Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
  • C08G59/02—Polycondensates containing more than one epoxy group per molecule
  • C08G59/04—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof
  • C08G59/06—Polycondensates containing more than one epoxy group per molecule of polyhydroxy compounds with epihalohydrins or precursors thereof of polyhydric phenols
• • 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
  • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
• • 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
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/02—Elements
  • C08K3/04—Carbon
• • 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
  • C08K7/00—Use of ingredients characterised by shape
  • C08K7/02—Fibres or whiskers
  • C08K7/04—Fibres or whiskers inorganic
  • C08K7/06—Elements
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

• the present invention relates to phenolic resins, epoxy resins, curable resin compositions, and cured products and carbon fiber reinforced composite materials obtained by curing these resins.
• Epoxy resins when cured with various curing agents, become cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties, and are used in a wide range of applications, including adhesives, paints, laminates, molding compounds, and casting materials.
• Carbon fiber reinforced composites (CFRP) made by impregnating and curing carbon fibers with epoxy resin and a curing agent as a matrix resin, offer lightweight and high strength properties.
• Demand for CFRP is increasing in recent years, as it has been widely used in aircraft structural components, wind turbine blades, automobile exterior panels, and computer applications such as IC trays and laptop housings.
• the lightweight and high strength properties of the molded products are particularly well-suited for use as matrix resins in aircraft applications.
• Thermosetting resin cured products such as epoxy resins used as matrix resins in CFRP and other materials, are generally brittle, and require high mechanical strength when used as structural materials for aerospace applications, vehicles, and other applications.
• a widely known method is to add a highly tough thermoplastic resin to the thermosetting resin matrix (Patent Documents 1 to 3).
• the flexural strength and toughness of prepregs are improved by combining particles of thermoplastic resins such as polyethersulfone, polyetherimide, and polyamide with the thermosetting resin matrix resin.
• CFRP CFRP
• bending strength and toughness are required when used as a structural material for aerospace applications and vehicles.
• Patent Document 4 discloses 1,3-di(2-(3,4-dihydroxyphenyl)-2-propyl)benzene, and indicates that the compound is in the form of crystals with a melting point of 133-137°C. Because recrystallization is required to synthesize the compound, a large amount of organic solvents and resins are discarded, posing cost and environmental issues when considering industrial production. Furthermore, in order to knead and melt the compound with other resins, it must be heated to over 140°C, posing issues in terms of handling and large amounts of energy consumption.
• the present invention was made in consideration of the above circumstances, and aims to provide a phenolic resin that offers excellent industrial productivity and ease of handling, an epoxy resin whose cured product has excellent flexural strength, a curable resin composition and its cured product, and a phenolic resin that can be used as a precursor.
• each of the multiple R 1s independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
• R 2 represents a hydrogen atom or a methyl group
• R 3 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
• Each of the multiple m's independently represents an integer of 0 to 2
• p represents an integer of 0 to 4.
• n represents the average number of repetitions and is a real number in the range of 1 ⁇ n ⁇ 15.
• n is the average number of repetitions and is a real number in the range of 1 ⁇ n ⁇ 15.
• a curable resin composition comprising the phenolic resin according to any one of the preceding items [1] to [3], and at least one selected from the group consisting of a curing accelerator, a polymerization initiator, an epoxy resin, an active ester compound, a phenolic resin other than the phenolic resin, a polyphenylene ether compound, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, and a benzoxazine compound.
• [6] An epoxy resin obtained by reacting the phenolic resin according to any one of the above items [1] to [3] with epihalohydrin.
• the epoxy resin according to the above item [4] having an epoxy equivalent of 190 g/eq. or more and 280 g/eq. or less.
• a curable resin composition comprising the epoxy resin according to the above item [6] or [7] and a curing agent.
• a curable resin composition comprising the epoxy resin according to the above item [6] or [7], and at least one selected from the group consisting of a curing accelerator, a polymerization initiator, an epoxy resin other than the above epoxy resin, an active ester compound, a phenolic resin, a polyphenylene ether compound, a compound having an ethylenically unsaturated bond, an isocyanate resin, a polyamide resin, a maleimide compound, a cyanate ester resin, a polyimide resin, polybutadiene and modified products thereof, polystyrene and modified products thereof, polyethylene and modified products thereof, and a benzoxazine compound.
• a cured product obtained by curing the curable resin composition according to the above item [8] or [9].
• a carbon fiber reinforced composite material obtained by curing the curable resin composition according to the above item [8] or [9].
• the present invention provides a phenolic resin that offers excellent industrial productivity and ease of handling, an epoxy resin whose cured product has excellent flexural strength, a curable resin composition, and a cured product thereof.
• 1 shows a GPC chart of the phenolic resin obtained in Synthesis Example 1.
• 1 shows a GPC chart of the epoxy resin obtained in Synthesis Example 2.
• 1 shows a GPC chart of the phenolic resin obtained in Synthesis Example 3.
• 1 shows a GPC chart of the epoxy resin obtained in Synthesis Example 4.
• 1 shows a GPC chart of the phenolic resin obtained in Synthesis Example 5.
• 1 shows a GPC chart of the epoxy resin obtained in Synthesis Example 6.
• 1 shows a GPC chart of the epoxy resin obtained in Synthesis Example 7.
• the phenolic resin of this embodiment is represented by the following formula (1):
• each of the multiple R1s independently represents a hydrogen atom, a hydrocarbon group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms.
• R2 represents a hydrogen atom or a methyl group
• R3 represents a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms.
• Each of the multiple m's independently represents an integer of 0 to 2
• p represents an integer of 0 to 4.
• n represents the average number of repetitions and is a real number in the range of 1 ⁇ n ⁇ 15.
• n can be calculated from the number average molecular weight determined by measurement using gel permeation chromatography (GPC, detector: RI) or the area ratio of each separated peak.
• n is preferably a real number in the range 1 ⁇ n ⁇ 15, more preferably 1 ⁇ n ⁇ 10, and particularly preferably 1 ⁇ n ⁇ 5.
• the softening point of the phenolic resin of this embodiment is preferably 60°C or higher and 120°C or lower, and more preferably 60°C or higher and 100°C or lower. Having a softening point within the above range provides excellent handleability.
• the phenolic resin of this embodiment preferably has a hydroxyl group equivalent of 100 to 140 g/eq., and more preferably 110 to 130 g/eq.
• the phenolic resin represented by formula (1) is more preferably represented by formula (3) below, and particularly preferably represented by formula (3-1) below.
• the phenolic resin of this embodiment may be mixed with the epoxy resin of this embodiment described below or various materials exemplified in this specification to form a curable resin composition.
• the phenolic resin of this embodiment can be obtained, for example, by reacting a catechol with a di-substituted benzene compound under acidic conditions.
• catechols include catechol, 3-methylcatechol, 4-methylcatechol, 4,5-dimethylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, and 3,5-di-t-butylcatechol, and these compounds may be used alone or in combination of two or more.
• di-substituted benzene compounds include ⁇ , ⁇ '-dihydroxy-1,3-diisopropylbenzene, ⁇ , ⁇ '-dihydroxy-1,4-diisopropylbenzene, 1,3-diisopropylbenzene, 1,4-diisopropylbenzene, 1,3-divinylbenzene, and 1,4-divinylbenzene, and these compounds may be used alone or in combination of two or more.
• Solvents include, but are not limited to, methanol, ethanol, propanol, isopropanol, toluene, xylene, methyl ethyl ketone, and methyl isobutyl ketone, and may be used alone or in combination of two or more.
• the amount used is preferably 5 to 500 parts by weight, and more preferably 10 to 300 parts by weight, per 100 parts by weight of the catechol compound.
• acidic catalysts include hydrochloric acid, phosphoric acid, sulfuric acid, formic acid, zinc chloride, ferric chloride, aluminum chloride, p-toluenesulfonic acid, methanesulfonic acid, activated clay, and ion exchange resins. These may be used alone or in combination of two or more.
• the amount of catalyst used is usually 0.1 to 50% by weight, preferably 1 to 30% by weight, based on the catechol compound used. If too much is used, the reaction solution will become too viscous and difficult to stir, and if too little is used, the reaction will proceed slowly.
• the epoxy resin of this embodiment can be obtained, for example, by reacting the phenolic resin with epihalohydrin.
• epihalohydrin examples include epichlorohydrin, ⁇ -methylepichlorohydrin, and epibromohydrin.
• the amount of epihalohydrin used is preferably 1.0 to 20 mol, more preferably 3.0 to 8.0 mol, and even more preferably 4.0 to 6.0 mol, per mol of hydroxyl groups in the phenolic resin.
• an alkali metal hydroxide can be used as a catalyst to promote the epoxidation step.
• Usable alkali metal hydroxides include sodium hydroxide and potassium hydroxide.
• a solid or an aqueous solution thereof may be used, but in this embodiment, the use of a solid formed into flakes is particularly preferred from the standpoints of solubility and handling.
• the amount of alkali metal hydroxide used is preferably 0.90 to 1.5 mol, more preferably 0.95 to 1.25 mol, and even more preferably 0.99 to 1.15 mol per mol of hydroxyl groups in the raw material phenol mixture.
• quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, or trimethylbenzylammonium chloride may be added as a catalyst.
• the amount of quaternary ammonium salt used is preferably 0.1 to 15 g, and more preferably 0.2 to 10 g, per mole of hydroxyl groups in the raw material phenol mixture.
• the reaction temperature is preferably 30 to 90°C, more preferably 35 to 80°C.
• the reaction time is preferably 0.5 to 10 hours, more preferably 1 to 8 hours, and particularly preferably 1 to 3 hours. If the reaction time is too short, the reaction will not proceed to completion, while if the reaction time is too long, by-products will be produced, which is undesirable.
• the reaction products of these epoxidation reactions are washed with water, or without washing, and then heated under reduced pressure to remove epihalohydrin and solvent.
• the recovered epoxy resin can be dissolved in a ketone compound having 4 to 7 carbon atoms (e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.) as a solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out the reaction, ensuring ring closure.
• a ketone compound having 4 to 7 carbon atoms e.g., methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone, etc.
• the amount of alkali metal hydroxide used is preferably 0.01 to 0.3 mol, more preferably 0.05 to 0.2 mol, per 1 mol of hydroxyl groups in the raw phenol mixture used in the epoxidation.
• the reaction temperature is preferably 50 to 120°C, and the reaction time is preferably 0.5 to 2 hours.
• the salt produced is removed by filtration, washing with water, etc., and the solvent is then distilled off under heating and reduced pressure to obtain the epoxy resin of this embodiment.
• R 1 , R 2 , R 3 , m, p, and n are the same as those in formula (1), and R 4 represents a hydrogen atom or a methyl group.
• the epoxy resin of this embodiment preferably has a softening point of 100°C or less, and more preferably 80°C or less.
• a softening point of 100°C or less provides excellent handleability.
• the lower limit of the softening point is preferably 40°C or more.
• the epoxy resin of this embodiment preferably has an epoxy equivalent of 190 g/eq. or more and 280 g/eq. or less, and more preferably 200 g/eq. or more and 240 g/eq. or less.
• the epoxy resin represented by formula (2) is more preferably represented by formula (4) below, and even more preferably represented by formula (4-1) below.
• the curable resin composition of this embodiment contains a curing agent.
• curing agents that can be used include amine-based curing agents, acid anhydride-based curing agents, amide-based curing agents, and phenol-based curing agents.
• an amine-based curing agent is preferred, as it can achieve a good balance between the resin viscosity of the curable resin composition and the heat resistance of the cured resin.
• amine-based curing agents include 3,3'-diaminodiphenyl sulfone (3,3'-DDS), 4,4'-diaminodiphenyl sulfone (4,4'-DDS), diaminodiphenylmethane (DDM), 3,3'-diisopropyl-4,4'-diaminodiphenylmethane, 3,3'-di-t-butyl-4,4'-diaminodiphenylmethane, 3,3'-diethyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-diisopropyl-5,5'-dimethyl-4,4'-diaminodiphenylmethane, 3,3'-d
• aniline novolak orthoethylaniline novolak
• aniline resins obtained by reacting aniline with xylylene chloride and aniline resins obtained by polycondensation of aniline with substituted biphenyls (such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl) or substituted phenyls (such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(hydroxymethyl)benzene).
• substituted biphenyls such as 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl
• substituted phenyls such as 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene and 1,4-bis(
• acid anhydride curing agents examples include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexahydrophthalic anhydride.
• Amide-based curing agents include dicyandiamide or polyamide resins synthesized from a linolenic acid dimer and ethylenediamine.
• Phenol-based curing agents include polyhydric phenols (bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-(1,1'-biphenyl)-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, etc.); phenols (e.g., phenol, alkyl-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, and dihydroxynaphthalene, etc.); and aldehydes (formaldehyde, acetaldehyde, benzaldehy
• Suitable phenols include phenolic resins obtained by condensation with hydroxybenzaldehyde and furfural, ketones (p-hydroxyacetophenone and o-hydroxyacetophenone), or dienes (dicyclopentadiene and tricyclopentadiene); phenolic resins obtained by polycondensation of the above phenols with substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl), or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene); modified products of the above phenols and/or the above phenolic resins; and halogenated phenols such as tetrabromobisphenol A and brominated phenolic resins.
• the amount of curing agent used is preferably 0.7 to 1.2 equivalents per equivalent of epoxy groups in the epoxy resin. If the amount is less than 0.7 equivalents per equivalent of epoxy groups or more than 1.2 equivalents, curing may be incomplete and good cured physical properties may not be obtained.
• the curable resin composition of this embodiment may also contain a curing accelerator, if necessary.
• the gelation time can also be adjusted by using a curing accelerator.
• curing accelerators that can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4-methylimidazole; tertiary amines such as 2-(dimethylaminomethyl)phenol and 1,8-diaza-bicyclo[5.4.0]undecene-7; phosphines such as triphenylphosphine; and metal compounds such as tin octoate.
• the curing accelerator is used in an amount of 0.01 to 5.0 parts by weight per 100 parts by weight of the epoxy resin, as needed.
• the curable resin composition of this embodiment may contain other epoxy resins.
• specific examples include phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, etc.).
• epoxy resins examples include polycondensates of bisphenols and aldehydes (e.g., 4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl), phenolic resins obtained by polycondensation of phenols and substituted biphenyls (e.g., 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, and 1,4-bis(hydroxymethyl)benzene), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins such as 4-vinyl-1-cyclohexene diepoxide and 3,4-epoxycyclohexylmethyl-3,4'-epoxycyclohexanecarboxylate, glycidylamine epoxy resins such as
• the curable resin composition of this embodiment can contain known additives as needed.
• usable additives include active ester compounds, phenolic resins, compounds having ethylenically unsaturated bonds, isocyanate resins, polyamide resins, benzoxazine compounds, polybutadiene and modified products thereof, modified acrylonitrile copolymers, polyphenylene ether compounds, polystyrene and modified products thereof, polyethylene and modified products thereof, polyimide resins, fluororesins, maleimide compounds, cyanate ester resins, silicone gels, silicone oils, inorganic fillers such as silica, alumina, calcium carbonate, quartz powder, aluminum powder, graphite, talc, clay, iron oxide, titanium oxide, aluminum nitride, asbestos, mica, and glass powder, surface treatment agents for fillers such as silane coupling agents, mold release agents, and colorants such as carbon black, phthalocyanine blue, and phthalocyanine green.
• active ester compounds include phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds.
• polyphenylene ether compounds examples include SA-9000 (manufactured by SABIC, a polyphenylene ether compound with a methacrylic group) and OPE-2St 1200 (manufactured by Mitsubishi Gas Chemical Company, a polyphenylene ether compound with a styrene structure).
• Examples of compounds having an ethylenically unsaturated bond include reaction products of phenol resins with ethylenically unsaturated halogenated compounds (chloromethylstyrene, allyl chloride, methallyl chloride, acrylic acid chloride, methacrylic acid chloride, etc.), reaction products of ethylenically unsaturated phenols (2-allylphenol, 2-propenylphenol, 4-allylphenol, 4-propenylphenol, eugenol, isoeugenol, etc.) with halogenated compounds (1,4-bis(chloromethyl)benzene, 4,4'-bis(chloromethyl)biphenyl, 4,4'-difluorobenzophenone, 4,4'-dichlorobenzophenone, 4,4'-dibromobenzophenone, cyanuric chloride, etc.), reaction products of epoxy resins or alcohols with (meth)acrylic acids (acrylic acid, methacrylic acid
• isocyanate resins 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 biuret derivatives of one or more isocyanate monomers or isocyanate derivatives obtained by trimerizing the above diisocyanate compounds; and polyiso
• 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, and 1,3-bis(4-maleimidophenoxy) benzene, Zylok-type maleimide compounds (Anilix Maleimide, manufactured by Mitsui Fine Chemicals, Inc.), biphenylaralkyl-type maleimide compounds (solidified by distilling off the solvent under reduced pressure from a resin solution containing the maleimide compound
• Cyanate ester resins include 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-dicyclopentadiene co-condensates in which the hydroxyl groups have been converted to cyanate groups.
• Polyimide resins include those prepared by combining the above diamines with tetracarboxylic dianhydrides (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-cyclohexene-1,2-dicarboxylic anhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 2,2',3,3'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenyl ...
• tetracarboxylic dianhydrides (4,4'-(hexafluoroisopropylidene)diphthalic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)
• diphthalic dianhydride 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, methylene-4,4'-diphthalic dianhydride, 1,1-ethylidene-4,4'-diphthalic dianhydride, 2,2'-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-di Phthalic dianhydride, 4,4'-oxydiphthalic dianhydride, thio-4,4'-diphthalic dianhydride, sulfonyl-4,4'-diphthalic dianhydride
• Polybutadiene and its modified products, polystyrene and its modified products, polyethylene and its modified products include polybutadiene, hydroxyl-terminated polybutadiene, (meth)acrylate-terminated polybutadiene, carboxylic acid-terminated polybutadiene, amine-terminated polybutadiene, styrene-butadiene rubber, RICON-100, RICON-181, RICON-184 (all manufactured by Cray Valley Corporation), 1,2-SBS (manufactured by Nippon Soda Co., Ltd.), B-1000, B-2000, B-3000 (all manufactured by Nippon Soda Co., Ltd.); polystyrene, styrene-2-isopropenyl-2-oxazoline copolymer (Epocross RP S-1005, RP-61, all manufactured by Nippon Shokubai Co., Ltd.), SEP (styrene-ethylene propylene copolymer: Sept
• SEP styrene-ethylene propylene copolymer: Septon ethylene-butylene-styrene block copolymer: Septon 8004, Septon 8006, Septon 8007L, all manufactured by Kuraray Co., Ltd.
• SEEPS-OH styrene-ethylene/ethylene-propylene-styrene block copolymer with a hydroxyl group at the end: Septon HG252, manufactured by Kuraray Co., Ltd.
• SIS styrene-isoprene-styrene block copolymer: Septon 5125, Septon 5127, all manufactured by Kuraray Co., Ltd.
• hydrogenated SIS hydrogenated styrene-isoprene-styrene block copolymer: Hybrar 7125F, Hybrar 7311F, all manufactured by Kuraray Co., Ltd.
• SIBS styrene-isobutylene
• suitable copolymers include ethylene
• benzoxazine compounds include benzoxazine P-d, Fa, and ALP-d (all manufactured by Shikoku Kasei Corporation), 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 uniformly mixing the above components.
• 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 to form a varnish-like composition (hereinafter simply referred to as a varnish).
• a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, or N-methylpyrrolidone
• a varnish-like composition hereinafter simply referred to as a varnish
• the solvent is used in an amount that 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.
• the above prepreg is cut into the desired shape and laminated, and then the curable resin composition is heated and cured while pressure is applied to the laminate using methods such as press molding, autoclave molding, or sheet winding molding, to obtain carbon fiber reinforced plastic (CFRP). Copper foil or organic film can also be laminated when laminating the prepreg.
• CFRP carbon fiber reinforced plastic
• CFRP can also be obtained by molding using known methods.
• resin transfer molding RTM
• a carbon fiber substrate usually woven carbon fiber fabric
• preform a preformed body before being impregnated with resin
• the preform is placed in a mold, the mold is closed, resin is injected to impregnate the preform and harden, and the mold is then opened to remove the molded product.
• RTM method such as the VaRTM method, SCRIMP (Seeman's Composite Resin Infusion Molding Process), or the CAPRI (Controlled Atmospheric Pressure Resin Infusion) method, which is described in JP-A-2005-527410, in which a resin supply tank is evacuated to a pressure lower than atmospheric pressure, cyclic compression is used, and the net molding pressure is controlled to more appropriately control the resin injection process, particularly the VaRTM method.
• VaRTM method such as the VaRTM method, SCRIMP (Seeman's Composite Resin Infusion Molding Process), or the CAPRI (Controlled Atmospheric Pressure Resin Infusion) method, which is described in JP-A-2005-527410, in which a resin supply tank is evacuated to a pressure lower than atmospheric pressure, cyclic compression is used, and the net molding pressure is controlled to more appropriately control the resin injection process, particularly the VaRTM method.
• Carbon fibers include acrylic, pitch, and rayon carbon fibers, with acrylic carbon fibers being preferred due to their high tensile strength.
• the carbon fiber can be in the form of twisted yarn, untwisted yarn, or untwisted yarn, but untwisted yarn or untwisted yarn is preferred due to the good balance between the formability and strength properties of the fiber-reinforced composite material.
• the cured product of the curable resin composition of this embodiment can be used for a variety of applications in addition to the above-mentioned applications such as CFRP, including adhesives, paints, coatings, molding materials (including sheets, films, CFRP, etc.), encapsulants for semiconductor elements, encapsulants for liquid crystal display elements, encapsulants for organic EL elements, printed wiring boards (BGA substrates, build-up substrates, etc.), and electrical and electronic components such as 3D printing, as well as additives for other resins, etc.
• CFRP including adhesives, paints, coatings, molding materials (including sheets, films, CFRP, etc.), encapsulants for semiconductor elements, encapsulants for liquid crystal display elements, encapsulants for organic EL elements, printed wiring boards (BGA substrates, build-up substrates, etc.), and electrical and electronic components such as 3D printing, as well as additives for other resins, etc.
• adhesives include those for civil engineering, construction, automotive, general office, and medical use, as well as adhesives for electronic materials.
• adhesives for electronic materials include interlayer adhesives for multilayer substrates such as build-up substrates, die bonding agents, semiconductor adhesives such as underfills, underfills for reinforcing BGAs, and mounting adhesives such as anisotropic conductive films (ACFs) and anisotropic conductive pastes (ACPs), making them applicable to a wide variety of uses.
• ACFs anisotropic conductive films
• ACPs anisotropic conductive pastes
• the curable resin composition of this embodiment is used as an encapsulant for semiconductor devices
• a lead frame equipped with a semiconductor device or a semiconductor package substrate is placed in a mold, and the curable resin composition of this embodiment is molded by melt casting, transfer molding, injection molding, compression molding, or other methods, and then heated at 80 to 200°C for 2 to 10 hours to obtain a cured product.
• Examples of semiconductor devices that can be manufactured using this encapsulant include potting, dipping, and transfer mold encapsulation for capacitors, transistors, diodes, light-emitting diodes, ICs, and LSIs; potting encapsulation for COB, COF, TAB, and other types of ICs and LSIs; underfill for flip chips; and encapsulation (including reinforcing underfill) for mounting IC packages such as QFP, BGA, and CSP.
• a prepreg can be obtained by heating and melting the composition to reduce viscosity and impregnating it into reinforcing fibers such as glass fiber or polyamide fiber.
• reinforcing fibers such as glass fiber or polyamide 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, and/or organic fibers.
• the shape of the substrate is not particularly limited, but examples include woven fabric, nonwoven fabric, roving, and chopped strand mat.
• Known weaving methods for woven fabric include plain weave, sieve weave, and twill weave, and these known methods can be selected appropriately depending on the intended application and performance.
• Woven fabrics that have been opened or surface-treated with a silane coupling agent or the like are also suitable.
• the thickness of the substrate is not particularly limited, but is preferably approximately 0.01 to 0.4 mm.
• prepreg can be obtained by impregnating reinforcing fibers with the varnish and then heating and drying it to produce a copper clad laminate (CCL).
• CCL copper clad laminate
• a laminate can also be produced using the curable resin composition of this embodiment by hot-press molding the resulting prepreg and CCL.
• the laminate is not particularly limited as long as it contains one or more prepregs, and may also contain any other layers.
• a sheet-like adhesive can be obtained by applying the varnish to a release film, removing the solvent under heat, and B-staging the varnish.
• This sheet-like adhesive can be used as an interlayer insulating layer in multilayer substrates or as an adhesive sheet for mounting semiconductors.
• the curable resin composition of this embodiment can also be used with specialized substrate materials such as package substrates and high-density interconnects (HDIs).
• Epoxy equivalent Measured by the method described in JIS K-7236, and expressed in g/eq.
• GPC gel permeation chromatography analysis
• Manufacturer Waters Column: Guard column SHODEX GPC KF-401HQ, KF-402HQ, KF-402.5HQ, KF-403HQ, Flow rate: 0.3ml/min.
• Detector RI (differential refractive index detector)
• Example 1 Comparative Example 1, Comparative Example 2
• DDS 4,4'-diaminodiphenyl sulfone
• Example 1 which used the epoxy resin of the present invention, was excellent in bending strength.

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• 2025
  • 2025-02-17 WO PCT/JP2025/005099 patent/WO2025187370A1/ja active Pending
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