Method for producing unsaturated urethane compounds

Abstract

To provide a method for producing unsaturated urethane compound under a normal reaction condition (reaction temperature, catalyst addition amount, etc.) without using an organic tin catalyst but using a catalyst having excellent reaction activity.SOLUTION: When producing an unsaturated urethane compound by reacting an alcohol compound with an isocyanate compound, by using an organic salt or complex of at least one metal element selected from the 1st to 3rd transition elements and the 13th to 15th group elements (excluding tin) as a catalyst, an urethane compound of good quality can efficiently be produced.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing an unsaturated urethane compound using an organic salt or complex of a specific metal element as a catalyst. [Background technology]

[0002] Urethane compounds having unsaturated bonds between carbon atoms (unsaturated urethane compounds) are widely used as raw materials for curable resin compositions because they have unsaturated groups between carbon atoms and a variety of skeletal structures of urethane compounds. In particular, when used in photocurable resin compositions, they can easily impart various properties to the cured product, such as flexibility, bendability, pliability, toughness, solvent resistance, and abrasion resistance, and are therefore widely used in a variety of fields, including adhesives, coatings, and inks.

[0003] Such unsaturated urethane compounds are usually synthesized by reacting a polyol with a polyisocyanate to obtain a polyurethane having hydroxyl groups or isocyanate groups at both ends, and then further reacting each of these with a hydroxyl group-containing unsaturated compound or an isocyanate group-containing unsaturated compound (Patent Documents 1 to 3).

[0004] Organotin compounds such as dibutyltin dilaurate and tertiary amines are often used as catalysts in the urethane reaction between isocyanate groups and hydroxyl groups. However, in the multi-step reactions often used in the synthesis of unsaturated urethane compounds, tertiary amines are not suitable due to their low catalytic activity. Organotin compounds, while showing good catalytic activity, are considered problematic as endocrine disruptors, and restrictions on their use have been accelerating in recent years.

[0005] Therefore, various new organometallic compounds have been investigated as urethane-forming catalysts as alternatives to organotin compounds. For example, when a urethane acrylate is synthesized in the presence of a zinc compound, and a curable composition composed of the resulting urethane acrylate and a hydroxyl group-containing acrylate is prepared, the inclusion of a zinc compound can suppress the viscosity loss (decrease in viscosity over time) of the composition, which occurs with tin catalysts (Patent Document 4). Furthermore, a zinc complex or its salt has been proposed as a new tin-free catalyst for producing polyurethane (Patent Document 5). However, these zinc catalysts have lower activity than conventional tin catalysts, and under normal conditions, the reaction proceeds extremely slowly. Even when the catalyst amount is increased by up to three times, the urethane-forming reaction does not reach completion, and the reaction product becomes discolored. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2010-267703 [Patent Document 2] WO2015 / 141537 publication [Patent Document 3] WO2017 / 047615 publication [Patent Document 4] Japanese Patent Application Laid-Open No. 2010-215774 [Patent Document 5] Special Publication No. 2012-511056 Summary of the Invention [Problem to be solved by the invention]

[0007] The present invention aims to provide a method for producing an unsaturated urethane compound under normal reaction conditions (reaction temperature, catalyst addition amount, etc.) using a catalyst with excellent reaction activity, without using an organotin catalyst. Another object of the present invention is to provide a method for producing an unsaturated urethane compound with good color and quality, using the catalyst, without causing problems with temperature control. [Means for solving the problem]

[0008] As a result of extensive research to solve the above problems, the present inventors have found that when an unsaturated urethane compound is produced by reacting an alcohol compound with an isocyanate compound, by using an organic salt or complex of at least one metal element selected from the group consisting of the 1st to 3rd transition elements and the 13th to 15th group elements (excluding tin) as a catalyst, an unsaturated urethane compound of good quality can be produced efficiently, leading to the completion of the present invention.

[0009] That is, the present invention (1) A method for producing an unsaturated urethane compound having an unsaturated bond between carbon atoms, comprising reacting an alcohol compound (A) with an isocyanate compound (B) in the presence of a catalyst (C), which is an organic salt or complex of at least one metal element selected from the group consisting of transition metals of groups 1 to 3 and elements of groups 13 to 15 (excluding tin); (2) A method for producing an unsaturated urethane compound according to (1) above, characterized in that the alcohol compound (A) is an alcohol compound (a1) having an unsaturated bond between carbon atoms and / or a polyol (a2) having two or more hydroxyl groups, the isocyanate compound (B) is an isocyanate compound (b1) having an unsaturated bond between carbon atoms and / or a polyisocyanate (b2) having two or more isocyanate groups, and the molar ratio of hydroxyl groups (OH) to isocyanate groups (NCO) is 0.9 to 1.1; (3) The method for producing an unsaturated urethane compound according to (1) or (2), wherein the unsaturated bond is one or more unsaturated bonds selected from the group consisting of a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, a (meth)allyl ether group, and a maleimide group. (4) The method for producing an unsaturated urethane compound according to any one of (1) to (3), wherein the catalyst (C) is an organic salt or complex of at least one metal element selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, aluminum, gallium, indium, thallium, lead, and bismuth; (5) A method for producing an unsaturated urethane compound according to any one of (1) to (4), characterized in that at least one of the alcohol compound (A), the isocyanate compound (B), and the catalyst (C) has an ether bond and / or an amide bond. (6) A method for producing an unsaturated urethane compound according to any one of (1) to (5) above, further comprising a compound (D) having an ether bond and / or an amide bond. (7) The method for producing an unsaturated urethane compound according to any one of (1) to (6), wherein the compound (D) is an aliphatic, alicyclic, or aromatic compound having no active hydrogen. (8) The method for producing an unsaturated urethane compound according to any one of (1) to (7), wherein the amount of the catalyst (C) blended is 0.001 to 5.0% (mass ratio) based on the total amount of the alcohol compound (A) and the isocyanate compound (B). (9) The method for producing an unsaturated urethane compound according to any one of (1) to (8), wherein the compound (D) is blended in an amount of 1 to 200% (mass ratio) based on the total amount of the alcohol compound (A) and the isocyanate compound (B). This provides: [Effects of the Invention]

[0010] According to the present invention, when an alcohol compound and an isocyanate compound are reacted to produce an unsaturated urethane compound having an unsaturated bond between carbon atoms, an organic salt or complex of at least one metal element selected from the group consisting of transition elements (1-3) and elements (13-15) of groups excluding tin is used as a catalyst, thereby enabling the efficient production of an unsaturated urethane compound under normal reaction conditions without using an organotin catalyst. Furthermore, the use of this novel catalyst makes it easy to control the reaction temperature, and enables the production of an unsaturated urethane compound with good color and quality.

[0011] The present invention will be described in detail below. The method for producing an unsaturated urethane compound of the present invention is characterized by reacting an alcohol compound (A) with an isocyanate compound (B) in the presence of a catalyst (C), which is an organic salt or complex of at least one metal element selected from the group consisting of transition metals of groups 1 to 3 and elements of groups 13 to 15 (excluding tin). Each component of the production method of the present invention will be described below.

[0012] The alcohol compound (A) used in the present invention is preferably an alcohol compound (a1) having an unsaturated bond between carbon atoms and / or a polyol (a2) having two or more hydroxyl groups.More preferably, the alcohol compound (a1) contains one or more unsaturated bonds selected from the group consisting of a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, a (meth)allyl ether group, and a maleimide group.

[0013] Examples of (a1) include hydroxyalkyl(meth)acrylates, hydroxyalkyl(meth)acrylamides, hydroxyalkyl vinyl ethers, hydroxyalkyl(methyl)vinyl ethers, hydroxyalkyl(meth)allyl ethers, and hydroxyalkylmaleimides, each of which has a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms; polyalkylene glycol(meth)acrylates, polyalkylene glycol(meth)acrylamides, polyalkylene glycol vinyl ethers, polyalkylene glycol(methyl)vinyl ethers, polyalkylene glycol(meth)allyl ethers, and polyalkylene glycol maleimides, each of which has an alkylene glycol having 1 to 9 carbon atoms and 1 to 23 repeating units; and the above-mentioned (meth)acrylic Examples of (a1) include N-alkyl(hydroxyalkyl)(meth)acrylamides, N-alkyl(polyalkylene glycol)(meth)acrylamides, and N-alkyl(hydroxyphenyl)(meth)acrylamides, in which a linear, branched, or cyclic alkyl or alkylene group having 1 to 8 carbon atoms has been introduced to the nitrogen atom of an amide monomer, as well as hydroxyphenyl(meth)acrylate, hydroxyphenyl(meth)acrylamide, hydroxyphenyl vinyl ether, hydroxyphenyl(methyl)vinyl ether, hydroxyphenyl(meth)allyl ether, and hydroxyphenylmaleimide. Among these, hydroxyalkyl(meth)acrylate and hydroxyalkyl(meth)acrylamide are preferred because they improve the polymerizability of the unsaturated urethane compound. These (a1)s can be used alone or in combination of two or more.

[0014] (a2) is preferably an alkylene polyol, polyether polyol, polyester polyol, polycarbonate polyol, hydrogenated polyalkadiene polyol, polyalkadiene polyol, or polyol having a silicone skeleton, having two or more hydroxyl groups in the molecule, and among these, an alkylene diol, polyether diol, polyester diol, polycarbonate diol, hydrogenated polyalkadiene diol, polyalkadiene diol, or polyol having a silicone skeleton, having two hydroxyl groups in the molecule, is more preferred. These (a2) can be used alone or in combination of two or more.

[0015] Examples of alkylene polyols include linear, branched, and cyclic alkylene diols, alkylene triols, and alkylene tetraols having 2 to 18 carbon atoms, and specific examples thereof include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, neopentyl glycol, 1,4-butanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,10-decanediol, 1,18-octadecanediol, glycerin, trimethylolpropane, and pentaerythritol.

[0016] Examples of polyether polyols include linear, branched, and cyclic polyalkylene glycols having 2 to 18 carbon atoms, and specific examples thereof include polyethylene glycol, glycerin tri(polyoxyethylene) ether, trimethylolpropane tri(polyoxyethylene) ether, pentaerythritol tetra(polyoxyethylene) ether, poly(oxy-1,3-propylene) glycol, glycerin tri(polyoxy-1,3-propylene) ether, trimethylolpropane tri(polyoxy-1,3-propylene) ether, and pentaerythritol tetra(polyoxyethylene) ether.

[0033] Examples of alkylene glycols include poly(oxy-1,3-propylene) ether, poly(oxy-1,2-propylene) glycol, glycerin tri(polyoxy-1,2-propylene) ether, trimethylolpropane tri(polyoxy-1,2-propylene) ether, pentaerythritol tetra(polyoxy-1,2-propylene) ether, poly(oxy-1,4-butylene) glycol, poly(oxy-1,5-pentylene) glycol, poly(oxy-3-methyl-1,5-pentylene) glycol, and poly(oxy-1,6-hexylene) glycol.

[0017] The polyester polyol is composed of a polycarboxylic acid and a polyol, contains a polyester skeleton in the molecule, and has a hydroxyl group at the end. Examples of the polycarboxylic acid component include phthalic acid, tetrahydrophthalic acid, terephthalic acid, isophthalic acid, 1,2-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, succinic acid, maleic acid, fumaric acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,2,4-butanetricarboxylic acid, hemimellitic acid, trimellitic acid, trimesic acid, cyclohexanetricarboxylic acid, pyromellitic acid, and cyclohexanetetracarboxylic acid. Examples of the polyol component include the alkylene polyols described in the above paragraph

[0015] .

[0018] The polycarbonate polyols include those composed of a carbonyl component and a polyol, containing a carbonate skeleton in the molecule, and having hydroxyl groups at the terminals. Examples of the carbonyl component include phosgene, chloroformate, dialkyl carbonate, diaryl carbonate, and alkylene carbonate, and examples of the polyol component include the alkylene polyols described in the above paragraph

[0015] .

[0019] Examples of hydrogenated polyalkadiene polyols include 1,2-hydrogenated polybutadiene diol, 1,4-hydrogenated polybutadiene diol, and hydrogenated polyisoprene polyol, and examples of polyalkadiene polyols include 1,2-polybutadiene diol, 1,4-polybutadiene diol, and polyisoprene polyol.

[0020] The polyol having a silicone skeleton is one that contains a siloxane bond in the main skeleton of the molecule and has two or more hydroxyl groups at both ends or on the side chain, and examples thereof include carbinol-modified silicones with side chain introduction, carbinol-modified silicones with both ends introduction, and carbinol-modified silicones with side chain and both ends introduction.

[0021] The isocyanate compound (B) used in the present invention is preferably an isocyanate compound (b1) having an unsaturated bond between carbon atoms and / or a polyisocyanate (b2) having two or more isocyanate groups.More preferably, the isocyanate compound (b1) contains one or more unsaturated bonds selected from the group consisting of a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, a (meth)allyl ether group, and a maleimide group.

[0022] Examples of (b1) include isocyanatoalkyl(meth)acrylates, isocyanatoalkyl(meth)acrylamides, isocyanatoalkylvinyl ethers, isocyanatoalkyl(methyl)vinyl ethers, isocyanatoalkyl(meth)allyl ethers, isocyanatoalkylmaleimides, isocyanatoalkoxyalkyl(meth)acrylates, isocyanatoalkoxyalkyl(meth)acrylamides, isocyanatoalkoxyalkylvinyl ethers, isocyanatoalkoxyalkyl(methyl)vinyl ethers, isocyanatoalkoxyalkyl(meth)allyl ethers, isocyanatoalkoxyalkylmaleimides, and the (meth)acrylamide-based monomers each having a linear, branched, or cyclic alkylene group having 1 to 18 carbon atoms introduced therein; Examples of (b1) include N-alkyl(isocyanatoalkyl)(meth)acrylamides, N-alkyl(isocyanatoalkoxyalkyl)(meth)acrylamides, and N-alkyl(isocyanatophenyl)(meth)acrylamides, each of which has a linear, branched, or cyclic alkyl or alkylene group of 1 to 8 introduced therein, as well as isocyanatophenyl(meth)acrylate, isocyanatophenyl(meth)acrylamide, isocyanatophenylvinyl ether, isocyanatophenyl(methyl)vinyl ether, isocyanatophenyl(meth)allyl ether, and isocyanatophenylmaleimide. Among these, isocyanatoalkyl(meth)acrylate and isocyanatoalkyl(meth)acrylamide are preferred because they improve the polymerizability of the unsaturated urethane compound. These (b1)s can be used alone or in combination of two or more.

[0023] Examples of (b2) include aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate; 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and 4, Examples of the diisocyanates include aromatic diisocyanates such as 4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, and xylylene diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, methylcyclohexylene diisocyanate, 2,5-norbornane diisocyanate, 2,6-norbornane diisocyanate, and 1,3-bis(isocyanatomethyl)cyclohexane, as well as adduct types, isocyanurate types, and biuret types thereof. These may be used alone or in combination of two or more.

[0024] When obtaining an unsaturated urethane compound by the production method of the present invention, the combination of the alcohol compound (A) and the isocyanate compound (B) can be any combination, but since the unsaturated urethane compound contains an unsaturated bond between carbon atoms, at least one of (A) and (B) has an unsaturated bond. Specifically, the method is characterized by containing an alcohol compound (a1) having an unsaturated bond and / or an isocyanate compound (b1) having an unsaturated bond. Furthermore, it is preferable to contain a polyol (a2) having two or more hydroxyl groups and a polyisocyanate (b2) having two or more isocyanate groups, because the molecular weight of the obtained unsaturated urethane compound can be adjusted as desired by changing the ratio of (a2) to (b2).

[0025] The combination of the alcohol compound (A) and the isocyanate compound (B) is arbitrary, but the molar ratio calculated from the total (moles) of hydroxyl groups contained in the alcohol compound (a1) having an unsaturated bond and / or the polyol (a2) having two or more hydroxyl groups and the total (moles) of isocyanate groups contained in the isocyanate compound (b1) having an unsaturated bond and / or the polyisocyanate (b2) having two or more isocyanate groups is preferably hydroxyl groups (OH) / isocyanate groups (NCO) = 0.9 to 1.1, and more preferably hydroxyl groups (OH) / isocyanate groups (NCO) = 1.0 to 1.1, in which the hydroxyl groups are in excess of the isocyanate groups, because remaining isocyanate groups in the resulting unsaturated urethane compound can cause instability by reacting with moisture in the air.

[0026] The catalyst (C) used in the present invention is an organic salt or complex of at least one metal element selected from the group consisting of transition metals 1 to 3 and elements of groups 13 to 15 (excluding tin). Specifically, it is preferably an organic salt or complex of at least one metal element selected from scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, yttrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, aluminum, gallium, indium, thallium, lead, and bismuth. Among these, titanium, iron, zirconium, hafnium, aluminum and bismuth are more preferable, and iron, zirconium and bismuth are particularly preferable.

[0027] Preferred examples of the organic salt of a metal element include salts of organic acids and metals, salts of organic acids and metal oxides, salts of organic acids and alkyl metals, and salts of organic acids and alkoxy metals. Examples of the organic acid include linear, branched, and cyclic alkylcarboxylic acids having 1 to 18 carbon atoms, formic acid, dodecylbenzenesulfonic acid, maleic acid, fumaric acid, lactic acid, oxalic acid, naphthenic acid, tartaric acid, citric acid, oleic acid, (meth)acrylic acid, pyridine-2-carboxylic acid, trifluoroacetic acid, and trifluoromethanesulfonic acid. In view of exhibiting good catalytic activity, organic salts of titanium, iron, zirconium, and bismuth are preferred, and examples thereof include iron(II) bis(acetate), iron(III) tris(2-ethylhexanoate), iron(II) bis(stearate), iron(III) tris(stearate), diisopropoxytitanium bis(dodecylbenzenesulfonate), zirconium tetrakis(2-ethylhexanoate), zirconium tetrakis(stearic acid), bismuth tris(2-ethylhexanoate), and bismuth tris(neodecanoate), with iron tris(stearate), bismuth tris(2-ethylhexanoate), bismuth tris(neodecanoate), zirconium tetrakis(2-ethylhexanoate), and zirconium tetrakis(stearic acid) being more preferred due to their low colorability.

[0028] The complex of the metal element is preferably a complex of a metal element, a complex of a metal oxide, a complex of an alkyl metal, a complex of an alkoxy metal, a complex of a metal halide, or the like. Specifically, an acetylacetonate complex, an ethylacetoacetate complex, a dimethoxyethane complex, a tetrahydrofuran complex, a 2,2,6,6-tetramethyl-3,5-heptanedionato complex, a trifluoroacetylacetonate complex, a hexafluoroacetylacetonate complex, a cyclopentadienyl complex, a pentafluorocyclopentadienyl complex, or the like is preferred. In terms of exhibiting good catalytic activity, complexes with titanium, iron, zirconium, hafnium, aluminum, or bismuth are preferred, and diisopropoxybis(ethylacetoacetate)titanium, tetrakis(acetylacetonate) Titanium, bis(cyclopentadienyl)iron, iron(II) bis(acetylacetonate), iron(III) tris(acetylacetonate), zirconium monoacetylacetonate, zirconium tetrakis(acetylacetonate)zirconium, zirconium ethylacetoacetate, tetrakis(acetylacetonate)hafnium, tris(acetylacetonate)aluminum, tris(acetylacetonate)bismuth are more preferred, and zirconium monoacetylacetonate, tetrakis(acetylacetonate)zirconium, zirconium ethylacetoacetate, and tetrachlorobis(tetrahydrofuran)zirconium are even more preferred due to their low coloring properties.

[0029] These catalysts (C) can be used alone or in combination of two or more. The amount of (C) used is preferably 0.001 to 5.0% by mass relative to the total of the alcohol compound (A) and the isocyanate compound (B). The use of 0.001% or more is preferred because the urethane reaction can proceed quickly, and the use of 5.0% or less is preferred because coloration caused by the catalyst can be suppressed. An amount of 0.01 to 1.0% is even more preferred.

[0030] The method for producing the unsaturated urethane compound of the present invention can be carried out by a known method in which an alcohol compound (A) and an isocyanate compound (B) are mixed as reaction components and a catalyst (C) is added. However, if a compound having an ether bond and / or an amide bond is included in the reaction system, the rate of the urethanization reaction is improved, making it possible to produce the unsaturated urethane compound at a low temperature or in a short time. In addition, the resulting unsaturated urethane compound has good color and quality, and production costs can be reduced by the low-temperature, short-time reaction, which is preferable.

[0031] Examples of methods for incorporating the compound having an ether bond and / or an amide bond into the reaction system include (1) a method in which the alcohol compound (A), the isocyanate compound (B), or the catalyst (C) used in the present invention has the bond, and (2) a method in which a compound (D) having the bond is added.

[0032] In the method (1) above, specific examples of compounds having an ether bond include the alcohol compound (A), polyalkylene glycol (meth)acrylate, polyalkylene glycol (meth)acrylamide, and polyether polyol, the isocyanate compound (B), 2-(2-isocyanatoethoxy)ethyl (meth)acrylate, and the catalyst (C), tetrachlorobis(tetrahydrofuran)zirconium. Among these, polyether polyol is preferred because it can introduce a larger amount of ether structure into the reaction system.

[0033] In the method (1), specific examples of the compound having an amide bond as the alcohol compound (A) include hydroxyalkyl (C1-18) (meth)acrylamides, polyalkylene glycol (meth)acrylamides in which the alkylene glycol has 2-6 carbon atoms and the alkylene glycol repeating units are 1-23, N-alkyl(hydroxyalkyl (C1-18)) (meth)acrylamides in which a linear, branched, or cyclic alkyl or alkylene group having 1-8 carbon atoms has been introduced to the nitrogen atom of the (meth)acrylamide-based monomer, polyalkylene glycol-N-alkyl(meth)acrylamides in which the alkylene glycol has 2-6 carbon atoms and the alkylene glycol repeating units are 1-23, and (hydroxyphenyl)-N-alkyl(meth)acrylamides. Of these, hydroxyalkyl (C1-18) (meth)acrylamides are more preferred, and N-(2-hydroxyethyl)acrylamide is particularly preferred because of its low skin irritation and high safety, with a PII of 0.0.

[0034] In the method (1) described above, the inclusion of an ether bond in one or more of the compounds (A), (B), and (C) improves catalytic activity, allowing the reaction to proceed at low temperatures and in a short time, and thus solving the problem of discoloration of the unsaturated urethane compounds of the present invention due to the unsaturated bonds. Furthermore, the inclusion of an amide bond in one or more of the compounds (A), (B), and (C) improves the reactivity of the hydroxyl group with the isocyanate group, thereby suppressing problems such as polymerization and thickening that tend to occur during the production process of the unsaturated urethane compound. Furthermore, the simultaneous presence of an ether bond and an amide bond in the reaction system using (A), (B), and (C) is even more preferable, since it allows for stable production of the unsaturated urethane compound and prevents discoloration of the resulting unsaturated urethane compound. The inventors speculate that the proximity of the intramolecular or intermolecular ether bond and amide bond enhances their respective specific effects through their interaction, further increasing the rate of the urethane reaction and enabling the reaction to be completed in a short time.

[0035] The compound (D) used in the method (2) is not particularly limited as long as it has an ether bond and / or an amide bond, but any compound that does not react with (A), (B), or (C) (i.e., does not have active hydrogen) can be used. The ether bond and / or amide bond in compound (D) has the same effect as described above. Furthermore, when the reaction system using (A), (B), and (C) does not contain either or both of an ether bond and an amide bond, adding compound (D) having either or both of an ether bond and an amide bond simultaneously allows both an ether bond and an amide bond to be simultaneously present in the reaction system, thereby providing a synergistic effect due to their interaction, as described above. Furthermore, using compound (D) having both an ether bond and an amide bond simultaneously is particularly preferred, as a high effect can be expected even when added in small amounts.

[0036] Examples of the compound (D) include aliphatic, alicyclic, and aromatic compounds containing an ether bond and / or an amide bond and no active hydrogen, and specific examples thereof include alkylene glycol dialkyl ethers, dialkylene glycol dialkyl ethers, trialkylene glycol dialkyl ethers, polyalkylene glycol dialkyl ethers, alkylene glycol alkyl ether acetates, dialkylene glycol alkyl ether acetates, trialkylene glycol alkyl ether acetates, polyalkylene glycol alkyl ether acetates, and alkylene glycol diaryl ethers, which are composed of an alkylene glycol having 1 to 4 carbon atoms and a linear, branched, or cyclic alkyl group or aryl group having 1 to 18 carbon atoms. glycols such as alkyl ether, dialkylene glycol diaryl ether, trialkylene glycol diaryl ether, polyalkylene glycol diaryl ether, alkylene glycol aryl ether acetate, dialkylene glycol aryl ether acetate, trialkylene glycol aryl ether acetate, polyalkylene glycol aryl ether acetate; amides such as dialkylformamide, dialkylacetamide, dialkylpropionamide; amide ethers such as morpholine acetamide, morpholinepropanamide, alkoxy-N,N-dialkylacetamide, alkoxy-N,N-dialkylpropanamide; tetrahydrofuran, 1,Cyclic ethers such as 4-dioxane, glycol (meth)acrylates such as alkylene glycol alkyl ether (meth)acrylate, dialkylene glycol alkyl ether (meth)acrylate, trialkylene glycol alkyl ether (meth)acrylate, polyalkylene glycol alkyl ether (meth)acrylate, aryl alkylene glycol (meth)acrylate, aryl dialkylene glycol (meth)acrylate, aryl trialkylene glycol (meth)acrylate, aryl polyalkylene glycol (meth)acrylate, alkylene glycol alkyl ether (meth)acrylamide, dialkylene glycol alkyl ether (meth)acrylamide, trialkylene glycol alkyl ether (meth)acrylamide, polyalkylene glycol alkyl ether (meth)acrylate Examples of suitable (meth)acrylamides include glycol (meth)acrylamides such as methacrylamide, alkylene glycol aryl ether (meth)acrylamide, dialkylene glycol aryl ether (meth)acrylamide, trialkylene glycol aryl ether (meth)acrylamide, and polyalkylene glycol aryl ether (meth)acrylamide; substituted (meth)acrylamides such as dialkyl (meth)acrylamide and diacetone acrylamide; cyclic ether group-introduced (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and cyclic trimethylolpropane formal (meth)acrylate; and cyclic ether group-introduced (meth)acrylamides such as tetrahydrofurfuryl (meth)acrylamide, cyclic trimethylolpropane formal (meth)acrylamide, and (meth)acryloylmorpholine. These may be used alone or in combination of two or more.

[0037] When the compound (D) used in the present invention contains both an ether bond and an amide bond in its molecular structure, the reactivity of the urethanization reaction becomes better. Therefore, it is more preferable to use an amide ether such as morpholine acetamide or methoxy-N,N-dimethylpropanamide, or a (meth)acrylamide having a cyclic ether group introduced therein such as acryloylmorpholine.

[0038] The amount of compound (D) blended is preferably 1.0 to 200.0% (mass ratio) of the total of the alcohol compound (A) and the isocyanate compound (B). A blending amount of 1.0% or more is preferred because the rate of the urethanization reaction is increased and the resulting unsaturated urethane compound has a low hue. A blending amount of 200.0% or less is preferred because the reaction-accelerating effect of compound (D) is balanced with the decrease in the reaction rate due to a decrease in the concentrations of the alcohol compound (A) and the isocyanate compound (B) in the reaction system, making it easier to control the reaction rate.

[0039] The reaction temperature in the method for producing the unsaturated urethane compound (F) of the present invention can be any temperature, but is preferably 20 to 100°C. A temperature of 20°C or higher allows the reaction to proceed quickly, while a temperature of 100°C or lower is preferred because coloration, thickening, and the like during production can be suppressed. A reaction temperature of 30 to 80°C is more preferred.

[0040] In the method for producing the unsaturated urethane compound (F) of the present invention, the procedure for mixing the reaction components is not particularly limited, and the reaction may be carried out all at once or in several stages. The production method of the present invention can be carried out without a solvent, but if necessary, the compound (D) or other component (E) not having an ether bond and / or an amide bond can be used as an organic solvent or a reactive diluent.

[0041] Among the other components (E), examples of organic solvents include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone, aprotic polar solvents such as dimethylformamide, dimethylacetamide, and dimethyl sulfoxide, ester solvents such as ethyl acetate and butyl acetate, and aliphatic hydrocarbon solvents such as hexane, cyclohexane, benzene, toluene, xylene, and petroleum ether. These may be used alone or in combination of two or more.

[0042] Among the other components (E), examples of reactive diluents include linear, branched, and cyclic alkyl(meth)acrylates having 1 to 18 carbon atoms, phenoxy(meth)acrylate, benzyl(meth)acrylate, linear, branched, and cyclic alkylene glycol di(meth)acrylates having 2 to 18 carbon atoms, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, styrene, α-methylstyrene, vinyl acetate, vinyl propionate, etc. These may be used alone or in combination of two or more.

[0043] The amount of (E) added may be appropriately determined depending on the unsaturated urethane compound (F). However, from the viewpoints of the viscosity of (F), ease of production, and economic efficiency, it is preferably 1.0 to 200.0% (mass ratio) of the total amount of the alcohol compound (A) and the isocyanate compound (B).

[0044] In the production method of the present invention, various additives can be used as needed. Examples of additives include ultraviolet sensitizers, thermal polymerization inhibitors, antioxidants, antioxidants, preservatives, phosphate ester and other flame retardants, surfactants, wetting and dispersing agents, antistatic agents, colorants, plasticizers, surface lubricants, leveling agents, softeners, thickeners, pigments, organic fillers, inorganic fillers, etc. In particular, it is preferable to add a thermal polymerization inhibitor in order to prevent polymerization of unsaturated bonds between carbon atoms.

[0045] Examples of thermal polymerization inhibitors include quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; alkylphenol-based polymerization inhibitors such as 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, 2-tert-butyl-4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, and 2,4,6-tri-tert-butylphenol; amine-based polymerization inhibitors such as alkylated diphenylamine, N,N'-diphenyl-p-phenylenediamine, and phenothiazine; N-oxyls such as 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl; and copper dithiocarbamate-based polymerization inhibitors such as copper dimethyldithiocarbamate, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate. These may be used alone or in combination of two or more.

[0046] The amount of the thermal polymerization inhibitor to be added may be appropriately determined depending on the type of unsaturated group, the unsaturated group equivalent, etc., but from the viewpoints of the polymerization-inhibiting effect, ease of production, and economy, the amount is usually preferably 0.001 to 5.0 mass%, and more preferably 0.01 to 1.0 mass%, based on the amount of the resulting unsaturated urethane compound (F).

[0047] The molecular weight of the unsaturated urethane compound (F) obtained by the production method of the present invention is not particularly limited, but a number-average molecular weight of 250 to 1,000,000 is preferred. (F) is used as a raw material for curable resin compositions, and can easily impart various properties, such as flexibility, bendability, pliability, toughness, solvent resistance, and abrasion resistance, to the cured product thereof. Therefore, (F) is widely used in a variety of fields, such as adhesives, coatings, and inks. For these applications, the number-average molecular weight is preferably 250 or more. Furthermore, in order to maintain good compatibility with polymerizable monomers and organic solvents and a viscosity suitable for operability, the number-average molecular weight is preferably 1,000,000 or less, and more preferably 400 to 100,000.

[0048] The unsaturated group equivalent of the unsaturated urethane compound (F) is not particularly limited, but is preferably 250 to 500,000. When the unsaturated group equivalent is 250 or more, the (F) molecule contains one or more unsaturated groups, making it suitable for use as a raw material for polymerizable or curable resins. When the unsaturated group equivalent is 500,000 or less, even a high-molecular-weight unsaturated urethane compound (F) contains two or more unsaturated groups in the molecule, resulting in cured products that are soft and flexible. In particular, cured products using urethane (meth)acrylamide containing a (meth)acrylamide group as the unsaturated group exhibit excellent toughness, solvent resistance, and abrasion resistance, making them particularly preferred. An unsaturated group equivalent of 400 to 50,000 is even more preferred.

[0049] The unsaturated urethane compound (F) can be mixed with other unsaturated monomers, unsaturated oligomers, etc. to prepare a polymerizable curable resin composition. Methods for adjusting the curability of the resin composition and the physical properties such as the strength and elongation of the resulting cured product depending on the intended use include a method of adjusting the type and amount of the unsaturated monomer or unsaturated oligomer added, and a method of adjusting the type of urethane skeleton of (F), the number of unsaturated bonds between carbon atoms, molecular weight, etc.

[0050] The polymerization method for the curable resin composition is not particularly limited, and any known method for polymerizing unsaturated groups can be used. Examples include radical polymerization, anionic polymerization, and cationic polymerization using active energy rays or heat. Specific examples of active energy rays include ultraviolet rays, visible light, infrared rays, X-rays, gamma rays, and electron beams.

[0051] The curable resin composition can be used in a variety of applications, including, but not limited to, coating materials used in paints and coating materials for automobiles, electrical appliances, furniture, etc., elastomer materials used in cushioning materials, packing, vibration-proofing materials, sound-absorbing materials, printing plates, sealants, abrasives, adhesives and pressure-sensitive adhesives such as transparent adhesive sheets and UV-curable pressure-sensitive adhesives, sealing materials and encapsulants, dental hygiene materials, optical materials, stereolithography materials, materials for reinforced plastics, and resin compositions for three-dimensional stereolithography. [Example]

[0052] The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. In the following, "parts" and "%" are all by mass unless otherwise specified.

[0053] Unsaturated urethane compounds (F-1) to (F-23) of the examples and urethane compounds (I-1) to (I-7) for comparison Example 1 Synthesis of Unsaturated Urethane Compound (F-1) A separable flask was charged with 50.0 parts by weight of diethylene glycol diethyl ether (D-1), 53.5 parts by weight of N-(2-hydroxyethyl)acrylamide (a1-1), 46.5 parts by weight of 2,4,4-trimethylhexamethylene diisocyanate (b2-1), 5.0 parts by weight of diisopropoxybis(ethylacetoacetate)titanium (Orgatix TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.) (C-1) as a catalyst, and 0.01 parts by weight of methoxyhydroquinone (H-1) as a polymerization inhibitor, and the mixture was stirred at 60°C. After 15 hours, infrared absorption (IR) spectroscopy analysis was performed, and the absorption (2260 cm) characteristic of the isocyanate group derived from b2-1 was confirmed. -1 The disappearance of the compound (near the water) was confirmed, and a solution of the unsaturated urethane compound (F-1) in D-1 was obtained.

[0054] Examples 2 to 9 Synthesis of unsaturated urethane compounds (F-2) to (F-9) Using the compositions shown in Table 1, the same operation as in Example 1 was carried out to obtain solutions of unsaturated urethane compounds (F-2) to (F-9) corresponding to Examples 2 to 9. The reaction temperatures and reaction times are shown in Table 1.

[0055] Comparative Example 1 The same reaction as in Example 1 was carried out except for omitting catalyst C-1. After 48 hours, infrared absorption (IR) spectroscopy revealed an absorption characteristic of an isocyanate group (2260 cm -1 It was confirmed that the urethane reaction hardly progressed at all.

[0056] Comparative Examples 2 and 3 Synthesis of Urethane Compounds (I-2) and (I-3) Using the compositions shown in Table 1, the same operation as in Example 1 was carried out to obtain solutions of urethane compounds (I-2) and (I-3) corresponding to Comparative Examples 2 and 3. The reaction temperatures and reaction times (time required for reaction completion) are shown in Table 1.

[0057] Example 10 Synthesis of Unsaturated Urethane Compound (F-10) A separable flask was charged with 58.0 parts by mass of Kuraray Polyol P-1012 (Kuraray Co., Ltd.) (a2-3), 25.8 parts by mass of isophorone diisocyanate (b2-2), 0.1 parts by mass of tetrakis(acetylacetonato)zirconium (C-6) as a catalyst, and 0.01 parts by mass of methoxyhydroquinone (H-1) as a polymerization inhibitor, and the mixture was stirred at 60°C. IR analysis was performed, and the absorption (2260 cm) specific to the isocyanate group derived from b2-2 was confirmed. -1 The first-stage reaction was terminated when the decrease in the hydroxyl group (approximately 100%) had stopped (24 hours after the start of the reaction). 16.2 parts by mass of hydroxyethyl acrylate (a1-7) was added to the resulting reaction solution, and the mixture was stirred at 60°C to initiate the second-stage reaction. Similarly, the disappearance of the isocyanate group was confirmed by IR analysis (12 hours after the start of the second-stage reaction), and the second-stage reaction was terminated to obtain an unsaturated urethane compound (F-10).

[0058] Example 16 Synthesis of unsaturated urethane compound (F-16) A separable flask was charged with 8.7 parts by mass of N-(2-hydroxyethyl)acrylamide (a1-1), 74.5 parts by mass of Kuraray Polyol P-2010 (a2-6), 16.8 parts by mass of isophorone diisocyanate (b2-2), 100 parts by mass of N-acryloylmorpholine (D-6), 0.05 parts by mass of bismuth tris(2-ethylhexanoic acid) (C-5) as a catalyst, and 0.05 parts by mass of 2,6-di-tert-butylphenol (H-2) as a polymerization inhibitor, and the resulting mixture was stirred for 6 hours at 60 ° C. Similarly, the completion of the reaction was confirmed by IR analysis, and a D-6 solution of unsaturated urethane compound (F-16) was obtained.

[0059] Examples 11 to 15, 17 to 23 Synthesis of unsaturated urethane compounds (F-11) to (F-15), (F-17) to (F-23) Using the compositions shown in Table 2, Examples 11 to 15 and 17 to 23 were carried out in the same manner as in Example 10 to obtain unsaturated urethane compounds (F-11) to (F-15) and (F-17) to (F-23). ​​The reaction temperatures and reaction times for the first and second stage reactions are shown in Table 2.

[0060] Comparative Example 4 Synthesis of Urethane Compound (I-4) The same procedure as in Example 10 was carried out using the composition and reaction conditions shown in Table 2 to synthesize a urethane compound (I-4) corresponding to Comparative Example 4. After 48 hours, infrared absorption (IR) spectroscopy revealed that the absorption characteristic of an isocyanate group (at 2260 cm -1 It was found that the initial state of the reaction mixture (around 1000 kJ / mol) hardly changed, and the first-step reaction hardly progressed.

[0061] Comparative Example 5 Synthesis of Urethane Compound (I-5) Using the composition shown in Table 2, the same operation as in Example 10 was carried out to obtain a solution of urethane compound (I-5) corresponding to Comparative Example 5. The reaction temperature and reaction time are shown in Table 2.

[0062] Comparative Examples 6 and 7 Synthesis of Urethane Compounds (I-6) and (I-7) Using the compositions shown in Table 2, the same procedure as in Example 16 was carried out to obtain solutions of urethane compounds (I-6) and (I-7) corresponding to Comparative Examples 6 and 7. The reaction temperatures and reaction times for each are shown in Table 2.

[0063] [Table 1]

[0064] [Table 2]

[0065] The raw materials used in the synthesis of the unsaturated urethane compound (F) and the urethane compound (I) are shown below. (Alcohol compound (a1) having an unsaturated bond between carbon atoms) a1-1: N-(2-hydroxyethyl)acrylamide (HEAA) (registered trademark "HEAA", registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) a1-2: 2-hydroxyethylmaleimide (HEMI) a1-3: Hydroxyethyl methacrylate (HEMA) a1-4: 4-hydroxybutyl acrylate (4HBA) a1-5: 4-Hydroxybutyl vinyl ether (4HBVE) a1-6: 2-hydroxyethyl allyl ether a1-7: Hydroxyethyl acrylate (HEA) a1-8: N-(2-hydroxypropyl)acrylamide (HPAA) a1-9: N-(2-hydroxyethyl) methacrylamide (HEMAA)

[0066] (Polyol (a2) having two or more hydroxyl groups) a2-1: Polytetramethylene glycol with a number average molecular weight of 650 (PTMG650, manufactured by Mitsubishi Chemical Corporation) a2-2: Polypropylene glycol, triol type, number average molecular weight 300 (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) a2-3: Polyester diol (condensate of 3-methyl-1,5-pentanediol / adipic acid / terephthalic acid) having a number average molecular weight of 1,000 (Kuraray Polyol P-1012, manufactured by Kuraray Co., Ltd.) a2-4: Polycarbonate diol (condensate of 3-methyl-1,5-pentanediol / 1,6-hexanediol / diethyl carbonate) having a number average molecular weight of 2,000 (Kuraray Polyol C-2090, manufactured by Kuraray Co., Ltd.) a2-5: Polyester polyol (3-methyl-1,5-pentanediol / adipic acid) with a number average molecular weight of 6,000 (Kuraray Polyol P-6010, manufactured by Kuraray Co., Ltd.) a2-6: Polyester polyol (3-methyl-1,5-pentanediol / adipic acid) with a number average molecular weight of 2,000 (Kuraray Polyol P-2010, manufactured by Kuraray Co., Ltd.) a2-7: Hydrogenated poly-1,2-butadienediol with a number average molecular weight of 1,000 (GI-1000, manufactured by Nippon Soda Co., Ltd.) a2-8: Carbinol-modified polyether silicone oil with a number-average molecular weight of 1,800 (KF-6001, manufactured by Shin-Etsu Chemical Co., Ltd.) a2-9: Polycarbonate diol (condensate of 3-methyl-1,5-pentanediol / 1,6-hexanediol / diethyl carbonate) having a number average molecular weight of 1,000 (Kuraray Polyol C-1090, manufactured by Kuraray Co., Ltd.)

[0067] (Isocyanate compound (b1) having an unsaturated bond between carbon atoms) b1-1: Isocyanatoethyl acrylate (Karens AOI, manufactured by Showa Denko K.K.)

[0068] (Polyisocyanate (b2) having two or more isocyanate groups) b2-1: 2,4,4-trimethylhexamethylene diisocyanate (TMHDI) b2-2: Isophorone diisocyanate (IPDI) b2-3: Isocyanurate of hexamethylene diisocyanate (HDI-I) b2-4: Hexamethylene diisocyanate (HDI) b2-5: Methylenebis(1,4-cyclohexanediyl)diisocyanate (hydrogenated MDI)

[0069] (Catalysts (C) and (G)) C-1: Diisopropoxybis(ethylacetoacetate)titanium (Orgatix TC-750, manufactured by Matsumoto Fine Chemical Co., Ltd.) C-2: Tris(acetylacetonate)aluminum (Orgatix AL-3100, manufactured by Matsumoto Fine Chemical Co., Ltd.) C-3: Tetrakis(acetylacetonato)hafnium (Fujifilm Wako Pure Chemical Industries, Ltd.) C-4: Zirconium tetrakis(2-ethylhexanoate) (Orgatix ZC-200, manufactured by Matsumoto Fine Chemical Co., Ltd.) C-5: Bismuth tris(2-ethylhexanoate) (Fujifilm Wako Pure Chemical Industries, Ltd.) C-6: Tris(acetylacetonato)iron(III) (Fujifilm Wako Pure Chemical Industries, Ltd.) C-7: Tetrakis(acetylacetonato)zirconium (Orgatix ZC-150, manufactured by Matsumoto Fine Chemical Co., Ltd.) C-8: Tris(iron stearate)(III) (Tokyo Chemical Industry Co., Ltd.) G-1: N,N,N,N-tetramethylethylenediamine G-2: Zinc bis(neodecanoate) (Borchi Kat22, manufactured by Matsuo Sangyo Co., Ltd.) G-3: Bis(acetylacetonato)zinc (Tokyo Chemical Industry Co., Ltd.) G-4: Dibutyltin dilaurate (Tokyo Chemical Industry Co., Ltd.)

[0070] (Compound (D)) D-1: Diethylene glycol diethyl ether D-2: Tetrahydrofurfuryl acrylate D-3: Tetrahydrofuran D-4: Morpholineacetamide D-5: Methoxy-N,N-dimethylpropanamide (registered trademark "KJCMPA", manufactured by KJ Chemicals Co., Ltd.) D-6: N-acryloylmorpholine (registered trademark "ACMO", registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) D-7: N,N-diethylacrylamide (registered trademark "DEAA", registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) D-8: Diacetone acrylamide (registered trademark "Kohshylmer", manufactured by KJ Chemicals Co., Ltd.) D-9: N,N-dimethylacetamide

[0071] (Other ingredients (E)) E-1: Isobornyl acrylate E-2: Ethyl acetate

[0072] (Polymerization inhibitor (H)) H-1: Methoxyhydroquinone H-2: 2,6-di-tert-butylphenol H-3: 4-hydroxy-2,2,6,6-tetramethylpiperidine-N-oxyl

[0073] Measurement of molecular weight and calculation of unsaturated group equivalent of products of Examples 1 to 9 and Comparative Examples 1 to 3 Since the unsaturated urethane compounds (F-1) to (F-9) obtained in Examples 1 to 9 and the urethane compounds (I-2) and (I-3) obtained in Comparative Examples 2 and 3 were obtained as single compounds, their molecular weights were measured by mass spectrometry using a TSQ Quantum Access MAX (Thermo Science) and an ESI probe (H-ESI2, positive measurement) using an infusion method (eluent: acetonitrile / 0.1% acetic acid aqueous solution = 9 / 1 (mass ratio)). The unsaturated group equivalent (molecular weight per unsaturated group) was also calculated (unsaturated group equivalent = molecular weight / number of unsaturated groups). In Comparative Example 1, the urethane reaction hardly progressed, so molecular weight measurement was not performed. These results are shown in Table 3.

[0074] Measurement of molecular weight and calculation of unsaturated group equivalent weight for products of Examples 10 to 21 and Comparative Examples 4 to 7 The unsaturated urethane compounds (F-10) to (F-21) obtained in Examples 10 to 21 and the urethane compounds (I-5) to (I-7) obtained in Comparative Examples 5 to 7 were polymers with molecular weight distributions. 7 Separation range: 100 to 2 × 10 7 The theoretical plate number was 10,000 plates / tube, and tetrahydrofuran was used as the eluent.) and the number average molecular weight was calculated in terms of standard polystyrene molecular weight. The unsaturated group equivalent (molecular weight per unsaturated group) was also calculated (unsaturated group equivalent = number average molecular weight / number of unsaturated groups). In Comparative Example 4, the urethanization reaction hardly progressed, so molecular weight measurement was not performed. These results are shown in Table 4.

[0075] (viscosity measurement) Using a Brookfield viscometer (device name: Digital Viscometer LV DV2T, manufactured by Eiko Seiki Co., Ltd.), the viscosity of the unsaturated urethane compound (F) and urethane compound (I) obtained in each example and comparative example, or the viscosity of a solution of the unsaturated urethane compound (F) and urethane compound (I), was measured at 60°C in accordance with JIS K5600-2-3. Furthermore, measurements were not performed in Comparative Examples 1 and 4 because the urethane reaction hardly progressed. The results of the viscosity measurements are shown in Tables 3 and 4.

[0076] (hue) The Hazen color number (APHA) was measured as the hue of the unsaturated urethane compound (F) and urethane compound (I) obtained in each Example and Comparative Example, or the hue of a solution of the unsaturated urethane compound (F) and urethane compound (I) using a transmission color measuring instrument (Nippon Denshoku TZ6000), and the following evaluations were made based on the APHA value. In Comparative Examples 1 and 4, the urethane reaction hardly progressed, so no measurement was performed. The results of the hue measurements are shown in Tables 3 and 4. ◎: APHA less than 50 ○: APHA is 50 or more and less than 100 △: APHA is 100 or more and less than 200 ×: APHA is 200 or more

[0077] (stability) The color of the unsaturated urethane compound (F) and the urethane compound (I) obtained in each Example and Comparative Example, or a solution of the unsaturated urethane compound (F) and the urethane compound (I) was stored at 60°C for one week, and the viscosity after storage was measured, and the stability was evaluated from the change in viscosity. In Comparative Examples 1 and 4, the urethane reaction hardly progressed, so no evaluation was performed. The results of the stability evaluation are shown in Tables 3 and 4. ◎: Viscosity change is less than ±10% ○: Viscosity change is more than ±10% and less than ±20% △: Viscosity change is more than ±20% and less than ±100% ×: Viscosity change is ±100% or more

[0078] [Table 3]

[0079] [Table 4]

[0080] The results of the production and evaluation of unsaturated urethane compounds with molecular weights of less than 1,000 are shown in Tables 1 and 3. As is clear from these results, the method of the present invention allows the production of unsaturated urethane compounds (F-1) to (F-9) at relatively low temperatures in a short time. Furthermore, the resulting compounds (F-1) to (F-9) had good color and thermal stability. On the other hand, in Comparative Example 1, where no catalyst was added, the reaction was incomplete. In Comparative Example 2, where a tertiary amine was used as a catalyst, a long reaction time at high temperature was required, and the resulting urethane compound (I-2) was brownish-red and had a poor color. Furthermore, the compound was prone to Michael addition between the amine and the unsaturated bond, and its stability was poor. In Comparative Example 3, where zinc bis(neodecanoate) derived from a Group 12 element was used as a catalyst, the catalytic activity was low, a long reaction time was required, and the resulting product (I-3) had a poor color and was also unstable, with the formation of insoluble matter.

[0081] The results of the production and evaluation of high-molecular-weight unsaturated urethane compounds with a molecular weight of 1,000 or more, obtained by combining a polyol (a2) having two or more hydroxyl groups and a polyisocyanate (b2) having two or more isocyanate groups, are shown in Tables 2 and 4. As is clear from these results, the method of the present invention demonstrated good reactivity, whether it was a multi-step reaction in which (a2) and (b2) were reacted with (a1) as in Example 10, or whether it was a reaction in which (a1), (a2), and (b2) were charged all at once as in Example 16. It was also found that the reaction was completed at a relatively low temperature and in a short time. Furthermore, it was possible to produce a wide variety of unsaturated urethane compounds, ranging from high molecular weight and high viscosity to low molecular weight and low viscosity. The resulting unsaturated urethane compounds (F-10) to (F-23) had excellent color and thermal stability. In Examples 11 and 12, which contained an amide bond in the reaction system, the reactivity was improved. Furthermore, in Examples 13 to 23, which contained both an ether bond and an amide bond in the reaction system, the reactivity was further improved, resulting in a lower hue and improved thermal stability of the resulting unsaturated urethane compound. On the other hand, in Comparative Example 4, which contained both an ether bond and an amide bond like in Example 14 but did not contain a catalyst, the reaction did not go to completion. In Comparative Example 5, which used a tertiary amine as a catalyst, the required reaction temperature was high and the reaction time was long, resulting in poor hue and thermal stability of the resulting urethane compound (I-5). Furthermore, Comparative Examples 6 and 7, which were based on Examples 2 and 1 in Patent Document 4 (JP 2010-215774 A), but used acryloylmorpholine (D-6), which contained both an ether bond and an amide bond as the diluent monomer, showed relatively good reactivity. However, Comparative Example 6, which used a zinc-based catalyst, showed severe coloration, and Comparative Example 7, which used a tin-based catalyst, showed slight coloration and a decrease in viscosity by approximately 30%. [Industrial Applicability]

[0082] As described above, the method for producing an unsaturated urethane compound of the present invention is characterized by using an organic salt or complex of at least one metal element selected from the group consisting of transition elements (1-3) and elements (13-15) (excluding tin) as a catalyst. Because the unsaturated urethane compound can be efficiently produced at low temperatures in a short time, it is possible to reduce costs and improve color and quality. Furthermore, because no toxic tin-based catalyst is used, the resulting unsaturated urethane compound is highly safe and can be suitably used as a raw material for curable resin compositions. The unsaturated urethane compound can be used in a variety of fields, including paints for automobiles, electrical appliances, and furniture, coating materials, buffer materials, packing, vibration-damping materials, sound-absorbing materials, printing plates, sealants, abrasives, transparent adhesive sheets, UV-curable pressure-sensitive adhesives and pressure-sensitive adhesives, sealing materials, encapsulants, dental hygiene materials, optical materials, stereolithography materials, reinforced plastic materials, and resin compositions for three-dimensional stereolithography.

Claims

1. A method for producing an unsaturated urethane compound having an unsaturated bond between carbon atoms, comprising reacting an alcohol compound (A) with an isocyanate compound (B) in the presence of a catalyst (C), which is an organic salt or complex of at least one metal element selected from the group consisting of titanium, iron, zirconium, hafnium, aluminum, and bismuth; The alcohol compound (A) contains an alcohol compound (a1) having an unsaturated bond, The isocyanate compound (B) is a polyisocyanate (b2) having two or more isocyanate groups, A method for producing an unsaturated urethane compound, wherein the alcohol compound (a1) having an unsaturated bond contains an alcohol compound having a (meth)acrylamide group.

2. 2. The method for producing an unsaturated urethane compound according to claim 1, wherein the alcohol compound (A) further contains a polyol (a2) having two or more hydroxyl groups.

3. 3. The method for producing an unsaturated urethane compound according to claim 1 or 2, wherein the alcohol compound (a1) having an unsaturated bond further contains one or more compounds selected from the group consisting of alcohol compounds having a (meth)acrylate group, alcohol compounds having a vinyl group, alcohol compounds having a vinyl ether group, alcohol compounds having a methyl vinyl ether group, alcohol compounds having an allyl group, alcohol compounds having a (meth)allyl ether group, and alcohol compounds having a maleimide group.

4. 4. The method for producing an unsaturated urethane compound according to claim 1, wherein a compound having an amide bond (excluding a1) is contained in the reaction system.

5. The method for producing an unsaturated urethane compound according to any one of claims 1 to 4, characterized in that the molar ratio of the hydroxyl group (OH) of the alcohol compound (A) to the isocyanate group (NCO) of the isocyanate compound (B) is 0.9 to 1.

1.

6. The method for producing an unsaturated urethane compound according to any one of claims 1 to 5, wherein the alcohol compound (A) further contains a polyol (a2) having two or more hydroxyl groups, and the alcohol compound (a1) having an unsaturated bond, the polyol (a2), the polyisocyanate (b2), and the catalyst (C) are all charged into a reactor at once and reacted.

7. The method for producing an unsaturated urethane compound according to any one of claims 1 to 5, wherein the alcohol compound (A) further contains a polyol (a2) having two or more hydroxyl groups, and the polyol (a2), the polyisocyanate (b2), and the catalyst (C) are charged into a reactor and reacted, and then the alcohol compound (a1) having an unsaturated bond is charged and further reacted.

8. The method for producing an unsaturated urethane compound according to any one of claims 1 to 7, further comprising one or more organic solvents selected from the group consisting of ketone solvents, aprotic polar solvents, ester solvents, and aliphatic hydrocarbon solvents.

9. The method for producing an unsaturated urethane compound according to any one of claims 1 to 8, further comprising one or more reactive diluents selected from the group consisting of linear, branched, and cyclic alkyl(meth)acrylates having 1 to 18 carbon atoms, phenoxy(meth)acrylate, benzyl(meth)acrylate, linear, branched, and cyclic alkylene glycol di(meth)acrylates having 2 to 18 carbon atoms, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, trimethylolpropane tri(meth)acrylate, styrene, α-methylstyrene, vinyl acetate, and vinyl propionate.

10. The method for producing an unsaturated urethane compound according to any one of claims 1 to 9, characterized in that the amount of the catalyst (C) blended is 0.001 to 5.0% (mass ratio) based on the total amount of the alcohol compound (A) and the isocyanate compound (B).

11. 9. The method for producing an unsaturated urethane compound according to claim 8, wherein the blending amount of the organic solvent is 1 to 200% (mass ratio) based on the total amount of the alcohol compound (A) and the isocyanate compound (B).

12. The method for producing an unsaturated urethane compound according to claim 9, wherein the amount of the reactive diluent blended is 1 to 200% (mass ratio) of the total amount of the alcohol compound (A) and the isocyanate compound (B).

Images