WO2021106963A1 - Composition de résine et procédé pour empêcher l'expansion d'un matériau durci - Google Patents

Composition de résine et procédé pour empêcher l'expansion d'un matériau durci Download PDF

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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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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

La présente invention aborde le problème de la fourniture d'une composition de résine dans laquelle l'expansion pendant le durcissement, en particulier dans des conditions de température et d'humidité élevées, est empêchée. La présente invention concerne également un procédé destiné à empêcher l'expansion d'un matériau durci à base de la composition de résine.　La composition de résine contient : (A) une résine époxy, (B) un agent de durcissement, (C) un élastomère d'uréthane et (D) au moins un composé choisi parmi les composés contenant du phosphore représentés par la formule (1) ou (2). (1) : pour plus d'informations sur m, R1, R2, R3, X1 et Y1 dans la formule (1), voir la description. (2) : pour plus d'informations sur n, R5 à R8, R9, X2 et Y2 dans la formule (2), voir la description.
PCT/JP2020/043906 2019-11-26 2020-11-25 Composition de résine et procédé pour empêcher l'expansion d'un matériau durci WO2021106963A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016121750A1 (fr) * 2015-01-29 2016-08-04 株式会社Adeka Composition ignifuge de résine époxyde, préimprégné formé en utilisant la composition et plaque de stratifié
WO2016152839A1 (fr) * 2015-03-23 2016-09-29 株式会社Adeka Composition de résine époxy
JP2018016767A (ja) * 2016-07-29 2018-02-01 株式会社Adeka 硬化性樹脂組成物、及び該組成物を用いた構造材料接合用接着剤
JP2018514616A (ja) * 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 エポキシ樹脂（ｉｉ）の硬化用の難燃作用を有する硬化剤および硬化促進剤
JP2019038989A (ja) * 2017-08-23 2019-03-14 株式会社Adeka 難燃性エポキシ樹脂組成物
JP2019038891A (ja) * 2017-08-23 2019-03-14 株式会社Adeka 難燃性エポキシ樹脂組成物、並びにそれを用いてなるプリプレグ及び積層板

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016121750A1 (fr) * 2015-01-29 2016-08-04 株式会社Adeka Composition ignifuge de résine époxyde, préimprégné formé en utilisant la composition et plaque de stratifié
WO2016152839A1 (fr) * 2015-03-23 2016-09-29 株式会社Adeka Composition de résine époxy
JP2018514616A (ja) * 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 エポキシ樹脂（ｉｉ）の硬化用の難燃作用を有する硬化剤および硬化促進剤
JP2018016767A (ja) * 2016-07-29 2018-02-01 株式会社Adeka 硬化性樹脂組成物、及び該組成物を用いた構造材料接合用接着剤
JP2019038989A (ja) * 2017-08-23 2019-03-14 株式会社Adeka 難燃性エポキシ樹脂組成物
JP2019038891A (ja) * 2017-08-23 2019-03-14 株式会社Adeka 難燃性エポキシ樹脂組成物、並びにそれを用いてなるプリプレグ及び積層板

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