JPH115887A - Resin composition for fiber-reinforced composite material, prepreg and fiber-reinforced composite material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain the subject composition giving prepregs excellent in tackiness, drape and windability on mandrels by including a thermosetting resin and a thermoplastic resin soluble in the thermosetting resin and having a specific weight-average mol.wt. SOLUTION: This resin composition comprises (A) 100 pts.wt. of a thermosetting resin (e.g. an epoxy resin) and (B) 0.1-20 pts.wt., preferably 0.1-10 pts.wt., of a thermoplastic resin which is soluble in the component A and has a weight- average mol.wt. of 200,000-5,000,000 and preferably further a glass transition temperature of >=80 deg.C or a melting point of >=80 deg.C. The resin composition preferably has a complex viscosity η of 200-2,000 Pa.s by the measurement of dynamic viscoelasticity at a measurement frequency of 0.5 Hz and at 50 deg.C and a storage elastic modules G' of 100-2,000 Pa, wherein η* and G' satisfy an relation of 0.9<=G'/η*<=2.0.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition for a fiber-reinforced composite material which gives a prepreg excellent in tackiness, drapability and wrapping around a mandrel (core metal), a prepreg using the same as a matrix resin, And a fiber-reinforced composite material (composite) obtained from the prepreg.

[0002]

2. Description of the Related Art Fiber-reinforced composite materials comprising a reinforcing fiber and a matrix resin are lightweight and have excellent mechanical properties, so that they are used for sports applications such as golf shafts, fishing rods and tennis rackets, aerospace applications, and general industries. Widely used for applications.

Conventionally, various methods have been used for producing a fiber-reinforced composite material. However, a method using a prepreg, which is a sheet-like intermediate substrate in which a reinforcing fiber is impregnated with a matrix resin, is widely used. Have been. According to this method, a fiber-reinforced composite material can be obtained as a molded product by laminating a plurality of prepregs and heating them.

[0004] As a matrix resin used for the prepreg, both a thermosetting resin and a thermoplastic resin are used. In most cases, a thermosetting resin is used. Among them, heat resistance, hardness and dimensional stability are used. Epoxy resins (cured products) having excellent mechanical and chemical properties such as properties and chemical resistance are mainly used. Here, the term thermosetting resin or epoxy resin is generally used in two senses: a prepolymer, and a cured product obtained by reacting a composition obtained by mixing a curing agent and other components with the prepolymer. Can be As used herein, the term thermosetting resin or epoxy resin refers to
Unless otherwise noted, it is used in the sense of prepolymer.

[0005] When prepregs using a thermosetting resin are used, problems often arise in tackiness (adhesion) between the prepregs and drapeability (flexibility) of the prepregs. These properties greatly affect the workability when handling the prepreg.

[0006] That is, if the tackiness of the prepreg is too small, the prepreg that has been laminated is immediately peeled off in the prepreg laminating step, which hinders the laminating operation. On the other hand, if the tackiness of the prepreg is too large, for example, if the prepreg is erroneously overlapped, it is difficult to peel off, and it is difficult to peel off and correct it. In addition, when the drape property of the prepreg is poor, the workability when laminating using a mold or a mandrel having a curved surface is significantly reduced.

In recent years, the weight has been reduced particularly for sports equipment such as golf shafts and fishing rods, and a prepreg suitable for a lightweight design has been demanded. In recent years, prepregs using high-modulus fibers, particularly high-modulus carbon fibers, as reinforcing fibers have been demanded in recent years, particularly in the market, because they can facilitate lightweight design. Also, the demand for prepregs having a high reinforcing fiber content is increasing.

However, when high modulus carbon fibers are used as the reinforcing fibers, the drapability of the prepreg decreases. Also, when the content of the reinforcing fibers increases, the amount of the resin distributed on the prepreg surface decreases, so that the tackiness tends to decrease. Therefore, the conventional prepreg using a matrix resin has a problem that tackiness, drapeability, or both are insufficient.

For this reason, as described later, several methods have been proposed for improving the resin composition in order to obtain good tackiness or drapability.
In general, there is a problem that the drapability is sacrificed when the tackiness is improved. Golf shafts and fishing rods are formed by winding a prepreg around a mandrel having a relatively small diameter. If the adhesive force (tacking property) between the prepregs exceeds the force for peeling the prepreg, the prepreg wound around the mandrel peels off, making the winding operation difficult. The force for peeling the prepreg increases as the drapability decreases. Therefore, even if tackiness is improved at the expense of drapeability, the mandrel winding operation itself is not significantly improved.

As a technique for improving the tackiness of a prepreg, it is known to mix a high molecular compound such as a thermoplastic resin or an elastomer with an epoxy resin. An example of blending a polymer compound with an epoxy resin is disclosed in
JP-A-8-8724 and JP-A-62-169829.
JP-A-55-27342, JP-A-55-27342, and JP-A-55-27342.
JP-A-5-108443 and JP-A-6-16675
6, a method of adding a polyvinyl acetal resin described in JP-A-5-117423, a method of blending a polyester polyurethane described in JP-A-5-117423, and a method of adding a poly (polyester) described in JP-A-54-99161. Method for blending a (meth) acrylate polymer
A method of blending polyvinyl ether described in 130156 and a method of blending nitrile rubber described in JP-A-2-20546 are known.

However, in the method of adding a polymer compound to an epoxy resin, even if the tackiness of the prepreg can be improved, there is a restriction that the viscosity of the resin increases and the drapability deteriorates. Therefore, it is difficult to find a resin satisfying both tackiness and drapability, particularly in a prepreg using a high elastic modulus carbon fiber and having a high reinforcing fiber content, and has a good wrapping property of the prepreg around a mandrel. Was difficult to achieve.

[0012]

SUMMARY OF THE INVENTION It is an object of the present invention to provide a resin composition for a fiber-reinforced composite material capable of obtaining a prepreg excellent in tackiness, drapeability and wrapping around a mandrel.

[0013]

The resin composition for a fiber-reinforced composite material of the present invention has the following constitution in order to achieve the above object. That is, the resin composition contains at least the following components A and B, and the component B is soluble in the component A.

A. Thermosetting resin B. Thermoplastic resin having a weight average molecular weight of 200,000 to 5,000,000 Further, the prepreg of the present invention is a prepreg obtained by impregnating the above-mentioned resin composition for a fiber-reinforced composite material into a reinforcing fiber, and the fiber-reinforced composite material of the present invention is: A fiber-reinforced composite material comprising a cured product of the thermosetting resin composition and reinforcing fibers.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The thermosetting resin of component A used in the resin composition for a fiber-reinforced composite material of the present invention includes epoxy resin, unsaturated polyester resin, vinyl ester resin, phenol resin, melamine resin, Examples thereof include urea resins, silicone resins, maleimide resins, cyanate ester resins, and resins obtained by prepolymerizing a maleimide resin and a cyanate ester resin. In the present invention, a mixture of these resins is also used.

Among them, an epoxy resin excellent in heat resistance, elastic modulus, and chemical resistance is particularly preferably used for a fiber reinforced composite material.

As the epoxy resin, a compound having one or more epoxy groups in a molecule, preferably a compound having two or more epoxy groups in a molecule is used. From the viewpoint of the balance between heat resistance and mechanical properties of the cured product, a mixture of a bifunctional epoxy resin (having two epoxy groups per molecule) and a trifunctional or higher epoxy resin (having three or more epoxy groups per molecule) It is particularly preferable to use them. In this case, if the amount of the trifunctional or higher epoxy resin is large,
The crosslink density of the cured product may be too high to obtain high toughness. Therefore, in the present invention, the epoxy resin 10
50 to 95 parts by weight of the bifunctional epoxy resin in 0 parts by weight,
It is preferable to use a trifunctional or higher functional epoxy resin in a mixing ratio of 5 to 50 parts by weight.

Further, phenols, amines, and / or
And an epoxy resin having a compound having a carbon-carbon double bond as a precursor is preferably used in view of mechanical properties of the cured product and reactivity with a curing agent.

An epoxy resin having phenols as a precursor is obtained by reacting phenols with epichlorohydrin. Examples of the precursor include bisphenols such as bisphenol A and bisphenol F, resorcinol, dihydroxynaphthalene, trihydroxynaphthalene, dihydroxybiphenyl, bishydroxyphenylfluorene, trishydroxyphenylmethane,
Examples include tetraxyhydroxyphenylethane, novolak, and condensates of dicyclopentadiene and phenol.

Epoxy resins using amines as precursors are:
Obtained by the reaction of amines with epichlorohydrin. Examples of precursors include tetraglycidyl diaminodiphenylmethane, aminophenol, aminocresol, xylenediamine, and the like.

An epoxy resin using a compound having a carbon-carbon double bond as a precursor can be obtained by oxidizing a carbon-carbon double bond in the precursor into an epoxy group. Its precursors include vinylcyclohexene and bis (3-
(Vinylcyclohexylmethyl) adipate, 3-vinylcyclohexylmethyl-3-vinylcyclohexanecarboxylate, and the like.

As the bisphenol A type epoxy resin (epoxy resin having bisphenol A as a precursor),
"Epicoat" (registered trademark) 825 (epoxy equivalent 17
2-178), "Epicoat" 828 (epoxy equivalent 1
84-194), "Epicoat" 834 (epoxy equivalent 230-270), "Epicoat" 1001 (epoxy equivalent 450-500), "Epicoat" 1002 (epoxy equivalent 600-700), "Epicoat" 1003
(Epoxy equivalent 670-770), "Epicoat" 10
04 (epoxy equivalent 875-975), "Epicoat"
1007 (epoxy equivalent 1750-2200), "Epicoat" 1009 (epoxy equivalent 2400-330)
0), "Epicoat" 1010 (epoxy equivalent 3000
~ 5000) (The above are made by Yuka Shell Epoxy Co., Ltd.)
And "Epototo" (registered trademark) YD-128 (epoxy equivalent: 184 to 194) "Epotote" YD-011
(Epoxy equivalent 450-500), "Epototo" YD
-014 (epoxy equivalent 900-1000), "Epototo" YD-017 (epoxy equivalent 1750-210)
0), "Epototo" YD-019 (epoxy equivalent 24
00-3000), "Epototo" YD-022 (epoxy equivalent 4000-6000) (Tohoku Kasei Co., Ltd.)
), "Epiclone" (registered trademark) 840 (epoxy equivalent 180-190), "Epiclon" 850 (epoxy equivalent 184-194), "Epiclon" 1050 (epoxy equivalent 450-500) (Dai Nippon Ink Chemicals, Inc.) Industrial Co., Ltd.), "Sumi Epoxy" (registered trademark) ELA
-128 (epoxy equivalents 184-194, manufactured by Sumitomo Chemical Co., Ltd.), DER331 (epoxy equivalents 182-19)
2, commercially available resins such as Dow Chemical Co., Ltd.). These resins have a chemical structure represented by the following formula (1).

[0023]

Embedded image Note that n in the above formula (1) represents a positive number.

As the bisphenol F type epoxy resin, “Epiclon” 830 (epoxy equivalent of 165 to 165) is used.
185, manufactured by Dainippon Ink and Chemicals, Inc.), "Epicoat" 806 (epoxy equivalent 160-170), "Epicoat" 807 (epoxy equivalent 160-175), "Epicoat" E4002P (epoxy equivalent 610), "Epicoat" E4003P (epoxy equivalent 800), “Epicoat” E4004P (epoxy equivalent 930), “Epicoat” E4007P (epoxy equivalent 2060), “Epicoat” E4009P (epoxy equivalent 3030),
"Epicoat" E4010P (epoxy equivalent 4400)
(Both manufactured by Yuka Shell Epoxy Co., Ltd.) and the like,
It has a chemical structure as shown in the following formula (2).

[0025]

Embedded image Note that n in the above equation (2) represents a positive number.

As the phenol novolak type epoxy resin, “Epicoat” 152 (epoxy equivalent: 172-1)
79), "Epicoat" 154 (epoxy equivalent 176-
181) (both manufactured by Yuka Shell Epoxy Co., Ltd.), DE
R438 (epoxy equivalent 176-181, manufactured by Dow Chemical Company), "Araldite" (registered trademark) EPN1138
(Epoxy equivalents 176-181), "Araldite" 1
139 (epoxy equivalents: 172 to 179, manufactured by Ciba) can be used, and these resins have a chemical structure represented by the following formula (3).

[0027]

Embedded image In addition, the following epoxy resins may be used.

"Epiclon" EXA-1514, a bisphenol S type epoxy resin (epoxy equivalent 290)
To 330, manufactured by Dainippon Ink and Chemicals, Inc.), "Denacol" (registered trademark) EX-251 (epoxy equivalent 18
9, Nagase Kasei Kogyo Co., Ltd.), "Epicoat" 5050 which is a tetrabromobisphenol A type epoxy resin
(Epoxy equivalent: 380-410, manufactured by Yuka Shell Epoxy Co., Ltd.), "Epiclon" 152 (epoxy equivalent: 34
0-380, manufactured by Dainippon Ink and Chemicals, Inc.), "Sumi-Epoxy" ESB-400T (epoxy equivalent: 380-380)
420, manufactured by Sumitomo Chemical Co., Ltd.), "Epototo" YB
D-360 (epoxy equivalent 350-370, manufactured by Toto Kasei Co., Ltd.), "Denacol" EX-201 (epoxy equivalent 118) which is a resorcin diglycidyl ether,
Hydroquinone diglycidyl ether “Denacol” EX-203 (epoxy equivalent: 112) (all manufactured by Nagase Kasei Kogyo Co., Ltd.), 4,4′-dihydroxy-3,3 ′,
5,5'-tetramethylbiphenyldiglycidyl ether "Epicoat" YX4000 (epoxy equivalent 18
0-192, manufactured by Yuka Shell Epoxy Co., Ltd.) "Epiclone" HP-4032H which is a diglycidyl ether of 1,6-dihydroxynaphthalene (epoxy equivalent: 25
0, manufactured by Dainippon Ink and Chemicals, Inc.), 9,9-bis (4
“EPON” HPT resin 1079 (epoxy equivalent 250-260, manufactured by Shell Co.) which is a diglycidyl ether of -hydroxyphenyl) fluorene, TACTIX 742 (epoxy equivalent 150-157) which is a triglycidyl ether of tris (p-hydroxyphenyl) methane ,
Dow Chemical Co., Ltd.), "Epicoat" 1031S, a tetraglycidyl ether of tetrakis (p-hydroxyphenyl) ethane (epoxy equivalent: 196, manufactured by Yuka Shell Epoxy Co., Ltd.), "Denacol" EX, a triglycidyl ether of glycerin -314 (epoxy equivalent 1
45, manufactured by Nagase Kasei Kogyo Co., Ltd.) "Denacol" E which is a tetraglycidyl ether of pentaerythritol
X-411 (epoxy equivalent 231; manufactured by Nagase Kasei Kogyo Co., Ltd.) and the like.

Further, specific examples of epoxy resins using amines as precursors include “Sumi-Epoxy” ELM434 (epoxy equivalent of 110 to 130, diglycidylaniline and tetraglycidyldiaminodiphenylmethane).
Sumitomo Chemical Co., Ltd.), tetraglycidyl m-xylylenediamine TETRAD-X (epoxy equivalent 9
0-105, manufactured by Mitsubishi Gas Chemical Co., Ltd.), triglycidyl
-Sumi-epoxy ELM which is m-aminophenol
120 (Epoxy equivalent 118, Sumitomo Chemical Co., Ltd.)
"Araldite" MY0510 which is a triglycidyl-p-aminophenol (epoxy equivalent 94
To 107, manufactured by Ciba Co., Ltd.). Polyepoxides obtained by oxidizing a compound having a plurality of double bonds in the molecule include Union Carbide ERL
-4206 (epoxy equivalent 70-74), ERL-42
21 (epoxy equivalents 131 to 143), ERL-423
4 (epoxy equivalents 133 to 154) and the like. Further, epoxidized soybean oil and the like can also be mentioned.

Other than these, glycidyl esters such as diglycidyl phthalate, diglycidyl terephthalate and diglycidyl dimer, and triglycidyl isocyanurate can also be used.

The thermoplastic resin having a weight average molecular weight of 200,000 to 5,000,000, which is the component B of the present invention, is blended with the matrix resin in order to control the viscoelasticity of the matrix resin and to achieve both tackiness and drapability of the prepreg. Is done.

As the high molecular weight compound to be added to the matrix resin for controlling the viscoelasticity, both a thermoplastic resin and an elastomer are used. However, when an elastomer is blended, there is a disadvantage that the heat resistance and the elastic modulus of the cured product of the matrix resin are reduced. Therefore, in the present invention, a thermoplastic resin having no such a problem is suitably used. In order to obtain good heat resistance, a thermoplastic resin that satisfies either a condition of a glass transition temperature of 80 ° C. or higher or a melting point of 80 ° C. or higher is preferably used.

The tackiness and drapability of the prepreg or the wrapping property around the mandrel depend on the prepreg production conditions, the type of reinforcing fibers, and the viscoelasticity of the matrix resin. The viscoelasticity of the matrix resin has a greater degree of freedom as compared with the prepreg manufacturing conditions and the reinforcing fibers, and is an important factor for controlling tackiness and drapability or improving the winding property around a mandrel.

Although there are several parameters relating to the viscoelasticity of the matrix resin, the complex viscosity η ^* and the storage elastic modulus G ′ are particularly important parameters for the tackiness or drapability of the prepreg. Complex viscosity η ^*
Is generally correlated with the drapability, and a prepreg using a matrix resin having a small complex viscosity η ^* tends to have a better drapability. On the other hand, the storage elastic modulus G 'generally has a correlation with tackiness, and a prepreg using a matrix resin having a large storage elastic modulus G' tends to have better tackiness.

For measuring the complex viscosity η ^* and the storage modulus G ′ of the matrix resin, a dynamic viscoelasticity measurement method using a parallel plate is usually used. Dynamic viscoelasticity changes depending on the measurement temperature and the measurement frequency. The parameters having a relatively good correlation with the tackiness or drapability of the prepreg near room temperature include a complex viscosity η ^* and a storage elastic modulus G ′ measured at a measurement temperature of 50 ° C. and a measurement frequency of 0.5 Hz. Is preferred.

When a thermoplastic resin is blended with the thermosetting resin used as the matrix resin of the prepreg, the storage modulus G 'increases with the increase in the blending amount, and the tackiness of the prepreg improves, but at the same time, the complex The viscosity η ^* also increases. For this reason, the drapability is reduced, and it is difficult to achieve both tackiness and drapability. Regarding the wrapping property of the prepreg on the mandrel, it is difficult to obtain a satisfactory wrapping property on the mandrel with the prepreg obtained by such a method because balance between tackiness and drapability is important.

However, the present inventors have found that when a high-molecular-weight thermoplastic resin is dissolved in a thermosetting resin, the increase in the storage modulus G ′ is significantly larger than that in the complex viscosity η ^*. It was found that the higher the molecular weight, the more remarkable. Based on this finding, by adding a relatively small amount of a high-molecular-weight thermoplastic resin to a thermosetting resin, it has become possible to significantly increase tackiness without sacrificing much drapability. This is a novel finding that has not been described or suggested in various documents relating to conventional matrix resins containing a high molecular weight compound.

When the molecular weight of the thermoplastic resin is small, the increase in the storage elastic modulus G ′ with respect to the increase in the complex viscosity η ^* cannot be made sufficiently large, so that the polymerization average molecular weight of the thermoplastic resin used in the present invention is , 200,000 or more, more preferably 350,000 or more.

On the other hand, if the molecular weight of the thermoplastic resin is too large, the change in the viscoelasticity is greatly dependent on the blending amount, which may make it difficult to control or dissolve the thermoplastic resin composition in the thermosetting resin composition. Therefore, the thermoplastic resin preferably has a weight average molecular weight of 5,000,000 or less, more preferably 1.7,000,000 or less.

The mechanism by which the thermoplastic resin of the component B exhibits the viscoelasticity improving effect as described above is considered to be due to the entanglement of the molecular chains of the thermoplastic resin dissolved in the thermosetting resin of the component A. Can be Therefore, the thermoplastic resin of component B must be soluble in the thermosetting resin of component A. Also, even if the thermoplastic resin is soluble in the thermosetting resin, if the compatibility of both is low, the molecular chain of the thermoplastic resin does not spread sufficiently and the effect of entanglement cannot be obtained, so that sufficient viscoelasticity is obtained. It is difficult to obtain improvement effects.

As an index of the solubility and the compatibility, a solubility parameter SP value which can be calculated from the molecular structure can be used. In order to obtain sufficient solubility and compatibility, the absolute value of the difference between the SP value of the thermoplastic resin used and the SP value of the thermosetting resin used is preferably in the range of 0 to 2.

The absolute value of the difference between the SP values can be reduced by appropriately selecting the raw materials of the thermosetting resin, optimizing the compounding ratio, and selecting the structure of the thermoplastic resin. . In addition, when the thermosetting resin of the component A is a mixture, the average value calculated as the sum of the values obtained by multiplying the SP value of each raw material by the weight fraction is used.

If the blending amount of the thermoplastic resin of the component B is small, a sufficient effect cannot be obtained. In addition, if the amount is too large, it is difficult to dissolve in the thermosetting resin. However, if an appropriate combination of the component A and the component B is selected as described above, the blending amount of the component B does not need to be too large. The blending amount of the thermoplastic resin of the component B is preferably in the range of 0.1 to 10 parts by weight, and more preferably in the range of 0.1 to 5 parts by weight, based on the thermosetting resin of the component A. Is more preferred.

Various known thermoplastic resins can be used as the thermoplastic resin of the component B. Among them, a polymer obtained by polymerizing a vinyl monomer is preferably used because a high molecular weight polymer is easily obtained. As used herein, the vinyl monomer means a low molecular weight compound having one polymerizable double bond in the molecule, and a polymer obtained by polymerizing a vinyl monomer refers to one or more vinyl monomers. A polymer obtained by polymerizing monomers, or a polymer obtained by polymerizing one or more kinds of vinyl monomers and one or more kinds of non-vinyl monomers, or a side chain of these polymers Means a polymer chemically modified by saponification or acetalization.

When a polymer obtained by polymerizing a vinyl monomer and a monomer other than the vinyl monomer is used, the ratio of the vinyl monomer to all the monomers is preferably at least 70 mol%.

When an epoxy resin composition is used as the thermosetting resin, the vinyl monomer has excellent compatibility with the epoxy resin and also has excellent physical properties of a cured product of the epoxy resin composition containing the same. (Meth) acrylic acid esters and vinylpyrrolidone are particularly preferably used. When a mixture of a plurality of types is used as the vinyl monomer, the content of (meth) acrylate or vinylpyrrolidone is particularly preferably at least 50 mol%, more preferably at least 80 mol%. In this specification, the expression (meth) acrylate is used to mean "methacrylate or acrylate". (Meth) acrylate is also used in the meaning of "methacrylate or acrylate". Specific examples of (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate,
Alkyl (meth) acrylates such as 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, propyl (meth) acrylate, amyl (meth) acrylate, lauryl (meth) acrylate, cyclohexyl (meth) acrylate, and hydroxyethyl (meth) Acrylates, hydroxyalkyl (meth) acrylates such as hydroxypropyl (meth) acrylate,
Glycidyl (meth) acrylate, benzyl acrylate and the like can be mentioned.

Of these, methyl (meth) acrylate is particularly preferred, and methyl (meth) acrylate in (meth) acrylate is preferably 50 mol%, more preferably 80 mol% or more. .

Vinyl monomers other than (meth) acrylic acid esters include (meth) acrylic acid, itaconic acid, maleic acid, maleic anhydride, maleimide, styrene, methylstyrene, (meth) acrylonitrile, (meth) acrylamide, Acryloyl morpholine, vinyl pyrrolidone, vinyl methyl ether, vinyl acetate, methyl vinyl ketone, vinyl chloride, vinylidene chloride, ethylene, propylene, 4-methylpentene, and the like.

Further, as the copolymerization component other than the vinyl monomer, dienes such as butadiene and isoprene, and acetylene and its substituent derivatives are used.

Further, as the thermoplastic resin, a polymer such as polyether, polyester, polyamide, polyimide, polyurethane, polyurea and the like are used in addition to the polymer obtained by polymerizing a vinyl monomer.
When an epoxy resin is used as the thermosetting resin, polyethers, particularly polyoxyalkylene, are preferably used because they are compatible with the epoxy resin and a polymer having a high molecular weight is easily obtained. Among polyoxyalkylenes, polyoxyethylene is preferably used.

Many commercial products can be used as the thermoplastic resin of the component B. For example, as commercial products of polymethyl methacrylate and a polymer mainly containing methyl methacrylate, MP-1450 (weight average molecular weight 250,000 to 500,000, Tg 128 ° C.), MP-14
51 (weight average molecular weight 500,000 to 1.5 million, Tg128
° C), MP-2200 (weight average molecular weight 1,000,000 to 15)
0,000, Tg128 ° C; manufactured by Soken Chemical Co., Ltd.), “Dianal” (registered trademark) BR-85 (weight average molecular weight 28)
10,000, Tg 105 ° C), “Dianal” BR-88 (weight average molecular weight 480,000, Tg 105 ° C), “Dianal” BR-108 (weight average molecular weight 550,000, Tg90)
° C) (above, manufactured by Mitsubishi Rayon Co., Ltd.), “Matsumoto Microsphere” M, M100, M500 (weight average molecular weight: 1,000,000 to 1,500,000, Tg105 ° C; manufactured by Matsumoto Yushi Seiyaku Co., Ltd.). it can.

As commercially available polyvinylpyrrolidone, "Rubiscol" (registered trademark) K80 (weight average molecular weight: 900,000, Tg: 150 to 185 ° C.), and "Rubiscol" K90 (weight average molecular weight: 1.2 million, Tg: 150 to 1)
85 ° C) (all made by BSF Japan Co., Ltd.)
And the like.

Further, as commercial products of polyoxyethylene, PEO-3 (weight average molecular weight of 600,000 to 1.1 million, melting point of 150 ° C. or more), PEO-8 (weight average molecular weight of 170
10,000 to 2.2 million, melting point 150 ° C. or higher) (all manufactured by Sumitomo Seika Co., Ltd.).

The thermosetting resin is often used in combination with a curing agent. As the curing agent, a compound having a functional group capable of reacting with the thermosetting resin or a compound serving as a catalyst for a polymerization reaction of the thermosetting resin is used.

As the curing agent used for the epoxy resin, aromatic amines such as diaminodiphenylmethane and diaminodiphenylsulfone, aliphatic amines, imidazole derivatives, dicyandiamide, tetramethylguanidine, thiourea-added amine, methylhexahydrophthalic anhydride Anhydrides, carboxylic acid hydrazides, carboxylic amides, polyphenol compounds, novolak resins, polymercaptans, and Lewis acid complexes such as boron fluoride ethylamine complex.

Further, an adduct having a curing activity obtained by reacting these curing agents with an epoxy resin is also used as the curing agent. Furthermore, those obtained by microencapsulating these curing agents are also preferably used in order to enhance the storage stability of the prepreg.

These curing agents can be used in combination with a suitable curing accelerator in order to enhance the curing activity. In the case of an epoxy resin, preferred examples include a combination of a urea derivative or an imidazole derivative as a curing accelerator with dicyandiamide as a curing agent, and a tertiary amine or imidazole derivative with a carboxylic anhydride or polyphenol compound as a curing agent. Examples of combinations as agents are given.

As the urea derivative, a compound obtained by reacting a secondary amine with an isocyanate, for example, a compound having a chemical structure represented by the following formula (4) is used.

[0059]

Embedded image Here, in the above formula (4), R ¹ and R ² are H, Cl, CH
₃ , OCH ₃ , NO ₂ represents any atom or group (n = 1 or 2).

Specifically, 3-phenyl-1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea (DCMU) and the like are preferably used. DCMU
Is represented by the following structural formula (5).

[0061]

Embedded image Among these combinations of a curing agent for epoxy resin and a curing accelerator, a combination of dicyandiamide, which cures at a relatively low temperature and has good storage stability, and a urea derivative of the above formula (4) is particularly preferably used.

The thermosetting resin composition, which is the resin composition for a fiber-reinforced composite material of the present invention, includes an improved adhesion between the matrix resin and the reinforcing fiber, an improved toughness of the matrix resin, and an improved impact resistance of the fiber-reinforced composite material. For the purpose of improvement or the like, a polymer compound that does not correspond to the above-described component B can be included.

When a thermoplastic resin having a highly polar group, particularly a hydrogen-bonding functional group, is used as such a polymer compound, the adhesion between the matrix resin and the reinforcing fibers is further improved.

Examples of the hydrogen bonding functional group include an alcoholic hydroxyl group, an amide group, an imide group, and a sulfonyl group.

Examples of the high molecular compound having an alcoholic hydroxyl group include polyvinyl acetal resins such as polyvinyl formal and polyvinyl butyral and phenoxy resins, and examples of the polymer having an amide group include polyamides.
Examples of the polymer having an imide group include polyimide, and examples of the polymer having a sulfonyl group include polysulfone. Polyamide, polyimide and polysulfone may have a functional group such as an ether bond or a carbonyl group in the main chain. Polyamide is
The nitrogen atom of the amide group may have a substituent.

Among these, polyamide, polyimide,
And polysulfone is also useful for improving the toughness of the matrix resin.

Examples of commercially available polymer compounds having a hydrogen bonding functional group which are soluble in an epoxy resin are as follows.

As the polyvinyl acetal resin, “Denka Butyral” and “Denka Formal” (manufactured by Denki Kagaku Kogyo KK), “Vinilec” (manufactured by Chisso Corporation)
"UCAR" PKHP (manufactured by Union Carbide) as a phenoxy resin. , "Macromelt" (made by Henkel Hakusui Co., Ltd.) as polyamide resin,
"Amilan" CM4000 (manufactured by Toray Industries, Inc.). "Ultem" (manufactured by General Electric) and "Matrimid" 5218 (manufactured by Ciba) as polyimides, "Victrex" (manufactured by Mitsui Toatsu Chemicals) and "UDEL" (manufactured by Union Carbide) as polysulfones. No. These resins have the following chemical structure.

[0069]

Embedded image

Embedded image

Embedded image

Embedded image

Embedded image (Here, D represents a hydrocarbon group having 32 carbon atoms in the dimer acid molecule.)

Embedded image

Embedded image As the polyvinyl acetal resin, a resin having polyvinyl formal having a vinyl formal portion of 60% by weight or more is preferable because of excellent mechanical properties of the composite.

As such a polymer compound, 25 ° C.
In the above, a compound having a flexural modulus of 10 MPa or more is preferred because it hardly reduces the elastic modulus of a cured product of the epoxy resin composition. Further, the thermoplastic resin of the present invention may contain additives such as a reactive diluent, an antioxidant, and organic or inorganic particles.

As the reactive diluent, a monofunctional epoxy compound is preferably used. Specifically, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, p-sec-butyl glycidyl ether, p-ter
t-butyl glycidyl ether and the like.

Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-p-cresol (BHT), butylated hydroxyanisole and tocophenol, and dilauryl 3,3'-thiodipropionate. , And sulfur-based antioxidants such as distearyl 3,3'-thiodipropionate are preferably used.

Further, as the organic particles, a thermoplastic resin,
A cured product of a thermosetting resin and fine particles made of an elastomer or the like can be used. These particles have the effect of improving the toughness of the resin and the impact resistance of the fiber-reinforced composite material.

As the thermoplastic resin used for the organic particles, there are polyamide and polyimide, and as the thermosetting resin, epoxy resin and phenol resin are preferably used. Examples of commercially available polyamide particles include SP-500 manufactured by Toray Industries, Inc. and “Orgasol” manufactured by ATOCHEM.

As the elastomer particles, crosslinked rubber particles, and core-shell type rubber particles obtained by graft-polymerizing a heterogeneous polymer on the surface of the crosslinked rubber particles are preferably used. Commercially available crosslinked rubber particles include XER-91 (manufactured by Nippon Synthetic Rubber Industry Co., Ltd.) comprising a crosslinked product of a carboxyl-modified butadiene-acrylonitrile copolymer, and CX-MN series (manufactured by Nippon Shokubai Co., Ltd.) comprising acrylic rubber fine particles. )) And YR-500 series (manufactured by Toto Kasei Co., Ltd.).

Examples of commercially available core-shell rubber particles include, for example, “Kureha paraloid” EXL-2655 composed of a butadiene / alkyl methacrylate / styrene copolymer.
(Made by Kureha Chemical Industry Co., Ltd.), "Staphyroid" composed of acrylate / methacrylate copolymer
AC-3355, TR-2122 (Takeda Pharmaceutical Co., Ltd.)
"PARALOID" EXL-261 comprising butyl acrylate / methyl methacrylate copolymer
1, EXL-3387 (manufactured by Rohm & Haas) and the like.

As the inorganic particles, silica, alumina, smectite, synthetic mica and the like are used. These inorganic particles are mainly blended for rheological control, that is, for thickening and imparting thixotropic properties.

In order for the prepreg to exhibit an appropriate drapability, the complex viscosity η ^* of the matrix resin must be 2
It is preferably from 00 to 2,000 Pa · s. If the complex viscosity η ^* exceeds this range, the prepreg may have insufficient drapability or may not be easily impregnated into the reinforcing fibers. Also, the complex viscosity η ^* is
If the amount is less than the above range, the shape retention of the prepreg may decrease.

On the other hand, the storage elastic modulus G ′ of the matrix resin
In general, a prepreg using a matrix resin having a large storage elastic modulus G ′ is recognized as having a correlation with tackiness.
It tends to have excellent tackiness. In order to develop a suitable tackiness, the storage elastic modulus G ′ should be 100 to 2,000P.
a is preferred. When the storage elastic modulus G ′ exceeds such a range, the tackiness is too large. For example, when a prepreg is erroneously overlapped, it is difficult to peel off and it becomes difficult to peel off and correct. . When the storage elastic modulus G 'is less than the above range, the tackiness is too small, and the prepregs stacked in the prepreg laminating step are easily peeled off, which hinders the laminating operation.

Since the balance between tackiness and drapability is important for the wrapping property of the prepreg around the mandrel, the ratio of the complex viscosity η ^* to the storage modulus G ′, that is, G ′
/ Η ^* can be used as an index for obtaining good winding properties. The ratio of G ′ to η ^* is 0.9 ≦ G ′ / η ^* ≦
Satisfying the relationship of 2.0 is preferable from the viewpoint of achieving both tackiness and drapability.

By impregnating the reinforcing fibers with the resin composition for a fiber-reinforced composite material of the present invention, a prepreg as an intermediate base material of the fiber-reinforced composite material is prepared.

As the reinforcing fibers used in the prepreg, carbon fibers, glass fibers, aramid fibers, boron fibers, alumina fibers, silicon carbide fibers and the like are used. These fibers may be used as a mixture of two or more kinds. The form and arrangement of the reinforcing fibers are not limited, and for example, fiber structures such as long fibers aligned in one direction, a single tow, a woven fabric, a knit, a nonwoven fabric, a mat, and a braid are used.

In order to produce light weight sports equipment such as golf shafts and fishing rods, it is preferable to use a reinforced fiber having a high elastic modulus in the prepreg so that a small amount of material can exhibit sufficient product rigidity. The elastic modulus of such a reinforcing fiber is preferably 200 GPa to 800 GPa.

In particular, when carbon fiber is used as the reinforcing fiber, the strength and elastic modulus of the obtained fiber-reinforced composite material are as follows:
It largely depends on the content of carbon fiber. Therefore, when a certain amount of reinforcing fiber is contained, as the amount of the matrix resin to be impregnated is reduced, the weight of the product can be reduced while the performance of the composite material and the final product is kept almost constant. For such a purpose, a prepreg having a high reinforcing fiber content is suitably used. In this case, the reinforcing fiber content of the prepreg is preferably 60 to 90% by weight, and more preferably 67 to 80% by weight.
When making a prepreg having a high reinforcing fiber content in this way, when the resin composition of the present invention is used, tackiness, drapability or handling properties such as winding property around a mandrel,
Furthermore, excellent properties, such as physical properties after curing, which could not be obtained conventionally can be obtained.

The tackiness T of the prepreg is 50 mm × 5
The prepreg samples of 0 mm can be quantified by the peel strength (MPa) after being pressed under a load of 0.11 MPa. The drapability D can be quantified as the reciprocal (GPa ^-1 ) of the 0 ° bending elastic modulus of the prepreg measured by the three-point bending test method.

The peel strength T of the prepreg was measured as follows.
50 mm x 50 mm prepreg samples are 0.1
It is determined by dividing the maximum load at that time by the area of the prepreg, after peeling off after pressure bonding at 1 MPa.

The flexural modulus of the prepreg was 85 m.
With respect to a prepreg sample of m (fiber direction) × 15 mm, the distance between supporting points is set to 40 mm, and a three-point bending measurement using an indenter having a diameter of 4 mm can be performed from a gradient of an initial linear portion of a load displacement curve obtained. .

These are all 23 ± 2 ° C.
It is measured under a measurement environment of 50 ± 5% RH.

In the present invention, the index T of the tackiness of the prepreg is preferably 0.05 to 0.20 MPa.

Further, the index D of the drapability of the prepreg
Is preferably 0.01 to 0.1 GPa ^-1 .

Further, the wrapping property of the prepreg on the mandrel is important because the balance between the tackiness and the drapability of the prepreg is important. Therefore, T and D are 2.3 × 10 ⁻³ ≦ D ·
It is preferable to satisfy the relationship of T ≦ 1.2 × 10 ⁻² .

In the present invention, the prepreg is prepared by dissolving the resin composition for a fiber-reinforced composite material in an organic solvent such as methyl ethyl ketone or methanol to reduce the viscosity and impregnating the reinforcing fibers (so-called wet method); The resin composition for a fiber-reinforced composite material can be manufactured by a method such as a method of lowering the viscosity by heating and impregnating the reinforcing fibers (a so-called hot melt method or a dry method).

The wet method is a method in which a reinforcing fiber is immersed in a solution of a resin composition, pulled up, and the solvent is evaporated using an oven or the like to obtain a prepreg. In the hot melt method, first, a resin film is prepared by coating a resin composition on a release paper or the like, and then the film is laminated from both sides or one side of the reinforcing fiber, and the resin is heated and pressed to form a resin film. Method of manufacturing a prepreg by impregnation, or while pulling out a reinforcing fiber bundle, without using a film created by coating the resin composition,
This is a method for producing a prepreg by directly impregnating a resin composition.

The solvent is likely to remain in the prepreg produced by the wet method, and this may cause voids in the composite. Therefore, in the present invention, it is preferable to use a hot melt method as a method for producing a prepreg.

After laminating a pattern obtained by cutting the prepreg obtained as described above and heating the resin while applying pressure to the laminate, a fiber-reinforced composite material is obtained. Methods for applying heat and pressure include a press molding method, an autoclave molding method, a bagging molding method, a sheet winding method, and an internal pressure molding method, and in particular, for sporting goods, the sheet winding method and the internal pressure molding method are preferably employed. Is done.

The sheet winding method is a method in which a prepreg is wound around a mandrel to form a cylindrical object, and is suitable for producing a rod-shaped body such as a golf shaft or a fishing rod. Specifically, a prepreg is wound around a mandrel, and the prepreg is fixed so as not to peel off from the mandrel, or a tape-like thermoplastic resin film (wrapping tape) is applied to the outside of the prepreg in order to apply molding pressure to the prepreg. After the resin is heated and cured in an oven, the core metal is removed to obtain a cylindrical molded body.

In the internal pressure forming method, a preform in which a prepreg is wound around an internal pressure applying body made of a thermoplastic resin is set in a mold, high-pressure air is introduced into the internal pressure applying body and pressurized. This is a method of forming a fiber-reinforced composite material by heating. The internal pressure molding method is suitably used when molding a complicated shape such as a golf shaft or bat having a special shape, particularly a racket such as tennis or badminton.

When the resin composition for a fiber-reinforced composite material of the present invention is used, even when a high-modulus carbon fiber is used as the reinforcing fiber or when the content of the reinforcing fiber is high, the tackiness and drape property are excellent. Further, it is possible to obtain a prepreg having a good winding property around the mandrel.

[0099]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. In addition, evaluation methods such as solubility parameter, dynamic viscoelasticity, tack-draping property of prepreg, and winding property around a mandrel were performed under the following conditions.

A. Solubility parameter Polym. Eng. Sci., 14 (2), 147-154
The solubility parameter SP value was determined based on the method of Fedors described in (1974).

B. Dynamic viscoelasticity The dynamic viscoelasticity was measured using a dynamic analyzer RDAII manufactured by Rheometrics. The measurement was performed using a parallel flat plate having a radius of 25 mm, and the complex viscosity η ^* and the storage elastic modulus G ′ were determined by a time / curing sweep under the conditions of a measurement frequency of 0.5 Hz and a heating rate of 1.5 ° C./min. Was.

C. Tackability of prepreg After the prepregs were pressed, they were peeled off, and the maximum load was divided by the sample area to determine the peeling strength T (MPa). "Instron" (registered trademark) 4 as a measuring device
The measurement was performed under the following conditions using a 201 type universal material testing machine (manufactured by Instron Japan Co., Ltd.).

Environment: 23 ± 2 ° C., 50 ± 5% RH Sample: 50 × 50 mm Load speed: 1 mm / min Adhesive load: 0.11 MPa Load time: 5 ± 2 sec Peeling speed: 10 mm / min D. Drapability of Prepreg Drapability in this example was evaluated by measuring flexural modulus of the prepreg. The measuring method of the flexural modulus generally followed JIS K7074 “Bending test method of fiber reinforced plastic”. "Instron" as a measuring device
The measurement was performed under the following conditions using a Model 4201 universal testing machine (Instron Japan Co., Ltd.).

・ Environment: 23 ± 2 ° C., 50 ± 5% RH ・ Sample: 85 mm (fiber direction) × 15 mm ・ Load speed: 5 mm / min ・ Distance between supporting points: 40 mm ・ Indenter diameter: 4 mmφ The obtained 0 ° bending The reciprocal D (GPa ^-1 ) of the elastic modulus was used as an index of drapability.

E. The wrapping property of the prepreg on the mandrel The wrapping property of the prepreg on the mandrel was evaluated as follows.

A prepreg left for 3 days in an atmosphere of a temperature of 23 ° C. and a humidity of 50% RH was immersed in a 10 mm diameter, 10 mm long.
A SUS cylinder with a diameter of 00 mm has a reinforcing fiber alignment direction,
The prepreg was wrapped at an angle of 45 ° with respect to the longitudinal direction of the cylinder, and the wrapping state of the prepreg after standing for 15 minutes was observed. The prepreg is classified as follows according to the maximum peeling height at the end of winding of the prepreg, and the peeling length is added for each of S, M, and L. Further, a mandrel winding index was calculated by the following equation, and the index was used as an index of the winding property.

S: maximum peel height of less than 2 mm M: maximum peel height of 2 mm or more and less than 4 mm L: maximum peel height of 4 mm or more Mandrel winding property index = S + 2M + 4L (Example 1) (1) Preparation of matrix resin composition The following raw materials were kneaded using a kneader to prepare a matrix resin composition.

Bisphenol A type epoxy resin ("Epicoat" 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 44 parts by weight Bisphenol A type epoxy resin ("Epicoat" 1001 manufactured by Yuka Shell Epoxy Co., Ltd.) 7 weight Part Bisphenol A type epoxy resin (Yuika Shell Epoxy Co., Ltd., "Epicoat" 1009) 14 parts by weight Phenol novolak type epoxy resin (Yuika Shell Epoxy Co., Ltd., "Epicoat" 154) 35 parts by weight Combined A (polymethyl methacrylate; weight average molecular weight 500,000; glass transition temperature 105 ° C) 2 parts by weight Dicyandiamide 4 parts by weight DCMU 4 parts by weight (2) Preparation of prepreg The above resin composition was separated using a reverse roll coater. A resin film was prepared by coating on a pattern. Next, carbon fiber "Treca" (registered trademark) T300B-12K (trademark) having a tensile modulus of 230 GPa arranged in one direction (Toray Industries, Inc.)
), Heat and pressure (130
C., 0.4 MPa) to impregnate the resin, thereby producing a unidirectional prepreg having a carbon fiber weight of 150 g / m ² and a matrix resin weight fraction of 35%.

The prepreg had good tackiness, drapability and wrapping around the mandrel. The results are shown in Table 1.

Example 2 (1) Preparation of Matrix Resin Composition The following raw materials were kneaded using a kneader to prepare a matrix resin composition.

45 parts by weight of bisphenol A type epoxy resin (“Epicoat” 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 7 parts by weight of bisphenol A type epoxy resin (“Epicoat” 1001 manufactured by Yuka Shell Epoxy Co., Ltd.) Part: 13 parts by weight of bisphenol A type epoxy resin ("Epicoat" 1009, manufactured by Yuka Shell Epoxy Co., Ltd.) 35 parts by weight of phenol novolak type epoxy resin ("Epicoat" 154, manufactured by Yuka Shell Epoxy Co., Ltd.) Combined B (polymethyl methacrylate; weight-average molecular weight 1.5 million; glass transition temperature 105 ° C) 2 parts by weight Dicyandiamide 4 parts by weight DCMU 4 parts by weight (2) Preparation of prepreg A prepreg was prepared in the same manner as in Example 1. The tackiness and drapability of the prepreg and the wrapping property around the mandrel were good. The results are shown in Table 1.

Example 3 (1) Preparation of Matrix Resin Composition The following raw materials were kneaded using a kneader to prepare a matrix resin composition.

45 parts by weight of bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat" 828) 7 parts by weight of bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat" 1001) Part: 13 parts by weight of bisphenol A type epoxy resin ("Epicoat" 1009, manufactured by Yuka Shell Epoxy Co., Ltd.) 35 parts by weight of phenol novolak type epoxy resin ("Epicoat" 154, manufactured by Yuka Shell Epoxy Co., Ltd.) Merged C (poly (methyl methacrylate / propyl acrylate); methyl methacrylate / propyl acrylate = 80/20 (mol / mol); weight average molecular weight 360,000; glass transition temperature 20 ° C.) 5 parts by weight Dicyandiamide 4 parts by weight DCMU 4 Parts by weight (2) Preparation of prepreg In the same manner as in Example 1, To prepare a prepreg. The tackiness and drapability of the prepreg and the wrapping property around the mandrel were good. The results are shown in Table 1.

Example 4 (1) Preparation of Matrix Resin Composition The following raw materials were kneaded using a kneader to prepare a matrix resin composition.

45 parts by weight of bisphenol A type epoxy resin (“Epicoat” 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 7 parts by weight of bisphenol A type epoxy resin (“Epicoat” 1001 manufactured by Yuka Shell Epoxy Co., Ltd.) Part: 13 parts by weight of bisphenol A type epoxy resin ("Epicoat" 1009, manufactured by Yuka Shell Epoxy Co., Ltd.) 35 parts by weight of phenol novolak type epoxy resin ("Epicoat" 154, manufactured by Yuka Shell Epoxy Co., Ltd.) Combined E (polyvinylpyrrolidone; weight average molecular weight 1.2 million; glass transition temperature 150 to 185 ° C) 2 parts by weight Dicyandiamide 4 parts by weight DCMU 4 parts by weight (2) Preparation of prepreg A prepreg was prepared in the same manner as in Example 1. . The tackiness and drapability of the prepreg and the wrapping property around the mandrel were good. The results are shown in Table 1.

Example 5 (1) Preparation of Matrix Resin Composition The following raw materials were kneaded using a kneader to prepare a matrix resin composition.

45 parts by weight of bisphenol A type epoxy resin ("Epicoat" 828, manufactured by Yuka Shell Epoxy) 7 parts by weight of bisphenol A type epoxy resin ("Epicoat" 1001) manufactured by Yuka Shell Epoxy Co., Ltd. Part: 13 parts by weight of bisphenol A type epoxy resin ("Epicoat" 1009, manufactured by Yuka Shell Epoxy Co., Ltd.) 35 parts by weight of phenol novolak type epoxy resin ("Epicoat" 154, manufactured by Yuka Shell Epoxy Co., Ltd.) Combined F (polyoxyethylene; weight average molecular weight 1.7 million to 2.2 million; melting point 150 ° C. or more) 2 parts by weight Dicyandiamide 4 parts by weight DCMU 4 parts by weight (2) Preparation of prepreg In the same manner as in Example 1, prepreg was prepared. Produced. The tackiness, drapeability and wrapping around the mandrel of the prepreg were good. Table 1 shows the results.

Comparative Example 1 (1) Preparation of Matrix Resin Composition The following raw materials were kneaded using a kneader to prepare a matrix resin composition.

44 parts by weight of bisphenol A type epoxy resin ("Epicoat" 828, manufactured by Yuka Shell Epoxy) 7 parts by weight of bisphenol A type epoxy resin ("Epicoat" 1001), manufactured by Yuka Shell Epoxy Co., Ltd. Part: bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat" 1009) 14 parts by weight phenol novolak type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat" 154) 35 parts by weight dicyandiamide 4 parts by weight DCMU 4 parts by weight (2) Preparation of prepreg A prepreg was prepared in the same manner as in Example 1. The tackiness of the prepreg was weak and the handling was poor. In addition, since the tackiness was weak, the wrapping property around the mandrel was poor. The results are shown in Table 2.

Comparative Example 2 (1) Preparation of Matrix Resin Composition The following materials were kneaded using a kneader to prepare a matrix resin composition.

Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat" 828) 45 parts by weight Bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat" 1001) 7 weight parts Part: 13 parts by weight of bisphenol A type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat" 1009) 35 parts by weight of phenol novolak type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat" 154) Combined D (polymethyl methacrylate; weight average molecular weight 100,000; glass transition temperature 105 ° C) 10 parts by weight Dicyandiamide 4 parts by weight DCMU 4 parts by weight (2) Preparation of prepreg A prepreg was prepared in the same manner as in Example 1. The tackiness of the prepreg was weak and the handling was poor. In addition, since the tackiness was weak, the winding property around the mandrel was poor. The results are shown in Table 2.

Comparative Example 3 (1) Preparation of Matrix Resin Composition The following raw materials were kneaded using a kneader to prepare a matrix resin composition.

35 parts by weight of bisphenol A type epoxy resin (“Epicoat” 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 30 parts by weight of bisphenol A type epoxy resin (“Epicoat” 1001 manufactured by Yuka Shell Epoxy Co., Ltd.) Part: Phenol novolak type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat" 154) 35 parts by weight polyvinyl formal resin (manufactured by Chisso Corporation, "Vinylec" K) 7 parts by weight Dicyandiamide 4 parts by weight DCMU 4 parts by weight Part (2) Preparation of Prepreg A prepreg was prepared in the same manner as in Example 1. The tackiness of the prepreg was good. However, the prepreg was hard and had poor drapability, so that the wrapping around the mandrel was poor. The results are shown in Table 2.

Comparative Example 4 (1) Preparation of Matrix Resin Composition The following raw materials were kneaded using a kneader to prepare a matrix resin composition.

35 parts by weight of bisphenol A type epoxy resin (“Epicoat” 828, manufactured by Yuka Shell Epoxy Co., Ltd.) 30 parts by weight of bisphenol A type epoxy resin (“Epicoat” 1001 manufactured by Yuka Shell Epoxy Co., Ltd.) Part: phenol novolak type epoxy resin (manufactured by Yuka Shell Epoxy Co., Ltd., "Epicoat" 154) 35 parts by weight polyvinyl formal resin (manufactured by Chisso Corporation, "Vinylec" K) 10 parts by weight dicyandiamide 4 parts by weight DCMU 4 parts by weight Part (2) Preparation of Prepreg A prepreg was prepared in the same manner as in Example 1. The tackiness of the prepreg was good. However, the prepreg was hard and had poor drapability, so that the wrapping around the mandrel was poor. The results are shown in Table 2.

[0126]

[Table 1]

[Table 2]

[0127]

As described above, according to the present invention,
By making a prepreg using a matrix resin mixed with a thermoplastic resin having a specific range of molecular weight soluble in thermosetting resin, it is possible to achieve both high tackiness and drapability of the prepreg at a high level, and a mandrel And the fiber reinforced composite material can be produced with good workability.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08L 33/12 C08L 33/12

Claims (20)

[Claims] 1. A resin composition for a fiber-reinforced composite material, comprising at least the following components A and B, wherein said component B is soluble in said component A: A. Thermosetting resin B. Thermoplastic resin with weight average molecular weight of 200,000 to 5,000,000 2. The thermoplastic resin has a weight average molecular weight of 200,000 or more.
The resin composition for a fiber-reinforced composite material according to claim 1, which is a polymer of 1.7 million. 3. A complex viscosity η ^* in a dynamic viscoelasticity measurement at a measurement frequency of 0.5 Hz and 50 ° C. is 200 to 2,000P.
a · s and the storage elastic modulus G ′ is 100 to 2,000P
The resin composition for a fiber reinforced composite material according to claim 1 or 2, which is a. 4. The resin for a fiber-reinforced composite material according to claim 3, wherein the complex viscosity η ^* (Pa · s) and the storage elastic modulus G ′ (Pa) satisfy the following relationship: Composition. 0.9 ≦ G ′ / η ^* ≦ 2.0 5. An absolute value of a difference between a solubility parameter SP value of the thermosetting resin and that of the thermoplastic resin is 0 to 2.
5. The resin composition for a fiber-reinforced composite material according to any one of items 4 to 4. 6. The thermoplastic resin has a glass transition temperature of 80 ° C.
Or a melting point of 80 ° C. or higher.
6. The resin composition for a fiber-reinforced composite material according to any one of items 5 to 5. 7. The resin composition for a fiber-reinforced composite material according to claim 1, wherein the thermoplastic resin is a polymer obtained by polymerizing a vinyl monomer. 8. The resin composition for a fiber-reinforced composite material according to claim 7, wherein at least 50 mol% of the vinyl monomer is a (meth) acrylate. 9. 50 mol% of (meth) acrylic acid ester
9. The resin composition for a fiber-reinforced composite material according to claim 8, wherein the above is methyl (meth) acrylate. 10. The resin composition for a fiber-reinforced composite material according to claim 7, wherein 50% by mole or more of the vinyl monomer is vinylpyrrolidone. 11. The resin composition for a fiber-reinforced composite material according to claim 1, wherein said thermoplastic resin is a polyether. 12. The resin composition for a fiber-reinforced composite material according to claim 11, wherein the polyether is a polyalkylene ether. 13. The thermosetting resin according to claim 10, wherein said thermoplastic resin is
The resin composition for a fiber-reinforced composite material according to any one of claims 1 to 12, which is contained in an amount of 0.1 to 20 parts by weight based on 0 part by weight. 14. The thermosetting resin according to claim 10, wherein said thermoplastic resin is
The resin composition for a fiber-reinforced composite material according to claim 13, which is contained in an amount of 0.1 to 10 parts by weight based on 0 part by weight. 15. The thermosetting resin comprises an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, a phenol resin, a melamine resin, a benzoguanamine resin, a urea resin, a silicone resin, a maleimide resin, a cyanate ester resin, and a maleimide resin. The resin composition for a fiber-reinforced composite material according to any one of claims 1 to 14, which is a thermosetting resin selected from a resin obtained by pre-polymerizing a cyanate ester resin or a mixture of these resins. 16. A prepreg obtained by impregnating reinforcing fibers with the resin composition for a fiber-reinforced composite material according to any one of claims 1 to 15. 17. A tackiness T representing an adhesiveness of 0.05 to 0.5.
20 MPa, drape property D representing flexibility is 0.01 to
0.1 GPa ^-1 and tackiness T and drapeability D
Satisfies the following relationship: 2.3 × 10 ⁻³ ≦ D · T ≦ 1.2 × 10 ⁻² 18. The reinforcing fiber is a carbon fiber, an aromatic polyamide fiber, a glass fiber, a silicon carbide fiber,
17. At least one selected from the group consisting of boron fibers, alumina fibers, and stainless steel fibers.
Or the prepreg according to 17. 19. The prepreg according to claim 18, wherein said reinforcing fibers are carbon fibers having an elastic modulus of 200 GPa or more. 20. A fiber-reinforced composite material comprising a cured product of the resin composition for a fiber-reinforced composite material according to claim 1 and reinforcing fibers.