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WO2017200082A1 - Composition pour résine renforcée par des fibres de carbone, composition de résine renforcée par des fibres de carbone, article durci - Google Patents

Composition pour résine renforcée par des fibres de carbone, composition de résine renforcée par des fibres de carbone, article durci Download PDF

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Publication number
WO2017200082A1
WO2017200082A1 PCT/JP2017/018799 JP2017018799W WO2017200082A1 WO 2017200082 A1 WO2017200082 A1 WO 2017200082A1 JP 2017018799 W JP2017018799 W JP 2017018799W WO 2017200082 A1 WO2017200082 A1 WO 2017200082A1
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Prior art keywords
carbon fiber
resin
fiber reinforced
meth
reinforced resin
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English (en)
Japanese (ja)
Inventor
一博 黒木
小林　健一
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Resonac Holdings Corp
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Showa Denko KK
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Priority to JP2018518381A priority Critical patent/JP6952686B2/ja
Priority to CN201780029122.5A priority patent/CN109071777B/zh
Priority to KR1020187032289A priority patent/KR102221532B1/ko
Priority to KR1020207003941A priority patent/KR20200017559A/ko
Publication of WO2017200082A1 publication Critical patent/WO2017200082A1/fr
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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
    • 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
    • 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

Definitions

  • the present invention provides a composition for carbon fiber reinforced resin that can be cured efficiently at a low temperature and in a short time, and in which a cured product having good adhesion between a resin component and carbon fiber is obtained, a carbon fiber reinforced resin composition containing the same, and It relates to the cured product.
  • a carbon fiber reinforced resin composition using an epoxy resin needs to be heated at a high temperature for a long time.
  • Some carbon fiber reinforced resin compositions contain a vinyl ester resin that can be cured at a low temperature in a short time.
  • the adhesion between the resin component and the carbon fiber in the cured product is insufficient, so that the interlayer shear strength of the cured product cannot be sufficiently obtained. There was a case.
  • Patent Document 1 describes a curable resin composition containing a resin having an epoxy group and a radically polymerizable unsaturated group and a hexaarylbiimidazole compound.
  • Patent Document 2 describes a composition containing an epoxy acrylate resin, a hexaarylbiimidazole compound, a mercapto compound, and a fiber reinforcing material.
  • JP 2005-281610 A Japanese Patent Laid-Open No. 9-278903
  • the conventional carbon fiber reinforced resin composition that can be cured at a low temperature and in a short time has insufficient adhesion between the resin component and the carbon fiber in the cured product. For this reason, there has been a demand for a carbon fiber reinforced resin composition that can be cured at a low temperature in a short time and that can provide a cured product having good adhesion between the resin component and the carbon fiber.
  • the present invention has been made in view of the above circumstances, and is a resin of a carbon fiber reinforced resin composition that can be cured at a low temperature and in a short time and that provides a cured product with good adhesion between the resin component and the carbon fiber. It aims at providing the composition for carbon fiber reinforced resin used as a component. Moreover, this invention makes it a subject to provide the carbon fiber reinforced resin composition containing the said composition for carbon fiber reinforced resins. Furthermore, this invention makes it a subject to provide the hardened
  • This inventor earnestly examined in order to solve the said subject and to provide the composition for carbon fiber reinforced resin which can be hardened
  • a composition containing (A) a radical reactive resin and (B) a radical polymerizable unsaturated monomer (C) a compound containing a mercapto group was used as a curing accelerator, and (D) one It has been found that by using an imidazole compound having only an imidazole ring and (E) an organic peroxide as a curing agent, an extremely high curing acceleration function can be obtained.
  • the present inventor has found that the cured product of the carbon fiber reinforced resin composition containing the composition containing (A) to (E) and the carbon fiber has good adhesion between the resin component and the carbon fiber.
  • the present invention has been conceived. That is, the present invention relates to the following matters.
  • a composition for carbon fiber reinforced resin comprising an organic peroxide.
  • the (D) imidazole compound is one in which one or two positions including the 2-position of the imidazole ring are substituted with an alkyl group, an aryl group, or an aralkyl group.
  • the composition for carbon fiber reinforced resin according to item.
  • the (A) radical reactive resin is at least one selected from an epoxy (meth) acrylate resin, an unsaturated polyester resin, a polyester (meth) acrylate resin, and a urethane (meth) acrylate resin.
  • the content of the epoxy (meth) acrylate resin having at least one epoxy group in the radical reactive resin (A) is 1 to 100% by mass, and any one of [1] to [7] The composition for carbon fiber reinforced resins described in 1.
  • composition for carbon fiber reinforced resin according to any one of [1] to [9], wherein the (E) organic peroxide is cumene hydroperoxide or t-butyl peroxybenzoate.
  • (G) metal soap is a manganese compound or a cobalt compound.
  • [12] 20 to 99% by mass of (A) radical reactive resin, (B) radical polymerizable, based on the total amount of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer. Containing 1-80% by weight of unsaturated monomer, 0.001 to 20 parts by mass of the (C) mercapto group-containing compound with respect to 100 parts by mass in total of the (A) radical reactive resin and the (B) radical polymerizable unsaturated monomer,
  • a carbon fiber reinforced resin composition comprising the carbon fiber reinforced resin composition according to any one of [1] to [12] and (F) a carbon fiber.
  • Resin composition [16] A cured product of the carbon fiber reinforced resin composition according to any one of [13] to [15].
  • the carbon fiber reinforced resin composition containing the composition for carbon fiber reinforced resin of the present invention can be efficiently cured at a low temperature and in a short time. Therefore, the carbon fiber reinforced resin composition of the present invention can be molded using a molding method that requires a high production cycle. Moreover, according to the carbon fiber reinforced resin composition of the present invention, a cured product having good adhesion between the resin component and the carbon fiber can be obtained by curing the resin composition.
  • the resin composition of the present embodiment includes a carbon fiber reinforced resin composition and carbon fibers.
  • the carbon fiber reinforced resin composition is preferably impregnated with (F) carbon fiber.
  • the composition for carbon fiber reinforced resin has (A) a radical reactive resin, (B) a radical polymerizable unsaturated monomer, (C) a mercapto group-containing compound, and (D) only one imidazole ring. An imidazole compound and (E) an organic peroxide.
  • the radical reactive resin is a resin having an ethylenic carbon-carbon double bond in the side chain and / or main chain. Specifically, at least one selected from (A1) epoxy (meth) acrylate resin, (A2) unsaturated polyester resin, (A3) polyester (meth) acrylate resin, and (A4) urethane (meth) acrylate resin Preferably there is.
  • (meth) acrylate means at least one selected from methacrylate and acrylate.
  • the (A1) epoxy (meth) acrylate resin is obtained by reacting all or part of the epoxy groups contained in the epoxy compound with an unsaturated monobasic acid, and has a radical-reactive carbon-carbon dicarboxylic acid in the side chain. Has a double bond. Since a representative example of the unsaturated monobasic acid is (meth) acrylic acid, it is referred to as an epoxy (meth) acrylate resin.
  • epoxy compound monomers, oligomers and polymers generally having two or more epoxy groups in one molecule can be used, and the molecular weight and molecular structure are not particularly limited.
  • biphenyl type epoxy resin bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, tetrabromobisphenol A type epoxy resin, tetramethylbisphenol F type epoxy resin, etc .
  • stilbene type epoxy Resin Novolak type epoxy resin such as phenol novolak type epoxy resin and cresol novolak type epoxy resin
  • Multifunctional epoxy resin such as triphenolmethane type epoxy resin and alkyl-modified triphenolmethane type epoxy resin
  • Known unsaturated monobasic acids can be used.
  • (meth) acrylic acid, crotonic acid, cinnamic acid and the like can be mentioned.
  • (meth) acrylic acid is preferable.
  • the unsaturated monobasic acid a reaction product of a compound having one hydroxy group and one or more (meth) acryloyl groups and a polybasic acid anhydride may be used.
  • the polybasic acid anhydride is used to increase the molecular weight of the epoxy resin, and known ones can be used.
  • succinic acid glutaric acid, adipic acid, sebacic acid, phthalic acid, fumaric acid, maleic acid, itaconic acid, tetrahydrophthalic acid, hexahydrophthalic acid, dimer acid, ethylene glycol 2 mol maleic anhydride adduct, polyethylene Glycol 2 mol maleic anhydride adduct, propylene glycol 2 mol maleic anhydride adduct, polypropylene glycol 2 mol maleic anhydride adduct, dodecanedioic acid, tridecanedioic acid, octadecanedioic acid, 1,16- (6 Examples include anhydrides such as -ethylhexadecane) dicarboxylic acid, 1,12- (6-ethyldodecane) dicarboxylic acid, carboxyl-terminated butadiene / acrylonitrile copolymer (trade name Hycar CTBN)
  • the (A) radical reactive resin includes an epoxy (meth) acrylate resin having at least one epoxy group.
  • the content of the epoxy (meth) acrylate resin having at least one epoxy group in the radical reactive resin is preferably 1 to 100% by mass, more preferably 20 to 90% by mass, and even more preferably 30 to 30% by mass. 70% by mass.
  • the epoxy (meth) acrylate resin having at least one epoxy group preferably has an epoxy equivalent of 140 to 9500, more preferably 190 to 5000.
  • an epoxy (meth) acrylate resin having at least one epoxy group has a radically polymerizable unsaturated group, it is cured at a low temperature in a short time. Moreover, since the epoxy (meth) acrylate resin which has at least 1 epoxy group has an epoxy group, it is excellent in adhesiveness with carbon fiber. Therefore, when (A) the radical reactive resin contains an epoxy (meth) acrylate resin having at least one epoxy group, the composition for carbon fiber reinforced resin is more excellent in fast curability and adhesion to carbon fibers. It becomes.
  • Unsaturated polyester resin is obtained by esterifying an unsaturated dibasic acid and, if necessary, a dibasic acid component containing a saturated dibasic acid and a polyhydric alcohol.
  • unsaturated dibasic acid include maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride and the like, and these may be used alone or in combination of two or more.
  • saturated dibasic acid examples include aliphatic dibasic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and isosebacic acid, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, and terephthalic acid.
  • aliphatic dibasic acids such as adipic acid, suberic acid, azelaic acid, sebacic acid, and isosebacic acid, phthalic acid, phthalic anhydride, halogenated phthalic anhydride, isophthalic acid, and terephthalic acid.
  • the polyhydric alcohol is not particularly limited.
  • a resin modified with a bridged cyclic hydrocarbon compound such as dicyclopentadiene may be used as long as the effects of the present invention are not impaired.
  • a modification method for example, after obtaining an addition product (sidedecanol monomaleate) of dicyclopentadiene and maleic acid, this is used as a monobasic acid and reacted with the unsaturated polyester to form a dicyclopentadiene skeleton.
  • Known methods such as introduction of the Among the above (A2) unsaturated polyester resins, ortho-type unsaturated polyester resins are preferable from the viewpoint of versatility and cost.
  • an oxidative polymerization (air curing) group such as an allyl group or a benzyl group
  • an oxidative polymerization (air curing) group such as an allyl group or a benzyl group
  • air curing an oxidative polymerization (air curing) group
  • an oxidative polymerization (air curing) group such as an allyl group or a benzyl group
  • limiting in particular in the introduction method of an oxidation polymerization group For example, the method etc. with which (A2) unsaturated polyester resin and the compound which has both a hydroxyl group and an allyl ether group are condensation-reacted are mentioned.
  • the (A1) epoxy (meth) acrylate resin and / or (A2) unsaturated polyester resin used in the present invention may be used by mixing with an oxidatively polymerizable group-containing polymer.
  • a reaction product obtained by reacting a reaction product of a compound having both a hydroxyl group and an allyl ether group with an acid anhydride and a compound having an epoxy group is used in the present invention.
  • (A1) Epoxy (meth) You may mix and use for an acrylate resin and / or (A2) unsaturated polyester resin.
  • the compound having an epoxy group include allyl glycidyl ether and 2,6-diglycidyl phenyl allyl ether.
  • the oxidative polymerization (air curing) group those having an allyl ether group or a benzyl ether group are particularly preferable.
  • the oxidative polymerization (air curing) in the present invention refers to cross-linking associated with the generation and decomposition of a peroxide by oxidation of a methylene bond between an ether bond and a double bond, such as found in an allyl ether group. .
  • Examples of the monomer forming the oxidatively polymerizable group-containing polymer include unsaturated compounds having an allyl ether group or a benzyl ether group. Specific examples include allyl methacrylate, vinyl benzyl butyl ether, vinyl benzyl hexyl ether, vinyl benzyl octyl ether, vinyl benzyl- (2-ethylhexyl) ether, vinyl benzyl ( ⁇ -methoxymethyl) ether, vinyl benzyl (n-butoxypropyl).
  • Examples include ether, vinyl benzyl cyclohexyl ether, vinyl benzyl- ( ⁇ -phenoxyethyl) ether, vinyl benzyl dicyclopentenyl ether, vinyl benzyl dicyclopentenyl oxyethyl ether, vinyl benzyl dicyclopentenyl methyl ether, and divinyl benzyl ether.
  • dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, or the like the drying property of the carbon fiber reinforced resin composition is improved.
  • the polyester (meth) acrylate resin is a polyester having a (meth) acryloyloxy group.
  • the polyester (meth) acrylate resin is obtained, for example, by the method (1) or (2) shown below. (1) An epoxy group-containing (meth) acrylate or a hydroxyl group-containing (meth) acrylate is reacted with a polyester having a terminal carboxyl group. (2) A polyester having a hydroxyl group at the end is reacted with (meth) acrylic acid or an isocyanato group-containing (meth) acrylate.
  • polyester having a carboxyl group at the end used as a raw material in the method (1) examples include those obtained from an excess amount of a saturated polybasic acid and / or an unsaturated polybasic acid and a polyhydric alcohol.
  • polyester having a hydroxyl group at the end used as a raw material in the method (2) examples include those obtained from a saturated polybasic acid and / or an unsaturated polybasic acid and an excess amount of a polyhydric alcohol.
  • Examples of the saturated polybasic acid used as a raw material for the polyester (meth) acrylate resin include polymerizable unsaturated bonds such as phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, adipic acid, and sebacic acid. Non-polybasic acid or its anhydride.
  • Examples of the unsaturated polybasic acid used as a raw material for the polyester (meth) acrylate resin include polymerizable unsaturated polybasic acids such as fumaric acid, maleic acid, and itaconic acid, or anhydrides thereof.
  • polyhydric alcohol component examples include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,2-butanediol, 1,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, cyclohexane-1,4-dimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, etc. Can be mentioned.
  • the epoxy group-containing (meth) acrylate used for the production of the polyester (meth) acrylate resin includes glycidyl (meth) acrylate.
  • Hydroxyl group-containing (meth) acrylate used for the production of polyester (meth) acrylate resin includes 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate 2-phenoxy-2-hydroxypropyl (meth) acrylate, 2- (meth) acryloyloxy-2-hydroxypropyl phthalate, and the like.
  • the isocyanato group-containing (meth) acrylate used for the production of the polyester (meth) acrylate resin includes 2-isocyanatoethyl (meth) acrylate.
  • polyester (meth) acrylate resins obtained by reacting glycidyl (meth) acrylate and 2-isocyanatoethyl (meth) acrylate are preferable from the viewpoint of versatility and cost. .
  • the urethane (meth) acrylate resin is a polyurethane having a (meth) acryloyloxy group. Specifically, after reacting a polyisocyanate with a polyhydroxy compound or a polyhydric alcohol, an unreacted isocyanato group is further reacted with a hydroxyl group-containing (meth) acryl compound and optionally a hydroxyl group-containing allyl ether compound. And a radically polymerizable unsaturated group-containing oligomer obtained in the above manner.
  • Examples of the polyisocyanate used as a raw material for the (A4) urethane (meth) acrylate resin include 2,4-tolylene diisocyanate and its isomer, diphenylmethane diisocyanate, hexamethylene disisocyanate, hydrogenated xylylene diisocyanate, and isophorone.
  • These polyisocyanates may be used alone or in combination of two or more.
  • diphenylmethane diisocyanate is preferably used from the viewpoint of cost.
  • Examples of the polyhydroxy compound used as a raw material for the (A4) urethane (meth) acrylate resin include polyester polyol, polyether polyol, and polycarbonate polyol. More specifically, glycerin-ethylene oxide adduct, glycerin-propylene oxide adduct, glycerin-tetrahydrofuran adduct, glycerin-ethylene oxide-propylene oxide adduct, trimethylolpropane-ethylene oxide adduct, trimethylolpropane-propylene oxide adduct , Trimethylolpropane-tetrahydrofuran adduct, trimethylolpropane-ethylene oxide-propylene oxide adduct, dipentaerythritol-ethylene oxide adduct, dipentaerythritol-propylene oxide adduct, dipentaerythritol-tetrahydrofuran adduct And dipentaerythri
  • polyhydric alcohol used as a raw material for the above (A4) urethane (meth) acrylate resin examples include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, 2-methyl- 1,3-propanediol, 1,3-butanediol, adducts of bisphenol A and propylene oxide or ethylene oxide, 1,2,3,4-tetrahydroxybutane, glycerin, trimethylolpropane, 1,3-butanediol, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, para-xylene glycol, bicyclohexyl-4,4-diol, 2,6-deca Glycol, such as 2,7-decalin glycol.
  • These polyhydric alcohols may be used alone or in combination of two or more.
  • a hydroxyl-containing (meth) acrylic compound used as a raw material of the said (A4) urethane (meth) acrylate resin a hydroxyl-containing (meth) acrylic ester is preferable.
  • These hydroxyl group-containing (meth) acrylic compounds may be used alone or in a mixture of two or more.
  • hydroxyl group-containing allyl ether compound used as a raw material for the (A4) urethane (meth) acrylate resin include ethylene glycol monoallyl ether, diethylene glycol monoallyl ether, and triethylene glycol monoallyl.
  • Ether polyethylene glycol monoallyl ether, propylene glycol monoallyl ether, dipropylene glycol monoallyl ether, tripropylene glycol monoallyl ether, polypropylene glycol monoallyl ether, 1,2-butylene glycol monoallyl ether, 1,3-butylene glycol Monoallyl ether, hexylene glycol monoallyl ether, octylene glycol monoallyl ether, trimethylolpropane di Rirueteru, Grilled syringe allyl ether, pentaerythritol triallyl ether.
  • These hydroxyl group-containing allyl ether compounds may be used alone or in a combination of two or more.
  • the content of the (A) radical reactive resin is preferably 20 to 99% by mass, more preferably 50 to 50%, based on the total amount of (A) the radical reactive resin and (B) the radical polymerizable unsaturated monomer. 90% by mass, more preferably 60-80% by mass.
  • composition for carbon fiber reinforced resin of this invention may contain resin components other than (A) radical reactive resin.
  • resin components other than (A) radical reactive resin Preferable examples include (A5) (meth) acrylate resin.
  • (A5) (meth) acrylate resins include those obtained by homopolymerization or copolymerization of (meth) acrylate monomers.
  • Examples of the (meth) acrylate monomer used as a raw material for the (A5) (meth) acrylate resin include methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, Isooctyl (meth) acrylate, n-nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate, lauryl (meth) acrylate, tridecyl (meth)
  • the (A5) (meth) acrylate resin it is preferable to use a homopolymer of methyl (meth) acrylate and a copolymer containing methyl (meth) acrylate as a main component from the viewpoint of the cost and reactivity of the polymer. .
  • (A) radical reactive resin (A1) epoxy (meth) acrylate resin, (A2) unsaturated polyester resin, (A3) polyester (meth) acrylate resin, (A4) urethane (meth) acrylate resin
  • A1 epoxy (meth) acrylate resin epoxy (meth) acrylate resin
  • A2) unsaturated polyester resin unsaturated polyester resin
  • A3) polyester (meth) acrylate resin polyester (meth) acrylate resin
  • (A4) urethane (meth) acrylate resin The catalyst and / or polymerization inhibitor used when synthesizing at least one or more of them may remain.
  • the catalyst examples include compounds containing tertiary nitrogen atoms such as triethylamine, pyridine derivatives, imidazole derivatives, and imidazole derivatives; amine salts such as tetramethylammonium chloride and triethylamine; and phosphorus compounds such as trimethylphosphine and triphenylphosphine. Is mentioned.
  • the polymerization inhibitor include hydroquinone, methylhydroquinone and phenothiazine.
  • the radical reactive resin contains a catalyst and / or a polymerization inhibitor
  • the content thereof is (A1) epoxy (meth) acrylate resin, (A2) unsaturated polyester resin, (A3) polyester (meth).
  • the amount is preferably 0.001 to 2 parts by mass with respect to 100 parts by mass in total of the acrylate resin and the (A4) urethane (meth) acrylate resin.
  • the (B) radical polymerizable unsaturated monomer is not particularly limited, but preferably has a vinyl group or a (meth) acryloyl group.
  • the “(meth) acryloyl group” means an acryloyl group and / or a methacryloyl group.
  • Examples of the (B) radical polymerizable unsaturated monomer having a vinyl group include styrene, p-chlorostyrene, vinyltoluene, ⁇ -methylstyrene, dichlorostyrene, divinylbenzene, t-butylstyrene, vinyl acetate, Examples include diallyl phthalate and triallyl isocyanurate.
  • Examples of the (B) radical polymerizable unsaturated monomer having a (meth) acryloyl group include (meth) acrylic acid esters.
  • Examples of (meth) acrylic acid esters include methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, lauryl (meth) acrylate, Cyclohexyl (meth) acrylate, benzyl (meth) acrylate, stearyl (meth) acrylate, tridecyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, phenoxyethyl (meth) acrylate, 2-hydroxyethyl ( (Meth) acrylate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl ether (meth) acrylate, ethylene
  • radical polymerizable unsaturated monomers can be used alone or in combination of two or more.
  • (B) radical polymerizable unsaturated monomers styrene is preferably used from the viewpoint of workability, curability and cost.
  • the content of the (B) radical polymerizable unsaturated monomer is 1 to 80% by mass with respect to the total amount of the (A) radical reactive resin and (B) the radical polymerizable unsaturated monomer. It is preferably 10 to 50% by mass, more preferably 20 to 40% by mass.
  • the mercapto group-containing compound functions as a curing accelerator.
  • the mercapto group-containing compound is one or more selected from a secondary thiol compound (C1) in which a mercapto group is bonded to a secondary carbon atom, or a tertiary thiol compound (C2) that is bonded to a tertiary carbon atom. It is preferable that (C) The mercapto group-containing compound is particularly preferably a secondary thiol compound (C1) in order to cure in a shorter time.
  • the secondary thiol compound (C1) has better storage stability than the primary thiol compound in which a mercapto group is arranged at the terminal.
  • the tertiary thiol compound (C2) is a compound in which a mercapto group is not arranged at the terminal, like the secondary thiol compound (C1). Therefore, the tertiary thiol compound (C2) has a function similar to that of the secondary thiol compound (C1) as a (C) mercapto group-containing compound.
  • the term “polyfunctional thiol” as used herein means a mercapto group-containing compound having two or more mercapto groups that are functional groups.
  • the mercapto group-containing compound is a polyfunctional thiol having two or more mercapto groups bonded to secondary or tertiary carbon atoms in the molecule in order to cure the carbon fiber reinforced resin composition in a shorter time.
  • the compound having two or more mercapto groups bonded to a secondary or tertiary carbon atom in the molecule is not particularly limited.
  • the compound has at least one structure represented by the following formula (Q).
  • a compound having two or more mercapto groups bonded to a secondary or tertiary carbon atom in the molecule including the mercapto group in the structure represented by the formula (Q) is preferable.
  • R 1 is any one of a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, and an aromatic group having 6 to 18 carbon atoms.
  • R 2 represents one to 1 carbon atoms.
  • 10 is an alkyl group or an aromatic group having 6 to 18 carbon atoms, * indicates that it is linked to an arbitrary organic group, and a is an integer of 0 to 2.
  • (C) As a mercapto group-containing compound, in particular, a mercapto having a structure represented by the formula (Q), wherein R 1 in the formula (Q) is a hydrogen atom, and bonded to a secondary carbon atom in the molecule More preferably, it is a compound having two or more groups. That is, the (C) mercapto group-containing compound has a structure represented by the formula (Q), and the secondary thiol compound (C1) in which the carbon atom to which the mercapto group in the formula (Q) is bonded is a secondary carbon atom. ) Is preferable.
  • the alkyl group having 1 to 10 carbon atoms in R 1 and R 2 in the formula (Q) may be linear or branched. Specific examples include a methyl group, an ethyl group, various propyl groups, various butyl groups, various pentyl groups, various hexyl groups, various heptyl groups, and various octyl groups.
  • the “various” means various isomers including n-, sec-, tert-, and iso-. Among these alkyl groups, a methyl group and an ethyl group are preferable.
  • examples of the aromatic group having 6 to 18 carbon atoms in R 1 and R 2 in the formula (Q) include a phenyl group, a benzyl group, a naphthyl group, an anthryl group, and a phenanthryl group.
  • these aromatic groups may be substituted with a halogen atom, an amino group, a nitro group, a cyano group, or the like.
  • a in the formula (Q) is an integer of 0 to 2, preferably 1.
  • the (C) mercapto group-containing compound preferably has at least one ester structure represented by the following formula (Q-1).
  • R 1 , R 2, * and a are, R 1, R 2 in the formula (Q), the same meanings as * and a.
  • a in formula (Q-1) is preferably 1.
  • a 1, it is preferable from the viewpoint of controlling the stability and curability of the resin composition.
  • R 1 is a hydrogen atom (the compound represented by (Q-1) is a secondary thiol compound (C1))
  • the formula (Q- A in 1) is preferably 1.
  • the ester structure represented by the formula (Q-1) is preferably derived from a mercapto group-containing carboxylic acid represented by the following formula (S) and a polyhydric alcohol.
  • R 1, R 2 and a have the same meanings as R 1, R 2 and a in the formula (Q).
  • polyhydric alcohol examples include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, neopentyl glycol, 1,2-propanediol, 1, 3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,2-pentanediol, 1,3-pentanediol, 2,3-pentanediol, 1,4-pentanediol, 1,5 -Pentanediol, 1,6-hexanediol, 1,9-nonanediol, tricyclodecane dimethanol, (2,2-bis (2-hydroxyethoxyphenyl) propane), bisphenol A alkylene o Sid adduct, bisphenol F alkylene oxide adduct, bisphenol S alkyl
  • divalent alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol; glycerin from the viewpoint of availability and improving curability
  • divalent alcohols such as ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol; glycerin from the viewpoint of availability and improving curability
  • Trihydric or higher alcohols such as trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, dipentaerythritol, 2,2-bis (2,3-dihydroxypropyloxyphenyl) propane; Polycarbonate diol and dimer acid polyester polyol are preferred.
  • 1,4-butanediol trimethylolethane, trimethylolpropane, tris (2-hydroxyethyl) isocyanurate, pentaerythritol, polycarbonate diol, dimer acid Polyester polyol is preferred.
  • the compound (C1) is a compound having an ester structure represented by the formula (Q-1)
  • the compound is represented by the polyhydric alcohol and the formula (S). It is preferably derived from a carboxylic acid containing a mercapto group bonded to a secondary carbon atom.
  • Examples of the mercapto group-containing carboxylic acid represented by the formula (S) include 2-mercaptopropionic acid, 3-mercaptobutyric acid, 3-mercapto-3-phenylpropionic acid, and the like.
  • secondary thiol compounds (C1) commercially available monofunctional secondary thiols include 3-mercaptobutanoic acid (manufactured by Showa Denko KK, product name: 3MBA), mercapto bonded to a secondary carbon atom in the molecule.
  • Examples of commercially available compounds having two or more groups include 1,4-bis (3-mercaptobutyryloxy) butane (manufactured by Showa Denko KK, Karenz MT (registered trademark) BD1), pentaerythritol tetrakis (3-mercapto Butyrate) (produced by Showa Denko KK, Karenz MT (registered trademark) PE1), 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 ( 1H, 3H, 5H) -trione (produced by Showa Denko KK, Karenz MT (registered trademark) NR1), trimethylolethane tris (3-mercaptobutyrate ) (Manufactured by Showa Denko KK, TEMB), trimethylolpropane tris (3-mercapto butyrate) (manufactured by Showa Denko KK, TPMB) and the like, it is
  • [Tertiary thiol compound (C2)] (C)
  • the mercapto group-containing compound is a tertiary thiol compound (C2) having the structure represented by the formula (Q)
  • specific examples thereof include di (2-mercaptoisobutyl) phthalate, ethylene glycol bis (2-mercaptoisobutyrate), propylene glycol bis (2-mercaptoisobutyrate), diethylene glycol bis (2-mercaptoisobutyrate), butanediol bis (2-mercaptoisobutyrate), octanediol bis (2- Mercaptoisobutyrate), trimethylolethane tris (2-mercaptoisobutyrate), trimethylolpropane tris (2-mercaptoisobutyrate), pentaerythritol tetrakis (2-mercaptoisobutyrate), dipentaerythritol hexakis ( 2-me Captoisobut
  • the compound (C2) is a compound having an ester structure represented by the formula (Q-1)
  • the compound is represented by the polyhydric alcohol and the formula (S). It is preferably derived from a carboxylic acid containing a mercapto group bonded to a tertiary carbon atom.
  • Examples of the mercapto group-containing carboxylic acid represented by the formula (S) include 2-mercaptoisobutyric acid and 3-mercapto-3-methylbutyric acid.
  • the (C) mercapto group-containing compound is preferably contained in an amount of 0.001 to 20 parts by mass with respect to a total of 100 parts by mass of the (A) radical reactive resin and the (B) radical polymerizable unsaturated monomer. . More preferred is 0.01 to 10 parts by mass, and further more preferred is 0.1 to 5 parts by mass.
  • the (D) imidazole compound contained in the resin composition of the present embodiment has only one imidazole ring, and does not include a compound having a plurality of imidazole rings.
  • the imidazole compound functions as a curing agent.
  • Examples of (D) imidazole compounds include imidazole, 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl- 2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-dia Mino-6- [2′-methylimidazolyl-
  • the alkyl group preferably has 1 to 6 carbon atoms, and more preferably has 1 to 3 carbon atoms.
  • the aryl group preferably has 6 to 20 carbon atoms, and more preferably has 6 to 12 carbon atoms.
  • the aralkyl group preferably has 7 to 20 carbon atoms, and more preferably has 7 to 12 carbon atoms.
  • Examples of such (D) imidazole compounds include 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole, and 2-methylimidazole. In particular, 2-ethyl-4-methylimidazole or 1-benzyl-2-methylimidazole is preferably used as the (D) imidazole compound.
  • the imidazole compound is preferably contained in an amount of 0.001 to 10 parts by mass with respect to a total of 100 parts by mass of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer. More preferred is 0.01 to 5 parts by mass, and still more preferred is 0.1 to 2 parts by mass.
  • (E) Organic peroxide functions as a curing agent.
  • curing agent can be used for (A) radical reactive resin and (B) radically polymerizable unsaturated monomer.
  • diacyl peroxides such as benzoyl peroxide, peroxyesters such as t-butylperoxybenzoate, hydroperoxides such as cumene hydroperoxide, dialkyl peroxides such as dicumyl peroxide, methyl ethyl ketone
  • peroxides ketone peroxides such as acetylacetone peroxide, peroxyketals, alkyl peresters, and carbonates
  • cumene hydroperoxide or t-butylperoxybenzoate is preferably used as the organic peroxide (E) from the viewpoint of stability after mixing with the resin.
  • Cumene hydroperoxide and t-butyl peroxybenzoate are both compounds having a (—O (oxygen) —O (oxygen) —) bond that decomposes upon curing to generate radicals.
  • the pot life can be increased as compared with the case of using cumene hydroperoxide.
  • the curing temperature may be set higher than when cumene hydroperoxide is used.
  • the organic peroxide is 0.1 to 10 parts by mass with respect to 100 parts by mass in total of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer, preferably 0.5 to 5 parts by mass, more preferably 0.5 to 2 parts by mass.
  • Carbon fiber As a carbon fiber, the arbitrary things manufactured with various manufacturing methods can be used. For example, carbon fibers such as pitch, PAN (polyacrylonitrile), and vapor phase growth can be used.
  • the shape of the carbon fiber is not particularly limited, and for example, a roving shape, a knitting shape, a cloth (cloth) shape, or a mat shape can be used alone or in combination.
  • the carbon fiber is preferably contained in the resin composition in an amount of 10 to 90% by mass, and more preferably 30 to 80% by mass. When the content of (F) carbon fiber is within the above range, the reinforcing effect by including (F) carbon fiber is sufficiently obtained.
  • the carbon fiber is preferably contained in the composition for carbon fiber reinforced resin so that the fiber volume content of the cured product is 40 to 70%.
  • the carbon fiber reinforced resin composition of this embodiment may contain the following components as needed in addition to the above-described components.
  • the metal soap functions as a curing accelerator.
  • a salt of a long chain fatty acid or an organic acid and a metal element is used.
  • the long chain fatty acid can be appropriately selected according to the type of the desired metal soap.
  • a fatty acid having 7 to 30 carbon atoms is preferable.
  • Saturated fatty acids such as acid, docosanoic acid, tetracosanoic acid, hexacosanoic acid, octacosanoic acid and triacontanoic acid, naphthenic acid, and unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid may also be used.
  • stearic acid 1,2-hydroxystearic acid, lauric acid, myristic acid, palmitic acid, behenic acid, rosin acid, linseed oil fatty acid, soybean oil fatty acid, tall oil acid, etc. may be used. it can.
  • the organic acid can be appropriately selected according to the type of the desired metal soap.
  • the organic acid those that are soluble in an organic solvent are preferable.
  • organic acids ascorbic acid, alpha acid, imidic acid, erythorbic acid, croconic acid, kojic acid, squaraine, which are used as weakly acidic compounds having sulfo group, hydroxy group, thiol group, and enol as characteristic groups
  • Acid, sulfinic acid, sulfonic acid, tycoic acid, thioacetic acid, dehydroacetic acid, delta acid, uric acid, hydroxamic acid, humic acid, fulvic acid, phosphonic acid, meldrum acid and the like can also be used.
  • long-chain fatty acids or organic acids long-chain fatty acids are preferable, linear or cyclic saturated fatty acids having 7 to 15 carbon atoms, or unsaturated fatty acids having 7 to 15 carbon atoms are more preferable, and octanoic acid and naphthenic acid are preferable. Further preferred.
  • Metal elements are vanadium, gold, silver, palladium, platinum, ruthenium, rhodium, tin, lead, zinc, iron, nickel, cobalt, lithium, aluminum, indium, neodymium, manganese, cerium, calcium, zirconium, copper, barium, Examples thereof include magnesium and rare earth.
  • Group 2 metal elements and Group 3-12 metal elements are preferable, barium, vanadium, manganese, iron, cobalt, copper, and zinc are more preferable, and manganese, iron, cobalt, copper And zinc are more preferred, and manganese and cobalt are even more preferred.
  • metal soap for example, metal soaps such as manganese naphthenate, manganese octylate, cobalt naphthenate, cobalt octylate, zinc octylate, vanadium octylate, copper naphthenate, barium naphthenate, etc. should be used. Can do.
  • a manganese compound or a cobalt compound as the (G) metal soap, and in particular, manganese naphthenate, manganese octylate, cobalt naphthenate, and cobalt octylate having high versatility are preferable.
  • the content of (G) metal soap in terms of metal component is 100 parts by mass in total of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer. On the other hand, it is preferably 0.0001 to 0.3 parts by mass, more preferably 0.001 to 0.2 parts by mass, and still more preferably 0.006 to 0.1 parts by mass. (G) It is preferable that the content of the metal soap in terms of metal component is in the range of 0.0001 to 0.3 parts by mass because the carbon fiber reinforced resin composition can be cured more efficiently at a low temperature and in a short time.
  • the resin composition of this embodiment may contain a polymerization inhibitor from the viewpoint of suppressing excessive polymerization of the resin composition and controlling the reaction rate.
  • a polymerization inhibitor examples include known ones such as hydroquinone, methylhydroquinone, catechols, and phenothiazine.
  • the resin composition of this embodiment may contain a curing retardant for the purpose of delaying the curing of the resin composition.
  • the curing retarder include free radical curing retarders such as 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical (TEMPO), 4-hydroxy-2,2, 6,6-tetramethylpiperidine 1-oxyl, free radical (4H-TEMPO), 4-oxo-2,2,6,6-tetramethyl-1-piperidinyloxy, free radical (4-Oxo-TEMPO) TEMPO derivatives such as Among these, 4-hydroxy-2,2,6,6-tetramethylpiperidine 1-oxyl and free radical (4H-TEMPO) are preferable from the viewpoint of cost and ease of handling.
  • free radical curing retarders such as 2,2,6,6-tetramethyl-1-piperidinyloxy, free radical (TEMPO), 4-hydroxy-2,2, 6,6-tetramethylpiperidine 1-oxyl, free radical (4H-TEMPO), 4-oxo-2,2,6,6-tetra
  • the resin composition of the present embodiment contains a polymerization inhibitor and / or a curing retarder as a constituent component
  • their contents are (A) a radical reactive resin and (B) a radical polymerizable unsaturated monomer.
  • the amount is 0.0001 to 10 parts by mass per 100 parts by mass in total.
  • the resin composition of the present embodiment includes (C) a mercapto group-containing compound, (D) an imidazole compound having only one imidazole ring, and (E) an organic peroxide.
  • other curing accelerators may be included.
  • curing accelerators examples include phosphorus compounds such as trimethylphosphine and triphenylphosphine, and amines such as amines and amine salts.
  • the other curing accelerator is preferably 0.01 to 10 parts by mass, more preferably 0 to 100 parts by mass in total of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer. It can be contained in the range of 1 to 5 parts by mass.
  • the resin composition of this embodiment may contain a photopolymerization initiator for the purpose of improving curability.
  • a photopolymerization initiator include a radical photopolymerization initiator, a cationic photopolymerization initiator, and a photoanionic polymerization initiator.
  • a radical photopolymerization initiator is used to improve the curability of an acrylic resin or monomer having a double bond.
  • photo radical polymerization initiators include benzoin ethers such as benzoin alkyl ether, benzophenones such as benzophenone, benzyl and methyl orthobenzoylbenzoate, benzyl dimethyl ketal, 2,2-diethoxyacetophenone, 2-hydroxy -2-Methylpropiophenone, 4-isopropyl-2-hydroxy-2-methylpropiophenone, acetophenone series such as 1,1-dichloroacetophenone, 2-chlorothioxanthone, 2-methylthioxanthone, 2-isopropylthioxanthone, etc.
  • a thioxanthone type is mentioned.
  • the cationic photopolymerization initiator is used to improve the curability of cyclic ether epoxy resin or the like and oxetane.
  • a photocationic polymerization initiator triarylsulfonium hexafluorophosphate, triarylsulfonium hexafluoroantimonate, triarylsulfonium salt, tricumyliodonium tetrakispentafluorophenylborate, 4-isobutylphenyl (4-methyl) Phenyl) iodonium hexafluorophosphate, triarylsulfonium hexafluorophosphate, triarylsulfonium tetrakis (pentafluorophenyl) borate and the like.
  • a photoanionic polymerization initiator is used in order to improve sclerosis
  • the photopolymerization initiator can be added in a range of 0.1 to 10 parts by mass with respect to 100 parts by mass in total of (A) the radical reactive resin and (B) the radical polymerizable unsaturated monomer. .
  • An antifoaming agent may be used in the resin composition of the present embodiment for the purpose of improving foam generation during molding and foam residue of the molded product.
  • the antifoaming agent include a silicon-based antifoaming agent and a polymer-based antifoaming agent.
  • the amount of the antifoaming agent used is preferably in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight as a total of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer. More preferably, it is 0.1 to 1 part by weight.
  • a coupling agent may be used for the purpose of improving moldability or for improving the adhesion to carbon fibers.
  • the coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent.
  • Examples of such a coupling agent include a silane coupling agent represented by R 3 —Si (OR 4 ) 3 .
  • R 3 include an aminopropyl group, a glycidyloxy group, a methacryloxy group, an N-phenylaminopropyl group, a mercapto group, and a vinyl group.
  • R 4 include a methyl group, an ethyl group, and the like. Groups and the like.
  • the amount of the coupling agent used is preferably in the range of 0.01 to 1 part by mass with respect to 100 parts by mass in total of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer.
  • a light stabilizer may be used for the purpose of improving the long-term durability of the molded product.
  • the light stabilizer include an ultraviolet absorber and a hindered amine light stabilizer. These may be used alone or in combination of two or more.
  • the ultraviolet absorber include benzotriazole, triazine, benzophenone, cyanoacrylate, salicylate, and the like.
  • the hindered amine light stabilizer NH type, NH3 type, And N-O alkyl type.
  • the amount of the light stabilizer used is in the range of 0.01 to 5 parts by mass with respect to 100 parts by mass in total of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer.
  • the amount is preferably 0.05 to 2 parts by mass.
  • the resin composition of this embodiment may contain a wax.
  • a wax paraffin waxes, polar waxes and the like can be used alone or in combination, and known ones having various melting points can be used.
  • polar waxes include those having both a polar group and a nonpolar group in the structure. Specific examples include NPS-8070, NPS-9125 (manufactured by Nippon Seiwa Co., Ltd.), Emanon 3199, 3299 (manufactured by Kao Corporation), and the like.
  • the wax is preferably contained in an amount of 0.05 to 4 parts by mass with respect to 100 parts by mass in total of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer, and 0.1 to 2 parts by mass. It is more preferable to contain 0.0 part by mass.
  • the resin composition of this embodiment may contain a flame retardant.
  • a flame retardant a brominated flame retardant, a chlorine flame retardant, a phosphorus flame retardant, an inorganic flame retardant, an intimate flame retardant, a silicon flame retardant, or the like can be used alone or in combination. Things can be used.
  • halogen-based flame retardants such as brominated flame retardants can be used in combination with antimony trioxide for the purpose of further improving flame retardancy.
  • the amount of flame retardant added varies depending on the system, it may be contained in an amount of 1 to 100 parts by mass with respect to a total of 100 parts by mass of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer. preferable.
  • fillers such as inorganic fillers and organic fillers may be blended for the purpose of controlling specific characteristics within a range that does not impair the effects of the present invention. These may be used alone or in combination of two or more.
  • the inorganic filler include inorganic hydroxides such as aluminum hydroxide that imparts flame retardancy, fumed silica that controls the fluidity of the resin composition, talc, and calcium carbonate, and titanium oxide and other colorants that perform coloring.
  • the organic filler include organic bentonites for the purpose of improving viscosity and imparting thixotropy.
  • the amount of the filler used is preferably in the range of 1 to 200 parts by mass with respect to 100 parts by mass in total of (A) radical reactive resin and (B) radical polymerizable unsaturated monomer.
  • the method for producing the resin composition of the present embodiment is not particularly limited, and (A) a radical reactive resin and (B) a radical polymerizable unsaturated monomer (or (A) a radical reactive resin and (B) a mixture of radically polymerizable unsaturated monomers), (C) a mercapto group-containing compound, (D) an imidazole compound having only one imidazole ring, (E) an organic peroxide, and It is obtained by mixing (G) metal soap (optional component) and other components contained in accordance with (F) and carbon fiber (F) by a known method.
  • the resin composition of the present embodiment is produced by a method in which (F) the above components other than carbon fiber are mixed to prepare a carbon fiber reinforced resin composition, and this is impregnated into (F) carbon fiber. It is preferable to do.
  • the cured product of the present embodiment is a cured product of the resin composition of the present embodiment.
  • a method for curing the resin composition of the present embodiment any method that can heat the resin composition at a temperature necessary for curing may be used.
  • a method of heating using a heating furnace or a heater can be used.
  • the temperature for curing the resin composition can be, for example, 5 to 200 ° C., preferably 15 to 150 ° C., more preferably 60 to 120 ° C.
  • the heating time can be, for example, 1 to 180 minutes, preferably 1 to 120 minutes, more preferably 1 to 60 minutes.
  • the resin composition of this embodiment has (A) a radical reactive resin, (B) a radical polymerizable unsaturated monomer, (C) a mercapto group-containing compound, and (D) only one imidazole ring. Since it contains an imidazole compound, (E) an organic peroxide, and (F) a carbon fiber, it can be cured efficiently at a low temperature and in a short time. In addition, the cured product of the resin composition of the present embodiment has sufficient adhesion between the resin component and the carbon fiber.
  • the curing rate of the resin composition can be adjusted by controlling the content of each of the imidazole compound having the above and (E) the organic peroxide.
  • the resin composition of the present embodiment is useful when producing a cured product that uses a general-purpose carbon fiber and requires a higher production cycle than an epoxy resin. Specifically, it is suitable for producing a molded product (cured product) using a molding method that requires a high production cycle, such as an automobile member produced by filament winding molding, resin transfer molding molding, press molding, or the like. .
  • the (A) radical reactive resin of (A1-1) (A1-2) (A2-1) (A4-1) was synthesized by the following method. Each of the obtained (A) radical reactive resins (A1-1), (A1-2), (A2-1) and (A4-1), and (B) styrene (Idemitsu) as a radical polymerizable unsaturated monomer. Manufactured by Kosan Co., Ltd.) to obtain a mixture of the component (A) and the component (B).
  • Epoxy methacrylate resin (A1-1) AER-2603 (Asahi Kasei Co., Ltd. bisphenol A type epoxy resin: epoxy equivalent 189): 1890 g, bisphenol A: 342 g, and tetradecyldimethylbenzylammonium were added to a reactor equipped with a stirrer, reflux condenser, gas inlet tube and thermometer. Chloride: 7 g was charged and reacted at 150 ° C. for 2 hours in a nitrogen gas atmosphere. After completion of the reaction, the reaction product was cooled to 90 ° C.
  • methacrylic acid 602 g
  • triphenylphosphine 9 g
  • hydroquinone 0.9 g
  • styrene 1000 g
  • the reaction was terminated when the acid value reached 11 mgKOH / g to obtain an epoxy methacrylate resin (A1-1).
  • the weight average molecular weight of the obtained epoxy methacrylate resin (A1-1) was measured by the method shown below. As a result, the weight average molecular weight of the epoxy methacrylate resin (A1-1) was 3395.
  • Method for measuring weight average molecular weight For the measurement of the weight average molecular weight, gel permeation chromatography (Shodex GPC-101 manufactured by Showa Denko KK) was used. The weight average molecular weight was measured at room temperature under the following conditions and calculated in terms of polystyrene. (Measurement condition) Column: Showa Denko LF-804, 2 Column temperature: 40 ° C Sample: 0.4 mass% tetrahydrofuran solution of the measurement object Flow rate: 1 ml / min Eluent: Tetrahydrofuran
  • Epoxy methacrylate resin having epoxy group (A1-2) AER-2603 (Bisphenol A type epoxy resin manufactured by Asahi Kasei Co., Ltd .: epoxy equivalent 189): 1890 g, methacrylic acid: 430 g, hydroquinone: 0.5 g, 1.2 g of triphenylphosphine was charged, heated to 100 ° C. while blowing air, and reacted for about 9 hours. The reaction was terminated when the acid value reached 0 mgKOH / g, and an epoxy methacrylate resin (A1-2) having at least one epoxy group was obtained.
  • the weight average molecular weight of the epoxy methacrylate resin (A1-2) having at least one epoxy group was measured in the same manner as the epoxy methacrylate resin (A1-1). As a result, the weight average molecular weight of the epoxy methacrylate resin (A1-2) having at least one epoxy group was 619. Further, 580 g of styrene (manufactured by Idemitsu Kosan) was added to the epoxy methacrylate resin (A1-2) having at least one epoxy group synthesized by the above method to obtain a mixture.
  • the weight average molecular weight of the urethane methacrylate resin (A4-1) was measured in the same manner as the epoxy methacrylate resin (A1-1). As a result, the weight average molecular weight of the urethane methacrylate resin (A4-1) was 5285. Further, 700 g of styrene (manufactured by Idemitsu Kosan) was added to the urethane methacrylate resin (A4-1) synthesized by the above method to obtain a mixture.
  • Tetrafunctional secondary thiol manufactured by Showa Denko KK, product name: Karenz MT PE1 (pentaerythritol tetrakis (3-mercaptobutyrate))
  • Cyanuric acid skeleton trifunctional secondary thiol manufactured by Showa Denko KK, product name: Karenz MT NR1 (1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine- 2,4,6 (1H, 3H, 5H) -trione)
  • Bifunctional secondary thiol manufactured by Showa Denko KK, product name: Karenz MT BD1 (1,4-bis (3-mercaptobutyryloxy) butane)
  • Monofunctional secondary thiol manufactured by Showa Denko KK, product name: 3MBA (3-mercaptobutanoic acid) (5) Tetrafunctional primary thiol, manufactured by SC Organic Chemical Co., Ltd
  • Imidazole compound (Imidazole compound having only one imidazole ring) (1) 2-ethyl-4-methylimidazole, manufactured by Shikoku Chemicals, product name: 2E4MZ (2) 1-benzyl-2-methylimidazole, manufactured by Shikoku Chemicals, product name: 1B2MZ (3) 2MZ-H; 2-methylimidazole, manufactured by Wako Pure Chemicals, product name: Wako primary 2-methylimidazole (imidazole compound having two or more imidazole rings) (4) 2,2′-bis (o-chlorophenyl) -4,5,4′5′-tetraphenyl-1,2 ′ biimidazole, manufactured by Kurokin Kasei, product name: biimidazole
  • T700SC-24000 manufactured by Toray (PAN-based carbon fiber, number of filaments: 24,000, tensile strength: 711 ksi (4900 MPa), elongation: about 2%)
  • Epoxy resins manufactured by Mitsubishi Chemical Corporation, product name: jER828
  • Curing agent acid anhydride, Hitachi Chemical Co., Ltd., product name: HN-5500 (mixture of 3-methylhexahydrophthalic anhydride and 4-methylhexahydrophthalic anhydride)
  • Other additives [Curing accelerator] Amine compound, manufactured by Tokyo Chemical Industry Co., Ltd., N, N-dimethylbenzylamine
  • Examples 1 to 7 A mixture of (A) radical reactive resin (A1-1) (A1-2) (A4-1) and (B) styrene as a radical polymerizable unsaturated monomer produced by the above method. If necessary, the radically polymerizable unsaturated monomer (B) shown in Table 1 was added. Thus, a mixture (a mixture of the component (A) and the component (B)) containing the (A) radical reactive resin and the (B) radical polymerizable unsaturated monomer at a ratio shown in Table 1 was obtained. .
  • the gelation time, curing temperature, and curing time were evaluated by the following evaluation methods.
  • the resin composition was placed in a test tube (outer diameter: 18 mm, length: 165 mm) at a depth of 100 mm at room temperature, placed in an oil bath heated to 80 ° C., and the temperature of the resin composition was measured with a thermocouple.
  • the time required for the temperature of the resin composition to reach 85 ° C. after the temperature reached 65 ° C. was measured and used as the gelation time.
  • the time until the resin composition reached the maximum exothermic temperature was defined as the curing time, and the exothermic temperature at that time was defined as the curing temperature, which was measured according to JIS K-6901.
  • the resin compositions of Examples 1 to 7 were found to have a short gel time and a short curing time, and could be cured efficiently even at a low curing temperature (80 ° C.).
  • Example 6 and Example 7 containing metal soap (G) had a shorter gelation time and curing time than Example 1 not containing metal soap (G) and could be cured efficiently.
  • (C) the resin composition of Comparative Example 1 that does not contain a mercapto group-containing compound has a longer gelation time and curing time than the resin compositions of Examples 1 to 7, and has a lower curing temperature. It has been found that it takes more time to cure.
  • Example 2 ⁇ Examples 8 to 9, Comparative Example 2> In the same manner as in Example 1, a mixture containing (A) a radical reactive resin and (B) a radical polymerizable unsaturated monomer at a ratio shown in Table 2 was obtained.
  • the resin composition which added the said (D) component to the mixture of the said (A) component and the said (B) component in the 25 degreeC environment and stirred for 2 minutes was made into the test body.
  • permeability was measured using the haze meter HM-150 by Murakami Color Research Laboratory, and the haze test was done.
  • the thickness of the cell at the time of measurement was 1 cm.
  • the transmittance and haze were measured three times for each specimen, and the average value of the results obtained was used for the evaluation shown in Table 2.
  • Example 1 As shown in Table 2, (D) the resin composition of Example 1 using 2-ethyl-4-methylimidazole as the imidazole compound, and the resin composition of Example 8 using 1-benzyl-2-methylimidazole.
  • the resin composition of Example 9 using 2-methylimidazole was transparent with a solubility evaluation of ⁇ or ⁇ .
  • the resin compositions of Example 1, Example 8, and Example 9 had high transmittance and low haze.
  • the (D) imidazole compound having only one imidazole ring used in Examples 1, 8, and 9 is a phase with (A) radical reactive resin and (B) radical polymerizable unsaturated monomer. It was found to be excellent in solubility.
  • (D) the resin composition of Example 1 using 2-ethyl-4-methylimidazole as the imidazole compound and the resin composition of Example 8 using 1-benzyl-2-methylimidazole were crystalline. The floating of the object was not recognized and solubility evaluation was favorable.
  • the resin composition of Comparative Example 2 using (D) biimidazole having two imidazole rings as the imidazole compound has a lower transmittance than the resin compositions of Examples 1, 8, and 9. The haze was high.
  • Example 10 to 13 In the same manner as in Example 1, a mixture containing (A) a radical reactive resin and (B) a radical polymerizable unsaturated monomer at a ratio shown in Table 3 was obtained.
  • the roving-like carbon fiber bundle was placed in a dipping tank filled with a resin composition (carbon fiber reinforced resin composition), and the carbon fiber bundle was impregnated with the resin composition to obtain a carbon fiber reinforced resin composition.
  • the obtained carbon fiber reinforced resin composition was wound 350 times around a mandrel provided with a flat plate so that the sample size had an axial length of 25 cm and a circumferential length of 21 cm. I arranged. Then, it was press-molded in a state wound around a mandrel, adjusted to a thickness of 3 mm, and cured at 80 ° C. for 1 hour and at 110 ° C. for 2 hours to obtain CFRP.
  • Comparative Example 4 was cured at 80 ° C. for 2 hours and at 110 ° C. for 3 hours to obtain CFRP. Thereafter, the CFRP was removed from the mandrel, and cut out from the CFRP with a predetermined dimension so that the 90 ° direction was the long side with respect to the orientation of the carbon fiber, thereby obtaining a CFRP specimen.
  • ⁇ Bending strength> From each CFRP, a CFRP test piece of length ⁇ width ⁇ thickness 140 mm ⁇ 15 mm ⁇ 3 mm was cut out. Regarding the cut CFRP test specimen, the bending strength was measured at a distance between fulcrums of 120 mm using Tensilon UTC-1T manufactured by Orientec in accordance with JIS K7074 in a test environment at a temperature of 23 ° C. and a humidity of 50%. The bending strength was measured three times for each CFRP. And the average value of the measurement result of 3 times was used for evaluation of bending strength.
  • a CFRP specimen was prepared according to JIS K 7165, a B-type test piece.
  • the produced CFRP test specimen was tested for tensile strength at a test temperature of 23 ° C. and humidity of 50% using an Instron 5900R according to JIS K 7161 at a grip length of 150 mm and a test speed of 1 mm / min. went.
  • Tensile strength was measured three times for each CFRP. And the average value of 3 times of measurement results was used for evaluation of tensile strength.
  • the CFRP specimens of Examples 10 to 13 had good interlaminar shear strength, bending strength, and tensile strength.
  • the CFRP specimens of Comparative Examples 3 and 5 had lower bending strength than the CFRP specimens of Examples 10-13. This is because the CFRP specimens of Examples 10 to 13 have better adhesion between the resin component and the carbon fiber than the CFRP specimens of Comparative Examples 3 and 5.
  • the CFRP test body of the comparative example 4 uses the conventional epoxy resin. As shown in Table 3, the CFRP specimens of Examples 10 to 13 can achieve the same strength as when using an epoxy resin.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • 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

L'invention concerne une composition pour une résine renforcée par des fibres de carbone, comprenant (A) une résine réactive aux radicaux, (B) un monomère insaturé polymérisable par voie radicalaire, (C) un composé contenant des groupes mercapto, (D) un composé imidazole n'ayant qu'un cycle imidazole, et (E) un peroxyde organique. La composition pour résine renforcée par des fibres de carbone peut également comprendre (G) un savon métallique.
PCT/JP2017/018799 2016-05-20 2017-05-19 Composition pour résine renforcée par des fibres de carbone, composition de résine renforcée par des fibres de carbone, article durci Ceased WO2017200082A1 (fr)

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JP2018518381A JP6952686B2 (ja) 2016-05-20 2017-05-19 炭素繊維強化樹脂用組成物、炭素繊維強化樹脂組成物、硬化物
CN201780029122.5A CN109071777B (zh) 2016-05-20 2017-05-19 碳纤维增强树脂用组合物、碳纤维增强树脂组合物、固化物
KR1020187032289A KR102221532B1 (ko) 2016-05-20 2017-05-19 탄소 섬유 강화 수지용 조성물, 탄소 섬유 강화 수지 조성물, 경화물
KR1020207003941A KR20200017559A (ko) 2016-05-20 2017-05-19 탄소 섬유 강화 수지용 조성물, 탄소 섬유 강화 수지 조성물, 경화물

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Publication number Priority date Publication date Assignee Title
WO2022210261A1 (fr) * 2021-03-30 2022-10-06 ナミックス株式会社 Composition de résine durcissable

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WO1999062977A1 (fr) * 1998-06-04 1999-12-09 Nippon Nsc Ltd. Compositions de materiaux a durcissement provoquee par polymerisation radicalaire, procede de renforcement de structures de beton et structures de beton ainsi renforcees
JP2002284860A (ja) * 2001-03-27 2002-10-03 Toyo Ink Mfg Co Ltd 硬化性エポキシ樹脂組成物、接着剤、及びシール剤
JP2009019099A (ja) * 2007-07-11 2009-01-29 Showa Highpolymer Co Ltd 繊維強化複合材料用樹脂組成物、それを用いた成形材料及び繊維強化複合材料
JP2014001291A (ja) * 2012-06-18 2014-01-09 Nagase Chemtex Corp 一液型エポキシ樹脂組成物

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JP3587932B2 (ja) 1996-04-17 2004-11-10 昭和電工株式会社 繊維強化複合材料の製造方法
JP2005281610A (ja) 2004-03-30 2005-10-13 Showa Highpolymer Co Ltd 硬化性樹脂組成物
EP1983017B1 (fr) * 2006-01-26 2012-04-18 Showa Denko K.K. Préparation durcissable contenant un thiol
JP5234632B2 (ja) * 2006-06-13 2013-07-10 昭和電工株式会社 重合促進剤、硬化性組成物および硬化物ならびにチオール化合物の製造方法

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WO1999062977A1 (fr) * 1998-06-04 1999-12-09 Nippon Nsc Ltd. Compositions de materiaux a durcissement provoquee par polymerisation radicalaire, procede de renforcement de structures de beton et structures de beton ainsi renforcees
JP2002284860A (ja) * 2001-03-27 2002-10-03 Toyo Ink Mfg Co Ltd 硬化性エポキシ樹脂組成物、接着剤、及びシール剤
JP2009019099A (ja) * 2007-07-11 2009-01-29 Showa Highpolymer Co Ltd 繊維強化複合材料用樹脂組成物、それを用いた成形材料及び繊維強化複合材料
JP2014001291A (ja) * 2012-06-18 2014-01-09 Nagase Chemtex Corp 一液型エポキシ樹脂組成物

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2022210261A1 (fr) * 2021-03-30 2022-10-06 ナミックス株式会社 Composition de résine durcissable
JPWO2022210261A1 (fr) * 2021-03-30 2022-10-06

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JPWO2017200082A1 (ja) 2019-03-14
TW201811855A (zh) 2018-04-01
CN109071777B (zh) 2022-06-10
CN109071777A (zh) 2018-12-21
TWI644938B (zh) 2018-12-21
KR102221532B1 (ko) 2021-02-26
JP6952686B2 (ja) 2021-10-20
KR20200017559A (ko) 2020-02-18

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