JPH04130141A - Fiber-reinforced resin composition - Google Patents

Abstract

PURPOSE:To prepare a fiber-reinforced resin composite material excellent in heat resistance, mechanical properties, and moldability, free from void and other defects, and having a high packing density by compounding an epoxy resin with specific compds. and molding the resulting compsn. by RIM or RTM method. CONSTITUTION:A fiber-reinforced resin compsn. is prepd. by compounding into the compsn. a reactive resin component comprising an epoxy resin having at least two epoxy groups in the molecule, a polyfunctional (meth)acrylate compd. having at least two (meth)acrylic groups in the molecule, a lip. carboxylic acid anhydride contg. a monofunctional carboxylic acid anhydride and/or a polycarboxylic acid anhydride obtd. by reacting a lower aliph. polyhydric alcohol with trimellitic acid or a deriv. thereof, a curing accelerator, and a radical polymn. initiator. A fiber-reinforced resin composite material excellent in heat resistance, mechanical properties, and moldability, free from void and other defects, and having a high packing density can be prepd. from this compsn. by reaction injection molding or by resin transfer molding.

Description

Detailed Description of the Invention [Industrial Application Field] The present invention relates to fiber reinforced resin compositions, particularly reaction injection molding (RIM) and R (reinforce) RIM.
, S(s)lactual) RIM or resin.

The present invention relates to a resin composition that provides a fiber-reinforced dendritic bonding material with excellent moldability and excellent resin properties for obtaining composite materials suitable for automobile parts, electrical parts, etc. by the transfer molding (RTM) method.

[Prior Art] Fiber-reinforced composite materials are used in a wide range of fields such as automobile parts, electrical equipment parts, building materials, ships, sporting goods, and aircraft parts, and are being made into plastics to reduce their weight. As the fiber reinforcing material, glass fiber, aramid fiber, carbon fiber, etc. are used, and as the matrix resin, various matrix resins such as urethane resin, unsaturated polyester resin, vinyl ester resin, and epoxy resin are used. Composite materials are also produced by various molding methods such as hand lay-up molding, filament winding molding, pultrusion molding, pressure molding using prepreg, BMC molding, and SMC molding. The reaction injection molding method is also a conventionally established molding method, but this method is an excellent molding method that has a short molding cycle time and can produce a wide variety of molded products through automation. In recent years, there has been an increasing demand for large-scale molding and complex-shaped products using this method, and there is also a growing demand for high mechanical properties, heat resistance, durability, etc. as structural materials.

Conventionally, various matrix resins have been used in fiber reinforced materials using reaction injection molding. The main characteristics and drawbacks of matrix resins are that urethane resin has a fast curing speed but insufficient heat resistance, and unsaturated polyester resin also has a fast curing speed but does not fully satisfy other characteristics. . Furthermore, although vinyl ester resins have excellent corrosion resistance and workability, they tend to have lower composite material properties and heat resistance than epoxy resins, resulting in deterioration of surface properties due to curing shrinkage.On the other hand, epoxy resins have relatively good properties. Although it has heat resistance, excellent corrosion resistance, and mechanical strength, it has drawbacks such as slow curing speed and high viscosity, and it has also been pointed out that it lacks impact resistance and toughness. Although studies are being conducted to further improve the properties of these epoxy resins, it is difficult to satisfy both low viscosity, heat resistance, and high toughness.Especially in the case of fiber-reinforced resin composites using reinforcing fibers, In order to fully exhibit the mechanical properties of the resin, the elongation at break of the cured resin must be greater than the elongation at break of the reinforcing fiber. especially,
In order to maintain sufficiently high fatigue properties of fiber-reinforced resin composites, the elongation of the cured product needs to be considerably higher than the elongation of the fibers. For example, when glass fiber with an elongation of 4% is used as a reinforcing material, the elongation at break of the resin must exceed this value, and there are almost no known resin compositions that fully satisfy these conditions. This is the current situation.

Regarding epoxy resins, JP-A No. 63-218325 describes a RIM manufacturing method for epoxy resins using an alicyclic amine curing agent that cures relatively quickly. Generally, the epoxy resin has an extremely high viscosity, so it has insufficient impregnating properties into reinforcing materials such as continuous fibers and fabrics, which causes voids or unimpregnated areas in the molded product. This tendency is particularly noticeable when the reinforcing material is packed with high density. In addition, particularly in the case of amine-based hardening materials, there may be problems in terms of safety and health, deterioration of the working environment, etc.

It is generally known to add reactive diluents such as aliphatic diglycidyl ethers and -functional epoxy compounds to epoxy resins for the purpose of lowering the viscosity and imparting flexibility to these resins. However, by adding a reactive diluent, heat resistance, mechanical properties, water resistance, etc. are significantly reduced, making it difficult to satisfy the required performance. JP 1-22848
The publication describes that viscosity and pot life are improved and heat resistance is improved by using a vinyl aromatic monohydrocarbon in a polycarboxylic acid anhydride curing agent system. However, with this method, although the heat resistance such as the heat distortion temperature is improved, the elongation at break of the cured product is insufficient and the strength is reduced. Unexamined Japanese Patent Publication 1986-
No. 170410 discloses that the workability and heat resistance of an epoxy resin and a polymerizable vinyl compound are improved by using an imidazole compound and a radical polymerization initiator, but these also have sufficient elongation at break while maintaining the heat resistance of the cured product. is difficult to obtain.

Further, Japanese Patent Publication No. 1-29815 and Japanese Patent Publication No. 1-29816 describe methods for producing prepregs and laminates using unsaturated polyester or epoxy vinyl ester resins as a polybasic acid anhydride curing agent system. Although these methods have improved the curing speed and properties of the cured product, these resin compositions have a relatively high viscosity, resulting in poor wettability and impregnation with the reinforcing fibers during RJM molding, which may cause voids to remain. becomes. Furthermore, it is difficult to obtain molded products with excellent surface smoothness.

Toughness has conventionally been improved by adding acrylic rubber or an acrylonitrile-butadiene copolymer having a terminal group such as a carboxyl group to an epoxy resin.

[Problems to be Solved by the Invention] However, in these methods, the mixed viscosity of the resin increases and the heat resistance, strength, elastic modulus, water resistance, etc. of the cured product decrease.

In particular, it is extremely difficult to obtain a fiber-reinforced resin composite material that has the low viscosity and fast curing properties required for RIM molding, satisfies the heat resistance and toughness of the cured product, and has excellent durability.

[Means for Solving the Problems] Therefore, as a result of intensive studies, the present inventors have made intensive studies to solve the problems in reaction injection molding using epoxy resins, and found that epoxy resins and specific polymerizable unsaturated groups By using the containing compound and a liquid carboxylic acid anhydride curing agent, it is possible to mold for a short time at a relatively low temperature of about 100 to 120°C, creating continuous fibers with high heat resistance, high toughness, and high packing density. The present invention has been completed based on the discovery that it is possible to quickly obtain a molded product having excellent composite properties that is substantially free of voids and unimpregnated areas and is reinforced by the above methods.

In other words, the purpose of the present invention is to shorten the molding cycle time by using reaction injection molding or RIM method, to increase the filling of reinforcing fibers by lowering the viscosity of the mixed resin, and to achieve high heat resistance by using an epoxy resin and a specific compound as the matrix resin. The present invention provides a fiber-reinforced resin composite material that has both high elasticity and toughness, and has excellent mechanical properties and durability.

The purpose of this is to mix the reactive resin components and immediately inject them into a mold on which the M&fiber reinforcement is placed to produce a fiber-reinforced resin composite material.The following A, B, This can be easily achieved using a fiber-reinforced resin composition containing C, D and E components as essential components.

Component A: An epoxy resin having two or more epoxy groups in one molecule.

Component B: A polyfunctional (meth)acrylate compound having two or more acrylic or methacrylic groups in one molecule.

Component C: A liquid carboxylic anhydride containing a monofunctional carboxylic anhydride and a polyfunctional carboxylic anhydride obtained by reacting l or lower aliphatic polyhydric alcohol with trimellitic acid or a derivative thereof.

D component: hardening accelerator E component: radical polymerization initiator The present invention will be explained in detail below.

The epoxy resin which is component A in the present invention is a compound having two or more epoxy groups at the end of the molecule. Generally, such epoxy resins contain a large excess of shrimp halohydrin (
For example, shrimp halohydrin is subjected to an addition reaction in epichlorohydrin) at a temperature below 1006 C, and then 40 to 10
A method of dropping an aqueous alkaline solution under reduced pressure at a temperature of 0°C and epoxidizing while distilling off water in the system azeotropically, and a method of epoxidizing unsaturated double bonds with peracetic acid, etc. It is generally synthesized with

Examples of this epoxy resin include bisphenol A1 bisphenol F, glycidyl ether type epoxy resin which is a reaction product of novolak resin, etc. and epichlorohydrin, glycidyl amine type epoxy resin, glycidyl ester type epoxy resin, heterocyclic epoxy resin, and halogenated epoxy resin. These are epoxy resins and the like, and one or more of these can be used in combination. However, in order to sufficiently achieve high impregnating properties, which is one of the objects of the present invention, it is preferable to use an epoxy resin that is liquid at room temperature and has a lower viscosity, either alone or as a mixture.

The polyfunctional (meth)acrylic compound which is component B in the present invention is a compound containing two or more radically polymerizable acrylic or methacrylic groups in one molecule. Examples of this include ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, 1,4-
Butanediol dimethacrylate, 1,6-hexanethiol di(meth)acrylate, trimethylolpropane trimethacrylate, glycerin dimethacrylate,
Triethylene glycol dimethacrylate, polyethylene glycol di(meth)acrylate, 1,3-butanediol dimethacrylate, neobentyl glycol di(meth)acrylate, 1,10-decanediol dimethacrylate, ethylene oxide adduct of bisphenol A (meth)acrylate, dibromoneopentyl glycol dimethacrylate, ethylene oxide adduct of tetrabromobisphenol A di(meth)acrylate, triethylene glycol diacrylate, ethylene oxide modified bisphenol A diacrylate, propylene oxide modified bisphenol A diacrylate, tri- Methylolpropane triacrylate, ethylene oxide modified trimethylolpropane triacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol hexaacrylate, hydrogenated dicyclopentajenyl diacrylate, propylene oxide modified bisphenol A diacrylate, trimethylol Examples include methane trimethacrylate and tetramethylolmethane triacrylate. This polyfunctional (meth)acrylate compound is appropriately selected depending on the type of epoxy resin used for component A, but when a vinyl aromatic hydrocarbon or a monofunctional (meth)acrylic compound is used, the physical properties are significantly deteriorated. However, by using a polyfunctional compound,
It is particularly effective in improving curing reactivity and toughness, which are one of the objectives of the present invention. Furthermore, the epoxy group and the unsaturated group can be simultaneously cured by heating using a combination of the epoxy resin which is the A component of the present invention and the liquid carboxylic acid anhydride curing agent which is the C component, and an addition polymerization curing accelerator and a radical polymerization initiator. By doing this, heat resistance (glass transition temperature = T
g) A tough cured resin product with improved elastic modulus while maintaining appropriate elongation of the cured product and excellent impact strength etc. can be obtained.

In the present invention, in addition to the above-mentioned compounds, monofunctional (meth)acrylate compounds, (meth)acrylate compounds having functional groups such as epoxy groups and hydroxyl groups, and polymerizable unsaturated monomer compounds 1. Unsaturated compounds such as T4 polyester and vinyl ester resins can also be used together. These resin compositions have curing reactivity,
Improvements have also been made in lowering the viscosity. Furthermore, curing shrinkage during molding, which is a drawback of radically polymerizable compounds having unsaturated groups, is small, and a fiber-reinforced resin composite material with good surface properties can be obtained.

The carboxylic acid anhydride curing agent which is component C in the present invention is liquid at room temperature, and is a polyfunctional carboxylic acid obtained by reacting a monofunctional carboxylic anhydride alone or a lower aliphatic polyhydric alcohol with trimellitic acid or a derivative thereof. It is used in combination with anhydride. Examples of monofunctional carboxylic anhydrides include 3-methyltetrahydrophthalic anhydride, 4-methyltetrahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylnadic anhydride, and dodecenyl anhydride. Examples include succinic acid and structural or geometric isomers thereof. The monofunctional carboxylic acid anhydride is preferably a liquid having a viscosity of 500 cps or less at 25°C. At 500 cps or more, it is difficult to achieve a sufficiently low viscosity.

Examples of polyfunctional carboxylic anhydrides include liquid modified products containing reaction products obtained by reacting lower aliphatic polyhydric alcohols with trimellitic acid or its derivatives; The lower aliphatic polyhydric alcohol which is a component of the product preferably has 2 carbon atoms.
It is preferable to use 1 to 10 of them, and examples thereof include ethylene glycol, propylene glycol, 1,4-butanediol, glycerol, trimethylolethane, trimethylolpropane, pentaerythritol, hexanetriol, and the like.

Examples of the curing accelerator used in the present invention as component D include Lewis acids, BF3/amine complexes, tertiary amines and their salts, imidazole and its complexes, and organic phosphine compounds. Preferred are imidazole and organic phosphine compounds, and examples of imidazole compounds include 2
-ethylimidazole, 2-undecylimidazole,
2-Pentadecylimidazole, 2-methyl-4-ethylimidazole, 1-butylimidazole, 1-propyl-2-methylimidazole, 1-cyanoethyl-2-
Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-azine-2-methylimidazole, 1-
Examples of organic phosphine compounds include tertiary phosphine compounds such as triphenylphosphine, tributylphosphine, tricyclohexylphosphine, methyldiphenylphosphine, butyrrhiphenylphosphine, diphenylphosphine, etc. Secondary phosphine compounds, primary phosphine compounds such as phenylphosphine, octylphosphine, and bis(diphenylphosphino)methane, 1,2-bis(
Examples include tertiary bisphosphine compounds such as diphenylphosphino)ethane, and one or more of these may be used in combination as required.

Examples of the radical polymerization initiator that is component E of the present invention include common organic peroxides that generate radicals and polymerize radically polymerizable groups of polyfunctional (meth)acrylate compounds by heating. Examples of organic peroxides include azo compounds such as azoisobutylnitrile, t-butylperbenzoate, t-butylperoxy-2-ethylhexanoate, (butylperoxyisopropylcarbonate), 1, 1-bis(t-butylperoxy)3,3
．． 5-) Limethylcyclohexane, n-butyl-4,
Examples include 4-bis(t-butylperoxy)valerate, benzoyl peroxide, t-bar octoate, acetoacetate peroxide, methyl ethyl ketone peroxide, dicumyl peroxide, t-butyl hydroperoxide, etc. Type 1 or 2
More than one species can be used, and it is also possible to add curing accelerators such as dimethyl para-toluidine, dimethylaniline, diethylaniline, laurin mercaptan, and cobalt naphthenate.

In the present invention, it is preferable to add 5 to 200 parts by weight of the polyfunctional (meth)acrylate compound as component B to 100 parts by weight of component A, and more preferably 20 to 1 part by weight.
It is 50 parts by weight. If the amount added is less than the above range, there will be little effect on lowering the viscosity, improving curing reactivity, heat resistance, elastic modulus, and toughness. Moreover, if it exceeds the above-mentioned range, curing shrinkage will increase, and the heat resistance and mechanical properties of the cured product will deteriorate, which is not preferable.

Further, in the liquid carboxylic anhydride curing agent which is component C, the equivalent ratio of the carboxylic anhydride functional group to the epoxy group of component A is preferably 1.070.3 to 1.0/1.4, and more preferably. is 1.0/0.4 to 1.0/1.2. If the equivalent ratio of the carboxylic acid anhydride is less than the above range, the heat resistance and elongation at break of the cured product will decrease, and the effect of lowering the viscosity will also decrease. Moreover, if it exceeds the above range, the heat resistance tends to deteriorate, which is not preferable. Furthermore, in terms of lowering the viscosity of the mixed resin, using a monofunctional carboxylic anhydride alone has a greater effect, but in order to improve faster curing and heat resistance, it is necessary to use a monofunctional carboxylic anhydride alone. It is preferable to use 2 to 80% by weight, preferably 5 to 40% by weight, based on the functional carboxylic acid anhydride. If this amount is less than the above range, it will not be very effective in improving fast curing properties and heat resistance, and if it is more than the above range, the viscosity will increase and it will be difficult to obtain the desired molded product, which is not preferable.

There is no particular restriction on the amount of curing accelerator added as component D, and the reaction rate is appropriately controlled. This curing accelerator is used by being uniformly dissolved in component C, but if it does not substantially promote the homopolymerization of the epoxy resin, A
It may also be used by mixing with component B. The curing accelerator is usually blended in an amount of 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, per 10 parts by weight of component A.

There is no particular restriction on the amount of radical polymerization initiator added as component E, but it is usually 0.05 to 100 parts by weight of component B.
It is blended so that it is 20 parts by weight, preferably 0.2 to 20 parts by weight.
It is 10 parts by weight.

The mixture of the three components A, B, and C has a relatively low viscosity, and a high-quality fiber-reinforced resin composite material with a high packing density can be obtained. improved toughness.

In RIM molding, liquid A/C consists of component A and component B.
The mixing ratio of component and B liquid consisting of D component and E component is 1
The closer it is to 1 part by volume, the better the measurement accuracy and mixing properties, but even in this respect, the carboxylic acid anhydride curing agent system of the present invention is superior to the amine curing agent system with less deviation in blending ratio. .

Molding is completed by mixing the reactive resin components of liquid A and liquid B at high speed using a mixing head or a static mixer, and then injecting the mixture into a mold heated and maintained at a predetermined temperature, curing, and demolding. The fiber reinforcing material may be in the form of a mat, fibers, etc., and if necessary, it is preset in a mold as a sandwich structure using a foam material such as urethane or epoxy as a core material. It is also possible to mix short fibers and the like with the resin and inject it. The molded article that is the object of the present invention is manufactured by a short molding cycle, and the time required from injection to demolding is within 10 minutes, preferably within 5 minutes, and more preferably within 3 minutes. The temperature and time actually required for molding are appropriately determined depending on the composition of the reactive resin, the shape and thickness of the molded product, etc. The resin composition of the present invention has high curing reactivity after gelling, and therefore has excellent demoldability. Further, by subjecting the molded product to a short heat treatment to complete curing as required, a fiber-reinforced resin composite material having excellent heat resistance and mechanical properties can be obtained.

In addition to these components, an epoxide-reactive diluent may be added to an extent that does not reduce reactivity, heat resistance, toughness, etc. Examples of reactive diluents include phenyl glycidyl ether, butyl glycidyl ether, alkyl glycidyl ether, styrene oxide, octylene oxide, and mixtures thereof.

In addition, additives such as coupling agents such as silane and titanate compounds, mold release agents such as higher fatty acids and waxes, flame retardant agents such as halogens and phosphorus compounds, antifoaming agents, and coloring agents are also used as necessary. 8 things are coming.

Continuous fiber reinforcement materials used in the present invention include glass fibers, aramid fibers, polyester fibers, carbon fibers, silicon carbide fibers, alumina fibers, etc., and these include tapes,
It is used in the form of sheets, mats, woven fabrics, knitted fabrics, etc., and in various combinations of these depending on the required characteristics.

Further, these short fiber reinforcing materials may also be used if necessary. The volume content of the fiber reinforcement is 2 to 2 of the total volume with the resin component.
70% is preferable, and its composition and amount are appropriately selected depending on the required characteristics.

Furthermore, the epoxy resin composition of the present invention can be processed by reaction injection molding, RT
Although it is suitable for M molding, it is also useful to mold it into a desired composite material by known molding methods such as filament winding method, pultrusion method, etc.

[Examples] The present invention will be described in more detail with reference to Examples below, but the present invention is not limited by these Examples unless the gist thereof is exceeded. Note that parts in the examples are based on weight unless otherwise specified, and the blending ratios of epoxy resin and carboxylic acid anhydride were all such that epoxy acid anhydride = 1.0 equivalent ratio.

The resin properties include gelation time at 120°C (
GT) was determined from the torque generation time using a JSR type Curastometer. In addition, the physical properties of the cured resin are 300
120° CI0 in oven using 300mm mold
．． After curing for 5 hours and at 150°C for 1 hour, a cast plate was prepared and measured. Fiber-reinforced composites are manufactured using reaction injection equipment (
“MC102-N” manufactured by Polyurethane Engineering Co., Ltd.
) and heated and held at 120'C.
The mold was demolded 5 minutes after injection into a 0x3 mm flat plate mold. The glass transition temperature (Tg) of the cured product was determined from the change in thermal expansion curve using the TMA method, and the breaking strain corresponding to the bending properties and toughness of the cured resin product and fiber-reinforced composite was determined according to ASTM-D 790. It was determined by a three-point bending test using "UTM-5T" manufactured by Toyo Baldwin Co., Ltd. in accordance with the following. The resin property evaluation results are shown in Table 1.

Example I As component A, bisphenol A diglycidether (
"Epicote 827", manufactured by Yuka Shell Co., Ltd.) 60 parts, trimethylolpropane triacrylate ("
NK ester TMPT”, manufactured by Shin Nakamura Chemical Co., Ltd.) 40 copies,
In addition, methyltetrahydrophthalic anhydride (“
55 parts of 2-ethyl-4-methylimidazole (2 parts of 4M
Z", manufactured by Shikoku Kasei Kogyo Co., Ltd.) 6 parts and 1 part as E component,
1 part of 1-bis(t-butylperoxy)3.3.5-)limethylcyclohexane ("Perhexa 3M", manufactured by NOF Corporation) was mixed, and after defoaming, it was placed in a mold heated to 80°C. A casting plate was prepared.

In addition, A liquid consisting of components A and B was heated to 60°C and kept defoamed, and C1D was heated to 60°C and sealed with nitrogen after defoaming.
Using a RIM device, liquid B consisting of component E was added to glass fiber continuous strand mat ("C3M8600").
”, manufactured by Asahi Fiber Glass Co., Ltd., weight of reinforcement material 2FAW=
600g/m2) were laminated in 4 plies [volume content of fiber reinforcement material, amount: Vf=30.2%], and after installation 20kg/
The mold was clamped to 0m2.

The molded product was substantially free of unimpregnated areas and voids, and had good surface properties. The bending strength of this composite material is 32.
At 4kg/mm2, the flexural modulus is 1.230kg/mm2.
It was mm'.

Example 2 Similarly to Example 1, component C "MT 500" was mixed with methyltetrahydrophthalic anhydride and a polyfunctional curing agent containing 15% trimellitic acid triglyceride ("MTA 15").
, manufactured by Shin Nippon Rika Co., Ltd.), and a casting plate was prepared instead of 58 parts.

Example 3 Similarly to Example 1, 50 parts of bisphenol F type diglycidyl ether ("Epiclon 830", manufactured by Dainippon Ink Chemical Co., Ltd.) was used as the A component, and tetramethylolmethanetetraacrylate ("NK ester A-") was used as the B component. TM
MT", manufactured by Shin Nakamura Chemical Co., Ltd.) 50 parts, "MT" as C component
500" 47 parts, D component and L Te" 2 parts 4MZ
A casting plate was prepared using 5 parts of ``Perhexa 3M'' and 1 part of E component ``Perhexa 3M''.

Furthermore, the bending strength of the composite material using "C8M 8600" formed by RIM molding was 34.3 kg/mm2, and the crushing elastic modulus was 1.270 kg/mm2.

Example 4 Similar to Example 1, “Epicron 830” was used as the A component.
and 70 parts of bisphenol F ethylene oxide adduct dimethacrylate (KAYARADR-7) as component B.
12" manufactured by Nippon Kayaku Co., Ltd.) 30 parts, C component "'MTA15
A casting plate was prepared using 71 parts of ``2 Parts 4MZ'' as the D component, 7 parts of ``2 Parts 4MZ'' as the D component, and 1 part of Hyperhexa 3M'' as the E component.

Example 5 Similarly to Example 1, 60 parts of tetraglycidyl metaxylylene diamine ("TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) was used as the A component, and 40 parts of "R-712" was used as the B component.
104 parts of "MTA15" was used as the C component, 6 parts of "2 parts 4MZ" as the D component, and 1 part of "Perhexa 3M" as the E component. The bending strength of the composite material is 32.
At 6 kg/mm2, the bending modulus is 1.450 kg
/ mm2.

Examples 6 and 7 Similarly to Example 1, “TETRAD-X” was used as the A component.
” and 50 parts of aliphatic ring-containing diacrylate (“KAYARAD R-604” manufactured by Nippon Kayaku Co., Ltd.) or hydrogenated dicyclopentadienyl diacrylate (“DC
50 parts of "P-A" (manufactured by Toagosei Kagaku Co., Ltd.), 93 parts of "MTA15" as component C, component D and L te" 2
Part 4MZ” is 5 parts, E component is “Parhexa 3M”
One part was used.

Comparative Example 1 As in Example 1, 55% of “Epicron 830” was added to the A component.
0 parts, 50 parts of styrene for B component, "MT50" for C component
A casting plate was prepared using 47 parts of "0", 5 parts of "2 part 4MZ" for the D component, and 1 part of Hexa 3M" for the E component.

In addition, by adjusting molding, "C8M 8600" was made into 4 pieces (
The bending strength of the composite material laminated with Vf=30.5% is 18
．． 2 kg/mm' and the bending modulus is 940 kg
/ mm2. The molded product had sink marks and cracks, and its surface properties were poor.

Comparative Examples 2 to 4 Similar to Example 1, “Epicron 830” was used as the A component.
and 50 parts of triallyl isocyanurate ("T") as component B.
AIC”) or t-butyl methacrylate (“Light Ester TB”, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) or 2
-Phenoxyethyl methacrylate (Light Ester P
O1 (manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd.) 50 parts, as component C “
A casting plate was prepared using 47 parts of ``MT 500'', 5 parts of ``2 parts 4MZ'' as the D component, and 1 part of ``Perhexa 3M'' as the E component.

Comparative Examples 5 and 6 Same as Example 1, “Evicron 830” which is component A
Or 100 parts of "TETRAD-X", 94 or 173 parts of "MT500" as C component, "
A casting plate was prepared using 10 parts of 2 parts of 4MZ''.

[Effects of the Invention] According to the present invention, a fiber-reinforced resin composite material having excellent heat resistance, mechanical properties, and moldability and having a high packing density and substantially free of voids and defects can be produced by reaction injection molding (RIM) or RTM.
It can be manufactured by the method.

Claims (1)

[Scope of Claims] 1) A fiber-reinforced resin composition containing the following components A, B, C, D, and E as essential components as reactive resin components. Component A: An epoxy resin having two or more epoxy groups in one molecule. Component B: A polyfunctional (meth)acrylate compound having two or more acrylic or methacrylic groups in one molecule. Component C: A liquid carboxylic anhydride containing a polyfunctional carboxylic anhydride obtained by reacting a monofunctional carboxylic anhydride and/or a lower aliphatic polyhydric alcohol with trimellitic acid or a derivative thereof. Component D: Curing accelerator Component E: Radical polymerization initiator 2) Fiber reinforced resin composition obtained by mixing the reactive resin component and immediately injecting the fiber reinforced resin composition into a mold in which the fiber reinforcing material is placed. The resin composition according to claim 1. 3) Claim 1, wherein the polyfunctional (meth)acrylate compound as component B is 5 to 200 parts by weight based on 100 parts by weight of component A.
The resin composition described. 4) The liquid carboxylic anhydride of component C has an equivalent ratio of carboxylic anhydride functional groups to the epoxy group of component A of 1.0/
The resin composition according to claim 1, which has a molecular weight in the range of 0.3 to 1.0/1.4. 5) The resin composition according to claim 1, wherein the polyfunctional carboxylic anhydride is contained in an amount of 2 to 80% by weight based on the monofunctional carboxylic anhydride.