KR20200017559A - The composition for the carbon fiber reinforced plastic, the carbon fiber reinforced resin composition, and the cured product - Google Patents

Abstract

(A) radical reactive resin, (B) radically polymerizable unsaturated monomer, (C) mercapto group containing compound, (D) imidazole compound which has only one imidazole ring, (E) organic peroxide containing It is set as the composition for carbon fiber reinforced resins. The composition for carbon fiber reinforced resin may further contain (G) metal soap.

Description

The composition for the carbon fiber reinforced plastic, the carbon fiber reinforced resin composition, and the cured product}

This invention relates to the composition for carbon fiber reinforced resins which can harden | cure efficiently at low temperature in a short time, and also the hardened | cured material with favorable adhesiveness of a resin component and carbon fiber, the carbon fiber reinforced resin composition containing this, and its hardened | cured material 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 that an epoxy resin with favorable adhesiveness with respect to carbon fiber and carbon fiber are included. However, the carbon fiber reinforced resin composition using an epoxy resin needs to perform heating for hardening for a long time, even at high temperature.

Moreover, there exist some which contain a vinyl ester resin which can harden | cure in a short time as a carbon fiber reinforced resin composition. However, in the carbon fiber reinforced resin composition using the conventional vinyl ester resin, since the adhesiveness of the resin component and carbon fiber in hardened | cured material is inadequate, the interlayer shear strength of hardened | cured material may not be fully obtained.

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

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

In addition, Patent Literature 2 describes a composition containing an epoxy acrylate resin, a hexaaryl biimidazole compound, a mercapto compound, and a fiber reinforcing material.

Japanese Patent Laid-Open No. 2005-281610 Japanese Patent Laid-Open No. 9-278903

However, the conventional carbon fiber reinforced resin composition which can be cured in a short time while being low temperature was inadequate in the adhesiveness of the resin component and carbon fiber in hardened | cured material. For this reason, the carbon fiber reinforced resin composition which can harden | cure at low time and is short, and also the hardened | cured material with favorable adhesiveness of a resin component and carbon fiber is obtained.

This invention is made | formed in view of the said situation, Carbon fiber reinforcement used as a resin component of the carbon fiber reinforced resin composition from which it can harden | cure in low time and a short time, and the hardened | cured material with favorable adhesiveness of a resin component and carbon fiber is obtained. Let it be a subject to provide the composition for resin.

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

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

MEANS TO SOLVE THE PROBLEM This inventor earnestly examined in order to solve the said subject and to provide the composition for carbon fiber reinforced resins which can be hardened in a short time at low temperature. As a result, about the composition containing (A) radical reactive resin and (B) radically polymerizable unsaturated monomer, the compound containing (C) mercapto group is used as a hardening accelerator, and only one (D) imidazole ring is used. By using the imidazole compound and (E) organic peroxide which have, as a hardening | curing agent, it turned out that remarkably high hardening promoting function is obtained.

Moreover, this inventor discovered that the hardened | cured material of the composition containing said (A)-(E) and carbon fiber reinforced resin composition containing carbon fiber is good that the adhesiveness of a resin component and carbon fiber is favorable, and this invention It was overlaid on.

That is, this invention relates to the following matters.

[1] (A) radical reactive resin, (B) radical polymerizable unsaturated monomer, (C) mercapto group-containing compound, (D) imidazole compound having only one imidazole ring, (E) organic peroxide Containing, composition for carbon fiber reinforced resin.

[2] The composition for carbon fiber reinforced resin as described in [1], which further contains (G) metal soap.

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

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

[5] The above-mentioned (D) imidazole compound is 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 resin of any one of Claims.

[6] The above (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 in any one of 5].

[7] The radical reactive resin (A) is at least one kind selected from an epoxy (meth) acrylate resin, an unsaturated polyester resin, a polyester (meth) acrylate resin, and a urethane (meth) acrylate resin. The composition for carbon fiber reinforced resins in any one of 1]-[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 (A) radical reactive resin is 1 to 100% by mass. Reinforcement resin composition.

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

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

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

[12] 20 to 99 mass% of (A) radical reactive resin and 1 to 80 of (B) radical polymerizable unsaturated monomer, based on the total amount of the (A) radical reactive resin and the (B) radical polymerizable unsaturated monomer Including mass%,

0.001-20 mass parts of said (C) mercapto-group-containing compounds, and only one said (D) imidazole ring with respect to a total of 100 mass parts of said (A) radical reactive resin and said (B) radically polymerizable unsaturated monomer The composition for carbon fiber reinforced resins in any one of [1]-[11] containing 0.001-10 mass parts of imidazole compounds which have, and 0.1-10 mass parts of (E) organic peroxides.

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

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

[15] The carbon fiber reinforced resin composition as described in [13] or [14] in which the composition for carbon fiber reinforced resins in any one of [1]-[12] is impregnated with the said (F) carbon fiber.

[16] The 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 this invention can be hardened | cured efficiently in a short time, even if it is low temperature. Therefore, the carbon fiber reinforced resin composition of this invention can be shape | molded using the shaping | molding method in which a high production cycle is calculated | required.

Moreover, according to the carbon fiber reinforced resin composition of this invention, hardened | cured material with favorable adhesiveness of a resin component and carbon fiber is obtained by hardening this.

BRIEF DESCRIPTION OF THE DRAWINGS It is a figure which shows the state of the mandrel which wound the carbon fiber bundle of roving shape.

Hereinafter, the carbon fiber reinforced resin composition (henceforth abbreviated as "resin composition") and hardened | cured material of this invention are demonstrated in detail.

(Carbon Fiber Reinforced Resin Composition)

The resin composition of this embodiment contains the composition for carbon fiber reinforced resins, and carbon fiber. As for the resin composition of this embodiment, it is preferable that the composition for carbon fiber reinforced resins is impregnated to (F) carbon fiber.

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

<(A) Radical Reactive Resin>

(A) A radical reactive resin is resin which has ethylenic carbon-carbon double bond in a side chain and / or a 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.

"(Meth) acrylate" means at least 1 sort (s) chosen from a methacrylate and an acrylate here.

(A1) The epoxy (meth) acrylate resin is obtained by reacting all or part of an epoxy group contained in an 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 said unsaturated monobasic acid is (meth) acrylic acid, it is called epoxy (meth) acrylate resin.

As said epoxy compound, the monomer, oligomer, and whole polymer which have two or more epoxy groups in 1 molecule can be used, The molecular weight and molecular structure are not specifically 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; Novolak-type epoxy resins, such as a phenol novolak-type epoxy resin and a cresol novolak-type epoxy resin; Polyfunctional epoxy resins such as triphenol methane type epoxy resins and alkyl-modified triphenol methane type epoxy resins; Phenol aralkyl type epoxy resins, such as a phenol aralkyl type epoxy resin which has a phenylene skeleton, and a phenol aralkyl type epoxy resin which has a biphenylene skeleton; Naphthol type epoxy resins such as an epoxy resin obtained by glycidyl ether dimer of dihydroxy naphthalene type epoxy resin and dihydroxy naphthalene; Triazine nucleus-containing epoxy resins such as triglycidyl isocyanurate and monoaryl diglycidyl isocyanurate; Alicyclic polyepoxy compounds such as alicyclic diepoxycetal, alicyclic diepoxydiate, alicyclic diepoxycarboxylate, and vinylcyclohexene dioxide; Conjugated cyclic hydrocarbon compound modified phenol type epoxy resins, such as a dicyclopentadiene modified phenol type epoxy resin; Glycidyl ester type epoxy resins obtained by reaction of polybasic acids such as dimer acid and epichlorohydrin; The oxazolidone ring containing epoxy resin obtained by making the said epoxy resin and diisocyanate react is mentioned.

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

Moreover, as said unsaturated monobasic acid, you may use the compound which has one hydroxyl group and one or more (meth) acryloyl groups, and the reaction product of polybasic acid anhydride.

The said polybasic acid anhydride is used in order to increase the molecular weight of the said epoxy resin, A well-known thing can 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, dodecane diacid, tridecane diacid, octadecane diacid, 1,16- ( And anhydrides such as 6-ethylhexadecane) dicarboxylic acid, 1,12- (6-ethyldodecane) dicarboxylic acid, and carboxyl terminal butadiene acrylonitrile copolymer (trade name Hycar CTBN).

Among said (A1) epoxy (meth) acrylate resins, bisphenol-A epoxy (meth) acrylate resin is preferable from a viewpoint of toughness provision, versatility, and cost.

Among the above, it is preferable that especially (A) radical reactive resin contains the epoxy (meth) acrylate resin which has at least one epoxy group. (A) 1-100 mass% is preferable, as for content of the epoxy (meth) acrylate resin which has at least one epoxy group in radical reactive resin, More preferably, it is 20-90 mass%, More preferably, it is 30- 70 mass%. As epoxy (meth) acrylate resin which has at least one epoxy group, it is preferable that epoxy equivalent is 140-9500, More preferably, it is 190-5000.

Since the epoxy (meth) acrylate resin having at least one epoxy group has a radically polymerizable unsaturated group, it is cured in a short time while being low temperature. Moreover, since the epoxy (meth) acrylate resin which has at least one epoxy group has an epoxy group, it is excellent in adhesiveness with carbon fiber. 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 resins which is further excellent in quick curing property and adhesiveness with carbon fiber.

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

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

As said saturated dibasic acid, For example, aliphatic dibasic acid, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, terephthalic acid, tetrachlorophthalic acid, such as adipic acid, subberic acid, azelaic acid, sebacic acid, isosebacic acid, etc. Tetrachloro phthalic anhydride, dimer acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid anhydride, 4 Aromatic dibasic acids, such as a 4 'biphenyl dicarboxylic acid or these dialkyl ester, a halogenated saturated dibasic acid, etc. are mentioned, These may be used individually or in combination of 2 or more types.

Although there is no restriction | limiting in particular as said polyhydric alcohol, 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, neopentylglycol, 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 and the like, and adducts of alkylene oxides represented by propylene oxide or ethylene oxide. Alcohol;

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

As unsaturated polyester resin (A2), you may use what was modified by the crosslinked cyclic hydrocarbon compound, such as dicyclopentadiene, in the range which does not impair the effect of this invention. As the modification method, for example, an adduct of dicyclopentadiene and maleic acid (sidedecanol monomaleate) is obtained, and then reacted with the unsaturated polyester using this as a monobasic acid to form a dicyclopentadiene skeleton. A well-known method, such as introducing, is mentioned.

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

Oxidation polymerization (air curing) groups, such as an allyl group or the benzyl group, can be introduce | transduced into the (A1) epoxy (meth) acrylate resin and / or (A2) unsaturated polyester resin used by this invention. Although there is no restriction | limiting in particular in the introduction method of an oxidative polymerization group, For example, the method of condensation-reacting the compound which has both (A2) unsaturated polyester resin and a hydroxyl group and an allyl ether group, etc. are mentioned.

You may use (A1) epoxy (meth) acrylate resin and / or (A2) unsaturated polyester resin used by this invention in mixture with an oxidizing polymer containing polymer.

Moreover, the reactant obtained by making the compound which has both a hydroxyl group and an allyl ether group, the reaction product of an acid anhydride, and the compound which has an epoxy group react with (A1) epoxy (meth) acrylate resin used by this invention, and / or (A2) ) You may mix and use in unsaturated polyester resin. As a compound which has an epoxy group, allyl glycidyl ether, 2, 6- diglycidyl phenyl allyl ether, etc. are mentioned.

By using an oxidizing polymerizer, when used as a composition for carbon fiber reinforced resins, there is an effect of greatly improving the dryness and making the finish of the coating film and the molding surface uniform. Especially as an oxidative polymerization (air hardening) group, what has an allyl ether group and a benzyl ether group is preferable.

In addition, oxidative polymerization (air hardening) in this invention refers to the bridge | crosslinking accompanying production | generation and decomposition | disassembly of the peroxide by oxidation of the methylene bond between the ether bond and a double bond shown, for example in an allyl ether group.

As a monomer which forms an oxidizing polymer containing polymer, the unsaturated compound which has an allyl ether group, a benzyl ether group, etc. is mentioned. 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.

Moreover, drying property of the composition for carbon fiber reinforced resins improves using dicyclopentenyl (meth) acrylate, dicyclopentenyl oxyethyl (meth) acrylate, etc. other than the above.

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

(1) An epoxy group containing (meth) acrylate or a hydroxyl group containing (meth) acrylate is made to react with polyester whose terminal is a carboxyl group.

(2) (meth) acrylic acid or isocyanato group containing (meth) acrylate is made to react with polyester whose terminal is a hydroxyl group.

As polyesters whose terminal is a carboxyl group used as a raw material in the method of said (1), what is obtained from an excess amount of saturated polybasic acid and / or unsaturated polybasic acid, and a polyhydric alcohol is mentioned.

As a polyester whose terminal is a hydroxyl group used as a raw material in the method of said (2), what is obtained from saturated polybasic acid and / or unsaturated polybasic acid, and excess polyhydric alcohol is mentioned.

As a saturated polybasic acid used as a raw material of (A3) polyester (meth) acrylate resin, it does not have polymerizable unsaturated bonds, such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, sebacic acid, for example. Polybasic acid or its anhydride is mentioned.

As unsaturated polybasic acid used as a raw material of polyester (meth) acrylate resin, polymeric unsaturated polybasic acids, such as fumaric acid, maleic acid, and itaconic acid, or its anhydride is mentioned, for example.

Examples of the polyhydric alcohol component include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, and 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, and the like. Can be mentioned.

As an epoxy group containing (meth) acrylate used for manufacture of (A3) polyester (meth) acrylate resin, glycidyl (meth) acrylate is mentioned.

As a hydroxyl group containing (meth) acrylate used for manufacture of (A3) polyester (meth) acrylate resin, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydrate Hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, etc. are mentioned.

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

Polyester (meth) obtained by making glycidyl (meth) acrylate and 2-isocyanatoethyl (meth) acrylate react in view of versatility and cost among said (A3) polyester (meth) acrylate resins, An acrylate resin is preferable.

The 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 further reacting a hydroxyl group-containing (meth) acryl compound and, if necessary, a hydroxyl group-containing allyl ether compound. A radically polymerizable unsaturated group containing oligomer is mentioned.

As a polyisocyanate used as a raw material of the said (A4) urethane (meth) acrylate resin, 2, 4- tolylene diisocyanate and its isomers, diphenylmethane diisocyanate, hexamethylene diisocyanate, hydrogenated xylylene di, for example. Isocyanate, isophorone diisocyanate, xylylene diisocyanate, dicyclohexyl methane diisocyanate, naphthalene diisocyanate, triphenylmethane triisocyanate, banox D-750, Crisbon NK (brand name; Dainippon ink Kagaku Kogyo KK) ), Test module L (brand name; manufactured by Sumitomo Bayer Corporation), coronate L (brand name; manufactured by Nippon Polyurethane Co., Ltd.), Takenate D102 (brand name; manufactured by Takeda Yakuhin Co., Ltd.), isonate 143L (trade name; manufactured by Mitsubishi Chemical Corporation), Dura Nate series (brand name; Asahi Kasei Chemical Co., Ltd.) etc. are mentioned.

These polyisocyanates may be used individually by 1 type, and may mix and use two or more types. Among these polyisocyanates, from the viewpoint of cost, it is preferable to use diphenylmethane diisocyanate.

As a polyhydroxy compound used for the raw material of said (A4) urethane (meth) acrylate resin, polyester polyol, polyether polyol, polycarbonate polyol, etc. are mentioned. 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-ethyleneoxide-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 individually by 1 type, and may mix and use two or more types.

As polyhydric alcohols used as a raw material of the said (A4) urethane (meth) acrylate resin, For example, ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2 -Methyl-1,3 propanediol, 1,3-butanediol, adducts of bisphenol A and 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 And 7-decalin glycol and the like.

These polyhydric alcohols may be used individually by 1 type, and may mix and use two or more types.

As a hydroxyl-containing (meth) acryl compound used as a raw material of the said (A4) urethane (meth) acrylate resin, a hydroxyl-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 acid di (meth) acrylate, pentaerythritol tri (meth) acrylate, glycerin (mono) (Meth) acrylate, Bremmer series (brand name; Nichiyu Corp. make), etc. are mentioned.

These hydroxyl group containing (meth) acryl compounds may be used individually by 1 type, and may mix and use two or more types.

As a hydroxyl group containing allyl ether compound used as needed as a raw material of the said (A4) urethane (meth) acrylate resin, 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, trimethylol propane diallyl ether, glycerin diallyl ether, penta erythritol triallyl ether, etc. are mentioned.

These hydroxyl-containing allyl ether compounds may be used individually by 1 type, and may mix and use two or more types.

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

In addition, the composition for carbon fiber reinforced resins of this invention may contain resin components other than (A) radical reactive resin. Suitable examples include (A5) (meth) acrylate resins.

As (A5) (meth) acrylate resin, what homopolymerized or copolymerized the (meth) acrylate monomer, for example is mentioned.

As a (meth) acrylate monomer used as a raw material of the said (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, 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) acryloyl morpholine, etc. are mentioned.

These (meth) acrylate monomers may be used individually by 1 type, and may mix and use two or more types.

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

In (A) radical reactive resin, it is from (A1) epoxy (meth) acrylate resin, (A2) unsaturated polyester resin, (A3) polyester (meth) acrylate resin, and (A4) urethane (meth) acrylate resin. The catalyst and / or polymerization inhibitor used when synthesizing at least one or more selected compounds may remain.

As a catalyst, For example, compounds containing tertiary nitrogen atoms, such as a triethylamine, a pyridine derivative, an imidazole derivative, an imidazole derivative; Amine salts such as tetramethylammonium chloride and triethylamine; And phosphorus compounds such as trimethylphosphine and triphenylphosphine.

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

(A) When 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 it is 0.001-2 mass parts respectively with respect to a total of 100 mass parts of acrylate resin and (A4) urethane (meth) acrylate resin.

<(B) radically polymerizable unsaturated monomer>

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

There is no restriction | limiting in particular as said (B) radically polymerizable unsaturated monomer, What has a vinyl group or a (meth) acryloyl group is preferable. In addition, in this specification, a "(meth) acryloyl group" means acryloyl group and / or methacryloyl group.

Examples of the (B) radically polymerizable unsaturated monomer having a vinyl group include styrene, p-chlorostyrene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, diallyl phthalate, Triallyl isocyanurate, etc. are mentioned.

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

As (meth) acrylic acid ester, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, (meth) acrylic acid, for example 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-hexanedioldi (meth) acrylate Neopentyl glycol di (meth) 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 modified (n = 2) di (meth) acrylate, isocyanuric acid EO modified (n = 3) di (meth) acrylate, trimethylolpropanedi (meth) acrylate, glycerin di (meth) acrylate, Trimethylolpropane tri (meth) acrylate, glycerin tri (meth) acrylate, pentaerythritol tetra (meth) acrylic Hite, dipentaerythritol hexa (meth) acrylate, pentaerythritol di (meth) acrylate monostearate, dicyclopentenyl (meth) acrylate, tricyclodecanyl (meth) acrylate, tricyclodecanyl (Meth) acrylate or tris (2-hydroxyethyl) isocyanur (meth) acrylate etc. are mentioned.

Further, the means having the above-described EO-modified refers to (poly) oxyethylene chain (-CH ₂ -CH ₂ -O-) and, n is the (poly) means the number of the oxyethylene chain.

These (B) radically polymerizable unsaturated monomers can be used individually or in combination of 2 or more types.

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

It is preferable that it is 1-80 mass% with respect to the total amount of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer, and, as for content of (B) radically polymerizable unsaturated monomer, it is 10-50 mass% more 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 hardening accelerator.

(C) The mercapto group-containing compound is at least one selected from secondary thiol compounds (C1) in which the mercapto group is bonded to secondary carbon atoms, or tertiary thiol compounds (C2) bonded to tertiary carbon atoms It is preferable. (C) It is especially preferable that a mercapto group containing compound is a secondary thiol compound (C1) in order to harden | cure in shorter time.

The secondary thiol compound (C1) has better storage stability than the primary thiol compound in which a mercapto group is arranged at the terminal. A tertiary thiol compound (C2) is a compound in which a mercapto group is not arrange | positioned at the terminal similarly to a secondary thiol compound (C1). For this reason, a tertiary thiol compound (C2) is a (C) mercapto group containing compound and has a function similar to a secondary thiol compound (C1).

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

In order to harden the composition for carbon fiber reinforced resins in a short time, it is especially preferable to use the trifunctional or more than trifunctional thiol which has three or more mercapto groups in a molecule | numerator as a (C) mercapto group containing compound.

(C) It is preferable that a mercapto-group containing compound is a polyfunctional thiol which has two or more mercapto groups couple | bonded with a secondary or tertiary carbon atom in a molecule | numerator in order to harden | cure the composition for carbon fiber reinforced resins in a short time.

Although there is no restriction | limiting in particular as a compound which has 2 or more mercapto groups couple | bonded with a secondary or tertiary carbon atom in a molecule | numerator, For example, it has at least 1 structure represented by a following formula (Q), and is a following formula (Q) Preferred are compounds having two or more mercapto groups bonded to secondary or tertiary carbon atoms in the molecule, including the mercapto group in the structure represented as.

(In formula (Q), R ¹ is either 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 carbon atoms. An aromatic group of 6 to 18. * represents an organic group connected to a. A is an integer of 0 to 2).

(C) As a mercapto group containing compound, the compound especially has a structure represented by Formula (Q), R <^1> in Formula (Q) is a hydrogen atom, and has 2 or more mercapto groups couple | bonded with a secondary carbon atom in a molecule | numerator. It is more preferable that is. That is, it is preferable that the (C) mercapto group containing compound has a structure represented by Formula (Q), and is the secondary thiol compound (C1) whose carbon atom which the mercapto group in formula (Q) couple | bonds is a secondary carbon atom. .

In addition, the C1-C10 alkyl group in R <^1> and R <^2> in 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, etc. are mentioned.

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

Moreover, as a C6-C18 aromatic group in R <^1> and R <^2> in Formula (Q), a phenyl group, benzyl group, a naphthyl group, anthryl group, phenanthryl group etc. are mentioned, for example. In addition, these aromatic groups may be substituted by 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.

Moreover, it is preferable that (C) mercapto-group containing compound has at least 1 ester structure represented by a 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 said a is 1, it is preferable from a viewpoint of controlling stability and curability of a 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 stability and curability of the resin composition, a in formula (Q-1) is It is preferable that it is 1.

It is preferable that the ester structure represented by Formula (Q-1) is derived from the mercapto group containing carboxylic acid and polyhydric alcohol represented by 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 Such as [4- (2-hydroxyethyl) phenyl] fluorene Dihydric alcohols; Glycerin, diglycerol, 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 them, dihydric alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, and 1,4-butanediol from the viewpoint of easy availability and sclerosis properties; Glycerin, Trimethylolethane, Trimethylolpropane, Tris (2-hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol, 2,2-bis (2,3-dihydroxypropyloxyphenyl) propane Trihydric or higher alcohols such as these; Polycarbonate diols and dimer acid polyester polyols are preferable. In particular, 1,4-butanediol, trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, and polycarbonate diol from the viewpoint of good workability at reactivity and low steam pressure And dimer acid polyester polyols are preferable.

[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 and 3-mercaptophthalic acid di (1-mercapto). Ethyl), phthalic acid di (2-mercaptopropyl), phthalic acid di (3-mercaptobutyl), ethylene glycol bis (3-mercaptobutyrate), propylene glycol bis (3-mercaptobutyrate), diethylene glycol bis ( 3-mercaptobutyrate), butanediolbis (3-mercaptobutyrate), octanediolbis (3-mercaptobutyrate), trimethylolethanetris (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 glycol bis (2-mercaptopropionate), butanedi Bis (2-mercaptopropionate), octanediolbis (2-mercaptopropionate), trimethylolpropane tris (2-mercaptopropionate), pentaerythritol tetrakis (2-mercaptopropionate) Nate), dipentaerythritol hexakis (2-mercaptopropionate), ethylene glycol bis (4-mercapto valerate), diethylene glycol bis (4- mercapto valerate), butanediol bis (4-mer) Capto valerate), octane diol bis (4-mercapto valerate), trimethylol propane tris (4- mercapto valerate), pentaerythritol tetrakis (4-mercapto valerate), dipentaerythritol hexakis (4-mercapto valerate), ethylene glycol bis (3-mercapto valerate), propylene glycol bis (3- mercapto valerate), diethylene glycol bis (3- mercapto valerate), butanediol bis (3 Mercapto valerate), octanediolbis (3-mercapto valerate), trimethylolpropane Tris (3-mercapto valerate), pentaerythritol tetrakis (3-mercapto valerate), dipentaerythritol hexakis (3- mercapto valerate), hydrogenated bisphenol A bis (3- mercapto butyrate) , Bisphenol A dihydroxyethyl ether-3-mercaptobutyrate, 4,4 '-(9-fluorenylidene) bis (2-phenoxyethyl (3-mercaptobutyrate)), ethylene glycol bis (3- Mercapto-3-phenylpropionate), propylene glycol bis (3-mercapto-3-phenylpropionate), diethylene glycol bis (3-mercapto-3-phenylpropionate), butanediolbis (3 Mercapto-3-phenylpropionate), octanediolbis (3-mercapto-3-phenylpropionate), trimethylolpropane tris (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 a secondary thiol compound (C1) is a compound which has an ester structure represented by the said Formula (Q-1), this compound is made to the said polyhydric alcohol and the secondary carbon atom represented by the said Formula (S). It is preferable that it is derived from the carboxylic acid containing the mercapto group couple | bonded. 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.

As a commercial item of a monofunctional secondary thiol, in a secondary thiol compound (C1), 3-mercaptobutanoic acid (made by Showa Denko Co., Ltd., product name: 3MBA), the mercapto group which couple | bonds with a secondary carbon atom in a molecule | numerator # 2 As a commercial item of the compound which has two or more, 1, 4-bis (3-mercapto butyryloxy) butane (made by Showa Denko KK, Carens MT (registered trademark) BD1), pentaerythritol tetrakis (3- Mercaptobutyrate) (made by Showa Denko KK, Carens MT (registered trademark) PE1), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine- 2,4,6 (1H, 3H, 5H) -trione (made by Showa Denko Co., Ltd., Karenz MT (registered trademark) NR1), trimethylol ethane tris (3-mercaptobutyrate) (Showa Denko Co., Ltd.) Shiki Kaisha, TEMB), trimethylol propane tris (3-mercaptobutyrate) (Showa Denko Co., Ltd., TPMB), etc. are mentioned, It is desirable to use 1 or more types of these. It is.

[Third-thiol compound (C2)]

(C) In the case where the mercapto group-containing compound is a tertiary thiol compound (C2) having a structure represented by the above formula (Q), specific examples thereof include diphthalic acid (2-mercaptoisobutyl) and ethylene glycol bis (2- Mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediolbis (2-mercaptoisobutyrate), octanediolbis (2-mercaptoy Sobutyrate), trimethylolethane tris (2-mercaptoisobutyrate), trimethylol propane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis (2-mercaptoisobutyrate), phthalic acid di (3-mercapto-3-methylbutyl), ethylene glycol bis (3-mercapto-3-methylbutyrate), propylene glycol bis (3-mercapto-3-methyl Butyrate), diethylene glycol bis (3-mercapto-3-methylbutyrate), part Diolbis (3-mercapto-3-methylbutyrate), octanediolbis (3-mercapto-3-methylbutyrate), trimethylolethanetris (3-mercapto-3-methylbutyrate), trimethylolpropanetris ( 3-mercapto-3-methylbutyrate), pentaerythritol tetrakis (3-mercapto-3-methylbutyrate), dipentaerythritol hexakis (3-mercapto-3-methylbutyrate), and the like. .

In addition, when a tertiary thiol compound (C2) is a compound which has an ester structure represented by the said Formula (Q-1), this compound is in addition to the said polyhydric alcohol and the tertiary carbon atom represented by the said Formula (S). It is preferable that it is derived from the carboxylic acid containing the mercapto group couple | bonded. Examples of the mercapto group-containing carboxylic acid represented by the above formula (S) include 2-mercaptoisobutyric acid and 3-mercapto-3-methylbutyric acid.

(C) It is preferable that a mercapto-group containing compound contains 0.001-20 mass parts with respect to a total of 100 mass parts of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. More preferably, it is 0.01-10 mass parts, More preferably, it is 0.1-5 mass parts.

<(D) imidazole compound>

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

As the (D) imidazole compound, for example, imidazole, 2-methylimidazole, 2-undecyl imidazole, 2-heptadecyl imidazole, 1,2-dimethylimidazole, 2-ethyl- 4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-sia 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 Aliphatic, 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-benzylimidazolium chloride, 2-phenylimidazoline, etc. are mentioned.

As the (D) imidazole compound, unlike a polyaddition type, since it is a catalyst type, hardening advances with a small amount of addition, and it is excellent in the function as a hardening accelerator, (A) radical reactive resin, and (B) radically polymerizable unsaturated monomer. In view of excellent compatibility, it is preferable to use one in which two or more 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.

It is preferable that it is C1-C6, and, as for the said alkyl group, it is more preferable that it is C1-C3. It is preferable that it is C6-C20, and, as for the said aryl group, it is more preferable that it is C6-C12. It is preferable that it is C7-20, and, as for the said aralkyl group, it is more preferable that it is C7-12.

As such (D) imidazole compound, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 2-methylimidazole are mentioned. In particular, it is preferable to use 2-ethyl-4-methylimidazole or 1-benzyl-2-methylimidazole as the (D) imidazole compound.

It is preferable to contain 0.001-10 mass parts of (D) imidazole compound with respect to a total of 100 mass parts 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 (E) organic peroxide, what is normally used as a radical hardening | curing agent can be used for (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. Specifically, diacyl peroxides, such as benzoyl peroxide, peroxy esters, such as t-butyl peroxy benzoate, hydroperoxides, such as cumene hydroperoxide, and dialkyl peroxides, such as dicumyl peroxide, Commonly known ones such as ketone peroxides, peroxy ketals, alkyl peresters and percarbonates, such as methyl ethyl ketone peroxide and acetylacetone peroxide.

It is preferable to use the thing whose 30-minute half life temperature is 30-170 degreeC especially among said thing, and it is more preferable to use what is 40 degreeC-160 degreeC.

Among the above, it is preferable to use cumene hydroperoxide or t-butylperoxy benzoate as (E) organic peroxide from the point of stability after mixing to resin especially. Cumene hydroperoxide and t-butylperoxybenzoate are both compounds having a (—O (oxygen) —O (oxygen) —) bond that decomposes upon curing to produce a radical. When t-butylperoxy benzoate is used, the pot life (availability time) can be lengthened compared with the case where cumene hydroperoxide is used. What is necessary is just to make hardening temperature higher than the case of using cumene hydroperoxide, in order to acquire the sclerosis | hardenability equivalent to cumene hydroperoxide using t-butyl peroxy benzoate.

(E) Organic peroxide is 0.1-10 mass parts with respect to a total of 100 mass parts of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer, Preferably it is 0.5-5 mass parts, More preferably, 0.5-2 mass parts.

<(F) carbon fiber>

(F) As carbon fiber, arbitrary things manufactured by various manufacturing methods can be used. For example, carbon fibers, such as a pitch system, a PAN (polyacrylonitrile) system, and a vapor phase growth system, can be used. The shape of (F) carbon fiber is not specifically limited, For example, a roving shape, a knitted fabric, a cloth (cloth) form, and a mat form can be used individually or in combination.

(F) It is preferable to contain 10-90 mass% in carbon resin, and it is more preferable to contain 30-80 mass%. Reinforcement effect by containing (F) carbon fiber is fully acquired as content of (F) carbon fiber is the said range.

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

<Other ingredients>

The carbon fiber reinforced resin composition of this embodiment may contain the following components as needed other than each said component.

<(G) metal soap>

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

Long-chain fatty acid can be suitably selected according to the kind of metal soap made into the objective. As the long-chain fatty acid, fatty acids having 7 to 30 carbon atoms are preferable, and for example, heptanoic acid, octanoic acid, nonanoic acid, decanoic acid, neodecanoic acid, undecanoic acid, dodecanoic acid, tetradecanoic acid, hexadecanoic acid, octa Saturated fatty acids such as decanoic acid, eicosanoic acid, docoic acid, tetracoic acid, hexacoic acid, octacoic acid and triacontanoic acid, naphthenic acid, and unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid may be used.

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

An organic acid can be suitably selected according to the kind of metal soap made into the objective. As an organic acid, it is preferable to melt | dissolve in an organic solvent, For example, formic acid, an acetic acid, a citric acid, an oxalic acid or benzoic acid, an amino acid, carboxylic acid ester, carboxylic acid salt, carboxylic acid chloride, dicarboxylic acid, a bile acid, a sugar acid, a hydride Those which generally have a carboxyl group, such as oxycinnamic acid, hydroxy acid, aromatic acid, thioester, folic acid, and classified into carboxylic acids can be used.

Ascorbic acid, α acid, imide acid, erythorbic acid, croconic acid, kojic acid, squaric acid, sulfinic acid, which are used as weakly acidic compounds having sulfo group, hydroxyl group, thiol group, and enol as characteristic groups as organic acids. , Sulfonic acid, tycoic acid, thioacetic acid, dehydroacetic acid, delta acid, uric acid, hydroxamic acid, humic acid, furboic acid, phosphonic acid, meldmic acid and the like can also be used.

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

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

Among these metal elements, group 2 metal elements and group 3 to 12 metal elements are preferable, and 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.

As the (G) metal soap, for example, metal soaps such as manganese naphthenate, manganese octylate, cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate and barium naphthenate can be used. .

Among these metal soaps, as the (G) metal soap, it is preferable to use a manganese compound or a cobalt compound, and in particular, manganese naphthenate, manganese octylate, cobalt naphthenate, and cobalt octynate having high versatility are preferable.

When (G) metal soap is contained, content by the metal component conversion of (G) metal soap becomes like this with respect to 100 mass parts of total of (A) radically reactive resin and (B) radically polymerizable unsaturated monomer preferably. 0.0001-0.3 mass parts, More preferably, it is 0.001-0.2 mass part, More preferably, it is 0.006-0.1 mass part. (G) Since content by the metal component conversion of metal soap exists in the range of 0.0001-0.3 mass part, since carbon fiber reinforced resin composition can be hardened more efficiently in a short time, it is preferable.

[Polymerization inhibitor]

The resin composition of this embodiment may contain a polymerization inhibitor from a viewpoint of suppressing excessive superposition | polymerization of a resin composition, and a viewpoint of controlling reaction rate. As a polymerization inhibitor, well-known things, such as hydroquinone, methyl hydroquinone, catechols, phenothiazine, are mentioned.

[Curing retardant]

The resin composition of this embodiment may also contain a hardening retarder for the purpose of delaying hardening of a resin composition. Examples of the curing retardant include free radical curing retardants, for example, 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical (TEMPO), 4-hydroxy-2, 2,6,6-tetramethylpiperidine1-oxyl, free radicals (4H-TEMPO), 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, free radicals (4- TEMPO derivatives, such as Oxo-TEMPO), are mentioned. Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl and free radicals (4H-TEMPO) are preferable at the point of cost and ease of handling.

When the resin composition of this embodiment contains a polymerization inhibitor and / or a curing retarder as a component, those content is 100 mass parts in total with respect to (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. Preferably it is 0.0001-10 mass parts, respectively.

[Other curing accelerators]

In the resin composition of this embodiment, the imidazole compound and (E) organic peroxide which have the above-mentioned (C) mercapto group containing compound, and (D) only one imidazole ring for the purpose of improving curability, In addition to the (G) metal soap which it contains, you may also contain another hardening accelerator.

As said other hardening accelerator, amines, such as phosphorus compounds, such as a trimethylphosphine and a triphenylphosphine, an amine, and an amine salt, are mentioned. 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 diethanol aniline, N, N-substituted-p-toluidine, 4- (N, N-substituted amino) benzaldehyde, and the like.

The other curing accelerator is preferably contained in the 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) radically reactive resin and (B) radically polymerizable unsaturated monomer. Can be.

[Photoinitiator]

The resin composition of this embodiment may contain a photoinitiator for the purpose of improving sclerosis | hardenability. As a photoinitiator, a radical photopolymerization initiator, a photocationic polymerization initiator, a photoanionic polymerization initiator, etc. are mentioned, for example.

An radical photopolymerization initiator is used in order to improve the curability of the acrylic resin and monomer which have a double bond.

Specific examples of the radical photopolymerization initiator include benzoin ethers such as benzoin alkyl ethers, benzophenones such as benzophenone, benzyl and methyl ortho benzoyl benzoate, benzyl dimethyl ketal, 2,2-diethoxy acetophenone, Acetophenones such as 2-hydroxy-2-methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone and 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2 Thioxanthone type | system | groups, such as -methyl thioxanthone and 2-isopropyl thioxanthone, are mentioned.

In addition, a photocationic polymerization initiator is used in order to improve the sclerosis | hardenability of epoxy resin of cyclic ether, etc., and oxetane.

Specifically, as a photocationic polymerization initiator, a triarylsulfonium hexafluoro phosphate, a triarylsulfonium hexafluoro antimonate, a triarylsulfonium salt, tolyl cumyl iodonium tetrakispentafluorophenyl borate, 4- Isobutylphenyl (4-methylphenyl) iodonium hexafluorophosphate, triarylsulfonium hexafluorophosphate, triarylsulfonium tetrakis (pentafluorophenyl) borate, etc. are mentioned.

In addition, a photoanionic polymerization initiator is used in order to improve sclerosis | hardenability, such as an epoxy resin.

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

[Defoamer]

In the resin composition of this embodiment, you may use an antifoamer for the purpose of improving the bubble generation at the time of shaping | molding, and the bubble residual of a molded article. Examples of the antifoaming agent include silicone antifoaming agents and polymer antifoaming agents.

The usage-amount of an antifoamer has a range of 0.01-5 weight part with respect to a total of 100 weight part of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. More preferably, it is 0.1-1 weight part.

[Coupling Agent]

In the resin composition of this embodiment, you may use a coupling agent for the purpose of improving moldability, or improving the adhesiveness with carbon fiber. As a coupling agent, a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, etc. are mentioned.

Examples of such coupling agents, for example, there may be mentioned a silane coupling agent represented by _{^{R 3 -Si (OR 4) 3}} . Moreover, as R <^3> , an aminopropyl group, glycidyloxy group, methacryloxy group, N-phenylaminopropyl group, a mercapto group, a vinyl group, etc. are mentioned, for example, As R <^4> , For example, a methyl group, Ethyl group etc. are mentioned.

As for the usage-amount of a coupling agent, the range of 0.01-1 mass part is good with respect to a total of 100 mass parts of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer.

[Light stabilizer]

In the resin composition of this embodiment, you may use an optical stabilizer for the purpose of improving the long-term durability of a molded article. As a light stabilizer, a ultraviolet absorber and a hindered amine light stabilizer are mentioned. You may use these individually or in combination of 2 or more types. Specifically, examples of the ultraviolet absorber include benzotriazole type, triazine type, benzophenone type, cyanoacrylate type, salicylate type, and the like. Examples of the hindered amine type light stabilizer include NH type and N-CH3 type. , NO alkyl type, and the like.

It is preferable that it is the range of 0.01-5 mass parts with respect to 100 mass parts of total amounts of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer, More preferably, it is 0.05-2 mass parts. .

[Wax]

The resin composition of this embodiment may contain a wax. As wax, paraffin wax, polar wax, etc. can be used individually or in combination, The well-known thing of various melting | fusing point can be used.

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

It is preferable to contain 0.05-4 mass parts with respect to a total of 100 mass parts of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer, and, as for a wax, it is more preferable to contain 0.1-2.0 mass parts.

[Flame retardant]

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

Moreover, halogen flame retardants, such as a bromine flame retardant, can be used in combination with antimony trioxide for the purpose of further improving flame retardance.

Although the addition amount of a flame retardant changes with system, it is preferable to contain 1-100 mass parts with respect to a total of 100 mass parts of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer.

〔filling〕

In the resin composition of this embodiment, you may mix | blend fillers, such as an inorganic filler and an organic filler, in order to control a specific characteristic in the range which does not impair the effect of this invention. You may use these individually or in combination of 2 or more types.

As an inorganic filler, inorganic pigments, such as aluminum hydroxide which provides a flame retardance, fumed silica which controls the fluidity | liquidity of a resin composition, talc, calcium carbonate, etc., and titanium oxide which performs coloring, and another coloring agent.

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

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

(Method for producing carbon fiber reinforced resin composition)

The method of manufacturing the resin composition of this embodiment is not specifically limited, (A) radically reactive resin and (B) radically polymerizable unsaturated monomer (or (A) radically reactive resin and (B) radically polymerizable unsaturated monomer) ), (C) mercapto group-containing compound, (D) imidazole compound having only one imidazole ring, (E) organic peroxide, and (G) metal soap (optional component) to be contained, if necessary And other components and (F) carbon fiber are obtained by mixing by a well-known method.

It is preferable that especially the resin composition of this embodiment mixes said each component except (F) carbon fiber, produces the composition for carbon fiber reinforced resins, and manufactures it by the method of impregnating this for (F) carbon fiber. .

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

As a method of hardening the resin composition of this embodiment, what is necessary is just a method which can heat a resin composition at the temperature required for hardening, For example, the method of heating using a heating furnace or a heater etc. can be used.

The temperature which hardens a resin composition can be 5-200 degreeC, for example, Preferably it is 15-150 degreeC, More preferably, it can be 60-120 degreeC. 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 this embodiment is (A) radical reactive resin, (B) radically polymerizable unsaturated monomer, (C) mercapto group containing compound, and (D) imidazole compound which has only one imidazole ring, Since it contains (E) organic peroxide and (F) carbon fiber, it can harden efficiently in a short time at low temperature. Moreover, the adhesiveness of a resin component and carbon fiber fully obtains the resin composition hardened | cured material of this embodiment.

Moreover, in the resin composition of this embodiment, the imidazole compound which has only (C) mercapto-group containing compound and (D) one imidazole ring with respect to the total amount of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer. By controlling each content of (E) and an organic peroxide, the hardening rate of a resin composition can be adjusted.

Therefore, the resin composition of this embodiment is useful when using general-purpose carbon fiber and manufacturing hardened | cured material which requires a production cycle higher than an epoxy resin. Specifically, it is suitable for producing molded articles (cured products) using molding methods requiring high production cycles, such as automobile members produced by filament winding molding, resin transfer molding molding, press molding, and the like.

Example

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated based on an Example. This invention is not restrict | limited at all by the Example shown below. The raw material used for the Example and comparative example shown below is as follows.

(Used raw materials)

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

(A) radical reactive resin of (A1-1) (A1-2) (A2-1) (A4-1) was synthesize | combined by the method shown below. The (A) radical reactive resin of each of (A1-1) (A1-2) (A2-1) (A4-1) obtained, and (B) styrene (Idemitsu alkyate) as a radically polymerizable unsaturated monomer are mixed, , (A) component and (B) component were obtained.

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

AER-2603 (Ashihi 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 degreeC for 2 hours in nitrogen gas atmosphere. After the reaction was completed, the reaction was cooled to 90 ° C. Thereafter, 602 g of methacrylic acid, 9 g of triphenylphosphine, 0.9 g of hydroquinone, and 1000 g of styrene were added to the reaction, and the reaction was further carried out at 90 ° C. for 20 hours while blowing air. The reaction was complete | finished when the acid value became 11 mgKOH / g, and the epoxy methacrylate resin (A1-1) was obtained.

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

`` Measurement method of weight average molecular weight ''

Gel-permeation-chromatography (Shodex GPC-101 by Showa Denko Co., Ltd.) was used for the measurement of a weight average molecular weight. The weight average molecular weight was measured at normal temperature on the following conditions, and was computed in polystyrene conversion.

(Measuring conditions)

Column: Showa Denko LF-804, 2

Column temperature: 40 ℃

Sample: 0.4% by mass of tetrahydrofuran solution

Flow rate: 1 ml / min

Eluent: tetrahydrofuran

Furthermore, 1857 g of styrene (made by Idemitsu Alkane) was added to the epoxy methacrylate resin (A1-1) synthesize | combined by said method, and the viscosity in 25 degreeC is 0.8 Pa.s and 50 mass% of solid content. A mixture was obtained.

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

AER-2603 (Ashihi Kasei Co., Ltd. bisphenol A type epoxy resin: epoxy equivalent 189): 1890 g, methacrylic acid: 430 g, hydroquinone: 0.5 g, tree 1.2 g of phenylphosphine was added, and it heated at 100 degreeC, blowing in air, and made it react for about 9 hours. The reaction was terminated when the acid value became 0 mgKOH / g to obtain an epoxy methacrylate resin (A1-2) having at least one epoxy group.

The weight average molecular weight of the epoxy methacrylate resin (A1-2) which has this at least one epoxy group was measured similarly to epoxy methacrylate resin (A1-1). As a result, the weight average molecular weight of the epoxy methacrylate resin (A1-2) which has at least one epoxy group was 619.

Furthermore, 580 g of styrene (made by Idemitsu Alkane) was added to the epoxy methacrylate resin (A1-2) which has the at least 1 epoxy group synthesize | combined by the said method, and the mixture was obtained.

Unsaturated polyester resin (A2-1)

Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 0.8 mol of isophthalic acid, 1.0 mol of 1,2-propanediol, and 1.8 mol of neopentylglycol were charged and heated under a nitrogen gas stream. It heated up to 190 degreeC, stirring. Then, it heated up gradually to 215 degreeC and made it esterify. It cooled to 120 degreeC when the acid value became 9.5 mgKOH / g. Next, maleic anhydride: 2.0 mol was added to the reaction material of esterification reaction, and esterification reaction was performed at 150 degreeC-210 degreeC. It cooled when the acid value became 9.8 mgKOH / g, and obtained unsaturated polyester (A2-1).

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

This was melt | dissolved in styrene (made by Idemitsu altitude), and the unsaturated polyester resin composition whose styrene content is 40 mass% was adjusted.

Urethane methacrylate resin (A4-1)

In a 3-liter four-necked flask equipped with a stirrer, a reflux condenser, a gas inlet tube, and a thermometer, diphenylmethane diisocyanate: 500 g, Actcol D-1000 (polyether polyol manufactured by Mitsui Chemicals, Inc .: weight average molecular weight 1000 ): 700 g, Toho polyethylene glycol # 600 (polyethylene glycol from Toho Kagaku Kogyo Co., Ltd .: weight average molecular weight 600): 180 g, and 0.2 g of dibutyl tin dilaurate were added thereto, and stirred at 60 ° C. for 4 hours. Reacted. Next, 260 g of 2-hydroxyethyl methacrylate was added dropwise to the reaction product over 2 hours, followed by stirring for 5 hours after completion of the dropwise addition to obtain a urethane methacrylate resin (A4-1).

The weight average molecular weight of this urethane methacrylate resin (A4-1) was measured similarly to epoxy methacrylate resin (A1-1). As a result, the weight average molecular weight of urethane methacrylate resin (A4-1) was 5285.

Furthermore, 700 g of styrene (made by Idemitsu alpine acid) was added to the urethane methacrylate resin (A4-1) synthesize | combined by the said method, and the mixture was obtained.

<(B) radically polymerizable unsaturated monomer>

Styrene (Idemitsu alpine)

<(C) mercapto group containing compound>

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

(2) cyanuric acid skeleton trifunctional secondary thiol, manufactured by Showa Denko Co., Ltd., product name: CARENS MT NR1 (1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3, 5-triazine-2,4,6 (1H, 3H, 5H) -trione)

(3) Bifunctional secondary thiols, manufactured by Showa Denko Co., Ltd., product name: Carenz 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 primary thiol, 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, Shikoku Kasei Co., product name: 2E4MZ

(2) 1-benzyl-2-methylimidazole, Shikoku Kasei, product name: 1B2MZ

(3) 2 MZ-H; 2-methylimidazole, Wako Junyakuje, product name: Waco primary 2-methylimidazole

(Imidazole Compounds Having Two or More Imidazole Rings)

(4) 2,2'-bis (o-chlorophenyl) -4,5,4'5'-tetraphenyl- 1,2 'biimidazole, a kurogane catase, a product name: biimidazole

<(E) Organic Peroxide>

Cumene hydroperoxide, Nichiyu Kabushiki Kaisha, product name: Park Mill H-80

<(F) carbon fiber>

(1) T700SC-24000: Toray agent (PAN-based carbon fiber, filament number: 24,000 pieces, tensile strength: 711 ksi (4900 MPa), elongation: about 2%)

<(G) metal soap>

(1) 6% manganese octylate, manufactured by Toei Chemical Co., Ltd., product name: Hexate manganese

(2) Naphthenic cobalt 8%, manufactured by Nippon Kagaku Sangyo Co., Ltd., product name: Naphtex Cobalt

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

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

Other additives; [Curing accelerator] Amine compound, manufactured by Tokyo Kasei Kogyo Co., Ltd., N, N-dimethylbenzylamine

<Examples 1 to 7>

To the mixture of each (A) radical reactive resin of (A1-1) (A1-2) (A4-1) manufactured by said method, and (B) styrene as a radically polymerizable unsaturated monomer, it is a table | surface as needed. (B) radically polymerizable unsaturated monomer shown in 1 was added. This obtained the mixture (mixture of (A) component and (B) component) containing (A) radical reactive resin and (B) radically polymerizable unsaturated monomer in the ratio shown in Table 1.

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

In addition, in the column of (A) radical reactive resin of Table 1, content of only (A) radical reactive resin in the mixture computed from the preparation amount of the raw material used for manufacture of the mixture of (A) component and (B) component was described. . (A) Content of radical reactive resin considered and calculated | required that the raw material used for manufacture of the mixture reacted 100%. In addition, in the column of the (B) radically polymerizable unsaturated monomer in Table 1, only the (B) radically polymerizable unsaturated monomer in the mixture computed from the preparation amount of the raw material used for manufacture of the mixture of (A) component and (B) component. Content was described. (B) Content of the radically polymerizable unsaturated monomer was computed considering the 100% reaction of the raw material used for manufacture of a mixture.

Next, (C) a mercapto group containing compound, (D) imidazole compound, and (E) organic peroxide with respect to a total of 100 mass parts of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer in this order The resin composition which does not contain (F) carbon fiber by adding and stirring in the ratio shown in Table 1 at the ratio shown in Table 1, and adding (G) metal soap as needed in the ratio shown in Table 1 as needed, and stirring Composition).

Comparative Example 1

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

About the composition for carbon fiber reinforced resin obtained in this way, gelation time, hardening time, and hardening temperature were measured in 80 degreeC environment by the following method, and sclerosis | hardenability was evaluated. The results are shown in Table 1.

<Measurement of Curability in 80 ° C Environment>

The evaluation method shown below evaluated gelation time, hardening temperature, and hardening time.

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

In addition, hardening time and the exothermic temperature at that time were defined as hardening temperature, and the time until the resin composition reaches | attains the highest exothermic temperature was measured according to JISK-6901.

As shown in Table 1, it turned out that the resin composition of Examples 1-7 has a short gelation time and hardening time, and can harden | cure efficiently even at low hardening temperature (80 degreeC).

In particular, it is understood that Examples 6 and 7 including (G) metal soap have a shorter gelling time and a curing time, and can be cured efficiently as compared with Example 1 without (G) metal soap. Could.

On the other hand, the resin composition of the comparative example 1 which does not contain the (C) mercapto group containing compound has a long gelling time and hardening time compared with the resin composition of Examples 1-7, and in order to harden | cure at low hardening temperature, 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 radical polymerizable unsaturated monomer was obtained at a ratio shown in Table 2.

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

In addition, in the column of (A) radical reactive resin of Table 2, content of only (A) radical reactive resin in the mixture computed from the preparation amount of the raw material used for manufacture of the mixture of (A) component and (B) component was described. . Content of (A) radical reactive resin considered and calculated | required that the raw material used for manufacture of the mixture reacted 100%. In addition, in the column of (B) radically polymerizable unsaturated monomer in Table 2, only (B) radically polymerizable unsaturated monomer in the mixture computed from the preparation amount of the raw material used for manufacture of the mixture of (A) component and (B) component. Content was described. (B) Content of the radically polymerizable unsaturated monomer considered and calculated | required that the raw material used for manufacture of the mixture reacted 100%.

Next, (C) a mercapto group containing compound, (D) imidazole compound, and (E) organic peroxide with respect to a total of 100 mass parts of (A) radical reactive resin and (B) radically polymerizable unsaturated monomer in this order In addition, it stirred at the ratio shown in Table 2, and obtained the resin composition (composition for carbon fiber reinforced resin) which does not contain (F) carbon fiber.

About each composition for carbon fiber reinforced resin obtained in this way, it carried out similarly to Example 1, the gelation time, hardening time, and hardening temperature were measured in 80 degreeC environment, and curability was evaluated. The results are shown in Table 2. In addition, evaluation of the curability of Example 1 is also shown in Table 2.

As shown in Table 2, it turned out that the resin composition of Examples 8-9 has short gelation time and hardening time, and can harden | cure at low hardening temperature efficiently.

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

<Solubility Evaluation of Resin Composition of Imidazole Compound>

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

Solubility Evaluation Criteria

(Circle): It melt | dissolved.

(Triangle | delta): It was transparent and the some crystal | crystallization which remained without melting was floating.

X: (D) A component did not melt | dissolve and the crystal | crystallization was suspended and turbid.

The resin composition which added the said (D) component to the mixture of the said (A) component and the said (B) component in 25 degreeC environment, and stirred for 2 minutes was made into the test body. About each test body, the haze test was performed while measuring the transmittance | permeability using the haze meter HM-150 by Murakami Shikisai Genju Co., Ltd. according to JISK7361 and K7136. The thickness of the cell at the time of the measurement was 1 cm. The transmittance | permeability and haze were measured 3 times, respectively about each test body, and the average value of the result obtained 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, and Example 8 using 1-benzyl-2-methylimidazole. In the resin composition of Example 9 using the resin composition and 2-methylimidazole, evaluation of solubility was (circle) or (triangle | delta) and was transparent. In addition, as shown in Table 2, the resin compositions of Example 1, Example 8, and Example 9 had high transmittance | permeability and low haze.

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

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

On the other hand, the resin composition of the comparative example 2 using the biimidazole which has two imidazole rings as (D) imidazole compound has low transmittance | permeability, and a haze is compared with the resin composition of Examples 1, 8, and 9 High.

<Examples 10 to 13>

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

In the column of styrene in Table 3, to the mixture of each (A) radical reactive resin and (B) radically polymerizable unsaturated monomer of said (A1-1) (A1-2) (A2-1) (A4-1) The styrene content contained previously and the styrene content as a (B) radically polymerizable unsaturated monomer added as needed were added together and described.

In addition, in the column of (A) radical reactive resin in Table 3, content of only (A) radical reactive resin in the mixture computed from the preparation amount of the raw material used for manufacture of the mixture of (A) component and (B) component was described. . (A) Content of radical reactive resin considered and calculated | required that the raw material used for manufacture of the mixture reacted 100%. In addition, in the column of the (B) radically polymerizable unsaturated monomer in Table 3, only (B) radically polymerizable unsaturated monomer in the mixture computed from the preparation amount of the raw material used for manufacture of the mixture of (A) component and (B) component. Content was described. (B) Content of the radically polymerizable unsaturated monomer was computed considering the 100% reaction of the raw material used for manufacture of a mixture.

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

<Comparative Examples 3 and 5>

(F) Carbon fiber which has a composition shown in Table 3 except having added the (C) mercapto-group containing compound and (D) imidazole compound and adding (G) metal soap, The resin composition (composition for carbon fiber reinforced resin) which did not contain was obtained.

<Comparative Example 4>

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

Thus, about each of the compositions for carbon fiber reinforced resins of Examples 10-13 and Comparative Examples 3-5 which were obtained in this way, it carried out similarly to Example 1, and measured gelation time, hardening time, and hardening temperature in 80 degreeC environment, and was curable 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 gelling time and a curing time, and were able to be cured efficiently at a low curing temperature.

On the other hand, the resin composition of the comparative example 4 using the epoxy resin which is the comparative examples 3 and 5 which do not contain the (C) mercapto-group-containing compound and (D) imidazole compound, and the other resin of Examples 10-13 Compared with the resin composition, it was found that the gelation time and the curing time are long, and more time is required for curing at a lower curing temperature.

Next, the carbon fiber reinforced resin composition in which the resin composition which does not contain the (F) carbon fiber of Examples 10-13 and Comparative Examples 3-5 was impregnated with the (F) carbon fiber shown in Table 3 was manufactured.

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

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

<Production method of CFRP test specimen>

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

As shown in FIG. 1, the obtained carbon fiber reinforced resin composition was wound around 350 laps in the mandrel provided with a flat plate so that the axial length might be 25 cm and the circumferential length was 21 cm. Then, it press-molded in the state wound on the mandrel, it adjusted to thickness 3mm, hardened at 80 degreeC for 1 hour, and 110 degreeC for 2 hours, and obtained CFRP. Moreover, about the comparative example 4, it hardened | cured at 80 degreeC for 2 hours, and 110 degreeC for 3 hours, and obtained CFRP. Then, CFRP was isolate | separated from a mandrel, it cut out from CFRP to predetermined dimension so that the direction of 90 degrees with respect to the orientation of carbon fiber might be long, and it was set as the CFRP test body.

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

From each CFRP, the CFRP test body 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 which measured the mass was burned by the muffle furnace for 4 hours at 400 degreeC, and then 600 degreeC for 20 minutes, and was made into carbon fiber powder only. The mass of the CFRP test body after combustion was measured, and the fiber volume content was calculated using the calculation formula described in JIS K 7075.

Interlayer Shear Strength

From each CFRP, the CFRP test body of length x width x thickness = 21 mm x 10 mm x 3 mm was cut out. About the cut CFRP test body, the interlaminar shear strength was measured using Tensilon UTC-1T made from Orient Tech, according to JISK7078 in the test environment of the temperature of 23 degreeC, and 50% of humidity. The interlaminar shear strength was measured three times for each CFRP. And the average value of three measurement results was used for evaluation of interlayer shear strength.

<Bending Strength>

From each CFRP, the CFRP test body of length x width x thickness = 140 mm x 15 mm x 3 mm was cut out. About the CFRP test piece cut out, bending strength was measured in 120 mm of point-to-point distances using Tensilon UTC-1T made from Orientech in accordance with JISK7074 in the test environment of the temperature of 23 degreeC, and 50% of humidity. The bending strength was measured three times for each CFRP. And the average value of the measurement result of 3 times was used for evaluation of bending strength.

Tensile Strength

A CFRP test body was produced in accordance with JIS K 7165 and a type B test piece. Tensile strength test was carried out on the produced CFRP test body at 150 mm between gripping portions and test speed of 1 mm / min using an Instron 5900R according to JIS K 7161 in a test environment having a temperature of 23 ° C. and a humidity of 50%. Was performed. The tensile strength was measured three times for each CFRP. And the average value of the measurement result of 3 times was used for evaluation of tensile strength.

As shown in Table 3, the CFRP test bodies 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 than the CFRP test bodies of Examples 10 to 13. This is because the CFRP test bodies of Examples 10 to 13 have good adhesiveness between the resin component and the carbon fiber, as compared with the CFRP test bodies of Comparative Examples 3 and 5.

In addition, the CFRP test body of Comparative Example 4 uses a conventional epoxy resin. As shown in Table 3, the CFRP test body of Examples 10-13 can implement the intensity | strength equivalent to the case where an epoxy resin is used.

Claims (14)

As a molded object which consists of hardened | cured material of a carbon fiber reinforced resin composition,
The carbon fiber reinforced resin composition includes (A) a radical reactive resin, (B) a radical polymerizable unsaturated monomer, (C) a mercapto group-containing compound, (D) an imidazole compound having only one imidazole ring, ( E) organic peroxides, and (F) carbon fibers,
The (C) mercapto group-containing compound is a polyfunctional thiol having two or more mercapto groups bonded to a secondary or tertiary carbon atom in the molecule, and all of the mercapto groups are structures represented by the following general formula (Q). Molded body.

(In formula (Q), R <^1> is either a hydrogen atom or an alkyl group of 1 to 10 carbon atoms. R <^2> is an alkyl group of 1 to 10 carbon atoms. * Shows that it is connected to arbitrary organic groups. a is an integer from 0 to 2) The method of claim 1,
The molded article wherein the carbon fiber reinforced resin composition further comprises (G) 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, trimethylolethanetris (3-mercaptobutyrate), trimethylolpropanetris (3 -Mercaptobutyrate). The method according to claim 1 or 2,
The molded article in which the (D) imidazole compound is substituted with an alkyl group, an aryl group or an aralkyl group in one or two positions including the second position of the imidazole ring. The method according to claim 1 or 2,
The molded article in which 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 molded article of the said (A) radical reactive resin is at least 1 sort (s) chosen from an epoxy (meth) acrylate resin, unsaturated polyester resin, polyester (meth) acrylate resin, and urethane (meth) acrylate resin. The method according to claim 1 or 2,
The molded object whose content of the epoxy (meth) acrylate resin which has at least one epoxy group in said (A) radical reactive resin is 1-100 mass%. The method according to claim 1 or 2,
The molded object whose 10-hour half life temperature of said (E) organic peroxide is 30-170 degreeC. The method according to claim 1 or 2,
The molded article wherein the organic peroxide (E) is cumene hydroperoxide or t-butylperoxybenzoate. The method of claim 2,
The molded object whose said (G) metal soap is a manganese compound or a cobalt compound. The method according to claim 1 or 2,
20-99 mass% of (A) radical reactive resins and 1-80 mass% of (B) radically polymerizable unsaturated monomers with respect to the total amount of said (A) radical reactive resin and said (B) radically polymerizable unsaturated monomer. and,
0.001-20 mass parts of said (C) mercapto-group-containing compounds, and only one said (D) imidazole ring with respect to a total of 100 mass parts of said (A) radical reactive resin and said (B) radically polymerizable unsaturated monomer A molded article comprising 0.001 to 10 parts by mass of the imidazole compound having and 0.1 to 10 parts by mass of the organic peroxide (E). The method according to claim 1 or 2,
The molded object whose content of said (F) carbon fiber is 10-90 mass% with respect to a carbon fiber reinforced resin composition. The method according to claim 1 or 2,
Molded body produced by filament winding molding, resin transfer molding molding, press molding. The method according to claim 1 or 2,
Molded products used as automotive parts.

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