TW202033660A - Resin composition for prepreg, prepreg and molded product prepared from urethane (meth)acrylate (A), polymerization initiator (B) and thermoplastic resin (C) as essential components - Google Patents

Abstract

This invention provides a resin composition for a prepreg, which is prepared from urethane (meth)acrylate (A) of a reactant of polyisocyanate (a1), polyol (a2) and hydroxyalkyl (meth)acrylate (a3), a polymerization initiator (B) and thermoplastic resin (C) as essential components. The resin composition of the prepreg is characterized in that the polyisocyanate (a1) is selected from more than one polyisocyanates selected from 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, a carbodiimide modified substance of 4,4'-diphenylmethane diisocyanate and polymethylene polyphenyl polyisocyanate. The resin composition for the prepreg, provided by this invention has excellent moldability and can obtain molded products with various physical properties such as flexibility, impact resistance and heat resistance, so that the resin composition for the prepreg may be preferably applied to the prepreg and a molded product thereof.

Description

Resin composition for prepreg, prepreg and molded product

The present invention relates to a prepreg that is excellent in handleability and formability, and can obtain a molded product excellent in various physical properties such as heat resistance, and a molded product thereof.

Fiber-reinforced resin composite materials reinforced with reinforcing fibers such as carbon fiber and glass fiber are attracting attention because of their light weight, excellent heat resistance and mechanical strength, and are used in various structural applications such as automobile and aircraft shells and various parts. The use of in is gradually expanding. As a molding method of the fiber-reinforced resin composite material, for example, an intermediate material called a prepreg in which a thermosetting resin is impregnated into the reinforcing fiber is used, and then it is cured and molded by autoclave molding and press molding. method.

As the resin for the prepreg, it is generally necessary to have both room temperature stability and curability by heating or the like. Generally, thermosetting resins such as epoxy resin compositions are often used. However, prepregs using epoxy resins harden at room temperature, and therefore have the problem that they must be stored under refrigeration.

In order to solve this problem, a molding material that can achieve high productivity and stability at room temperature is being developed (for example, refer to Patent Document 1). Although the molding material contains a urethane (forma The base) acrylate compound and reinforcing fiber have the problem that the moldability required for the prepreg is insufficient.

Therefore, there is a demand for a material that has excellent moldability and can obtain molded products excellent in various physical properties such as flexibility, impact resistance, and heat resistance.

Prior art literature Patent literature

Patent Document 1 JP 2016-29133 A

The problem to be solved by the present invention is to provide a resin composition for prepregs, prepregs, and moldings thereof that are excellent in formability and can obtain molded products having excellent various physical properties such as flexibility, impact resistance, and heat resistance. Product.

The inventors of the present case have discovered that a resin composition for prepreg and a prepreg using a specific urethane (meth)acrylate, a polymerization initiator, and a thermoplastic resin as essential raw materials have excellent moldability and can be obtained Molded products having excellent various physical properties, such as flexibility, impact resistance, and heat resistance, have further completed the present invention.

That is, it relates to a resin composition for prepreg, which is a urethane (a1), a polyol (a2), and a hydroxyalkyl (meth)acrylate (a3) reactant. Pre-impregnation with meth)acrylate (A), polymerization initiator (B) and thermoplastic resin (C) as essential components A resin composition for materials, characterized in that: the polyisocyanate (a1) is selected from 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyl One or more polyisocyanates of carbodiimide modified products of methylmethane diisocyanate and polymethylene polyphenyl polyisocyanate; and prepregs and molded products thereof.

The molded product obtained from the resin composition for prepreg and the prepreg of the present invention has excellent flexibility, impact resistance, heat resistance, etc., and can be applied to automobile parts, railway vehicle parts, aerospace aircraft parts, ship parts, etc. Housing equipment parts, sporting goods parts, light-use vehicle parts, construction and civil engineering parts, OA equipment, etc.

The form used to implement the invention

The resin composition for prepreg of the present invention is a urethane (meth)acrylate which is a reactant of polyisocyanate (a1), polyol (a2), and hydroxyalkyl (meth)acrylate (a3) (A), a polymerization initiator (B), and a thermoplastic resin (C) as essential components for a prepreg resin composition, wherein the polyisocyanate (a1) is selected from 2,4'-diphenylmethane two One or more polyisocyanates of isocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, a carbodiimide modified product, and polymethylene polyphenyl polyisocyanate.

This urethane (meth)acrylate (A) is a reaction product of polyisocyanate (a1), polyol (a2), and hydroxyalkyl (meth)acrylate (a3).

The polyisocyanate (a1) is a carbodiimide modified from 2,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate One or more types of polyisocyanates of the substrate and polymethylene polyphenyl polyisocyanate, but from the viewpoint of further improving the heat resistance of the molded article, it is preferable to contain polymethylene polyphenyl polyisocyanate.

As an isocyanate raw material of this urethane (meth)acrylate (A), other polyisocyanates other than this polyisocyanate (a1) can be used together. As other polyisocyanates, for example, cyanurate (nurate) modification, biuret (burette) modification, urethane imine modification, diethylene glycol, or diphenylmethane diisocyanate can be used. Polyol modifier modified by polyol with a number average molecular weight of 1,000 or less such as dipropylene glycol, toluene diisocyanate (TDI), toluidine diisocyanate, xylylene diisocyanate, 1,5-naphthalene diisocyanate, tetra Aromatic polyisocyanates such as methylxylene diisocyanate; alicyclic polyisocyanates such as isophorone diisocyanate (IPDI), hydrogenated diphenylmethane diisocyanate, hydrogenated xylylene diisocyanate, norbornene diisocyanate Isocyanates; aliphatic polyisocyanates such as hexamethylene diisocyanate, hexamethylene diisocyanate modified isocyanurate, biuret modified, adduct, dimer acid diisocyanate, etc. .

The polyisocyanate (a1) is preferably 20% by mass or more in the isocyanate raw material of the urethane (meth)acrylate (A), more preferably 50% by mass or more.

Although not particularly limited as the polyol (a2), for example, an alkylene oxide adduct of bisphenol A, an alkylene oxide adduct of an aromatic diol can be used. Products, polyester polyol, acrylic polyol, polyether polyol, polycarbonate polyol, polyalkylene polyol, etc. These polyols (a2) may be used alone or in combination of two or more kinds.

As the hydroxyalkyl (meth)acrylate (a3), for example, 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxyn-butyl (meth)acrylate Ester, 2-hydroxypropyl (meth)acrylate, 2-hydroxyn-butyl (meth)acrylate, 3-hydroxyn-butyl (meth)acrylate, etc., but preferably 2-hydroxypropyl (meth)acrylate Ethyl ester. In addition, these hydroxyalkyl (meth)acrylates (a3) may be used alone or in combination of two or more kinds.

The hydroxyalkyl (meth)acrylate (a3) is preferably in the range of 5 to 50% by mass in the resin composition for prepreg.

The molar ratio (NCO/OH) of the isocyanate group (NCO) of the isocyanate compound used as the raw material of the urethane (meth)acrylate (A) and the hydroxyl group (OH) of the compound having a hydroxyl group (NCO/OH) is preferably 0.7 ~1.5, more preferably 0.8~1.3, still more preferably 0.8~1.0.

The polymerization initiator (B) is not particularly limited, and is preferably an organic peroxide. For example, diacetoxy peroxide compounds, peroxy ester compounds, hydroperoxide compounds, and ketone peroxide compounds are mentioned. , Alkyl peroxy ester compounds, percarbonate compounds, peroxy ketals, etc., can be appropriately selected according to the molding conditions. In addition, these polymerization initiators (B) may be used alone or in combination of two or more kinds.

In addition, among these, it is preferable to use a polymerization initiator whose temperature is 70°C or more and 100°C or less for the purpose of shortening the molding time in order to obtain a 10-hour half-life. If it is above 70℃ and below 100℃, then The prepreg has a long life at room temperature and can be cured in a short time (within 5 minutes) by heating, and is therefore preferred. By combining with the prepreg of the present invention, the curability and formability are more excellent. As such a polymerization initiator, for example, 1,6-bis(tertiarybutylperoxycarbonyloxy)hexane, 1,1-bis(tertiarybutylperoxy)cyclohexane, 1,1 -Bis (tertiary pentyl peroxy) cyclohexane, 1,1-bis (tertiary hexyl peroxy) cyclohexane, peroxydiethyl acetate tertiary butyl ester, peroxy isopropyl carbonate tertiary butyl Ester, tertiary amyl peroxyisopropyl carbonate, tertiary hexyl peroxyisopropyl carbonate, di-tertiary butylperoxyhexahydroterephthalate, tertiary peroxytrimethylhexanoic acid Amyl ester, tertiary hexyl peroxy-2-ethylhexanoate, etc.

The content of the polymerization initiator (B) is preferably in the range of 0.3 to 3% by mass in the resin composition for prepregs from the viewpoint of excellent curing characteristics and storage stability.

As the thermoplastic resin (C), for example, polyurethane resin, polyamide resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polycarbonate resin, Polypropylene resins, polyethylene resins, polystyrene resins, acrylic resins, polybutadiene resins, polyisoprene resins, and those modified by copolymerization, etc., among them, are more improved From the viewpoints of the flexibility, impact resistance, and heat resistance of the resulting molded product, a thermoplastic polyurethane resin is preferred, and a thermoplastic polyurethane resin containing polyalkylene ether polyol as an essential raw material is more preferred. Acid ester. These thermoplastic resins may be used alone or in combination of two or more kinds.

In addition, the thermoplastic resin (C) may be added in the form of particles and used, or may be used after melt mixing. Use particulate thermoplastic resin In the case of, from the viewpoint of fiber dispersibility, the particle diameter is preferably 30 μm or less, more preferably 20 μm.

The content of the thermoplastic resin (C) is preferably 1 to 25% by mass in the resin composition for prepreg from the viewpoint of improving the flexibility, impact resistance, and heat resistance of the molded product obtained Range.

啉(甲基)丙烯酸酯、丙烯酸苯基苯氧基乙酯、(甲基)丙烯酸苯基苄酯、丙烯酸苯基甲酯、(甲基)丙烯酸二環戊烯酯、(甲基)丙烯酸二環戊烯氧基乙酯、丙烯酸二環戊基甲酯等的單官能(甲基)丙烯酸酯化合物；(甲基)丙烯酸羥基乙酯、(甲基)丙烯酸羥基丙酯、(甲基)丙烯酸羥基丁酯等的含羥基之(甲基)丙烯酸酯化合物；乙二醇二(甲基)丙烯酸酯、丙二醇二(甲基)丙烯酸酯、1,4-丁二醇二(甲基)丙烯酸酯、1,6-己二醇二(甲基)丙烯酸酯、雙酚二(甲基)丙烯酸酯、1,4-環己烷二甲醇二(甲基)丙烯酸酯等的二(甲基)丙烯酸酯化合物等。該等可單獨使用，亦可併用2種以上。 In addition, as a raw material of the resin composition for prepregs of the present invention, ethylenically unsaturated monomers can also be used as required. As these ethylenically unsaturated monomers, for example, styrene compounds such as styrene, methylstyrene, halogenated styrene, and divinylbenzene; methyl (meth)acrylate, (meth)acrylic acid, etc. Ethyl, propyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, ( Benzyl (meth)acrylate, methylbenzyl (meth)acrylate, phenoxyethyl (meth)acrylate, methylphenoxyethyl (meth)acrylate,

Phospholine (meth)acrylate, phenylphenoxyethyl acrylate, phenylbenzyl (meth)acrylate, phenylmethyl acrylate, dicyclopentenyl (meth)acrylate, di(meth)acrylate Monofunctional (meth)acrylate compounds such as cyclopentenoxyethyl and dicyclopentylmethyl acrylate; hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, (meth)acrylic acid Hydroxyl-containing (meth)acrylate compounds such as hydroxybutyl ester; ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate , 1,6-hexanediol di(meth)acrylate, bisphenol di(meth)acrylate, 1,4-cyclohexanedimethanol di(meth)acrylate and other di(meth)acrylic acid Ester compounds, etc. These can be used individually or in combination of 2 or more types.

Among them, from the viewpoints of handling of odors and hazardous substances in the operating environment, and the mechanical strength and heat resistance of the molded body, monofunctional (meth)acrylates with a molecular weight of 150 to 250, (former) Phenoxyethyl (meth)acrylate, methylphenoxyethyl (meth)acrylate, benzyl (meth)acrylate, methylbenzyl (meth)acrylate, more preferably phenoxy (meth)acrylate Ethyl, benzyl (meth)acrylate.

The ethylenically unsaturated monomer in the resin composition for prepreg of the present invention is preferably 50% by mass or less, more preferably from the balance of handleability (adhesiveness), heat resistance, and curability 30% by mass or less.

As the components of the resin composition for prepregs of the present invention, those other than those described above may also be used. For example, thermosetting resins, polymerization inhibitors, hardening accelerators, fillers, low shrinkage agents, release agents, Tackifiers, viscosity reducers, pigments, antioxidants, plasticizers, flame retardants, antibacterial agents, ultraviolet stabilizers, reinforcing materials, light hardeners, etc.

Examples of the thermosetting resin include vinyl ester resins, unsaturated polyester resins, phenol resins, melamine resins, and furan resins. In addition, these thermosetting resins may be used alone or in combination of two or more kinds.

As the polymerization inhibitor, for example, hydroquinone, trimethylhydroquinone, p-tertiary butyl catechol, tertiary butyl hydroquinone, methyl hydroquinone, p- Benzoquinone, naphthoquinone, hydroquinone monomethyl ether, phenothiazine, copper naphthenate, copper chloride, etc. These polymerization inhibitors may be used alone or in combination of two or more kinds.

啉、哌啶、二乙醇苯胺等。該等的硬化促進劑可單獨使用，亦可併用2種以上。 As the hardening accelerator, for example, metal soaps such as cobalt naphthenate, cobalt octenate, vanadium octenate, copper naphthenate, barium naphthenate, etc., vanadium acetyl acetate, cobalt acetyl acetate, Metal chelating compounds such as acetyl iron acetate. Also, as amines, N,N-dimethylaminop-benzaldehyde, N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N -Ethyl m-toluidine, triethanolamine, m-toluidine, ethylene triamine, pyridine, phenyl

Morpholine, piperidine, diethanolaniline, etc. These hardening accelerators may be used alone or in combination of two or more kinds.

As the filler, there are inorganic compounds and organic compounds, which can be used to adjust physical properties such as the strength, elastic modulus, impact strength, and fatigue durability of the molded article.

As the inorganic compound, for example, calcium carbonate, magnesium carbonate, barium sulfate, mica, talc, kaolinite, clay, monetite, asbestos, barite, barium oxide, silicon dioxide, silica sand , Dolomite limestone, gypsum, aluminum powder, hollow sphere, alumina, glass powder, aluminum hydroxide, white marble, zirconia, antimony trioxide, titanium oxide, molybdenum dioxide, iron powder, etc.

As the organic compound, there are natural polysaccharide powders such as cellulose and chitin, and synthetic resin powder. As the synthetic resin powder, hard resin, soft rubber, elastomer or polymer (copolymer) can be used. Organic powder or particles with a core-shell type and other multilayer structure. Specifically, polyacrylic particles, polyamide particles, particles containing butadiene rubber and/or acrylic rubber, urethane rubber, silicone rubber, etc., polyimide resin powder, fluororesin powder, Phenol resin powder, etc. These fillers may be used alone or in combination of two or more kinds.

As this release agent, zinc stearate, calcium stearate, paraffin wax, polyethylene wax, carnauba wax, etc. are mentioned, for example. Preferably, paraffin wax, polyethylene wax, carnauba wax, etc. are mentioned. These release agents may be used alone or in combination of two or more kinds.

As the thickener, for example, metal oxides and metal hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide, calcium hydroxide, etc., acrylic resin-based fine particles, etc., can be used according to the prepreg of the present invention. Appropriate selection of handling. These thickeners may be used alone, or two or more of them may be used in combination.

The prepreg of the present invention contains the resin composition for the prepreg and the reinforcing fiber (D). Among them, the reinforcing fiber (D) includes carbon fiber, glass fiber, silicon carbide fiber, alumina fiber, and boron fiber , Metal fiber, amide fiber, vinylon (Vinylon) fiber, Tetoron (Tetoron) fiber and other organic fibers. From the viewpoint of obtaining higher strength and high elasticity molded products, carbon fiber or Glass fiber, more preferably carbon fiber. These reinforcing fibers (D) may be used alone or in combination of two or more kinds.

As the carbon fiber, various materials such as polyacrylonitrile-based, pitch-based, and rayon-based materials can be used. Among these, polyacrylonitrile-based materials are preferred from the viewpoint of obtaining high-strength carbon fibers.

The shape of the reinforcing fiber (D) is not particularly limited, and examples include reinforcing fiber tows in which reinforcing fiber threads have been bundled, unidirectional materials in which reinforcing fiber tows are arranged unidirectionally in parallel, woven textiles, or cut shorts. Reinforced fibers, or non-woven fabrics or papers containing cut reinforced fibers, are preferably used because unidirectional materials are used as reinforcing fibers and laminated and molded to obtain high mechanical properties.

In the case of using cut reinforcement fibers, it is preferable to use carbon fibers cut to a size of 2.5-50 mm from the viewpoint of further improving the fluidity in the mold during molding and the appearance of the molded product.

For textiles, examples include plain weave, twill weave, satin weave, or non-crimp fabric (non crimp fabric), which does not disassemble the sheet material with unidirectional parallel arrangement of fiber bundles and the laminated sheet material by changing the angle. Stitched suture sheet, etc.

The weight per unit area of the reinforcing fiber (weight per 1 m ² of the fiber) is not particularly limited, but is preferably 10 g/m ² to 650 g/m ² . If the weight per unit area is 10 g/m ² or more, the unevenness of the fiber width decreases and the mechanical properties become good, which is preferable. If the weight per unit area is 650 g/m ² or less, the impregnation of the resin becomes good, which is preferable. The weight per unit area is more preferably 50 to 500 g/m ² , particularly preferably 50 to 300 g/m ² .

In the prepreg of the present invention, the content of the reinforcing fiber (D) is preferably in the range of 20 to 85% by mass, more preferably 40 to 80 from the viewpoint of further improving the mechanical strength of the molded article obtained. The range of mass %.

The prepreg of the present invention is, for example, obtained by the following two steps: Step 1: The reinforcing fiber (D) is impregnated in the polyisocyanate using a conventional mixer such as a planetary mixer or a kneader. (a1), the polyol (a2), the hydroxyalkyl (meth)acrylate (a3), the polymerization initiator (B) and the thermoplastic resin (C) mixed resin solution, and then sandwich the release PET film from above Live, roll by a rolling mill to obtain a sheet; Step 2, put it at room temperature to 50 ℃, make the polyisocyanate (a1) The isocyanate group possessed, the polyol (a2), and the hydroxyl group possessed by the hydroxyalkyl (meth)acrylate (a3) react. In addition, in step 1, within a range that does not impair the impregnation of the fiber, a part of the polyisocyanate (a1), the polyol (a2) and the hydroxyalkyl (meth)acrylate (a3) can be used in advance. Responder.

The thickness of the prepreg of the present invention is preferably 0.02 to 1.0 mm. If the thickness is 0.02 mm or more, the handling of the build-up layer becomes easy, which is preferable. If the thickness is 1 mm or less, the impregnation of the resin becomes good, which is preferable. More preferably, it is 0.05 to 0.5 mm.

As a method of obtaining a molded product from the prepreg obtained above, for example, the following method can be used: the prepreg is peeled from the release PET film, 8 to 16 prepregs are laminated, and then heated to 110 The mold at ℃~160℃ is closed with a compression molding machine, the prepreg is shaped and the molding pressure is maintained at 0.1-10MPa to harden the prepreg, and then the molded product is taken out to obtain a molded product. In this case, it is preferable to use the following manufacturing method: in a mold with a shear edge, the mold temperature is 120°C to 160°C, and the thickness of the molded product is maintained for a predetermined time of 1 to 2 minutes per 1 mm. 1~8MPa molding pressure for heating compression molding.

The molded product obtained from the prepreg of the present invention has excellent interlaminar shear strength, heat resistance, etc., so it can be applied to automobile parts, railway vehicle parts, aerospace aircraft parts, ship parts, housing equipment parts, sporting goods parts, and light weight Car parts, construction and civil engineering parts, OA equipment, etc.

Example

Specific examples are given below to illustrate the present invention in detail.

(Synthesis example 1: Production of thermoplastic resin (C-1))

Mix 71 parts of PTMG1000 (manufactured by Mitsubishi Chemical Co., Ltd.: polytetramethylene ether glycol) with 3 parts of 1,4-butanediol and 26 parts of 4,4'-diphenylmethane diisocyanate, and cast It was made to react under the conditions of 90 degreeC and 24 hours in a vat, and the thermoplastic resin (C-1) was produced. The weight average molecular weight of the thermoplastic resin (C-1) is 50,000.

(Synthesis example 2: Production of thermoplastic resin (C-2))

Mix 73 parts of PTMG1000 (manufactured by Mitsubishi Chemical Co., Ltd.: polytetramethylene ether glycol) with 3 parts of 1,4-butanediol and 24 parts of 4,4'-diphenylmethane diisocyanate, and cast It was made to react under the conditions of 90 degreeC and 24 hours in a tank, and the thermoplastic resin (C-2) was produced. The weight average molecular weight of the thermoplastic resin (C-2) is 10,000.

(Synthesis Example 3: Production of Thermoplastic Resin (C-3))

Mix 74 parts of PTMG1000 (manufactured by Mitsubishi Chemical Co., Ltd.: polytetramethylene ether glycol) with 2 parts of 1,4-butanediol and 24 parts of 4,4'-diphenylmethane diisocyanate, and cast In the tank, it was made to react under the conditions of 90 degreeC and 24 hours, and the thermoplastic resin (C-3) was produced. The weight average molecular weight of the thermoplastic resin (C-3) is 150,000.

(Example 1: Production and evaluation of resin composition (1) for prepreg)

19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164g/eq), and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: bisphenol EO adduct of A, hydroxyl equivalent; 204g/eq), 44 parts of thermoplastic resin (C-1) were mixed at 150℃, after cooling, 79 parts of hydroxyethyl methacrylate and 3 parts of hydroxyethyl methacrylate were polymerized Starter ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic peroxide), 20 parts of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate (made by TOSOH Co., Ltd. Millionate MR-200") was mixed with 80 parts of 4,4'-diphenylmethane diisocyanate, poured into a mold with a thickness of 2mm and 6mm, and cured at 45°C for 24 hours to obtain prepreg Resin composition for objects (1).

In addition, 19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164 g/eq) and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 204g/eq), 44 parts of thermoplastic resin (C-1) were mixed at 150°C, after cooling, 79 parts of hydroxyethyl methacrylate, 3 parts of Polymerization initiator ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic peroxide), 20 parts of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate (TOSOH Co., Ltd. "Millionate MR-200") was mixed with 80 parts of 4,4'-diphenylmethane diisocyanate, coated on one side of the release PET film, and then impregnated with carbon fiber (Mitsubishi Rayon Co., Ltd.) Made "TRK979PQRW") to make the carbon fiber content 55%, cover the same release PET film, and then heat it at 45℃, 24 The aging treatment was carried out under hour conditions to produce the prepreg (1). The molar ratio (NCO/OH) of the raw materials other than the carbon fiber in this prepreg (1) was 0.93. Also, the thickness is 0.25 mm.

[Evaluation of flexibility]

The resin composition (1) for a prepreg having a thickness of 2 mm obtained above was cured at 150°C for 30 minutes to obtain a cured product. According to JIS K 7161, the elongation of the obtained cured product was measured and evaluated according to the following standards.

○: 4% or more

×: less than 4%

[Evaluation of impact resistance]

The resin composition (1) for a prepreg having a thickness of 6 mm obtained above was cured at 150°C for 30 minutes to obtain a cured product. The obtained hardened product was cut into a width of 12.7 mm and a length of 150 mm with a diamond cutter, and the fracture toughness was measured in accordance with ASTM D5045-99, and evaluated according to the following standards.

○: 1.8MPa. m ^0.5 or more

×: Less than 1.8MPa. m ^0.5

[Production of molded products]

Laminate 8 pieces of the prepreg (1) obtained above, and use a 300mm×300mm×3mm plate mold to heat and press for 5 minutes under the conditions of a mold temperature of 140°C and a mold closing pressure of 0.98MPa to obtain a molding品(1).

[Evaluation of formability]

The difference between the carbon fiber content of the prepreg (1) and the carbon fiber content of the molded article (1) obtained above was measured, and the moldability was evaluated according to the following criteria.

○: The difference in carbon fiber content is less than 5%

△: The difference in carbon fiber content is more than 5% and less than 10%

×: The difference in carbon fiber content is more than 10%

[Evaluation of the heat resistance of molded products]

A test piece with a width of 5 mm and a length of 55 mm was cut out from the molded product (1) obtained above. For this test piece, the "DMS6100" manufactured by SII•Nanotechnology was used to measure the measurement frequency of 1 Hz, the heating rate of 3°C/min, and the Dynamic viscoelasticity bent from both ends of the hardened material. The intersection of the approximate straight line of the glass range of the obtained storage elastic modulus graph and the tangent line of the transition range was taken as the glass transition temperature, and the heat resistance was evaluated according to the following criteria.

○: The glass transition temperature is above 120℃

△: The glass transition temperature is above 100℃ but below 120℃

×: The glass transition temperature is less than 100℃

[Evaluation of flexibility of molded products]

A test piece with a width of 15 mm and a length of 60 mm was cut out from the above-obtained molded product (1). For this test piece, the bending strength in the orthogonal direction (90°) of the unidirectional fiber material was measured according to JIS K7017, according to the following Standard for evaluation.

○: Flexural strength above 90MPa

△: The bending strength is above 70MPa but less than 90MPa

×: The bending strength is less than 70MPa

(Example 2: Production and evaluation of resin composition (2) for prepreg)

19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164g/eq), and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: bisphenol EO adduct of A, hydroxyl equivalent; 204g/eq), 22 parts of thermoplastic resin (C-1) were mixed at 150°C, after cooling, 79 parts of hydroxyethyl methacrylate and 3 parts of hydroxyethyl methacrylate were polymerized Starter ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic peroxide), 20 parts of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate (made by TOSOH Co., Ltd. Millionate MR-200") was mixed with 80 parts of 4,4'-diphenylmethane diisocyanate, poured into a mold with a thickness of 2mm and 6mm, and cured at 45°C for 24 hours to obtain prepreg Resin composition for objects (2).

In addition, 19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164 g/eq) and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 204g/eq), 22 parts of thermoplastic resin (C-1) were mixed at 150°C, after cooling, 79 parts of hydroxyethyl methacrylate, 3 parts of Polymerization initiator ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic peroxide), 20 parts of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate A mixture of esters ("Millionate MR-200" manufactured by TOSOH Co., Ltd.) is mixed with 80 parts of 4,4'-diphenylmethane diisocyanate. After coating on one side of the release PET film, it is impregnated by hand Carbon fiber ("TRK979PQRW" manufactured by Mitsubishi Rayon Co., Ltd.) with carbon fiber content of 55%, covered with the same release PET film, and cured at 45°C for 24 hours to produce a prepreg (2 ). The molar ratio (NCO/OH) of the raw materials other than the carbon fiber in this prepreg (2) was 0.93. Also, the thickness is 0.25 mm.

(Example 3: Production and evaluation of resin composition (3) for prepreg)

19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164g/eq), and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: bisphenol EO adduct of A, hydroxyl equivalent; 204g/eq), 11 parts of thermoplastic resin (C-1) were mixed at 150°C, and after cooling, 79 parts of hydroxyethyl methacrylate and 22 parts of polyamide Amine particles ("2001UD" manufactured by ARKEMA), 3 parts of polymerization initiator ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic peroxide), 20 parts of polymethylene polyphenyl polyisocyanate and A mixture of diphenylmethane diisocyanate ("Millionate MR-200" manufactured by TOSOH Co., Ltd.) was mixed with 80 parts of 4,4'-diphenylmethane diisocyanate and poured into a mold with a thickness of 2mm and 6mm. The aging treatment was performed under the conditions of ℃ and 24 hours to obtain the resin composition (3) for prepregs.

In addition, 19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164 g/eq), 24 Parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 204g/eq), 11 parts of thermoplastic resin (C-1) were mixed at 150°C, and after cooling, 79 parts of hydroxyethyl methacrylate, 22 parts of polyamide particles ("2001UD" manufactured by ARKEMA) and 3 parts of polymerization initiator ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd.), organic peroxide ), 20 parts of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate ("Millionate MR-200" manufactured by TOSOH Co., Ltd.) and 80 parts of 4,4'-diphenylmethane After mixing with diisocyanate, coating on one side of the release PET film, impregnating carbon fiber ("TRK979PQRW" manufactured by Mitsubishi Rayon Co., Ltd.) by manual method to make the carbon fiber content 55%, and covering the same release PET film , The aging treatment was carried out at 45° C. and 24 hours to produce the prepreg (3). The molar ratio (NCO/OH) of the raw materials other than the carbon fiber in this prepreg (3) was 0.93. Also, the thickness is 0.25 mm.

(Example 4: Manufacture and evaluation of resin composition (4) for prepreg)

19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164g/eq), and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: bisphenol EO adduct of A, hydroxyl equivalent; 204g/eq), 22 parts of thermoplastic resin (C-2) were mixed at 150°C, after cooling, 79 parts of hydroxyethyl methacrylate and 3 parts of hydroxyethyl methacrylate were polymerized Starter ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic peroxide), 20 parts of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate The mixture ("Millionate MR-200" manufactured by TOSOH Co., Ltd.) was mixed with 80 parts of 4,4'-diphenylmethane diisocyanate, and it was poured into a mold with a thickness of 2mm and 6mm at 45°C for 24 hours. The aging treatment is performed to obtain a resin composition (4) for prepreg.

In addition, 19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164 g/eq) and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 204g/eq), 22 parts of thermoplastic resin (C-2) were mixed at 150°C, after cooling, 79 parts of hydroxyethyl methacrylate, 3 parts of Polymerization initiator ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic peroxide), 20 parts of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate (TOSOH Co., Ltd. "Millionate MR-200") was mixed with 80 parts of 4,4'-diphenylmethane diisocyanate, coated on one side of the release PET film, and then impregnated with carbon fiber (Mitsubishi Rayon Co., Ltd.) "TRK979PQRW") was made so that the carbon fiber content was 55%, and after covering the same release PET film, it was cured at 45°C for 24 hours to produce a prepreg (4). The molar ratio (NCO/OH) of the raw materials other than the carbon fiber in this prepreg (4) was 0.93. Also, the thickness is 0.25 mm.

(Example 5: Production and evaluation of resin composition (5) for prepreg)

19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164g/eq), and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: bisphenol A EO adduct, hydroxyl equivalent; 204g/eq), 16 parts of thermoplastic resin (C-3) are mixed at 150℃, after cooling, 79 parts of hydroxyethyl methacrylate, 3 parts of polymerization start Agent ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic peroxide), 20 parts of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate (made by TOSOH Co., Ltd. "Millionate MR-200") was mixed with 80 parts of 4,4'-diphenylmethane diisocyanate, poured into a mold with a thickness of 2mm and 6mm, and aged at 45°C for 24 hours to obtain a prepreg Use resin composition (5).

In addition, 19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164 g/eq) and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 204g/eq), 16 parts of thermoplastic resin (C-3) were mixed at 150°C, after cooling, 79 parts of hydroxyethyl methacrylate, 3 parts of Polymerization initiator ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic peroxide), 20 parts of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate (TOSOH Co., Ltd. "Millionate MR-200") was mixed with 80 parts of 4,4'-diphenylmethane diisocyanate, coated on one side of the release PET film, and then impregnated with carbon fiber (Mitsubishi Rayon Co., Ltd.) "TRK979PQRW") was made so that the carbon fiber content was 55%, and after covering the same release PET film, the prepreg (5) was made by curing at 45°C for 24 hours. The molar ratio (NCO/OH) of the raw materials other than the carbon fiber in this prepreg (5) was 0.93. Also, the thickness is 0.25 mm.

(Comparative example 1: Preparation and evaluation of resin composition (R1) for prepreg)

19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164g/eq), and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: bisphenol EO adduct of A, hydroxyl equivalent; 204g/eq), 79 parts of hydroxyethyl methacrylate, 3 parts of polymerization initiator ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic peroxide ), 20 parts of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate (TOSOH Co., Ltd. "Millionate MR-200") and 80 parts of 4,4'-diphenylmethane diisocyanate The isocyanate was mixed, poured into a mold having a thickness of 2 mm and 6 mm, and subjected to an aging treatment at 45°C for 24 hours to obtain a resin composition (R1) for prepreg.

In addition, 19 parts of NEWPOL BPE-20 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 164 g/eq) and 24 parts of NEWPOL BPE-40 (manufactured by Sanyo Chemical Co., Ltd.: EO adduct of bisphenol A, hydroxyl equivalent; 204g/eq), 79 parts of hydroxyethyl methacrylate, 3 parts of polymerization initiator ("TRIGONOX 122-C80" manufactured by KAYAKU AKUZO Co., Ltd., organic Oxide), 20 parts of a mixture of polymethylene polyphenyl polyisocyanate and diphenylmethane diisocyanate ("Millionate MR-200" manufactured by TOSOH Co., Ltd.) and 80 parts of 4,4'-diphenyl After mixing methane diisocyanate and coating on one side of the release PET film, the carbon fiber is impregnated by manual method ("TRK979PQRW" manufactured by Mitsubishi Rayon Co., Ltd.) The amount became 55%, and after covering the same release PET film, the aging treatment was performed under the conditions of 45°C for 24 hours to produce a prepreg (R1). The molar ratio (NCO/OH) of the raw materials other than the carbon fiber in this prepreg (R1) was 0.93. Also, the thickness is 0.25 mm.

Except that the resin composition (1) for prepreg used in Example 1 was changed to the resin composition (2) to (5) and (R1) for prepreg, it was the same as Example 1 Evaluate flexibility and impact resistance.

In addition, except that the prepreg (1) used in Example 1 was changed to prepregs (2) to (5) and (R1), a molded product (2) was produced in the same manner as in Example 1. )~(5) and (R1), evaluate the formability and heat resistance.

The evaluation results of the resin compositions (1) to (5) and (R1) for prepregs obtained above are shown in Table 1.

It was confirmed that the resin composition for prepreg of the present invention of Examples 1 to 6 can provide a cured product having excellent flexibility and impact resistance, a prepreg having excellent moldability, and a molded product having excellent heat resistance and flexibility.

On the other hand, Comparative Example 1 is an example that does not contain the thermoplastic resin as an essential component of the present invention, and it can be confirmed that the flexibility and impact resistance of the cured product and the flexibility of the molded product are insufficient.

Claims (6)

A resin composition for prepreg, which is a urethane (meth)acrylate that is a reactant of polyisocyanate (a1), polyol (a2), and hydroxyalkyl (meth)acrylate (a3) (A), a polymerization initiator (B), and a thermoplastic resin (C) as essential components of a resin composition for prepreg, characterized in that the polyisocyanate (a1) is selected from 2,4'-diphenyl One or more of methane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate carbodiimide modification, and polymethylene polyphenyl polyisocyanate Polyisocyanate. The resin composition for prepreg according to claim 1, wherein the thermoplastic resin (C) is a thermoplastic polyurethane resin using polyalkylene ether polyol as an essential raw material. The resin composition for prepregs of claim 1 or 2, wherein the weight average molecular weight of the thermoplastic resin (C) is 5,000 to 1,000,000. The resin composition for prepreg according to any one of claims 1 to 3, wherein the thermoplastic resin (C) is in the range of 1-25% by mass. A prepreg characterized in that it contains the resin composition for prepreg according to any one of claims 1 to 4 and reinforcing fibers (D). A molded product characterized in that it is a hardened product of the prepreg according to claim 5.