WO2014203797A1 - Composition de résine époxyde et article durci associé, préimprégné et matériau composite renforcé par des fibres - Google Patents

Composition de résine époxyde et article durci associé, préimprégné et matériau composite renforcé par des fibres Download PDF

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Publication number
WO2014203797A1
WO2014203797A1 PCT/JP2014/065585 JP2014065585W WO2014203797A1 WO 2014203797 A1 WO2014203797 A1 WO 2014203797A1 JP 2014065585 W JP2014065585 W JP 2014065585W WO 2014203797 A1 WO2014203797 A1 WO 2014203797A1
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Prior art keywords
resin composition
epoxy resin
compound
group
polyvinyl acetal
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English (en)
Japanese (ja)
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中村亮太
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Daicel Corp
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Daicel Corp
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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
    • 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
    • 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
    • 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
    • C08J2429/00—Characterised by the use of homopolymers or 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 an alcohol, ether, aldehydo, ketonic, acetal, or ketal radical; Hydrolysed polymers of esters of unsaturated alcohols with saturated carboxylic acids; Derivatives of such polymer
    • C08J2429/14—Homopolymers or copolymers of acetals or ketals obtained by polymerisation of unsaturated acetals or ketals or by after-treatment of polymers of unsaturated alcohols

Definitions

  • the present invention relates to an epoxy resin composition and a cured product thereof, a prepreg obtained by impregnating or coating a reinforcing fiber with the epoxy resin composition, and a fiber-reinforced composite material obtained by curing the prepreg.
  • epoxy resin compositions containing epoxy compounds have been widely used for a wide variety of applications such as adhesives and structural materials.
  • development of a fiber-reinforced composite material obtained by further reinforcing a cured product obtained by curing the epoxy resin composition with reinforcing fibers such as carbon fibers has been energetically advanced.
  • the above fiber reinforced composite material utilizes its light weight and tough properties, for example, automobile parts, civil engineering and building equipment, wind power blades, sports equipment, aircraft, ships, robots, cable materials, high pressure tanks, etc. Application as various components is expected.
  • Examples of the epoxy resin composition for forming the fiber reinforced composite material include, as a base material resin, bisphenol A type epoxy resin (bisphenol A diglycidyl ether), a curing agent, and a reactive diluent for epoxy resin.
  • An epoxy resin composition or the like is known (see Patent Document 1).
  • an epoxy resin composition containing an epoxy compound having a glycidyl group, such as a bisphenol A type epoxy resin needs to be heated at a high temperature for a long time in order to be cured, which is problematic in terms of the productivity of the fiber-reinforced composite material. Had. Furthermore, the cured product obtained by curing the epoxy resin composition has low heat resistance and low mechanical strength such as low elongation (tensile elongation at break). From the viewpoint of mechanical properties of the fiber-reinforced composite material Had a problem.
  • epoxy resin compositions for forming fiber reinforced composite materials can be applied to a variety of molding methods, from liquid to solid, and in the case of liquids from low viscosity to high. It is required that the desired properties and viscosity can be easily controlled, such as those having a viscosity.
  • the object of the present invention is to easily control the properties and viscosity, can be cured at a low temperature in a short time, has excellent mechanical properties such as high tensile elongation at break, and has high heat resistance. It is providing the epoxy resin composition which can form, and its hardened
  • the present inventor has an epoxy resin composition containing a specific epoxy compound, a specific compound having a hydroxyl group, and a polyvinyl formal resin, and the control of properties and viscosity is easy. It was found that it can be cured at a low temperature and in a short time, and by further curing, a cured product having excellent mechanical properties such as high tensile fracture elongation and high heat resistance can be formed, and the present invention has been completed. I let you.
  • the present invention relates to an alicyclic epoxy compound (A), at least one compound (B) selected from the group consisting of a lactone addition compound (B1) having a hydroxyl group and a polycarbonate polyol (B2), and polyvinyl acetal.
  • An epoxy resin composition comprising a resin (C) is provided.
  • the epoxy resin composition is provided in which the content of the compound (B) is 5 to 60 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A).
  • the above epoxy resin composition which is a resin composition for fiber reinforced composite materials.
  • the present invention also provides a cured product obtained by curing the above epoxy resin composition.
  • the present invention also provides a prepreg obtained by impregnating or coating the above-mentioned epoxy resin composition on reinforcing fibers.
  • the present invention also provides a fiber-reinforced composite material obtained by curing the prepreg.
  • the present invention relates to the following.
  • the epoxy resin composition characterized by including this.
  • the alicyclic epoxy compound (A) is (i) a compound having an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring, and (ii) an epoxy group on the alicyclic ring.
  • the epoxy resin composition according to [1] which is at least one selected from the group consisting of compounds directly bonded by a single bond.
  • a compound in which an epoxy group is directly bonded to the alicyclic ring by a single bond is a compound represented by the following formula (II): [wherein R ′ is a p-valent in the structural formula Is an organic group (organic residue) formed by removing p hydroxyl groups (—OH) from the alcohol, and p and n each represent a natural number. ]
  • the epoxy resin composition according to any one of [2] to [4].
  • the ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the alicyclic epoxy compound (A), the compound (B), and the polyvinyl acetal resin (C) is 25 to 95% by weight.
  • the epoxy resin composition according to any one of [1] to [6].
  • the lactone addition compound (B1) having a hydroxyl group has a structure in which two or more lactone units are repeatedly directly bonded (polymerized), and the number of repeating lactone units (degree of polymerization) in the structure is 2 to 20 [ [1] The epoxy resin composition according to any one of [9]. [11] The epoxy resin composition according to any one of [1] to [10], wherein the lactone addition compound (B1) having a hydroxyl group has 2 to 10 hydroxyl groups in the molecule (total number). .
  • a lactone addition compound (B1) having a hydroxyl group is a compound represented by the following formula (1): [wherein r represents an integer of 1 to 20; R 1 represents an organic group (organic residue) formed by removing r hydroxyl groups from a compound [R 1 (OH) r ] having r hydroxyl groups in the molecule in the structural formula. q represents an integer of 0 to 10. R 2 represents an alkylene group. ] The epoxy resin composition according to any one of [1] to [11]. [13] The epoxy resin composition according to any one of [1] to [12], wherein the number (total number) of hydroxyl groups in the polycarbonate polyol (B2) is 2 to 10.
  • the polyvinyl acetal resin (C) is a structural unit represented by the following formula (i) [in the formula (i), R 11 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the epoxy resin composition according to [19] which is a polyvinyl acetal resin (C2) containing a structural unit represented by formulas (i) to (iii) as an essential structural unit and having a carboxyl group in the molecule.
  • the total content (total content) of the structural units represented by the formulas (i) to (iii) in the polyvinyl acetal resin (C1) is the total structural unit (100% by weight) constituting the polyvinyl acetal resin (C1). %)), The epoxy resin composition according to [20].
  • the content (content) of the structural unit represented by the formula (i) in the polyvinyl acetal resin (C1) is based on the total structural units (100 mol%) constituting the polyvinyl acetal resin (C1).
  • the content (content) of the structural unit represented by the formula (ii) in the polyvinyl acetal resin (C1) is based on the total structural units (100 mol%) constituting the polyvinyl acetal resin (C1).
  • the content (content) of the structural unit represented by the formula (iii) in the polyvinyl acetal resin (C1) is based on the total structural units (100 mol%) constituting the polyvinyl acetal resin (C1).
  • the polyvinyl acetal resin (C2) is a structural unit represented by the following formula (vi) in addition to the structural units represented by the formulas (i) to (iii) [in the formula (vi), R 12 represents Represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • the content (content) of the structural unit represented by the formula (ii) in the polyvinyl acetal resin (C2) is based on the total structural units (100 mol%) constituting the polyvinyl acetal resin (C2).
  • the content (content) of the structural unit represented by the formula (iii) in the polyvinyl acetal resin (C2) is based on the total structural units (100 mol%) constituting the polyvinyl acetal resin (C2).
  • the content (content) of the structural unit represented by the formula (vi) in the polyvinyl acetal resin (C2) is based on the total structural units (100 mol%) constituting the polyvinyl acetal resin (C2).
  • the epoxy resin composition of the present invention Since the epoxy resin composition of the present invention has the above-described configuration, it can be cured at a low temperature and in a short time, and the properties and viscosity can be easily controlled. Furthermore, by curing the epoxy resin composition of the present invention, a cured product having excellent mechanical properties such as high tensile elongation at break and having high heat resistance can be formed with high productivity. Moreover, the fiber reinforced composite material excellent in productivity, heat resistance, and toughness can be obtained by hardening the prepreg obtained by coating or impregnating the reinforcing fiber with the epoxy resin composition of the present invention.
  • the epoxy resin composition (curable epoxy resin composition) of the present invention is at least one selected from the group consisting of an alicyclic epoxy compound (A), a lactone addition compound (B1) having a hydroxyl group, and a polycarbonate polyol (B2). It is a resin composition containing the seed compound (B) and the polyvinyl acetal resin (C) as essential components.
  • the epoxy resin composition of the present invention may contain other components such as a curing catalyst (D) described later.
  • the alicyclic epoxy compound (A) in the epoxy resin composition of the present invention is a compound having at least an alicyclic (aliphatic hydrocarbon ring) structure and an epoxy group in the molecule (in one molecule).
  • an epoxy group composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring when referred to as “alicyclic epoxy group”
  • a compound in which an epoxy group is directly bonded to the alicyclic ring with a single bond when referred to as “alicyclic epoxy group”.
  • the compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (i) is arbitrarily selected from known or commonly used compounds. Can be used. Especially, as said alicyclic epoxy group, a cyclohexene oxide group is preferable.
  • a cyclohexene oxide group is used as the compound having an epoxy group (alicyclic epoxy group) composed of two adjacent carbon atoms and oxygen atoms constituting the alicyclic ring (i).
  • a compound (alicyclic epoxy compound) represented by the following formula (I) is preferable.
  • X represents a single bond or a linking group (a divalent group having one or more atoms).
  • the linking group include divalent hydrocarbon groups, alkenylene groups in which part or all of carbon-carbon double bonds are epoxidized, carbonyl groups, ether bonds, ester bonds, carbonate groups, amide groups, and the like. And a group in which a plurality of are connected.
  • Examples of the compound in which X in the above formula (I) is a single bond include 3,4,3 ′, 4′-diepoxybicyclohexane and the like.
  • Examples of the divalent hydrocarbon group include a linear or branched alkylene group having 1 to 18 carbon atoms and a divalent alicyclic hydrocarbon group.
  • Examples of the linear or branched alkylene group having 1 to 18 carbon atoms include a methylene group, a methylmethylene group, a dimethylmethylene group, an ethylene group, a propylene group, and a trimethylene group.
  • divalent alicyclic hydrocarbon group examples include 1,2-cyclopentylene group, 1,3-cyclopentylene group, cyclopentylidene group, 1,2-cyclohexylene group, 1,3-cyclopentylene group, And divalent cycloalkylene groups (including cycloalkylidene groups) such as cyclohexylene group, 1,4-cyclohexylene group, and cyclohexylidene group.
  • alkenylene group in the alkenylene group in which part or all of the carbon-carbon double bond is epoxidized include, for example, vinylene group, propenylene group, 1-butenylene group And straight-chain or branched alkenylene groups having 2 to 8 carbon atoms such as 2-butenylene group, butadienylene group, pentenylene group, hexenylene group, heptenylene group and octenylene group.
  • the epoxidized alkenylene group is preferably an alkenylene group in which all of the carbon-carbon double bonds are epoxidized, more preferably 2 to 4 carbon atoms in which all of the carbon-carbon double bonds are epoxidized. Alkenylene group.
  • the linking group X is particularly preferably a linking group containing an oxygen atom, specifically, —CO—, —O—CO—O—, —COO—, —O—, —CONH—, epoxidation.
  • Representative examples of the alicyclic epoxy compounds represented by the above formula (I) include compounds represented by the following formulas (I-1) to (I-10), bis (3,4-epoxycyclohexylmethyl) ) Ether, 1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 1,2-epoxy-1,2-bis (3,4-epoxycyclohexane-1-yl) ethane, 2,2 -Bis (3,4-epoxycyclohexane-1-yl) propane and the like.
  • l and m each represents an integer of 1 to 30.
  • R in the following formula (I-5) is an alkylene group having 1 to 8 carbon atoms, and is a methylene group, ethylene group, propylene group, isopropylene group, butylene group, isobutylene group, s-butylene group, pentylene group, hexylene.
  • linear or branched alkylene groups such as a group, heptylene group, and octylene group.
  • linear or branched alkylene groups having 1 to 3 carbon atoms such as a methylene group, an ethylene group, a propylene group, and an isopropylene group are preferable.
  • N1 to n6 in the following formulas (I-9) and (I-10) each represents an integer of 1 to 30.
  • Examples of the compound (ii) in which the epoxy group is directly bonded to the alicyclic ring with a single bond include compounds represented by the following formula (II).
  • R ′ is an organic group (organic residue) formed by removing p hydroxyl groups (—OH) from a p-valent alcohol in the structural formula, and p and n each represent a natural number.
  • the p-valent alcohol [R ′ (OH) p ] include polyhydric alcohols such as 2,2-bis (hydroxymethyl) -1-butanol (such as alcohols having 1 to 15 carbon atoms) described later And compounds having r hydroxyl groups.
  • p is preferably 1 to 6, and n is preferably 1 to 30.
  • n in each group in () (inside the outer parenthesis) may be the same or different.
  • the alicyclic epoxy compound (A) can be used alone or in combination of two or more.
  • the alicyclic epoxy compound (A) for example, commercially available products such as trade names “Celoxide 2021P” and “Celoxide 2081” (manufactured by Daicel Corporation) may be used.
  • Examples of the alicyclic epoxy compound (A) include compounds represented by the above formula (I-1) [3,4-epoxycyclohexylmethyl (3,4-epoxy) cyclohexanecarboxylate; for example, trade name “Celoxide 2021P”. (Daicel Co., Ltd.) etc. are particularly preferred.
  • the content (blending amount) of the alicyclic epoxy compound (A) in the epoxy resin composition of the present invention is not particularly limited, but is preferably 25 to 95% by weight with respect to the epoxy resin composition (100% by weight). More preferably, it is 35 to 85% by weight, still more preferably 45 to 80% by weight.
  • the ratio of the alicyclic epoxy compound (A) to the total amount (100% by weight) of the alicyclic epoxy compound (A), the compound (B), and the polyvinyl acetal resin (C) is: Although not particularly limited, it is preferably 25 to 95% by weight, more preferably 35 to 85% by weight, and still more preferably 45 to 80% by weight.
  • the ratio of the alicyclic epoxy compound (A) is 25% by weight or more, the curability of the epoxy resin composition tends to be further improved, and the heat resistance of the cured product tends to be further improved.
  • the ratio of the alicyclic epoxy compound (A) is 95% by weight or less, the mechanical properties tend to be improved, for example, the tensile strength at break of the cured product is increased.
  • the compound (B) in the epoxy resin composition of the present invention is at least one compound selected from the group consisting of a lactone addition compound (B1) having a hydroxyl group and a polycarbonate polyol (B2).
  • a lactone addition compound (B1) having a hydroxyl group and a polycarbonate polyol (B2).
  • the epoxy resin composition of the present invention contains the compound (B) as an essential component, the mechanical strength of the cured product tends to be improved, for example, the tensile elongation at break is increased.
  • the lactone addition compound (B1) having a hydroxyl group is a structural unit having one or more hydroxyl groups in the molecule and formed by a ring-opening addition reaction (including ring-opening addition polymerization) of a lactone compound (lactone).
  • lactone compound include known and commonly used lactone compounds and are not particularly limited, and examples thereof include 4- to 10-membered ring lactone compounds such as ⁇ -butyrolactone, ⁇ -valerolactone, and ⁇ -caprolactone.
  • ⁇ -caprolactone is preferable as the lactone compound. That is, as the lactone addition compound (B1) having a hydroxyl group, a structural unit having one or more hydroxyl groups in the molecule and formed by a ring-opening addition reaction (including ring-opening addition polymerization) of ⁇ -caprolactone.
  • a compound ( ⁇ -caprolactone addition compound) having at least [—C (O) — (CH 2 ) 5 —O—] in the molecule is preferred.
  • the lactone addition compound (B1) having a hydroxyl group may have only one kind of the lactone unit, or may have two or more kinds.
  • the number (total number) of lactone units in the molecule of the lactone addition compound (B1) having a hydroxyl group is not particularly limited as long as it is 1 or more, but 2 or more (for example, 2 to 40) is preferable. Further, when the lactone addition compound (B1) having a hydroxyl group has a structure in which two or more lactone units are repeatedly directly bonded (polymerized), the number of repeating lactone units (degree of polymerization) in the structure is not particularly limited. ⁇ 20 are preferred. Moreover, the addition form of the lactone unit in the said structure is not specifically limited, A random type may be sufficient and a block type may be sufficient.
  • the number (total number) of hydroxyl groups in the molecule of the lactone addition compound (B1) having a hydroxyl group is not particularly limited as long as it is 1 or more, but is preferably 2 or more (for example, 2 to 10), more preferably. Is 2-4.
  • the lactone addition compound (B1) having a hydroxyl group is not particularly limited.
  • the lactone compound in the presence of a compound (initiator) having one or more hydroxyl groups in the molecule, the lactone compound is subjected to a ring-opening addition reaction (also known as ring-opening addition polymerization). To be included).
  • Examples of the compound having one or more hydroxyl groups in the molecule include aliphatic alcohols such as methanol, ethanol, propanol, butanol, pentanol, hexanol and octanol; aromatic alcohols such as benzyl alcohol; ethylene glycol, diethylene glycol, Triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, pentanediol, methylpentanediol, 2,4-diethylpentanediol, 1,6-hexanediol, 2-ethyl-1,3-hexanediol, neopentyl glycol, neopentyl glycol ester, cyclohexanedimethanol, glycerin, diglycerin, polyglycerin, Polyhydric alcohols such as l
  • Phenols polyvinyl alcohol, polyvinyl acetate partial hydrolyzate, starch, acrylic Cellulose polymers such as all, styrene-allyl alcohol copolymer resin, polyester polyol, polycaprolactone polyol, polypropylene polyol, polytetramethylene glycol, polycarbonate polyol, polybutadiene having a hydroxyl group, cellulose, cellulose acetate, cellulose acetate butyrate, and hydroxyethyl cellulose Examples thereof include oligomers or polymers having a hydroxyl group.
  • the lactone addition compound (B1) having a hydroxyl group includes a lactone addition compound having two or more hydroxyl groups in the molecule (particularly, ⁇ -caprolactone addition).
  • Compound and more preferably, a lactone addition compound having two or more structures having a hydroxyl group at the end of the lactone unit (that is, —C (O) —R L —OH) in the molecule.
  • the ring-opening addition reaction of the lactone compound can be carried out by a known or conventional method, and is not particularly limited.
  • the lactone compound is stirred and mixed in the presence of an initiator while heating as necessary. Can be implemented.
  • the usage-amount (preparation amount) of an initiator and a lactone compound can be suitably adjusted according to the molecular weight etc. of the target lactone adduct, and is not specifically limited.
  • a known or conventional catalyst such as tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, dibutyltin oxide, dibutyltin laurate, tin octylate, stannous chloride is used as necessary.
  • a catalyst can be suitably selected according to the kind of initiator, a lactone compound, reaction conditions, etc., and is not specifically limited.
  • Polycarbonate polyol (B2) is a compound having two or more hydroxyl groups in the molecule and at least a carbonate skeleton in the molecule.
  • Polycarbonate polyol (B2) can be prepared by the same phosgene method as in the usual method for producing carbonate polyol, or a carbonate exchange reaction using dialkyl carbonate or diphenyl carbonate such as dimethyl carbonate and diethyl carbonate (Japanese Patent Laid-Open Nos. 62-187725 and 2). -175721, JP-A-2-49025, JP-A-3-220233, JP-A-3-252420, etc.). Since the carbonate bond is difficult to undergo thermal decomposition, the cured product of the resin composition containing the polycarbonate polyol (B2) tends to exhibit excellent stability even under high temperature and high humidity.
  • the polyol used in the carbonate exchange reaction together with the dialkyl carbonate includes 1,6-hexanediol, ethylene glycol, diethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3- Butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,4-cyclohexanedimethanol, 1,12-dodecanediol, butadiene diol, neopentyl glycol, tetramethylene glycol, propylene glycol, Examples include dipropylene glycol.
  • the number (total number) of hydroxyl groups in the polycarbonate polyol (B2) is not particularly limited as long as it is 2 or more, but is preferably 2 to 10, more preferably 2 to 4.
  • examples of the compound (B) include a compound represented by the following formula (1) and a compound represented by the following formula (2).
  • r represents an integer of 1 to 20. r is preferably an integer of 2 to 4.
  • R 1 is an organic group (organic residue) formed by removing r hydroxyl groups from a compound [R 1 (OH) r ] having r hydroxyl groups in the molecule in the structural formula. Indicates. Examples of the organic group include an organic group formed by removing r hydroxyl groups from a compound having one or more (r groups) hydroxyl groups in the above-described molecule in the structural formula.
  • q means the number of repetitions of the structure (lactone unit) in parentheses with q, and represents an integer of 0 to 10. However, the total number of q in Formula (1) is an integer of 1 or more. In addition, when r is an integer greater than or equal to 2, several q may be the same and may differ.
  • R 2 in the formula (1) represents an alkylene group, and has, for example, methylene group, methylmethylene group, dimethylmethylene group, ethylene group, propylene group, trimethylene group, tetramethylene group, pentamethylene group, etc. -18 linear or branched alkylene groups.
  • R 2 a pentamethylene group is preferable.
  • R ⁇ 2 > exists in Formula (1), these may be the same and may differ.
  • the addition form of the structure (lactone unit) in parentheses to which q is attached is not particularly limited, and may be a random type or a block type.
  • s represents an integer of 2 to 50.
  • R 3 in formula (2) is the same or different and represents an alkylene group, and examples thereof are the same as those for R 2 in formula (1).
  • subjected s may be the same, and may differ.
  • the addition form of the structure in the parentheses to which s is attached is not particularly limited, and may be a random type or a block type.
  • the hydroxyl value of the compound (B) is not particularly limited, but is preferably 10 to 800 mgKOH / g, more preferably 50 to 600 mgKOH / g. By setting the hydroxyl value to 10 mgKOH / g or more, the heat resistance of the cured product tends to be further improved. On the other hand, when the hydroxyl value is 800 mgKOH / g or less, the mechanical properties of the cured product tend to be further improved.
  • the hydroxyl value of the compound (B) can be measured according to JIS K0070.
  • the molecular weight of the compound (B) is not particularly limited, but is preferably 200 to 10000, more preferably 300 to 3000. By setting the molecular weight to 200 or more, there is a tendency that the effects of lowering the elastic modulus and improving the bending strength can be enjoyed more efficiently. On the other hand, when the molecular weight is 10,000 or less, the heat resistance and mechanical strength of the cured product tend to be further improved. In addition, the molecular weight of a compound (B) can be measured as a molecular weight of standard polystyrene conversion by gel permeation chromatography.
  • Compound (B) may be liquid at 25 ° C. or may be solid.
  • the viscosity (25 ° C.) is not particularly limited, but is preferably 100 to 25000 mPa ⁇ s, more preferably 500 to 10000 mPa ⁇ s.
  • the compound (B) can be used alone or in combination of two or more.
  • the compound (B) for example, trade names “Placcel 205”, “Placcel 205U”, “Placcel L205AL”, “Placcel 208”, “Placcel 210”, “Placcel 210N”, “Placcel 212”, “Placcel” L212AL, Plaxel 220, Plaxel 220N, Plaxel 220NP1, Plaxel L220AL, Plaxel 230, Plaxel 230N, Plaxel 240, Plaxel 303, Plaxel 305, Plaxel "308", "Placcel 312", “Placcel L320AL”, “Placcel 405D", "Placcel CD205", “Placcel CD210", “Placcel CD220”, “Placcel CD205PL”, “Placcel C” "205HL”, “Plaxel CD210PL”, “Plaxel CD210HL”, “Plaxel CD220PL
  • the content (blending amount) of the compound (B) in the epoxy resin composition of the present invention is not particularly limited, but is preferably 5 to 60 parts by weight with respect to 100 parts by weight of the alicyclic epoxy compound (A).
  • the amount is preferably 10 to 60 parts by weight, more preferably 15 to 55 parts by weight, and particularly preferably 20 to 50 parts by weight.
  • the polyvinyl acetal resin (C) in the epoxy resin composition of the present invention is obtained by reacting a polyvinyl alcohol resin containing at least a structural unit corresponding to vinyl alcohol (sometimes referred to as “vinyl alcohol structural unit”) with an aldehyde, It is a compound (polymer) containing one or two or more structures in which adjacent vinyl alcohol structural units in the polyvinyl alcohol resin are acetalized.
  • the epoxy resin composition of the present invention contains the polyvinyl acetal resin (C) as an essential component, and in particular, while maintaining excellent mechanical strength of the cured product such as high tensile breaking elongation, the glass transition temperature and the thermal decomposition temperature. Tends to improve the heat resistance of the cured product. Furthermore, the property and viscosity of the epoxy resin composition can be easily controlled by selecting the molecular weight of the polyvinyl acetal resin (C).
  • Examples of the polyvinyl acetal resin (C) include known or conventional polyvinyl acetal resins, and are not particularly limited.
  • the structural unit represented by the following formula (i) the structural unit represented by the following formula (ii)
  • a polyvinyl acetal resin containing a structural unit represented by the following formula (iii) as an essential structural unit More specifically, examples of the polyvinyl acetal resin (C) include polyvinyl formal resins in which R 11 in the following formula (i) is a hydrogen atom.
  • the structural unit represented by the above formula (i) is a structural unit having an acetal moiety, and can be formed, for example, by a reaction between a continuous (adjacent) vinyl alcohol structural unit and an aldehyde (R 11 —CHO).
  • R 11 in the structural unit represented by the formula (i) is an arbitrary group or atom, and examples thereof include a hydrogen atom, an alkyl group, an alkoxy group, and an aryl group.
  • R 11 in the structural unit represented by the formula (i) is a bulky group (for example, a hydrocarbon group having a large number of carbon atoms)
  • the softening point of the polyvinyl acetal resin (C) tends to decrease.
  • the epoxy resin composition containing the polyvinyl acetal resin (C) having a low softening point may have a viscosity that is greatly reduced at a high temperature and the resin may flow too much.
  • the polyvinyl acetal resin (C) in which R 11 is a bulky group has high solubility in a solvent, but on the other hand, tends to be inferior in chemical resistance.
  • R 11 in the formula (i) is preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • alkyl group having 1 to 5 carbon atoms examples include linear or branched alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • the structural unit represented by the above formula (ii) is a structural unit corresponding to vinyl acetate
  • the structural unit represented by the above formula (iii) is a structural unit corresponding to vinyl alcohol.
  • the structural unit corresponding to vinyl acetate is formed by polymerization of vinyl acetate
  • the structural unit corresponding to vinyl alcohol is formed by saponifying the structural unit corresponding to vinyl acetate.
  • the polyvinyl acetal resin (C) includes structural units represented by formulas (i) to (iii) (a structural unit represented by formula (i), a structural unit represented by formula (ii), and a formula (iii) It may have a structural unit other than the structural unit represented by Examples of such a structural unit include a structural unit represented by the following formula (iv) (intermolecular acetal unit) and a structural unit represented by the following formula (v) (hemiacetal unit).
  • R 11 in formula (iv) and formula (v) is the same as that in formula (i).
  • polyvinyl acetal resin (C) for example, a polyvinyl acetal containing a structural unit represented by formulas (i) to (iii) as an essential structural unit and having no carboxyl group in the molecule.
  • Resin sometimes referred to as “polyvinyl acetal resin (C1)”
  • Resin may be referred to as “polyvinyl acetal resin (C2)”) and the like.
  • the total content (total content) of the structural units represented by the above formulas (i) to (iii) in the polyvinyl acetal resin (C1) is not particularly limited, but all the structural units constituting the polyvinyl acetal resin (C1) 80 to 100% by weight is preferable with respect to (100% by weight).
  • the structural units represented by the formulas (i) to (iii) may be regularly arranged or randomly arranged. That is, the polyvinyl acetal resin (C1) may be a block copolymer, an alternating copolymer or the like, or a random copolymer. Among them, it is preferable that they are arranged at random.
  • content (content rate) of the structural unit represented by Formula (i) in polyvinyl acetal resin (C1) is not specifically limited, With respect to all the structural units (100 mol%) which comprise polyvinyl acetal resin (C1). Therefore, 50 to 80 mol% is preferable. When the content of the structural unit represented by the formula (i) is 50 mol% or more, the chemical resistance, flexibility, wear resistance, and mechanical strength of the polyvinyl acetal resin (C1) tend to be further improved. There is. On the other hand, making the structural unit represented by formula (i) higher than 80 mol% tends to be difficult in production.
  • the structural unit represented by the formula (i) in the polyvinyl acetal resin (C1) is formed by acetalizing a vinyl alcohol structural unit existing continuously (adjacent) in the molecular chain in the polyvinyl alcohol resin.
  • discontinuous vinyl alcohol structural units cannot be acetalized, and as a result, it is difficult to make the content of the structural unit represented by the formula (i) higher than 80 mol%.
  • content (content rate) of the structural unit represented by Formula (ii) in polyvinyl acetal resin (C1) is not specifically limited, With respect to all the structural units (100 mol%) which comprise polyvinyl acetal resin (C1).
  • the content is preferably 0.1 to 49.9 mol%, more preferably 1 to 30 mol%.
  • the amount of the structural unit represented by the formula (i) can be relatively increased, and the polyvinyl acetal resin ( The chemical resistance, flexibility, wear resistance, and mechanical strength of C1) are further improved, and the expected performance tends to be exhibited more easily.
  • content (content rate) of the structural unit represented by Formula (iii) in polyvinyl acetal resin (C1) is not specifically limited, With respect to all the structural units (100 mol%) which comprise polyvinyl acetal resin (C1).
  • the content is preferably 0.1 to 49.9 mol%, more preferably 1 to 30 mol%.
  • the structural unit represented by the formula (ii) and the formula (iii) are used. Since the structural unit is in an equilibrium relationship, the content of the structural unit represented by the formula (iii) is usually 0.1 mol% or more.
  • each structural unit for example, structural units represented by formulas (i) to (iii)
  • the content of each structural unit (for example, structural units represented by formulas (i) to (iii)) in the polyvinyl acetal resin (C1) can be measured according to JIS K6729.
  • the polyvinyl acetal resin (C2) is a polyvinyl acetal resin having a carboxyl group in the molecule.
  • the polyvinyl acetal resin (C2) for example, in addition to the structural units represented by the above formulas (i) to (iii), a polyvinyl acetal resin containing a structural unit represented by the following formula (vi) (by copolymerization) And a polyvinyl acetal resin having a carboxyl group introduced therein (sometimes referred to as a “carboxyl group-introduced polyvinyl acetal resin”).
  • R 12 represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.
  • alkyl group having 1 to 5 carbon atoms include linear or branched alkyl groups having 1 to 5 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group.
  • Structural units represented by formulas (i) to (iii) and (vi) in the polyvinyl acetal resin (C2) (constituent units represented by formulas (i) to (iii) and a structure represented by formula (vi))
  • the total content (total content) of the units is not particularly limited, but is preferably 80 to 100% by weight with respect to all the structural units (100% by weight) constituting the polyvinyl acetal resin (C2).
  • the polyvinyl acetal resin (C2) may further contain other structural units such as the structural unit represented by the above formula (iv) and the structural unit represented by the formula (v).
  • the structural units represented by the formulas (i) to (iii) and (vi) may be arranged with regularity or may be arranged randomly. That is, the polyvinyl acetal resin (C2) may be a block copolymer, an alternating copolymer or the like, or a random copolymer. Among them, it is preferable that they are arranged at random.
  • content (content rate) of the structural unit represented by Formula (i) in polyvinyl acetal resin (C2) is not specifically limited, With respect to all the structural units (100 mol%) which comprise polyvinyl acetal resin (C2). Therefore, 49.9 to 80 mol% is preferable. By setting the content of the structural unit represented by formula (i) to 49.9 mol% or more, the chemical resistance, flexibility, wear resistance, and mechanical strength of the polyvinyl acetal resin (C2) are further improved. Tend to. On the other hand, making the structural unit represented by formula (i) higher than 80 mol% tends to be difficult in production.
  • the structural unit represented by the formula (i) in the polyvinyl acetal resin (C2) is formed by acetalizing a vinyl alcohol structural unit existing continuously (adjacent) in the molecular chain in the polyvinyl alcohol resin.
  • discontinuous vinyl alcohol structural units cannot be acetalized, and as a result, it is difficult to make the content of the structural unit represented by the formula (i) higher than 80 mol%.
  • content (content rate) of the structural unit represented by Formula (ii) in polyvinyl acetal resin (C2) is not specifically limited, With respect to all the structural units (100 mol%) which comprise polyvinyl acetal resin (C2).
  • the content is preferably 0.1 to 49.9 mol%, more preferably 1 to 30 mol%.
  • the amount of the structural unit represented by the formula (i) can be relatively increased, and the polyvinyl acetal resin ( The chemical resistance, flexibility, wear resistance, and mechanical strength of C2) tend to be further improved, and the expected performance tends to be exhibited more easily.
  • content (content rate) of the structural unit represented by Formula (iii) in polyvinyl acetal resin (C2) is not specifically limited, With respect to all the structural units (100 mol%) which comprise polyvinyl acetal resin (C2).
  • the content is preferably 0.1 to 49.9 mol%, more preferably 1 to 30 mol%.
  • content (content rate) of the structural unit represented by Formula (vi) in polyvinyl acetal resin (C2) is not specifically limited, With respect to all the structural units (100 mol%) which comprise polyvinyl acetal resin (C2).
  • the content is preferably 0.1 to 49.9 mol%, more preferably 1 to 30 mol%.
  • the amount of the structural unit represented by the formula (i) can be relatively increased, and a polyvinyl acetal resin ( The chemical resistance, flexibility, wear resistance, and mechanical strength of C2) tend to be further improved, and the expected performance tends to be exhibited more easily.
  • Each content of each structural unit (for example, structural units represented by formulas (i) to (iii) and (vi)) in the polyvinyl acetal resin (C2) can be measured according to JIS K6729.
  • the weight average molecular weight of the polyvinyl acetal resin (C) is not particularly limited, but is preferably 40,000 to 140,000, more preferably 40,000 to 80,000.
  • the weight average molecular weight is 40000 or more, the moldability of the epoxy resin composition is further improved, and the bending strength and tensile strength of the cured product and the fiber-reinforced composite material tend to be further improved.
  • the weight average molecular weight is 140000 or less, workability is ensured without excessively increasing the viscosity of the epoxy resin composition while ensuring sufficient solubility in the alicyclic epoxy compound (A) and the like. There is a tendency to improve.
  • the polyvinyl acetal resin (C) can be used alone or in combination of two or more.
  • the polyvinyl acetal resin (C) include, for example, trade names “VINYREC PVF-K”, “VINYREC PVF-L”, “VINYREC PVF-H”, “VINYREC PVF-E”, “VINYREC C” (above, Commercial products such as JNC Co., Ltd.) can also be used.
  • the content (blending amount) of the polyvinyl acetal resin (C) in the epoxy resin composition of the present invention can be appropriately adjusted according to the desired properties and viscosity of the epoxy resin composition, and is not particularly limited.
  • the amount is preferably 1 to 40 parts by weight, more preferably 1 to 30 parts by weight, and still more preferably 1 to 20 parts by weight with respect to 100 parts by weight of the cyclic epoxy compound (A).
  • the viscosity of the epoxy resin composition can be controlled to an appropriate range, so that the width of the molding method to which the epoxy resin composition can be applied is expanded.
  • the mechanical strength of the cured product and the fiber-reinforced composite material tends to be further improved.
  • the epoxy resin composition can be made into a liquid, and furthermore, the viscosity can be controlled to an appropriate range, so that it can be applied. There is a tendency for the width of the molding method to expand.
  • the epoxy resin composition of the present invention may further contain a curing catalyst (D).
  • the curing catalyst (D) in the epoxy resin composition of the present invention functions to cure the epoxy resin composition by initiating and / or accelerating a curing reaction (polymerization reaction) such as the alicyclic epoxy compound (A). It is a compound that has.
  • the curing catalyst (D) is not particularly limited.
  • a cationic polymerization initiator photocation polymerization initiator, thermal cation polymerization, which initiates polymerization by generating cationic species by applying light irradiation or heat treatment). Initiators, etc.
  • Lewis acid / amine complexes Bronsted acid salts, imidazoles and the like.
  • Examples of the photocationic polymerization initiator as the curing catalyst (D) include hexafluoroantimonate salts, pentafluorohydroxyantimonate salts, hexafluorophosphate salts, hexafluoroarsenate salts, and more specifically.
  • triarylsulfonium hexafluorophosphate eg, p-phenylthiophenyldiphenylsulfonium hexafluorophosphate
  • sulfonium salts such as triarylsulfonium hexafluoroantimonate (particularly, triarylsulfonium salts)
  • diaryl iodonium hexafluorophosphate Diaryl iodonium hexafluoroantimonate, bis (dodecylphenyl) iodonium tetrakis (pentafluorophenyl) borate
  • iodonium salts such as donium [4- (4-methylphenyl-2-methylpropyl) phenyl] hexafluorophosphate
  • phosphonium salts such as tetrafluorophosphonium hexafluorophosphate
  • pyridinium salts such as N-hexy
  • cationic photopolymerization initiator examples include, for example, trade names “UVACURE 1590” (manufactured by Daicel Cytec Co., Ltd.); trade names “CD-1010”, “CD-1011”, “CD-1012” (above, the United States). Sartomer); trade name “Irgacure 264” (manufactured by BASF); trade name “CIT-1682” (manufactured by Nippon Soda Co., Ltd.); trade name “PHOTOINITIATOR 2074” (manufactured by Rhodia Japan) It can also be preferably used.
  • thermal cationic polymerization initiator as the curing catalyst (D) include aryldiazonium salts, aryliodonium salts, arylsulfonium salts, allene-ion complexes, etc., and trade names “PP-33”, “CP-66”.
  • thermal cationic polymerization initiator a compound of a chelate compound of a metal such as aluminum or titanium and acetoacetic acid or diketones and a silanol such as triphenylsilanol, or a metal such as aluminum or titanium and acetoacetic acid or diketone
  • a compound of a chelate compound with a phenol and a phenol such as bisphenol S.
  • a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited.
  • a known or commonly used Lewis acid / amine complex-based curing catalyst can be used, and is not particularly limited.
  • Bronsted acid salts as the curing catalyst (D), known or commonly used Bronsted acid salts can be used, and are not particularly limited.
  • imidazole as the curing catalyst (D), known or commonly used imidazoles can be used, and are not particularly limited.
  • the curing catalyst (D) can be used singly or in combination of two or more.
  • the content (blending amount) of the curing catalyst (D) in the epoxy resin composition of the present invention is not particularly limited, but is a cationic curable compound (for example, alicyclic epoxy compound (A)) contained in the epoxy resin composition. Is preferably 0.01 to 15 parts by weight, more preferably 0.01 to 12 parts by weight, still more preferably 0.05 to 10 parts by weight, and particularly preferably 0.05 to 8 parts by weight with respect to 100 parts by weight as a whole. Part.
  • the curing catalyst (D) within the above range, the curing rate of the epoxy resin composition is increased, and the balance between the heat resistance and the transparency of the cured product tends to be improved.
  • the epoxy resin composition of the present invention may further contain a curing agent (E) (for example, instead of the curing catalyst (D)).
  • the curing agent (E) in the epoxy resin composition of the present invention is a compound having a function of curing the epoxy resin composition by reacting with the alicyclic epoxy compound (A) or the like.
  • a known or conventional curing agent can be used as a curing agent for epoxy resin, and is not particularly limited.
  • acid anhydrides (acid anhydride curing agents), amines ( Amine curing agents), polyamide resins, imidazoles (imidazole curing agents), polymercaptans (polymercaptan curing agents), phenols (phenolic curing agents), polycarboxylic acids, dicyandiamides, organic acid hydrazides, etc.
  • acid anhydrides (acid anhydride curing agents)
  • amines Amine curing agents
  • polyamide resins imidazoles (imidazole curing agents)
  • polymercaptans polymercaptan curing agents
  • phenols phenolic curing agents
  • polycarboxylic acids dicyandiamides
  • organic acid hydrazides etc.
  • acid anhydrides as the curing agent (E), known or commonly used acid anhydride-based curing agents can be used, and are not particularly limited.
  • methyltetrahydrophthalic anhydride Acids (4-methyltetrahydrophthalic anhydride, 3-methyltetrahydrophthalic anhydride, etc.
  • methylhexahydrophthalic anhydride (4-methylhexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, etc.
  • dodecenyl anhydride Acid methylendomethylenetetrahydrophthalic anhydride, phthalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylcyclohexene dicarboxylic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride Products, n
  • acid anhydrides for example, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, dodecenyl succinic anhydride, methylendomethylenetetrahydrophthalic anhydride, etc.
  • acid anhydride that is solid at 25 ° C. for example, can be dissolved in a liquid acid anhydride at 25 ° C. to form a liquid mixture, and as a curing agent (E) in the epoxy resin composition of the present invention. There is a tendency that the handleability of is improved.
  • saturated monocyclic hydrocarbon dicarboxylic acid anhydrides (including those in which a substituent such as an alkyl group is bonded to the ring) are preferable from the viewpoint of heat resistance and transparency of the cured product.
  • amines as the curing agent (E), known or conventional amine-based curing agents can be used, and are not particularly limited.
  • phenols phenolic curing agent
  • curing agent (E) known or commonly used phenolic curing agents can be used, and are not particularly limited.
  • novolac type phenol resins cresol type novolac resins
  • cresol type novolac resins examples include paraxylylene-modified phenol resins, aralkyl resins such as paraxylylene / metaxylylene-modified phenol resins, terpene-modified phenol resins, dicyclopentadiene-modified phenol resins, and triphenol propane.
  • polyamide resin as the curing agent (E) examples include a polyamide resin having one or both of a primary amino group and a secondary amino group in the molecule.
  • imidazole (imidazole curing agent) as the curing agent (E) a known or commonly used imidazole curing agent can be used, and is not particularly limited.
  • Examples of the polymercaptans (polymercaptan-based curing agent) as the curing agent (E) include liquid polymercaptan and polysulfide resin.
  • polycarboxylic acids examples include adipic acid, sebacic acid, terephthalic acid, trimellitic acid, carboxyl group-containing polyester, and the like.
  • curing agent (E) can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • a commercial item can also be used as a hardening
  • acid anhydride-based curing agents include trade names “Licacid MH-700”, “Licacid MH-700F” (manufactured by Shin Nippon Rika Co., Ltd.); trade name “HN-5500” (Hitachi) Kasei Kogyo Co., Ltd.).
  • the content (blending amount) of the curing agent (E) in the epoxy resin composition of the present invention is not particularly limited, but is 50 to 200 with respect to 100 parts by weight of the total amount of the cationic curable compound contained in the epoxy resin composition. Part by weight is preferred, more preferably 80 to 150 parts by weight. More specifically, when acid anhydrides are used as the curing agent (E), cationic polymerization in all cationic polymerizable compounds (for example, compounds having an epoxy group) contained in the epoxy resin composition of the present invention. It is preferably used at a ratio of 0.5 to 1.5 equivalents per equivalent of a group (for example, epoxy group).
  • the curing accelerator (F) is a compound having a function of accelerating the reaction rate when a cationic curable compound (particularly a compound having an epoxy group) reacts with the curing agent (E).
  • a known or conventional curing accelerator can be used as the curing accelerator (F).
  • 1,8-diazabicyclo [5.4.0] undecene-7 DBU or a salt thereof (for example, phenol) Salt, octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); 1,5-diazabicyclo [4.3.0] nonene-5 (DBN) or a salt thereof (eg, phenol salt, Octylate, p-toluenesulfonate, formate, tetraphenylborate, etc.); tertiary such as benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, N, N-dimethylcyclohexylamine Amines; imidazoles such as 2-ethyl-4-methylimidazole and 1-cyanoethyl-2-ethyl-4-methylimidazole; Acid esters; phosphines such as triphenylphosphine
  • the content (blending amount) of the curing accelerator (F) in the epoxy resin composition of the present invention is not particularly limited, but is 0.1% relative to 100 parts by weight of the total amount of the cationic curable compound contained in the epoxy resin composition.
  • the amount is preferably 01 to 5 parts by weight, more preferably 0.03 to 3 parts by weight, still more preferably 0.03 to 2 parts by weight.
  • the epoxy resin composition of the present invention may contain various additives within a range not impairing the effects of the present invention.
  • a compound having a hydroxyl group such as ethylene glycol, diethylene glycol, propylene glycol, or glycerin
  • the reaction can be allowed to proceed slowly.
  • Other silane coupling agents such as silicone-based and fluorine-based antifoaming agents, leveling agents, ⁇ -glycidoxypropyltrimethoxysilane and 3-mercaptopropyltrimethoxysilane as long as the viscosity and transparency are not impaired.
  • Surfactants such as silica and alumina, flame retardants, colorants, antioxidants, ultraviolet absorbers, ion adsorbers, pigments, phosphors (eg, YAG phosphor fine particles, silicate phosphors)
  • Conventional additives such as fine inorganic particles such as fine particles), release agents, solvents (for example, ⁇ -butyrolactone, etc.), thickeners, stabilizers, and the like can be used.
  • the epoxy resin composition of the present invention may further contain a compound having one or more oxetanyl groups in the molecule (sometimes referred to as “oxetane compound”).
  • oxetane compound a compound having one or more oxetanyl groups in the molecule
  • various effects such as an effect of increasing the curing rate, an effect of increasing the conversion rate and the degree of polymerization, and an effect of improving the heat resistance and breaking strength of the cured product tend to be obtained.
  • the oxetane compound may be a known or commonly used oxetane compound, and is not particularly limited.
  • the epoxy resin composition of the present invention is not particularly limited, but can be prepared by stirring and mixing each of the above-described components as necessary.
  • the epoxy resin composition of the present invention can be used as a one-component composition in which each component is mixed in advance, for example, two or more components prepared separately are used before use. It can also be used as a multi-component (for example, two-component) composition used by mixing at a predetermined ratio.
  • the stirring / mixing method is not particularly limited, and for example, known or conventional stirring / mixing means such as various mixers such as a dissolver and a homogenizer, a kneader, a roll, a bead mill, and a self-revolving stirrer can be used. Further, after stirring and mixing, defoaming may be performed under vacuum.
  • the epoxy resin composition of the present invention is preferably liquid at 25 ° C.
  • the viscosity (25 ° C.) of the epoxy resin composition of the present invention is not particularly limited, but is preferably less than 25000 Pa ⁇ s, more preferably less than 10,000 Pa ⁇ s, still more preferably 500 to 50000 mPa ⁇ s, and particularly preferably 2000 to 30000 mPa. -S.
  • the range of applicable molding methods tends to be expanded.
  • the epoxy resin composition of the present invention is preferably liquid at 30 ° C.
  • the viscosity (30 ° C.) of the epoxy resin composition of the present invention is not particularly limited, but is preferably less than 10,000 Pa ⁇ s, more preferably 500 to 50000 mPa ⁇ s, and further preferably 2000 to 30000 mPa ⁇ s. By setting the viscosity at 30 ° C. to less than 10,000 Pa ⁇ s, the range of applicable molding methods tends to be expanded.
  • the viscosity of the epoxy resin composition at 30 ° C. and 25 ° C.
  • the epoxy resin composition of the present invention is solid at 25 ° C. or solid at 30 ° C., for example, a cured product or a cured product by a molding method (for example, transfer molding method) in which heat is applied to melt A molded body of a fiber reinforced composite material can be obtained.
  • the epoxy resin composition of the present invention can be easily controlled in properties and viscosity, can be cured at a low temperature in a short time, and is further heat resistant by curing the epoxy resin composition.
  • Resin composition for forming a composite material (fiber reinforced composite material) of the cured product and reinforcing fibers (resin composition for fiber reinforced composite materials) Can be preferably used.
  • a prepreg obtained by impregnating or coating a reinforcing fiber with the epoxy resin composition of the present invention (sometimes referred to as “the prepreg of the present invention”), a fiber-reinforced composite material (“ May be referred to as “the fiber-reinforced composite material of the present invention”). Since the fiber-reinforced composite material of the present invention has the above configuration, it is excellent in productivity, heat resistance, and toughness.
  • reinforcing fiber known or commonly used reinforcing fiber can be used, and is not particularly limited.
  • carbon fiber, glass fiber, aramid fiber, boron fiber, graphite fiber, silicon carbide fiber, high-strength polyethylene fiber examples thereof include tungsten carbide fibers and polyparaphenylene benzoxazole fibers (PBO fibers).
  • the carbon fiber include polyacrylonitrile (PAN) -based carbon fiber, pitch-based carbon fiber, and vapor-grown carbon fiber.
  • PAN polyacrylonitrile
  • carbon fibers, glass fibers, and aramid fibers are preferable from the viewpoint of mechanical properties (toughness and the like), and carbon fibers are particularly preferable.
  • the epoxy resin composition of the present invention can be preferably used particularly as a resin composition (resin composition for carbon fiber reinforced composite material) for forming a carbon fiber reinforced composite material.
  • the said reinforced fiber can also be used individually by 1 type, and can also be used in combination of 2 or more type.
  • the form of the reinforcing fiber is not particularly limited, and examples thereof include a filament (long fiber) form, a tow form, a unidirectional material form in which tows are arranged in one direction, a woven form, and a non-woven form. It is done.
  • reinforced fiber fabrics include stitches that prevent unraveling sheets that are aligned in one direction, such as plain weave, twill weave, satin weave, or non-crimp fabric, or sheets that are laminated at different angles. Stitched sheets and the like.
  • the content of reinforcing fiber in the prepreg of the present invention is not particularly limited and can be adjusted as appropriate.
  • the method for impregnating or coating the reinforcing fiber with the epoxy resin composition of the present invention is not particularly limited, and can be carried out by an impregnation or coating method in a known or commonly used prepreg manufacturing method.
  • the prepreg of the present invention is obtained by impregnating or coating the reinforcing resin with the epoxy resin composition of the present invention, and further performing heating, active energy ray irradiation, etc.
  • the fiber-reinforced composite material of the present invention can be obtained by curing the prepreg of the present invention, and its production method is not particularly limited, but known or conventional methods such as a hand layup method, It can be produced by a prepreg method, RTM method, SMC molding method, pultrusion method, filament winding method, spray-up method, pultrusion method and the like. That is, as the fiber reinforced composite material of the present invention, a material molded by the prepreg method, a material molded by the RTM method, a material molded by the SMC molding method (for example, C-SMC; Carbon-fiber-reinforced Sheet Molding Compound).
  • 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 also be preferably used as a constituent material for high-pressure tanks such as hydrogen tanks and liquefied natural gas (LNG) tanks.
  • LNG liquefied natural gas
  • Example 1 As shown in Table 1, 100 parts by weight of an alicyclic epoxy compound (trade name “Celoxide 2021P”, manufactured by Daicel Corporation), polyester polyol (trade name “Placcel 305”, polycaprolactone triol, manufactured by Daicel Corporation) 30 parts by weight, 7 parts by weight of polyvinyl acetal resin (trade name “Vinylec C”, manufactured by JNC Corporation), and 1 part by weight of thickening inhibitor (trade name “ADK STAB PEP-36”, manufactured by ADEKA Corporation) Stir into a flask, mix by heating and stirring at 100 ° C.
  • an alicyclic epoxy compound trade name “Celoxide 2021P”, manufactured by Daicel Corporation
  • polyester polyol trade name “Placcel 305”, polycaprolactone triol, manufactured by Daicel Corporation
  • 7 parts by weight of polyvinyl acetal resin trade name “Vinylec C”, manufactured by JNC Corporation
  • thickening inhibitor trade name “ADK STAB PEP-
  • Examples 2 to 9, Comparative Examples 1 to 3 An epoxy resin composition was prepared in the same manner as in Example 1 except that the constituent components and blending ratio of the epoxy resin composition were changed as shown in Table 1. Next, the cured product was prepared by putting the epoxy resin composition obtained above into a molding die (a casting mold having a thickness of 4 mm and 0.5 mm) and heating under the curing conditions shown in Table 1. .
  • Viscosity change rate (%) ⁇ (V2 ⁇ V1) / V1 ⁇ ⁇ 100
  • the epoxy resin compositions obtained in the examples were able to form a cured product by curing at a low temperature in a short time. Moreover, the epoxy resin composition obtained in the Example had a small viscosity change rate and had a long pot life. Furthermore, the cured product of the epoxy resin composition obtained in the examples was excellent in mechanical properties such as tensile properties, and had high heat resistance (glass transition temperature and thermal decomposition temperature). On the other hand, the epoxy resin composition obtained in the comparative example was inferior in each characteristic such as extremely short pot life, low tensile elongation at break and low heat resistance.
  • Example and the comparative example is as follows.
  • PLACCEL 305 Polycaprolactone triol, manufactured by Daicel Corporation
  • PLACCEL 205 Polycaprolactone diol, manufactured by Daicel Corporation
  • PLACCEL 405D Polycaprolactone tetraol, manufactured by Daicel Corporation [polyvinyl acetal resin]
  • Vinylec C Carboxyl group-introduced polyvinyl formal resin, manufactured by JNC Corporation
  • Vinylec PVF-L Polyvinyl formal resin, manufactured by JNC Corporation [Thickening inhibitor]
  • ADK STAB PEP-36 Bis (2,6-di-tert-butyl-4-methylphenyl)
  • the epoxy resin composition of the present invention can be preferably used as a resin composition for fiber reinforced composite materials.
  • a fiber-reinforced composite material can be obtained.
  • the fiber-reinforced composite material is, for example, an aircraft fuselage, main wing, tail wing, moving wing, fairing, cowl, door, etc .; spacecraft motor case, main wing, etc .; satellite structure; automobile parts such as automobile chassis; Rail vehicle structure; bicycle structure; ship structure; wind power blade; pressure vessel; fishing rod; tennis racket; golf shaft; robot arm; cable (for example, cable core material, etc.) Can be used.
  • the fiber-reinforced composite material of the present invention can also be preferably used as a constituent material for high-pressure tanks such as hydrogen tanks and liquefied natural gas (LNG) tanks.
  • LNG liquefied natural gas

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  • Epoxy Resins (AREA)
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Abstract

La présente invention concerne une composition de résine époxyde dont les qualités et la viscosité sont facilement régulées, qu'il est possible de faire durcir facilement sur une courte durée et à basse température et qui permet de former un article durci ayant d'exceptionnelles caractéristiques mécaniques telles qu'un allongement en traction élevé à la rupture et une haute résistance à la chaleur, ainsi qu'un article durci associé (article de résine durcie). La composition de résine époxyde selon la présente invention est caractérisée en ce qu'elle comprend (A) un composé époxy alicyclique, (B) au moins un type de composé choisi dans le groupe constitué par (B1) des composés d'addition de lactone ayant des groupes hydroxyles et (B2) des polyols de polycarbonate et (C) une résine de poly(acétal de vinyle).
PCT/JP2014/065585 2013-06-19 2014-06-12 Composition de résine époxyde et article durci associé, préimprégné et matériau composite renforcé par des fibres Ceased WO2014203797A1 (fr)

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Cited By (4)

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WO2019189226A1 (fr) * 2018-03-28 2019-10-03 積水化学工業株式会社 Composition de résine époxyde
WO2019202762A1 (fr) * 2018-04-20 2019-10-24 Jnc株式会社 Préimprégné et matériau composite renforcé par des fibres utilisant celui-ci
WO2020066592A1 (fr) * 2018-09-26 2020-04-02 積水化学工業株式会社 Composition de résine époxyde
JP2022153282A (ja) * 2021-03-29 2022-10-12 東レ株式会社 エポキシ樹脂組成物、表面保護中間基材および繊維強化複合材料中間体

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CN107200995A (zh) * 2016-03-16 2017-09-26 住友电木株式会社 环氧树脂组合物和半导体装置
TWI861274B (zh) * 2019-12-11 2024-11-11 日商三鍵有限公司 陽離子硬化性組成物、硬化物及接合體

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JP2001302823A (ja) * 2000-04-24 2001-10-31 Nippon Mitsubishi Oil Corp 繊維強化複合材料用樹脂組成物、プリプレグおよび繊維強化複合材料
JP2007284613A (ja) * 2006-04-19 2007-11-01 Daicel Chem Ind Ltd 活性エネルギー線硬化性コーティング剤およびその用途
JP2008189699A (ja) * 2007-01-31 2008-08-21 Daicel Chem Ind Ltd 硬化性樹脂組成物及び光導波路
WO2008146386A1 (fr) * 2007-05-31 2008-12-04 Toray Industries, Inc. Intermédiaire pour un matériau composite renforcé par des fibres de carbone
JP2012001690A (ja) * 2010-06-21 2012-01-05 Adeka Corp 光硬化性樹脂組成物

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JP2001302823A (ja) * 2000-04-24 2001-10-31 Nippon Mitsubishi Oil Corp 繊維強化複合材料用樹脂組成物、プリプレグおよび繊維強化複合材料
JP2007284613A (ja) * 2006-04-19 2007-11-01 Daicel Chem Ind Ltd 活性エネルギー線硬化性コーティング剤およびその用途
JP2008189699A (ja) * 2007-01-31 2008-08-21 Daicel Chem Ind Ltd 硬化性樹脂組成物及び光導波路
WO2008146386A1 (fr) * 2007-05-31 2008-12-04 Toray Industries, Inc. Intermédiaire pour un matériau composite renforcé par des fibres de carbone
JP2012001690A (ja) * 2010-06-21 2012-01-05 Adeka Corp 光硬化性樹脂組成物

Cited By (13)

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EP3778694A4 (fr) * 2018-03-28 2021-12-29 Sekisui Chemical Co., Ltd. Composition de résine époxyde
CN111868137A (zh) * 2018-03-28 2020-10-30 积水化学工业株式会社 环氧树脂组合物
JPWO2019189226A1 (ja) * 2018-03-28 2021-02-12 積水化学工業株式会社 エポキシ樹脂組成物
WO2019189226A1 (fr) * 2018-03-28 2019-10-03 積水化学工業株式会社 Composition de résine époxyde
US11603456B2 (en) 2018-03-28 2023-03-14 Sekisui Chemical Co., Ltd. Epoxy resin composition
JP7291075B2 (ja) 2018-03-28 2023-06-14 積水化学工業株式会社 エポキシ樹脂組成物
CN111868137B (zh) * 2018-03-28 2023-08-15 积水化学工业株式会社 环氧树脂组合物
WO2019202762A1 (fr) * 2018-04-20 2019-10-24 Jnc株式会社 Préimprégné et matériau composite renforcé par des fibres utilisant celui-ci
WO2020066592A1 (fr) * 2018-09-26 2020-04-02 積水化学工業株式会社 Composition de résine époxyde
JPWO2020066592A1 (ja) * 2018-09-26 2021-08-30 積水化学工業株式会社 エポキシ樹脂組成物
JP7402048B2 (ja) 2018-09-26 2023-12-20 積水化学工業株式会社 エポキシ樹脂組成物
US12291632B2 (en) 2018-09-26 2025-05-06 Sekisui Chemical Co., Ltd. Epoxy resin composition
JP2022153282A (ja) * 2021-03-29 2022-10-12 東レ株式会社 エポキシ樹脂組成物、表面保護中間基材および繊維強化複合材料中間体

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