KR102221532B1 - Composition for carbon fiber reinforced resin, carbon fiber reinforced resin composition, cured product - Google Patents

Abstract

(A) a radical 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) an organic peroxide. It is set as the composition for carbon fiber reinforced resin. The composition for carbon fiber reinforced resin may further contain (G) metal soap.

Description

Composition for carbon fiber reinforced resin, carbon fiber reinforced resin composition, cured product

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

This application claims priority based on Japanese Patent Application No. 2016-101352 for which it applied to Japan on May 20, 2016, and uses the content here.

Conventionally, as a carbon fiber reinforced resin composition, it is known to contain an epoxy resin having good adhesion to carbon fibers and carbon fibers. However, the carbon fiber reinforced resin composition using an epoxy resin needs to be heated for a long time at a high temperature for curing.

Moreover, as a carbon fiber reinforced resin composition, there is a thing containing a vinyl ester resin which can harden in a short time at low temperature. However, in the conventional carbon fiber-reinforced resin composition using a vinyl ester resin, since the adhesion between the resin component in the cured product and the carbon fiber is insufficient, the interlayer shear strength of the cured product may not be sufficiently obtained.

Moreover, as a carbon fiber reinforced resin composition, the composition described in patent document 1 and patent document 2 is proposed.

In Patent Document 1, a curable resin composition containing a resin having an epoxy group and a radically polymerizable unsaturated group and a hexaarylbiimidazole compound is described.

In addition, in Patent Document 2, a composition containing an epoxy acrylate resin, a hexaarylbiimidazole compound, a mercapto compound, and a fiber reinforcing material is described.

Japanese Patent Publication No. 2005-281610 Japanese Patent Publication No. Hei 9-278903

However, the conventional carbon fiber reinforced resin composition capable of curing at a low temperature in a short time has insufficient adhesion between the resin component in the cured product and the carbon fiber. For this reason, a carbon fiber reinforced resin composition that can be cured at a low temperature in a short time and obtains a cured product having good adhesion between the resin component and the carbon fiber is required.

The present invention has been made in view of the above circumstances, and can be cured at a low temperature in a short time, and a carbon fiber reinforced resin composition used as a resin component in which a cured product having good adhesion between the resin component and the carbon fiber is obtained. It makes it a subject to provide the composition for resin.

In addition, the present invention makes it a subject to provide a carbon fiber reinforced resin composition containing the composition for carbon fiber reinforced resins.

Moreover, the present invention makes it a subject to provide a cured product of the carbon fiber reinforced resin composition.

The present inventors have made intensive studies in order to solve the above problems and provide a composition for carbon fiber reinforced resins that can be cured at a low temperature in a short time. As a result, for a composition containing (A) a radical reactive resin and (B) a radically polymerizable unsaturated monomer, (C) a compound containing a mercapto group was used as a curing accelerator, and (D) only one imidazole ring was used. It was found that a remarkably high curing accelerating function was obtained by using the possessed imidazole compound and (E) organic peroxide as a curing agent.

In addition, the present inventors found out that the cured product of the composition containing the above (A) to (E) and the carbon fiber-reinforced resin composition containing carbon fibers has good adhesion between the resin component and the carbon fiber, and the present invention I thought about it.

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

[1] (A) a radical 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) an organic peroxide. Containing a carbon fiber reinforced resin composition.

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

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

[4] The composition for carbon fiber reinforced resins according to any one of [1] to [3], wherein the mercapto group in the (C) mercapto group-containing compound is secondary or tertiary.

[5] In the above (D) imidazole compound, any one of [1] to [4], wherein one or two positions including the second position of the imidazole ring are substituted with an alkyl group, an aryl group, or an aralkyl group. The composition for carbon fiber reinforced resins according to claim 1.

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

[7] The (A) radical reactive resin is at least one selected from epoxy (meth) acrylate resin, unsaturated polyester resin, polyester (meth) acrylate resin, and urethane (meth) acrylate resin, [ The composition for carbon fiber reinforced resins according to any one of 1] to [6].

[8] The carbon fiber according to any one of [1] to [7], wherein the content of the epoxy (meth)acrylate resin having at least one epoxy group in the radical reactive resin (A) is 1 to 100% by mass. Composition for reinforcing resin.

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

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

[12] With respect to the total amount of the (A) radical reactive resin and the (B) radically polymerizable unsaturated monomer, (A) 20 to 99% by mass of the radical reactive resin, and (B) 1 to 80 of the radically polymerizable unsaturated monomer. Including mass%,

0.001 to 20 parts by mass of the (C) mercapto group-containing compound, and only one of the (D) imidazole rings with respect to 100 parts by mass of the total of the (A) radical reactive resin and the (B) radically polymerizable unsaturated monomer. The composition for carbon fiber reinforced resins according to any one of [1] to [11], comprising 0.001 to 10 parts by mass of the imidazole compound and 0.1 to 10 parts by mass of (E) organic peroxide.

[13] A carbon fiber reinforced resin composition comprising the composition for carbon fiber reinforced resins according to any one of [1] to [12] and (F) carbon fibers.

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

[15] The carbon fiber reinforced resin composition according to [13] or [14], in which the composition for carbon fiber reinforced resin according to any one of [1] to [12] is impregnated with the carbon fiber (F).

[16] A cured product of the carbon fiber reinforced resin composition according to any one of [13] to [15].

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

Further, according to the carbon fiber reinforced resin composition of the present invention, by curing this, a cured product having good adhesion between the resin component and the carbon fiber is obtained.

1 is a diagram showing a state of a mandrel wound around a bundle of roving-shaped carbon fibers.

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

(Carbon fiber reinforced resin composition)

The resin composition of this embodiment contains a composition for carbon fiber reinforced resins and carbon fibers. In the resin composition of the present embodiment, it is preferable that the composition for carbon fiber reinforced resin is impregnated with (F) carbon fibers.

The composition for carbon fiber reinforced resin comprises (A) a radical reactive resin, (B) a radically polymerizable unsaturated monomer, (C) a mercapto group-containing compound, (D) an imidazole compound having only one imidazole ring, (E) It contains an organic peroxide.

<(A) radical reactive resin>

(A) The radical reactive resin is a resin having an ethylenic carbon-carbon double bond in the side chain and/or the main chain. Specifically, at least 1 selected from (A1) epoxy (meth)acrylate resin, (A2) unsaturated polyester resin, (A3) polyester (meth)acrylate resin, and (A4) urethane (meth)acrylate resin It is preferable that it is a kind.

Here, "(meth)acrylate" means at least 1 type selected from methacrylate and acrylate.

(A1) The epoxy (meth)acrylate resin is obtained by reacting all or part of the epoxy groups contained in the epoxy compound with an unsaturated monobasic acid, and has a radically reactive carbon-carbon double bond in the side chain. Since the representative example of the unsaturated monobasic acid is (meth)acrylic acid, it is referred to as an epoxy (meth)acrylate resin.

As the epoxy compound, monomers, oligomers, and all polymers having two or more epoxy groups in one molecule can be used, and the molecular weight and molecular structure are not particularly limited. For example, biphenyl type epoxy resin; Bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin, and tetramethyl bisphenol F type epoxy resin; Stilbene type epoxy resin; Novolac-type epoxy resins such as phenol novolac-type epoxy resins and cresol novolac-type epoxy resins; Polyfunctional epoxy resins such as triphenolmethane type epoxy resin and alkyl-modified triphenolmethane type epoxy resin; Phenol aralkyl type epoxy resins such as a phenol aralkyl type epoxy resin having a phenylene skeleton and a phenol aralkyl type epoxy resin having a biphenylene skeleton; Naphthol-type epoxy resins such as dihydroxynaphthalene-type epoxy resins and epoxy resins obtained by glycidyl etherification of a dimer of dihydroxynaphthalene; Triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoaryl diglycidyl isocyanurate; Alicyclic polyepoxy compounds such as alicyclic diepoxycetal, alicyclic diepoxydipate, alicyclic diepoxycarboxylate, and vinylcyclohexene dioxide; A cross-linked cyclic hydrocarbon compound-modified phenol-type epoxy resin such as dicyclopentadiene-modified phenol-type epoxy resin; Glycidyl ester type epoxy resin obtained by reaction of a polybasic acid such as dimer acid and epichlorohydrin; An oxazolidone ring-containing epoxy resin obtained by reacting the above epoxy resin and diisocyanate is mentioned.

As the unsaturated monobasic acid, a known one can be used. For example, (meth)acrylic acid, crotonic acid, cinnamic acid, etc. are mentioned. Among these, (meth)acrylic acid is preferable.

Further, as the unsaturated monobasic acid, a reaction product of a compound having one hydroxy group and one or more (meth)acryloyl groups and a polybasic acid anhydride may be used.

The polybasic acid anhydride is used to increase the molecular weight of the epoxy resin, and a known one may be used. For example, succinic acid, glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol, 2-mol maleic anhydride adduct, polyethylene Glycol·2 mol maleic anhydride adduct, propylene glycol·2 mol maleic anhydride adduct, polypropylene glycol·2 mol maleic anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16-( And anhydrides such as 6-ethylhexadecane)dicarboxylic acid, 1,12-(6-ethyldodecane)dicarboxylic acid, and carboxyl group terminal butadiene/acrylonitrile copolymer (trade name Hycar CTBN).

Among the above (A1) epoxy (meth)acrylate resins, a bisphenol A type epoxy (meth)acrylate resin is preferred from the viewpoint of imparting toughness, versatility, and cost.

Among the above, it is particularly preferable to include an epoxy (meth)acrylate resin having at least one epoxy group as the radical reactive resin (A). (A) The content of the epoxy (meth)acrylate resin having at least one epoxy group in the radical reactive resin is preferably 1 to 100% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to It is 70% by mass. As the epoxy (meth)acrylate resin having at least one epoxy group, the epoxy equivalent is preferably 140 to 9500, more preferably 190 to 5000.

Since the epoxy (meth)acrylate resin having at least one epoxy group has a radically polymerizable unsaturated group, it is cured at a low temperature and in a short time. Further, since the epoxy (meth)acrylate resin having at least one epoxy group has an epoxy group, it is excellent in adhesion to carbon fibers. Therefore, when (A) radical reactive resin contains the epoxy (meth)acrylate resin which has at least one epoxy group, it becomes the composition for carbon fiber reinforced resin which is more excellent in fast curing property and adhesiveness with carbon fiber.

(A2) The unsaturated polyester resin is obtained by esterifying a dibasic acid component containing an unsaturated dibasic acid and, if necessary, a saturated dibasic acid, and a polyhydric alcohol.

As said unsaturated dibasic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, etc. are mentioned, for example, These may be used individually or in combination of 2 or more types.

Examples of the saturated dibasic acid include aliphatic dibasic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and isosebasic acid, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, Tetrachloro phthalic anhydride, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic anhydride, 4 And aromatic dibasic acids such as ,4'-biphenyldicarboxylic acid or dialkyl esters thereof, and saturated halogenated dibasic acids, and these may be used alone or in combination of two or more.

The polyhydric alcohol is not particularly limited, but, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentane Diol, 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-pentanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1 ,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, paraxylene glycol, bicyclohexyl-4,4'-diol, 2,6 -Dihydric alcohols such as decalin glycol and 2,7-decalin glycol;

Divalent phenols such as hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol A, bisphenol F, bisphenol S, tetrabromobisphenol A, etc. and adducts of alkylene oxides typified by propylene oxide or ethylene oxide Alcohol;

And trihydric or higher alcohols such as 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane and pentaerythritol.

(A2) As the unsaturated polyester resin, one modified with a cross-linked cyclic hydrocarbon compound such as dicyclopentadiene may be used as long as the effect of the present invention is not impaired. As a modification method, for example, after obtaining an addition product of dicyclopentadiene and maleic acid (sidecanol monomaleate), this is used as a monobasic acid and reacted with the unsaturated polyester to form a dicyclopentadiene skeleton. A known method such as introduction is mentioned.

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

In the (A1) epoxy (meth)acrylate resin and/or (A2) unsaturated polyester resin used in the present invention, an oxidation polymerization (air curing) group such as an allyl group or a benzyl group can be introduced. Although there is no restriction|limiting in particular in the introduction method of an oxidation polymerization group, For example, (A2) a method of condensation reaction of an unsaturated polyester resin and a compound which has both a hydroxyl group and an allyl ether group, etc. are mentioned.

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

In addition, a reaction product 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 obtained by reacting the (A1) epoxy (meth)acrylate resin and/or (A2) used in the present invention. ) You may mix it with an unsaturated polyester resin and use it. Examples of the compound having an epoxy group include allyl glycidyl ether and 2,6-diglycidylphenyl allyl ether.

By introducing an oxidation polymerization reactor, when used as a composition for carbon fiber reinforced resins, there is an effect of significantly improving drying properties and making the finish of the coating film and the molded surface uniform. As the oxidation polymerization (air curing) group, it is particularly preferable to have an allyl ether group and a benzyl ether group.

In addition, the oxidative polymerization (air curing) in the present invention refers to crosslinking accompanying the generation and decomposition of peroxide by oxidation of the methylene bond between the ether bond and the double bond, for example, seen in an allyl ether group.

Examples of the monomer forming the oxidation polymerization group-containing polymer include an unsaturated compound 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, vinyl benzyl (β-methoxymethyl) ether, vinyl benzyl (n- Butoxypropyl) ether, vinylbenzylcyclohexyl ether, vinylbenzyl-(β-phenoxyethyl) ether, vinylbenzyldicyclopentenyl ether, vinylbenzyldicyclopentenyloxyethyl ether, vinylbenzyldicyclopentenyl methyl ether And divinyl benzyl ether.

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

(A3) Polyester (meth)acrylate resin is polyester which has a (meth)acryloyloxy group. (A3) Polyester (meth)acrylate resin is obtained, for example by the method of (1) or (2) shown below.

(1) An epoxy group-containing (meth)acrylate or a hydroxyl group-containing (meth)acrylate is reacted with polyester having a carboxyl group at the terminal.

(2) A (meth)acrylic acid or an isocyanato group-containing (meth)acrylate is reacted with a polyester whose terminal is a hydroxyl group.

Examples of the polyester having a terminal carboxyl group used as a raw material in the method (1) above include those obtained from an excess amount of saturated polybasic acid and/or unsaturated polybasic acid and polyhydric alcohol.

Examples of the polyester having a terminal hydroxyl group used as a raw material in the method (2) above include those obtained from a saturated polybasic acid and/or an unsaturated polybasic acid and an excessive amount of polyhydric alcohol.

(A3) As the saturated polybasic acid used as the raw material of the polyester (meth)acrylate resin, for example, it does not have a polymerizable unsaturated bond such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, etc. Polybasic acids or anhydrides thereof.

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

As a polyhydric alcohol component, for example, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2- Methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, etc. Can be mentioned.

(A3) Glycidyl (meth)acrylate is mentioned as an epoxy group-containing (meth)acrylate used for manufacture of a polyester (meth)acrylate resin.

(A3) As a hydroxyl group-containing (meth)acrylate used in the production of a polyester (meth)acrylate resin, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxy Roxybutyl (meth)acrylate, 2-phenoxy-2-hydroxypropyl (meth)acrylate, 2-(meth)acryloyloxy-2-hydroxypropylphthalate, etc. are mentioned.

(A3) As an isocyanato group-containing (meth)acrylate used for manufacture of a polyester (meth)acrylate resin, 2-isocyanatoethyl (meth)acrylate is mentioned.

Among the above (A3) polyester (meth)acrylate resins, polyester (meth) obtained by reacting glycidyl (meth)acrylate or 2-isocyanatoethyl (meth)acrylate from the viewpoint of versatility and cost An acrylate resin is preferred.

(A4) Urethane (meth)acrylate resin is a polyurethane having a (meth)acryloyloxy group. Specifically, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, it is obtained by reacting an unreacted isocyanato group with a hydroxyl group-containing (meth)acrylic compound and, if necessary, a hydroxyl group-containing allyl ether compound. And oligomers containing radically polymerizable unsaturated groups.

As the polyisocyanate used as the raw material of the (A4) urethane (meth)acrylate resin, for example, 2,4-tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylenedi Isocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexylmethane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, Banoc D-750, Crisbone NK (trade name; Dai-Nippon Ink Chemical Co., Ltd. make ), Test Module L (brand name; manufactured by Sumitomo Bayer Corporation), Coronate L (brand name; manufactured by Nippon Polyurethane Corporation), Takeda D102 (brand name; manufactured by Takeda Yakuhin Corporation), Isonate 143L (brand name; manufactured by Mitsubishi Chemical Corporation), Dura Nate series (brand name; Asahi Kasei Chemical Co., Ltd.), etc. are mentioned.

These polyisocyanates may be used singly or in combination of two or more. Among these polyisocyanates, it is preferable to use diphenylmethane diisocyanate from the viewpoint of cost.

Examples of the polyhydroxy compound used for the raw material of the (A4) urethane (meth)acrylate resin include polyester polyol, polyether polyol, and polycarbonate polyol. More specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct , Trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol -Propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct, dipentaerythritol-ethylene oxide-propylene oxide adduct, etc. are mentioned.

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

Examples of polyhydric alcohols used as raw materials for the (A4) urethane (meth)acrylate resin include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2 -Methyl-1,3propanediol, 1,3-butanediol, bisphenol A and adduct of propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1, 3-butanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, paraxylene glycol, bicyclohexyl-4,4-diol, 2,6-decalin glycol, 2 , 7-decalin glycol, etc. are mentioned.

These polyhydric alcohols may be used singly or in combination of two or more.

As the hydroxyl group-containing (meth)acrylic compound used as a raw material for the (A4) urethane (meth)acrylate resin, a hydroxyl group-containing (meth)acrylic acid ester is preferable.

Specifically, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate , Polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, tris(hydroxyethyl)isocyanuric di(meth)acrylate, pentaerythritol tri(meth)acrylate, glycerin(mono) (Meth)acrylate, Bremmer series (brand name; Nichiyu Corporation make), etc. are mentioned.

These hydroxyl group-containing (meth)acrylic compounds may be used singly or in combination of two or more.

As a raw material for the (A4) urethane (meth)acrylate resin, as a hydroxyl group-containing allyl ether compound used as needed, specifically, for example, ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, triethylene glycol mono Allyl ether, polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3 -Butylene glycol monoallyl ether, hexylene glycol monoaryl ether, octylene glycol monoaryl ether, trimethylolpropane diallyl ether, glycerin diallyl ether, pentaesteritol triallyl ether, and the like.

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

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

Moreover, the composition for carbon fiber reinforced resin of this invention may contain resin components other than (A) radical reactive resin. As a suitable example, (A5) (meth)acrylate resin is mentioned.

As (A5) (meth)acrylate resin, the thing obtained by homopolymerizing or copolymerizing a (meth)acrylate monomer is mentioned, for example.

As a (meth)acrylate monomer used as a raw material for the (A5) (meth)acrylate resin, for example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (Meth)acrylate, i-butyl (meth)acrylate, t-butyl (meth)acrylate, amyl (meth)acrylate, hexyl (meth)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 )Acrylate, tridecyl (meth)acrylate, stearyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, dicyclopentenyl (meth)acrylate, 2-dicyclopentene Oxyethyl (meth)acrylate, isobornyl (meth)acrylate, methoxyethyl (meth)acrylate, ethoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, tetrahydrofurfuryl (meth) )Acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylic acid, (meth)acryloylmorpholine And the like.

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

(A5) As the (meth)acrylate resin, it is preferable to use a homopolymer of methyl (meth)acrylate and a copolymer containing methyl (meth)acrylate as a main component from the viewpoint of cost and reactivity of the polymer.

Among (A) radical reactive resins, (A1) epoxy (meth)acrylate resin, (A2) unsaturated polyester resin, (A3) polyester (meth)acrylate resin, (A4) urethane (meth)acrylate resin The catalyst and/or polymerization inhibitor used when at least one or more selected types are synthesized may remain.

Examples of the catalyst include compounds containing a tertiary nitrogen atom such as triethylamine, pyridine derivative, imidazole derivative, and imidazole derivative; Amine salts such as tetramethylammonium chloride and triethylamine; And phosphorus compounds such as trimethylphosphine and triphenylphosphine.

As a polymerization inhibitor, hydroquinone, methyl hydroquinone, phenothiazine, etc. are mentioned, for example.

(A) When the radical reactive resin contains a catalyst and/or a polymerization inhibitor, the content is (A1) epoxy (meth)acrylate resin, (A2) unsaturated polyester resin, (A3) polyester (meth) It is preferable that they are 0.001-2 mass parts, respectively, with respect to 100 mass parts in total of the acrylate resin and (A4) urethane (meth)acrylate resin.

<(B) radically polymerizable unsaturated monomer>

(B) The radically polymerizable unsaturated monomer is used to lower the viscosity of the resin composition and improve hardness, strength, chemical resistance, water resistance, and the like.

Although there is no restriction|limiting in particular as said (B) The radical polymerizable unsaturated monomer, It is preferable to have a vinyl group or a (meth)acryloyl group. In addition, in this specification, the "(meth)acryloyl group" means an acryloyl group and/or a methacryloyl group.

As (B) radically polymerizable unsaturated monomer having a vinyl group, for example, styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diallylphthalate, Triallyl isocyanurate, and the like.

As (B) radically polymerizable unsaturated monomer which has a (meth)acryloyl group, (meth)acrylic acid ester etc. are mentioned, for example.

Examples of (meth)acrylic acid esters include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, and (meth)acrylic acid. Cyclohexyl, 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 mono2-ethylhexyl ether (meth)acrylic Rate, 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, polytetramethylene ether glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate )Acrylate, 2-hydroxy-1,3-di(meth)acryloxypropane, 2,2-bis[4-(methacryloylethoxy)phenyl]propane, 2,2-bis[4-( Methacryloxy·diethoxy)phenyl]propane, 2,2-bis[4-(methacryloxy·polyethoxy)phenyl]propane, tetraethylene glycol di(meth)acrylate, bisphenol AEO modification (n=2) Di(meth)acrylate, isocyanuric acid EO modified (n=3) di(meth)acrylate, trimethylolpropanedi(meth)acrylate, glycerin di(meth)acrylate, trimethylolpropanetri(meth) Acrylate, glycerin tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, pentaerythritol di(meth)acrylate monostearate, dicyclopentenyl ( Meth)acrylate, tricyclodecanyl (meth)acrylate, tricyclodecanyl (meth)acrylate, or tris(2-hydroxyethyl)isocyanure (meth)acrylate, and the like.

In addition, the EO modification mentioned above means having a (poly)oxyethylene chain (-CH ₂ -CH ₂ -O-), and n means the number of (poly) oxyethylene chains.

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

Among the above (B) radically polymerizable unsaturated monomers, it is preferable to use styrene from the viewpoints of workability, curability and cost.

(B) The content of the radically polymerizable unsaturated monomer is preferably 1 to 80% by mass, more preferably 10 to 50% by mass, based on the total amount of the (A) radical reactive resin and (B) the radically polymerizable unsaturated monomer. It is preferable, and it is more preferable that it is 20-40 mass %.

<(C) Mercapto group-containing compound>

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

(C) The mercapto group-containing compound is at least one selected from a secondary thiol compound (C1) in which a mercapto group is bonded to a secondary carbon atom, or a tertiary thiol compound (C2) bonded to a tertiary carbon atom. It is desirable. (C) The mercapto group-containing compound is particularly preferably a secondary thiol compound (C1) in order to cure it in a shorter time.

The secondary thiol compound (C1) has good storage stability compared to the primary thiol compound in which a mercapto group is disposed at the terminal. Like the secondary thiol compound (C1), the tertiary thiol compound (C2) is a compound in which a mercapto group is not disposed at the terminal. For this reason, the tertiary thiol compound (C2) is a (C) mercapto group-containing compound and has a function similar to that of the secondary thiol compound (C1).

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

The "polyfunctional thiol" as used herein means a mercapto group-containing compound having two or more mercapto groups as a functional group.

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

(C) The mercapto group-containing compound is preferably a polyfunctional thiol having two or more mercapto groups bonded to secondary or tertiary carbon atoms in the molecule in order to cure the composition for carbon fiber reinforced resin in a shorter time.

The compound having two or more mercapto groups bonded to secondary or tertiary carbon atoms in the molecule is not particularly limited, but, for example, has at least one structure represented by the following formula (Q), and the following formula (Q) A compound having two or more mercapto groups bonded to a secondary or tertiary carbon atom in the molecule, including the mercapto group in the structure represented as is preferred.

(In formula (Q), R ¹ is 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 or a carbon atom number. It is an aromatic group of 6 to 18. * indicates that it is connected to an arbitrary organic group. a is an integer of 0 to 2)

(C) As the mercapto group-containing compound, particularly, a compound having a structure represented by formula (Q), R ¹ in formula (Q) is a hydrogen atom, and having two or more mercapto groups bonded to secondary carbon atoms in the molecule It is more preferable that it is. That is, it is preferable that the (C) mercapto group-containing compound has a structure represented by the formula (Q), and the carbon atom to which the mercapto group in the formula (Q) is bonded is a secondary thiol compound (C1) in which a secondary carbon atom is used. .

Further, the alkyl group having 1 to 10 carbon atoms ^{in R 1} and R ² in the formula (Q) may be linear or branched. Specifically, a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, various octyl groups, and the like are mentioned.

In addition, "various kinds" means various isomers including n-, sec-, tert-, and iso-. Among these alkyl groups, a methyl group and an ethyl group are preferable.

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

A in formula (Q) is an integer of 0-2, Preferably it is 1.

In addition, it is preferable that the (C) mercapto group-containing compound has at least one ester structure represented by the following formula (Q-1).

(Formula (Q-1) being of, R ^1, R ^2, * and a are the formula (Q) R ^1, R ^2, * and a and agree in)

It is preferable that a in formula (Q-1) is 1. When a is 1, it is preferable from the viewpoint of controlling the stability and curability of the resin composition. 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 controlling the stability and curability of the resin composition, a in formula (Q-1) is It is preferably 1.

It is preferable that the ester structure represented by formula (Q-1) is derived from a mercapto group-containing carboxylic acid and a polyhydric alcohol represented by the following formula (S).

(Formula (S) being of, R ^1, R ² and a are, R ^1, R ² and a and agreed in the formula (Q))

Examples of the polyhydric alcohol include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-propanediol, 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-hydroxyethoxyphenyl)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 Dihydric alcohols such as [4-(2-hydroxyethyl)phenyl]fluorene; Glycerin, diglycerin, trimethylolethane, trimethylolpropane, ditrimethylolpropane, tris(2-hydroxyethyl)isocyanurate, hexanetriol, sorbitol, pentaerythritol, dipentaerythritol, sucrose, 2, Trihydric or higher alcohols such as 2-bis(2,3-dihydroxypropyloxyphenyl)propane; In addition, polycarbonate diol, dimer acid polyester polyol, etc. are mentioned.

Among these, dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol from the viewpoint of availability and improving curability; Glycerin, trimethylolethane, trimethylolpropane, tris(2-hydroxyethyl)isocyanurate, pentaerythritol, dipentaerythritol, 2,2-bis(2,3-dihydroxypropyloxyphenyl)propane Trihydric or higher alcohols such as; Polycarbonate diol and dimer acid polyester polyol are preferable. In particular, 1,4-butanediol, trimethylolethane, trimethylolpropane, tris(2-hydroxyethyl)isocyanurate, pentaerythritol, polycarbonate diol from the viewpoint of reactivity and good workability at low vapor pressure , Dimer acid polyester polyol is preferred.

(Secondary thiol compound (C1))

(C) When the mercapto group-containing compound is a secondary thiol compound (C1) having a structure represented by the above formula (Q), specific examples thereof include 3-mercaptobutyric acid, 3-mercaptophthalic acid di(1-mercapto). Ethyl), di phthalate (2-mercaptopropyl), di phthalate (3-mercaptobutyl), ethylene glycol bis (3-mercapto butyrate), propylene glycol bis (3-mercapto butyrate), diethylene glycol bis ( 3-mercaptobutyrate), butanediolbis(3-mercaptobutyrate), octanediolbis(3-mercaptobutyrate), trimethylolethantris(3-mercaptobutyrate), trimethylolpropanetris(3-mercaptobutyrate) ), pentaerythritol tetrakis (3-mercaptobutyrate), dipentaerythritol hexakis (3-mercaptobutyrate), ethylene glycol bis (2-mercaptopropionate), propylene glycol bis (2-mercapto) Propionate), diethylene glycolbis(2-mercaptopropionate), butanediolbis(2-mercaptopropionate), octanediolbis(2-mercaptopropionate), trimethylolpropanetris(2) -Mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate), dipentaerythritol hexakis (2-mercaptopropionate), ethylene glycolbis (4-mercaptovalerate) , Diethylene glycol bis(4-mercaptovalerate), butanediolbis(4-mercaptovalerate), octanediolbis(4-mercaptovalerate), trimethylolpropane tris(4-mercaptovalerate), Pentaerythritol Tetrakis (4-mercaptovalerate), Dipentaerythritol Hexakis (4-mercaptovalerate), Ethylene glycolbis (3-mercaptovalerate), Propylene glycolbis (3-mercaptovalerate) Rate), diethylene glycolbis (3-mercaptovalerate), butanediolbis (3-mercaptovalerate), octanediolbis (3-mercaptovalerate), trimethylolpropanetris (3-mercaptovalerate) ), pentaerythritol tetrakis (3-mercaptovalerate), dipentaerythritol hexakis (3-mercaptovalerate), hydrogenated bisphenol A bis(3-mercaptobutyrate), bisphenol A dihydroxyethyl ether -3-mercaptobutyrate, 4,4'-(9-fluorenylidene)bis(2-phenoxyethyl(3-mercaptobutyrate)), ethylene glycolbis(3-mercapto- 3-phenylpropionate), propylene glycolbis(3-mercapto-3-phenylpropionate), diethylene glycolbis(3-mercapto-3-phenylpropionate), butanediolbis(3-mercapto) -3-phenylpropionate), octanediolbis(3-mercapto-3-phenylpropionate), trimethylolpropanetris(3-mercapto-3-phenylpropionate), tris-2-(3 -Mercapto-3-phenylpropionate)ethyl isocyanurate, pentaerythritol tetrakis (3-mercapto-3-phenylpropionate), dipentaerythritol hexakis (3-mercapto-3- Phenylpropionate) and the like.

In addition, when the secondary thiol compound (C1) is a compound having an ester structure represented by the formula (Q-1), the compound is added to the polyhydric alcohol and a secondary carbon atom represented by the formula (S). It is preferable that it is derived from a carboxylic acid containing a mercapto group to be bound. Examples of the mercapto group-containing carboxylic acid represented by the above formula (S) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, and 3-mercapto-3-phenylpropionic acid.

Among the secondary thiol compounds (C1), as commercially available products of monofunctional secondary thiols, 3-mercaptobutanoic acid (manufactured by Showa Denko Corporation, product name: 3MBA), a mercapto group bonded to a secondary carbon atom in a molecule 　2 As commercially available products of compounds having more than two, 1,4-bis(3-mercaptobutyryloxy)butane (Showa Denko Corporation make, Karenz MT (registered trademark) BD1), pentaerythritol tetrakis (3- Mercaptobutyrate) (Showa Denko Corporation make, Karenz MT (registered trademark) PE1), 1,3,5-tris (3-mercaptobutyryloxyethyl)-1,3,5-triazine- 2,4,6(1H, 3H, 5H)-trione (Showa Denko Corporation make, Karenz MT (registered trademark) NR1), trimethylolethane tris (3-mercaptobutyrate) (Showa Denko Corporation) TEMB), trimethylolpropane tris (3-mercaptobutyrate) (made by Showa Denko, TPMB), and the like, and it is preferable to use one or more of them.

(Tertiary thiol compound (C2))

(C) When the mercapto group-containing compound is a tertiary thiol compound (C2) having a structure represented by the above formula (Q), specific examples thereof include di (2-mercaptoisobutyl) phthalate, and ethylene glycol bis (2- Mercaptoisobutyrate), propylene glycolbis(2-mercaptoisobutyrate), diethylene glycolbis(2-mercaptoisobutyrate), butanediolbis(2-mercaptoisobutyrate), octanediolbis(2-mercaptoy) Sobutyrate), trimethylolethantris (2-mercaptoisobutyrate), trimethylolpropanetris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), diphthalate (3-mercapto-3-methylbutyl), ethylene glycol bis (3-mercapto-3-methylbutyrate), propylene glycol bis (3-mercapto-3-methyl) Butyrate), diethylene glycolbis(3-mercapto-3-methylbutyrate), butanediolbis(3-mercapto-3-methylbutyrate), octanediolbis(3-mercapto-3-methylbutyrate), trimethylol Ethanetris (3-mercapto-3-methylbutyrate), trimethylolpropanetris (3-mercapto-3-methylbutyrate), pentaerythritol tetrakis (3-mercapto-3-methylbutyrate), dipentaeryth Litholhexakis (3-mercapto-3-methylbutyrate), etc. are mentioned.

In addition, when the tertiary thiol compound (C2) is a compound having an ester structure represented by the formula (Q-1), the compound is added to the polyhydric alcohol and a tertiary carbon atom represented by the formula (S). It is preferable that it is derived from a carboxylic acid containing a mercapto group to be bound. Examples of the mercapto group-containing carboxylic acid represented by the above formula (S) include 2-mercaptoisobutyric acid and 3-mercapto-3-methylbutyric acid.

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

<(D) imidazole compound>

Only one (D) imidazole compound contained in the resin composition of this embodiment has an imidazole ring, and a compound having a plurality of imidazole rings is not included. (D) The imidazole compound functions as a curing agent.

(D) As an imidazole compound, for example, imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl- 4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cya Noethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenyl Imidazole, 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'-methyl Imidazolyl-(1′)]-ethyl-s-triazineisocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 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-phenylimidazoline, and the like.

(D) As an imidazole compound, unlike the polyaddition type, since it is a catalyst type, curing proceeds with a small amount of addition, and has excellent function as a curing accelerator, and (A) a radical reactive resin and (B) a radical polymerizable unsaturated monomer. From the viewpoint of excellent compatibility, it is preferable to use one in which one or two positions including the second position of the 5-membered ring of imidazole are substituted with an alkyl group, an aryl group or an aralkyl group.

The alkyl group preferably has 1 to 6 carbon atoms, and more preferably 1 to 3 carbon atoms. The aryl group preferably has 6 to 20 carbon atoms, and more preferably 6 to 12 carbon atoms. The aralkyl group preferably has 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 imidazole compound (D), it is preferable to use 2-ethyl-4-methylimidazole or 1-benzyl-2-methylimidazole.

(D) The imidazole compound is preferably contained in an amount of 0.001 to 10 parts by mass with respect to 100 parts by mass of the total of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. More preferably, it is 0.01-5 mass parts, More preferably, it is 0.1-2 mass parts.

<(E) Organic peroxide>

(E) The organic peroxide functions as a curing agent. As the (E) organic peroxide, what is usually used as a radical curing agent for (A) a radical reactive resin and (B) a radically polymerizable unsaturated monomer can be used. Specifically, diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, and dialkyl peroxides such as dicumyl peroxide , Ketone peroxides such as methyl ethyl ketone peroxide and acetylacetone peroxide, peroxy ketals, alkyl peresters, and percarbonates.

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

Among the above, it is particularly preferable to use cumene hydroperoxide or t-butylperoxybenzoate as the organic peroxide (E) from the viewpoint of stability after mixing with the resin. Both cumene hydroperoxide and t-butylperoxybenzoate are compounds having a (-O(oxygen)-O(oxygen)-) bond that decomposes upon curing to generate a radical. When t-butylperoxybenzoate is used, compared with the case of using cumene hydroperoxide, the pot life (potable time) can be lengthened. In order to obtain a curability equivalent to cumene hydroperoxide using t-butylperoxybenzoate, the curing temperature may be higher than that in the case of using cumene hydroperoxide.

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

<(F) carbon fiber>

(F) As the carbon fiber, any one manufactured by various manufacturing methods can be used. For example, carbon fibers such as pitch-based, PAN (polyacrylonitrile)-based, and vapor-phase growth method-based 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, and a mat shape may be used alone or in combination.

(F) It is preferable to contain 10 to 90 mass% in resin composition, and, as for (F) carbon fiber, it is more preferable to contain 30 to 80 mass %. (F) When the content of the carbon fiber is within the above range, the reinforcing effect by including the carbon fiber (F) is sufficiently obtained.

(F) It is preferable to contain the carbon fiber in the composition for carbon fiber reinforced resins so that the fiber volume content rate of a hardened|cured material may become 40-70%.

<Other ingredients>

The carbon fiber reinforced resin composition of the present embodiment may contain the following components as necessary in addition to the above components.

<(G) Metal soap>

(G) Metal soap functions as a curing accelerator. (G) As the metal soap, a salt of a long chain fatty acid or an organic acid and a metal element is used.

The long-chain fatty acid can be appropriately selected according to the type of the target metal soap. As the long-chain fatty acid, a fatty acid having 7 to 30 carbon atoms is preferable. For example, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octanoic acid Saturated fatty acids such as decanoic acid, eiconic acid, docosanic acid, tetrachoic acid, hexacoic acid, octacoic acid, and triaconic acid, naphthenic acid, and unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid may be used.

In addition, as long-chain fatty acids, stearic acid, 1,2-hydroxystearic acid, lauric acid, myristic acid, palmitic acid, behenic acid, rosin acid, linseed oil fatty acid, soybean oil acid, tall oil acid, etc. can also be used. .

The organic acid can be appropriately selected depending on the type of metal soap to be used. As the organic acid, it is preferable to dissolve in an organic solvent, for example, formic acid, acetic acid, citric acid, oxalic acid or benzoic acid, amino acids, carboxylic acid esters, carboxylic acid salts, carboxylic acid chlorides, dicarboxylic acids, bile acids, sugar acids, hydrides Those generally having a carboxyl group such as hydroxycinnamic acid, hydroxy acid, aromatic acid, thioester, folic acid and the like and classified as carboxylic acids can be used.

In addition, ascorbic acid, α acid, imide acid, erythorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid used as weakly acidic compounds having sulfo group, hydroxy group, thiol group, and enol as characteristic groups as organic acids. , Sulfonic acid, taico acid, thioacetic acid, dehydroacetic acid, delta acid, uric acid, hydroxamic acid, humic acid, furboic acid, phosphonic acid, meldrum acid, and the like can also be used.

Among the long-chain fatty acids or organic acids, long-chain fatty acids are preferable, linear or cyclic saturated fatty acids having 7 to 15 carbon atoms, or unsaturated fatty acids having 7 to 15 carbon atoms are more preferable, and octanoic acid and naphthenic acid are still more preferable.

Metal elements are vanadium, gold, silver, palladium, platinum, ruthenium, rhodium, tin, lead, zinc, iron, nickel, cobalt, lithium, aluminum, indium, neodymium, manganese, cerium, calcium, zirconium, copper, barium, Magnesium and rare earths are mentioned.

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

(G) As the metal soap, for example, metal soaps such as manganese naphthenate, manganese octylate, cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, barium naphthenate, etc. 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 naphthenate, manganese octylate, cobalt naphthenate, and cobalt octylate are preferable.

In the case of containing (G) metal soap, the content in terms of the metal component of (G) metal soap is based on 100 parts by mass of the total of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer, preferably 0.0001 to 0.3 parts by mass, more preferably 0.001 to 0.2 parts by mass, still more preferably 0.006 to 0.1 parts by mass. (G) When the content of the metal soap in terms of the metal component is in the range of 0.0001 to 0.3 parts by mass, the carbon fiber reinforced resin composition can be cured more efficiently in a short time while at a low temperature, which 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 from the viewpoint of controlling the reaction rate. As a polymerization inhibitor, well-known things, such as hydroquinone, methyl hydroquinone, catechols, and phenothiazine, are mentioned.

[Hardening retardant]

The resin composition of this embodiment may contain a curing retardant for the purpose of delaying curing of the resin composition. Examples of the curing retardant include a free radical curing retardant, for example 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical (TEMPO), 4-hydroxy-2, 2,6,6-tetramethylpiperidine 1-oxyl, free radical (4H-TEMPO), 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, free radical (4- Oxo-TEMPO) and other TEMPO derivatives are mentioned. Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl and free radicals (4H-TEMPO) are preferable in terms of cost and ease of handling.

When the resin composition of the present embodiment contains a polymerization inhibitor and/or a curing retardant as a constituent component, the content thereof is based on 100 parts by mass of the total of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. , Preferably 0.0001 to 10 parts by mass, respectively.

[Other hardening accelerators]

In the resin composition of the present embodiment, for the purpose of improving curability, the above-described (C) mercapto group-containing compound, (D) an imidazole compound having only one imidazole ring, (E) an organic peroxide, and if necessary In addition to the (G) metal soap contained therein, other hardening accelerators may be included.

Examples of the other curing accelerator 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-toluidine, diethylenetriamine, pyridine, phenylmorpholine, piperidine, N,N- Amines such as N,N-substituted aniline such as bis(hydroxyethyl)aniline and diethanolaniline, N,N-substituted-p-toluidine, and 4-(N,N-substituted amino)benzaldehyde, etc. can be used.

The other curing accelerator is preferably contained in a range of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, based on 100 parts by mass of the total of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. I can.

[Photopolymerization initiator]

The resin composition of the present embodiment may contain a photoinitiator for the purpose of improving curability. As a photoinitiator, a photoradical polymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator, etc. are mentioned, for example.

The photo-radical polymerization initiator is used in order to improve the curability of an acrylic resin or monomer having a double bond.

Specifically, examples of the photo-radical polymerization initiator include benzoin ethers such as benzoin alkyl ethers, benzophenones such as benzophenone, benzyl, and methylorthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, Acetophenones such as 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, and 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2 -Thioxanthone-type things, such as methyl thioxanthone and 2-isopropyl thioxanthone, are mentioned.

In addition, a photo cationic polymerization initiator is used in order to improve curability of an epoxy resin of a cyclic ether, or oxetane.

Specifically, as a photo cationic polymerization initiator, triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium salt, tolycumyliodonium tetrakispentafluorophenylborate, 4- Isobutylphenyl (4-methylphenyl) iodonium hexafluorophosphate, triarylsulfonium hexafluorophosphate, triarylsulfonium tetrakis (pentafluorophenyl) borate, and the like.

In addition, a photoanionic polymerization initiator is used in order to improve curability of an epoxy resin or the like.

The photoinitiator can be added in a range of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer.

[Antifoam]

In the resin composition of the present embodiment, a defoaming agent may be used for the purpose of improving the generation of bubbles during molding and the remaining of bubbles in the molded article. Examples of the antifoaming agent include silicone antifoaming agents and polymer antifoaming agents.

The amount of the antifoaming agent used is preferably in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total of (A) radical reactive resin and (B) 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 for the purpose of improving adhesion to carbon fibers. As a coupling agent, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc. are mentioned.

As such a coupling agent, a silane coupling agent represented by ^{R 3} -Si(OR ⁴ ) _{3 is mentioned, for example.} In addition, ^{examples of R 3} include aminopropyl group, glycidyloxy group, methacryloxy group, N-phenylaminopropyl group, mercapto group, and vinyl group, ^{and examples of R 4} include methyl group, Ethyl group, etc. are mentioned.

The amount of the coupling agent used is preferably in the range of 0.01 to 1 part by mass with respect to 100 parts by mass in total of the radical reactive resin (A) and the radical polymerizable unsaturated monomer (B).

[Light stabilizer]

In the resin composition of the present embodiment, a light stabilizer may be used for the purpose of improving the long-term durability of the molded article. Examples of the light stabilizer include an ultraviolet absorber and a hindered amine light stabilizer. These may be used alone or in combination of two or more. Specifically, examples of the ultraviolet absorber include benzotriazole-based, triazine-based, benzophenone-based, cyanoacrylate-based, salicylate-based, and the like, and hindered amine-based light stabilizers include NH type, N-CH3 type And NO alkyl type.

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

〔Wax〕

The resin composition of this embodiment may contain a wax. As the wax, paraffin waxes, polar waxes, and the like can be used alone or in combination, and known ones having various melting points can be used.

Examples of polar waxes include those having both a polar group and a non-polar group in the structure. Specifically, NPS-8070, NPS-9125 (made by Nippon Seiro), Emanon 3199, 3299 (made by Kao), etc. are mentioned.

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, based on 100 parts by mass of the total of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer.

〔Flame Retardant〕

The resin composition of this embodiment may contain a flame retardant. As the flame retardant, a bromine flame retardant, a chlorine flame retardant, a phosphorus flame retardant, an inorganic flame retardant, an intramethod flame retardant, a silicone flame retardant or the like can be used alone or in combination, and a known one can be used.

Further, halogen-based flame retardants such as brominated flame retardants can be used in combination with antimony trioxide for the purpose of further improving flame retardancy.

Although the addition amount of the flame retardant varies depending on the system, it is preferable to contain 1 to 100 parts by mass with respect to 100 parts by mass in total of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer.

〔filling〕

In the resin composition of the present embodiment, a filler such as an inorganic filler and an organic filler may be blended for the purpose of controlling specific properties within a range that does not impair the effects of the present invention. These may be used alone or in combination of two or more.

Examples of the inorganic filler include inorganic pigments such as aluminum hydroxide that imparts flame retardancy, fumed silica that controls the fluidity of the resin composition, talc, calcium carbonate, and the like, and titanium oxide and other colorants to color.

Moreover, as an organic filler, organic bentonites, etc. are mentioned for the purpose of improving viscosity and imparting thixotropy.

The amount of the filler used is preferably in the range of 1 to 200 parts by mass with respect to 100 parts by mass in total of the radical reactive resin (A) and the radical polymerizable unsaturated monomer (B).

(Method of manufacturing carbon fiber reinforced resin composition)

The method for producing the resin composition of the present embodiment is not particularly limited, and (A) a radical reactive resin and (B) a radically polymerizable unsaturated monomer (or (A) a radical reactive resin and (B) a radically polymerizable unsaturated monomer) A mixture of), (C) a mercapto group-containing compound, (D) an imidazole compound having only one imidazole ring, (E) an organic peroxide, and (G) a metal soap (optional component) containing as needed. And other components, and (F) carbon fibers are mixed by a known method.

The resin composition of the present embodiment is particularly preferably prepared by mixing the above components except for (F) carbon fibers to prepare a composition for carbon fiber reinforced resin, and then impregnating this with (F) carbon fibers. .

The cured product of this embodiment is a cured product of the resin composition of this embodiment.

As a method of curing the resin composition of the present embodiment, any method capable of heating the resin composition at a temperature required for curing may be used. For example, a method of heating using a heating furnace or a heater can be used.

The temperature at which the resin composition is cured can be, for example, 5 to 200°C, preferably 15 to 150°C, and more preferably 60 to 120°C. The heating time can be, for example, 1 to 180 minutes, preferably 1 to 120 minutes, and more preferably 1 to 60 minutes.

The resin composition of the present embodiment includes (A) a radical reactive resin, (B) a radically polymerizable unsaturated monomer, (C) a mercapto group-containing compound, (D) an imidazole compound having only one imidazole ring, Since (E) organic peroxide and (F) carbon fiber are contained, it can harden efficiently in a short time at low temperature. In addition, in the cured resin composition of the present embodiment, sufficient adhesion between the resin component and the carbon fiber is obtained.

In addition, in the resin composition of the present embodiment, (C) a mercapto group-containing compound and (D) an imidazole compound having only one imidazole ring relative to the total amount of (A) a radical reactive resin and (B) a radically polymerizable unsaturated monomer. And (E) By controlling each content of the organic peroxide, the curing rate of the resin composition can be adjusted.

Therefore, the resin composition of this embodiment is useful in the case of producing a cured product requiring a higher production cycle than an epoxy resin by using a general-purpose carbon fiber. Specifically, it is suitable for manufacturing a molded article (cured product) using a molding method requiring a high production cycle, such as an automobile member produced by filament winding molding, resin transfer molding, press molding, or the like.

Example

Hereinafter, the present invention will be described based on examples. The present invention is not limited at all by the examples shown below. The raw materials used in Examples and Comparative Examples shown below are as follows.

(Used raw materials)

<(A) Mixture of radical reactive resin and (B) radically polymerizable unsaturated monomer>

The radical reactive resin (A) of (A1-1) (A1-2) (A2-1) (A4-1) was synthesized by the method shown below. Each (A) radical reactive resin of the obtained (A1-1) (A1-2) (A2-1) (A4-1) and (B) styrene (manufactured by Idemitsu Kosan) as a radically polymerizable unsaturated monomer were mixed. , A mixture of component (A) and component (B) was obtained.

"Epoxy methacrylate resin (A1-1)"

To a reaction device equipped with a stirrer, reflux condenser, gas introduction tube and thermometer, AER-2603 (Asahi Kasei Co., Ltd. bisphenol A type epoxy resin: epoxy equivalent: 189): 1890 g, bisphenol A: 342 g and tetradecyldimethylbenzyl ammonium chloride: 7 g was added and reacted at 150°C for 2 hours in a nitrogen gas atmosphere. After completion of the reaction, 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 product, and reacted at 90° C. for 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"

For the measurement of the weight average molecular weight, gel permeation chromatography (Showa Denko Corporation Shodex GPC-101) was used. The weight average molecular weight was measured at room temperature under the following conditions and calculated in terms of polystyrene.

(Measuring conditions)

Column: Showa Denko LF-804, 2 pcs.

Column temperature: 40°C

Sample: 0.4 mass% tetrahydrofuran solution of the object to be measured

Flow rate: 1ml/min

Eluent: Tetrahydrofuran

Further, 1857 g of styrene (made by Idemitsu Kosan) was added to the epoxy methacrylate resin (A1-1) synthesized by the above method, and the viscosity at 25°C was 0.8 Pa·s and the solid content was 50% by mass. A mixture was obtained.

"Epoxy methacrylate resin having an epoxy group (A1-2)"

To a reaction device equipped with a stirrer, reflux condenser, gas inlet pipe and thermometer, AER-2603 (Asahi Kasei Co., Ltd. bisphenol A type epoxy resin: epoxy equivalent 189): 1890 g, methacrylic acid: 430 g, hydroquinone: 0.5 g, tri 1.2 g of phenylphosphine was added and heated at 100° C. while blowing air, and reacted for about 9 hours. When the acid value became 0 mgKOH/g, the reaction was terminated, and an epoxy methacrylate resin (A1-2) having at least one epoxy group was obtained.

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.

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

"Unsaturated polyester resin (A2-1)"

Into a 4-neck flask equipped with a thermometer, stirrer, inert gas inlet and reflux cooler, isophthalic acid: 0.8 mol, 1,2-propanediol: 1.0 mol, and neopentyl glycol: 1.8 mol were added, and heated under a nitrogen gas stream. The temperature was raised to 190°C while stirring. After that, 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 was added to the reaction product of the esterification reaction, and the esterification reaction was carried out at 150°C to 210°C. It cooled when the acid value became 9.8 mgKOH/g, and unsaturated polyester (A2-1) was obtained.

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

This was dissolved in styrene (made 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 3L 4-neck flask equipped with a stirrer, reflux condenser, gas inlet tube, and thermometer, diphenylmethane diisocyanate: 500g, Actcol D-1000 (Mitsui Chemical Co., Ltd. polyether polyol: weight average molecular weight 1000 ): 700 g, Toho polyethylene glycol #600 (Toho Chemical Industry Co., Ltd. polyethylene glycol: weight average molecular weight 600): 180 g, and dibutyl tin dilaurate: 0.2 g was added and stirred at 60°C for 4 hours. Reacted. Next, to the reaction product, 2-hydroxyethyl methacrylate: 260 g was added dropwise over 2 hours while stirring, and after completion of the dropwise addition, the mixture was stirred for 5 hours and reacted 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 in the epoxy methacrylate resin (A1-1). As a result, the weight average molecular weight of the urethane methacrylate resin (A4-1) was 5285.

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

<(B) radically polymerizable unsaturated monomer>

Styrene (Idemitsu Kosan)

<(C) Mercapto group-containing compound>

(1) 4-functional secondary thiol, manufactured by Showa Denko Co., Ltd., product name: Karenz MT PE1 (pentaerythritol tetrakis (3-mercaptobutyrate))

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

(3) Bifunctional secondary thiol, manufactured by Showa Denko Corporation, product name: Karenz MT BD1 (1,4-bis(3-mercaptobutyryloxy)butane)

(4) Monofunctional secondary thiol, manufactured by Showa Denko Co., Ltd., product name: 3MBA (3-mercapto butanoic acid)

(5) 4-functional first grade thiol, manufactured by SC Yuki Chemical Co., Ltd., product name: PEMP (pentaerythritol tetrakis (3-mercaptopropionate))

<(D) imidazole compound>

(Imidazole compound having only one imidazole ring)

(1) 2-ethyl-4-methylimidazole, manufactured by Shikoku Kasei, Product name: 2E4MZ

(2) 1-Benzyl-2-methylimidazole, manufactured by Shikoku Kasei, Product Name: 1B2MZ

(3) 2MZ-H; 2-Methylimidazole, Wako Junyaku, Product name: Wako 1st grade 2methylimidazole

(Imidazole compound having two or more imidazole rings)

(4) 2,2'-bis(o-chlorophenyl)-4,5,4'5'-tetraphenyl-1,2'biimidazole, Kurogane Gasase, Product Name: Biimidazole

<(E) Organic peroxide>

Cumene Hydroperoxide, manufactured by Nichiyu Corporation, Product Name: Parkmill H-80

<(F) carbon fiber>

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

<(G) Metal soap>

(1) Manganese octylate 6%, manufactured by Toei Chemical Co., Ltd., Product name: Manganese hexoate

(2) Naphthenic acid cobalt 8%, manufactured by Nippon Chemical Industry Co., Ltd., product name: Naphtex Cobalt

Other resins; Epoxy resin, manufactured by Mitsubishi Chemical Co., Ltd., product name: jER828

Other additives; [Curing agent] Acid anhydride, Hitachi Kasei Co., Ltd., product name: HN-5500 (mixture of 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride)

Other additives; [Cure Accelerator] Amine compound, manufactured by Tokyo Kasei Kogyo, N,N-dimethylbenzylamine

<Examples 1 to 7>

In the mixture of each (A) radical reactive resin of (A1-1) (A1-2) and (A4-1) prepared by the above method and styrene as a radically polymerizable unsaturated monomer, as necessary, the table (B) The radically polymerizable unsaturated monomer shown in 1 was added. Thereby, a mixture (a mixture of component (A) and component (B)) containing (A) a radical 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, styrene preliminarily contained in a mixture of (A) radical reactive resins and (B) radically polymerizable unsaturated monomers in (A1-1) (A1-2) (A4-1) above. The content and the styrene content as the radically polymerizable unsaturated monomer (B) added as necessary were summed and described.

In addition, in the column of (A) radical reactive resin in Table 1, the content of only the radical reactive resin (A) in the mixture calculated from the input amount of the raw material used for preparing the mixture of the component (A) and the component (B) is described. . (A) The content of the radical reactive resin was calculated by considering that the raw materials used for preparing the mixture reacted 100%. In addition, in the column of (B) radically polymerizable unsaturated monomer in Table 1, only (B) radically polymerizable unsaturated monomers in the mixture calculated from the input amount of the raw materials used for preparing the mixture of component (A) and component (B). The content is described. (B) The content of the radically polymerizable unsaturated monomer was calculated by considering that the raw materials used for preparing the mixture reacted 100%.

Next, (C) a mercapto group-containing compound, (D) an imidazole compound, and (E) an organic peroxide, in this order, per 100 parts by mass of the total of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. By adding and stirring at the ratio shown in Table 1, and adding and stirring (G) metal soap as needed at the ratio shown in Table 1, (F) a resin composition containing no carbon fiber (for carbon fiber reinforced resin Composition) was obtained.

<Comparative Example 1>

(C) Except not containing the mercapto group-containing compound, it carried out similarly to Example 1, and (F) the resin composition (composition for carbon fiber reinforced resin) which does not contain carbon fiber was obtained.

For each composition for carbon fiber reinforced resin thus obtained, the gelation time, curing time, and curing temperature were measured in an 80° C. environment by the following method, and curability was evaluated. The results are shown in Table 1.

<Measurement of curability under 80℃ environment>

The gelation time, curing temperature, and curing time were evaluated by the evaluation method shown below.

The resin composition was put in a test tube (outer diameter 18 mm, length 165 mm) to a depth of 100 mm at room temperature, installed in an oil bath heated at 80°C, and the temperature of the resin composition was measured with a thermocouple. The time taken from the temperature of the resin composition to 65°C to 85°C was measured, and it was set as the gelation time.

In addition, the time until the resin composition reaches the maximum exothermic temperature was defined as the curing time, and the exothermic temperature at that time was defined as the curing temperature, and measured according to JIS K-6901.

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

In particular, it was found that (G) Example 6 and Example 7 containing metal soap had shorter gelation time and curing time than Example 1 without (G) metal soap, and thus can be efficiently cured. Could

On the other hand, (C) the resin composition of Comparative Example 1 that does not contain a mercapto group-containing compound has a longer gelation time and a longer curing time than that of the resin compositions of Examples 1 to 7, and is more difficult to cure at a lower curing temperature. I could see that it took a lot of time.

<Examples 8 to 9, Comparative Example 2>

In the same manner as in Example 1, a mixture containing (A) a radical reactive resin and (B) a radically polymerizable unsaturated monomer in the ratio shown in Table 2 was obtained.

In the column of styrene in Table 2, styrene preliminarily contained in the mixture of (A) radical reactive resins and (B) radically polymerizable unsaturated monomers in (A1-1) (A1-2) (A4-1) above. The content and the styrene content as the radically polymerizable unsaturated monomer (B) added as necessary were summed and described.

In addition, in the column of (A) radical reactive resin in Table 2, the content of only the radical reactive resin (A) in the mixture calculated from the input amount of the raw material used for preparing the mixture of the component (A) and the component (B) is described. . (A) The content of the radical reactive resin was calculated by considering that the raw materials used for preparing the mixture reacted 100%. In addition, in the column of (B) radically polymerizable unsaturated monomer in Table 2, only (B) radically polymerizable unsaturated monomers in the mixture calculated from the input amount of the raw materials used for preparing the mixture of component (A) and component (B). The content is described. (B) The content of the radically polymerizable unsaturated monomer was calculated by considering that the raw materials used for preparing the mixture reacted 100%.

Next, (C) a mercapto group-containing compound, (D) an imidazole compound, and (E) an organic peroxide, in this order, per 100 parts by mass of the total of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. By adding and stirring at the ratio shown in Table 2 (F), the resin composition (composition for carbon fiber reinforced resin) which does not contain carbon fiber was obtained.

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

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

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

<Evaluation of solubility of imidazole compound in resin composition>

In the 25 degreeC environment, (D) imidazole compound was added in the ratio shown in Table 2 with respect to 100 mass parts of a mixture of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer shown in Table 2, and stirred. Then, the (D) component was added to the mixture of the component (A) and the component (B), and the state of the resin composition 2 minutes after starting stirring was visually observed, and the ( The solubility (compatibility) of the component D) was evaluated. The results are shown in Table 2.

「Solubility Evaluation Criteria」

○: It dissolved.

?: It was transparent, and some crystals left without melting were floating.

×: The component (D) was not dissolved, and the crystals were floating and cloudy.

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

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

From this, the (D) imidazole compound having only one imidazole ring used in Examples 1, 8 and 9 has excellent compatibility with (A) a radical reactive resin and (B) a radically polymerizable unsaturated monomer. Could know.

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

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

<Examples 10 to 13>

In the same manner as in Example 1, a mixture containing (A) a radical reactive resin and (B) a radically polymerizable unsaturated monomer in the ratio shown in Table 3 was obtained.

In the column of styrene in Table 3, in the mixture of (A) radical reactive resins and (B) radically polymerizable unsaturated monomers in (A1-1) (A1-2) (A2-1) (A4-1) above. The styrene content contained in advance and the styrene content as the radically polymerizable unsaturated monomer (B) added as needed were summed and described.

In addition, in the column of (A) radical reactive resin in Table 3, the content of only the radical reactive resin (A) in the mixture calculated from the input amount of the raw material used for preparing the mixture of the component (A) and the component (B) is described. . (A) The content of the radical reactive resin was calculated by considering that the raw materials used for preparing the mixture reacted 100%. In addition, in the column of (B) radically polymerizable unsaturated monomer in Table 3, only (B) radically polymerizable unsaturated monomers in the mixture calculated from the input amount of the raw materials used for preparing the mixture of component (A) and component (B). The content is described. (B) The content of the radically polymerizable unsaturated monomer was calculated by considering that the raw materials used for preparing the mixture reacted 100%.

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

<Comparative Examples 3 and 5>

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

<Comparative Example 4>

To 100 parts by mass of the other resins (epoxy resins) shown in Table 3, an acid anhydride and an amine compound as other additives were added in the proportions shown in Table 3 and stirred, (F) a resin composition containing no carbon fibers ( A composition for carbon fiber reinforced resin) was obtained.

For each carbon fiber reinforced resin composition of Examples 10 to 13 and Comparative Examples 3 to 5 thus obtained, in the same manner as in Example 1, the gelation time, curing time, and curing temperature were measured in an 80°C environment, and curability Was evaluated. The results are shown in Table 3.

As shown in Table 3, it was found that the resin compositions of Examples 10 to 13 had a short gelation time and a short curing time, and could be efficiently cured at a low curing temperature.

On the other hand, the resin compositions of Comparative Examples 3 and 5, which do not contain (C) a mercapto group-containing compound and (D) an imidazole compound, and of Comparative Example 4 using an epoxy resin, which are other resins, are Compared with the resin composition, the gelation time and curing time were longer, and it was found that more time was required to cure at a lower curing temperature.

Next, a carbon fiber-reinforced resin composition in which the resin composition (F) containing no carbon fibers of Examples 10 to 13 and Comparative Examples 3 to 5 was impregnated with the carbon fibers (F) shown in Table 3 was prepared.

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

For the CFRP test specimens of Examples 10 to 13 and Comparative Examples 3 to 5 thus obtained, the fiber volume content (content of carbon fibers in the carbon fiber reinforced resin composition), interlayer shear strength, bending strength, and tensile strength were as follows. It evaluated by the method shown. The results are shown in Table 3.

<Method of manufacturing CFRP test specimen>

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

As shown in FIG. 1, the obtained carbon fiber reinforced resin composition was wound and aligned 350 turns on a mandrel with a flat plate so that the sample size in the axial direction was 25 cm and the length in the circumferential direction was 21 cm. Then, by press-forming in a state wound around a mandrel, it was adjusted to a thickness of 3 mm, and cured at 80°C for 1 hour and 110°C for 2 hours to obtain CFRP. In addition, for Comparative Example 4, it was cured at 80°C for 2 hours and at 110°C for 3 hours to obtain CFRP. Thereafter, the CFRP was separated from the mandrel, and the CFRP was cut into a predetermined dimension so that the direction of 90° with respect to the orientation of the carbon fiber became a long side, and a CFRP test specimen was obtained.

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

From each CFRP, a CFRP test specimen of length x width x thickness = 35 mm x 25 mm x 3 mm was cut out, and the mass was measured. Next, the CFRP test body whose mass was measured was burned at 400°C for 4 hours, then at 600°C for 20 minutes, with a muffle furnace to obtain only carbon fiber content. The mass of the CFRP test body after combustion was measured, and the fiber volume content rate was calculated using the calculation formula described in JIS K 7075.

<Interlayer shear strength>

From each CFRP, a CFRP test specimen of length x width x thickness = 21 mm x 10 mm x 3 mm was cut out. The cut-out 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 Tensilon UTC-1T manufactured by Orientec. The interlaminar shear strength was measured three times for each CFRP. And the average value of the three measurement results was used for evaluation of the interlaminar shear strength.

<Bending strength>

From each CFRP, a CFRP test specimen of length x width x thickness = 140 mm x 15 mm x 3 mm was cut out. With respect to the cut out CFRP test specimen, the bending strength was measured at a distance of 120 mm between points using Tensilon UTC-1T manufactured by Orientech in accordance with JIS K 7074 in a test environment at a temperature of 23°C and a humidity of 50%. The measurement of the bending strength was performed three times for each CFRP. And the average value of the three measurement results was used for evaluation of the bending strength.

<Tensile strength>

A CFRP test specimen was produced according to JIS K 7165 and B-type test pieces. With respect to the produced CFRP test body, in a test environment of 23°C and 50% humidity, according to JIS K 7161, tensile strength test at a length of 150 mm between grips and a test speed of 1 mm/min using Instron 5900R Was done. The measurement of the tensile strength was performed three times for each CFRP. And the average value of the three measurement results was used for evaluation of the tensile strength.

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

On the other hand, the CFRP test bodies of Comparative Example 3 and Comparative Example 5 had a lower bending strength compared to the CFRP test bodies of Examples 10 to 13. This is because the CFRP test bodies of Examples 10 to 13 have good adhesion between the resin component and the carbon fiber as compared with the CFRP test bodies of Comparative Example 3 and Comparative Example 5.

In addition, the CFRP test body 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 strength equivalent to that in the case of using an epoxy resin.

Claims (16)

(A) a radical 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) an organic peroxide. As a composition for carbon fiber reinforced resin,
The (C) mercapto group-containing compound is a polyfunctional thiol having two or more mercapto groups bonded to secondary or tertiary carbon atoms in the molecule, and the mercapto groups are all of the structure represented by the following general formula (Q). Composition for carbon fiber reinforced resin.

(In formula (Q), R ¹ is either a hydrogen atom or an alkyl group having ^{1 to 10 carbon atoms. R 2} is an alkyl group having 1 to 10 carbon atoms. * represents connected to an arbitrary organic group. a is an integer from 0 to 2) The method of claim 1,
(G) The composition for carbon fiber reinforced resins further containing a metal soap. The method according to claim 1 or 2,
The (C) mercapto group-containing compound is 1,4-bis(3-mercaptobutyryloxy)butane, pentaerythritol tetrakis(3-mercaptobutyrate), 1,3,5-tris(3-mer) Captobutyryloxyethyl)-1,3,5-triazine-2,4,6 (1H, 3H, 5H)-trione, trimethylolethantris (3-mercaptobutyrate) or trimethylolpropanetris (3 -Mercaptobutyrate) carbon fiber reinforced resin composition. The method according to claim 1 or 2,
In the above (D) imidazole compound, one or two positions including the second position of the imidazole ring are substituted with an alkyl group, an aryl group, or an aralkyl group. The method according to claim 1 or 2,
The composition for carbon fiber reinforced resins wherein the (D) imidazole compound is any of 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 2-methylimidazole. The method according to claim 1 or 2,
The (A) radical reactive resin is at least one selected from epoxy (meth) acrylate resin, unsaturated polyester resin, polyester (meth) acrylate resin, and urethane (meth) acrylate resin for carbon fiber reinforced resin Composition. The method according to claim 1 or 2,
The composition for carbon fiber reinforced resins, wherein the content of the epoxy (meth)acrylate resin having at least one epoxy group in the radical reactive resin (A) is 1 to 100% by mass. The method according to claim 1 or 2,
The composition for carbon fiber reinforced resins wherein the (E) organic peroxide has a 10-hour half-life temperature of 30 to 170°C. The method according to claim 1 or 2,
The composition for carbon fiber reinforced resins wherein the (E) organic peroxide is cumene hydroperoxide or t-butyl peroxybenzoate. The method of claim 2,
The composition for carbon fiber reinforced resins wherein the (G) metal soap is a manganese compound or a cobalt compound. The method according to claim 1 or 2,
(A) 20 to 99% by mass of radical reactive resin, (B) 1 to 80% by mass of radically polymerizable unsaturated monomer with respect to the total amount of the (A) radical reactive resin and the (B) radically polymerizable unsaturated monomer and,
0.001 to 20 parts by mass of the (C) mercapto group-containing compound, and only one of the (D) imidazole rings with respect to 100 parts by mass of the total of the (A) radical reactive resin and the (B) radically polymerizable unsaturated monomer. A composition for carbon fiber-reinforced resins comprising 0.001 to 10 parts by mass of an imidazole compound and (E) 0.1 to 10 parts by mass of an organic peroxide. A carbon fiber reinforced resin composition comprising the composition for carbon fiber reinforced resins according to claim 1 or 2 and (F) carbon fibers. The method of claim 12,
The carbon fiber reinforced resin composition in which the content of the carbon fiber (F) is 10 to 90% by mass based on the carbon fiber reinforced resin composition. The method of claim 12,
The carbon fiber reinforced resin composition in which the composition for carbon fiber reinforced resin is impregnated with the carbon fiber (F). A cured product of the carbon fiber reinforced resin composition according to claim 12. delete

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