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  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
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  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
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  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
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  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
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  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/282—Alkanols, cycloalkanols or arylalkanols including terpenealcohols
  • C08G18/2825—Alkanols, cycloalkanols or arylalkanols including terpenealcohols having at least 6 carbon atoms
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  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
  • C08G18/4804—Two or more polyethers of different physical or chemical nature
  • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
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  • C08G18/4829—Polyethers containing at least three hydroxy groups
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/48—Polyethers
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
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  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
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  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/80—Masked polyisocyanates
  • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
  • C08G18/8064—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds
  • C08G18/8067—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with monohydroxy compounds phenolic compounds
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  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
  • C08L75/04—Polyurethanes
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  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
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  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J175/00—Adhesives based on polyureas or polyurethanes; Adhesives based on derivatives of such polymers
  • C09J175/04—Polyurethanes
  • C09J175/08—Polyurethanes from polyethers

Definitions

• the problem to be solved by the present invention is to provide a curable composition capable of forming a cured product having excellent adhesiveness, a cured product of the curable composition, and an adhesive.
• the inventors of the present invention have made intensive studies to solve the above problems, and found that a blocked isocyanate prepolymer containing a specific polyol compound, a specific amount of polyisocyanate compound, a specific amount of branching agent, and a blocking agent as essential raw materials and an epoxy resin, and a curing agent or a curing accelerator.
• the present invention provides a blocked isocyanate prepolymer (A) comprising a polyol compound (a1), a polyisocyanate compound (a2), a branching agent (a3), and a blocking agent (a4) as essential raw materials, and an epoxy resin (B ), a curing agent (C1) and/or a curing accelerator (C2), wherein the polyol compound (a1) is polytetramethylene glycol, and the branching agent (a3 ) is a compound having at least three reactive functional groups capable of reacting with the isocyanate groups of the polyisocyanate compound (a2), and the number of moles of the isocyanate groups of the polyisocyanate compound (a2) is equal to the polyol compound
• the reactive functional group amount of the branching agent (a3) is 2 mol or less per 1 mol of the total of the reactive functional groups capable of reacting with the hydroxyl groups of (a1) and the isocyanate groups of the branching agent (a3). is more than
• the curable composition of the present invention can form a cured product having excellent adhesiveness, it can be used as a coating agent or an adhesive, and can be particularly suitably used as an adhesive.
• the curable composition of the present invention is characterized by containing a blocked isocyanate prepolymer (A), an epoxy resin (B), a curing agent (C1) and/or a curing accelerator (C2). do.
• the blocked isocyanate prepolymer (A) comprises a polyol compound (a1), a polyisocyanate compound (a2), a branching agent (a3), and a blocking agent (a4) as essential raw materials.
• Polytetramethylene glycol is used as the polyol compound (a1).
• the number average molecular weight of the polytetramethylene glycol is preferably in the range of 1,000 to 4,000, and 3,000 to 4 ,000 range is more preferred.
• polyol compound (a1) other polyol compounds can be used in addition to the polytetramethylene glycol, if necessary.
• the polyisocyanate compound (a2) is preferably a compound having at least two isocyanate groups in one molecule, and from the viewpoint of facilitating adjustment of the molecular weight of the isocyanate prepolymer (A), 2 to 4 isocyanate groups. It is more preferred that the compound has a diisocyanate.
• polyisocyanate compound (a2) examples 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), xyl diisocyanate, metatetramethylxylylene diisocyanate, isophorone diisocyanate (3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate), 1,3- or 1,4-bis(isocyanatomethyl)cyclohexane, diphenylmethane-4,
• hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane-4,4 are preferred because the reaction with the polyol compound (a1) is easily controlled and raw materials are easily available.
• '-diisocyanate is preferred and isophorone diisocyanate is more preferred.
• the amount of the polyisocyanate compound (a2) used is such that the molecular weight of the resulting prepolymer can be easily adjusted, and from the viewpoint of reducing unreacted polyisocyanate, the polyol compound (a1) contains a hydroxyl group and a branching agent (a3 ) has 2 mol or less of isocyanate groups with respect to the total 1 mol of reactive functional groups capable of reacting with isocyanate groups, and a curable composition capable of forming a cured product having excellent adhesiveness can be obtained. , the range of 1.6 to 1.8 mol is preferred.
• branching agent (a3) a compound having at least three reactive functional groups capable of reacting with the isocyanate groups of the polyisocyanate compound (a2) is used.
• reactive functional groups that can react with the polyisocyanate compound (a2) include hydroxyl groups, amino groups, and carboxyl groups. These reactive functional groups may be present singly or in combination of two or more.
• branching agent (a3) examples include polyether triol, polyether triamine, and trimer acid. These branching agents can be used alone or in combination of two or more. Among these, polyether triols are preferable because a curable composition capable of forming a cured product having excellent adhesiveness can be obtained.
• the number-average molecular weight of the branching agent (a3) is preferably in the range of 300 to 3,000, since a curable composition capable of forming a cured product with excellent adhesiveness can be obtained.
• the reactive functional group content of the branching agent (a3) is more than 50 mol% of the total of the hydroxyl groups of the polyol compound (a1) and the reactive functional groups of the branching agent (a3), and the resulting block
• the range of 55 to 65 mol % is preferable because it is possible to obtain a curable composition capable of suppressing an increase in the viscosity of the isocyanate prepolymer, maintaining workability, and forming a cured product having excellent adhesiveness.
• the blocking agent (a4) examples include active methylene compounds such as malonic acid diesters (diethyl malonate, etc.), acetylacetone, acetoacetic esters (ethyl acetoacetate, etc.); Oxime compounds such as isobutyl ketoxime (MIBK oxime); amine compounds such as diisopropylamine, benzylamine, dicyclohexylamine; phenol, cresol, ethylphenol, n-propylphenol, isopropylphenol, butylphenol, tert-butylphenol, octylphenol, nonylphenol, Monohydric phenol compounds such as dodecylphenol, cardanol, cyclohexylphenol, chlorophenol, and bromophenol; dihydric phenol compounds such as resorcinol, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, and naphthol; ⁇ -caprolactone,
• the method for producing the blocked isocyanate prepolymer (A) is not particularly limited. ) is allowed to react so that the isocyanate groups of ) become excessive, and then the excess isocyanate groups are blocked using the blocking agent (a4).
• the reaction of the polyol compound (a1), the polyisocyanate compound (a2) and the branching agent (a3) is not particularly limited, and can be carried out by a normal urethanization reaction.
• the reaction temperature in the above reaction is preferably in the range of 40 to 140°C, more preferably in the range of 60 to 130°C.
• a urethane polymerization catalyst can also be used to promote the reaction.
• urethane polymerization catalyst examples include organometallic compounds such as dioctyltin dilaurate, dibutyltin dilaurate, stannous octoate, stannous octoate, lead octylate, lead naphthenate, and zinc octylate, triethylenediamine, triethylamine, and the like. and tertiary amine compounds of. These urethane polymerization catalysts can be used alone or in combination of two or more.
• a known blocking reaction method can be used as a method for blocking using the blocking agent (a4).
• a range of 1 to 2 equivalents is preferred, and a range of 1.05 to 1.5 equivalents is more preferred, relative to the group.
• the blocking reaction with the blocking agent (a4) usually takes a method of adding the blocking agent (a4) in the final reaction of the urethane polymerization, but the blocking agent (a4) is added at any stage of the urethane polymerization. can be reacted to obtain a blocked isocyanate prepolymer.
• the blocking agent (a4) can be added at the end of a predetermined polymerization, at the beginning of the polymerization, or by adding a portion at the beginning of the polymerization and adding the remainder at the end of the polymerization. However, it is preferably added at the end of the polymerization. In this case, the isocyanate % may be used as a standard as a guideline for the completion of a predetermined polymerization.
• the reaction temperature for adding the blocking agent is generally 50 to 150°C, preferably 60 to 120°C.
• the reaction time is usually about 1 to 7 hours.
• the urethane polymerization catalyst may be added to promote the reaction. Any amount of plasticizer may be added during the reaction.
• the weight average molecular weight of the blocked isocyanate prepolymer (A) is preferably in the range of 4,000 to 15,000, more preferably 5,000 to 15,000, from the viewpoint of good handling when the curable composition is used as an adhesive. A range of 10,000 is more preferred.
• a weight average molecular weight (Mw) is a value measured by a gel permeation chromatography (GPC).
• the epoxy resin (B) is not particularly limited, and various types can be used. When used as an adhesive, it is preferably an epoxy resin that is liquid at room temperature.
• Aliphatic polyol polyglycidyl ether such as butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; diglycidylaniline, resorcinol diglycidyl ether, hydrogenation Ring structure-containing polyglycidyl compounds such as bisphenol A diglycidyl ether; ring structure-containing monofunctional glycidyl compounds such as alkylphenol monoglycidyl ether; polyglycidyl ester compounds such as neodecanoic acid glycidyl ester; Among these, it is preferable to use
• the ratio of the bisphenol-type epoxy resin to the total mass of the epoxy resin (B) is preferably 50% by mass or more, more preferably 70% by mass or more.
• these epoxy resins can be used alone or in combination of two or more.
• Examples of the bisphenol-type or biphenol-type epoxy resins include those obtained by using various bisphenol compounds or biphenol compounds and epihalohydrin as resin raw materials. Specifically, they are represented by the following structural formula (1). things are mentioned. These bisphenol type or biphenol type epoxy resins can be used alone or in combination of two or more.
• X is each independently a structural moiety represented by any one of the following structural formulas (2-1) to (2-8), and n represents the number of repetitions. ]
• each R 2 is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms
• each R 3 is independently a It is either an alkyl group of ⁇ 4 or an alkoxy group of 1 to 4 carbon atoms.
• X in Structural Formula (1) is a structural moiety represented by any of Structural Formulas (2-1) to (2-8), and multiple Xs present in the molecule are the same structural moiety. There may be one or different structural sites. Among these, the structural site represented by the general formula (2-1) or (2-2) is preferable because a curable composition capable of forming a cured product having excellent adhesiveness can be obtained. .
• Examples of the bisphenol compound or biphenol compound used in method 1 or 2 include compounds represented by any of the following structural formulas (3-1) to (3-8).
• each R 2 is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms
• each R 3 is independently a It is either an alkyl group of ⁇ 4 or an alkoxy group of 1 to 4 carbon atoms.
• These bisphenol compounds or biphenol compounds can be used alone or in combination of two or more.
• the compounds represented by general formula (3-1) or (3-2) are preferable because a curable composition capable of forming a cured product having excellent adhesiveness can be obtained.
• the reaction ratio between the bisphenol compound or the biphenol compound and these diglycidyl ether compounds is preferably in the range of 50/50 to 5/95 by mass.
• the reaction temperature is preferably about 120 to 160° C., and a reaction catalyst such as tetramethylammonium chloride may be used.
• the epoxy equivalent of the epoxy resin (B) is preferably in the range of 150 to 250 g/equivalent, more preferably in the range of 160 to 200 g/equivalent, since a curable composition capable of forming a cured product having excellent adhesiveness can be obtained. is preferred.
• epoxy resin (B) a bisphenol-type or biphenol-type epoxy resin and a flexible epoxy resin such as a urethane-modified epoxy resin or a rubber-modified epoxy resin can be used together, if necessary.
• polyhydroxy compounds examples include polyether polyols, polyester polyols, adducts of hydroxycarboxylic acids and alkylene oxides, polybutadiene polyols, and polyolefin polyols.
• the weight average molecular weight of the polyhydroxy compound is preferably in the range of 300 to 5,000, more preferably in the range of 500 to 2,000.
• the polyisocyanate is not particularly limited as long as it is a compound having two or more isocyanate groups. Examples thereof include aliphatic polyisocyanates, aromatic polyisocyanates, and polyisocyanates having aromatic hydrocarbon groups. Among these, aromatic polyisocyanates are preferred. Examples of the aromatic polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, and the like.
• the epoxy equivalent of the urethane-modified epoxy resin is preferably in the range of 200 to 250 g/equivalent.
• the rubber-modified epoxy resin is not particularly limited as long as it has two or more epoxy groups and has a rubber skeleton.
• examples of the rubber forming the skeleton include polybutadiene, acrylonitrile-butadiene rubber (NBR), carboxyl group-terminated NBR (CTBN), and the like.
• the rubber-modified epoxy resins may be used alone or in combination of two or more.
• the epoxy equivalent of the rubber-modified epoxy resin is preferably in the range of 200-350 g/equivalent.
• the method for producing the rubber-modified epoxy resin is not particularly limited, and examples thereof include a method of producing by reacting rubber and epoxy in a large amount of epoxy.
• the epoxy (eg, epoxy resin) used in producing the rubber-modified epoxy resin is not particularly limited.
• Examples of the curing agent (C1) include polyamine compounds, amide compounds, acid anhydrides, phenolic hydroxyl group-containing resins, phosphorus compounds, imidazole compounds, imidazoline compounds, urea compounds, organic acid metal salts, Lewis acids, and amines. complex salts and the like.
• polyamine compound examples include trimethylenediamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N,N,N',N'-tetra methylpropylenediamine, tetramethylenediamine, pentanediamine, hexamethylenediamine, trimethylhexamethylenediamine, N,N,N',N'-tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, diethylenetriamine, triethylenetetramine, Tetraethylenepentamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminopropylamine, 1,4-diazabicyclo(2,2,2) octane (triethylenediamine), polyoxyethylenediamine, polyoxypropylenediamine, bis(2- dimethylamin
• aromatic amines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylylenediamine, pyridine, picoline, ⁇ -methylbenzylmethylamine; Compound;
• Epoxy compound-added polyamine Michael-added polyamine, Mannich-added polyamine, Thiourea-added polyamine, Ketone-capped polyamine, Dicyandiamide, Guanidine, Organic acid hydrazide, Diaminomaleonitrile, Amine imide, Boron trifluoride-piperidine complex, Boron trifluoride-mono Examples include modified amine compounds such as ethylamine complexes.
• Examples of the amide compound include dicyandiamide and polyamidoamine.
• Examples of the polyamidoamine include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid and azelaic acid, carboxylic acid compounds such as fatty acids and dimer acid, and aliphatic polyamines and polyoxyalkylenes. Examples thereof include those obtained by reacting polyamines having chains.
• Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, methylhexa hydrophthalic anhydride and the like.
• phenolic hydroxyl group-containing resin examples include phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Zyloc resin), and naphthol aralkyl resin.
• trimethylolmethane resin trimethylolmethane resin, tetraphenylolethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co-condensed novolac resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group ), biphenyl-modified naphthol resins (polyhydric naphthol compounds with phenolic nuclei linked by bismethylene groups), aminotriazine-modified phenolic resins (polyhydric phenolic compounds with phenolic nuclei linked by melamine, benzoguanamine, etc.) and aromatic rings containing alkoxy groups.
• polyhydric phenol compounds such as modified novolac resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
• Examples of the phosphorus compounds include alkylphosphines such as ethylphosphine and butylphosphine, primary phosphines such as phenylphosphine; dialkylphosphines such as dimethylphosphine and dipropylphosphine; secondary phosphines such as diphenylphosphine and methylethylphosphine; Tertiary phosphines such as phosphine, triethylphosphine, and triphenylphosphine are included.
• alkylphosphines such as ethylphosphine and butylphosphine
• primary phosphines such as phenylphosphine
• dialkylphosphines such as dimethylphosphine and dipropylphosphine
• secondary phosphines such as diphenylphosphine and methylethylphosphine
• imidazole compound examples include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethylimidazole, 2-ethylimidazole, 3-ethylimidazole, 4-ethylimidazole, 5-ethylimidazole, 1-n-propylimidazole, 2-n-propylimidazole, 1-isopropylimidazole, 2-isopropylimidazole, 2-isopropylimidazole, 1-n-butylimidazole, 2-n-butylimidazole, 1- isobutylimidazole, 2-isobutylimidazole, 2-undecyl-1H-imidazole, 2-heptadecyl-1H-imidazole, 1,2-dimethylimidazole, 1,3-dimethylimidazole, 2,4-dimethylimi
• imidazoline compound examples include 2-methylimidazoline and 2-phenylimidazoline.
• urea compound examples include p-chlorophenyl-N,N-dimethylurea, 3-phenyl-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-N,N-dimethylurea, N-( 3-chloro-4-methylphenyl)-N',N'-dimethylurea and the like.
• curing agents can be used alone or in combination of two or more.
• dicyandiamide is preferred because it yields a curable composition capable of forming a cured product having excellent adhesiveness.
• Examples of the curing accelerator (C2) include amine compounds, imidazole compounds, and urea compounds.
• Examples of the amine compound include N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N' -tetramethylhexamethylenediamine, N,N-dimethylcyclohexylamine, 1,4-diazabicyclo(2,2,2)octane (triethylenediamine), bis(2-dimethylaminoethyl) ether, dimethylaminoethoxyethoxyethanol, tri ethanolamine, dimethylaminohexanol, and the like.
• the same ones as those exemplified as the imidazole compounds described above can be used.
• urea compound the same urea compound as exemplified above can be used.
• the curable composition of the present invention may optionally contain an organic solvent, an ultraviolet absorber, an antioxidant, a silicone additive, a fluorine additive, a flame retardant, a plasticizer, a silane coupling agent, organic beads, Inorganic fine particles, inorganic fillers, rheology control agents, defoaming agents, anti-fogging agents, colorants and the like may be contained. These various components can be added in arbitrary amounts depending on the desired performance.
• the blocked isocyanate prepolymer (A), the epoxy resin (B), the curing agent (C1) and / or the curing accelerator (C2), and if necessary are uniformly mixed using a pot mill, ball mill, bead mill, roll mill, homogenizer, super mill, homodisper, universal mixer, Banbury mixer, kneader, etc. It can be prepared.
• the application of the curable composition of the present invention is not particularly limited, and it can be used in various applications such as paints, coating agents, molding materials, insulating materials, sealing agents, sealing agents, and fiber binding agents. Among these, it can be suitably used as an adhesive for structural members in the fields of automobiles, trains, civil engineering and construction, electronics, aircraft and the aerospace industry, taking advantage of the excellent flexibility and toughness of the cured product.
• the adhesive of the present invention can maintain high adhesiveness without being affected by changes in the temperature environment, causing peeling and the like. hard.
• the adhesive of the present invention can also be used as an adhesive for general office, medical, carbon fiber, and electronic materials.
• Interlayer adhesives for multi-layer substrates such as substrates, optical component bonding adhesives, optical disc bonding adhesives, printed wiring board mounting adhesives, die bonding adhesives, semiconductor adhesives such as underfill, underfill for BGA reinforcement Mounting adhesives such as fills, anisotropic conductive films, and anisotropic conductive pastes can be used.
• the number average molecular weight (Mn) is a value measured under the following conditions using a gel permeation chromatograph (GPC).
• HLC-8220 manufactured by Tosoh Corporation Column; "Guard Column H XL -H” manufactured by Tosoh Corporation + “TSKgel G5000HXL” manufactured by Tosoh Corporation + “TSKgel G4000HXL” manufactured by Tosoh Corporation + “TSKgel G3000HXL” manufactured by Tosoh Corporation + “TSKgel G2000HXL” manufactured by Tosoh Corporation Detector; RI (differential refractometer) Data processing: “SC-8010” manufactured by Tosoh Corporation Measurement conditions: Column temperature 40°C Solvent Tetrahydrofuran Flow rate 1.0 ml/min Standard; Polystyrene Sample; A tetrahydrofuran solution of 0.4% by mass in terms of resin solid content filtered through a microfilter (100 ⁇ l)
• Table 1 shows the compositions of the blocked isocyanate prepolymers prepared in Synthesis Examples 1-8.
• PTMG-2000 polytetramethylene glycol
• PTMG-2000 polytetramethylene glycol
• PTMG-3000 polytetramethylene glycol
• PTMG-3000 manufactured by Mitsubishi Chemical Corporation
• TMP Trimethylolpropane
• TMP (flake) Trimethylolpropane
• T-400 polypropylene glycol
• T-700 polypropylene glycol
• T-700 manufactured by Mitsui Chemicals & SKC Polyurethane
• T-1500 polypropylene glycol (manufactured by Mitsui Chemicals & SKC Polyurethane Co., Ltd.
• T-1500 Mw: 1500, number of functional groups: 3
• HDI Hexamethylene diisocyanate (“Desmodur H” manufactured by Sumika Covestro Urethane Co., Ltd.)
• IPDI isophorone diisocyanate (“Desmodur I” manufactured by Sumika Covestro Urethane Co., Ltd.)
• TDI tolylene diisocyanate (“T-80” manufactured by Mitsui Chemicals & SKC Polyurethane)
• PTBP para-tertiary butyl phenol (“DIC-PTBP” manufactured by DIC Corporation)
• NX-2026 cardanol ("NX-2026” manufactured by Cardolite)
• DMP 3,5-dimethylpyrazole ("3,5-dimethylpyrazole” manufactured by Otsuka Chemical Co., Ltd.)
• the “NCO group amount” in Table 1 is the mole of the isocyanate group of the polyisocyanate compound (a2) per 1 mole of the hydroxyl group of the polyol compound (a1) and the reactive functional group of the branching agent (a3). indicate the number.
• the “amount of reactive functional groups of the branching agent (a3)" in Table 1 is the branching agent (a3) in the total of the reactive functional groups of the hydroxyl groups of the polyol compound (a1) and the branching agent (a3). shows the amount of reactive functional groups in
• Example 1 Preparation of curable composition (1)
• 20 parts by mass of the blocked isocyanate prepolymer (1) obtained in Synthesis Example 1 80 parts by mass of bisphenol A type epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation), 5 parts by mass of dicyandiamide as a curing agent, and a curing accelerator 1 part by mass of 3,4-dichlorophenyl-N,N-dimethylurea and 20 parts by mass of calcium carbonate as a filler were mixed to obtain a curable composition (1).
• bisphenol A type epoxy resin (“EPICLON 850-S” manufactured by DIC Corporation)
• 5 parts by mass of dicyandiamide as a curing agent 5 parts by mass of dicyandiamide as a curing agent
• a curing accelerator 1 part by mass of 3,4-dichlorophenyl-N,N-dimethylurea and 20 parts by mass of calcium carbonate as a filler were mixed to obtain a curable composition (1).
• Example 2 Preparation of curable composition (2)
• 20 parts by mass of the blocked isocyanate prepolymer (1) obtained in Synthesis Example 1 70 parts by mass of bisphenol A type epoxy resin (“EPICLON 850-S” manufactured by DIC Corporation), rubber-modified epoxy resin (“EPICLON TSR” manufactured by DIC Corporation -601") 10 parts by mass, 5 parts by mass of dicyandiamide as a curing agent, 1 part by mass of 3,4-dichlorophenyl-N,N-dimethylurea as a curing accelerator, and 20 parts by mass of calcium carbonate as a filler, to obtain a curable composition.
• Adhesion was evaluated based on tensile shear tests and T-peel tests.
• Table 2 shows the compositions and evaluation results of the curable compositions (1) to (6) prepared in Examples 1 to 6 and the curable compositions (R1) to (R3) prepared in Comparative Examples 1 to 3.
• TSR-601 rubber-modified epoxy resin ("EPICLON TSR-601" manufactured by DIC Corporation)
• 850-S Bisphenol A type epoxy resin
• DICY dicyandiamide
• DCMU 3,4-dichlorophenyl-N,N-dimethylurea
• Examples 1 to 6 shown in Table 2 are examples of curable compositions containing the blocked isocyanate prepolymer of the present invention. It was confirmed that these curable compositions had excellent adhesion.
• Comparative Examples 1 and 2 shown in Table 2 are examples of curable compositions containing blocked isocyanate prepolymers using no branching agent (a3).
• Comparative Example 3 is a blocked isocyanate in which the amount of reactive functional groups in the branching agent (a3) is 50 mol% of the total of the hydroxyl groups in the polyol compound (a1) and the reactive functional groups in the branching agent (a3).
• An example of a curable composition containing a prepolymer It was confirmed that these curable compositions had insufficient adhesion.

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