WO2014189029A1 - 繊維強化複合材料用組成物、プリプレグ、及び繊維強化複合材料 - Google Patents
繊維強化複合材料用組成物、プリプレグ、及び繊維強化複合材料 Download PDFInfo
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- WO2014189029A1 WO2014189029A1 PCT/JP2014/063295 JP2014063295W WO2014189029A1 WO 2014189029 A1 WO2014189029 A1 WO 2014189029A1 JP 2014063295 W JP2014063295 W JP 2014063295W WO 2014189029 A1 WO2014189029 A1 WO 2014189029A1
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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
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/10—Esters
- C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
- C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/06—Fibrous reinforcements only
-
- 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
- C08J5/24—Impregnating materials with prepolymers which can be polymerised in situ, e.g. manufacture of prepregs
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
- C08L63/04—Epoxynovolacs
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- 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
- C08J2363/00—Characterised by the use of epoxy resins; Derivatives of epoxy resins
Definitions
- the present invention relates to a composition for fiber reinforced composite material, a prepreg, and a fiber reinforced composite material. More specifically, a composition for forming a composite material (composite material of fiber and resin) reinforced with fibers (reinforced fibers) such as carbon fiber and glass fiber, prepreg, and the composite material (fiber reinforced composite material) About.
- a fiber reinforced composite material is a composite material composed of reinforced fiber and resin (matrix resin).
- matrix resin reinforced fiber and resin
- the reinforcing fiber in the fiber reinforced composite material for example, glass fiber, aramid fiber, carbon fiber, boron fiber and the like are used.
- the matrix resin in the fiber reinforced composite material a thermosetting resin that can be easily impregnated into the reinforcing fiber is often used.
- a thermosetting resin for example, an epoxy resin, an unsaturated polyester resin, a vinyl ester resin, a phenol resin, a maleimide resin, a cyanate resin, or the like is used.
- Examples of the material for forming the fiber-reinforced composite material include a curable resin composition containing a glycidylamine type epoxy resin, a thermosetting resin composition containing a bisphenol F type epoxy resin, and an acid anhydride curing agent.
- a curable resin composition containing a glycidylamine type epoxy resin a thermosetting resin composition containing a bisphenol F type epoxy resin
- an acid anhydride curing agent Is known (see Patent Document 1).
- a prepreg for a fiber reinforced composite material including a thermosetting resin composition containing an alicyclic epoxy resin, a monoallyl diglycidyl isocyanurate compound, and a flame retardant reinforcing fiber containing a curing agent. It is known (see Patent Document 2).
- epoxy resin curing agent As an epoxy resin curing agent, amines such as imidazole derivatives and acid anhydrides such as methylhymic anhydride have been used. However, these curing agents have a wide temperature response range, and the reaction proceeds gradually even at room temperature, so that the pot life is short, and the curing agent must be added immediately before use, resulting in poor work stability. It was.
- the composite material composition As a material for forming a fiber reinforced composite material, it has a sufficient pot life, has excellent work stability, and can be rapidly cured when cured (fiber reinforced composition)
- the present condition is that the composite material composition) has not yet been obtained.
- the materials are required to have high heat resistance (for example, heat resistance that can withstand use in a high temperature environment such as 200 ° C.).
- high heat resistance for example, heat resistance that can withstand use in a high temperature environment such as 200 ° C.
- a composition capable of forming a fiber-reinforced composite material having such high heat resistance, excellent in work stability, and having a high curing rate has not yet been obtained.
- an object of the present invention is to provide a composition for a fiber-reinforced composite material that can form a fiber-reinforced composite material having a long pot life, excellent work stability, and high heat resistance.
- Another object of the present invention is to provide a prepreg which is formed by impregnating a reinforcing fiber with the above-mentioned composition for fiber reinforced composite material and can form a fiber reinforced composite material having high heat resistance.
- the other object of this invention is to provide the fiber reinforced composite material which has high heat resistance.
- the present inventors have found that a composition containing a specific radical polymerizable compound, a specific cation polymerizable compound, a specific radical polymerization initiator, and a specific acid generator, The present inventors have found that a fiber reinforced composite material having a long pot life, excellent work stability and high heat resistance can be formed.
- the present invention relates to a radical polymerizable compound (A) having two or more radical polymerizable groups in one molecule, a cationic polymerizable compound (B) having two or more cationic polymerizable groups in one molecule, and 10 hours.
- A radical polymerizable compound having two or more radical polymerizable groups in one molecule
- B cationic polymerizable compound having two or more cationic polymerizable groups in one molecule
- 10 hours When measured at a heating rate of 10 ° C./min using a radical polymerization initiator (C) having a half-life decomposition temperature of 85 ° C. or higher and a differential scanning calorimeter (DSC), the heat generation starting temperature is 100 ° C. or higher.
- the composition for fiber reinforced composite materials which contains the acid generator (D) used as this, and the viscosity in 25 degreeC is 10000 mPa * s or more is provided.
- the cationically polymerizable compound (B) may be at least one compound selected from the group consisting of epoxy compounds, oxetane compounds, and vinyl ether compounds.
- the ratio (weight ratio) [(A) / (B)] of the radical polymerizable compound (A) and the cationic polymerizable compound (B) is preferably larger than 0/100 and not larger than 80/20.
- the content of the radical polymerization initiator (C) is, for example, 0.01 to 10 parts by weight with respect to 100 parts by weight of the total amount of the radical polymerizable compound (A) and the cationic polymerizable compound (B).
- the content of the acid generator (D) is, for example, 0.1 to 20 parts by weight with respect to 100 parts by weight of the total amount of the radical polymerizable compound (A) and the cationic polymerizable compound (B).
- the radical polymerizable compound (A) is preferably a compound having a cyclic structure.
- the radical polymerizable compound (A) is preferably a compound having a tricyclodecane skeleton.
- the cationically polymerizable compound (B) is preferably a compound having a cyclic structure.
- the cationically polymerizable compound (B) is preferably a compound having a tricyclodecane skeleton.
- composition for fiber-reinforced composite material preferably has a pot life at 25 ° C. (time for the viscosity to be twice the initial viscosity) of 14 days or more.
- the present invention also provides a prepreg formed by impregnating the reinforcing fiber (E) with the composition for fiber-reinforced composite material.
- the fiber mass content (Wf) of the reinforcing fiber (E) is preferably 50 to 90% by weight.
- the reinforcing fiber (E) may be at least one selected from the group consisting of carbon fiber, glass fiber, and aramid fiber.
- the present invention further provides a fiber-reinforced composite material obtained by curing the prepreg.
- the present invention relates to the following.
- composition for fiber-reinforced composite material according to (1) wherein the cationically polymerizable compound (B) is at least one compound selected from the group consisting of an epoxy compound, an oxetane compound, and a vinyl ether compound.
- the ratio (weight ratio) [(A) / (B)] of the radical polymerizable compound (A) and the cationic polymerizable compound (B) is greater than 0/100 and not greater than 80/20 (1) Or the composition for fiber reinforced composite materials as described in (2).
- Composition for reinforced composite materials wherein the content of the radical polymerizable compound (A) is 10 to 75% by weight relative to the total amount (100% by weight) of the composition.
- the content of the acid generator (D) is 0.1 to 20 parts by weight based on 100 parts by weight of the total amount of the radical polymerizable compound (A) and the cationic polymerizable compound (B) (1
- the radical polymerizable compound (A) has two radical polymerizable groups in one molecule and has a cyclic structure in the molecule, and one molecule
- the composition for fiber-reinforced composite material according to any one of (1) to (7) which is at least one selected from the group consisting of radically polymerizable compounds (A-2) having three or more radically polymerizable groups object.
- composition for fiber-reinforced composite material according to (8) wherein the ratio of the radical polymerizable compound (A-1) to the whole radical polymerizable compound (A) is 30% by weight or more.
- (11) The composition for fiber-reinforced composite material according to any one of (1) to (10), wherein the radical polymerizable compound (A) is a compound having a tricyclodecane skeleton.
- the radical polymerizable compound (A) is at least one selected from the group consisting of dimethylol dicyclopentane di (meth) acrylate and tricyclodecanediol di (meth) acrylate (1) to (11)
- the cation polymerizable compound (B) is a bisphenol type epoxy resin, a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a resorcinol type epoxy resin, a phenol alkyl type epoxy resin, a dicyclopentadiene type epoxy resin (tricyclodecane) Any one of (1) to (14) selected from the group consisting of an epoxy resin having a skeleton), an epoxy compound having a biphenyl skeleton, an epoxy compound having a naphthalene skeleton, and an epoxy compound having a fluorene skeleton
- the radical polymerization initiator (C) is 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-t-butylperoxycyclohexyl) propane, 2,2 -Bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexyne-3, Di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, dicumyl peroxide, ⁇ , ⁇ '-bis (t-butyl Peroxy) diisopropylbenzene, t-butyl hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, 1,1,3,3
- the acid generator (D) is triallylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, diaryliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (dodecylphenyl) iodoniumtetrakis (pentafluorophenyl)
- the fiber reinforcement according to any one of (1) to (18), which is at least one selected from the group consisting of borate and iodonium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate Composition for composite material.
- the reinforcing fiber (E) is made of carbon fiber, glass fiber, aramid fiber, boron fiber, graphite fiber, silicon carbide fiber, high-strength polyethylene fiber, tungsten carbide fiber, and polyparaphenylene benzoxazole fiber (PBO fiber).
- a fiber-reinforced composite material obtained by curing the prepreg according to any one of (21) to (24).
- the composition for fiber-reinforced composite material of the present invention has the above-described configuration, the pot life is long and the work stability is excellent.
- a fiber-reinforced composite material having high heat resistance can be formed by curing.
- the fiber-reinforced composite material obtained by curing the composition for fiber-reinforced composite material or the prepreg of the present invention is excellent in production stability and has high heat resistance.
- composition for fiber reinforced composite material of the present invention (sometimes simply referred to as “the composition of the present invention”) is a radical polymerizable compound (A) having two or more radical polymerizable groups in one molecule, one molecule Using a cationically polymerizable compound (B) having two or more cationically polymerizable groups therein, a radical polymerization initiator (C) having a 10-hour half-life decomposition temperature of 85 ° C. or higher, and a differential scanning calorimeter (DSC) And the acid generator (D) having an exotherm starting temperature of 100 ° C. or higher when measured at a temperature rising rate of 10 ° C./min, and a viscosity at 25 ° C. of 10,000 mPa ⁇ s or higher.
- A radical polymerizable compound having two or more radical polymerizable groups in one molecule, one molecule
- a radical polymerization initiator (C) having a 10-hour half-life decomposition temperature of 85 ° C
- radical polymerizable compound (A) in the composition of the present invention is a compound having two or more radical polymerizable groups in one molecule.
- the radical polymerizable group possessed by the radical polymerizable compound (A) is not particularly limited as long as it is a functional group capable of causing a radical polymerization reaction, and examples thereof include a group containing a carbon-carbon unsaturated double bond. Specific examples include a vinyl group, a (meth) allyl group, and a (meth) acryloyl group.
- the 2 or more radically polymerizable group which a radically polymerizable compound (A) has may be the same respectively, and may differ.
- the number of radical polymerizable groups in the molecule of the radical polymerizable compound (A) is not particularly limited as long as it is 2 or more, preferably 2 to 20, more preferably 2 to 15, and still more preferably. Is 2-10.
- radical polymerizable compound (A) examples include vinyl compounds such as divinylbenzene; ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 1,3-butanediol di (meth) ) Acrylate, 1,4-butanediol di (meth) acrylate, tetramethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, Bisphenol A epoxy di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, nonanediol di (meth) acrylate, diethylene glycol di (meth) acrylate Polyethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate
- the radical polymerizable compound (A) has two radical polymerizable groups in one molecule and has a cyclic structure [monocyclic or polycyclic aromatic ring such as benzene ring or naphthalene ring in the molecule]. Radical polymerization having a monocyclic alicyclic skeleton such as a cyclohexane ring, a polycyclic alicyclic skeleton such as a tricyclodecane ring, a monocyclic or polycyclic heterocyclic ring, etc. (especially a polycyclic ring structure)
- the compound (A-1) and the radically polymerizable compound (A-2) having three or more radically polymerizable groups in one molecule are preferable.
- the compound (A-1) include divinylbenzene, bisphenol A epoxy di (meth) acrylate, 9,9-bis [4- (2- (meth) acryloyloxyethoxy) phenyl] fluorene, and dimethylol.
- the compound (A-2) include trimethylolpropane tri (meth) acrylate, trimethylolethane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, and pentaerythritol tetra (meth) acrylate.
- the radical polymerizable compound (A) has two radical polymerizable groups in one molecule. And a radically polymerizable compound (A-1) having a cyclic structure (aromatic ring, monocyclic or polycyclic aliphatic ring, monocyclic or polycyclic heterocycle, etc.) in the molecule.
- a radically polymerizable compound (A-1) having a cyclic structure (aromatic ring, monocyclic or polycyclic aliphatic ring, monocyclic or polycyclic heterocycle, etc.) in the molecule.
- radical polymerization having two radically polymerizable groups in one molecule and a polycyclic aliphatic ring skeleton (particularly, a tricyclodecane skeleton) in the molecule.
- the ratio of the radical polymerizable compound (A-1) [or (A-11)] to the whole radical polymerizable compound (A) is preferably 30% by weight or more, more preferably 50% by weight or more. Especially preferably, it is 70 weight% or more.
- the functional group equivalent of the radically polymerizable group of the radically polymerizable compound (A) is, for example, 50 to 300, preferably 70 to 280, more preferably 80 to 260.
- the functional group equivalent is less than 50, the mechanical strength of the cured product or fiber-reinforced composite material tends to decrease.
- the functional group equivalent exceeds 300, the heat resistance and mechanical properties of the cured product and the fiber-reinforced composite material are likely to deteriorate.
- the functional group equivalent of the radically polymerizable group of the radically polymerizable compound (A) can be calculated by the following formula.
- [Functional group equivalent of radical polymerizable group] [Molecular weight of radical polymerizable compound (A)] / [Number of radical polymerizable groups possessed by radical polymerizable compound (A)]
- the radical polymerizable compound (A) can be used alone or in combination of two or more.
- the content (blending amount) of the radical polymerizable compound (A) in the composition of the present invention is not particularly limited, but is preferably 10 to 75% by weight, more preferably based on the total amount (100% by weight) of the composition. Is 30 to 65% by weight, more preferably 35 to 60% by weight.
- the content is less than 10% by weight, the curing rate may decrease or the heat resistance of the cured product may decrease.
- the content exceeds 75% by weight the interface strength between the cured product and the fiber may be lowered.
- composition of the present invention may contain a radical polymerizable compound other than the radical polymerizable compound (A).
- radical polymerizable compound other than the radical polymerizable compound (A) include compounds having one radical polymerizable group in one molecule.
- Examples of the compound having one radical polymerizable group in one molecule include vinyl compounds such as styrene, 2-chlorostyrene, 2-bromostyrene, methoxystyrene, 1-vinylnaphthalene and 2-vinylnaphthalene; 2-phenoxy Ethyl (meth) acrylate, benzyl (meth) acrylate, o-phenylphenol (meth) acrylate, nonylphenoxypolyethylene glycol (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, triethylene glycol mono (meth) acrylate, 1,3 -Butanediol mono (meth) acrylate, tetramethylene glycol mono (meth) acrylate, propylene glycol mono (meth) acrylate (eg, 1,2-propanediol-1- (meth) acrylate), Opentyl glycol mono (meth) acrylate, methoxy
- the cationically polymerizable compound (B) in the composition of the present invention is a compound having two or more cationically polymerizable groups in one molecule.
- the cationically polymerizable group of the cationically polymerizable compound (B) is not particularly limited as long as it is a functional group capable of causing a cationic polymerization reaction, and examples thereof include an epoxy group, an oxetanyl group, and a vinyl ether group.
- the cationically polymerizable compound (B) has two or more cationically polymerizable groups, and these cationically polymerizable groups may be the same or different.
- the number of cationically polymerizable groups in the molecule of the cationically polymerizable compound (B) is not particularly limited as long as it is 2 or more, preferably 2 to 20, more preferably 2 to 15, particularly preferably. Is 2-10.
- Examples of the cationic polymerizable compound (B) include an epoxy compound (a compound having two or more epoxy groups in one molecule), an oxetane compound (a compound having two or more oxetanyl groups in one molecule), And vinyl ether compounds (compounds having two or more vinyl ether groups in one molecule).
- epoxy compound examples include bisphenol A type epoxy resins (bisphenol A diglycidyl ether, etc.), bisphenol F type epoxy resins (bisphenol F diglycidyl ether, etc.), and bisphenol S type epoxy resins (bisphenol S diester).
- Glycidyl ether, etc. halogen substituted products thereof (for example, brominated epoxy resins such as brominated bisphenol A diglycidyl ether, brominated bisphenol F diglycidyl ether, brominated bisphenol S diglycidyl ether), alkyl substituted products, Or bisphenol-type epoxy resins such as hydrogenated products (for example, hydrogenated bisphenol A diglycidyl ether, hydrogenated bisphenol F diglycidyl ether, hydrogenated bisphenol S diglycidyl ether, etc.); Resole novolac type epoxy resin, phenol novolac type epoxy resin, resorcinol type epoxy resin, phenol alkyl type epoxy resin, dicyclopentadiene type epoxy resin (epoxy resin having tricyclodecane skeleton; for example, phenol-dicyclopentadiene type epoxy resin, Alkylphenol-dicyclopentadiene-type epoxy resin, etc.), epoxy compounds having a biphenyl skeleton (eg
- oxetane compound examples include 3,3-bis (chloromethyl) oxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, bis ⁇ [1-ethyl (3-oxetanyl)] methyl ⁇ ether, 4,4′-bis [(3-ethyl-3-oxetanyl) methoxymethyl] bicyclohexyl, 1,4-bis [(3-ethyl-3-oxetanyl) methoxymethyl] Cyclohexane, 1,4-bis ⁇ [(3-ethyl-3-oxetanyl) methoxy] methyl ⁇ benzene, 3-ethyl-3 ⁇ [(3-ethyloxetane-3-yl) methoxy] methyl) ⁇ oxetane, xylylene Bisoxetane, 3-ethyl-3- ⁇ [[3
- vinyl ether compound examples include 3,3-bis (vinyloxymethyl) oxetane, 1,6-hexanediol divinyl ether, 1,4-cyclohexanedimethanol divinyl ether, and 1,3-cyclohexanedi Methanol divinyl ether, 1,2-cyclohexanedimethanol divinyl ether, p-xylene glycol divinyl ether, m-xylene glycol divinyl ether, o-xylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, tetraethylene glycol divinyl ether , Pentaethylene glycol divinyl ether, oligoethylene glycol divinyl ether, polyethylene glycol divinyl ether, di Lopylene glycol divinyl ether, tripropylene glycol divinyl ether, tetrapropylene glycol divinyl ether, pentapropy
- the cationically polymerizable compound (B) one or more cyclic structures are formed in one molecule from the viewpoint that the pot life of the composition can be lengthened, and the curing speed and the heat resistance of the cured product or fiber reinforced composite material.
- the cationically polymerizable compound (B) is preferably a compound having a tricyclodecane skeleton such as a dicyclopentadiene type epoxy resin.
- Examples of commercially available phenol novolac epoxy resins include trade names “N-740”, “N-770”, “N-775” (manufactured by DIC).
- a commercial product of a resorcinol type epoxy resin a trade name “EX-201” (manufactured by Nagase Chemtech Co., Ltd.) and the like can be mentioned.
- Commercially available products of dicyclopentadiene type epoxy resins include trade names “HP-7200”, “HP-7200L”, “HP-7200H” (above, manufactured by DIC).
- Examples of commercially available epoxy compounds having a biphenyl skeleton include trade names “YX-4000” and “YX-4000H” (above, manufactured by Mitsubishi Chemical Corporation).
- Examples of commercial products of the oxetane compound include trade name “OXT-221” (manufactured by Toagosei Co., Ltd.), trade name “OXT-121” (manufactured by Toagosei Co., Ltd.), and the like.
- the functional group equivalent of the cationically polymerizable group of the cationically polymerizable compound (B) is not particularly limited, but is preferably 50 to 400, more preferably 80 to 350, and still more preferably 100 to 300. If the functional group equivalent is less than 50, the toughness of the cured product or fiber-reinforced composite material may be insufficient. On the other hand, when the functional group equivalent exceeds 400, the heat resistance and mechanical properties of the cured product and the fiber-reinforced composite material may be deteriorated.
- the functional group equivalent of the cation polymerizable group of the cation polymerizable compound (B) can be calculated by the following formula.
- the cationically polymerizable compound (B) can be used alone or in combination of two or more.
- the content (blending amount) of the cationically polymerizable compound (B) in the composition of the present invention is not particularly limited, but is preferably 10 to 75% by weight, more preferably based on the total amount (100% by weight) of the composition. Is 30 to 65% by weight, more preferably 35 to 60% by weight.
- the content is less than 10% by weight, the interfacial strength between the cured product and the fiber may decrease, or the heat resistance of the cured product may decrease.
- the content exceeds 75% by weight, the curing rate of the composition may decrease or the heat resistance of the cured product may decrease.
- composition of this invention may contain cationically polymerizable compounds other than the said cationically polymerizable compound (B).
- cationic polymerizable compound other than the cationic polymerizable compound (B) include compounds having one cationic polymerizable group in one molecule.
- a compound having one cationic polymerizable group in one molecule an epoxy compound having one epoxy group in one molecule, an oxetane compound having one oxetanyl group in one molecule, and one vinyl ether group in one molecule.
- the vinyl ether compound which has individual is mentioned.
- Examples of the epoxy compound include cyclohexene oxide, 3,4-epoxycyclohexylmethyl alcohol, 3,4-epoxycyclohexylethyltrimethoxysilane, epoxyhexahydrophthalate dioctyl, epoxyhexahydrophthalate di-2-ethylhexyl, aliphatic Examples thereof include monoglycidyl ethers of higher alcohols; monoglycidyl ethers of polyether alcohols obtained by adding alkylene oxide to phenol, cresol, butylphenol, and glycidyl esters of higher fatty acids.
- oxetane compound examples include 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane, 3-ethyl-3- (hydroxymethyl) oxetane, 3-ethyl-3- [(Phenoxy) methyl] oxetane, 3-ethyl-3- (hexyloxymethyl) oxetane, 3-ethyl-3- (chloromethyl) oxetane and the like.
- vinyl ether compound examples include 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroxypropyl vinyl ether, 2-hydroxyisopropyl vinyl ether, 4-hydroxybutyl vinyl ether, 3-hydroxybutyl vinyl ether, 2-hydroxybutyl vinyl ether, 3 -Hydroxyisobutyl vinyl ether, 2-hydroxyisobutyl vinyl ether, 1-methyl-3-hydroxypropyl vinyl ether, 1-methyl-2-hydroxypropyl vinyl ether, 1-hydroxymethylpropyl vinyl ether, 4-hydroxycyclohexyl vinyl ether, 1,6-hexanediol Monovinyl ether, 1,4-cyclohexanedimethanol monovinyl ether 1,3-cyclohexanedimethanol monovinyl ether, 1,2-cyclohexanedimethanol monovinyl ether, p-xylene glycol monovinyl ether, m-xylene glycol monovinyl ether, o-xy
- the ratio (weight ratio) [radical polymerizable compound (A) / cation polymerizable compound (B)] of the radical polymerizable compound (A) and the cationic polymerizable compound (B) in the composition of the present invention is not particularly limited. Is more than 0/100 and not more than 80/20, more preferably 10/90 to 70/30, still more preferably 30/70 to 60/40.
- the ratio of the radically polymerizable compound (A) ratio to the total amount (100% by weight) of the radically polymerizable compound (A) and the cationically polymerizable compound (B)] is 0% by weight, the curing rate decreases.
- the proportion of the radical polymerizable compound (A) exceeds 80% by weight, the mechanical strength of the cured product or fiber-reinforced composite material may be decreased, or the interface strength between the cured product and the fiber may be decreased.
- the radical polymerization initiator (C) in the composition of the present invention is a radical polymerization initiator having a 10-hour half-life decomposition temperature (a temperature at which the amount of active oxygen becomes half of the original in 10 hours) of 85 ° C. or more.
- the 10-hour half-life decomposition temperature of the radical polymerization initiator (C) is preferably 88 ° C or higher, more preferably 90 ° C or higher.
- the radical polymerization initiator (C) functions to initiate a polymerization reaction (radical polymerization reaction) of a compound having a radical polymerizable group (radical polymerizable compound (A)) among the curable compounds in the composition.
- radical polymerization initiator having a 10-hour half-life decomposition temperature of less than 85 ° C. is not preferable because the pot life of the composition is shortened.
- the radical polymerization initiator (C) is not particularly limited as long as the 10-hour half-life decomposition temperature is 85 ° C. or higher, and for example, a thermal radical polymerization initiator can be used.
- the upper limit of the 10-hour half-life decomposition temperature is, for example, 180 ° C., more preferably 150 ° C., and particularly preferably 110 ° C.
- thermal radical polymerization initiator examples include organic peroxides.
- organic peroxide a dialkyl peroxide, an acyl peroxide, a hydroperoxide, a ketone peroxide, a peroxy ester etc.
- organic peroxide having a 10-hour half-life decomposition temperature of 85 ° C. or higher include, for example, 1,1-bis (t-butylperoxy) cyclohexane, 2,2-bis (4,4-di-).
- t-butylperoxycyclohexyl) propane 2,2-bis (t-butylperoxy) butane, n-butyl 4,4-bis (t-butylperoxy) valerate, 2,5-dimethyl-2,5- Bis (t-butylperoxy) hexyne-3, di-t-butyl peroxide, t-butylcumyl peroxide, 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane, dicumylper Oxide, ⁇ , ⁇ ⁇ quote -bis (t-butylperoxy) diisopropylbenzene, t-butylhydroperoxide, p-menthane hydroperoxide, diisopropylbenzene Hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl peroxyisopropyl monocarbonate, t-
- an azo compound may be used in addition to the organic peroxide.
- the azo compound having a 10-hour half-life decomposition temperature of 85 ° C. or higher include 2- (carbamoylazo) isobutyronitrile, 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile, 2,2 ′ -Azobis (2,4,4-trimethylpentane), 2,2'-azobis (2-methyl-N-2-propenylpropanamide), 2,2'-azobis (N-butyl-2-methylpropionamide) Etc.
- inorganic peroxides such as persulfates (for example, potassium persulfate, ammonium persulfate, etc.) may be used or used in combination.
- a radical polymerization initiator (C) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- the content (blending amount) of the radical polymerization initiator (C) in the composition of the present invention is not particularly limited, but is 100 parts by weight based on the total amount of the radical polymerizable compound (A) and the cationic polymerizable compound (B). 0.01 to 10 parts by weight, more preferably 0.05 to 8 parts by weight, still more preferably 0.1 to 5 parts by weight. When the content is less than 0.01 part by weight, the progress of the curing reaction may be insufficient. On the other hand, if the content exceeds 10 parts by weight, the heat resistance of the cured product or fiber-reinforced composite material may be insufficient depending on the application. In addition, when using together 2 or more types of radical polymerization initiator (C), it is preferable to control the total amount of this radical polymerization initiator (C) in the said range.
- the heat generation start temperature is 100 ° C. or higher (preferably, 110.degree. C. or higher, more preferably 120.degree. C. or higher).
- the acid generator (D) serves to initiate a polymerization reaction (cationic polymerization reaction) of a compound having a cationically polymerizable group (cationic polymerizable compound (B)) among the curable compounds in the composition.
- a polymerization reaction cationic polymerization reaction
- cationic polymerizable compound (B) cationic polymerizable compound (B)
- Use of an acid generator having an exotherm starting temperature of less than 100 ° C. is not preferable because the pot life of the composition is shortened.
- an acid generator that has an exotherm starting temperature of 100 ° C. or higher when measured at a temperature rising rate of 10 ° C./min using a differential scanning calorimeter (DSC) is particularly suitable.
- a thermal acid generator etc. are mentioned.
- the upper limit of the heat generation start temperature is, for example, 200 ° C., more preferably 150 ° C., and particularly preferably 130 ° C.
- Examples of the acid generator (D) include compounds that generate an acid upon heating or irradiation with active energy rays, specifically, sulfonium salts such as triallylsulfonium hexafluorophosphate and triarylsulfonium hexafluoroantimonate; Iodonium salts such as iodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate, iodonium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate Phosphonium salts such as tetrafluorophosphonium hexafluorophosphate; pyridium salts; diazonium salts; selenium salts; ammonium salts .
- an acid generator (D) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
- the content (blending amount) of the acid generator (D) in the composition of the present invention is not particularly limited, but relative to 100 parts by weight of the total amount of the radical polymerizable compound (A) and the cationic polymerizable compound (B).
- the amount is preferably 0.1 to 20 parts by weight, more preferably 0.2 to 15 parts by weight, still more preferably 0.3 to 5 parts by weight.
- the content is less than 0.1 part by weight, the progress of the curing reaction may be insufficient.
- the content exceeds 20 parts by weight, the heat resistance of the cured product or fiber-reinforced composite material may be insufficient depending on the application.
- additives may be added as necessary within a range not impairing the effects of the present invention.
- Other additives include, for example, curing-expandable monomers, photosensitizers (anthracene sensitizers, etc.), resins, adhesion improvers, reinforcing agents, softeners, plasticizers, viscosity modifiers, solvents, inorganic Or well-known various conventional additives, such as organic particle
- the composition of the present invention comprises the above-described constituent components (radical polymerizable compound (A), cationic polymerizable compound (B), radical polymerization initiator (C), acid generator (D), additive, etc.), It can manufacture by mix
- the mixing of each of the above components can be carried out using a known or conventional stirring device (mixing device) and the like, and is not particularly limited.
- the viscosity of the composition of the present invention at 25 ° C. may be 10,000 mPa ⁇ s or more.
- the viscosity at 25 ° C. of the composition of the present invention is preferably 10,000 to 50000 mPa ⁇ s, more preferably 10,000 to 45000 mPa ⁇ s, and further preferably 11000 to 40000 mPa ⁇ s from the viewpoints of handleability and workability.
- the viscosity at 25 ° C. of the composition can be measured using, for example, a viscosity measuring device (trade name “TV-22H”, manufactured by Toki Sangyo Co., Ltd.) (eg, rotor: 1 ° 34 ′ ⁇ R24). , Rotation speed: 1.0 rpm, measurement temperature: 25 ° C.).
- the composition of the present invention has a viscosity immediately after preparation (25 ° C.) (viscosity measured within 1 hour after preparation; sometimes referred to as “initial viscosity”), and after preparation.
- the viscosity after standing at 25 ° C. for 14 days (25 ° C.) is preferably in the above-mentioned range.
- the pot life at 25 ° C. (the time during which the viscosity is twice the initial viscosity) is preferably 14 days or longer.
- the viscosity (25 ° C.) after standing for 14 days at 25 ° C. after preparation is preferably 1.5 times or less (particularly 1.3 times or less) of the initial viscosity.
- the viscosity immediately after the preparation is controlled within the above range, but when the viscosity after the preparation is left at 25 ° C. for 14 days exceeds twice the initial viscosity, the curing proceeds during storage. There is a possibility that the work stability is remarkably lowered, and the quality of the cured product (particularly, the fiber reinforced composite material) may be lowered.
- the composition of the present invention is cured and cured by polymerizing the radical polymerizable compound (A) and the cationic polymerizable compound (B) in the composition of the present invention (more specifically, radical polymerization and cationic polymerization).
- a product (cured resin product) can be obtained.
- the means for initiating the polymerization reaction can be appropriately selected according to the type and content of the radical polymerization initiator (C) and the acid generator (D), and is not particularly limited. Examples include irradiation with active energy rays (for example, ultraviolet rays, infrared rays, visible rays, electron beams).
- the polymerization reaction is preferably started by heating using a thermal radical polymerization initiator as the radical polymerization initiator (C) and a thermal acid generator as the acid generator (D).
- Conditions for curing the composition of the present invention can be appropriately selected according to the type and content of the radical polymerization initiator (C) and the acid generator (D), and are not particularly limited.
- the heating temperature is 60 to 280 ° C.
- the heating time is 0.1 to 5 hours (more preferably 0.5 to 4 hours, still more preferably 1 to 3 hours). preferable. If the heating temperature is too low or the heating time is too short, curing may be insufficient and the heat resistance and mechanical properties of the cured product may be reduced. On the other hand, if the heating temperature is too high or the heating time is too long, decomposition or deterioration of components in the composition may occur.
- the temperature condition may be increased stepwise.
- the temperature may be increased stepwise in which heating is performed at a temperature of 60 to 185 ° C. for 0.1 to 3 hours (preferably 0.5 to 2 hours).
- a cured product may be obtained through a secondary curing step of heating at a temperature exceeding 185 ° C. and not more than 280 ° C. for 0.1 to 2 hours (preferably 0.2 to 1.5 hours).
- the glass transition temperature (Tg) of the cured product obtained by curing the composition of the present invention is not particularly limited, but is preferably 100 ° C. or higher (for example, 100 to 300 ° C.), more preferably 140 ° C. or higher (for example, 140 to 300 ° C.), more preferably 150 ° C. or more, and particularly preferably 180 ° C. or more. If the glass transition temperature is less than 100 ° C., the heat resistance of the fiber-reinforced composite material may be insufficient depending on the application.
- the glass transition temperature is measured in accordance with, for example, JIS K7244-4, more specifically, dynamic viscoelasticity measurement (for example, heating rate: 5 ° C./min, measuring temperature: 25 to 350 ° C., deformation mode) : Dynamic viscoelasticity measurement under the tensile mode condition) and the temperature at the peak top of tan ⁇ (loss tangent).
- dynamic viscoelasticity measurement for example, heating rate: 5 ° C./min, measuring temperature: 25 to 350 ° C., deformation mode
- Dynamic viscoelasticity measurement under the tensile mode condition Dynamic viscoelasticity measurement under the tensile mode condition
- prepreg fiber reinforced composite material
- the reinforcing fiber (E) is not particularly limited.
- the carbon fiber include polyacrylonitrile (PAN) -based carbon fiber, pitch-based carbon fiber, and vapor-grown carbon fiber.
- PAN polyacrylonitrile
- carbon fiber, glass fiber, and aramid fiber are preferable from the viewpoint of mechanical properties.
- the reinforcing fiber (E) can be used alone or in combination of two or more.
- the form of the reinforcing fiber (E) in the prepreg of the present invention is not particularly limited.
- the woven fabric of the reinforcing fibers (E) for example, a sheet in which fiber bundles represented by plain weave, twill weave, satin weave, or non-crimp fabric are aligned in one direction or a sheet laminated at different angles cannot be unraveled. Stitching sheets that are stitched like this.
- the content of (E) in the reinforcing fiber (sometimes referred to as “fiber mass content (Wf)”) in the prepreg of the present invention is not particularly limited, but is preferably 50 to 90% by weight, more preferably 60 to It is 85% by weight, more preferably 65 to 80% by weight. If the content is less than 50% by weight, the mechanical strength and heat resistance of the fiber-reinforced composite material may be insufficient depending on the application. On the other hand, if the content exceeds 90% by weight, the mechanical strength (for example, toughness) of the fiber-reinforced composite material may be insufficient depending on the application.
- the composition of the present invention after impregnating the reinforcing fiber (E) with the composition of the present invention, further heating or active energy ray irradiation is performed to cure a part of the curable compound in the composition (that is, , Semi-cured).
- the method of impregnating the reinforcing fiber (E) with the composition of the present invention is not particularly limited, and can be carried out by a method of impregnation in a known or conventional prepreg manufacturing method.
- a fiber-reinforced composite material can be obtained by curing the prepreg of the present invention.
- the fiber reinforced composite material has very excellent mechanical strength and heat resistance because the cured product of the composition of the present invention is reinforced by the reinforcing fiber (E).
- Conditions for curing the prepreg of the present invention are not particularly limited. For example, conditions similar to the conditions for curing the above-described composition of the present invention can be employed.
- a pultrusion method (pultrusion method) can be employed.
- the reinforcing fiber (E) is impregnated with the composition of the present invention by continuously passing the reinforcing fiber (E) through a resin tank (resin tank filled with the composition of the present invention), and then A prepreg (the prepreg of the present invention) is formed by passing a squeeze die as necessary, and then, for example, a fiber reinforced composite material is obtained by curing while continuously pulling and forming with a tension machine through a heating mold. be able to.
- the obtained fiber reinforced composite material may be further subjected to heat treatment (post-bake) using an oven or the like.
- the prepreg and fiber-reinforced composite material of the present invention are not limited to the above-described molding method (pulling-molding method), and known or commonly used prepreg and fiber-reinforced composite material manufacturing methods such as hand layup method, prepreg method, RTM It can also be produced by a method, a pultrusion method, a filament winding method, a spray-up method or the like.
- the fiber-reinforced composite material of the present invention can be used as a material for various structures, and is not particularly limited.
- the fiber-reinforced composite material of the present invention can be preferably used, for example, as a core material for electric wires used as aerial wiring.
- the composite material has high strength, is lightweight and has a low coefficient of linear expansion, and therefore reduces the number of steel towers and improves transmission capacity. Can be achieved.
- the fiber reinforced composite material of this invention has high heat resistance, it can be preferably used also as a core material for high-voltage electric wires (high-voltage electric wires) that are likely to generate heat.
- the core material can be formed by a known method such as a pultrusion method or a stranded wire method.
- Viscosity The viscosity (mPa ⁇ s) at 25 ° C. of the compositions for fiber-reinforced composite materials obtained in Examples and Comparative Examples was measured immediately after the composition was prepared (within 1 hour after preparation). The results are shown in the column “Initial viscosity of composition” in Table 1. Moreover, after preparing the said composition for fiber reinforced composite materials, after storing for 14 days in a 25 degreeC environment, the viscosity (mPa * s) was measured. The results are shown in the column of “Viscosity of composition after storage at 25 ° C. for 14 days” in Table 1. The viscosity measuring apparatus and measurement conditions are as follows.
- Measuring device Viscosity measuring device (trade name “TV-22H”, manufactured by Toki Sangyo Co., Ltd.) Measurement temperature: 25 ° C Rotor: 1 ° 34 ' ⁇ R24 Rotation speed: 1.0rpm
- Measuring device Solid viscoelasticity measuring device (“RSAIII”, manufactured by TA INSTRUMENTS) Atmosphere: Nitrogen Temperature range: 25-350 ° C Temperature rising temperature: 5 ° C./min Deformation mode: Tensile mode The peak top temperature of tan ⁇ (loss tangent) measured by the dynamic viscoelasticity measurement was determined as the glass transition temperature (Tg) of the cured product. The results are shown in the “Tg” column of Table 1.
- the fiber-reinforced composite material composition of the present invention was excellent in work stability with almost no change in the viscosity immediately after preparation and the viscosity after storage at 25 ° C. for 14 days.
- the composition of the comparative example was inferior in work stability because the viscosity after storage for 14 days at 25 ° C. increased more than 3 times compared to the viscosity immediately after preparation.
- cured material obtained by hardening the composition for fiber reinforced composite materials of this invention had a high glass transition temperature.
- Example and the comparative example is as follows.
- EBECRYL 130 Diacrylate having a tricyclodecane skeleton (manufactured by Daicel Cytec)
- N-670-EXP-S Orthocresol novolac type epoxy resin (manufactured by DIC, functional group equivalent: 200-210)
- HP-7200 Dicyclopentadiene type epoxy resin (manufactured by DIC, functional group equivalent: 250-280)
- YD-128 bisphenol type epoxy resin (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., functional group equivalent: 184-194)
- the composition for fiber-reinforced composite material of the present invention has the above-described configuration, the pot life is long and the work stability is excellent.
- a fiber-reinforced composite material having high heat resistance can be formed by curing.
- the fiber-reinforced composite material obtained by curing the composition for fiber-reinforced composite material or the prepreg of the present invention is excellent in production stability and has high heat resistance.
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Abstract
Description
また、本発明の他の目的は、上記の繊維強化複合材料用組成物を強化繊維に含浸させて形成され、高い耐熱性を有する繊維強化複合材料を形成できるプリプレグを提供することにある。
さらに、本発明の他の目的は、高い耐熱性を有する繊維強化複合材料を提供することにある。
(1)一分子中にラジカル重合性基を2個以上有するラジカル重合性化合物(A)、一分子中にカチオン重合性基を2個以上有するカチオン重合性化合物(B)、10時間半減期分解温度が85℃以上のラジカル重合開始剤(C)、及び示差走査型熱量測定装置(DSC)を用いて昇温速度10℃/分で測定した際に、発熱開始温度が100℃以上となる酸発生剤(D)を含み、25℃における粘度が10000mPa・s以上の繊維強化複合材料用組成物。
(2)前記カチオン重合性化合物(B)が、エポキシ化合物、オキセタン化合物、及びビニルエーテル化合物からなる群より選択される少なくとも一種の化合物である(1)に記載の繊維強化複合材料用組成物。
(3)前記ラジカル重合性化合物(A)とカチオン重合性化合物(B)の割合(重量比)[(A)/(B)]が0/100より大きく且つ80/20以下である(1)又は(2)に記載の繊維強化複合材料用組成物。
(4)前記ラジカル重合性化合物(A)の含有量が、組成物の全量(100重量%)に対して、10~75重量%である(1)~(3)のいずれかに記載の繊維強化複合材料用組成物。
(5)前記カチオン重合性化合物(B)の含有量が、組成物の全量(100重量%)に対して、10~75重量%である(1)~(4)のいずれかに記載の繊維強化複合材料用組成物。
(6)前記ラジカル重合開始剤(C)の含有量が、ラジカル重合性化合物(A)とカチオン重合性化合物(B)の総量100重量部に対して、0.01~10重量部である(1)~(5)のいずれかに記載の繊維強化複合材料用組成物。
(7)前記酸発生剤(D)の含有量が、ラジカル重合性化合物(A)とカチオン重合性化合物(B)の総量100重量部に対して、0.1~20重量部である(1)~(6)のいずれかに記載の繊維強化複合材料用組成物。
(8)前記ラジカル重合性化合物(A)が、一分子中に2個のラジカル重合性基を有し、且つ分子内に環状構造を有するラジカル重合性化合物(A-1)、及び一分子中に3個以上のラジカル重合性基を有するラジカル重合性化合物(A-2)からなる群より選択される少なくとも一種である(1)~(7)のいずれかに記載の繊維強化複合材料用組成物。
(9)前記ラジカル重合性化合物(A-1)のラジカル重合性化合物(A)全体に占める割合が30重量%以上である(8)に記載の繊維強化複合材料用組成物。
(10)前記ラジカル重合性化合物(A)が環状構造を有する化合物である(1)~(9)のいずれかに記載の繊維強化複合材料用組成物。
(11)前記ラジカル重合性化合物(A)がトリシクロデカン骨格を有する化合物である(1)~(10)のいずれかに記載の繊維強化複合材料用組成物。
(12)前記ラジカル重合性化合物(A)がジメチロールジシクロペンタンジ(メタ)アクリレート、及びトリシクロデカンジオールジ(メタ)アクリレートからなる群より選択される少なくとも一種である(1)~(11)のいずれかに記載の繊維強化複合材料用組成物。
(13)ラジカル重合性化合物(A)のラジカル重合性基の官能基当量が、50~300である(1)~(12)のいずれかに記載の繊維強化複合材料用組成物。
(14)前記カチオン重合性化合物(B)が環状構造を有する化合物である(1)~(13)のいずれかに記載の繊維強化複合材料用組成物。
(15)前記カチオン重合性化合物(B)がビスフェノール型エポキシ樹脂、クレゾールノボラック型エポキシ樹脂、フェノールノボラック型エポキシ樹脂、レゾルシノール型エポキシ樹脂、フェノールアルキル型エポキシ樹脂、ジシクロペンタジエン型エポキシ樹脂(トリシクロデカン骨格を有するエポキシ樹脂)、ビフェニル骨格を有するエポキシ化合物、ナフタレン骨格を有するエポキシ化合物、及びフルオレン骨格を有するエポキシ化合物からなる群より選択される少なくとも一種である(1)~(14)のいずれかに記載の繊維強化複合材料用組成物。
(16)前記カチオン重合性化合物(B)がトリシクロデカン骨格を有する化合物である(1)~(15)のいずれかに記載の繊維強化複合材料用組成物。
(17)カチオン重合性化合物(B)のカチオン重合性基の官能基当量が、50~400である(1)~(16)のいずれかに記載の繊維強化複合材料用組成物。
(18)ラジカル重合開始剤(C)が、1,1-ビス(t-ブチルパーオキシ)シクロヘキサン、2,2-ビス(4,4-ジ-t-ブチルパーオキシシクロヘキシル)プロパン、2,2-ビス(t-ブチルパーオキシ)ブタン、n-ブチル4,4-ビス(t-ブチルパーオキシ)バレレート、2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキシン-3、ジ-t-ブチルパーオキサイド、t-ブチルクミルパーオキシド、2,5-ジメチル-2,5-ビス(t-ブチルパーオキシ)ヘキサン、ジクミルパーオキシド、α,α’-ビス(t-ブチルパーオキシ)ジイソプロピルベンゼン、t-ブチルヒドロパーオキサイド、p-メンタンヒドロパーオキサイド、ジイソプロピルベンゼンヒドロパーオキサイド、1,1,3,3-テトラメチルブチルヒドロパーオキサイド、クメンヒドロパーオキサイド、t-ヘキシルパーオキシイソプロピルモノカーボネート、t-ブチルパーオキシマレイックアシッド、t-ブチルパーオキシ3,5,5-トリメチルヘキサノエート、t-ブチルパーオキシラウレート、t-ブチルパーオキシイソプロピルモノカーボネート、t-ブチルパーオキシ2-エチルヘキシルモノカーボネート、t-ヘキシルパーオキシベンゾエート、2,5-ジメチル-2,5-ビス(ベンゾイルパーオキシ)ヘキサン、t-ブチルパーオキシアセテート、t-ブチルパーオキシ-m-トルオイルベンゾエート、t-ブチルパーオキシベンゾエート、2-(カルバモイルアゾ)イソブチロニトリル、2-フェニルアゾ-4-メトキシ-2,4-ジメチルバレロニトリル、2,2′-アゾビス(2,4,4-トリメチルペンタン)、2,2′-アゾビス(2-メチル-N-2-プロペニルプロパンアミド)、及び2,2′-アゾビス(N-ブチル-2-メチルプロピオンアミド)からなる群より選択される少なくとも一種である(1)~(17)のいずれかに記載の繊維強化複合材料用組成物。
(19)酸発生剤(D)が、トリアリルスルホニウムヘキサフルオロホスフェート、トリアリールスルホニウムヘキサフルオロアンチモネート、ジアリールヨードニウムヘキサフルオロホスフェート、ジフェニルヨードニウムヘキサフルオロアンチモネート、ビス(ドデシルフェニル)ヨードニウムテトラキス(ペンタフルオロフェニル)ボレート、及びヨードニウム[4-(4-メチルフェニル-2-メチルプロピル)フェニル]ヘキサフルオロホスフェートからなる群より選択される少なくとも一種である(1)~(18)のいずれかに記載の繊維強化複合材料用組成物。
(20)25℃におけるポットライフ(粘度が初期粘度の2倍になる時間)が、14日以上である(1)~(19)のいずれかに記載の繊維強化複合材料用組成物。
(21)(1)~(20)のいずれかに記載の繊維強化複合材料用組成物を強化繊維(E)に含浸させて形成されるプリプレグ。
(22)強化繊維(E)の繊維質量含有率(Wf)が50~90重量%である(21)に記載のプリプレグ。
(23)強化繊維(E)が、炭素繊維、ガラス繊維、アラミド繊維、ボロン繊維、黒鉛繊維、炭化珪素繊維、高強度ポリエチレン繊維、タングステンカーバイド繊維、及びポリパラフェニレンベンズオキサゾール繊維(PBO繊維)からなる群より選択される少なくとも一種である(21)又は(22)に記載のプリプレグ。
(24)強化繊維(E)が、炭素繊維、ガラス繊維、及びアラミド繊維からなる群より選択される少なくとも一種である(21)~(23)のいずれかに記載のプリプレグ。
(25)(21)~(24)のいずれかに記載のプリプレグを硬化させて得られる繊維強化複合材料。
本発明の繊維強化複合材料用組成物(単に「本発明の組成物」と称する場合がある)は、一分子中にラジカル重合性基を2個以上有するラジカル重合性化合物(A)、一分子中にカチオン重合性基を2個以上有するカチオン重合性化合物(B)、10時間半減期分解温度が85℃以上のラジカル重合開始剤(C)、及び示差走査型熱量測定装置(DSC)を用いて昇温速度10℃/分で測定した際に、発熱開始温度が100℃以上となる酸発生剤(D)を含み、25℃における粘度が10000mPa・s以上である。
本発明の組成物における前記ラジカル重合性化合物(A)は、一分子中に2個以上のラジカル重合性基を有する化合物である。
[ラジカル重合性基の官能基当量]=[ラジカル重合性化合物(A)の分子量]/[ラジカル重合性化合物(A)が有するラジカル重合性基の数]
本発明の組成物における前記カチオン重合性化合物(B)は、一分子中にカチオン重合性基を2個以上有する化合物である。
[カチオン重合性基の官能基当量]=[カチオン重合性化合物(B)の分子量]/[カチオン重合性化合物(B)が有するカチオン重合性基の数]
本発明の組成物におけるラジカル重合開始剤(C)は、10時間半減期分解温度(活性酸素量が10時間で元の半分になる温度)が85℃以上のラジカル重合開始剤である。前記ラジカル重合開始剤(C)の10時間半減期分解温度は、好ましくは88℃以上、より好ましくは90℃以上である。ラジカル重合開始剤(C)は、組成物における硬化性化合物の中でも、ラジカル重合性基を有する化合物(ラジカル重合性化合物(A))の重合反応(ラジカル重合反応)を開始させる働きをする。10時間半減期分解温度が85℃未満のラジカル重合開始剤を用いると、組成物のポットライフが短くなるので好ましくない。ラジカル重合開始剤(C)としては、10時間半減期分解温度が85℃以上のラジカル重合開始剤であれば特に限定されず、例えば、熱ラジカル重合開始剤などを使用できる。なお、ラジカル重合開始剤(C)において、前記10時間半減期分解温度の上限は、例えば180℃、より好ましくは150℃、特に好ましくは110℃である。
本発明の組成物における酸発生剤(D)は、示差走査型熱量測定装置(DSC)を用いて昇温速度10℃/分で測定した際に、発熱開始温度が100℃以上(好ましくは、110℃以上、さらに好ましくは120℃以上)となる酸発生剤である。酸発生剤(D)は、組成物における硬化性化合物の中でも、カチオン重合性基を有する化合物(カチオン重合性化合物(B))の重合反応(カチオン重合反応)を開始させる働きをする。前記発熱開始温度が100℃未満の酸発生剤を用いると、組成物のポットライフが短くなるので好ましくない。酸発生剤(D)としては、示差走査型熱量測定装置(DSC)を用いて昇温速度10℃/分で測定した際に、発熱開始温度が100℃以上となる酸発生剤であれば特に限定されないが、例えば、熱酸発生剤などが挙げられる。なお、酸発生剤(D)において、前記発熱開始温度の上限は、例えば200℃、より好ましくは150℃、特に好ましくは130℃である。
本発明の組成物を強化繊維(E)に含浸させることにより、プリプレグ(「本発明のプリプレグ」と称する場合がある)が形成される。即ち、本発明のプリプレグは、本発明の組成物と強化繊維(E)とを必須成分として含む。
[繊維強化複合材料用組成物及び硬化物の製造]
表1に示す配合組成(単位:重量部)に従って、各成分を配合し、自転公転型ミキサーで攪拌・混合することにより、繊維強化複合材料用組成物を得た。
また、上記で得た繊維強化複合材料用組成物をガラス板に挟み込み、表1に記載の条件で加熱処理することにより、硬化物を得た。
実施例及び比較例で得られた繊維強化複合材料用組成物及び硬化物について、以下の評価を行った。
実施例及び比較例で得られた繊維強化複合材料用組成物の25℃における粘度(mPa・s)を、該組成物を調製した直後(調製後1時間以内)に測定した。結果を表1の「組成物の初期粘度」の欄に示す。
また、上記繊維強化複合材料用組成物を調製後、25℃の環境下で14日間保管した後、粘度(mPa・s)を測定した。結果を表1の「組成物の25℃ラ14日間保管後の粘度」の欄に示す。
なお、粘度の測定装置、測定条件は下記の通りである。
<測定装置及び測定条件>
測定装置:粘度測定装置(商品名「TV-22H」、東機産業社製)
測定温度:25℃
ローター:1°34'×R24
回転数:1.0rpm
実施例及び比較例で得られた硬化物(厚み:0.5mm)を幅4mm、長さ3cmに切り出し、これをサンプルとして使用した。
上記で得たサンプルの動的粘弾性測定(DMA)を、下記の条件で実施した。
<測定装置及び測定条件>
測定装置:固体粘弾性測定装置(「RSAIII」、TA INSTRUMENTS社製)
雰囲気:窒素
温度範囲:25~350℃
昇温温度:5℃/分
変形モード:引っ張りモード
上記動的粘弾性測定で測定されたtanδ(損失正接)のピークトップの温度を硬化物のガラス転移温度(Tg)として求めた。結果を表1の「Tg」の欄に示した。
また、本発明の繊維強化複合材料用組成物を硬化させて得られた硬化物は、高いガラス転移温度を有していた。
[ラジカル重合性化合物(A)]
IRR214-K:ジメチロールジシクロペンタンジアクリレート(ダイセル・サイテック社製、分子量:304、一分子中のアクリロイル基の数:2個、官能基当量:152)
EBECRYL 130:トリシクロデカン骨格を有するジアクリレート(ダイセル・サイテック社製)
[カチオン重合性化合物(B)]
N-670-EXP-S:オルソクレゾールノボラック型エポキシ樹脂(DIC社製、官能基当量:200-210)
HP-7200:ジシクロペンタジエン型エポキシ樹脂(DIC社製、官能基当量:250-280)
YD-128:ビスフェノール型エポキシ樹脂(新日鉄住金化学社製、官能基当量:184-194)
[ラジカル重合開始剤]
パーヘキサC(S):1,1-ジ(t-ブチルパーオキシ)シクロヘキサン(日油社製;10時間半減期分解温度:90.7℃)(前記ラジカル重合開始剤(C)に該当する)
パーブチルO:tert-ブチル 2-エチルペルオキシヘキサノアート(日油社製;10時間半減期分解温度:72.1℃)
[酸発生剤]
サンエイドSI-100L:芳香族スルホニウム塩(三新化学工業社製;示差走査型熱量測定装置(DSC)を用いて昇温速度10℃/分で測定した際の発熱開始温度:124.1℃)(前記酸発生剤(D)に該当する)
サンエイドSI-60L:芳香族スルホニウム塩(三新化学工業社製;示差走査型熱量測定装置(DSC)を用いて昇温速度10℃/分で測定した際の発熱開始温度:97.6℃)
Claims (14)
- 一分子中にラジカル重合性基を2個以上有するラジカル重合性化合物(A)、一分子中にカチオン重合性基を2個以上有するカチオン重合性化合物(B)、10時間半減期分解温度が85℃以上のラジカル重合開始剤(C)、及び示差走査型熱量測定装置(DSC)を用いて昇温速度10℃/分で測定した際に、発熱開始温度が100℃以上となる酸発生剤(D)を含み、25℃における粘度が10000mPa・s以上の繊維強化複合材料用組成物。
- 前記カチオン重合性化合物(B)が、エポキシ化合物、オキセタン化合物、及びビニルエーテル化合物からなる群より選択される少なくとも一種の化合物である請求項1に記載の繊維強化複合材料用組成物。
- 前記ラジカル重合性化合物(A)とカチオン重合性化合物(B)の割合(重量比)[(A)/(B)]が0/100より大きく且つ80/20以下である請求項1又は2に記載の繊維強化複合材料用組成物。
- 前記ラジカル重合開始剤(C)の含有量が、ラジカル重合性化合物(A)とカチオン重合性化合物(B)の総量100重量部に対して、0.01~10重量部である請求項1~3のいずれか一項に記載の繊維強化複合材料用組成物。
- 前記酸発生剤(D)の含有量が、ラジカル重合性化合物(A)とカチオン重合性化合物(B)の総量100重量部に対して、0.1~20重量部である請求項1~4のいずれか一項に記載の繊維強化複合材料用組成物。
- 前記ラジカル重合性化合物(A)が環状構造を有する化合物である請求項1~5のいずれか一項に記載の繊維強化複合材料用組成物。
- 前記ラジカル重合性化合物(A)がトリシクロデカン骨格を有する化合物である請求項1~6のいずれか一項に記載の繊維強化複合材料用組成物。
- 前記カチオン重合性化合物(B)が環状構造を有する化合物である請求項1~7のいずれか一項に記載の繊維強化複合材料用組成物。
- 前記カチオン重合性化合物(B)がトリシクロデカン骨格を有する化合物である請求項1~8のいずれか一項に記載の繊維強化複合材料用組成物。
- 25℃におけるポットライフ(粘度が初期粘度の2倍になる時間)が、14日以上である請求項1~9のいずれか一項に記載の繊維強化複合材料用組成物。
- 請求項1~10のいずれか一項に記載の繊維強化複合材料用組成物を強化繊維(E)に含浸させて形成されるプリプレグ。
- 強化繊維(E)の繊維質量含有率(Wf)が50~90重量%である請求項11に記載のプリプレグ。
- 強化繊維(E)が、炭素繊維、ガラス繊維、及びアラミド繊維からなる群より選択される少なくとも一種である請求項11又は12に記載のプリプレグ。
- 請求項11~13のいずれか一項に記載のプリプレグを硬化させて得られる繊維強化複合材料。
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BR112015028360A BR112015028360A2 (pt) | 2013-05-24 | 2014-05-20 | Composição para um material compósito reforçado com fibra, prepreg, e material compósito reforçado com fibra |
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WO2021131566A1 (ja) * | 2019-12-25 | 2021-07-01 | Dic株式会社 | プリプレグ及び成形品 |
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EP3517558B1 (en) * | 2016-09-26 | 2021-09-15 | Mitsubishi Chemical Corporation | Laminated film for fiber adhesion and/or fiber sheet surface protection and thermosetting composition for fiber adhesion and/or fiber sheet surface protection |
US10851232B2 (en) * | 2016-12-09 | 2020-12-01 | Lg Chem, Ltd. | Encapsulating composition, organic electronic device and method for manufacturing thereof |
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