Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/38—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation
  • C08F2/40—Polymerisation using regulators, e.g. chain terminating agents, e.g. telomerisation using retarding agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F22/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides or nitriles thereof
  • C08F22/36—Amides or imides
  • C08F22/40—Imides, e.g. cyclic imides
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/04—Oxygen-containing compounds
  • C08K5/13—Phenols; Phenolates
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L35/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least one other carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons

Definitions

• the present invention relates to a curable resin composition and its cured product, which are suitable for use in electrical and electronic components such as semiconductor encapsulants, printed wiring boards, and build-up laminates, lightweight, high-strength materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, and 3D printing applications.
• CPUs central processing units
• Patent Document 1 discloses a curable resin composition containing bisvinylphenylethane (BVPE) and thermosetting polyphenylene ether (Patent Document 1).
• BVPE bisvinylphenylethane
• Patent Document 1 thermosetting polyphenylene ether
• This curable resin composition uses a polymerization inhibitor to improve the storage stability of the resin composition, and 2,5-bis(1,1-dimethylbutyl)hydroquinone is used as the polymerization inhibitor.
• the storage stability improves as the amount added increases, but there is a trade-off in that the dielectric properties deteriorate. Furthermore, the optimal polymerization inhibitor changes depending on the compound for which storage stability needs to be improved, making selection both a difficult and important issue.
• polymerization inhibitors examples include phenol-based, sulfur-based, phosphorus-based, hindered amine-based, nitroso-based, and nitroxyl radical-based inhibitors.
• phenolic polymerization inhibitors include, for example, monophenols such as 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)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, and 2,4-bis[(octylthio)methyl]-o-cresol; t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), 4,4'-thiobis(3-methyl-6-t-butylphenol),
• Examples of the phosphorus-based polymerization inhibitors include triphenyl phosphite, diphenyl isodecyl phosphite, phenyl diisodecyl phosphite, tris(nonylphenyl) phosphite, diisodecyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(octadecyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbis(2,4-di-t-butyl-4-methylphenyl) phosphite, bis[2- Examples of suitable phosphites include t-buty
• Examples of the above hindered amine polymerization inhibitors include ADK STAB LA-40MP, ADK STAB LA-40Si, ADK STAB LA-402AF, ADK STAB LA-87, ADK STAB LA-82, ADK STAB LA-81, ADK STAB LA-77Y, ADK STAB LA-77G, ADK STAB LA-72, ADK STAB LA-68, ADK STAB LA-63P, ADK STAB LA-57, ADK STAB Examples include, but are not limited to, LA-52, Chimassorb 2020FDL, Chimassorb 944FDL, Chimassorb 944LD, Tinuvin 622SF, Tinuvin PA144, Tinuvin 765, Tinuvin 770DF, Tinuvin XT55FB, Tinuvin 111FDL, Tinuvin 783FDL, and Tinuvin 791FB.
• the curability of the curable resin composition of the present embodiment can be improved by adding a curing accelerator.
• a curing accelerator an anionic curing accelerator that accelerates the curing reaction by generating anions upon irradiation with ultraviolet light or visible light or heating, or a cationic curing accelerator that accelerates the curing reaction by generating cations upon irradiation with ultraviolet light or visible light or heating, is preferred.
• anionic curing accelerators examples include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; trialkylamines such as triethylamine and tributylamine; 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.
• imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole
• trialkylamines such as triethylamine and tributylamine
• 4-dimethylaminopyridine benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol
• phosphines such as triphenylphosphine
• quaternary ammonium salts such as tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, and hexadecyltrimethylammonium hydroxide. These may be used alone or in combination.
• the amount of inorganic filler used is preferably 80 to 92 parts by mass, and more preferably 83 to 90 parts by mass, per 100 parts by mass of the curable resin composition. Furthermore, when obtaining a curable resin composition for use as an interlayer insulating layer forming material or a substrate material such as copper-clad laminates, prepregs, or RCC, the amount of inorganic filler used is preferably 5 to 80 parts by mass, and more preferably 10 to 60 parts by mass, per 100 parts by mass of the curable resin composition.
• azo compounds examples include, but are not limited to, azobisisobutyronitrile, 4,4'-azobis(4-cyanovaleric acid), and 2,2'-azobis(2,4-dimethylvaleronitrile). These compounds may be used alone or in combination.
• the phosphorus-based flame retardants may be either reactive or additive.
• Specific examples include, but are not limited to, phosphate esters such as trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylenyl phosphate, 1,3-phenylenebis(dixylenyl phosphate), 1,4-phenylenebis(dixylenyl phosphate), and 4,4'-biphenyl(dixylenyl phosphate); phosphanes such as 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide and 10(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide; phosphorus-containing epoxy compounds obtained by reacting epoxy resin with the active hydrogen of the above-mentioned
• the content of flame retardant is preferably in the range of 0.1 to 0.6 parts by mass per 100 parts by mass of the curable resin composition. If it is less than 0.1 part by mass, the flame retardancy may be insufficient, and if it is more than 0.6 part by mass, it may have a negative effect on the moisture absorption and dielectric properties of the cured product.
• the curable resin composition of this embodiment may contain a light stabilizer.
• a hindered amine-based light stabilizer particularly a HALS, is preferred as the light stabilizer.
• HALS include a reaction product of dibutylamine, 1,3,5-triazine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, and N-(2,2,6,6-tetramethyl-4-piperidyl)butylamine, a reaction product of dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and 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-4-piperidyl)buty
• Suitable hydroxybenzyl compounds include, but are not limited to, bis(1,2,2,6,6-pentamethyl-4-piperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl)sebacate, and bis(1,2,2,6,6-pentamethyl-4-piperidyl) 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonate. These compounds may be used alone or in combination.
• the content of the light stabilizer is preferably in the range of 0.001 to 0.1 parts by mass per 100 parts by mass of the curable resin composition. Less than 0.001 parts by mass may be insufficient to achieve light stabilization, while more than 0.1 parts by mass may have a negative impact on the moisture absorption and dielectric properties of the cured product.
• the curable resin composition of this embodiment may use a binder resin.
• binder resins include, but are not limited to, butyral-based resins, acetal-based resins, acrylic-based resins, epoxy-nylon-based resins, NBR-phenol-based resins, epoxy-NBR-based resins, and silicone-based resins. These may be used alone or in combination.
• the amount of binder resin used is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is preferably 0.05 to 50 parts by mass, and more preferably 0.05 to 20 parts by mass, per 100 parts by mass of the curable resin composition, as needed.
• the curable resin composition of the present embodiment may contain additives, such as modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
• additives such as modified acrylonitrile copolymers, polyethylene, fluororesins, silicone gels, silicone oils, surface treatment agents for fillers such as silane coupling agents, release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
• polyphenylene ether compounds compounds having an ethylenically unsaturated bond, cyanate ester resins, polybutadiene and modified products thereof, and polystyrene and modified products thereof.
• the inclusion of these compounds can improve the brittleness of the cured product and adhesion to metals, and can suppress package cracking during reliability tests such as solder reflow and thermal cycling.
• the amount of the above compounds used is preferably 10 times by mass or less, more preferably 5 times by mass or less, and particularly preferably 3 times by mass or less, relative to the compound represented by formula (1) above.
• the preferred lower limit is 0.1 times by mass or more, more preferably 0.25 times by mass or more, and even more preferably 0.5 times by mass or more.
• epoxy resin Preferred examples of epoxy resins include, but are not limited to, the following.
• the epoxy resin may be liquid or solid, and may be used alone or in combination.
• liquid epoxy resins examples include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AF type epoxy resins, naphthalene type epoxy resins, glycidyl ester type epoxy resins, glycidyl amine type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, and epoxy resins having a butadiene structure.
• solid epoxy resins include bixylenol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins, and examples of suitable solid epoxy resins include naphthol-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, and biphenyl-type epoxy resins.
• An active ester compound refers to a compound containing at least one ester bond in its structure, with an aliphatic chain, an aliphatic ring, or an aromatic ring bonded to both sides of the ester bond.
• Examples of active ester compounds include compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. These compounds are obtained by a condensation reaction between at least one of a carboxylic acid compound, an acid chloride, or a thiocarboxylic acid compound and at least one of a hydroxy compound or a thiol compound.
• active ester compounds are preferably obtained from a carboxylic acid compound or an acid chloride and a hydroxy compound, and the hydroxy compound is preferably a phenol compound or a naphthol compound. Active ester compounds may be used alone or in combination of two or more.
• carboxylic acid compound examples include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.
• Examples of the acid chlorides include acetyl chloride, acrylic acid chloride, methacrylic acid chloride, malonyl chloride, succinic acid dichloride, diglycolyl chloride, glutaric acid dichloride, suberic acid dichloride, sebacic acid dichloride, adipic acid dichloride, dodecandioyl dichloride, azelaic acid chloride, 2,5-furandicarbonyl dichloride, phthaloyl chloride, isophthaloyl chloride, terephthaloyl chloride, trimesic acid chloride, bis(4-chlorocarbonylphenyl) ether, 4,4'-diphenyldicarbonyl chloride, and 4,4'-azodibenzoyl dichloride.
• phenol compounds and naphthol compounds examples include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, ⁇ -naphthol, ⁇ -naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, benzenetriol, dicyclopentadiene-type diphenol compounds, phenol novolac, and the phenolic resins described below.
• dicyclopentadiene-type diphenol compounds refer to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.
• active ester compounds include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated phenol novolac, active ester compounds containing a benzoylated phenol novolac, the compound described in Example 2 of WO 2020/095829, and the compounds disclosed in WO 2020/059625.
• active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred.
• the dicyclopentadiene-type diphenol structure refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.
• active ester compounds include, for example, "EXB9451,” “EXB9460,” “EXB9460S,” “HPC-8000-65T,” “HPC-8000H-65TM,” “EXB-8000L-65TM,” and “EXB-8150-65T” (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure, “EXB9416-70BK” (manufactured by DIC Corporation) as an active ester compound containing a naphthalene structure, and “EXB9416-70BK” (manufactured by DIC Corporation) as a phenolic compound.
• active ester compounds containing acetylated volac examples include “DC808” (manufactured by Mitsubishi Chemical Corporation), active ester compounds containing benzoylated phenol novolac include “YLH1026,” “YLH1030,” and “YLH1048” (manufactured by Mitsubishi Chemical Corporation), active ester curing agents that are acetylated phenol novolac include “DC808” (manufactured by Mitsubishi Chemical Corporation), and phosphorus atom-containing active ester curing agents include "EXB-9050L-62M” (manufactured by DIC Corporation).
• the ratio ( ⁇ / ⁇ ) of the active ester equivalent ( ⁇ ) to the epoxy equivalent ( ⁇ ) is preferably 0.5 to 1.5, more preferably 0.8 to 1.2, and even more preferably 0.90 to 1.10. If the ratio is outside this range, excess epoxy groups or active ester groups may remain in the system, which may result in deterioration of properties in high-temperature storage tests (e.g., 150°C, 1000 hours) or long-term reliability tests under high-temperature, high-humidity conditions (e.g., temperature: 85°C, humidity: 85%).
• Phenol alkyl-substituted phenol, aromatic-substituted phenol, hydroquinone, resorcinol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.
• ⁇ Aldehydes > Formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, furfural, and the like.
• ⁇ Diene compounds Dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, and the like.
• ⁇ Ketones Acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, fluorenone, etc.
• ⁇ Substituted biphenyls > 4,4'-bis(chloromethyl)-1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 4,4'-bis(hydroxymethyl)-1,1'-biphenyl, and the like.
• ⁇ Substituted phenyls > 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene, and the like.
• the polyphenylene ether compound is preferably a polyphenylene ether compound having an ethylenically unsaturated bond, and more preferably a polyphenylene ether compound having an acrylic group, a methacrylic group, or a styrene structure.
• Commercially available products include SA-9000 (manufactured by SABIC Corporation, a polyphenylene ether compound having a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Company, Inc., a polyphenylene ether compound having a styrene structure).
• the number average molecular weight (Mn) of the polyphenylene ether compound is preferably 500 to 5,000, more preferably 2,000 to 5,000, and even more preferably 2,000 to 4,000. If the molecular weight is less than 500, the heat resistance of the cured product tends to be insufficient. On the other hand, if the molecular weight is greater than 5,000, the melt viscosity increases, and sufficient fluidity cannot be obtained, which tends to result in molding defects. In addition, the reactivity decreases, the curing reaction takes a long time, and the amount of unreacted material that is not incorporated into the curing system increases, which tends to lower the glass transition temperature of the cured product and reduce the heat resistance of the cured product.
• the number average molecular weight of the polyphenylene ether compound is 500 to 5000, it is possible to exhibit excellent heat resistance, moldability, etc. while maintaining excellent dielectric properties.
• the number average molecular weight here can be specifically measured using gel permeation chromatography or the like.
• poly(2,6-dimethyl-1,4-phenylene ether) or the like can be used as a high-molecular-weight polyphenylene ether compound that undergoes the redistribution reaction.
• the phenolic compound used in the redistribution reaction is not particularly limited, but preferred are, for example, multifunctional phenolic compounds having two or more phenolic hydroxyl groups per molecule, such as bisphenol A, phenol novolac, and cresol novolac. These compounds may be used alone or in combination.
• aniline resins include, but are not limited to, aniline resins disclosed in Japanese Patent No. 6,429,862, reaction products of aniline and substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl), reaction products of aniline and substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene), 4,4'-(1,3-phenylenediisopropylidene)bisaniline, 4,4'-(1,4-phenylenediisopropylidene)bisaniline, reaction products of aniline and diisopropenylbenzene, and dimer diamine. These may be used alone or in combination.
• the compound containing an ethylenically unsaturated bond is a compound having one or more ethylenically unsaturated bonds in the molecule that can be polymerized by heat or light, regardless of whether a polymerization initiator is used or not.
• An isocyanate resin is a compound having two or more isocyanate groups in the molecule.
• the isocyanate resin include aromatic diisocyanates such as p-phenylene diisocyanate, m-phenylene diisocyanate, p-xylene diisocyanate, m-xylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and naphthalene diisocyanate; aliphatic or alicyclic diisocyanates such as isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hydrogenated xylene diisocyanate, norbornene diisocyanate, and lysine diisocyanate; polyisocyanates such as one or more biuret compounds
• polyamide resin examples include reaction products of one or more of diamines, diisocyanates, and oxazolines with dicarboxylic acids, reaction products of diamines with acid chlorides, and ring-opening polymerization products of lactam compounds. These may be used alone or in combination. Specific examples of the above raw materials are given below, but are not limited to these.
• ⁇ Diisocyanate> benzene diisocyanate, toluene diisocyanate, 1,3-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)cyclohexane, bis(4-isocyanatophenyl)methane, isophorone diisocyanate, 1,3-bis(2-isocyanato-2-propyl)benzene, 2,2-bis(4-isocyanatophenyl)hexafluoropropane, dicyclohexylmethane-4,4'-diisocyanate, and the like.
• ⁇ Dicarboxylic acid> Oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 5-hydroxyisophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, cyclohexanedicarboxylic acid, biphenyldicarboxylic acid, naphthalenedicarboxylic acid, benzophenonedicarboxylic acid, furandicarboxylic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfide, and the like.
• the curable resin composition of this embodiment may contain a maleimide compound.
• a maleimide compound is a compound having one or more maleimide groups in the molecule.
• maleimide compounds include 4,4'-diphenylmethane bismaleimide, polyphenylmethane maleimide, m-phenylene bismaleimide, 2,2'-bis[4-(4-maleimidophenoxy)phenyl]propane, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide, 4,4'-diphenylether bismaleimide, 4,4'-diphenylsulfone bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene), and Xyloc-type maleimide compounds (anilix).
• the cyanate ester resin is a cyanate ester compound obtained by reacting a phenolic resin with a cyanogen halide.
• a cyanogen halide include, but are not limited to, dicyanatobenzene, tricyanatobenzene, dicyanatonaphthalene, dicyanatobiphenyl, 2,2'-bis(4-cyanatophenyl)propane, bis(4-cyanatophenyl)methane, bis(3,5-dimethyl-4-cyanatophenyl)methane, 2,2'-bis(3,5-dimethyl-4-cyanatophenyl)propane, 2,2'-bis(4-cyanatophenyl)ethane, 2,2'-bis(4-cyanatophenyl)hexafluoropropane, bis(4-cyanatophenyl)sulfone, bis(4-cyanatophenyl)thioether, phenol novolac cyanate, and phenol
• the catalyst is preferably used in an amount of 0.0001 to 0.10 parts by mass, and preferably 0.00015 to 0.0015 parts by mass, per 100 parts by mass of the cyanate ester resin and curable resin composition.
• Polybutadiene and its modified products are polybutadiene or compounds having a structure derived from polybutadiene in the molecule.
• the unsaturated bonds in the polybutadiene-derived structure may be partially or entirely converted to single bonds by hydrogenation.
• Examples of polybutadiene and modified polybutadienes include, but are not limited to, polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, and styrene-butadiene rubber. These may be used alone or in combination.
• polybutadiene or styrene-butadiene rubber is preferred from the viewpoint of dielectric properties.
• styrene-butadiene rubber examples include RICON-100, RICON-181, and RICON-184 (all manufactured by Cray Valley Chemical Industries, Ltd.) and 1,2-SBS (manufactured by Nippon Soda Co., Ltd.).
• polybutadienes examples include B-1000, B-2000, and B-3000 (all manufactured by Nippon Soda Co., Ltd.).
• the molecular weight of polybutadiene and styrene-butadiene rubber is preferably a weight-average molecular weight of 500 to 10,000, more preferably 750 to 7,500, and even more preferably 1,000 to 5,000.
• the amount of volatilization is high, making it difficult to adjust the solids content during prepreg production.
• compatibility with other curable resins deteriorates.
• compounds containing heteroatoms such as oxygen and nitrogen such as bismaleimides and polymaleimides, have difficulty ensuring compatibility with low-polarity compounds, such as compounds composed primarily of hydrocarbons or compounds composed solely of hydrocarbons, due to their polarity.
• the compound of this embodiment does not have a skeleton design that actively incorporates heteroatoms such as oxygen and nitrogen, and therefore exhibits excellent compatibility with materials with low polarity and low dielectric properties, as well as compounds composed solely of hydrocarbons.
• Polystyrene and its modified products are polystyrene or compounds having a structure derived from polystyrene in the molecule.
• examples of polystyrene and modified products thereof include polystyrene, styrene-2-isopropenyl-2-oxazoline copolymers (Epocross RPS-1005, RP-61, both manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene-propylene copolymer: Septon 1020, manufactured by Kuraray Co., Ltd.), SEPS (styrene-ethylene-propylene-styrene copolymer: Septon 2002, Septon 2004F, Septon 2005, Septon 2006, Septon 2063, Septon 2104, all manufactured by Kuraray Co., Ltd.), SEEPS (styrene-ethylene/ethylene-propylene-styrene block copolymer: Septon 4003,
• Suitable block copolymers include SEPTON 8004, SEPTON 8006, and SEPTON 8007L, all manufactured by Kuraray Co., Ltd.), SEEPS-OH (a styrene-ethylene/ethylene propylene-styrene block copolymer having a hydroxyl group at its terminal: SEPTON HG252, manufactured by Kuraray Co., Ltd.), SIS (styrene-isoprene-styrene block copolymer: SEPTON 5125 and SEPTON 5127, both manufactured by Kuraray Co., Ltd.), hydrogenated SIS (hydrogenated styrene-isoprene-styrene block copolymer: HYBRAR 7125F and HYBRAR 7311F, both manufactured by Kuraray Co., Ltd.), and SIBS (styrene-isobutylene-styrene block copolymer: SIBSTAR073T, SIBSTAR102T, and SIBSTAR103T
• Polystyrene and modified products thereof are preferably free of unsaturated bonds because they have higher heat resistance and are less susceptible to oxidative degradation.
• the weight-average molecular weight of polystyrene and modified products thereof is not particularly limited as long as it is 10,000 or more. However, if it is too large, compatibility with polyphenylene ether compounds, low-molecular-weight components with a weight-average molecular weight of about 50 to 1,000, and oligomer components with a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, a weight-average molecular weight of about 10,000 to 300,000 is preferred.
• Polyethylene and its modified products are compounds having polyethylene or a structure derived from polyethylene in the molecule.
• Examples of polyethylene and modified polyethylenes include ethylene-propylene copolymers, ethylene-styrene copolymers, ethylene-propylene-ethylidene norbornene copolymers (EBT: K-8370EM, K-9330M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-propylene-vinyl norbornene copolymers (VNB-EPT: PX-006M, PX-008M, PX-009M, etc., manufactured by Mitsui Chemicals, Inc.), ethylene-vinyl alcohol copolymers, and ethylene-vinyl acetate copolymers, but are not limited thereto.
• ethylene-propylene-ethylidene norbornene copolymers or ethylene-propylene-vinyl norbornene copolymers containing a crosslinkable structure may be used alone or in combination.
• weight-average molecular weight of polyethylene and modified polyethylenes thereof there are no particular restrictions on the weight-average molecular weight of polyethylene and modified polyethylenes thereof as long as it is 10,000 or more.
• compatibility with not only the polyphenylene ether compound but also low-molecular-weight components having a weight-average molecular weight of about 50 to 1,000 and oligomer components having a weight-average molecular weight of about 1,000 to 5,000 deteriorates, making it difficult to ensure mixing and solvent stability. Therefore, it is preferably about 10,000 to 300,000.
• any compound may be used as long as it is a compound obtained by reacting a compound having a phenolic hydroxyl group, a compound having an amino group, or a compound having an aldehyde group.
• the compound having a phenolic hydroxyl group is not particularly limited, but for example, the above-mentioned phenolic resin, phenols (which may have a substituent such as an alkenyl group or an alkyl group), and bisphenols can be used.
• the compound having an amino group is not particularly limited, but the above-mentioned amine resin, diamine, and anilines (which may have a substituent such as an alkenyl group or an alkyl group) can be used.
• the aldehyde compound for example, the above-mentioned aldehydes can be used, but formaldehyde is preferably used.
• benzoxazine compounds may be used, and examples thereof include benzoxazine P-d, Fa, and ALP-d (all manufactured by Shikoku Chemical Industry Co., Ltd.), JBZ-BA100N, JBZ-FA100N, JBZ-DP100N, JBZ-OP100N, JBZ-OP100D, and JBZ-OP100I (all manufactured by JFE Chemical Corporation), and BTBz (manufactured by Japan Material Technology Co., Ltd.).
• the curable resin composition of this embodiment can be obtained by preparing the above components in the specified ratios, pre-curing at 130-180°C for 30-500 seconds, and then post-curing at 150-200°C for 2-15 hours, allowing the curing reaction to proceed sufficiently and producing the cured product of this embodiment.
• the components of the curable resin composition can be uniformly dispersed or dissolved in a solvent, etc., and then cured after removing the solvent.
• the method for preparing the curable resin composition of this embodiment is not particularly limited, but the components may be simply mixed uniformly, or may be prepolymerized.
• a mixture containing the compound of this embodiment is prepolymerized by heating it in the presence or absence of a curing accelerator or polymerization initiator, and in the presence or absence of a solvent.
• compounds such as amine compounds, compounds having ethylenically unsaturated bonds, maleimide compounds, cyanate ester compounds, polybutadiene and modified products thereof, polystyrene and modified products thereof, inorganic fillers, and other additives may be added and prepolymerized.
• the components may be mixed or prepolymerized using, for example, an extruder, kneader, or rolls in the absence of a solvent, or a reaction vessel equipped with a stirrer in the presence of a solvent.
• the uniform mixing method involves kneading the components using a device such as a kneader, roll, or planetary mixer at a temperature within the range of 50 to 100°C to obtain a uniform resin composition.
• the resulting resin composition is then pulverized and molded into cylindrical tablets using a molding machine such as a tablet machine, or into a granular powder or powder molded body.
• these compositions can be melted on a surface support and molded into a sheet with a thickness of 0.05 mm to 10 mm to obtain a molded curable resin composition.
• the resulting molded body is non-sticky at 0 to 20°C, and there is little decrease in fluidity or curability even when stored at -25 to 0°C for one week or more.
• the resulting molded article can be molded into a cured product using a transfer molding machine or a compression molding machine.
• the curable resin composition of this embodiment can also be made into a varnish-like composition (hereinafter simply referred to as varnish) by adding an organic solvent.
• the curable resin composition of this embodiment can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone, as needed, to form a varnish.
• This varnish can then be impregnated into a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, or paper, and heated and dried to produce a prepreg.
• This prepreg can then be hot-press molded to form a cured product of the curable resin composition of this embodiment.
• the solvent used in this case accounts for 10 to 70% by weight, preferably 15 to 70% by weight, of the mixture of the curable resin composition of this embodiment and the solvent.
• a cured product containing carbon fiber can be obtained directly, for example, by the RTM method.
• the curable resin composition of this embodiment can also be used as a modifier for film-type compositions. Specifically, it can be used to improve flexibility, etc., in the B-stage.
• a film-type resin composition can be obtained as a sheet-like adhesive by applying the curable resin composition of this embodiment as a varnish onto a release film, removing the solvent under heat, and then performing B-stage formation.
• This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates, etc.
• the curable resin composition of this embodiment can also be used to obtain a prepreg by heating and melting it to reduce its viscosity and impregnating it into reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber.
• reinforcing fibers such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, and alumina fiber.
• specific examples include, but are not limited to, glass fibers such as E-glass cloth, D-glass cloth, S-glass cloth, Q-glass cloth, spherical glass cloth, NE-glass cloth, and T-glass cloth; inorganic fibers other than glass; and organic fibers such as polyparaphenylene terephthalamide (Kevlar (registered trademark), manufactured by DuPont), wholly aromatic polyamide, polyester, polyparaphenylene benzoxazole, polyimide, and carbon fiber.
• Kevlar registered trademark
• the shape of the substrate is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, and chopped strand mat.
• woven fabrics include plain weave, sieve weave, and twill weave, and these can be selected appropriately from these known methods depending on the intended application and performance.
• woven fabrics that have been subjected to fiber opening treatment and glass woven fabrics that have been surface-treated with a silane coupling agent or the like.
• the thickness of the substrate is not particularly limited, but is preferably approximately 0.01 to 0.4 mm. Prepreg can also be obtained by impregnating reinforcing fibers with the varnish and drying them by heating.
• a laminate can also be manufactured using the prepreg.
• the laminate is not particularly limited as long as it comprises one or more prepregs, and may also have any other layers.
• the method for manufacturing the laminate can be any generally known method, and is not particularly limited. For example, when molding a metal foil-clad laminate, a multi-stage press, a multi-stage vacuum press, a continuous molding machine, an autoclave molding machine, or the like can be used.
• the prepregs are laminated together and then heated and pressure molded to obtain a laminate.
• the heating temperature is not particularly limited, but is preferably 65 to 300°C, and more preferably 120 to 270°C.
• the pressure applied is also not particularly limited, but if the pressure is too high, it becomes difficult to adjust the solid content of the resin in the laminate, resulting in unstable quality. If the pressure is too low, air bubbles will form and adhesion between the laminate layers will be poor. Therefore, a pressure of 2.0 to 5.0 MPa is preferred, and 2.5 to 4.0 MPa is more preferred.
• the laminate of this embodiment, having a layer made of metal foil can be suitably used as a metal foil-clad laminate, as described below.
• the prepreg is cut into a desired shape and laminated with copper foil or the like as needed.
• the laminate is then heated and cured while applying pressure to the laminate by press molding, autoclave molding, sheet winding molding, or the like, to obtain an electrical and electronic laminate (printed wiring board) or a carbon fiber reinforced material.
• the curable resin composition of this embodiment can also be made into a resin sheet.
• One method for obtaining a resin sheet from the curable resin composition of this embodiment is to apply the curable resin composition to a support film (support), followed by drying to form a resin composition layer on the support film.
• the film softens under the lamination temperature conditions (70°C to 140°C) used in vacuum lamination and exhibits fluidity (resin flow) that allows resin to fill via holes or through holes in the circuit board simultaneously with lamination of the circuit board. It is preferable to blend the above-mentioned components to achieve this characteristic.
• the resulting resin sheet or circuit board (such as a copper-clad laminate) must have a uniform appearance to ensure consistent performance at any given location without experiencing locally varying property values due to phase separation or other factors.
• the diameter of the through holes in the circuit board is 0.1 to 0.5 mm, and the depth is 0.1 to 1.2 mm, and it is preferable to be able to fill them with resin within this range. Furthermore, if both sides of the circuit board are laminated, it is desirable to fill about half of the through holes.
• a specific method for producing the above-mentioned resin sheet includes preparing a resin composition varnished by blending an organic solvent, applying the varnished resin composition to the surface of a support film (Y), and then drying the organic solvent by heating or blowing hot air onto the resin composition to form a resin composition layer (X).
• the organic solvents used here preferably include, for example, ketones such as acetone, methyl ethyl ketone, and cyclohexanone; acetate esters such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; carbitols such as cellosolve and butyl carbitol; aromatic hydrocarbons such as toluene and xylene; dimethylformamide, dimethylacetamide, and N-methylpyrrolidone. It is also preferable to use organic solvents in such a way that the nonvolatile content is 30 to 60% by mass of the total.
• the thickness of the resin composition layer (X) formed must be equal to or greater than the thickness of the conductor layer of the circuit board onto which the resin composition layer (X) is laminated. Since the thickness of the conductor layer of the circuit board is in the range of 5 to 70 ⁇ m, the thickness of the resin composition layer (X) is preferably 10 to 100 ⁇ m.
• the resin composition layer (X) in this embodiment may be protected with a protective film, which will be described later. Protection with a protective film can prevent the adhesion of dust and other particles to the surface of the resin composition layer (X) and scratches.
• the support film and protective film can be made of polyolefins such as polyethylene, polypropylene, and polyvinyl chloride; polyesters such as polyethylene terephthalate (PET) and polyethylene naphthalate; polycarbonate; polyimide; and even release paper and metal foils such as copper foil and aluminum foil.
• the support film and protective film may be subjected to a mud treatment, corona treatment, or release treatment. There are no particular restrictions on the thickness of the support film, but it is generally between 10 and 150 ⁇ m, and preferably between 25 and 50 ⁇ m.
• the thickness of the protective film is preferably between 1 and 40 ⁇ m.
• the support film (Y) is peeled off after the resin composition layer (X) has been laminated onto the circuit board, or after the resin composition layer (X) has been heat-cured to form an insulating layer. Peeling off the support film (Y) after the resin composition layer (X) that constitutes the resin sheet has been heat-cured can prevent the adhesion of dust and other particles during the curing process. If the support film (Y) is to be peeled off after the resin composition layer (X) has been cured, a release treatment is applied to the support film (Y) beforehand.
• a multilayer printed circuit board can be produced from the resin sheet obtained as described above.
• the protective film is peeled off, and then the resin composition layer (X) is laminated to one or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum lamination method.
• the lamination method may be a batch method or a continuous method using a roll. If necessary, the resin sheet and circuit board may be heated (preheated) before lamination.
• a pressure bonding temperature (lamination temperature) of 70 to 140°C is preferred, a pressure bonding pressure of 1 to 11 kgf/cm 2 (9.8 ⁇ 10 4 to 107.9 ⁇ 10 4 N/m 2 ) is preferred, and lamination is preferably performed under reduced pressure of 20 mmHg (26.7 hPa) or less.
• the curable resin composition of this embodiment can be used to manufacture semiconductor devices.
• semiconductor devices include DIP (dual in-line package), QFP (quad flat package), BGA (ball grid array), CSP (chip size package), SOP (small outline package), TSOP (thin small outline package), and TQFP (thin quad flat package).
• the curable resin composition and its cured product of this embodiment can be used in a wide range of fields. Specifically, they can be used in a variety of applications, including molding materials, adhesives, composite materials, and paints. Because the cured product of the curable resin composition described in this embodiment exhibits excellent heat resistance and dielectric properties, it is suitable for use in electrical and electronic components such as encapsulants for semiconductor elements, encapsulants for liquid crystal display elements, encapsulants for organic EL elements, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), lightweight, high-strength structural composite materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing, etc.
• electrical and electronic components such as encapsulants for semiconductor elements, encapsulants for liquid crystal display elements, encapsulants for organic EL elements, laminates (printed wiring boards, BGA substrates, build-up substrates, etc.), lightweight, high-strength structural composite materials such as carbon fiber reinforced plastics and glass fiber reinforced plastics, 3D printing
• the curable resin composition of the present invention is suitably used for electric and electronic parts such as semiconductor encapsulants, printed wiring boards, and build-up laminates.

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