Resin composition for fiber-reinforced plastic, and fiber-reinforced plastic

Abstract

A purpose of the present invention is to provide a resin composition for fiber-reinforced plastics which is suitable for improving the strength of fiber-reinforced plastics, has an excellent balance between pot life and curability, and has excellent non-coloring properties.　This resin composition comprises (A) component, which is an epoxy resin, (B) component, which is a polyoxyalkylene-polyamine, and (C) component, which is at least one compound selected from among compounds represented by formula (1). (In formula (1), R1 to R6 each independently represent a C1-C10 hydrocarbon group and X1 to X4 each independently represent an oxygen atom or a sulfur atom.)

Description

Resin composition for fiber-reinforced plastics, and fiber-reinforced plastics

[0001] The present invention relates to a resin composition for fiber-reinforced plastics and a fiber-reinforced plastic obtained using the composition, and more particularly to a fiber-reinforced plastic containing an epoxy resin, a polyoxyalkylene polyamine, and a salt compound that is liquid at room temperature.

[0002] A method for producing molded articles using a thermosetting epoxy resin, unsaturated polyester, polyamide resin, or phenolic resin as a reinforcing material for fibrous materials such as carbon fiber or glass fiber is well known. Fiber-reinforced plastics produced using this method are widely used in structural materials for aircraft and ships, as well as in sporting goods such as tennis rackets and golf clubs. Epoxy resins used as reinforcing materials are often used as a well-balanced material because they are inexpensive and have excellent adhesive properties, heat resistance, and chemical resistance.

[0003] Patent Documents 1 to 3 propose epoxy resin compositions for fiber reinforcement, which are composed of an epoxy resin, an acid anhydride, and a curing catalyst, and describe an imidazole-based catalyst as the curing catalyst.

[0004] Japanese Patent Laid-Open No. 8-156115 Japanese Patent Laid-Open No. 2008-38082 Japanese Patent Laid-Open No. 2015-3938

[0005] The methods proposed so far have had the problem of discoloration of the material. Therefore, an object of the present invention is to provide a resin composition for fiber-reinforced plastics, which is suitable for improving the strength of fiber-reinforced plastics, has an excellent balance between pot life and curability, and is excellent in non-discoloration properties.

[0006] The present inventors have conducted extensive research to achieve the above-mentioned objects and have discovered that a resin composition for fiber-reinforced plastics that is excellent in curability and non-colorability can be obtained by combining an epoxy resin, a polyoxyalkylene polyamine, and a specific phosphonium salt, thereby arriving at the present invention.

[0007] That is, the present invention provides a resin composition for fiber-reinforced plastics, which contains component (A): an epoxy resin, component (B): a polyoxyalkylene polyamine, and component (C): at least one compound selected from the group consisting of a compound represented by the following formula (1):

[0008] (In the formula, R １ ~R ６ each independently represents a hydrocarbon group having 1 to 10 carbon atoms; X １ ~X ４ each independently represents an oxygen atom or a sulfur atom.

[0009] The present invention also provides a fiber-reinforced plastic containing the resin composition for fiber-reinforced plastic.

[0010] The resin composition for fiber-reinforced plastics of the present invention has excellent curability and non-coloring properties, and the fiber-reinforced plastics obtained from it can provide various molded articles with excellent appearances because of their excellent non-coloring properties.

[0011] Examples of the epoxy resin as component (A) include polyglycidyl ether compounds of mononuclear polyhydric phenol compounds such as hydroquinone, resorcinol, pyrocatechol, and phloroglucinol; and polynuclear polyhydric phenol compounds such as dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis(ortho-cresol), ethylidenebisphenol, isopropylidenebisphenol (bisphenol A), isopropylidenebis(ortho-cresol), tetrabromobisphenol A, 1,3-bis(4-hydroxycumylbenzene), 1,4-bis(4-hydroxycumylbenzene), 1,1,3-tris(4-hydroxyphenyl)butane, 1,1,2,2-tetra(4-hydroxyphenyl)ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcinol novolac, and terpene phenols. Polyglycidyl ether compounds of phenol compounds; polyglycidyl ether compounds of polyhydric alcohol compounds such as ethylene glycol, propylene glycol, butylene glycol, neopentyl glycol, hexanediol, polyethylene glycol, polypropylene glycol, thioglycol, dicyclopentadiene dimethanol, 2,2-bis(4-hydroxycyclohexyl)propane (hydrogenated bisphenol A), glycerin, trimethylolpropane, pentaerythritol, sorbitol, and bisphenol A-alkylene oxide adducts; glycidyl ester compounds of aliphatic, aromatic, or alicyclic polybasic acids such as maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid, trimer acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid, tetrahydrophthalic acid, and endomethylenetetrahydrophthalic acid, and homopolymers or copolymers of glycidyl methacrylate;Epoxy compounds having a glycidylamino group such as N,N-diglycidylaniline, bis(4-(N-methyl-N-glycidylamino)phenyl)methane, diglycidyl orthotoluidine, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)-2-methylaniline, N,N-bis(2,3-epoxypropyl)-4-(2,3-epoxypropoxy)aniline, and N,N,N',N'-tetra(2,3-epoxypropyl)-4,4-diaminodiphenylmethane; vinylcyclohexene diepoxide, Examples of epoxy resins include epoxidized cyclic olefin compounds such as cyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-6-methylcyclohexylmethyl-6-methylcyclohexanecarboxylate, and bis(3,4-epoxy-6-methylcyclohexylmethyl)adipate; epoxidized conjugated diene polymers such as epoxidized polybutadiene and epoxidized styrene-butadiene copolymers; and heterocyclic compounds such as triglycidyl isocyanurate. These epoxy resins may be internally crosslinked with a prepolymer of a terminal isocyanate, or may be polymerized with a polyvalent active hydrogen compound (such as a polyphenol, polyamine, a carbonyl group-containing compound, or a polyphosphate ester). These epoxy resins may be used alone or in combination of two or more. In the present invention, epoxy resins having an average of more than 1.1 epoxy groups per molecule are preferred, and epoxy resins having two or more epoxy groups per molecule are particularly preferred.

[0012] Among the epoxy resins, those containing at least one of a polyglycidyl ether compound of a polynuclear polyhydric phenol compound and a polyglycidyl ether compound of a polyhydric alcohol compound are preferred, and those containing a polyglycidyl ether compound of a polynuclear polyhydric phenol compound as the main component are more preferred. It is particularly preferred that the epoxy resin contains a bisphenol-type epoxy resin as the main component. Here, "main component" refers to a component whose content in the epoxy resin exceeds 50% by mass. Bisphenol-type epoxy resins refer to those having a bisphenol structure, such as polyglycidyl ether compounds of bisphenols such as bisphenol A. Those containing a bisphenol-type epoxy resin as the main component are preferred because they provide excellent curability and physical properties of the cured product. Furthermore, when the resin composition of the present invention is used in fiber-reinforced plastics, it is preferable to use an epoxy resin that is liquid at 25°C in terms of its ability to penetrate fiber materials.

[0013] The amount of the epoxy resin used is not particularly limited, but is preferably 10 to 90 parts by mass, more preferably 15 to 85 parts by mass, and even more preferably 20 to 80 parts by mass, per 100 parts by mass of the resin composition for fiber-reinforced plastics.

[0014] The polyoxyalkylene polyamine, component (B) used in the present invention, is a compound having a polyoxyalkylene skeleton and two or more amino groups, and there are no particular limitations on the molecular structure, molecular weight, etc.

[0015] Examples of the polyoxyalkylene polyamines include polyoxypropylene diamine, trimethylolpropane poly(oxypropylene) triamine, glyceryl poly(oxypropylene) triamine, polyoxyethylene diamine, trimethylolpropane poly(oxyethylene) triamine, and glyceryl poly(oxyethylene) triamine.

[0016] In the present invention, it is preferable to use polyoxypropylenediamine as the component (B) from the viewpoint of improving the curability and the physical properties of the cured product.

[0017] From the viewpoint of improving curability and the physical properties of the cured product, the weight average molecular weight of the polyoxyalkylene polyamine, component (B), is preferably 200 to 5000, more preferably 200 to 2000, and particularly preferably 200 to 500. The weight average molecular weight refers to the weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC).

[0018] Examples of commercially available products of the component (B) include Jeffamine D-230, Jeffamine D-400, Jeffamine D-2000, Jeffamine D-4000, Jeffamine T-403, Jeffamine T-3000, and Jeffamine T-5000, all of which are manufactured by Huntsman.

[0019] The amount of polyoxyalkylene polyamine (B) used is preferably 1 to 50 parts by mass, and particularly preferably 5 to 30 parts by mass, per 100 parts by mass of epoxy resin (A). By using 1 part by mass or more of polyoxyalkylene polyamine (B), curing proceeds sufficiently, and by using 50 parts by mass or less, excellent physical properties of the cured product can be obtained.

[0020] The amount of polyoxyalkylene polyamine used as component (B) is not particularly limited, but is preferably 0.01 to 50 mass %, more preferably 0.05 to 40 mass %, and particularly preferably 0.1 to 30 mass %, in the resin composition for fiber-reinforced plastics.

[0021] The component (C) used in the present invention is a compound represented by the following formula (1), which functions as a curing catalyst for the components (A) and (B).

[0022] (In formula (1), R １ ~R ６ each independently represents a hydrocarbon group having 1 to 10 carbon atoms; X １~X ４ each independently represents an oxygen atom or a sulfur atom.

[0023] In the formula (1), R １ ~R ６ Examples of the hydrocarbon group having 1 to 10 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, an isooctyl group, a tert-octyl group, a 2-ethylhexyl group, a nonyl group, an isononyl group, a decyl group, an isodecyl group, a phenyl group, a benzyl group, and a cyclohexyl group. １ ~R ４ are each independently a methyl group or a butyl group, and R ５ and R ６ are each preferably independently a methyl group or an ethyl group, since this allows for the production of a resin composition that is well balanced between curability and non-coloring properties.

[0024] Specific examples of the compound represented by general formula (1) which is component (C) include compounds represented by the following general formula (1a) or (1b).

[0025]

[0026]

[0027] The amount of the compound represented by general formula (1) as component (C) is not particularly limited, but is 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass, and particularly preferably 0.1 to 10 parts by mass, per 100 parts by mass of the polyoxyalkylene polyamine as component (B). By using 0.01 part by mass or more of the compound represented by general formula (1) as component (C), sufficient curability can be obtained, and by using 20 parts by mass or less, sufficient storage stability can be obtained.

[0028] The amount of the compound represented by general formula (1) used as component (C) is not particularly limited, but is preferably 0.005 to 10 mass %, more preferably 0.01 to 8 mass %, and particularly preferably 0.05 to 5 mass %, in the resin composition for fiber-reinforced plastics.

[0029] In the present invention, it is preferable to further contain a silane coupling agent as component (D) because good adhesion to the fiber material can be obtained. Examples of the silane coupling agent include γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-γ-aminopropyltriethoxysilane, N-β-(aminoethyl)-N'-β-(aminoethyl)-γ-aminopropyltriethoxysilane, γ-anilinopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, vinyltriethoxysilane, N-β-(N-vinylbenzylaminoethyl)-γ-aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, and γ-isocyanatopropyltriethoxysilane;Isopropyl triisostearoyl titanate, isopropyl tri-n-dodecylbenzenesulfonyl titanate, isopropyl tris(dioctylpyrophosphate) titanate, tetraisopropyl bis(dioctylphosphite) titanate, tetraoctyl bis(ditridecylphosphite) titanate, tetra(2,2-diallyloxymethyl-1-butyl)bis(di-tridecyl)phosphite titanate, bis(dioctylpyrophosphate)oxyacetate titanate, bis(dioctylpyrophosphate)ethylene titanate, isopropyl trioctanoyl titanate, isopropyl dimethacryloylisostearoyl titanate, isopropyl isostearoyl diacryl titanate, isopropyl tri(dioctylphosphate) titanate, isopropyl tricumylphenyl titanate, isopropyl Titanium coupling agents such as tri(N-aminoethyl-aminoethyl)titanate, tetraisopropyl titanate, tetra normal butyl titanate, butyl titanate dimer, tetrakis(2-ethylhexyl)titanate, tetrastearyl titanate, tetramethyl titanate, diethoxybis(acetylacetonato)titanium, diisopropylbis(acetylacetonato)titanium, diisopropoxybis(ethylacetoacetate)titanium, isopropoxy(2-ethyl-1,3-hexanediolato)titanium, di(2-ethylhexoxy)bis(2-ethyl-1,3-hexanediolato)titanium, di-n-butoxybis(triethanolaminato)titanium, tetraacetylacetonate titanium, hydroxybis(lactato)titanium, dicumylphenyloxyacetate titanate, and diisostearoylethylene titanate;Zirconium tributoxystearate, tetra(2,2-diallyloxymethyl)butyl di(ditridecyl)phosphito zirconate, neopentyl(diallyl)oxytrineodecanoyl zirconate, neopentyl(diallyl)oxytri(dodecyl)benzene-sulfonyl zirconate, neopentyl(diallyl)oxytri(dioctyl)phosphato zirconate, neopentyl(diallyl)oxytri(dioctyl)pyro-phosphato zirconate, neopentyl(diallyl)oxytri(N-ethylenediamino)ethyl zirconate, neopentyl(diallyl)oxytri(m-amino)phenyl zirconate, neopentyl(diallyl)oxytrimethacryl zirconate, neopentyl(diallyl)oxytrimethacryl zirconate, neopentyl(diallyl)oxytrimethacryl Examples of the silane coupling agent include zirconium coupling agents such as acrylate zirconate, dineopentyl(diallyl)oxydipara-aminobenzoyl zirconate, dineopentyl(diallyl)oxydi(3-mercapto)propyl zirconate, tetra-normal-propoxy zirconium, tetra-normal-butoxy zirconium, zirconium 2,2-bis(2-propenolatomethyl)butyrate, zirconium tetraacetylacetonate, zirconium tributoxyacetylacetonate, zirconium dibutoxybis(acetylacetonate), zirconium dibutoxybis(acetylacetonate), zirconium tributoxyethylacetoacetate, and zirconium monobutoxyacetylacetonate bis(ethylacetoacetate). Among the above-mentioned silane coupling agents, the addition of γ-aminopropyltrimethoxysilane and / or γ-glycidoxypropyltrimethoxysilane is more preferred, and the addition of γ-glycidoxypropyltrimethoxysilane is most preferred, in view of their ease of availability and low cost. ;

[0030] The amount of the silane coupling agent (D) is not particularly limited, but is preferably 0.1 to 50 parts by mass per 100 parts by mass of the epoxy resin (A). From the viewpoints of good miscibility with the resin and improved adhesion to the fiber, it is particularly preferred to add 0.5 to 30 parts by mass, and more particularly 1 to 20 parts by mass.

[0031] The amount of the silane coupling agent, component (D), used is not particularly limited, but is preferably 0.005 to 10 mass %, more preferably 0.01 to 8 mass %, and particularly preferably 0.05 to 5 mass %, in the resin composition for fiber-reinforced plastics.

[0032] In the present invention, a reactive diluent, which is component (E), may be used in combination to adjust the viscosity to a desired level. The reactive diluent is incorporated into the cured product after curing of the resin composition and does not affect the physical properties of the cured product. Examples of reactive diluents for epoxy resin compositions include diluents having an epoxy group in the molecule. Examples of such reactive diluents include n-butyl glycidyl ether, C １２ ~C １４ alkyl glycidyl ethers of the above, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, glycidyl methacrylate, and monoglycidyl ether compounds such as tertiary carboxylic acid glycidyl esters.

[0033] The resin composition for fiber-reinforced plastics of the present invention may further contain additives, if necessary. Examples of the additives include commonly used additives such as non-reactive diluents (plasticizers) such as dioctyl phthalate, dibutyl phthalate, benzyl alcohol, and coal tar; pigments; lubricants such as candelilla wax, carnauba wax, Japan wax, Ibota wax, beeswax, lanolin, spermaceti, montan wax, petroleum wax, fatty acid wax, fatty acid esters, fatty acid ethers, aromatic esters, and aromatic ethers; thickeners; thixotropic agents; antioxidants; light stabilizers; ultraviolet absorbers; flame retardants; antifoaming agents; and rust inhibitors.

[0034] Since the resin composition for fiber-reinforced plastics of the present invention is used for fiber-reinforced plastics, it is preferably liquid at 25° C., and in particular, it is preferable that its viscosity is 100 to 3000 Pa·s.

[0035] The resin composition for fiber-reinforced plastics of the present invention is suitable as a matrix resin for fiber-reinforced plastics using carbon fiber, glass fiber, etc. as reinforcing fibers. The type of reinforcing fiber is not particularly limited, and for example, carbon fiber, glass fiber, aramid fiber, boron fiber, alumina fiber, silicone carbide fiber, etc. may be used alone or as a hybrid fiber of two or more types.

[0036] Examples of the form of the reinforcing fibers include a so-called tow sheet in which high-strength, high-elasticity fibers are aligned in one direction, a unidirectional fabric or a bidirectional fabric in which the fiber filaments are aligned in one or two directions, a triaxial fabric in which the fibers are aligned in three directions, a multiaxial fabric in which the fibers are aligned in multiple directions, etc. In the tow sheet, the fibers are preferably aligned so as to ensure appropriate gaps between the strands in order to improve resin impregnation into the substrate.

[0037] The method for molding a fiber-reinforced plastic using the resin composition for fiber-reinforced plastic of the present invention is not particularly limited, and examples thereof include extrusion molding, blow molding, compression molding, vacuum molding, injection molding, RTM (Resin Transfer Molding), VaRTM (Vaccum Assist Resin Transfer Molding), laminate molding, hand lay-up molding, and filament winding molding.

[0038] The amount of the cured product of the resin composition for fiber-reinforced plastics contained in the fiber-reinforced plastic is preferably 5 to 95 mass %, particularly preferably 10 to 80 mass %, and even more preferably 20 to 70 mass %. Use within this range is preferred because excellent physical properties can be exhibited.

[0039] Fiber-reinforced plastics obtained using the resin composition for fiber-reinforced plastics of the present invention can be used in a variety of applications, including general industrial applications such as structural materials for mobile bodies such as automobiles, ships, and railway vehicles, drive shafts, leaf springs, wind turbine blades, pressure vessels, flywheels, papermaking rollers, roofing materials, cables, and repair and reinforcement materials; aerospace applications such as fuselages, main wings, tails, moving surfaces, fairings, cowls, doors, seats, interior materials, motor cases, and antennas; and sports applications such as golf shafts, fishing rods, tennis and badminton rackets, hockey sticks, and ski poles.

[0040] The present invention will now be described in more detail with reference to examples.

[0041] Example 1 To a 500 mL disposable cup were added 98.6 g of ADEKA RESIN EP-4100E (manufactured by ADEKA Corporation; bisphenol A-type epoxy resin, epoxy equivalent: 190 g / eq.), 32 g of JEFFAMINE D-230 (manufactured by Huntsman; polypropylene polyamine), 2 g of HISHICHOLIN PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.; tetrabutylphosphonium O,O-diethylphosphorodithioate), and 1.4 g of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.; γ-glycidoxypropyltrimethoxysilane), and the mixture was stirred with a spatula at 25° C. for 5 minutes. The mixture was then further stirred using a planetary stirrer to obtain a resin composition.

[0042] Example 2 To a 500 mL disposable cup, 83.9 g of ADEKA Resin EP-4100E (manufactured by ADEKA Corporation; bisphenol A type epoxy resin, epoxy equivalent: 190 g / eq.), 14.8 g of ADEKA Glycilol ED-523T (manufactured by ADEKA Corporation; neopentyl glycol type epoxy resin: epoxy equivalent 140 g / eq.), 32 g of Jeffamine D-230 (manufactured by Huntsman; polypropylene polyamine), 2 g of Hishicolin PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.; tetrabutylphosphonium O,O-diethylphosphorodithioate), and 1.3 g of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.; γ-glycidoxypropyltrimethoxysilane) were added and stirred with a spatula at 25°C for 5 minutes. Thereafter, the mixture was further stirred using a planetary stirrer to obtain a resin composition.

[0043] Example 3 To a 500 mL disposable cup, 79.0 g of ADEKA Resin EP-4100E (manufactured by ADEKA Corporation; bisphenol A type epoxy resin, epoxy equivalent: 190 g / eq.), 30.6 g of Jeffamine D-230 (manufactured by Huntsman; polypropylene polyamine), 2 g of Hishicolin PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.; tetrabutylphosphonium O,O-diethylphosphorodithioate), 1.2 g of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.; γ-glycidoxypropyltrimethoxysilane), and 19.8 g of ADEKA Glysilol ED-509E (manufactured by ADEKA Corporation; t-butylphenyl glycidyl ether: epoxy equivalent: 210 g / eq.) were added and stirred with a spatula at 25 ° C. for 5 minutes. Thereafter, the mixture was further stirred using a planetary stirrer to obtain a resin composition.

[0044] [Example 4] To a 500 mL disposable cup, 74.0 g of ADEKA Resin EP-4100E (manufactured by ADEKA Corporation; bisphenol A type epoxy resin, epoxy equivalent: 190 g / eq.), 30.6 g of Jeffamine D-230 (manufactured by Huntsman; polypropylene polyamine), 2 g of Hishicolin PX-4ET (manufactured by Nippon Chemical Industry Co., Ltd.; tetrabutylphosphonium O,O-diethylphosphorodithioate), 1.2 g of KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., γ-glycidoxypropyltrimethoxysilane), and 24.8 g of ADEKA Glysilol ED-509E (manufactured by ADEKA Corporation; t-butylphenyl glycidyl ether: epoxy equivalent: 210 g / eq.) were added and stirred with a spatula at 25 ° C. for 5 minutes. Thereafter, further stirring was performed using a planetary stirrer to obtain a resin composition.

[0045] Comparative Example 1 A resin composition was obtained in the same manner as in Example 2, except that 2 g of 2-ethyl-4-methylimidazole was used instead of Hishicolin PX-4ET.

[0046] Comparative Example 2 A resin composition was obtained in the same manner as in Example 2, except that Hishicolin PX-4ET was not used.

[0047] [Evaluation Results] The resin compositions obtained in the Examples and Comparative Examples were evaluated as follows. The results are shown in Table 1.

[0048] <Curability> 20 g of each of the resin compositions obtained in the above Examples and Comparative Examples was weighed into an aluminum cup and then heat-cured at 80°C for 80 minutes. The degree of cure of the obtained sample was measured according to the method in accordance with JIS K 7148-1. At this time, a degree of cure of 90% or more was rated as +, and a degree of cure of less than 90% was rated as -.

[0049] <Non-coloring property> 33 g of the resin compositions obtained in the above Examples and Comparative Examples were mixed with glass fiber (UE-1200 g / m) using a roller. ２The resin was impregnated into 100 g of glass fiber (1300 mm diameter, manufactured by Saertex). The resin-impregnated glass fiber was then placed in a thermostatic chamber at 80°C and heated and cured for 80 minutes. The resulting fiber-reinforced plastic was visually inspected for coloration. A rating of + was given for cases where it was determined that the color had not changed from before curing, and a rating of - was given for cases where a color change from before curing was confirmed.

[0050]

[0051] In Table 1, *1 to *7 are as follows: *1: ADEKA Corporation's ADEKA Resin: bisphenol-type epoxy resin, epoxy equivalent 190 g / eq. *2: ADEKA Corporation's ADEKA Glycilol: neopentyl glycol-type epoxy resin, epoxy equivalent 140 g / eq. *3: Huntsman Chemical Industries' Jeffamine: polyoxypropylenediamine *4: Nippon Chemical Industry Co., Ltd.'s Hishicolin: tetrabutylphosphonium O,O-diethylphosphorodithioate *5: Shin-Etsu Silicones' γ-glycidoxypropyltrimethoxysilane *6: ADEKA Corporation's ADEKA Glycilol: p-tert-butylphenyl glycidyl ether *7: 2-ethyl-4-methylimidazole

[0052] As can be seen from Table 1, the resin composition for fiber-reinforced plastics of the present invention has excellent curability, and the fiber-reinforced plastics obtained using the same have excellent non-coloring properties.

[0053] The resin composition for fiber-reinforced plastics of the present invention can provide fiber-reinforced plastics that are excellent in curability and non-colorability, and therefore can provide molded articles with excellent appearance.

Claims

1. A resin composition for fiber-reinforced plastics, comprising: (A) component: an epoxy resin; (B) component: a polyoxyalkylene polyamine; and (C) component: at least one compound selected from the group consisting of compounds represented by the following formula (1): 【Chemistry 1】 (In the formula, R １ ~R ６ each independently represents a hydrocarbon group having 1 to 10 carbon atoms; X １ ~X ４ each independently represents an oxygen atom or a sulfur atom.

2. 2. The resin composition for fiber-reinforced plastics according to claim 1, wherein the polyoxyalkylene polyamine (B) is a polyoxypropylene polyamine having a weight-average molecular weight of 200 to 5,000.

3. 2. The resin composition for fiber-reinforced plastics according to claim 1, wherein the content of the component (C) is 0.01 to 20 parts by mass per 100 parts by mass of the component (B).

4. The resin composition for fiber-reinforced plastics according to claim 1, further comprising a component (D): a silane coupling agent.

5. The resin composition for fiber-reinforced plastics according to claim 1, further comprising component (E): a reactive diluent.

6. A fiber-reinforced plastic comprising a cured product of the resin composition for fiber-reinforced plastics according to any one of claims 1 to 5.

7. A fiber-reinforced plastic obtained by curing a composition containing the resin composition for fiber-reinforced plastics according to any one of claims 1 to 5 and reinforcing fibers.

Images