TW201224240A - Fiber reinforcing resin complex material - Google Patents

Abstract

The fiber with reinforcing resin of the present invention is a fiber that is treated the surface by epoxyated polydiene based resin. Preferably, the aforementioned fiber is a carbon fiber or a glass fiber. The fiber reinforcing resin complex material of the present invention is constituted of the aforementioned fiber with reinforcing resin and matrix resin; preferably, the aforementioned matrix resin is an epoxy based thermosetting resin. According to the fiber with reinforcing resin of the present invention, the absorption energy(elasticity energy) until the most high loading of fiber reinforcing resin complex material and absorption energy(movement energy) after the most high loading of fiber reinforcing resin complex material can be enhanced simultaneously.

Description

[Technical Field] The present invention relates to a resin-reinforcing fiber useful for producing a fiber-reinforced composite material, a fiber-reinforced resin composite material using the resin-reinforcing fiber, and a composite of the fiber-reinforced resin. A structure made of materials. [Prior Art] The fiber-reinforced resin composite material is a composite material composed of a reinforcing fiber and a matrix resin, and is used in automobile parts, civil construction products, blades for wind power generation, sports &, aircraft, ships, robots, cable materials, and the like. Widely used in the field. As the reinforcing fiber, glass fiber, guanamine fiber, carbon fiber, boron fiber or the like is used. As the matrix resin, a thermosetting resin which is easily impregnated into the reinforcing fibers is often used. As the thermosetting resin, an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, a phenol resin, a maleimide resin, a cyanate resin, or the like is used, and among them, the most commonly used one has excellent heat resistance, elastic modulus, and resistance. Chemical resistance, and epoxy resin with small shrinkage. In the carbon fiber reinforced resin composite material having excellent impact properties, a carbon fiber reinforced resin composite material is disclosed in the patent document No. 3 1 36883 (Patent Document No.), and the carbon fiber reinforced resin composite material is characterized in that the specific gravity is 1.75 or less. The elastic modulus and the tensile strength are specific enthalpy, and the nitrogen concentration N/C and the surface oxygen concentration 〇/c are in a specific range, and the carbon fiber unit weight includes an epoxy oxime composed of an aliphatic compound having a plurality of epoxy groups. The sizing agent is 0.01 to 5%, and is reinforced with carbon fibers having a sheet end peel strength of 22 kgf/mm2 or more. The above epoxy-based polymerization agent is an aliphaticated 201224240 compound having a number of epoxy groups of 2 to 4 and a molecular weight of 1 Å to 2 Å. In Japanese Patent No. 3003521 (Patent Document 2), a sizing agent is adhered to the sizing agent, and the change in the force is small, and the carbon fiber and the adhesive force are improved, and the mechanical properties of the composite material are excellent. There is no carbon fiber, a sizing agent composed of bisphenol A diglycidyl ether or a plurality of epoxy groups, and the thickness of the sizing agent is the maximum 値 and minimum thickness of the slurry in a specific range. The prior art document [Patent Document] [Patent Document 1] Japanese Patent No. 3 1 36883 [Patent Document 2] Japanese Patent Publication No. 3003521 [Abstract] [Problems to be Solved by the Invention] However, in the reinforced fiber described in the above document, the number of epoxy groups in the molecule attached to the slurry is small, and the sizing is small, and it is difficult to sufficiently increase the reinforcing fiber and the matrix resin. The impact resistance of the resin composite material is simultaneously increased, and the absorption energy (elastic energy) below the maximum load and the absorption energy of the load (progressive energy). That is, there is a so-called enhancement of the adhesion of the resin to increase the absorption energy of the maximum load below the maximum load, and the absorption energy of the maximum load is decreased. On the contrary, when the absorption energy is larger than the maximum load, the absorption energy below the maximum load is lowered. SUMMARY OF THE INVENTION An object of the present invention is to provide a matrix resin which can be simultaneously provided to provide a matrix resin stability and which is attached to the compound. The molecular weight above the fibers is also in close contact. When the sex is more than the maximum fiber and the base, the bipolar phase strengthening tree larger than the maximum load is -4- 201224240. The absorption energy (elastic energy) below the maximum load of the doubled material is greater than the maximum: the absorption of the weight A resin for reinforcing fibers of 忐 (progressive energy), a fiber-reinforced resin composite material using the fiber for reinforcing eucalyptus, and a structure composed of the fiber-reinforced resin composite material. [Means for Solving the Problem] The results of the study of the above-mentioned purpose, such as the use of the epoxidized polydiene resin on the surface: At the same time, the absorption energy below the weight of the fiber-reinforced resin composite material and the absorption energy greater than the maximum load are improved. T—that is, the present invention provides a resin-reinforced fiber obtained by subjecting a fiber to an epoxidized polydiene resin. The aforementioned fibers are preferably carbon fibers or glass fibers. Further, the present invention provides a fiber-reinforced resin composite material comprising the resin reinforcing fiber and a matrix resin. The matrix resin is preferably an epoxy thermosetting resin. The present invention further provides a structure comprising the aforementioned fiber-reinforced resin composite material. [Effects of the Invention] The fiber for fiber reinforcement according to the present invention is used as a fiber because the surface of the fiber is treated by an epoxidized polydiene resin having a rubber core elasticity and a plurality of epoxy groups in the molecule. When the resin composite material is reinforced, an interface phase which is extremely excellent in adhesion to the matrix resin (close contact) and which is particularly excellent in flexibility is formed between the fiber and the matrix resin. Therefore, the absorption energy (elastic energy) below the maximum load of the fiber-reinforced resin composite material and the absorption energy (progressive energy) of the maximum load of 201224240 at the maximum load of the fiber-reinforced resin composite material are simultaneously improved, that is, it is difficult to achieve at the same time. Dynamic strength and static strength ~ speed! To improve at the same time. As a result, compared with the previous ones that can withstand transient impacts, 〇, ##like has the disadvantage of embrittlement after party impact, the fiber strengthening Jiang of the present invention

The reinforced tree sapwood composite has adhesive strength, and JL can not only withstand strong impact, but also maintain high strength after strong and strong impact. [Embodiment] [Resin reinforcing fiber] The resin reinforcing fiber of the present invention is obtained by subjecting a fiber to an epoxidized polydiene resin. The fiber is not particularly limited as long as it is a fiber generally used for the fiber-reinforced resin composite material, and examples thereof include carbon fiber, glass fiber, guanamine fiber, and boron fiber. Among them, carbon fiber and glass fiber are particularly preferred. The fibers may be used singly or in combination of two or more. As the carbon fiber, for example, polyacrylonitrile (pAN)-based carbon fiber montmorillonite anti-fiber, vapor-grown carbon fiber or the like can be used. As the glass fiber, glass fiber generally used for resin reinforcement can be used. As the epoxidized polyalkylene oxime resin, for example, an epoxide of a copolymer of a polybutadiene, a polyisoprene or a compound having a butadiene structure or an isoprene structure in the molecule can be used. As an epoxide of a copolymer having a butadiene structure or an isoprene structure in a molecule, an epoxide of a copolymerized polyene having a butadiene structure (for example, styrene/butadiene/benzene) can be exemplified. An epoxide of an ethylene copolymer or the like, an epoxide of a copolymerized polyene having an isoprene structure (for example, an epoxide of a styrene/isoprene/styrene copolymer, etc.). The terminal group of the 201224240 copolymer of the above polybutadiene, polyisoprene, a compound having a butadiene structure or an isoprene structure in the molecule may have a hydroxyl group and a terminal group in addition to a hydrogen atom. It is a hydrogen atom or a hydroxyl group. As the epoxidized polyester, preferred among these are epoxidized polybutadiene, epoxidized alkene, epoxidized styrene/butadiene/styrene copolymer, cycloolefin/isoprene/styrene copolymer, It is particularly preferable that the epoxidized polyepoxidized polydiene resin may be used singly or in combination of two or more. The epoxidized polydiene resin can be obtained by reacting a compound having a butadiene structure or an isoprene structure in polybutadiene or polyisomer with an epoxidizing agent. The steric structure of the copolymer portion of the compound of polybutadiene, polyisoprene, butadiene-structured or isoprene as a raw material may be cis-1,4, anti-purine, 4, anti-丨, 2, any one. Also, the ratio of them is any. The epoxidizing agent may, for example, be an organic hydrogen peroxide such as peroxyacetic acid, peroxyformic acid, tris-peroxyacetic acid or 35 oxypropionic acid, a tertiary butyl peroxide or a cumene cyanide or the like. As the organic peroxyacid, in order to increase the oxygen concentration of the target, it is preferred that the organic peroxyacid is substantially free of water (for example, 8% by weight or less). Among the above epoxidizing agents, the acid is commercially available at a low cost and has a high degree of stability. Catalyst can be used for epoxidation. When the epoxidizing agent is used, an alkali such as sodium carbonate or hydrogen peroxide can be used as the epoxidizing agent. When an organic acid or an acid such as sulfuric acid is used, a tungstic acid azole group or the like can be used. A gynecological tree polyisobutyl benzene butyl bromide. The above-mentioned combined pentadiene, the copolymer of the copolymer has medium, double-bond-1, 2, peroxybenzene, peroxygen hydroperoxide ethylene oxide moisture content can be used as peroxyethylene peroxygen Acidic, when the catalyst. Mixture with sodium hydroxide 201224240 or organic acid as a catalyst. Further, when an organic hydroperoxide such as a tertiary butyl peroxide is used, molybdenum hexacarbonyl can be used as a catalyst. The epoxidation reaction can be carried out in an inert solvent. The inert solvent may, for example, be an aliphatic hydrocarbon such as hexane or heptane; an alicyclic hydrocarbon such as cyclohexane; an aromatic hydrocarbon such as benzene, methyl benzene or diphenyl; an ether; an ester such as ethyl acetate; chloroform or tetrachloro Toxic hydrocarbons such as carbon; such mixed solvents and the like. The reaction temperature of the epoxidation can be appropriately selected depending on the kind of the epoxidizing agent. When peracetic acid is used as the epoxidizing agent, the reaction temperature is, for example, 20 to 80 °C. When a tertiary butyl peroxide is used as the epoxidizing agent, the reaction temperature is, for example, 20 to 150. (3. The molar ratio of the epoxidizing agent to the raw material (polybutadiene, polyisoprene, copolymer having a butadiene structure or a isoprene structure in the molecule) may be based on the target epoxidation degree. Appropriately selected. Relative to the raw material, the double bond 1 mole is added with an epoxidizing agent, preferably 1 to 2 moles. The epoxidized polydiene resin formed can be formed by a suitable method, for example, a poor solvent. The method of precipitating, separating the polymer into hot water under stirring, distilling off the solvent, directly removing the solvent, etc., and separating the oxidized polydiphenyl resin by a number average molecular weight of, for example, 500 to 50000' More weifa, preferably 2500~30000, more preferably 3500~20000. % Oxidation poly, said & alpha, the oxygen concentration of ethylene oxide of the olefinic resin is, for example, 3 to 15%, preferably disk < Further, if the number of epoxy groups in the molecule is preferably 5 or more, more preferably 10 or more, and even more preferably 20 201224240 [Resin reinforcing fiber, resin of the invention) The implementation table can be, for example, single (knit), charm (mat) The method of not specifically limiting the surface of the olefinic resin solution or the resin solution or the fiber surface is appropriately selected when the temperature is dried, and examples thereof: as a solvent for preparing the ring, a guanamine, a dimercapto or a lactone; Such as the preparation of epoxy requirements (especially for the use of monthly agents, dispersants, etc.. Active agent, non-ionic any. Interface or two or more treatments, epoxidized dispersion. Resin strengthening amount (attachment) Modulation] The fiber for aging can be obtained by treating the fiber with epoxidized polyhedral. The fiber form is not limited to any of fibers, yarns, strands, fabrics, braids, and the like. For the surface treatment, for example, the fibers may be impregnated into the epoxidized polydispersion liquid, or the fibers may be sprayed with an epoxidized polydiene dispersion to adhere the epoxidized polydiene resin to the like. After spraying, etc., it is suitable to remove/treat. The drying temperature may be 35 to 350 ° C, preferably 40 to 250 depending on the type of solvent. (: 左右. Oxidized polydiene resin solution or dispersion Liquid time Such as water; alcohols such as decyl alcohol and ethanol; decylamine or decylamine such as dimethylformamide; g-like such as acetone; cool mixed liquid, etc. When concentrating a rare resin solution or dispersion, it can be regarded as 3 water. In the case of a solvent, a surfactant and emulsification may be used as a surfactant. An active agent such as an anionic interface surfactant or a cationic surfactant, an emulsifier, a dispersant, or the like may be used alone or in combination. The surface of the fiber ^ A thin resin can also be used in the capsule-emulsified fiber, the treatment of the epoxidized polydiene resin '100 parts by weight of the fiber, for example, 〇. 〇1~5 201224240 It is preferably 0.1 to 4 parts by weight, more preferably 3 to 3 parts by weight. When the amount of the fiber-reinforced resin composite material is too large, the adhesion of the shellfish is likely to decrease. If too much, the thick layer of the cured product of the epoxidized polydiene resin occupies between the fiber and the matrix resin. And there is a change in the characteristics of the composite material. [Fiber-reinforced resin composite material] The March fiber-reinforced resin composite material is composed of the above-mentioned resin-reinforced dicar resin. The matrix resin may be any of thermosetting resins and thermoplastics, and is preferably a thermosetting resin from the viewpoint of being easily impregnated with reinforcing fibers. As the thermosetting resin, an epoxy J:: an unsaturated polyester resin, an ethylene vinegar resin, a enamel resin, a male virgin resin, a cyanic acid S resin, or the like can be used. In terms of matrix resin, the above resin: small = resistant? It is excellent in properties, modulus of elasticity, chemical resistance, and hardening, and is preferably an epoxy-based thermosetting resin. The % oxygen-based thermosetting resin is not particularly preferred as an epoxy compound, and preferably has a two-component epoxy compound in the molecule. Needle, +, household ^ More than two or more decyloxy groups The oxygenate can be used in combination of one type of I alone or more. For dry sputum or two kinds, there are two or more epoxies in the molecule, which are specifically limited, and can be used as a #H y & gas-based oxime compound, an oxygen compound, and a fat _ > Rolled material, bisphenol type bicyclic epoxy resin, and the like. , cerium alcohol polyglycidyl ether, polyglycidamine amine-like aliphatic skeleton and two (4) fixed 'only preferred (1) ring, as long as it is a compound having a ring in the molecule, there is no special cyclic aliphatic skeleton An epoxy compound having two or more valence ring epoxy groups formed by containing two adjacent carbon atoms of -10-201224240. The alicyclic epoxy compound may, for example, be a compound represented by the following formula (1).

(1) The alicyclic epoxy compound represented by the above formula (1) is produced by oxidizing a corresponding alicyclic olefin compound with an aliphatic peroxycarboxylic acid or the like, and a perhydrate-free aliphatic peroxycarboxylic acid is used. The manufacturer is preferred from the viewpoint of having a high epoxidation ratio. VIII In the above formula (1), γ represents a single bond or a linking group. The linking group may, for example, be a divalent hydrocarbon group, a carbonyl group (-CO-), an ether bond (-0-), an ester bond (-COO-), a urethane bond (_c〇NH_), or a carboxylate bond (〇) C〇〇) and a group in which a plurality of such groups are linked. As the above-mentioned divalent hydrocarbon group, a linear or branched alkyl group or a divalent alicyclic hydrocarbon group having a number of from 1 to 18 (particularly from 1 to 6) can be preferably used (particularly A 1 ^ 引马2 price extension) Cycloalkyl), etc., the above-mentioned linear or branched extension group can be used; ^ m J methylene, methyl fluorenylene, dimethyl fluorenyl group , a sign of dimethylene and so on. Further, the divalent alicyclic hydrocarbon group may, for example, be a 1,2-cyclopentyl group, an i, 3, a cyclopentyl group, a cyclopentene group, a 1,2-extended cyclohexyl group, a 1,3-extension ring,丞丨, 4-cyclohexyl group, cyclohexyl group, etc. As the alicyclic epoxy compound of the formula (1彳矣_ V J), the following compounds can be specifically exemplified. -11 - 201224240

ο

ο

ο

ο

ο ο ο

〇Jn

ο In the above formula, η is an integer of 1 to 3 0. As the alicyclic epoxy compound, in addition to the above (i), (ii) one of only two epoxy groups may be used to form a cyclic aliphatic skeleton and contain two adjacent carbon atoms. An epoxy compound having an alicyclic epoxy group (for example, a limonene diepoxide), (iii) an epoxy compound constituting an epoxy group and a carbon atom constituting the cyclic aliphatic skeleton bonded by a single bond, ( Iv) a glycidyl ether compound (for example, a glycidyl ether type epoxy compound having a cyclic aliphatic skeleton and a glycidyl-12-201224240 oleyl ether group). Specific examples of the above compounds include the following compounds.

In the above formula, R represents a group in which q OH groups are removed by a q-valent alcohol [R-(OH)q], P represents an integer of 1 to 50, and q represents an integer of 1 to 10. Among the groups in the q parentheses, p may be the same or different. The q-valent alcohol [R-(OH)q] may, for example, be a monohydric alcohol such as decyl alcohol, ethanol, 1-propanol, isopropanol or 1-butanol; ethylene glycol, 1,2-propanediol, 1, a glycol such as 3-propanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, dipropylene glycol or polypropylene glycol; A trihydric or higher alcohol such as glycerin, diglycerin, erythritol, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol or sorbitol. The aforementioned alcohols may also be polyether polyols, polyester polyols, polycarbonate polyols, polyolefin polyols -13-201224240, and the like. The above alcohol is preferably an aliphatic alcohol having 1 to 10 carbon atoms (particularly an aliphatic polyol such as trimethylolpropane). Further, (V) a polyfunctional epoxy compound having three or more epoxy groups may be used in addition to the above. Specifically, the following compounds can be exemplified. C0-^0-(CH2>jC0^0-CH, co-f o-(ch2)^co ^0-CH, ch2—CO -fo —(ch2)^· co 0—CH, CH—C〇- {-〇—(CH2)^-C0 〇—CHr CH—CO —f 0 —(CH2)^· CO ^ 0—CH, CH 2 —CO —f 0 —(CH 2 )^· CO 0—CH;

In the above formula, a, b, c, d, e, and f are integers 0 to 30. As the bisphenol type diepoxy compound, a conventional product may be used, and examples thereof include a bisphenol A type epoxy resin (bisphenol A diglycidyl ether; and a bisphenol A and an epichlorohydrin having a glycidyl ether group at both terminals). a condensed product, etc.), a bisphenol F type epoxy resin (bisphenol F diglycidyl ether; a condensation product of bisphenol F and epichlorohydrin having a glycidyl ether group at both ends), and a bisphenol S ring An oxygen resin (bisphenol S diglycidyl ether; a condensation product of bisphenol S and epichlorohydrin having a glycidyl ether group at both ends). -14- 201224240 The aforementioned aliphatic polyglycol polyglycidyl ether is not - is an "aliphatic" in the polyglycidyl bond of the aliphatic polyol. For example, such as ethylene glycol, hydrazine, 2-propylene glycol , 丨, 3 • propylene glycol 夕凡一” ιλ D 1,3 · butanediol, I, 4-butanol, 1,5-pentanediol, neopentyl glycol, hydrazine. Hexanediol, diethylene glycol: ethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol: diol such as propylene glycol; glycerin, diglycerol' such as ganyl/yellow, erythritol, three It is a ternary or higher alcohol such as methyl ketone, trimethoprim, and neopentyl alcohol. #—a representative example of neopentyl alcohol ether

= alcohol diglycidyl as an aliphatic polyol polycondensed water, exemplified 1,6-hexanediol diglycidyl shunt, bond, two methyl propane polyglycidyl ether, diethylene glycol diglycidyl ether, neopentyl Glycol diglycidyl ether, propylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and the like. The polyglycidylamine pear epoxy resin may, for example, be N, N, N, N, _tetraglycidyl-4, 4'-fluorenylene-dibenzoguanamine or the like. From the viewpoint of improving the workability at the time of blending and the production of the fiber-reinforced resin composite material, the epoxy compound is preferably liquid. However, even if the monomer is a solid epoxy compound, the viscosity of the curable composition after blending the respective components (25. 〇 may be used as long as it is, for example, 20 〇〇〇 mPa·s or less. The viscosity (25) of the compound (all the epoxy compound/ester compound used) is, for example, 5,000 mPa·s or less, preferably 300 00 mPa·s or less, more preferably 2 Å. 〇〇mPa · s or less. If the viscosity is too large, the workability and the like are easily lowered. [Production of fiber-reinforced resin composite material] If the matrix resin is a thermosetting resin, the fiber-reinforced tree of the present invention can be borrowed from the present invention. The resin for reinforcing the above-mentioned resin of the present invention is produced by curing a mixed material comprising a curable composition (a composition before curing) of a matrix resin. The curing is generally carried out by heating when the fiber-reinforced resin composite material is to be produced. Conventional methods such as a prepreg method, a hand lay up method, a wire-making method, an RTM (Hesin Transfer Molding) method, a pultrusion method, a vacuum suction method can be applied. A method such as a vacuum infusion method. The curable composition is generally composed of a curable compound (such as an epoxy compound), a curing agent, a curing accelerator, or a curing catalyst, and various additives blended as required. When the curable compound is a cyclic ruthenium compound or the like, an acid anhydride, a polyamine or the like is preferably used as the curing agent. The curing agent may be used singly or in combination of two or more kinds. The anhydride can be selected and used. For example, it can be exemplified by formic anhydride, dodecanoic anhydride, etc. The adverse effects of the phthalic anhydride and the fluorenyl ring-bonded two-times are used in a liquid form. The product name "usually used as an acid anhydride for the curing agent for %_oxy resin" is preferably liquid at room temperature, specifically methyltetrahydrophthalic anhydride, methylhexahydrophthalic acid Anhydrous anhydride, fluorenyl fluorenyl sulfhydryl tetrahydron-butyrene can be used as an acid anhydride at room temperature in the absence of impregnation of the epoxy resin composition, such as o-tetrahydro-o-stup An anhydride, a hexahydrophthalic anhydride, a 'carboxylic acid anhydride, etc.. It is preferably used as a solid acid anhydride at room temperature in a liquid anhydride at room temperature, and is preferably used as an acid anhydride hardener. RIKACID MH-700" (manufactured by Nippon Chemical and Chemical Co., Ltd.), -16-201224240 Trade name "RIKACID ΜΗ" (manufactured by Shin Sakamoto Chemical Co., Ltd.), trade name "ΗΝ-5 5 00" (manufactured by Kyori Chemical Co., Ltd.) Commercially available products The polyamine can be arbitrarily selected and used as a curing agent for epoxy resins, and the polyamine is preferably liquid at normal temperature. When a polyamine which is solid at a normal temperature is used, it is preferably used in a polyamine which is dissolved in a liquid at a normal temperature to form a liquid mixture at normal temperature. As a specific example of the polyamine, a chain aliphatic polyamine such as diethylenetriamine, triethylenetetramine, tetraethyleneamine, dipropylenediamine or diethylaminopropylamine can be exemplified; a cyclic aliphatic polyamine such as aminoethyl phenanthrene, menthene diamine or isophorone diamine; polyether polyamine [e.g., trade name "JEFFAMINE D-230", "JEFFAMINE D-400" "JEFFAMINE D-2000", "JEFFAMINE D-4000", "JEFFAMINE ED-600", "JEFFAMINE ED-900", "JEFFAMINE ED-2003", "JEFF AMINE EDR-1 48", "JEFFAMINE EDR-" 176", "JEFFAMINE T-403", "JEFFAMINE T-3000", "JEFFAMINE T-5000" (above, manufactured by Huntsman), etc. The blending amount of the curing agent such as the acid anhydride-based curing agent or the polyamine-based curing agent is preferably an effective amount which can exert the effect as a curing agent, that is, generally 1 equivalent of the epoxy compound in the epoxy resin composition. The base is used in a ratio of, for example, 0.5 to 1.5 anhydride equivalents (or amine equivalents, etc.). The hardening accelerator is not particularly limited as long as it is a curing accelerator which is generally used for curing an epoxy compound or the like, and for example, a tertiary amine, a tertiary amine salt, an imidazole, an organophosphorus compound, or a quaternary ammonium salt can be used. , four grades of salt, organic metal salts, boron compounds, etc. The hardening accelerator may be used -17-201224240 alone or in combination of two or more. The tertiary amine may, for example, be lauryl diamine, N,N-didecylcyclohexylamine, hydrazine, hydrazine-dimethylphenyl guanamine, hydrazine, hydrazine-didecyl aniline, (Ν, Ν- Dimethylaminomethyl)phenol, 2,4,6-tris(Ν,Ν-dimethylaminodecyl)phenol, 1,8-diazabicyclo[5_4.0]undec-7-ene (DBU , 1,5-diazabicyclo[4.3.0]non-5-ene (DBN), and the like. The tertiary amine salt may, for example, be a carboxylate, a sulfonate or a mineral acid salt of the above tertiary amine. The carboxylate may, for example, be a salt of a carboxylic acid having a carbon number of 1 to 30 (particularly a carbon number of 1 to 10) such as an octanoate (particularly a salt of a fatty acid). The sulfonate may, for example, be p-toluenesulfonate, besylate, sulfonate or ethanesulfonate. A representative example of the tertiary amine salt is, for example, a salt of 1,8-diazabicyclo [5.4.0]undec-7-ene (DBU) (e.g., p-toluenesulfonate, octoate) or the like. The imidazoles may, for example, be 2-mercaptoimidazole, 2-ethylimidazole, 1,2-dimercaptoimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl- 4-methylimidazole, 1-benzyl-2-methylimidazole, and the like. The organophosphorus compound may, for example, be triphenylphosphine or triphenylphosphite. The quaternary ammonium salt may, for example, be tetraethylammonium bromide or tetrabutylammonium bromide. The fourth-order scale salt may, for example, be tetrabutyl sulphonate, tetrabutyl laurate, tetrabutyl sulfonium myristate, tetrabutyl palmitate, tetrabutyl cation and bicyclo [ 2.2.1] a salt formed by the anion of heptane-2,3-dicarboxylic acid and/or methylbicyclo[2.2.1]heptane-2,3-dicarboxylic acid; tetrabutyl squaride and 1,2 a 201224240 salt formed by an anion of 4,5-cyclohexanetetracarboxylic acid; an anionic form of a salt sulfonium cation and a sulfonic acid formed by an anion of a tetrabutyl cation and a methanesulfonic acid: a salt formed by an anion; a salt formed by an anion of tetrabutyl cation cation blood κ 夂 四 'tetrabutyl cation cation — a salt formed by an anion of a benzene sulfonic acid. — The organic metal salt may, for example, be a zinc octylate, zinc octoate, dibutyltin acid or an aluminum acetonate complex. The boron compound may, for example, be boron trifluoride or triphenylborane. Commercially available products such as "^ S A - 5 〇 6", "U-C A T S A 1 η 7 r CAT SA·102", and "U_CAT 5003" (manufactured by Ma-Apr Co., Ltd.) can be used as the hardening accelerator. The blending amount of the hardening accelerator is also 0.01 to 15 parts by weight, preferably °·1~, depending on the type of the hardening agent (the acid liver hardener or the like). 10 parts by weight, more preferably 0.5 to 8 parts by weight. As the curing catalyst, for example, a cationic polymerization initiator may be used. The cationic polymerization initiator is an initiator which releases a substance which initiates cationic polymerization by heating. The cationic polymerization initiator may, for example, be an aryldiazonium salt [for example, PP_33 (manufactured by ADEKA Co., Ltd.), an arylsulfonium salt, a salt (for example, FC.509 (made by 3M), UVEi). 〇14 (ge (share) system), 66 CP-77 (above ADEKA (share) system), si-60L, SI-80L, I 100L, SI-ll〇L (above is Sanxin Chemical Industry Co., Ltd.) )), etc., relative to, for example, a curable compound (epoxy compound, etc.) 100 weight damage, the amount of the hardening catalyst is 0 01 to 15 parts by weight, preferably 〇〇 5 to 12 parts by weight 'more preferably 0.1 〜10 parts by weight. As the above various additives, a low molecular weight -19 to 201224240 compound having a hydroxyl group can be exemplified. The molecular compound is subjected to a hardening reaction. The compound having a trans-group can be used to retard a polyol such as a diol or a glycerin. Alcohol, diethylene, and, in addition, in a curable composition, a fiber-reinforced resin The composite material) can be mixed with various additives in the hard shell. As such, it can be: c-fan active agent, internal mold release agent, colorant, and resistance: such as interface coupling agent, Filler, antioxidant, //packaging agent, decane H external absorbent, deuterated composition, based on the weight of the various additives: preferably 10% or less (especially 5% or less). The hardening of the curable composition, the + m refining/dish degree is also different depending on the curable compound, and is, for example, 40 to 25 Torr, preferably 8 Å to 2 Torr (rc. The fiber reinforced resin compound thus obtained The material (hard transfer temperature is, for example, 9 (TC or more, preferably i2 〇t or more. The glass fiber volume in the quasi-reinforced resin composite material is also different depending on the use, but ~8 G%, preferably 35 to 7〇%. The fiber-reinforced resin composite material of the present invention The elastic energy and progress can be simultaneously improved. 'Not only impact resistance, but also the strength after impact, which is suitable for the aircraft body, main wing, tail wing, flight control device, fairing, cowl, P1, etc. Motor case, main wing, etc., body structure of artificial satellite, automobile parts such as chassis of automobile, body structure of railway vehicle, body structure of bicycle, hull structure of ship, blade of wind power generation, pressure vessel , fishing rods, tennis rackets, golf clubs, mechanical + f, cable construction. [Examples] -20-201224240 Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited thereto. Example 1 A carbon fiber cloth [made of Toray Co., Ltd., a plain weave fabric made of carbon fiber Τ70〇] was impregnated with 1 part by weight of acetone in 2 parts by weight of epoxidized polybutadiene [Daicel Chemical Industries] (Stock) system, the product name "EPOLEAD PB3 6 00" 'Ethylene oxide oxygen concentration 7.8%, number average molecular weight 5 9000' of the solution is taken out after about 1 〇 seconds, in the dryer, 6 0 C Dry at temperature for 30 minutes. The weight of the dried carbon fiber cloth was increased by 1.5% compared with that before the impregnation, and it was confirmed that the epoxidized polybutadiene was coated on the carbon fiber. Secondly, the 3,4-epoxycyclohexyldecyl (3,4-epoxy)cyclohexanone acid 6 is used by hand method [Daicel Chemical Industries, Ltd., trade name "CELLOXIDE 2021P"] 1 part by weight, mixed with 13 parts by weight of a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride [New 曰 理 理 ( ' ' 商品 商品 商品 R R R R R R R R R R R R R R R R R R R R 700"], 〇. 6 5 parts by weight of ethylene glycol, 0.6 parts by weight of octanoic acid of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as a hardening accelerator The liquid (curable composition) of salt [San-Apiro Co., Ltd., trade name "SA-102"] is impregnated into a single layer or a two-layer laminate of carbon fiber cloth after dipping and drying. After hardening at 11 ° C for 2 hours in the furnace and further hardening at 170 ° C for 2 hours, a carbon fiber reinforced resin was obtained. As a result of measuring the fiber volume fraction (V [) of the chiral fiber reinforced resin, the monolayer was 54.0%', and the 12-layer laminate was 6〇9%. -21 - 201224240 Comparative Example 1 Carbon fiber reinforced with a single layer and a 12 layer laminate in the same manner as in Example 1 except that the carbon fiber cloth was not impregnated with the epoxidized polybutadiene solution. Resin. The fiber volume content (Vf) of the carbon fiber-reinforced resin obtained by the measurement was 5·0% for the single layer and 64 to 3% for the 12-layer laminate. [Evaluation Test 1) The carbon fiber reinforced tree 曰 曰 tensile test of the single layer body obtained in the yoke example 1 and the comparative example ,, and the elastic modulus (4) and the tensile strong sound (MPa) heart test system were measured. It is carried out according to the Japanese Industrial Standard κ7〇73. In addition, the test piece size of the single layer body is 200 mm long, 2 mm wide, and 40 mm 35 mm. The results are shown in the table. ,Table 1. In Table 1, the increase rate is 値 from the following formula - 比较 of Comparative Example 1 / Comparative Example Increasing Rate (%) = [(Example 1 値) X 1 0 0 [Assessment Test 21 vs. Example 1 and Comparison In Example 1, the layer of the θ ^ Α 侍 has 12 layers of ruthenium-reinforced reinforced resin for the drop hammer impact test, and the remedy of the maximum energy of the children. The absorption energy of the maximum Π 以下 以下 ( ( 泸 泸 泸 泸 泸 泸 泸 泸 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 The test piece size water was set to a thickness of 2 mm. The results are shown in Table 2. Table: Length l〇〇mrn 'width 10 〇 mm, obtained. Medium, the increase rate is obtained by the following formula] X 10 increase rate (% ) = [(Example 1 / Comparative Example 1) / Comparative Example 22 - 201224240 [Table 1]

It is known from Tables 1 and 2 that the composite material of the resin for fat strengthening (execution) is used in comparison with the oxidized polydiene resin. Resin-treated resin-reinforced resin-reinforced sigma material (comparative example), the tensile strength is greatly improved, and the elastic energy and progress can be simultaneously increased. [Industrial Applicability] The resin for reinforcing fibers of the present invention can simultaneously increase the absorption energy (elastic energy) below the maximum load of the fiber-reinforced resin composite material and the absorption energy (progressive energy) larger than the maximum load, and is used as Manufacturing materials for fiber reinforced composite materials -23- 201224240 used in the fields of automotive parts, civil engineering supplies, blades for wind power generation, sporting goods, aircraft, ships, robots, and cable materials. [Simple description of the diagram] None. [Main component symbol description]

Claims (1)

201224240 201224240 VII. Scope of application for patents·· 桝 曰 曰 曰 曰 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ 纤维 纤维 纤维 纤维 纤维 纤维 。 。 。 。 。 The fiber reinforced fiber of the first item of the fiber Γ patent dry circumference, wherein the above 3, 糸 is carbon fiber or glass fiber. The 1st-dimensional reinforced resin composite material is composed of a resin-reinforcing fiber and a matrix resin as claimed in the patent application. A fiber-reinforced resin composite material according to item 3 of the patent scope, wherein the matrix resin is an epoxy-based thermosetting resin. The scorpion scorpion &matter' is composed of a fiber reinforced resin composite material as disclosed in the patent application 帛4 item. -25- 201224240 IV. Designated representative map: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None 0. If there is a chemical formula in this case, please disclose the chemical formula that best shows the characteristics of the invention: