JP5724409B2 - Blocking agent dissociation catalyst comprising metal binuclear complex and its use - Google Patents

Description

  The present invention comprises a catalyst for dissociating a polyisocyanate blocking agent comprising a metal binuclear complex (hereinafter sometimes referred to as “blocking agent dissociation catalyst”), and a one-component thermosetting composition using the same. Related to things.

  Polyurethane resin coatings have very good wear resistance, chemical resistance and stain resistance. A general polyurethane resin coating 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. However, since 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. Further, since the polyisocyanate and water easily react, it is impossible to use in a water-based paint such as an electrodeposition paint. As described above, the conventional two-pack type polyurethane resin paint has many limitations in its use.

  In order to improve the above-mentioned problems, a method is known that uses a blocked isocyanate that is inactivated by reacting a polyisocyanate with an active hydrogen group-containing compound (blocking agent). 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. For this reason, the pot life is not limited, and it is possible to preliminarily blend both into a coating material to form a single solution or to apply to a water-based coating material.

  As compounds used as a polyisocyanate blocking agent, for example, ε-caprolactam, methyl ethyl ketone oxime, phenol and the like are known. However, 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. there were.

  For this reason, attempts have been made to lower the baking temperature by using a catalyst (blocking agent dissociation catalyst). As such a catalyst, organic tin such as dibutyltin dilaurate is known (for example, see Non-Patent Document 1), but its use is not preferred because of toxicity problems. In addition, bismuth salts (for example, see Patent Document 1), zinc salts (for example, see Patent Document 2) and the like have been reported as catalysts, but the decrease in dissociation temperature is not sufficient, and dissociation at low temperatures. An effective blocking agent dissociation catalyst has not yet been reported.

  Various metal binuclear complexes and production methods thereof have been reported (for example, see Non-Patent Document 2 to Non-Patent Document 4), but examples in which these metal binuclear complexes are applied as dissociation catalysts for blocking agents are still reported. It has not been.

Japanese Patent No. 3293633 Japanese Patent No. 337536

Progress in Organic Coatings 36, 148-172 (1999) Journal of Materials Chemistry Volume 14, pages 3150-3157 (2004) Dalton Transactions 544-550 (2003) Chemical Communications 1213-1222 (2003)

  The present invention has been made in view of the above-mentioned background art, and an object thereof is to provide a dissociation catalyst for a blocking agent having a high dissociation effect at a low temperature and its use.

  As a result of intensive studies to solve the above problems, the present inventors have found that a specific metal binuclear complex containing two or more metals becomes a dissociation catalyst for a blocking agent having a high dissociation effect at low temperatures, The present invention has been completed.

  That is, 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.

  [1] A blocking agent dissociation catalyst containing a metal binuclear complex containing two or more metals.

  [2] The blocking agent according to the above [1], wherein the metal contained in the metal binuclear complex is two or more kinds of metals selected from the group consisting of aluminum, zinc, cobalt, nickel, manganese and copper Dissociation catalyst.

  [3] The above [1], wherein 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 The blocking agent dissociation catalyst according to [2].

  [4] The blocking agent dissociation catalyst according to any one of [1] to [3], 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], wherein the metal binuclear complex contains a β-diketone and an alkoxy group as a ligand.

  [6] The above-mentioned [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. [5] The blocking agent dissociation catalyst according to any one of [5].

  [7] 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.

  [8] The blocking agent dissociation catalyst according to any one of the above [1] to [7], comprising an organic solvent.

  [9] The organic solvent is one or more compounds selected from the group consisting of ketones, ethers, esters, aliphatic hydrocarbons, aromatic hydrocarbons, and alicyclic hydrocarbons. The blocking agent dissociation catalyst according to [8] above, wherein 5 to 70% by weight of the metal binuclear complex is dissolved with respect to the entire blocking agent dissociation catalyst.

  [10] 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.

  [11] The one-component thermosetting composition as described in [10] above, wherein the compound having an isocyanate-reactive group is a polyol.

  [12] The above-mentioned feature, wherein the amount of the blocking agent dissociation catalyst according to any one of [1] to [9] is in the range of 0.1 to 15% by weight with respect to the blocked isocyanate The one-component thermosetting composition according to [10] or [11].

  [13] 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].

  Since 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.

  In addition, 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.

  Hereinafter, the present invention will be described in more detail.

  In the present invention, the blocking agent dissociation catalyst contains a metal binuclear complex containing two or more metals. In the present invention, the “metal binuclear complex” refers to a complex containing two or more metals in one molecule. Although it does not specifically limit about the preparation method of a metal binuclear complex, For example, it can prepare by the method as described in the above-mentioned nonpatent literature 2-nonpatent literature 4. Specifically, a metal alkoxide and a metal chelate compound (other than a metal alkoxide) may be prepared by adding an organic compound as a ligand and reacting in a solvent in some cases. it can.

  Suitable examples of the metal in the metal alkoxide used here include aluminum, zinc, cobalt, nickel, manganese, copper, and the like. Moreover, as an alkoxy group in a metal alkoxide, an isopropoxy group, n-propoxy group, an ethoxy group, a methoxy group etc. are mentioned as a suitable thing, for example. Taking aluminum as an example of the metal in the metal alkoxide, 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. As the chelate ligand in the metal chelate compound, acetylacetone, 3,5-heptanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1,5,5,5 Β-diketones such as hexafluoro-2,4-pentanedione; β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate, isopropyl acetoacetate; dimethyl malonate, diethyl malonate, etc. Malonic acid diesters; β-ketoamides such as acetoacetanilide; and carboxylic acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, and 2-ethylhexanoic acid. Taking zinc as an example of the metal in the metal chelate compound, specific examples of the metal chelate compound 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 thereof 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. Β-diketones such as 1,5,5-hexafluoro-2,4-pentanedione; carboxylic acids such as acetic acid, propionic acid, butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid and 2-ethylhexanoic acid Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol and tert-butanol; β-ketoesters such as methyl acetoacetate, ethyl acetoacetate, n-propyl acetoacetate and isopropyl acetoacetate Malonic acid diesters such as dimethyl malonate and diethyl malonate; acetoacetanilide Β-ketoamides and the like.

  Examples of the solvent used here 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, and diethylene glycol dimethyl ether. Can be mentioned. In the preparation of the metal binuclear complex, insoluble matter may be generated due to the mixing of moisture. In such a case, operations such as centrifugation, filtration, and decantation may be performed as separation methods thereof.

  Although it does not specifically limit as a metal contained in a metal binuclear complex, Aluminum, zinc, cobalt, nickel, manganese, copper etc. are illustrated as a suitable thing. 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 amount of aluminum contained in the metal binuclear complex is preferably in the range of 1 to 3 as an atomic ratio with respect to the total amount of metals other than aluminum contained in the metal binuclear complex. It is particularly preferable that the range is That is, [amount of aluminum contained in metal binuclear complex] / [total amount of metal other than aluminum contained in metal binuclear complex] = 1 to 3 (atomic ratio), preferably 1.2 to 2.5 (Atom ratio) is particularly preferred. When this atomic ratio is less than 1 or exceeds 3, a metal binuclear complex may not be formed.

  The metal binuclear complex preferably contains a β-diketone and an alkoxy group as ligands.

  Examples of β-diketone 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-1,3-pentanedione, 1,3-dione Phenyl-1,3-propanedione, 1-phenyl-5,5-dimethyl-2,4-hexanedione, 1- (4-biphenyl) -1,3-butanedione, 1-phenyl-3- (2-methoxy) Phenyl) -1,3-propanedione, 1- (4-nitrophenyl) -1,3-butanedione, 1- (2-furyl) -1,3-butanedione, 1- (tetrahydro-2-furyl) -1 , 3-butanedione and the like.

  Among these β-diketones, 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 a methoxy group, an ethoxy group, an isopropoxy group, an n-propoxy group, an n-butoxy group, an n-pentoxy group, an n-hexyloxy group, and a 1-methoxy-2-propoxy group. As mentioned.

  In the present invention, a part of the alkoxy group may be substituted with a carboxyl group. The carboxyl group is not particularly limited. For example, formic acid group, acetic acid group, propionic acid group, butanoic acid group, pentanoic acid group, hexanoic acid group, heptanoic acid group, octanoic acid group, 2-ethylhexanoic acid 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 group of unsaturated fatty acids such as acid group, methacrylic acid group, acrylic acid, carboxyl group of aromatic fatty acids such as benzoic acid group, phthalic acid group, isophthalic acid group, terephthalic acid group, salicylic acid group, lactic acid group, Examples thereof include carboxyl groups of hydroxycarboxylic acids such as malic acid group and citric acid group.

  The metal binuclear complex of the present invention is characterized by high solubility in an organic solvent. 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 in the blocking agent dissociation catalyst is not particularly limited, but is preferably in the range of 5 to 70% by weight and more preferably in the range of 10 to 50% by weight with respect to the entire blocking agent dissociation catalyst. preferable. Therefore, the solubility of the metal binuclear complex in the organic solvent is preferably 5 to 230 [g / 100 g-solvent], and more preferably 10 to 100 [g / 100 g-solvent].

  Examples of the organic solvent include ketones, ethers, esters, aliphatic hydrocarbons, aromatic hydrocarbons, alicyclic hydrocarbons, and the like. Specifically, 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, tripropylene glycol monomethyl ether, propylene glycol mono n-propyl ether, dipropylene glycol mono n-propyl ether, propylene glycol mono n-butyl ether, tripropylene glycol mono n-butyl ether, propylene In addition to glycol monoalkyl ethers such as glycol monomethyl ether and diethylene glycol monoethyl ether, methyl ethyl ketone, toluene, ethyl acetate, isopropyl acetate, n-propyl acetate, isobutyl acetate, s-butyl acetate, n-butyl acetate, methyl acetate, acetone , Ethanol, hexane, diethyl ether and the like are exemplified, but not limited thereto.

  On the other hand, the solubility of the metal alkoxide, which is a raw material compound 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]. Thus, it can be said that 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.

In the present invention, as the metal binuclear complex, specifically, ZnAl ₂ (C ₅ H ₇ O ₂ ) ₃ (C ₃ H ₇ O) ₄ (CH ₃ COO), Zn ₂ Al ₂ (C ₅ H ₇ O) _{2) 4 (C 3 H 7} O) 6, Zn 2 Al 2 (C 5 H 7 O 2) 4 (C 2 H 5 O) 5 (C 3 H 7 O), Zn 5 Al 4 (C 5 H 7 O ₂ ) ₂₀ (C ₂ H ₅ O) ₁₁ (C ₃ H ₇ O), Zn ₂ Al ₃ (C ₅ H ₇ O ₂ ) ₄ (C ₂ H ₅ O) ₈ (C ₃ H ₇ O), Zn ₂ Al ₄ (C ₅ H ₇ O ₂ ) ₄ (C ₂ H ₅ O) ₁₁ (C ₃ H ₇ O), Zn ₂ Al ₆ (C ₅ H ₇ O ₂ ) ₄ (C ₂ H ₅ O) ₁₆ ( _{C 3 H 7 O) 2,} Zn 2 Al 7 (C 5 H 7 O 2) 4 (C 2 H 5 O) 19 (C 3 H 7 O) 2, ZnA _{l 2 (C 7 H 11 O} 2) 3 (C 3 H 7 O) 4 (CH 3 COO), Zn 2 Al 3 (C 5 H 7 O 2) 4 (CH 3 OC 3 H 6 O) 7, CoAl ₂ (C ₅ H ₇ O ₂ ) ₄ (C ₃ H ₇ O) ₄ , Co ₂ Al ₂ (C ₅ H ₇ O ₂ ) ₄ (C ₃ H ₇ O) ₆ , CoAl ₂ (C ₅ H ₇ O ₂ ) ₃ (C ₃ H ₇ O) ₄ (CH ₃ COO), NiAl ₂ (C ₅ H ₇ O ₂ ) ₄ (C ₃ H ₇ O) ₄ , MnAl ₂ (C ₅ H ₇ O ₂ ) ₃ (C ₃ Examples thereof include compounds represented by molecular formulas such as H ₇ O) ₄ (CH ₃ COO) and CuAl ₂ (C ₅ H ₇ O ₂ ) ₂ (C ₃ H ₇ O) ₆ .

Here, 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. However, in order to further improve the catalytic activity at low temperature, 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, and aluminum bisacetylacetate. Nate ethoxide, aluminum bisacetylacetonate n-butoxide, aluminum bisacetylacetonate sec-butoxide, aluminum bisacetylacetonate tert-butoxide, aluminum tris (3,5-heptanedionate) The Of these, aluminum trisacetylacetonate is particularly preferred.

  Next, the one-component thermosetting composition of the present invention will be described.

  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.

  In the one-component thermosetting composition of the present invention, examples of the block isocyanate include non-aqueous blocked isocyanate and aqueous blocked isocyanate.

  Examples of non-aqueous blocked isocyanate 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 ε-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. Rukoto can.

  Here, as a well-known isocyanate compound, aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, araliphatic polyisocyanate etc. are mentioned, for example.

  Examples of the aliphatic polyisocyanate 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.

  Examples of the alicyclic polyisocyanate 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.

  Examples of aromatic polyisocyanates 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, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.

  Moreover, as 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.

  On the other hand, 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. . Examples of the hydrophilic group include ionic groups such as cations and anions, and nonionic groups. Examples of the nonionic compound for introducing a nonionic group into the polyisocyanate include polyalkylene ether alcohols and polyoxyalkylene fatty acid esters.

  In the one-component thermosetting composition of the present invention, examples of the compound having an isocyanate-reactive group include a polyol. In the present invention, 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.

  Examples of the polymerizable monomer having one or more active hydrogens in one molecule 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 and methacrylic acid-2-hydroxybutyl; 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 ε-caprolactone with these active hydrogens.

  Examples of the monomer copolymerizable with the polymerizable monomer include acrylic acid esters such as methyl acrylate, ethyl acrylate, isopropyl acrylate, acrylic acid-n-butyl, and acrylic acid-2-ethylhexyl; 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.

  Examples of polyester polyols include condensed polyester polyols, polycarbonate polyols, and polylactone polyols.

  Examples of the condensed polyester polyol 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, naphthalenedicarbo Reaction products of dicarboxylic acids such as acid.

  Specifically, polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyneopentylene adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexamethylene adipate diol, poly (polytetramethylene ether) ) Adipate-type condensed polyester diols such as adipate diol, and azelate-type condensed polyester diols such as polyethylene azelate diol and polybutylene azelate diol.

  Examples of the polycarbonate polyol 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. Specifically, polytetramethylene carbonate diol, poly 3-methylpentamethylene carbonate diol, polyhexamethylene carbonate diol and the like are exemplified.

  Examples of polylactone polyols include ring-opening polymers of ε-caprolactone, γ-butyrolactone, γ-valerolactone, and mixtures of two or more thereof. Specific examples include polycaprolactone diol.

  Examples of the polyether polyol 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. In the case of a 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, β-methyl epichloro type, cyclic oxirane type, glycidyl ether type, glycol ether type, aliphatic unsaturated compound epoxy type, epoxidized fatty acid ester type, polyvalent carboxylic acid ester type, amino acid Examples include glycidyl type, halogenated type, and resorcin type epoxy polyols.

  Moreover, as non-aqueous polyols other than those described above, for example, OH-terminated prepolymers produced by reacting these polyols with isocyanate compounds can also be used.

  On the other hand, 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. Examples of neutralizers include ammonia and water-soluble amino compounds such as monoethanolamine, ethylamine, dimethylamine, diethylamine, triethylamine, propylamine, dipropylamine, isopropylamine, diisopropylamine, triethanolamine, and butylamine. , Dibutylamine, 2-ethylhexylamine, methylethanolamine, dimethylethanolamine, diethylethanolamine, morpholine and the like. Among these, tertiary amines such as triethylamine and dimethylethanolamine are preferably used.

  In the one-component thermosetting composition of the present invention, 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. By setting the hydroxyl value to 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.

  In the one-component thermosetting composition of the present invention, 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. Although normally used as a composition, solid content means a polyol, a neutralizing agent, and antioxidant among these.

  The hydroxyl value of the 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 neutralizing titrating a 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. In the present invention, "solid content" represents a component other than the solvent in the one-component thermosetting composition. For example, in the case of a non-aqueous 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. In the case of an aqueous one-component thermosetting composition, 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 | water-based blocked isocyanate, is represented. Sufficient low-temperature curability can be obtained by setting the amount of the metal binuclear complex to 0.05% by weight or more based on the solid content. On the other hand, even if the amount of the metal binuclear complex exceeds 10% by weight based on the solid content, no further improvement in low-temperature curability is observed, which is economically disadvantageous.

  In the one-component thermosetting composition of the present invention, additives, pigments, solvents and the like commonly used in the technical field can be used as necessary.

  Examples of the additive include, but are not limited to, UV absorbers such as hindered amine, benzotriazole, and benzophenone, hindered phenol, phosphorus, sulfur, hydrazide, and other antioxidants, tin Examples include urethanization catalysts such as those based on zinc, amine and amine, leveling agents, rheology control agents, pigment dispersants and the like.

  Examples of the pigment 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, other carbon pigments, and metal foils. And pigments such as pigments and rust preventive pigments.

  Although it does not specifically limit as a solvent, For example, Hydrocarbons, such as benzene, toluene, xylene, a cyclohexane, mineral spirit, naphtha; Ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone; Ethyl acetate, acetic acid-n -Esters, such as butyl and cellosolve acetate, are mentioned, These solvents may be used independently and may use 2 or more types together.

  When storage at a high temperature or the like is assumed, 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.

  The following examples further illustrate the present invention, but the present invention is not limited to these examples.

  In the following examples, baking of a one-pack type thermosetting composition, measurement of solvent resistance, and identification of a metal binuclear complex were carried out as shown below.

<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.

<Measurement of solvent resistance>
The above-mentioned baked coating film was peeled off from the polypropylene plate and immersed in methyl ethyl ketone for 12 hours. The gel fraction was determined from the weight residual ratio of the coating film after immersion in methyl ethyl ketone as follows, and the solvent resistance was evaluated.

  Gel fraction (%) = weight of coating film after immersion / weight of coating film before immersion × 100.

<Identification of metal binuclear complex>
Confirmed by ¹ H NMR. The measurement was performed in deuterated chloroform (CDCl ₃ ) solvent using gemini200 (200 MHz) manufactured by Varian Technologies Japan Limited. The following abbreviations were used for peak notation. s = singlet, d = doublelet, t = triplet, st = septet, m = multiplet. In addition, the number (chemical shift) described in each production example shown below is expressed in δ (ppm).

Production Example 1
(Preparation of metal binuclear complex)
A metal binuclear complex was prepared according to the description in Non-Patent Document 2 [Journal of Materials Chemistry Vol. 14, pages 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. Thereafter, the mixture was cooled to room temperature, and 0.435 g of acetic acid and 0.680 g of acetylacetone were added with vigorous stirring. Then, the inside of the container was reduced to 50 ° C. under reduced pressure to remove the solvent, and 4.50 g of Al—Zn binuclear complex 1 was obtained (molecular formula: ZnAl ₂ (C ₅ H ₇ O ₂ ) ₃ (C ₃ H ₇ O) ₄ (CH ₃ COO), ¹ H NMR: 5.48 (s, 3H, C ₅ H ₇ O ₂ ), 4.02 (st, 4H, C ₃ H ₇ O), 1.99 (s, 3H, CH ₃ COO), 1.98 to 1.84 (m, 18 H, C ₅ H ₇ O ₂ ), 1.30 to 0.92 (m, 24 H, C ₃ H ₇ O)).

Production Example 2
(Preparation of metal binuclear complex)
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. under reduced pressure to remove the solvent, and 2.80 g of Al—Zn binuclear complex 2 was obtained (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), 1.99~1.85 (m, 24H} , C 5 H 7 O 2), 1.30~1.04 (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. . Thereafter, the inside of the container was reduced to 50 ° C. under reduced pressure to remove the solvent, and 2.80 g of Al—Zn binuclear complex 3 was obtained (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), 1.99~1.82 (m, 24H, C 5 H 7 O 2), 1.28~0.90 (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. . Thereafter, the inside of the container was reduced to 50 ° C. under reduced pressure to remove the solvent, and 2.60 g of Al—Zn binuclear complex 4 was obtained (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), 1.99~1.80 (m, 120H, C 5 H 7 O 2), 1.30~0.88 (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. under reduced pressure to remove the solvent, and 3.44 g of Al—Zn binuclear complex 5 was obtained (molecular formula: Zn ₂ Al ₃ (C ₅ H ₇ O ₂ ) ₄ (C ₂ H ₅ O). ) ₈ (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 _{.36 (m, 16H, C 2} H 5 O), 1.99~1.80 (m, 24H, C 5 H 7 O 2), 1.30~0.88 (m, 24H, C 2 H 5 _{O, m, 6H, C 3} H 7 O)).

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. . Thereafter, the inside of the container was brought to 50 ° C. under reduced pressure to remove the solvent, and 4.04 g of Al—Zn binuclear complex 6 was obtained (molecular formula: Zn ₂ Al ₄ (C ₅ H ₇ O ₂ ) ₄ (C ₂ H ₅ O). ) ₁₁ (C ₃ H ₇ O), ¹ H NMR: 5.36 (s, 4H, C ₅ H ₇ O ₂ ), 4.02 (st, 1H, C ₃ H ₇ O), 3.90-3 _{.30 (m, 22H, C 2} H 5 O), 1.99~1.75 (m, 24H, C 5 H 7 O 2), 1.35~0.80 (m, 33H, C 2 H 5 _{O, m, 6H, C 3} H 7 O)).

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. . Then, the inside of the container was reduced to 50 ° C. under reduced pressure to remove the solvent, and 5.23 g of Al—Zn binuclear complex 7 was obtained (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), 1.99~1.75 (m, 24H, C 5 H 7 O 2), 1.35~0.80 (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. . Thereafter, the inside of the container was reduced to 50 ° C. under reduced pressure to remove the solvent, and 5.83 g of Al—Zn binuclear complex 8 was obtained (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), 4.000 _{3.28 (m, 38H, C 2} H 5 O), 1.99~1.75 (m, 24H, C 5 H 7 O 2), 1.35~0.78 (m, 57H, C 2 H _{5 O, m, 12H, C} 3 H 7 O)).

Production Example 9
(Preparation of metal binuclear complex)
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. After adding 1.17 g of acetylacetone with stirring, the inside of the container was reduced to 50 ° C. under reduced pressure to remove the solvent, and 3.21 g of an Al—Co binuclear complex was obtained (molecular formula: CoAl ₂ (C ₅ H ₇ O ₂ )). ₄ (C ₃ H ₇ O) ₄ ), ¹ H NMR: 5.48 (s, 4H, C ₅ H ₇ O ₂ ), 4.02 (st, 4H, C ₃ H ₇ O), 2.00 _{1.90 (m, 24H, C 5} H 7 O 2), 1.26~1.02 (m, 24H, C 3 H 7 O)).

Production Example 10
(Preparation of zinc bisheptanedionate monohydrate)
In a beaker, 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. In another beaker, 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.

(Preparation of metal binuclear complex)
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. Thereafter, the mixture was cooled to room temperature, and 0.189 g of acetic acid and 0.379 g of 3,5-heptanedione were added with vigorous stirring. Then, the inside of the container to remove the solvent to a reduced pressure of 50 ° C., to obtain 0.87g of the Al-Zn binuclear complex 9 (molecular _{formula: ZnAl 2 (C 7 H 11} O 2) 3 (C 3 H 7 O) 4 (CH ₃ COO), ¹ H NMR: 5.46 (s, 3H, C ₇ H ₁₁ O ₂ ), 4.02 (st, 4H, C ₃ H ₇ O), 2.26 to 2.01 (m _{, 12H, C 7 H 11 O} 2), 2.03 (s, 3H, CH 3 COO), 1.28~0.92 (m, 42H, C 7 H 11 O 2, C 3 H 7 O)) .

Production Example 11
(Preparation of metal binuclear complex)
A reflux condenser was attached to a four-necked flask equipped with a nitrogen blowing tube, and the inside of the container was brought to a nitrogen atmosphere. Next, 2.61 g of aluminum trisisopropoxide, 2.24 g of zinc bisacetylacetonate monohydrate, and 12.0 mL of dehydrated propylene glycol monomethyl ether acetate are charged in a container and refluxed at 130 ° C. for 300 minutes. Reacted. Then, the inside of the container was reduced to 50 ° C., and the solvent was concentrated for 30 minutes to obtain 7.80 g of a propylene glycol monomethyl ether acetate solution of Al—Zn binuclear complex 10.

The obtained solution was collected in a 0.50 g aluminum cup, dried at 100 ° C. for 60 minutes to remove propylene glycol monomethyl ether acetate, and the residual weight was 0.28 g. Accordingly, the solid content concentration of the obtained solution was 56% by weight. 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 ( ¹ H 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), was _{1.24~1.05 (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.

実施例２〜実施例１１．
実施例１と同様の方法により、製造例２〜製造例１１で得られた金属複核錯体の、プロピレングリコールモノメチルエーテルアセテート又はメチルエチルケトンへの溶解度を測定した。結果を表１、及び表２に併せて示す。

Example 2 to Example 11.
By the same method as in Example 1, the solubility of the metal binuclear complex obtained in Production Example 2 to Production Example 11 in propylene glycol monomethyl ether acetate or methyl ethyl ketone was measured. The results are shown in Table 1 and Table 2.

比較例１〜比較例６．
（複核錯体原料の溶媒への溶解度測定）
実施例１と同様の方法により、製造例１〜製造例５、及び製造例８〜製造例１１で使用した金属複核錯体の原料である金属化合物の、プロピレングリコールモノメチルエーテルアセテート又はメチルエチルケトンへの溶解度を測定した。結果を表３、及び表４に併せて示す。

Comparative Example 1 to Comparative Example 6
(Measurement of solubility of binuclear complex raw materials in solvent)
In the same manner as in Example 1, the solubility of the metal compound, which is the raw material of the metal binuclear complex used in Production Example 1 to Production Example 5 and Production Example 8 to Production Example 11, in propylene glycol monomethyl ether acetate or methyl ethyl ketone was measured. It was measured. The results are also shown in Table 3 and Table 4.

表１〜表４から明らかなとおり、金属複核錯体の原料の金属化合物は溶媒にほとんど溶解せず、本発明の金属複核錯体は、金属複核の錯体を形成したことで高い溶媒度を獲得したことが理解される。

As is clear from Tables 1 to 4, 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 solvent degree by forming the metal binuclear complex. Is understood.

Production Example 12.
(Preparation of non-aqueous polyol)
In 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. Next, 13.1 g of neopentyl glycol, 79.3 g of hexamethylene diisocyanate, and 149 g of methyl ethyl ketone were added to the reactor and reacted at 80 ° C. for 3 hours. Thereafter, 106 g of methyl ethyl ketone was added to the reactor, and the reaction was continued at 80 ° C. for 3 hours. When the residual amount of isocyanate reached 1.06% by weight, the reaction was stopped by cooling to room temperature. Thereafter, 341 g of acetone and 22.6 g of diethanolamine were added to the reactor while stirring to obtain a non-aqueous polyol. The obtained non-aqueous polyol had a solid content concentration of 50% by weight and a hydroxyl value of 35.0 mgKOH / g based on the solid content.

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. Thereafter, 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. When no isocyanate was detected, the reaction was stopped by cooling to room temperature 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.

  Here, 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. Thereafter, 18.6 g of 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. When no isocyanate was detected, the reaction was stopped by cooling to room temperature.

  To 100 g of the obtained composition, 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)
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 with the composition shown in Table 5, the Al-Zn binuclear complex 1 obtained in Production Example 1 A 5 wt% acetone solution of was added with stirring to obtain a non-aqueous one-component thermosetting composition containing a metal binuclear complex.

  Table 5 shows the results of measuring the solvent resistance after baking the obtained non-aqueous one-component thermosetting composition at 110 ° C, 120 ° C and 130 ° C.

実施例１３〜実施例２０．
表５、及び表６に示す組成で、実施例１２と同様の方法により、金属複核錯体を含有する非水性一液型熱硬化性組成物を得た。

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.

  The obtained non-aqueous one-component thermosetting composition was baked at 110 ° C., 120 ° C., and 130 ° C., and then the solvent resistance measurement was performed.

比較例７．
（非水性一液型熱硬化性組成物における触媒無添加の硬化性評価）
表７に示す組成で、製造例１２で得られた非水性ポリオール、製造例１３で得られた非水性ブロックイソシアネート、及びメチルエチルケトンを混合し、触媒を含有しない非水性一液型熱硬化性組成物を得た。

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.

  Table 7 shows the results of measuring the solvent resistance after baking the obtained non-aqueous one-component thermosetting composition at 110 ° C, 120 ° C, and 130 ° C.

表５〜表７から明らかなとおり、比較例７の１３０℃のゲル分率と実施例１２、１３、及び１９の１１０℃のゲル分率は同程度であり、Ａｌ−Ｚｎ複核錯体１、２、及び８の添加によりブロック剤の解離温度が約２０℃低下したことがわかる。

As is apparent from Tables 5 to 7, the gel fraction at 130 ° C. of Comparative Example 7 and the gel fractions at 110 ° C. of Examples 12, 13, and 19 are comparable, and Al—Zn binuclear complexes 1, 2 It can be seen that the dissociation temperature of the blocking agent was reduced by about 20 ° C. by addition of 8 and 8.

  In addition, the gel fraction at 120 ° C. in Examples 14 and 15 greatly exceeds the gel fraction at 130 ° C. in Comparative Example 7, and the dissociation temperature of the blocking agent is increased by the addition of the Al—Zn binuclear complexes 3 and 4. It can be seen that the temperature decreased by 10 ° C or more.

  Furthermore, the gel fraction at 110 ° C. of Examples 16 to 18 and 20 greatly exceeds the gel fraction of 130 ° C. of Comparative Example 7, and the blocking agent dissociation is caused by the addition of Al—Zn binuclear complexes 5 to 8 and 10. 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)
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 with the composition shown in Table 7, a 5 wt% acetone solution of dibutyltin dilaurate, which is a known catalyst, is used. Was added with stirring to obtain a non-aqueous one-component thermosetting composition containing a known catalyst.

  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 7.

  As is clear from Tables 5 to 7, the gel fractions of Examples 12 to 20 were higher at each temperature than Comparative Example 8. This shows that the Al—Zn binuclear complexes 1 to 8 and 10 have a blocking agent low-temperature dissociation activity superior to that of dibutyltin dilaurate.

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)
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 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 baking the obtained non-aqueous one-component thermosetting composition 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)
In 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. Next, 16.9 g of dimethylolpropionic acid, 79.3 g of hexamethylene diisocyanate, and 149 g of methyl ethyl ketone were added to the reactor and reacted at 80 ° C. for 3 hours. Thereafter, 106 g of methyl ethyl ketone was added, and the reaction was continued at 80 ° C. for 3 hours. When the residual amount of isocyanate reached 1.10% by weight, the reaction was stopped by cooling to room temperature. While stirring, 341 g of acetone and 23.5 g of diethanolamine were added to the reactor to obtain an OH-terminated prepolymer solution.

  In the composition shown in Table 8, IRGANOX 1010 (hindered phenol antioxidant, manufactured by Ciba Japan), triethylamine, and catalyst solution were 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.

  Thereafter, the aqueous blocked isocyanate obtained in Production Example 14 with the composition shown in Table 8 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.

(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.

比較例９．
（水性一液型熱硬化性組成物における触媒無添加の硬化性評価）
表８に示した組成で、実施例２２と同様の方法により、触媒を含有しない水性一液型熱硬化性組成物を得た。得られた水性一液型熱硬化性組成物は固形分濃度３１重量％の安定な分散液であった。

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, compared with Comparative Example 9, Examples 22 to 25 had higher gel fractions at each temperature. 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)
With the composition shown in Table 9, 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.

表８、表９から明らかなとおり、比較例１０〜１２に比べ、実施例２２〜２５の方が１２０℃においてゲル分率が高かった。これより、金属複核錯体は公知触媒より優れたブロック剤低温解離活性を持つことがわかる。

As is clear from Tables 8 and 9, the gel fraction was higher in Examples 22-25 than at Comparative Examples 10-12 at 120 ° C. This shows that the metal binuclear complex has a blocking agent low-temperature dissociation activity superior to that of known catalysts.

Comparative Example 13 to Comparative Example 14.
(Evaluation of catalytic activity of metal compounds constituting binuclear complexes in aqueous one-component thermosetting compositions)
With the composition shown in Table 9, an aqueous one-component thermosetting composition containing an Al compound or a Zn compound, which is a constituent metal of the Al—Zn binuclear complex, 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.

  Table 9 shows the results of solvent resistance measurement after the obtained aqueous one-component thermosetting composition was baked at 120 ° C and 130 ° C.

  As is clear from Table 8 and Table 9, Examples 22 to 25 had higher gel fractions at each temperature than Comparative Examples 13 to 14. From these results, it can be seen that 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.

Claims (10)

For blocked isocyanate containing a metal dinuclear complex containing aluminum and one or more metals selected from the group consisting of zinc, cobalt, nickel, manganese and copper and having β-diketone and alkoxy group as ligands Block agent dissociation catalyst. The blocking agent dissociation catalyst for blocked isocyanate according to claim 1, wherein the metal contained in the metal binuclear complex is aluminum and zinc or cobalt. To the total amount of aluminum than the metal contained in the metal polynuclear complex, the amount of aluminum contained in the metal polynuclear complex is according to claim 1 or claim 2, characterized in that in the range of 1 to 3 in atomic ratio Blocking agent dissociation catalyst for blocked isocyanate . The blocking agent dissociation catalyst for blocked isocyanate according to any one of claims 1 to 3 , comprising a metal compound other than the metal binuclear complex. The blocking agent dissociation catalyst for blocked isocyanate according to any one of claims 1 to 4 , comprising 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; and 6. The blocking agent dissociation catalyst for blocked isocyanate according to claim 5 , wherein 5 to 70% by weight of a metal binuclear complex is dissolved with respect to the entire blocking agent dissociation catalyst. A one-component thermosetting composition comprising the blocked isocyanate dissociation catalyst for blocked isocyanate according to any one of claims 1 to 6 , the blocked isocyanate, and a compound having an isocyanate-reactive group. The one-component thermosetting composition according to claim 7 , wherein the compound having an isocyanate-reactive group is a polyol. The amount of the blocking agent dissociation catalyst for blocked isocyanate according to any one of claims 1 to 6 is in the range of 0.1 to 15% by weight as the amount of metal binuclear complex used for the blocked isocyanate. The one-component thermosetting composition according to claim 7 or 8 . A method for dissociating a blocking agent, comprising heating the blocked isocyanate in the presence of the blocking agent dissociation catalyst for blocked isocyanate according to any one of claims 1 to 6 .