JPH10237196A - Tow prepreg - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a tow prepreg improved in processability into high speed rotators and in performances in operations, especially strength in the radial direction, namely tensile strength at an angle of 90 deg.C by impregnating reinforcing fibers with a resin composition containing acrylic resin particles. SOLUTION: Reinforcing fibers (e.g. PAN-based carbon fibers) are impregnated with an epoxy resin composition comprising (A) an epoxy resin, (B) acrylic resin particles capable of being dissolved in or swollen with the epoxy resin at high temperatures and having a particles diameter of <=1.0μm at 25 deg.C, (C) a curing agent (e.g. methylhexahydrophthalic acid), and (D) a curing accelerator (e.g. 1-methylimidazole) and having a viscosity of 0.5-20Pa.s at 25 deg.C. The content of the resin in the objective prepreg is preferably 25-40wt.%.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a tow prepreg obtained by impregnating a reinforcing fiber with an epoxy resin composition comprising an epoxy resin, an acrylic resin-based fine particle, a curing agent and a curing accelerator.

[0002]

2. Description of the Related Art Fiber reinforced plastic (FRP) is a material excellent in both specific strength and specific elastic modulus, and research and development of flywheels utilizing these characteristics have been promoted. As fiber materials used for these, carbon fibers, glass fibers, and aramid fibers, which are very excellent in specific strength and specific elastic modulus, are generally used. As matrix resins thereof, epoxy resins, unsaturated polyester resins, and the like are generally used. In recent years, light weight and high speed have been demanded as a demand for a rotating body. As a fiber material meeting these demands, high-strength polyacrylonitrile (hereinafter referred to as PAN) -based carbon fiber,
There are pitch-based carbon fibers and the like. In order to make effective use of the strength of the reinforcing fiber, a filament winding method is used as a molding method.
応 力 direction stress has very weak point. To compensate for these,
Conventionally, a design was made to increase the number of reinforcing fibers rather than improving the matrix.

Conventionally, as a matrix resin, a conventional epoxy resin compound uses a low molecular weight epoxy resin to improve workability by lowering the viscosity, so that a cured product obtained is hard and brittle. In order to increase flexibility, a liquid reactive rubber component is partially used. However, due to an increase in viscosity, air bubbles are involved during processing, which causes defects such as voids in a molded product, which is not a preferable method.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the foregoing circumstances, and has been made in view of the above-described circumstances.
Particularly, the present invention provides a tow prepreg obtained by impregnating reinforcing fibers with an epoxy resin composition for a high-speed rotating body composite material, which has improved radial strength, that is, tensile strength in a 90 ° direction.

[0005]

In order to solve the above-mentioned problems, the present inventors have studied the workability of a high-speed rotating body or the like, the performance during operation, particularly the strength in the radial direction, that is, the tensile strength in the 90 ° direction. As a result of various studies to improve the above, the present invention has been completed.

That is, the present invention relates to an epoxy resin composition comprising an epoxy resin, acrylic fine particles having a particle size of 1.0 μm or less at 25 ° C. which dissolve or swell in the epoxy resin at a high temperature, a curing agent and a curing accelerator. And a tow prepreg obtained by impregnating a reinforcing fiber.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail.

The epoxy resin used in the present invention is 25
A liquid epoxy resin at ℃, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, alicyclic epoxy resin And the like, and a mixture of two or more of these epoxy resins can be used.

Bisphenol A type epoxy resins include Epicoat 825, Epicoat 827, Epicoat 828 (all manufactured by Yuka Shell Epoxy), Araldite GY250, Araldite GY260 (all manufactured by Ciba-Geigy), Dow Epoxy DER330, Dow Epoxy DER331 (all Dow Chemical Company), Epicron 8
40, Epicron 850 (all manufactured by Dainippon Ink and Chemicals, Inc.), Epototo YD127, Epotote YD128
(Manufactured by Toto Kasei Co., Ltd.) or the like can be used.

As the bisphenol F type epoxy resin, Epicoat 807 (manufactured by Yuka Shell Epoxy), Epicron 830 (manufactured by Dainippon Ink and Chemicals, Inc.), YDF
170 (manufactured by Toto Kasei) EP-4900 (manufactured by Asahi Denka Kogyo), PY-306 (manufactured by Asahi Ciba) and the like can be used.

As the phenol novolak type epoxy resin, Epicoat 152, Epicoat 154 (all manufactured by Yuka Shell Epoxy), Araldite EPN1138,
Araldite EPN1139 (from Ciba-Geigy), Dow Epoxy DEN431 (from Dow Chemical), EPPN201 (from Nippon Kayaku), Epicron N
740 (manufactured by Dainippon Ink and Chemicals, Inc.), Epototo YD
PN638 (manufactured by Toto Kasei), TACTIX785 (manufactured by Dow Chemical Japan), or the like can be used.

As the cresol novolak type epoxy resin, ECN1280, ECN1299 (all manufactured by Ciba-Geigy), EOCN102 (Nippon Kayaku) and the like can be used.

Glycidylamine type epoxy resins include Araldite MY720 and Araldite MY051
0 (from Ciba-Geigy), GAN, GOT (from Nippon Kayaku), Epotote YH434 (from Toto Kasei), ELM120, ELM434 (from Sumitomo Chemical), TETRAD-C, TETRAD-X (Manufactured by Mitsubishi Gas Chemical Company) or the like can be used.

As the glycidyl ester type epoxy resin, Epicoat 191P, Epicoat 190P, Kadura E10 (all manufactured by Yuka Shell Epoxy), AK-6
01 (manufactured by Nippon Kayaku Co., Ltd.), Araldite CY183, Araldite CY182 (all manufactured by Ciba-Geigy), Denacol EX-721 (manufactured by Nagase Kasei Kogyo), Epototo YD171 (manufactured by Toto Kasei) and the like can be used.

As the alicyclic epoxy resin, ERL424 is used.
9 (manufactured by Union Carbide), ERL4221 (manufactured by Union Carbide), Araldite CY179 (manufactured by Ciba Geigy), Daicel Celloxide 2021 (manufactured by Daicel Chemical Industries), ERL4206 (manufactured by Union Carbide), Epicoat RX- 21 (manufactured by Yuka Shell Epoxy), or the like.

These epoxy resins can be used alone, but as a mixture of two or more selected from the above epoxy resins, the composition has a viscosity of 20 Pa · s at 25 ° C.
Can be used within a range not exceeding.

Further, another epoxy resin such as a high-viscosity, semi-solid or solid epoxy resin at 25 ° C. can be mixed with the low-viscosity epoxy resin.
And can be used as an epoxy resin composition having a viscosity not exceeding 20 Pa · s. Further, various plastics and rubbers can be added to improve the toughness of the epoxy resin. In this case, the viscosity of the obtained epoxy resin composition at 25 ° C. does not exceed 20 Pa · s. .

For example, plastics include polycarbonate, polyether sulfone, phenoxy resin, polyvinyl formal, polyvinyl butyral, polyethylene terephthalate and the like. Rubbers include butadiene-acrylonitrile rubber, styrene-butadiene rubber, acrylonitrile-butadiene-styrene resin, and silicone resin.

Further, in order to further improve the toughness, other polymer fine particles can be added in combination. Styrene resin, divinylbenzene resin, styrene-divinylbenzene resin, benzoguanamine resin, melamine resin, benzoguanamine-melamine co-condensation resin, urea resin, silicone resin, ethylene-acrylic acid copolymer resin, methyl methacrylate resin, n- Butyl acrylate resin, acrylic-urethane resin, polyamide resin,
There are aromatic polyester resins and the like.

At the high temperature used in the present invention, it dissolves or swells in the epoxy resin and has a particle size of 1.0 at 25 ° C.
Acrylic acid fine particles of μm or less include acrylic acid,
Methacrylic acid, methyl acrylate, ethyl acrylate,
It is obtained by applying any conventionally known emulsion polymerization method using acrylic acid derivatives such as methyl methacrylate and ethyl methacrylate as raw materials. Although any of a shell-type system may be used, a core-shell type system is particularly preferable.

Further, a part of the shell part is cross-linked,
It is particularly preferable because the change in viscosity before temperature rise is small in the epoxy resin.

The size of the acrylic resin fine particles may be 1 μm or less, preferably 0.1 to 1 μm. When it is larger than 1 μm, it is difficult to impregnate the reinforcing fibers into the inside when impregnating the reinforcing fibers, which is not preferable.
When the thickness is less than 0.1 μm, the handling of the acrylic fine particle powder becomes poor.

The amount of the acrylic resin particles which dissolve or swell in the epoxy resin at a high temperature and have a particle size of 1.0 μm or less at 25 ° C. is 5 to 35 parts by weight, preferably 8 to 100 parts by weight of the epoxy resin. １５15 parts by weight. When the amount is less than 5 parts by weight, the physical properties at 90 ° in the case of the composite material are insufficient, and when it exceeds 35 parts by weight, the mixing property of the resin composition is insufficient.
Neither is preferred. Examples of the curing agent used in the present invention include, for example, any of methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl phthalic anhydride, and methylnadic anhydride which are liquid at room temperature. Can be used. When solid tetrahydroanhydride, hexahydroanhydride, and nadic anhydride are used together, it is preferable to uniformly disperse them with an epoxy resin and / or another liquid curing agent. In particular, when methylhexahydrophthalic anhydride is used, the molded article has good hygroscopicity, weather resistance, and durability, which is preferable.

The curing agent can be used in an amount of 75 to 230 parts by weight, preferably 75 to 110 parts by weight, per 100 parts by weight of the epoxy resin. If the added amount is less than 75 parts by weight or exceeds 230 parts by weight, the glass transition temperature of the cured resin composition decreases, which is not preferable.

The curing accelerator used in the present invention includes:
Various imidazoles, tertiary amines and the like can be mentioned. Examples of these are 1-methylimidazole, 1-benzylimidazole, 2-ethyl-4-methylimidazole,
BF3.monoethylamine, BCl3.monoethylamine, dimethylbenzylamine, trisdiaminophenol, diazabicycloundecene, and the like.

The curing accelerator is added in an amount of 0.5 to 10 parts by weight, preferably 1.0 to 3 parts by weight, based on 100 parts by weight of the epoxy resin. When the addition amount is less than 0.5 part by weight, the curing becomes insufficient, and when it exceeds 10 parts by weight, the storage stability of the intermediate material, that is, the tow prepreg becomes poor, and both are not preferable.

When the epoxy resin composition obtained in the present invention is heated, the resin composition starts to gel due to the dissolution or swelling action of the acrylic resin-based fine particles, and the viscosity can be rapidly increased at a certain temperature. .

In this case, the resin composition is added at 2 ° C./min.
The ratio between the lowest viscosity shown when the temperature is raised and the viscosity at a temperature higher by 10 to 15 ° C. (referred to as gelling viscosity) from the temperature at which the lowest viscosity is shown (usually 60 to 110 ° C.), that is, abrupt stepwise When the viscosity increases, the viscosity increase ratio is 1.2 to 100.
0, preferably 1.2-100, most preferably 1.5
-10. When the viscosity increase ratio is less than 1.2, the resin flows out of the tow, making it difficult to adjust the fiber volume content Vf to a target value. It becomes difficult to improve.

The epoxy resin composition obtained according to the present invention comprises 2
The viscosity at 5 ° C. is preferably 0.5 to 20 Pa · s.

The fibers can be suitably impregnated within this viscosity range.

The reinforcing fiber used in the present invention is PA
N-based carbon fibers, pitch-based carbon fibers, glass fibers, aramid fibers, boron fibers, and the like can be used, and preferably PAN-based carbon fibers having high strength and high elasticity can be used.

Although it is common to use these reinforcing fibers alone, a hybrid lamination using two or more kinds of fibers can also be used depending on the application.

The resin content of the tow prepreg is from 25 to
40% by weight, preferably 28-35% by weight, are used.

In the present invention, a reaction diluent, various fillers, a plasticizer, a foam stabilizer, a colorant, and the like can be mixed as other additives.

The method for producing a prepreg according to the present invention can be carried out as follows. That is, the important steps in the production of the epoxy resin composition for high-speed rotating body composite material,
1) the order of addition of the components and 2) the mixing method.

Any mixer can be used as long as it does not generate heat during mixing. Among them, three rolls for ink are preferable.

When mixing the epoxy resin, the acrylic fine particles, the curing agent and the curing accelerator, the epoxy resin, the acrylic fine particles and the curing agent are first mixed, sufficiently mixed, and then vacuum defoamed in order to suppress an increase in viscosity during the mixing. Preferably, a curing accelerator is added, and the mixture is further mixed so that air bubbles are not involved.

In dispersing the acrylic resin fine particles in the epoxy resin, the epoxy resin is added to the emulsion after the emulsion polymerization, and the dispersion medium such as water is degassed.
A method of dispersing a powder obtained by spray-drying an emulsion after emulsion polymerization in an epoxy resin while applying a high shear thereto, and a method of dispersing an epoxy resin and acrylic fine particles at the time of use and dispersing them by a three-roll or the like. And any of them can be used.

In particular, the fine particle powder is mixed with an epoxy resin,
Those dispersed by three rolls or the like are preferable because gelation (pseudo-curability) of the epoxy resin composition due to dissolution or swelling of fine particles is large.

An epoxy resin is added to the emulsion after emulsion polymerization, and a dispersion medium such as water is degassed.
It is also possible to further add another acrylic fine particle powder to the one obtained by dispersing the powder obtained by spray-drying the emulsion after the emulsion polymerization in the epoxy resin while applying a high shear in the epoxy resin. It is possible.

When the curing accelerator is added from the beginning and the whole process takes a long time, the viscosity of the mixture increases, the resin content of the tow prepreg as the next intermediate material changes, and the fiber content of the final cured product increases. It is not preferable because the rate changes.

The water in the air at the time of mixing reacts with the curing agent,
It is preferable to mix them in a dry atmosphere because they cause curing inhibition.

With respect to the mixing method, if the shearing force is applied too much, the temperature of the mixture increases due to frictional heat, the reaction of the epoxy resin proceeds, the viscosity increases, and bubbles are entrapped. is important.

The viscosity at the time of mixing is preferably 0.5 to 20 Pa · s. If the viscosity is too high, the handleability during production of the tow prepreg as an intermediate material is poor, and the impregnation into the reinforcing fibers is insufficient, which is not preferable.

The mixing temperature is usually at room temperature, and the upper limit is a temperature below the minimum viscosity of the resin composition, that is, a temperature at which the acrylic resin-based fine particles swell or dissolve and the resin composition does not gel. It is preferable to carry out in.

The resulting resin composition is preferably degassed in a vacuum to remove air bubbles in the resin.
It is sufficient to perform the treatment under mHg for 10 to 20 minutes.
It is more preferable to have a mixer with vacuum degassing.

The method of producing the tow prepreg as an intermediate by impregnating the degassed resin composition with the reinforcing fibers is not particularly limited. However, in order to control the resin impregnation amount, the fiber tow is mixed with the epoxy resin composition. After passing through the impregnating tank containing, a method of controlling the amount of adhered resin through a drawing die, a part of a rotating drum having a doctor blade is impregnated in an impregnating tank containing epoxy resin, and a fiber tow is placed on the rotating drum. A method of controlling the amount of adhered resin by passing the epoxy resin and a part of the curing agent from the first dispenser, the curing agent and the curing accelerator continuously and in the same place on the reinforcing fiber tow moving from the second dispenser. A method of controlling the amount of adhered resin by dropping it quantitatively. And a curing accelerator are charged into the second tank, and the amount of the adhered resin is controlled by continuously and quantitatively dropping the reinforced fiber tow from the first dispenser and the second dispenser via a mixer, respectively, and the like. There is.

The resin composition when impregnated into these tow prepregs can be heated at room temperature or moderately. However, when the resin composition is excessively heated, the resin composition gels due to dissolution or swelling of the acrylic resin fine particles, and the viscosity increases. You need to avoid it.

The tow prepreg obtained by impregnating the resin composition is usually stored in a refrigerator or a freezer, except that it is immediately laminated by filament winding. If the curing agent is continuously exposed to moisture, etc., it changes from acid anhydride to dicarboxylic acid, causing curing inhibition.Therefore, it is necessary to store the fiber tow in a bag such as polyethylene to the extent that it does not come into strong contact with the fiber tow. is there.

The tow prepreg can be obtained by dissolving or swelling the acrylic resin-based fine particles before molding to form a resin composition into a gel. However, the tow prepreg is usually not gelled because the handleability of the tow prepreg deteriorates. It is preferred to gel for the first time during curing molding.

The method of winding with a filament winder, a drum winder or the like is not particularly limited, but the method of winding in the circumferential direction is preferable for a high-speed rotating body. When winding, tow requires a moderate tension,
If it is too weak, it causes voids and loose winding, and if it is too strong, the resin content in the fiber becomes small, which causes undesired delamination.

The curing condition of the uncured molded product after winding depends on the size of the uncured molded product, but is usually 10 times.
0 ° C, 10 to 20 hours, 100 for short-time curing
After も C and 4 hours, it is also possible to set 140 ゜ C and 4 hours. At the time of curing, when acrylic resin-based fine particles that dissolve or swell in the epoxy resin at a high temperature and have a particle size of 1.0 μm or less at 25 ° C. are used, 60 to 110 ° C.
In this case, an increase in viscosity occurs, and dripping of the resin from the molded body can be prevented.

The tow prepreg of the present invention can be formed into a flat plate, a curved plate,
It can be applied to any of a tubular shape and a rod shape.

Examples of these uses include shafts, rods and pipes for various sports.

[0055]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto.

Example 1 Bisphenol F type epoxy resin (trade name: YDF17)
0, manufactured by Toto Kasei Co., Ltd.), 4500 parts by weight, particle size 0.3
Acrylic core-shell type fine particles having a particle size of 500 μm (trade name: ZEON F351, manufactured by Zeon Corporation) and methylhexahydrophthalic anhydride (trade name: H
Y917J, Ciba Specialty Chemicals Co., Ltd.
4000 parts by weight). After thorough mixing, 50 parts by weight of 1-methylimidazole was added and mixed at 25 ° C. In order to remove bubbles in the resin from the mixture, the mixture was degassed in a vacuum deaerator under the conditions of room temperature, 10 mmHg, and 10 min. The obtained mixture is put into an impregnation tank equipped with a rotating drum, and a tow of carbon fiber (M-40J, 12000 filament, manufactured by Toray Industries, Inc.) is brought into contact with the resin formed into a thin film by a doctor blade attached to the rotating drum. Thereby, the resin was continuously impregnated.

The amount of the adhered resin was 35% by weight. The tow prepreg obtained above was treated with a filament winding device having a mandrel having a diameter of 260 mm to a diameter of 46 mm.
A cylindrical body having a length of 0 mm and a body length of 200 mm was formed. These are put in a curing oven for 100 while rotating at 20 rpm.
゜ C, cured for 12 hours. After curing, the molded product was obtained by gradually cooling and de-centering. After cutting the end with a cutter, the surface was polished and the surface was observed. As a result, no delamination or voids were found between the layers. No resin dripping was observed at the time of curing. Table 1 shows the performance of the obtained resin composition and molded article.
Shown in

Example 2 The tow prepreg obtained in Example 1 was prepared with a diameter of 300 mm.
It was wound on a drum of a drum winder having a width of 300 mm to obtain a sheet-shaped prepreg having a basis weight of 350 g / m ² . These were laminated in one direction and cured under the same conditions as in Example 1 to obtain a cured plate. Length 140mm, width 20mm,
A specimen having a thickness of 2 mm and a fiber direction of 90 ° was subjected to a tensile test without a tab. Table 1 shows the properties of the obtained resin composition and the molded article.

Example 3 Bisphenol F type epoxy resin (trade name: YDF17)
0, manufactured by Toto Kasei Co., Ltd.), 4000 parts by weight, particle size 0.3
1000 parts by weight of an acrylic core-shell type fine particle having a μm (trade name: ZEON F351, manufactured by ZEON CORPORATION) were mixed, deaerated, and then charged into a first tank. 4000 parts by weight of methylhexahydrophthalic anhydride (trade name: HY917J, manufactured by Ciba Specialty Chemicals Co., Ltd.) and 50 parts by weight of 1-methylimidazole were added, mixed, degassed, and charged in the second tank. The resin in the first tank and the curing agent in the second tank respectively passed through a metering pump, passed through a mixer and a metering valve, and passed through a carbon fiber (M-4).
0J, 12000 filament, manufactured by Toray Industries, Inc.) to continuously impregnate the resin. The amount of the adhered resin was 35% by weight. The tow prepreg obtained above was 460 mm in diameter and 20 mm in body length using a filament winding device having a mandrel having a diameter of 260 mm.
A 0 mm cylinder was molded. These were cured in a curing furnace at 100 ° C. for 3 hours, and further at 140 ° C. for 4 hours while applying a rotation of 20 rpm. After curing, the molded product was obtained by gradually cooling and de-centering. After cutting this end with a cutting machine, polishing and observing the surface, delamination between layers,
No void was seen. No resin dripping was observed at the time of curing. Table 1 shows the properties of the obtained resin composition and the molded article.

Example 4 The tow prepreg obtained in Example 3 was prepared with a diameter of 300 mm.
It was wound on a drum of a drum winder having a width of 300 mm to obtain a sheet-shaped prepreg having a basis weight of 350 g / m ² . These were laminated in one direction and cured under the same conditions as in Example 1 to obtain a cured plate. Length 140mm, width 20mm,
A specimen having a thickness of 2 mm and a fiber direction of 90 ° was subjected to a tensile test without a tab. Table 1 shows the properties of the obtained resin composition and the molded article.

Example 5 Bisphenol F type epoxy resin (trade name: YDF17)
0, manufactured by Toto Kasei Co., Ltd.), 4500 parts by weight, particle size 0.3
Acrylic core-shell type fine particles having a particle size of 500 μm (trade name: MP1000, manufactured by Soken Chemical Co., Ltd.) and methylhexahydrophthalic anhydride (trade name: HY9)
17J, Ciba Specialty Chemicals Co., Ltd.)
4000 parts by weight were mixed. After thorough mixing, 50 parts by weight of 1-methylimidazole was added and mixed.

A cylinder having a diameter of 460 mm and a body length of 200 mm was formed from these mixtures in the same manner as in Example 1.
After cutting the end with a cutter, the surface was polished and the surface was observed. As a result, no delamination or voids were found between the layers. In addition,
No resin was found at the time of curing. Table 1 shows the properties of the obtained resin composition and the molded article.

Example 6 The tow prepreg obtained in Example 5 was prepared with a diameter of 300 mm.
It was wound on a drum of a drum winder having a width of 300 mm to obtain a sheet-shaped prepreg having a basis weight of 350 g / m ² . These were laminated in one direction and cured under the same conditions as in Example 1 to obtain a cured plate. Length 140mm, width 20mm,
A specimen having a thickness of 2 mm and a fiber direction of 90 ° was subjected to a tensile test without a tab. Table 1 shows the properties of the obtained resin composition and the molded article.

Comparative Example 1 Bisphenol F type epoxy resin (trade name: YDF17)
0, manufactured by Toto Kasei Co., Ltd.) and 4,500 parts by weight of methylhexahydrophthalic anhydride (trade name: HY917J,
Ciba Specialty Chemicals Co., Ltd.) 4000
Parts by weight were mixed. After thorough mixing, 45 parts by weight of dimethylbenzylamine was added and mixed at 25 ° C. In order to remove bubbles in the resin from the mixture, the mixture was degassed in a vacuum deaerator under the conditions of room temperature, 10 mmHg, and 10 min. The obtained mixture was put into an impregnation tank equipped with a rotary drum, and the carbon fiber tow of Example 1 was continuously impregnated with the resin by bringing the tow of the carbon fiber into contact with a thin film resin by a doctor blade attached to the rotary drum. The amount of the adhered resin was 35% by weight. The tow prepreg obtained as described above is
A cylindrical body having a diameter of 460 mm and a body length of 200 mm was formed by a filament winding device having a 0 mm mandrel. These were rotated at 20 rpm in a curing furnace at 100 ° C. for 3 hours, and further at 100 ° C.
Cured for 12 hours. After curing, the molded product was obtained by gradually cooling and de-centering. After cutting the end with a cutter, the surface was polished and the surface was observed. As a result, delamination was observed in part.
In addition, dripping of the resin at the time of curing was observed. Table 1 shows the properties of the obtained resin composition and the molded article.

Comparative Example 2 The tow prepreg obtained in Comparative Example 1 was prepared by
It was wound on a drum of a drum winder having a width of 300 mm to obtain a sheet-shaped prepreg having a basis weight of 350 g / m ² . These were laminated in one direction and cured under the same conditions as in Example 1 to obtain a cured plate. Length 140mm, width 20mm,
A specimen having a thickness of 2 mm and a fiber direction of 90 ° was subjected to a tensile test without a tab. Table 1 shows the results.

Comparative Example 3 Bisphenol F type epoxy resin (trade name: YDF17)
0, manufactured by Toto Kasei Co., Ltd.), 4000 parts by weight, particle size 1 μm
Polyamide-based fine particles (trade name: Olgasol 2)
001 Nippon Rilsan Co., Ltd.) 1000 parts by weight and methyl hexahydrophthalic anhydride (trade name: HY917)
J, Ciba Specialty Chemicals Co., Ltd.) 40
00 parts by weight were mixed. After thorough mixing, 50 parts by weight of 1-methylimidazole was added and mixed. In order to remove bubbles in the resin from the mixture, the mixture was degassed in a vacuum deaerator under the conditions of room temperature, 10 mmHg, and 10 min.
The obtained mixture is put into an impregnation tank equipped with a rotating drum, and a tow of carbon fiber (M-40J, 12000 filament, manufactured by Toray Industries, Inc.) is brought into contact with the resin formed into a thin film by a doctor blade attached to the rotating drum. Thereby, the resin was continuously impregnated. The amount of the adhered resin was 35% by weight.
A cylindrical body having a diameter of 460 mm and a body length of 200 mm was formed from the tow prepreg obtained above using a filament winding apparatus having a mandrel having a diameter of 260 mm. These were cured in a curing furnace at 100 ° C. for 12 hours while applying a rotation of 20 rpm. After curing, the molded product was obtained by gradually cooling and de-centering. After cutting the end with a cutting machine, the surface was polished and the surface was observed. As a result, no peeling between layers and no voids were observed, but dripping of the resin during curing was observed. Table 1 shows the properties of the obtained resin composition and the molded article.

Comparative Example 4 The tow prepreg obtained in Comparative Example 3 was prepared with a diameter of 300 mm.
It was wound on a drum of a drum winder having a width of 300 mm to obtain a sheet-shaped prepreg having a basis weight of 350 g / m ² . These were laminated in one direction and cured under the same conditions as in Example 1 to obtain a cured plate. Length 140mm, width 20mm,
A specimen having a thickness of 2 mm and a fiber direction of 90 ° was subjected to a tensile test without a tab. Table 1 shows the properties of the obtained resin composition and the molded article.

[0068]

[Table 1]

[0069]

As described above, according to the present invention, according to the present invention, an epoxy resin, acrylic resin-based fine particles having a particle size of 1.0 μm or less at 25 ° C. which dissolve or swell in the epoxy resin at a high temperature, Prepreg obtained by impregnating a reinforcing fiber with a resin composition for a high-speed rotating body composite material, comprising a reinforcing agent and a curing accelerator, and by molding the same, no resin dripping during curing, 90 ° direction A high-speed rotating body composite material having improved tensile strength can be obtained.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Noboru Hirano 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Japan Nippon Oil Corporation

Claims (1)

[Claims] (A) an epoxy resin, (B) an acrylic resin-based fine particle which dissolves or swells in the epoxy resin at a high temperature and has a particle size of 1.0 μm or less at 25 ° C., (C) a curing agent and D) Tow prepreg obtained by impregnating a reinforcing fiber with an epoxy resin composition characterized by having a viscosity at 25 ° C. of 0.5 to 20 Pa · s comprising a curing accelerator.