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
  • C08G59/20—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
• • 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
• • 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

Definitions

• the present invention relates to a curable composition that is fast-curing and has excellent heat resistance and toughness in the cured product, a cured product, a fiber-reinforced composite material, and a fiber-reinforced resin molded product made of the curable composition.
• 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. Practical use is progressing in various applications as a resin for fiber-reinforced composite materials.
• epoxy resins for fiber-reinforced composite materials have the disadvantage that the cured product tends to be hard and brittle compared to other resin systems.
• a resin composition capable of improving this brittleness and giving a cured product having excellent toughness.
• the problem to be solved by the present invention is to provide a curable composition having long fluidity and excellent rapid curing properties, and excellent heat resistance and toughness in the cured product, a cured product made of the curable composition, and a fiber
• An object of the present invention is to provide a reinforced composite material and a fiber-reinforced resin molded product.
• the present inventors have found a curable composition containing an epoxy resin, a specific amine compound, and a thermoplastic resin, wherein the epoxy group in the epoxy resin is
• the above problems can be solved by using a curable composition in which the ratio [H/E] of the number of moles E to the number of moles H of active hydrogen in the amine compound is in the range of 1 to 1.2. , completed the present invention.
• the present invention provides a curable composition containing an epoxy resin (A), an amine compound (B), and a thermoplastic resin (C), wherein the mol of epoxy groups in the epoxy resin (A) is The ratio [H/E] between the number E and the number H of moles of active hydrogen in the amine compound (B) is in the range of 1 to 1.2, and the amine compound (B) is an alicyclic amine compound.
• the present invention relates to a curable composition, a cured product made of the curable composition, a fiber-reinforced composite material, and a fiber-reinforced resin molded product, characterized by comprising:
• the curable composition of the present invention has long fluidity and excellent fast curing properties, and has excellent heat resistance and toughness in the cured product, so it is suitably used for fiber reinforced composite materials and fiber reinforced resin molded articles. be able to.
• the "long fluidity" in the present invention is the time required for the viscosity of the curable composition in the curing reaction to reach 200 mPa s (80 ° C) from the initial viscosity of less than 200 mPa s (80 ° C).
• “Excellent rapid curability” means that the viscosity of the curable composition reaches from 200 mPa ⁇ s to 5,000 mPa ⁇ s (80°C) in a short time.
• the curable composition of the present invention is characterized by containing an epoxy resin (A), an amine compound (B), and a thermoplastic resin (C).
• Examples of the epoxy resin (A) include aliphatic epoxy resins, bisphenol-type epoxy resins, phenylene ether-type epoxy resins, naphthylene ether-type epoxy resins, biphenyl-type epoxy resins, triphenylmethane-type epoxy resins, and phenol novolak-type epoxy resins.
• cresol novolak type epoxy resin bisphenol novolac type epoxy resin, naphthol novolac type epoxy resin, naphthol-phenol co-condensation novolac type epoxy resin, naphthol-cresol co-condensation novolac type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy Resin, dicyclopentadiene-phenol addition reaction type epoxy resin, biphenylaralkyl type epoxy resin, fluorene type epoxy resin, xanthene type epoxy resin, dihydroxybenzene type epoxy resin, trihydroxybenzene type epoxy resin, oxazolidone type epoxy resin, glycidylamine type Epoxy resins, bis(hydroxynaphthalene)-type epoxy resins, and the like are included.
• epoxy resins (A) can be used alone or in combination of two or more.
• the aliphatic epoxy resin, the bisphenol-type epoxy resin, and the bisphenol-type epoxy resin are more preferred, since a curable composition having long fluidity and excellent heat resistance in the cured product can be obtained.
• the ratio of the bisphenol type epoxy resin to the total weight of the epoxy resin (A) is preferably 50% by mass or more, more preferably 70% or more. 80% or more is particularly preferred.
• Examples of the aliphatic epoxy resin include glycidyl etherification products of various aliphatic polyol compounds.
• Examples of the aliphatic polyol compound include ethylene glycol, propylene glycol, 1,3-propanediol, 2-methylpropanediol, 1,2,2-trimethyl-1,3-propanediol, 2,2-dimethyl-3 -isopropyl-1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 3-methyl-1,3-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentane Aliphatic diol compounds such as diols, neopentyl glycol, 1,6-hexanediol, 1,4-bis(hydroxymethyl)cyclohexane, 2,2,4-trimethyl-1,3-pentanediol; tri- or more functional alipha
• bisphenol type epoxy resin examples include bisphenol A type epoxy resin, bisphenol AP type epoxy resin, bisphenol B type epoxy resin, bisphenol BP type epoxy resin, bisphenol E type epoxy resin, bisphenol F type epoxy resin, and bisphenol S type epoxy resin. Resins, hydrogenated bisphenol type epoxy resins obtained by hydrogenating these resins, and the like.
• biphenyl type epoxy resin examples include 4,4′-dihydroxybiphenyl type epoxy resin, 2,2′-dihydroxybiphenyl type epoxy resin, tetramethyl-4,4′-dihydroxybiphenyl type epoxy resin, tetramethyl-2 , 2'-dihydroxybiphenyl-type epoxy resins, and hydrogenated biphenyl-type epoxy resins obtained by hydrogenating these.
• triphenylmethane-type epoxy resin examples include those having a structural site represented by the following structural formula (1) as a repeating structural unit.
• R 1 and R 2 are each independently a hydrogen atom or a bonding point that connects the structural site represented by the structural formula (1) via a methine group marked with *. . n is an integer of 1 or more. ]
• a glycidyloxybenzene or glycidyloxynaphthalene structure is at a structural site represented by any of the following structural formulas (2-1) to (2-3). and those having a molecular structure knotted together.
• X is an alkylene group having 2 to 6 carbon atoms, an ether bond, a carbonyl group, a carbonyloxy group, a sulfide group, or a sulfone group.
• Examples of the glycidylamine type epoxy resin include N,N-diglycidylaniline, 4,4′-methylenebis[N,N-diglycidylaniline], triglycidylaminophenol, N,N,N′,N′- tetraglycidylxylylenediamine and the like.
• Examples of the bis(hydroxynaphthalene) type epoxy resin include those represented by any of the following structural formulas (3-1) to (3-3).
• the epoxy equivalent weight of the epoxy resin (A) is in the range of 155 to 195 g/equivalent, since a curable composition having long fluidity and excellent rapid curability and excellent heat resistance in the cured product can be obtained. is preferred, and a range of 160 to 190 g/equivalent is more preferred.
• the amine compound (B) is used as a curing agent or curing accelerator for the epoxy resin (A), and is essentially an alicyclic amine compound.
• alicyclic amine compounds examples include cyclohexylamine, dimethylaminocyclohexane, mensendiamine, isophoronediamine, norbornenediamine, bis(aminomethyl)cyclohexane, diaminodicyclohexylmethane, methylenebis(methylcyclohexanamine), and the like. These alicyclic amine compounds can be used alone or in combination of two or more. Also, among these, bis(aminomethyl)cyclohexane is preferred because it has excellent rapid curability and provides a curable composition having excellent heat resistance and toughness in the cured product, and 1,3-bis (Aminomethyl)cyclohexane is more preferred.
• the amine compound (B) can also be used in combination with an amine compound other than the alicyclic amine compound (hereinafter abbreviated as "other amine compound”), if necessary.
• the content of the alicyclic amine compound has excellent rapid curability, and a curable composition having excellent heat resistance and toughness in the cured product can be obtained. is preferably 50% or more, more preferably 70% or more, and particularly preferably 80% or more.
• Examples of the other amine compound (B) include ethylenediamine, N,N,N',N'-tetramethylethylenediamine, propylenediamine, N,N,N',N'-tetramethylpropylenediamine, dimethylaminopropyl Amines, diethylaminopropylamine, dibutylaminopropylamine, diethylenetriamine, N,N,N',N'',N'-pentamethyldiethylenetriamine, triethylenetetramine, tetraethylenepentamine, 3,3'-diaminodipropylamine , butanediamine, pentanediamine, hexanediamine, trimethylhexanediamine, N,N,N',N'-tetramethylhexanediamine, bis(2-dimethylaminoethyl)ether, dimethylaminoethoxyethoxyethanol, triethanolamine, dimethyl Aliphatic amine compounds such as aminohexanol
• Amine compounds having a polyoxyalkylene structure in the molecular structure such as polyoxyethylenediamine and polyoxypropylenediamine;
• imidazole 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethyl imidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1-isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimidazole, 2-ethy
• imidazoline compounds such as 2-methylimidazoline and 2-phenylimidazoline.
• the amount of the amine curing agent (B) used is such that the ratio [H/E] of the number of moles E of epoxy groups in the epoxy resin (A) to the number of moles H of active hydrogen in the amine compound (B) is , is used so as to be in the range of 1 to 1.2, and has long fluidity and excellent fast curing properties, and a curable composition having excellent heat resistance and toughness in the cured product is obtained. , 1.05 to 1.15.
• thermoplastic resin (C) examples include acrylic resin (C1) and core-shell type rubber particles (C2). These thermoplastic resins (C) can be used alone or in combination of two or more.
• the acrylic resin (C1) its constituent monomers, polymerization method, etc. are appropriately selected depending on the desired performance.
• the constituent monomers include methyl (meth)acrylate, ethyl (meth)acrylate, ( (meth)acrylic acid alkyl esters such as butyl methacrylate 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 acrylate; (meth)acrylic acid (fluoro)alkyl esters such as 2-trifluoroethyl (meth)acrylate; (meth)acrylic acid, (anhydrous) malein acid, acid group-containing monomers such as maleic anhydride; hydroxyl group-containing monomers such as hydroxyethyl (meth)acrylate,
• the acrylic resin (C1) is preferably a block copolymer obtained by copolymerizing a plurality of block polymers having different monomer constitutions.
• the block copolymer include an AB type diblock type, an ABA type or an ABC type triblock type, and the like. Among these, a curable composition having excellent rapid curability and excellent heat resistance and toughness in the cured product can be obtained.
• a curable composition having excellent rapid curability and excellent heat resistance and toughness in the cured product can be obtained.
• the weight average molecular weight (Mw) of the acrylic resin (C1) is preferably in the range of 1,000 to 500,000.
• a weight average molecular weight (Mw) shows the value measured by the gel permeation chromatography (GPC) method.
• the core-shell type rubber particles (C2) specifically refer to core-shell type rubber particles, in which a polymer different from the core component is added to the surface of a particulate core component containing a crosslinked rubbery polymer as a main component. It refers to rubber particles in which part or all of the surface of the particulate core component is covered with a shell component by graft polymerization.
• 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.
• C2 Commercially available products of the core-shell type rubber particles (C2) include, for example, “Paraloid (registered trademark)” EXL-2655 (manufactured by Kureha Chemical Industry Co., Ltd.) composed of butadiene/alkyl methacrylate/styrene copolymer, acrylic ester ⁇ “Staphyloid (registered trademark)” AC-3355 and TR-2122 (manufactured by Takeda Pharmaceutical Co., Ltd.) composed of methacrylic acid ester copolymers, “PARALOID (registered trademark)” composed of butyl acrylate/methyl methacrylate copolymer )” EXL-2611, EXL-3387 (manufactured by Rohm & Haas), “Kane Ace (registered trademark)” MX series (manufactured by Kaneka Corporation), and the like.
• Paraloid (registered trademark)” EXL-2655 manufactured by Kureha Chemical
• the core-shell type rubber particles (C2) have a volume average particle diameter of low viscosity, good impregnation into fibers, and a curable composition capable of forming a cured product having excellent heat resistance and toughness. It is preferably in the range of 50 to 1,000 nm, more preferably 50 to 500 nm, because it is possible to obtain a good product.
• the curable composition of the present invention preferably contains 1 to 10 parts by mass of the core-shell type rubber particles (C2) with respect to 100 parts by mass of the total amount of the curable composition (excluding the organic solvent). It is more preferably 9 parts by mass, and even more preferably 3 to 8 parts by mass. By using it within the above range, 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 toughness can be formed. A sexual composition is obtained and is useful.
• the content of the thermoplastic resin (C) has long fluidity and excellent rapid curability, and a curable composition having excellent toughness in the cured product is obtained, so the epoxy resin (A), It is preferably in the range of 0.5 to 10% by mass, more preferably in the range of 2.0 to 8.0% by mass, based on the total mass of the amine compound (B) and the thermoplastic resin (C).
• the curable composition of the present invention has a long fluidity and excellent fast curing property, and a curable composition having excellent heat resistance and toughness in the cured product is obtained, so the initial viscosity at 80 ° C. is 200 mPa. * It is preferable that it is less than s.
• a curable composition having long fluidity and excellent fast curing property, and excellent heat resistance and toughness in the cured product can be obtained.
• ° C.) is preferably 180 seconds or longer, and the time (b) from 200 mPa s to 5,000 mPa s (80 ° C.) is 180 seconds or less. is preferred.
• the time (a) and the time (b) However, those satisfying the following formula (1) are particularly preferable.
• the curable composition of the present invention can contain flame retardants/flame retardant aids, fillers, additives, organic solvents, etc. within limits that do 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. Among them, it is preferable to use them by mixing them in an appropriate order, since a curable composition having long fluidity and excellent rapid curability and excellent heat resistance and toughness in the cured product can be obtained.
• a blending method of premixing the epoxy resin (A) and the thermoplastic resin (C) and then adding the amine compound (B) is preferred.
• the viscosity of the mixture of the epoxy resin (A) and the thermoplastic resin (C) at 25° C. has excellent rapid curability, and the cured composition has excellent heat resistance and toughness. is obtained, the range of 1,000 to 50,000 mPa ⁇ s is preferable, and the range of 2,000 to 40,000 mPa ⁇ s is more preferable.
• kneading can be performed 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.
• Various members that can be contained in the curable composition of the present invention are described below.
• 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.
• hydrotalcite magnesium hydroxide, boric compounds, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc.
• hydrotalcite magnesium hydroxide
• boric compounds zirconium oxide
• black dye calcium carbonate
• zeolite zeolite
• zinc molybdate activated carbon
• 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 parts by mass to 10 parts by mass, and particularly preferably 0.1 parts by mass 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. 0.05 parts by mass 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-OF 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. 0.05 parts by mass to 20 parts by mass, and particularly preferably 0.5 parts by mass to 15 parts by mass, per 100 parts by mass of the total 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 preferable to mix 0.005 parts by mass to 10 parts by mass with respect to the total 100 parts by mass of the resin components of the curable composition.
• the curable composition of the present invention may contain a filler.
• 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 present 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, and hydrolysis inhibitors.
• agents lubricants, impact agents, slidability improvers, compatibilizers, nucleating agents, reinforcing agents, reinforcing agents, flow control agents, dyes, sensitizers, coloring pigments, rubbery polymers, thickeners , an anti-settling agent, an anti-sagging agent, an anti-foaming agent, a coupling agent, an anti-rust agent, an anti-bacterial/anti-mold agent, an anti-fouling agent, a conductive polymer and the like can be added.
• the curable composition of the present invention may contain an organic solvent, for example, when a fiber-reinforced resin molded article is produced by a filament winding method.
• organic solvents 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 of the cured product. can be done.
• the curable composition of the present invention can be suitably used for fiber-reinforced composite materials, fiber-reinforced resin moldings, and the like, in addition to applications where the composition itself is cured. These are described below.
• the method of obtaining a cured product from the curable composition of the present invention may conform to a general curing method for epoxy resin compositions. It may be selected as appropriate depending on the type, application, and the like. For example, a method of heating the curable composition at a temperature in the range of room temperature to about 250°C can be used. 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 fiber-reinforced composite material of the present invention is a material in a state before curing after impregnating reinforcing fibers with a 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 the fiber-reinforced composite material.
• 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.
• 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 the reinforcing fibers with respect to the total volume of the fiber-reinforced composite material is preferably 40% to 85%, and in terms of strength, it is in the range of 50% to 70%. is more preferred. 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 fiber-reinforced resin molded article of the present invention 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 in the range of 40% to 85%, and from the viewpoint of strength, it is 50% to 70%. A range is particularly preferred.
• fiber-reinforced resin molded products examples 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 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.
• a fiber-reinforced composite material including unidirectional fibers
• the fiber-reinforced composite material is preferably molded by thermosetting at a temperature range of 50° C. to 250° C., and more preferably molded at a temperature range of 70° C. 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° C. to 100° C. to obtain a tack-free cured product, and then further treated at a temperature condition of 120° C. to 200° C., in two steps. A method of curing, etc. can be mentioned.
• 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 the product is airtightly sealed in a vacuum. (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.
• Example 1 Preparation of curable composition (1)
• Using an evaporator set at 100 ° C. 85 parts by mass of bisphenol A type epoxy resin (manufactured by DIC Corporation "EPICLON 840S”) and 40% polybutadiene rubber particles dispersed bisphenol A type epoxy resin (manufactured by Kaneka Corporation "Kaneace 15 parts by mass of MX-154”) was added and stirred for 30 minutes to obtain a mixture.
• 19 parts by mass of 1,3-bis(aminomethyl)cyclohexane was added and stirred for 1 minute with a spatula to obtain a curable composition (1).
• Example 5 Preparation of curable composition (5)
• a mixture was obtained by throwing in 6 parts by mass of "NANOSTRENGTH D51N” manufactured by the company and stirring for 120 minutes.
• 19.9 parts by mass of 1,3-bis(aminomethyl)cyclohexane was added and stirred for 1 minute with a spatula to obtain a curable composition (5).
• Example 6 Preparation of curable composition (6)
• a bisphenol A type epoxy resin (“EPICLON 840S” manufactured by DIC Corporation) and a polymethyl methacrylate block-polybutyl acrylate block diblock acrylic resin ( 3 parts by mass of "NANOSTRENGTH D51N” manufactured by Arkema Co., Ltd.) is added and stirred for 120 minutes, then the temperature is lowered to 100 ° C., and polybutadiene rubber particles are dispersed 40% bisphenol A type epoxy resin ("Kaneace MX-154" manufactured by Kaneka Corporation). A mixture was obtained by throwing in 7.5 parts by mass and stirring for 30 minutes. Next, after cooling the mixture to room temperature, 20 parts by mass of 1,3-bis(aminomethyl)cyclohexane was added and stirred for 1 minute with a spatula to obtain a curable composition (6).
• EPICLON 840S manufactured by DIC Corporation
• Curable compositions (R2) to (R4) were obtained in the same manner as in Comparative Example 1 at the blending ratios shown in Table 3.
• ⁇ Rheometer measurement> Using a rheometer ("MCR302" manufactured by Anton Paar), 0.6 ml of the curable composition was placed immediately after blending each component in the proportions shown in Tables 1 to 3, and the viscosity over time was measured.
• the measurement conditions were a temperature of 80° C., a shear rate of 10 (1/s), an atmospheric gas of Air, a cone of 20 mm, a Dispo parallel plate, and a gap of 2 mm.
• compositions and evaluation results of the curable compositions (1) to (14) prepared in Examples 1 to 14 and the curable compositions (R1) to (R4) prepared in Comparative Examples 1 to 4 are shown in Tables 1 to 3. shown in
• Examples 1 to 14 shown in Tables 1 and 2 are examples of the curable composition of the present invention. It was confirmed that these curable compositions have long fluidity and excellent rapid curability, and have heat resistance and toughness in cured products.
• Comparative Example 3 is an example that does not use an alicyclic amine compound. This curable composition was not cured and could not be evaluated.
• Comparative Example 4 is an example in which no thermoplastic resin is used. This curable composition was confirmed to have insufficient toughness in a cured product.

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• 2022
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