WO2022102332A1 - 硬化性組成物、硬化物及び接着剤 - Google Patents

硬化性組成物、硬化物及び接着剤 Download PDF

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Publication number
WO2022102332A1
WO2022102332A1 PCT/JP2021/037984 JP2021037984W WO2022102332A1 WO 2022102332 A1 WO2022102332 A1 WO 2022102332A1 JP 2021037984 W JP2021037984 W JP 2021037984W WO 2022102332 A1 WO2022102332 A1 WO 2022102332A1
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WIPO (PCT)
Prior art keywords
curable composition
compound
epoxy resin
composition according
adhesive
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2021/037984
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English (en)
French (fr)
Japanese (ja)
Inventor
亮介 小澤
肇 菅沼
剛 山崎
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DIC Corp
Original Assignee
DIC Corp
Dainippon Ink and Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by DIC Corp, Dainippon Ink and Chemicals Co Ltd filed Critical DIC Corp
Priority to CN202180076359.5A priority Critical patent/CN116406392A/zh
Priority to US18/035,798 priority patent/US20240010782A1/en
Priority to EP21891579.1A priority patent/EP4245785A4/en
Priority to JP2022549674A priority patent/JP7180822B2/ja
Publication of WO2022102332A1 publication Critical patent/WO2022102332A1/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C08G18/485—Polyethers containing oxyethylene units and other oxyalkylene units containing mixed oxyethylene-oxypropylene or oxyethylene-higher oxyalkylene end groups
    • C—CHEMISTRY; METALLURGY
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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
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08G18/08—Processes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08G18/2805—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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
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    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4825—Polyethers containing two hydroxy groups
    • C—CHEMISTRY; METALLURGY
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    • C08G18/40—High-molecular-weight compounds
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    • C08G18/4829—Polyethers containing at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
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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
    • C08G18/4833—Polyethers containing oxyethylene units
    • C08G18/4837—Polyethers containing oxyethylene units and other oxyalkylene units
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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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
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
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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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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4028—Isocyanates; Thioisocyanates
    • C—CHEMISTRY; METALLURGY
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    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/44—Amides
    • C08G59/46—Amides together with other curing agents
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    • C08G65/00—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule
    • C08G65/02—Macromolecular compounds obtained by reactions forming an ether link in the main chain of the macromolecule from cyclic ethers by opening of the heterocyclic ring
    • C08G65/32—Polymers modified by chemical after-treatment
    • C08G65/329—Polymers modified by chemical after-treatment with organic compounds
    • C08G65/333—Polymers modified by chemical after-treatment with organic compounds containing nitrogen
    • C08G65/33348—Polymers modified by chemical after-treatment with organic compounds containing nitrogen containing isocyanate group
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    • C09J163/00—Adhesives based on epoxy resins; Adhesives based on derivatives of epoxy resins
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    • C09J171/00—Adhesives based on polyethers obtained by reactions forming an ether link in the main chain; Adhesives based on derivatives of such polymers
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    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
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    • C09J2475/00—Presence of polyurethane

Definitions

  • the present invention relates to a curable composition, a cured product and an adhesive.
  • An object to be solved by the present invention is to provide a curable composition capable of forming a cured product having excellent adhesiveness and moisture heat resistance, a cured product of the curable composition, and an adhesive.
  • the present inventors have found a blocked isocyanate prepolymer containing a polyol compound, a polyisocyanate compound, and a specific blocking agent as essential raw materials, an epoxy resin, and a curing agent.
  • the present invention has been completed by finding that the above-mentioned problems can be solved by using a curable composition containing the above-mentioned.
  • the present invention comprises a blocked isocyanate prepolymer (A) containing a polyol compound (a1), a polyisocyanate compound (a2), and a blocking agent (a3) as essential raw materials, an epoxy resin (B), and a curing agent (C).
  • the curable composition of the present invention can form a cured product having excellent adhesiveness and moisture resistance, it can be used as a coating agent or an adhesive, and can be particularly preferably used as an adhesive.
  • the curable composition of the present invention is characterized by containing a blocked isocyanate prepolymer (A), an epoxy resin (B), and a curing agent (C).
  • the blocked isocyanate prepolymer (A) contains a polyol compound (a1), a polyisocyanate compound (a2), and a blocking agent (a3) as essential raw materials.
  • polyol compound (a1) examples include polyether polyols such as polyethylene glycol, polypropylene glycol and polytetramethylene glycol, polyester polyols, polycarbonate polyols and acrylic polyols.
  • a polyether polyol is preferable, and a polyol containing a polyoxyethylene unit and a polyoxypropylene unit is more preferable because a curable composition capable of forming a cured product having excellent adhesiveness and moisture heat resistance can be obtained.
  • the inclusion of the polyoxyethylene unit makes it possible to take in some water into the adhesive layer (cured product) when used as an adhesive, and as a result, suppresses interfacial peeling even if peeling occurs.
  • the polyoxyethylene unit and the polyoxypropylene unit are contained as compared with the case where only the polyoxytetramethylene unit, which has excellent moisture and heat resistance but tends to lack flexibility and easily causes interfacial peeling, is used as a raw material. This is because the performance balance as an adhesive becomes excellent. Further, the polyoxyethylene unit and the polyoxypropylene unit do not need to be present in the same molecule. For example, a polyol containing only the polyoxyethylene unit and a polyol containing only the polyoxypropylene unit are used in combination to be described later. It may be reacted with the isocyanate compound (a2).
  • polyol containing the polyoxyethylene unit and the polyoxypropylene unit examples include a polyoxyethylene-polyoxypropylene copolymer and the like.
  • the polyoxyethylene-polyoxypropylene copolymer is preferably a trifunctional or higher functional copolymer from the viewpoint of being more excellent in adhesiveness.
  • the repeating unit of the oxyethylene unit in polyoxyethylene is in the range of 2 to 10, from the viewpoint of excellent adhesion to the substrate when used as an adhesive and an excellent balance between mechanical strength and moisture heat resistance. preferable.
  • the mass ratio [(polyoxyethylene unit) / (polyoxypropylene unit)] of the polyoxyethylene unit and the polyoxypropylene unit in the polyol containing the polyoxyethylene unit and the polyoxypropylene unit has excellent adhesiveness.
  • the range is preferably 40/60 to 1/99.
  • the polyol containing the polyoxyethylene unit and the polyoxypropylene unit may contain units other than polyoxyethylene and polyoxypropylene (hereinafter, referred to as "other units").
  • the other units include, for example, aliphatic dihydric alcohols such as neopentane glycol; glycerin, trioxyisobutane, 1,2,3-butanetriol, 1,2,3-pentanetriol, 2-methyl-1.
  • 2,3-Propanetriol 2-methyl-2,3,4-butanetriol, 2-ethyl-1,2,3-butanetriol, 2,3,4-pentanetriol, 2,3,4-hexane Triol, 4-propyl-3,4,5-heptanetriol, 2,4-dimethyl-2,3,4-pentanetriol, pentamethylglycerin, pentaglycerin, 1,2,4-butanetriol, 1,2, Trihydric alcohols such as 4-pentanetriol, trimethylolpropane; erythrite, pentaerythrit, 1,2,3,4-pentantetrol, 2,3,4,5-hexanetetrol, 1,2,3 Four-valent alcohols such as 5-pentane tetrol and 1,3,4,5-hexanetetrol; pentavalent alcohols such as adnit, arabit and xylit; hexavalent alcohols such as sorbit, mannit and igit alone.
  • the polyol compound (a1) preferably contains 2 to 4 functional components, and particularly preferably contains trifunctional components from the viewpoint of excellent adhesion to the substrate.
  • the number average molecular weight of the polyol (a1) is preferably in the range of 1,000 to 5,000, and more preferably in the range of 2,000 to 4,000.
  • the polyisocyanate compound (a2) is preferably a compound having at least two isocyanate groups in one molecule, and has 2 to 4 isocyanate groups from the viewpoint that the molecular weight of the isocyanate prepolymer (A) can be easily adjusted. It is more preferably a compound having one, and particularly preferably a diisocyanate.
  • polyisocyanate compound (a2) examples include propane-1,2-diisocyanate, 2,3-dimethylbutane-2,3-diisocyanate, 2-methylpentane-2,4-diisocyanate, and octane-3,6-.
  • These polyisocyanate compounds may
  • hexamethylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane-4,4 are easy to control the reaction with the polyol compound (a1), and from the viewpoint of easy availability of raw materials.
  • '-Diisocyanate is preferable, and isophorone diisocyanate is more preferable.
  • isocyanate is given to 1 mol of the hydroxyl group of the polyol compound (a1) from the viewpoint of easy adjustment of the molecular weight of the obtained prepolymer and reduction of unreacted polyisocyanate.
  • the group is preferably in the range of 1.80 to 3.50 mol.
  • the blocking agent (a3) one containing a phenol compound having a hydrocarbon group having 12 or more carbon atoms is used.
  • the number of carbon atoms is preferably 12 or more and 20 or less, and more preferably 12 or more and 18 or less, because a curable composition capable of forming a cured product having excellent adhesiveness and moisture heat resistance can be obtained.
  • the hydrocarbon group an aliphatic hydrocarbon group is preferable, and an alkyl group is more preferable.
  • Examples of the phenol compound having a hydrocarbon group having 12 or more carbon atoms include dodecylphenol, cardanol, cardol and the like.
  • cardanol is preferable because a curable composition capable of forming a cured product having excellent adhesiveness and moisture heat resistance can be obtained.
  • the blocking agent (a3) a blocking agent other than the phenol compound having a hydrocarbon group having 12 or more carbon atoms (hereinafter, may be referred to as “other blocking agent”) is used. You can also.
  • the other blocking agent examples include active methylene compounds such as phenol diester (diethyl phenol and the like), acetylacetone, and acetacetic acid ester (ethyl acetate and the like); acetoxime, methylethylketooxime (MEK oxime), and methylisobutyl.
  • Oxim compounds such as ketooxym (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 these.
  • 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, isopropylphenol , Butylphenol, Tertiary butylphenol, octylphenol, nonylphenol, dodecylphenol, cyclohexylphenol, chlorophenol, bromophenol and other monovalent phenolic compounds, resorcin, catechol, hydroquinone, bisphenol A, bisphenol S, bisphenol F, naphthol and the like. Phenolic compounds; ⁇ -caprolactone, ⁇ -caprolactam and the like. These other blocking agents may be used alone or in combination of two or more.
  • the method for producing the blocked isocyanate prepolymer (A) is not particularly limited, but the hydroxyl group of the polyol compound (a1) is reacted so that the isocyanate group of the polyisocyanate compound (a2) becomes excessive. Then, a method of blocking the excess isocyanate group with a blocking agent (a3) and the like can be mentioned.
  • the reaction between the polyol compound (a1) and the polyisocyanate compound (a2) is not particularly limited, and can be carried out by a normal urethanization reaction.
  • the reaction temperature in the 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.
  • Examples of the catalyst for urethane polymerization include organic metal compounds such as dioctyltin dilaurate, dibutyltin dilaurate, stannous octate, stanas octate, lead octylate, lead naphthenate, zinc octylate, triethylenediamine, triethylamine and the like. Examples thereof include tertiary amine compounds. These urethane polymerization catalysts can be used alone or in combination of two or more.
  • a known blocking reaction method can be used, and the amount of the blocking agent (a3) used is an excess of isocyanate groups, that is, free isocyanate.
  • the range of 1 to 2 equivalents is preferable with respect to the group, and the range of 1.05 to 1.5 equivalents is more preferable.
  • the blocking reaction with the blocking agent (a3) usually takes the method of adding the blocking agent (a3) in the final reaction of the urethane polymerization, but the blocking agent (a3) is added at any stage of the urethane polymerization. It can also be reacted to obtain a blocked isocyanate prepolymer.
  • the blocking agent (a3) As a method of adding the blocking agent (a3), it is possible to add it at the end of a predetermined polymerization, add it at the initial stage of polymerization, or add a part at the initial stage of polymerization and add the rest at the end of polymerization. However, it is preferably added at the end of polymerization. In this case, the isocyanate% may be used as a reference as a guideline at the end of the predetermined polymerization.
  • the reaction temperature at the time of adding the blocking agent is usually 50 to 150 ° C, preferably 60 to 120 ° C.
  • the reaction time is usually about 1 to 7 hours.
  • the urethane polymerization catalyst At the time of the reaction, it is also possible to add the urethane polymerization catalyst to accelerate the reaction. Further, an arbitrary amount of the 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, preferably 5,000 to 10, from the viewpoint of good handling when the curable composition is used as an adhesive. A range of 000 is more preferred.
  • the weight average molecular weight (Mw) is a value measured by gel permeation chromatography (GPC).
  • the epoxy resin (B) is not particularly limited, and various ones can be used. When used as an adhesive, it is preferably an epoxy resin that is liquid at room temperature, for example, a bisphenol type or biphenol type epoxy resin such as a tetramethylbiphenol type epoxy resin, a bisphenol A type epoxy resin, or a bisphenol F type epoxy resin; Adipose polyol polyglycidyl ethers such as butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, hexanediol diglycidyl ether, trimethylolpropane triglycidyl ether, glycerin triglycidyl ether; diglycidyl aniline, resorcinol diglycidyl ether, hydrogenation.
  • a bisphenol type or biphenol type epoxy resin such as a tetramethylbiphenol type epoxy resin, a bisphenol A type epoxy resin, or a bisphenol
  • 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 and the like can be mentioned.
  • a bisphenol type or biphenol type epoxy resin because a curable composition capable of forming a cured product having excellent adhesiveness and moisture heat resistance can be obtained, and from the viewpoint of industrial availability.
  • a bisphenol type epoxy resin is preferably 50% by mass or more, and 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 resin include those obtained by using various bisphenol compounds or biphenol compounds and epihalohydrin as resin raw materials, and specifically, it is represented by the following structural formula (1). Things can be mentioned. These bisphenol type or biphenol type epoxy resins can be used alone or in combination of two or more.
  • X is a structural part represented by any of the following structural formulas (2-1) to (2-8) independently, and n represents the number of repetitions. ]
  • R 2 is independently any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms
  • R 3 is independently having 1 carbon atom. It is either an alkyl group of up to 4 or an alkoxy group having 1 to 4 carbon atoms.
  • X in the structural formula (1) is a structural part represented by any of the structural formulas (2-1) to (2-8), and a plurality of Xs existing in the molecule are the same structural part. It may be present, or it may be a different structural part. Among these, it is a structural part represented by the general formula (2-1) or (2-2) because a curable composition capable of forming a cured product having excellent adhesiveness and moisture heat resistance can be obtained. Is preferable.
  • the bisphenol type or biphenol type epoxy resin can be produced by a method using various bisphenol compounds or biphenol compounds and epihalohydrin as resin raw materials.
  • a method (method 1) in which a diglycidyl ether compound obtained by reacting a bisphenol compound or a biphenol compound with epihalohydrin is further reacted with a bisphenol compound or a biphenol compound, or a bisphenol compound or a biphenol compound and epihalohydrin are used.
  • Examples thereof include a method (method 2) of directly obtaining an epoxy resin by reacting.
  • the method 1 is preferable because the reaction is easy to control and the epoxy equivalent of the obtained epoxy resin (B) can be easily controlled to the preferable value.
  • Examples of the bisphenol compound or biphenol compound used in the method 1 or 2 include compounds represented by any of the following structural formulas (3-1) to (3-8).
  • R 2 is independently any of a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms
  • R 3 is independently having 1 carbon atom. It is either an alkyl group of up to 4 or an alkoxy group having 1 to 4 carbon atoms.
  • bisphenol compounds or biphenol compounds can be used alone or in combination of two or more.
  • the compound represented by the general formula (3-1) or (3-2) is preferable because a curable composition capable of forming a cured product having excellent adhesiveness and moisture heat resistance can be obtained.
  • the reaction ratio between the bisphenol compound or the biphenol compound and these diglycidyl ether compounds is preferably in the mass ratio of 50/50 to 5/95.
  • 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 / eq, preferably 160 to 200 g / eq, because a curable composition capable of forming a cured product having excellent adhesiveness and moisture heat resistance can be obtained.
  • the range of eq 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 in combination, if necessary.
  • the urethane-modified epoxy resin is not particularly limited as long as it is a resin having a urethane bond and two or more epoxy groups in the molecule.
  • a urethane bond-containing compound having an isocyanate group obtained by reacting a polyhydroxy compound with a polyisocyanate and a hydroxy group-containing epoxy compound can be efficiently introduced into one molecule of a urethane bond and an epoxy group. It is preferable that the resin is obtained by reacting with.
  • polyhydroxy compound examples include polyether polyols, polyester polyols, additives of hydroxycarboxylic acid and alkylene oxide, polybutadiene polyols, polyolefin polyols and the like.
  • 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.
  • an aliphatic polyisocyanate, an aromatic polyisocyanate, a polyisocyanate having an aromatic hydrocarbon group, and the like can be mentioned.
  • aromatic polyisocyanates are preferable.
  • the aromatic polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate and the like.
  • a urethane prepolymer containing a free isocyanate group at the terminal is obtained.
  • an epoxy resin having at least one hydroxyl group in one molecule for example, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, diglycidyl ether of aliphatic polyhydric alcohol and glycidol.
  • a urethane-modified epoxy resin can be obtained.
  • the epoxy equivalent of the urethane-modified epoxy resin is preferably in the range of 200 to 250 g / eq.
  • the rubber-modified epoxy resin is not particularly limited as long as it has two or more epoxy groups and the skeleton is rubber.
  • the rubber forming the skeleton include polybutadiene, acrylonitrile butadiene rubber (NBR), and carboxyl group terminal NBR (CTBN).
  • the rubber-modified epoxy resin 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 to 350 g / eq.
  • the method for producing the rubber-modified epoxy resin is not particularly limited, and examples thereof include a method for producing the rubber by reacting the rubber with the epoxy in a large amount of epoxy.
  • the epoxy (for example, epoxy resin) used in producing the rubber-modified epoxy resin is not particularly limited.
  • curing agent (C) examples include polyamine compounds, amide compounds, acid anhydrides, phenolic hydroxyl group-containing resins, phosphorus compounds, imidazole compounds, imidazoline compounds, urea compounds, organic acid metal salts, and Lewis acids. Amine complex salt and the like can be mentioned.
  • polyamine compound examples include trimethylenediamine, ethylenediamine, N, N, N', N'-tetramethylethylenediamine, pentamethyldiethylenetriamine, triethylenediamine, dipropylenediamine, N, N, N', N'-tetra.
  • DBU undecene
  • Aromatic amines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzylmethylamine, dimethylbenzylamine, m-xylenediamine, pyridine, picoline, ⁇ -methylbenzylmethylamine Compound;
  • Epoxy compound-added polyamines Epoxy compound-added polyamines, Michael-added polyamines, Mannig-added polyamines, thiourea-added polyamines, ketone-blocking polyamines, dicyandiamides, guanidines, organic acid hydrazides, diaminomaleonitriles, amineimides, boron trifluoride-piperidin complexes, boron trifluoride-mono Examples thereof include modified amine compounds such as ethylamine complexes.
  • Examples of the amide compound include dicyandiamide and polyamideamine.
  • Examples of the polyamide amine include aliphatic dicarboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid and azelaic acid, carboxylic acid compounds such as fatty acids and dimer acids, and aliphatic polyamines and polyoxyalkylenes. Examples thereof include those obtained by reacting a polyamine having a chain or the like.
  • Examples of the acid anhydride include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, hexahydrophthalic anhydride, and methylhexa.
  • Examples include hydrophthalic anhydride.
  • phenolic hydroxyl group-containing resin examples include phenol novolac resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadienephenol-added resin, phenol aralkyl resin (Zyroc resin), and naphthol aralkyl resin.
  • polyhydric phenol compounds such as modified novolak resins (polyhydric phenol compounds in which a phenol nucleus and an alkoxy group-containing aromatic ring are linked with formaldehyde).
  • Examples of the phosphorus compound include alkylphosphine such as ethylphosphine and butylphosphine, first phosphine such as phenylphosphine; dialkylphosphine such as dimethylphosphine and dipropylphosphine; second phosphine such as diphenylphosphine and methylethylphosphine; trimethyl.
  • alkylphosphine such as ethylphosphine and butylphosphine
  • first phosphine such as phenylphosphine
  • dialkylphosphine such as dimethylphosphine and dipropylphosphine
  • second phosphine such as diphenylphosphine and methylethylphosphine
  • trimethyl examples thereof include a third phosphine such as phosphine, triethylphosphine, and triphenylphosphine.
  • imidazole compound examples include imidazole, 1-methylimidazole, 2-methylimidazole, 3-methylimidazole, 4-methylimidazole, 5-methylimidazole, 1-ethyl imidazole, 2-ethyl imidazole and 3-ethyl imidazole.
  • 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 and N- ( Examples thereof include 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 preferable because a curable composition capable of forming a cured product having excellent adhesiveness and moisture heat resistance can be obtained.
  • the ratio of the blocked isocyanate prepolymer (A) to the epoxy resin (B) is such that a curable composition capable of forming a cured product having excellent adhesiveness and moisture heat resistance can be obtained.
  • the mass ratio represented by (A) / (B) is preferably in the range of 5/95 to 40/60, and more preferably in the range of 10/90 to 30/70.
  • the mixing ratio of the epoxy resin (B) and the curing agent (C) is such that when a curing agent having a functional group capable of reacting with the epoxy group is used, the mixing ratio is based on 1 mol of the epoxy group of the epoxy resin (B).
  • the functional group in the curing agent in a ratio of 0.5 to 1.1 mol.
  • a curing accelerator may be used, and when the curing accelerator is used, it is preferably blended in a ratio of 0.5 to 10 parts by mass with respect to 100 parts by mass of the epoxy resin (B).
  • the curable composition of the present invention includes, if necessary, an organic solvent, an ultraviolet absorber, an antioxidant, a silicon-based additive, a fluorine-based additive, a flame retardant, a plasticizer, a silane coupling agent, an organic bead, and the like. It may contain inorganic fine particles, an inorganic filler, a rheology control agent, a defoaming agent, an antifogging agent, a coloring agent and the like. Any amount of these various components can be added depending on the desired performance.
  • the blocked isocyanate prepolymer (A), the epoxy resin (B), the curing agent (C), and various optional components that can be contained as needed can be prepared by a method of uniformly mixing using a pot mill, a ball mill, a bead mill, a roll mill, a homogenizer, a super mill, a homodisper, a universal mixer, a Banbury mixer, a kneader or the like.
  • the use of the curable composition of the present invention is not particularly limited, and it can be used for various uses such as paints, coating agents, molding materials, insulating materials, encapsulants, sealants, and fiber binding agents. Among these, taking advantage of the excellent flexibility and toughness of the cured product, 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 space industry.
  • the adhesive of the present invention can be used not only for structural members but also as an adhesive for general office work, medical use, carbon fiber, electronic material, etc., and as an adhesive for electronic material, for example, build-up Adhesives for multilayer boards such as substrates, adhesives for joining optical components, adhesives for bonding optical disks, adhesives for mounting printed wiring boards, die bonding adhesives, adhesives for semiconductors such as underfills, and underscores for BGA reinforcement. Examples thereof include a fill, an anisotropic conductive film, and an adhesive for mounting such as an anisotropic conductive paste.
  • the weight average molecular weight (Mw) is a value measured under the following conditions using a gel permission chromatograph (GPC).
  • Tables 1 and 2 show the compositions of the blocked isocyanate prepolymers prepared in Synthesis Examples 1 to 13.
  • EP-530 Polyoxyethylene-polyoxypropylene copolymer
  • EP-530 manufactured by Mitsui Chemical & SKC Polyurethane, Mw: 3000, number of functional groups: 3
  • ED-37A Polyoxyethylene-polyoxypropylene copolymer
  • T-3000 Polypropylene glycol (Mitsui Chemical & SKC Polyurethane "T-3000", Mw: 3000, number of functional groups: 3)
  • EP-3033 Polypropylene glycol (Mitsui Chemical & SKC Polyurethane "EP-3033", Mw: 6600, number of functional groups: 4)
  • PTMG-3000 Polytetramethylene glycol
  • PTMG-3000 manufactured by Mitsubishi Chemical Corporation, Mw: 3000, number of functional groups: 2)
  • T5652 Polycarbonate polyol
  • Example 1 Preparation of curable composition (1)
  • 20 parts by mass of the blocked isocyanate prepolymer (1) obtained in Synthesis Example 1 5 parts by mass of a rubber-modified epoxy resin (“EPICLON TSR-601” manufactured by DIC Co., Ltd.), and a bisphenol A type epoxy resin (“EPICLON 850” manufactured by DIC Co., Ltd.).
  • -S 75 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 form a curable composition. I got the thing (1).
  • Example 2 to 8 Preparation of curable compositions (2) to (8)
  • the blocked isocyanate prepolymers (2) to (8) obtained in Synthesis Examples 2 to 8 were used in the blending amounts shown in Table 3 instead of the blocked isocyanate prepolymer (1) used in Example 1.
  • Curable compositions (2) to (8) were obtained in the same manner as in Example 1.
  • ⁇ Tension shear test> The tensile shear strength of the test piece was measured using "AUTOGRAPH AG-XPlus 100 kN" manufactured by Shimadzu Corporation under the condition of 25 ° C. by the method of JIS K6859 (1994) (creep rupture test of adhesive).
  • ⁇ T-shaped peeling test> The peel strength of the test piece was measured using "AUTOGRAPH AG-IS 1kN" manufactured by Shimadzu Corporation under the condition of 25 ° C. by the method of JIS K6854-3 (1999) (adhesive peeling adhesive strength test).
  • Tables 3 and 4 show the compositions and evaluation results of the curable compositions (1) to (8) prepared in Examples 1 to 8 and the curable compositions (R1) to (R5) prepared in Comparative Examples 1 to 5. show.
  • TSR-601 Rubber-modified epoxy resin ("EPICLON TSR-601" manufactured by DIC Corporation)
  • 850-S Bisphenol A type epoxy resin
  • EPICLON 850-S Bisphenol F type liquid epoxy resin
  • DICY dicyandiamide
  • DCMU 3,4-dichlorophenyl-N, N-dimethylurea
  • Examples 1 to 8 shown in Table 3 are examples of curable compositions containing a blocked isocyanate prepolymer using a phenol compound having a hydrocarbon group having 12 or more carbon atoms as a blocking agent. It was confirmed that these curable compositions have excellent adhesiveness and moisture heat resistance.
  • Comparative Examples 1 to 5 shown in Table 4 are examples of a curable composition containing a blocked isocyanate prepolymer which does not use a phenol compound having a hydrocarbon group having 12 or more carbon atoms as a blocking agent. be. It was confirmed that these curable compositions had insufficient adhesiveness and also insufficient moisture and heat resistance.

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