JP2000313750A - Fiber-reinforced resin and composition therefor - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain both a composition for a fiber-reinforced resin which is a resin for impregnating carbon fibers used for reinforcing and repairing a concrete structure and is better in low-temperature curability, impregnating properties and adhesion to carbon fibers than those of an epoxy resin and further better in impact and heat resistances and surface drying properties than those of a conventional epoxy acrylate resin and the fiber-reinforced resin. SOLUTION: This fiber-reinforced resin comprises a composition for the fiber-reinforced resin comprising (a) an epoxy acrylate prepared by reacting a bisphenol A type and/or a bisphenol F' type epoxy resin with bisphenol A and/or bisphenol F using a trialkylamine compound as a catalyst and then reacting the resultant epoxy resin having 400-1,000 g/equivalent epoxy equivalents with (meth)acrylic acid and (b) a copolymerizable monomer of styrene or an acrylic or a methacrylic ester and reinforcing fibers.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a composition for a fiber-reinforced resin and a fiber-reinforced resin, and more particularly to a composition for a fiber-reinforced resin suitably used for reinforcing and repairing a concrete building, and a composition for the fiber-reinforced resin. The present invention relates to a fiber-reinforced resin using the composition. More specifically, impregnation with reinforcing fibers,
The present invention relates to a composition for a fiber-reinforced resin having excellent adhesion, low-temperature curability, and excellent surface dryness, and a fiber-reinforced resin using the composition for a fiber-reinforced resin.

[0002]

2. Description of the Related Art An epoxy acrylate resin (vinyl) obtained by dissolving an epoxy acrylate obtained from an epoxy resin and methacrylic acid or acrylic acid (hereinafter referred to as (meth) acrylic acid) in a copolymerizable monomer such as styrene. Ester resins are also known for their excellent curability, chemical resistance, and mechanical properties.
It is used as a lining material such as a chemical solution dilution tank, a chemical solution storage tank, a concrete shield, iron, and stainless steel, and recently as a matrix resin for sports equipment such as a helmet. Further, those obtained by dissolving epoxy acrylate in acrylic acid ester and incorporating a photopolymerizable initiator can be cured by irradiating ultraviolet rays, and are used for printing inks, paints, solder resist materials and the like.

[0003] On the other hand, carbon fiber has the property of being lightweight and having high specific strength. A composite material obtained by combining carbon fiber and a thermosetting resin has a light weight and a high modulus of elasticity. It is widely used as a reinforcing material for parts, automobiles, railway vehicles, sporting goods, and the like.

At present, after the Great Hanshin Earthquake, concrete buildings in Japan are frequently repaired and reinforced by using a material combining carbon fiber and thermosetting resin. . For such repair and reinforcement, a construction method in which carbon fibers arranged in one direction and an impregnated resin are directly attached to concrete and laminated is mainly adopted. In general, carbon fibers have a high tensile strength, and carbon fibers arranged in one direction used for such reinforcement and repair have a very strong strength in the 0 ° direction with respect to the carbon fibers and a sufficient strength against stress. Having.

However, when carbon fibers arranged in one direction are attached to, for example, a concrete column, it is necessary to always overlap the carbon fibers (overlap). At this time, the strength of the overlapping part (lap strength)
Needs to be about the same as the intensity in the 0 ° direction.

At this time, when an impregnated resin having poor adhesion to carbon fibers is used, interfacial peeling occurs at such an overlapped portion, and the strength is reduced. Therefore, when reinforcing and repairing a concrete pillar with carbon fiber, it is important to select an impregnated resin having high adhesiveness to carbon fiber in order to bring out the strength of the overlapping portion.

Conventionally used impregnating resins include:
It is common to use an epoxy resin that exhibits excellent adhesion to carbon fibers. However, epoxy resins have several disadvantages. The biggest drawback is poor curability and workability at low temperatures. Since the epoxy resin has a considerably high viscosity even at ordinary temperature, it is difficult to impregnate the carbon fiber, and the work is troublesome. In particular, when the work site is at a low temperature, the viscosity is further increased, so that the operation of impregnating the carbon fibers becomes more difficult. Further, at a low temperature, the curability of the epoxy resin is extremely reduced, and it may take several hours to cure, or one day or more at 10 ° C. or less. As described above, at a low temperature, the curing time becomes longer, causing problems such as resin dripping and a longer construction period.

[0008] Further, when an epoxy resin is cured, an amine compound is used as a curing agent, so that an operator may cause allergic symptoms. There are problems such as recurrence of symptoms. Therefore, when epoxy resin is used to reinforce and repair concrete structures,
Improvements in these problems are needed.

Also, unsaturated polyester resins and unsaturated polyester acrylate resins in which the ends of unsaturated polyester are sealed with acrylic groups are less expensive than epoxy resins, have a lower resin viscosity, and have a lower curing time at lower temperatures. It can be adjusted by the amount and the amount of the accelerator, and therefore, the operation of impregnating the carbon fibers becomes easy. These resins are used as matrices for fishing boats, bathtubs, chemical tanks, etc., and exhibit good chemical resistance to water and acids.However, composite materials combined with carbon fiber are more expensive than epoxy resins. Therefore, the adhesion to carbon fibers tends to be poor.

JP-B-60-26132 and JP-B-60-26133 disclose that urethane acrylate resins having an acrylic double bond at the end have a low resin viscosity, like unsaturated polyester resins, and are hardened. It is described that the time can be adjusted by the amount of the curing agent or the amount of the accelerator. Although such resins have better mechanical properties than unsaturated polyester resins, -NHCO
Since the O-group is present in a large amount in the molecule, the water absorption is also large,
Water resistance tends to be inferior to unsaturated polyester resin, and is not suitable for reinforcement and repair of bridge piers used in severe outdoor natural environments. In addition, since the -NHCOO- group is weak against an acid, there is a problem in durability when the influence of acid rain is considered.

Epoxy acrylate resins used together with unsaturated polyester resins as matrices for leisure boats, bathtubs, pipes of chemical equipment, tanks, etc. are characterized by their low-temperature workability, curability, and acid resistance, which are characteristic of unsaturated polyester resins. It has excellent alkali resistance and is superior in adhesiveness (lap strength) to unsaturated polyester resin to a fiber reinforcing material, but tends to be lower in adhesiveness to epoxy resin to carbon fiber.

Further, urethane acrylate resins and epoxy acrylate resins have a (meth) acryloyl group at a molecular terminal, and thus have a polymerization inhibitory effect due to oxygen in the air, so that the surface is apt to be uncured, sticky and workable. In many cases, a method of adding paraffin wax to such a resin and forming a paraffin wax film on the surface of the resin during curing has been adopted for the purpose of preventing polymerization inhibition due to air, which causes deterioration in appearance. I have. But,
What added paraffin wax in such a resin,
Although a surface with good dryness can be obtained, if carbon fiber is further impregnated on the surface to reinforce it, not only may the adhesion between the upper and lower layers be reduced, but also no adhesion may occur.

[0013]

SUMMARY OF THE INVENTION An object of the present invention is to provide a reinforcing fiber impregnating resin used for reinforcing and repairing concrete structures, which has a lower temperature curing property, impregnating property and adhesion to carbon fibers than epoxy resins. It is an object of the present invention to provide a composition for a fiber reinforced resin and a fiber reinforced resin which are excellent in properties and more excellent in impact resistance, surface drying property and heat resistance than conventional epoxy acrylate resins.

[0014]

Means for Solving the Problems The present inventors have studied to solve the above problems, and as a result, have found that an epoxy acrylate obtained by a reaction between an epoxy resin synthesized using a specific catalyst and (meth) acrylic acid. Was solved by using an epoxy acrylate resin dissolved in styrene or (meth) acrylic acid ester or the like, thereby achieving the present invention.

That is, the composition for a fiber-reinforced resin according to claim 1 is obtained by reacting a bisphenol A type and / or bisphenol F type epoxy resin with bisphenol A and / or bisphenol F using a trialkylamine compound as a catalyst, The obtained epoxy equivalent of 400 to 1000 g
/ Equiv., Characterized by containing an epoxy acrylate (a) obtained by reacting an epoxy resin with (meth) acrylic acid and a styrene or (meth) acrylic ester copolymerizable monomer (b).

The composition for a fiber-reinforced resin according to claim 2 is
The composition for a fiber-reinforced resin according to claim 1, further comprising an organic peroxide (c), an organic cobalt compound (d), and an N, N-dialkylalinine compound (e).

The composition for a fiber-reinforced resin according to claim 3 is
The composition for a fiber-reinforced resin according to claim 1 or 2, further comprising:
It is characterized by containing 0.1 to 10 parts by weight of (meth) acrylic acid based on 100 parts by weight of the total of the epoxy acrylate (a) and the polymerizable monomer (b).

The composition for a fiber-reinforced resin according to claim 4 is
The composition for fiber reinforced resin according to any one of claims 1 to 3, further comprising a compound having at least one hydroxyl group and at least one (meth) acryloyl group in one molecule, the epoxy acrylate (a). And 1 to 10 parts by weight based on a total of 100 parts by weight of the polymerizable monomer (b).

The composition for a fiber-reinforced resin according to claim 5 is
The composition for a fiber-reinforced resin according to any one of claims 1 to 4, further comprising a polyamide-based organic thixotropic agent.

The fiber reinforced resin according to the sixth aspect is the first aspect.
A fiber-reinforced resin comprising the composition for a fiber-reinforced resin according to any one of Items 1 to 5, and a reinforcing fiber.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION In the present specification, (meth) acrylic acid means acrylic acid, methacrylic acid or a mixture thereof, and (meth) acrylic ester means acrylic ester, methacrylic ester or a mixture thereof. Means a mixture of

The composition for a fiber-reinforced resin of the present invention is obtained by using a bisphenol A type and / or bisphenol F type epoxy resin and bisphenol A and / or bisphenol F as a catalyst with a trialkylamine compound (having 1 to 3 carbon atoms) as a catalyst. And the obtained epoxy equivalent of 400 to 10
It contains an epoxy acrylate (a) obtained by reacting 00g / equiv. Of an epoxy resin with (meth) acrylic acid and a styrene or (meth) acrylic ester copolymerizable monomer (b).

The epoxy acrylate (a) used in the composition for a fiber-reinforced resin of the present invention may be, for example, an epoxy equivalent having an epoxy equivalent of 160 or more having two or more epoxy groups in one molecule.
~ 200 g / equiv. Of bisphenol A and / or bisphenol F type epoxy resin and bisphenol A and / or bisphenol F in the presence of a trialkylamine catalyst (1 to 3 carbon atoms) at 140 to 170 ° C for 0.5
React for ~ 2.0 hours, epoxy equivalent 400 ~ 100
0 g / equiv. Of epoxy resin was synthesized, and the obtained epoxy resin was mixed with (meth) acrylic acid at 100 to 140 ° C. for 1 to 10 by using a known polymerization inhibitor or a known esterification catalyst.
It can be prepared by reacting for hours. The above-mentioned reaction between the epoxy resin and the (meth) acrylic acid can be carried out by introducing nitrogen gas or air or the like. If necessary, styrene or (meth) acrylic ester polymerizable monomer may be used for the purpose of reducing the viscosity of the reaction system. The reaction can be carried out by adding a monomer or an organic solvent.

The bisphenol A type and / or bisphenol F type epoxy resin used in the present invention can be obtained from the reaction of bisphenol A and / or bisphenol F with epichlorohydrin. Alternatively, the epoxy resin having an epoxy equivalent in the range of 160 to 200 g / equiv. Can be used.

Examples of such an epoxy resin include Epicoat 825, 827, 828 and the like manufactured by Yuka Shell Co., Ltd.
Epicron 840, a product name of Dainippon Ink and Chemicals, Inc.
, 850 etc., Araldite 250, 260 manufactured by Asahi Ciba Co., Ltd.
Bisphenol A type epoxy compounds synthesized from the reaction of epichlorohydrin with bisphenol A,
Yuko Shell Co., Ltd. product name Epicoat 806, 807 etc. or Dainippon Ink & Chemicals, Inc. product name Epicron 83
And bisphenol F type epoxy compounds synthesized from the reaction of epichlorohydrin such as 830S and bisphenol F, etc., and these can be used alone or as a blend of two or more.

As the bisphenol A and / or bisphenol F, bisphenol A obtained from the reaction of phenol with acetone and bisphenol F obtained from the reaction of phenol with formaldehyde can be used. Although the compound exists in a form, it is possible to use a pure substance or a mixture of the respective isomers.

The reaction of the above bisphenol A type and / or bisphenol F type epoxy resin with bisphenol A and / or bisphenol F is carried out in the presence of a trialkylamine with an epoxy equivalent of 160 to 200 g / equiv. Bisphenol A and / or bisphenol F are compounded in the range of 20.0 to 53.8 parts by weight with respect to 100.0 parts by weight of the epoxy resin of the type, and reacted at 140 to 170 ° C. to obtain the desired epoxy equivalent of 400 to 170 ° C. 1000 g / equiv. Of epoxy resin can be prepared. At this time, it is preferable to replace the inside of the kettle with nitrogen or air.

The trialkylamine used in the present invention is
It has an action as a catalyst for reacting bisphenol A and / or bisphenol F type epoxy resin with bisphenol A and / or bisphenol F. When this catalyst is used, an epoxy resin having a wide molecular weight distribution can be obtained. The trialkylamine used in the present invention includes one having 1 carbon atom.
~ 3, trimethylamine, triethylamine, tripropylamine and the like can be used. When the number of carbon atoms is more than 3, the boiling point becomes high, and the trialkylamine remains in the system at the completion of the reaction, which is not preferable because it may gel. In particular, it is preferable to use trimethylamine and triethylamine which are easily available industrially and have a low boiling point. These trialkylamines can be used alone or in combination of two or more.

In order to synthesize an epoxy resin having a desired epoxy equivalent, the amount of the above trialkylamine compound to be added is a combination of bisphenol A and / or bisphenol F type epoxy resin and bisphenol A and / or bisphenol F. For 100 parts by weight,
Used in the range of 0.01 to 2 parts by weight. If the amount is less than 0.01 part by weight, the effect as a catalyst is low, and if it is more than 2.0 parts by weight, it remains in the system, gelling or a compound having a molecular weight larger than the intended molecular weight is not preferable.

Further, when triphenylphosphine, lithium hydroxide, sodium hydroxide, or the like is used as a catalyst, the molecular weight distribution of the obtained epoxy resin becomes narrower than when a trialkylamine is used, and the intended machine is used. Properties such as adhesion to reinforcing fibers such as carbon fibers, impact resistance, and surface dryness cannot be obtained.

The epoxy resin obtained from the above reaction of bisphenol A type and / or F type epoxy resin with bisphenol A and / or bisphenol F has an epoxy equivalent in the range of 400 to 1000 g / equiv. It has excellent adhesiveness, excellent impact resistance and excellent surface dryness. If the epoxy equivalent is less than 400 / equiv., The impact resistance and the adhesion to reinforcing fibers such as carbon fibers tend to be low, while the epoxy equivalent is 1000 g / equiv.
If the value exceeds v., the viscosity at the time of synthesis is high, gelation occurs at the time of synthesis, the viscosity of the obtained resin is high, and the impregnating property to the fiber reinforcing material tends to be poor, which is not preferable.

The reaction between the epoxy resin thus obtained and (meth) acrylic acid can be carried out using a known esterification catalyst. Known esterification catalysts include triphenylphosphine, tertiary amine having a tertiary nitrogen in the molecule, alkyl-substituted imidazole, N, N-dialkylaniline, 2,4,6-tris (dimethylaminomethyl) phenol, Dimethylaminoethyl methacrylate and the like can be mentioned, and these can be used alone or as a mixture of two or more. Particularly preferred among these esterification catalysts are:
N, N-dimethylaniline, 2,4,6-tris (dimethylaminomethyl) phenol and the like.

The addition amount of these esterification catalysts is
An epoxy resin having an epoxy equivalent of 400 to 1000 g / equiv. And (meth) acrylic acid in a range of 0.01 to 10 parts by weight, preferably 0.1 to 10 parts by weight, based on 100 parts by weight.
It can be used in the range of 0.5 to 5 parts by weight. 0.0
If the amount is less than 1 part by weight, the esterification reaction becomes extremely slow. If the amount exceeds 10 parts by weight, the esterification reaction becomes extremely fast.

The (meth) acrylic acid is used in an amount of 1 to 1 equivalent of the epoxy group in the epoxy resin.
1.1 It can be used in a range of chemical equivalents. If the (meth) acrylic acid is less than 1 chemical equivalent, the storage stability after the synthesis becomes poor, while if it exceeds 1.1 chemical equivalent, the odor of the acid is so strong that it is difficult to work, which is not preferable.

The above reaction between the epoxy resin and the (meth) acrylic acid is performed in order to stably synthesize without gelling.
Known polymerization inhibitors can be used. Examples of the polymerization inhibitor include hydroquinones, monomethyl ether hydroquinone, hydroquinones such as toluhydroquinone,
Examples thereof include phenols such as 2,6-tert-butyl 4-methylphenol, phenothiazine, and copper salts.
The addition amount is a combination of an epoxy resin having an epoxy equivalent of 400 to 1000 g / equiv. And (meth) acrylic acid.
It can be used in the range of 0.0001 to 1 part by weight, preferably 0.001 to 0.5 part by weight, based on 00 parts by weight. If it is less than 0.0001 part by weight, it gels at the time of synthesis, and if it exceeds 1 part by weight, curing of the obtained resin becomes extremely slow, which is not practical. Also,
These polymerization inhibitors can be added to adjust the gelation time of the resin composition.

The epoxy acrylate (a) thus prepared is used by dissolving it in a copolymerizable polymerizable monomer (b) selected from styrene or (meth) acrylic ester. Styrene or (meth) which can be used in the present invention
Examples of the polymerizable monomer (b) selected from acrylic esters include styrene, an aromatic vinyl compound such as vinyltoluene, or methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, (Meta)
Alkyl (meth) acrylates such as butyl acrylate and isobutyl (meth) acrylate, or bifunctional or polyfunctional such as ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, and trimethylolpropane tri (meth) acrylate Functional (meth) acrylates and the like can be mentioned, and these can be used alone or in combination of two or more. In particular, methyl styrene methacrylate is preferred because it is effective in handling, cost, and reducing the viscosity of the resin.

In addition, in order to reinforce the inside of a concrete building, such a polymerizable monomer is liable to volatilize, so that it is necessary to take measures against odor. For this reason, it is necessary to reduce the content of styrene and methyl methacrylate. , Pt-butylstyrene, cyclohexyl methacrylate, benzyl methacrylate, lauryl methacrylate, phenoxyethyl acrylate, methoxyethyl methacrylate, ethoxyethyl methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, 1,3 butanediol Dimethacrylate, 1,4-butanediol dimethacrylate, tripropylene glycol di (meth) acrylate, acrylic morpholine, Nn-butoxymethylacrylamide, butyl methacrylate, isobutyl methacrylate, ethylene glycol Methacrylate, diethylene glycol di (meth) acrylate, and the like, or a mixture of relatively low odors, or using these (meth) acrylates instead of styrene or methyl methacrylate to form the above polymerizable monomer ( b).

The polymerizable monomer (b) selected from styrene or (meth) acrylic ester can be used in an amount of 50 to 350 parts by weight based on 100 parts by weight of the epoxy acrylate (a). Particularly, in consideration of the impregnating property to the fiber reinforcing material, the handling property, and the mechanical properties, 80 to 30
It is preferable to use it in the range of 0 parts by weight. If the amount is less than 50 parts by weight, the viscosity of the obtained resin is high, handling at low temperature is poor, and impregnating property to carbon fibers is reduced, which causes a reduction in strength as a composite material. If the amount exceeds 350 parts by weight, the characteristics of the epoxy acrylate (a) are lost, the adhesiveness to carbon fibers is reduced, and the curability is also undesirably reduced.

Preferably, in the present invention, a compound having one or more hydroxyl groups and one or more (meth) acryloyl groups in one molecule can be further added. A compound having one or more hydroxyl groups and one or more (meth) acryloyl groups in one molecule has a function of increasing the curing rate and a function of improving the surface curability. In particular, the effect is remarkable at a low temperature of 10 ° C. or less, and is effective for accelerating the curing at a low temperature. Although the reaction mechanism of the compound is not clear, it is presumed that the compound forms a complex with an organic peroxide, a cobalt salt of an organic acid, a tertiary amine, or the like.

As a compound having one or more hydroxyl groups and one or more (meth) acryloyl groups in one molecule, use is made of 2-hydroxylethyl (meth) acrylate, 2-hydroxylpropyl (meth) acrylate or the like. These can be used alone or in combination of two or more.

The addition amount of the compound having one or more hydroxyl groups and one or more (meth) acryloyl groups in one molecule may be epoxy acrylate (a) and styrene or (meth) acrylic ester polymerizable monomer. (B) and a total of 10
1 to 10 parts by weight, preferably 1 to 5 parts by weight, based on 0 parts by weight
It can be added in the range of parts by weight. When the addition amount of the compound having one or more hydroxyl groups and one or more (meth) acryloyl groups in one molecule is less than 1 part by weight, it has no effect on low-temperature curing and surface drying, and 10 parts by weight is not effective. If it exceeds, the curing time is too fast due to the acceleration effect, and the working time cannot be secured.

Preferably, in the present invention, (meth)
Acrylic acid (f) can be added. Such (meth) acrylic acid is effective for increasing the adhesion to the reinforcing fiber and increasing the wrap strength. The addition amount is 0.1 to 10 parts by weight, preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the total of the epoxy acrylate (a) and the styrene or (meth) acrylic ester polymerizable monomer (b). ~ 5
It can be added in the range of parts by weight. When the amount of (meth) acrylic acid is less than 0.1 part by weight, no significant improvement effect is obtained. When the amount exceeds 10 parts by weight, adhesion to reinforcing fibers is improved, but irritation to skin and the like is increased. It is not preferable because the workability is reduced.

The organic peroxide (c) used in the present invention is
In the presence of metal salts and amine compounds at room temperature, they form redox with them and generate radicals. This radical is composed of epoxy acrylate (a) and styrene or (meth)
It reacts with a terminal double bond of a copolymerizable monomer (b) such as an acrylate ester, and has an effect that a crosslinking reaction proceeds.
Examples of the organic peroxide include ketone peroxides such as methyl ethyl ketone peroxide and acetoacetate peroxide, hydroperoxides such as cumene hydroperoxide, and bis- (4-t-butylcyclohexyl) peroxy. Peroxycarbonates such as carbonate, 1,1-di-t-butylperoxy 3,3,5 trimethylcyclohexanone, 1,1-di-
Peroxy ketals such as t-butyl peroxycyclohexanone, diacyl peroxides such as t-butyl veroxy-2-ethylhexanoate and benzoyl peroxide, t-butyl veroxy benzoate, t-butyl Peroxyesters such as butylperoxy-2-ethylhexanoate can be used. Organic peroxides commercially available as epoxy acrylate resin-specific curing agents can also be used. Examples of such epoxy acrylate resin-specific curing agents include Nippon Oil & Fats Co., Ltd. product names Percure K and Percure VL. , Percure V
S, 328E and 328EM manufactured by Kazo Akzo Co., Ltd., and the like. Among these, benzoyl peroxide and a curing agent dedicated to epoxy acrylate resin are effective in curing the resin of the present invention. These can be used alone or in combination of two or more.

The amount of the organic peroxide (c) used is 0.1 parts by weight based on 100 parts by weight of the total of the epoxy acrylate (a) and the styrene or (meth) acrylic ester polymerizable monomer (b). It can be used in the range of up to 5 parts by weight. If the amount is less than 0.1 part by weight, the curing is extremely slow, which is not practical. If the amount exceeds 10 parts by weight, the mechanical properties, water resistance and heat resistance of the cured product are undesirably reduced.

The organic cobalt compound (d) used in the present invention forms redox with the organic peroxide (c),
It has a function of helping the organic peroxide to decompose at room temperature to generate radicals and a function of improving the drying property of the coating film surface, and examples thereof include cobalt naphthenate and cobalt octenoate. The amount of the organic cobalt compound (d) used in the present invention is 0.1 to 0.1 parts by weight of the total of the epoxy acrylate (a) and the styrene or (meth) acrylic ester polymerizable monomer (b). ~
It can be used in the range of 5 parts by weight. If the amount is less than 0.1 part by weight, the surface hardening becomes slow, which is not practical. If the amount exceeds 5 parts by weight, the pot life becomes short, which is not preferable.

The N, N-dialkylaniline (e) used in the present invention forms a redox with the organic peroxide (c), and helps to decompose the organic peroxide at room temperature to generate radicals. Has an action, for example, N, N-dimethylalkylaniline, N, N-diethylaniline, N, N
-Diethanolaniline, N, N-dimethyl-p-toluidine, N, N-dihydroxyethyl-p-toluidine and the like. The amount of the N, N-dialkylaniline (e) used in the present invention is based on 100 parts by weight of the total of the epoxy acrylate (a) and the styrene or (meth) acrylic ester polymerizable monomer (b). 0.
It can be used in the range of 001 to 5 parts by weight. 0.
If the amount is less than 001 parts by weight, the curing is extremely slow, which is not practical. If the amount exceeds 5 parts by weight, the curing is abruptly performed, and heat generation causes deformation and warpage, which is not preferable.

Particularly effective combinations for curing the composition for a fiber-reinforced resin of the present invention include a combination of benzoyl peroxide, N, N-dimethylaniline and a cobalt salt of an organic acid, or an epoxy acrylate-only combination. There is a combination of a curing agent, N, N-dimethylaniline and a cobalt salt of an organic acid, which are easy to set the curing time, have good curability, dryness, and have good mechanical properties of the obtained cured product. It is preferable because of its existence.

In the composition for a fiber-reinforced resin of the present invention, a polyamide organic thixotropic agent can be used for the purpose of preventing resin dripping. For the purpose of preventing resin dripping, silica is generally used.Since silica is dispersed in the resin, silica is impregnated with a reinforcing fiber such as carbon fiber. It causes a filter effect and prevents the resin from impregnating between the monofilaments. For this reason, it becomes a cause of lowering the adhesiveness between the reinforcing fiber and the resin, which is not preferable.

Examples of the polyamide organic thixotropic agent that can be used in the present invention include DISPARON # 6900-10S (trade name, manufactured by Kusumoto Kasei Co., Ltd.). The polyamide organic thixotropic agent is added in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total of the epoxy acrylate (a) and the styrene or (meth) acrylic ester polymerizable monomer (b). Can be. If the amount is less than 1 part by weight, there is no sufficient effect to prevent sagging. If the amount is more than 10 parts by weight, the cost is increased and the chemical resistance of the impregnated resin is undesirably reduced.

Further, the fiber reinforced resin composition of the present invention may contain a releasing agent, a pigment, an antifoaming agent and the like, if necessary.

As the reinforcing fibers used in the fiber-reinforced resin of the present invention, carbon fibers, glass fibers, and aramid fibers can be used.
Chopped strand or matte,
Alternatively, a roving cloth or a roving cloth knitted with a roving can be used. Further, a hybrid type fiber reinforced material combining carbon fiber, glass fiber and aramid fiber can also be used. These reinforcing fibers can be used alone or in combination of two or more.

The fiber reinforced resin of the present invention is obtained by dissolving epoxy acrylate (a) in styrene or (meth) acrylic ester polymerizable monomer (b), and adding an organic peroxide (c) and an organic cobalt compound (d). , An N, N-dialkylaniline compound (e), and if necessary, (meth) acrylic acid, a compound having at least one hydroxyl group and at least one (meth) acryloyl group in one molecule, It is obtained by molding and curing in the range of -20 to 60 ° C using the composition for a reinforced resin obtained by blending a polyamide-based organic thixotropic agent and the above-mentioned reinforcing fiber.

The method for molding the composition for a fiber-reinforced resin of the present invention includes a hand lay-up molding method, a spray-up molding method, a casting method, a filament winding molding method, a resin transfer molding method, a bag molding method, and a drawing molding. , A preform matched die molding method, a cold press method and the like.

[0054]

The present invention will be described below with reference to the following examples and comparative examples. Synthesis Example 1 91.5 bisphenol A was placed in a four-neck flask equipped with a stirrer, thermometer, cooling tower, and gas inlet tube.
g bisphenol A type epoxy compound having an epoxy equivalent of 188, manufactured by Asahi Ciba Co., Ltd., trade name Araldite #
260 296 g and triethylamine 0.78 g were charged, and the temperature was raised to 140 ° C. while paying attention to heat generation.
The reaction was carried out at 160 ° C. for about 1 hour to obtain an epoxy compound having an epoxy equivalent of 500. Subsequently, the internal temperature was cooled to 100 ° C. or lower, and toluhydroquinone 0.19 as a polymerization inhibitor was used.
g, 73.7 g of methacrylic acid, and 1.35 g of 2,4,6-tris (dimethylaminomethyl) phenol as an esterification catalyst.
For 2.5 hours to obtain an epoxy arylate having an acid value of 6. 450 g of this epoxy acrylate is mixed with styrene 3
This was dissolved in 68 g to obtain an epoxy acrylate resin (A-1).

Synthesis Example 2 Bisphenol F is placed in a four-necked flask equipped with a stirrer, thermometer, cooling tower and gas inlet tube.
Was added, 381 g of a bisphenol F type epoxy compound having an epoxy equivalent of 174 manufactured by Dainippon Ink and Chemicals, Inc., 381 g of trade name Ebicron 830S, and 0.50 g of triethylamine were added, and the temperature was raised to 140 ° C. while paying attention to heat generation. The reaction was carried out at about 160 ° C. for about 1 hour to obtain an epoxy compound having an epoxy equivalent of 450. Subsequently, the internal temperature was cooled to 100 ° C. or lower, and 0.23 g of toluhydroquinone, 72 g of methacrylic acid, 2,4,6
-Tris (dimethylaminomethyl) phenol 1.21
g) and reacted at 120 ° C. for 2.5 hours with vigorous stirring to obtain an epoxy acrylate having an acid value of 9. 500 g of this epoxy acrylate and 200 g of styrene,
It was dissolved in 209 g of methyl methacrylate to obtain an epoxy acrylate resin (A-2).

Synthesis Example 3 Bisphenol A in a four-necked flask equipped with a stirrer, thermometer, cooling tower and gas inlet tube
153 g of epoxy equivalent <18 as epoxy equivalent manufactured by Asahi Ciba Co., Ltd.
8, bisphenol A type epoxy compound, trade name Araldite # 260 347 g, trimethylamine 0.82
g, and heated to 140 ° C while paying attention to heat generation,
Reaction was carried out at 150-160 ° C for about 1 hour, and epoxy equivalent 1
000 epoxy compounds were obtained. Subsequently, the internal temperature was set to 100
After cooling to 0.1 ° C. or lower, 0.19 g of toluhydroquinone, 43 g of methacrylic acid, and 1.9 g of 2-methylimidazole were charged as polymerization inhibitors, and 120 g of the mixture was stirred with vigorous stirring.
The reaction was performed at 2.5 ° C. for 2.5 hours to obtain an epoxy acrylate having an acid value of 5. 450 g of this epoxy acrylate was dissolved in 275 g of styrene and 275 g of methyl methacrylate to obtain an epoxy acrylate resin (A-3).

Synthesis Example 4 Bisphenol A in a four-necked flask equipped with a stirrer, thermometer, cooling tower and gas inlet tube
100 g, epoxy equivalent 18 manufactured by Asahi Chiba Co., Ltd.
8 bisphenol A type epoxy compound, trade name Araldite # 260 400 g and triethylamine 0.78 g were charged, and the temperature was raised to 140 ° C. while paying attention to the heat generation.
The reaction was carried out at 160 ° C. for about 1 hour to obtain an epoxy compound having an epoxy equivalent of 400. Subsequently, the internal temperature was cooled to 100 ° C. or lower, and toluhydroquinone 0.19 as a polymerization inhibitor was used.
g, 107.5 g of methacrylic acid, and 1.35 g of 2,4,6-tris (dimethylaminomethyl) phenol as an esterification catalyst <120 ° C. with vigorous stirring.
For 2.5 hours to obtain an epoxy acrylate having an acid value of 8. 450 g of this epoxy acrylate was dissolved in 368 g of styrene to obtain an epoxy acrylate resin (A-4).

Synthesis Example 5 Bisphenol A in a four-necked flask equipped with a stirrer, thermometer, cooling tower and gas inlet tube
91.5g, and an epoxy equivalent of 1 manufactured by Asahi Ciba Co., Ltd.
No. 88 bisphenol A type epoxy compound, trade name Araldite # 260 296 g, triphenylphosphine 0.40
g while paying attention to heat generation in a nitrogen gas stream.
Temperature to 150-160 ° C for about 1 hour,
An epoxy compound having an epoxy equivalent of 500 was obtained. continue,
Replace the system with air, cool the internal temperature to 100 ° C or less,
0.19 g of hydroquinone as a polymerization inhibitor, 73.7 g of methacrylic acid, and 1.35 g of 2,4,6-tris (dimethylaminomethyl) phenol as an esterification catalyst were reacted at 120 ° C. for 2.5 hours with vigorous stirring. Thus, an epoxy acrylate having an acid value of 6 was obtained. 450 g of this epoxy acrylate was dissolved in 368 g of styrene to obtain an epoxy acrylate resin (A-5).

Synthesis Example 6 Bisphenol A in a four-necked flask equipped with a stirrer, thermometer, cooling tower and gas inlet tube
And 153 g of an epoxy equivalent of 18 from Asahi Chiba Co., Ltd.
8 bisphenol A type epoxy compound, 347 g of Araldite # 260 trade name and 0.8 g of triphenylphosphine were charged, and the temperature was raised to 140 ° C. in a nitrogen stream while paying attention to heat generation, followed by reaction at 150 to 160 ° C. for about 1 hour. Thus, an epoxy compound having an epoxy equivalent of 1,000 was obtained. Subsequently, the inside of the system was replaced with air, the internal temperature was cooled to 100 ° C. or lower, and 0.19 g of toluhydroquinone, 43 g of methacrylic acid, and 1.9 g of 2-methylimidazole were charged as polymerization inhibitors.
Reaction at 120 ° C. for 2.5 hours with vigorous stirring,
An epoxy acrylate having an acid value of 4 was obtained. 450 g of this epoxy acrylate was dissolved in 275 g of styrene and 275 g of methyl methacrylate, and an epoxy acrylate resin (A
-6) was obtained.

Synthesis Example 7 Bisphenol A in a four-necked flask equipped with a stirrer, thermometer, cooling tower and gas inlet tube
165 g, and an epoxy equivalent of 18 manufactured by Asahi Ciba Co., Ltd.
Bisphenol A type epoxy compound No. 8, 355 g of Araldite # 260 (trade name) and 0.82 g of triethylamine were charged, and the temperature was raised to 140 ° C. while paying attention to heat generation in a nitrogen stream, and reacted at 150 to 160 ° C. for about 1 hour. An epoxy compound having an equivalent weight of 1500 was obtained. Subsequently, the inside of the system was replaced with air, the internal temperature was cooled to 100 ° C. or lower, and 0.19 g of toluhydroquinone, 28.7 g of methacrylic acid, and 1.9 g of 2-methylimidazole were charged as polymerization inhibitors and vigorously stirred. While the reaction was carried out at 120 ° C., the resin had a high viscosity and gelled during the reaction. Since the viscosity at the time of synthesis was high, 226 g of styrene was added during the methacrylic acid reaction, and the reaction was carried out until the target acid value of 3 was reached while introducing air from the gas pipe, but the gel was formed in the middle.

Synthesis Example 8 A four-necked flask equipped with a stirrer, a thermometer, a cooling tower, a gas inlet tube, and a dropping funnel is charged with 300 g of methylene diisocyanate (MDI), 0.03 g of dibutyltin dilaurate as a urethanization catalyst, and 0.28 g of monomethyl ether hydroquinone. While blowing dry air, 314 g of 2-hydroxypropyl methacrylate and 15 parts of dipropylene glycol were added to the dropping funnel.
g was added dropwise over about 0.75 hours while paying attention to heat generation. Reaction at 70 ° C for about 2 hours.
The reaction is continued until the absorption due to -NCO at 2270 cm ^-1 disappears. After reacting for about 1.5 hours, the mixture was cooled to obtain urethane acrylate. This urethane acrylate 6
200 g of styrene, 200 g of methyl methacrylate
g) to obtain a urethane acrylate resin (A-8).

Synthesis Example 9 Bisphenol A in a four-necked flask equipped with a stirrer, thermometer, cooling tower and gas inlet tube
97.5 g, and an epoxy equivalent of 1 manufactured by Asahi Ciba Co., Ltd.
Bisphenol A type epoxy compound of No. 88, trade name Araldite # 260 460.0 g, triethylamine 0.5
6 g was charged, the temperature was raised to 140 ° C. while paying attention to heat generation, and the mixture was reacted at 150 to 160 ° C. for about 1 hour to obtain an epoxy compound having an epoxy equivalent of 350. Then, the internal temperature was set to 10
After cooling to 0 ° C. or lower, 0.14 g of toluhydroquinone as a polymerization inhibitor, 142.5 g of methacrylic acid,
6-tris (dimethylaminomethyl) phenol 1.4
0 g, 2.5 g at 120 ° C. with vigorous stirring.
The reaction was carried out for an hour to obtain an epoxy acrylate having an acid value of 10. 500 g of this epoxy acrylate is added to styrene 23
The resultant was dissolved in 3 g to obtain an epoxy acrylate resin (A-9).

Examples 1 to 10 and Comparative Examples 1 to 7 For the resins (A-1 to 9) synthesized in Synthesis Examples 1 to 9, compositions for fiber reinforced resins were prepared according to the formulations shown in Tables 1 and 2. CFRP (Fiber Reinforced Plastic) Using Carbon Fibers, Liquid Properties, Casting Board Retention of the Composition for Fiber Reinforced Resin Obtained
Composite characteristics were measured by the following methods. The results are shown in Tables 1 and 2.

(1) Liquid Properties Liquid compositions such as molecular weight distribution, curability and viscosity were measured for the compositions for fiber reinforced resin prepared in the above Examples and Comparative Examples. Viscosity and whisking degree Each composition for fiber reinforced resin was placed in a 450 ml mayonnaise bottle and placed in a bottle.
Weigh 100 g, immerse it in a thermostatic bath containing water adjusted to the temperature to be measured (25 ° C.) for 30 minutes or more, and confirm with a thermometer that the temperature of the composition for fiber-reinforced resin has reached the measurement temperature. And a B-type rotational viscometer. The measuring method is JI
It was based on SK6901. The degree of thixation is 60 at 25 ° C.
The T value at the rotation and the T 'value at the six rotations are obtained, and the degree of fluctuation = T'
/ T. However, the viscosity and thixotropic degree were measured without adding an organic peroxide.

Curability In accordance with JIS K6901, the curing characteristics of each fiber reinforced resin composition were measured. The measurement was performed at 5, 10, 25 ° C.

Molecular weight distribution Using a GPC detector manufactured by Waters (elution solvent: tetrahydrofuran, flow rate: 1 ml / min), the number average molecular weight (Mn) and the weight average molecular weight (Mw) were determined from the calibration curve of polystyrene by the refractive index. ) Was measured.

[0067] Place the PET film on the desk of the impregnation property plane, placing the three unidirectional carbon fiber 20cm width of the 300 g / m ² thereon, then carbon 2 of impregnating resin 400 g / m ² The fiber was hung on the fiber and impregnated with a defoaming roller. After curing, the PET film was peeled off, and it was visually confirmed whether the impregnated resin had penetrated to the bottom. Evaluation ：: The entire carbon fiber is impregnated. ×: Not partially impregnated.

The sagging property The impregnated resin (400 g / m ² ) obtained by dispersing a thixotropic agent in one unidirectional carbon fiber (300 g / m ² ) was impregnated into a vertical concrete by a defoaming roller. The degree of sagging was visually evaluated. Evaluation ：: The resin does not sag until the impregnated resin is cured. ×: Dripping until the impregnated resin is cured. Surface dryness Measured according to JIS K5400 dry-to-touch operation. Evaluation ：: No stickiness even when strongly rubbed with finger pad. ：: No stickiness even when lightly rubbed with a finger. Δ: Lightly touched with finger, finger is not stained. X: Lightly touched with a finger and sticky.

(2) Properties of Casting Plate With respect to 100 parts by weight of the fiber reinforced resin compositions prepared in the above Examples and Comparative Examples, Nippon Oil & Fats Co., Ltd. was used as a curing catalyst.
1 part by weight of "Percure K" or 2 parts by weight of 40% benzoyl peroxide was mixed and stirred, poured into a flat 3 mm thick tempered glass cell to which cellophane for release was attached, and cured at room temperature for 16 hours. At 120 ° C. for 2 hours to produce respective casting plates. The impact resistance and tensile properties of this cast plate were measured.

Impact resistance The cast product was processed into a size of 65 mm x 12.7 mm x 3 mm and JIS K6901
The breaking strength was measured with an Izod impact strength measuring device according to the standard. Measured without notch, edgewise. The obtained energy was divided by the cross-sectional area of the test piece to obtain the impact strength.

Tensile Properties and Elongation A test piece was cut out from the cast product in accordance with JIS K7113, and the tensile properties were measured.

(3) CFRP properties Tensile properties A unidirectional carbon fiber of 300 g / m ² was impregnated with a composition for a fiber-reinforced resin in which a curing catalyst and an accelerator were blended.
After curing at 7 ° C. for 7 days, a test piece having a width of 12.5 mm and a length of 200 mm was cut out and examined for tensile properties in the 0 ° direction. The tensile strength was calculated as a value obtained by dividing the stress obtained in the tensile measurement by the cross-sectional area.

Lap strength Two pieces of unidirectional carbon fiber having a width of 300 g / m ^{2 and} a width of 20 cm were overlapped with each other by 10 cm in the fiber direction, and laminated with each composition for fiber reinforced resin. After lamination, leave to cure at 23 ° C for 7 days, width 12.5mm x 20
The sheet was cut to 0 mm, and the strength of the overlap portion was measured by a tensile test. The lap strength was calculated as a value obtained by dividing the stress obtained by the tensile measurement by the cross-sectional area. At this time, in addition to the lap strength, the destruction state was also evaluated. In the destruction state, cohesive failure of the base material or the lap portion is good adhesiveness. Evaluation base material destruction: Destruction of base material (good adhesion between impregnated resin and carbon fiber) Base material / aggregation: Destruction or cohesion failure of base material (good adhesion between impregnated resin and carbon fiber) : The destruction state is peeling at the wrap portion (poor adhesion between the impregnated resin and carbon fiber)

[0074]

[Table 1]

[0075]

[Table 2]

[0076]

The composition for fiber-reinforced resin and the fiber-reinforced resin of the present invention have lower curing properties, impregnation properties and fiber-reinforced materials than commercially available epoxy compounds or epoxy acrylate resins synthesized by conventional methods. Excellent adhesion, excellent impact resistance, surface dryness and heat resistance.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification FI FI Theme Court ゛ (Reference) // B29K 25:00 33:00 63:00 C08L 63:10 F-term (Reference) 4F072 AB06 AB09 AB10 AD33 AD34 AD44 AE01 AE02 AF17 AF27 AH21 AK03 AL17 4F205 AA13 AA21 AA39 AA43 AD04 AE10 AH33 AH35 AH47 HA19 HA42 HB01 HC02 HC04 HC14 HC16 HC17 HF01 4J011 PA03 PA15 PA36 PA88 PA96 PB04 PB30 CA04 AJ04 CB04 FB13 GA29 JA13

Claims (6)

[Claims] 1. A bisphenol A-type and / or bisphenol F-type epoxy resin is reacted with bisphenol A and / or bisphenol F using a trialkylamine compound as a catalyst.
Epoxy acrylate (a) obtained by reacting 1000 g / equiv. Of epoxy resin with (meth) acrylic acid
And a composition for a fiber-reinforced resin comprising styrene or a (meth) acrylic ester copolymerizable monomer (b). 2. The fiber-reinforced resin composition according to claim 1, further comprising an organic peroxide (c), an organic cobalt compound (d), and an N, N-dialkylaniline compound (e). object. 3. The composition according to claim 1, further comprising 0.1 to 10 parts by weight of (meth) acrylic acid based on 100 parts by weight of the total of the epoxy acrylate (a) and the polymerizable monomer (b). The composition for a fiber-reinforced resin according to claim 1 or 2, wherein 4. The method according to claim 1, wherein one or more hydroxyl groups are contained in one molecule.
A compound having at least one (meth) acryloyl group in an amount of 1 to 10 parts by weight based on 100 parts by weight of the total of the epoxy acrylate (a) and the polymerizable monomer (b). Item 4. The composition for a fiber-reinforced resin according to any one of Items 1 to 3. 5. The composition for a fiber-reinforced resin according to claim 1, further comprising a polyamide-based thixotropic agent. 6. A fiber reinforced resin comprising the composition for a fiber reinforced resin according to claim 1 and reinforcing fibers.