TW201811855A - Composition for carbon fiber reinforced resin, carbon fiber reinforced resin composition, and hardened material - Google Patents

Abstract

A composition for a carbon fiber reinforced resin of the present application includes (A) a radical reactive resin, (B) a radical polymerizable unsaturated monomer, (C) a mercapto group containing compound, (D) an imidazole compound containing only one imidazole ring, and (E) an organic peroxide. The composition for the carbon fiber reinforced resin may further include (G) a metallic soap.

Description

   Carbon fiber reinforced resin composition, carbon fiber reinforced resin composition, hardened material   

The present invention relates to a carbon fiber-reinforced resin composition, a carbon fiber-reinforced resin composition containing the same, and a cured product thereof, which can be efficiently cured at low temperature and in a short time, and which can obtain a hardened product having good adhesion between the resin component and the carbon fiber.

This application is based on Japanese Patent Application No. 2016-101352, filed in Japan on May 20, 2016, and claims priority to this content.

Conventionally, it has been known that a carbon fiber-reinforced resin composition includes an epoxy resin and a carbon fiber having good adhesion to carbon fibers. However, a carbon fiber-reinforced resin composition using an epoxy resin must be heated at a high temperature for a long time for heating.

The carbon fiber-reinforced resin composition includes a vinyl ester resin that can be cured at a low temperature for a short time. However, a carbon fiber-reinforced resin composition using a conventional vinyl ester resin may have insufficient adhesion between the resin component of the hardened material and the carbon fiber, and thus may not sufficiently obtain the interlayer shear strength of the hardened material.

Further, as the carbon fiber-reinforced resin composition, the compositions described in Patent Literature 1 and Patent Literature 2 have been proposed.

Patent Document 1 describes a curable resin composition containing a resin having an epoxy group and a radical polymerizable unsaturated group, and a hexaarylbiimidazole compound.

Further, Patent Document 2 describes a composition including an epoxy acrylate resin, a hexaaryl biimidazole compound, a mercapto compound, and a fiber-reinforced material.

[Prior technical literature]

[Patent Literature]

[Patent Document 1] JP 2005-281610

[Patent Document 2] Japanese Unexamined Patent Publication No. 9-278903

However, in the conventional carbon fiber-reinforced resin composition that can be hardened at a low temperature for a short time, the adhesion between the resin component and the carbon fiber in the hardened material is insufficient. Therefore, the carbon fiber-reinforced resin composition can be cured at low temperature and in a short time, and a hardened product having good adhesion between the resin component and the carbon fiber can be obtained.

The present invention has been made in view of the above circumstances, and the present invention provides a carbon fiber used as a resin component for a carbon fiber-reinforced resin composition that can be cured at low temperature and in a short time, and can obtain a hardened material having good adhesion between the resin component and the carbon fiber. The subject of reinforcing the resin composition is a problem.

Moreover, this invention makes it a subject to provide the carbon fiber reinforced resin composition containing the said composition for carbon fiber reinforced resins.

Moreover, this invention makes it a subject to provide the hardened | cured material of the said carbon fiber reinforced resin composition.

In order to solve the above-mentioned problems, the present inventors have carefully examined and provided a composition for a carbon fiber reinforced resin that can be hardened at a low temperature for a short time. As a result, it was found that (D) has a compound having (A) a radically reactive resin and (B) a radically polymerizable unsaturated monomer by using (C) a mercapto group-containing compound as a hardening accelerator, When an imidazole compound having only one imidazole ring and (E) an organic peroxide are used as a hardener, a very high hardening promoting function can be obtained.

In addition, the present inventors have found that the cured product of the carbon fiber-reinforced resin composition containing the composition (A) to (E) and the carbon fiber has good adhesion between the resin component and the carbon fiber, and completed the present invention.

That is, the present invention relates to the following matters.

[1] A composition for a carbon fiber reinforced resin, comprising (A) a radically reactive resin, (B) a radically polymerizable unsaturated monomer, (C) a mercapto group-containing compound, and (D) having only one An imidazole compound of the imidazole ring and (E) an organic peroxide.

[2] The composition for a carbon fiber-reinforced resin according to [1], further containing (G) a metal soap.

[3] The composition for a carbon fiber reinforced resin according to [1] or [2], wherein the compound (C) containing a mercapto group contains two or more mercapto groups in the molecule.

[4] The composition for a carbon fiber-reinforced resin according to any one of [1] to [3], wherein the mercapto group in the compound (C) containing a mercapto group is a second-order or a third-order.

[5] The composition for a carbon fiber-reinforced resin according to any one of [1] to [4], wherein the (D) imidazole compound contains one or two positions of the two positions of the imidazole ring via an alkyl group or an aromatic group. Radical or aralkyl.

[6] The carbon fiber-reinforced resin composition according to any one of [1] to [5], wherein the (D) imidazole compound is 2-ethyl-4-methylimidazole, 1-benzyl-2-methyl Any of imidazole and 2-methylimidazole.

[7] The composition for a carbon fiber-reinforced resin according to any one of [1] to [6], wherein the (A) radically reactive resin is selected from the group consisting of epoxy (meth) acrylate resin and unsaturated polymer At least one type of ester resin, polyester (meth) acrylate resin, and urethane (meth) acrylate resin.

[8] The composition for a carbon fiber-reinforced resin according to any one of [1] to [7], wherein the epoxy group (methyl) having at least one epoxy group in the (A) radically reactive resin described above The content of the acrylate resin is 1 to 100% by mass.

[9] The composition for a carbon fiber reinforced resin according to any one of [1] to [8], wherein the 10-hour half-life temperature of the organic peroxide (E) is 30 to 170 ° C.

[10] The composition for a carbon fiber reinforced resin according to any one of [1] to [9], wherein the organic peroxide (E) is cumene hydroperoxide or third butyl peroxybenzoate.

[11] The composition for a carbon fiber reinforced resin according to any one of [2] to [10], wherein the metal soap (G) is a manganese compound or a cobalt compound.

[12] The composition for a carbon fiber-reinforced resin according to any one of [1] to [11], wherein the total amount of the radically reactive resin (A) and the radically polymerizable unsaturated monomer (B) The amount of (A) the radically reactive resin contains 20 to 99% by mass, and (B) the radically polymerizable unsaturated monomer contains 1 to 80% by mass. ) A total of 100 parts by mass of the radically polymerizable unsaturated monomer. The (C) mercapto group-containing compound contains 0.001 to 20 parts by mass, the (D) imidazole compound having only one imidazole ring contains 0.001 to 10 parts by mass, (E) The organic peroxide contains 0.1 to 10 parts by mass.

[13] A carbon fiber-reinforced resin composition comprising the carbon fiber-reinforced resin composition according to any one of [1] to [12], and (F) a carbon fiber.

[14] The carbon fiber-reinforced resin composition according to [13], wherein the content of the (F) carbon fiber is 10 to 90% by mass relative to the carbon fiber-reinforced resin composition.

[15] The carbon fiber-reinforced resin composition according to [13] or [14], wherein the carbon fiber-reinforced resin composition according to any one of [1] to [12] is impregnated into the carbon fiber (F).

[16] A hardened product of a carbon fiber-reinforced resin composition according to any one of [13] to [15].

The carbon fiber-reinforced resin composition containing the composition for a carbon fiber-reinforced resin of the present invention can be efficiently cured at low temperature and in a short time. Therefore, the carbon fiber-reinforced resin composition of the present invention can be molded using a molding method that requires a high production cycle.

When the carbon fiber-reinforced resin composition according to the present invention is hardened, a hardened product having good adhesion between the resin component and the carbon fiber can be obtained.

FIG. 1 is a view showing a state in which a mandrel (roving) -shaped carbon fiber bundle is wound.

Hereinafter, the carbon fiber-reinforced resin composition of the present invention (hereinafter sometimes referred to as a "resin composition") and the cured product will be described in detail.

(Carbon fiber reinforced resin composition)

The resin composition of this embodiment includes a composition for a carbon fiber reinforced resin and carbon fibers. In the resin composition of this embodiment, the carbon fiber-reinforced resin composition is preferably impregnated with (F) carbon fibers.

A carbon fiber-reinforced resin composition comprising (A) a radically reactive resin, (B) a radically polymerizable unsaturated monomer, (C) a mercapto group-containing compound, (D) an imidazole compound having only one imidazole ring, and (E) Organic peroxide.

<(A) radical reactive resin>

(A) A radically reactive resin is a resin having an ethylenic carbon-carbon double bond in a side chain and / or a main chain. Specifically, it is selected from (A1) epoxy (meth) acrylate resin, (A2) unsaturated polyester resin, (A3) polyester (meth) acrylate resin, (A4) urethane At least one type of (meth) acrylate resin is preferred.

Here, "(meth) acrylate" means at least 1 sort (s) chosen from a methacrylate and an acrylate.

(A1) An epoxy (meth) acrylate resin is a carbon-carbon double bond having a radical reactivity in a side chain in which all or a part of epoxy groups contained in an epoxy compound is reacted with an unsaturated monoacid. . A representative example of the aforementioned unsaturated monobasic acid is (meth) acrylic acid, so it is called an epoxy (meth) acrylate resin.

As the epoxy compound, all monomers, oligomers, and polymers having two or more epoxy groups in one molecule can be used, and the molecular weight and molecular structure are not particularly limited. Examples include biphenyl epoxy resin; bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, tetrabromobisphenol A epoxy resin, and tetramethylbisphenol F. Epoxy resins such as bisphenol epoxy resins; fluorene epoxy resins; phenol novolac epoxy resins, cresol novolac epoxy resins and other novolac epoxy resins; trisphenol methane Polyfunctional epoxy resins such as epoxy resins, alkyl modified triphenol methane epoxy resins; phenol aralkyl epoxy resins with phenylene skeleton, phenol aralkyls with biphenylene skeleton Phenol aralkyl-type epoxy resins such as epoxy resins; naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by dipropylene naphthalene dimerization; Triglycidyl tripolyisocyanate, monoallyl diglycidyl polyisocyanate, and other epoxy resins containing a triazine core; alicyclic diepoxy acetal, alicyclic diepoxy adipate Alicyclic polyepoxides such as esters, alicyclic diepoxy carboxylates, vinyl cyclohexene dioxide, etc .; bicyclic Bridged cyclic hydrocarbon compounds such as diene modified phenol type epoxy resins and phenol type epoxy resins; epoxy propyl ester type epoxy resins obtained by reacting polybasic acids such as dimer acids with epichlorohydrin Resin; epoxy resin containing an oxazolidone ring obtained by reacting the aforementioned epoxy resin with a diisocyanate.

Known unsaturated monobasic acids can be used. Examples include (meth) acrylic acid, crotonic acid, and cinnamic acid. Among these, (meth) acrylic acid is preferred.

In addition, as the unsaturated monobasic acid, a compound having one hydroxyl group and one or more (meth) acrylfluorenyl groups, and a reactant of a polybasic acid anhydride may be used.

As the polybasic acid anhydride, a known material for increasing the molecular weight of the epoxy resin can be used. Examples thereof include succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, and dicarboxylic acid. Polyacid, ethylene glycol. 2 Mol maleic anhydride adduct, polyethylene glycol. 2 Mol maleic anhydride adduct, propylene glycol. 2 Mol maleic anhydride adduct, polypropylene glycol. 2Mole maleic anhydride adduct, dodecanedioic acid, tridecanedicarboxylic acid, octadecanoic acid, 1,16- (6-ethylhexadecane) dicarboxylic acid, 1,12- ( 6-ethyldodecane) dicarboxylic acid, terminal carboxybutadiene. Acid anhydrides such as acrylonitrile copolymer (trade name Hycar CTBN).

Among the above (A1) epoxy (meth) acrylate resins, bisphenol A type epoxy (meth) acrylate resins are preferred from the viewpoints of imparting toughness, versatility, and cost.

Among the above, the (A) radically reactive resin is particularly preferably an epoxy (meth) acrylate resin having at least one epoxy group. (A) The content of the epoxy (meth) acrylate resin having at least one epoxy group in the radically reactive resin is preferably 1 to 100% by mass, and more preferably 20 to 90% by mass. It is more preferably 30 to 70% by mass. The epoxy (meth) acrylate resin having at least one epoxy group is preferably one having an epoxy equivalent of 140 to 9,500, and more preferably 190 to 5000.

Since an epoxy (meth) acrylate resin having at least one epoxy group has a radical polymerizable unsaturated group, it can be cured at a low temperature for a short time. In addition, since an epoxy (meth) acrylate resin having at least one epoxy group has an epoxy group, it has excellent adhesion to carbon fibers. Therefore, when (A) the radically reactive resin is an epoxy (meth) acrylate resin having at least one epoxy group, it becomes a carbon fiber reinforced resin that has faster curing properties and excellent adhesion to carbon fibers. Using composition.

(A2) Unsaturated polyester resin means an unsaturated dibasic acid and, if necessary, a dibasic acid component containing a saturated dibasic acid and a polyhydric alcohol by esterification reaction.

Examples of the unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, and itaconic anhydride. These may be used alone or in combination of two or more.

Examples of the saturated dibasic acid include aliphatic dibasic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and isosebacic acid, phthalic acid, phthalic anhydride, and halogenated orthophthalic acid. Phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, tetrachlorophthalic anhydride, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid Acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4,4'-biphenyl dicarboxylic acid, or dialkyl esters thereof, aromatic dibasic acids, halogenated saturated dicarboxylic acids, etc. These acids can be used alone or in combination of two or more kinds.

The aforementioned polyol is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, and 1, 5-pentanediol, 1,6-hexanediol, neopentyl glycol, 2-methyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2,2-dimethyl -1,3-propanediol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 3-methyl-1,5- Pentylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 1,4-cyclohexane Binaries of alkanedimethanol, p-xylene glycol, bicyclohexyl-4,4'-diol, 2,6-decahydronaphthalene glycol, 2,7-decahydronaphthalene glycol, etc. Alcohols; dihydric phenols represented by hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc., and propylene oxide or ethylene oxide Diols such as alkylene oxide adducts; 1,2,3,4-tetrahydroxybutane, glycerol, trimethylolpropane, neopentyl tetraol and the like.

(A2) The unsaturated polyester resin can be modified by a bridged cyclic hydrocarbon compound such as dicyclopentadiene within a range that does not impair the effects of the present invention. Examples of the modification method include, for example, obtaining an addition product of dicyclopentadiene and maleic acid (cyclodecanol monomaleate), using this as a monobasic acid, reacting with the unsaturated polyester, and introducing Cyclopentadiene skeleton and other known methods.

Among the above-mentioned (A2) unsaturated polyester resins, from the viewpoint of versatility and cost, an ortho unsaturated polyester resin is preferred.

In the (A1) epoxy (meth) acrylate resin and / or (A2) unsaturated polyester resin used in the present invention, an oxidative polymerization (air-hardening) group such as an allyl group or a benzyl group can be introduced. The method for introducing the oxidative polymerization group is not particularly limited, and examples thereof include a method in which a (A2) unsaturated polyester resin is subjected to a condensation reaction with a compound having both a hydroxyl group and an allyl ether group.

The (A1) epoxy (meth) acrylate resin and / or (A2) unsaturated polyester resin used in the present invention may be used in combination with a polymer containing an oxidative polymerization group.

Further, a reactant obtained by reacting a compound having both a hydroxyl group and an allyl ether group with an acid anhydride and a compound having an epoxy group is mixed with the (A1) epoxy group (methyl) used in the present invention. Acrylic resin and / or (A2) unsaturated polyester resin. Examples of the compound having an epoxy group include allyl glycidyl ether and 2,6-diglycidyl phenyl allyl ether.

When an oxidative polymerization group is introduced, when it is used as a composition for a carbon fiber reinforced resin, it has the effects of greatly improving the drying property and making the coating film and the molding surface uniform. The oxidative polymerization (air hardening) group is particularly preferably one having an allyl ether group or a benzyl ether group.

The oxidative polymerization (air hardening) of the present invention refers to a methylene bond between an ether bond and a double bond, such as an allyl ether group, which is oxidized to generate a peroxide and cross-linking accompanying decomposition.

Examples of the monomer forming the polymer containing an oxidative polymerization group include unsaturated compounds having an allyl ether group or a benzyl ether group. Specific examples include allyl methacrylate, vinyl benzyl butyl ether, vinyl benzyl hexyl ether, vinyl benzyl octyl ether, vinyl benzyl- (2-ethylhexyl) ether, and vinyl Benzyl (β-methoxymethyl) ether, vinyl benzyl (n-butoxypropyl) ether, vinyl benzyl cyclohexyl ether, vinyl benzyl- (β-phenoxyethyl) Ether, vinyl benzyl dicyclopentenyl ether, vinyl benzyl dicyclopentenyl ether, vinyl benzyl dicyclopentenyl methyl ether, divinyl benzyl ether, and the like.

Further, in addition to the above, by using a dicyclopentenyl (meth) acrylate, a dicyclopentenyloxyethyl (meth) acrylate, or the like, the drying property of the composition for a carbon fiber reinforced resin can be improved.

(A3) The polyester (meth) acrylate resin is a polyester having a (meth) acrylic acid group. (A3) A polyester (meth) acrylate resin can be obtained by the method of (1) or (2) shown below, for example.

(1) A polyester having a carboxyl terminal is reacted with a (meth) acrylate containing an epoxy group or a (meth) acrylate containing a hydroxyl group.

(2) A polyester having a hydroxyl group at its terminal is allowed to react with (meth) acrylic acid or (meth) acrylate containing an isocyanate group.

In the method (1), the polyester having a carboxyl terminal used as a raw material includes those obtained from an excessive amount of a saturated polybasic acid and / or an unsaturated polybasic acid and a polyol.

In the method (2), the polyester whose terminal end is a hydroxy group used as a raw material includes those obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and an excessive amount of a polyhydric alcohol.

Examples of the saturated polybasic acid used as a raw material of the (A3) polyester (meth) acrylate resin include phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, and adipic acid. Polybasic acids or anhydrides thereof having no polymerizable unsaturated bond, such as sebacic acid or the like.

Examples of the unsaturated polybasic acid used as a raw material of the polyester (meth) acrylate resin include polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid, and econic acid, or anhydrides thereof.

Examples of the polyol component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, and 1,6-hexane. Diethylene glycol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adducts of bisphenol A , Propylene oxide adduct of bisphenol A, etc.

(A3) An epoxy group-containing (meth) acrylate used for producing a polyester (meth) acrylate resin includes an epoxy propyl (meth) acrylate.

(A3) Hydroxyl-containing (meth) acrylates used in the production of polyester (meth) acrylate resins include 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate Ester, 4-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloxy-2-hydroxypropylbenzene Formate and so on.

(A3) The isocyanate group-containing (meth) acrylate used in the production of polyester (meth) acrylate resins includes 2-isocyanate ethyl (meth) acrylate.

Among the above-mentioned (A3) polyester (meth) acrylate resins, from the viewpoint of general versatility or cost, it is preferable to use epoxypropyl (meth) acrylate or 2-isocyanatoethyl (methyl (Meth) acrylate (meth) acrylate resin.

(A4) A urethane (meth) acrylate resin refers to a polyurethane having a (meth) acrylic acid group. Specific examples include reacting a polyisocyanate with a polyhydroxy compound or a polyol, and then reacting an unreacted isocyanate group with a (meth) acrylic compound containing a hydroxyl group and, if necessary, an allyl ether compound containing a hydroxyl group. The obtained radical polymerizable unsaturated group contains an oligomer.

Examples of the polyisocyanate that can be used as a raw material for the (A4) urethane (meth) acrylate resin include 2,4-methylphenyl diisocyanate and its isomers, and diphenylmethane diisocyanate. , Hexamethylene diisocyanate, hydrogenated xylylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Burnock D -750, Crisvon NK (trade name; manufactured by Dainippon Ink Chemical Industry Co., Ltd.) Desmodur L (trade name; manufactured by Sumitomo Bayer), coronate L (trade name; manufactured by Nippon Polyurethane), Takenate D102 (trade name; Takeda Pharmaceuticals) Company), Isoneto 143L (trade name; manufactured by Mitsubishi Chemical Corporation), duranate series (trade name; Asahi Kasei Chemical Co., Ltd.), and the like.

These polyisocyanates can be used singly or in combination of two or more kinds. Among these polyisocyanates, diphenylmethane diisocyanate is preferably used from the viewpoint of cost.

Examples of the polyhydroxy compound that can be used as a raw material for the (A4) urethane (meth) acrylate resin include polyester polyols, polyether polyols, and polycarbonate polyols. More specifically, glycerol-ethylene oxide adduct, glycerol-propylene oxide adduct, glycerol-tetrahydrofuran adduct, glycerol-ethylene oxide-epoxy Propane adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-cyclo Ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethylene oxide-epoxy Propane adducts and so on.

These polyhydroxy compounds can be used singly or in combination of two or more kinds.

Polyols that can be used as a raw material for the (A4) urethane (meth) acrylate resin include, for example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, Dipropylene glycol, polypropylene glycol, 2-methyl-1,3 propylene glycol, 1,3-butanediol, adduct of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-butane Tetraol, glycerol, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, p-benzene Dimethanol, dicyclohexyl-4,4-diol, 2,6-decahydronaphthalene glycol, 2,7-decahydronaphthalene glycol, and the like.

These polyols can be used alone or in combination of two or more.

The (meth) acrylic compound containing a hydroxyl group, which can be used as a raw material for the (A4) urethane (meth) acrylate resin, is preferably a (meth) acrylate containing a hydroxyl group.

Specific examples include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (methyl Base) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, ginsyl (hydroxyethyl) isotricyanate di (meth) acrylate, pentaerythritol tris (methyl) Base) acrylate, glycerol (mono) (meth) acrylate, Bren Mar series (trade name; manufactured by Nippon Oil Corporation), and the like.

These hydroxy (meth) acrylic compounds may be used alone or in combination of two or more.

As a raw material of the (A4) urethane (meth) acrylate resin, a hydroxyl-containing allyl ether compound can be used if necessary, and specific examples thereof include ethylene glycol monoallyl ether and diethyl ether. Glycol monoallyl ether, triethylene glycol monoallyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether Ether, 1,2-butanediol monoallyl ether, 1,3-butanediol monoallyl ether, hexanediol monoallyl ether, octanediol monoallyl ether, trimethylolpropane diallyl Ether, glycerin diallyl ether, pentaerythritol triallyl ether, and the like.

These allyl ether compounds containing a hydroxyl group may be used alone or in combination of two or more.

The content of the (A) radically reactive resin is preferably 20 to 99% by mass, more preferably 50 to the total amount of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer. ~ 90% by mass, and more preferably 60 ~ 80% by mass.

The composition for a carbon fiber-reinforced resin of the present invention may contain a resin component other than the radically reactive resin (A). Preferable examples include (A5) (meth) acrylate resin.

(A5) The (meth) acrylate resin includes, for example, a (meth) acrylate monomer that is separately polymerized or copolymerized.

Examples of the (meth) acrylate monomer used as a raw material of the (A5) (meth) acrylate resin include meth (meth) acrylate, ethyl (meth) acrylate, and propyl (methyl) Acrylate), n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (methyl Acrylate), heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, n-nonyl (Meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth) acrylate, octadecane (Meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, dicyclopentenyl (meth) acrylate, 2-dicyclopentenyloxyethyl (methyl Base) acrylate, isoamyl (meth) acrylate, methoxyethyl (meth) acrylate, ethoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, 2-hydroxy Ethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, (meth) acrylic acid, (meth) acrylfluorenyl morpholine, etc. .

These (meth) acrylate monomers may be used singly or in combination of two or more kinds.

(A5) The (meth) acrylate resin is preferably a homopolymer of meth (meth) acrylate and mainly a meth (meth) acrylate from the viewpoint of the cost or reactivity of the polymer. Copolymer of ingredients.

(A) The radically reactive resin is selected from (A1) epoxy (meth) acrylate resin, (A2) unsaturated polyester resin, (A3) polyester (meth) acrylate resin, ( A4) The catalyst and / or polymerization inhibitor used in the synthesis of at least one or more urethane (meth) acrylate resins may remain.

Examples of the catalyst include compounds containing tertiary nitrogen atoms such as triethylamine, pyridine derivatives, imidazole derivatives, and imidazole derivatives; amine salts such as tetramethylammonium chloride and triethylamine; and trimethylphosphine, triethylamine Phosphine compounds such as phenylphosphine.

Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, and phenothiazine.

(A) When the radically reactive resin contains a catalyst and / or a polymerization inhibitor, the content is based on (A1) epoxy (meth) acrylate resin, (A2) unsaturated polyester resin, (A3) The total of 100 parts by mass of the polyester (meth) acrylate resin and (A4) the urethane (meth) acrylate resin is preferably 0.001 to 2 parts by mass.

<(B) radical polymerizable unsaturated monomer>

In order to reduce the viscosity of the resin composition and improve hardness, strength, chemical resistance, water resistance, etc., (B) a radically polymerizable unsaturated monomer can be used.

The (B) radically polymerizable unsaturated monomer is not particularly limited, and preferably has a vinyl group or a (meth) acrylfluorenyl group. In addition, in the present specification, "(meth) acrylfluorenyl" means acrylfluorenyl and / or methacrylfluorenyl.

The (B) radical polymerizable unsaturated monomer having a vinyl group includes, for example, styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t -Butylstyrene, vinyl acetate, diallyl phthalate, triallyl isotricyanate, and the like.

Examples of the (B) radical polymerizable unsaturated monomer having a (meth) acrylfluorenyl group include a (meth) acrylate.

Examples of the (meth) acrylate include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (methyl) (Lauryl) lauryl acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyloxyethyl (Meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (Meth) acrylate, ethylene glycol monohexyl ether (meth) acrylate, ethylene glycol mono 2-ethylhexyl ether (meth) acrylate, diethylene glycol monomethyl ether (meth) acrylate , Diethylene glycol monoethyl ether (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, polytetraethylene Methylene ether glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate (Meth) acrylate, 2-hydroxy-1,3-di (meth) acrylic acid Propane, 2,2-bis [4- (methacrylfluorenylethoxy) phenyl] propane, 2,2-bis [4- (methacrylfluorenyloxy.diethoxy) phenyl] propane , 2,2-bis [4- (methacryl fluorenyloxy. Polyethoxy) phenyl] propane, tetraethylene glycol di (meth) acrylate, bisphenol AEO modified (n = 2), (Meth) acrylate, isotricyanic acid EO modified (n = 3) di (meth) acrylate, trimethylolpropane di (meth) acrylate, glycerol di (meth) acrylic acid Ester, trimethylolpropane tri (meth) acrylate, glycerol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, pentaerythritol di (methyl) ) Acrylate monostearate, dicyclopentenyl (meth) acrylate, tricyclodecyl (meth) acrylate, tricyclodecyl (meth) acrylate or ginseng (2-hydroxyethyl) ) Isotricyanic acid (meth) acrylate and the like.

The EO modification refers to those having a (poly) oxyethylene chain (-CH ₂ -CH ₂ -O-), and n represents the number of (poly) oxyethylene chains.

These (B) radical polymerizable unsaturated monomers can be used alone or in combination of two or more kinds.

Among the (B) radically polymerizable unsaturated monomers, styrene is preferably used from the viewpoints of workability, hardenability, and cost.

The content of (B) the radically polymerizable unsaturated monomer is preferably 1 to 80% by mass relative to the total amount of the (A) radically reactive resin and (B) the radically polymerizable unsaturated monomer. It is preferably 10 to 50% by mass, and even more preferably 20 to 40% by mass.

<(C) Mercapto-containing compound>

(C) The mercapto group-containing compound functions as a hardening accelerator.

(C) A mercapto group-containing compound is preferably selected from the group consisting of a secondary thiol compound (C1) having a thiol group bonded to a secondary carbon atom, or a tertiary thiol compound (C2) having a tertiary carbon atom. More than that. (C) The mercapto group-containing compound is particularly preferably a secondary thiol compound (C1) in order to harden in a shorter time.

The secondary thiol compound (C1) has better storage stability than the primary thiol compound in which a mercapto group is disposed at the terminal. The tertiary thiol compound (C2) is the same as the secondary thiol compound (C1), and a compound having no mercapto group disposed at the terminal. Therefore, the tertiary thiol compound (C2) is a thiol group-containing compound (C) and has a function similar to that of the secondary thiol compound (C1).

(C) Since the compound containing a mercapto group has an excellent function as a hardening accelerator, it is preferable to use a polyfunctional thiol containing two or more mercapto groups in the molecule.

The "polyfunctional thiol" as used herein refers to a compound containing two or more mercapto groups.

In order to harden the carbon fiber-reinforced resin composition in a shorter time, (C) a compound containing a mercapto group is particularly preferably a trifunctional or higher thiol having three or more mercapto groups in the molecule.

(C) A compound containing a mercapto group is a polyfunctional thiol having two or more thiol groups bonded to a secondary or tertiary carbon atom in order to harden the composition for a carbon fiber reinforced resin in a shorter time. .

The compound having two or more thiol groups bonded to a secondary or tertiary carbon atom in the molecule is not particularly limited. For example, the compound has at least one structure represented by the following formula (Q), and includes the following formula (Q) The thiol group in the structure is preferably a compound having two or more thiol groups bonded to a secondary or tertiary carbon atom in the molecule.

(In the formula (Q), R ¹ is any of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aromatic group having 6 to 18 carbon atoms. R ² is an alkyl group having 1 to 10 carbon atoms Group, or an aromatic group having 6 to 18 carbon atoms. * Indicates a bond to an arbitrary organic group. A is an integer of 0 to 2.)

(C) A compound containing a mercapto group, especially a compound having a structure represented by the formula (Q), wherein R ¹ in the formula (Q) is a hydrogen atom, the compound having two or more sulfhydryl groups bonded to a secondary carbon atom is more good. That is, the compound having a mercapto group (C) has a structure represented by the formula (Q), and a secondary thiol compound (C1) having a carbon atom bonded to a mercapto group in the formula (Q) as a secondary carbon atom is preferred.

Moreover, the alkyl group having 1 to 10 carbon atoms in R ¹ and R ² in formula (Q) may be linear or branched. Specific examples include methyl, ethyl, various propyl, various butyl, various pentyl, various hexyl, various heptyl, and various octyl groups.

The "various" means various isomers including n-, sec-, tert-, and iso-. Among these alkyl groups, methyl and ethyl are preferred.

Examples of the aromatic group having 6 to 18 carbon atoms in R ¹ and R ² in formula (Q) include phenyl, benzyl, naphthyl, anthracenyl, and phenanthryl. In addition, these aromatic groups may be substituted with a halogen atom, an amine group, a nitro group, a cyano group, or the like.

A in the formula (Q) is an integer of 0 to 2, and is preferably 1.

The (C) mercapto group-containing compound preferably has at least one ester structure represented by the following formula (Q-1).

(In formula (Q-1), R ¹ , R ² , *, and a are synonymous with R ¹ , R ² , *, and a in the aforementioned formula (Q).)

A in formula (Q-1) is preferably 1. The case where a is 1 is preferable from the viewpoint of stability of the resin composition or control of hardenability. In particular, when R ¹ is a hydrogen atom (the compound represented by (Q-1) is a secondary thiol compound (C1)), from the viewpoint of stability of the resin composition or control of hardening properties, in formula (Q-1) A is preferably 1.

The ester structure represented by the formula (Q-1) is preferably derived from a mercapto group-containing carboxylic acid and a polyol represented by the following formula (S).

(In the formula (S), R ¹ , R ² and a are synonymous with R ¹ , R ² and a in the aforementioned formula (Q).)

Examples of the polyol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, and 1,2-propylene glycol. , 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4 -Pentanediol, 1,5-pentanediol, 1,6-hexanediol, 1,9-nonanediol, tricyclodecanedimethanol, (2,2-bis (2-hydroxyethoxybenzene) Group) propane), bisphenol A alkylene oxide adduct, bisphenol F alkylene oxide adduct, bisphenol S alkylene oxide adduct, 1,4-cyclohexanediol, 1, 4-cyclohexanedimethanol, 1,2-hexanediol, 1,3-hexanediol, 2,3-hexanediol, 1,4-hexanediol, 2,4-hexanediol, 3, 4-hexanediol, 1,5-hexanediol, 2,5-hexanediol, 1,6-hexanediol, 9,9-bis [4- (2-hydroxyethyl) phenyl] fluorene, etc. Glycols; glycerol, diglycerol, trimethylolethane, trimethylolpropane, bis (trimethylol) propane, ginseng (2-hydroxyethyl) trimer isocyanate, hexane Triol, sorbitol, pentaerythritol, dipentaerythritol, sucrose, 2,2-bis (2,3-dihydroxypropoxyphenyl) propene Alcohols such as alkanes, etc .; others include polycarbonate diols, dimer acid polyester polyols, and the like.

Among these, glycols such as ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, and 1,4-butanediol are preferable from the viewpoint of easiness of acquisition and the viewpoint of improvement of hardenability. ; Glycerol, trimethylolethane, trimethylolpropane, ginseng (2-hydroxyethyl) trimer isocyanate, pentaerythritol, dipentaerythritol, 2,2-bis (2,3-dihydroxypropoxy) Trivalent or higher alcohols such as phenyl) propane; polycarbonate diols, dimer acid polyester polyols. In particular, from the standpoint of good reactivity or workability under low vapor pressure, 1,4-butanediol, trimethylolethane, trimethylolpropane, and ginseng (2-hydroxyethyl) triamine are preferred. Polyisocyanate, pentaerythritol, polycarbonate diol, dimer acid polyester polyol.

[Secondary thiol compound (C1)]

(C) In the case where the compound containing a mercapto group is a secondary thiol compound (C1) having a structure represented by the aforementioned formula (Q), specific examples include 3-mercaptobutyric acid and 3-mercaptophthalate di ( 1-mercaptoethyl), bis (2-mercaptopropyl) phthalate, bis (3-mercaptobutyl) phthalate, ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3 -Mercaptobutyrate), diethylene glycol bis (3-mercaptobutyrate), butanediol bis (3-mercaptobutyrate), octanediol bis (3-mercaptobutyrate), trimethylol Ethyl ethane (3-mercaptobutyrate), trimethylolpropane (3-mercaptobutyrate), pentaerythritol (3-mercaptobutyrate), dipentaerythritol hexa (3-mercaptobutyrate) , Ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercaptopropionate), diethylene glycol bis (2-mercaptopropionate), butanediol bis (2-mercaptopropionate) ), Octanediol bis (2-mercaptopropionate), trimethylolpropane ginseng (2-mercaptopropionate), pentaerythritol (2-mercaptopropionate), dipentaerythritol hexa (2-mercaptopropionate) Ester), ethylene glycol bis (4-mercaptovalerate), diethylene glycol bis (4-mercaptovalerate), butanediol bis (4-mercaptovalerate) ), Octanediol bis (4-mercaptovalerate), trimethylolpropane (4-mercaptovalerate), pentaerythritol (4-mercaptovalerate), dipentaerythritol hexa (4-mercaptovalerate) Ester), ethylene glycol bis (3-mercaptovalerate), propylene glycol bis (3-mercaptovalerate), diethylene glycol bis (3-mercaptovalerate), butanediol bis (3-mercaptopentanoate) Acid ester), octanediol bis (3-mercaptovalerate), trimethylolpropane (3-mercaptovalerate), pentaerythritol (3-mercaptovalerate), dipentaerythritol hexa (3-mercapto) Valerate), hydrogenated bisphenol A bis (3-mercaptobutyrate), bisphenol A dihydroxyether-3-mercaptobutyrate, 4,4 '-(9-fluorenylidene) bis ( 2-phenoxyethyl (3-mercaptobutyrate)), ethylene glycol bis (3-mercapto-3-phenylpropionate), propylene glycol bis (3-mercapto-3-phenylpropionate) , Diethylene glycol bis (3-mercapto-3-phenylpropionate), butanediol bis (3-mercapto-3-phenylpropionate), octanediol bis (3-mercapto-3-benzene Propionate), trimethylolpropane ginseng (3-mercapto-3-phenylpropionate), gins-2- (3-mercapto-3-phenylpropionate) ethyltrimeric isocyanate, pentaerythritol (3-mercapto-3-phenylpropionate), dipentapentyl Hexa (3-mercapto-3-phenyl propionate) and the like.

In the case where the secondary thiol compound (C1) is a compound having an ester structure represented by the aforementioned formula (Q-1), the compound is preferably derived from the aforementioned polyhydric alcohol and bonded to the group containing the compound represented by the aforementioned formula (S). Carboxylic acid of secondary carbon atom. Examples of the mercapto-containing carboxylic acid represented by the formula (S) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, and 3-mercapto-3-phenylpropionic acid.

Among the secondary thiol compounds (C1), commercially available monofunctional secondary thiols include 3-mercaptobutyric acid (manufactured by Showa Denko Corporation, product name: 3MBA). The molecule has two or more bonds. Commercial products of a mercapto compound having a secondary carbon atom include 1,4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko Corporation, Karenz MT (registered trademark) BD1), and pentaerythritol. (3-mercaptobutyrate) (manufactured by Showa Denko Corporation, Karenz MT (registered trademark) PE1), 1,3,5-ginseng (3-mercaptobutyryloxyethyl) -1,3,5- Triazine-2,4,6 (1H, 3H, 5H) -trione (manufactured by Showa Denko Corporation, Karenz MT (registered trademark) NR1), trimethylolethane (3-mercaptobutyrate) ( Showa Denko Corporation, TEMB), trimethylolpropane ginseng (3-mercaptobutyrate) (Showa Denko Corporation, TPMB), etc., it is preferable to use one or more of these.

[Tertiary thiol compound (C2)]

(C) In the case where the compound containing a mercapto group is a tertiary thiol compound (C2) having a structure represented by the aforementioned formula (Q), specific examples thereof include bis (2-mercaptoisobutyl) phthalate, and Diethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate) Acid ester), octanediol bis (2-mercaptoisobutyrate), trimethylolethane ginseng (2-mercaptoisobutyrate), trimethylolpropane ginseng (2-mercaptoisobutyrate) , Pentaerythritol (2-mercaptoisobutyrate), dipentaerythritol hexa (2-mercaptoisobutyrate), bis (3-mercapto-3-methylbutyl) phthalate, ethylene glycol bis (3 -Mercapto-3-methylbutyrate), propylene glycol bis (3-mercapto-3-methylbutyrate), diethylene glycol bis (3-mercapto-3-methylbutyrate), butanediol Bis (3-mercapto-3-methylbutanoate), octanediol bis (3-mercapto-3-methylbutanoate), trimethylolethane (3-mercapto-3-methylbutanoate) Acid ester), trimethylolpropane (3-mercapto-3-methylbutyrate), pentaerythritol (3-mercapto-3-methylbutyrate), dipentaerythritol hexa (3-mercapto-3- Methyl butyrate) and the like.

In the case where the tertiary thiol compound (C2) is a compound having an ester structure represented by the aforementioned formula (Q-1), the compound is preferably derived from the aforementioned polyol and the group containing Grade carbon atom thiol carboxylic acid. Examples of the mercapto group-containing carboxylic acid represented by the formula (S) include 2-mercaptoisobutyric acid and 3-mercapto-3-methylbutanoic acid.

(C) The mercapto group-containing compound is preferably contained in an amount of 0.001 to 20 parts by mass based on 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer. It is more preferably 0.01 to 10 parts by mass, and still more preferably 0.1 to 5 parts by mass.

<(D) imidazole compound>

The (D) imidazole compound contained in the resin composition of this embodiment has only one imidazole ring, and does not include a compound having a plurality of imidazole rings. (D) The imidazole compound functions as a hardener.

(D) Imidazole compounds include, for example, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methyl Imidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2 -Methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole , 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6 -[2'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2,4-diamino-6- [2'-undecylimidazolyl- (1')] -Ethyl-s-triazine, 2,4-diamino-6- [2'-ethyl-4'-methylimidazolyl- (1 ')]-ethyl-s-triazine, 2, 4-diamino-6- [2'-methylimidazolyl- (1 ')]-ethyl-s-triazine isotricyanic acid adduct, 2-phenylimidazole isotricyanic acid addition Product, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo- [1, 2-a] benzimidazole, 1-dodecyl-2-methyl-3-benzyl Imidazolium chloride, 2-phenyl imidazoline.

(D) The imidazole compound is different from the addition polymerization type in that it is a catalyst type. Therefore, the imidazole compound is hardened with a small amount of addition. From the viewpoint of excellent function as a hardening accelerator, it is compatible with (A) a radically reactive resin and (B). ) From the viewpoint of excellent compatibility of free radically polymerizable unsaturated monomers, it is preferred to use one or two positions of the 2-position of the 5-membered ring of the imidazole, and substitute with an alkyl group, an aryl group, or an aralkyl group. .

The aforementioned alkyl group is preferably 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. The aryl group is preferably 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. The aralkyl group is preferably 7 to 20 carbon atoms, and more preferably 7 to 12 carbon atoms.

Examples of such (D) imidazole compounds include 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 2-methylimidazole. In particular, as the (D) imidazole compound, 2-ethyl-4-methylimidazole or 1-benzyl-2-methylimidazole is preferably used.

(D) The imidazole compound is preferably contained in an amount of 0.001 to 10 parts by mass based on 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer. It is more preferably 0.01 to 5 parts by mass, and still more preferably 0.1 to 2 parts by mass.

<(E) Organic peroxide>

(E) The organic peroxide system functions as a hardener. (E) As an organic peroxide, (A) a radically reactive resin and (B) a radically polymerizable unsaturated monomer can be used as a radical hardener user. Specific examples include difluorenyl peroxides such as benzamidine peroxide, peroxide esters such as tert-butyl peroxide benzoate, hydrogen peroxide systems such as cumene hydrogen peroxide, and the like. Dialkyl oxides such as cumyl peroxide, ketone peroxides such as methyl ethyl ketone peroxide, acetone acetone peroxide, peroxy acetals, alkyl peroxy acid esters, Percarbonate and the like are known to the public.

Among the above, it is particularly preferable to use a 10-hour half-life temperature of 30 to 170 ° C, and more preferably to use a temperature of 40 ° C to 160 ° C.

Among the above, particularly from the viewpoint of stability of the resin after mixing, it is preferable to use cumene hydroperoxide or third butyl peroxybenzoate as the (E) organic peroxide. Both cumene hydroperoxide and tert-butyl peroxybenzoate have compounds (-O (oxy) -O (oxy)-) bonds that are decomposed during hardening to generate free radicals. When tert-butyl peroxybenzoate is used, it can be used for a longer period of time (pot life) than when using cumene hydrogen peroxide. When tert-butyl peroxybenzoate is used, in order to obtain a hardenability equivalent to that of cumene hydrogen peroxide, the curing temperature may be increased as compared with the case where cumene hydrogen peroxide is used.

(E) The organic peroxide is 0.1 to 10 parts by mass, preferably 0.5 to 5 parts by mass based on 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer. Parts, more preferably 0.5 to 2 parts by mass.

<(F) carbon fiber>

(F) Any of carbon fibers can be produced by various production methods. For example, pitch-based, PAN (polyacrylonitrile) -based, and vapor-phase growth-based carbon fibers can be used. (F) The shape of the carbon fiber is not particularly limited, and for example, a roving shape, a knitted fabric shape, a cloth shape, or a fiber mat shape may be used alone or in combination.

(F) The content of carbon fiber in the resin composition is preferably 10 to 90% by mass, and more preferably 30 to 80% by mass. When the content of the (F) carbon fiber is within the above range, a reinforcing effect containing the (F) carbon fiber can be sufficiently obtained.

The carbon fiber-reinforced resin composition preferably contains (F) carbon fibers so that the fiber volume content of the hardened material is preferably 40 to 70%.

<Other ingredients>

The carbon fiber-reinforced resin composition of this embodiment may contain the following components in addition to the above-mentioned components, if necessary.

<(G) Metal soap>

(G) The metal soap system functions as a hardening accelerator. (G) The metal soap is a salt of a long-chain fatty acid or an organic acid with a metal element.

The long-chain fatty acid can be appropriately selected according to the type of the metal soap to be used. The long-chain fatty acid is preferably a fatty acid having 7 to 30 carbon atoms. For example, heptanoic acid, caprylic acid, nonanoic acid, capric acid, neodecanoic acid, undecanoic acid, dodecanoic acid, myristic acid, hexadecanoic acid, ten Saturated fatty acids such as octanoic acid, behenic acid, behenic acid, docosaic acid, hexacosanoic acid, octacosanoic acid, and decanoic acid. Unsaturated fatty acids such as linoleic acid.

Further, as long-chain fatty acids, stearic acid, 1,2-hydroxystearic acid, lauric acid, myristic acid, palmitic acid, amaric acid, rosin acid, linseed oil fatty acid, soybean fatty acid, and tall oil can also be used. Acid etc.

The organic acid can be appropriately selected according to the type of the metal soap used. Organic acids are preferably soluble in organic solvents. For example, formic acid, acetic acid, citric acid, oxalic acid or benzoic acid and amino acids, carboxylic acid esters, carboxylic acid salts, carboxylic acid chlorides, dicarboxylic acids, and bile acids can be used. , Sugar acid, hydroxycinnamic acid, hydroxy acid, aromatic acid, thioester, folic acid, etc. generally have a carboxyl group and are classified as carboxylic acids.

As the organic acid, ascorbic acid, alpha acid, amidinic acid, erythorbic acid, ketoacid, osmic acid, square acid, ascorbic acid, a weakly acidic compound having a sulfo group, a hydroxyl group, a mercapto group, and an enol group as characteristic groups can be used. Sulfuric acid, sulfonic acid, Teicohoic acids, Thioacetic acid, dehydroacetic acid, delta acid, uric acid, hydroxamic acid, humic acid ), Fulvic acid, phosphonic acid, Meldrum's acid, and the like.

Among the long-chain fatty acids or organic acids, long-chain fatty acids are preferred, chain-like or cyclic saturated fatty acids having 7 to 15 carbon atoms, or unsaturated fatty acids having 7 to 15 carbon atoms, and octanoic acid, And decalin.

Examples of the metal element include vanadium, gold, silver, palladium, platinum, ruthenium, rhodium, tin, lead, zinc, iron, nickel, cobalt, lithium, aluminum, indium, neodymium, manganese, cerium, calcium, zirconium, copper, barium, Magnesium or rare earths.

Among these metal elements, metal elements of Group 2 and metal elements of Groups 3 to 12 are preferable, and barium, vanadium, manganese, iron, cobalt, copper, and zinc are more preferable, and manganese, Iron, cobalt, copper, and zinc, and more preferably manganese and cobalt.

(G) Metal soaps such as manganese decalinate, manganese octoate, cobalt decalinate, cobalt octoate, zinc octoate, vanadium octoate, copper decalinate, barium decalinate and the like can be used.

Among these metal soaps, it is preferable to use a manganese compound or a cobalt compound as the (G) metal soap, and particularly manganese decalinate, manganese octoate, cobalt decalinate, and cobalt octoate, which are highly versatile.

When (G) metal soap is contained, the content of metal component conversion of (G) metal soap is 100 parts by mass relative to the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer. It is preferably 0.0001 to 0.3 parts by mass, more preferably 0.001 to 0.2 parts by mass, and even more preferably 0.006 to 0.1 parts by mass. Since the content of the metal component conversion of the (G) metal soap is in the range of 0.0001 to 0.3 parts by mass, the carbon fiber-reinforced resin composition can be more efficiently hardened at a low temperature and in a short time, so it is preferable.

[Polymerization inhibitor]

The resin composition of this embodiment may contain a polymerization inhibitor from the viewpoint of suppressing excessive polymerization of the resin composition and controlling the reaction rate. Examples of the polymerization inhibitor include hydroquinone, methylhydroquinone, catechols, and phenothiazines.

[Hardening delay agent]

The resin composition of this embodiment may contain a hardening retarder in order to delay the hardening of the resin composition. Examples of the hardening retarder include free radical hardening retarders, and examples thereof include 2,2,6,6-tetraalkyl-1-piperidinyloxy, free radical (TEMPO), 4-hydroxy-2, 2,6,6-tetramethylpiperidine 1-oxide, free radical (4H-TEMPO), 4-lanthoxy-2,2,6,6-tetraalkyl-1-piperidyloxy, free radical (4-Oxo-TEMPO) and other TEMPO derivatives. Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxide and free radical (4H-TEMPO) are preferred from the viewpoint of cost and ease of use.

When the resin composition of the present embodiment contains a polymerization inhibitor and / or a hardening retarder as constituent components, their contents are relative to (A) a radically reactive resin and (B) a radically polymerizable unsaturated resin. The total of the monomers is 100 parts by mass, preferably 0.0001 to 10 parts by mass, respectively.

[Other hardening accelerators]

In order to improve the hardenability in the resin composition of this embodiment, in addition to the (C) mercapto group-containing compound and (D) the imidazole compound having only one imidazole ring and (E) an organic peroxide, ( G) In addition to metal soaps, other hardening accelerators may be contained.

Examples of the other hardening accelerators include phosphorus compounds such as trimethylphosphine and triphenylphosphine, and amines such as amines and amine salts. Specifically, aniline, N, N-dimethylaniline, N, N-diethylaniline, p-toluidine, N, N-dimethyl-p-toluidine, N, N-bis ( 2-hydroxyethyl) -p-toluidine, 4- (N, N-dimethylamino) benzaldehyde, 4- [N, N-bis (2-hydroxyethyl) amino] benzaldehyde, 4 -(N-methyl-N-hydroxyethylamino) benzaldehyde, N, N-bis (2-hydroxypropyl) -p-toluidine, N-ethyl-m-toluidine, triethanolamine, m -N, N-substituted anilines, N, N-substituted-anilines, such as toluidine, ethylenediamine, pyridine, phenylmorpholine, piperidine, N, N-bis (hydroxyethyl) aniline, diethanolaniline- p-toluidine, 4- (N, N-substituted amino) benzaldehyde, and other amines.

Other hardening accelerators are preferably contained in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer, and more preferably may contain 0.1 to 5 parts by mass.

[Photopolymerization initiator]

The resin composition of this embodiment may contain a photopolymerization initiator in order to improve hardenability. Examples of the photopolymerization initiator include a photoradical polymerization initiator, a photocationic polymerization initiator, and a photoanionic polymerization initiator.

In order to improve the curability of an acrylic resin or monomer having a double bond, a photoradical polymerization initiator may be used.

Specific examples of the photo-radical polymerization initiator include diphenyl ethers such as benzoin ethers of benzoin alkyl ethers, benzophenone, benzyl, methyl-o-benzoyl benzoate, and the like Methyl ketone system, benzyl dimethyl acetal, 2,2-diethoxyacetophenone, 2-hydroxy-2-methylphenylacetone, 4-isopropyl-2-hydroxy-2-methylbenzene Acetophenones such as acetone, 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, and 2-isothioxanthone.

In order to improve the curability of epoxy resins such as cyclic ethers or oxetane, a photocationic polymerization initiator can be used.

Specific examples of the photocationic polymerization initiator include triarylphosphonium hexafluorophosphate, triarylphosphonium hexafluoroantimonate, triarylphosphonium salt, tricumylphosphonium tetrakis (pentafluorophenyl) borate, and -Isobutylphenyl (4-methylphenyl) 錪. Hexafluorophosphate, triarylphosphonium hexafluorophosphate, triarylphosphonium (pentafluorophenyl) borate and the like.

Moreover, in order to improve the hardenability of an epoxy resin etc., a photoanion polymerization initiator can be used.

The photopolymerization initiator may be added in a range of 0.1 to 10 parts by mass based on 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer.

[Defoaming agent]

In the resin composition of this embodiment, an antifoaming agent can be used in order to improve the generation of air bubbles during molding and the remaining air bubbles in a molded product. Examples of the defoaming agent include a silicon-based defoamer and a polymer-based defoamer.

The amount of the defoaming agent used may be in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer. More preferably, it is 0.1 to 1 part by weight.

[Coupling agent]

In the resin composition of the present embodiment, a coupling agent may be used for the purpose of improving moldability or improving adhesion to carbon fibers. Examples of the coupling agent include a silane-based coupling agent, a titanate-based coupling agent, and an aluminum-based coupling agent.

Examples of such a coupling agent include a silane coupling agent represented by R ³ -Si (OR ⁴ ) ₃ . Examples of R ³ include aminopropyl, glycidyloxy, methacryloxy, N-phenylaminopropyl, mercapto, and vinyl. Examples of R ⁴ include methyl and ethyl. Base etc.

The amount of the coupling agent is in the range of 0.01 to 1 part by mass based on 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer.

[Light stabilizer]

In the resin composition of this embodiment, in order to improve the long-term durability of a molded product, a light stabilizer may be used. Examples of the light stabilizer include an ultraviolet absorber and a hindered amine light stabilizer. These can be used alone or in combination of two or more. Specific examples of the ultraviolet absorber include benzotriazole-based, triazine-based, benzophenone-based, cyanoacrylate-based, and salicylate-based, and hindered amine-based light stabilizers, and NH-type , N-CH3 type, NO alkyl type and so on.

The amount of the light stabilizer is relative to 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer, preferably in the range of 0.01 to 5 parts by mass, and more preferably 0.05. ~ 2 parts by mass.

[Wax]

The resin composition of this embodiment may contain wax. Waxes such as paraffin waxes, polar waxes, etc. may be used alone or in combination, and conventional materials having various melting points may be used.

The polar waxes include those having both a polar group and a non-polar group in the structure. Specific examples include NPS-8070, NPS-9125 (manufactured by Nippon Fine Wax Corporation), EMANON 3199, 3299 (manufactured by Kao Corporation), and the like.

The wax is preferably contained in an amount of 0.05 to 4 parts by mass, and more preferably 0.1 to 2.0 parts by mass with respect to 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer.

[Flame retardant]

The resin composition of this embodiment may contain a flame retardant. Flame retardants such as bromine flame retardants, chlorine flame retardants, phosphorus flame retardants, inorganic flame retardants, intumescent flame retardants, and silicon flame retardants can be used alone or in combination. , Can also use the knowledgeable person.

In addition, halogen-based flame retardants such as bromine-based flame retardants can be used in combination with antimony triacid in order to further improve flame resistance.

The amount of the flame retardant to be added varies depending on the system, but it is better to contain 1 to 100 parts by mass relative to 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer.

[Filling material]

In the resin composition of this embodiment, fillers such as inorganic fillers and organic fillers may be blended for the purpose of controlling specific characteristics within a range that does not hinder the effects of the present invention. These can be used individually or in combination of 2 or more types.

Examples of the inorganic filler include inorganic pigments such as flame retardant aluminum hydroxide, smoked silicon dioxide, talc, calcium carbonate and the like which control the fluidity of the resin composition, titanium oxide and other coloring agents which are colored.

Examples of the organic filler include organic bentonites for the purpose of improving viscosity or imparting thixotropy.

The amount of the filler is in the range of 1 to 200 parts by mass based on 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer.

(Production method of carbon fiber reinforced resin composition)

The method for producing the resin composition of this embodiment is not particularly limited, and (A) a radically reactive resin and (B) a radically polymerizable unsaturated monomer (or (A) a radical) can be mixed by a conventional method. Reactive resin and (B) a mixture of radically polymerizable unsaturated monomers) and (C) a thiol-containing compound and (D) an imidazole compound having only one imidazole ring and (E) an organic peroxide When necessary, it is obtained by containing (G) metal soap (optional component) and other components with (F) carbon fiber.

The resin composition of the present embodiment is particularly preferably produced by a method for producing a carbon fiber-reinforced resin composition by mixing the above-mentioned components not containing (F) carbon fibers, and impregnating (F) carbon fibers.

The hardened | cured material of this embodiment is a hardened | cured material of the resin composition of this embodiment.

The method of hardening the resin composition of this embodiment may be a method of heating at a temperature necessary for curing the resin composition, and for example, a method of heating using a heating furnace or a heater may be used.

The temperature for curing the resin composition may be, for example, 5 to 200 ° C, preferably 15 to 150 ° C, and more preferably 60 to 120 ° C. The heating time may be, for example, 1 to 180 minutes, preferably 1 to 120 minutes, and more preferably 1 to 60 minutes.

The resin composition of this embodiment contains (A) a radically reactive resin, (B) a radically polymerizable unsaturated monomer, (C) a mercapto group-containing compound, and (D) an imidazole having only one imidazole ring. The compound, (E) organic peroxide, and (F) carbon fiber can be effectively hardened at low temperature and in a short time. Moreover, the hardened | cured material of the resin composition of this embodiment can fully acquire the adhesiveness of a resin component and carbon fiber.

In addition, the resin composition of this embodiment can control the respective contents of (C) a mercapto group-containing compound and (D) an imidazole compound having only one imidazole ring and (E) an organic peroxide, relative to (A). ) The total amount of the radically reactive resin and (B) the radically polymerizable unsaturated monomer can adjust the hardening rate of the resin composition.

Therefore, the resin composition of this embodiment can be used in the case of using a general-purpose carbon fiber to produce a hardened product requiring a higher production cycle than an epoxy resin. Specifically, it is suitable for manufacturing molded parts (hardened products) using molding methods that require high production cycles, such as automotive components produced by Filament Winding, Resin Transfer Molding, and compression molding. situation.

    [Embodiment]    

[Example]

Hereinafter, the present invention will be described based on examples. The present invention is not limited to the examples shown below. The raw materials used in the examples and comparative examples shown below are as follows.

(Using raw materials)

<A mixture of (A) a radically reactive resin and (B) a radically polymerizable unsaturated monomer>

(A) (A1-1) (A1-2) (A2-1) (A4-1) (A4-1) radical reactive resin was synthesized by the method shown below. Each (A) of the obtained (A1-1) (A1-2) (A2-1) (A4-1) radically reactive resin and (B) a radically polymerizable unsaturated monomer of styrene (Idemitsu (Produced by Industrial Co., Ltd.) to obtain a mixture of the component (A) and the component (B).

`` Epoxy methacrylate resin (A1-1) ''

In a reaction device equipped with a stirrer, a reflux cooler, a gas introduction tube, and a thermometer, AER-2603 (bisphenol A epoxy resin manufactured by Asahi Kasei Corporation: epoxy equivalent 189): 1890 g, bisphenol A: 342 g, and Tetradecyl dimethyl benzyl ammonium chloride: 7 g, and reacted at 150 ° C. for 2 hours under a nitrogen atmosphere. After the reaction was completed, the reaction was cooled to 90 ° C. Then, methacrylic acid: 602 g, triphenylphosphine: 9 g, hydroquinone: 0.9 g, and styrene: 1000 g were added to the reaction, and the reaction was performed at 90 ° C. for another 20 hours while blowing air. When the acid value became 11 mgKOH / g, the reaction was terminated to obtain an epoxy methacrylate resin (A1-1).

The weight average molecular weight of the obtained epoxy methacrylate resin (A1-1) was measured by the method shown below. As a result, the weight average molecular weight of the epoxy methacrylate resin (A1-1) was 3395.

`` Measurement method of weight average molecular weight ''

The weight average molecular weight was measured by gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko Corporation). The weight average molecular weight is calculated under the following conditions, measured at room temperature, and converted to polystyrene.

(Measurement conditions)

Column: Showa Denko LF-804, 2

Column temperature: 40 ℃

Sample: 0.4% by mass of tetrahydrofuran solution

Flow: 1ml / min

Eluent: Tetrahydrofuran

In addition, 1857 g of styrene (manufactured by Idemitsu Kosan) was added to the epoxy methacrylate resin (A1-1) synthesized by the above method to obtain a viscosity of 0.8 Pa at 25 ° C. s. A mixture having a solid content of 50% by mass.

"Epoxy methacrylate resin with epoxy group (A1-2)"

AER-2603 (Bisphenol A epoxy resin manufactured by Asahi Kasei Corporation: epoxy equivalent 189): 1890 g, methacrylic acid: 430 g, hydrogen Quinone: 0.5 g, 1.2 g of triphenylphosphine, and heated to 100 ° C. while blowing air, and allowed to react for about 9 hours. When the acid value became 0 mgKOH / g, the reaction was terminated to obtain an epoxy methacrylate resin (A1-2) having at least one epoxy group.

The weight average molecular weight of the epoxy methacrylate resin (A1-2) having at least one epoxy group was measured in the same manner as the epoxy methacrylate resin (A1-1). As a result, the weight average molecular weight of the epoxy methacrylate resin (A1-2) having at least one epoxy group was 619.

To the epoxy methacrylate resin (A1-2) having at least one epoxy group synthesized by the above method, 580 g of styrene (manufactured by Idemitsu Kosan Co., Ltd.) was added to obtain a mixture.

"Unsaturated polyester resin (A2-1)"

In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux cooler, put isophthalic acid: 0.8 mol, 1,2-propylene glycol: 1.0 mol, and neopentyl glycol: 1.8 mol. Under nitrogen flow, the temperature was raised to 190 ° C while heating and stirring. Then, the temperature was gradually raised to 215 ° C, and an esterification reaction was performed. When the acid value became 9.5 mgKOH / g, it was cooled to 120 ° C. Next, maleic anhydride: 2.0 mol is added to the reaction product of the esterification reaction, and the esterification reaction is performed at 150 ° C to 210 ° C. When the acid value became 9.8 mgKOH / g, cooling was performed to obtain an unsaturated polyester (A2-1).

Next, hydroquinone was added to this unsaturated polyester (A2-1): 0.5 part by mass. The proportion of fumaric acid (proportion of fumaric acid transferred from maleic anhydride) in the unsaturated dibasic acid component was 90 mol%.

This was dissolved in styrene (manufactured by Idemitsu Kosan) to prepare an unsaturated polyester resin composition having a styrene content of 40% by mass.

"Urethane methacrylate resin (A4-1)"

In a 3 L 4-necked flask equipped with a stirrer, reflux condenser, gas introduction tube, and thermometer, diphenylmethane diisocyanate: 500 g, ACTCOL D-1000 (polyether polyol made by Mitsui Chemicals Co., Ltd .: weight) Average molecular weight 1000): 700 g, Toho Polyethylene Glycol # 600 (polyethylene glycol produced by Toho Chemical Industry Co., Ltd .: weight average molecular weight 600): 180 g, and dibutyltin dilaurate: 0.2 g, stirred at 60 ° C for 4 Hour makes the reaction. Next, while stirring 260 g of 2-hydroxyethyl methacrylate to the reactant over a period of 2 hours, the mixture was stirred. After completion of the dropwise addition, the reaction was stirred for 5 hours to obtain a urethane methacrylate resin ( A4-1).

The weight average molecular weight of this urethane methacrylate resin (A4-1) was measured in the same manner as the epoxy methacrylate resin (A1-1). As a result, the weight average molecular weight of the urethane methacrylate resin (A4-1) was 5,285.

Further, 700 g of styrene (manufactured by Idemitsu Kosan) was added to the urethane methacrylate resin (A4-1) synthesized by the above method to obtain a mixture.

<(B) radical polymerizable unsaturated monomer>

Styrene (made by Idemitsu Kosan)

<(C) Mercapto-containing compound>

(1) 4-functional secondary mercaptan, manufactured by Showa Denko Corporation, product name: Karenz MT PE1 (Pentaerythritol (3-mercaptobutyrate))

(2) Trifunctional cyanuric acid skeleton trifunctional secondary mercaptan, manufactured by Showa Denko Corporation, product name: Karenz MT NR1 (1,3,5-ginseng (3-mercaptobutyryloxyethyl) -1,3 , 5-triazine-2,4,6 (1H, 3H, 5H) -trione)

(3) 2-functional secondary mercaptan, manufactured by Showa Denko Corporation, product name: Karenz MT BD1 (1,4-bis (3-mercaptobutoxy) butane)

(4) Monofunctional secondary mercaptan, manufactured by Showa Denko Corporation, product name: 3MBA (3-mercaptobutyric acid)

(5) 4-functional thiol, manufactured by SC Organic Chemicals Co., Ltd., product name: PEMP (Pentaerythritol (3-mercaptopropionate))

<(D) imidazole compound>

(Imidazole compound with only 1 imidazole ring)

(1) 2-Ethyl-4-methylimidazole, manufactured by Shikoku Chemicals, product name: 2E4MZ

(2) 1-benzyl-2-methylimidazole, manufactured by Shikoku Chemicals, product name: 1B2MZ

(3) 2MZ-H; 2-methylimidazole, manufactured by Wako Pure Chemical Industries, Ltd., product name: Wako first grade 2methylimidazole

(Imidazole compound having two or more imidazole rings)

(4) 2,2'-bis (o-chlorophenyl) -4,5,4'5'-tetraphenyl-1,2'biimidazole, manufactured by Heijin Chemical Co., Ltd. Product name: biimidazole

<(E) Organic peroxide>

Cumene Hydroperoxide, made by Japan Oil Corporation, product name: Percumyl H-80

<(F) carbon fiber>

(1) T700SC-24000: made by Toray (PAN-based carbon fiber, number of fiber filaments: 24,000, tensile strength: 711ksi (4900MPa), elongation: about 2%)

<(G) Metal soap>

(1) Manganese octoate 6%, manufactured by Dongrong Chemical Co., Ltd., product name: hexoate manganese

(2) Cobalt decalinate 8%, manufactured by Japan Chemical Industry Co., Ltd., product name: Naf Tex cobalt

Other resins; epoxy resin, made by Mitsubishi Chemical Corporation, product name: jER828

Other additives; [hardener] acid anhydride, Hitachi Chemical Co., Ltd., product name: HN-5500 (mixture of 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride)

Other additives; [hardening accelerator] amine compound, manufactured by Tokyo Chemical Industry Co., Ltd., N, N-dimethylbenzylamine

<Examples 1 to 7>

The (A), (A1-1), (A1-2), (A4-1) and (A) each of (A) a radically reactive resin and (B) a radically polymerizable unsaturated monomer of styrene To the mixture, a (B) radical polymerizable unsaturated monomer shown in Table 1 is added if necessary. Thereby, a mixture (a mixture of a component (A) and a component (B)) containing (A) a radically reactive resin and (B) a radically polymerizable unsaturated monomer in the ratio shown in Table 1 was obtained.

In the column of styrene in Table 1, each of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer of (A1-1) (A1-2) (A4-1) described above is used. In the mixture, the styrene content contained in advance and the styrene content added as a (B) radically polymerizable unsaturated monomer as necessary are recorded together.

In addition, in the column (A) of the radically reactive resin in Table 1, it is described that only the radical (A) is reacted in the mixture calculated from the input amount of raw materials used in the production of the mixture of the component (A) and the component (B). Content of sexual resin. (A) The content of the radically reactive resin is calculated by considering the raw materials used in the production of the mixture as a 100% reaction. In addition, in the column of (B) radically polymerizable unsaturated monomers in Table 1, only (B) of the mixture calculated from the input amount of raw materials used in the production of the mixture of the (A) component and the (B) component is described. Content of free radically polymerizable unsaturated monomer. (B) The content of the radically polymerizable unsaturated monomer is calculated by considering the raw materials used in the production of the mixture as a 100% reaction.

Next, with respect to 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer, (C) a mercapto group-containing compound, (D) an imidazole compound, and (E) an organic compound. The order of the oxides is added in the proportion shown in Table 1 and stirred, and then (G) metal soap is added and stirred as necessary in the proportion shown in Table 1, to obtain a resin composition containing (F) carbon fibers. (Composition for carbon fiber reinforced resin).

<Comparative example 1>

A resin composition (composition for carbon fiber reinforced resin) containing no (F) carbon fiber was obtained in the same manner as in Example 1 except that the compound containing no (C) mercapto group was not contained.

About each of the carbon fiber-reinforced resin compositions thus obtained, the gelation time, the hardening time, and the hardening temperature were measured in an environment of 80 ° C. by the following method to evaluate the hardenability. The results are shown in Table 1.

<Measurement of hardenability at 80 ° C>

The gelation time, hardening temperature, and hardening time were evaluated by the evaluation methods shown below.

The resin composition was placed in a test tube (outer diameter of 18 mm and length of 165 mm) to a depth of 100 mm at room temperature, and the resin composition was placed on an oil bath heated to 80 ° C., and the temperature of the resin composition was measured by thermoelectric pair. The time required for the temperature of the resin composition to be 65 ° C to 85 ° C was measured as the gelation time.

In addition, the time when the resin composition reaches the maximum heating temperature is defined as the curing time, and the heating temperature at this time is defined as the curing temperature, which is measured in accordance with JIS K-6901.

As shown in Table 1, it was found that the resin compositions of Examples 1 to 7 had short gelation time and hardening time, and that they could be hardened efficiently even at a low hardening temperature (80 ° C).

In particular, when compared with Example 1 not containing (G) metal soap, Examples 6 and 7 containing (G) metal soap had shorter gelation time and hardening time, and could harden efficiently.

In contrast, the resin composition of Comparative Example 1 not containing (C) a mercapto group-containing compound has a longer gelation time and hardening time than the resin composition of Examples 1 to 7, and has a low gelation time. The hardening temperature requires more time for hardening.

<Examples 8 to 9, Comparative Example 2>

As in Example 1, a mixture containing (A) a radically reactive resin and (B) a radically polymerizable unsaturated monomer was obtained in the proportion shown in Table 2.

In the column of styrene in Table 2, each of the (A) radically reactive resin and (B) the radically polymerizable unsaturated monomer of the above (A1-1) (A1-2) (A4-1) The styrene content previously contained in the mixture and the styrene content added as a (B) radical polymerizable unsaturated monomer as necessary are recorded together.

In addition, in the column (A) of the radically reactive resin in Table 2, it is described that only (A) of the mixture calculated from the input amount of raw materials used in the production of the mixture of the (A) component and the (B) component is free. The content of the base reactive resin. (A) The content of the radically reactive resin is calculated by considering the raw materials used in the production of the mixture as a 100% reaction. In addition, in the column of (B) radically polymerizable unsaturated monomer in Table 2, it is described that only (B) of the mixture calculated from the input amount of raw materials used in the production of the mixture of the (A) component and the (B) component Content of free radically polymerizable unsaturated monomer. (B) The content of the radically polymerizable unsaturated monomer is calculated by considering the raw materials used in the production of the mixture as a 100% reaction.

Next, with respect to 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer, (C) a mercapto group-containing compound, (D) an imidazole compound, and (E) an organic compound. The order of the oxides was added using the ratio shown in Table 2 and stirred to obtain a resin composition (composition for carbon fiber reinforced resin) containing no (F) carbon fibers.

About each of the carbon fiber-reinforced resin compositions thus obtained, in the same manner as in Example 1, the gelation time, curing time, and curing temperature were measured in an environment at 80 ° C, and the curability was evaluated. The results are shown in Table 2. In Table 2, the curability of Example 1 was also evaluated.

As shown in Table 2, it was found that the resin compositions of Examples 8 to 9 had short gelation time and hardening time, and could be hardened efficiently even at a low hardening temperature.

On the other hand, the resin composition of Comparative Example 2 using biimidazole as the (D) imidazole compound has longer gelation time and hardening time than the resin composition of Examples 1, 8, and 9.

<Evaluation of solubility of imidazole compound in resin composition>

In a 25 ° C environment, (D) is added at a ratio shown in Table 2 to 100 parts by mass of a mixture of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer shown in Table 2 The imidazole compound is stirred. Then, the component (D) was added to the mixture of the component (A) and the component (B), and the state of the resin composition 2 minutes after the start of stirring was visually observed, and the above-mentioned ( D) The solubility (compatibility) of the ingredients. The results are shown in Table 2.

`` Solubility Evaluation Criteria ''

○: Dissolved.

△: It is transparent, and some residual crystals dissolved are floating.

×: (D) The component is not dissolved, and the crystals float and become cloudy.

In a 25 ° C environment, a resin composition in which the component (D) was added to a mixture of the component (A) and the component (B), and the mixture was stirred for 2 minutes as a test body. For each test body, a haze test was performed while measuring transmittance using a haze meter HM-150 manufactured by Murakami Color Technology Research Institute in accordance with JIS K 7361 and K 7136. The thickness of the cell during measurement was 1 cm. The transmittance and haze are measured three times for each test body, and the average value of the obtained results is used for evaluation shown in Table 2.

As shown in Table 2, as the (D) imidazole compound, the resin composition of Example 1 using 2-ethyl-4-methylimidazole and the resin of Example 8 using 1-benzyl-2-methylimidazole The composition and the resin composition of Example 9 using 2-methylimidazole had a solubility evaluation of ○ or △ and were transparent. As shown in Table 2, the resin compositions of Examples 1, 8, and 9 had high transmittance and low haze.

From this, it can be seen that the phase of the (D) imidazole compound having only one imidazole ring used in Examples 1, 8, and 9 and the radically reactive resin (A) and the radically polymerizable unsaturated monomer (B) Excellent solubility.

In particular, as the (D) imidazole compound, the resin composition of Example 1 using 2-ethyl-4-methylimidazole and the resin composition of Example 8 using 1-benzyl-2-methylimidazole were not prepared. Seeing the floating of crystals, the solubility evaluation was good.

On the other hand, as the (D) imidazole compound, the resin composition of Comparative Example 2 using biimidazole having two imidazole rings has a lower transmittance than the resin composition of Examples 1, 8, and 9, And the haze is high.

<Examples 10 to 13>

As in Example 1, a mixture containing (A) a radically reactive resin and (B) a radically polymerizable unsaturated monomer in a proportion shown in Table 3 was obtained.

In the column of styrene in Table 3, each of (A) the radically reactive resin and (B) the radically polymerizable properties of the above (A1-1), (A1-2), (A2-1), (A4-1) In the mixture of unsaturated monomers, the styrene content contained in advance and the styrene content added as a (B) radically polymerizable unsaturated monomer when necessary are recorded together.

In addition, in the column of (A) radically reactive resin in Table 3, only the (A) radical reaction is performed in the mixture calculated from the input amount of the raw materials used in the production of the mixture of the (A) component and the (B) component. Content of sexual resin. (A) The content of the radically reactive resin is calculated by considering the raw materials used in the production of the mixture as a 100% reaction. In addition, in the column (B) of the radically polymerizable unsaturated monomer in Table 3, only the (B) of the mixture calculated from the input amount of the raw materials used in the production of the mixture of the (A) component and the (B) component is described. Content of free radically polymerizable unsaturated monomer. (B) The content of the radically polymerizable unsaturated monomer is calculated by considering the raw materials used in the production of the mixture as a 100% reaction.

Next, (C) a mercapto group-containing compound and (D) imidazole were added at a ratio shown in Table 3 to 100 parts by mass of the total of (A) the radically reactive resin and (B) the radically polymerizable unsaturated monomer. The compound and the (E) organic peroxide are stirred to obtain a resin composition (a composition for a carbon fiber-reinforced resin) that does not contain (F) carbon fibers.

<Comparative Examples 3 and 5>

A resin composition containing (F) carbon fiber-free resin having the composition shown in Table 3 was obtained in the same manner as in Example 1 except that (C) a mercapto group-containing compound and (D) an imidazole compound were not added, and (G) a metal soap. (Composition for carbon fiber reinforced resin).

<Comparative Example 4>

With respect to 100 parts by mass of other resins (epoxy resins) shown in Table 3, as the other additives, an acid anhydride and an amine compound are added in a ratio shown in Table 3, and the resin composition (carbon fiber) containing (F) carbon fibers is not stirred. Composition for reinforcing resin).

For each of the carbon fiber-reinforced resin compositions obtained in Examples 10 to 13 and Comparative Examples 3 to 5, the gelation time, hardening time, and hardening temperature were measured at 80 ° C in the same manner as in Example 1, and the hardenability was evaluated. . The results are shown in Table 3.

As shown in Table 3, it can be seen that the resin compositions of Examples 10 to 13 have short gelation time and hardening time, and can be effectively hardened at a low hardening temperature.

In contrast, the resin compositions of Comparative Examples 3 and 5 that do not contain (C) a mercapto group-containing compound and (D) an imidazole compound, and Comparative Example 4 using an epoxy resin of other resins are compared with Examples 10 to 13 In the case of the resin composition, it is found that the gelation time and the curing time are longer, and in order to cure at a lower curing temperature, more time is required.

Next, carbon fiber-reinforced resin compositions containing (F) carbon fibers shown in Table 3 were impregnated in the resin compositions not containing (F) carbon fibers in Examples 10 to 13 and Comparative Examples 3 to 5.

Then, using the obtained carbon fiber-reinforced resin composition, a CFRP (carbon fiber reinforced plastic) test body was produced by the method shown below.

The CFRP test bodies of Examples 10 to 13 and Comparative Examples 3 to 5 thus obtained were evaluated for the fiber volume fraction (content of carbon fiber to carbon fiber reinforced resin composition) and shear strength by the methods shown below. strength), flexural strength, tensile strength. The results are shown in Table 3.

<Production method of CFRP test body>

The roving-shaped carbon fiber bundle was put in an immersion tank filled with a resin composition (composition for carbon fiber reinforced resin), and the carbon fiber bundle was impregnated with the resin composition as a carbon fiber reinforced resin composition.

The obtained carbon fiber-reinforced resin composition was wound on a mandrel provided with a flat plate as shown in FIG. 1, and wound 350 turns and arranged neatly so that the sample had a length of 25 cm in the axial direction and a length of 21 cm in the circumferential direction. size. Then, the state of being wound around the mandrel was adjusted to a thickness of 3 mm by press molding, and was cured at 80 ° C. for 1 hour and at 110 ° C. for 2 hours to obtain CFRP. In Comparative Example 4, CFRP was obtained by curing at 80 ° C for 2 hours and 110 ° C for 3 hours. Then, the CFRP was removed from the mandrel, the long side was formed in a direction of 90 ° with respect to the orientation of the carbon fiber, and a predetermined size was cut from the CFRP to be a CFRP test body.

<Fiber volume content ratio (content of carbon fiber to carbon fiber reinforced resin composition)>

From each CFRP, a CFRP test body of length × width × thickness = 35 mm × 25 mm × 3 mm was cut, and the mass was measured. Next, the CFRP test body after the mass measurement was burned at 400 ° C. for 4 hours in a high-temperature furnace (Muffle Furnace), and then burned at 600 ° C. for 20 minutes to become only carbon fiber components. The mass of the CFRP test body after combustion was measured, and the fiber volume fraction was calculated using the calculation formula described in JIS K 7075.

<Interlayer Shear Strength>

From each CFRP, a CFRP test body of length × width × thickness = 21 mm × 10 mm × 3 mm was cut. The cut CFRP test body was measured for interlaminar shear strength in a test environment at a temperature of 23 ° C. and a humidity of 50% in accordance with JIS K 7078 using TENSILONUTC-1T manufactured by ORIENTEC. Interlayer shear strength was measured three times for each CFRP. Then, the average of the three measurement results was used to evaluate the interlayer shear strength.

<Bending strength>

From each CFRP, a CFRP test body having a length × width × thickness of 140 mm × 15 mm × 3 mm was cut. For the cut CFRP test body, the bending strength was measured at a distance of 120 mm between the fulcrum points in a test environment at a temperature of 23 ° C. and a humidity of 50% in accordance with JIS K 7074 using TENSILONUTC-1T manufactured by ORIENTEC. The bending strength was measured three times for each CFRP. Then, the average of the three measurement results was used to evaluate the bending strength.

<Tensile strength>

A CFRP test body was produced in accordance with JIS K 7165, type B test pieces. The produced CFRP test body was subjected to a tensile strength test in a test environment at a temperature of 23 ° C and a humidity of 50%, in accordance with JIS K 7161, using a 5900R manufactured by Instron, with a gap length of 150 mm, and a test speed of 1 mm / min. The tensile strength was measured three times for each CFRP. Then, the average of the three measurement results was used to evaluate the tensile strength.

As shown in Table 3, the CFRP test bodies of Examples 10 to 13 had good interlaminar shear strength, flexural strength, and tensile strength.

In contrast, the CFRP test bodies of Comparative Examples 3 and 5 have lower bending strength than the CFRP test bodies of Examples 10 to 13. This is the CFRP test specimens of Examples 10 to 13. Compared with the CFRP test specimens of Comparative Examples 3 and 5, the adhesion between the resin component and the carbon fiber is good.

The CFRP test system of Comparative Example 4 used a conventional epoxy resin. As shown in Table 3, the CFRP test bodies of Examples 10 to 13 can achieve the same strength as when using epoxy resin.

Claims (16)

    A composition for a carbon fiber reinforced resin, comprising (A) a radically reactive resin, (B) a radically polymerizable unsaturated monomer, (C) a mercapto group-containing compound, and (D) a compound having only one imidazole ring Imidazole compounds and (E) organic peroxides.         The carbon fiber-reinforced resin composition according to claim 1, further comprising (G) a metal soap.         The carbon fiber-reinforced resin composition according to claim 1 or claim 2, wherein the compound (C) containing a mercapto group contains two or more mercapto groups in the molecule.         The carbon fiber-reinforced resin composition according to any one of Claims 1 to 3, wherein the mercapto group in the (C) mercapto group-containing compound is the second or third order.         The carbon fiber-reinforced resin composition according to any one of claim 1 to claim 4, wherein the (D) imidazole compound contains one or two positions of the two positions of the imidazole ring via an alkyl group, an aryl group, or an aromatic group. Alkyl substituted.         The carbon fiber-reinforced resin composition according to any one of claim 1 to claim 5, wherein the (D) imidazole compound is 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, Any of 2-methylimidazole.         The carbon fiber-reinforced resin composition according to any one of claim 1 to claim 6, wherein the (A) radical reactive resin is selected from the group consisting of epoxy (meth) acrylate resin, unsaturated polyester resin, At least one type of polyester (meth) acrylate resin and urethane (meth) acrylate resin.         The composition for a carbon fiber-reinforced resin according to any one of claim 1 to claim 7, wherein the epoxy (meth) acrylate resin having at least one epoxy group in the (A) radically reactive resin described above The content is 1 to 100% by mass.         The carbon fiber-reinforced resin composition according to any one of claim 1 to claim 8, wherein the 10-hour half-life temperature of the (E) organic peroxide is 30 to 170 ° C.         The carbon fiber-reinforced resin composition according to any one of claim 1 to claim 9, wherein the (E) organic peroxide is cumene hydroperoxide or third butyl peroxybenzoate.         The carbon fiber-reinforced resin composition according to any one of claim 2 to claim 10, wherein the (G) metal soap is a manganese compound or a cobalt compound.         The carbon fiber-reinforced resin composition according to any one of claim 1 to claim 11, wherein the total amount of the (A) radically reactive resin and the (B) radically polymerizable unsaturated monomer is ( A) The radically reactive resin contains 20 to 99% by mass, and (B) the radically polymerizable unsaturated monomer contains 1 to 80% by mass, compared with the aforementioned (A) radically reactive resin and the aforementioned (B) radical A total of 100 parts by mass of the polymerizable unsaturated monomer, the (C) mercapto group-containing compound contains 0.001 to 20 parts by mass, the (D) imidazole compound having only one imidazole ring contains 0.001 to 10 parts by mass, (E) The organic peroxide contains 0.1 to 10 parts by mass.         A carbon fiber-reinforced resin composition comprising the carbon fiber-reinforced resin composition according to any one of claim 1 to claim 12 and (F) carbon fiber.         The carbon fiber reinforced resin composition according to claim 13, wherein the content of the (F) carbon fiber is 10 to 90% by mass based on the carbon fiber reinforced resin composition.         The carbon fiber-reinforced resin composition according to claim 13 or claim 14, wherein the carbon fiber-reinforced resin composition according to any one of claim 1 to claim 12 is impregnated into the carbon fiber (F).         The hardened | cured material of the carbon fiber reinforced resin composition as described in any one of Claims 13-15.