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
  • C08G59/18—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
  • C08G59/5006—Amines aliphatic
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
• • 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
  • C08G59/18—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
  • C08G59/5006—Amines aliphatic
  • C08G59/502—Polyalkylene polyamines
• • 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
  • C08G59/18—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
  • C08G59/5026—Amines cycloaliphatic
• • 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
  • C08G59/18—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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
  • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
• • 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
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/34—Heterocyclic compounds having nitrogen in the ring
  • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
  • C08K5/3445—Five-membered rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2463/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
  • C08J2463/02—Polyglycidyl ethers of bis-phenols

Definitions

• the present invention relates to a curable composition that is fast-curing and has good heat resistance and toughness in a cured product, a cured product thereof, a fiber-reinforced composite material, and a fiber-reinforced resin molded product.
• Fiber-reinforced composite materials using carbon fiber, aramid fiber, etc. as reinforcing fibers are widely used in general industrial applications such as automobiles and wind turbines, aerospace industry applications, and sports applications, taking advantage of their high specific strength and specific modulus.
• fiber-reinforced composite materials have been actively developed as a way to reduce the weight of metals.
• Thermosetting resins such as unsaturated polyester resins, vinyl ester resins, and epoxy resins are mainly used as matrix resins for fiber-reinforced composite materials.
• a cured product obtained from a curable composition containing an epoxy resin has excellent heat resistance, high strength, high elastic modulus, adhesion, chemical resistance, and good moldability.
• As a fiber-reinforced composite material it is being put to practical use in various applications.
• Epoxy resin compositions using aromatic amine-based curing components which are used particularly in the field of aircraft, are more excellent in heat resistance and the like of the resulting cured product.
• the use of an epoxy resin composition has been proposed in which a compound and an alcohol compound having a main chain composed of 2 to 6 carbon atoms and an alcohol compound having two or more hydroxyl groups are blended in a specific ratio (for example, Patent Document 1 reference).
• Patent Document 1 reference a compound and an alcohol compound having a main chain composed of 2 to 6 carbon atoms and an alcohol compound having two or more hydroxyl groups
• the problem to be solved by the present invention is a curable composition that is fast-curing and has good heat resistance and toughness in the cured product, a cured product thereof, a fiber-reinforced composite material, and a fiber-reinforced resin It is to provide a molded product.
• a curable composition containing an epoxy resin uses a specific amine compound and an imidazole compound as curing agents in combination, and further contains core-shell particles.
• the inventors have found that the above problems can be solved by blending the epoxy groups in the epoxy resin and the active hydrogen in the specific amine compound at a specific ratio (molar ratio), and have completed the present invention.
• the present invention contains an epoxy resin (A), an aliphatic amine compound and/or an alicyclic amine compound (B), core-shell particles (C), and an imidazole compound (D), and the epoxy resin (A ) and the ratio H/E of the number of moles E of epoxy groups in the aliphatic amine compound and/or the number of moles H of active hydrogen in the alicyclic amine compound (B) is 0.3 to 0.9. relating to sexual compositions.
• the epoxy resin (A) preferably contains a bisphenol F type epoxy resin.
• the viscosity of the mixture of the epoxy resin (A) and the core-shell particles (C) at 25°C is preferably 1,000 to 100,000 mPa ⁇ s.
• the aliphatic amine compound and/or alicyclic amine compound (B) is selected from the group consisting of triethylenetetramine, 1,3-bis(aminomethyl)cyclohexane, and isophoronediamine. At least one selected is preferred.
• the curable composition of the present invention preferably contains 1 to 10 parts by mass of the core-shell particles (C) with respect to 100 parts by mass of the total amount of the curable composition.
• the core-shell particles (C) preferably have a volume average particle size of 50 to 1,000 nm.
• the curable composition of the present invention preferably contains 0.2 to 4 parts by mass of the imidazole compound (D) with respect to 100 parts by mass of the epoxy resin (A).
• the imidazole compound (D) is selected from the group consisting of imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, and 2-ethyl-4-methylimidazole. At least one selected is preferred.
• the epoxy resin (A) preferably contains a naphthalene-type epoxy resin and/or a biphenyl-type epoxy resin.
• the present invention relates to a cured product of the curable composition.
• the present invention relates to a fiber-reinforced composite material containing the curable composition and reinforcing fibers.
• the present invention relates to a fiber-reinforced resin molded article containing the cured product and reinforcing fibers.
• a curable composition a cured product thereof, a fiber-reinforced composite material, and a fiber-reinforced resin molded product, which is fast-curing and has excellent heat resistance and toughness in the cured product. can.
• the present invention contains an epoxy resin (A), an aliphatic amine compound and/or an alicyclic amine compound (B), core-shell particles (C), and an imidazole compound (D), and the epoxy resin (A) contains A curable composition in which the ratio H/E of the number of moles E of epoxy groups to the number of moles H of active hydrogen in the aliphatic amine compound and/or alicyclic amine compound (B) is 0.3 to 0.9. Regarding.
• Epoxy resin (A) The epoxy resin (A) used in the present invention can be used without particular limitation as long as it is an epoxy resin having two or more epoxy groups in the molecule.
• the epoxy resin (A) include bisphenol Bisphenol-type epoxy resins such as A-type epoxy resins, bisphenol S-type epoxy resins, bisphenol F-type epoxy resins; biphenyl-type epoxy resins; naphthalene-type epoxy resins; triphenylmethane-type epoxy resins; glycidylamine-type epoxy resins; , cresol novolac type epoxy resins, novolac type epoxy resins such as bisphenol type novolak; epoxidized products of various dicyclopentadiene-modified phenol resins obtained by reacting dicyclopentadiene with various phenols; epoxy resins having a fluorene skeleton; Phosphorus-containing epoxy resin synthesized using (2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphen
• a curable composition having excellent mechanical strength can be obtained, and in particular, from the viewpoint of low viscosity and toughness, it is more preferable to contain a bisphenol F type epoxy resin, and furthermore, in addition to the bisphenol F type epoxy resin , From the viewpoint of toughness, it is more preferable to contain a biphenyl-type epoxy resin and/or a naphthalene-type epoxy resin.
• the bisphenol F type epoxy resin is preferably contained in the epoxy resin (A) from the viewpoint of low viscosity and toughness.
• the bisphenol F type epoxy resin for example, trade name "EPICLON 830-S” (manufactured by DIC, epoxy equivalent: 165 to 180 g/equivalent, viscosity (25°C): 3,000 to 4,500 mPa s), Trade name "JER 807” (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 160-175 g/equivalent), trade name "YDF-170” (manufactured by Nippon Steel Chemical & Materials, epoxy equivalent: 160-180 g/equivalent), etc. be done.
• the naphthalene-type epoxy resin is preferably contained in the epoxy resin (A) from the viewpoint of toughness.
• examples of the naphthalene-type epoxy resin include the trade name "EPICLON HP-4032D” (manufactured by DIC, epoxy equivalent: 136-150 g/equivalent, viscosity (50°C): 250-850 mPa ⁇ s), trade name "EPICLON HP-4032D”.
• the biphenyl-type epoxy resin is preferably contained in the epoxy resin (A) from the viewpoint of toughness.
• the biphenyl type epoxy resin for example, trade name "XY4000” (manufactured by Mitsubishi Chemical Corporation, epoxy equivalent: 180 to 192 g / equivalent), trade name "NC-3000” (manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent: 265 to 285 g/equivalent).
• the epoxy equivalent of the epoxy resin (A) is preferably 160 to 200 g/equivalent, more preferably 160 to 195 g/equivalent, and more preferably 160 to 190 g/equivalent. Equivalent amounts are more preferred.
• the viscosity of the mixture of the epoxy resin (A) and the core-shell particles (C) at 25° C. is preferably 1,000 to 100,000 mPa ⁇ s, more preferably 1,000 to 50,000 mPa ⁇ s. and more preferably 1,000 to 15,000 mPa ⁇ s. Being within the above range is preferable from the viewpoint of the fluidity of the curable composition and the impregnation of reinforcing fibers and the like.
• amine compound (B) The aliphatic amine compound and/or alicyclic amine compound (B) (hereinafter sometimes referred to as "amine compound (B)") is used as a curing agent for the epoxy resin (A).
• amine compound (B) aliphatic amine compound and/or alicyclic amine compound in the present invention are those in which the carbon atom to which the amino group is bonded does not have aromaticity, and even if it is a compound having an aromatic ring in the structure good.
• the aliphatic amine compound and/or alicyclic amine compound (B) is an amine having one or more active hydrogens in one molecule, and an aliphatic or alicyclic amine is used from the viewpoint of rapid curing. .
• polyamines having two or more active hydrogens in one molecule are preferred.
• aliphatic amine compounds include alkylenediamines such as ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,3-diaminobutane and 1,4-diaminobutane; diethylenetriamine and triethylenetetramine; , polyalkylpolyamines such as tetraethylenepentamine; N,N-dimethylaminopropylamine, N,N-diethylaminopropylamine, N,N-diisopropylaminopropylamine, N,N-diallylaminopropylamine, N,N -bisaminopropyl allylamine, bis[3-(N,N-dimethylaminopropyl)]amine, bis[3-(N,N-diethylaminopropyl)]amine, bis[3-(N,N-diisopropylaminopropyl) ] amine amine
• diethylenetriamine triethylenetetramine
• tetraethylenepentamine from the viewpoint of the viscosity of the composition when combined with the epoxy resin (A), rapid curability, and the mechanical strength of the resulting cured product.
• triethylenetetramine is particularly preferred.
• Examples of the alicyclic amine compounds include N,N-dimethylbisaminocyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,2-diaminocyclohexane, 1 ,4-diamino-3,6-diethylcyclohexane, N,N-cyclohexylmethylaminoethylamine, N,N-dicyclohexylaminoethylamine, N,N-cyclohexylmethylaminopropylamine, N,N-dicyclohexylaminopropylamine, N, N-bisaminopropylcyclohexylamine, isophoronediamine, N,N,-dimethylisophoronediamine, etc., may be used alone or in combination of two or more.
• the amine compound (B) includes triethylenetetramine, At least one selected from the group consisting of 1,3-bis(aminomethyl)cyclohexane and isophoronediamine is preferred, and 1,3-bis(aminomethyl)cyclohexane is more preferred.
• the amine compound (B) and various epoxy resins such as glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether or glycidyl esters of carboxylic acid.
• glycidyl ethers such as phenyl glycidyl ether, butyl glycidyl ether, bisphenol A-diglycidyl ether, bisphenol F-diglycidyl ether or glycidyl esters of carboxylic acid.
• polyepoxy addition-modified products produced by reacting amidation-modified products produced by reacting these organic polyamines with carboxylic acids such as phthalic acid, isophthalic acid and dimer acid; , mannichylated modified products prepared by reacting with aldehydes such as formaldehyde; Mannich-modified products produced by reacting a phenol having a site with the amine compound can also be used as the amine compound (B).
• the blending ratio of the epoxy resin (A) and the amine compound (B) is determined by the number of moles E of the epoxy in the epoxy resin (A) and the aliphatic amine compound and/or the oil.
• the cyclic amine compound (B) is characterized in that the ratio H/E of the number of moles H of active hydrogen in the cyclic amine compound (B) is 0.3 to 0.9.
• the ratio H/E is within the range, the epoxy groups derived from the epoxy resin (A) become excessive, resulting in an addition reaction between the epoxy groups and the amino groups derived from the amine compound (B).
• the ratio H/E is 0.3 to 0.8.
• the core-shell particles (C) specifically refer to core-shell type rubber particles, in which a polymer different from the core component is graft-polymerized on the surface of a particulate core component containing a crosslinked rubbery polymer as a main component. It means a rubber particle in which part or all of the surface of the particulate core component is covered with the shell component.
• the core component examples include crosslinked rubber particles.
• the type of rubber is not limited, and examples thereof include butadiene rubber, acrylic rubber, silicone rubber, butyl rubber, nitrile rubber, styrene rubber, synthetic natural rubber, ethylene propylene rubber and the like.
• the shell component examples include polymers polymerized from one or more monomers selected from the group consisting of acrylic acid esters, methacrylic acid esters and aromatic vinyl compounds.
• the shell component is preferably graft-polymerized to the core component and chemically bonded to the polymer constituting the core component.
• a crosslinked rubbery polymer composed of a polymer of styrene and butadiene is used as the core component
• a polymer of methyl methacrylate, which is a methacrylic acid ester, and styrene, which is an aromatic vinyl compound is used as the shell component. is preferably used.
• Examples of commercially available core-shell type rubber particles include “Paraloid (registered trademark)” EXL-2655 (manufactured by Kureha Chemical Industry Co., Ltd.) composed of butadiene/alkyl methacrylate/styrene copolymer, acrylic acid ester/methacrylic acid “Staphyloid (registered trademark)” AC-3355 and TR-2122 (manufactured by Takeda Pharmaceutical Co., Ltd.) composed of ester copolymers, and “PARALOID (registered trademark)” EXL composed of butyl acrylate/methyl methacrylate copolymer -2611, EXL-3387 (manufactured by Rohm & Haas), and "Kane Ace (registered trademark)” MX series (manufactured by Kaneka Corporation).
• Paraloid (registered trademark)” EXL-2655 manufactured by Kureha Chemical Industry Co., Ltd.
• the volume average particle size of the core-shell particles (C) is low in viscosity, and the epoxy resin composition has good impregnability into fibers, and can form a cured product having excellent heat resistance and mechanical properties. is obtained, the range is preferably 50 to 1,000 nm, more preferably 50 to 500 nm.
• the curable composition of the present invention preferably contains 1 to 10 parts by mass, more preferably 2 to 9 parts by mass, of the core-shell particles (C) with respect to 100 parts by mass of the total amount of the curable composition. Preferably, 3 to 8 parts by mass is more preferable.
• a curable composition having a low viscosity and good impregnation into reinforcing fibers can be obtained, and a cured product having excellent heat resistance and mechanical properties (such as toughness) can be obtained.
• Formable curable compositions are obtained and useful.
• the epoxy resin (A) contains the bisphenol F-type epoxy resin, and by using these together, a cured product with high toughness is obtained, and the high heat resistance is obtained.
• a curable composition that becomes a cured product having both high toughness and high heat resistance can be obtained, which is useful.
• the imidazole compound (D) used in the present invention is used as a curing agent for the epoxy resin (A).
• the imidazole compound (D) is not particularly limited, and examples thereof include imidazole, 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-isopropyl imidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-aminopropylimidazole, etc., and may be used alone or in combination of two or more. .
• imidazole 1-methylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, and 2- It is preferable to use at least one selected from the group consisting of ethyl-4-methylimidazole.
• the curable composition of the present invention preferably contains 0.2 to 4 parts by mass of the imidazole compound (D) with respect to 100 parts by mass of the epoxy resin (A), and 0.3 to 3 parts by mass. more preferably 0.4 to 2 parts by mass. By using it within the above range, a curable composition capable of exhibiting rapid curing can be obtained, which is useful.
• the curable composition of the present invention uses the epoxy resin (A), the aliphatic amine compound and/or the alicyclic amine compound (B) in a specific ratio, and in addition to the core-shell particles (C), the imidazole It is characterized by containing the compound (D), and may further contain other components.
• Other components include, for example, acid-modified polybutadiene, polyethersulfone resin, polycarbonate resin, polyphenylene ether resin, and acrylic resin.
• the acid-modified polybutadiene is a component having reactivity with the epoxy resin (A), and by using the acid-modified polybutadiene in combination, the resulting cured product exhibits excellent mechanical strength, heat resistance, and resistance to moist heat. be able to.
• Examples of the acid-modified polybutadiene include those having a skeleton derived from 1,3-butadiene or 2-methyl-1,3-butadiene in the butadiene skeleton.
• Those derived from 1,3-butadiene include those having any one of 1,2-vinyl, 1,4-trans, and 1,4-cis structures, and those having two or more of these structures. mentioned.
• Those derived from 2-methyl-1,3-butadiene have a structure of either 1,2-vinyl type, 3,4-vinyl type, 1,4-cis type or 1,4-trans type. and those having two or more of these structures.
• the acid-modified component of the acid-modified polybutadiene is not particularly limited, but unsaturated carboxylic acids can be mentioned.
• unsaturated carboxylic acid acrylic acid, methacrylic acid, maleic acid, maleic anhydride, itaconic acid, and itaconic anhydride are preferable. From the viewpoint of reactivity, itaconic anhydride and maleic anhydride are preferable, and maleic anhydride is more preferable. .
• the content of the unsaturated carboxylic acid in the acid-modified polybutadiene is determined from the viewpoint of reactivity with the epoxy resin (A).
• the acid value is preferably 5-400 mgKOH/g, more preferably 20-300 mgKOH/g, even more preferably 50-200 mgKOH/g.
• the unsaturated carboxylic acid component is not limited as long as it is copolymerized in the acid-modified polybutadiene. Examples thereof include random copolymerization, block copolymerization, graft copolymerization (graft modification), and the like.
• the weight average molecular weight (Mw) of acid-modified polybutadiene is preferably 1,000 to 100,000.
• the acid-modified polybutadiene is obtained by modifying polybutadiene with an unsaturated carboxylic acid, but commercially available products may be used as they are.
• commercially available products include maleic anhydride-modified liquid polybutadiene (Polyvest MA75, Polyvest EP MA120, etc.) manufactured by Evonik Degussa, and maleic anhydride-modified polyisoprene (LIR-403, LIR-410) manufactured by Kuraray. can do.
• the content of the acid-modified polybutadiene in the curable composition is such that the total mass of the resin components in the curable composition is 100 parts by mass, because the elongation, heat resistance, and moist heat resistance of the resulting cured product are good. It is preferably contained in a proportion of 1 to 40 parts by mass, more preferably in a proportion of 3 to 30 parts by mass.
• the polyethersulfone resin is a thermoplastic resin, and in the curing reaction of the curable composition, it is not included in the crosslinked network, but due to its excellent modifier effect having a high Tg, in the cured product obtained, Excellent mechanical strength and heat resistance can be expressed.
• the total mass of the resin components in the curable composition was set to 100 parts by mass in order to improve the mechanical strength and heat resistance of the resulting cured product. It is preferably contained in a proportion of 1 to 30 parts by mass, more preferably in a proportion of 3 to 20 parts by mass.
• polycarbonate resin examples include a polycondensate of divalent or bifunctional phenol and carbonyl halide, or a product obtained by polymerizing divalent or bifunctional phenol and carbonic acid diester by transesterification. be done.
• dihydric or bifunctional phenol examples include 4,4′-dihydroxybiphenyl, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4 -hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4- hydroxyphenyl)cyclohexane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, hydroquinone, resorcinol, catechol and the like.
• bis(hydroxyphenyl)alkanes are preferred, and 2,2-bis(4-hydroxyphenyl)propane as
• carbonyl halides or diesters of carbonic acid to be reacted with dihydric or difunctional phenols are, for example, phosgene; and aliphatic carbonate compounds such as dimethyl carbonate, diethyl carbonate, diisopropyl carbonate, dibutyl carbonate, diamyl carbonate and dioctyl carbonate.
• the polycarbonate resin may have a branched structure in addition to having a linear molecular structure of the polymer chain.
• a branched structure can be obtained by using 1,1,1-tris(4-hydroxyphenyl)ethane, ⁇ , ⁇ ', ⁇ ′′-tris(4-hydroxyphenyl)-1,3,5-triisopropylbenzene, It can be introduced by using phloroglucin, trimellitic acid, isatin bis(o-cresol), and the like.
• the polyphenylene ether resins include, for example, poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-14-phenylene) ether, poly(2,6-diethyl-1, 4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4-phenylene) ether, poly(2- methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene) ) ether and the like.
• poly(2,6-dimethyl-1,4-phenylene) ether is preferable, and 2-(dialkylaminomethyl)-6-methylphenylene ether unit and 2-(N-alkyl-N-phenylaminomethyl)-
• a polyphenylene ether containing a 6-methylphenylene ether unit or the like as a partial structure may also be used.
• the polyphenylene ether resin has a reactive functional group such as a carboxyl group, an epoxy group, an amino group, a mercapto group, a silyl group, a hydroxyl group, and an anhydride dicarboxyl group added to its resin structure by any method such as graft reaction or copolymerization.
• the modified polyphenylene ether resin introduced in (1) can also be used as long as the object of the present invention is not impaired.
• the acrylic resin can be added for the purpose of improving the mechanical strength, especially fracture toughness, of the cured product.
• constituent monomers, polymerization method, etc. of the acrylic resin are appropriately selected according to the desired performance.
• constituent monomers include (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate; (Meth)acrylic acid esters having an alicyclic structure such as cyclohexyl (meth)acrylate and cyclohexyl methacrylate; (meth)acrylic acid esters having an aromatic ring such as benzyl (meth)acrylate; (meth)acrylic acid 2- (Meth)acrylic acid (fluoro)alkyl esters such as trifluoroethyl; acid group-containing monomers such as (meth)acrylic acid, (anhydride) maleic acid, and maleic anhydride; hydroxyethyl (meth)acrylate, (meth)acryl hydroxyl
• the acrylic resin is preferably a block copolymer obtained by copolymerizing a plurality of block polymers having different monomer configurations.
• the block copolymer include an AB type diblock type, an ABA type or an ABC type triblock type, and the like. Among them, since it becomes a curable composition having even more excellent mechanical strength in the cured product, it is necessary to have both a block containing methyl (meth)acrylate as a main component and a block containing butyl (meth)acrylate as a main component. is preferred.
• a triblock acrylic resin consisting of a polymethyl methacrylate block-polybutyl acrylate block-polymethyl methacrylate block, and a diblock acrylic resin consisting of a polymethyl methacrylate block-polybutyl acrylate block are preferred.
• Acrylic resins are particularly preferred.
• the acrylic resin preferably has a weight average molecular weight (Mw) of 1,000 to 500,000.
• the content of the acrylic resin in the curable composition is not particularly limited, and is appropriately adjusted according to the desired performance of the cured product. Among them, since it becomes a curable composition that is even more excellent in mechanical strength in the cured product, when the total mass of the resin components of the curable composition is 100 parts by mass, 0.1 to 20 parts by mass of the acrylic resin is included. more preferably 0.5 to 10 parts by mass.
• the curable composition of the present invention can contain flame retardants, fillers, additives, organic solvents, and the like within a range that does not impair the effects of the present invention.
• the order of blending in producing the curable composition is not particularly limited as long as the effects of the present invention can be achieved. That is, all components may be mixed in advance and used, or may be mixed in order as appropriate.
• kneading can be carried out using a kneader such as an extruder, a heating roll, a kneader, a roller mixer, or a Banbury mixer.
• a kneader such as an extruder, a heating roll, a kneader, a roller mixer, or a Banbury mixer.
• the curable composition of the present invention may contain a non-halogen flame retardant that does not substantially contain halogen atoms in order to exhibit flame retardancy.
• non-halogen flame retardants examples include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, organic metal salt flame retardants, and the like.
• a single flame retardant may be used, or a plurality of flame retardants of the same type may be used, or flame retardants of different types may be used in combination.
• inorganic and organic flame retardants can be used as the phosphorus-based flame retardant.
• inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphoramide. .
• the red phosphorus is preferably surface-treated for the purpose of preventing hydrolysis, etc.
• surface treatment methods include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water (ii) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and the like, and A method of coating with a mixture of a thermosetting resin such as a phenolic resin, (iii) a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc. is coated with a thermosetting resin such as a phenolic resin. A method of double-coating with a resin and the like can be mentioned.
• the phosphorus-based flame retardant when used, the phosphorus-based flame retardant is used, the phosphorus-based flame retardant is used in combination with hydrotalcite, magnesium hydroxide, boric compounds, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. good too.
• nitrogen-based flame retardant examples include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazine, etc. Triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferred.
• triazine compound examples include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, melamine polyphosphate, triguanamine, and guanylmelamine sulfate, melem sulfate, and melam sulfate.
• examples thereof include aminotriazine sulfate compounds, the above aminotriazine-modified phenol resins, and products obtained by further modifying the aminotriazine-modified phenol resins with tung oil, isomerized linseed oil, and the like.
• cyanuric acid compound examples include cyanuric acid and melamine cyanurate.
• the amount of the nitrogen-based flame retardant is appropriately selected depending on the type of nitrogen-based flame retardant, other components of the curable composition, and the desired degree of flame retardancy. 0.05 to 10 parts by mass, particularly preferably 0.1 to 5 parts by mass, per 100 parts by mass of the total resin components.
• a metal hydroxide, a molybdenum compound, or the like may be used in combination.
• any organic compound containing a silicon atom can be used as the silicone-based flame retardant without particular limitation, and examples thereof include silicone oil, silicone rubber, and silicone resin.
• the amount of the silicone flame retardant to be blended is appropriately selected depending on the type of silicone flame retardant, other components of the curable composition, and the desired degree of flame retardancy. It is preferable to mix 0.05 to 20 parts by mass with respect to 100 parts by mass of the total resin components. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.
• inorganic flame retardants examples include metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass.
• metal hydroxide examples include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, and zirconium hydroxide.
• metal oxides include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. , bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide, and the like.
• metal carbonate compounds include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.
• the metal powder examples include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.
• boron compound examples include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.
• low-melting glass examples include Seapley (Bokusui Brown Co.), hydrated glass SiO 2 —MgO—H 2 O, PbO—B 2 O 3 system, ZnO—P 2 O 5 —MgO system, P2O5-B2O3 - PbO-MgO system, P-Sn - O - F system, PbO - V2O5 - TeO2 system , Al2O3 - H2O system, lead borosilicate system, etc. can be mentioned.
• the amount of the inorganic flame retardant compounded is appropriately selected depending on the type of the inorganic flame retardant, other components of the curable composition, and the desired degree of flame retardancy. It is preferably blended in the range of 0.05 to 20 parts by mass, particularly preferably in the range of 0.5 to 15 parts by mass, with respect to the total of 100 parts by mass of the resin components.
• organometallic salt-based flame retardants examples include ferrocene, acetylacetonate metal complexes, organometallic carbonyl compounds, organic cobalt salt compounds, organic sulfonate metal salts, metal atoms and aromatic compounds or heterocyclic compounds in ionic bonds or Coordinate bonded compounds and the like can be mentioned.
• the amount of the organometallic salt-based flame retardant to be blended is appropriately selected depending on the type of the organometallic salt-based flame retardant, other components of the curable composition, and the desired degree of flame retardancy. It is preferably blended in the range of 0.005 to 10 parts by mass with respect to a total of 100 parts by mass of the resin components of the curable composition.
• the curable composition of the present invention may contain fillers.
• the curable composition of the present invention contains a filler, the resulting cured product can exhibit excellent mechanical properties.
• fillers include titanium oxide, glass beads, glass flakes, glass fibers, calcium carbonate, barium carbonate, calcium sulfate, barium sulfate, potassium titanate, aluminum borate, magnesium borate, fused silica, crystalline silica, alumina, nitride
• fibrous reinforcing agents such as silicon, aluminum hydroxide, kenaf fiber, carbon fiber, alumina fiber, quartz fiber, and non-fibrous reinforcing agents. These may be used individually by 1 type, or may use 2 or more types together. Moreover, these may be coated with an organic substance, an inorganic substance, or the like.
• glass fiber when used as a filler, it can be selected from long fiber type rovings, short fiber type chopped strands, milled fibers, and the like. It is preferable to use a glass fiber surface-treated for the resin to be used.
• the strength of the incombustible layer (or carbonized layer) generated during combustion can be further improved.
• the incombustible layer (or carbonized layer) once formed during combustion is less likely to be damaged, and a stable heat insulating ability can be exhibited, resulting in a greater flame retardant effect.
• a high stiffness can be imparted to the material.
• the curable composition of the invention may contain additives.
• additives include, for example, plasticizers, antioxidants, ultraviolet absorbers, stabilizers such as light stabilizers, antistatic agents, conductivity imparting agents, stress relaxation agents, release agents, crystallization accelerators, hydrolysis Inhibitors, lubricants, impact agents, slidability improvers, compatibilizers, nucleating agents, reinforcing agents, reinforcing agents, flow control agents, dyes, sensitizers, coloring pigments, rubbery polymers, thickeners Agents, anti-settling agents, anti-sagging agents, anti-foaming agents, coupling agents, anti-rust agents, anti-bacterial/anti-mold agents, anti-fouling agents, conductive polymers and the like can also be added.
• the curable composition of the present invention may contain an organic solvent when producing a fiber-reinforced resin molding by a filament winding method.
• organic solvents that can be used here include methyl ethyl ketone acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, and the like. can be appropriately selected depending on the application.
• the curable composition of the present invention has a very high curing speed, and can be used in various applications such as paints, electrical and electronic materials, adhesives, and molded products, taking advantage of the excellent heat resistance and mechanical strength (high toughness, etc.) of the cured product. It can be used for various purposes. Moreover, the curable composition can be suitably used for fiber-reinforced composite materials, fiber-reinforced resin molded articles, and the like, in addition to applications in which it is used by curing itself. These are described below.
• the present invention relates to a cured product of the curable composition.
• a cured product obtained using the curable composition has high heat resistance and high toughness, and is useful.
• the method for obtaining the cured product may conform to a general curing method for epoxy resin compositions.
• the heating temperature conditions may be appropriately selected depending on the type of curing agent to be combined and the application.
• a method of heating the curable composition in a temperature range of about room temperature (25°C) to about 250°C can be mentioned.
• a general method for a curable composition can be used as a molding method, and conditions specific to the curable composition of the present invention are unnecessary.
• the present invention relates to a fiber-reinforced composite material containing the curable composition and reinforcing fibers.
• a fiber-reinforced composite material containing the curable composition and reinforcing fibers.
• the fiber-reinforced composite material is a material in a state before curing after impregnating reinforcing fibers with the curable composition.
• the reinforcing fibers may be twisted yarns, untwisted yarns, or untwisted yarns, but untwisted yarns and untwisted yarns are preferable because they have excellent moldability in fiber-reinforced composite materials.
• the form of the reinforcing fibers those in which the fiber direction is aligned in one direction or a woven fabric can be used.
• the woven fabric can be freely selected from plain weave, satin weave, etc., depending on the site and application. Specifically, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicon carbide fiber, etc., which are excellent in mechanical strength and durability, can be used, and two or more of these can be used in combination. .
• carbon fiber is particularly preferable because the strength of the molded article is excellent, and various types of carbon fiber such as polyacrylonitrile, pitch, and rayon can be used.
• the method for obtaining a fiber-reinforced composite material from the curable composition of the present invention is not particularly limited.
• a method of immersing unidirectional reinforcing fibers in which the reinforcing fibers are aligned in one direction in the varnish (before curing by the pultrusion method or filament winding method), or overlapping the reinforcing fiber fabrics and setting them in a concave shape Then, after sealing with a convex mold, a method of injecting resin and impregnating under pressure (state before curing by RTM method) can be used.
• the curable composition does not necessarily impregnate the inside of the fiber bundle, and even if the curable composition is localized near the surface of the fiber. good.
• the volume content of reinforcing fibers relative to the total volume of the fiber-reinforced composite material is preferably 40 to 85%, and more preferably 50 to 70% in terms of strength. . If the volume content is less than 40%, the content of the curable composition is too large, resulting in insufficient flame retardancy of the resulting cured product, or is required for fiber-reinforced composite materials with excellent specific elastic modulus and specific strength. In some cases, it may not be possible to satisfy various characteristics. Moreover, when the volume content exceeds 85%, the adhesiveness between the reinforcing fibers and the resin composition may deteriorate.
• the present invention relates to a fiber-reinforced resin molded product containing the cured product and reinforcing fibers.
• the cured product By using the cured product to produce the fiber-reinforced resin molded product, it has excellent impregnation properties into reinforcing fibers and rapid curing.
• the fiber-reinforced composite material has high heat resistance, excellent mechanical strength (such as high toughness), and is useful.
• the fiber-reinforced resin molded article is a molded article having reinforcing fibers and a cured product of a curable composition, and is obtained by thermosetting a fiber-reinforced composite material.
• the volume content of the reinforcing fibers in the fiber-reinforced molded product is preferably 40 to 85%, and from the viewpoint of strength, it is preferably 50 to 70%. more preferred.
• Examples of such fiber-reinforced resin molded products include automobile parts such as front subframes, rear subframes, front pillars, center pillars, side members, cross members, side sills, roof rails and propeller shafts, core members for electric cables, Examples include pipe materials for submarine oil fields, roll and pipe materials for printers, robot fork materials, primary structural materials for aircraft, secondary structural materials, and the like.
• the method for obtaining a fiber-reinforced molded article from the curable composition of the present invention is not particularly limited, it is preferable to use a pultrusion method (pultrusion method), a filament winding method, an RTM method, or the like.
• the pultrusion molding method is a method of molding a fiber reinforced resin molded product by introducing a fiber reinforced composite material into a mold, heating and curing it, and then pulling it out with a drawing device. is a method in which a fiber-reinforced composite material (including unidirectional fibers) is wound while rotating around an aluminum liner, a plastic liner, etc., and then cured by heating to form a fiber-reinforced resin molded product.
• the fiber-reinforced composite material is preferably heat-cured at a temperature range of 50 to 250°C, and more preferably molded at a temperature range of 70 to 220°C. This is because if the molding temperature is too low, sufficient rapid curing may not be obtained, and if it is too high, warping due to thermal strain may easily occur.
• the fiber-reinforced composite material is precured at 50 to 100° C. to obtain a tack-free cured product, and then cured in two stages, such as by treatment at a temperature of 120 to 200° C. methods and the like.
• Other methods for obtaining a fiber-reinforced molded article from the curable composition of the present invention include a hand lay-up method and a spray-up method in which a fiber aggregate is laid in a mold and the varnish and fiber aggregate are laminated in multiple layers; Using either a male or female mold, the base material made of reinforcing fibers is impregnated with varnish and stacked and molded, covered with a flexible mold that can apply pressure to the molded product, and vacuum-sealed. (Reduced pressure)
• the vacuum bag method for molding, the SMC press method for compressing and molding a sheet of varnish containing reinforcing fibers in advance with a mold, and the like can be used.
• Examples 1 to 9 and Comparative Examples 1 to 7 According to the formulations shown in Tables 1 and 2 below, each component was blended and uniformly stirred to obtain a curable composition. Furthermore, a cured product was obtained using the curable composition. Various evaluation tests were performed on the curable composition and the cured product in the following manner. The evaluation results are shown in Tables 1 and 2.
• the reaction mixture was washed with water three times, and it was confirmed that the washing water had a neutral pH. Then, the reaction mixture was azeotropically dehydrated, passed through microfiltration, and the solvent was distilled off under reduced pressure to obtain a biphenyl type epoxy resin (A-1).
• the epoxy equivalent of the obtained epoxy resin (A-1) was 230 g/equivalent (epoxy resin "A-1" in Tables 1 and 2).
• the gel time is preferably shorter (for example, less than 180 seconds) from the viewpoint of rapid curing. A: Less than 180 seconds B: Less than 180 to 360 seconds C: 360 seconds or more
• the dynamic viscoelasticity was measured under the following conditions: room temperature (25° C.) to glass transition temperature +50° C., temperature increase rate of 3° C./min, frequency of 1 Hz, and strain amplitude of 25 ⁇ m.
• the glass transition temperature preferably exceeds 120° C., which is the temperature at which the curable composition is cured, and is preferably higher from the viewpoint of heat resistance.
• the curable composition obtained above was poured into a mold having a thickness of 6 mm and heated at 120° C. for 5 minutes to obtain a cured product.
• the obtained cured product was cut with a diamond cutter into a width of 12 mm and a length of 55 mm to prepare a test piece according to ASTM D-5045.
• a fracture toughness test was conducted according to ASTM D-5045.
• the fracture toughness value K IC /2 was measured to evaluate the fracture toughness. From the viewpoint of toughness, the fracture toughness value is preferably higher.
• Comparative Example 7 does not use an aliphatic amine compound and/or an alicyclic amine compound (B).
• "Epoxy group (H/E)" is not a value based on "aliphatic amine compound and/or alicyclic amine compound (B)" as in other examples and comparative examples.
• the number of moles E of epoxy groups in the epoxy resin (A) and the number of moles of active hydrogen in the aliphatic amine compound and/or alicyclic amine compound (B) The ratio H/E of the number H is within the range of 0.3 to 0.9, and by containing imidazole (D), it can be confirmed that the gel time is short and the cured product is fast curing. It was confirmed that the glass transition temperature is high, the heat resistance is high, the fracture toughness value is high, and the toughness is high. In particular, it has been confirmed that both high heat resistance and high toughness can be achieved, excellent effects can be expressed, and it is useful.
• Comparative Examples a curable composition using desired raw materials was not used, or the ratio H/E was out of the desired range, resulting in faster curability than in Examples. It was confirmed that the glass transition temperature was low and the heat resistance was poor, and the fracture toughness was low and the toughness was poor. Especially in Comparative Example 7, no aliphatic amine compound and/or alicyclic amine compound was used, and the ratio H/E was not within the desired range. could not.

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