WO2011093466A1 - Catalyseur pour dissociation d'agent de blocage comportant un complexe métallique polynucléaire et son procédé d'utilisation - Google Patents

Catalyseur pour dissociation d'agent de blocage comportant un complexe métallique polynucléaire et son procédé d'utilisation Download PDF

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WO2011093466A1
WO2011093466A1 PCT/JP2011/051803 JP2011051803W WO2011093466A1 WO 2011093466 A1 WO2011093466 A1 WO 2011093466A1 JP 2011051803 W JP2011051803 W JP 2011051803W WO 2011093466 A1 WO2011093466 A1 WO 2011093466A1
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metal
blocking agent
binuclear complex
dissociation catalyst
acid
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PCT/JP2011/051803
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English (en)
Japanese (ja)
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裕志 藤原
真治 尾添
前浜　誠司
隆夫 蒲原
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東ソー株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
    • B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
    • B01J31/143—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron of aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
    • B01J31/0201—Oxygen-containing compounds
    • B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
    • B01J31/0212—Alkoxylates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2234—Beta-dicarbonyl ligands, e.g. acetylacetonates
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
    • B01J31/2208—Oxygen, e.g. acetylacetonates
    • B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
    • B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
    • B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
    • 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
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/222—Catalysts containing metal compounds metal compounds not provided for in groups C08G18/225 - C08G18/26
    • 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
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C08G18/2815—Monohydroxy compounds
    • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • 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
    • C08G18/285—Nitrogen containing compounds
    • C08G18/286—Oximes
    • 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
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • 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
    • C08G18/703—Isocyanates or isothiocyanates transformed in a latent form by physical means
    • C08G18/705—Dispersions of isocyanates or isothiocyanates in a liquid medium
    • C08G18/706—Dispersions of isocyanates or isothiocyanates in a liquid medium the liquid medium being water
    • 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
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • 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
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds
    • C08G18/8077—Oximes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
    • B01J2531/0213—Complexes without C-metal linkages
    • B01J2531/0219—Bimetallic complexes, i.e. comprising one or more units of two metals, with metal-metal bonds but no all-metal (M)n rings, e.g. Cr2(OAc)4
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
    • B01J2531/26—Zinc
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
    • B01J2531/72—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
    • B01J2531/80—Complexes comprising metals of Group VIII as the central metal
    • B01J2531/84—Metals of the iron group
    • B01J2531/847—Nickel

Definitions

  • the present invention relates to a catalyst composed of a metal binuclear complex for dissociating a blocking agent of polyisocyanate (hereinafter sometimes referred to as “blocking agent dissociation catalyst”), and a one-component thermosetting composition using the same.
  • blocking agent dissociation catalyst a blocking agent of polyisocyanate
  • Polyurethane resin paint has very excellent wear resistance, chemical resistance, stain resistance and the like.
  • a general polyurethane resin paint is a two-component type composed of a polyol component and a polyisocyanate component, and each is stored separately and mixed for use during coating.
  • the paint once mixed is cured in a short time, there is a problem in terms of workability at the time of painting because the pot life is short.
  • the polyisocyanate and water easily react, it is impossible to use in a water-based paint such as an electrodeposition paint.
  • the conventional two-pack type polyurethane resin paint has many limitations in its use.
  • a method using a blocked isocyanate which is inactivated by reacting a polyisocyanate with an active hydrogen group-containing compound (blocking agent) is known.
  • This blocked isocyanate does not react with the polyol at room temperature, but when heated, the blocking agent dissociates to regenerate the isocyanate group, and the crosslinking reaction with the polyol proceeds.
  • the pot life is not limited, and it is possible to preliminarily blend both into a paint to make a single solution or to apply to a water-based paint.
  • ⁇ -caprolactam methyl ethyl ketone oxime
  • phenol phenol
  • blocked isocyanates using these require a high baking temperature of 140 ° C. or higher to dissociate the blocking agent, which is disadvantageous in terms of energy and cannot be applied to plastic substrates with low heat resistance. was there.
  • a catalyst blocking agent dissociation catalyst
  • organic tin such as dibutyltin dilaurate
  • bismuth salts for example, see Patent Document 1
  • zinc salts for example, see Patent Document 2
  • An effective blocking agent dissociation catalyst has not yet been reported.
  • Non-Patent Document 2 to Non-Patent Document 4
  • examples in which these metal binuclear complexes are applied as dissociation catalysts for blocking agents are still reported. It has not been.
  • the present invention has been made in view of the background art described above, and an object thereof is to provide a dissociation catalyst for a blocking agent having a high dissociation effect at low temperatures and its use.
  • this invention is a block agent dissociation catalyst which consists of a metal binuclear complex as shown below, and a one-pack type thermosetting composition using the same.
  • a blocking agent dissociation catalyst comprising a metal binuclear complex containing two or more metals.
  • the metal contained in the metal binuclear complex is one or two or more metals selected from the group consisting of aluminum and zinc, cobalt, nickel, manganese, and copper.
  • [4] The blocking agent dissociation catalyst according to [1] above, wherein the metal contained in the metal binuclear complex is aluminum and zinc.
  • [5] The blocking agent dissociation catalyst according to any one of [1] to [4] above, wherein the metal binuclear complex contains a ⁇ -diketone and an alkoxy group as ligands.
  • [6] The above [1] to [1], wherein the amount of aluminum contained in the metal binuclear complex with respect to the total amount of metals other than aluminum contained in the metal binuclear complex is in the range of 1 to 3 in atomic ratio.
  • the blocking agent dissociation catalyst according to any one of [1] to [6] above which contains a metal compound other than a metal binuclear complex containing two or more metals.
  • the blocking agent dissociation catalyst according to any one of [1] to [7] above which contains an organic solvent.
  • the organic solvent is one or more compounds selected from the group consisting of ketones, ethers, esters, aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons.
  • a one-component thermosetting composition comprising the blocking agent dissociation catalyst according to any one of [1] to [9], a blocked isocyanate, and a compound having an isocyanate-reactive group.
  • the use amount of the blocking agent dissociation catalyst according to [10] or [11] is in the range of 0.1 to 15% by weight as the use amount of the metal binuclear complex with respect to the blocked isocyanate.
  • a method for dissociating a blocking agent comprising heating the blocked isocyanate in the presence of the blocking agent dissociation catalyst according to any one of [1] to [9].
  • the blocking agent dissociation catalyst comprising the metal binuclear complex of the present invention exhibits a blocking agent dissociation catalytic activity that exceeds that of known catalysts such as organotin, it is extremely useful industrially.
  • the one-component thermosetting composition of the present invention uses a blocking agent dissociation catalyst that has a high dissociation effect at low temperatures, which is advantageous in terms of energy and can be applied to a substrate having low heat resistance. It is.
  • the blocking agent dissociation catalyst contains a metal binuclear complex containing two or more metals.
  • the “metal binuclear complex” refers to a complex containing two or more metals in one molecule.
  • the method for preparing the metal binuclear complex is not particularly limited. For example, it can be prepared by the methods described in Non-Patent Document 2 to Non-Patent Document 4 described above. Specifically, it can be prepared by adding a metal alkoxide and a metal chelate compound other than the metal alkoxide, in some cases, further adding an organic compound serving as a ligand and reacting them in a solvent.
  • Suitable examples of the metal in the metal alkoxide used here include aluminum, zinc, cobalt, nickel, manganese, copper, and the like.
  • preferable examples of the alkoxy group in the metal alkoxide include an isopropoxy group, an n-propoxy group, an ethoxy group, and a methoxy group.
  • specific examples of the metal alkoxide include aluminum trisisopropoxide, aluminum tris n-propoxide, aluminum trisethoxide, and aluminum trismethoxide.
  • Examples of the metal in the metal chelate compound used here include aluminum, zinc, cobalt, nickel, manganese, and copper.
  • Examples of the chelate ligand in the metal chelate compound include acetylacetone, 3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5.
  • ⁇ -diketones such as hexafluoro-2,4-pentanedione; ⁇ -ketoesters such as methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate; dimethyl malonate, diethyl malonate, etc.
  • Malonic acid diesters such as acetoacetanilide
  • ⁇ -ketoamides such as acetoacetanilide
  • carboxylic acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, and 2-ethylhexanoic acid.
  • the metal chelate compound examples include zinc bisacetylacetonate, zinc bis3,5-heptanedionate, zinc bis1,1,1-trifluoro- 2,4-pentanedionate, zinc bis-1,1,1,5,5,5-hexafluoro-2,4-pentanedionate, methyl zinc bisacetoacetate, ethyl zinc bisacetoacetate, n-propyl zinc bisacetoacetate, Isopropyl zinc bisacetoacetate, dimethyl zinc bismalonate, diethyl zinc bismalonate, zinc bisacetoacetanilide, zinc bisacetic acid, zinc bispropionic acid, zinc bisbutanoic acid, zinc bispentanoic acid, zinc bishexanoic acid, zinc bisheptanoic acid, zinc bisoctanoic acid, zinc Examples include bis-2-ethylhexanoic acid
  • Examples of the organic compound used as a ligand used here include acetylacetone, 3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5. , 5,5-hexafluoro-2,4-pentanedione and other ⁇ -diketones; acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, 2-ethylhexanoic acid and other carboxylic acids Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol; ⁇ -ketoesters such as methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate and isopropyl acetoacetate Mal
  • solvent used here examples include toluene, benzene, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, methyl ethyl ketone, propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dimethyl ether and the like.
  • solvent used here examples include toluene, benzene, methyl acetate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, methyl ethyl ketone, propylene glycol monomethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol dimethyl ether and the like.
  • insoluble matters may be generated due to the mixing of moisture. In such a case, operations such as centrifugation, filtration, and decantation may be
  • the metal contained in the metal binuclear complex is not particularly limited, but aluminum, zinc, cobalt, nickel, manganese, copper and the like are preferable examples. In these, since aluminum has high low-temperature dissociation activity of a blocking agent, it is preferable that a metal binuclear complex contains aluminum.
  • the metal binuclear complex more preferably contains aluminum and zinc.
  • the metal binuclear complex preferably contains a ⁇ -diketone and an alkoxy group as ligands.
  • ⁇ -diketones include acetylacetone, 2,4-hexanedione, 3,5-heptanedione, 2,4-octanedione, 2,4-decanedione, 2,4-tridecanedione, 1,1,1 -Trifluoro-2,4-pentanedione, 1,1,1,5,5,5-hexafluoro-2,4-pentanedione, 5-methyl-2,4-hexanedione, 5,5-dimethyl- 2,4-hexanedione, 2,2-dimethyl-3,5-nonanedione, 2,2,6,6-tetramethyl-3,5-heptanedione, 1,3-cyclopentanedione, 1,3-cyclohexane Dione, 1-cyclohexyl-1,3-butanedione, 1-phenyl-1,3-butanedione (1-benzoylacetone), 1-phenyl
  • acetylacetone 3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5 are usually used.
  • 5-hexafluoro-2,4-pentanedione, and acetylacetone is particularly preferably used.
  • Preferred examples of the alkoxy group include isopropoxy group, n-propoxy group, ethoxy group, methoxy group, n-butoxy group, n-pentoxy group, n-hexyloxy group, 1-methoxy-2-propoxy group and the like. As mentioned.
  • a part of the alkoxy group may be substituted with a carboxyl group.
  • the carboxyl group is not particularly limited.
  • Carboxyl group of saturated fatty acids such as nonanoic acid group, decanoic acid group, dodecanoic acid group, tetradecanoic acid group, hexadecanoic acid group, heptadecanoic acid group, octadecanoic acid group; oleic acid group, linoleic acid group, linolenic acid group, arachidone
  • Carboxyl groups of unsaturated fatty acids such as acid groups, methacrylic acid groups and acrylic acids
  • carboxyl groups of aromatic fatty acids such
  • the metal binuclear complex of the present invention is characterized by high solubility in organic solvents. Mixing with blocked isocyanate is facilitated by dissolving in an organic solvent. However, mixing with powder is also possible.
  • the content of the metal binuclear complex with respect to the entire blocking agent dissociation catalyst containing the organic solvent is not particularly limited, but is preferably 5 to 70% by weight, and more preferably 10 to 50% by weight. Therefore, the solubility of the metal binuclear complex in the organic solvent is preferably 5 to 230 [g / 100 g-solvent], more preferably 10 to 100 [g / 100 g-solvent].
  • organic solvent examples include ketones, ethers, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, and the like.
  • glycol monoalkyl ether acetates such as propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, ethylene glycol monomethyl ether acetate;
  • propylene Glycol diacetates such as glycol diacetate, 1,3-butylene glycol diacetate, and 1,6-hexanediol diacetate;
  • Glycol dialkyl ethers such as dipropylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dimethyl ether; Mono n-butyl ether, dipropylene glycol monomethyl ether, tripropy
  • the solubility of the metal alkoxide of the metal binuclear complex and the metal chelate compound other than the metal alkoxide in an organic solvent is generally less than 1 [g / 100 g-solvent].
  • the metal binuclear complex is not a single metal compound, but they are combined to form a metal binuclear complex, so that high solubility is obtained.
  • C 5 H 7 O 2 , C 3 H 7 O, CH 3 COO, C 2 H 5 O, and CH 3 OC 3 H 6 O are acetylacetone, isopropoxy, acetic acid, ethoxy, 1- Represents a methoxy-2-propoxy group.
  • the blocking agent dissociation catalyst of the present invention can sufficiently achieve the object of the present invention by containing only the above-described metal binuclear complex.
  • Other metal compounds may be included. Specific examples of such metal compounds include aluminum trisacetylacetonate, aluminum bisacetylacetonate isopropoxide, aluminum bisacetylacetonate n-propoxide, aluminum bisacetylacetonate methoxide, aluminum bisacetylacetate.
  • the one-component thermosetting composition of the present invention contains the above-described blocking agent dissociation catalyst of the present invention, a blocked isocyanate, and a compound having an isocyanate-reactive group.
  • examples of the block isocyanate include non-aqueous blocked isocyanate and aqueous blocked isocyanate.
  • non-aqueous blocked isocyanate examples include known blocking agents (eg, alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, tert-butanol; phenol, cresol, nitrophenol, chloro Phenols such as phenol and resorcinol; thiols such as benzenethiol; caprolactams such as ⁇ -caprolactam; carbamates such as ethyl carbamate; ketoenols such as acetylacetone; ketoximes such as methyl ethyl ketone oxime; diisopropylamine, triazole, 3, Amines such as 5-dimethylpyrazole; sodium bisulfite, etc.), and known isocyanate compounds or compounds obtained by blocking their prepolymers.
  • blocking agents eg, alcohols such as methanol, ethanol, n-propanol
  • Rukoto can.
  • isocyanate compound aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate etc. are mentioned, for example.
  • aliphatic polyisocyanate examples include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, And dimer acid diisocyanate.
  • alicyclic polyisocyanates examples include 1,3-bis (isocyanatomethyl) cyclohexane, 1,4-bis (isocyanatomethyl) cyclohexane, 3-isocyanatomethyl-3,3,5-trimethylcyclohexane (IPDI). , Isophorone diisocyanate), bis- (4-isocyanatocyclohexyl) methane (hydrogenated MDI), norbornane diisocyanate, and the like.
  • aromatic polyisocyanate examples include 2,4′-diphenylmethane diisocyanate, 4,4′-diphenylmethane diisocyanate, crude MDI, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, and 2,6-tolylene diisocyanate. 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate and the like.
  • Examples of the araliphatic polyisocyanate include 1,3-xylylene diisocyanate, 1,4-xylylene diisocyanate, ⁇ , ⁇ , ⁇ ′, ⁇ ′-tetramethylxylylene diisocyanate, and the like.
  • isocyanate compounds other than the above for example, isocyanate group-terminated compounds by reaction of isocyanate compounds with active hydrogen group-containing compounds, reaction products of these compounds (for example, adduct-type polyisocyanates, allophanatization reactions, carbodiimidization reactions, Uretodione reaction, isocyanurate reaction, ureton iminate reaction, isocyanate-modified product by biuret reaction, etc.), or a mixture thereof.
  • reaction products of these compounds for example, adduct-type polyisocyanates, allophanatization reactions, carbodiimidization reactions, Uretodione reaction, isocyanurate reaction, ureton iminate reaction, isocyanate-modified product by biuret reaction, etc.
  • the aqueous blocked isocyanate can be obtained, for example, by reacting a polyisocyanate with a hydrophilic group having at least one active hydrogen group capable of reacting with an isocyanate group and blocking it with a known blocking agent.
  • a hydrophilic group include ionic groups such as cations and anions, and nonionic groups.
  • nonionic compound for introducing a nonionic group into the polyisocyanate include polyalkylene ether alcohols and polyoxyalkylene fatty acid esters.
  • examples of the compound having an isocyanate-reactive group include a polyol.
  • the polyol refers to a compound containing two or more hydroxyl groups having reactivity with an isocyanate group, and specific examples include non-aqueous polyols and aqueous polyols.
  • examples of the non-aqueous polyol include acrylic polyol, polyester polyol, polyether polyol, and epoxy polyol.
  • examples of the acrylic polyol include a copolymer of a polymerizable monomer having one or more active hydrogens in one molecule and a monomer copolymerizable therewith.
  • polymerizable monomers having one or more active hydrogens in one molecule examples include acrylic acid hydroxy esters such as 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, and 2-hydroxybutyl acrylate.
  • Methacrylic acid hydroxyesters such as methacrylic acid-2-hydroxyethyl, methacrylic acid-2-hydroxypropyl, methacrylic acid-2-hydroxybutyl, etc .; acrylic acid monoester or methacrylic acid monoester of glycerin, acrylic acid of trimethylolpropane Monoester or methacrylic acid monoester, or a monomer obtained by ring-opening polymerization of ⁇ -caprolactone with these active hydrogens.
  • Examples of the monomer copolymerizable with the polymerizable monomer include acrylates such as methyl acrylate, ethyl acrylate, isopropyl acrylate, n-butyl acrylate, and 2-ethylhexyl acrylate; methyl methacrylate , Methacrylates such as ethyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-hexyl methacrylate, cyclohexyl methacrylate, lauryl methacrylate, glycidyl methacrylate; acrylic acid, methacrylic acid Unsaturated carboxylic acids such as maleic acid and itaconic acid; unsaturated amides such as acrylamide, N-methylolacrylamide and diacetoneacrylamide; styrene, vinyltoluene, vinyl acetate, acrylonitrile and the like It is
  • polyester polyol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,6- Dioxanes such as hexanediol, neopentyl glycol, butylethylpropane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, and succinic acid, adipic acid, azelaic acid, sebacic acid, Dodecanedicarboxylic acid, maleic anhydride, fumaric acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, naphthalenedicar Reaction products
  • Adipate type condensed polyester diol such as adipate diol
  • Azelate type condensed polyester diol such as polyethylene azelate diol and polybutylene azelate diol.
  • polycarbonate polyol examples include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,6-hexane.
  • examples include diols, neopentyl glycol, butyl ethyl propane diol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol and other diols and dimethyl carbonate and other dialkyl carbonates. It is done.
  • Specific examples include polytetramethylene carbonate diol, poly 3-methylpentamethylene carbonate diol, polyhexamethylene carbonate diol and the like.
  • polylactone polyol examples include ring-opening polymers of ⁇ -caprolactone, ⁇ -butyrolactone, ⁇ -valerolactone, and mixtures of two or more thereof. Specific examples include polycaprolactone diol.
  • polyether polyol examples include ethylene glycol, propylene glycol, 1,3-butylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, catechol, hydroquinone, bisphenol A, and the like.
  • examples include a reaction product obtained by addition polymerization of monomers such as ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin, tetrahydrofuran, and cyclohexylene, using a compound containing two or more hydrogen atoms as an initiator.
  • reaction product obtained by addition polymerization of two or more monomers block addition, random addition, or a mixed system of both may be used.
  • Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene ether glycol and the like.
  • Examples of the epoxy polyol include novolak type, ⁇ -methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycol ether type, epoxy type of aliphatic unsaturated compound, epoxidized fatty acid ester type, polyvalent carboxylic acid ester type, amino acid Examples include glycidyl type, halogenated type, and resorcin type epoxy polyols.
  • non-aqueous polyols other than those described above, for example, OH-terminated prepolymers produced by reacting these polyols with isocyanate compounds can be used as well.
  • examples of the aqueous polyol include compounds obtained by emulsifying, dispersing, or dissolving the above-described non-aqueous polyol in water.
  • examples of the method of emulsifying, dispersing or dissolving in water include a method of neutralizing by introducing a carboxyl group, a sulfone group or the like.
  • neutralizers include ammonia and water-soluble amino compounds such as monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, triethanolamine, and butylamine.
  • tertiary amines such as triethylamine and dimethylethanolamine are preferably used.
  • the hydroxyl value of the polyol is not particularly limited, but is preferably in the range of 10 to 300 mgKOH / g, more preferably 20 to 250 mgKOH / g per solid content. It is a range.
  • the hydroxyl value is 10 mgKOH / g or more, the strength of the obtained resin is improved, and by setting it to 300 mgKOH / g or less, the plasticity of the obtained resin is improved.
  • the polyol component contains a polyol (a compound containing two or more hydroxyl groups having reactivity with an isocyanate group), a neutralizing agent, an antioxidant, and water.
  • a polyol a compound containing two or more hydroxyl groups having reactivity with an isocyanate group
  • a neutralizing agent a compound containing two or more hydroxyl groups having reactivity with an isocyanate group
  • an antioxidant an antioxidant
  • water water
  • solid content means a polyol, a neutralizing agent, and an antioxidant among these.
  • the hydroxyl value of polyol can be measured by the method defined in JIS-K0070. That is, it can be measured by adding and dissolving acetic anhydride and pyridine to a sample, allowing to cool, and then performing neutralization titration on a titration sample solution prepared by adding water and toluene with an ethanol solution of potassium hydroxide.
  • the hydroxyl value is represented by the number of mg of potassium hydroxide required to neutralize acetic acid consumed to acetylate the hydroxyl group contained in a 1 g sample.
  • the equivalent ratio ([hydroxyl group] / [isocyanate group]) of the hydroxyl group and isocyanate group of the polyol in the one-component thermosetting composition of the present invention is determined by the required coating film properties and is not particularly limited. Is usually in the range of 0.2-2.
  • the amount of the blocking agent dissociation catalyst of the present invention used in the one-component thermosetting composition of the present invention is the amount of metal binuclear complex used relative to the amount of blocked isocyanate used ([the amount of metal binuclear complex used] / [block The amount of isocyanate used]) is usually in the range of 0.1 to 15% by weight, preferably 0.5 to 10% by weight, more preferably 1 to 5% by weight. Sufficient low-temperature curability can be obtained by setting the amount of the metal binuclear complex used to 0.1% by weight or more based on the amount of the blocked isocyanate. On the other hand, even if the amount of the metal binuclear complex exceeds 15% by weight relative to the amount of the blocked isocyanate, no further improvement in low-temperature curability is observed, which is economically disadvantageous.
  • the amount of the blocking agent dissociation catalyst of the present invention used in the one-component thermosetting composition of the present invention is the amount of the metal binuclear complex used relative to the solid content ([the amount of metal binuclear complex used] / [solid content] ]) Is usually in the range of 0.05 to 10% by weight, preferably 0.25 to 5% by weight, more preferably 0.5 to 3% by weight.
  • solid content represents a component other than the solvent in the one-component thermosetting composition.
  • methyl ethyl ketone in the non-aqueous polyol Represents the sum of components other than solvents such as acetone and components other than solvents such as methyl ethyl ketone in non-aqueous blocked isocyanate.
  • methyl ethyl ketone and acetone in an OH-terminated prepolymer solution The total of components other than solvents, such as IRGANOX1010 and triethylamine, and components other than solvents, such as water in aqueous
  • thermosetting composition of the present invention additives, pigments, solvents and the like commonly used in the technical field can be used as necessary.
  • ultraviolet absorbers such as a hindered amine type, a benzotriazole type, and a benzophenone type
  • Antioxidants such as a hindered phenol type, a phosphorus type, a sulfur type, a hydrazide type
  • Tin Urethanization catalysts such as those based on zinc, zinc and amine
  • leveling agents such as those based on zinc, zinc and amine
  • rheology control agents pigment dispersants and the like.
  • the pigment examples include, but are not limited to, organic pigments such as quinacridone, azo, and phthalocyanine; inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and silica; And pigments such as pigments and rust preventive pigments.
  • organic pigments such as quinacridone, azo, and phthalocyanine
  • inorganic pigments such as titanium oxide, barium sulfate, calcium carbonate, and silica
  • pigments such as pigments and rust preventive pigments.
  • the solvent examples include, but are not limited to, hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha; ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ethyl acetate, acetic acid-n -Esters such as butyl and cellosolve acetate, and these solvents may be used alone or in combination of two or more.
  • hydrocarbons such as benzene, toluene, xylene, cyclohexane, mineral spirit, and naphtha
  • ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone
  • ethyl acetate, acetic acid-n -Esters such as butyl and cellosolve acetate
  • the one-part thermosetting composition of the present invention is divided into a block socyanate and a compound having an isocyanate-reactive group as a two-part thermosetting composition. It is also possible to use it.
  • the one-component thermosetting composition of the present invention is a pre-coated metal such as a metal coating for automobile top and middle coatings, chipping-resistant coatings, electrodeposition coatings, automotive parts coatings, automotive repair coatings, home appliances and office equipment, etc.
  • -It can be used as a rust-proof steel plate, a paint for building materials, a paint for plastics, an adhesive, an adhesion-imparting agent, and a sealing agent.
  • thermosetting composition baking of the one-component thermosetting composition, measurement of solvent resistance, and identification of the metal binuclear complex were carried out as shown below.
  • thermosetting composition ⁇ Baking of one-component thermosetting composition>
  • the one-component thermosetting composition was applied to a polypropylene plate, preliminarily dried in an oven at 50 ° C. for 30 minutes, and then baked in an oven at a predetermined temperature for 30 minutes.
  • a metal binuclear complex was prepared according to the description in Non-Patent Document 2 [Journal of Materials Chemistry Vol. 14, pp. 3150-3157 (2004)]. That is, a reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was made a nitrogen atmosphere. Next, 2.77 g of aluminum trisisopropoxide, 1.86 g of zinc bisacetylacetonate monohydrate, and 50.0 mL of dehydrated toluene were charged into the container, and the mixture was reacted by refluxing at 130 ° C. for 30 minutes.
  • a metal binuclear complex was prepared according to the description in Non-Patent Document 3 [Dalton Transactions 544-550 (2003)]. That is, a reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was made a nitrogen atmosphere. Next, 1.48 g of aluminum trisisopropoxide, 2.01 g of zinc bisacetylacetonate monohydrate, and 30.0 mL of dehydrated toluene were charged into the container, and the reaction was performed by refluxing at 130 ° C. for 30 minutes. Then, the inside of the container was reduced to 50 ° C.
  • Al—Zn binuclear complex 2 (molecular formula: Zn 2 Al 2 (C 5 H 7 O 2 ) 4 (C 3 H 7 O ) 6 , 1 H NMR: 5.47 (s, 4H, C 5 H 7 O 2 ), 4.21 (st, 2H, C 3 H 7 O), 3.92 (st, 4H, C 3 H 7 O), 1.99 to 1.85 (m, 24H, C 5 H 7 O 2 ), 1.30 to 1.04 (m, 36H, C 3 H 7 O)).
  • Production Example 3 (Preparation of metal binuclear complex) A metal binuclear complex was prepared in the same manner as in Production Example 2 except that the solvent was changed from toluene to ethyl acetate. That is, a reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was made a nitrogen atmosphere. Next, 1.48 g of aluminum trisisopropoxide, 2.01 g of zinc bisacetylacetonate monohydrate, and 30.0 mL of dehydrated ethyl acetate were charged into the container, and the reaction was performed by refluxing at 100 ° C. for 120 minutes. . Then, the inside of the container was reduced to 50 ° C.
  • Al—Zn binuclear complex 3 (molecular formula: Zn 2 Al 2 (C 5 H 7 O 2 ) 4 (C 2 H 5 O ) 5 (C 3 H 7 O), 1 H NMR: 5.38 (s, 4H, C 5 H 7 O 2 ), 4.02 (st, 1H, C 3 H 7 O), 3.80-3 .22 (m, 10H, C 2 H 5 O), 1.99 to 1.82 (m, 24H, C 5 H 7 O 2 ), 1.28 to 0.90 (m, 15H, C 2 H 5 O, m, 6H, C 3 H 7 O)).
  • Production Example 4 (Preparation of metal binuclear complex) A metal binuclear complex was prepared in the same manner as in Production Example 3 except that the Al / Zn molar ratio of the raw material was changed from 1.0 to 0.8. That is, a reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was made a nitrogen atmosphere. Next, 1.17 g of aluminum trisisopropoxide, 2.01 g of zinc bisacetylacetonate monohydrate, and 30.0 mL of dehydrated ethyl acetate were charged into the container and reacted by refluxing at 100 ° C. for 120 minutes. .
  • Al—Zn binuclear complex 4 (molecular formula: Zn 5 Al 4 (C 5 H 7 O 2 ) 20 (C 2 H 5 O ) 11 (C 3 H 7 O), 1 H NMR: 5.38 (s, 20 H, C 5 H 7 O 2 ), 4.02 (st, 1 H, C 3 H 7 O), 3.80-3 .36 (m, 22H, C 2 H 5 O), 1.99 to 1.80 (m, 120H, C 5 H 7 O 2 ), 1.30 to 0.88 (m, 33H, C 2 H 5 O, m, 6H, C 3 H 7 O)).
  • Production Example 5 (Preparation of metal binuclear complex) A metal binuclear complex was prepared in the same manner as in Production Example 3 except that the Al / Zn molar ratio of the raw material was changed from 1.0 to 1.5. That is, a reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was made a nitrogen atmosphere. Next, 2.19 g of aluminum trisisopropoxide, 2.01 g of zinc bisacetylacetonate monohydrate, and 30.0 mL of dehydrated ethyl acetate were charged into the container and reacted by refluxing at 100 ° C. for 120 minutes. . Then, the inside of the container was reduced to 50 ° C.
  • Production Example 6 (Preparation of metal binuclear complex) A metal binuclear complex was prepared in the same manner as in Production Example 3 except that the Al / Zn molar ratio of the raw material was changed from 1.0 to 2.0. That is, a reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was made a nitrogen atmosphere. Next, 2.92 g of aluminum trisisopropoxide, 2.01 g of zinc bisacetylacetonate monohydrate, and 30.0 mL of dehydrated ethyl acetate were charged into the container, and the mixture was reacted by refluxing at 100 ° C. for 120 minutes. .
  • Production Example 7 (Preparation of metal binuclear complex) A metal binuclear complex was prepared in the same manner as in Production Example 3 except that the Al / Zn molar ratio of the raw material was changed from 1.0 to 3.0. That is, a reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was made a nitrogen atmosphere. Next, 4.37 g of aluminum trisisopropoxide, 2.01 g of zinc bisacetylacetonate monohydrate, and 30.0 mL of dehydrated ethyl acetate were charged into the container, and reacted by refluxing at 100 ° C. for 120 minutes. .
  • Al—Zn binuclear complex 7 (molecular formula: Zn 2 Al 6 (C 5 H 7 O 2 ) 4 (C 2 H 5 O ) 16 (C 3 H 7 O) 2 , 1 H NMR: 5.36 (s, 4H, C 5 H 7 O 2 ), 4.02 (st, 2H, C 3 H 7 O), 4.00- 3.30 (m, 32H, C 2 H 5 O), 1.99 to 1.75 (m, 24H, C 5 H 7 O 2 ), 1.35 to 0.80 (m, 48H, C 2 H 5 O, m, 12H, C 3 H 7 O)).
  • Production Example 8 (Preparation of metal binuclear complex) A metal binuclear complex was prepared in the same manner as in Production Example 3 except that the Al / Zn molar ratio of the raw material was changed from 1.0 to 3.5. That is, a reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was made a nitrogen atmosphere. Next, 5.10 g of aluminum trisisopropoxide, 2.01 g of zinc bisacetylacetonate monohydrate, and 30.0 mL of dehydrated ethyl acetate were charged into the container, and reacted by refluxing at 100 ° C. for 120 minutes. .
  • Al—Zn binuclear complex 8 (molecular formula: Zn 2 Al 7 (C 5 H 7 O 2 ) 4 (C 2 H 5 O ) 19 (C 3 H 7 O) 2 , 1 H NMR: 5.35 (s, 4H, C 5 H 7 O 2 ), 4.02 (st, 2H, C 3 H 7 O), 4.00- 3.28 (m, 38H, C 2 H 5 O), 1.99 to 1.75 (m, 24H, C 5 H 7 O 2 ), 1.35 to 0.78 (m, 57H, C 2 H 5 O, m, 12H, C 3 H 7 O)).
  • a metal binuclear complex was prepared according to the description in Non-Patent Document 3 [Dalton Transactions 544-550 (2003)]. That is, a reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was made a nitrogen atmosphere. Next, 2.38 g of aluminum trisisopropoxide, 1.47 g of cobalt bisacetylacetonate, and 25.0 mL of dehydrated toluene were charged into the container and reacted at 130 ° C. for 10 minutes under reflux. Then, it cooled at 4 degreeC in the refrigerator for 2 hours.
  • Production Example 10 (Preparation of zinc bisheptanedionate monohydrate)
  • 0.622 g of sodium hydroxide, 7.50 mL of water, and 2.00 g of 3,5-heptanedione were added and stirred until a uniform yellow transparent solution was obtained.
  • 2.27 g of zinc sulfate heptahydrate was dissolved in 7.50 mL of water, and the yellow transparent solution was added dropwise thereto. Thereafter, this was stirred at room temperature for 1 hour, and the resulting pale yellow precipitate was filtered and washed with 300 mL of water. The mixture was dried at 50 ° C. for 2 hours to obtain 1.74 g of zinc bisheptanedionate monohydrate as a pale yellow powder.
  • a metal binuclear complex was prepared in the same manner as in Production Example 1 except that acetylacetone was changed to 3,5-heptanedione. That is, a reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was made a nitrogen atmosphere. Next, 1.17 g of aluminum trisisopropoxide, 0.917 g of zinc bisheptanedionate monohydrate, and 25.0 mL of dehydrated toluene were charged into the container, and the mixture was reacted by refluxing at 130 ° C. for 30 minutes.
  • the molecular formula of the Al—Zn binuclear complex 10 is Zn 2 Al 3 (C 5 H 7 O 2 ) 4 (CH 3 OC 3 H 6 O) 7 (1H NMR: 5.38 (s, 4H, C 5 H 7 O 2 ), 4.06 (m, 7H, CH 3 OC 3 H 6 O), 3.50 to 3.20 (m, 35H, CH 3 OC 3 H 6 O), 2.00 to 1.80 (m , 24H, C 5 H 7 O 2 ), 1.24 to 1.05 (m, 21H, CH 3 OC 3 H 6 O)).
  • Example 1 (Measurement of solubility of dinuclear complex in solvent) The solubility of the Al—Zn binuclear complex 1 obtained in Production Example 1 in propylene glycol monomethyl ether acetate or methyl ethyl ketone was measured. The results are shown in Table 1.
  • Example 2 to Example 11 In the same manner as in Example 1, the solubility of the metal binuclear complexes obtained in Production Examples 2 to 11 in propylene glycol monomethyl ether acetate or methyl ethyl ketone was measured. The results are shown in Table 1 and Table 2.
  • the metal compound of the metal binuclear complex was hardly dissolved in the solvent, and the metal binuclear complex of the present invention obtained a high degree of solvent by forming the metal binuclear complex. Is understood.
  • Production Example 13 (Preparation of non-aqueous blocked isocyanate) A stirring blade was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the vessel was made into a nitrogen atmosphere. Then, Coronate HX (manufactured by Nippon Polyurethane Co., Ltd., hexamethylene diisocyanate trimer, NCO 21.3 wt% ) 50.2 g and dehydrated methyl ethyl ketone 114 g were charged and stirred at 40 ° C. for 5 minutes.
  • Coronate HX manufactured by Nippon Polyurethane Co., Ltd., hexamethylene diisocyanate trimer, NCO 21.3 wt%
  • a dropping funnel was attached to the container, and 22.2 g of methyl ethyl ketone oxime was dropped into the container over 1 hour while maintaining the temperature at 40 ° C. Thereafter, a reflux condenser was attached to the container and reacted at 70 ° C. for 1 hour.
  • the reactor was cooled to room temperature, and the reaction was stopped to obtain a non-aqueous blocked isocyanate.
  • the obtained non-aqueous blocked isocyanate had a solid concentration of 40% by weight and an effective NCO of 1.36 mmol / g.
  • the effective NCO means the amount of isocyanate groups (NCO) that can be reacted by heating the blocked isocyanate to dissociate the blocking agent. That is, an effective NCO of 1.36 mmol / g means that 1.36 mmol of isocyanate groups are potentially contained in 1 g of blocked isocyanate (regenerated by dissociation of the blocking agent).
  • Production Example 14 (Preparation of aqueous blocked isocyanate) A stirring blade and a reflux condenser were attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the vessel was made a nitrogen atmosphere. Next, 49.0 g of Coronate HX (manufactured by Nippon Polyurethane, hexamethylene diisocyanate trimer, NCO 21.3% by weight) and 13.7 g of polyethylene glycol monomethyl ether (manufactured by Aldrich, average molecular weight 550) were charged in the container. And reacted at 80 ° C. for 9 hours.
  • Coronate HX manufactured by Nippon Polyurethane, hexamethylene diisocyanate trimer, NCO 21.3% by weight
  • polyethylene glycol monomethyl ether manufactured by Aldrich, average molecular weight 550
  • methyl ethyl ketone oxime and 20.0 g of methyl ethyl ketone were added to the container and reacted at 80 ° C. for 3 hours.
  • the reaction mixture was cooled to room temperature to stop the reaction.
  • 150 g of water was gradually added with stirring, and the aqueous blocked isocyanate was emulsified and dispersed in water. Residual methyl ethyl ketone was removed from the obtained emulsified dispersion with an evaporator.
  • the obtained aqueous blocked isocyanate was a stable dispersion having a solid content of 39% by weight and an effective NCO of 1.19 mmol / g.
  • Example 12 Evaluation of catalytic activity of metal binuclear complex in non-aqueous one-component thermosetting composition
  • the non-aqueous blocked isocyanate obtained in Production Example 13 and methyl ethyl ketone with the composition shown in Table 5
  • the Al—Zn binuclear complex 1 obtained in Production Example 1 was mixed.
  • a 5 wt% acetone solution of was added with stirring to obtain a non-aqueous one-component thermosetting composition containing a metal binuclear complex.
  • the solvent resistance was measured. The results are shown in Table 5.
  • Example 13 to Example 20 With the compositions shown in Table 5 and Table 6, a non-aqueous one-component thermosetting composition containing a metal binuclear complex was obtained in the same manner as in Example 12. After the obtained non-aqueous one-component thermosetting composition was baked at 110 ° C., 120 ° C., and 130 ° C., the solvent resistance was measured. The results are shown in Table 5 and Table 6.
  • Comparative Example 7 (Curability evaluation without addition of catalyst in non-aqueous one-component thermosetting composition) A non-aqueous one-component thermosetting composition containing the composition shown in Table 7 and containing the non-aqueous polyol obtained in Production Example 12, the non-aqueous blocked isocyanate obtained in Production Example 13 and methyl ethyl ketone, and containing no catalyst. Got. After the obtained non-aqueous one-component thermosetting composition was baked at 110 ° C., 120 ° C., and 130 ° C., the solvent resistance was measured. The results are shown in Table 7.
  • the gel fraction at 130 ° C. in Comparative Example 7 and the gel fraction at 110 ° C. in Examples 12, 13, and 19 are comparable, and Al—Zn binuclear complexes 1, 2
  • the dissociation temperature of the blocking agent was reduced by about 20 ° C. by addition of 8 and 8.
  • the gel fraction at 120 ° C. of Examples 14 and 15 greatly exceeded the gel fraction at 130 ° C. of Comparative Example 7, and the dissociation temperature of the blocking agent by the addition of Al—Zn binuclear complexes 3 and 4
  • the gel fraction at 110 ° C. of Examples 16 to 18 and 20 is significantly higher than the gel fraction at 130 ° C. of Comparative Example 7, and the addition of Al—Zn binuclear complexes 5 to 8 and 10 dissociates the blocking agent. It can be seen that the temperature has dropped by 20 ° C. or more.
  • Comparative Example 8 Evaluation of curability of known catalysts in non-aqueous one-component thermosetting compositions
  • Table 7 After mixing the non-aqueous polyol obtained in Production Example 12, the non-aqueous blocked isocyanate obtained in Production Example 13 and methyl ethyl ketone, stirring a 5 wt% acetone solution of dibutyltin dilaurate
  • the obtained non-aqueous one-component thermosetting composition was baked at 110 ° C., 120 ° C., and 130 ° C., the solvent resistance was measured.
  • Example 21 (Curability evaluation of a system containing a metal compound in addition to the metal binuclear complex in a non-aqueous one-component thermosetting composition)
  • the non-aqueous polyol obtained in Production Example 12 the non-aqueous blocked isocyanate obtained in Production Example 13 and methyl ethyl ketone with the composition shown in Table 6, the Al—Zn binuclear complex 2 obtained in Production Example 2 was mixed. 5 wt% acetone solution and aluminum trisacetylacetonate 5 wt% acetone solution were added with stirring to obtain a non-aqueous one-component thermosetting composition containing a metal compound in addition to the metal binuclear complex. After the obtained non-aqueous one-component thermosetting composition was baked at 110 ° C., 120 ° C., and 130 ° C., the solvent resistance was measured. The composition and results are also shown in Table 6.
  • Example 22 to Example 25 (Preparation of aqueous bicomponent thermosetting composition containing metal binuclear complex)
  • aqueous bicomponent thermosetting composition containing metal binuclear complex prepared by a four-necked flask equipped with a nitrogen blowing tube.
  • 500 g of polytetramethylene glycol (PTG-2000SN, manufactured by Hodogaya Chemical Co., Ltd., number average molecular weight 1993) was charged and dried under reduced pressure at 130 ° C. for 1 hour. After the temperature in the reactor was lowered to make the inside of the reactor a nitrogen atmosphere, a stirring blade and a reflux condenser were attached to the reactor.
  • PTG-2000SN polytetramethylene glycol
  • IRGANOX 1010 hindered phenol antioxidant, manufactured by Ciba Japan
  • triethylamine triethylamine
  • catalyst solution was added to the obtained OH-terminated prepolymer solution while stirring, and then stirred.
  • the mixture was emulsified and dispersed in water by gradually adding water.
  • Methyl ethyl ketone and acetone remaining in the evaporator were removed from the obtained emulsified dispersion.
  • the resulting aqueous polyol was a stable dispersion having a solid content concentration of 30% by weight and a hydroxyl value of 35.0 mgKOH / g based on the solid content.
  • the aqueous blocked isocyanate obtained in Production Example 14 was added and mixed to obtain an aqueous one-component thermosetting composition containing a metal binuclear complex.
  • the obtained aqueous one-component thermosetting composition was a stable dispersion having a solid concentration of 31% by weight.
  • thermosetting composition (Evaluation of catalytic activity of metal binuclear complex in aqueous one-component thermosetting composition)
  • the aqueous one-component thermosetting composition obtained above was baked at 120 ° C. and 130 ° C., and then the solvent resistance was measured.
  • the composition and results are also shown in Table 8.
  • Comparative Example 9 (Curability evaluation without addition of catalyst in aqueous one-component thermosetting composition) With the composition shown in Table 8, an aqueous one-component thermosetting composition containing no catalyst was obtained in the same manner as in Example 22. The obtained aqueous one-component thermosetting composition was a stable dispersion having a solid concentration of 31% by weight. After the obtained aqueous one-component thermosetting composition was baked at 120 ° C. and 130 ° C., the solvent resistance was measured. The composition and results are also shown in Table 8. As is apparent from Table 8, the gel fraction was higher in Examples 22 to 25 at each temperature than in Comparative Example 9. This shows that the dissociation temperature of the blocking agent was lowered by the addition of the metal binuclear complex.
  • Comparative Example 10 to Comparative Example 12. Evaluation of catalytic activity of known catalysts in aqueous one-component thermosetting compositions
  • an aqueous one-component thermosetting composition containing a known catalyst was obtained in the same manner as in Example 22.
  • the obtained aqueous one-component thermosetting composition was a stable dispersion having a solid concentration of 31% by weight.
  • After the obtained aqueous one-component thermosetting composition was baked at 120 ° C. and 130 ° C., the solvent resistance was measured.
  • the composition and results are shown in Table 9.
  • Comparative Examples 13 to 14 Evaluation of catalytic activity of metal compounds constituting binuclear complexes in aqueous one-component thermosetting compositions
  • the obtained aqueous one-component thermosetting composition was a stable dispersion having a solid concentration of 31% by weight.
  • Table 9 shows the results of measurement of solvent resistance after baking the obtained aqueous one-component thermosetting composition at 120 ° C and 130 ° C.
  • the metal binuclear complex of the present invention has a higher blocking agent low-temperature dissociation activity than the compound of the constituent metal, and a high activity was obtained by using a binuclear complex.
  • the blocking agent dissociation catalyst comprising the metal binuclear complex of the present invention exhibits a blocking agent dissociation catalytic activity that exceeds that of known dissociation catalysts, it is extremely useful in industry, and is a one-part heat containing the blocking agent dissociation catalyst of the present invention
  • the curable composition has a high dissociation effect at a low temperature, is advantageous in terms of energy, and is highly applicable to a substrate having low heat resistance.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Paints Or Removers (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne un catalyseur pour la dissociation d'un agent de blocage avec lequel il est possible de dissocier un agent de blocage de polyisocyanate à basse température. Le catalyseur pour la dissociation de l'agent de blocage contient un complexe métallique polynucléaire comportant au moins deux métaux. Une composition thermodurcissable de type à un seul liquide est obtenue d'un composé contenant des groupes isocyanate bloqués et des groupes pouvant réagir avec les isocyanates en utilisant le catalyseur pour la dissociation de l'agent de blocage.
PCT/JP2011/051803 2010-01-29 2011-01-28 Catalyseur pour dissociation d'agent de blocage comportant un complexe métallique polynucléaire et son procédé d'utilisation WO2011093466A1 (fr)

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Cited By (2)

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JP2011173116A (ja) * 2010-01-29 2011-09-08 Tosoh Corp 金属複核錯体からなるブロック剤解離触媒及びその用途
JP7557339B2 (ja) 2020-10-28 2024-09-27 旭化成株式会社 ブロックポリイソシアネート組成物、一液型コーティング組成物、塗膜及び塗装物品

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011173116A (ja) * 2010-01-29 2011-09-08 Tosoh Corp 金属複核錯体からなるブロック剤解離触媒及びその用途
JP7557339B2 (ja) 2020-10-28 2024-09-27 旭化成株式会社 ブロックポリイソシアネート組成物、一液型コーティング組成物、塗膜及び塗装物品

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