WO2021241288A1 - Epoxy resin composition and cured object obtained therefrom - Google Patents

Epoxy resin composition and cured object obtained therefrom Download PDF

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Publication number
WO2021241288A1
WO2021241288A1 PCT/JP2021/018452 JP2021018452W WO2021241288A1 WO 2021241288 A1 WO2021241288 A1 WO 2021241288A1 JP 2021018452 W JP2021018452 W JP 2021018452W WO 2021241288 A1 WO2021241288 A1 WO 2021241288A1
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Prior art keywords
epoxy resin
resin composition
mass
less
epoxy
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PCT/JP2021/018452
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French (fr)
Japanese (ja)
Inventor
謙一 竹内
洋史 加藤
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住友化学株式会社
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Publication of WO2021241288A1 publication Critical patent/WO2021241288A1/en

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    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • 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
    • C08G59/40—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
    • C08G59/62—Alcohols or phenols
    • 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

Definitions

  • the present invention relates to an epoxy resin composition and a cured product thereof.
  • Epoxy resin is applied to various applications such as fiber reinforced plastics, electronic parts, adhesives, paints, etc. because its cured product has excellent heat resistance, strength, chemical resistance, adhesiveness, etc. ing.
  • a composition containing an epoxy resin (hereinafter referred to as "epoxy resin composition”) usually contains a curing agent for curing the composition, and may further contain a curing accelerator [for example,. , Japanese Patent Application Laid-Open No. 2015-083634 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2013-032510 (Patent Document 2)].
  • the epoxy resin composition is required to have characteristics according to the application to which it is applied. Generally, the epoxy resin composition is required to have a long pot life from the viewpoint of workability.
  • An object of the present invention is to provide an epoxy resin composition having a long pot life and a cured product thereof.
  • the present invention provides the following epoxy resin compositions, cured products, and the like.
  • An epoxy resin composition containing an epoxy resin (A), a curing agent (B), and an imidazole adduct-type curing accelerator (C).
  • the curing agent (B) has the following formula (B-1):
  • R 1 represents a hydrogen atom, a halogen atom, a methoxy group or a hydrocarbon group having 1 to 12 carbon atoms.
  • compound (B-1) represented by An epoxy resin composition having a chlorine content of 1600 mass ppm or less.
  • the content of the imidazole adduct-type curing accelerator (C) is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A), according to [1] or [2].
  • Epoxy resin composition has the following components: Epoxy resin (A), Curing agent (B) and imidazole adduct-type curing accelerator (C) including.
  • the curing agent (B) contains a compound represented by the above formula (B-1) (hereinafter, also referred to as “compound (B-1)”).
  • each component contained in or may be contained in the epoxy resin composition and the epoxy resin composition will be described in detail.
  • the compounds exemplified as the components contained in or may be contained in the epoxy resin composition in the present specification may be used alone or in combination of two or more.
  • Epoxy resin (A) is not particularly limited as long as it has one or more epoxy groups in the molecule, but is preferably in the molecule from the viewpoint of curability of the epoxy resin composition and heat resistance and strength of the cured product. It contains an epoxy resin having two or more epoxy groups, and more preferably contains an epoxy resin having two epoxy groups in the molecule.
  • Examples of the epoxy resin having two or more epoxy groups in the molecule include, for example. Obtained by reacting a polyhydric phenol compound such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, biphenyldiol, naphthalenediol, novolak resin obtained by condensing or cocondensing phenols with aldehydes, and epichlorohydrin.
  • a polyhydric phenol compound such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, biphenyldiol, naphthalenediol, novolak resin obtained by condensing or cocondensing phenols with aldehydes, and epichlorohydrin.
  • Aromatic glycidyl ether type epoxy resin that can be used; An aliphatic glycidyl obtained by reacting a polyhydric alcohol compound such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, neopentyl glycol, glycerin, pentaerythritol, and sorbitol with epichlorohydrin.
  • a polyhydric alcohol compound such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, neopentyl glycol, glycerin, pentaerythritol, and sorbitol with epichlorohydrin.
  • Ether type epoxy resin A glycidyl ester type epoxy resin that can be obtained by reacting a polybasic acid such as phthalic acid, hexahydrophthalic acid, or dimer acid with epichlorohydrin; A glycidylamine type epoxy resin obtained by reacting amines such as aniline, toluidine, diaminodiphenylmethane, p-aminophenol, and p-aminocresol with epichlorohydrin; Olefin compounds having two or more unsaturated bonds in the molecule such as soybean oil and polybutadiene, inden, 4-vinyl-1-cyclohexene, 3-cyclohexene-1-carboxylic acid (3-cyclohexenyl) methyl and the like.
  • Examples thereof include an alicyclic epoxy resin obtained by oxidizing a cyclic olefin compound having two or more unsaturated bonds in a molecule with a peracid (peracetic acid or the like).
  • the above-exemplified epoxy resin can be an epoxy resin having two epoxy groups in the molecule.
  • Examples of the aromatic glycidyl ether type epoxy resin having two epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, and biphenyldiol type epoxy resin. , Naphthalene diol type epoxy resin can be mentioned.
  • Examples of the aliphatic glycidyl ether type epoxy resin having two epoxy groups in the molecule include hydrogenated bisphenol A type epoxy resin, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polyethylene.
  • Examples thereof include glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether.
  • Examples of the glycidyl ester type epoxy resin having two epoxy groups in the molecule include phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and dimer acid diglycidyl ester.
  • Examples of the glycidylamine type epoxy resin having two epoxy groups in the molecule include glycidylaniline and glycidyltoluidine.
  • the epoxy resin (A) preferably contains an aromatic glycidyl ether type epoxy resin from the viewpoints of the viscosity of the epoxy resin, and thus the viscosity and pot life of the epoxy resin composition, the curability, and the heat resistance and strength of the cured product. , More preferably contains a bisphenol type epoxy resin, and more preferably contains a bisphenol A type epoxy resin.
  • the epoxy resin (A) preferably contains a liquid epoxy resin, and more preferably, when the epoxy resin (A) contains one or more kinds of epoxy resins, the epoxy resin (A) as a whole is liquid. ..
  • the term "liquid” means to exhibit fluidity at 25 ° C.
  • Substances that are "liquid” in the present specification usually show viscosity, and the viscosity is measured by an E-type viscometer in a viscosity range that cannot be measured by a viscometer (EMS viscometer) using an electromagnetic spinning method or an EMS viscometer.
  • the viscosity at 25 ° C. may be 0.0001 Pa ⁇ s to 1000 Pa ⁇ s and may be 0.001 Pa ⁇ s to 500 Pa ⁇ s.
  • it When it is "liquid", it includes a state in which one or more components are dispersed in other components.
  • Examples of the case where the epoxy resin (A) is liquid as a whole include the following cases. a) When the epoxy resin (A) is made of one kind of liquid epoxy resin b) When the epoxy resin (A) is a mixture of two or more kinds of liquid epoxy resins c) When the epoxy resin (A) is one or more kinds of liquid When the epoxy resin is a mixture of one or more solid epoxy resins and the mixture is liquid d) When the epoxy resin (A) is a mixture of two or more solid epoxy resins and the mixture is liquid
  • the epoxy resin (A) may contain a solid epoxy resin.
  • solid means a solid at 25 ° C.
  • the solid epoxy resin may be dissolved or dispersed in the liquid epoxy resin. In order to carry out the curing reaction uniformly, it is preferable that the solid epoxy resin is uniformly dissolved.
  • the viscosity of the epoxy resin (A) (when two or more kinds of epoxy resins are contained, the viscosity as a mixture of the two or more kinds of epoxy resins) is determined.
  • the viscosity at 25 ° C. according to the EMS viscosity meter is preferably 50 Pa ⁇ s or less, more preferably 40 Pa ⁇ s or less, and further preferably 20 Pa ⁇ s or less.
  • the viscosity of the epoxy resin (A) at 25 ° C. is usually 0.01 Pa ⁇ s or more, may be 0.1 Pa ⁇ s or more, or may be 1 Pa ⁇ s or more.
  • the viscosity of the epoxy resin (A) is the viscosity at 25 ° C. by an EMS viscometer, preferably 0.01 Pa ⁇ s or more and 50 Pa ⁇ s or less, more preferably 0.1 Pa ⁇ s or more and 40 Pa ⁇ s or less, and 1 Pa ⁇ s. More than 20 Pa ⁇ s or less is more preferable.
  • epoxy resin having two or more epoxy groups in the molecule only one type may be used, or two or more types may be used in combination.
  • the combined use of the bisphenol A type epoxy resin and the biphenyl type epoxy resin is preferable because it may be advantageous in achieving both good heat resistance and good tensile properties.
  • the epoxy resin (A) preferably contains an epoxy resin having two epoxy groups in the molecule.
  • the epoxy resin (A) is selected from the group consisting of an epoxy resin having two epoxy groups in the molecule, an epoxy resin having one epoxy group in the molecule, and an epoxy resin having three or more epoxy groups in the molecule. It may contain one or more epoxy resins.
  • the content of the epoxy resin having two epoxy groups in the molecule of the epoxy resin (A) is, for example, 50 parts by mass or more in 100 parts by mass of the epoxy resin (A), and the characteristics of the cured product of the epoxy resin composition ( From the viewpoint of heat resistance and / or tensile properties, etc.), it is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, still more preferably 90 parts by mass. As mentioned above, it may be 100 parts by mass.
  • the epoxy equivalent of the epoxy resin (A) (when two or more kinds of epoxy resins are contained, the epoxy equivalent as a mixture of the two or more kinds of epoxy resins) is the tensile property and heat resistance of the cured product of the epoxy resin composition. From the viewpoint of strength and the like, it is preferably 30 g / eq or more and 500 g / eq or less, more preferably 40 g / eq or more and 400 g / eq or less, still more preferably 50 g / eq or more and 300 g / eq or less, and further. It is preferably 50 g / eq or more and 250 g / eq or less.
  • the epoxy equivalent of the epoxy resin can be measured according to JIS K 7236.
  • the curing agent (B) contains a compound capable of cross-linking and curing the epoxy resin (A).
  • the curing agent (B) contains the compound (B-1) represented by the above formula (B-1).
  • the curing agent (B) may contain one kind of compound (B-1) or two or more kinds.
  • R 1 represents a hydrogen atom, a halogen atom, a methoxy group or a hydrocarbon group having 1 to 12 carbon atoms.
  • the halogen atom in R 1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • the hydrocarbon group having 1 to 12 carbon atoms in R 1 includes an aliphatic group (alkyl group, etc.), an alicyclic group group (cycloalkyl group, etc.), an aromatic group, and a combination of an alicyclic group and an alicyclic group.
  • Examples thereof include a hydrocarbon group composed of, and a hydrocarbon group composed of a combination of an aromatic group and an aliphatic group and / or an alicyclic group.
  • the hydrocarbon group preferably has 1 to 8 carbon atoms.
  • the hydrocarbon group is a methyl group or a 1-phenylethyl group.
  • R 1 is preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom.
  • the positional relationship between the two OH groups of the compound (B-1) may be any of the ortho-position, the meta-position, and the para-position, but from the viewpoint of reducing the viscosity of the epoxy resin composition and in the epoxy resin composition. From the viewpoint of suppressing crystal precipitation in the above, the ortho-position or the meta-position is preferable, and the meta-position is more preferable.
  • the compound (B-1) has a viewpoint of reducing the viscosity of the epoxy resin composition, suppressing crystal precipitation in the epoxy resin composition, and lowering the melting temperature when preparing the epoxy resin composition.
  • a compound having a melting point of 150 ° C. or lower is preferable, and a compound having a melting point of 130 ° C. or lower is more preferable.
  • Examples of the compound (B-1) having a melting point of 150 ° C. or lower include catechol (1,2-dihydroxybenzene), resorcin (1,3-dihydroxybenzene), 4-fluoro-1,3-dihydroxybenzene, 2-.
  • compound (B-1) comprises 1,3-dihydroxybenzene.
  • the inclusion of the compound (B-1) in the epoxy resin composition is advantageous in improving the properties (heat resistance and / or tensile properties, etc.) of the cured product of the epoxy resin composition.
  • the epoxy resin composition may further contain a compound having three or more phenolic hydroxyl groups. By containing the compound, the properties (heat resistance and / or tensile properties, etc.) of the cured product of the epoxy resin composition may be improved.
  • Examples of the compound having three or more phenolic hydroxyl groups include a compound in which one of the hydrogen atoms directly bonded to the benzene ring of the compound (B-1) is replaced with a hydroxyl group, a phenol resin, a novolak resin and the like.
  • the epoxy resin composition may contain a compound having one phenolic hydroxyl group.
  • the compound having one phenolic hydroxyl group include phenol, cresol, xylenol, t-butylphenol and the like.
  • the molar ratio of the phenolic hydroxyl group content to the epoxy group content in the epoxy resin composition is, for example, 0.20 or more and 0.75 or less, which improves the properties of the cured product (heat resistance and / or tensile properties, etc.). From the viewpoint, it is preferably 0.25 or more and 0.67 or less, more preferably 0.3 or more and 0.6 or less, still more preferably 0.35 or more and 0.55 or less, and further preferably 0. 4 or more and 0.5 or less.
  • epoxy group content in the epoxy resin composition refers to the number (number of moles) of epoxy groups contained in the epoxy resin (A).
  • the "phenolic hydroxyl group content” is the phenolic hydroxyl group content in the epoxy resin composition, other than the number of phenolic hydroxyl groups (number of moles) of the compound (B-1) and the compound (B-1). It refers to the total number of phenolic hydroxyl groups (number of moles) of the phenolic compound having phenolic hydroxyl groups.
  • the content of the compound (B-1) in the epoxy resin composition is preferably an amount in which the molar ratio is within the above range, and is, for example, 1 part by mass or more and 30 parts by mass with respect to 100 parts by mass of the epoxy resin (A). It is 5 parts by mass or more, preferably 25 parts by mass or less, and more preferably 8 parts by mass or more and 22 parts by mass or less.
  • the curing agent (B) has the following formula (B-2):
  • the compound represented by hereinafter, also referred to as “compound (B-2)” may be further contained.
  • the curing agent (B) may contain one kind of compound (B-2) or two or more kinds.
  • R 2 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group.
  • the halogen atom in R 2 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
  • R 2 from the viewpoint of the melting point, preferably a hydrogen atom, a methyl group or a methoxy group, more preferably a hydrogen atom.
  • Incorporating the compound (B-2) in the epoxy resin composition may be advantageous in reducing the viscosity of the epoxy resin composition. Further, the inclusion of the compound (B-2) in the epoxy resin composition may be advantageous in enhancing the tensile properties in the cured product of the epoxy resin composition. At this time, the breaking elongation property can be improved without lowering the heat resistance of the cured product.
  • the compound comprises (B-1) is a 1,3-dihydroxybenzene and a compound (B-2) is Dihydrocoumarin: containing (R 2 a hydrogen atom).
  • the content of the compound (B-2) in the epoxy resin composition is, for example, 0.1 part by mass or more with respect to 100 parts by mass of the epoxy resin (A). From the viewpoint of more effectively exhibiting the above effects, the amount is preferably 1 part by mass or more, and more preferably 2 parts by mass or more.
  • the content of the compound (B-2) in the epoxy resin composition is excessively large, the curing of the epoxy resin composition may be insufficient. Therefore, when the epoxy resin composition contains the compound (B-2), the content of the compound (B-2) in the epoxy resin composition is preferably 50 parts by mass with respect to 100 parts by mass of the epoxy resin (A). It is less than or equal to, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less.
  • the compound with respect to the content of the compound (B-1) in the epoxy resin composition from the viewpoint of curability of the epoxy resin composition (
  • the content ratio of B-2) is preferably 0.20 to 0.95, more preferably 0.20 to 0.75, and further preferably 0.20 to 0.50 in terms of mass ratio. Is.
  • the epoxy resin composition may further contain other curing agents for epoxy resins other than those described above.
  • the other curing agent for epoxy resin may be a conventionally known curing agent.
  • the content of the curing agent for other epoxy resins in the curing agent (B) is the curing agent.
  • the total amount of (B) is 100 parts by mass, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 1 part by mass. The following (for example, 0 parts by mass).
  • Imidazole adduct-type curing accelerator refers to an agent having a function of accelerating a curing reaction.
  • promotion as used herein includes the case of initiating a curing reaction.
  • the imidazole adduct-type curing accelerator (C) is used among the curing accelerators.
  • the use of the imidazole adduct-type curing accelerator (C) may be advantageous in achieving both the pot life of the epoxy resin composition and the curing property (fast curing property, etc.).
  • the imidazole adduct-type curing accelerator (C) has an effect of the curing reaction between the epoxy resins (A) and the curing reaction between the epoxy resin (A) and the compound (B-1) and / or the compound (B-2). It is presumed that this is because the imidazole adduct-type curing accelerator (C) generally has potential and thus works favorably for prolonging the pot life. Will be done.
  • the imidazole adduct-type curing accelerator (C) as the curing accelerator is advantageous in enabling the curing reaction at a relatively low temperature, and also in improving the storage stability of the epoxy resin composition. But it is advantageous.
  • the imidazole adduct type curing accelerator (C) only one kind may be used, or two or more kinds may be used in combination.
  • “Potential” means that the product can be stably stored at room temperature (25 ° C.) even in the presence of an epoxy resin or an epoxy resin and a curing agent, while promoting the curing reaction by heat, light, pressure, or the like. A property that can express a function.
  • the imidazole adduct-type curing accelerator (C) used in the present invention preferably has a property (thermal potential) capable of exhibiting a function of accelerating the curing reaction by heat.
  • the imidazole adduct-type curing accelerator (C) is a compound in which an adduct is added to the imidazole compound.
  • the addition of the adduct gives the potential.
  • the adduct is, for example, a compound that can be bonded to the N atom of the imidazole ring, preferably the N atom at the 1-position, by reacting with the imidazole compound.
  • the bond is usually a covalent bond.
  • the adduct is preferably a compound that can impart good potential, and examples thereof include epoxy compounds, isocyanate compounds, (meth) acrylic compounds, and urea compounds.
  • the imidazole adduct-type curing accelerator (C) is preferably a polymer compound obtained by reacting the imidazole compound with the above adduct. Further, the adduct may be further made into a solid solution with a phenol resin or the like, or may be surface-treated with an organic acid, a boric acid compound or the like.
  • the imidazole adduct-type curing accelerator (C) thus produced is usually pulverized to a particle size of about 0.5 to 50 ⁇ m and dispersed in an epoxy resin for use. Since the imidazole adduct-type curing accelerator (C) generally has low solubility in an epoxy resin at room temperature, the imidazole adduct-type curing accelerator (C) mixed with the epoxy resin often exhibits thermal potential.
  • the imidazole adduct-type curing accelerator (C) is described in known patent documents, for example, JP-A-59-053526, JP-A-60-004524, JP-A-60-072917, JP-A-2005-206744. It can be produced by the methods described in JP-A-06-0731556, JP-A-06-172495, JP-A-2008-214567, JP-A-2014-177525, and the like.
  • a commercially available product may be used as the imidazole adduct-type curing accelerator (C).
  • the commercially available products of the imidazole ADEKA duct type curing accelerator (C) are all trade names, "Fujicure FXR-1020", “FXR-1030", “FXR-1032", “FXR-1081”, and "Fujicure FXR-1020".
  • the epoxy resin composition may contain one or more curing accelerators other than the imidazole adduct-type curing accelerator (C) as long as the effects of the present invention are not impaired.
  • the other curing accelerator is not particularly limited, and is, for example, a tertiary amine compound and a salt thereof, an imidazole compound (non-adduct type), an imidazolium salt, a phosphorus compound such as triphenylphosphine or a phosphonium salt, and a metal carboxylate. Examples thereof include salts, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole (TBZ) and the like.
  • the content of the other curing accelerator in the curing accelerator is preferably 20 parts by mass or less, more preferably 20 parts by mass or less, when the total amount of the curing accelerator is 100 parts by mass. It is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less (for example, 0 parts by mass).
  • the content of the imidazole adduct-type curing accelerator (C) in the epoxy resin composition is, for example, 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A), and the above effect can be more effectively achieved. From the viewpoint of expression, it is preferably 2 parts by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less, still more preferably 5 parts by mass or more and 20 parts by mass or less, and even more preferably. It is 5 parts by mass or more and 15 parts by mass or less.
  • the epoxy resin composition may further contain other compounding components other than the above-mentioned components.
  • Other compounding components include, for example, rubber particles, inorganic particles (particles composed of a metal such as aluminum and a metal compound such as calcium carbonate and silica), a flame retardant, a surface treatment agent, a mold release agent, an antibacterial agent, and a leveling agent. Examples thereof include defoaming agents, rocking agents, heat stabilizers, light stabilizers, ultraviolet absorbers, colorants, coupling agents, surfactants, metal alkoxides, thermoplastic resins, diluents and the like.
  • As the other compounding ingredients only one kind may be used, or two or more kinds may be used in combination.
  • the rubber particles include core-shell type acrylic rubber particles, surface-modified acrylic rubber particles, crosslinked NBR particles, silicone rubber particles, and the like. These rubber particles may be conventionally known.
  • the average particle size of the rubber particles is, for example, 0.05 ⁇ m or more and 1 ⁇ m or less, preferably 0.2 ⁇ m or more and 0.5 ⁇ m or less. Only one type of rubber particles may be used, or two or more types may be used in combination.
  • a commercially available product may be used as the rubber particles, or a dispersed product in which the rubber particles are dispersed in an epoxy resin in advance may be used.
  • the trade names are "Acryset BPA328" (manufactured by Nippon Catalyst Corporation); "Kaneace MX-153", “MX-154", "MX-257".
  • the content of the rubber particles in the epoxy resin composition is, for example, 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A), and is preferable from the viewpoint of more effectively exhibiting the above effect. It is 5 parts by mass or more and 80 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass or less.
  • the content of the rubber particles in the epoxy resin composition is, for example, 1% by mass or more and 50% by mass or less with respect to the entire composition, and from the viewpoint of more effectively exhibiting the above effect, it is preferably 2% by mass or more and 30% by mass. It is 1% by mass or less, more preferably 2% by mass or more and 20% by mass or less.
  • Epoxy resin composition has a chlorine content of 1600 mass ppm (mg / kg) or less.
  • the epoxy resin composition can have an excellent pot life as compared with an epoxy resin composition having a chlorine content of more than 1600 mass ppm.
  • the chlorine content means the total chlorine content according to JIS K 7243-3: 2005, and is measured according to the same standard.
  • the chlorine content of the epoxy resin composition is preferably 1500 mass ppm or less, more preferably 1450 mass ppm or less, still more preferably 1400 mass ppm or less, and further preferably 1400 mass ppm or less, from the viewpoint of further improving the pot life. It is preferably 1350 mass ppm or less, and particularly preferably 1300 mass ppm or less (for example, 1250 mass ppm or less).
  • the chlorine content of the epoxy resin composition may be zero, for example, 100 mass ppm or more, 200 mass ppm or more, 500 mass ppm or more, or 1000 mass ppm or more.
  • the chlorine content of the epoxy resin composition is preferably 100% by mass or more and 1500% by mass or less, more preferably 200% by mass or more and 1450% by mass or less, and further preferably 500% by mass or more and 1400% by mass or less. Further, it is more preferably 1000 mass ppm or more and 1350 mass ppm or less, and particularly preferably 1000 mass ppm or more and 1300 mass ppm or less.
  • the epoxy resin (A) contained in the epoxy resin composition is preferably composed of an epoxy resin having two epoxy groups in the molecule, and from the viewpoint of improving the pot life of the epoxy resin composition, the epoxy resin contains chlorine.
  • the amount (in the case of containing two or more kinds of epoxy resins, the chlorine content as a mixture of the two or more kinds of epoxy resins) is preferably 1700 mass ppm or less, more preferably 1500 mass ppm or less. It is more preferably 1450 mass ppm or less, further preferably 1400 mass ppm or less, and particularly preferably 1350 mass ppm or less.
  • the chlorine content of the epoxy resin may be zero, and may be, for example, 100 mass ppm or more, 200 mass ppm or more, 500 mass ppm or more, or 1000 mass ppm or more.
  • the chlorine content of the epoxy resin (A) is preferably 100% by mass or more and 1700% by mass or less, more preferably 200% by mass or more and 1500% by mass or less, and further preferably 500% by mass or more and 1450% by mass or less. Yes, more preferably 1000 mass ppm or more and 1400 mass ppm or less, and particularly preferably 1000 mass ppm or more and 1350 mass ppm or less.
  • the epoxy resin composition according to the present invention containing the epoxy resin (A), the compound (B-1) and the imidazole adduct-type curing accelerator (C), and other components optionally added is preferably liquid.
  • the meaning of "liquid” is as described above.
  • all the components contained therein may be in a dissolved state, or one or more components may be dispersed in other components.
  • the liquid epoxy resin composition according to the present invention can have a low viscosity.
  • the low viscosity can improve the productivity and workability of products using the epoxy resin composition.
  • a method for producing a molding material (composition) containing a cured product of an epoxy resin composition and a fiber or the like includes a step of impregnating a fiber woven fabric or a fiber bundle with the epoxy resin composition, and has a low viscosity.
  • the viscosity at 25 ° C. by an EMS viscometer is preferably 50 Pa ⁇ s or less, more preferably 40 Pa ⁇ s or less, and further. It is preferably 30 Pa ⁇ s or less, more preferably 25 Pa ⁇ s or less, and particularly preferably 20 Pa ⁇ s or less.
  • the viscosity of the epoxy resin composition at 25 ° C. is usually 0.01 Pa ⁇ s or more, may be 0.1 Pa ⁇ s or more, or may be 1 Pa ⁇ s or more.
  • the viscosity of the epoxy resin composition is preferably 0.01 Pa ⁇ s or more and 50 Pa ⁇ s or less, more preferably 0.1 Pa ⁇ s or more and 40 Pa ⁇ s or less, and 1 Pa ⁇ s or more, based on the viscosity at 25 ° C. by an EMS viscometer. It is more preferably 30 Pa ⁇ s or less, still more preferably 1 Pa ⁇ s or more and 25 Pa ⁇ s or less, and particularly preferably 1 Pa ⁇ s or more and 20 Pa ⁇ s or less.
  • the epoxy resin composition according to the present invention can have an excellent pot life.
  • Each viscosity in the above formula is the viscosity at 25 ° C. by the EMS viscometer. The above storage is carried out at 25 ° C.
  • the viscosity ratio may be 1.00 or more.
  • the epoxy resin composition according to the present invention can exhibit good curability. That is, the epoxy resin composition can be sufficiently cured in a relatively short thermosetting time and / or at a relatively low temperature.
  • the cured product according to the present invention is obtained by curing the epoxy resin composition according to the present invention.
  • the cured product according to the present invention can have good heat resistance, or can have even better tensile properties.
  • the cured product according to the present invention can exhibit, for example, a glass transition temperature of 110 ° C. or higher, further 115 ° C. or higher, further 120 ° C. or higher, and further 125 ° C. or higher.
  • the cured product according to the present invention has a breaking elongation of, for example, 4.5% or more, further 5.5% or more, and further 6.5 in the tensile properties conforming to JIS K 7161-1 and JIS K 7161-2. % Or more, even 7.0% or more, and even 7.5% or more.
  • the epoxy resin composition and the cured product thereof according to the present invention can be applied to various uses, and can be used, for example, as an adhesive, a resin composition for encapsulating electronic parts, and a resin composition for impregnating fibers.
  • the epoxy resin composition according to the present invention has a low chlorine content and is therefore suitable for electronic materials such as encapsulants.
  • the present invention also relates to a product or part containing the cured product.
  • An example of the product is a molded product (composition) containing the cured product and fibers and the like.
  • the product or component containing the cured product may contain components other than the epoxy resin composition-derived component (cured product), such as fibers.
  • the epoxy resin composition according to the present invention is used as a resin composition for impregnating fibers.
  • fibers such as PAN-based carbon fiber, pitch-based carbon fiber, glass fiber, aramid fiber, and kenaf fiber can be used.
  • a known sizing treatment may be applied to the surface of the fiber.
  • a known method can be used as a method for producing a molded product by combining the epoxy resin composition and the fiber according to the present invention.
  • a known method can be used.
  • Wet filament winding method in which fibers are impregnated with an epoxy resin composition, wound around a molding die such as a mandrel, molded, and heat-cured.
  • a dry filament winding method in which a tuple preg in which fibers are pre-impregnated with an epoxy resin composition is prepared, the tuprepreg is wound around a molding die such as a mandrel, molded, and heat-cured.
  • a resin transfer molding method in which a fiber woven fabric is prepared, the fiber woven fabric is laminated on a mold, and a preform prepared by pressing and pressing is vacuum-impregnated with an epoxy resin composition and heat-cured.
  • a sheet winding method in which a prepreg impregnated with an epoxy resin composition in a fiber woven fabric is prepared, wound around a molding die such as a mandrel, molded, and heat-cured.
  • a press molding method in which a prepreg impregnated with an epoxy resin composition in a fiber woven fabric is prepared, the prepreg is laminated on a mold, and the prepreg is heated and pressure-cured by a press.
  • An autoclave molding method in which a prepreg impregnated with an epoxy resin composition in a fiber woven fabric is prepared, the prepreg is placed on a molding tool, covered with a bag film, and heated and pressure-cured in an autoclave. And so on.
  • Epoxy resin 1 Liquid epoxy resin manufactured by ADEKA Co., Ltd. Product name "Adecaledin EP-4300E” (bisphenol A type epoxy resin, epoxy equivalent: 185 g / eq, viscosity: 8 Pa ⁇ s (25 ° C))
  • Epoxy resin 2 Liquid epoxy resin manufactured by Kokuto Kagaku, trade name "EPOKUKDO YD-127” (bisphenol A type epoxy resin, epoxy equivalent: 180-190 g / eq, viscosity: 8-111 Pa ⁇ s (25 ° C))
  • Epoxy resin 3 Liquid epoxy resin manufactured by Kokuto Kagaku, trade name "EPOKUKDO YD-128” (bisphenol A type epoxy resin, epoxy equivalent: 184-194 g / eq, viscosity: 11-15 Pa ⁇ s (25 ° C))
  • Epoxy resin 4 Liquid epoxy resin manufactured by Kokuto Kagaku, trade name "EPOKUKDO YD-128”
  • Curing agent 1 1,3-dihydroxybenzene (resorcin)
  • Curing agent 2 Dihydrocoumarin
  • Curing accelerator 1 Imidazole adduct-type curing accelerator manufactured by ADEKA Corporation
  • Product name "ADEKA HANDNER EH-5011S” potential

Abstract

Provided is an epoxy resin composition which comprises an epoxy resin (A), a hardener (B), and an imidazole adduct type hardening accelerator (C), wherein the hardener (B) includes a compound (B-1) represented by formula (B-1) [wherein R1 represents a hydrogen atom, a halogen atom, a methoxy group, or a hydrocarbon group having 1-12 carbon atoms], the epoxy resin composition having a chlorine content of 1,500 mass ppm or less.

Description

エポキシ樹脂組成物及びその硬化物Epoxy resin composition and its cured product
　本発明は、エポキシ樹脂組成物及びその硬化物に関する。 The present invention relates to an epoxy resin composition and a cured product thereof.
　エポキシ樹脂は、その硬化物が耐熱性、強度、耐薬品性、接着性等に優れていることから、繊維強化材用、電子部品用、接着剤用、塗料用等、様々な用途に適用されている。
　各種用途において、エポキシ樹脂を含む組成物（以下、「エポキシ樹脂組成物」という。）は通常、該組成物を硬化させるための硬化剤を含み、硬化促進剤をさらに含有させることもある〔例えば、特開２０１５－０８３６３４号公報（特許文献１）及び特開２０１３－０３２５１０号公報（特許文献２）〕。 Epoxy resin is applied to various applications such as fiber reinforced plastics, electronic parts, adhesives, paints, etc. because its cured product has excellent heat resistance, strength, chemical resistance, adhesiveness, etc. ing.
In various applications, a composition containing an epoxy resin (hereinafter referred to as "epoxy resin composition") usually contains a curing agent for curing the composition, and may further contain a curing accelerator [for example,. , Japanese Patent Application Laid-Open No. 2015-083634 (Patent Document 1) and Japanese Patent Application Laid-Open No. 2013-032510 (Patent Document 2)].
特開２０１５－０８３６３４号公報Japanese Unexamined Patent Publication No. 2015-083634 特開２０１３－０３２５１０号公報Japanese Unexamined Patent Publication No. 2013-032510
　エポキシ樹脂組成物には、その適用される用途に応じた特性が求められる。一般的に、エポキシ樹脂組成物には、作業性の観点から、長いポットライフが求められる。 The epoxy resin composition is required to have characteristics according to the application to which it is applied. Generally, the epoxy resin composition is required to have a long pot life from the viewpoint of workability.
　本発明の目的は、長いポットライフを有するエポキシ樹脂組成物及びその硬化物を提供することにある。 An object of the present invention is to provide an epoxy resin composition having a long pot life and a cured product thereof.
　本発明は、以下に示すエポキシ樹脂組成物及び硬化物等を提供する。
　［１］　エポキシ樹脂（Ａ）、硬化剤（Ｂ）及びイミダゾールアダクト型硬化促進剤（Ｃ）を含むエポキシ樹脂組成物であって、
　前記硬化剤（Ｂ）は、下記式（Ｂ－１）： The present invention provides the following epoxy resin compositions, cured products, and the like.
[1] An epoxy resin composition containing an epoxy resin (A), a curing agent (B), and an imidazole adduct-type curing accelerator (C).
The curing agent (B) has the following formula (B-1):
Figure JPOXMLDOC01-appb-C000002
［式中、Ｒ１は、水素原子、ハロゲン原子、メトキシ基又は炭素数１～１２の炭化水素基を表す。］
で表される化合物（Ｂ－１）を含み、
　塩素含有量が１６００質量ｐｐｍ以下である、エポキシ樹脂組成物。
　［２］　前記エポキシ樹脂組成物中のエポキシ基含有量に対するフェノール性水酸基含有量のモル比が０．２０～０．７５である、［１］に記載のエポキシ樹脂組成物。
　［３］　前記イミダゾールアダクト型硬化促進剤（Ｃ）の含有量は、前記エポキシ樹脂（Ａ）１００質量部に対して１質量部以上５０質量部以下である、［１］又は［２］に記載のエポキシ樹脂組成物。
　［４］　前記エポキシ樹脂（Ａ）は、分子内にエポキシ基を２個有するエポキシ樹脂を含む、［１］～［３］のいずれかに記載のエポキシ樹脂組成物。
　［５］　前記エポキシ樹脂（Ａ）は、分子内にエポキシ基を２個有するエポキシ樹脂からなり、該エポキシ樹脂の塩素含有量が１７００質量ｐｐｍ以下である、［４］に記載のエポキシ樹脂組成物。
　［６］　［１］～［５］のいずれかに記載のエポキシ樹脂組成物の硬化物。
　［７］　［１］～［５］のいずれかに記載のエポキシ樹脂組成物と繊維を含むプリプレグ。
　［８］　［１］～［５］のいずれかに記載のエポキシ樹脂組成物の硬化物と繊維を含む組成物。
Figure JPOXMLDOC01-appb-C000002
[In the formula, R 1 represents a hydrogen atom, a halogen atom, a methoxy group or a hydrocarbon group having 1 to 12 carbon atoms. ]
Includes compound (B-1) represented by
An epoxy resin composition having a chlorine content of 1600 mass ppm or less.
[2] The epoxy resin composition according to [1], wherein the molar ratio of the phenolic hydroxyl group content to the epoxy group content in the epoxy resin composition is 0.20 to 0.75.
[3] The content of the imidazole adduct-type curing accelerator (C) is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A), according to [1] or [2]. Epoxy resin composition.
[4] The epoxy resin composition according to any one of [1] to [3], wherein the epoxy resin (A) contains an epoxy resin having two epoxy groups in the molecule.
[5] The epoxy resin composition according to [4], wherein the epoxy resin (A) is composed of an epoxy resin having two epoxy groups in the molecule, and the chlorine content of the epoxy resin is 1700 mass ppm or less. ..
[6] A cured product of the epoxy resin composition according to any one of [1] to [5].
[7] A prepreg containing the epoxy resin composition according to any one of [1] to [5] and a fiber.
[8] A composition containing a cured product and fibers of the epoxy resin composition according to any one of [1] to [5].
　長いポットライフを有するエポキシ樹脂組成物及びその硬化物を提供することができる。 It is possible to provide an epoxy resin composition having a long pot life and a cured product thereof.
　＜エポキシ樹脂組成物＞
　本発明に係るエポキシ樹脂組成物（以下、「エポキシ樹脂組成物」ともいう。）は、下記成分：
　エポキシ樹脂（Ａ）、
　硬化剤（Ｂ）、及び
　イミダゾールアダクト型硬化促進剤（Ｃ）
を含む。
　硬化剤（Ｂ）は、上記式（Ｂ－１）で表される化合物（以下、「化合物（Ｂ－１）」ともいう。）を含む。 <Epoxy resin composition>
The epoxy resin composition according to the present invention (hereinafter, also referred to as “epoxy resin composition”) has the following components:
Epoxy resin (A),
Curing agent (B) and imidazole adduct-type curing accelerator (C)
including.
The curing agent (B) contains a compound represented by the above formula (B-1) (hereinafter, also referred to as “compound (B-1)”).
　以下、エポキシ樹脂組成物に含まれる又は含まれ得る各成分及びエポキシ樹脂組成物について詳細に説明する。
　なお、本明細書においてエポキシ樹脂組成物に含まれる又は含まれ得る各成分として例示する化合物は、特に断りのない限り、単独で、又は、複数種を組み合わせて使用することができる。 Hereinafter, each component contained in or may be contained in the epoxy resin composition and the epoxy resin composition will be described in detail.
Unless otherwise specified, the compounds exemplified as the components contained in or may be contained in the epoxy resin composition in the present specification may be used alone or in combination of two or more.
　〔１〕エポキシ樹脂（Ａ）
　エポキシ樹脂（Ａ）としては、分子内にエポキシ基を１個以上有する限り特に制限されないが、エポキシ樹脂組成物の硬化性並びに硬化物の耐熱性及び強度等の観点から、好ましくは、分子内にエポキシ基を２個以上有するエポキシ樹脂を含み、より好ましくは、分子内にエポキシ基を２個有するエポキシ樹脂を含む。 [1] Epoxy resin (A)
The epoxy resin (A) is not particularly limited as long as it has one or more epoxy groups in the molecule, but is preferably in the molecule from the viewpoint of curability of the epoxy resin composition and heat resistance and strength of the cured product. It contains an epoxy resin having two or more epoxy groups, and more preferably contains an epoxy resin having two epoxy groups in the molecule.
　分子内にエポキシ基を２個以上有するエポキシ樹脂としては、例えば、
　ビスフェノールＡ、ビスフェノールＦ、ビスフェノールＡＤ、ビスフェノールＳ、ビフェニルジオール、ナフタレンジオール、フェノール類とアルデヒド類とを縮合又は共縮合させて得られるノボラック樹脂等の多価フェノール化合物と、エピクロルヒドリンとの反応によって得ることができる芳香族グリシジルエーテル型エポキシ樹脂；
　１，４－ブタンジオール、１，６－ヘキサンジオール、ポリエチレングリコール、ポリプロピレングリコール、ネオペンチルグリコール、グリセリン、ペンタエリスリトール、ソルビトール等の多価アルコール化合物と、エピクロルヒドリンとの反応によって得ることができる脂肪族グリシジルエーテル型エポキシ樹脂；
　フタル酸、ヘキサヒドロフタル酸、ダイマー酸等の多塩基酸と、エピクロルヒドリンとの反応によって得ることができるグリシジルエステル型エポキシ樹脂；
　アニリン、トルイジン、ジアミノジフェニルメタン、ｐ－アミノフェノール、ｐ－アミノクレゾール等のアミンと、エピクロルヒドリンとの反応によって得ることができるグリシジルアミン型エポキシ樹脂；
　大豆油、ポリブタジエン等の分子内に２個以上の不飽和結合を有するオレフィン系化合物や、インデン、４－ビニル－１－シクロヘキセン、３－シクロヘキセン－１－カルボン酸（３－シクロヘキセニル）メチル等の分子内に２個以上の不飽和結合を有する環状オレフィン化合物を過酸（過酢酸等）で酸化することによって得ることができる脂環エポキシ樹脂
等が挙げられる。
　上記例示のエポキシ樹脂は、分子内にエポキシ基を２個有するエポキシ樹脂であり得る。 Examples of the epoxy resin having two or more epoxy groups in the molecule include, for example.
Obtained by reacting a polyhydric phenol compound such as bisphenol A, bisphenol F, bisphenol AD, bisphenol S, biphenyldiol, naphthalenediol, novolak resin obtained by condensing or cocondensing phenols with aldehydes, and epichlorohydrin. Aromatic glycidyl ether type epoxy resin that can be used;
An aliphatic glycidyl obtained by reacting a polyhydric alcohol compound such as 1,4-butanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, neopentyl glycol, glycerin, pentaerythritol, and sorbitol with epichlorohydrin. Ether type epoxy resin;
A glycidyl ester type epoxy resin that can be obtained by reacting a polybasic acid such as phthalic acid, hexahydrophthalic acid, or dimer acid with epichlorohydrin;
A glycidylamine type epoxy resin obtained by reacting amines such as aniline, toluidine, diaminodiphenylmethane, p-aminophenol, and p-aminocresol with epichlorohydrin;
Olefin compounds having two or more unsaturated bonds in the molecule such as soybean oil and polybutadiene, inden, 4-vinyl-1-cyclohexene, 3-cyclohexene-1-carboxylic acid (3-cyclohexenyl) methyl and the like. Examples thereof include an alicyclic epoxy resin obtained by oxidizing a cyclic olefin compound having two or more unsaturated bonds in a molecule with a peracid (peracetic acid or the like).
The above-exemplified epoxy resin can be an epoxy resin having two epoxy groups in the molecule.
　分子内にエポキシ基を２個有する芳香族グリシジルエーテル型エポキシ樹脂としては、例えば、ビスフェノールＡ型エポキシ樹脂、ビスフェノールＦ型エポキシ樹脂、ビスフェノールＡＤ型エポキシ樹脂、ビスフェノールＳ型エポキシ樹脂、ビフェニルジオール型エポキシ樹脂、ナフタレンジオール型エポキシ樹脂が挙げられる。
　分子内にエポキシ基を２個有する脂肪族グリシジルエーテル型エポキシ樹脂としては、例えば、水添ビスフェノールＡ型エポキシ樹脂、１，４－ブタンジオールジグリシジルエーテル、１，６－ヘキサンジオールジグリシジルエーテル、ポリエチレングリコールジグリシジルエーテル、ポリプロピレングリコールジグリシジルエーテル、ネオペンチルグリコールジグリシジルエーテルが挙げられる。
　分子内にエポキシ基を２個有するグリシジルエステル型エポキシ樹脂としては、例えば、フタル酸ジグリシジルエステル、ヘキサヒドロフタル酸ジグリシジルエステル、ダイマー酸ジグリシジルエステルが挙げられる。
　分子内にエポキシ基を２個有するグリシジルアミン型エポキシ樹脂としては、例えば、グリシジルアニリン、グリシジルトルイジン等が挙げられる。 Examples of the aromatic glycidyl ether type epoxy resin having two epoxy groups in the molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, bisphenol S type epoxy resin, and biphenyldiol type epoxy resin. , Naphthalene diol type epoxy resin can be mentioned.
Examples of the aliphatic glycidyl ether type epoxy resin having two epoxy groups in the molecule include hydrogenated bisphenol A type epoxy resin, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and polyethylene. Examples thereof include glycol diglycidyl ether, polypropylene glycol diglycidyl ether, and neopentyl glycol diglycidyl ether.
Examples of the glycidyl ester type epoxy resin having two epoxy groups in the molecule include phthalic acid diglycidyl ester, hexahydrophthalic acid diglycidyl ester, and dimer acid diglycidyl ester.
Examples of the glycidylamine type epoxy resin having two epoxy groups in the molecule include glycidylaniline and glycidyltoluidine.
　エポキシ樹脂の粘度、ひいてはエポキシ樹脂組成物の粘度及びポットライフ、硬化性並びに硬化物の耐熱性及び強度等の観点から、エポキシ樹脂（Ａ）は、好ましくは、芳香族グリシジルエーテル型エポキシ樹脂を含み、より好ましくはビスフェノール型エポキシ樹脂を含み、さらに好ましくはビスフェノールＡ型エポキシ樹脂を含む。 The epoxy resin (A) preferably contains an aromatic glycidyl ether type epoxy resin from the viewpoints of the viscosity of the epoxy resin, and thus the viscosity and pot life of the epoxy resin composition, the curability, and the heat resistance and strength of the cured product. , More preferably contains a bisphenol type epoxy resin, and more preferably contains a bisphenol A type epoxy resin.
　エポキシ樹脂（Ａ）は、好ましくは、液状エポキシ樹脂を含み、より好ましくは、エポキシ樹脂（Ａ）が１種又は２種以上のエポキシ樹脂を含む場合において、エポキシ樹脂（Ａ）全体として液状である。
　本明細書において「液状」とは、２５℃において流動性を示すことをいう。本明細書において「液状」である物質は通常、粘性を示し、その粘度は、電磁スピニング法を用いた粘度計（ＥＭＳ粘度計）又はＥＭＳ粘度計では測定できない粘度範囲においてはＥ型粘度計による２５℃での粘度で、０．０００１Ｐａ・ｓ～１０００Ｐａ・ｓであり得、０．００１Ｐａ・ｓ～５００Ｐａ・ｓであってもよい。
　「液状」である場合には、１以上の成分が他の成分に分散している状態が含まれる。 The epoxy resin (A) preferably contains a liquid epoxy resin, and more preferably, when the epoxy resin (A) contains one or more kinds of epoxy resins, the epoxy resin (A) as a whole is liquid. ..
As used herein, the term "liquid" means to exhibit fluidity at 25 ° C. Substances that are "liquid" in the present specification usually show viscosity, and the viscosity is measured by an E-type viscometer in a viscosity range that cannot be measured by a viscometer (EMS viscometer) using an electromagnetic spinning method or an EMS viscometer. The viscosity at 25 ° C. may be 0.0001 Pa · s to 1000 Pa · s and may be 0.001 Pa · s to 500 Pa · s.
When it is "liquid", it includes a state in which one or more components are dispersed in other components.
　エポキシ樹脂（Ａ）全体として液状である場合としては、例えば以下の場合が挙げられる。
　ａ）エポキシ樹脂（Ａ）が１種の液状エポキシ樹脂からなる場合
　ｂ）エポキシ樹脂（Ａ）が２種以上の液状エポキシ樹脂の混合物である場合
　ｃ）エポキシ樹脂（Ａ）が１種以上の液状エポキシ樹脂と１種以上の固体エポキシ樹脂との混合物であり、該混合物が液状である場合
　ｄ）エポキシ樹脂（Ａ）が２種以上の固体エポキシ樹脂の混合物であり、該混合物が液状である場合 Examples of the case where the epoxy resin (A) is liquid as a whole include the following cases.
a) When the epoxy resin (A) is made of one kind of liquid epoxy resin b) When the epoxy resin (A) is a mixture of two or more kinds of liquid epoxy resins c) When the epoxy resin (A) is one or more kinds of liquid When the epoxy resin is a mixture of one or more solid epoxy resins and the mixture is liquid d) When the epoxy resin (A) is a mixture of two or more solid epoxy resins and the mixture is liquid
　したがって、エポキシ樹脂（Ａ）は、固体エポキシ樹脂を含み得る。本明細書において「固体」とは、２５℃において固体であることをいう。固体エポキシ樹脂は、液状エポキシ樹脂に溶解していてもよいし、分散されていてもよい。硬化反応を均一に行うために、固体エポキシ樹脂は均一に溶解していることが好ましい。 Therefore, the epoxy resin (A) may contain a solid epoxy resin. As used herein, the term "solid" means a solid at 25 ° C. The solid epoxy resin may be dissolved or dispersed in the liquid epoxy resin. In order to carry out the curing reaction uniformly, it is preferable that the solid epoxy resin is uniformly dissolved.
　エポキシ樹脂組成物の粘度を好ましい範囲に調整する観点から、エポキシ樹脂（Ａ）の粘度（２種以上のエポキシ樹脂を含む場合には、該２種以上のエポキシ樹脂の混合物としての粘度）は、ＥＭＳ粘度計による２５℃での粘度で、好ましくは５０Ｐａ・ｓ以下であり、より好ましくは４０Ｐａ・ｓ以下であり、さらに好ましくは２０Ｐａ・ｓ以下である。
　エポキシ樹脂（Ａ）の２５℃での粘度は、通常０．０１Ｐａ・ｓ以上であり、０．１Ｐａ・ｓ以上であってもよく、１Ｐａ・ｓ以上であってもよい。
　エポキシ樹脂（Ａ）の粘度は、ＥＭＳ粘度計による２５℃での粘度で、０．０１Ｐａ・ｓ以上５０Ｐａ・ｓ以下が好ましく、０．１Ｐａ・ｓ以上４０Ｐａ・ｓ以下がより好ましく、１Ｐａ・ｓ以上２０Ｐａ・ｓ以下がさらに好ましい。 From the viewpoint of adjusting the viscosity of the epoxy resin composition to a preferable range, the viscosity of the epoxy resin (A) (when two or more kinds of epoxy resins are contained, the viscosity as a mixture of the two or more kinds of epoxy resins) is determined. The viscosity at 25 ° C. according to the EMS viscosity meter is preferably 50 Pa · s or less, more preferably 40 Pa · s or less, and further preferably 20 Pa · s or less.
The viscosity of the epoxy resin (A) at 25 ° C. is usually 0.01 Pa · s or more, may be 0.1 Pa · s or more, or may be 1 Pa · s or more.
The viscosity of the epoxy resin (A) is the viscosity at 25 ° C. by an EMS viscometer, preferably 0.01 Pa · s or more and 50 Pa · s or less, more preferably 0.1 Pa · s or more and 40 Pa · s or less, and 1 Pa · s. More than 20 Pa · s or less is more preferable.
　分子内にエポキシ基を２個以上有するエポキシ樹脂は、１種のみを用いてもよいし、２種以上を併用してもよい。
　ビスフェノールＡ型エポキシ樹脂とビフェニル型エポキシ樹脂を併用すると、良好な耐熱性と良好な引張特性との両立に有利に働くことがあるので好ましい。 As the epoxy resin having two or more epoxy groups in the molecule, only one type may be used, or two or more types may be used in combination.
The combined use of the bisphenol A type epoxy resin and the biphenyl type epoxy resin is preferable because it may be advantageous in achieving both good heat resistance and good tensile properties.
　エポキシ樹脂（Ａ）は、分子内にエポキシ基を２個有するエポキシ樹脂を含むことが好ましい。
　エポキシ樹脂（Ａ）は、分子内にエポキシ基を２個有するエポキシ樹脂と、分子内にエポキシ基を１個有するエポキシ樹脂及び分子内にエポキシ基を３個以上有するエポキシ樹脂からなる群より選ばれる１種以上のエポキシ樹脂とを含んでいてもよい。
　エポキシ樹脂（Ａ）における分子内にエポキシ基を２個有するエポキシ樹脂の含有量は、エポキシ樹脂（Ａ）１００質量部中、例えば５０質量部以上であり、エポキシ樹脂組成物の硬化物の特性（耐熱性及び／又は引張特性等）等の観点から、好ましくは６０質量部以上であり、より好ましくは７０質量部以上であり、さらに好ましくは８０質量部以上であり、なおさらに好ましくは９０質量部以上であり、１００質量部であってもよい。 The epoxy resin (A) preferably contains an epoxy resin having two epoxy groups in the molecule.
The epoxy resin (A) is selected from the group consisting of an epoxy resin having two epoxy groups in the molecule, an epoxy resin having one epoxy group in the molecule, and an epoxy resin having three or more epoxy groups in the molecule. It may contain one or more epoxy resins.
The content of the epoxy resin having two epoxy groups in the molecule of the epoxy resin (A) is, for example, 50 parts by mass or more in 100 parts by mass of the epoxy resin (A), and the characteristics of the cured product of the epoxy resin composition ( From the viewpoint of heat resistance and / or tensile properties, etc.), it is preferably 60 parts by mass or more, more preferably 70 parts by mass or more, still more preferably 80 parts by mass or more, still more preferably 90 parts by mass. As mentioned above, it may be 100 parts by mass.
　エポキシ樹脂（Ａ）のエポキシ当量（２種以上のエポキシ樹脂を含む場合には、該２種以上のエポキシ樹脂の混合物としてのエポキシ当量）は、エポキシ樹脂組成物の硬化物の引張特性、耐熱性及び強度等の観点から、好ましくは３０ｇ／ｅｑ以上５００ｇ／ｅｑ以下であり、より好ましくは４０ｇ／ｅｑ以上４００ｇ／ｅｑ以下であり、さらに好ましくは５０ｇ／ｅｑ以上３００ｇ／ｅｑ以下であり、なおさらに好ましくは５０ｇ／ｅｑ以上２５０ｇ／ｅｑ以下である。
　エポキシ樹脂のエポキシ当量は、ＪＩＳ　Ｋ　７２３６に従って測定することができる。 The epoxy equivalent of the epoxy resin (A) (when two or more kinds of epoxy resins are contained, the epoxy equivalent as a mixture of the two or more kinds of epoxy resins) is the tensile property and heat resistance of the cured product of the epoxy resin composition. From the viewpoint of strength and the like, it is preferably 30 g / eq or more and 500 g / eq or less, more preferably 40 g / eq or more and 400 g / eq or less, still more preferably 50 g / eq or more and 300 g / eq or less, and further. It is preferably 50 g / eq or more and 250 g / eq or less.
The epoxy equivalent of the epoxy resin can be measured according to JIS K 7236.
　〔２〕硬化剤（Ｂ）
　硬化剤（Ｂ）は、エポキシ樹脂（Ａ）を架橋硬化させることができる化合物を含む。該化合物として、硬化剤（Ｂ）は、上記式（Ｂ－１）で表される化合物（Ｂ－１）を含む。
　硬化剤（Ｂ）は、化合物（Ｂ－１）を１種含んでいてもよいし、２種以上含んでいてもよい。 [2] Hardener (B)
The curing agent (B) contains a compound capable of cross-linking and curing the epoxy resin (A). As the compound, the curing agent (B) contains the compound (B-1) represented by the above formula (B-1).
The curing agent (B) may contain one kind of compound (B-1) or two or more kinds.
　上記式（Ｂ－１）中、Ｒ１は、水素原子、ハロゲン原子、メトキシ基又は炭素数１～１２の炭化水素基を表す。
　Ｒ１におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
　Ｒ１における炭素数１～１２の炭化水素基としては、脂肪族基（アルキル基等）、脂環族基（シクロアルキル基等）、芳香族基、脂肪族基と脂環族基との組み合わせからなる炭化水素基、並びに、芳香族基と脂肪族基及び／又は脂環族基との組み合わせからなる炭化水素基等が挙げられる。
　炭化水素基の炭素数は、好ましくは１～８である。エポキシ樹脂組成物の粘度の観点から炭化水素基はメチル基又は１－フェニルエチル基である。
　Ｒ１は、好ましくは、水素原子又は炭化水素基であり、より好ましくは水素原子である。 In the above formula (B-1), R 1 represents a hydrogen atom, a halogen atom, a methoxy group or a hydrocarbon group having 1 to 12 carbon atoms.
Examples of the halogen atom in R 1 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
The hydrocarbon group having 1 to 12 carbon atoms in R 1 includes an aliphatic group (alkyl group, etc.), an alicyclic group group (cycloalkyl group, etc.), an aromatic group, and a combination of an alicyclic group and an alicyclic group. Examples thereof include a hydrocarbon group composed of, and a hydrocarbon group composed of a combination of an aromatic group and an aliphatic group and / or an alicyclic group.
The hydrocarbon group preferably has 1 to 8 carbon atoms. From the viewpoint of the viscosity of the epoxy resin composition, the hydrocarbon group is a methyl group or a 1-phenylethyl group.
R 1 is preferably a hydrogen atom or a hydrocarbon group, and more preferably a hydrogen atom.
　化合物（Ｂ－１）が有する２つのＯＨ基の位置関係は、オルト位、メタ位、パラ位のいずれであってもよいが、エポキシ樹脂組成物の粘度を低減する観点及びエポキシ樹脂組成物中での結晶析出を抑制する観点から、好ましくは、オルト位又はメタ位であり、より好ましくはメタ位である。 The positional relationship between the two OH groups of the compound (B-1) may be any of the ortho-position, the meta-position, and the para-position, but from the viewpoint of reducing the viscosity of the epoxy resin composition and in the epoxy resin composition. From the viewpoint of suppressing crystal precipitation in the above, the ortho-position or the meta-position is preferable, and the meta-position is more preferable.
　化合物（Ｂ－１）は、エポキシ樹脂組成物の粘度を低減する観点、エポキシ樹脂組成物中での結晶析出を抑制する観点、及びエポキシ樹脂組成物を調製する際の溶解温度を低くする観点から、好ましくは、融点が１５０℃以下の化合物であり、より好ましくは、融点が１３０℃以下の化合物である。 The compound (B-1) has a viewpoint of reducing the viscosity of the epoxy resin composition, suppressing crystal precipitation in the epoxy resin composition, and lowering the melting temperature when preparing the epoxy resin composition. A compound having a melting point of 150 ° C. or lower is preferable, and a compound having a melting point of 130 ° C. or lower is more preferable.
　融点が１５０℃以下の化合物（Ｂ－１）としては、例えば、カテコール（１，２－ジヒドロキシベンゼン）、レゾルシン（１，３－ジヒドロキシベンゼン）、４－フルオロ－１，３－ジヒドロキシベンゼン、２－クロロ－１，３－ジヒドロキシベンゼン、４－クロロ－１，３－ジヒドロキシベンゼン、２－メトキシ－１，３－ジヒドロキシベンゼン、４－メトキシ－１，３－ジヒドロキシベンゼン、５－メトキシ－１，３－ジヒドロキシベンゼン、４－メチル－１，３－ジヒドロキシベンゼン、５－メチル－１，３－ジヒドロキシベンゼン、２－エチル－１，３－ジヒドロキシベンゼン、４－エチル－１，３－ジヒドロキシベンゼン、５－エチル－１，３－ジヒドロキシベンゼン、４－（１－フェニルエチル）－１，３－ジヒドロキシベンゼン等が挙げられる。
　１つの好ましい実施形態に係るエポキシ樹脂組成物において、化合物（Ｂ－１）は、１，３－ジヒドロキシベンゼンを含む。 Examples of the compound (B-1) having a melting point of 150 ° C. or lower include catechol (1,2-dihydroxybenzene), resorcin (1,3-dihydroxybenzene), 4-fluoro-1,3-dihydroxybenzene, 2-. Chloro-1,3-dihydroxybenzene, 4-chloro-1,3-dihydroxybenzene, 2-methoxy-1,3-dihydroxybenzene, 4-methoxy-1,3-dihydroxybenzene, 5-methoxy-1,3- Dihydroxybenzene, 4-methyl-1,3-dihydroxybenzene, 5-methyl-1,3-dihydroxybenzene, 2-ethyl-1,3-dihydroxybenzene, 4-ethyl-1,3-dihydroxybenzene, 5-ethyl Examples thereof include -1,3-dihydroxybenzene and 4- (1-phenylethyl) -1,3-dihydroxybenzene.
In the epoxy resin composition according to one preferred embodiment, compound (B-1) comprises 1,3-dihydroxybenzene.
　エポキシ樹脂組成物に化合物（Ｂ－１）を含有させることは、エポキシ樹脂組成物の硬化物の特性（耐熱性及び／又は引張特性等）を改善させるうえで有利である。
　エポキシ樹脂組成物は、フェノール性水酸基を３個以上有する化合物をさらに含んでいてもよい。該化合物を含有させることにより、エポキシ樹脂組成物の硬化物の特性（耐熱性及び／又は引張特性等）を改善できることがある。 The inclusion of the compound (B-1) in the epoxy resin composition is advantageous in improving the properties (heat resistance and / or tensile properties, etc.) of the cured product of the epoxy resin composition.
The epoxy resin composition may further contain a compound having three or more phenolic hydroxyl groups. By containing the compound, the properties (heat resistance and / or tensile properties, etc.) of the cured product of the epoxy resin composition may be improved.
　フェノール性水酸基を３個以上有する化合物としては、化合物（Ｂ－１）が有するベンゼン環に直接結合する水素原子の１個を水酸基で置換した化合物、フェノール樹脂、ノボラック樹脂等が挙げられる。 Examples of the compound having three or more phenolic hydroxyl groups include a compound in which one of the hydrogen atoms directly bonded to the benzene ring of the compound (B-1) is replaced with a hydroxyl group, a phenol resin, a novolak resin and the like.
　また、エポキシ樹脂組成物は、フェノール性水酸基を１個有する化合物を含んでいてもよい。フェノール性水酸基を１個有する化合物としては、フェノール、クレゾール、キシレノール、ｔ－ブチルフェノール等が挙げられる。 Further, the epoxy resin composition may contain a compound having one phenolic hydroxyl group. Examples of the compound having one phenolic hydroxyl group include phenol, cresol, xylenol, t-butylphenol and the like.
　エポキシ樹脂組成物中のエポキシ基含有量に対するフェノール性水酸基含有量のモル比は、例えば０．２０以上０．７５以下であり、硬化物の特性（耐熱性及び／又は引張特性等）を改善させる観点から、好ましくは０．２５以上０．６７以下であり、より好ましくは０．３以上０．６以下であり、さらに好ましくは０．３５以上０．５５以下であり、なおさらに好ましくは０．４以上０．５以下である。 The molar ratio of the phenolic hydroxyl group content to the epoxy group content in the epoxy resin composition is, for example, 0.20 or more and 0.75 or less, which improves the properties of the cured product (heat resistance and / or tensile properties, etc.). From the viewpoint, it is preferably 0.25 or more and 0.67 or less, more preferably 0.3 or more and 0.6 or less, still more preferably 0.35 or more and 0.55 or less, and further preferably 0. 4 or more and 0.5 or less.
　「エポキシ樹脂組成物中のエポキシ基含有量」とは、エポキシ樹脂（Ａ）が有するエポキシ基の数（モル数）をいう。
　「フェノール性水酸基含有量」とは、エポキシ樹脂組成物中のフェノール性水酸基含有量であり、化合物（Ｂ－１）が有するフェノール性水酸基の数（モル数）と、化合物（Ｂ－１）以外のフェノール性水酸基を有するフェノール系化合物が有するフェノール性水酸基の数（モル数）との合計をいう。 The "epoxy group content in the epoxy resin composition" refers to the number (number of moles) of epoxy groups contained in the epoxy resin (A).
The "phenolic hydroxyl group content" is the phenolic hydroxyl group content in the epoxy resin composition, other than the number of phenolic hydroxyl groups (number of moles) of the compound (B-1) and the compound (B-1). It refers to the total number of phenolic hydroxyl groups (number of moles) of the phenolic compound having phenolic hydroxyl groups.
　エポキシ樹脂組成物における化合物（Ｂ－１）の含有量は、好ましくは上記モル比が上記範囲内となる量であり、エポキシ樹脂（Ａ）１００質量部に対して、例えば１質量部以上３０質量部以下であり、好ましくは５質量部以上２５質量部以下であり、より好ましくは８質量部以上２２質量部以下である。 The content of the compound (B-1) in the epoxy resin composition is preferably an amount in which the molar ratio is within the above range, and is, for example, 1 part by mass or more and 30 parts by mass with respect to 100 parts by mass of the epoxy resin (A). It is 5 parts by mass or more, preferably 25 parts by mass or less, and more preferably 8 parts by mass or more and 22 parts by mass or less.
　硬化剤（Ｂ）は、下記式（Ｂ－２）：
Figure JPOXMLDOC01-appb-C000003
で表される化合物（以下、「化合物（Ｂ－２）」ともいう。）をさらに含んでいてもよい。
　硬化剤（Ｂ）は、化合物（Ｂ－２）を１種含んでいてもよいし、２種以上含んでいてもよい。 The curing agent (B) has the following formula (B-2):
Figure JPOXMLDOC01-appb-C000003
The compound represented by (hereinafter, also referred to as “compound (B-2)”) may be further contained.
The curing agent (B) may contain one kind of compound (B-2) or two or more kinds.
　上記式（Ｂ－２）中、Ｒ２は、水素原子、ハロゲン原子、メチル基又はメトキシ基を表す。
　Ｒ２におけるハロゲン原子としては、フッ素原子、塩素原子、臭素原子、ヨウ素原子が挙げられる。
　Ｒ２は、融点の観点から、好ましくは、水素原子、メチル基又はメトキシ基であり、より好ましくは水素原子である。 In the above formula (B-2), R 2 represents a hydrogen atom, a halogen atom, a methyl group or a methoxy group.
Examples of the halogen atom in R 2 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.
R 2, from the viewpoint of the melting point, preferably a hydrogen atom, a methyl group or a methoxy group, more preferably a hydrogen atom.
　エポキシ樹脂組成物に化合物（Ｂ－２）を含有させることは、エポキシ樹脂組成物の低粘度化に有利となり得る。
　また、エポキシ樹脂組成物に化合物（Ｂ－２）を含有させることは、エポキシ樹脂組成物の硬化物において、引張特性を高めるうえで有利となり得る。この際、硬化物の耐熱性を低下させることなく、破断伸び特性を高め得る。 Incorporating the compound (B-2) in the epoxy resin composition may be advantageous in reducing the viscosity of the epoxy resin composition.
Further, the inclusion of the compound (B-2) in the epoxy resin composition may be advantageous in enhancing the tensile properties in the cured product of the epoxy resin composition. At this time, the breaking elongation property can be improved without lowering the heat resistance of the cured product.
　１つの好ましい実施形態に係るエポキシ樹脂組成物において、化合物（Ｂ－１）が１，３－ジヒドロキシベンゼンを含み、かつ、化合物（Ｂ－２）がジヒドロクマリン（Ｒ２：水素原子）を含む。 In the epoxy resin composition according to one preferred embodiment, the compound comprises (B-1) is a 1,3-dihydroxybenzene and a compound (B-2) is Dihydrocoumarin: containing (R 2 a hydrogen atom).
　エポキシ樹脂組成物が化合物（Ｂ－２）を含む場合、エポキシ樹脂組成物における化合物（Ｂ－２）の含有量は、エポキシ樹脂（Ａ）１００質量部に対して、例えば０．１質量部以上であり、上記効果をより効果的に発現させる観点から、好ましくは１質量部以上であり、より好ましくは２質量部以上である。 When the epoxy resin composition contains the compound (B-2), the content of the compound (B-2) in the epoxy resin composition is, for example, 0.1 part by mass or more with respect to 100 parts by mass of the epoxy resin (A). From the viewpoint of more effectively exhibiting the above effects, the amount is preferably 1 part by mass or more, and more preferably 2 parts by mass or more.
　エポキシ樹脂組成物における化合物（Ｂ－２）の含有量が過度に大きいと、エポキシ樹脂組成物の硬化が不十分となり得る。したがって、エポキシ樹脂組成物が化合物（Ｂ－２）を含む場合、エポキシ樹脂組成物における化合物（Ｂ－２）の含有量は、エポキシ樹脂（Ａ）１００質量部に対して、好ましくは５０質量部以下であり、より好ましくは４０質量部以下であり、さらに好ましくは３０質量部以下である。 If the content of the compound (B-2) in the epoxy resin composition is excessively large, the curing of the epoxy resin composition may be insufficient. Therefore, when the epoxy resin composition contains the compound (B-2), the content of the compound (B-2) in the epoxy resin composition is preferably 50 parts by mass with respect to 100 parts by mass of the epoxy resin (A). It is less than or equal to, more preferably 40 parts by mass or less, still more preferably 30 parts by mass or less.
　エポキシ樹脂組成物が化合物（Ｂ－１）とともに化合物（Ｂ－２）を含む場合、エポキシ樹脂組成物の硬化性の観点から、エポキシ樹脂組成物における化合物（Ｂ－１）の含有量に対する化合物（Ｂ－２）の含有量の比は、質量比で、好ましくは０．２０～０．９５であり、より好ましくは０．２０～０．７５であり、さらに好ましくは０．２０～０．５０である。 When the epoxy resin composition contains the compound (B-2) together with the compound (B-1), the compound with respect to the content of the compound (B-1) in the epoxy resin composition from the viewpoint of curability of the epoxy resin composition ( The content ratio of B-2) is preferably 0.20 to 0.95, more preferably 0.20 to 0.75, and further preferably 0.20 to 0.50 in terms of mass ratio. Is.
　エポキシ樹脂組成物は、上記した以外の他のエポキシ樹脂用硬化剤をさらに含んでいてもよい。他のエポキシ樹脂用硬化剤は、従来公知の硬化剤であってよい。
　ただし、エポキシ樹脂組成物の粘度若しくはポットライフ、硬化物の特性（耐熱性及び／又は引張特性等）の観点から、硬化剤（Ｂ）における他のエポキシ樹脂用硬化剤の含有量は、硬化剤（Ｂ）の全体量を１００質量部とするとき、好ましくは２０質量部以下であり、より好ましくは１０質量部以下であり、さらに好ましくは５質量部以下であり、なおさらに好ましくは１質量部以下（例えば０質量部）である。 The epoxy resin composition may further contain other curing agents for epoxy resins other than those described above. The other curing agent for epoxy resin may be a conventionally known curing agent.
However, from the viewpoint of the viscosity or pot life of the epoxy resin composition and the characteristics of the cured product (heat resistance and / or tensile characteristics, etc.), the content of the curing agent for other epoxy resins in the curing agent (B) is the curing agent. When the total amount of (B) is 100 parts by mass, it is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, still more preferably 5 parts by mass or less, still more preferably 1 part by mass. The following (for example, 0 parts by mass).
　〔３〕イミダゾールアダクト型硬化促進剤（Ｃ）
　本明細書において「硬化促進剤」とは、硬化反応を促進させる機能を有する剤をいう。ここでいう「促進」には、硬化反応を開始させる場合も含まれる。
　本発明では、硬化促進剤の中でも、イミダゾールアダクト型硬化促進剤（Ｃ）を用いる。イミダゾールアダクト型硬化促進剤（Ｃ）の使用は、エポキシ樹脂組成物のポットライフと硬化性（速硬化性等）との両立に有利となり得る。これは、イミダゾールアダクト型硬化促進剤（Ｃ）がエポキシ樹脂（Ａ）同士の硬化反応並びにエポキシ樹脂（Ａ）と化合物（Ｂ－１）及び／又は化合物（Ｂ－２）との硬化反応を効果的に開始及び／又は促進させることができるとともに、イミダゾールアダクト型硬化促進剤（Ｃ）が一般的には潜在性を有しているために、ポットライフの延長に有利に働くためであると推定される。 [3] Imidazole adduct-type curing accelerator (C)
As used herein, the term "curing accelerator" refers to an agent having a function of accelerating a curing reaction. The term "promotion" as used herein includes the case of initiating a curing reaction.
In the present invention, the imidazole adduct-type curing accelerator (C) is used among the curing accelerators. The use of the imidazole adduct-type curing accelerator (C) may be advantageous in achieving both the pot life of the epoxy resin composition and the curing property (fast curing property, etc.). This is because the imidazole adduct-type curing accelerator (C) has an effect of the curing reaction between the epoxy resins (A) and the curing reaction between the epoxy resin (A) and the compound (B-1) and / or the compound (B-2). It is presumed that this is because the imidazole adduct-type curing accelerator (C) generally has potential and thus works favorably for prolonging the pot life. Will be done.
　また、硬化促進剤としてイミダゾールアダクト型硬化促進剤（Ｃ）を用いることは、比較的低温での硬化反応を可能にするうえでも有利であり、また、エポキシ樹脂組成物の保存安定性を高めるうえでも有利である。
　イミダゾールアダクト型硬化促進剤（Ｃ）は、１種のみを用いてもよいし、２種以上を併用してもよい。 Further, using the imidazole adduct-type curing accelerator (C) as the curing accelerator is advantageous in enabling the curing reaction at a relatively low temperature, and also in improving the storage stability of the epoxy resin composition. But it is advantageous.
As the imidazole adduct type curing accelerator (C), only one kind may be used, or two or more kinds may be used in combination.
　「潜在性」とは、エポキシ樹脂の存在下、又は、エポキシ樹脂及び硬化剤の存在下においても室温（２５℃）では安定に貯蔵できる一方で、熱、光又は圧力等により硬化反応を促進させる機能を発現することができる性質をいう。
　本発明に用いられるイミダゾールアダクト型硬化促進剤（Ｃ）は、好ましくは、熱により硬化反応を促進させる機能を発現することができる性質（熱潜在性）を有する。 "Potential" means that the product can be stably stored at room temperature (25 ° C.) even in the presence of an epoxy resin or an epoxy resin and a curing agent, while promoting the curing reaction by heat, light, pressure, or the like. A property that can express a function.
The imidazole adduct-type curing accelerator (C) used in the present invention preferably has a property (thermal potential) capable of exhibiting a function of accelerating the curing reaction by heat.
　イミダゾールアダクト型硬化促進剤（Ｃ）は、イミダゾール化合物に付加体が付加した化合物である。付加体の付加によって潜在性が付与される。付加体は、例えば、イミダゾール化合物との反応によりイミダゾール環のＮ原子、好ましくは１－位のＮ原子に結合することができる化合物である。該結合は、通常、共有結合である。
　付加体は、良好な潜在性を付与できる化合物であることが好ましく、例えば、エポキシ化合物、イソシアネート化合物、（メタ）アクリル系化合物、尿素化合物等が挙げられる。 The imidazole adduct-type curing accelerator (C) is a compound in which an adduct is added to the imidazole compound. The addition of the adduct gives the potential. The adduct is, for example, a compound that can be bonded to the N atom of the imidazole ring, preferably the N atom at the 1-position, by reacting with the imidazole compound. The bond is usually a covalent bond.
The adduct is preferably a compound that can impart good potential, and examples thereof include epoxy compounds, isocyanate compounds, (meth) acrylic compounds, and urea compounds.
　イミダゾールアダクト型硬化促進剤（Ｃ）は、イミダゾール化合物に上記付加体を反応させることによって得られる高分子化合物であることが好ましい。
　また、上記付加体をさらにフェノール樹脂等との固溶体としたり、有機酸やホウ酸化合物等で表面処理をしてもよい。
　このようにして製造されたイミダゾールアダクト型硬化促進剤（Ｃ）は、通常、０．５～５０μｍ程度の粒径に粉砕され、エポキシ樹脂に分散して使用される。
　イミダゾールアダクト型硬化促進剤（Ｃ）は、一般にエポキシ樹脂に対する常温における溶解性が低いことから、エポキシ樹脂と混合されたイミダゾールアダクト型硬化促進剤（Ｃ）は、熱潜在性を示す場合が多い。 The imidazole adduct-type curing accelerator (C) is preferably a polymer compound obtained by reacting the imidazole compound with the above adduct.
Further, the adduct may be further made into a solid solution with a phenol resin or the like, or may be surface-treated with an organic acid, a boric acid compound or the like.
The imidazole adduct-type curing accelerator (C) thus produced is usually pulverized to a particle size of about 0.5 to 50 μm and dispersed in an epoxy resin for use.
Since the imidazole adduct-type curing accelerator (C) generally has low solubility in an epoxy resin at room temperature, the imidazole adduct-type curing accelerator (C) mixed with the epoxy resin often exhibits thermal potential.
　イミダゾールアダクト型硬化促進剤（Ｃ）は、公知の特許文献、例えば、特開昭５９－０５３５２６号公報、特開昭６０－００４５２４号公報、特開昭６０－０７２９１７号公報、特開２００５－２０６７４４号公報、特開平０６－０７３１５６号公報、特開平０６－１７２４９５号公報、特開２００８－２１４５６７号公報、特開２０１４－１７７５２５号公報等に記載されている方法で製造することができる。 The imidazole adduct-type curing accelerator (C) is described in known patent documents, for example, JP-A-59-053526, JP-A-60-004524, JP-A-60-072917, JP-A-2005-206744. It can be produced by the methods described in JP-A-06-0731556, JP-A-06-172495, JP-A-2008-214567, JP-A-2014-177525, and the like.
　イミダゾールアダクト型硬化促進剤（Ｃ）として市販品が用いられてもよい。イミダゾールアダクト型硬化促進剤（Ｃ）の市販品としては、いずれも商品名で、「フジキュアー　ＦＸＲ－１０２０」、「同　ＦＸＲ－１０３０」、「同　ＦＸＲ－１０３２」、「同　ＦＸＲ－１０８１」、「同　ＦＸＲ－１１２１」、「同　ＦＸＲ－１１３１」（以上、株式会社Ｔ＆Ｋ　ＴＯＫＡ製）；「アデカハードナー　ＥＨ－５０１１Ｓ」、「同　ＥＨ－５０４６Ｓ」（以上、株式会社ＡＤＥＫＡ製）；「キュアダクト　Ｐ－０５０５」（四国化成工業株式会社製）；「アミキュア　ＰＮ－２３」、「同　ＰＮ－２３Ｊ」、「同　ＰＮ－３１」、「同　ＰＮ－３１Ｊ」、「同　ＰＮ－４０」、「同　ＰＮ－４０Ｊ」、「同　ＰＮ－５０」、「同　ＰＮ－Ｆ」、「同　ＰＮ－Ｈ」（以上、味の素ファインテクノ株式会社製）等が挙げられる。 A commercially available product may be used as the imidazole adduct-type curing accelerator (C). The commercially available products of the imidazole ADEKA duct type curing accelerator (C) are all trade names, "Fujicure FXR-1020", "FXR-1030", "FXR-1032", "FXR-1081", and "Fujicure FXR-1020". Same FXR-1121 "," Same FXR-1131 "(above, T & K TOKA Co., Ltd.);" Adeka Hardener EH-5011S "," Same EH-5046S "(above, ADEKA Co., Ltd.);" Cure Duct P- 0505 "(manufactured by Shikoku Kasei Kogyo Co., Ltd.);" Amicure PN-23 "," Same PN-23J "," Same PN-31 "," Same PN-31J "," Same PN-40 "," Same PN- Examples include "40J", "Same PN-50", "Same PN-F", "Same PN-H" (all manufactured by Ajinomoto Fine Techno Co., Ltd.).
　エポキシ樹脂組成物は、本発明の効果を阻害しない限り、イミダゾールアダクト型硬化促進剤（Ｃ）以外の他の硬化促進剤を１種又は２種以上含んでいてもよい。
　他の硬化促進剤としては特に制限されず、例えば、第３級アミン化合物及びその塩、イミダゾール化合物（非アダクト型）、イミダゾリウム塩、トリフェニルホスフィンやホスホニウム塩等のリン系化合物、カルボン酸金属塩、２，３－ジヒドロ－１Ｈ－ピロロ［１，２－ａ］ベンズイミダゾール（ＴＢＺ）等が挙げられる。 The epoxy resin composition may contain one or more curing accelerators other than the imidazole adduct-type curing accelerator (C) as long as the effects of the present invention are not impaired.
The other curing accelerator is not particularly limited, and is, for example, a tertiary amine compound and a salt thereof, an imidazole compound (non-adduct type), an imidazolium salt, a phosphorus compound such as triphenylphosphine or a phosphonium salt, and a metal carboxylate. Examples thereof include salts, 2,3-dihydro-1H-pyrrolo [1,2-a] benzimidazole (TBZ) and the like.
　上記効果をより効果的に発現させる観点から、硬化促進剤における他の硬化促進剤の含有量は、硬化促進剤の全体量を１００質量部とするとき、好ましくは２０質量部以下であり、より好ましくは１０質量部以下であり、さらに好ましくは５質量部以下であり、なおさらに好ましくは１質量部以下（例えば０質量部）である。 From the viewpoint of more effectively exhibiting the above effects, the content of the other curing accelerator in the curing accelerator is preferably 20 parts by mass or less, more preferably 20 parts by mass or less, when the total amount of the curing accelerator is 100 parts by mass. It is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, still more preferably 1 part by mass or less (for example, 0 parts by mass).
　エポキシ樹脂組成物におけるイミダゾールアダクト型硬化促進剤（Ｃ）の含有量は、エポキシ樹脂（Ａ）１００質量部に対して、例えば１質量部以上５０質量部以下であり、上記効果をより効果的に発現させる観点から、好ましくは２質量部以上４０質量部以下であり、より好ましくは３質量部以上３０質量部以下であり、さらに好ましくは５質量部以上２０質量部以下であり、なおさらに好ましくは５質量部以上１５質量部以下である。 The content of the imidazole adduct-type curing accelerator (C) in the epoxy resin composition is, for example, 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A), and the above effect can be more effectively achieved. From the viewpoint of expression, it is preferably 2 parts by mass or more and 40 parts by mass or less, more preferably 3 parts by mass or more and 30 parts by mass or less, still more preferably 5 parts by mass or more and 20 parts by mass or less, and even more preferably. It is 5 parts by mass or more and 15 parts by mass or less.
　〔４〕その他の配合成分
　エポキシ樹脂組成物は、上述した成分以外の他の配合成分をさらに含むことができる。
　他の配合成分としては、例えば、ゴム粒子、無機粒子（アルミニウム等の金属、炭酸カルシウムやシリカ等の金属化合物からなる粒子）、難燃剤、表面処理剤、離型剤、抗菌剤、レベリング剤、消泡剤、揺変剤、熱安定剤、光安定剤、紫外線吸収剤、着色剤、カップリング剤、界面活性剤、金属アルコキシド、熱可塑性樹脂、希釈剤等が挙げられる。
　他の配合成分は、１種のみを用いてもよいし、２種以上を併用してもよい。 [4] Other compounding components The epoxy resin composition may further contain other compounding components other than the above-mentioned components.
Other compounding components include, for example, rubber particles, inorganic particles (particles composed of a metal such as aluminum and a metal compound such as calcium carbonate and silica), a flame retardant, a surface treatment agent, a mold release agent, an antibacterial agent, and a leveling agent. Examples thereof include defoaming agents, rocking agents, heat stabilizers, light stabilizers, ultraviolet absorbers, colorants, coupling agents, surfactants, metal alkoxides, thermoplastic resins, diluents and the like.
As the other compounding ingredients, only one kind may be used, or two or more kinds may be used in combination.
　ゴム粒子の添加により、エポキシ樹脂組成物の硬化物において、良好な耐熱性を維持しながら、靱性を向上させることが可能となる。 The addition of rubber particles makes it possible to improve the toughness of the cured product of the epoxy resin composition while maintaining good heat resistance.
　ゴム粒子としては、例えば、コアシェル型アクリルゴム粒子、表面修飾型アクリルゴム粒子、架橋ＮＢＲ粒子、シリコーンゴム粒子等が挙げられる。これらのゴム粒子は、従来公知のものであってよい。
　ゴム粒子の平均粒子径は、例えば、０．０５μｍ以上１μｍ以下であり、好ましくは０．２μｍ以上０．５μｍ以下である。
　ゴム粒子は、１種のみを用いてもよいし、２種以上を併用してもよい。 Examples of the rubber particles include core-shell type acrylic rubber particles, surface-modified acrylic rubber particles, crosslinked NBR particles, silicone rubber particles, and the like. These rubber particles may be conventionally known.
The average particle size of the rubber particles is, for example, 0.05 μm or more and 1 μm or less, preferably 0.2 μm or more and 0.5 μm or less.
Only one type of rubber particles may be used, or two or more types may be used in combination.
　ゴム粒子として市販品が用いられてもよいし、あらかじめエポキシ樹脂にゴム粒子が分散された分散品を用いてもよい。ゴム粒子又は該分散品の市販品としては、いずれも商品名で、「アクリセット　ＢＰＡ３２８」（株式会社日本触媒製）；「カネエース　ＭＸ－１５３」、「同　ＭＸ－１５４」、「同　ＭＸ－２５７」、「同　ＭＸ－９６０」（以上、株式会社カネカ製）；「スタフィロイド　ＡＣ」シリーズ（アイカ工業株式会社製）；「パラロイド　ＥＸＬ」シリーズ（ダウ社製）；「メタブレン」（三菱ケミカル株式会社製）；「ＸＥＲ－９１」（ＪＳＲ株式会社製）；「ＧＥＮＩＯＰＥＲＬ　Ｐ５２」（旭化成ワッカーシリコーン株式会社製）等が挙げられる。 A commercially available product may be used as the rubber particles, or a dispersed product in which the rubber particles are dispersed in an epoxy resin in advance may be used. As commercial products of rubber particles or the dispersed products, the trade names are "Acryset BPA328" (manufactured by Nippon Catalyst Corporation); "Kaneace MX-153", "MX-154", "MX-257". , "Same MX-960" (above, Kaneka Co., Ltd.); "Staphyroid AC" series (Aika Kogyo Co., Ltd.); "Pararoid EXL" series (Dow); "Metabren" (Mitsubishi Chemical Co., Ltd.) ); "XER-91" (manufactured by JSR Corporation); "GENIOPERL P52" (manufactured by Asahi Kasei Wacker Silicone Co., Ltd.) and the like.
　エポキシ樹脂組成物におけるゴム粒子の含有量は、エポキシ樹脂（Ａ）１００質量部に対して、例えば１質量部以上１００質量部以下であり、上記効果をより効果的に発現させる観点から、好ましくは５質量部以上８０質量部以下であり、より好ましくは１０質量部以上５０質量部以下である。 The content of the rubber particles in the epoxy resin composition is, for example, 1 part by mass or more and 100 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A), and is preferable from the viewpoint of more effectively exhibiting the above effect. It is 5 parts by mass or more and 80 parts by mass or less, and more preferably 10 parts by mass or more and 50 parts by mass or less.
　エポキシ樹脂組成物におけるゴム粒子の含有量は、組成物全体に対して、例えば１質量％以上５０質量％以下であり、上記効果をより効果的に発現させる観点から、好ましくは２質量％以上３０質量％以下であり、より好ましくは２質量％以上２０質量％以下である。 The content of the rubber particles in the epoxy resin composition is, for example, 1% by mass or more and 50% by mass or less with respect to the entire composition, and from the viewpoint of more effectively exhibiting the above effect, it is preferably 2% by mass or more and 30% by mass. It is 1% by mass or less, more preferably 2% by mass or more and 20% by mass or less.
　〔５〕エポキシ樹脂組成物
　エポキシ樹脂組成物は、塩素含有量が１６００質量ｐｐｍ（ｍｇ／ｋｇ）以下である。該エポキシ樹脂組成物は、塩素含有量が１６００質量ｐｐｍを超えるエポキシ樹脂組成物に比べて、優れたポットライフを有することができる。
　上記塩素含有量は、ＪＩＳ　Ｋ　７２４３－３：２００５に従う全塩素量を意味し、同規格に準拠して測定される。 [5] Epoxy resin composition The epoxy resin composition has a chlorine content of 1600 mass ppm (mg / kg) or less. The epoxy resin composition can have an excellent pot life as compared with an epoxy resin composition having a chlorine content of more than 1600 mass ppm.
The chlorine content means the total chlorine content according to JIS K 7243-3: 2005, and is measured according to the same standard.
　エポキシ樹脂組成物の塩素含有量は、ポットライフをさらに向上させる観点から、好ましくは１５００質量ｐｐｍ以下であり、より好ましくは１４５０質量ｐｐｍ以下であり、さらに好ましくは１４００質量ｐｐｍ以下であり、なおさらに好ましくは１３５０質量ｐｐｍ以下であり、特に好ましくは１３００質量ｐｐｍ以下（例えば１２５０質量ｐｐｍ以下）である。
　エポキシ樹脂組成物の塩素含有量はゼロであってもよく、例えば１００質量ｐｐｍ以上、２００質量ｐｐｍ以上、５００質量ｐｐｍ以上又は１０００質量ｐｐｍ以上であってもよい。
　エポキシ樹脂組成物の塩素含有量は、好ましくは１００質量ｐｐｍ以上１５００質量ｐｐｍ以下であり、より好ましくは２００質量ｐｐｍ以上１４５０質量ｐｐｍ以下であり、さらに好ましくは５００質量ｐｐｍ以上１４００質量ｐｐｍ以下であり、なおさらに好ましくは１０００質量ｐｐｍ以上１３５０質量ｐｐｍ以下であり、特に好ましくは１０００質量ｐｐｍ以上１３００質量ｐｐｍ以下である。 The chlorine content of the epoxy resin composition is preferably 1500 mass ppm or less, more preferably 1450 mass ppm or less, still more preferably 1400 mass ppm or less, and further preferably 1400 mass ppm or less, from the viewpoint of further improving the pot life. It is preferably 1350 mass ppm or less, and particularly preferably 1300 mass ppm or less (for example, 1250 mass ppm or less).
The chlorine content of the epoxy resin composition may be zero, for example, 100 mass ppm or more, 200 mass ppm or more, 500 mass ppm or more, or 1000 mass ppm or more.
The chlorine content of the epoxy resin composition is preferably 100% by mass or more and 1500% by mass or less, more preferably 200% by mass or more and 1450% by mass or less, and further preferably 500% by mass or more and 1400% by mass or less. Further, it is more preferably 1000 mass ppm or more and 1350 mass ppm or less, and particularly preferably 1000 mass ppm or more and 1300 mass ppm or less.
　エポキシ樹脂組成物に含まれるエポキシ樹脂（Ａ）は、分子内にエポキシ基を２個有するエポキシ樹脂からなることが好ましく、エポキシ樹脂組成物のポットライフを向上させる観点から、該エポキシ樹脂の塩素含有量（２種以上のエポキシ樹脂を含む場合には、該２種以上のエポキシ樹脂の混合物としての塩素含有量）は、好ましくは１７００質量ｐｐｍ以下であり、より好ましくは１５００質量ｐｐｍ以下であり、さらに好ましくは１４５０質量ｐｐｍ以下であり、なおさらに好ましくは１４００質量ｐｐｍ以下であり、特に好ましくは１３５０質量ｐｐｍ以下である。該エポキシ樹脂の塩素含有量はゼロであってもよく、例えば１００質量ｐｐｍ以上、２００質量ｐｐｍ以上、５００質量ｐｐｍ以上又は１０００質量ｐｐｍ以上であってもよい。
　エポキシ樹脂（Ａ）の塩素含有量は、好ましくは１００質量ｐｐｍ以上１７００質量ｐｐｍ以下であり、より好ましくは２００質量ｐｐｍ以上１５００質量ｐｐｍ以下であり、さらに好ましくは５００質量ｐｐｍ以上１４５０質量ｐｐｍ以下であり、なおさらに好ましくは１０００質量ｐｐｍ以上１４００質量ｐｐｍ以下であり、特に好ましくは１０００質量ｐｐｍ以上１３５０質量ｐｐｍ以下である。 The epoxy resin (A) contained in the epoxy resin composition is preferably composed of an epoxy resin having two epoxy groups in the molecule, and from the viewpoint of improving the pot life of the epoxy resin composition, the epoxy resin contains chlorine. The amount (in the case of containing two or more kinds of epoxy resins, the chlorine content as a mixture of the two or more kinds of epoxy resins) is preferably 1700 mass ppm or less, more preferably 1500 mass ppm or less. It is more preferably 1450 mass ppm or less, further preferably 1400 mass ppm or less, and particularly preferably 1350 mass ppm or less. The chlorine content of the epoxy resin may be zero, and may be, for example, 100 mass ppm or more, 200 mass ppm or more, 500 mass ppm or more, or 1000 mass ppm or more.
The chlorine content of the epoxy resin (A) is preferably 100% by mass or more and 1700% by mass or less, more preferably 200% by mass or more and 1500% by mass or less, and further preferably 500% by mass or more and 1450% by mass or less. Yes, more preferably 1000 mass ppm or more and 1400 mass ppm or less, and particularly preferably 1000 mass ppm or more and 1350 mass ppm or less.
　エポキシ樹脂（Ａ）、化合物（Ｂ－１）及びイミダゾールアダクト型硬化促進剤（Ｃ）、並びに任意で添加されるその他の成分を含む本発明に係るエポキシ樹脂組成物は、好ましくは液状である。「液状」の意味は上述のとおりである。
　液状のエポキシ樹脂組成物において、それに含まれるすべての成分は、溶解している状態であってもよいし、１以上の成分が他の成分に分散されている状態であってもよい。 The epoxy resin composition according to the present invention containing the epoxy resin (A), the compound (B-1) and the imidazole adduct-type curing accelerator (C), and other components optionally added is preferably liquid. The meaning of "liquid" is as described above.
In the liquid epoxy resin composition, all the components contained therein may be in a dissolved state, or one or more components may be dispersed in other components.
　本発明に係る液状のエポキシ樹脂組成物は、低粘度を有することができる。低粘度であることによって、エポキシ樹脂組成物を用いた製品の生産性及び作業性を向上させ得る。例えば、エポキシ樹脂組成物の硬化物と繊維等とを含む成形材（組成物）を製造するための方法は、繊維の織物や繊維束にエポキシ樹脂組成物を含浸させる工程を含むところ、低粘度のエポキシ樹脂組成物を用いることにより、エポキシ樹脂組成物の含浸性を高めることができる。 The liquid epoxy resin composition according to the present invention can have a low viscosity. The low viscosity can improve the productivity and workability of products using the epoxy resin composition. For example, a method for producing a molding material (composition) containing a cured product of an epoxy resin composition and a fiber or the like includes a step of impregnating a fiber woven fabric or a fiber bundle with the epoxy resin composition, and has a low viscosity. By using the epoxy resin composition of the above, the impregnation property of the epoxy resin composition can be enhanced.
　液状であるエポキシ樹脂組成物の粘度は、該組成物の調製直後において、ＥＭＳ粘度計による２５℃での粘度で、好ましくは５０Ｐａ・ｓ以下であり、より好ましくは４０Ｐａ・ｓ以下であり、さらに好ましくは３０Ｐａ・ｓ以下であり、なおさらに好ましくは２５Ｐａ・ｓ以下であり、特に好ましくは２０Ｐａ・ｓ以下である。エポキシ樹脂組成物の２５℃での粘度は、通常０．０１Ｐａ・ｓ以上であり、０．１Ｐａ・ｓ以上であってもよく、１Ｐａ・ｓ以上であってもよい。
　エポキシ樹脂組成物の粘度は、ＥＭＳ粘度計による２５℃での粘度で、０．０１Ｐａ・ｓ以上５０Ｐａ・ｓ以下が好ましく、０．１Ｐａ・ｓ以上４０Ｐａ・ｓ以下がより好ましく、１Ｐａ・ｓ以上３０Ｐａ・ｓ以下がさらに好ましく、１Ｐａ・ｓ以上２５Ｐａ・ｓ以下がなおさらに好ましく、１Ｐａ・ｓ以上２０Ｐａ・ｓ以下が特に好ましい。 Immediately after the preparation of the liquid epoxy resin composition, the viscosity at 25 ° C. by an EMS viscometer is preferably 50 Pa · s or less, more preferably 40 Pa · s or less, and further. It is preferably 30 Pa · s or less, more preferably 25 Pa · s or less, and particularly preferably 20 Pa · s or less. The viscosity of the epoxy resin composition at 25 ° C. is usually 0.01 Pa · s or more, may be 0.1 Pa · s or more, or may be 1 Pa · s or more.
The viscosity of the epoxy resin composition is preferably 0.01 Pa · s or more and 50 Pa · s or less, more preferably 0.1 Pa · s or more and 40 Pa · s or less, and 1 Pa · s or more, based on the viscosity at 25 ° C. by an EMS viscometer. It is more preferably 30 Pa · s or less, still more preferably 1 Pa · s or more and 25 Pa · s or less, and particularly preferably 1 Pa · s or more and 20 Pa · s or less.
　上述のように、本発明に係るエポキシ樹脂組成物は、優れたポットライフを有することができる。ポットライフは、例えば、エポキシ樹脂組成物調製時からの保管経過日数を横軸とし、該組成物のＥＭＳ粘度計による２５℃での粘度を縦軸とするグラフの傾きによって評価することができる。この傾きが小さいほどポットライフに優れるといえる。
　より具体的には、ポットライフは、例えば、下記式：
　粘度比＝（エポキシ樹脂組成物調製から保管Ｘ日後の粘度）／（エポキシ樹脂組成物調製直後の粘度）
によって評価することができる。Ｘは１以上の整数である。該粘度比が小さいほどポットライフに優れるといえる。上記式中の各粘度は、ＥＭＳ粘度計による２５℃での粘度である。上記保管は、２５℃で行われる。 As described above, the epoxy resin composition according to the present invention can have an excellent pot life. The pot life can be evaluated, for example, by the slope of a graph having the number of days of storage since the preparation of the epoxy resin composition as the horizontal axis and the viscosity of the composition at 25 ° C. as the vertical axis. It can be said that the smaller this inclination is, the better the pot life is.
More specifically, the pot life is, for example, the following formula:
Viscosity ratio = (viscosity after X days of storage from epoxy resin composition preparation) / (viscosity immediately after epoxy resin composition preparation)
Can be evaluated by. X is an integer of 1 or more. It can be said that the smaller the viscosity ratio, the better the pot life. Each viscosity in the above formula is the viscosity at 25 ° C. by the EMS viscometer. The above storage is carried out at 25 ° C.
　本発明に係るエポキシ樹脂組成物は、Ｘ＝２（日）における上記粘度比が、好ましくは１．３５未満であり、より好ましくは１．３３以下であり、さらに好ましくは１．３０以下である。上記粘度比は、１．００以上であってもよい。 The epoxy resin composition according to the present invention has a viscosity ratio of preferably less than 1.35, more preferably 1.33 or less, still more preferably 1.30 or less at X = 2 (day). .. The viscosity ratio may be 1.00 or more.
　本発明に係るエポキシ樹脂組成物は、良好な硬化性を示すことができる。すなわち、エポキシ樹脂組成物は、比較的短い熱硬化時間で、及び／又は、比較的低温で、十分に硬化することができる。 The epoxy resin composition according to the present invention can exhibit good curability. That is, the epoxy resin composition can be sufficiently cured in a relatively short thermosetting time and / or at a relatively low temperature.
　＜硬化物＞
　本発明に係る硬化物は、上記本発明に係るエポキシ樹脂組成物を硬化させてなるものである。本発明に係る硬化物は、良好な耐熱性を有することができ、あるいはさらに良好な引張特性を有することができる。 <Curing product>
The cured product according to the present invention is obtained by curing the epoxy resin composition according to the present invention. The cured product according to the present invention can have good heat resistance, or can have even better tensile properties.
　本発明に係る硬化物は、例えば、１１０℃以上、さらには１１５℃以上、さらには１２０℃以上、さらには１２５℃以上のガラス転移温度を示すことができる。
　本発明に係る硬化物は、ＪＩＳ　Ｋ　７１６１－１及びＪＩＳ　Ｋ　７１６１－２に準拠する引張特性における破断伸びが、例えば、４．５％以上、さらには５．５％以上、さらには６．５％以上、さらには７．０％以上、さらには７．５％以上であり得る。 The cured product according to the present invention can exhibit, for example, a glass transition temperature of 110 ° C. or higher, further 115 ° C. or higher, further 120 ° C. or higher, and further 125 ° C. or higher.
The cured product according to the present invention has a breaking elongation of, for example, 4.5% or more, further 5.5% or more, and further 6.5 in the tensile properties conforming to JIS K 7161-1 and JIS K 7161-2. % Or more, even 7.0% or more, and even 7.5% or more.
　本発明に係るエポキシ樹脂組成物及びその硬化物は、様々な用途に適用することができ、例えば、接着剤、電子部品の封止、繊維への含浸用樹脂組成物として使用することができる。とりわけ、本発明に係るエポキシ樹脂組成物は、塩素含有量が低いため、封止剤など電子材料向けに好適である。
　本発明は、上記硬化物を含む製品又は部品にも関する。該製品の一例は、上記硬化物と繊維等とを含む成形物（組成物）である。上記硬化物を含む製品又は部品は、例えば繊維のように、エポキシ樹脂組成物由来成分（硬化物）以外の成分を含んでいてもよい。 The epoxy resin composition and the cured product thereof according to the present invention can be applied to various uses, and can be used, for example, as an adhesive, a resin composition for encapsulating electronic parts, and a resin composition for impregnating fibers. In particular, the epoxy resin composition according to the present invention has a low chlorine content and is therefore suitable for electronic materials such as encapsulants.
The present invention also relates to a product or part containing the cured product. An example of the product is a molded product (composition) containing the cured product and fibers and the like. The product or component containing the cured product may contain components other than the epoxy resin composition-derived component (cured product), such as fibers.
　本発明に係るエポキシ樹脂組成物を繊維への含浸用樹脂組成物として使用する場合について以下に説明する。
　本発明に係るエポキシ樹脂組成物と併用する繊維としては、ＰＡＮ系炭素繊維、ピッチ系炭素繊維、ガラスファイバー、アラミド繊維、ケナフ繊維等の繊維を使用することができる。繊維の表面には公知のサイジング処理を実施してもよい。 The case where the epoxy resin composition according to the present invention is used as a resin composition for impregnating fibers will be described below.
As the fiber used in combination with the epoxy resin composition according to the present invention, fibers such as PAN-based carbon fiber, pitch-based carbon fiber, glass fiber, aramid fiber, and kenaf fiber can be used. A known sizing treatment may be applied to the surface of the fiber.
　本発明に係るエポキシ樹脂組成物と繊維とを複合化して成形物を作製する方法としては、公知の方法を用いることができる。具体的には、
　繊維にエポキシ樹脂組成物を含浸して、マンドレル等の成型金型に巻き付けて成形し、加熱硬化させる、ウェットフィラメントワインディング法；
　繊維にエポキシ樹脂組成物を予め含浸させたトゥプリプレグを準備し、トゥプリプレグをマンドレル等の成型金型に巻き付けて成形し、加熱硬化させる、ドライフィラメントワインディング法；
　繊維の織物を作製し、金型に繊維織物を積層してプレス加圧して作製したプリフォームに、エポキシ樹脂組成物を真空含浸して、加熱硬化する、レジントランスファーモールド法；
　繊維の織物にエポキシ樹脂組成物を予め含浸させたプリプレグを準備し、マンドレル等の成型金型に巻き付けて成形し、加熱硬化させる、シートワインディング法；
　繊維の織物にエポキシ樹脂組成物を予め含浸させたプリプレグを準備し、金型にプリプレグを積層し、プレスで加熱・加圧硬化させる、プレス成形法；
　繊維の織物にエポキシ樹脂組成物を予め含浸させたプリプレグを準備し、プリプレグを成形冶具に載せてバッグフィルムで覆い、オートクレーブ中で加熱・加圧硬化させる、オートクレーブ成形法；
等が挙げられる。 As a method for producing a molded product by combining the epoxy resin composition and the fiber according to the present invention, a known method can be used. In particular,
Wet filament winding method in which fibers are impregnated with an epoxy resin composition, wound around a molding die such as a mandrel, molded, and heat-cured.
A dry filament winding method in which a tuple preg in which fibers are pre-impregnated with an epoxy resin composition is prepared, the tuprepreg is wound around a molding die such as a mandrel, molded, and heat-cured.
A resin transfer molding method in which a fiber woven fabric is prepared, the fiber woven fabric is laminated on a mold, and a preform prepared by pressing and pressing is vacuum-impregnated with an epoxy resin composition and heat-cured.
A sheet winding method in which a prepreg impregnated with an epoxy resin composition in a fiber woven fabric is prepared, wound around a molding die such as a mandrel, molded, and heat-cured.
A press molding method in which a prepreg impregnated with an epoxy resin composition in a fiber woven fabric is prepared, the prepreg is laminated on a mold, and the prepreg is heated and pressure-cured by a press.
An autoclave molding method in which a prepreg impregnated with an epoxy resin composition in a fiber woven fabric is prepared, the prepreg is placed on a molding tool, covered with a bag film, and heated and pressure-cured in an autoclave.
And so on.
　以下、実施例を示して本発明をさらに具体的に説明するが、本発明はこれらの例によって限定されるものではない。例中、含有量ないし使用量を表す％及び部は、特記ない限り、質量基準である。 Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. In the examples,% and parts representing the content or the amount used are based on mass unless otherwise specified.
　＜実施例１～４、比較例１～２＞
　（１）エポキシ樹脂組成物の調製
　下記表１に示される各成分を、下記表１に示される配合量で混合して、エポキシ樹脂組成物を調製した。表１において、各成分の配合量の単位は質量部である。すべての実施例及び比較例において、得られたエポキシ樹脂組成物は、液状であった（２５℃で流動性あり）。 <Examples 1 to 4, Comparative Examples 1 to 2>
(1) Preparation of Epoxy Resin Composition An epoxy resin composition was prepared by mixing each component shown in Table 1 below in the blending amount shown in Table 1 below. In Table 1, the unit of the blending amount of each component is a mass part. In all Examples and Comparative Examples, the resulting epoxy resin composition was liquid (fluid at 25 ° C.).
　表１の「ＯＨ／ＥＰモル比」の欄に、仕込み量から算出される、エポキシ樹脂組成物中のエポキシ基含有量に対するフェノール性水酸基含有量のモル比を記載した。 In the column of "OH / EP molar ratio" in Table 1, the molar ratio of the phenolic hydroxyl group content to the epoxy group content in the epoxy resin composition calculated from the charged amount is described.
　表１に示される各配合成分の詳細は次のとおりである。
　〔ａ〕エポキシ樹脂１：株式会社ＡＤＥＫＡ製の液状エポキシ樹脂　商品名「アデカレジンＥＰ－４３００Ｅ」（ビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８５ｇ／ｅｑ、粘度：８Ｐａ・ｓ（２５℃））
　〔ｂ〕エポキシ樹脂２：國都化学製の液状エポキシ樹脂　商品名「ＥＰＯＫＵＫＤＯ　ＹＤ－１２７」（ビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８０－１９０ｇ／ｅｑ、粘度：８－１１Ｐａ・ｓ（２５℃））
　〔ｃ〕エポキシ樹脂３：國都化学製の液状エポキシ樹脂　商品名「ＥＰＯＫＵＫＤＯ　ＹＤ－１２８」（ビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８４－１９４ｇ／ｅｑ、粘度：１１－１５Ｐａ・ｓ（２５℃））
　〔ｄ〕エポキシ樹脂４：三菱ケミカル株式会社製の液状エポキシ樹脂　商品名「ｊＥＲ８２８」（ビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８４－１９４ｇ／ｅｑ、粘度：１２－１５Ｐａ・ｓ（２５℃））
　〔ｅ〕エポキシ樹脂５：國都化学製の液状エポキシ樹脂　商品名「ＥＰＯＫＵＫＤＯ　ＹＤ－１２８Ｍ」（ビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８４－１９６ｇ／ｅｑ、粘度：１２－１４Ｐａ・ｓ（２５℃））
　〔ｆ〕エポキシ樹脂６：株式会社ＡＤＥＫＡ製の液状エポキシ樹脂　商品名「ＥＰ－４３００」（ビスフェノールＡ型エポキシ樹脂、エポキシ当量：１８０－２００ｇ／ｅｑ、粘度：１０．４　Ｐａ・ｓ（２５℃））
　〔ｇ〕硬化剤１：１，３－ジヒドロキシベンゼン（レゾルシン）
　〔ｈ〕硬化剤２：ジヒドロクマリン
　〔ｉ〕硬化促進剤１：株式会社ＡＤＥＫＡ製のイミダゾールアダクト型硬化促進剤　商品名「アデカハードナー　ＥＨ－５０１１Ｓ」（潜在性） The details of each compounding ingredient shown in Table 1 are as follows.
[A] Epoxy resin 1: Liquid epoxy resin manufactured by ADEKA Co., Ltd. Product name "Adecaledin EP-4300E" (bisphenol A type epoxy resin, epoxy equivalent: 185 g / eq, viscosity: 8 Pa · s (25 ° C))
[B] Epoxy resin 2: Liquid epoxy resin manufactured by Kokuto Kagaku, trade name "EPOKUKDO YD-127" (bisphenol A type epoxy resin, epoxy equivalent: 180-190 g / eq, viscosity: 8-111 Pa · s (25 ° C)) )
[C] Epoxy resin 3: Liquid epoxy resin manufactured by Kokuto Kagaku, trade name "EPOKUKDO YD-128" (bisphenol A type epoxy resin, epoxy equivalent: 184-194 g / eq, viscosity: 11-15 Pa · s (25 ° C)) )
[D] Epoxy resin 4: Liquid epoxy resin manufactured by Mitsubishi Chemical Corporation Trade name "jER828" (bisphenol A type epoxy resin, epoxy equivalent: 184-194 g / eq, viscosity: 12-15 Pa · s (25 ° C.))
[E] Epoxy resin 5: Liquid epoxy resin manufactured by Kokuto Kagaku, trade name "EPOKUKDO YD-128M" (bisphenol A type epoxy resin, epoxy equivalent: 184-196 g / eq, viscosity: 12-14 Pa · s (25 ° C)) )
[F] Epoxy resin 6: Liquid epoxy resin manufactured by ADEKA Co., Ltd. Product name "EP-4300" (bisphenol A type epoxy resin, epoxy equivalent: 180-200 g / eq, viscosity: 10.4 Pa · s (25 ° C)) )
[G] Curing agent 1: 1,3-dihydroxybenzene (resorcin)
[H] Curing agent 2: Dihydrocoumarin [i] Curing accelerator 1: Imidazole adduct-type curing accelerator manufactured by ADEKA Corporation Product name "ADEKA HANDNER EH-5011S" (potential)
　（２）測定・評価
　（２－１）エポキシ樹脂及びエポキシ樹脂組成物の塩素含有量
　ＪＩＳ　Ｋ　７２４３－３：２００５に準拠して、エポキシ樹脂及びエポキシ樹脂組成物の塩素含有量をそれぞれ測定した。結果を表１に示す。 (2) Measurement / Evaluation (2-1) Chlorine content of epoxy resin and epoxy resin composition The chlorine content of epoxy resin and epoxy resin composition was measured according to JIS K 7243-3: 2005, respectively. The results are shown in Table 1.
　（２－２）エポキシ樹脂組成物の粘度及びポットライフ
　エポキシ樹脂組成物の調製直後及び２５℃恒温槽内で所定の期間保管したエポキシ樹脂組成物のそれぞれについて、約２ｇのエポキシ樹脂組成物を４．７ｍｍアルミニウム球状プローブとともに試料管に封入した。この試験管を２５℃に設定された京都電子工業株式会社製　ＥＭＳ粘度計（ＥＭＳ－１０００）にセットし、モーター回転数１０００ｒｐｍ、測定時間２分、測定間隔３０秒の条件でエポキシ樹脂組成物の粘度を測定した。結果を表１に示す。表１において「－」は、その保管期間において粘度の測定を行わなかったことを意味する。 (2-2) Viscosity and Pot Life of Epoxy Resin Composition About 2 g of epoxy resin composition was added to each of the epoxy resin compositions immediately after preparation of the epoxy resin composition and stored in a constant temperature bath at 25 ° C. for a predetermined period. It was encapsulated in a sample tube together with a 0.7 mm aluminum spherical probe. This test tube was set in an EMS viscometer (EMS-1000) manufactured by Kyoto Denshi Kogyo Co., Ltd. set at 25 ° C., and the epoxy resin composition was prepared under the conditions of a motor rotation speed of 1000 rpm, a measurement time of 2 minutes, and a measurement interval of 30 seconds. The viscosity was measured. The results are shown in Table 1. In Table 1, "-" means that the viscosity was not measured during the storage period.
　エポキシ樹脂組成物のポットライフは、下記式：
　粘度比＝（エポキシ樹脂組成物調製から保管Ｘ日後の粘度）／（エポキシ樹脂組成物調製直後の粘度）
によって評価することができる。Ｘ＝２（日）における粘度比を表１に示す。該粘度比が小さいほどポットライフに優れるといえる。
　比較例１～２のエポキシ樹脂組成物は、Ｘ＝２（日）における粘度比が、実施例と比べて高い。 The pot life of the epoxy resin composition is as follows:
Viscosity ratio = (viscosity after X days of storage from epoxy resin composition preparation) / (viscosity immediately after epoxy resin composition preparation)
Can be evaluated by. Table 1 shows the viscosity ratio at X = 2 (day). It can be said that the smaller the viscosity ratio, the better the pot life.
The epoxy resin compositions of Comparative Examples 1 and 2 have a higher viscosity ratio at X = 2 (day) than that of Examples.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004

Claims (8)

  1. 　エポキシ樹脂（Ａ）、硬化剤（Ｂ）及びイミダゾールアダクト型硬化促進剤（Ｃ）を含むエポキシ樹脂組成物であって、
    　前記硬化剤（Ｂ）は、下記式（Ｂ－１）：
    Figure JPOXMLDOC01-appb-C000001
    ［式中、Ｒ１は、水素原子、ハロゲン原子、メトキシ基又は炭素数１～１２の炭化水素基を表す。］
    で表される化合物（Ｂ－１）を含み、
    　塩素含有量が１６００質量ｐｐｍ以下である、エポキシ樹脂組成物。     An epoxy resin composition containing an epoxy resin (A), a curing agent (B), and an imidazole adduct-type curing accelerator (C).
    The curing agent (B) has the following formula (B-1):
    Figure JPOXMLDOC01-appb-C000001
    [In the formula, R 1 represents a hydrogen atom, a halogen atom, a methoxy group or a hydrocarbon group having 1 to 12 carbon atoms. ]
    Includes compound (B-1) represented by
    An epoxy resin composition having a chlorine content of 1600 mass ppm or less.
  2. 　前記エポキシ樹脂組成物中のエポキシ基含有量に対するフェノール性水酸基含有量のモル比が０．２０～０．７５である、請求項１に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1, wherein the molar ratio of the phenolic hydroxyl group content to the epoxy group content in the epoxy resin composition is 0.20 to 0.75.
  3. 　前記イミダゾールアダクト型硬化促進剤（Ｃ）の含有量は、前記エポキシ樹脂（Ａ）１００質量部に対して１質量部以上５０質量部以下である、請求項１又は２に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 1 or 2, wherein the content of the imidazole adduct-type curing accelerator (C) is 1 part by mass or more and 50 parts by mass or less with respect to 100 parts by mass of the epoxy resin (A). ..
  4. 　前記エポキシ樹脂（Ａ）は、分子内にエポキシ基を２個有するエポキシ樹脂を含む、請求項１～３のいずれか１項に記載のエポキシ樹脂組成物。 The epoxy resin composition according to any one of claims 1 to 3, wherein the epoxy resin (A) contains an epoxy resin having two epoxy groups in the molecule.
  5. 　前記エポキシ樹脂（Ａ）は、分子内にエポキシ基を２個有するエポキシ樹脂からなり、該エポキシ樹脂の塩素含有量が１７００質量ｐｐｍ以下である、請求項４に記載のエポキシ樹脂組成物。 The epoxy resin composition according to claim 4, wherein the epoxy resin (A) is composed of an epoxy resin having two epoxy groups in the molecule, and the chlorine content of the epoxy resin is 1700 mass ppm or less.
  6. 　請求項１～５のいずれか１項に記載のエポキシ樹脂組成物の硬化物。 The cured product of the epoxy resin composition according to any one of claims 1 to 5.
  7. 　請求項１～５のいずれか１項に記載のエポキシ樹脂組成物と繊維を含むプリプレグ。 A prepreg containing the epoxy resin composition and fiber according to any one of claims 1 to 5.
  8. 　請求項１～５のいずれか１項に記載のエポキシ樹脂組成物の硬化物と繊維を含む組成物。 A composition containing a cured product and fibers of the epoxy resin composition according to any one of claims 1 to 5.
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JP2003096273A (en) * 2001-09-25 2003-04-03 Sumitomo Bakelite Co Ltd Epoxy resin composition and semiconductor device
JP2011174005A (en) * 2010-02-25 2011-09-08 Dic Corp Epoxy resin composition, cured product thereof, resin composition for sealing optical semiconductor, optical semiconductor device, fiber-reinforced composite material, and fiber-reinforced resin molded article
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