trademark)
• Example 9 and Comparative Example 4 ⁇ Dielectric property test and heat resistance test>
• the curing agent composition and the epoxy resin obtained as described above were blended in the proportions (parts by weight) shown in Table 2, and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing.
• This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
• the tableted epoxy resin composition was transfer-molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation.
• cured material was measured in the following ways.
• Example 10 and Comparative Example 5 ⁇ Heat resistance test / dielectric property test>
• the curing agent composition and the epoxy resin obtained above were blended in the proportions (parts by weight) shown in Table 3, and mixed and kneaded uniformly using a mixing roll to obtain an epoxy resin composition for sealing.
• This epoxy resin composition was pulverized with a mixer and further tableted with a tablet machine.
• the tableted epoxy resin composition was transfer-molded (175 ° C. ⁇ 60 seconds), and after demolding, cured under the conditions of 160 ° C. ⁇ 2 hours + 180 ° C. ⁇ 6 hours to obtain a test piece for evaluation.
• cured material was measured in the following ways.
• Dielectric constant / dielectric loss tangent Cavity resonator method Equipment used Kanto Electric Application Development Cavity resonator 1 GHz Reference Teflon (registered trademark) ⁇ Heat resistance (DMA) Dynamic viscoelasticity measuring instrument: TA-instruments, DMA-2980 Measurement temperature range: -30 to 280 ° C Temperature rate: 2 ° C./min Test piece size: 5 mm ⁇ 50 mm cut out (thickness is about 800 ⁇ m) Tg: Tan- ⁇ peak point was Tg. Heat resistance (TMA): Measured in accordance with JIS K 7244.
• the curable resin composition of the present invention is excellent in heat resistance as compared with those using H'-1 and H'-2 having a similar structure as a curing agent (composition). It was clear that the dielectric constant and dielectric loss tangent were good as compared with those using other curing agents, and it was confirmed that they have excellent dielectric properties.
• the polyphenylene ether novolak resin of the present invention is useful as a curing agent for an epoxy resin
• the epoxy resin composition containing the polyphenylene ether novolak resin as a curing agent includes an insulating material for electrical and electronic parts and a laminate (printed wiring board, It is useful for various composite materials such as build-up substrates) and CFRP, adhesives, paints and the like.

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• 2013
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