Classifications

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  • 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
  • C08G59/10—Polycondensates containing more than one epoxy group per molecule of polyamines with epihalohydrins or precursors thereof
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  • 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
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  • 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
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/22—Di-epoxy compounds
  • C08G59/24—Di-epoxy compounds carbocyclic
  • C08G59/245—Di-epoxy compounds carbocyclic aromatic
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  • 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
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/3227—Compounds containing acyclic nitrogen atoms
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  • 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
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
  • C08G59/32—Epoxy compounds containing three or more epoxy groups
  • C08G59/38—Epoxy compounds containing three or more epoxy groups together with di-epoxy compounds
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  • 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
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
  • C08G59/4014—Nitrogen containing compounds
  • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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  • 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
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
  • C08G59/50—Amines
  • C08G59/5033—Amines aromatic
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  • 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
  • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
  • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
  • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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  • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/21—Urea; Derivatives thereof, e.g. biuret
• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/10—Encapsulations, e.g. protective coatings characterised by their shape or disposition
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
  • H10W74/00—Encapsulations, e.g. protective coatings
  • H10W74/40—Encapsulations, e.g. protective coatings characterised by their materials
  • H10W74/47—Encapsulations, e.g. protective coatings characterised by their materials comprising organic materials, e.g. plastics or resins
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  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2170/00—Compositions for adhesives
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2203/00—Applications
  • C08L2203/20—Applications use in electrical or conductive gadgets
  • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Definitions

• SiC semiconductors have been considered useful in place of Si semiconductors in the power semiconductor field. Since SiC has a dielectric breakdown field strength about 10 times higher than Si, even in device structures such as Schottky barrier diodes and MOSFETs, the thickness of the depletion layer can be thinned while maintaining voltage resistance. As a result, SiC power devices can simultaneously achieve high voltage resistance, high-speed switching characteristics, and low on-resistance. Furthermore, since SiC has a band gap about three times wider than Si, it can provide power devices that can operate even at high temperatures.
• the epoxy resin used as a raw material for semiconductor encapsulation materials it is necessary for the epoxy resin used as a raw material for semiconductor encapsulation materials to have excellent heat resistance when mixed with a hardener and cured, so that the cured product obtained by curing the epoxy resin is excellent in heat resistance in anticipation of use in high-temperature environments.
• CFRP is required to have a high elastic modulus because it is used as a base material for aircraft and cars.
• epoxy resins with rigid molecular frameworks or multifunctional epoxy resins In order to increase the glass transition point of the cured product, it is common to use epoxy resins with rigid molecular frameworks or multifunctional epoxy resins. However, depending on the formulation, even if a multifunctional epoxy resin is used, the elastic modulus may not increase, and there has been a demand for epoxy resins that can achieve both a high glass transition temperature and a high elastic modulus.
• Patent Document 1 discloses a tetraglycidylamine derivative of m-tolidine as an epoxy resin with a rigid and multifunctional molecular structure.
• a liquid crystal alignment agent containing this compound has good storage stability, is highly transparent, and can form a liquid crystal alignment film with good liquid crystal alignment properties.
• tetraglycidylamine derivatives of m-tolidine are evaluated as additives for liquid crystal alignment agents.
• epoxy resins are generally used by mixing with other epoxy resins and hardeners when producing paints, adhesives, prepregs, semiconductor sealants, etc.
• tetraglycidylamine derivatives of m-tolidine contain a biphenyl skeleton, there was concern that they would become highly viscous when produced by commonly used production methods, resulting in poor miscibility.
• R 1 to R 4 may be the same or different and are a hydrogen atom or a hydrocarbon group, which may contain a heteroatom; R 1 to R 4 may be bonded to each other to form a ring; and at least one of R 1 to R 4 is a hydrocarbon group.
• the epoxy resin according to the first embodiment of the present invention (hereinafter, sometimes simply referred to as the present epoxy resin) is an epoxy resin containing a compound X represented by the following formula (1).
• the epoxy resin according to this embodiment is an epoxy resin containing a compound X having a diaminobiphenyl skeleton, and the content ratio of an oligomer consisting of the compound X in the epoxy resin is 0.01 to 19.0 area % when the total area of the peaks detected in a reversed-phase HPLC measurement using a UV detector at 280 nm is taken as 100 area %.
• the epoxy resin is a concept including an epoxy compound, and is also a composition (composition) consisting of multiple types of substances, that is, a composition (composition) containing at least the epoxy compound X and an oligomer consisting of the epoxy compound X.
• composition composition consisting of multiple types of substances, that is, a composition (composition) containing at least the epoxy compound X and an oligomer consisting of the epoxy compound X.
• the cured product obtained by curing the following compound X using a curing agent or the like exhibits good heat resistance and elastic modulus.
• R 1 to R 4 may be the same or different and are a hydrogen atom or a hydrocarbon group, which may contain a heteroatom; R 1 to R 4 may be bonded to each other to form a ring; and at least one of R 1 to R 4 is a hydrocarbon group.
• the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a tert-butyl group, a phenyl group, and a trifluoromethyl group.
• examples of the structure include a ring formed by bonding these hydrocarbon groups to each other.
• the upper limit of the viscosity of the present epoxy resin at 150° C. is preferably 100 mPa ⁇ s or less, more preferably 80 mPa ⁇ s or less, even more preferably 70 mPa ⁇ s or less, and particularly preferably 60 mPa ⁇ s or less. If the viscosity at 150° C. is equal to or less than the above upper limit, it becomes easy to mix uniformly, and a cured product of uniform quality can be produced.
• the lower limit of the viscosity of the present epoxy resin at 150° C. is preferably 1 mPa ⁇ s or more, more preferably 10 mPa ⁇ s or more, and particularly preferably 20 mPa ⁇ s or more. If the viscosity at 150° C. is equal to or more than the above lower limit, mixing can be performed by applying shear, making it easy to mix uniformly.
• the viscosity of the epoxy resin at 150° C. can be measured, for example, by the method described in the examples described below.
• the epoxy equivalent, viscosity at 50°C, and viscosity at 150°C of this epoxy resin are measured by the method described in the Examples section below.
• the present epoxy resin may contain an easily saponifiable halogen, and specifically, the easily saponifiable halogen usually includes chlorine, bromine, etc.
• the amount of easily saponifiable halogen in the epoxy resin can be measured in accordance with JIS K7243-2.
• the upper limit of the amount of easily saponifiable halogen in the present epoxy resin is preferably 20,000 ppm by mass or less, more preferably 11,000 ppm by mass or less, even more preferably 9,000 ppm by mass or less, still more preferably 3,000 ppm by mass or less, still more preferably 1,000 ppm by mass or less, still more preferably 500 ppm by mass or less, and particularly preferably 200 ppm by mass or less.
• the amount of easily saponifiable halogen is the above lower limit or less, when the epoxy resin is used as an electronic material, corrosion of metal parts used in wiring of the product can be prevented.
• the lower limit of the amount of easily saponifiable halogen in the present epoxy resin is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, and particularly preferably 50 ppm by mass or more.
• the present epoxy resin can be produced by an economical process using epihalohydrin.
• the upper limit of the total halogen content of the present epoxy resin is preferably 50,000 mass ppm or less, more preferably 20,000 mass ppm or less, even more preferably 15,000 mass ppm or less, still more preferably 10,000 mass ppm or less, and particularly preferably 7,000 mass ppm or less. If the total halogen content is the lower limit or less, corrosion of metal parts used in wiring of products can be prevented when the epoxy resin is used as an electronic material.
• the lower limit of the total halogen content of the present epoxy resin is preferably 1 ppm by mass or more, more preferably 10 ppm by mass or more, further preferably 100 ppm by mass or more, and particularly preferably 500 ppm by mass or more.
• the epoxy resin can be produced by an economical process using epihalohydrin.
• the total halogen content in the epoxy resin can be measured in accordance with JIS K7243-3.
• the preferred ranges of the amount of easily saponifiable halogen and the total amount of halogen described above may be adopted as the ranges of the amount of each halogen alone (for example, in the case of chlorine, the amount of easily saponifiable chlorine and the total amount of chlorine, respectively).
• the lower limit of the content of oligomers consisting of compound X when the total area of detected peaks is taken as 100 area % is preferably 0.01 area % or more, more preferably 0.1 area % or more, even more preferably 0.5 area % or more, and even more preferably 1.0 area % or more.
• the reaction time it is necessary to increase the reaction time infinitely, which is not realistic. If the content is equal to or more than the lower limit, the reaction can be carried out in a realistic production time, and process stability can be improved.
• an oligomer made of compound X is an oligomer that can be produced as a by-product in the manufacture of compound X.
• it is an oligomer produced by addition of an epoxy group in compound X to an active hydrogen-containing compound, or an oligomer produced by anionic polymerization in which compound X itself acts as a tertiary amine catalyst.
• an oligomer made of compound X is a compound group that has a longer retention time than that of compound X in reversed-phase HPLC measurement.
• the lower limit of the content of compound X in the epoxy resin is not particularly limited, but is preferably 60 area% or more, more preferably 70 area% or more, even more preferably 80 area% or more, and particularly preferably 85 area% or more. If the content is equal to or more than the above lower limit, the epoxy group content per unit weight increases, and as a result, the crosslink density increases when the epoxy resin is cured, and the heat resistance improves.
• the upper limit of the content of compound X in the present epoxy resin is not particularly limited, but may be 99 area % or less, 95 area % or less, or 90 area % or less.
• the content of compound X in the present epoxy resin is preferably 100 area %, but as described above, it is not realistic to eliminate oligomers consisting of compound X, so the above upper limit may be used.
• Examples of low molecular weight components other than compound X include compounds in which the glycidyl group of compound X is substituted with at least one of the following groups or atoms: ⁇ -glycol group, 1,2-halohydrin group, 1,3-halohydrin group, a group in which epihalohydrin is added to the ⁇ -OH of an ⁇ -glycol group, a group in which epihalohydrin is added to the ⁇ -OH of an ⁇ -glycol group, a group in which epihalohydrin is added to the ⁇ -OH of a 1,2-halohydrin group, a group in which epihalohydrin is added to the ⁇ -OH of a 1,3-halohydrin group, a group in which alcohol of the reaction solvent is ⁇ -added to a glycidyl group, and a hydrogen atom.
• the epoxy resin produced as described above may be purified to a high degree by reacting it again with an alkali to drive the ring-closing reaction of the remaining 1,2-halohydrin, by recrystallization, or by distillation. These methods may be used in combination. From an economical standpoint, purification by reaction with an alkali is preferred.
• a solvent may be used in the reaction process or purification process for producing this epoxy resin. Any solvent may be used as long as it dissolves the raw materials. Usually, this is an organic solvent, but water may also be used.
• the content of the curing agent is preferably 0.1 to 1000 parts by weight per 100 parts by weight of the total epoxy resin components as solids. Also, it is more preferably 500 parts by weight or less, and even more preferably 300 parts by weight or less.
• solids refers to components excluding solvents, and includes not only solid epoxy resins, but also semi-solid and viscous liquids.
• total epoxy resin components corresponds to the amount of epoxy resin contained in the curable resin composition, and in the case where this epoxy resin and other epoxy resins are included, it corresponds to the sum of the epoxy resin in this epoxy resin and the other epoxy resins.
• the curable resin composition of this embodiment can obtain excellent heat resistance, stress resistance, moisture absorption resistance, flame retardancy, and the like.
• imidazoles from the viewpoint of sufficiently progressing the curing reaction and improving heat resistance.
• polyhydric phenol resins obtained by the condensation reaction of various phenols with various aldehydes such as benzaldehyde, hydroxybenzaldehyde, crotonaldehyde, or glyoxal; polyhydric phenol resins obtained by the condensation reaction of xylene resin and phenols; co-condensation resins of heavy oils or pitches with phenols and formaldehydes; phenol-benzaldehyde-xylylene dimethoxide polycondensates; phenol-benzaldehyde-xylylene dihalide polycondensates; phenol-benzaldehyde-4,4'-dimethoxide biphenyl polycondensates; or phenol-benzaldehyde-4,4'-dihalide biphenyl polycondensates.
• These phenol-based curing agents may be used alone or in any combination of two or more kinds in any blend ratio.
• the amount of the phenol-based hardener is preferably 0.1 to 1,000 parts by weight, more preferably 500 parts by weight or less, even more preferably 300 parts by weight or less, and particularly preferably 100 parts by weight or less, per 100 parts by weight of the total epoxy resin components in the hardenable resin composition.
• alicyclic amines examples include isophorone diamine, methacenediamine, N-aminoethylpiperazine, bis(4-amino-3-methyldicyclohexyl)methane, bis(aminomethyl)cyclohexane, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraoxaspiro(5,5)undecane, and norbornene diamine.
• organic phosphines or phosphonium salts are preferred, and organic phosphines are most preferred.
• the curing accelerators may be used alone or in any combination and ratio of two or more. When dicyandiamide is used as the curing agent, it is preferable to use aromatic urea or aliphatic urea as the curing accelerator.
• the average particle size of the inorganic filler is usually 1 to 50 ⁇ m, preferably 1.5 to 40 ⁇ m, and more preferably 2 to 30 ⁇ m. If the average particle size is equal to or greater than the lower limit above, the melt viscosity will not be too high and the flowability will not decrease, which is preferable. If the average particle size is equal to or less than the upper limit above, the filler will not clog the narrow gaps in the mold during molding, which is preferable because the filling properties of the material will be improved.
• the amount of the coupling agent is preferably 0.1 to 3.0 parts by weight per 100 parts by weight of the total epoxy resin components.
• the amount of the coupling agent is equal to or greater than the lower limit above, the effect of improving the adhesion between the epoxy resin matrix and the inorganic filler by adding the coupling agent tends to be improved.
• the amount of the coupling agent is equal to or less than the upper limit above, the coupling agent is less likely to bleed out from the obtained cured product, which is preferable.
• thermoplastic resin examples include polyamide, polyester, polycarbonate, polyethersulfone, polyphenylene ether, polyphenylene sulfide, polyetheretherketone, polyetherketone, polyetherimide, polyimide, polytetrafluoroethylene, polyether, polyolefin, liquid crystal polymer, polyarylate, polysulfone, polyacrylonitrilestyrene, polystyrene, polyacrylonitrile, polymethyl methacrylate, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-ethylene-propylene-diene-styrene copolymer (AES resin), acrylonitrile-styrene-alkyl (meth)acrylate copolymer (ASA resin), polyvinyl chloride, polyvinyl formal, phenoxy resin, and block polymer, but are not limited thereto. These thermoplastic resins may be used alone or in combination of two or more.
• the curable resin composition of the present embodiment can be blended with reinforcing fibers.
• the reinforcing fibers include glass fibers, carbon fibers, aramid fibers, and boron fibers. From the viewpoint of the mechanical properties and weight reduction of the resulting fiber-reinforced plastic, carbon fibers are preferred as the reinforcing fibers.
• the number of carbon fibers in the carbon fiber bundle used in the reinforcing fiber substrate is preferably 1,000 to 70,000.
• a sheet-shaped reinforcing fiber substrate can be formed by using a plurality of carbon fiber bundles and aligning the fibers in one direction.
• the curable resin composition of the present embodiment may contain components other than those described above (sometimes referred to as "other compounding components" in the present disclosure).
• other compounding components include flame retardants, plasticizers, reactive diluents, pigments, etc., and these may be appropriately compounded as needed.
• the curable resin composition of the present embodiment does not in any way prevent the compounding of components other than those listed above.
• the lower limit of the storage modulus of the cured product is preferably more than 3.0 GPa, more preferably more than 3.7 GPa, and particularly preferably more than 4.0 GPa. When the storage modulus is equal to or greater than the lower limit, it is possible to ensure rigidity that can withstand practical use.
• the upper limit of the storage modulus is preferably 10 GPa or less, more preferably 8 GPa or less, and particularly preferably 5 GPa or less. When preparing a cured product having a storage modulus equal to or greater than the upper limit, the curing temperature and the composition of the cured product may not be compatible with the current general process.
• the storage modulus of the cured product can be measured by a known method, for example, by the method described in the Examples below.
• the first embodiment of the present invention relates to an epoxy resin that has excellent miscibility with other epoxy resins and curing agents and gives a cured product having good heat resistance and elastic modulus.
• the second embodiment of the present invention relates to a curable resin composition containing this epoxy resin and a cured product thereof.
• B-1 m-tolidine (4,4'-Diamino-2,2'-dimethylbiphenyl, m-TB-HG manufactured by Seika Corporation)
• the total chlorine content of the epoxy resin was determined by a method that detects the same amount of chlorine as the method according to JIS K7243-3. That is, the measurement was performed according to the following procedure. After accurately weighing 0.05 to 0.2 g of the sample into a beaker, 25 ml of a toluene/dimethyl cellosolve/butyl cellosolve mixed solution was added. Nitrogen bubbling was performed while stirring. 5 to 10 ml of sodium biphenyl was added and the mixture was left for 3 to 5 minutes. Nitrogen bubbling was stopped and 1 ml of 6% hydrogen peroxide solution was added. 20 mL of acetic acid was added, and then potentiometric titration was performed with 1/100N silver nitrate solution. The total chlorine content of the epoxy resin shown in Table 1 is based on mass.
• the heat resistance in the examples and comparative examples was measured using a dynamic viscoelasticity measuring device "DMS6100" manufactured by Seiko Instruments Inc., raising the temperature from 30 to 300°C at 5°C/min.
• the deformation mode was double-support bending, and the measurement frequency was 1 Hz.
• the elastic modulus in the examples and comparative examples was measured using a dynamic viscoelasticity measuring device "DMS6100" manufactured by Seiko Instruments Inc., raising the temperature from 30 to 300°C at 5°C/min.
• the deformation mode was double-support bending, and the measurement frequency was 1 Hz.
• the elastic modulus was measured using the storage modulus E' at a measurement temperature of 40°C for curing system 1, and the storage modulus E' at a measurement temperature of 50°C for curing system 2.
• the storage elastic modulus E' at a measurement temperature of 250° C. for curing system 1 and the storage elastic modulus E' at a measurement temperature of 180° C. for curing system 2 were used as an index of high temperature elastic modulus.

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• 2023
  • 2023-12-20 CN CN202380087118.XA patent/CN120380050A/zh active Pending
  • 2023-12-20 TW TW112149827A patent/TW202438552A/zh unknown
  • 2023-12-20 EP EP23907073.3A patent/EP4640733A4/en active Pending
  • 2023-12-20 KR KR1020257020963A patent/KR20250123141A/ko active Pending
  • 2023-12-20 WO PCT/JP2023/045630 patent/WO2024135713A1/ja not_active Ceased
  • 2023-12-20 JP JP2024566097A patent/JPWO2024135713A1/ja active Pending
• 2025
  • 2025-06-18 US US19/242,925 patent/US20250368773A1/en active Pending

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