WO2021106963A1 - Resin composition and method for suppressing foaming of cured material - Google Patents

Resin composition and method for suppressing foaming of cured material Download PDF

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Publication number
WO2021106963A1
WO2021106963A1 PCT/JP2020/043906 JP2020043906W WO2021106963A1 WO 2021106963 A1 WO2021106963 A1 WO 2021106963A1 JP 2020043906 W JP2020043906 W JP 2020043906W WO 2021106963 A1 WO2021106963 A1 WO 2021106963A1
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group
atom
resin composition
sulfur atom
oxygen atom
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PCT/JP2020/043906
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French (fr)
Japanese (ja)
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将太 小林
健一 玉祖
啓介 太田
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株式会社Adeka
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L85/00—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers
    • C08L85/02—Compositions of macromolecular compounds obtained by reactions forming a linkage in the main chain of the macromolecule containing atoms other than silicon, sulfur, nitrogen, oxygen and carbon; Compositions of derivatives of such polymers containing phosphorus

Definitions

  • the present invention relates to a method for suppressing foaming of a resin composition and a cured product.
  • Structural adhesives are widely used as bonding agents for metal members in a wide range of fields such as automobiles, ships, aviation, space, civil engineering, and construction.
  • a thermosetting type structural adhesive obtained by modifying an epoxy resin with an elastomer or the like as a base is widely used.
  • structural adhesives are required to have excellent adhesiveness to various base materials. Further, since the structural adhesive may be stored under high temperature and high humidity, it is desired that the structural adhesive has high adhesiveness even when used after being stored under high temperature and high humidity, that is, good moisture and heat resistance. There is. Furthermore, since structural adhesives are expected to be used in all environments, they maintain excellent adhesiveness without foaming even when exposed to a wide range from low temperature to high temperature and even under high humidity. Is desired.
  • Patent Document 1 proposes a curable epoxy block urethane composition obtained from an epoxy resin, a blocked isocyanate compound, and a latent curing agent.
  • Patent Document 2 proposes a curable resin composition containing a urethane-modified epoxy resin, block urethane, and a latent curing agent.
  • Patent Document 3 includes an epoxy resin, a blocked urethane polymer obtained by blocking an isocyanate group bonded to a secondary or tertiary aliphatic carbon atom with a specific imino compound, and a curing agent. Room temperature curable resin compositions have been proposed.
  • Patent Document 4 proposes a curable resin composition containing a polyepoxy compound, a urethane-modified chelated epoxy resin, block urethane, and a latent curing agent.
  • the resin compositions proposed in these cases may have an adverse effect on adhesiveness due to foaming or a decrease in strength when cured under high temperature and high humidity.
  • phosphorus-containing compounds having reactivity with epoxy groups are known to be effective as flame retardants (for example, Patent Documents 5 and 6). It is described in the same document that the phosphorus-containing compound improves the glass transition temperature (Tg) of the cured resin product and also imparts flame retardancy. However, there is no description or suggestion in the same document that the use of a phosphorus-containing compound suppresses foaming of a curable resin composition obtained by mixing an epoxy resin and an elastomer during curing.
  • Japanese Unexamined Patent Publication No. 5-155973 US2009 / 131605A1 Japanese Unexamined Patent Publication No. 2007-23238 Japanese Unexamined Patent Publication No. 2008-239890 US2016 / 152643A1 US2018 / 037014A1
  • the problem to be solved by the present invention is to provide a resin composition which is excellent in adhesiveness, suppresses foaming of the obtained cured product, and can be suitably used as a structural adhesive for automobile applications and the like. That is.
  • Another object of the present invention is to provide a method for suppressing foaming of a cured product.
  • the present invention is a resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a urethane elastomer, and (D) a phosphorus-containing compound represented by the following formula (1) or (2). Is to provide.
  • m represents an integer from 1 to 10.
  • R 1 and R 2 independently represent an alkyl group or an aryl group, respectively.
  • R 3 represents a hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a sulfur atom. It may be substituted with a substituent containing a nitrogen atom.
  • X 1 represents an oxygen atom or a sulfur atom and represents Y 1 is an oxygen atom, a sulfur atom, or -NR 4 - represents, R 4 represents a hydrogen atom, an alkyl group or an aryl group.
  • n represents an integer from 1 to 10.
  • R 5 , R 6 , R 7 and R 8 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively.
  • R 9 represents a hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a sulfur atom. It may be substituted with a substituent containing a nitrogen atom.
  • X 2 represents an oxygen atom or a sulfur atom
  • Y 2 represents an oxygen atom, a sulfur atom, or -NR 10-
  • R 10 represents a hydrogen atom, an alkyl group, or an aryl group.
  • the present invention is represented by (D) the above formula (1) or (2) prior to curing the resin composition composed of (A) epoxy resin, (B) curing agent and (C) urethane elastomer.
  • the present invention provides a method for suppressing foaming of a cured product in which a phosphorus-containing compound is contained in the composition.
  • composition of the present invention has excellent adhesiveness and suppresses foaming of the obtained cured product, and can be suitably used for structural adhesives for automobiles.
  • FIG. 1 is a photograph of the peeled surface of the test piece made of the resin composition obtained in Example 1 from the base material.
  • FIG. 2 is a photograph of the peeled surface of the test piece made of the resin composition obtained in Comparative Example 1 from the base material.
  • the resin composition of the present invention will be described below.
  • the resin composition of the present invention comprises (A) an epoxy resin, (B) an amine-based latent curing agent, (C) blocked urethane, and (D) a phosphorus-containing compound represented by the following formula (1) or (2). Contains.
  • the epoxy resin which is the component (A) contained in the resin composition of the present invention a known epoxy resin having at least two epoxy groups in the molecule can be used, and the molecular structure, molecular weight and the like thereof are particularly limited. Absent. It is preferable to use the epoxy resin composition properly depending on the use of the resin composition.
  • Examples of the epoxy resin include a polyglycidyl ether compound of a mononuclear polyvalent phenol compound, a polyglycidyl ether compound of a polynuclear polyvalent phenol compound, a polyglycidyl ether compound of a polyhydric alcohol compound, and a glycidyl ester compound of an aliphatic polybasic acid.
  • Aromatic polybasic acid glycidyl ester compound Aromatic polybasic acid glycidyl ester compound, alicyclic polybasic acid glycidyl ester compound, glycidyl methacrylate homopolymer or copolymer, epoxy compound having glycidyl amino group, epoxidized cyclic olefin compound, epoxidation Examples include conjugated diene polymers and heterocyclic epoxy compounds. These epoxy resins may be internally crosslinked with a prepolymer of terminal isocyanate, or have a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). You may. In the resin composition of the present invention, one type of epoxy resin may be used alone, or two or more types may be used in combination.
  • Examples of the mononuclear polyhydric phenol compound include hydroquinone, resorcin, pyrocatechol, fluoroglucosinol and the like.
  • polynuclear polyvalent phenol compound examples include dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), etylidenebisphenol, isopropyridenebisphenol (bisphenol A), isopropyridenebis (orthocresol), and tetrabromo.
  • Bisphenol A 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1, Examples thereof include 2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac and terpenphenol.
  • polyhydric alcohol compound examples include hexanediol, polyethylene glycol, polypropylene glycol, thioglycol, dicyclopentadiene dimethanol, 2,2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A), pentaerythritol and the like.
  • examples thereof include sorbitol and bisphenol A-alkylene oxide adduct.
  • alicyclic polybasic acid examples include maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid and trimer acid.
  • aromatic polybasic acid examples include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid and pyromellitic acid.
  • Examples of the alicyclic polybasic acid include tetrahydrophthalic acid and endomethylene tetrahydrophthalic acid.
  • Examples of the epoxy compound having a glycidylamino group include N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine, and N, N-bis ( 2,3-epoxypropyl) -4- (2,3-epoxypropoxy) -2-methylaniline, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline and Examples thereof include N, N, N', N'-tetra (2,3-epoxypropyl) -4,4-diaminodiphenylmethane and the like.
  • cyclic olefin compound examples include vinylcyclohexene diepoxide, cyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-6-methylcyclohexylmethyl-6.
  • -Methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate and the like can be mentioned.
  • epoxidized conjugated diene polymer examples include epoxidized polybutadiene and epoxidized styrene-butadiene copolymer.
  • heterocyclic epoxy compound examples include triglycidyl isocyanurate.
  • the epoxy resin as the component (A) may be a modified epoxy resin obtained by reacting the above-mentioned epoxy resin with CTBN, ATBN, a phosphoric acid compound and / or an isocyanate compound.
  • the content of the modified epoxy resin in the resin composition of the present invention is preferably 3 to 30% by mass, more preferably 5 to 20% by mass. This is because the adhesiveness of the resin composition is further improved by setting the content of the modified epoxy resin in the above range.
  • epoxy resin As the epoxy resin as the component (A), a bisphenol type epoxy resin such as bisphenol A diglycidyl ether is preferable because it can be obtained at a low price.
  • the content of the epoxy resin of the component (A) in the resin composition of the present invention is preferably 95 to 40% by mass, more preferably 90 to 45% by mass, because the adhesiveness is further improved. It is preferably 85 to 50% by mass, more preferably 85 to 50% by mass.
  • the curing agent which is the component (B) contained in the resin composition of the present invention
  • examples of the (B) curing agent include phenol resins, aliphatic amines, aromatic amines, amine-based latent curing agents, and acid anhydrides.
  • One of these curing agents may be used alone, or two or more thereof may be used in combination.
  • phenol resins examples include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, and trisphenylol methane resin.
  • polyhydric phenol compounds such as novolak resin (polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
  • the amount of the (B) curing agent composed of the phenol resins to the (A) epoxy resin is not particularly limited, but the hydroxyl group in the phenol resins is 0 with respect to 1 equivalent of the epoxy groups in the epoxy resin. It is preferable to mix the epoxy to 1.5 equivalents, and more preferably 0.8 to 1.2 equivalents.
  • aliphatic amines examples include ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, and 1, 4-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylpropane, bis (4-aminocyclohexyl) sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexyl Examples thereof include methane, isophoronediamine, norbornenediamine, and metaxylenediamine.
  • amine modification method examples include dehydration condensation with carboxylic acid, addition reaction with epoxy resin, addition reaction with isocyanate, Michael addition reaction, Mannich reaction, condensation reaction with urea, and condensation reaction with ketone. These can be used alone or in combination at any ratio.
  • the amount of the (B) curing agent composed of the aliphatic amines to be added to the (A) epoxy resin is not particularly limited, but the amount of active hydrogen in the aliphatic amine is relative to one equivalent of the epoxy group in the epoxy resin. Is preferably blended so as to have an amount of 0.6 to 1.5 equivalents, and more preferably 0.8 to 1.2 equivalents.
  • aromatic amines examples include diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminebenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3.
  • aromatic amines include diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminebenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3.
  • Examples include 5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,5,3', 5'-tetramethyl-4,4'-diaminodiphenylmethane. Be done. Further, it may be a modified product of these amines.
  • Examples of the amine modification method include dehydration condensation with carboxylic acid, addition reaction with epoxy resin, addition reaction with isocyanate, Michael addition reaction, Mannich reaction, condensation reaction with urea, and condensation reaction with ketone. These can be used alone or in combination at any ratio.
  • the amount of the (B) curing agent composed of the aromatic amines to be added to the (A) epoxy resin is not particularly limited, but the amount of active hydrogen in the aromatic amine is relative to one equivalent of the epoxy group in the epoxy resin. Is preferably blended so as to have an amount of 0.6 to 1.5 equivalents, and more preferably 0.8 to 1.2 equivalents.
  • amine-based latent curing agent one having a small change in viscosity or physical properties of the mixture when mixed with an epoxy resin at room temperature can be preferably used.
  • examples of such amine-based latent curing agents include dicyandiamide-type latent curing agents, imidazole-type latent curing agents, and polyamine-type latent curing agents.
  • Examples of the dicyandiamide-type latent curing agent include dicyandiamide.
  • the imidazole-type latent curing agent can be obtained, for example, by reacting an imidazole compound containing active hydrogen with an epoxy compound.
  • the reaction between the imidazole compound and the epoxy compound may be carried out at 50 to 150 ° C. for 1 to 20 hours.
  • a solvent may be used for the reaction between the imidazole compound and the epoxy compound. When a solvent is used, the solvent is removed at 80 to 200 ° C. under normal pressure or reduced pressure after the reaction is completed.
  • Examples of the imidazole compound used in the production of the imidazole-type latent curing agent include alkylimidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 2-heptadecylimidazole, and Examples thereof include arylimidazole such as 2-phenylimidazole.
  • Examples of the epoxy compound used in the production of the imidazole-type latent curing agent include the compounds exemplified in the epoxy resin (A).
  • Examples of the solvent used for producing the imidazole-type latent curing agent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone and propylene glycol monomethyl ether acetate; and aliphatic hydrocarbons such as cyclohexane.
  • Ethers such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether; esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene Examples include halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene and methylene chloride; halogenated aromatic hydrocarbons such as chlorobenzene.
  • the polyamine-type latent curing agent can be obtained, for example, by reacting a polyamine with an epoxy compound.
  • the reaction between the polyamine and the epoxy compound may be carried out at 50 to 150 ° C. for 1 to 20 hours.
  • a solvent may be used for the reaction between the polyamine and the epoxy compound. When a solvent is used, the solvent is removed at 80 to 200 ° C. under normal pressure or reduced pressure after the reaction is completed.
  • Examples of the polyamine used in the production of the polyamine-type latent curing agent include compounds exemplified by the aliphatic amines and aromatic amines.
  • the epoxy compound and solvent used in the production of the polyamine-type latent curing agent the same ones as those used in the production of the imidazole-type latent curing agent can be used.
  • the amine-based latent curing agent and the above-exemplified phenol resins may be used in combination.
  • a commercially available product can be used as the amine-based latent curing agent as the component (B).
  • Commercially available products include ADEKA HANDNER EH-3636AS (manufactured by ADEKA Corporation; deciandiamide type latent curing agent), ADEKA HANDNER EH-4351S (manufactured by ADEKA Corporation; deciandiamide type latent curing agent), and ADEKA HANDNER EH-5011S (stock).
  • the blending amount of the curing agent (B) composed of the amine-based latent curing agent with respect to the epoxy resin (A) is not particularly limited, but is 1 to 70 parts by mass with respect to 100 parts by mass of the epoxy resin. Is preferable, and the amount is more preferably 3 to 60 parts by mass. It is preferable that the content of the amine-based latent curing agent (B) is in the above range because the internal reactivity for exhibiting excellent adhesion is exhibited.
  • Examples of the acid anhydrides as the component (B) include hymic anhydride, phthalic anhydride, maleic anhydride, methyl hymic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Acids, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, benzophenone tetracarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, hydride methylnadic anhydride, etc. Be done.
  • the amount of the curing agent (B) composed of the acid anhydrides to be blended with the epoxy resin (A) is not particularly limited, but the acid in the acid anhydrides is relative to one equivalent of the epoxy group in the epoxy resin.
  • the number of anhydride groups is preferably 0.7 to 1.6 equivalents, more preferably 0.9 to 1.2 equivalents.
  • an amine-based latent curing agent it is preferable to use an amine-based latent curing agent because various modifications can be made according to the required characteristics.
  • urethane elastomer As the urethane elastomer as the component (C) contained in the resin composition of the present invention, an elastomer having a urethane structure obtained by using a polyol, a polyisocyanate, and if necessary, a chain extender can be used without particular limitation. it can. In the present invention, it is preferable to use, for example, block urethane as the urethane elastomer because it is possible to provide an elastomer having excellent flexibility-imparting effect, adhesion-imparting effect and the like.
  • the resin composition of the present invention is preferably obtained by blocking an excess of isocyanate groups in polyurethane having an isocyanate group with a blocking agent.
  • the isocyanate group of polyurethane is excessive means that the isocyanate (NCO) content of polyurethane is 0.1% by mass or more.
  • the blocked urethane obtained by blocking polyurethane having an isocyanate (NCO) content of 0.1 to 10% by mass, preferably 1 to 8% by mass as the blocked urethane with a (C2) blocking agent. is preferably used. It is preferable to use such polyurethane because it exhibits internal reactivity for exhibiting excellent adhesion.
  • the (c-1) polyhydroxy compound and the (c-2) polyisocyanate compound have an excess of isocyanate groups contained in the polyisocyanate compound with respect to the hydroxy groups contained in the polyhydroxy compound. It is preferable to use the one obtained by quantitative reaction.
  • Examples of the (c-1) polyhydroxy compound include polyether polyols, polyester polyols, polycarbonate polyols, polyesteramide polyols, acrylic polyols, polyurethane polyols and the like.
  • an alkylene oxide adduct of a polyhydric alcohol having a molecular weight of about 100 to 5500 is preferably used.
  • polyhydric alcohol used for producing the polyether polyol examples include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butylene glycol (tetramethylene glycol), and neopentane glycol; glycerin, trioxyisobutane, and the like.
  • a dihydric to tetravalent alcohol as the polyhydric alcohol, and it is more preferable to use an alkylene glycol such as propylene glycol and 1,4-butylene glycol or a trivalent alcohol such as glycerin.
  • the polyether polyol can be produced by adding an alkylene oxide having 2 to 4 carbon atoms to a polyhydric alcohol as exemplified above so as to have a desired molecular weight by a conventional method.
  • alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide (tetramethylene oxide), and propylene oxide and butylene oxide are particularly preferable.
  • polyester polyol examples include conventionally known polyesters produced from polycarboxylic acids and polyhydric alcohols, polyesters obtained from lactams, and the like.
  • polycarboxylic acid examples include benzenetricarboxylic acid, adipic acid, amber acid, suberic acid, sebacic acid, itaconic acid, methyladic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, and thio.
  • Dipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or any suitable carboxylic acid similar thereto can be used.
  • polyhydric alcohol used in the production of the polyester polyol examples include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, and 1,6-hexanediol. , Bis (hydroxymethylchlorohexane), diethylene glycol, polytetramethylene glycol, polyether polyols such as polycaprolactone glycol, 2,2-dimethylpropylene glycol, 1,3,6-hexanetriol, trimethylolpropane, pentaerythritol, sorbitol , Glycerin or any suitable polyhydric alcohol similar thereto can be used.
  • polycarbonate polyol examples include those obtained by a dephenolization reaction between a diol and a diphenyl carbonate, a dealcoholization reaction between a diol and a dialkyl carbonate, a deglycolation reaction between a diol and an alkylene carbonate, and the like.
  • diol used for producing the polycarbonate polyol examples include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4.
  • polyether polyol a resin composition having good moisture and heat resistance can be obtained.
  • Examples of the (c-2) polyisocyanate compound include propane-1,2-diisocyanate, 2,3-dimethylbutane-2,3-diisocyanate, 2-methylpentane-2,4-diisocyanate, octane-3, 6-Diisocyanate, 3,3-dinitropentane-1,5-diisocyanate, octane-1,6-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, lysine diisocyanate, tolylene diisocyanate (TDI) , Xylylene diisocyanate, metatetramethylxylylene diisocyanate, isophorone diisocyanate (3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate), 1,3- or 1,4-bis (isocyanatemethyl) cyclohexane, diphenylme
  • These polyisocyanate compounds may be isocyanulates formed by trimerization.
  • these polyisocyanate compounds it is strong against a metal substrate to use at least one selected from the group consisting of 1,6-hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and these isocyanul compounds. It is preferable because a resin composition exhibiting adhesiveness can be obtained.
  • the production of the (C1) polyurethane from the (c-1) polyhydroxy compound and the (c-2) polyisocyanate compound can be carried out by a conventional method.
  • the amount of the component (c-1) and the component (c-2) used is an amount in which the component (c-2) is excessive with respect to the component (c-1), specifically, (c-1). ),
  • the amount of the isocyanate group of (c-2) in excess of 1 equivalent of the hydroxyl group preferably 1.2 to 5 equivalents, particularly preferably 1.5 to 2.5 equivalents.
  • the isocyanate content of the obtained polyurethane is preferably 1 to 8% by mass.
  • the isocyanate content can be measured according to JIS K 1603-1.
  • the reaction temperature at the time of producing the (C1) polyurethane is usually 40 to 140 ° C, preferably 60 to 130 ° C.
  • known catalysts for urethane polymerization to promote the reaction such as organic metals such as dioctyltin dilaurate, dibutyltin dilaurate, stannous octate, stanas octoate, lead octylate, lead naphthenate, zinc octylate, etc. It is also possible to use a compound, a tertiary amine compound such as triethylenediamine or triethylamine.
  • Examples of the (C2) blocking agent include active methylene compounds such as malonic acid diester (diethyl malonate, etc.), acetylacetone, and acetacetic acid ester (ethyl acetate acetate, etc.); Oxim compounds such as isobutyl ketooxime (MIBK oxime); monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, heptyl alcohol, hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, stearyl alcohol or the like.
  • active methylene compounds such as malonic acid diester (diethyl malonate, etc.), acetylacetone, and acetacetic acid ester (ethyl acetate acetate, etc.); Oxim compounds such as isobutyl ketooxime (MIBK oxime); monohydric alcohols such as methyl alcohol, eth
  • glycol derivatives such as methyl glycol, ethyl glycol, ethyl diglycol, ethyl triglycol, butyl glycol, butyl diglycol; amine compounds such as dicyclohexylamine; phenol, cresol, ethylphenol, n-propylphenol, isopropyl
  • Monophenols such as phenol, butylphenol, tertiary butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol and bromophenol, diphenols such as resorcin, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F and naphthol.
  • Phenols such as ⁇ -caprolactone, ⁇ -caprolactam and the like.
  • these blocking agents using one or more selected from the group consisting of amine compounds, diphenols, ⁇ -caprolactone and ⁇ -caprolactam ensures a curable resin composition having strong adhesiveness. It is preferable because it can be obtained in.
  • the amine compound it is preferable to use dicyclohexylamine.
  • the amount of the (C2) blocking agent used is arbitrary, but usually, about the equivalent amount is used with respect to the isocyanate group of the (C1) polyurethane.
  • the blocking reaction of (C1) polyurethane with (C2) blocking agent is usually a method of adding (C2) blocking agent in the final reaction of polymerization of (C1) polyurethane, but (C1) polymerization of polyurethane.
  • Blocked polyurethane can also be obtained by adding and reacting the (C2) blocking agent at any stage of.
  • (C2) As a method of adding the blocking agent, a method of adding at the end of a predetermined polymerization, adding at the beginning of polymerization, adding a part at the beginning of polymerization, and adding the rest at the end of polymerization is possible. However, it is preferably added at the end of polymerization. In this case, the isocyanate content (%) (measured according to JIS K 1603-1) may be used as a reference at the end of the predetermined polymerization.
  • the reaction temperature when the blocking agent is added is usually 50 to 150 ° C, preferably 60 to 120 ° C.
  • the reaction time is usually about 1 to 7 hours. At the time of the reaction, it is also possible to add the above-mentioned known catalyst for urethane polymerization to accelerate the reaction. In addition, an arbitrary amount of plasticizer may be added during the reaction.
  • the blending amount of the block polyurethane of the component (C) used in the resin composition of the present invention is preferably 1 to 50 parts by mass, particularly 1 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin as the component (A). It is preferably 10 parts by mass.
  • the content of the block urethane as the component (C) is within the above range, the adhesiveness of the coating film to the substrate, the cold resistance of the coating film, and the strength of the coating film are good, and the prepared resin composition It is preferable because the viscosity does not become too high and the workability at the time of coating is improved.
  • m represents an integer from 1 to 10.
  • R 1 and R 2 independently represent an alkyl group or an aryl group, respectively.
  • R 3 represents a hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a sulfur atom. It may be substituted with a substituent containing a nitrogen atom.
  • X 1 represents an oxygen atom or a sulfur atom and represents Y 1 is an oxygen atom, a sulfur atom, or -NR 4 - represents, R 4 represents a hydrogen atom, an alkyl group or an aryl group.
  • m is preferably 2 to 7, and more preferably 2 to 5.
  • m is 2 or more, the number of functional groups that react with the epoxy group is 2 or more, and the glass transition temperature and strength of the cured product when the epoxy resin is cured are high, which is preferable.
  • m is 7 or less, the viscosity does not increase when the phosphorus-containing compound is produced, and the phosphorus-containing compound can be easily produced, which is preferable.
  • Examples of the alkyl group represented by R 1 , R 2 and R 4 in the formula (1) include a linear alkyl group.
  • Examples of the linear alkyl group include an alkyl group having 1 to 12 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a nonyl group and a decyl group.
  • Examples of the alkyl group represented by R 1 , R 2 and R 4 include a branched alkyl group. Examples of the branched alkyl group include those having 1 to 12 carbon atoms.
  • a linear alkyl group because the firing of the obtained cured product is further suppressed.
  • the number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 2 to 5, and even more preferably 2 to 4.
  • the linear alkyl group is preferably an ethyl group or a propyl group.
  • the aryl group represented by R 1 , R 2 and R 4 in the formula (1) may be a monocyclic ring or a condensed ring.
  • Examples of the monocyclic aryl group include a phenyl group.
  • Examples of the aryl group of the fused ring include a naphthyl group and the like.
  • the aryl group preferably has 6 to 32 carbon atoms, more preferably 7 to 11 carbon atoms.
  • the hydrocarbon group represented by R 3 includes an alkyl group, an aryl group, an alkanediyl group, an alkanetriyl group, a residue obtained by removing a hydroxyl group from a mononuclear polyvalent phenol compound, and a polynuclear group. Residues obtained by removing the hydroxyl group from the polyvalent phenol compound can be mentioned.
  • the alkyl group represented by R 3 include a linear alkyl group. Examples of the linear alkyl group include those having 1 to 12 carbon atoms.
  • examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a nonyl group and a decyl group.
  • examples of the alkyl group represented by R 3 include a branched alkyl group. Examples of the branched alkyl group include those having 1 to 12 carbon atoms.
  • the aryl group represented by R 3 may be a monocyclic ring or a condensed ring. Examples of the monocyclic aryl group include a phenyl group. Examples of the aryl group of the fused ring include a naphthyl group and the like.
  • the aryl group preferably has 6 to 32 carbon atoms, more preferably 7 to 11 carbon atoms.
  • Examples of the alkanediyl group represented by R 3 include a methylene group, an ethylene group, a propylene group, an ethanediyl group, an octanediyl group and the like.
  • Examples of the alkanetriyl group represented by R 3 include a methanetriyl group and a 1,1,2-ethanetriyl group.
  • Examples of the alkanetetrayl group represented by R 3 include 1,1,2,2-ethanetetrayl and the like.
  • Examples of the mononuclear polyhydric phenol compound represented by R 3 include hydroquinone, resorcin, pyrocatechol, fluoroglucosinol and the like.
  • Examples of the polynuclear polyvalent phenol compound represented by R 3 include dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), etylidene bisphenol, isopropyridene bisphenol (bisphenol A), and isopropylidene (orthocresol).
  • Tetrabromobisphenol A 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 1,1,3-tris (4-hydroxyphenyl) butane
  • examples thereof include 1,1,2,2-tetra (4-hydroxyphenyl) ethane, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac and terpenphenol.
  • R 3 Represented by R 3, 1 or 2 or more methylene groups the oxygen atom in the hydrocarbon group, the radicals substituted with a sulfur atom or a nitrogen atom, for example, thiobisphenols, sulfonyloxy bisphenol, oxy bisphenol, is ..
  • X 1 in the general formula (1) is an oxygen atom from the viewpoint that a raw material for production is easily available. From the same viewpoint, it is preferable that Y 1 is an oxygen atom.
  • a phosphorus-containing compound represented by the formula (1) is preferably a compound containing at least one aromatic ring in the skeleton, Table by R 3 It is particularly preferable that the hydrocarbon group to be formed is selected from the group consisting of the groups represented by the following formulas (a-1) to (i-1).
  • hydrocarbon groups represented by R 3 is the following structure.
  • n represents an integer from 1 to 10.
  • R 5 , R 6 , R 7 and R 8 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively.
  • R 9 represents a hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a sulfur atom. It may be substituted with a substituent containing a nitrogen atom.
  • X 2 represents an oxygen atom or a sulfur atom
  • Y 2 represents an oxygen atom, a sulfur atom, or -NR 10-
  • R 10 represents a hydrogen atom, an alkyl group, or an aryl group.
  • n is preferably 2 to 7, and more preferably 2 to 5.
  • n is 2 or more, the number of functional groups that react with the epoxy group is 2 or more, and the glass transition temperature and strength of the cured product when the epoxy resin is cured are high, which is preferable.
  • m is 7 or less, the viscosity does not increase when the phosphorus-containing compound is produced, and the phosphorus-containing compound can be easily produced, which is preferable.
  • Examples of the alkyl group represented by R 5 , R 6 , R 7 , R 8 and R 10 in the formula (2) include a linear alkyl group.
  • Examples of the linear alkyl group include an alkyl group having 1 to 12 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a nonyl group and a decyl group.
  • Examples of the alkyl group represented by R 5 , R 6 , R 7 , R 8 and R 10 include a branched alkyl group. Examples of the branched alkyl group include those having 1 to 10 carbon atoms.
  • a linear alkyl group because the firing of the obtained cured product is further suppressed.
  • the number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 2 to 5, and even more preferably 2 to 4.
  • the linear alkyl group is preferably an ethyl group or a propyl group.
  • the aryl group represented by R 5 , R 6 , R 7 , R 8 and R 10 in the formula (2) may be a monocyclic ring or a condensed ring.
  • Examples of the monocyclic aryl group include a phenyl group.
  • Examples of the aryl group of the fused ring include a naphthyl group and the like.
  • the aryl group preferably has 6 to 32 carbon atoms, more preferably 7 to 11 carbon atoms.
  • the hydrocarbon group represented by R 9 includes an alkyl group, an aryl group, an alkanediyl group, an alkanetriyl group, a residue obtained by removing a hydroxyl group from a mononuclear polyvalent phenol compound, and a polynuclear group. Residues obtained by removing the hydroxyl group from the polyvalent phenol compound can be mentioned.
  • the alkyl group represented by R 3 include a linear alkyl group. Examples of the linear alkyl group include those having 1 to 12 carbon atoms.
  • examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a nonyl group and a decyl group.
  • examples of the alkyl group represented by R 3 include a branched alkyl group. Examples of the branched alkyl group include those having 1 to 12 carbon atoms.
  • the aryl group represented by R 3 may be a monocyclic ring or a condensed ring. Examples of the monocyclic aryl group include a phenyl group. Examples of the aryl group of the fused ring include a naphthyl group and the like.
  • the aryl group preferably has 6 to 32 carbon atoms, more preferably 7 to 11 carbon atoms.
  • Examples of the alkanediyl group represented by R 3 include a methylene group, an ethylene group, a propylene group, an ethanediyl group, an octanediyl group and the like.
  • Examples of the alkanetriyl group represented by R 3 include a methanetriyl group and a 1,1,2-ethanetriyl group.
  • Examples of the alkanetetrayl group represented by R 3 include 1,1,2,2-ethanetetrayl and the like.
  • Examples of the mononuclear polyhydric phenol compound represented by R 3 include hydroquinone, resorcin, pyrocatechol, fluoroglucosinol and the like.
  • Examples of the polynuclear polyvalent phenol compound represented by R 3 include dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), etylidene bisphenol, isopropyridene bisphenol (bisphenol A), and isopropylidene (orthocresol).
  • Tetrabromobisphenol A 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 1,1,3-tris (4-hydroxyphenyl) butane
  • examples thereof include 1,1,2,2-tetra (4-hydroxyphenyl) ethane, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac and terpenphenol.
  • R 9 Represented by R 9, 1 or 2 or more methylene groups the oxygen atom in the hydrocarbon group, the radicals substituted with a sulfur atom or a nitrogen atom, for example, thiobisphenols, sulfonyloxy bisphenol, oxy bisphenol, is ..
  • X 2 in the general formula (2) is an oxygen atom from the viewpoint that a raw material for production is easily available. From the same viewpoint, it is preferable that Y 2 is an oxygen atom.
  • a phosphorus-containing compound represented by the formula (2) is preferably a compound containing at least one aromatic ring in the skeleton, tables in R 9 It is particularly preferable that the hydrocarbon group to be formed is selected from the group consisting of the groups represented by the following formulas (a-2) to (i-2).
  • a 2 in formula (a-2), from the viewpoint of the physical properties of a cured product obtained by curing is preferably 2, 3 and 4.
  • P 2 in the formula (g-2) is preferably 0 to 1 from the viewpoint of the physical properties of the cured product.
  • the hydrocarbon group represented by R 9 is preferably of the formula (b-2) or (g-2), and particularly preferably has the following structure, from the viewpoint of easy availability.
  • R 5 - R 8 are each independently, 1 hydrogen atom or a carbon atoms 6 It is more preferable that R 5 and R 7 are independently alkyl groups, and R 6 and R 8 are hydrogen atoms.
  • the blending amount of the phosphorus-containing compound of the component (D) in the resin composition of the present invention is not particularly limited, but is 2 to 40 mass by mass with respect to the total amount of the components (C) and (D). %, More preferably 5 to 30% by mass.
  • the content of the component (D) is in the above range, the moisture and heat resistance of the resin composition is further improved, the foaming of the cured product is further suppressed, and the water resistance is improved, which is preferable.
  • the resin composition of the present invention may contain (E) a rubber component in addition to the above-mentioned (A) component, (B) component, (C) component and (D) component.
  • the rubber component (E) is a component having a skeleton obtained by polymerizing monomers such as isoprene, butadiene, styrene, acrylonitrile, and chloroprene.
  • the rubber component (E) include liquid rubber and powdered rubber.
  • liquid rubber examples include polybutadiene, acrylonitrile butadiene rubber (NBR), butadiene-acrylonitrile rubber (CTBN) having carboxyl groups at both ends, and butadiene-acrylonitrile rubber (ATBN) having amino groups at both ends.
  • NBR acrylonitrile butadiene rubber
  • CBN butadiene-acrylonitrile rubber
  • ATBN butadiene-acrylonitrile rubber
  • powdered rubber examples include acrylonitrile butadiene rubber (NBR), carboxylic acid-modified NBR, hydrogenated NBR, core-shell type rubber, styrene-butadiene rubber, and acrylic rubber.
  • NBR acrylonitrile butadiene rubber
  • carboxylic acid-modified NBR carboxylic acid-modified NBR
  • hydrogenated NBR hydrogenated NBR
  • core-shell type rubber styrene-butadiene rubber
  • acrylic rubber examples include acrylic rubber.
  • the core-shell type rubber is a rubber in which particles have a core layer and a shell layer.
  • a two-layer structure in which the outer shell layer is a glassy polymer and the inner core layer is a rubbery polymer or Examples thereof include a three-layer structure in which the outer shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a glassy polymer.
  • the glassy polymer is composed of, for example, a polymer of methyl methacrylate, a polymer of methyl acrylate, a polymer of styrene, etc.
  • the rubbery polymer layer is, for example, a butyl acrylate polymer (butyl rubber), silicone rubber, polybutadiene, etc. It is composed.
  • liquid rubber and core-shell type rubber are preferable from the viewpoint of further improving the adhesiveness of the resin composition.
  • the content of the rubber component (E) in the resin composition of the present invention is preferably 3 to 30% by mass, more preferably 5 to 20% by mass. This is because the adhesiveness of the resin composition is further improved by setting the content of the rubber component (E) in the above range.
  • the resin composition of the present invention may contain a reactive diluent in order to adjust the viscosity of the resin composition to a desired value.
  • the reactive diluent preferably has at least one epoxy group from the viewpoint of suppressing a decrease in heat resistance and glass transition temperature of the cured product when the epoxy resin composition is cured.
  • the number of epoxy groups contained in the reactive diluent may be one or two or more, and is not particularly limited.
  • Reactive diluents having one epoxy group include, for example, n-butyl glycidyl ether, C12-C14 alkyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, and cresyl.
  • Reactive diluents with two epoxy groups include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether. And so on.
  • the reactive diluent having three epoxy groups include trimethylolpropane triglycidyl ether and glycerin triglycidyl ether.
  • the resin composition of the present invention preferably contains an epoxy resin curing accelerator.
  • an epoxy resin curing accelerator By containing the epoxy resin curing accelerator, the curing temperature of the adhesive can be lowered, which is preferable.
  • the curing accelerator include phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole.
  • imidazole salts which are salts of the imidazoles with trimellitic acid, isocyanuric acid, boron and the like; benzyldimethylamine, 2,4,6-tris (dimethylamino).
  • Amines such as methyl) phenol; quaternary ammonium salts such as trimethylammonium chloride; 3- (p-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, Examples of ureas such as 3-phenyl-1,1-dimethylurea, isophoronediisocyanate-dimethylurea, and tolylene diisocyanate-dimethylurea; and complex compounds of boron trifluoride with amines and ether compounds are exemplified. be able to. These curing accelerators may be used alone or in combination of two or more.
  • the content of the epoxy resin curing accelerator in the flame-retardant epoxy resin composition of the present invention is not particularly limited and can be appropriately set according to the use of the resin composition.
  • the content of the epoxy resin curing accelerator in the resin composition of the present invention is preferably 1 to 35% by mass, more preferably 3 to 30% by mass, and 5 to 5 to 30% by mass with respect to the (B) curing agent. It is more preferably 25% by mass.
  • the resin composition of the present invention may contain an organic solvent as a viscosity modifier, if necessary.
  • the organic solvent includes amides such as N, N-dimethylformamide; ethers such as ethylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol and ethanol; aromatics such as benzene and toluene. Examples include group hydrocarbons.
  • the resin composition of the present invention preferably contains an inorganic filler.
  • an inorganic filler By containing an inorganic filler, it can be expected to impart thixotropy, viscosity, and improve water resistance.
  • examples of such an inorganic filler include fused silica such as hydrophobic fumed silica, silica such as crystalline silica; magnesium hydroxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbonate, calcium silicate, and titanium.
  • Examples thereof include powders of potassium acid, verilia, zirconia, zircone, fosterite, steatite, spinel, mulite, titania and the like, beads obtained by spheroidizing these, and glass fibers, pulp fibers, synthetic fibers, ceramic fibers and the like. ..
  • These inorganic fillers may be used alone or in combination of two or more.
  • the content of the inorganic filler in the resin composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass.
  • the resin composition of the present invention may contain additives other than the above, if necessary.
  • additives include non-reactive diluents (plasticizers) such as dioctylphthalate, dibutylphthalate, benzyl alcohol, and coaltal; reinforcing materials such as glass cloth, aramid cloth, and carbon fiber; pigments; ⁇ -aminopropyltri.
  • the resin composition of the present invention has excellent adhesion to various substrates and has excellent flexibility in a wide range from low temperature to high temperature, it has a wide range of fields such as automobiles, ships, aerospace, space, civil engineering, and construction. In various fields, it can be suitably used as a structural adhesive used for joining various structural members, and in particular, it can be suitably used as an automobile structural adhesive. Further, as a matter of course, the resin composition of the present invention can be used not only for structural adhesives but also for various paints, various adhesives, various molded products and the like.
  • the resin composition of the present invention can be cured by heating.
  • the heating conditions such as the heating time and the heating temperature are not particularly limited, and known conditions can be adopted. Specifically, it can be cured by heating at 160 to 200 ° C., preferably 170 to 190 ° C. for 20 to 40 minutes, preferably 30 to 40 minutes.
  • the cured product at the time of curing is prepared by containing the component (D) in the composition prior to curing the resin composition containing the components (A) to (C).
  • This is a method of suppressing foaming.
  • block urethane which has a particularly remarkable effect, is used as the component (C)
  • the composition containing the components (A) to (C) is cured, it is blocked in the block urethane which is the component (C).
  • the agent is dissociated by heat to temporarily generate NCO groups.
  • the water content in the composition containing the components (A) to (C) or the water content in the air existing in the vicinity of the composition is NCO.
  • the phosphorus-containing compound as the component (D) suppresses the reaction between the NCO group and water.
  • the components (A) to (D) used in the foaming suppressing method correspond to the components (A) to (D) used in the resin composition.
  • the component (D) is contained in the composition prior to curing the composition containing the components (A) to (C). is there.
  • the cured product produced by the method for producing a cured product of the present invention has foaming suppressed.
  • the solvent and excess raw materials were removed by an evaporator, and the residue was dissolved in 300 mL of chloroform and transferred to a separatory funnel.
  • the organic layer was washed twice with 100 mL of distilled water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by an evaporator to obtain 18.8 g (yield 85.3%) of the phosphorus-containing compound 1. Since the phosphorus-containing compound is considered to be a by-product having e of 1 or more in P-2 in addition to the phosphorus-containing compound represented by the formula P-1, 31P-NMR measurement was performed and the integrated value was used. , E in P-2 was calculated to be 0.13.
  • A-1 Bisphenol A type epoxy resin (Product name: EP-4100E, manufactured by ADEKA Corporation, epoxy equivalent: 190 g / eq.)
  • A-2 Chelate-modified epoxy resin (Product name: EP-49-10P2, manufactured by ADEKA Corporation, epoxy equivalent: 300 g / eq.)
  • A-3 Rubber-modified epoxy resin (Product name: EPR-1630, manufactured by ADEKA Corporation)
  • B Dicyandiamide type latent curing agent (Product name: EH-3636AS, manufactured by ADEKA Corporation)
  • C Block urethane (block urethane equivalent: 1400 g / eq.)
  • D Phosphorus-containing compound 1 produced in Production Example 1.
  • G-1 Inorganic filler (calcium carbonate)
  • G-2 Inorganic filler (hydrophobic fumed silica, product name: RY-200S, manufactured by Nippon Aerosil Co., Ltd.)
  • the block urethane of C is manufactured by the following procedure. 300.0 g of propylene glycol glyceryl ether (product name: ADEKApolyether G-3000B, manufactured by ADEKA Corporation) in a 1 L 5-port separable round bottom flask equipped with a diisocyanate, a stirring blade and a nitrogen line (number of moles of hydroxyl groups: 0.294 mol) and 66.4 g of IPDI (isophorone diisocyanate) (number of moles of isocyanate groups: 0.596 mol) were added, and the mixture was reacted at 100 to 110 ° C. for 3 hours.
  • propylene glycol glyceryl ether product name: ADEKApolyether G-3000B, manufactured by ADEKA Corporation
  • IPDI isophorone diisocyanate
  • Pre-wet heat peeling test The resin compositions of Examples and Comparative Examples were placed in a mold of a test piece and cured by heating at 180 ° C. for 30 minutes to prepare a test piece. The T-type peel strength (kN / m) of the prepared test piece was measured. For the T-type peel strength, iron was used as the adherend, and the T-type peel strength at ⁇ 40 ° C. was measured using the above-mentioned test piece according to JIS K 6854-3.
  • test piece was evaluated according to the following criteria. When evaluating the test piece, since a plurality of voids may be continuous due to the appearance of many voids, the evaluation was made in consideration of not only the number of voids but also the generated area.
  • the cured product of the resin composition of Example 1 had a higher strength retention rate than the cured product of the resin composition of Comparative Example 1. From this result, it is clear that the resin composition of the present invention has excellent moisture and heat resistance. Further, the cured product of the resin composition of Example 1 had less voids than the cured product of the resin composition of Comparative Example 1. From this result, it is clear that the resin composition of the present invention suppresses firing during curing.

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Abstract

The present invention addresses the problem of providing a resin composition in which foaming during curing, especially in high-temperature and high-humidity conditions, is suppressed. The present invention also provides a method for suppressing foaming of a cured material of the resin composition.　The resin composition contains (A) an epoxy resin, (B) a curing agent, (C) a urethan elastomer, and (D) at least one compound selected from among the phosphorus-containing compounds represented by formula (1) or (2). (1): For details of m, R1, R2, R3, X1, and Y1 in formula (1), see the specification. (2): For details of n, R5 through R8, R9, X2, and Y2 in formula (2), see the specification.

Description

樹脂組成物、及び硬化物の発泡抑制方法Method for suppressing foaming of resin composition and cured product
　本発明は、樹脂組成物、及び硬化物の発泡抑制方法に関するものである。 The present invention relates to a method for suppressing foaming of a resin composition and a cured product.
　構造用接着剤は、自動車、船舶、航空、宇宙、土木、建築分野等の広範な分野において金属部材等の接合剤として汎用されている。構造用接着剤としては、エポキシ樹脂をベースとしエラストマー等で変性して得られる熱硬化型の構造用接着剤が、広く使用されている。 Structural adhesives are widely used as bonding agents for metal members in a wide range of fields such as automobiles, ships, aviation, space, civil engineering, and construction. As the structural adhesive, a thermosetting type structural adhesive obtained by modifying an epoxy resin with an elastomer or the like as a base is widely used.
　構造用接着剤に対しては、各種基材の接着性に優れていることが当然要求される。更に、構造用接着剤は、高温多湿下で保存される可能性があるため、高温多湿下で保存された後に使用された場合でも高い接着性を有すること、すなわち良好な耐湿熱性が望まれている。更に、構造用接着剤はあらゆる環境下での使用が想定されるため、低温から高温までの広い範囲、更に高湿度下にさらされた場合においても発泡することなく、優れた接着性を維持することが望まれている。 Naturally, structural adhesives are required to have excellent adhesiveness to various base materials. Further, since the structural adhesive may be stored under high temperature and high humidity, it is desired that the structural adhesive has high adhesiveness even when used after being stored under high temperature and high humidity, that is, good moisture and heat resistance. There is. Furthermore, since structural adhesives are expected to be used in all environments, they maintain excellent adhesiveness without foaming even when exposed to a wide range from low temperature to high temperature and even under high humidity. Is desired.
　特許文献１には、エポキシ樹脂、ブロックドイソシアネート化合物及び潜在性硬化剤から得られる硬化性エポキシブロックウレタン組成物が提案されている。特許文献２には、ウレタン変性エポキシ樹脂、ブロックウレタン及び潜在性硬化剤を含有してなる硬化性樹脂組成物が提案されている。特許文献３には、エポキシ樹脂と、第二級又は第三級の脂肪族炭素原子に結合しているイソシアネート基を、特定のイミノ化合物でブロック化して得られるブロックウレタンポリマー、硬化剤とを有する室温硬化性樹脂組成物が提案されている。特許文献４には、ポリエポキシ化合物、ウレタン変性キレートエポキシ樹脂、ブロックウレタン、潜在性硬化剤を含有してなる硬化性樹脂組成物が提案されている。しかしながら、これらで提案された樹脂組成物は、高温・高湿度下において硬化させた場合に発泡を生じたり、強度が低下することによって、接着性に悪影響を与えるおそれがあった。 Patent Document 1 proposes a curable epoxy block urethane composition obtained from an epoxy resin, a blocked isocyanate compound, and a latent curing agent. Patent Document 2 proposes a curable resin composition containing a urethane-modified epoxy resin, block urethane, and a latent curing agent. Patent Document 3 includes an epoxy resin, a blocked urethane polymer obtained by blocking an isocyanate group bonded to a secondary or tertiary aliphatic carbon atom with a specific imino compound, and a curing agent. Room temperature curable resin compositions have been proposed. Patent Document 4 proposes a curable resin composition containing a polyepoxy compound, a urethane-modified chelated epoxy resin, block urethane, and a latent curing agent. However, the resin compositions proposed in these cases may have an adverse effect on adhesiveness due to foaming or a decrease in strength when cured under high temperature and high humidity.
　一方、エポキシ基と反応性を有する含リン化合物が難燃剤として有効であることが知られている（例えば、特許文献５及び６）。含リン化合物によって樹脂硬化物のガラス転移温度（Ｔｇ）を良好とし、且つ難燃性も付与することが同文献に記載されている。しかしながら、同文献には、含リン化合物を使用することによって、エポキシ樹脂とエラストマーとを混合して得られる硬化性樹脂組成物の硬化時の発泡が抑制されることに関しては記載も示唆もない。 On the other hand, phosphorus-containing compounds having reactivity with epoxy groups are known to be effective as flame retardants (for example, Patent Documents 5 and 6). It is described in the same document that the phosphorus-containing compound improves the glass transition temperature (Tg) of the cured resin product and also imparts flame retardancy. However, there is no description or suggestion in the same document that the use of a phosphorus-containing compound suppresses foaming of a curable resin composition obtained by mixing an epoxy resin and an elastomer during curing.
特開平５－１５５９７３号公報Japanese Unexamined Patent Publication No. 5-155973 ＵＳ２００９／１３１６０５Ａ１US2009 / 131605A1 特開２００７－２３２３８号公報Japanese Unexamined Patent Publication No. 2007-23238 特開２００８－２３９８９０号公報Japanese Unexamined Patent Publication No. 2008-239890 ＵＳ２０１６／１５２６４３Ａ１US2016 / 152643A1 ＵＳ２０１８／０３７０１４Ａ１US2018 / 037014A1
　従って、本発明が解決しようとする課題は、接着性に優れ、得られる硬化物の発泡が抑制された、自動車用途などの構造用接着剤として好適に使用することができる樹脂組成物を提供することである。また、硬化物の発泡を抑制する方法を提供することである。 Therefore, the problem to be solved by the present invention is to provide a resin composition which is excellent in adhesiveness, suppresses foaming of the obtained cured product, and can be suitably used as a structural adhesive for automobile applications and the like. That is. Another object of the present invention is to provide a method for suppressing foaming of a cured product.
　そこで本発明者等は鋭意検討し、エポキシ樹脂、硬化剤、ウレタンエラストマー及び特定の含リン化合物を含有する樹脂組成物が前記目的を達成することを見出した。 Therefore, the present inventors have diligently studied and found that a resin composition containing an epoxy resin, a curing agent, a urethane elastomer and a specific phosphorus-containing compound achieves the above object.
　すなわち、本発明は、（Ａ）エポキシ樹脂、（Ｂ）硬化剤、（Ｃ）ウレタンエラストマー、及び（Ｄ）下記式（１）又は（２）で表される含リン化合物を含有する樹脂組成物を提供するものである。 That is, the present invention is a resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a urethane elastomer, and (D) a phosphorus-containing compound represented by the following formula (1) or (2). Is to provide.
Figure JPOXMLDOC01-appb-C000008
Figure JPOXMLDOC01-appb-C000008
　式中、ｍは１～１０の整数を表し、
　Ｒ１及びＲ２は、それぞれ独立に、アルキル基又はアリール基を表し、
　Ｒ３は、炭化水素基、又は該炭化水素基中の１若しくは２以上のメチレン基が酸素原子、硫黄原子若しくは窒素原子で置換された基を表し、該炭化水素基は酸素原子、硫黄原子又は窒素原子を含む置換基で置換されていてもよく、
　Ｘ１は酸素原子又は硫黄原子を表し、
　Ｙ１は酸素原子、硫黄原子、又は－ＮＲ４－を表し、
　Ｒ４は、水素原子、アルキル基又はアリール基を表す。 In the formula, m represents an integer from 1 to 10.
R 1 and R 2 independently represent an alkyl group or an aryl group, respectively.
R 3 represents a hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a sulfur atom. It may be substituted with a substituent containing a nitrogen atom.
X 1 represents an oxygen atom or a sulfur atom and represents
Y 1 is an oxygen atom, a sulfur atom, or -NR 4 - represents,
R 4 represents a hydrogen atom, an alkyl group or an aryl group.
Figure JPOXMLDOC01-appb-C000009
Figure JPOXMLDOC01-appb-C000009
　式中、ｎは１～１０の整数を表し、
　Ｒ５、Ｒ６、Ｒ７及びＲ８は、それぞれ独立に、水素原子、アルキル基、又はアリール基を表し、
　Ｒ９は、炭化水素基、又は該炭化水素基中の１若しくは２以上のメチレン基が酸素原子、硫黄原子若しくは窒素原子で置換された基を表し、該炭化水素基は酸素原子、硫黄原子又は窒素原子を含む置換基で置換されていてもよく、
　Ｘ２は酸素原子又は硫黄原子を表し、
　Ｙ２は、酸素原子、硫黄原子、又は－ＮＲ１０－を表し、Ｒ１０は水素原子、アルキル基、又はアリール基を表す。 In the formula, n represents an integer from 1 to 10.
R 5 , R 6 , R 7 and R 8 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively.
R 9 represents a hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a sulfur atom. It may be substituted with a substituent containing a nitrogen atom.
X 2 represents an oxygen atom or a sulfur atom
Y 2 represents an oxygen atom, a sulfur atom, or -NR 10- , and R 10 represents a hydrogen atom, an alkyl group, or an aryl group.
　また、前記樹脂組成物から得られる硬化物を提供するものである。 It also provides a cured product obtained from the resin composition.
　更に、本発明は、（Ａ）エポキシ樹脂、（Ｂ）硬化剤及び（Ｃ）ウレタンエラストマーからなる樹脂組成物を硬化させるのに先立ち、（Ｄ）前記式（１）又は（２）で表される含リン化合物を該組成物中に含有させておく、硬化物の発泡抑制方法を提供するものである。 Further, the present invention is represented by (D) the above formula (1) or (2) prior to curing the resin composition composed of (A) epoxy resin, (B) curing agent and (C) urethane elastomer. The present invention provides a method for suppressing foaming of a cured product in which a phosphorus-containing compound is contained in the composition.
　本発明の組成物は、接着性に優れ、得られる硬化物の発泡が抑制されており、自動車用構造用接着剤用途に好適に使用することができる。 The composition of the present invention has excellent adhesiveness and suppresses foaming of the obtained cured product, and can be suitably used for structural adhesives for automobiles.
図１は、実施例１で得られた樹脂組成物からなる試験片の基材からの剥離面を撮影した写真である。FIG. 1 is a photograph of the peeled surface of the test piece made of the resin composition obtained in Example 1 from the base material. 図２は、比較例１で得られた樹脂組成物からなる試験片の基材からの剥離面を撮影した写真である。FIG. 2 is a photograph of the peeled surface of the test piece made of the resin composition obtained in Comparative Example 1 from the base material.
　以下に、本発明の樹脂組成物について説明する。本発明の樹脂組成物は、（Ａ）エポキシ樹脂、（Ｂ）アミン系潜在性硬化剤、（Ｃ）ブロックウレタン、及び（Ｄ）下記式（１）又は（２）で表される含リン化合物を含有する。 The resin composition of the present invention will be described below. The resin composition of the present invention comprises (A) an epoxy resin, (B) an amine-based latent curing agent, (C) blocked urethane, and (D) a phosphorus-containing compound represented by the following formula (1) or (2). Contains.
　本発明の樹脂組成物に含まれる（Ａ）成分であるエポキシ樹脂としては、分子中にエポキシ基を少なくとも２つ有する公知のエポキシ樹脂を使用することができ、その分子構造や分子量等に特に制限ない。該エポキシ樹脂組成物は、樹脂組成物の用途によって使い分けることが好ましい。 As the epoxy resin which is the component (A) contained in the resin composition of the present invention, a known epoxy resin having at least two epoxy groups in the molecule can be used, and the molecular structure, molecular weight and the like thereof are particularly limited. Absent. It is preferable to use the epoxy resin composition properly depending on the use of the resin composition.
　前記エポキシ樹脂としては、例えば、単核多価フェノール化合物のポリグリシジルエーテル化合物、多核多価フェノール化合物のポリグリシジルエーテル化合物、多価アルコール化合物のポリグリシジルエーテル化合物、脂肪族多塩基酸のグリシジルエステル化合物、芳香族多塩基酸のグリシジルエステル化合物、脂環族多塩基酸のグリシジルエステル化合物、グリシジルメタクリレートの単独重合体又は共重合体、グリシジルアミノ基を有するエポキシ化合物、環状オレフィン化合物のエポキシ化物、エポキシ化共役ジエン重合体、及び複素環エポキシ化合物が挙げられる。これらのエポキシ樹脂は、末端イソシアネートのプレポリマーにより内部架橋されていてもよく、あるいは多価の活性水素化合物（多価フェノール、ポリアミン、カルボニル基含有化合物、ポリリン酸エステル等）で高分子量化されていてもよい。本発明の樹脂組成物においては、エポキシ樹脂は１種を単独で用いてもよく、２種以上を併用してもよい。 Examples of the epoxy resin include a polyglycidyl ether compound of a mononuclear polyvalent phenol compound, a polyglycidyl ether compound of a polynuclear polyvalent phenol compound, a polyglycidyl ether compound of a polyhydric alcohol compound, and a glycidyl ester compound of an aliphatic polybasic acid. , Aromatic polybasic acid glycidyl ester compound, alicyclic polybasic acid glycidyl ester compound, glycidyl methacrylate homopolymer or copolymer, epoxy compound having glycidyl amino group, epoxidized cyclic olefin compound, epoxidation Examples include conjugated diene polymers and heterocyclic epoxy compounds. These epoxy resins may be internally crosslinked with a prepolymer of terminal isocyanate, or have a high molecular weight with a polyvalent active hydrogen compound (polyhydric phenol, polyamine, carbonyl group-containing compound, polyphosphate ester, etc.). You may. In the resin composition of the present invention, one type of epoxy resin may be used alone, or two or more types may be used in combination.
　前記単核多価フェノール化合物としては、例えば、ハイドロキノン、レゾルシン、ピロカテコール及びフロログルクシノール等が挙げられる。 Examples of the mononuclear polyhydric phenol compound include hydroquinone, resorcin, pyrocatechol, fluoroglucosinol and the like.
　前記多核多価フェノール化合物としては、例えば、ジヒドロキシナフタレン、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデンビス（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミルベンゼン）、１，４－ビス（４－ヒドロキシクミルベンゼン）、１，１，３－トリス（４－ヒドロキシフェニル）ブタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン、チオビスフェノール、スルホビスフェノール、オキシビスフェノール、フェノールノボラック、オルソクレゾールノボラック、エチルフェノールノボラック、ブチルフェノールノボラック、オクチルフェノールノボラック、レゾルシンノボラック及びテルペンフェノール等が挙げられる。 Examples of the polynuclear polyvalent phenol compound include dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), etylidenebisphenol, isopropyridenebisphenol (bisphenol A), isopropyridenebis (orthocresol), and tetrabromo. Bisphenol A, 1,3-bis (4-hydroxycumylbenzene), 1,4-bis (4-hydroxycumylbenzene), 1,1,3-tris (4-hydroxyphenyl) butane, 1,1, Examples thereof include 2,2-tetra (4-hydroxyphenyl) ethane, thiobisphenol, sulfobisphenol, oxybisphenol, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac and terpenphenol.
　前記多価アルコール化合物としては、例えば、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、チオグリコール、ジシクロペンタジエンジメタノール、２，２－ビス（４－ヒドロキシシクロヘキシル）プロパン（水素化ビスフェノールＡ）、ペンタエリスリトール及びソルビトール、及びビスフェノールＡ－アルキレンオキシド付加物等が挙げられる。 Examples of the polyhydric alcohol compound include hexanediol, polyethylene glycol, polypropylene glycol, thioglycol, dicyclopentadiene dimethanol, 2,2-bis (4-hydroxycyclohexyl) propane (hydrogenated bisphenol A), pentaerythritol and the like. Examples thereof include sorbitol and bisphenol A-alkylene oxide adduct.
　前記脂環族多塩基酸としては、例えば、マレイン酸、フマル酸、イタコン酸、コハク酸、グルタル酸、スベリン酸、アジピン酸、アゼライン酸、セバシン酸、ダイマー酸及びトリマー酸が挙げられる。 Examples of the alicyclic polybasic acid include maleic acid, fumaric acid, itaconic acid, succinic acid, glutaric acid, suberic acid, adipic acid, azelaic acid, sebacic acid, dimer acid and trimer acid.
　前記芳香族多塩基酸としては、例えば、フタル酸、イソフタル酸、テレフタル酸、トリメリット酸、トリメシン酸及びピロメリット酸が挙げられる。 Examples of the aromatic polybasic acid include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid and pyromellitic acid.
　前記脂環族多塩基酸としては、例えば、テトラヒドロフタル酸及びエンドメチレンテトラヒドロフタル酸等が挙げられる。 Examples of the alicyclic polybasic acid include tetrahydrophthalic acid and endomethylene tetrahydrophthalic acid.
　前記グリシジルアミノ基を有するエポキシ化合物としては、例えば、Ｎ，Ｎ－ジグリシジルアニリン、ビス（４－（Ｎ－メチル－Ｎ－グリシジルアミノ）フェニル）メタン、ジグリシジルオルトトルイジン、Ｎ，Ｎ－ビス（２，３－エポキシプロピル）－４－（２，３－エポキシプロポキシ）－２－メチルアニリン、Ｎ，Ｎ－ビス（２，３－エポキシプロピル）－４－（２，３－エポキシプロポキシ）アニリン及びＮ，Ｎ，Ｎ’，Ｎ’－テトラ（２，３－エポキシプロピル）－４，４－ジアミノジフェニルメタン等が挙げられる。 Examples of the epoxy compound having a glycidylamino group include N, N-diglycidylaniline, bis (4- (N-methyl-N-glycidylamino) phenyl) methane, diglycidyl orthotoluidine, and N, N-bis ( 2,3-epoxypropyl) -4- (2,3-epoxypropoxy) -2-methylaniline, N, N-bis (2,3-epoxypropyl) -4- (2,3-epoxypropoxy) aniline and Examples thereof include N, N, N', N'-tetra (2,3-epoxypropyl) -4,4-diaminodiphenylmethane and the like.
　前記環状オレフィン化合物としては、例えば、ビニルシクロヘキセンジエポキシド、シクロペンタンジエンジエポキサイド、３，４－エポキシシクロヘキシルメチル－３，４－エポキシシクロヘキサンカルボキシレート、３，４－エポキシ－６－メチルシクロヘキシルメチル－６－メチルシクロヘキサンカルボキシレート及びビス（３，４－エポキシ－６－メチルシクロヘキシルメチル）アジペート等が挙げられる。 Examples of the cyclic olefin compound include vinylcyclohexene diepoxide, cyclopentanediene diepoxide, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, and 3,4-epoxy-6-methylcyclohexylmethyl-6. -Methylcyclohexanecarboxylate and bis (3,4-epoxy-6-methylcyclohexylmethyl) adipate and the like can be mentioned.
　前記エポキシ化共役ジエン重合体としては、例えば、エポキシ化ポリブタジエン及びエポキシ化スチレン－ブタジエン共重合物等が挙げられる。 Examples of the epoxidized conjugated diene polymer include epoxidized polybutadiene and epoxidized styrene-butadiene copolymer.
　前記複素環エポキシ化合物としては、例えば、トリグリシジルイソシアヌレート等が挙げられる。 Examples of the heterocyclic epoxy compound include triglycidyl isocyanurate.
　（Ａ）成分であるエポキシ樹脂は、上述のエポキシ樹脂と、ＣＴＢＮ、ＡＴＢＮ、リン酸化合物及び／又はイソシアネート化合物とを反応させて得られる変性エポキシ樹脂であってもよい。本発明の樹脂組成物における変性エポキシ樹脂の含有量は、３～３０質量％が好ましく、５～２０質量％がより好ましい。変性エポキシ樹脂の含有量を上述の範囲とすることによって、樹脂組成物の接着性が一層良好になるからである。 The epoxy resin as the component (A) may be a modified epoxy resin obtained by reacting the above-mentioned epoxy resin with CTBN, ATBN, a phosphoric acid compound and / or an isocyanate compound. The content of the modified epoxy resin in the resin composition of the present invention is preferably 3 to 30% by mass, more preferably 5 to 20% by mass. This is because the adhesiveness of the resin composition is further improved by setting the content of the modified epoxy resin in the above range.
　前記（Ａ）成分であるエポキシ樹脂としては、低価格で入手可能なものであることから、ビスフェノールＡジグリシジルエーテルなどのビスフェノール型エポキシ樹脂が好ましい。 As the epoxy resin as the component (A), a bisphenol type epoxy resin such as bisphenol A diglycidyl ether is preferable because it can be obtained at a low price.
　本発明の樹脂組成物における（Ａ）成分のエポキシ樹脂の含有量は、接着性が一層良好になることから、９５～４０質量％であることが好ましく、９０～４５質量％であることがより好ましく、８５～５０質量％であることが更に好ましい。 The content of the epoxy resin of the component (A) in the resin composition of the present invention is preferably 95 to 40% by mass, more preferably 90 to 45% by mass, because the adhesiveness is further improved. It is preferably 85 to 50% by mass, more preferably 85 to 50% by mass.
　次に、本発明の樹脂組成物に含まれる（Ｂ）成分である硬化剤について説明する。（Ｂ）硬化剤としては、フェノール樹脂類、脂肪族アミン類、芳香族アミン類、アミン系潜在性硬化剤、及び酸無水物類が挙げられる。これらの硬化剤は１種を単独で使用してもよく、２種以上を併用してもよい。 Next, the curing agent which is the component (B) contained in the resin composition of the present invention will be described. Examples of the (B) curing agent include phenol resins, aliphatic amines, aromatic amines, amine-based latent curing agents, and acid anhydrides. One of these curing agents may be used alone, or two or more thereof may be used in combination.
　前記フェノール樹脂類としては、フェノールノボラック樹脂、クレゾールノボラック樹脂、芳香族炭化水素ホルムアルデヒド樹脂変性フェノール樹脂、ジシクロペンタジエンフェノール付加型樹脂、フェノールアラルキル樹脂（ザイロック樹脂）、ナフトールアラルキル樹脂、トリスフェニロールメタン樹脂、テトラフェニロールエタン樹脂、ナフトールノボラック樹脂、ナフトール－フェノール共縮合ノボラック樹脂、ナフトール－クレゾール共縮合ノボラック樹脂、ビフェニル変性フェノール樹脂（ビスメチレン基でフェノール核が連結された多価フェノール化合物）、ビフェニル変性ナフトール樹脂（ビスメチレン基でフェノール核が連結された多価ナフトール化合物）、アミノトリアジン変性フェノール樹脂（フェノール骨格、トリアジン環及び１級アミノ基を分子構造中に有する化合物）、及び、アルコキシ基含有芳香環変性ノボラック樹脂（ホルムアルデヒドでフェノール核及びアルコキシ基含有芳香環が連結された多価フェノール化合物）等の多価フェノール化合物が挙げられる。 Examples of the phenol resins include phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), naphthol aralkyl resin, and trisphenylol methane resin. , Tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol cocondensation novolac resin, naphthol-cresol cocondensation novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nuclei are linked by bismethylene groups), biphenyl-modified naphthol Resin (a polyvalent naphthol compound in which a phenol nucleus is linked with a bismethylene group), an aminotriazine-modified phenol resin (a compound having a phenol skeleton, a triazine ring and a primary amino group in its molecular structure), and an alkoxy group-containing aromatic ring modification. Examples thereof include polyhydric phenol compounds such as novolak resin (polyhydric phenol compound in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
　前記フェノール樹脂類からなる（Ｂ）硬化剤の（Ａ）エポキシ樹脂に対する配合量は、特に限定されるものではないが、エポキシ樹脂中のエポキシ基１当量に対し、フェノール樹脂類中の水酸基が０．３～１．５当量になるように配合することが好ましく、０．８～１．２当量になるように配合することがより好ましい。 The amount of the (B) curing agent composed of the phenol resins to the (A) epoxy resin is not particularly limited, but the hydroxyl group in the phenol resins is 0 with respect to 1 equivalent of the epoxy groups in the epoxy resin. It is preferable to mix the epoxy to 1.5 equivalents, and more preferably 0.8 to 1.2 equivalents.
　前記脂肪族アミン類としては、エチレンジアミン、ヘキサメチレンジアミン、１，４－ジアミノシクロヘキサン、１，３－ジアミノシクロヘキサン、４，４’－ジアミノジシクロヘキシルメタン、１，３－ビス（アミノメチル）シクロヘキサン、１，４－ビス（アミノメチル）シクロヘキサン、４，４’－ジアミノジシクロヘキシルプロパン、ビス（４－アミノシクロヘキシル）スルホン、４，４’－ジアミノジシクロヘキシルエーテル、２，２’－ジメチル－４，４’－ジアミノジシクロヘキシルメタン、イソホロンジアミン、ノルボルネンジアミン、及びメタキシレンジアミン等が挙げられる。また、これらアミン類の変性物であってもよい。アミンの変性方法としては、カルボン酸との脱水縮合、エポキシ樹脂との付加反応、イソシアネートとの付加反応、マイケル付加反応、マンニッヒ反応、尿素との縮合反応、ケトンとの縮合反応などが挙げられる。これらは、単独で使用することもできるし、任意の割合で組み合わせて使用することもできる。 Examples of the aliphatic amines include ethylenediamine, hexamethylenediamine, 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, 1,3-bis (aminomethyl) cyclohexane, and 1, 4-bis (aminomethyl) cyclohexane, 4,4'-diaminodicyclohexylpropane, bis (4-aminocyclohexyl) sulfone, 4,4'-diaminodicyclohexyl ether, 2,2'-dimethyl-4,4'-diaminodicyclohexyl Examples thereof include methane, isophoronediamine, norbornenediamine, and metaxylenediamine. Further, it may be a modified product of these amines. Examples of the amine modification method include dehydration condensation with carboxylic acid, addition reaction with epoxy resin, addition reaction with isocyanate, Michael addition reaction, Mannich reaction, condensation reaction with urea, and condensation reaction with ketone. These can be used alone or in combination at any ratio.
　前記脂肪族アミン類からなる（Ｂ）硬化剤の（Ａ）エポキシ樹脂に対する配合量は、特に限定されるものではないが、エポキシ樹脂中のエポキシ基１当量に対し、脂肪族アミン中の活性水素が０．６～１．５当量になるように配合することが好ましく、０．８～１．２当量になるように配合することがより好ましい。 The amount of the (B) curing agent composed of the aliphatic amines to be added to the (A) epoxy resin is not particularly limited, but the amount of active hydrogen in the aliphatic amine is relative to one equivalent of the epoxy group in the epoxy resin. Is preferably blended so as to have an amount of 0.6 to 1.5 equivalents, and more preferably 0.8 to 1.2 equivalents.
　前記芳香族アミン類としては、ジエチルトルエンジアミン、１－メチル－３，５－ジエチル－２，４－ジアミンベンゼン、１－メチル－３，５－ジエチル－２，６－ジアミノベンゼン、１，３，５－トリエチル－２，６－ジアミノベンゼン、３，３’－ジエチル－４，４’－ジアミノジフェニルメタン、及び３，５，３’、５’－テトラメチル－４，４‘－ジアミノジフェニルメタンなどが挙げられる。また、これらアミン類の変性物であってもよい。アミンの変性方法としては、カルボン酸との脱水縮合、エポキシ樹脂との付加反応、イソシアネートとの付加反応、マイケル付加反応、マンニッヒ反応、尿素との縮合反応、ケトンとの縮合反応などが挙げられる。これらは、単独で使用することもできるし、任意の割合で組み合わせて使用することもできる。 Examples of the aromatic amines include diethyltoluenediamine, 1-methyl-3,5-diethyl-2,4-diaminebenzene, 1-methyl-3,5-diethyl-2,6-diaminobenzene, 1,3. Examples include 5-triethyl-2,6-diaminobenzene, 3,3'-diethyl-4,4'-diaminodiphenylmethane, and 3,5,3', 5'-tetramethyl-4,4'-diaminodiphenylmethane. Be done. Further, it may be a modified product of these amines. Examples of the amine modification method include dehydration condensation with carboxylic acid, addition reaction with epoxy resin, addition reaction with isocyanate, Michael addition reaction, Mannich reaction, condensation reaction with urea, and condensation reaction with ketone. These can be used alone or in combination at any ratio.
　前記芳香族アミン類からなる（Ｂ）硬化剤の（Ａ）エポキシ樹脂に対する配合量は、特に限定されるものではないが、エポキシ樹脂中のエポキシ基１当量に対し、芳香族アミン中の活性水素が０．６～１．５当量になるように配合することが好ましく、０．８～１．２当量になるように配合することがより好ましい。 The amount of the (B) curing agent composed of the aromatic amines to be added to the (A) epoxy resin is not particularly limited, but the amount of active hydrogen in the aromatic amine is relative to one equivalent of the epoxy group in the epoxy resin. Is preferably blended so as to have an amount of 0.6 to 1.5 equivalents, and more preferably 0.8 to 1.2 equivalents.
　前記アミン系潜在性硬化剤としては、室温でエポキシ樹脂と混合したときに、混合物の粘度変化や物性変化が小さいものを好適に使用することができる。そのようなアミン系潜在性硬化剤としては、例えば、ジシアンジアミド型潜在性硬化剤、イミダゾール型潜在性硬化剤及びポリアミン型潜在性硬化剤が挙げられる。 As the amine-based latent curing agent, one having a small change in viscosity or physical properties of the mixture when mixed with an epoxy resin at room temperature can be preferably used. Examples of such amine-based latent curing agents include dicyandiamide-type latent curing agents, imidazole-type latent curing agents, and polyamine-type latent curing agents.
　前記ジシアンジアミド型潜在性硬化剤としては、ジシアンジアミドが挙げられる。 Examples of the dicyandiamide-type latent curing agent include dicyandiamide.
　前記イミダゾール型潜在性硬化剤は、例えば、活性水素を含有したイミダゾール化合物と、エポキシ化合物とを反応させることによって得ることができる。イミダゾール化合物とエポキシ化合物との反応は５０～１５０℃にて１～２０時間行えばよい。イミダゾール化合物とエポキシ化合物との反応には、必要に応じて溶媒を用いてもよい。溶媒を用いた場合は、反応終了後、溶媒を８０～２００℃、常圧若しくは減圧により除去する。
　前記イミダゾール型潜在性硬化剤の製造に用いられるイミダゾール化合物としては、例えば、２－メチルイミダゾール、２－エチル－４－メチルイミダゾール、２－ウンデシルイミダゾール、２－ヘプタデシルイミダゾール等のアルキルイミダゾール、並びに２－フェニルイミダゾール等のアリールイミダゾールが挙げられる。
　前記イミダゾール型潜在性硬化剤の製造に用いられる前記エポキシ化合物としては、例えば、前記（Ａ）エポキシ樹脂にて例示した化合物が挙げられる。
　前記イミダゾール型潜在性硬化剤の製造に用いられる前記溶媒としては、メチルエチルケトン、メチルアミルケトン、ジエチルケトン、アセトン、メチルイソプロピルケトン及びプロピレングリコールモノメチルエーテルアセテート等のケトン類；シクロヘキサン等の脂肪族炭化水素類；テトラヒドロフラン、１，２－ジメトキシエタン、１，２－ジエトキシエタン、プロピレングリコールモノメチルエーテル等のエーテル類；酢酸エチル、酢酸ｎ－ブチル等のエステル類；ベンゼン、トルエン、キシレン等の芳香族炭化水素；四塩化炭素、クロロホルム、トリクロロエチレン、塩化メチレン等のハロゲン化脂肪族炭化水素；クロロベンゼン等のハロゲン化芳香族炭化水素が挙げられる。 The imidazole-type latent curing agent can be obtained, for example, by reacting an imidazole compound containing active hydrogen with an epoxy compound. The reaction between the imidazole compound and the epoxy compound may be carried out at 50 to 150 ° C. for 1 to 20 hours. If necessary, a solvent may be used for the reaction between the imidazole compound and the epoxy compound. When a solvent is used, the solvent is removed at 80 to 200 ° C. under normal pressure or reduced pressure after the reaction is completed.
Examples of the imidazole compound used in the production of the imidazole-type latent curing agent include alkylimidazoles such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, and 2-heptadecylimidazole, and Examples thereof include arylimidazole such as 2-phenylimidazole.
Examples of the epoxy compound used in the production of the imidazole-type latent curing agent include the compounds exemplified in the epoxy resin (A).
Examples of the solvent used for producing the imidazole-type latent curing agent include ketones such as methyl ethyl ketone, methyl amyl ketone, diethyl ketone, acetone, methyl isopropyl ketone and propylene glycol monomethyl ether acetate; and aliphatic hydrocarbons such as cyclohexane. Ethers such as tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane, propylene glycol monomethyl ether; esters such as ethyl acetate and n-butyl acetate; aromatic hydrocarbons such as benzene, toluene and xylene Examples include halogenated aliphatic hydrocarbons such as carbon tetrachloride, chloroform, trichloroethylene and methylene chloride; halogenated aromatic hydrocarbons such as chlorobenzene.
　前記ポリアミン型潜在性硬化剤は、例えば、ポリアミンとエポキシ化合物とを反応させることによって得ることができる。ポリアミンとエポキシ化合物との反応は、５０～１５０℃にて、１～２０時間行えばよい。ポリアミンとエポキシ化合物との反応には、必要に応じて、溶媒を用いてもよい。溶媒を用いた場合、反応終了後、溶媒を８０～２００℃、常圧若しくは減圧により除去する。
　前記ポリアミン型潜在性硬化剤の製造に用いられる前記ポリアミンとしては、例えば、前記脂肪族アミン類、芳香族アミン類で例示した化合物が挙げられる。前記ポリアミン型潜在性硬化剤の製造に用いられるエポキシ化合物及び溶媒としては、前記イミダゾール型潜在性硬化剤の製造に用いられるものと同様なものを用いることができる。 The polyamine-type latent curing agent can be obtained, for example, by reacting a polyamine with an epoxy compound. The reaction between the polyamine and the epoxy compound may be carried out at 50 to 150 ° C. for 1 to 20 hours. If necessary, a solvent may be used for the reaction between the polyamine and the epoxy compound. When a solvent is used, the solvent is removed at 80 to 200 ° C. under normal pressure or reduced pressure after the reaction is completed.
Examples of the polyamine used in the production of the polyamine-type latent curing agent include compounds exemplified by the aliphatic amines and aromatic amines. As the epoxy compound and solvent used in the production of the polyamine-type latent curing agent, the same ones as those used in the production of the imidazole-type latent curing agent can be used.
　組成物の貯蔵安定性を向上させるために、前記アミン系潜在性硬化剤と、前記例示したフェノール樹脂類とを併用してもよい。 In order to improve the storage stability of the composition, the amine-based latent curing agent and the above-exemplified phenol resins may be used in combination.
　（Ｂ）成分であるアミン系潜在性硬化剤としては市販品を用いることができる。市販品としては、アデカハードナー　ＥＨ－３６３６ＡＳ（株式会社ＡＤＥＫＡ製；ジシアンジアミド型潜在性硬化剤）、アデカハードナー　ＥＨ－４３５１Ｓ（株式会社ＡＤＥＫＡ製；ジシアンジアミド型潜在性硬化剤）、アデカハードナー　ＥＨ－５０１１Ｓ（株式会社ＡＤＥＫＡ製；イミダゾール型潜在性硬化剤）、アデカハードナー　ＥＨ－５０４６Ｓ（株式会社ＡＤＥＫＡ製；イミダゾール型潜在性硬化剤）、アデカハードナー　ＥＨ－４３５７Ｓ（株式会社ＡＤＥＫＡ製；ポリアミン型潜在性硬化剤）、アデカハードナー　ＥＨ－５０５７Ｐ（株式会社ＡＤＥＫＡ製；ポリアミン型潜在性硬化剤）、アデカハードナー　ＥＨ－５０５７ＰＫ（株式会社ＡＤＥＫＡ製；ポリアミン型潜在性硬化剤）、アミキュアＰＮ－２３（味の素ファインテクノ株式会社製；アミンアダクト系潜在性硬化剤）、アミキュアＰＮ－４０（味の素ファインテクノ株式会社製；アミンアダクト系潜在性硬化剤）、アミキュアＶＤＨ（味の素ファインテクノ株式会社製；ヒドラジド系潜在性硬化剤）、フジキュアＦＸＲ－１０２０（株式会社Ｔ＆Ｋ　ＴＯＫＡ製；潜在性硬化剤）等が挙げられる。これら市販品は１種を単独で使用してもよく、２種以上を組み合わせて使用してもよい。 A commercially available product can be used as the amine-based latent curing agent as the component (B). Commercially available products include ADEKA HANDNER EH-3636AS (manufactured by ADEKA Corporation; deciandiamide type latent curing agent), ADEKA HANDNER EH-4351S (manufactured by ADEKA Corporation; deciandiamide type latent curing agent), and ADEKA HANDNER EH-5011S (stock). Company ADEKA; ADEKA latent curing agent), ADEKA Hardener EH-5046S (ADEKA Corporation; imidazole type latent curing agent), ADEKA Hardener EH-4357S (ADEKA Corporation; polyamine type latent curing agent), ADEKA HANDNER EH-5057P (manufactured by ADEKA Corporation; polyamine type latent curing agent), ADEKA HANDNER EH-5057PK (manufactured by ADEKA Corporation; polyamine type latent curing agent), Amicure PN-23 (manufactured by Ajinomoto Fine Techno Co., Ltd .;) Amine Adact Latent Hardener), Amicure PN-40 (Ajinomoto Fine Techno Co., Ltd .; Amine Adact Latent Hardener), Amicure VDH (Ajinomoto Fine Techno Co., Ltd .; Hydrazide Latent Hardener), Fujicure FXR -1020 (manufactured by T & K TOKA Corporation; latent curing agent) and the like can be mentioned. One of these commercially available products may be used alone, or two or more thereof may be used in combination.
　前記アミン系潜在性硬化剤からなる硬化剤（Ｂ）のエポキシ樹脂（Ａ）に対する配合量は、特に限定されるものではないが、エポキシ樹脂１００質量部に対して１～７０質量部であることが好ましく、３～６０質量部であることがより好ましい。（Ｂ）成分であるアミン系潜在性硬化剤の含有量を上述の範囲とすることで、優れた密着性を発現するための内部反応性を発揮するため好ましい。 The blending amount of the curing agent (B) composed of the amine-based latent curing agent with respect to the epoxy resin (A) is not particularly limited, but is 1 to 70 parts by mass with respect to 100 parts by mass of the epoxy resin. Is preferable, and the amount is more preferably 3 to 60 parts by mass. It is preferable that the content of the amine-based latent curing agent (B) is in the above range because the internal reactivity for exhibiting excellent adhesion is exhibited.
　前記（Ｂ）成分である酸無水物類としては、無水ハイミック酸、無水フタル酸、無水マレイン酸、無水メチルハイミック酸、無水コハク酸、テトラヒドロ無水フタル酸、ヘキサヒドロ無水フタル酸、メチルテトラヒドロ無水フタル酸、メチルヘキサヒドロ無水フタル酸、トリアルキルテトラヒドロ無水フタル酸－無水マレイン酸付加物、ベンゾフェノンテトラカルボン酸無水物、無水トリメリット酸、無水ピロメリット酸、及び水素化メチルナジック酸無水物等が挙げられる。
　前記酸無水物類からなる硬化剤（Ｂ）のエポキシ樹脂（Ａ）に対する配合量は、特に限定されるものではないが、エポキシ樹脂中のエポキシ基１当量に対し、酸無水物類中の酸無水物基の数が０．７～１．６当量であることが好ましく、０．９～１．２当量であることがより好ましい。 Examples of the acid anhydrides as the component (B) include hymic anhydride, phthalic anhydride, maleic anhydride, methyl hymic anhydride, succinic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, and methyltetrahydrophthalic anhydride. Acids, methylhexahydrophthalic anhydride, trialkyltetrahydrophthalic anhydride-maleic anhydride adduct, benzophenone tetracarboxylic acid anhydride, trimellitic anhydride, pyromellitic anhydride, hydride methylnadic anhydride, etc. Be done.
The amount of the curing agent (B) composed of the acid anhydrides to be blended with the epoxy resin (A) is not particularly limited, but the acid in the acid anhydrides is relative to one equivalent of the epoxy group in the epoxy resin. The number of anhydride groups is preferably 0.7 to 1.6 equivalents, more preferably 0.9 to 1.2 equivalents.
　前記に挙げられた硬化剤の中でもアミン系潜在性硬化剤を使用することが、要求特性に応じて各種変性可能であることから好ましい。 Among the curing agents listed above, it is preferable to use an amine-based latent curing agent because various modifications can be made according to the required characteristics.
　本発明の樹脂組成物に含まれる（Ｃ）成分であるウレタンエラストマーとしては、ポリオール、ポリイソシアネート、必要に応じて鎖伸長剤を使用して得られるウレタン構造を有するエラストマーを特に制限なく用いることができる。本発明においては、ウレタンエラストマーとして、例えば、ブロックウレタンを使用することが、柔軟性付与効果、密着性付与効果などに優れたものを提供することができるため好ましい。 As the urethane elastomer as the component (C) contained in the resin composition of the present invention, an elastomer having a urethane structure obtained by using a polyol, a polyisocyanate, and if necessary, a chain extender can be used without particular limitation. it can. In the present invention, it is preferable to use, for example, block urethane as the urethane elastomer because it is possible to provide an elastomer having excellent flexibility-imparting effect, adhesion-imparting effect and the like.
　本発明の樹脂組成物は（Ｃ）成分であるブロックウレタンとしては、イソシアネート基を有するポリウレタン中の過剰のイソシアネート基をブロック化剤を用いてブロック化して得られるものを用いることが好ましい。本明細書において「ポリウレタンのイソシアネート基が過剰である」とは、ポリウレタンのイソシアネート（ＮＣＯ）含有量が０．１質量％以上であることを意味する。本発明においては、ブロックウレタンとして、イソシアネート（ＮＣＯ）含有量が０．１～１０質量％、好ましくは１～８質量％であるポリウレタンを、（Ｃ２）ブロック化剤でブロックして得られるブロックウレタンが好ましく用いられる。かかるポリウレタンを用いることによって、優れた密着性を発現するための内部反応性を発揮するため好ましい。ポリウレタンとして、（ｃ－１）ポリヒドロキシ化合物と、（ｃ－２）ポリイソシアネート化合物とを、該ポリヒドロキシ化合物に含まれるヒドロキシ基に対して、該ポリイソシアネート化合物に含まれるイソシアネート基が過剰となる量反応させて得られるものを用いることが好ましい。 As the block urethane as the component (C), the resin composition of the present invention is preferably obtained by blocking an excess of isocyanate groups in polyurethane having an isocyanate group with a blocking agent. In the present specification, "the isocyanate group of polyurethane is excessive" means that the isocyanate (NCO) content of polyurethane is 0.1% by mass or more. In the present invention, the blocked urethane obtained by blocking polyurethane having an isocyanate (NCO) content of 0.1 to 10% by mass, preferably 1 to 8% by mass as the blocked urethane with a (C2) blocking agent. Is preferably used. It is preferable to use such polyurethane because it exhibits internal reactivity for exhibiting excellent adhesion. As the polyurethane, the (c-1) polyhydroxy compound and the (c-2) polyisocyanate compound have an excess of isocyanate groups contained in the polyisocyanate compound with respect to the hydroxy groups contained in the polyhydroxy compound. It is preferable to use the one obtained by quantitative reaction.
　前記（ｃ－１）ポリヒドロキシ化合物としては、例えば、ポリエーテルポリオール、ポリエステルポリオール、ポリカーボネートポリオール、ポリエステルアミドポリオール、アクリルポリオール、ポリウレタンポリオール等が挙げられる。 Examples of the (c-1) polyhydroxy compound include polyether polyols, polyester polyols, polycarbonate polyols, polyesteramide polyols, acrylic polyols, polyurethane polyols and the like.
　前記ポリエーテルポリオールとしては、分子量１００～５５００程度の多価アルコールのアルキレンオキサイド付加物が好ましく使用される。 As the polyether polyol, an alkylene oxide adduct of a polyhydric alcohol having a molecular weight of about 100 to 5500 is preferably used.
　前記ポリエーテルポリオールの製造に用いられる多価アルコールとしては、例えば、エチレングリコール、プロピレングリコール、１，４－ブチレングリコール（テトラメチレングリコール）、ネオペンタングリコール等の２価アルコール；グリセリン、トリオキシイソブタン、１，２，３－ブタントリオール、１，２，３－ペンタントリオール、２－メチル－１，２，３－プロパントリオール、２－メチル－２，３，４－ブタントリオール、２－エチル－１，２，３－ブタントリオール、２，３，４－ペンタントリオール、２，３，４－ヘキサントリオール、４－プロピル－３，４，５－ヘプタントリオール、２，４－ジメチル－２，３，４－ペンタントリオール、ペンタメチルグリセリン、ペンタグリセリン、１，２，４－ブタントリオール、１，２，４－ペンタントリオール、トリメチロールプロパン等の３価アルコール；エリトリット、ペンタエリトリット、１，２，３，４－ペンタンテトロール、２，３，４，５－ヘキサンテトロール、１，２，３，５－ペンタンテトロール、１，３，４，５－ヘキサンテトロール等の４価アルコール；アドニット、アラビット、キシリット等の５価アルコール；ソルビット、マンニット、イジット等の六価アルコール等が挙げられる。
　本発明においては、前記多価アルコールとして２～４価のアルコールを用いることが好ましく、プロピレングリコール及び１，４－ブチレングリコール等のアルキレングリコール又はグリセリン等の３価のアルコールを用いることより好ましい。 Examples of the polyhydric alcohol used for producing the polyether polyol include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butylene glycol (tetramethylene glycol), and neopentane glycol; glycerin, trioxyisobutane, and the like. 1,2,3-butanetriol, 1,2,3-pentantriol, 2-methyl-1,2,3-propanetriol, 2-methyl-2,3,4-butanetriol, 2-ethyl-1, 2,3-Butantriol, 2,3,4-Pentantriol, 2,3,4-Hexanetriol, 4-propyl-3,4,5-Heptanetriol, 2,4-dimethyl-2,3,4- Trivalent alcohols such as pentantriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2,4-pentantriol, trimethylpropane; erythrit, pentaerytrit, 1,2,3,4 -Pentantetrol, 2,3,4,5-hexanetetrol, 1,2,3,5-pentanetetrol, 1,3,4,5-hexanetetrol and other tetravalent alcohols; adnit, arabite, Pentavalent alcohols such as xylit; hexavalent alcohols such as sorbit, mannit, and igit can be mentioned.
In the present invention, it is preferable to use a dihydric to tetravalent alcohol as the polyhydric alcohol, and it is more preferable to use an alkylene glycol such as propylene glycol and 1,4-butylene glycol or a trivalent alcohol such as glycerin.
　前記ポリエーテルポリオールは、前記に例示したごとき多価アルコールに、常法により炭素数２～４個のアルキレンオキサイドを、所望の分子量となるように付加することによって製造することができる。炭素数２～４個のアルキレンオキサイドとしては、例えば、エチレンオキサイド、プロピレンオキサイド、ブチレンオキサイド（テトラメチレンオキサイド）が挙げられるが、特にプロピレンオキサイド、ブチレンオキサイドを使用するのが好ましい。 The polyether polyol can be produced by adding an alkylene oxide having 2 to 4 carbon atoms to a polyhydric alcohol as exemplified above so as to have a desired molecular weight by a conventional method. Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, and butylene oxide (tetramethylene oxide), and propylene oxide and butylene oxide are particularly preferable.
　前記ポリエステルポリオールとしては、例えば、ポリカルボン酸及び多価アルコールから製造される従来公知のポリエステルあるいはラクタム類から得られるポリエステル等が挙げられる。
　前記ポリカルボン酸としては、例えば、ベンゼントリカルボン酸、アジピン酸、琥珀酸、スベリン酸、セバシン酸、蓚酸、メチルアジピン酸、グルタル酸、ピメリン酸、アゼライン酸、フタル酸、テレフタル酸、イソフタル酸、チオジプロピオン酸、マレイン酸、フマル酸、シトラコン酸、イタコン酸又はこれらに類する任意の適当なカルボン酸を使用することができる。 Examples of the polyester polyol include conventionally known polyesters produced from polycarboxylic acids and polyhydric alcohols, polyesters obtained from lactams, and the like.
Examples of the polycarboxylic acid include benzenetricarboxylic acid, adipic acid, amber acid, suberic acid, sebacic acid, itaconic acid, methyladic acid, glutaric acid, pimelic acid, azelaic acid, phthalic acid, terephthalic acid, isophthalic acid, and thio. Dipropionic acid, maleic acid, fumaric acid, citraconic acid, itaconic acid or any suitable carboxylic acid similar thereto can be used.
　前記ポリエステルポリオールの製造に使用される多価アルコールとしては、例えば、エチレングリコール、プロピレングリコール、１，４－ブタンジオール、１，３－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、ビス（ヒドロキシメチルクロルヘキサン）、ジエチレングリコール、ポリテトラメチレングリコール、ポリカプロラクトングリコール等のポリエーテルポリオール、２，２－ジメチルプロピレングリコール、１，３，６－ヘキサントリオール、トリメチロールプロパン、ペンタエリスリトール、ソルビトール、グリセリン又はこれらに類する任意の適当な多価アルコールを使用することができる。 Examples of the polyhydric alcohol used in the production of the polyester polyol include ethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, and 1,6-hexanediol. , Bis (hydroxymethylchlorohexane), diethylene glycol, polytetramethylene glycol, polyether polyols such as polycaprolactone glycol, 2,2-dimethylpropylene glycol, 1,3,6-hexanetriol, trimethylolpropane, pentaerythritol, sorbitol , Glycerin or any suitable polyhydric alcohol similar thereto can be used.
　前記ポリカーボネートポリオールとしては、例えば、ジオールとジフェニルカーボネートとの脱フェノール反応、ジオールとジアルキルカーボネートとの脱アルコール反応、あるいはジオールとアルキレンカーボネートとの脱グリコール反応等で得られるものが挙げられる。前記ポリカーボネートポリオールの製造に使用されるジオールとしては、例えは、エチレングリコール、１，２－プロピレングリコール、１，３－プロピレングリコール、１，２－ブタンジオール、１，３－ブタンジオール、１，４－ブタンジオール、１，５－ペンタンジオール、１，６－ヘキサンジオール、１，４－シクロヘキサンジオール、１，４－シクロヘキサンジメタノール、１，７－ヘプタンジオール、１，８－オクタンジオール、１，９－ノナンジオール、１，１０－デカンジオール、ネオペンチルグリコール、３－メチル－１，５－ペンタンジオール、３，３－ジメチロールヘプタン等が挙げられる。 Examples of the polycarbonate polyol include those obtained by a dephenolization reaction between a diol and a diphenyl carbonate, a dealcoholization reaction between a diol and a dialkyl carbonate, a deglycolation reaction between a diol and an alkylene carbonate, and the like. Examples of the diol used for producing the polycarbonate polyol include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, and 1,4. -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,7-heptanediol, 1,8-octanediol, 1,9 Examples thereof include -nonanediol, 1,10-decanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, and 3,3-dimethylol heptane.
　前記ポリヒドロキシ化合物の中でも、ポリエーテルポリオールを使用することが、耐湿熱性が良好な樹脂組成物が得られるため好ましい。 Among the polyhydroxy compounds, it is preferable to use a polyether polyol because a resin composition having good moisture and heat resistance can be obtained.
　前記（ｃ－２）ポリイソシアネート化合物としては、例えば、プロパン－１，２－ジイソシアネート、２，３－ジメチルブタン－２，３－ジイソシアネート、２－メチルペンタン－２，４－ジイソシアネート、オクタン－３，６－ジイソシアネート、３，３－ジニトロペンタン－１，５－ジイソシアネート、オクタン－１，６－ジイソシアネート、１，６－ヘキサメチレンジイソシアネート（ＨＤＩ）、トリメチルヘキサメチレンジイソシアネート、リジンジイソシアネート、トリレンジイソシアネート（ＴＤＩ）、キシリレンジイソシアネート、メタテトラメチルキシリレンジイソシアネート、イソホロンジイソシアネート（３－イソシアネートメチル－３，５，５－トリメチルシクロヘキシルイソシアネート）、１，３－又は１，４－ビス（イソシアネートメチル）シクロヘキサン、ジフェニルメタン－４，４’－ジイソシアネート（ＭＤＩ）、ジシクロヘキシルメタン－４，４’－ジイソシアネート（水添ＭＤＩ）、水添トリレンジイソシアネート等、及びこれらの混合物が挙げられる。これらのポリイソシアネート化合物は、三量化してなるイソシアヌル体であってもよい。
　これらのポリイソシアネート化合物の中でも、１，６－ヘキサメチレンジイソシアネート、トリレンジイソシアネート、イソホロンジイソシアネート、及びこれらのイソシアヌル体からなる群から選ばれる少なくとも１種を使用することが、金属基材に対して強い接着性を示す樹脂組成物が得られるため好ましい。 Examples of the (c-2) polyisocyanate compound include propane-1,2-diisocyanate, 2,3-dimethylbutane-2,3-diisocyanate, 2-methylpentane-2,4-diisocyanate, octane-3, 6-Diisocyanate, 3,3-dinitropentane-1,5-diisocyanate, octane-1,6-diisocyanate, 1,6-hexamethylene diisocyanate (HDI), trimethylhexamethylene diisocyanate, lysine diisocyanate, tolylene diisocyanate (TDI) , Xylylene diisocyanate, metatetramethylxylylene diisocyanate, isophorone diisocyanate (3-isocyanatemethyl-3,5,5-trimethylcyclohexylisocyanate), 1,3- or 1,4-bis (isocyanatemethyl) cyclohexane, diphenylmethane-4 , 4'-Diisocyanate (MDI), dicyclohexylmethane-4,4'-diisocyanate (hydrogenated MDI), hydrogenated tolylene diisocyanate and the like, and mixtures thereof. These polyisocyanate compounds may be isocyanulates formed by trimerization.
Among these polyisocyanate compounds, it is strong against a metal substrate to use at least one selected from the group consisting of 1,6-hexamethylene diisocyanate, tolylene diisocyanate, isophorone diisocyanate, and these isocyanul compounds. It is preferable because a resin composition exhibiting adhesiveness can be obtained.
　ここで、前記（ｃ－１）ポリヒドロキシ化合物及び前記（ｃ－２）ポリイソシアネート化合物からの（Ｃ１）ポリウレタンの製造は、常法により行うことができる。
　前記（ｃ－１）成分と前記（ｃ－２）成分との使用量は、（ｃ－１）成分に対し（ｃ－２）成分が過剰となる量、具体的には、（ｃ－１）成分の水酸基１当量に対して、（ｃ－２）のイソシアネート基が過剰となる量、好ましくは１．２～５当量、特に好ましくは１．５～２．５当量とする。前記の使用量とすることにより、イソシアネート含有量が０．１～１０質量％であるポリウレタンを得ることが可能となる。得られたポリウレタンのイソシアネート含有量は、１～８質量％であることが好ましい。
　ここでイソシアネート含有量は、ＪＩＳ　Ｋ　１６０３－１に順じて測定することができる。 Here, the production of the (C1) polyurethane from the (c-1) polyhydroxy compound and the (c-2) polyisocyanate compound can be carried out by a conventional method.
The amount of the component (c-1) and the component (c-2) used is an amount in which the component (c-2) is excessive with respect to the component (c-1), specifically, (c-1). ), The amount of the isocyanate group of (c-2) in excess of 1 equivalent of the hydroxyl group, preferably 1.2 to 5 equivalents, particularly preferably 1.5 to 2.5 equivalents. By using the above amount, it is possible to obtain polyurethane having an isocyanate content of 0.1 to 10% by mass. The isocyanate content of the obtained polyurethane is preferably 1 to 8% by mass.
Here, the isocyanate content can be measured according to JIS K 1603-1.
　前記（Ｃ１）ポリウレタンを製造する際の反応温度は、通常４０～１４０℃、好ましくは６０～１３０℃である。また、反応を促進するために公知のウレタン重合用触媒、例えば、ジオクチルスズジラウレート、ジブチルスズジラウレート、第一スズオクトエート、スタナスオクトエート、オクチル酸鉛、ナフテン酸鉛、オクチル酸亜鉛等の有機金属化合物、トリエチレンジアミン、トリエチルアミン等の第三級アミン系化合物を使用することも可能である。 The reaction temperature at the time of producing the (C1) polyurethane is usually 40 to 140 ° C, preferably 60 to 130 ° C. Also, known catalysts for urethane polymerization to promote the reaction, such as organic metals such as dioctyltin dilaurate, dibutyltin dilaurate, stannous octate, stanas octoate, lead octylate, lead naphthenate, zinc octylate, etc. It is also possible to use a compound, a tertiary amine compound such as triethylenediamine or triethylamine.
　前記（Ｃ２）ブロック化剤としては、例えば、マロン酸ジエステル（マロン酸ジエチル等）、アセチルアセトン、アセト酢酸エステル（アセト酢酸エチル等）等の活性メチレン化合物；アセトオキシム、メチルエチルケトオキシム（ＭＥＫオキシム）、メチルイソブチルケトオキシム（ＭＩＢＫオキシム）等のオキシム化合物；メチルアルコール、エチルアルコール、プロピルアルコール、ブチルアルコール、ヘプチルアルコール、ヘキシルアルコール、オクチルアルコール、２－エチルヘキシルアルコール、イソノニルアルコール、ステアリルアルコール等の１価アルコール又はこれらの異性体；メチルグリコール、エチルグリコール、エチルジグリコール、エチルトリグリコール、ブチルグリコール、ブチルジグリコール等のグリコール誘導体；ジシクロヘキシルアミン等のアミン化合物；フェノール、クレゾール、エチルフェノール、ｎ－プロピルフェノール、イソプロピルフェノール、ブチルフェノール、第三ブチルフェノール、オクチルフェノール、ノニルフェノール、ドデシルフェノール、シクロヘキシルフェノール、クロロフェノール、ブロモフェノール等のモノフェノール類、レゾルシン、カテコール、ハイドロキノン、ビスフェノールＡ、ビスフェノールＳ、ビスフェノールＦ、ナフトール等のジフェノール類等のフェノール類；ε－カプロラクトン、ε－カプロラクタム等が挙げられる。
　これらのブロック化剤の中でも、アミン化合物、ジフェノール類、ε－カプロラクトン及びε－カプロラクタムからなる群から選択される１種以上を使用することが、強い接着性を有する硬化性樹脂組成物が確実に得られるため好ましい。アミン化合物としては、ジシクロヘキシルアミンを用いることが好ましい。 Examples of the (C2) blocking agent include active methylene compounds such as malonic acid diester (diethyl malonate, etc.), acetylacetone, and acetacetic acid ester (ethyl acetate acetate, etc.); Oxim compounds such as isobutyl ketooxime (MIBK oxime); monohydric alcohols such as methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, heptyl alcohol, hexyl alcohol, octyl alcohol, 2-ethylhexyl alcohol, isononyl alcohol, stearyl alcohol or the like. These isomers; glycol derivatives such as methyl glycol, ethyl glycol, ethyl diglycol, ethyl triglycol, butyl glycol, butyl diglycol; amine compounds such as dicyclohexylamine; phenol, cresol, ethylphenol, n-propylphenol, isopropyl Monophenols such as phenol, butylphenol, tertiary butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol and bromophenol, diphenols such as resorcin, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F and naphthol. Phenols such as ε-caprolactone, ε-caprolactam and the like.
Among these blocking agents, using one or more selected from the group consisting of amine compounds, diphenols, ε-caprolactone and ε-caprolactam ensures a curable resin composition having strong adhesiveness. It is preferable because it can be obtained in. As the amine compound, it is preferable to use dicyclohexylamine.
　（Ｃ２）ブロック化剤の使用量は任意であるが、通常は（Ｃ１）ポリウレタンのイソシアネート基に対し、当量程度が使用する。 The amount of the (C2) blocking agent used is arbitrary, but usually, about the equivalent amount is used with respect to the isocyanate group of the (C1) polyurethane.
　（Ｃ２）ブロック化剤による（Ｃ１）ポリウレタンのブロック化反応は、通常、（Ｃ１）ポリウレタンの重合の最終の反応で（Ｃ２）ブロック化剤を添加する方法をとるが、（Ｃ１）ポリウレタンの重合の任意の段階で（Ｃ２）ブロック化剤を添加し反応させて、ブロックポリウレタンを得ることもできる。 The blocking reaction of (C1) polyurethane with (C2) blocking agent is usually a method of adding (C2) blocking agent in the final reaction of polymerization of (C1) polyurethane, but (C1) polymerization of polyurethane. Blocked polyurethane can also be obtained by adding and reacting the (C2) blocking agent at any stage of.
　（Ｃ２）ブロック化剤の添加方法としては、所定の重合終了時に添加するか、重合初期に添加するか、又は重合初期に一部添加し重合終了時に残部を添加する等の方法が可能であるが、好ましくは重合終了時に添加する。この場合、所定の重合終了時の目安としては、イソシアネート含有量（％）（ＪＩＳ　Ｋ　１６０３－１に順じて測定したもの）を基準とすればよい。ブロック化剤を添加する際の反応温度は、通常５０～１５０℃であり、好ましくは６０～１２０℃である。反応時間は通常１～７時間程度とする。反応に際し、前掲の公知のウレタン重合用触媒を添加して反応を促進することも可能である。また、反応に際し、可塑剤を任意の量加えてもよい。 (C2) As a method of adding the blocking agent, a method of adding at the end of a predetermined polymerization, adding at the beginning of polymerization, adding a part at the beginning of polymerization, and adding the rest at the end of polymerization is possible. However, it is preferably added at the end of polymerization. In this case, the isocyanate content (%) (measured according to JIS K 1603-1) may be used as a reference at the end of the predetermined polymerization. The reaction temperature when the blocking agent is added is usually 50 to 150 ° C, preferably 60 to 120 ° C. The reaction time is usually about 1 to 7 hours. At the time of the reaction, it is also possible to add the above-mentioned known catalyst for urethane polymerization to accelerate the reaction. In addition, an arbitrary amount of plasticizer may be added during the reaction.
　本発明の樹脂組成物に使用する、（Ｃ）成分のブロックポリウレタンの配合量は、（Ａ）成分であるエポキシ樹脂１００質量部に対して１～５０質量部であることが好ましく、特に１～１０質量部であることが好ましい。（Ｃ）成分であるブロックウレタンの含有量が上述の範囲であると、基材に対する塗膜の接着性、塗膜の耐寒性、及び塗膜強度が良好となり、且つ調製された樹脂組成物の粘度が高くなりすぎず、塗布する際の作業性が良好となるため好ましい。 The blending amount of the block polyurethane of the component (C) used in the resin composition of the present invention is preferably 1 to 50 parts by mass, particularly 1 to 50 parts by mass with respect to 100 parts by mass of the epoxy resin as the component (A). It is preferably 10 parts by mass. When the content of the block urethane as the component (C) is within the above range, the adhesiveness of the coating film to the substrate, the cold resistance of the coating film, and the strength of the coating film are good, and the prepared resin composition It is preferable because the viscosity does not become too high and the workability at the time of coating is improved.
　次に、本発明の樹脂組成物に含まれる下記の式（１）で表される（Ｄ）成分の含リン化合物について説明する。 Next, the phosphorus-containing compound of the component (D) represented by the following formula (1) contained in the resin composition of the present invention will be described.
Figure JPOXMLDOC01-appb-C000010
Figure JPOXMLDOC01-appb-C000010
　式中、ｍは１～１０の整数を表し、
　Ｒ１及びＲ２は、それぞれ独立に、アルキル基又はアリール基を表し、
　Ｒ３は、炭化水素基、又は該炭化水素基中の１若しくは２以上のメチレン基が酸素原子、硫黄原子若しくは窒素原子で置換された基を表し、該炭化水素基は酸素原子、硫黄原子又は窒素原子を含む置換基で置換されていてもよく、
　Ｘ１は酸素原子又は硫黄原子を表し、
　Ｙ１は酸素原子、硫黄原子、又は－ＮＲ４－を表し、
　Ｒ４は、水素原子、アルキル基又はアリール基を表す。 In the formula, m represents an integer from 1 to 10.
R 1 and R 2 independently represent an alkyl group or an aryl group, respectively.
R 3 represents a hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a sulfur atom. It may be substituted with a substituent containing a nitrogen atom.
X 1 represents an oxygen atom or a sulfur atom and represents
Y 1 is an oxygen atom, a sulfur atom, or -NR 4 - represents,
R 4 represents a hydrogen atom, an alkyl group or an aryl group.
　前記式（１）中、ｍは２～７であることが好ましく、２～５であることがより好ましい。ｍが２以上であると、エポキシ基と反応する官能基が２以上となり、エポキシ樹脂を硬化したときの硬化物のガラス転移温度や強度が高くなるため好ましい。ｍが７以下であると、含リン化合物を製造する際に、粘度が高くならず、含リン化合物の製造が容易になるため好ましい。 In the above formula (1), m is preferably 2 to 7, and more preferably 2 to 5. When m is 2 or more, the number of functional groups that react with the epoxy group is 2 or more, and the glass transition temperature and strength of the cured product when the epoxy resin is cured are high, which is preferable. When m is 7 or less, the viscosity does not increase when the phosphorus-containing compound is produced, and the phosphorus-containing compound can be easily produced, which is preferable.
　前記式（１）中のＲ１、Ｒ２及びＲ４で表されるアルキル基としては、直鎖状のアルキル基が挙げられる。直鎖状のアルキル基としては、炭素原子数１～１２のアルキル基が挙げられる。その具体例としては、メチル基、エチル基、プロピル基、ブチル基、アミル基、ヘキシル基、オクチル基、ノニル基及びデシル基が挙げられる。
　またＲ１、Ｒ２及びＲ４で表されるアルキル基としては、分岐状のアルキル基が挙げられる。分岐状のアルキル基としては、炭素原子数１～１２のものが挙げられる。その具体例としては、イソプロピル基、イソブチル基、第三ブチル基、イソアミル基、第三アミル基、イソヘキシル基、２－エチルヘキシル基及び第三オクチル基が挙げられる。
　本発明においては、得られる硬化物の発砲が一層抑制されることから、直鎖状のアルキル基を用いることが好ましい。同様の観点から、アルキル基の炭素原子数は１～６であることが好ましく、２～５であることがより好ましく、２～４であることが更に好ましい。直鎖状のアルキル基は、エチル基又はプロピル基であることが好ましい。 Examples of the alkyl group represented by R 1 , R 2 and R 4 in the formula (1) include a linear alkyl group. Examples of the linear alkyl group include an alkyl group having 1 to 12 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a nonyl group and a decyl group.
Examples of the alkyl group represented by R 1 , R 2 and R 4 include a branched alkyl group. Examples of the branched alkyl group include those having 1 to 12 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tertiary butyl group, an isoamyl group, a tertiary amyl group, an isohexyl group, a 2-ethylhexyl group and a tertiary octyl group.
In the present invention, it is preferable to use a linear alkyl group because the firing of the obtained cured product is further suppressed. From the same viewpoint, the number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 2 to 5, and even more preferably 2 to 4. The linear alkyl group is preferably an ethyl group or a propyl group.
　前記式（１）中のＲ１、Ｒ２及びＲ４で表されるアリール基は、単環であってもよく、縮合環であってもよい。単環のアリール基としては、例えば、フェニル基が挙げられる。縮合環のアリール基としては、例えばナフチル基等が挙げられる。該アリール基の炭素原子数は６～３２であることが好ましく、７～１１であることがより好ましい。 The aryl group represented by R 1 , R 2 and R 4 in the formula (1) may be a monocyclic ring or a condensed ring. Examples of the monocyclic aryl group include a phenyl group. Examples of the aryl group of the fused ring include a naphthyl group and the like. The aryl group preferably has 6 to 32 carbon atoms, more preferably 7 to 11 carbon atoms.
　前記式（１）中、Ｒ３で表される炭化水素基としては、アルキル基、アリール基、アルカンジイル基、アルカントリイル基、単核多価フェノール化合物から水酸基を除いた残基、及び多核多価フェノール化合物から水酸基を除いた残基が挙げられる。
　Ｒ３で表されるアルキル基としては、直鎖状のアルキル基が挙げられる。直鎖状のアルキル基としては、炭素原子数１～１２のものが挙げられる。その具体例としては、メチル基、エチル基、プロピル基、ブチル基、アミル基、ヘキシル基、オクチル基、ノニル基及びデシル基等が挙げられる。
　またＲ３で表されるアルキル基としては、分岐状のアルキル基が挙げられる。分岐状のアルキル基としては、炭素原子数１～１２のものが挙げられる。その具体例としては、イソプロピル基、イソブチル基、第三ブチル基、イソアミル基、第三アミル基、イソヘキシル基、２－エチルヘキシル基及び第三オクチル基が挙げられる。
　Ｒ３で表されるアリール基は、単環であってもよく、縮合環であってもよい。単環のアリール基としては、例えば、フェニル基が挙げられる。縮合環のアリール基としては、例えばナフチル基等が挙げられる。該アリール基の炭素原子数は６～３２であることが好ましく、７～１１であることがより好ましい。
　Ｒ３で表されるアルカンジイル基としては、例えば、メチレン基、エチレン基、プロピレン基、エタンジイル基及びオクタンジイル基等が挙げられる。
　Ｒ３で表されるアルカントリイル基としては、メタントリイル及び１，１，２－エタントリイル基等が挙げられる。
　Ｒ３で表されるアルカンテトライル基としては、例えば、１，１，２，２－エタンテトライル等が挙げられる。
　Ｒ３で表される単核多価フェノール化合物としては、例えば、ハイドロキノン、レゾルシン、ピロカテコール及びフロログルクシノール等が挙げられる。
　Ｒ３で表される多核多価フェノール化合物としては、例えば、ジヒドロキシナフタレン、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデン（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミル）ベンゼン、１，４－ビス（４－ヒドロキシクミル）ベンゼン、１，１，３－トリス（４－ヒドロキシフェニル）ブタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン、フェノールノボラック、オルソクレゾールノボラック、エチルフェノールノボラック、ブチルフェノールノボラック、オクチルフェノールノボラック、レゾルシンノボラック及びテルペンフェノールが挙げられる。 In the above formula (1), the hydrocarbon group represented by R 3 includes an alkyl group, an aryl group, an alkanediyl group, an alkanetriyl group, a residue obtained by removing a hydroxyl group from a mononuclear polyvalent phenol compound, and a polynuclear group. Residues obtained by removing the hydroxyl group from the polyvalent phenol compound can be mentioned.
Examples of the alkyl group represented by R 3 include a linear alkyl group. Examples of the linear alkyl group include those having 1 to 12 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a nonyl group and a decyl group.
Further, examples of the alkyl group represented by R 3 include a branched alkyl group. Examples of the branched alkyl group include those having 1 to 12 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tertiary butyl group, an isoamyl group, a tertiary amyl group, an isohexyl group, a 2-ethylhexyl group and a tertiary octyl group.
The aryl group represented by R 3 may be a monocyclic ring or a condensed ring. Examples of the monocyclic aryl group include a phenyl group. Examples of the aryl group of the fused ring include a naphthyl group and the like. The aryl group preferably has 6 to 32 carbon atoms, more preferably 7 to 11 carbon atoms.
Examples of the alkanediyl group represented by R 3 include a methylene group, an ethylene group, a propylene group, an ethanediyl group, an octanediyl group and the like.
Examples of the alkanetriyl group represented by R 3 include a methanetriyl group and a 1,1,2-ethanetriyl group.
Examples of the alkanetetrayl group represented by R 3 include 1,1,2,2-ethanetetrayl and the like.
Examples of the mononuclear polyhydric phenol compound represented by R 3 include hydroquinone, resorcin, pyrocatechol, fluoroglucosinol and the like.
Examples of the polynuclear polyvalent phenol compound represented by R 3 include dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), etylidene bisphenol, isopropyridene bisphenol (bisphenol A), and isopropylidene (orthocresol). ), Tetrabromobisphenol A, 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 1,1,3-tris (4-hydroxyphenyl) butane, Examples thereof include 1,1,2,2-tetra (4-hydroxyphenyl) ethane, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac and terpenphenol.
　Ｒ３で表される、炭化水素基中の１若しくは２以上のメチレン基が酸素原子、硫黄原子又は窒素原子で置換された基としては、例えば、チオビスフェノール、スルホニルビスフェノール、オキシビスフェノール、が挙げられる。 Represented by R 3, 1 or 2 or more methylene groups the oxygen atom in the hydrocarbon group, the radicals substituted with a sulfur atom or a nitrogen atom, for example, thiobisphenols, sulfonyloxy bisphenol, oxy bisphenol, is ..
　本発明の樹脂組成物においては、製造するための原料が容易に入手可能であるという観点から、一般式（１）中のＸ１が酸素原子であることが好ましい。同様の観点から、Ｙ１が酸素原子であることが好ましい。 In the resin composition of the present invention, it is preferable that X 1 in the general formula (1) is an oxygen atom from the viewpoint that a raw material for production is easily available. From the same viewpoint, it is preferable that Y 1 is an oxygen atom.
　本発明の樹脂組成物を硬化させた硬化物の物性の観点から、式（１）で表される含リン化合物は骨格に芳香環を少なくとも１個含む化合物であることが好ましく、Ｒ３で表される炭化水素基が下記式（ａ－１）～（ｉ－１）で表される基からなる群から選択されるものであることが特に好ましい。 From the viewpoint of the physical properties of the cured product obtained by curing the resin composition of the present invention, a phosphorus-containing compound represented by the formula (1) is preferably a compound containing at least one aromatic ring in the skeleton, Table by R 3 It is particularly preferable that the hydrocarbon group to be formed is selected from the group consisting of the groups represented by the following formulas (a-1) to (i-1).
Figure JPOXMLDOC01-appb-C000011
Figure JPOXMLDOC01-appb-C000011
　式中、＊は結合手を表す。 In the formula, * represents a bond.
　特に、入手が容易である点から、Ｒ３で表される炭化水素基が下記の構造であることが特に好ましい。 In particular, from the viewpoint of easy availability, it is particularly preferred hydrocarbon groups represented by R 3 is the following structure.
Figure JPOXMLDOC01-appb-C000012
Figure JPOXMLDOC01-appb-C000012
　式中、＊は結合手を表す。 In the formula, * represents a bond.
　次に、本発明の樹脂組成物に含まれる、下記式（２）で表される含リン化合物について説明する。 Next, the phosphorus-containing compound represented by the following formula (2) contained in the resin composition of the present invention will be described.
Figure JPOXMLDOC01-appb-C000013
Figure JPOXMLDOC01-appb-C000013
　式中、ｎは１～１０の整数を表し、
　Ｒ５、Ｒ６、Ｒ７及びＲ８は、それぞれ独立に、水素原子、アルキル基、又はアリール基を表し、
　Ｒ９は、炭化水素基、又は該炭化水素基中の１若しくは２以上のメチレン基が酸素原子、硫黄原子若しくは窒素原子で置換された基を表し、該炭化水素基は酸素原子、硫黄原子又は窒素原子を含む置換基で置換されていてもよく、
　Ｘ２は酸素原子又は硫黄原子を表し、
　Ｙ２は、酸素原子、硫黄原子、又は－ＮＲ１０－を表し、Ｒ１０は水素原子、アルキル基、又はアリール基を表す。 In the formula, n represents an integer from 1 to 10.
R 5 , R 6 , R 7 and R 8 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively.
R 9 represents a hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a sulfur atom. It may be substituted with a substituent containing a nitrogen atom.
X 2 represents an oxygen atom or a sulfur atom
Y 2 represents an oxygen atom, a sulfur atom, or -NR 10- , and R 10 represents a hydrogen atom, an alkyl group, or an aryl group.
　前記式（２）中、ｎは２～７であることが好ましく、２～５であることがより好ましい。ｎが２以上であると、エポキシ基と反応する官能基が２以上となり、エポキシ樹脂を硬化したときの硬化物のガラス転移温度や強度が高くなるため好ましい。ｍが７以下であると、含リン化合物を製造する際に、粘度が高くならず、含リン化合物の製造が容易になるため好ましい。 In the above formula (2), n is preferably 2 to 7, and more preferably 2 to 5. When n is 2 or more, the number of functional groups that react with the epoxy group is 2 or more, and the glass transition temperature and strength of the cured product when the epoxy resin is cured are high, which is preferable. When m is 7 or less, the viscosity does not increase when the phosphorus-containing compound is produced, and the phosphorus-containing compound can be easily produced, which is preferable.
　前記式（２）中のＲ５、Ｒ６、Ｒ７、Ｒ８及びＲ１０で表されるアルキル基としては、直鎖状のアルキル基が挙げられる。直鎖状のアルキル基としては、炭素原子数１～１２のアルキル基が挙げられる。その具体例としては、メチル基、エチル基、プロピル基、ブチル基、アミル基、ヘキシル基、オクチル基、ノニル基及びデシル基が挙げられる。
　またＲ５、Ｒ６、Ｒ７、Ｒ８及びＲ１０で表されるアルキル基としては、分岐状のアルキル基が挙げられる。分岐状のアルキル基としては、炭素原子数１～１０のものが挙げられる。その具体例としては、イソプロピル基、イソブチル基、第三ブチル基、イソアミル基、第三アミル基、イソヘキシル基、２－エチルヘキシル基及び第三オクチル基が挙げられる。
　本発明においては、得られる硬化物の発砲が一層抑制されることから、直鎖状のアルキル基を用いることが好ましい。同様の観点から、アルキル基の炭素原子数は１～６であることが好ましく、２～５であることがより好ましく、２～４であることが更に好ましい。直鎖状のアルキル基は、エチル基又はプロピル基であることが好ましい。 Examples of the alkyl group represented by R 5 , R 6 , R 7 , R 8 and R 10 in the formula (2) include a linear alkyl group. Examples of the linear alkyl group include an alkyl group having 1 to 12 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a nonyl group and a decyl group.
Examples of the alkyl group represented by R 5 , R 6 , R 7 , R 8 and R 10 include a branched alkyl group. Examples of the branched alkyl group include those having 1 to 10 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tertiary butyl group, an isoamyl group, a tertiary amyl group, an isohexyl group, a 2-ethylhexyl group and a tertiary octyl group.
In the present invention, it is preferable to use a linear alkyl group because the firing of the obtained cured product is further suppressed. From the same viewpoint, the number of carbon atoms of the alkyl group is preferably 1 to 6, more preferably 2 to 5, and even more preferably 2 to 4. The linear alkyl group is preferably an ethyl group or a propyl group.
　前記式（２）中のＲ５、Ｒ６、Ｒ７、Ｒ８及びＲ１０で表されるアリール基は、単環であってもよく、縮合環であってもよい。単環のアリール基としては、例えば、フェニル基が挙げられる。縮合環のアリール基としては、例えばナフチル基等が挙げられる。該アリール基の炭素原子数は６～３２であることが好ましく、７～１１であることがより好ましい。 The aryl group represented by R 5 , R 6 , R 7 , R 8 and R 10 in the formula (2) may be a monocyclic ring or a condensed ring. Examples of the monocyclic aryl group include a phenyl group. Examples of the aryl group of the fused ring include a naphthyl group and the like. The aryl group preferably has 6 to 32 carbon atoms, more preferably 7 to 11 carbon atoms.
　前記式（２）中、Ｒ９で表される炭化水素基としては、アルキル基、アリール基、アルカンジイル基、アルカントリイル基、単核多価フェノール化合物から水酸基を除いた残基、及び多核多価フェノール化合物から水酸基を除いた残基が挙げられる。
　Ｒ３で表されるアルキル基としては、直鎖状のアルキル基が挙げられる。直鎖状のアルキル基としては、炭素原子数１～１２のものが挙げられる。その具体例としては、メチル基、エチル基、プロピル基、ブチル基、アミル基、ヘキシル基、オクチル基、ノニル基及びデシル基等が挙げられる。
　またＲ３で表されるアルキル基としては、分岐状のアルキル基が挙げられる。分岐状のアルキル基としては、炭素原子数１～１２のものが挙げられる。その具体例としては、イソプロピル基、イソブチル基、第三ブチル基、イソアミル基、第三アミル基、イソヘキシル基、２－エチルヘキシル基及び第三オクチル基が挙げられる。
　Ｒ３で表されるアリール基は、単環であってもよく、縮合環であってもよい。単環のアリール基としては、例えば、フェニル基が挙げられる。縮合環のアリール基としては、例えばナフチル基等が挙げられる。該アリール基の炭素原子数は６～３２であることが好ましく、７～１１であることがより好ましい。
　Ｒ３で表されるアルカンジイル基としては、例えば、メチレン基、エチレン基、プロピレン基、エタンジイル基及びオクタンジイル基等が挙げられる。
　Ｒ３で表されるアルカントリイル基としては、メタントリイル及び１，１，２－エタントリイル基等が挙げられる。
　Ｒ３で表されるアルカンテトライル基としては、例えば、１，１，２，２－エタンテトライル等が挙げられる。
　Ｒ３で表される単核多価フェノール化合物としては、例えば、ハイドロキノン、レゾルシン、ピロカテコール及びフロログルクシノール等が挙げられる。
　Ｒ３で表される多核多価フェノール化合物としては、例えば、ジヒドロキシナフタレン、ビフェノール、メチレンビスフェノール（ビスフェノールＦ）、メチレンビス（オルトクレゾール）、エチリデンビスフェノール、イソプロピリデンビスフェノール（ビスフェノールＡ）、イソプロピリデン（オルトクレゾール）、テトラブロモビスフェノールＡ、１，３－ビス（４－ヒドロキシクミル）ベンゼン、１，４－ビス（４－ヒドロキシクミル）ベンゼン、１，１，３－トリス（４－ヒドロキシフェニル）ブタン、１，１，２，２－テトラ（４－ヒドロキシフェニル）エタン、フェノールノボラック、オルソクレゾールノボラック、エチルフェノールノボラック、ブチルフェノールノボラック、オクチルフェノールノボラック、レゾルシンノボラック及びテルペンフェノールが挙げられる。 In the above formula (2), the hydrocarbon group represented by R 9 includes an alkyl group, an aryl group, an alkanediyl group, an alkanetriyl group, a residue obtained by removing a hydroxyl group from a mononuclear polyvalent phenol compound, and a polynuclear group. Residues obtained by removing the hydroxyl group from the polyvalent phenol compound can be mentioned.
Examples of the alkyl group represented by R 3 include a linear alkyl group. Examples of the linear alkyl group include those having 1 to 12 carbon atoms. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, an amyl group, a hexyl group, an octyl group, a nonyl group and a decyl group.
Further, examples of the alkyl group represented by R 3 include a branched alkyl group. Examples of the branched alkyl group include those having 1 to 12 carbon atoms. Specific examples thereof include an isopropyl group, an isobutyl group, a tertiary butyl group, an isoamyl group, a tertiary amyl group, an isohexyl group, a 2-ethylhexyl group and a tertiary octyl group.
The aryl group represented by R 3 may be a monocyclic ring or a condensed ring. Examples of the monocyclic aryl group include a phenyl group. Examples of the aryl group of the fused ring include a naphthyl group and the like. The aryl group preferably has 6 to 32 carbon atoms, more preferably 7 to 11 carbon atoms.
Examples of the alkanediyl group represented by R 3 include a methylene group, an ethylene group, a propylene group, an ethanediyl group, an octanediyl group and the like.
Examples of the alkanetriyl group represented by R 3 include a methanetriyl group and a 1,1,2-ethanetriyl group.
Examples of the alkanetetrayl group represented by R 3 include 1,1,2,2-ethanetetrayl and the like.
Examples of the mononuclear polyhydric phenol compound represented by R 3 include hydroquinone, resorcin, pyrocatechol, fluoroglucosinol and the like.
Examples of the polynuclear polyvalent phenol compound represented by R 3 include dihydroxynaphthalene, biphenol, methylenebisphenol (bisphenol F), methylenebis (orthocresol), etylidene bisphenol, isopropyridene bisphenol (bisphenol A), and isopropylidene (orthocresol). ), Tetrabromobisphenol A, 1,3-bis (4-hydroxycumyl) benzene, 1,4-bis (4-hydroxycumyl) benzene, 1,1,3-tris (4-hydroxyphenyl) butane, Examples thereof include 1,1,2,2-tetra (4-hydroxyphenyl) ethane, phenol novolac, orthocresol novolac, ethylphenol novolac, butylphenol novolac, octylphenol novolac, resorcin novolac and terpenphenol.
　Ｒ９で表される、炭化水素基中の１若しくは２以上のメチレン基が酸素原子、硫黄原子又は窒素原子で置換された基としては、例えば、チオビスフェノール、スルホニルビスフェノール、オキシビスフェノール、が挙げられる。 Represented by R 9, 1 or 2 or more methylene groups the oxygen atom in the hydrocarbon group, the radicals substituted with a sulfur atom or a nitrogen atom, for example, thiobisphenols, sulfonyloxy bisphenol, oxy bisphenol, is ..
　本発明の樹脂組成物においては、製造するための原料が容易に入手可能であるという観点から、一般式（２）中のＸ２が酸素原子であることが好ましい。同様の観点から、Ｙ２が酸素原子であることが好ましい。 In the resin composition of the present invention, it is preferable that X 2 in the general formula (2) is an oxygen atom from the viewpoint that a raw material for production is easily available. From the same viewpoint, it is preferable that Y 2 is an oxygen atom.
　本発明の樹脂組成物を硬化させた硬化物の物性の観点から、式（２）で表される含リン化合物は骨格に芳香環を少なくとも１個含む化合物であることが好ましく、Ｒ９で表される炭化水素基が下記式（ａ－２）～（ｉ－２）で表される基からなる群から選択されるものであることが特に好ましい。 From the viewpoint of the physical properties of the cured product obtained by curing the resin composition of the present invention, a phosphorus-containing compound represented by the formula (2) is preferably a compound containing at least one aromatic ring in the skeleton, tables in R 9 It is particularly preferable that the hydrocarbon group to be formed is selected from the group consisting of the groups represented by the following formulas (a-2) to (i-2).
Figure JPOXMLDOC01-appb-C000014
Figure JPOXMLDOC01-appb-C000014
　式中、＊は結合手を表す。 In the formula, * represents a bond.
　式（ａ－２）中のａ２は、硬化させた硬化物の物性の観点から、２、３及び４であることが好ましい。
　式（ｇ－２）中のｐ２は、硬化させた硬化物の物性の観点から、０～１であることが好ましい。 A 2 in formula (a-2), from the viewpoint of the physical properties of a cured product obtained by curing is preferably 2, 3 and 4.
P 2 in the formula (g-2) is preferably 0 to 1 from the viewpoint of the physical properties of the cured product.
　特に、入手が容易である点から、Ｒ９で表される炭化水素基が、式（ｂ－２）又は（ｇ－２）であることが好ましく、下記の構造であることが特に好ましい。 In particular, the hydrocarbon group represented by R 9 is preferably of the formula (b-2) or (g-2), and particularly preferably has the following structure, from the viewpoint of easy availability.
Figure JPOXMLDOC01-appb-C000015
Figure JPOXMLDOC01-appb-C000015
　式中、＊は結合手を表す。 In the formula, * represents a bond.
　式（２）で表される化合物は、接着性が良好となり、且つ得られる硬化物の発砲が抑制されることから、Ｒ５～Ｒ８は、それぞれ独立に、水素原子又は炭素数１～６のアルキル基であることが好ましく、Ｒ５及びＲ７は、それぞれ独立に、アルキル基であり、且つＲ６及びＲ８は水素原子であることがより好ましい。 The compound represented by formula (2), the adhesiveness is improved, and since the firing is suppressed of the cured product obtained, R 5 - R 8 are each independently, 1 hydrogen atom or a carbon atoms 6 It is more preferable that R 5 and R 7 are independently alkyl groups, and R 6 and R 8 are hydrogen atoms.
　本発明の樹脂組成物中における前記（Ｄ）成分の含リン化合物の配合量は、特に限定されるものではないが、（Ｃ）成分及び（Ｄ）成分の合計量に対し、２～４０質量％であることが好ましく、５～３０質量％であることが更に好ましい。（Ｄ）成分の含有量が上述の範囲であると、樹脂組成物の耐湿熱性が一層良好となり硬化物の発泡が一層抑制され、且つ耐水性が良好になるため好ましい。 The blending amount of the phosphorus-containing compound of the component (D) in the resin composition of the present invention is not particularly limited, but is 2 to 40 mass by mass with respect to the total amount of the components (C) and (D). %, More preferably 5 to 30% by mass. When the content of the component (D) is in the above range, the moisture and heat resistance of the resin composition is further improved, the foaming of the cured product is further suppressed, and the water resistance is improved, which is preferable.
　本発明の樹脂組成物は、前記（Ａ）成分、（Ｂ）成分、（Ｃ）成分及び（Ｄ）成分に加え、（Ｅ）ゴム成分を含んでもよい。樹脂組成物に（Ｅ）ゴム成分を含有させることによって、樹脂組成物の接着性をより向上させることができる。本発明において「ゴム成分」とは、イソプレン、ブタジエン、スチレン、アクリロニトリル、クロロプレンなどのモノマーを重合させた骨格を有する成分である。（Ｅ）ゴム成分としては、液状ゴム及び粉末状ゴムが挙げられる。 The resin composition of the present invention may contain (E) a rubber component in addition to the above-mentioned (A) component, (B) component, (C) component and (D) component. By including the rubber component (E) in the resin composition, the adhesiveness of the resin composition can be further improved. In the present invention, the "rubber component" is a component having a skeleton obtained by polymerizing monomers such as isoprene, butadiene, styrene, acrylonitrile, and chloroprene. Examples of the rubber component (E) include liquid rubber and powdered rubber.
　前記液状ゴムは、例えば、ポリブタジエン、アクリロニトリルブタジエンゴム（ＮＢＲ）、両末端にカルボキシル基を有するブタジエン－アクリロニトリルゴム（ＣＴＢＮ）、両末端にアミノ基を有するブタジエン－アクリロニトリルゴム（ＡＴＢＮ）などが挙げられる。 Examples of the liquid rubber include polybutadiene, acrylonitrile butadiene rubber (NBR), butadiene-acrylonitrile rubber (CTBN) having carboxyl groups at both ends, and butadiene-acrylonitrile rubber (ATBN) having amino groups at both ends.
　前記粉末状ゴムとしては、例えば、アクリロニトリルブタジエンゴム（ＮＢＲ）、カルボン酸変性ＮＢＲ、水素添加ＮＢＲ、コアシェル型ゴム、スチレンブタジエンゴム、アクリルゴムなどが挙げられる。 Examples of the powdered rubber include acrylonitrile butadiene rubber (NBR), carboxylic acid-modified NBR, hydrogenated NBR, core-shell type rubber, styrene-butadiene rubber, and acrylic rubber.
　前記コアシェル型ゴムとは、粒子がコア層とシェル層を有するゴムのことであり、例えば、外層のシェル層がガラス状ポリマー、内層のコア層がゴム状ポリマーで構成される２層構造、又は外層のシェル層がガラス状ポリマー、中間層がゴム状ポリマー、コア層がガラス状ポリマーで構成される３層構造のもの等が挙げられる。ガラス状ポリマーは例えば、メタクリル酸メチルの重合物、アクリル酸メチルの重合物、スチレンの重合物等で構成され、ゴム状ポリマー層は例えば、ブチルアクリレート重合物（ブチルゴム）、シリコーンゴム、ポリブタジエン等で構成される。 The core-shell type rubber is a rubber in which particles have a core layer and a shell layer. For example, a two-layer structure in which the outer shell layer is a glassy polymer and the inner core layer is a rubbery polymer, or Examples thereof include a three-layer structure in which the outer shell layer is a glassy polymer, the intermediate layer is a rubbery polymer, and the core layer is a glassy polymer. The glassy polymer is composed of, for example, a polymer of methyl methacrylate, a polymer of methyl acrylate, a polymer of styrene, etc., and the rubbery polymer layer is, for example, a butyl acrylate polymer (butyl rubber), silicone rubber, polybutadiene, etc. It is composed.
　本発明においては、これらのゴム成分の中でも、樹脂組成物の接着性をより向上させるという観点から、液状ゴム、コアシェル型ゴムが好ましい。本発明の樹脂組成物における（Ｅ）ゴム成分の含有量は、３～３０質量％が好ましく、５～２０質量％がより好ましい。（Ｅ）ゴム成分の含有量を上述の範囲とすることによって、樹脂組成物の接着性が一層良好になるからである。 In the present invention, among these rubber components, liquid rubber and core-shell type rubber are preferable from the viewpoint of further improving the adhesiveness of the resin composition. The content of the rubber component (E) in the resin composition of the present invention is preferably 3 to 30% by mass, more preferably 5 to 20% by mass. This is because the adhesiveness of the resin composition is further improved by setting the content of the rubber component (E) in the above range.
　本発明の樹脂組成物は、樹脂組成物の粘度を所望の数値に調整するために、反応性希釈剤を含有していてもよい。反応性希釈剤としては、エポキシ樹脂組成物を硬化させたときの、硬化物の耐熱性やガラス転移温度の低下を抑制する観点から、エポキシ基を少なくとも１つ有するものが好ましい。 The resin composition of the present invention may contain a reactive diluent in order to adjust the viscosity of the resin composition to a desired value. The reactive diluent preferably has at least one epoxy group from the viewpoint of suppressing a decrease in heat resistance and glass transition temperature of the cured product when the epoxy resin composition is cured.
　前記反応性希釈剤に含まれるエポキシ基の数は、１つでも２つ以上でもよく、特に限定されるものではない。エポキシ基の数が１個の反応性希釈剤としては、例えば、ｎ－ブチルグリシジルエーテル、Ｃ１２－Ｃ１４のアルキルグリシジルエーテル、アリルグリシジルエーテル、２－エチルヘキシルグリシジルエーテル、スチレンオキシド、フェニルグリシジルエーテル、クレジルグリシジルエーテル、ｐ－ｓｅｃ－ブチルフェニルグリシジルエーテル、ｔ－ブチルフェニルグリシジルエーテル、グリシジルメタクリレート、及び三級カルボン酸グリシジルエステル等が挙げられる。エポキシ基が２個の反応性希釈剤としては、例えば、エチレングリコールジグリシジルエーテル、プロピレングリコールジグリシジルエーテル、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、及びネオペンチルグリコールジグリシジルエーテル等が挙げられる。エポキシ基が３個の反応性希釈剤としては、例えば、トリメチロールプロパントリグリシジルエーテル、及びグリセリントリグリシジルエーテル等が挙げられる。 The number of epoxy groups contained in the reactive diluent may be one or two or more, and is not particularly limited. Reactive diluents having one epoxy group include, for example, n-butyl glycidyl ether, C12-C14 alkyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether, styrene oxide, phenyl glycidyl ether, and cresyl. Examples thereof include glycidyl ether, p-sec-butylphenyl glycidyl ether, t-butylphenyl glycidyl ether, glycidyl methacrylate, and tertiary carboxylic acid glycidyl ester. Reactive diluents with two epoxy groups include, for example, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, and neopentyl glycol diglycidyl ether. And so on. Examples of the reactive diluent having three epoxy groups include trimethylolpropane triglycidyl ether and glycerin triglycidyl ether.
　本発明の樹脂組成物は、エポキシ樹脂硬化促進剤を含有することが好ましい。エポキシ樹脂硬化促進剤を含有することによって、接着剤の硬化温度を下げることができるため好ましい。硬化促進剤の具体例としては、トリフェニルホスフィン等のホスフィン類；テトラフェニルホスホニウムブロマイド等のホスホニウム塩；２－メチルイミダゾール、２－フェニルイミダゾール、２－エチル－４－メチルイミダゾール、２－ウンデシルイミダゾール、１－シアノエチル－２－メチルイミダゾール等のイミダゾール類；前記イミダゾール類と、トリメリット酸、イソシアヌル酸、ホウ素等との塩であるイミダゾール塩類；ベンジルジメチルアミン、２，４，６－トリス（ジメチルアミノメチル）フェノール等のアミン類；トリメチルアンモニウムクロライド等の４級アンモニウム塩類；３－（ｐ－クロロフェニル）－１，１－ジメチルウレア、３－（３，４－ジクロロフェニル）－１，１－ジメチルウレア、３－フェニル－１，１－ジメチルウレア、イソホロンジイソシアネート－ジメチルウレア、トリレンジイソシアネート－ジメチルウレア等のウレア類；及び、三フッ化ホウ素と、アミン類やエーテル化合物等との錯化合物等を例示することができる。これらの硬化促進剤は、単独で使用してもよいし、２種以上を併用してもよい。本発明の難燃性エポキシ樹脂組成物におけるエポキシ樹脂硬化促進剤の含有量は特に制限なく、樹脂組成物の用途に応じて適宜設定することができる。本発明の樹脂組成物におけるエポキシ樹脂硬化促進剤の含有量は、（Ｂ）硬化剤に対して１～３５質量％であることが好ましく、３～３０質量％であることがより好ましく、５～２５質量％であることが更に好ましい。 The resin composition of the present invention preferably contains an epoxy resin curing accelerator. By containing the epoxy resin curing accelerator, the curing temperature of the adhesive can be lowered, which is preferable. Specific examples of the curing accelerator include phosphines such as triphenylphosphine; phosphonium salts such as tetraphenylphosphonium bromide; 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole. , 1-Cyanoethyl-2-methylimidazole and other imidazoles; imidazole salts which are salts of the imidazoles with trimellitic acid, isocyanuric acid, boron and the like; benzyldimethylamine, 2,4,6-tris (dimethylamino). Amines such as methyl) phenol; quaternary ammonium salts such as trimethylammonium chloride; 3- (p-chlorophenyl) -1,1-dimethylurea, 3- (3,4-dichlorophenyl) -1,1-dimethylurea, Examples of ureas such as 3-phenyl-1,1-dimethylurea, isophoronediisocyanate-dimethylurea, and tolylene diisocyanate-dimethylurea; and complex compounds of boron trifluoride with amines and ether compounds are exemplified. be able to. These curing accelerators may be used alone or in combination of two or more. The content of the epoxy resin curing accelerator in the flame-retardant epoxy resin composition of the present invention is not particularly limited and can be appropriately set according to the use of the resin composition. The content of the epoxy resin curing accelerator in the resin composition of the present invention is preferably 1 to 35% by mass, more preferably 3 to 30% by mass, and 5 to 5 to 30% by mass with respect to the (B) curing agent. It is more preferably 25% by mass.
　本発明の樹脂組成物は、必要に応じて、粘度調整剤として有機溶剤を含有している場合がある。この場合の有機溶剤としては、Ｎ，Ｎ－ジメチルホルムアミド等のアミド類；エチレングリコールモノメチルエーテル等のエーテル類；アセトン、メチルエチルケトン等のケトン類；メタノール、エタノール等のアルコール類；ベンゼン、トルエン等の芳香族炭化水素類等が挙げられる。 The resin composition of the present invention may contain an organic solvent as a viscosity modifier, if necessary. In this case, the organic solvent includes amides such as N, N-dimethylformamide; ethers such as ethylene glycol monomethyl ether; ketones such as acetone and methyl ethyl ketone; alcohols such as methanol and ethanol; aromatics such as benzene and toluene. Examples include group hydrocarbons.
　本発明の樹脂組成物は、無機充填剤を含有することが好ましい。無機充填剤を含有することによって、チキソ性、粘度の付与や耐水性の向上などが期待できる。このような無機充填剤としては、例えば、疎水性ヒュームドシリカ等の溶融シリカ、結晶シリカ等のシリカ；水酸化マグネシウム、水酸化アルミニウム、モリブデン酸亜鉛、炭酸カルシウム、炭酸ケイ素、ケイ酸カルシウム、チタン酸カリウム、べリリア、ジルコニア、ジルコン、フォステライト、ステアタイト、スピネル、ムライト、チタニア等の粉体、又はこれらを球形化したビーズ、及びガラス繊維、パルプ繊維、合成繊維、セラミック繊維等が挙げられる。これらの無機充填剤は、１種を単独で使用してもよく、２種以上を併用してもよい。本発明の樹脂組成物における無機充填剤の含有量は、５～５０質量％が好ましく、１０～４５質量％がより好ましく、１５～４０質量％であることが更に好ましい。無機充填剤の含有量を上述の範囲とすることによって、接着性などの性能を低下させることなく、チキソ性等の効果を付与することができるため好ましい。 The resin composition of the present invention preferably contains an inorganic filler. By containing an inorganic filler, it can be expected to impart thixotropy, viscosity, and improve water resistance. Examples of such an inorganic filler include fused silica such as hydrophobic fumed silica, silica such as crystalline silica; magnesium hydroxide, aluminum hydroxide, zinc molybdate, calcium carbonate, silicon carbonate, calcium silicate, and titanium. Examples thereof include powders of potassium acid, verilia, zirconia, zircone, fosterite, steatite, spinel, mulite, titania and the like, beads obtained by spheroidizing these, and glass fibers, pulp fibers, synthetic fibers, ceramic fibers and the like. .. These inorganic fillers may be used alone or in combination of two or more. The content of the inorganic filler in the resin composition of the present invention is preferably 5 to 50% by mass, more preferably 10 to 45% by mass, and even more preferably 15 to 40% by mass. By setting the content of the inorganic filler in the above range, it is possible to impart effects such as thixotropy without deteriorating performance such as adhesiveness, which is preferable.
　また、本発明の樹脂組成物には、必要に応じて、前記以外の添加剤を含有する場合がある。前記添加剤としては、ジオクチルフタレート、ジブチルフタレート、ベンジルアルコール、コールタール等の非反応性の希釈剤（可塑剤）；ガラスクロス、アラミドクロス、カーボンファイバー等の補強材；顔料；γ－アミノプロピルトリエトキシシラン、Ｎ－β－（アミノエチル）－γ－アミノプロピルトリエトキシシラン、Ｎ－β－（アミノエチル）－Ｎ‘－β－（アミノエチル）－γ－アミノプロピルトリエトキシシラン、γ－アニリノプロピルトリエトキシシラン、γ－グリシドキシプロピルトリエトキシシラン、β－（３，４－エポキシシクロヘキシル）エチルトリエトキシシラン、ビニルトリエトキシシラン、Ｎ－β－（Ｎ－ビニルベンジルアミノエチル）－γ－アミノプロピルトリエトキシシラン、γ－メタクリロキシプロピルトリメトキシシラン、γ－クロロプロピルトリメトキシシラン、γ－メルカプトプロピルトリメトキシシラン等のシランカップリング剤；キャンデリラワックス、カルナウバワックス、木ろう、イボタロウ、みつろう、ラノリン、鯨ろう、モンタンワックス、石油ワックス、脂肪族ワックス、脂肪族エステル、脂肪族エーテル、芳香族エステル、芳香族エーテル等の潤滑剤；増粘剤；チキソトロピック剤；酸化防止剤；光安定剤；紫外線吸収剤；消泡剤；防錆剤；コロイダルシリカ、コロイダルアルミナ等の常用の添加剤を挙げることができる。本発明においては、更に、キシレン樹脂、石油樹脂等の粘着性の樹脂類を併用することもできる。 Further, the resin composition of the present invention may contain additives other than the above, if necessary. Examples of the additive include non-reactive diluents (plasticizers) such as dioctylphthalate, dibutylphthalate, benzyl alcohol, and coaltal; reinforcing materials such as glass cloth, aramid cloth, and carbon fiber; pigments; γ-aminopropyltri. Ethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -N'-β- (aminoethyl) -γ-aminopropyltriethoxysilane, γ-ani Renopropyltriethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, vinyltriethoxysilane, N-β- (N-vinylbenzylaminoethyl) -γ -Silane coupling agents such as aminopropyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-chloropropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane; candelilla wax, carnauba wax, wood wax, Ibotaro Lubricants such as mitsuro, lanolin, whale wax, montane wax, petroleum wax, aliphatic wax, aliphatic ester, aliphatic ether, aromatic ester, aromatic ether; thickener; thixotropic agent; antioxidant; Examples include light stabilizers; ultraviolet absorbers; antifoaming agents; rust preventives; commonly used additives such as colloidal silica and colloidal alumina. In the present invention, adhesive resins such as xylene resin and petroleum resin can also be used in combination.
　本発明の樹脂組成物は、各種基材との密着性に優れ、低温から高温までの広い範囲で優れた柔軟性を有することから、自動車、船舶、航空、宇宙、土木、建築分野等の広範な分野において、各種構造部材を接合するのに用いられる構造用接着剤として好適に使用することができ、とりわけ自動車構造用接着剤として好適に使用することができる。また、当然のことながら、本発明の樹脂組成物は、構造用接着剤以外に、各種塗料、各種接着剤、各種成形品等の用途にも用いることができる。 Since the resin composition of the present invention has excellent adhesion to various substrates and has excellent flexibility in a wide range from low temperature to high temperature, it has a wide range of fields such as automobiles, ships, aerospace, space, civil engineering, and construction. In various fields, it can be suitably used as a structural adhesive used for joining various structural members, and in particular, it can be suitably used as an automobile structural adhesive. Further, as a matter of course, the resin composition of the present invention can be used not only for structural adhesives but also for various paints, various adhesives, various molded products and the like.
　本発明の樹脂組成物は加熱によって硬化させることができる。加熱時間や加熱温度等の加熱条件に特に制限はなく、公知の条件を採用することができる。具体的には、１６０～２００℃、好ましくは１７０～１９０℃で、２０～４０分、好ましくは３０～４０分加熱することによって硬化させることができる。 The resin composition of the present invention can be cured by heating. The heating conditions such as the heating time and the heating temperature are not particularly limited, and known conditions can be adopted. Specifically, it can be cured by heating at 160 to 200 ° C., preferably 170 to 190 ° C. for 20 to 40 minutes, preferably 30 to 40 minutes.
　次に、本発明の樹脂組成物により得られる硬化物の発泡抑制方法を詳述する。 Next, the method for suppressing foaming of the cured product obtained by the resin composition of the present invention will be described in detail.
　本発明の発泡抑制方法は、（Ａ）～（Ｃ）成分を含む樹脂組成物を硬化させるのに先立ち、前記（Ｄ）成分を該組成物中に含有させておく、硬化時の硬化物の発泡を抑制する方法である。（Ｃ）成分として、とりわけ顕著な効果が得られるブロックウレタンを使用した場合においては、（Ａ）～（Ｃ）成分を含む組成物の硬化時には、（Ｃ）成分であるブロックウレタン中のブロック化剤が熱により解離し、ＮＣＯ基が一時的に生成するが、このとき、（Ａ）～（Ｃ）成分を含む組成物中の水分、若しくは組成物の近傍に存在する空気中の水分がＮＣＯ基と反応し、その後脱炭酸反応が進行することがある。本発明の硬化物の発泡抑制方法においては、（Ｄ）成分である含リン化合物が前記ＮＣＯ基と水との反応を抑制しているものと推定している。 In the method for suppressing foaming of the present invention, the cured product at the time of curing is prepared by containing the component (D) in the composition prior to curing the resin composition containing the components (A) to (C). This is a method of suppressing foaming. When block urethane, which has a particularly remarkable effect, is used as the component (C), when the composition containing the components (A) to (C) is cured, it is blocked in the block urethane which is the component (C). The agent is dissociated by heat to temporarily generate NCO groups. At this time, the water content in the composition containing the components (A) to (C) or the water content in the air existing in the vicinity of the composition is NCO. It may react with the group and then the decarboxylation reaction may proceed. In the method for suppressing foaming of a cured product of the present invention, it is presumed that the phosphorus-containing compound as the component (D) suppresses the reaction between the NCO group and water.
　前記発泡抑制方法に使用される（Ａ）～（Ｄ）成分は、前記樹脂組成物に使用される（Ａ）～（Ｄ）成分に相当するものである。 The components (A) to (D) used in the foaming suppressing method correspond to the components (A) to (D) used in the resin composition.
　本発明の発泡が抑制された硬化物の製造方法は、（Ａ）～（Ｃ）成分を含む組成物を硬化させるのに先立ち、（Ｄ）成分を該組成物中に含有させておくものである。本発明の発泡抑制方法と同様の理由により、本発明の硬化物の製造方法で製造された硬化物は発泡が抑制されたものとなる。 In the method for producing a cured product in which foaming is suppressed in the present invention, the component (D) is contained in the composition prior to curing the composition containing the components (A) to (C). is there. For the same reason as the foaming suppression method of the present invention, the cured product produced by the method for producing a cured product of the present invention has foaming suppressed.
　次に、本発明の実施例及び比較例により、更に詳細に説明するが、本発明はこれら実施例により何ら限定されるものではない。尚、以下の実施例等における％は、特に記載がない限り質量基準である。 Next, the present invention will be described in more detail with reference to Examples and Comparative Examples of the present invention, but the present invention is not limited to these Examples. In addition,% in the following Examples and the like is based on mass unless otherwise specified.
〔製造例１〕　含リン化合物１の製造
＜含リン塩化物の合成＞
　回転子、還流管、温度計及び窒素導入口を備えた３００ｍＬの丸底フラスコに、ビスフェノールＡを２２．８ｇ（０．１ｍｏｌ）、塩化ホスホリルを３０６．７ｇ（２．０ｍｏｌ）及び無水塩化マグネシウムを０．３ｇ（３．０ｍｍｏｌ）入れて、反応溶液が還流するまで加熱し、２４時間撹拌した。その際、反応で発生する塩化水素ガスを、還流管上部から水酸化ナトリウム水溶液に導入してトラップした。反応終了後、エバポレーターを用いて過剰の塩化ホスホリルを除去し、含リン塩化物を得た。得られた含リン塩化物をテトラヒドロフラン（ＴＨＦ）１００ｍＬに溶解させ、含リン塩化物のＴＨＦ溶液を得た。 [Production Example 1] Production of Phosphorus-Containing Compound 1 <Synthesis of Phosphorus-Containing Chloride>
22.8 g (0.1 mol) of bisphenol A, 306.7 g (2.0 mol) of phosphoryl chloride and anhydrous magnesium chloride are placed in a 300 mL round bottom flask equipped with a rotor, a reflux tube, a thermometer and a nitrogen inlet. 0.3 g (3.0 mmol) was added, the mixture was heated until the reaction solution refluxed, and the mixture was stirred for 24 hours. At that time, the hydrogen chloride gas generated in the reaction was introduced into the sodium hydroxide aqueous solution from the upper part of the reflux tube and trapped. After completion of the reaction, excess phosphoryl chloride was removed using an evaporator to obtain a phosphorus-containing chloride. The obtained phosphorus-containing chloride was dissolved in 100 mL of tetrahydrofuran (THF) to obtain a phosphorus-containing chloride THF solution.
＜塩化物とアミンの反応＞
　撹拌羽、還流管、滴下漏斗及び温度計を備えた５００ｍＬの丸底フラスコに、メチルアミンのＴＨＦ溶液を２１０ｍＬ（２．０ｍｏｌ／Ｌ、メチルアミン：０．４２ｍｏｌ）及びトリエチルアミンを４２．５ｇ（０．４２ｍｏｌ）入れた。窒素雰囲気下で、反応溶液を撹拌・冷却しながら、前記で作製した含リン塩化物のＴＨＦ溶液を反応温度が０℃を超えないように滴下し、滴下終了後、２５℃で２４時間撹拌した。反応終了後、エバポレーターで溶媒及び過剰の原料を除去し、残渣をクロロホルム３００ｍＬで溶解して分液漏斗に移した。蒸留水１００ｍＬで２回洗浄し、有機層を無水硫酸マグネシウムで乾燥し、エバポレーターで溶媒を除去して含リン化合物１を１８．８ｇ（収率８５．３％）得た。
　前記含リン化合物は、式Ｐ－１で表される含リン化合物の他に副生成物としてＰ－２においてｅが１以上のものが考えるため、３１Ｐ－ＮＭＲの測定を行い、この積分値から、Ｐ－２におけるｅは０．１３と算出された。 <Reaction of chloride and amine>
210 mL (2.0 mol / L, methylamine: 0.42 mol) of a THF solution of methylamine and 42.5 g (0) of triethylamine in a 500 mL round-bottom flask equipped with a stirring blade, a reflux tube, a dropping funnel and a thermometer. .42 mol) was added. While stirring and cooling the reaction solution in a nitrogen atmosphere, the phosphorus-containing chloride THF solution prepared above was added dropwise so that the reaction temperature did not exceed 0 ° C., and after completion of the addition, the mixture was stirred at 25 ° C. for 24 hours. .. After completion of the reaction, the solvent and excess raw materials were removed by an evaporator, and the residue was dissolved in 300 mL of chloroform and transferred to a separatory funnel. The organic layer was washed twice with 100 mL of distilled water, the organic layer was dried over anhydrous magnesium sulfate, and the solvent was removed by an evaporator to obtain 18.8 g (yield 85.3%) of the phosphorus-containing compound 1.
Since the phosphorus-containing compound is considered to be a by-product having e of 1 or more in P-2 in addition to the phosphorus-containing compound represented by the formula P-1, 31P-NMR measurement was performed and the integrated value was used. , E in P-2 was calculated to be 0.13.
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000016
Figure JPOXMLDOC01-appb-C000017
Figure JPOXMLDOC01-appb-C000017
　下記〔表１〕に示した原料を５００ｍｌディスポカップに加え、２５℃で５分間、スパチュラで撹拌した後、遊星式攪拌機を使用して更に撹拌し、実施例１及び比較例１の樹脂組成物を得た。得られた樹脂組成物について下記の評価を実施した。得られた結果を〔表１〕に示す。〔表１〕中の符号は下記の成分を表す。また、〔表１〕中の各成分の数値は質量部基準である。 The raw materials shown in [Table 1] below are added to a 500 ml disposable cup, stirred at 25 ° C. for 5 minutes with a spatula, and then further stirred using a planetary stirrer to further stir the resin compositions of Example 1 and Comparative Example 1. Got The following evaluation was carried out on the obtained resin composition. The obtained results are shown in [Table 1]. The reference numerals in [Table 1] represent the following components. The numerical values of each component in [Table 1] are based on parts by mass.
Ａ－１：ビスフェノールＡ型エポキシ樹脂（製品名：ＥＰ－４１００Ｅ、株式会社ＡＤＥＫＡ製、エポキシ当量：１９０ｇ／ｅｑ．）
Ａ－２：キレート変性エポキシ樹脂（製品名：ＥＰ－４９－１０Ｐ２、株式会社ＡＤＥＫＡ製、エポキシ当量：３００ｇ／ｅｑ．）
Ａ－３：ゴム変性エポキシ樹脂（製品名：ＥＰＲ－１６３０、株式会社ＡＤＥＫＡ製）
Ｂ：ジシアンジアミド型潜在性硬化剤（製品名：ＥＨ－３６３６ＡＳ、株式会社ＡＤＥＫＡ製）
Ｃ：ブロックウレタン（ブロックウレタン当量：１４００ｇ／ｅｑ．）
Ｄ：製造例１で製造された含リン化合物１
Ｆ：硬化促進剤（３－フェニル－１，１－ジメチルウレア）
Ｇ－１：無機充填剤（炭酸カルシウム）
Ｇ－２：無機充填剤（疎水性ヒュームドシリカ、製品名：ＲＹ－２００Ｓ、日本アエロジル（株）製） A-1: Bisphenol A type epoxy resin (Product name: EP-4100E, manufactured by ADEKA Corporation, epoxy equivalent: 190 g / eq.)
A-2: Chelate-modified epoxy resin (Product name: EP-49-10P2, manufactured by ADEKA Corporation, epoxy equivalent: 300 g / eq.)
A-3: Rubber-modified epoxy resin (Product name: EPR-1630, manufactured by ADEKA Corporation)
B: Dicyandiamide type latent curing agent (Product name: EH-3636AS, manufactured by ADEKA Corporation)
C: Block urethane (block urethane equivalent: 1400 g / eq.)
D: Phosphorus-containing compound 1 produced in Production Example 1.
F: Curing accelerator (3-phenyl-1,1-dimethylurea)
G-1: Inorganic filler (calcium carbonate)
G-2: Inorganic filler (hydrophobic fumed silica, product name: RY-200S, manufactured by Nippon Aerosil Co., Ltd.)
　Ｃのブロックウレタンは、下記の手順で製造されたものである。
　ジムロート、撹拌羽根及び窒素ラインを装着した１Ｌの５つ口セパラブル丸底フラスコに、プロピレングリコールグリセリルエーテル（製品名：アデカポリエーテルＧ－３０００Ｂ、株式会社ＡＤＥＫＡ製）を３００．０ｇ（水酸基モル数：０．２９４モル）、ＩＰＤＩ（イソホロンジイソシアネート）を６６．４ｇ（イソシアネート基モル数：０．５９６モル）加え、１００～１１０℃で３時間反応させた。反応系中のポリウレタンのＮＣＯ含有量が３．４６質量％であることを確認し、反応系にＰＴＢＰ（ｐ－ｔｅｒｔ－ブチルフェノール）を４８．９ｇ（０．３２５モル）添加し、更に９０～１００℃で３時間反応させた。ＩＲ吸収スペクトルにてＮＣＯの吸収が消失したことを確認して反応を終了させ、ブロックウレタンＣを得た。 The block urethane of C is manufactured by the following procedure.
300.0 g of propylene glycol glyceryl ether (product name: ADEKApolyether G-3000B, manufactured by ADEKA Corporation) in a 1 L 5-port separable round bottom flask equipped with a diisocyanate, a stirring blade and a nitrogen line (number of moles of hydroxyl groups: 0.294 mol) and 66.4 g of IPDI (isophorone diisocyanate) (number of moles of isocyanate groups: 0.596 mol) were added, and the mixture was reacted at 100 to 110 ° C. for 3 hours. After confirming that the NCO content of polyurethane in the reaction system was 3.46% by mass, 48.9 g (0.325 mol) of PTBP (p-tert-butylphenol) was added to the reaction system, and further 90 to 100 was added. The reaction was carried out at ° C. for 3 hours. After confirming that the absorption of NCO had disappeared from the IR absorption spectrum, the reaction was terminated to obtain blocked urethane C.
〔湿熱前剥離試験〕
　実施例及び比較例の樹脂組成物を試験片の型に入れて、１８０℃で３０分加熱することによって硬化させ、試験片を作成した。作成した試験片のＴ型剥離強度（ｋＮ／ｍ）を測定した。
　Ｔ型剥離強度は、被着材として鉄を使用し、ＪＩＳ　Ｋ　６８５４－３に従い、前記の試験片を用いて、－４０℃におけるＴ型剥離強度を測定した。 [Pre-wet heat peeling test]
The resin compositions of Examples and Comparative Examples were placed in a mold of a test piece and cured by heating at 180 ° C. for 30 minutes to prepare a test piece. The T-type peel strength (kN / m) of the prepared test piece was measured.
For the T-type peel strength, iron was used as the adherend, and the T-type peel strength at −40 ° C. was measured using the above-mentioned test piece according to JIS K 6854-3.
〔湿熱後剥離試験〕
　実施例及び比較例の樹脂組成物を試験片の型に入れて、５０℃で８５％ＲＨで３日間放置した。その後、樹脂組成物を１８０℃で３０分加熱してすることによって硬化させ、試験片を作成した。作成した試験片のＴ型剥離強度（ｋＮ／ｍ）を上述の方法で測定した。 [Peeling test after moist heat]
The resin compositions of Examples and Comparative Examples were placed in a mold of a test piece and left at 50 ° C. and 85% RH for 3 days. Then, the resin composition was cured by heating at 180 ° C. for 30 minutes to prepare a test piece. The T-type peel strength (kN / m) of the prepared test piece was measured by the above method.
〔強度保持率〕
　湿熱前剥離試験結果及び湿熱後剥離試験結果から、下記に式に基づき、強度保持率を算出した。強度保持率が高いほど、耐湿熱性が高いことを意味する。

　（湿熱後剥離強度）／（湿熱前剥離強度）×１００　（％）
[Strength retention rate]
From the results of the pre-wet heat peeling test and the results of the post-wet heat peeling test, the strength retention rate was calculated based on the following formula. The higher the strength retention rate, the higher the moisture and heat resistance.

(Peeling strength after moist heat) / (Peel strength before moist heat) x 100 (%)
〔ボイド観察〕
　湿熱後剥離試験を行った試験片の基材からの剥離面を写真撮影し、該写真を観察してボイドの有無を確認した。評価基準は、１～４の４段階で示し、４ではボイドが全く見られない状態を表し、数値が小さいものほどボイドが多く見られることを表す。この数値が大きいほど硬化物の発泡が抑制されたことを示す。具体的には、下記の基準で試験片を評価した。尚、試験片を評価するのに際し、ボイドが多く出現することで複数のボイドが連続する場合もあるため、単にボイドの数だけではなくその発生面積も考慮して評価した。

４：剥離面にボイドがほとんど見られない。
３：剥離面に小さなボイドが少し見られる。
２：剥離面に小さなボイドが広範囲に見られる。
１：剥離面に小さなボイドが全体に見られ、大きなボイドをいくつか見られる。
[Void observation]
The peeled surface of the test piece subjected to the moist heat post-peeling test from the base material was photographed, and the presence or absence of voids was confirmed by observing the photograph. The evaluation criteria are shown in 4 stages from 1 to 4, with 4 indicating a state in which no voids are observed, and the smaller the numerical value, the more voids are observed. The larger this value is, the more the foaming of the cured product is suppressed. Specifically, the test piece was evaluated according to the following criteria. When evaluating the test piece, since a plurality of voids may be continuous due to the appearance of many voids, the evaluation was made in consideration of not only the number of voids but also the generated area.

4: Almost no voids are seen on the peeled surface.
3: A few small voids can be seen on the peeled surface.
2: Small voids are widely seen on the peeled surface.
1: Small voids can be seen on the peeled surface as a whole, and some large voids can be seen.
Figure JPOXMLDOC01-appb-T000018
Figure JPOXMLDOC01-appb-T000018
　表１から明らかなように、実施例１の樹脂組成物の硬化物は比較例１の樹脂組成物の硬化物に比べて、強度保持率が高いもであった。この結果から、本発明の樹脂組成物は、耐湿熱性に優れたものであることが明らかである。また、実施例１の樹脂組成物の硬化物は比較例１の樹脂組成物の硬化物に比べて、ボイドが少ないものであった。この結果から、本発明の樹脂組成物は硬化時の発砲が抑制されたものであることが明らかである。 As is clear from Table 1, the cured product of the resin composition of Example 1 had a higher strength retention rate than the cured product of the resin composition of Comparative Example 1. From this result, it is clear that the resin composition of the present invention has excellent moisture and heat resistance. Further, the cured product of the resin composition of Example 1 had less voids than the cured product of the resin composition of Comparative Example 1. From this result, it is clear that the resin composition of the present invention suppresses firing during curing.

Claims (15)

  1. 　（Ａ）エポキシ樹脂、（Ｂ）硬化剤、（Ｃ）ウレタンエラストマー、及び（Ｄ）下記式（１）又は（２）で表される含リン化合物を含有する樹脂組成物。
    Figure JPOXMLDOC01-appb-C000001
     　式中、ｍは１～１０の整数を表し、
    　Ｒ１及びＲ２は、それぞれ独立に、アルキル基又はアリール基を表し、
    　Ｒ３は、炭化水素基、又は該炭化水素基中の１若しくは２以上のメチレン基が酸素原子、硫黄原子若しくは窒素原子で置換された基を表し、該炭化水素基は酸素原子、硫黄原子又は窒素原子を含む置換基で置換されていてもよく、
    　Ｘ１は酸素原子又は硫黄原子を表し、
    　Ｙ１は酸素原子、硫黄原子、又は－ＮＲ４－を表し、
    　Ｒ４は、水素原子、アルキル基又はアリール基を表す。
    Figure JPOXMLDOC01-appb-C000002
     　式中、ｎは１～１０の整数を表し、
    　Ｒ５、Ｒ６、Ｒ７及びＲ８は、それぞれ独立に、水素原子、アルキル基、又はアリール基を表し、
    　Ｒ９は、炭化水素基、又は該炭化水素基中の１若しくは２以上のメチレン基が酸素原子、硫黄原子若しくは窒素原子で置換された基を表し、該炭化水素基は酸素原子、硫黄原子又は窒素原子を含む置換基で置換されていてもよく、
    　Ｘ２は酸素原子又は硫黄原子を表し、
    　Ｙ２は、酸素原子、硫黄原子、又は－ＮＲ１０－を表し、Ｒ１０は水素原子、アルキル基、又はアリール基を表す。     A resin composition containing (A) an epoxy resin, (B) a curing agent, (C) a urethane elastomer, and (D) a phosphorus-containing compound represented by the following formula (1) or (2).
    Figure JPOXMLDOC01-appb-C000001
     In the formula, m represents an integer from 1 to 10.
    R 1 and R 2 independently represent an alkyl group or an aryl group, respectively.
    R 3 represents a hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a sulfur atom. It may be substituted with a substituent containing a nitrogen atom.
    X 1 represents an oxygen atom or a sulfur atom and represents
    Y 1 is an oxygen atom, a sulfur atom, or -NR 4 - represents,
    R 4 represents a hydrogen atom, an alkyl group or an aryl group.
    Figure JPOXMLDOC01-appb-C000002
     In the formula, n represents an integer from 1 to 10.
    R 5 , R 6 , R 7 and R 8 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively.
    R 9 represents a hydrocarbon group or a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a sulfur atom. It may be substituted with a substituent containing a nitrogen atom.
    X 2 represents an oxygen atom or a sulfur atom
    Y 2 represents an oxygen atom, a sulfur atom, or -NR 10- , and R 10 represents a hydrogen atom, an alkyl group, or an aryl group.
  2. 　（Ａ）成分であるエポキシ樹脂がビスフェノール型エポキシ樹脂である、請求項１に記載の樹脂組成物。 The resin composition according to claim 1, wherein the epoxy resin as the component (A) is a bisphenol type epoxy resin.
  3. 　前記含リン化合物が、前記式（２）で表される含リン化合物であり、
    　前記式（２）中のＸ２及びＹ２が酸素原子である、請求項１又は２に記載の樹脂組成物。     The phosphorus-containing compound is a phosphorus-containing compound represented by the formula (2).
    The resin composition according to claim 1 or 2, wherein X 2 and Y 2 in the formula (2) are oxygen atoms.
  4. 　前記式（２）中のＲ５～Ｒ８が、それぞれ独立に、水素原子又は炭素数１～６のアルキル基である、請求項３に記載の樹脂組成物。 The resin composition according to claim 3, wherein R 5 to R 8 in the formula (2) are independently hydrogen atoms or alkyl groups having 1 to 6 carbon atoms.
  5. 　前記式（２）中のＲ５及びＲ７が、それぞれ独立に、アルキル基であり、Ｒ６及びＲ８が水素原子である、請求項３又は４に記載の樹脂組成物。 The resin composition according to claim 3 or 4, wherein R 5 and R 7 in the formula (2) are independently alkyl groups, and R 6 and R 8 are hydrogen atoms.
  6. 　前記式（２）中のＲ９が、下記の式（ａ－２）～（ｉ－２）で表される基からなる群から選択されるものである、請求項３～５の何れか１項に記載の樹脂組成物。
    Figure JPOXMLDOC01-appb-C000003
     　式中、＊は結合手を表す。     Any one of claims 3 to 5, wherein R 9 in the formula (2) is selected from the group consisting of groups represented by the following formulas (a-2) to (i-2). The resin composition according to the item.
    Figure JPOXMLDOC01-appb-C000003
     In the formula, * represents a bond.
  7. 　（Ｂ）成分である硬化剤が、アミン系潜在性硬化剤である、請求項１～６の何れか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 6, wherein the curing agent as the component (B) is an amine-based latent curing agent.
  8. 　前記アミン系潜在性硬化剤がジシアンジアミド型潜在性硬化剤である、請求項７に記載の樹脂組成物。 The resin composition according to claim 7, wherein the amine-based latent curing agent is a dicyandiamide-type latent curing agent.
  9. 　（Ｃ）成分であるウレタンエラストマーがブロックウレタンである、請求項１～８の何れか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 8, wherein the urethane elastomer as the component (C) is block urethane.
  10. 　前記ブロックウレタンが、（Ｃ１）イソシアネート含有量が０．１～１０質量％であるポリウレタン中のイソシアネート基を、（Ｃ２）ブロック化剤でブロックして得られるブロックウレタンであり、
    　（Ｃ１）であるポリウレタンが、（ｃ－１）ポリヒドロキシ化合物と、（ｃ－２）ポリイソシアネート化合物とを、該ポリヒドロキシ化合物に含まれるヒドロキシ基に対して、該ポリイソシアネート化合物に含まれるイソシアネート基が過剰となる量反応させて得られるものである、請求項９に記載の樹脂組成物。     The blocked urethane is a blocked urethane obtained by blocking an isocyanate group in polyurethane having an (C1) isocyanate content of 0.1 to 10% by mass with a (C2) blocking agent.
    The polyurethane (C1) is a polyhydroxy compound (c-1) and a polyisocyanate compound (c-2), and the isocyanate contained in the polyisocyanate compound is compared with the hydroxy group contained in the polyhydroxy compound. The resin composition according to claim 9, which is obtained by reacting an amount of an excess group.
  11. 　前記（ｃ－１）成分であるポリヒドロキシ化合物がポリエーテルポリオールであり、
    　前記（ｃ－２）成分であるポリイソシアネート化合物が、１，６－ヘキサメチレンジイソシアネート、トリレンジイソシアネート及びイソホロンジイソシアネートからなる群から選ばれる少なくとも１種である、請求項１０に記載の樹脂組成物。     The polyhydroxy compound which is the component (c-1) is a polyether polyol.
    The resin composition according to claim 10, wherein the polyisocyanate compound as the component (c-2) is at least one selected from the group consisting of 1,6-hexamethylene diisocyanate, tolylene diisocyanate and isophorone diisocyanate.
  12. 　構造用接着剤に使用される、請求項１～１１の何れか１項に記載の樹脂組成物。 The resin composition according to any one of claims 1 to 11, which is used for a structural adhesive.
  13. 　請求項１～１１の何れか１項に記載の樹脂組成物を硬化させてなる硬化物。 A cured product obtained by curing the resin composition according to any one of claims 1 to 11.
  14. 　（Ａ）エポキシ樹脂、（Ｂ）硬化剤及び（Ｃ）ウレタンエラストマーからなる樹脂組成物を硬化させるのに先立ち、（Ｄ）下記式（１）又は（２）で表される含リン化合物を該組成物中に含有させておく、硬化物の発泡抑制方法。
    Figure JPOXMLDOC01-appb-C000004
     　式中、ｍは１～１０の整数を表し、
    　Ｒ１及びＲ２は、それぞれ独立に、アルキル基又はアリール基を表し、
    　Ｒ３は、炭化水素基、該炭化水素基中の１又は２以上のメチレン基が酸素原子、硫黄原子又は窒素原子で置換された基を表し、該炭化水素基は酸素原子、硫黄原子又は窒素原子を含む置換基で置換されていてもよく、
    　Ｘ１は酸素原子又は硫黄原子を表し、
    　Ｙ１は酸素原子、硫黄原子、又は－ＮＲ４－を表し、
    　Ｒ４は、水素原子、アルキル基又はアリール基を表す。
    Figure JPOXMLDOC01-appb-C000005
     　式中、ｎは１～１０の整数を表し、
    　Ｒ５、Ｒ６、Ｒ７及びＲ８は、それぞれ独立に、水素原子、アルキル基、又はアリール基を表し、
    　Ｒ９は、炭化水素基、該炭化水素基中の１又は２以上のメチレン基が酸素原子、硫黄原子又は窒素原子で置換された基を表し、該炭化水素基は酸素原子、硫黄原子又は窒素原子を含む置換基で置換されていてもよく、
    　Ｘ２は酸素原子又は硫黄原子を表し、
    　Ｙ２は、酸素原子、硫黄原子、又は－ＮＲ１０－を表し、Ｒ１０は水素原子、アルキル基、又はアリール基を表す。     Prior to curing the resin composition composed of (A) epoxy resin, (B) curing agent and (C) urethane elastomer, (D) a phosphorus-containing compound represented by the following formula (1) or (2) is applied. A method for suppressing foaming of a cured product, which is contained in the composition.
    Figure JPOXMLDOC01-appb-C000004
     In the formula, m represents an integer from 1 to 10.
    R 1 and R 2 independently represent an alkyl group or an aryl group, respectively.
    R 3 represents a hydrocarbon group, a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a nitrogen. It may be substituted with a substituent containing an atom,
    X 1 represents an oxygen atom or a sulfur atom and represents
    Y 1 is an oxygen atom, a sulfur atom, or -NR 4 - represents,
    R 4 represents a hydrogen atom, an alkyl group or an aryl group.
    Figure JPOXMLDOC01-appb-C000005
     In the formula, n represents an integer from 1 to 10.
    R 5 , R 6 , R 7 and R 8 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively.
    R 9 represents a hydrocarbon group, a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a nitrogen. It may be substituted with a substituent containing an atom,
    X 2 represents an oxygen atom or a sulfur atom
    Y 2 represents an oxygen atom, a sulfur atom, or -NR 10- , and R 10 represents a hydrogen atom, an alkyl group, or an aryl group.
  15. 　（Ａ）エポキシ樹脂、（Ｂ）硬化剤及び（Ｃ）ウレタンエラストマーからなる樹脂組成物を硬化させるのに先立ち、（Ｄ）下記式（１）又は（２）で表される含リン化合物を該組成物中に含有させておく、発泡が抑制された硬化物の製造方法。
    Figure JPOXMLDOC01-appb-C000006
     　式中、ｍは１～１０の整数を表し、
    　Ｒ１及びＲ２は、それぞれ独立に、アルキル基又はアリール基を表し、
    　Ｒ３は、炭化水素基、該炭化水素基中の１又は２以上のメチレン基が酸素原子、硫黄原子又は窒素原子で置換された基を表し、該炭化水素基は酸素原子、硫黄原子又は窒素原子を含む置換基で置換されていてもよく、
    　Ｘ１は酸素原子又は硫黄原子を表し、
    　Ｙ１は酸素原子、硫黄原子、又は－ＮＲ４－を表し、
    　Ｒ４は、水素原子、アルキル基又はアリール基を表す。
    Figure JPOXMLDOC01-appb-C000007
     　式中、ｎは１～１０の整数を表し、
    　Ｒ５、Ｒ６、Ｒ７及びＲ８は、それぞれ独立に、水素原子、アルキル基、又はアリール基を表し、
    　Ｒ９は、炭化水素基、該炭化水素基中の１又は２以上のメチレン基が酸素原子、硫黄原子又は窒素原子で置換された基を表し、該炭化水素基は酸素原子、硫黄原子又は窒素原子を含む置換基で置換されていてもよく、
    　Ｘ２は酸素原子又は硫黄原子を表し、
    　Ｙ２は、酸素原子、硫黄原子、又は－ＮＲ１０－を表し、Ｒ１０は水素原子、アルキル基、又はアリール基を表す。     Prior to curing the resin composition composed of (A) epoxy resin, (B) curing agent and (C) urethane elastomer, (D) a phosphorus-containing compound represented by the following formula (1) or (2) is applied. A method for producing a cured product in which foaming is suppressed, which is contained in the composition.
    Figure JPOXMLDOC01-appb-C000006
     In the formula, m represents an integer from 1 to 10.
    R 1 and R 2 independently represent an alkyl group or an aryl group, respectively.
    R 3 represents a hydrocarbon group, a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a nitrogen. It may be substituted with a substituent containing an atom,
    X 1 represents an oxygen atom or a sulfur atom and represents
    Y 1 is an oxygen atom, a sulfur atom, or -NR 4 - represents,
    R 4 represents a hydrogen atom, an alkyl group or an aryl group.
    Figure JPOXMLDOC01-appb-C000007
     In the formula, n represents an integer from 1 to 10.
    R 5 , R 6 , R 7 and R 8 independently represent a hydrogen atom, an alkyl group, or an aryl group, respectively.
    R 9 represents a hydrocarbon group, a group in which one or more methylene groups in the hydrocarbon group are substituted with an oxygen atom, a sulfur atom or a nitrogen atom, and the hydrocarbon group is an oxygen atom, a sulfur atom or a nitrogen. It may be substituted with a substituent containing an atom,
    X 2 represents an oxygen atom or a sulfur atom
    Y 2 represents an oxygen atom, a sulfur atom, or -NR 10- , and R 10 represents a hydrogen atom, an alkyl group, or an aryl group.
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016121750A1 (en) * 2015-01-29 2016-08-04 株式会社Adeka Flame-retardant epoxy resin composition, prepreg formed using this, and laminate plate
WO2016152839A1 (en) * 2015-03-23 2016-09-29 株式会社Adeka Epoxy resin composition
JP2018016767A (en) * 2016-07-29 2018-02-01 株式会社Adeka Curable resin composition, and adhesive for structural material bonding prepared with the composition
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JP2019038989A (en) * 2017-08-23 2019-03-14 株式会社Adeka Flame-retardant epoxy resin composition
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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016121750A1 (en) * 2015-01-29 2016-08-04 株式会社Adeka Flame-retardant epoxy resin composition, prepreg formed using this, and laminate plate
WO2016152839A1 (en) * 2015-03-23 2016-09-29 株式会社Adeka Epoxy resin composition
JP2018514616A (en) * 2015-04-17 2018-06-07 アルツケム アクチエンゲゼルシャフトＡｌｚＣｈｅｍ ＡＧ Curing agent and curing accelerator having flame retardancy for curing epoxy resin (II)
JP2018016767A (en) * 2016-07-29 2018-02-01 株式会社Adeka Curable resin composition, and adhesive for structural material bonding prepared with the composition
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