Classifications

• • 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
• • 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

Definitions

• the present invention uses a urethanization reaction catalyst having a high catalytic ability, a urethane compound obtained by using the urethanization reaction catalyst, a curable composition, a cured product, and the urethanization catalyst regardless of the type of reaction raw material.
• the present invention relates to a method for producing a urethane compound.
• Urethane resin is generally widely used in various fields such as paints, adhesives, and electronic materials because it has excellent characteristics such as high flexibility, elongation, and impact resistance.
• a urethanization catalyst used in producing a urethane resin it is known that a metal compound such as zinc, magnesium, or aluminum can be used in addition to an organotin compound (see Patent Document 1 below).
• Patent Document 1 describes a technique of using an acetylacetone compound such as zinc, magnesium, or aluminum as a urethanization catalyst, but these urethanization reaction catalysts do not have sufficient catalytic ability, and in particular, a urethanization reaction.
• an isocyanate group remains in the reaction system and turbidity occurs in the reaction system.
• the problem to be solved by the present invention is a urethanization reaction catalyst having a high catalytic ability, a urethane compound obtained by using the urethanization reaction catalyst, a curable composition, and a cured product, regardless of the type of reaction raw material. , And a method for producing a urethane compound using the urethanization catalyst.
• the present inventors have used a zirconium compound and another metal compound in combination as a urethanization catalyst, and zirconium in the zirconium compound and other in the other metal compound.
• a zirconium compound and another metal compound in combination as a urethanization catalyst, and zirconium in the zirconium compound and other in the other metal compound.
• the present invention contains the zirconium compound (A) and the other metal compound (B) other than the zirconium compound (A), and is based on 100 parts by mass of the total mass of zirconium in the zirconium compound (A).
• the present invention relates to a urethanization reaction catalyst characterized in that the total mass of other metals in the other metal compound (B) is in the range of 10 to 80 parts by mass.
• the present invention further relates to a urethane compound obtained by using the urethanization reaction catalyst.
• the present invention further relates to a curable composition containing the urethane compound.
• the present invention further relates to a cured product of the curable composition.
• the present invention further relates to a method for producing a urethane compound using the urethanization reaction catalyst.
• a urethanization reaction catalyst having a high catalytic ability a urethane compound obtained by using the urethanization reaction catalyst, a curable composition, a cured product, and the urethanization catalyst.
• the urethanization reaction catalyst of the present invention contains a zirconium compound (A) and a metal compound (B) other than the zirconium compound (A), and the total mass of zirconium in the zirconium compound (A) is 100 mass. It is characterized in that the total mass of the other metal in the other metal compound (B) with respect to the portion is in the range of 10 to 80 parts by mass.
• the zirconium compound (A) is not particularly limited as long as it is a compound having a zirconium atom, and a wide variety of compounds can be used. Further, in the present invention, one type of the zirconium compound (A) may be used alone, or two or more types may be used in combination.
• examples of the inorganic zirconium compound include zirconium oxide, zirconium hydride, and zirconium chloride.
• examples of the organic zirconium compound include compounds represented by any of the following general formulas (1) to (6).
• Zr (OR 1 ) 4 ... General formula (1)
• Zr (R 2 COH 2 COR 3 ) 4 ...
• General formula (2) Zr (OR 1 ) m (R 2 COCH 2 COR 3 ) n ...
• General formula (3) Zr (OR 1 ) m (R 4 COCH 2 COOR 5 ) n ...
• R 1 and R 6 are independently aliphatic hydrocarbon groups having 1 to 20 carbon atoms.
• R2 , R3 , R4 , and R5 are independently aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
• m and n are integers of 1 to 3 respectively, and the sum of m and n is 4.
• R 1 and R 6 are independently aliphatic hydrocarbon groups having 1 to 20 carbon atoms. Of these, an aliphatic hydrocarbon group having 3 to 6 carbon atoms is preferable because it is more excellent in catalytic ability.
• R 2 , R 3 , R 4 and R 5 are independently aliphatic hydrocarbon groups having 1 to 10 carbon atoms. Of these, an aliphatic hydrocarbon group having 1 to 4 carbon atoms is preferable because it is more excellent in catalytic ability.
• the compounds represented by any of the general formulas (1) to (4) are preferable because they are more excellent in catalytic ability, and are represented by the general formula (2) or (4). Compounds are more preferred.
• the metal compound (B) other than the zirconium compound (A) is not particularly limited, and a wide variety of compounds can be used. Further, in the present invention, as the other metal compound (B), one kind may be used alone, or two or more kinds may be used in combination. Specific examples of the other metal compound (B) include zinc compounds, titanium compounds, iron compounds, aluminum compounds, calcium compounds, magnesium compounds and the like. Among them, at least one of a zinc compound, a titanium compound, and an iron compound is preferable, and a zinc compound is particularly preferable, because it is more excellent in catalytic ability.
• the total mass of the zirconium compound (A), the zinc compound, the titanium compound, and the iron compound is preferably 80 parts by mass or more in 100 parts by mass of the total mass of the urethanization reaction catalyst. , 90 parts by mass or more is more preferable, and 95 parts by mass or more is particularly preferable.
• examples of the inorganic zinc compound include zinc oxide, zinc hydroxide, zinc chloride and the like.
• examples of the organozinc compound include compounds represented by any of the following general formulas (7) to (10), zinc complexes other than these, and the like.
• General formula (8) Zn (R 10 COCH 2 COOR 11 ) 2 ...
• General formula (9) Zn (OCOR 12 ) 2 ...
• R 7 and R 12 are independently aliphatic hydrocarbon groups having 1 to 20 carbon atoms.
• R8, R9 , R10, and R11 are independently aliphatic hydrocarbon groups having 1 to 10 carbon atoms.
• R 7 and R 12 are independently aliphatic hydrocarbon groups having 1 to 20 carbon atoms. Of these, an aliphatic hydrocarbon group having 3 to 10 carbon atoms is preferable because it is more excellent in catalytic ability.
• R 8 , R 9 , R 10 and R 11 are independently aliphatic hydrocarbon groups having 1 to 10 carbon atoms. Of these, an aliphatic hydrocarbon group having 1 to 4 carbon atoms is preferable because it is more excellent in catalytic ability.
• the ligand for the zinc complex include imidazole-type ligands such as imidazole and 2-methylimidazole; and pyridine-type coordinations such as pyridine, 2,2'-bipyridine, and 1,10-phenanthroline. Child; phosphine ligands such as trimethylphosphine, triphenylphosphine, 1,2-bis (diphenylphosphino) ethane and the like can be mentioned.
• a complex prepared in advance may be used, or the compound represented by any of the general formulas (7) to (10) is arranged in the reaction system of the urethanization reaction.
• a compound to be a coordinate may be added to form a complex in the reaction system.
• the compound represented by the general formula (8) or (10) or the zinc complex having an imidazole-type ligand is preferable because it is more excellent in catalytic ability, and is represented by the general formula (10).
• Compounds or zinc complexes having an imidazole-type ligand are more preferable.
• examples of the inorganic titanium compound include titanium oxide, zinc hydroxide, titanium chloride and the like.
• examples of the organic titanium compound include compounds represented by any of the following general formulas (11) to (15).
• Ti (OR 13 ) 4 ... General formula (11) Ti (R 14 COH 2 COR 15 ) 4 ...
• General formula (12) Ti (OR 13 ) m (R 14 COCH 2 COR 15 ) n ...
• General formula (13) Ti (OR 13 ) m (R 16 COCH 2 COOR 17 ) n ...
• R 13 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms.
• R 14 , R 15 , R 16 and R 17 are independently aliphatic hydrocarbon groups having 1 to 10 carbon atoms. ]
• R 13 is an aliphatic hydrocarbon group having 1 to 20 carbon atoms. Among them, an aliphatic hydrocarbon group having 1 to 10 carbon atoms is preferable, and an aliphatic hydrocarbon group having 1 to 4 carbon atoms is more preferable, because it is more excellent in catalytic ability. Further, R 14 , R 15 , R 16 and R 17 are independently aliphatic hydrocarbon groups having 1 to 10 carbon atoms. Of these, an aliphatic hydrocarbon group having 1 to 4 carbon atoms is preferable because it is more excellent in catalytic ability.
• the compound represented by any of the general formulas (11) to (14) is preferable, and the compound represented by the general formula (14) is more preferable, because the titanium compound is more excellent in catalytic ability.
• examples of the inorganic iron compound include iron oxide, iron hydroxide, iron chloride and the like.
• examples of the organic iron compound include compounds represented by the following general formula (16).
• General formula (16) [In the above general formula (16), R 18 and R 19 are independently aliphatic hydrocarbon groups having 1 to 10 carbon atoms. ]
• R 18 and R 19 are independently aliphatic hydrocarbon groups having 1 to 10 carbon atoms. Of these, an aliphatic hydrocarbon group having 1 to 4 carbon atoms is preferable because it is more excellent in catalytic ability.
• the total mass of other metals in the other metal compound (B) is in the range of 10 to 80 parts by mass with respect to 100 parts by mass of the total mass of zirconium in the zirconium compound (A).
• the total mass of other metals in the other metal compound (B) is preferably in the range of 10 to 70 parts by mass with respect to 100 parts by mass of the total mass of zirconium in the zirconium compound (A). It is more preferably in the range of about 50 parts by mass.
• the urethanization reaction catalyst of the present invention has high catalytic ability regardless of the type of reaction raw material. Therefore, in the method for producing a urethane compound using the urethanization reaction catalyst of the present invention, the reaction raw materials are not particularly limited, and a wide variety of reaction raw materials can be used. Further, the urethanization reaction catalyst of the present invention can be widely used as a catalyst for any urethanization reaction.
• the urethane compound produced by using the urethanization reaction of the present invention is, for example, a curable urethane resin having a reactive group such as a polymerizable unsaturated bond, a two-component curable urethane resin having a hydroxyl group or an isocyanate group, and a high-grade urethane compound.
• a curable urethane resin having a reactive group such as a polymerizable unsaturated bond
• a two-component curable urethane resin having a hydroxyl group or an isocyanate group and a high-grade urethane compound.
• thermoplastic urethane resins having a molecular weight examples thereof include thermoplastic urethane resins having a molecular weight.
• reaction raw material examples include a polyisocyanate compound (X), an alcoholic hydroxyl group-containing compound (Y-1), and a phenolic hydroxyl group-containing compound (Y-2). ..
• the zirconium compound, zinc compound, and titanium compound which have been conventionally known as urethanization reaction catalysts, tend to have low catalytic activity, especially when the phenolic hydroxyl group-containing compound (Y-2) is used as a reaction raw material.
• the urethanization reaction catalyst of the present invention exhibits high catalytic ability even when the phenolic hydroxyl group-containing compound (Y-2) is used as a reaction raw material.
• the polyisocyanate compound (X) is an aliphatic diisocyanate compound such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate; Alicyclic diisocyanate compounds such as diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane diisocyanate; aromatic diisocyanates such as phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, naphthalenedi isocyanate and the like.
• Alicyclic diisocyanate compounds such as diisocyanate, isophorone diisocyanate, hydrogenated x
• R 20 is either a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms, respectively.
• Each of R 21 is an alkyl group having 1 to 4 carbon atoms independently, or a bond point connected to a structural site represented by the structural formula (1) via a methylene group marked with *.
• m is 0 or an integer of 1 to 3
• l is an integer of 1 or more.
• the alcoholic hydroxyl group-containing compound (Y-1) is, for example, a monool monomer, a diol monomer, a trifunctional or higher-functional polyol monomer, a polyolefin polyol compound, a polyether polyol compound, a polyester polyol compound, a lactone-modified polyol compound, or a polycarbonate polyol compound. And so on.
• the alcoholic hydroxyl group-containing compound (Y-1) may be used alone or in combination of two or more.
• the monool monomer is, for example, a lower alcohol compound such as methanol, ethanol, propanol, butanol, pentanol, hexanol; a higher alcohol compound such as lauryl alcohol, myristyl alcohol, stearyl alcohol, oleyl alcohol, linolyl alcohol; cyclohexanol and the like.
• a lower alcohol compound such as methanol, ethanol, propanol, butanol, pentanol, hexanol
• a higher alcohol compound such as lauryl alcohol, myristyl alcohol, stearyl alcohol, oleyl alcohol, linolyl alcohol
• cyclohexanol and the like examples thereof include monool compounds containing an alicyclic structure.
• the diol monomer is, for example, ethylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonane.
• Linear aliphatic diol compounds such as diol, 1,10-decanediol, 1,11-undecanediol, and 1,12-dodecanediol; propylene glycol, 2-methyl-1,3-propanediol, neopentyl glycol, 2-ethyl-1,3-propanediol, 2-methyl-1,4-butanediol, 2-ethyl-2-methyl-1,3-propanediol, 2-ethylbutane-14-butanediol, 2,3- Didimethyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2,4-dimethyl-1,5-pentanediol, 3,3-dimethylpentane-1,5-diol, 2,2- Diethyl-1,3-propanediol, 3-propylpentane-1,5-d
• trifunctional or higher functional polyol monomer examples include trifunctional or higher functional aliphatic polyol compounds such as trimethylolethane, trimethylolpropane, glycerin, hexanetriol, and pentaerythritol.
• polyolefin polyol compound examples include polyol compounds having a polyolefin structure and a polydiene structure. Specific examples thereof include polyethylene-based polyols, polypropylene-based polyols, polybutadiene polyols, hydrogenated polybutadiene polyols, polyisoprene polyols, hydrogenated polyisoprene polyols and the like.
• the molecular weight of the polyolefin polyol compound is not particularly limited, but in general, those having a number average molecular weight (Mn) in the range of 500 to 5,000 are widely used.
• the polyether polyol compound includes the diol monomer, a trifunctional or higher functional polyol monomer, and a cyclic ether compound such as ethylene oxide, propylene oxide, tetrahydrofuran, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, and allyl glycidyl ether. Examples thereof include those obtained by ring-opening polymerization with.
• the molecular weight of the polyether polyol compound is not particularly limited, but in general, those having a number average molecular weight (Mn) in the range of 500 to 5,000 are widely used.
• polyester polyol compound examples include those using the diol monomer, a trifunctional or higher functional polyol monomer, and a polybasic acid compound as reaction raw materials.
• the polybasic acid compound is, for example, an aliphatic dicarboxylic acid compound such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and Derivatives of these acid anhydrides, acid halides, alkyl esters, etc .; alicyclic dicarboxylic acid compounds such as trahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, and these acid anhydrides, acid halides, etc.
• alkyl esters such as alkyl esters; aromatic dicarboxylic acid compounds such as phthalic acid, isophthalic acid and terephthalic acid, and derivatives such as these acid anhydrides, acid halides and alkyl esters; Trifunctional or higher aliphatic polycarboxylic acid compounds, and derivatives such as these acid anhydrides, acid halides, and alkyl esters; trifunctional or higher functional alicyclic polycarboxylic acid compounds such as 1,2,4-cyclohexanetricarboxylic acid.
• polyester polyol compound is not particularly limited, but generally, a polyester polyol compound having a number average molecular weight (Mn) in the range of 500 to 5,000 is widely used.
• lactone-modified polyol compound examples include a ring-opening polymer of a lactone compound such as ⁇ -caprolactone and ⁇ -butyrolactone, and a polymer of the diol monomer or a trifunctional or higher functional polyol monomer and the lactone compound.
• the molecular weight of the lactone-modified polyol compound is not particularly limited, but in general, those having a number average molecular weight (Mn) in the range of 500 to 4,000 are widely used.
• polycarbonate polyol compound examples include those using the diol monomer, a trifunctional or higher functional polyol monomer, and a carbonylating agent as reaction raw materials.
• the carbonylating agent include phosgene, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate and the like.
• the molecular weight of the polycarbonate polyol compound is not particularly limited, but in general, those having a number average molecular weight (Mn) in the range of 500 to 5,000 are widely used.
• the phenolic hydroxyl group-containing compound (Y-2) is, for example, an aromatic monohydroxy compound, an aromatic dihydroxy compound, a trifunctional or higher functional aromatic polyhydroxy compound, a phenol resin, a polyether polyol compound, a polyester polyol compound, or a polycarbonate polyol. Examples include compounds.
• the phenolic hydroxyl group-containing compound (Y-2) may be used alone or in combination of two or more.
• aromatic monohydroxy compound examples include phenol, cresol, xylenol, trimethylphenol, ethylphenol, propylphenol, butylphenol, pentylphenol, hexylphenol, octylphenol, nonylphenol, and naphthol.
• the pre-aromatic dihydroxy compound is, for example, dihydroxybenzene, dihydroxynaphthalene, biphenol, tetramethylbiphenol, bisphenol A, bisphenol F. , Bisphenol S and the like.
• trifunctional or higher functional aromatic polyhydroxy compound examples include trihydroxybenzene, trihydroxynaphthalene, trihydroxytriphenylmethane, and trihydroxytriphenylethane.
• the phenolic resin may be, for example, various novolak resins made from one or more of the aromatic monohydroxy compound, the aromatic dihydroxy compound, and the trifunctional or higher functional aromatic polyhydroxy compound, and dicyclopentadiene. Examples thereof include a phenol-added resin, a phenol aralkyl resin, a naphthol aralkyl resin, and a triphenol methane type resin.
• the molecular weight of the raphenol resin is not particularly limited, but generally, a raphenol resin having a number average molecular weight (Mn) in the range of 300 to 3,000 is widely used.
• the polyether polyol compound may be, for example, one or more of the aromatic monohydroxy compound, the aromatic dihydroxy compound, and the trifunctional or higher functional aromatic polyhydroxy compound, and ethylene oxide, propylene oxide, tetrahydrofuran, and ethyl glycidyl ether. , Ppropylglycidyl ether, butyl glycidyl ether, phenyl glycidyl ether, allyl glycidyl ether and the like obtained by ring-opening polymerization with a cyclic ether compound.
• the molecular weight of the polyether polyol compound is not particularly limited, but in general, those having a number average molecular weight (Mn) in the range of 500 to 5,000 are widely used.
• the polyester polyol compound is, for example, one or a plurality of the aromatic monohydroxy compound, the aromatic dihydroxy compound, the trifunctional or higher functional aromatic polyhydroxy compound, and a polybasic acid compound as a reaction raw material.
• the polybasic acid compound is, for example, an aliphatic dicarboxylic acid compound such as oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacic acid, and Derivatives of these acid anhydrides, acid halides, alkyl esters, etc .; alicyclic dicarboxylic acid compounds such as trahydrophthalic acid, hexahydrophthalic acid, methyltetrahydrophthalic acid, and these acid anhydrides, acid halides, etc.
• alkyl esters such as alkyl esters; aromatic dicarboxylic acid compounds such as phthalic acid, isophthalic acid and terephthalic acid, and derivatives such as these acid anhydrides, acid halides and alkyl esters; Trifunctional or higher aliphatic polycarboxylic acid compounds, and derivatives such as these acid anhydrides, acid halides, and alkyl esters; trifunctional or higher functional alicyclic polycarboxylic acid compounds such as 1,2,4-cyclohexanetricarboxylic acid.
• polyester polyol compound is not particularly limited, but generally, a polyester polyol compound having a number average molecular weight (Mn) in the range of 500 to 5,000 is widely used.
• the polycarbonate polyol compound may be, for example, one or a plurality of the aromatic monohydroxy compound, the aromatic dihydroxy compound, the trifunctional or higher functional aromatic polyhydroxy compound, and a carbonylating agent as a reaction raw material.
• a carbonylating agent include phosgene, ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, diphenyl carbonate and the like.
• the molecular weight of the polycarbonate polyol compound is not particularly limited, but in general, those having a number average molecular weight (Mn) in the range of 500 to 5,000 are widely used.
• the urethanization catalyst of the present invention can be used in the same manner as the conventionally known urethanization catalyst, and the urethanization reaction using the urethanization catalyst of the present invention can be carried out under the same conditions as the general urethanization reaction. can. Specific examples thereof include a method in which the reaction raw material is heated to about 40 to 160 ° C. and reacted for about 1 to 20 hours.
• the addition amount of the urethanization catalyst of the present invention is preferably in the range of 0.01 to 0.09% by mass with respect to the total mass of the reaction raw materials of the urethane compound, and is 0. It is preferably in the range of 0.03 to 0.07% by mass.
• the urethane compound may be produced in a solvent if necessary.
• the solvent used here is, for example, a polar organic solvent such as dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, dimethylsulfoxide, sulfolane, ⁇ -butyrolactone; ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether and the like.
• Ethylene glycol dialkyl ethers Diethylene glycol dialkyl ethers such as diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol dibutyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, triethylene glycol dibutyl ether; ethylene glycol monomethyl ether acetate, ethylene glycol Ethylene glycol monoalkyl ether acetates such as monoethyl ether acetate and ethylene glycol monobutyl ether acetate; diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate , Polyethylene glycol monoalkyl ether acetates such as triethylene glycol monobutyl ether acetate; propylene glycol dialkyl ether
• Glycol monoalkyl ether acetates dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monobutyl ether acetate, tripropylene glyco Polypropylene glycol monoalkyl ether acetates such as lumonomethyl ether acetate, tripropylene glycol monoethyl ether acetate, tripropylene glycol monobutyl ether acetate; dialkyl ethers of copolymerized polyether glycols such as low molecular weight ethylene-propylene copolymer; Monoacetate monoalkyl ethers of copolymerized polyether glycols; alkyl esters of copolymerized polyether glycols; and monoalkyl esters of copolymerized polyether glycols Monoalkyl ethers; esters such as ethyl acetate and butyl acetate; acetone, Ketones
• the molar ratio of the isocyanate group to the hydroxyl group in the reaction raw material is appropriately adjusted according to the desired performance of the obtained urethane compound, the application, etc., but is generally (isocyanate group).
• the molar ratio) / (molar ratio of hydroxyl groups) 1 / 0.95 to 1 / 5.0 is preferable.
• the order of charging the reaction raw materials of the urethane compound is as follows, depending on the desired performance of the obtained urethane compound, the application, etc. Can be mentioned.
• the urethanization catalyst of the present invention exhibits higher catalytic ability than the conventionally known urethanization catalyst, particularly when the phenolic hydroxyl group-containing compound (Y-2) is used as a reaction raw material.
• the polyisocyanate compound (X) is reacted with the alcoholic hydroxyl group-containing compound (Y-1) to obtain an isocyanate group-containing intermediate.
• Step 1 a method for producing a urethane compound (hereinafter abbreviated as production method (1)) in which the intermediate is reacted with the phenolic hydroxyl group-containing compound (Y-2) (step 2) can be mentioned.
• the entire amount of the urethanization catalyst may be added in the first step, or may be added in portions in a plurality of steps. ..
• the amount of the urethanization catalyst added is preferably in the range of 0.01 to 0.09% by mass, preferably 0.03 to 0.09% by mass, based on the total mass of the reaction raw materials of the urethane compound, as described above. It is preferably in the range of 0.07% by mass.
• the reaction ratio between the polyisocyanate compound (X) and the alcoholic hydroxyl group-containing compound (Y-1) is the reaction ratio of the alcoholic hydroxyl group-containing compound (Y-1) in the alcoholic hydroxyl group-containing compound (Y-1).
• the condition may be such that the isocyanate group in the polyisocyanate compound (X) is excessive with respect to the hydroxyl group, and the specific ratio is appropriately adjusted according to the desired performance of the obtained urethane compound, application, and the like. ..
• the polyisocyanate compound (X) is compared with 1 mol of the hydroxyl group in the alcoholic hydroxyl group-containing compound (Y-1). ) Is preferably in a proportion of 1.2 to 2.3 mol of isocyanate groups.
• the reaction temperature in the step 1 is appropriately changed depending on the types of the polyisocyanate compound (X) and the alcoholic hydroxyl group-containing compound (Y-1) to be used, but since the reaction proceeds efficiently, 40
• the temperature is preferably in the range of -80 ° C.
• the reaction time is preferably in the range of 1 to 10 hours, more preferably in the range of 1 to 6 hours.
• step 2 of the production method (1) the reaction ratio between the intermediate obtained in step 1 and the phenolic hydroxyl group-containing compound (Y-2) is determined by the desired performance of the obtained urethane compound, applications, and the like. It is adjusted appropriately according to. Above all, since the obtained urethane compound is excellent in the cured material properties when used for a curable composition, the phenolic hydroxyl group-containing compound (Y-2) contains 1 mol of the isocyanate group in the intermediate. The ratio of hydroxyl groups is preferably 2.0 to 7.0 mol.
• the reaction temperature in the step 1 is appropriately changed depending on the type of the polyisocyanate compound (X), the alcoholic hydroxyl group-containing compound (Y-1), the phenolic hydroxyl group-containing compound (Y-2), and the like. Since the reaction proceeds efficiently, the temperature is preferably in the range of 100 to 160 ° C. The reaction time is preferably in the range of 1 to 10 hours.
• the specific structure, molecular weight, etc. of the urethane compound obtained by the production method (1) are appropriately adjusted according to the type of reaction raw material, desired performance of the urethane compound, application, and the like.
• the weight average molecular weight (Mw) is preferably in the range of 5,000 to 50,000 because the obtained urethane compound is excellent in the cured physical properties when used for a curable composition.
• the weight average molecular weight (Mw) of the urethane compound is measured by gel permeation chromatography (GPC) under the measurement conditions described in Examples.
• the urethane compound obtained by using the urethanization reaction catalyst of the present invention can be used for various purposes like a general urethane compound.
• the urethane compound (or urethane resin) obtained by using the phenolic hydroxyl group-containing compound (Y-2) as the reaction raw material of the urethane compound the urethane bond between the phenolic hydroxyl group and the isocyanate group is dissociated under high temperature conditions. Therefore, it can be used as a curable composition by combining with a compound capable of reacting with a phenolic hydroxyl group or an isocyanate group.
• An epoxy resin is mentioned as an example of a compound that can react with the phenolic hydroxyl group or the isocyanate group.
• the epoxy resin may have any specific structure and may be used without particular limitation.
• phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol novolak type epoxy resin, biphenol novolak type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin examples thereof include a triphenol methane type epoxy resin, a tetraphenol ethane type epoxy resin, a dicyclopentadiene-phenol addition reaction type epoxy resin, a phenol aralkyl type epoxy resin, and a naphthol aralkyl type epoxy resin.
• the blending ratio of the urethane compound and the epoxy resin is appropriately adjusted according to the desired cured physical properties and the like.
• the epoxy resin is in the range of 10 to 1000 parts by mass with respect to 100 parts by mass of the urethane compound.
• the curable composition may contain other compounds or resin components, and various additives such as a curing accelerator, a solvent, a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, and an emulsifier, if necessary. May be contained.
• various additives such as a curing accelerator, a solvent, a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, and an emulsifier, if necessary. May be contained.
• binder resins such as polyester resin, phenoxy resin, PPS resin, PPE resin, and polyarylane resin; phenol resin, melamine resin, alkoxysilane-based curing agent, polybasic acid anhydride, cyanate compound, and the like. Examples thereof include reactive compounds of.
• the curing accelerator examples include a urethanization reaction catalyst of the present invention, a phosphorus compound such as triphenylphosphine, and a tertiary amine such as 1,8-diazabicyclo- [5.4.0] -undecene (DBU).
• a phosphorus compound such as triphenylphosphine
• a tertiary amine such as 1,8-diazabicyclo- [5.4.0] -undecene (DBU).
• DBU 1,8-diazabicyclo- [5.4.0] -undecene
• Examples thereof include imidazole compounds, pyridine compounds such as 4-dimethylaminopyridine, organic acid metal salts, Lewis acids, amine complex salts and the like.
• One type of these high-acceleration agents may be used alone, or two or more types may be used in combination.
• the amount of these curing accelerators added is preferably in the range of 0.001 to 5% by mass with
• the solvent examples include various solvents exemplified as the reaction solvent of the production method (1).
• the amount of the solvent used is preferably such that the non-volatile content of the curable composition is 10 to 80% by mass.
• the curable composition can be heated to obtain a cured product.
• the heating temperature is preferably in the range of 150 to 220 ° C.
• a heat-drying time for drying the solvent may be provided in advance. The temperature for heating and drying is appropriately adjusted depending on the solvent used, but is preferably in the range of 50 to 120 ° C.
• the use of the curable composition is not limited, and it can be used in the same manner as a general thermosetting resin material.
• the urethane compound obtained by the production method (1) has flexibility or toughness as a urethane resin and heat resistance due to the phenolic hydroxyl group-containing compound (Y-2), and thus is particularly an electronic material. It can be suitably used for heat-resistant materials and the like.
• Isocyanate group content [mass%] 42.02 x (V1-V2) x 0.0005 x 100/2 (Explanation of symbols and numbers in the formula)
• V1 Titration of hydrochloric acid when measured with a blank without adding urethane prepolymer [ml] 0.0005: Hydrochloric acid concentration [mol / ml] 42.02: Molecular weight of isocyanate group [g / mol]
• IR infrared absorption spectrum
• Example 1 Production of Urethane Resin (1) (Step 1) Propylene glycol monomethyl ether acetate 283.9 g, isophorone diisocyanate 23.6 g (0.106 mol), polybutadiene diol (0.106 mol) in a flask equipped with a stirrer, a thermometer, and a condenser.
• Step 2 Next, the reaction solution was heated to 80 ° C., and 75.3 g (0.113 mol) of orthocresol novolak resin (weight average molecular weight 668) was added. After raising the temperature to 140 ° C., the mixture was stirred for 4 hours, and it was confirmed that the increase in viscosity had subsided to obtain a urethane resin (1).
• the ratio of the total mass of zinc in the zinc complex to the total mass of zirconium in zirconium dibutoxybis (ethylacetoacetate) was 31%.
• Example 2 Production of Urethane Resin (2) (Step 1) In a flask equipped with a stirrer, a thermometer, and a condenser, 283.9 g of propylene glycol monomethyl ether acetate, 23.6 g (0.106 mol) of isophorone diisocyanate, and polybutadiene diol (.
• Step 2 Next, the reaction solution was heated to 80 ° C., and 75.3 g (0.113 mol) of orthocresol novolak resin (weight average molecular weight 668) was added. After raising the temperature to 140 ° C., the mixture was stirred for 7 hours, and it was confirmed that the increase in viscosity had subsided to obtain a urethane resin (2).
• the ratio of the total mass of titanium in titanium diisopropoxybis (ethylacetate acetate) to the total mass of zirconium in zirconium dibutoxybis (ethylacetate acetate) was 25%.
• Example 3 Production of Urethane Resin (3) (Step 1) In a flask equipped with a stirrer, a thermometer, and a condenser, 283.9 g of propylene glycol monomethyl ether acetate, 23.6 g (0.106 mol) of isophoron diisocyanate, and polybutadiene diol (.
• Step 2 Next, the reaction solution was heated to 80 ° C., and 75.3 g (0.113 mol) of orthocresol novolak resin (weight average molecular weight 668) was added. After raising the temperature to 140 ° C., the mixture was stirred for 6 hours, and it was confirmed that the increase in viscosity had subsided to obtain a urethane resin (3).
• the ratio of the total mass of iron in iron (III) acetylacetonate to the total mass of zirconium in zirconium tetraacetylacetonate was 23%.
• Example 4 Production of Urethane Resin (4) (Step 1) In a flask equipped with a stirrer, a thermometer, and a condenser, 283.9 g of propylene glycol monomethyl ether acetate, 23.6 g (0.106 mol) of isophorone diisocyanate, and polybutadiene diol (.
• Step 2 Next, the reaction solution was heated to 80 ° C., and 75.3 g (0.113 mol) of orthocresol novolak resin (weight average molecular weight 668) was added. After raising the temperature to 140 ° C., the mixture was stirred for 5 hours, and it was confirmed that the increase in viscosity had subsided to obtain a urethane resin (4).
• the ratio of the total mass of zinc in zinc 2-ethylhexanoate to the total mass of zirconium in zirconium tetraacetylacetonate was 20%.
• Step 2 After raising the temperature to 60 ° C., the mixture was stirred for 4 hours to obtain a urethane prepolymer (1') having an isocyanate group.
• the isocyanate group content of the urethane prepolymer (1') was 0.940% by mass.
• Step 2 Next, the reaction solution was heated to 80 ° C., and 75.3 g (0.113 mol) of orthocresol novolak resin (weight average molecular weight 668) was added. After raising the temperature to 140 ° C., the mixture was stirred for 11 hours, and it was confirmed that the increase in viscosity had subsided, and a urethane resin (1') was obtained.
• Step 2 After raising the temperature to 60 ° C., the mixture was stirred for 4 hours to obtain a urethane prepolymer (2') having an isocyanate group.
• the isocyanate group content of the urethane prepolymer (2') was 0.962% by mass.
• Step 2 Next, the reaction solution was heated to 80 ° C., and 75.3 g (0.113 mol) of orthocresol novolak resin (weight average molecular weight 668) was added. After raising the temperature to 140 ° C., the mixture was stirred for 11 hours, and it was confirmed that the increase in viscosity had subsided, and a urethane resin (2') was obtained.
• Step 2 After raising the temperature to 60 ° C., the mixture was stirred for 4 hours to obtain a urethane prepolymer (3') having an isocyanate group.
• the isocyanate group content of the urethane prepolymer (3') was 1.455% by mass.
• Step 2 Next, the reaction solution was heated to 80 ° C., and 75.3 g (0.113 mol) of orthocresol novolak resin (weight average molecular weight 668) was added. After raising the temperature to 140 ° C., the mixture was stirred for 11 hours, and it was confirmed that the increase in viscosity had subsided, and a urethane resin (3') was obtained.
• Step 2 After raising the temperature to 60 ° C., the mixture was stirred for 4 hours to obtain a urethane prepolymer (4') having an isocyanate group.
• the isocyanate group content of the urethane prepolymer (4') was 1.576% by mass.
• Step 2 Next, the reaction solution was heated to 80 ° C., and 75.3 g (0.113 mol) of orthocresol novolak resin (weight average molecular weight 668) was added. After raising the temperature to 140 ° C., the mixture was stirred for 11 hours, and it was confirmed that the increase in viscosity had subsided, and a urethane resin (4') was obtained.
• reaction time during urethane resin production and evaluation of residual isocyanate groups For Examples 1 to 4 and Comparative Examples 1 to 4, the reaction time (reaction time in step 2) required to produce urethane resin from urethane prepolymer is shown. I summarized it in 1. Further, it was confirmed by the infrared absorption spectrum measured under the above conditions whether or not the isocyanate group remained in the obtained urethane resin.

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