CN109071777A - Carbon fiber-reinforced resin composition, carbon fiber-reinforced resin composition, solidfied material - Google Patents

Carbon fiber-reinforced resin composition, carbon fiber-reinforced resin composition, solidfied material Download PDF

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CN109071777A
CN109071777A CN201780029122.5A CN201780029122A CN109071777A CN 109071777 A CN109071777 A CN 109071777A CN 201780029122 A CN201780029122 A CN 201780029122A CN 109071777 A CN109071777 A CN 109071777A
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carbon fiber
methyl
resin composition
acid
reinforced resin
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CN109071777B (en
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黑木博
黑木一博
小林健
小林健一
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Lishennoco Co ltd
Resonac Holdings Corp
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Showa Denko KK
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/01—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to unsaturated polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
    • C08L33/04—Homopolymers or copolymers of esters
    • C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
    • C08L33/08—Homopolymers or copolymers of acrylic acid esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/042—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with carbon fibres
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
    • C08K5/3445—Five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/37—Thiols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/02—Fibres or whiskers
    • C08K7/04—Fibres or whiskers inorganic
    • C08K7/06—Elements

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  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Manufacturing & Machinery (AREA)
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  • Inorganic Chemistry (AREA)
  • Macromonomer-Based Addition Polymer (AREA)
  • Reinforced Plastic Materials (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Epoxy Resins (AREA)

Abstract

The present invention is the carbon fiber-reinforced resin composition only comprising (A) free-radical reactive resin, (B) free-radical polymerised unsaturated monomer, (C) compounds containing thiol groups, (D) with the imidazolium compounds and (E) organic peroxide of 1 imidazole ring.Carbon fiber-reinforced resin composition can also include (G) metallic soap.

Description

Carbon fiber-reinforced resin composition, carbon fiber-reinforced resin composition, solidfied material
Technical field
The present invention relates to can be in low temperature and the short time expeditiously solidifies and can get resin component and carbon fiber The good solidfied material of adaptation carbon fiber-reinforced resin composition, the carbon comprising the carbon fiber-reinforced resin composition Fiber-reinforced resin composition and its solidfied material.
The application based on May 20th, 2016 Japanese publication Patent 2016-101352 CLAIM OF PRIORITY, by its content It quotes herein.
Background technique
In the past, as carbon fiber-reinforced resin composition, it is known that comprising to carbon fiber the good epoxy resin of adaptation, With the composition of carbon fiber.However, the carbon fiber-reinforced resin composition of epoxy resin has been used to need to carry out high temperature and length Time is used for cured heating.
In addition, as carbon fiber-reinforced resin composition, have comprising can be in low temperature and short time cured vinyl The composition of ester resin.However, for it is previous used the carbon fiber-reinforced resin composition of vinyl ester resin for, Gu The adaptation of resin component and carbon fiber in compound is insufficient, therefore the interlayer shear that cannot sufficiently obtain solidfied material sometimes is strong Degree.
In addition, proposing combination documented by patent document 1 and patent document 2 as carbon fiber-reinforced resin composition Object.
It is described in patent document 1 containing resin and six aryl with epoxy group and free-radical polymerised unsaturated group The hardening resin composition of united imidazole.
In addition, being described in patent document 2 containing Epocryl, six aryl united imidazoles, sulfhydrylation Close the composition of object and fiber reinforcement material.
Existing technical literature
Patent document
Patent document 1: Japanese Unexamined Patent Publication 2005-281610 bulletin
Patent document 2: Japanese Unexamined Patent Publication 9-278903 bulletin
Summary of the invention
Problems to be solved by the invention
However, previous can be in low temperature and short time cured carbon fiber-reinforced resin composition, solidfied material The adaptation of resin component and carbon fiber is insufficient.It is therefore desirable in low temperature and short time solidification and tree can be can get The carbon fiber-reinforced resin composition of the good solidfied material of the adaptation of rouge ingredient and carbon fiber.
The present invention is to propose in view of the foregoing, and project is to provide, can be in low temperature and the short time solidifies, and And can get resin component and carbon fiber the good solidfied material of adaptation carbon fiber-reinforced resin composition, as resin Ingredient and the carbon fiber-reinforced resin composition used.
In addition, the subject of the invention is to provide the carbon fiber-reinforced resins comprising above-mentioned carbon fiber-reinforced resin composition Composition.
Further, the subject of the invention is to provide the solidfied materials of above-mentioned carbon fiber-reinforced resin composition.
The method used for solving the problem
The present inventor in order to solve the above problems, and provide can be in low temperature and short time cured fibre reinforced tree Rouge composition, has made intensive studies.Itself as a result, it has been found that, by relative to comprising (A) free-radical reactive resin and (B) from By the composition of base polymerism unsaturated monomer, uses the compound of (C) comprising sulfydryl as curing accelerator, use (D) only Imidazolium compounds and (E) organic peroxide with 1 imidazole ring promote as curing agent to can get significantly high solidification Into function.
It further, the inventors discovered that, include to contain above-mentioned (the A)~composition of (E) and the fibre reinforced of carbon fiber The adaptation of the solidfied material of resin combination, resin component and carbon fiber is good, to contemplate the present invention.
That is, the present invention relates to following scheme.
[1] a kind of carbon fiber-reinforced resin composition, it includes (A) free-radical reactive resins, (B) free radical polymerization Property unsaturated monomer, (C) compounds containing thiol groups, (D) only with 1 imidazole ring imidazolium compounds and (E) organic peroxy Object.
[2] the carbon fiber-reinforced resin composition according to [1] also includes (G) metallic soap.
[3] the carbon fiber-reinforced resin composition according to [1] or [2], above-mentioned (C) compounds containing thiol groups are in molecule It inside include 2 or more sulfydryls.
[4] the carbon fiber-reinforced resin composition according to any one of [1]~[3], above-mentioned (C) chemical combination containing sulfydryl Sulfydryl in object is secondary sulfydryl or tertiary sulfydryl.
[5] the carbon fiber-reinforced resin composition according to any one of [1]~[4], above-mentioned (D) imidazolium compounds For imidazole ring comprising 1 including 2 or 2 positions by alkyl, aryl or aralkyl instead of imidazolium compounds.
[6] the carbon fiber-reinforced resin composition according to any one of [1]~[5], above-mentioned (D) imidazolium compounds For any one of 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 2-methylimidazole.
[7] the carbon fiber-reinforced resin composition according to any one of [1]~[6], above-mentioned (A) radical reaction Property resin be selected from epoxy (methyl) acrylate, unsaturated polyester resin, polyester (methyl) acrylate, amino It is at least one kind of in formic acid esters (methyl) acrylate.
[8] the carbon fiber-reinforced resin composition according to any one of [1]~[7], above-mentioned (A) radical reaction Property resin in epoxy (methyl) acrylate at least one epoxy group content be 1~100 mass %.
[9] the carbon fiber-reinforced resin composition according to any one of [1]~[8], above-mentioned (E) organic peroxy 10 hours half life temperatures of object are 30~170 DEG C.
[10] the carbon fiber-reinforced resin composition according to any one of [1]~[9], above-mentioned (E) organic peroxy Compound is cumyl hydroperoxide or peroxidized t-butyl perbenzoate.
[11] the carbon fiber-reinforced resin composition according to any one of [2]~[10], above-mentioned (G) metallic soap are Manganese compound or cobalt compound.
[12] the carbon fiber-reinforced resin composition according to any one of [1]~[11], certainly relative to above-mentioned (A) It include (A) free-radical reactive resin 20 by the total amount of base reaction resin and above-mentioned (B) free-radical polymerised unsaturated monomer ~99 mass %, (B) free-radical polymerised 1~80 mass % of unsaturated monomer,
Total 100 relative to above-mentioned (A) free-radical reactive resin and above-mentioned (B) free-radical polymerised unsaturated monomer Mass parts, comprising above-mentioned 0.001~20 mass parts of (C) compounds containing thiol groups, above-mentioned (D) only with the imidazoles of 1 imidazole ring Close 0.001~10 mass parts of object, 0.1~10 mass parts of (E) organic peroxide.
[13] a kind of carbon fiber-reinforced resin composition, it includes the fibre reinforceds described in any one of [1]~[12] Resin-forming composition and (F) carbon fiber.
[14] carbon fiber-reinforced resin composition according to [13], the content of above-mentioned (F) carbon fiber is relative to carbon fiber Dimension reinforced resin composition is 10~90 mass %.
[15] carbon fiber-reinforced resin composition according to [13] or [14], described in any one of [1]~[12] Carbon fiber-reinforced resin composition, which is contained, to be immersed in above-mentioned (F) carbon fiber.
[16] a kind of solidfied material is the solidification of described in any item carbon fiber-reinforced resin compositions of [13]~[15] Object.
Invention effect
Carbon fiber-reinforced resin composition comprising carbon fiber-reinforced resin composition of the invention can be at low temperature And the short time expeditiously solidifies.Therefore, requirement high production week can be used in carbon fiber-reinforced resin composition of the invention The forming method of phase forms.
In addition, carbon fiber-reinforced resin composition according to the present invention can get resin component and carbon by making its solidification The good solidfied material of the adaptation of fiber.
Detailed description of the invention
Fig. 1 is the figure of the state of mandrel made of the carbon fiber bundle circumvolution indicated rove shape (mandrel).
Specific embodiment
Hereinafter, to carbon fiber-reinforced resin composition of the invention (hereinafter, being abbreviated as " resin combination " sometimes.) and it is solid Compound is described in detail.
(carbon fiber-reinforced resin composition)
The resin combination of present embodiment includes carbon fiber-reinforced resin composition and carbon fiber.Present embodiment Resin combination preferably make carbon fiber-reinforced resin composition containing being immersed in (F) carbon fiber.
Carbon fiber-reinforced resin composition includes (A) free-radical reactive resin, (B) free-radical polymerised unsaturated list Body, (C) compounds containing thiol groups, (D) are only with the imidazolium compounds and (E) organic peroxide of 1 imidazole ring.
< (A) free-radical reactive resin >
(A) free-radical reactive resin is the resin for having olefinic carbon-to-carbon double bond in side chain and/or main chain.Specifically, It is preferably selected from (A1) epoxy (methyl) acrylate, (A2) unsaturated polyester resin, (A3) polyester (methyl) acrylic acid It is at least one kind of in ester resin, (A4) carbamate (methyl) acrylate.
Here so-called " (methyl) acrylate ", refers at least one kind of in methacrylate and acrylate.
(A1) epoxy (methyl) acrylate is all or part of for the epoxy group for making epoxide be included Epoxy obtained by reacting with unsaturated monoacid (methyl) acrylate has the carbon-to-carbon of free-radical reactive in side chain Double bond.The typical example of above-mentioned unsaturation monoacid is (methyl) acrylic acid, because of referred to herein as epoxy (methyl) acrylate.
As above-mentioned epoxide, monomer, oligomer, polymerization that 1 intramolecular has 2 or more epoxy groups can be used Object is whole, and molecular weight and molecular structure are not particularly limited.It can enumerate for example, biphenyl type epoxy resin；Bisphenol type epoxy tree Rouge, bisphenol f type epoxy resin, bisphenol-s epoxy resin, tetrabromobisphenol A type epoxy resin, tetramethyl bisphenol f type epoxy resin Equal bisphenol-type epoxy resins；Stilbene (Stilbene) type epoxy resin；Phenol novolak type epoxy resin, cresol novolak type The phenolic resin varnish type epoxy resins such as epoxy resin；Triphenol methane type epoxy resin, alkyl-modified triphenol methane type epoxy resin etc. Polyfunctional epoxy resin；Phenol aralkyl-type epoxy resin with phenylene skeleton, the phenol aralkyl with biphenylene skeleton The phenol aralkyl-type epoxy resin such as type epoxy resin；Dihydroxy naphthalene type epoxy resin, 2 aggressiveness of dihydroxy naphthlene shrink it is sweet Oil base is etherified and the naphthol type epoxy resins such as epoxy resin of acquisition；Triglycidyl isocyanurate, monoallyl two shrink The epoxy resin containing triazine core such as glyceryl isocyanuric acid ester；Alicyclic diepoxy acetal, alicyclic diepoxy adipate, The ester ring types polyepoxides such as alicyclic diepoxy carboxylate, vinyl cyclohexene dioxide；Dicyclopentadiene-modified phenol The bridgings ring-type hydrocarbon compound such as type epoxy resin is modified phenol-type epoxy resin；Pass through reacting for the polyacids such as dimeric dibasic acid and epichlorohydrin And the glycidyl esters type epoxy resin obtained；Make above-mentioned epoxy resin and di-isocyanate reaction and containing for obtaining The epoxy resin of oxazolidone ring.
As above-mentioned unsaturated monoacid, well known unsaturated monoacid can be used.It can be cited for example that (methyl) third Olefin(e) acid, crotonic acid, cinnamic acid etc..Wherein, preferably (methyl) acrylic acid.
In addition, can be used as above-mentioned unsaturated monoacid with a hydroxyl and more than one (methyl) acryloyl The compound of base, the reactant with multi-anhydride.
Above-mentioned multi-anhydride can be used in order to increase the molecular weight of above-mentioned epoxy resin and well known to using it is polynary Acid anhydrides.It can enumerate for example, succinic acid, glutaric acid, adipic acid, decanedioic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, four Hydrogen phthalate, hexahydro phthalic acid, dimeric dibasic acid, -2 moles of -2 mol maleic anhydride addition product of ethylene glycol, polyethylene glycol Malaysias Acid anhydride adduct, -2 mol maleic anhydride addition product of propylene glycol, -2 mol maleic anhydride addition product of polypropylene glycol, dodecane two Acid, tridecandioic acid, octadecane diacid, 1,16- (6- ethyl hexadecane) dioctyl phthalate, 1,12- (6- ethyl dodecane) dioctyl phthalate, The acid anhydrides of carboxyl terminal hycar (trade name Hycar CTBN) etc..
In above-mentioned (A1) epoxy (methyl) acrylate, from the viewpoint of toughness imparting, versatility, cost, Preferably bisphenol type epoxy (methyl) acrylate.
Wherein, as (A) free-radical reactive resin, particularly preferably comprising the epoxy (first at least one epoxy group Base) acrylate.(A) epoxy (methyl) acrylate at least one epoxy group in free-radical reactive resin The content of resin is preferably 1~100 mass %, further preferably 20~90 mass %, is even more preferably 30~70 matter Measure %.As epoxy (methyl) acrylate at least one epoxy group, preferably epoxide equivalent is 140~9500 Epoxy (methyl) acrylate, more preferably 190~5000.
Since epoxy (methyl) acrylate at least one epoxy group has free-radical polymerised unsaturation Base, thus at low temperature and the short time solidify.Further, since epoxy (methyl) acrylate at least one epoxy group Resin has epoxy group, therefore the excellent adhesion with carbon fiber.It therefore, include to have extremely in (A) free-radical reactive resin In the case where epoxy (methyl) acrylate of few 1 epoxy group, become rapidly-curable and the adaptation with carbon fiber More excellent carbon fiber-reinforced resin composition.
So-called (A2) unsaturated polyester resin is two made comprising unsaturated dibasic acid and monounsaturated dicarboxylic acid as needed First sour component, the unsaturated polyester resin for carrying out esterification with polyalcohol and obtaining.
As above-mentioned unsaturated dibasic acid, it can be cited for example that, maleic acid, maleic anhydride, fumaric acid, itaconic acid, clothing health Acid anhydrides etc., they may be used singly or in combination of two or more.
As above-mentioned monounsaturated dicarboxylic acid, it can be cited for example that, adipic acid, suberic acid, azelaic acid, decanedioic acid, isosebacic acid Equal aliphatic dibasic acids, phthalic acid, phthalic anhydride, halophthalic acid acid anhydride, M-phthalic acid, terephthaldehyde Acid, tetrachlorophthalic acid, tetrachlorophthalic tetrachlorophthalic anhydrid, dimeric dibasic acid, 2,6- naphthalenedicarboxylic acid, 2,7- naphthalenedicarboxylic acid, 2,3- naphthalene two The aromatic acids such as formic acid, 2,3- naphthalic anhydride, 4,4 '-biphenyl dicarboxylic acids or their dialkyl ester, halogenated saturation two First acid etc., they may be used singly or in combination of two or more.
As above-mentioned polyalcohol, be not particularly limited, can enumerate for example, ethylene glycol, propylene glycol, diethylene glycol (DEG), dipropylene glycol, 1,2- butanediol, 1,3 butylene glycol, 1,4- butanediol, 1,5- pentanediol, 1,6-HD, neopentyl glycol, 2- methyl-1,3- third Glycol, 2- methyl-1,4- butanediol, 2,2- dimethyl -1,3- propylene glycol, 2,2,4- trimethyl -1,3- pentanediol, 2- ethyl - 2- butyl -1,3- propylene glycol, 3- methyl-1,5- pentanediol, triethylene glycol, polyethylene glycol, polypropylene glycol, 1,2- cyclohexane diol, 1,3- cyclohexane diol, 1,4- cyclohexane diol, 1,4 cyclohexane dimethanol, terephthalyl alcohol, connection cyclohexyl -4,4 '-glycol, The dihydric alcohols such as 2,6- decahydronaphthalenes glycol, 2,7- decahydronaphthalenes glycol；
With hydrogenated bisphenol A, cyclohexanedimethanol, bisphenol-A, Bisphenol F, bisphenol S, tetrabromobisphenol A etc. for representative 2 yuan of phenol with Using propylene oxide or ethylene oxide as dihydric alcohols such as the addition products of oxyalkylene (alkylene oxide) of representative；
Alcohol the etc. more than ternarys such as 1,2,3,4- erythritol, glycerol, trimethylolpropane, pentaerythrite.
As (A2) unsaturated polyester resin, within the scope of the effect of the invention, can be used through two rings The unsaturated polyester resin that the bridgings ring-type hydrocarbon compound such as pentadiene is modified.As method of modifying, can enumerate for example, Obtaining the addition product of bicyclopentadiene and maleic acid, (ring decyl alcohol list maleate, Japanese original text are シ デ カ ノ ー Le モ ノ マ レ ー ト) after, it uses it as monoacid and is reacted with above-mentioned unsaturated polyester (UP), import the public affairs such as bicyclopentadiene skeleton The method known.
In above-mentioned (A2) unsaturated polyester resin, from the viewpoint of versatility, cost, preferably ortho position system is unsaturated Polyester resin.
It, can in (A1) epoxy (methyl) acrylate and/or (A2) unsaturated polyester resin used in the present invention To import the oxidation polymerizations such as allyl or benzyl (air curing) base.The introduction method of oxidation polymerization base is not particularly limited, can It enumerates for example, making (A2) unsaturated polyester resin, carrying out condensation reaction with the compound with both hydroxyl and allyl ether Method etc..
(A1) epoxy (methyl) acrylate and/or (A2) unsaturated polyester resin used in the present invention can be with Mixed with polymers containing oxidation polymerization base uses.
In addition, making the reactant of the compound with both hydroxyl and allyl ether and acid anhydrides and there is epoxy group Compound is reacted and obtains reactant, which can be mixed in (A1) epoxy (methyl) third used in the present invention It is used in alkene acid ester resin and/or (A2) unsaturated polyester resin.As the compound with epoxy group, allyl contracting can be enumerated Water glyceryl ether, 2,6- diglycidyl phenyl allyl ether etc..
By importing oxidation polymerization base, as carbon fiber-reinforced resin composition and in the case where use, having makes Drying property greatly improves, and furthermore makes the uniform effect of finishing of film, forming surface.As oxidation polymerization (air curing) base, The particularly preferably group with allyl ether, benzyl ether.
In addition, the so-called oxidation polymerization (air curing) in the present invention, refer in such as allyl ether it is visible, by The adjoint crosslinking of the generation and decomposition of peroxide caused by the oxidation of existing methene key between ehter bond and double bond.
As the monomer for forming the polymer containing oxidation polymerization base, can enumerate with allyl ether, benzyl ether etc. Unsaturated compound.As concrete example, allyl methacrylate, vinyl benzyl butyl ether, vinyl benzyl can be enumerated Hexyl ether, vinyl benzyl Octyl Ether, vinyl benzyl-(2- ethylhexyl) ether, vinyl benzyl ('beta '-methoxy methyl) ether, Vinyl benzyl (n-butoxy propyl) ether, vinyl benzyl cyclohexyl ether, vinyl benzyl-(beta-phenoxy ethyl) ether, second Alkenyl benzyl dicyclopentenyl ether, vinyl benzyl dicyclopentenyl oxygroup ethylether, vinyl benzyl dicyclopentenyl ylmethyl Ether, divinyl benzylic ether etc..
In addition, than that described above, by using (methyl) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid dicyclopentenyl Oxygroup ethyl ester etc., so that the drying property of carbon fiber-reinforced resin composition improves.
(A3) polyester (methyl) acrylate is the polyester with (methyl) acryloxy.(A3) polyester (methyl) Acrylate is for example obtained by the method for (1) or (2) as shown below.
(1) make (methyl) acrylate containing epoxy group or (methyl) acrylate containing hydroxyl and end carboxyl Pet reaction.
(2) make (methyl) acrylic acid or (methyl) acrylate containing isocyanate group and the polyester of end hydroxyl anti- It answers.
As the polyester used in the method for above-mentioned (1) as raw material, end is carboxyl, can enumerate by excess quantity Saturated polybasic acid and/or the polyester that obtains of unsaturated polyacid and polyalcohol.
As the polyester used in the method for above-mentioned (2) as raw material, end is hydroxyl, can enumerate more by being saturated The polyester that the polyalcohol of first acid and/or unsaturated polyacid and excess quantity obtains.
As the saturated polybasic acid for the raw material for being used as (A3) polyester (methyl) acrylate, can enumerate for example, adjacent benzene It is unsaturated that dioctyl phthalate, M-phthalic acid, terephthalic acid (TPA), tetrahydrophthalic acid, adipic acid, decanedioic acid etc. do not have polymerism The polyacid of key or its acid anhydrides.
As be used as polyester (methyl) acrylate raw material unsaturated polyacid, can enumerate for example, fumaric acid, The polymerisms unsaturation polyacid such as maleic acid, itaconic acid or its acid anhydrides.
As polyol component, can enumerate for example, ethylene glycol, propylene glycol, diethylene glycol (DEG), dipropylene glycol, 1,2- butanediol, 1, 3- butanediol, 1,5- pentanediol, 1,6-HD, 2- methyl-1,3-propanediol, 2,2- dimethyl -1,3- propylene glycol, hexamethylene Alkane -1,4- dimethanol, the ethylene oxide adduct of bisphenol-A, propylene oxide adduct of bisphenol-A etc..
(methyl) acrylic acid containing epoxy group used in manufacture as (A3) polyester (methyl) acrylate Ester can enumerate (methyl) glycidyl acrylate.
(methyl) acrylate containing hydroxyl used in manufacture as (A3) polyester (methyl) acrylate, Can enumerate (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxybutyl, (methyl) acrylic acid 2- phenoxy group -2- hydroxy-propyl ester, 2- (methyl) acryloxy -2- hydroxypropyl phthalate Deng.
(methyl) third containing isocyanate group used in manufacture as (A3) polyester (methyl) acrylate Olefin(e) acid ester can enumerate 2- isocyanatoethyl (methyl) acrylate.
In above-mentioned (A3) polyester (methyl) acrylate, from the viewpoint of versatility, cost, preferably make (methyl) glycidyl acrylate, 2- isocyanatoethyl (methyl) acrylate reactions and the polyester (methyl) third obtained Alkene acid ester resin.
So-called (A4) carbamate (methyl) acrylate, for the polyurethane with (methyl) acryloxy. Specifically, can enumerate after reacting polyisocyanates with polyol or polyalcohols, further make containing hydroxyl (methyl) acyclic compound and the allyl ether compound containing hydroxyl as needed and unreacted isocyanate group The oligomer containing free-radical polymerised unsaturated group of reaction and acquisition.
As the polyisocyanates for the raw material for being used as above-mentioned (A4) carbamate (methyl) acrylate, can enumerate For example, 2,4- toluene di-isocyanate(TDI)s and its isomers, methyl diphenylene diisocyanate, hexamethylene diisocyanate, hydrogen Change benzene dimethylene diisocyanate, isophorone diisocyanate, benzene dimethylene diisocyanate, dicyclohexyl methyl hydride two Isocyanates, naphthalene diisocyanate, triphenylmethane triisocyanate, バ ノ ッ Network D-750, Network リ ス ボ Application NK (trade name；Greatly Japanese イ Application キ chemical industry Co. Ltd. system) テ ス モ ジ ュ ー Le L (trade name；Sumitomo バ イ エ Le society system), U ロ ネ ー ト L (trade name；Japanese Port リ ウ レ タ Application system), タ ケ ネ ー ト D102 (trade name；Wu Tian drug society system), イ ソ ネ ー ト 143L (trade name；Society of Mitsubishi Chemical system), デ ュ ラ ネ ー ト シ リ ー ズ (trade name；ケ ミ カ Le Co., Ltd. of Asahi Chemical Industry) etc..
One kind can be only used alone in these polyisocyanates, can also be used in mixed way two kinds or more.These polyisocyanic acid In ester, it is preferable to use methyl diphenylene diisocyanate from the viewpoint of cost.
Polyol used in raw material as above-mentioned (A4) carbamate (methyl) acrylate, can Enumerate polyester polyol, polyether polyol, polycarbonate polyol etc..More specifically, glycerol-ethylene oxide addition can be enumerated Object, glycerine-propylene oxide addition product, glycerol-tetrahydrofuran addition product, glycerol-ethylene oxide-propylene oxide addition product, three hydroxyls Methylpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct, trimethylolpropane-tetrahydrofuran addition Object, trimethylolpropane-ethylene oxide-propylene oxide addition product, dipentaerythritol-ethylene oxide adduct, dipentaerythritol- Propylene oxide adduct, dipentaerythritol-tetrahydrofuran addition product, dipentaerythritol-ethylene oxide-propylene oxide addition product Deng.
One kind can be only used alone in these polyols, can also be used in mixed way two kinds or more.
As the polyalcohols for the raw material for being used as above-mentioned (A4) carbamate (methyl) acrylate, example can be enumerated Such as, ethylene glycol, diethylene glycol (DEG), triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2- methyl-1,3 propylene glycol, 1, The addition product of 3- butanediol, bisphenol-A and propylene oxide or ethylene oxide, 1,2,3,4- erythritol, glycerol, trihydroxy methyl third Alkane, 1,3 butylene glycol, 1,2- cyclohexane diol, 1,3- cyclohexane diol, 1,4- cyclohexane diol, terephthalyl alcohol, connection hexamethylene Base -4,4- glycol, 2,6- decahydronaphthalenes glycol, 2,7- decahydronaphthalenes glycol etc..
One kind can be only used alone in these polyalcohols, can also be used in mixed way two kinds or more.
(methyl) containing hydroxyl as the raw material for being used as above-mentioned (A4) carbamate (methyl) acrylate Acyclic compound, preferably (methyl) acrylate containing hydroxyl.
Specifically, can enumerate for example, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (first Base) acrylic acid 3- hydroxybutyl, (methyl) acrylic acid 4- hydroxybutyl, polyethyleneglycol (methyl) acrylate, polypropylene glycol Single (methyl) acrylate, two (methyl) acrylate of three (hydroxyethyl) isocyanuric acids, pentaerythrite three (methyl) propylene Acid esters, glycerol (list) (methyl) acrylate, Block レ ン マ ー シ リ ー ズ (trade name；Japan Oil Co's system) etc..
One kind can be only used alone in these (methyl) acyclic compounds for containing hydroxyl, can also be used in mixed way two kinds More than.
Contain hydroxyl as the raw material for being used as above-mentioned (A4) carbamate (methyl) acrylate as needed Allyl ether compound, specifically, can enumerate for example, ethylene glycol monoallyl ether, diglycol monotertiary allyl ether, triethylene glycol Mono allyl ether, polyethylene glycol mono allyl ether, propylene glycol mono allyl ether, dipropylene glycol mono allyl ether, tripropylene glycol list Allyl ether, polypropylene glycol mono allyl ether, 1,2- butanediol mono allyl ether, 1,3 butylene glycol mono allyl ether, hexylene glycol Mono allyl ether, ethohexadiol mono allyl ether, trimethylolpropane allyl ether, glycerol diallyl ether, pentaerythrite three Allyl ether etc..
One kind can be only used alone in these allyl ether compounds for containing hydroxyl, can also be used in mixed way two kinds with On.
(A) content of free-radical reactive resin is free-radical polymerised not relative to (A) free-radical reactive resin and (B) It is saturated the total amount of monomer, preferably 20~99 mass %, more preferably 50~90 mass %, further preferably 60~80 matter Measure %.
In addition, other than carbon fiber-reinforced resin of the invention may include (A) free-radical reactive resin with composition Resin component.As suitable example, (A5) (methyl) acrylate can be enumerated.
As (A5) (methyl) acrylate, can enumerate for example, by the homopolymerization of (methyl) acrylate monomer or copolymerization Obtained by (methyl) acrylate.
As (methyl) acrylate monomer for the raw material for being used as above-mentioned (A5) (methyl) acrylate, example can be enumerated Such as, (methyl) methyl acrylate, (methyl) ethyl acrylate, (methyl) propyl acrylate, (methyl) n-butyl acrylate, (first Base) isobutyl acrylate, (methyl) tert-butyl acrylate, (methyl) amyl acrylate, (methyl) Hexyl 2-propenoate, (methyl) third Olefin(e) acid heptyl ester, (methyl) 2-EHA, (methyl) n-octyl, (methyl) Isooctyl acrylate monomer, (methyl) The positive nonyl ester of acrylic acid, the different nonyl ester of (methyl) acrylic acid, (methyl) decyl acrylate, (methyl) lauryl acrylate, (methyl) Tridecyl acrylate, (methyl) stearyl acrylate base ester, (methyl) cyclohexyl acrylate, (methyl) benzyl acrylate, (first Base) acrylic acid dicyclopentenyl ester, (methyl) acrylic acid 2- dicyclopentenyl oxygroup ethyl ester, (methyl) isobornyl acrylate, (first Base) methoxyethyl acrylate, (methyl) ethoxyethyl acrylate, (methyl) acrylate, butoxy ethyl, (methyl) propylene Sour tetrahydro furfuryl ester, (methyl) acrylic acid 2- hydroxy methacrylate, (methyl) acrylic acid 2- hydroxy propyl ester, (methyl) acrylic acid 4- hydroxyl Butyl ester, (methyl) acrylic acid, (methyl) acryloyl morpholine etc..
One kind can be only used alone in these (methyl) acrylate monomers, can also be used in mixed way two kinds or more.
As (A5) (methyl) acrylate, from the cost, reactivity of polymer from the viewpoint of, it is preferable to use first The homopolymer of base (methyl) acrylate and using methyl (methyl) acrylate as the copolymer of principal component.
(A) in free-radical reactive resin, synthesis is unsaturated poly- selected from (A1) epoxy (methyl) acrylate, (A2) It is ester resin, (A3) polyester (methyl) acrylate, at least one kind of in (A4) carbamate (methyl) acrylate Used catalyst and/or polymerization inhibitor can remain when above.
As catalyst, can enumerate for example, triethylamine, pyridine derivate, imdazole derivatives, imdazole derivatives etc. contain uncle The compound of nitrogen-atoms；The amine salt such as tetramethyl ammonium chloride, triethylamine；With the phosphorus compounds such as trimethyl-phosphine, triphenylphosphine etc..
As polymerization inhibitor, can enumerate for example, quinhydrones, methylnaphthohydroquinone and phenthazine etc..
In the case where (A) free-radical reactive resin contains catalyst and/or polymerization inhibitor, content is relative to (A1) ring Oxygen (methyl) acrylate, (A2) unsaturated polyester resin, (A3) polyester (methyl) acrylate and (A4) amino Total 100 mass parts of formic acid esters (methyl) acrylate, are respectively preferably 0.001~2 mass parts.
The free-radical polymerised unsaturated monomer > of < (B)
(B) free-radical polymerised unsaturated monomer makes hardness, intensity, chemically-resistant to reduce the viscosity of resin combination Moral character, water resistance etc. are improved and are used.
As above-mentioned (B) free-radical polymerised unsaturated monomer, it is not particularly limited, it is however preferred to have vinyl or (first Base) acryloyl group free-radical polymerised unsaturated monomer.In addition, so-called in the present specification " (methyl) acryloyl group ", is Refer to acryloyl group and/or methylacryloyl.
As (B) free-radical polymerised unsaturated monomer with vinyl, can enumerate for example, styrene, to chlorobenzene second Alkene, vinyltoluene, α-methylstyrene, dichlorostyrene, divinylbenzene, t-butyl styrene, vinyl acetate, benzene two Formic acid diallyl, triallyl isocyanurate etc..
As (B) free-radical polymerised unsaturated monomer with (methyl) acryloyl group, can enumerate for example, (methyl) third Olefin(e) acid ester etc..
As (methyl) acrylate, can enumerate for example, (methyl) methyl acrylate, (methyl) ethyl acrylate, (first Base) n-butyl acrylate, (methyl) 2-EHA, (methyl) lauryl acrylate, (methyl) acrylate Ester, (methyl) benzyl acrylate, (methyl) stearyl acrylate base ester, (methyl) tridecyl acrylate, (methyl) acrylic acid Dicyclopentenyl oxygroup ethyl ester, (methyl) phenoxyethyl acrylate, (methyl) acrylic acid 2- hydroxy methacrylate, ethylene glycol list first Base ether (methyl) acrylate, ethylene glycol monomethyl ether (methyl) acrylate, ethylene glycol mono hexyl ether (methyl) acrylate, Ethylene glycol single 2-ethyl hexyl ether (methyl) acrylate, diethylene glycol monomethyl ether (methyl) acrylate, diethylene glycol monoethyl Ether (methyl) acrylate, diethylene glycol (deg) two (methyl) acrylate, dipropylene glycol two (methyl) acrylate, polyethylene glycol two (methyl) acrylate, polytetramethylene ether diol two (methyl) acrylate, 1,3 butylene glycol two (methyl) acrylate, 1, 6- hexylene glycol two (methyl) acrylate, neopentyl glycol two (methyl) acrylate, 2- hydroxyl -1,3- two (methyl) acryloyl-oxy Base propane, 2,2- bis- (4- (methacryl base oxethyl) phenyl propanes, the bis- (4- (methacryloxies/diethoxy of 2,2- Base) phenyl propane, 2,2- bis- (4- (methacryloxy/more ethyoxyls) phenyl propanes, tetraethylene glycol two (methyl) acrylic acid Modified (n=2) two (methyl) acrylate of ester, bisphenol-A EO, isocyanuric acid EO modified (n=3) two (methyl) acrylate, three Hydroxymethyl-propane two (methyl) acrylate, glycerol two (methyl) acrylate, trimethylolpropane tris (methyl) acrylate, Glycerol three (methyl) acrylate, pentaerythrite four (methyl) acrylate, dipentaerythritol six (methyl) acrylate, season penta (methyl) acrylate of tetrol two monostearate, dicyclopentenyl (methyl) acrylate, (methyl) tricyclodecyl acrylate, (methyl) tricyclodecyl acrylate or three (2- hydroxyethyl) isocyanuric acid (methyl) acrylate etc..
In addition, above-mentioned so-called EO is modified, referring to has (poly-) oxyethylene chain (- CH2-CH2- O-), n refers to (poly-) oxygen second The number of alkene chain.
These (B) free-radical polymerised unsaturated monomers can be used alone or two or more is applied in combination.
It is excellent from the viewpoint of operability, curability and cost in above-mentioned (B) free-radical polymerised unsaturated monomer Choosing uses styrene.
(B) content of free-radical polymerised unsaturated monomer is relative to (A) free-radical reactive resin and (B) radical polymerization The total amount of conjunction property unsaturated monomer, preferably 1~80 mass %, more preferably 10~50 mass %, further preferably 20~ 40 mass %.
< (C) compounds containing thiol groups >
(C) compounds containing thiol groups work as curing accelerator.
(C) compounds containing thiol groups are preferably selected from secondary mercaptan compound (C1) or sulfydryl of the sulfydryl in conjunction with secondary carbon One or more of tertiary mercaptan compound (C2) in conjunction with tertiary carbon atom.(C) compounds containing thiol groups are in order to solid in shorter time Change, particularly preferably secondary mercaptan compound (C1).
For secondary mercaptan compound (C1) compared with the primary mercaptan compound of end configuration sulfydryl, storage stability is good.Tertiary sulphur Alcoholic compound (C2) is the compound that sulfydryl is not configured in end in the same manner as secondary mercaptan compound (C1).Therefore, tertiary mercaptan chemical combination Object (C2) is used as (C) compounds containing thiol groups, has the function similar with secondary mercaptan compound (C1).
In order to keep the function as curing accelerator excellent, (C) compounds containing thiol groups it is preferable to use intramolecular include 2 with The multi-functional thiol of upper sulfydryl.
Here so-called " multi-functional thiol " refers to the compounds containing thiol groups that the sulfydryl as functional group is 2 or more.
It is especially excellent as (C) compounds containing thiol groups in order to solidify carbon fiber-reinforced resin composition in shorter time Choosing uses mercaptan more than 3 functions in molecule with 3 or more sulfydryls.
About (C) compounds containing thiol groups, in order to solidify carbon fiber-reinforced resin composition in shorter time, preferably With the multi-functional thiol of 2 or more the sulfydryls in conjunction with secondary carbon or tertiary carbon atom in molecule.
As the compound in molecule with 2 or more the sulfydryls in conjunction with secondary carbon or tertiary carbon atom, without special Limitation preferably for example, having structure shown at least one following formula (Q), and includes in structure shown in following formula (Q) Including sulfydryl, with the compound of 2 or more the sulfydryls in conjunction with secondary carbon or tertiary carbon atom in molecule.
(in formula (Q), R1Among aromatic series base for hydrogen atom, the alkyl of carbon atom number 1~10 and carbon atom number 6~18 It is any.R2For the alkyl of carbon atom number 1~10 or the aromatic series base of carbon atom number 6~18.* indicate with arbitrarily it is organic Base connection.The integer that a is 0~2.)
As (C) compounds containing thiol groups, in particular, more preferably there is structure shown in formula (Q), and the R in formula (Q)1 For hydrogen atom, with the compound of 2 or more the sulfydryls in conjunction with secondary carbon in molecule.That is, (C) compounds containing thiol groups are preferred It is the secondary mercaptan compound of secondary carbon for the carbon atom that the sulfydryl with structure shown in formula (Q), and in formula (Q) combines (C1)。
In addition, the R in formula (Q)1And R2In carbon atom number 1~10 alkyl can for straight-chain may be branched. Specifically, methyl, ethyl, various propyl, various butyl, various amyls, various hexyls, various heptyl, various pungent can be enumerated Base etc..
In addition, it is so-called " various ", refer to comprising n-, sec-, tert-, iso- various isomers.In these alkyl, preferably Methyl and ethyl.
In addition, as the R in formula (Q)1And R2In carbon atom number 6~18 aromatic series base, can enumerate for example, phenyl, benzyl Base, naphthalene, anthryl, phenanthryl etc..In addition, these aromatic series bases can be replaced by halogen atom, amino, nitro, cyano etc..
The integer that a in formula (Q) is 0~2, preferably 1.
Further, (C) compounds containing thiol groups preferably have ester structure shown at least one following formula (Q-1).
(in formula (Q-1), R1、R2, R in * and a and above-mentioned formula (Q)1、R2, * with a meaning it is identical.)
A in formula (Q-1) is preferably 1.Stability, solidification in the case where above-mentioned a is 1, from control resin combination It is preferred from the viewpoint of property.In particular, in R1For hydrogen atom ((Q-1) compound represented is secondary mercaptan compound (C1)) In the case where, from the viewpoint of the control stability of resin combination, curability, a in formula (Q-1) is preferably 1.
Ester structure shown in formula (Q-1) be preferably using contain shown in following formula (S) sulfydryl carboxylic acid and polyalcohol as The ester structure in source.
(in formula (S), R1、R2With the R in a and above-mentioned formula (Q)1、R2It is identical with a meaning.)
As above-mentioned polyalcohol, ethylene glycol, diethylene glycol (DEG), triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, double third can be enumerated Glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2- propylene glycol, 1,3- propylene glycol, 1,3 butylene glycol, 1,4- butanediol, 1,2- pentanediol, 1,3- pentanediol, 2,3- pentanediol, 1,4- pentanediol, 1,5- pentanediol, 1,6-HD, 1,9- nonanediol, Tricyclodecane Dimethanol, (bis- (2- hydroxyethoxyphenyl) propane of 2,2-), bisphenol-A alkylen oxide adducts, Bisphenol F oxyalkylene add At object, bisphenol S alkylen oxide adducts, 1,4- cyclohexanediol, 1,4 cyclohexane dimethanol, 1,2- hexylene glycol, 1,3- hexylene glycol, 2, 3- hexylene glycol, 1,4- hexylene glycol, 2,4- hexylene glycol, 3,4- hexylene glycol, 1,5- hexylene glycol, 2,5-HD, 1,6-HD, 9, The dihydric alcohols such as bis- [4- (2- hydroxyethyl) phenyl] fluorenes of 9-；Glycerol, diglycerol, trimethylolethane, trimethylolpropane, double three Hydroxymethyl-propane, isocyanuric acid three (2- hydroxyethyl) ester, hexane triol, D-sorbite, pentaerythrite, dipentaerythritol, sugarcane The alcohol more than ternarys such as sugar, bis- (the 2,3- dihydroxypropyl phenyl) propane of 2,2-；Other polycarbonate glycol, dimeric dibasic acid Polyester polyol etc..
Wherein, from the viewpoint of accessibility and from the viewpoint of improving curability, preferably ethylene glycol, 1,2- third The dihydric alcohols such as glycol, 1,3- propylene glycol, 1,4- butanediol；Glycerol, trimethylolethane, trimethylolpropane, isocyanuric acid three The ternarys such as bis- (the 2,3- dihydroxypropyl phenyl) propane of (2- hydroxyethyl) ester, pentaerythrite, dipentaerythritol, 2,2- with On alcohol；Polycarbonate glycol, dimer acid polyester polyhydric alcohols.In particular, from reactivity, under low-vapor pressure operability it is good this From the viewpoint of sample, preferably 1,4-butanediol, trimethylolethane, trimethylolpropane, (the 2- hydroxyl second of isocyanuric acid three Base) ester, pentaerythrite, polycarbonate glycol, dimer acid polyester polyhydric alcohols.
(secondary mercaptan compound (C1))
In the case where (C) compounds containing thiol groups are secondary mercaptan compound (C1) with structure shown in above-mentioned formula (Q), As its concrete example, 3- mercaptobutyric acid, 3- sulfydryl phthalic acid two (1- mercaptoethyl) ester, (the 2- mercapto of phthalic acid two can be enumerated Base propyl) ester, phthalic acid two (3- mercaptobutyl) ester, ethylene glycol bis- (3- mercaptobutylates), bis- (the 3- mercaptobutyric acids of propylene glycol Ester), diethylene glycol (DEG) bis- (3- mercaptobutylates), butanediol bis- (3- mercaptobutylates), ethohexadiol bis- (3- mercaptobutylates), three hydroxyls Methyl ethane three (3- mercaptobutylate), trimethylolpropane tris (3- mercaptobutylate), (the 3- mercaptobutyric acid of pentaerythrite four Ester), dipentaerythritol six (3- mercaptobutylate), ethylene glycol bis- (2 mercaptopropionic acid esters), propylene glycol bis- (2 mercaptopropionic acid esters), Diethylene glycol (DEG) bis- (2 mercaptopropionic acid esters), butanediol bis- (2 mercaptopropionic acid esters), ethohexadiol bis- (2 mercaptopropionic acid esters), trihydroxy methyl Propane three (2 mercaptopropionic acid ester), pentaerythrite four (2 mercaptopropionic acid ester), dipentaerythritol six (2 mercaptopropionic acid ester), second two Alcohol bis- (4- mercaptopentanoic acid esters), diethylene glycol (DEG) bis- (4- mercaptopentanoic acid esters), butanediol bis- (4- mercaptopentanoic acid esters), the bis- (4- of ethohexadiol Mercaptopentanoic acid ester), trimethylolpropane tris (4- mercaptopentanoic acid ester), pentaerythrite four (4- mercaptopentanoic acid ester), dipentaerythritol Six (4- mercaptopentanoic acid esters), ethylene glycol bis- (3- mercaptopentanoic acid esters), propylene glycol bis- (3- mercaptopentanoic acid esters), bis- (the 3- mercaptos of diethylene glycol (DEG) Base valerate), butanediol bis- (3- mercaptopentanoic acid esters), ethohexadiol bis- (3- mercaptopentanoic acid esters), trimethylolpropane tris (3- sulfydryl Valerate), pentaerythrite four (3- mercaptopentanoic acid ester), dipentaerythritol six (3- mercaptopentanoic acid ester), bis- (the 3- mercaptos of hydrogenated bisphenol A Base butyrate), bisphenol-A dihydroxy ethyl ether -3- mercaptobutylate, bis- (2- Phenoxyethyl (the 3- mercaptos of 4,4 '-(9- fluorenylidenes) Base butyrate)), ethylene glycol bis- (3- sulfydryl -3- phenylpropionic acid esters), propylene glycol bis- (3- sulfydryl -3- phenylpropionic acid esters), diethylene glycol (DEG) Bis- (3- sulfydryl -3- phenylpropionic acid esters), butanediol bis- (3- sulfydryl -3- phenylpropionic acid esters), the bis- (3- sulfydryl -3- phenyl of ethohexadiol Propionic ester), trimethylolpropane tris (3- sulfydryl -3- phenylpropionic acid ester), three -2- (3- sulfydryl -3- phenylpropionic acid ester) ethyl it is different Cyanurate, pentaerythrite four (3- sulfydryl -3- phenylpropionic acid ester), dipentaerythritol six (3- sulfydryl -3- phenylpropionic acid ester) etc..
In addition, in the case where secondary mercaptan compound (C1) is the compound with ester structure shown in above-mentioned formula (Q-1), The compound is preferably to be made with the carboxylic acid containing the sulfydryl in conjunction with secondary carbon shown in above-mentioned polyalcohol and above-mentioned formula (S) For the compound in source.As the carboxylic acid containing sulfydryl shown in above-mentioned formula (S), can enumerate 2 mercaptopropionic acid, 3- mercaptobutyric acid, 3- sulfydryl -3- phenylpropionic acid etc..
Among secondary mercaptan compound (C1), as the commercially available product of the secondary mercaptan of simple function, 3- mercaptobutyric acid (Showa electricity can be enumerated Work Co. Ltd. system, product name: 3MBA), as the compound in molecule with 2 or more the sulfydryls in conjunction with secondary carbon Commercially available product can enumerate bis- (the 3- sulfydryl butyryl acyloxy) butane of Isosorbide-5-Nitrae-(Showa Denko K. K's system, カ レ Application ズ MT (registrar Mark) BD1), pentaerythrite four (3- mercaptobutylate) (Showa Denko K. K's system, カ レ Application ズ MT (registered trademark) PE1), 1,3,5- tri- (3- sulfydryl butyryl acyloxy ethyl) -1,3,5- triazine -2,4,6 (1H, 3H, 5H)-triketone (Showa Denko K. K System, カ レ Application ズ MT (registered trademark) NR1), trimethylolethane trimethacrylate (3- mercaptobutylate) (Showa Denko K. K's system, TEMB), trimethylolpropane tris (3- mercaptobutylate) (Showa Denko K. K's system, TPMB) etc. is, it is preferable to use their 1 Kind or more.
(tertiary mercaptan compound (C2))
In the case where (C) compounds containing thiol groups are tertiary mercaptan compound (C2) with structure shown in above-mentioned formula (Q), As its concrete example, phthalic acid two (2- mercapto-isobutyl) ester, ethylene glycol bis- (2- mercaptoisobutanoic acid esters), propylene glycol can be enumerated Bis- (2- mercaptoisobutanoic acid esters), diethylene glycol (DEG) bis- (2- mercaptoisobutanoic acid esters), butanediol bis- (2- mercaptoisobutanoic acid esters), ethohexadiol are double (2- mercaptoisobutanoic acid esters), trimethylolethane trimethacrylate (2- mercaptoisobutanoic acid esters), trimethylolpropane tris (2- mercaptoisobutyric acid Ester), pentaerythrite four (2- mercaptoisobutanoic acid esters), dipentaerythritol six (2- mercaptoisobutanoic acid esters), (the 3- mercapto of phthalic acid two Base -3- methyl butyl) ester, ethylene glycol bis- (3- sulfydryls -3 Methylbutanoic acid ester), propylene glycol bis- (3- sulfydryls -3 Methylbutanoic acid ester), Diethylene glycol (DEG) bis- (3- sulfydryls -3 Methylbutanoic acid ester), butanediol bis- (3- sulfydryls -3 Methylbutanoic acid ester), bis- (the 3- sulfydryls-of ethohexadiol 3 Methylbutanoic acid ester), trimethylolethane trimethacrylate (3- sulfydryl -3 Methylbutanoic acid ester), trimethylolpropane tris (3- sulfydryl -3- first Base butyrate), pentaerythrite four (3- sulfydryl -3 Methylbutanoic acid ester), dipentaerythritol six (3- sulfydryl -3 Methylbutanoic acid ester) Deng.
In addition, in the case where tertiary mercaptan compound (C2) is the compound with ester structure shown in above-mentioned formula (Q-1), The compound is preferably to be made with the carboxylic acid containing the sulfydryl in conjunction with tertiary carbon atom shown in above-mentioned polyalcohol and above-mentioned formula (S) For the compound in source.As the carboxylic acid containing sulfydryl shown in above-mentioned formula (S), 2- mercaptoisobutyric acid, 3- sulfydryl -3- can be enumerated Methylbutanoic acid etc..
(C) compounds containing thiol groups are relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Total 100 mass parts, preferably comprise 0.001~20 mass parts.More preferably 0.01~10 mass parts, further preferably 0.1 ~5 mass parts.
< (D) imidazolium compounds >
(D) imidazolium compounds that the resin combination of present embodiment is included only has 1 imidazole ring, not comprising having The compound of multiple imidazole rings.(D) imidazolium compounds works as curing agent.
As (D) imidazolium compounds, can enumerate for example, imidazoles, 2-methylimidazole, 2- undecyl imidazole, 2- heptadecane Base imidazoles, DMIZ 1,2 dimethylimidazole, 2-ethyl-4-methylimidazole, 2- phenylimidazole, 2- phenyl -4-methylimidazole, 1- benzyl - 2-methylimidazole, 1- benzyl -2- phenylimidazole, 1- cyano ethyl -2-methylimidazole, 1- cyano ethyl -2- undecyl imidazole, 1- cyano ethyl -2-ethyl-4-methylimidazole, 1- cyano ethyl -2- phenylimidazole, 1- cyano ethyl -2- undecyl imidazoleTrimellitic acid salt, 1- cyano ethyl -2- phenylimidazoleTrimellitic acid salt, 2,4- diamino -6- [2 '-methylimidazolyls - (1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-undecyl imidazole base-(1 ')]-ethyl-s-triazine, 2,4- diamino Base -6- [2 '-ethyls -4 '-methylimidazolyl-(1 ')]-ethyl-s-triazine, 2,4- diamino -6- [2 '-methylimidazolyls - (1 ')]-ethyl-s-triazine isocyanuric acid adduct, 2- phenylimidazole isocyanuric acid adduct, 2- phenyl -4,5- dihydroxy first Base imidazoles, 2- phenyl -4- methyl -5- hydroxymethylimidazole, 2,3- dihydro -1H- pyrrolo--[1,2-a] benzimidazole, 1- 12 Alkyl -2- methyl-3-benzyl imidazoleChloride, 2- benzylimidazoline etc..
As (D) imidazolium compounds, from it is different from polyaddition type, due to being therefore catalyst type is carried out with a small amount of additive amount Solidify, the aspect excellent as the function of curing accelerator, and (A) free-radical reactive resin and (B) it is free-radical polymerised Unsaturated monomer it is excellent in compatibility from the aspect of, it is preferable to use 5 member rings of imidazoles include 1 or 2 positions including 2 Set by alkyl, aryl or aralkyl instead of imidazolium compounds.
Abovementioned alkyl is preferably carbon atom number 1~6, more preferably carbon atom number 1~3.Above-mentioned aryl is preferably carbon atom Number 6~20, more preferably carbon atom number 6~12.Above-mentioned aralkyl is preferably carbon atom number 7~20, more preferably carbon atom number 7 ~12.
As such (D) imidazolium compounds, 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 2- can be enumerated Methylimidazole.As (D) imidazolium compounds, 2-ethyl-4-methylimidazole or 1 benzyl 2 methyl imidazole are particularly preferably used.
(D) conjunction of the imidazolium compounds relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer 100 mass parts are counted, 0.001~10 mass parts are preferably comprised.More preferably 0.01~5 mass parts, further preferably 0.1~2 Mass parts.
< (E) organic peroxide >
(E) organic peroxide works as curing agent.As (E) organic peroxide, in general, can be used for (A) organic mistake that free-radical reactive resin and (B) free-radical polymerised unsaturated monomer are used as free radical curing agent Oxide.Specifically, the peroxidating such as the peroxidating two acyls such as benzoyl peroxide base system, peroxidized t-butyl perbenzoate can be enumerated The dialkyls systems such as the hydroperoxides such as ester system, cumyl hydroperoxide system, cumyl peroxide, methyl ethyl ketone mistake The ketone peroxides such as oxide, acetylacetone peroxide system, ketal peroxide system, alkyl super-acid ester system, peroxocarbonate system etc. Public organic peroxide.
The organic peroxide for the use of 10 hours half life temperatures being particularly preferably wherein 30~170 DEG C, more preferably uses 40 DEG C~160 DEG C of organic peroxide.
It is excellent as (E) organic peroxide wherein in particular, from the aspect of the mixed stability to resin Choosing uses cumyl hydroperoxide or peroxidized t-butyl perbenzoate.Cumyl hydroperoxide and peroxidized t-butyl perbenzoate are all It is with the compound that free radical (- O (oxygen)-O (oxygen) -) key is decomposed and generated when solidifying.Perbenzoic acid is used The case where tert-butyl ester, compared with the case where having used cumyl hydroperoxide, is able to extend service life (storage period, pot life).When obtaining the curability same with cumyl hydroperoxide using peroxidized t-butyl perbenzoate, as long as than using The case where hydrogen oxide isopropylbenzene, improves solidification temperature.
(E) organic peroxide is relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Total 100 mass parts are 0.1~10 mass parts, preferably 0.5~5 mass parts, more preferably 0.5~2 mass parts.
< (F) carbon fiber >
As (F) carbon fiber, any carbon fiber manufactured by various manufacturing methods can be used.Can be used for example, The carbon fiber of asphalt series, PAN (polyacrylonitrile) system, the vapor phase growth genealogy of law etc..(F) shape of carbon fiber is not particularly limited, can To be used alone or in combination for example, the shape of rove shape, knitted fabric shape, cloth (cloth) shape, felt (mat) shape.
(F) carbon fiber contains 10~90 mass %, further preferably 30~80 mass % preferably in resin combination.Such as The content of fruit (F) carbon fiber is above range, then fully obtains the reinforcing effect by generating comprising (F) carbon fiber.
(F) carbon fiber is preferably included in carbon fiber in such a way that the containing rate of fiber volume of solidfied material becomes 40~70% and increases In strong resin-forming composition.
The other ingredient > of <
The carbon fiber-reinforced resin composition of present embodiment is other than above-mentioned each ingredient, as needed also comprising following Ingredient.
< (G) metallic soap >
(G) metallic soap works as curing accelerator.As (G) metallic soap, using long chain fatty acids or organic acid, with The salt of metallic element.
Long chain fatty acids can suitably be selected according to the type of the metallic soap as target.It is excellent as long chain fatty acids It is selected as the fatty acid of carbon atom number 7~30, can be for example, enanthic acid, octanoic acid, n-nonanoic acid, capric acid, neodecanoic acid, hendecanoic acid, 12 Alkanoic acid, tetradecanoic acid, hexadecanoic acid, octadecanoid acid, arachic acid, behenic acid, lignoceric acid, hexacosoic acid, two The unsaturated fatty acids such as the saturated fatty acids such as octadecanoid acid, melissic acid, aphthenic acids and oleic acid, linoleic acid, linolenic acid.
In addition, as long chain fatty acids, also can be used stearic acid, 1,2-hydroxystearic acid, lauric acid, myristic acid, Palmitinic acid, mountainAcid, rosin acid, linseed oil fatty acid, soya-bean oil resin acid, tall oil acid etc..
Organic acid can suitably be selected according to the type of the metallic soap as target.It is preferably solvable as organic acid In the organic acid of organic solvent, can be used for example, formic acid, acetic acid, citric acid, oxalic acid, benzoic acid, also amino acid, carboxylic acid Ester, carboxylate, carboxyl acyl chloride, dicarboxylic acids, bile acid, saccharic acid, hydroxycinnamic acid, carboxylic acid, aromatic acid, thioesters (thioester), folic acid etc. generally has carboxyl and is classified as the organic acid etc. of carboxylic acid.
In addition, as organic acid, also can be used as with sulfo group, hydroxyl, mercapto, enol base as characteristic base Acidic Compounds and ascorbic acid, α acid, acid imide acid, arabo-ascorbic acid, crocic acid (croconic as use Acid), kojic acid, squaric acid, sulfinic acid, sulfonic acid, teichoic acid, thioacetic acid, dehydroactic acid, δ acid, uric acid, hydroxamic acid, humic Acid, fulvic acid, phosphonic acids, meldrum's acid (Meldrum's acid) etc..
In long chain fatty acids or organic acid, preferably long chain fatty acids, the more preferably chain or ring of carbon atom number 7~15 The saturated fatty acid of shape or the unsaturated fatty acid of carbon atom number 7~15, further preferably octanoic acid and aphthenic acids.
Metallic element can enumerate vanadium, gold, silver, palladium, platinum, ruthenium, rhodium, tin, lead, zinc, iron, nickel, cobalt, lithium, aluminium, indium, neodymium, manganese, Cerium, calcium, zirconium, copper, barium, magnesium, terres rares etc..
In these metallic elements, the preferably metallic element of the metallic element of the 2nd race and the 3rd~12 race, more preferably Barium, vanadium, manganese, iron, cobalt, copper and zinc, further preferably manganese, iron, cobalt, copper and zinc are still more preferably manganese and cobalt.
As (G) metallic soap, can be used for example, manganese naphthenate, manganese octoate, cobalt naphthenate, cobalt octoate, zinc octoate, pungent The metal soaps such as sour vanadium, copper naphthenate, barium naphthanate.
In these metallic soaps, as (G) metallic soap, it is preferable to use manganese compound or cobalt compound, particularly preferably general The high manganese naphthenate of property, manganese octoate, cobalt naphthenate, cobalt octoate.
In the case where containing (G) metallic soap, the content to be converted by metal component of (G) metallic soap is relative to (A) Total 100 mass parts of free-radical reactive resin and (B) free-radical polymerised unsaturated monomer, preferably 0.0001~0.3 Mass parts, more preferably 0.001~0.2 mass parts, further preferably 0.006~0.1 mass parts.By making (G) metallic soap The content to be converted by metal component 0.0001~0.3 mass parts range, so as in low temperature and short time Carbon fiber-reinforced resin composition is more efficiently solidified, therefore preferably.
(polymerization inhibitor)
From the viewpoint of inhibiting the viewpoint of resin combination excessively polymerizeing, controlling reaction speed, present embodiment Resin combination may include polymerization inhibitor.As polymerization inhibitor, can enumerate known in quinhydrones, methylnaphthohydroquinone, pyrocatechol, phenthazine etc. Polymerization inhibitor.
(cure retarder)
For the purpose for the solidification delay for making resin combination, the resin combination of present embodiment may include solidification and prolong Slow agent.As cure retarder, free base system cure retarder can be enumerated, can be enumerated for example, 2,2,6,6- tetramethyl -1- piperidines Base oxygroup, free radical (TEMPO), 4- hydroxyl -2,2,6,6- tetramethyl piperidine 1- oxygroup, free radical (4H-TEMPO), 4- oxo - 2,2,6,6- tetramethyl -1- piperidyl oxygroup, the TEMPO derivative such as free radical (4-Oxo-TEMPO).Wherein, in terms of cost, From the aspect of handling easiness, 4- hydroxyl -2,2,6,6- tetramethyl piperidine 1- oxygroups, free radical (4H-TEMPO) is preferred 's.
Contain the case where polymerization inhibitor and/or cure retarder are as constituent in the resin combination of present embodiment Under, total 100 matter of their content relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Measure part, preferably respectively 0.0001~10 mass parts.
(other curing accelerators)
In the resin combination of present embodiment, to improve curability as a purpose, in addition to above-mentioned (C) chemical combination containing sulfydryl Object, (D) only with the imidazolium compounds of 1 imidazole ring, (E) organic peroxide and (G) metallic soap that contains as needed with Outside, other curing accelerators be may include.
As above-mentioned other curing accelerators, the amine such as the phosphorus compounds such as trimethyl-phosphine, triphenylphosphine, amine, amine salt can be enumerated Class.Specifically, aniline, n,N-Dimethylaniline, N can be used, and N- diethylaniline, para-totuidine, N, N- dimethyl-right Toluidines, N, bis- (2- the hydroxyethyl)-para-totuidine of N-, 4- (N, N- dimethylamino) benzaldehyde, 4- [bis- (the 2- hydroxyls of N, N- Ethyl) amino] benzaldehyde, 4- (N- methyl-N-hydroxy ethylamino) benzaldehyde, N, bis- (2- the hydroxypropyl)-para-totuidine of N-, N- ethyl-meta-aminotoluene, triethanolamine, meta-aminotoluene, diethylenetriamines, pyridine, phenylmorpholine, piperidines, N, the bis- (hydroxyls of N- Ethyl) N such as aniline, diethanolaniline, N- substituted aniline, N, N- substitution-para-totuidine, 4- (N, N- substituted-amino) benzaldehyde etc. Amine etc..
Other curing accelerators are relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Total 100 mass parts are preferably contained with 0.01~10 mass parts, more preferably with the range of 0.1~5 mass parts.
(Photoepolymerizationinitiater initiater)
For the purpose for improving curability, the resin combination of present embodiment may include Photoepolymerizationinitiater initiater.Make For Photoepolymerizationinitiater initiater, can enumerate for example, optical free radical polymerization initiator, light cationic polymerization initiator, time ionic polymerization Initiator etc..
Optical free radical polymerization initiator makes to improve the curability of the acrylic resin with double bond, monomer With.
Specifically, benzoin ether system, two as benzoin alkylether can be enumerated as optical free radical polymerization initiator Benzophenone series, benzil dimethyl ketal, the 2,2- diethoxies such as Benzophenone, benzil, methyl o-benzoylbenzoic acid ester The benzene second such as acetophenone, 2- hydroxy-2-methyl propiophenone, 4- isopropyl -2- hydroxy-2-methyl propiophenone, 1,1- dichloroacetophenone The optical free radical polymerization initiator of the thioxanthones systems such as ketone system, 2-chlorothioxanthone, 2- methyl thioxanthones, 2-isopropylthioxanthone.
In addition, curability of the light cationic polymerization initiator for epoxy resin for improving cyclic ether etc., oxetanes And it uses.
Specifically, triaryl matte hexafluorophosphate, triaryl matte hexafluoro can be enumerated as light cationic polymerization initiator Stibate, triarylsulfonium salt, tolylcumyl iodineFour (pentafluorophenyl group) borates, 4- isobutyl phenenyl (4- aminomethyl phenyl) IodineHexafluorophosphate, triaryl matte hexafluorophosphate, triaryl matte four (pentafluorophenyl group) borate etc..
In addition, time cation polymerization initiator uses to improve the curability of epoxy resin etc..
Conjunction of the Photoepolymerizationinitiater initiater relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer 100 mass parts are counted to add with the range of 0.1~10 mass parts.
(defoaming agent)
In the resin combination of present embodiment, the gas bubbles left of bubble generation, molded product when for improvement molding Defoaming agent can be used in purpose.As defoaming agent, silicon systems defoaming agent, polymer system defoaming agent etc. can be enumerated.
The usage amount of defoaming agent is relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Total 100 parts by weight, the range of 0.01~5 parts by weight is preferably.More preferably 0.1~1 parts by weight.
(coupling agent)
In the resin combination of present embodiment, in the purpose for improving mouldability or make to mention with the adaptation of carbon fiber Under high purpose, coupling agent can be used.As coupling agent, silane series coupling agent, titanate esters system coupling agent, aluminium system can be enumerated Coupling agent etc..
As such coupling agent, it can be cited for example that, R3-Si(OR4)3Shown in silane coupling agent.In addition, as R3, It can enumerate for example, aminopropyl, glycidyl oxygroup, methacryloxy, N- phenyl amino propyl, sulfydryl and ethylene Base etc., as R4, can enumerate for example, methyl, ethyl etc..
The usage amount of coupling agent is relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Total 100 mass parts, the range of 0.01~1 mass parts is preferably.
(light stabilizer)
In the resin combination of present embodiment, for the purpose for improving the long durability of molded product, it can be used Light stabilizer.As light stabilizer, ultraviolet absorbing agent, amine system of being obstructed light stabilizer can be enumerated.They can be used alone, Two or more can be applied in combination.Specifically, enumerate BTA system, triazine system, hexichol first can be enumerated as ultraviolet absorbing agent Ketone system, cyanoacrylate system, salicylate system etc. can enumerate N-H type, N-CH3 type, N-O as the amine system light stabilizer that is obstructed Alkyl type etc..
The usage amount of light stabilizer is relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Total 100 mass parts, the preferably range of 0.01~5 mass parts, more preferably 0.05~2 mass parts.
(wax)
The resin combination of present embodiment can wrap the content of wax.As wax, it can be used alone or and use paraffin class (paraffin), the known object of various fusing points can be used in polarity wax class etc..
As polarity wax class, the polarity wax class that polar group and nonpolar base are had both in structure can be enumerated.Specifically, can lift NPS-8070, NPS-9125 (Japanese Jing La society system), エ マ ノ ー Application 3199,3299 (Hua Wang society system) etc. out.
Total 100 mass of the wax relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Part, preferably comprise 0.05~4 mass parts, further preferably 0.1~2.0 mass parts.
(fire retardant)
The resin combination of present embodiment may include fire retardant.As fire retardant, it can be used alone or and use bromine Flame retardant, chlorine-based flame retardant, phosphorus flame retardant, inorganic flame retardant, expansion flame retardant, silicon-series five-retardant etc., can make With well known fire retardant.
In addition, the halogen-system fire retardants such as bromide fire retardant can be with three oxidations for the purpose for further increasing anti-flammability Antimony is used in combination.
The additive amount of fire retardant is different according to system, but relative to (A) free-radical reactive resin and (B) radical polymerization Total 100 mass parts of conjunction property unsaturated monomer, preferably comprise 1~100 mass parts.
(filling material)
In the resin combination of present embodiment, in the range that does not impair the effects of the present invention, in control specific feature Inorganic filler and organic filler etc. can be cooperated to fill material under purpose.They may be used alone, can also be used in combination 2 kinds with On.
As inorganic filler, the pyrolysis of the mobility of the aluminium hydroxide for assigning anti-flammability, control resin combination can be enumerated Method silica, talcum, calcium carbonate etc. and the inorganic pigments such as the titanium oxide coloured, other colorants.
In addition, as organic filler, for the purpose of the raising of viscosity, imparting thixotroping, organobentonite class etc. can be enumerated.
The usage amount of material is filled relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Total 100 mass parts, the range of 1~200 mass parts is preferably.
(manufacturing method of carbon fiber-reinforced resin composition)
The method for manufacturing the resin combination of present embodiment is not particularly limited, by utilizing well known method by (A) Free-radical reactive resin and (B) free-radical polymerised unsaturated monomer (or (A) free-radical reactive resin and (B) free radical The mixture of polymerism unsaturated monomer), (C) compounds containing thiol groups, (D) only with 1 imidazole ring imidazolium compounds, (E) Organic peroxide, (G) metallic soap (any ingredient) contained as needed and other ingredients and (F) carbon fiber are mixed To obtain.
The resin combination of present embodiment particularly preferably passes through will be in addition to above-mentioned each ingredient other than (F) carbon fiber mixes And carbon fiber-reinforced resin composition is made, make it containing the method being dipped into (F) carbon fiber to manufacture.
The solidfied material of present embodiment is the solidfied material of the resin combination of present embodiment.
As the cured method of resin combination for making present embodiment, as long as can be by resin combination in solidification institute The method heated at a temperature of needing, it is, for example, possible to use the methods that heating furnace or heater etc. are heated.
Alloing the cured temperature of resin combination is for example, 5~200 DEG C, preferably 15~150 DEG C, more preferably 60 ~120 DEG C.Heating time can be for example, 1~180 minute, preferably 1~120 minute, more preferably 1~60 minute.
The resin combination of present embodiment is due to including (A) free-radical reactive resin, (B) free-radical polymerised insatiable hunger With monomer, (C) compounds containing thiol groups, (D) only with imidazolium compounds, (E) organic peroxide and (F) carbon of 1 imidazole ring Fiber, therefore can be in low temperature and the short time efficiently solidifies.In addition, the solidfied material of the resin combination of present embodiment The adaptation of resin component and carbon fiber can sufficiently be obtained.
In addition, in the resin combination of present embodiment, by controlling relative to (A) free-radical reactive resin and (B) (C) compounds containing thiol groups, (D) of the total amount of free-radical polymerised unsaturated monomer only have the imidazoles chemical combination of 1 imidazole ring Each content of object, (E) organic peroxide, can adjust the curing rate of resin combination.
Therefore, the resin combination of present embodiment manufactured using general carbon fiber require it is more higher than epoxy resin It is useful in the case where the solidfied material of production cycle.Specifically, being suitable for through fiber winding forming, resin transfer moulding Molding, extrusion forming etc. and the forming method of automobile component etc., requirement high production cycle that produces come the product of being manufactured (Gu Compound) the case where.
Embodiment
Hereinafter, illustrating the present invention based on embodiment.The present invention is not by embodiment described below any restrictions.It is as shown below Embodiment and comparative example used in raw material it is as described below.
(using raw material)
The mixture > of < (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer
By method as shown below, (A) the free-radical reactive tree of (A1-1) (A1-2) (A2-1) (A4-1) has been synthesized Rouge.By each (A) free-radical reactive resin of resulting (A1-1) (A1-2) (A2-1) (A4-1) and as (B) radical polymerization Styrene (the emerging production system of light out) mixing of conjunction property unsaturated monomer, obtains the mixture of (A) ingredient Yu (B) ingredient.
" epoxy methacrylates resin (A1-1) "
In the reaction unit for having blender, reflux cooler, gas introduction tube and thermometer, AER-2603 is added (society of Asahi Chemical Industry bisphenol A type epoxy resin: epoxide equivalent 189): 1890g, bisphenol-A: 342g and myristyl benzyl dimethyl Ammonium chloride: 7g reacts 2 hours at 150 DEG C in a nitrogen atmosphere.After the completion of reaction, reactant is cooling until 90 DEG C. Then, methacrylic acid is added in reactant: 602g, triphenylphosphine: 9g, quinhydrones: 0.9g and styrene: 1000g, on one side Air is blown into further to react at 90 DEG C 20 hours on one side.Reaction was completed at the time of acid value becomes 11mgKOH/g, obtains Epoxy methacrylates resin (A1-1).
The weight average molecular weight of resulting epoxy methacrylates resin (A1-1) is measured by method as shown below.Its As a result, the weight average molecular weight of epoxy methacrylates resin (A1-1) is 3395.
" measuring method of weight average molecular weight "
In the measurement of weight average molecular weight, gel permeation chromatography (Showa Denko K. K Shodex GPC- has been used 101).Weight average molecular weight measures at normal temperature under the following conditions, is converted and is calculated using polystyrene.
(determination condition)
Column: Showa electrician LF-804,2
Column temperature: 40 DEG C
Sample: 0.4 mass % tetrahydrofuran solution of determinand
Flow: 1ml/ minutes
Eluent: tetrahydrofuran
In addition, styrene (light out is added in the epoxy methacrylates resin (A1-1) synthesized by the above method Emerging production system) 1857g, obtain the mixture that the viscosity at 25 DEG C is 0.8Pas, solid component is 50 mass %.
" the epoxy methacrylates resin (A1-2) with epoxy group "
In the reaction unit for having blender, reflux cooler, gas introduction tube and thermometer, AER-2603 is added (society of Asahi Chemical Industry bisphenol A type epoxy resin: epoxide equivalent 189): 1890g, methacrylic acid: 430g, quinhydrones: 0.5g, triphen Base phosphine 1.2g, is blown into air on one side, is heated to 100 DEG C on one side, reacts about 9 hours.Knot at the time of acid value becomes 0mgKOH/g Shu Fanying obtains the epoxy methacrylates resin (A1-2) at least one epoxy group.
It is operated in the same way with epoxy methacrylates resin (A1-1) and determines the ring at least one epoxy group The weight average molecular weight of oxygen methacrylate resin (A1-2).As a result, the epoxy methacrylic acid at least one epoxy group The weight average molecular weight of ester resin (A1-2) is 619.
In addition, in the epoxy methacrylates resin (A1- at least one epoxy group synthesized by the above method 2) styrene (the emerging production system of light out) 580g is added in, obtains mixture.
" unsaturated polyester resin (A2-1) "
In the four-hole boiling flask for having thermometer, blender, non-active gas introducing port and reflux cooler, isophthalic is added Dioctyl phthalate: 0.8 mole, 1,2-PD: 1.0 moles and neopentyl glycol: 1.8 moles, one side heating stirring under stream of nitrogen gas It is heated up on one side until 190 DEG C.Then, it slowly heats up and has carried out esterification until 215 DEG C.Become 9.5mgKOH/g in acid value At the time of it is cooling until 120 DEG C.Next, maleic anhydride is added in the reactant of esterification: 2.0 moles, 150 DEG C~ Esterification has been carried out at 210 DEG C.It is cooling at the time of acid value becomes 9.8mgKOH/g, obtain unsaturated polyester (UP) (A2-1).
Next, adding quinhydrones: 0.5 mass parts in the unsaturated polyester (UP) (A2-1).Fumaric acid is in unsaturated dibasic acid Shared ratio (ratio of the fumaric acid changed from maleic anhydride) is 90 moles of % in ingredient.
It makes it dissolve in styrene (the emerging production system of light out), adjusts out the unsaturated polyester (UP) tree that styrene-content is 40 mass % Oil/fat composition.
" urethane methacrylate resin (A4-1) "
In the 4 mouthfuls of flasks for the 3L for having blender, reflux cooling tube, gas introduction tube and thermometer, diphenyl is added Methane diisocyanate: 500g, ア Network ト コ ー Le D-1000 (Mitsui Chemicals (strain) polyether polyol processed: weight average molecular weight 1000): 700g, ト ー ホ ー Port リ エ チ レ Application グ リ コ ー Le #600 (eastern nation's chemical industry (strain) polyethylene glycol processed: divides equally again 600) son is measured: 180g and dibutyl tin dilaurate: 0.2g, stirring 4 hours at 60 DEG C makes its reaction.Then, in its reactant In, on one side through 2 hours dropwise addition 2-hydroxyethyl methacrylates: being stirred while 260g, stirring 5 hours after completion of dropwise addition makes it Reaction, obtains urethane methacrylate resin (A4-1).
It is operated in the same way with epoxy methacrylates resin (A1-1) and determines the carbamate methacrylic acid The weight average molecular weight of ester resin (A4-1).As a result, the weight average molecular weight of urethane methacrylate resin (A4-1) It is 5285.
In addition, benzene second is added in the urethane methacrylate resin (A4-1) synthesized by the above method Alkene (the emerging production system of light out) 700g, obtains mixture.
The free-radical polymerised unsaturated monomer > of < (B)
Styrene (the emerging production system of light out)
< (C) compounds containing thiol groups >
(1) the 4 secondary mercaptan of function, Showa Denko K. K's system, product name: カ レ Application ズ MT PE1 (four (3- of pentaerythrite Mercaptobutylate))
(2) the secondary mercaptan of 3 function of cyanurate skeleton, Showa Denko K. K's system, product name: カ レ Application ズ MT NR1 (1, 3,5- tri- (3- sulfydryl butyryl acyloxy ethyl) -1,3,5- triazine -2,4,6 (1H, 3H, 5H)-triketone)
(3) the 2 secondary mercaptan of function, Showa Denko K. K's system, product name: カ レ Application ズ MT BD1 (bis- (the 3- sulfydryls of Isosorbide-5-Nitrae- Butyryl acyloxy) butane)
(4) the secondary mercaptan of simple function, Showa Denko K. K's system, product name: 3MBA (3- mercaptobutyric acid)
(5) the 4 primary mercaptan of function, SC organic chemistry Co. Ltd. system, product name: PEMP ((the 3- mercaptopropionic acid of pentaerythrite four Ester))
< (D) imidazolium compounds >
(only with the imidazolium compounds of 1 imidazole ring)
(1) 2-ethyl-4-methylimidazole, four countries' chemical conversion system, product name: 2E4MZ
(2) 1 benzyl 2 methyl imidazole, four countries' chemical conversion system, product name: 1B2MZ
(3)2MZ-H；2-methylimidazole and the pure medicine system of light, product name: and 2 methylimidazole of light level-one (has 2 or more miaows The imidazolium compounds of azoles ring)
(4) 2,2 '-bis- (Chloro-O-Phenyl) -4,5,4 ' 5 '-tetraphenyl -1,2 ' bisglyoxalines, dark fund chemical conversion system, product name: connection Imidazoles
< (E) organic peroxide >
Cumyl hydroperoxide, Japan Oil Co's system, product name: パ ー Network ミ Le H-80
< (F) carbon fiber >
(1) T700SC-24000: eastern レ system (PAN based carbon fiber, long filament number: 24,000, tensile strength: 711ksi (4900MPa), elongation: about 2%)
< (G) metallic soap >
(1) manganese octoate 6%, Dong Rong Chemical Co., Ltd system, product name: ヘ キ ソ エ ー ト マ Application ガ Application
(2) cobalt naphthenate 8%, chemistry Industry Co., Ltd of Japan system, product name: Na Off テ ッ Network ス U バ Le ト
Other resins；Epoxy resin, Mitsubishi chemical Co., Ltd's system, product name: jER828
Other additives；(curing agent) acid anhydrides, Hitachi Chemical Co., Ltd., product name: (3- methyl hexahydro is adjacent by HN-5500 The mixture of phthalate anhydride and 4- methylhexahydrophthalic anhydride)
Other additives；(curing accelerator) amine compounds, Tokyo Chemical Industry Co., Ltd's system, N, N- dimethyl benzyl Amine
< Examples 1 to 7 >
Each (A) free-radical reactive resin and conduct in (A1-1) (A1-2) (A4-1) manufactured by the above method (B) in the mixture of the styrene of free-radical polymerised unsaturated monomer, (B) radical polymerization shown in table 1 is added as needed Conjunction property unsaturated monomer.Being obtained as a result, with ratio shown in table 1 includes (A) free-radical reactive resin and (B) radical polymerization The mixture (mixture of (A) ingredient and (B) ingredient) of conjunction property unsaturated monomer.
[table 1]
In styrene column in table 1, by each (A) free-radical reactive resin of above-mentioned (A1-1) (A1-2) (A4-1) with (B) styrene-content for including in advance and the conduct being added as needed in the mixture of free-radical polymerised unsaturated monomer (B) styrene-content of free-radical polymerised unsaturated monomer adds up to and records.
In addition, describing in (A) free-radical reactive resin column in table 1 by the mixing of (A) ingredient and (B) ingredient The only content of (A) free-radical reactive resin in the mixture that the additional amount of raw material used in the manufacture of object calculates.(A) freely The content of base reaction resin is that raw material used in the manufacture of mixture is considered as 100% and has reacted and calculated.In addition, table 1 In the free-radical polymerised unsaturated monomer column (B) in, describing is made by (A) ingredient and the manufacture of the mixture of (B) ingredient The content of only (B) free-radical polymerised unsaturated monomer in mixture that the additional amount of raw material calculates.(B) radical polymerization The content of conjunction property unsaturated monomer is that raw material used in the manufacture of mixture is considered as 100% and has reacted and calculated.
Then, total 100 matter relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Measure part, by (C) compounds containing thiol groups, (D) imidazolium compounds, (E) organic peroxide successively with ratio shown in table 1 be added into Row stirring, further (G) metallic soap is added with ratio shown in table 1 as needed and is stirred, be free of (F) carbon fiber Resin combination (carbon fiber-reinforced resin composition).
1 > of < comparative example
It is operated similarly with example 1 in addition to this without (C) compounds containing thiol groups, is free of (F) carbon fiber Resin combination (carbon fiber-reinforced resin composition).
Each carbon fiber-reinforced resin composition that such operate is obtained, through following methods, under 80 DEG C of environment Gelation time, curing time, solidification temperature are measured, curability is had rated.It the results are shown in table 1.
Curability under 80 DEG C of environment of < measures >
By evaluation assessment as shown below, gelation time, solidification temperature, the evaluation of curing time have been carried out.
Resin combination is added to test tube (outer diameter 18mm, length 165mm) at room temperature until depth 100mm, setting The temperature of resin combination is determined by thermocouple in the oil bath for being heated to 80 DEG C.The temperature of measurement resin combination becomes Until becoming 85 DEG C of the time it takes after 65 DEG C, it is set as gelation time.
In addition, the timing definition until resin combination is reached highest heating temperature is curing time, by hair at this time Hot temperature is defined as solidification temperature, measures according to JIS K-6901.
As shown in Table 1, the gelation time of the resin combination of Examples 1 to 7 and curing time are short, even if low Solidification temperature (80 DEG C) under also can efficiently solidify.
Especially it is found that embodiment 6 and embodiment 7 comprising (G) metallic soap and 1 phase of embodiment for being free of (G) metallic soap Than gelation time and curing time are short, can efficiently solidify.
In contrast it is found that the tree of the resin combination of the comparative example 1 without (C) compounds containing thiol groups and Examples 1 to 7 Oil/fat composition is compared, and gelation time and curing time are long, in order to make its solidification under low solidification temperature, when needing more Between.
< embodiment 8~9,2 > of comparative example
It operates similarly with example 1, obtaining with ratio shown in table 2 includes (A) free-radical reactive resin and (B) The mixture of free-radical polymerised unsaturated monomer.
[table 2]
In the styrene column in table 2, by each (A) free-radical reactive resin of above-mentioned (A1-1) (A1-2) (A4-1) With the styrene-content for including in advance in the mixture of (B) free-radical polymerised unsaturated monomer and the work being added as needed Styrene-content for (B) free-radical polymerised unsaturated monomer adds up to and records.
In addition, describing in (A) free-radical reactive resin column in table 2 by the mixing of (A) ingredient and (B) ingredient The content of only (A) free-radical reactive resin in mixture that the additional amount of raw material used in the manufacture of object calculates.(A) certainly Content as base reaction resin is that raw material used in the manufacture of mixture is considered as 100% and has reacted and calculated.In addition, In free-radical polymerised unsaturated monomer column (B) in table 2, the manufacture institute of the mixture by (A) ingredient Yu (B) ingredient is described The content of only (B) free-radical polymerised unsaturated monomer in mixture that the additional amount of the raw material used calculates.(B) free radical The content of polymerism unsaturated monomer is that raw material used in the manufacture of mixture is considered as 100% and has reacted and calculated.
Then, total 100 matter relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Measure part, by (C) compounds containing thiol groups, (D) imidazolium compounds, (E) organic peroxide successively with ratio shown in table 2 be added into Row stirring, is free of the resin combination (carbon fiber-reinforced resin composition) of (F) carbon fiber.
Each carbon fiber-reinforced resin composition obtained to such operate, operates similarly with example 1, at 80 DEG C Gelation time, curing time, solidification temperature are measured under environment, have rated curability.It the results are shown in table 2.In addition, table In 2, the evaluation of the curability of embodiment 1 is also shown together.
As shown in Table 2, the gelation time of the resin combination of embodiment 8~9 and curing time are short, consolidate in low Also can efficiently it solidify at a temperature of change.
In contrast, used bisglyoxaline as the comparative example 2 of (D) imidazolium compounds resin combination and embodiment 1, 8,9 resin combination is compared, and gelation time and curing time are long.
Dissolubility of the < imidazolium compounds in resin combination evaluates >
Under 25 DEG C of environment, relative to (A) free-radical reactive resin shown in table 2 and (B) free-radical polymerised insatiable hunger With 100 mass parts of mixture of monomer, (D) imidazolium compounds is stirred with the addition of ratio shown in table 2.In turn, upper It states in the mixture of (A) ingredient and above-mentioned (B) ingredient and above-mentioned (D) ingredient is added, start after stirring to see by visual observation after 2 minutes The state for examining resin combination passes through the dissolubility (compatibility) of above-mentioned (D) ingredient of following benchmark evaluations.It the results are shown in In table 2.
" dissolubility evaluation criteria "
Zero: dissolution.
△: it is transparent, it dissolves remaining several crystals and suspends.
×: (D) ingredient is insoluble, and crystal suspends and muddy.
Will under 25 DEG C of environment, be added in the mixture of above-mentioned (A) ingredient and above-mentioned (B) ingredient above-mentioned (D) ingredient into The resin combination that 2 minutes stir of having gone is set as test body.To each test body, according to JIS K 7361, K 7136, using in village Dye technology studies made haze meter HM-150 and measures transmissivity, and has carried out haze test.Unit (cell) when measurement With a thickness of 1cm.About transmissivity and mist degree, each test body is measured 3 times respectively, the average value of resulting result is used in It is evaluated shown in table 2.
As shown in table 2, used 2-ethyl-4-methylimidazole as the resin combination of the embodiment 1 of (D) imidazolium compounds Object, used 1 benzyl 2 methyl imidazole as the embodiment 8 of (D) imidazolium compounds resin combination, used 2- methyl Imidazoles is evaluated as zero or △ as the deliquescent of resin combination of the embodiment 9 of (D) imidazolium compounds, is transparent.This Outside, as shown in table 2, the transmissivity of the resin combination of embodiment 1, embodiment 8, embodiment 9 is high, and mist degree is low.
Thus, it can be known that used in the embodiment 1,8,9 only (D) imidazolium compounds with 1 imidazole ring with (A) from By the excellent in compatibility of base reaction resin and (B) free-radical polymerised unsaturated monomer.
In particular, having used the resin combination of the embodiment 1 of 2-ethyl-4-methylimidazole as (D) imidazolium compounds Object does not confirm the suspension of crystal, dissolubility with the resin combination of the embodiment 8 of 1 benzyl 2 methyl imidazole has been used Evaluation is good.
In contrast, used the bisglyoxaline with 2 imidazole rings as the resin of the comparative example 2 of (D) imidazolium compounds For composition compared with the resin combination of embodiment 1,8,9, transmissivity is low, and mist degree is high.
10~13 > of < embodiment
It operates similarly with example 1, obtaining with ratio shown in table 3 includes (A) free-radical reactive resin and (B) The mixture of free-radical polymerised unsaturated monomer.
[table 3]
In the styrene column in table 3, by each (A) radical reaction of above-mentioned (A1-1) (A1-2) (A2-1) (A4-1) The styrene-content that includes in advance in property resin and the mixture of (B) free-radical polymerised unsaturated monomer and add as needed The styrene-content as (B) free-radical polymerised unsaturated monomer added adds up to and records.
In addition, describing in (A) free-radical reactive resin column in table 3 by the mixing of (A) ingredient and (B) ingredient The content of only (A) free-radical reactive resin in mixture that the additional amount of raw material used in the manufacture of object calculates.(A) certainly Content as base reaction resin is that raw material used in the manufacture of mixture is considered as 100% and has reacted and calculated.In addition, In free-radical polymerised unsaturated monomer column (B) in table 3, the manufacture institute of the mixture by (A) ingredient Yu (B) ingredient is described The content of only (B) free-radical polymerised unsaturated monomer in mixture that the additional amount of the raw material used calculates.(B) free radical The content of polymerism unsaturated monomer is that raw material used in the manufacture of mixture is considered as 100% and has reacted and calculated.
Then, total 100 matter relative to (A) free-radical reactive resin and (B) free-radical polymerised unsaturated monomer Part is measured, (C) compounds containing thiol groups, (D) imidazolium compounds, (E) organic peroxide are stirred with the addition of ratio shown in table 3 It mixes, is free of the resin combination (carbon fiber-reinforced resin composition) of (F) carbon fiber.
< comparative example 3,5 >
(C) compounds containing thiol groups, (D) imidazolium compounds are added without, joined (G) metallic soap, in addition to this, with embodiment 1 operates in the same way, and obtains the resin combination (carbon fiber-reinforced resin without (F) carbon fiber with composition shown in table 3 With composition).
4 > of < comparative example
Relative to 100 mass parts of other resins (epoxy resin) shown in table 3, by the acid anhydrides and amine as other additives Compound is stirred with the addition of ratio shown in table 3, is free of the resin combination (fibre reinforced of (F) carbon fiber Resin-forming composition).
Each carbon fiber-reinforced resin composition of embodiment 10~13, comparative example 3~5 that such operate is obtained, It operates similarly with example 1, gelation time, curing time, solidification temperature is measured under 80 DEG C of environment, has rated solidification Property.It the results are shown in table 3.
As shown in Table 3, the gelation time of the resin combination of embodiment 10~13 and curing time are short, Neng Gou Efficiently solidify under low solidification temperature.
In contrast it is found that being free of the comparative example 3,5 of (C) compounds containing thiol groups and (D) imidazolium compounds and having used work For the epoxy resin of other resins comparative example 4 resin combination compared with the resin combination of embodiment 10~13, gel Change the time and curing time is long, in order to solidify under low solidification temperature, needs the more time.
Then, produce embodiment 10~13, comparative example 3~5 the resin combination without (F) carbon fiber by containing being immersed in Carbon fiber-reinforced resin composition in (F) carbon fiber shown in table 3.
Then, using resulting carbon fiber-reinforced resin composition, CFRP (carbon fiber is produced by method as shown below Tie up reinforced plastics) test body.
Embodiment 10~13, the CFRP test body of comparative example 3~5 obtained about such operate, by as shown below Method to have rated containing rate of fiber volume (content of the carbon fiber relative to carbon fiber-reinforced resin composition), interlayer shear strong Degree, bending strength, tensile strength.It the results are shown in table 3.
The production method > of < CFRP test body
The carbon fiber bundle of rove shape is put into the leaching filled with resin combination (carbon fiber-reinforced resin composition) In stain slot, resin combination is made to be impregnated in carbon fiber bundle, carbon fiber-reinforced resin composition is made.
As shown in Figure 1, resulting carbon fiber-reinforced resin composition is become axial long around the mandrel for being provided with plate Degree is 25cm, the mode circumvolution 350 for the sample size that circumferential lengths are 21cm circle carries out and silk.Then, in circumvolution in mandrel It is press-formed under state, so as to adjust for thickness 3mm, solidifies 1 hour at 80 DEG C, solidify 2 hours at 110 DEG C, obtain Obtained CFRP.In addition, solidifying 2 hours at 80 DEG C about comparative example 4, solidifies 3 hours at 110 DEG C, obtain CFRP.So Afterwards, CFRP is removed from mandrel, from CFRP to provide in a manner of becoming long side relative to the direction for being oriented to 90 ° of carbon fiber Size cut out, CFRP test body is made.
< containing rate of fiber volume (content of the carbon fiber relative to carbon fiber-reinforced resin composition) >
From each CFRP cut-out length × width × thickness=35mm × 25mm × 3mm CFRP test body, quality is determined. Next, the CFRP test body for determining quality is burnt 4 hours at 400 DEG C by Muffle furnace, then, fired at 600 DEG C It burns 20 minutes, only carbon-fibre component is made.The quality of CFRP test body after measurement burning, the meter recorded using JIS K 7075 Formula calculates containing rate of fiber volume.
< interlaminar shear strength >
From each CFRP cut-out length × width × thickness=21mm × 10mm × 3mm CFRP test body.To what is cut out CFRP test body uses オ リ エ Application テ ッ Network テ according to JIS K 7078 in the experimental enviroment of 23 DEG C of temperature, humidity 50% Application シ ロ Application UTC-1T, determines interlaminar shear strength.The measurement of interlaminar shear strength carries out each CFRP each 3 times.In turn, will The average value of 3 measurement results is used in the evaluation of interlaminar shear strength.
< bending strength >
From each CFRP cut-out length × width × thickness=140mm × 15mm × 3mm CFRP test body.To what is cut out CFRP test body, 23 DEG C of temperature, humidity 50% experimental enviroment under, according to JIS K 7074, use オ リ エ Application テ ッ Network system テ Application シ ロ Application UTC-1T, determines bending strength with distance between the fulcrum 120mm.The measurement of bending strength carries out each CFRP each 3 times.In turn, the average value of 3 measurement results is used in the evaluation of bending strength.
< tensile strength >
CFRP test body is made according to JIS K 7165, Type B test film.To the CFRP test body of production, 23 DEG C of temperature, Under the experimental enviroment of humidity 50%, according to JIS K 7161, using イ Application ス ト ロ Application 5900R, with length 150mm between fixture, Test for tensile strength is carried out within test speed 1mm/ minutes.The measurement of tensile strength carries out each CFRP each 3 times.In turn, by 3 times The average value of measurement result be used in the evaluation of tensile strength.
As shown in table 3, the interlaminar shear strength of the CFRP test body of embodiment 10~13, bending strength, tensile strength are good It is good.
In contrast, the CFRP test body of comparative example 3 and comparative example 5 is compared with the CFRP test body of embodiment 10~13, Bending strength is low.This is because the CFRP test body phase of the CFRP test body of embodiment 10~13 and comparative example 3 and comparative example 5 Than the adaptation of resin component and carbon fiber is good.
In addition, the CFRP test body of comparative example 4 is to have used the test body of previous epoxy resin.As shown in table 3, implement The same intensity of the case where CFRP test body of example 10~13 may be implemented and use epoxy resin.

Claims (16)

1. a kind of carbon fiber-reinforced resin composition, it includes (A) free-radical reactive resin, (B) are free-radical polymerised not Monomer, (C) compounds containing thiol groups, (D) are saturated only with the imidazolium compounds and (E) organic peroxide of 1 imidazole ring.
2. carbon fiber-reinforced resin composition according to claim 1 also includes (G) metallic soap.
3. carbon fiber-reinforced resin composition according to claim 1 or 2, (C) compounds containing thiol groups are in molecule It inside include 2 or more sulfydryls.
4. carbon fiber-reinforced resin composition described in any one of claim 1 to 3, (C) chemical combination containing sulfydryl Sulfydryl in object is secondary sulfydryl or tertiary sulfydryl.
5. carbon fiber-reinforced resin composition according to any one of claims 1 to 4, (D) imidazolium compounds For imidazole ring comprising 1 including 2 or 2 positions by alkyl, aryl or aralkyl instead of imidazolium compounds.
6. carbon fiber-reinforced resin composition according to any one of claims 1 to 5, (D) imidazolium compounds For any one of 2-ethyl-4-methylimidazole, 1 benzyl 2 methyl imidazole, 2-methylimidazole.
7. carbon fiber-reinforced resin composition described according to claim 1~any one of 6, (A) radical reaction Property resin be selected from epoxy (methyl) acrylate, unsaturated polyester resin, polyester (methyl) acrylate, amino It is at least one kind of in formic acid esters (methyl) acrylate.
8. carbon fiber-reinforced resin composition according to any one of claims 1 to 7, (A) radical reaction Property resin in epoxy (methyl) acrylate at least one epoxy group content be 1~100 mass %.
9. carbon fiber-reinforced resin composition described according to claim 1~any one of 8, (E) organic peroxy 10 hours half life temperatures of object are 30~170 DEG C.
10. carbon fiber-reinforced resin composition described according to claim 1~any one of 9, (E) organic peroxy Object is cumyl hydroperoxide or peroxidized t-butyl perbenzoate.
11. the carbon fiber-reinforced resin composition according to any one of claim 2~10, (G) metallic soap are Manganese compound or cobalt compound.
12. carbon fiber-reinforced resin composition described according to claim 1~any one of 11, certainly relative to (A) It include (A) free-radical reactive resin 20 by the total amount of base reaction resin and (B) the free-radical polymerised unsaturated monomer ~99 mass %, (B) free-radical polymerised 1~80 mass % of unsaturated monomer,
Total 100 mass relative to (A) the free-radical reactive resin and (B) the free-radical polymerised unsaturated monomer Part, comprising 0.001~20 mass parts of described (C) compounds containing thiol groups, (D) only with the imidazolium compounds of 1 imidazole ring 0.001~10 mass parts, 0.1~10 mass parts of (E) organic peroxide.
13. a kind of carbon fiber-reinforced resin composition, it includes the fibre reinforced trees described in any one of claim 1~12 Rouge composition and (F) carbon fiber.
14. carbon fiber-reinforced resin composition according to claim 13, the content of (F) carbon fiber is relative to carbon fiber Dimension reinforced resin composition is 10~90 mass %.
15. carbon fiber-reinforced resin composition described in 3 or 14 according to claim 1, described in any one of claim 1~12 Carbon fiber-reinforced resin composition by containing being immersed in described (F) carbon fiber.
16. a kind of solidfied material is the solidification of carbon fiber-reinforced resin composition described in any one of claim 13~15 Object.
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