JP7498478B2 - Method for producing unsaturated urethane compound - Google Patents

Description

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.

Urethane compounds with 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, by using them in photocurable resin compositions, it is possible to easily impart various properties to the cured product, such as flexibility, bendability, softness, toughness, solvent resistance, and abrasion resistance, and they are widely used in various fields such as adhesives, coatings, and inks.

Such unsaturated urethane compounds are usually synthesized by reacting a polyol with a polyisocyanate to obtain a polyurethane having hydroxyl or isocyanate groups at both ends, which is then further reacted with a hydroxyl-containing unsaturated compound or an isocyanate-containing unsaturated compound, respectively (Patent Documents 1 to 3).

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, and while organotin compounds show good catalytic activity, they are problematic as endocrine disruptors, and restrictions on their use have been accelerating in recent years.

Therefore, various organometallic compounds have been newly studied as urethane catalysts to replace organotin compounds. For example, a urethane acrylate is synthesized in the presence of a zinc compound, and in a curable composition composed of the obtained urethane acrylate and a hydroxyl group-containing acrylate, the inclusion of a zinc compound can suppress the problem of viscosity reduction (viscosity decrease over time) of the composition that occurs with tin catalysts (Patent Document 4). In addition, 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 progresses extremely slowly, and even if the amount of catalyst added is increased by up to three times, the urethane reaction does not complete, and the reaction product becomes discolored.

JP 2010-267703 A Publication No. WO2015/141537 Patent Publication No. WO2017/047615 JP 2010-215774 A JP 2012-511056 A

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 aim is to provide a method for producing an unsaturated urethane compound with good hue and quality using the catalyst without problems in temperature control.

As a result of intensive research conducted by the inventors to solve the above problems, they discovered that when an alcohol compound is reacted with an isocyanate compound to produce an unsaturated urethane compound, an unsaturated urethane compound of good quality can be produced efficiently by using an organic salt or complex of at least one metal element selected from the group consisting of transition elements of the first to third groups and elements of the thirteenth to fifteenth groups (excluding tin) as a catalyst, and thus completed the present invention.

That is, the present invention relates to (1) a method for producing an unsaturated urethane compound having an unsaturated bond between carbon atoms, which comprises 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 elements belonging to groups 1 to 3 and elements belonging to 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 the hydroxyl group (OH) to the isocyanate group (NCO) is 0.9 to 1.1;
(3) A method for producing an unsaturated urethane compound according to (1) or (2) above, characterized in that 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) above, 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), 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).
(9) The method for producing an unsaturated urethane compound according to any one of (1) to (8), characterized in that the blending amount of the compound (D) is 1 to 200% (mass ratio) based on the total amount of the alcohol compound (A) and the isocyanate compound (B).
This provides:

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 1st to 3rd transition elements and the 13th to 15th group elements (excluding tin) is used as a catalyst, making it possible to efficiently produce an unsaturated urethane compound under normal reaction conditions without using an organotin catalyst. In addition, by using a novel catalyst, the reaction temperature can be easily controlled, and an unsaturated urethane compound with good hue and quality can be obtained.

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

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. It is more preferable that 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.

Examples of (a1) include hydroxyalkyl (meth)acrylates, hydroxyalkyl (meth)acrylamides, hydroxyalkyl vinyl ethers, hydroxyalkyl (methyl) vinyl ethers, hydroxyalkyl (meth)allyl ethers, and hydroxyalkyl maleimides, in which a linear, branched, or cyclic alkylene group having 1 to 20 carbon atoms has been introduced; polyalkylene glycol (meth)acrylates in which the alkylene glycol has 1 to 9 carbon atoms and the alkylene glycol has 1 to 23 repeating units; polyalkylene glycol (meth)acrylamides, polyalkylene glycol vinyl ethers, polyalkylene glycol (methyl) vinyl ethers, polyalkylene glycol (meth)allyl ethers, and polyalkylene glycol maleimides; and the above (meth)acrylic Examples of the N-alkyl(hydroxyalkyl)(meth)acrylamides, N-alkyl(polyalkylene glycol)(meth)acrylamides, and N-alkyl(hydroxyphenyl)(meth)acrylamides, which are amide monomers having a linear, branched or cyclic alkyl group or alkylene group having 1 to 8 carbon atoms introduced into the nitrogen atom, include hydroxyphenyl(meth)acrylates, hydroxyphenyl(meth)acrylamides, hydroxyphenylvinyl ethers, hydroxyphenyl(methyl)vinyl ethers, hydroxyphenyl(meth)allyl ethers, and hydroxyphenylmaleimides. Among these, the use of hydroxyalkyl(meth)acrylates and hydroxyalkyl(meth)acrylamides is preferred because they improve the polymerization properties of the unsaturated urethane compound. These (a1)s can be used alone or in combination of two or more.

As (a2), it is preferable that the polyol has two or more hydroxyl groups in the molecule, and is an alkylene polyol, a polyether polyol, a polyester polyol, a polycarbonate polyol, a hydrogenated polyalkadiene polyol, a polyalkadiene polyol, or a polyol having a silicone skeleton, and among these, it is more preferable that the polyol has two hydroxyl groups in the molecule, and is an alkylene diol, a polyether diol, a polyester diol, a polycarbonate diol, a hydrogenated polyalkadiene diol, a polyalkadiene diol, or a polyol having a silicone skeleton. These (a2) can be used alone or in combination of two or more.

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 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.

Examples of polyether polyols include linear, branched, and cyclic polyalkylene glycols having 2 to 18 carbon atoms, specifically 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, pentaerythritol tetra(polyoxy 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.

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 item [0015].

Examples of polycarbonate polyols include those that are composed of a carbonyl component and a polyol, contain a carbonate skeleton in the molecule, and have hydroxyl groups at the ends. Examples of the carbonyl component include phosgene, chloroformate ester, dialkyl carbonate, diaryl carbonate, and alkylene carbonate, and examples of the polyol component include the alkylene polyols described in the above item [0015].

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

Polyols having a silicone skeleton are those that contain a siloxane bond in the main skeleton of the molecule and have two or more hydroxyl groups at both ends or on the side chain, and examples 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.

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. It is more preferable that 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.

(b1) includes isocyanatoalkyl (meth)acrylates, isocyanatoalkyl (meth)acrylamides, isocyanatoalkyl vinyl ethers, isocyanatoalkyl (methyl) vinyl ethers, isocyanatoalkyl (meth)allyl ethers, isocyanatoalkyl maleimides, isocyanatoalkoxyalkyl (meth)acrylates, isocyanatoalkoxyalkyl (meth)acrylamides, isocyanatoalkoxyalkyl vinyl ethers, isocyanatoalkoxyalkyl (methyl) vinyl ethers, isocyanatoalkoxyalkyl (meth)allyl ethers, isocyanatoalkoxyalkyl maleimides, and the (meth)acrylamide monomers having a carbon number of 1 to 18 introduced into the nitrogen atom. Examples of the N-alkyl(isocyanatoalkyl)(meth)acrylamides, N-alkyl(isocyanatoalkoxyalkyl)(meth)acrylamides, and N-alkyl(isocyanatophenyl)(meth)acrylamides having 1 to 8 linear, branched, or cyclic alkyl or alkylene groups introduced therein, as well as isocyanatophenyl(meth)acrylates, isocyanatophenyl(meth)acrylamides, isocyanatophenylvinyl ethers, isocyanatophenyl(methyl)vinyl ethers, isocyanatophenyl(meth)allyl ethers, and isocyanatophenylmaleimides, are mentioned. Among these, the use of isocyanatoalkyl(meth)acrylates and isocyanatoalkyl(meth)acrylamides is preferred because the polymerizability of the unsaturated urethane compound is improved. These (b1)s can be used alone or in combination of two or more.

(b2) may, for example, be 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, 4, Examples of such 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 alicyclic diisocyanates such as 1,3-bis(isocyanatomethyl)cyclohexane, and adduct types, isocyanurate types, and biuret types of these. These can be used alone or in combination of two or more.

When obtaining an unsaturated urethane compound by the manufacturing method of the present invention, the combination of the alcohol compound (A) and the isocyanate compound (B) is arbitrary, 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, it 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, since the molecular weight of the obtained unsaturated urethane compound can be adjusted arbitrarily by the ratio of (a2) and (b2).

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, since remaining isocyanate groups in the resulting unsaturated urethane compound will react with moisture in the air and cause instability.

The catalyst (C) used in the present invention is an organic salt or complex of at least one metal element selected from the group 1 to 3 transition elements and the group 13 to 15 elements (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 especially preferable.

Preferred organic salts of the metal elements 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 organic acids include linear, branched, and cyclic alkyl carboxylic 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 terms of exhibiting good catalytic activity, organic salts of titanium, iron, zirconium, and bismuth are preferred, including 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), and tris(stearate) is more preferred because of its low colorability.

As the complex of the metal element, 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, etc. are preferable. 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, etc. are preferable. In terms of exhibiting good catalytic activity, complexes with titanium, iron, zirconium, hafnium, aluminum, and bismuth are preferable. Diisopropoxybis(ethylacetoacetate)titanium, tetrakis(acetylacetonate)titanium, etc. More preferred are 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, and tris(2,2,6,6-tetramethyl-3,5-heptanedionato)bismuth, and even more preferred are zirconium monoacetylacetonate, tetrakis(acetylacetonate)zirconium, zirconium ethylacetoacetate, and tetrachlorobis(tetrahydrofuran)zirconium, due to their low coloring properties.

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). Using 0.001% or more is preferred because it allows the urethane reaction to proceed quickly, and using 5.0% or less is preferred because it prevents discoloration caused by the catalyst. An amount of 0.01 to 1.0% is even more preferred.

The method for producing the unsaturated urethane compound of the present invention can be carried out by a known method of mixing an alcohol compound (A) and an isocyanate compound (B) as reaction components and adding a catalyst (C). 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 color and quality of the resulting unsaturated urethane compound are good, and production costs can be reduced by the low temperature and short reaction time, which is preferable.

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

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

In the method (1), specific examples of the compound having an amide bond include the alcohol compound (A), hydroxyalkyl (1-18 carbon atoms) (meth)acrylamide, polyalkylene glycol (meth)acrylamide in which the alkylene glycol has 2-6 carbon atoms and the repeating unit of the alkylene glycol is 1-23, N-alkyl (hydroxyalkyl (1-18 carbon atoms)) (meth)acrylamide in which a linear, branched or cyclic alkyl group or alkylene group having 1-8 carbon atoms is introduced to the nitrogen atom of the (meth)acrylamide monomer, polyalkylene glycol-N-alkyl (meth)acrylamide in which the alkylene glycol has 2-6 carbon atoms and the repeating unit of the alkylene glycol is 1-23, and (hydroxyphenyl)-N-alkyl (meth)acrylamide. Of these, hydroxyalkyl (1-18 carbon atoms) (meth)acrylamide is more preferable, and N-(2-hydroxyethyl)acrylamide is particularly preferable because it has low skin irritation with a PII of 0.0 and is highly safe.

In the method (1), by having an ether bond in one or more of the compounds (A), (B) and (C), the catalytic activity can be improved, the reaction can be carried out at a low temperature in a short time, and the problem of the unsaturated urethane compound relating to the present invention being prone to coloring due to the unsaturated bond can be solved, which is preferable. In addition, by having an amide bond in one or more of the compounds (A), (B) and (C), the reactivity of the hydroxyl group and the isocyanate group is improved, and as a result, problems such as polymerization and thickening that tend to occur in the manufacturing process in the production of the unsaturated urethane compound can be suppressed, which is preferable. Furthermore, when an ether bond and an amide bond are simultaneously present in the reaction system using (A), (B) and (C), the unsaturated urethane compound can be stably produced, and coloring of the obtained unsaturated urethane compound can be prevented, which is more preferable. It is speculated by the present inventors that when an ether bond and an amide bond are close to each other within a molecule or between molecules, their interaction increases the specific effects of each, and at the same time, the speed of the urethane reaction is further increased, and the reaction can be completed in a short time.

The compound (D) used in the method (2) is not particularly limited as long as it is a compound having an ether bond and/or an amide bond, but any compound that does not react with (A), (B), or (C) (has no active hydrogen) can be suitably used. The ether bond and/or amide bond in the compound (D) has the same effect as above, and when the reaction system using (A), (B), and (C) does not have either or both of an ether bond and an amide bond, it is more preferable to include a compound (D) having either or both of an ether bond and an amide bond, since the ether bond and the amide bond are simultaneously included in the reaction system, and a synergistic effect due to their interaction can be provided as described above. Furthermore, it is particularly preferable to use a compound (D) having both an ether bond and an amide bond, since a high effect can be expected even when added in small amounts.

Examples of compound (D) include aliphatic, alicyclic, and aromatic compounds that contain an ether bond and/or an amide bond and have no active hydrogen, and specifically 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, alkylene glycol diaryl ethers, dialkylene glycol diaryl ethers, Glycols such as trialkylene glycol diaryl ether, polyalkylene glycol diaryl ether, alkylene glycol aryl ether acetate, dialkylene glycol aryl ether acetate, trialkylene glycol aryl ether acetate, and polyalkylene glycol aryl ether acetate; amides such as dialkylformamide, dialkylacetamide, and dialkylpropionamide; amide ethers such as morpholine acetamide, morpholine propanamide, alkoxy-N,N-dialkylacetamide, and alkoxy-N,N-dialkylpropanamide; cyclic ethers such as tetrahydrofuran and 1,4-dioxane; alkylene glycol alkyl ether (meth)acrylate; glycol (meth)acrylates such as aryl 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, and 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)acrylamide, and alkylene glycol aryl ether Examples of such compounds include glycol (meth)acrylamides such as (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 compounds may be used alone or in combination of two or more.

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

The amount of compound (D) is preferably 1.0 to 200.0% (mass ratio) based on the total of alcohol compound (A) and isocyanate compound (B). If it is 1.0% or more, the speed of the urethanization reaction is improved and the hue of the resulting unsaturated urethane compound is low, which is preferable. If it is 200.0% or less, the reaction promotion effect of compound (D) is balanced with the decrease in the reaction rate due to the decrease in the concentration of alcohol compound (A) and isocyanate compound (B) in the reaction system, making it easier to control the reaction rate, which is preferable.

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. If the temperature is 20°C or higher, the reaction can proceed quickly, and if the temperature is 100°C or lower, coloring, thickening, and the like that may occur during production can be suppressed, which is preferable. It is more preferable that the reaction temperature is 30 to 80°C.

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

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

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, and vinyl propionate. These may be used alone or in combination of two or more.

The amount of (E) added may be set appropriately depending on the amount of unsaturated urethane compound (F), but from the standpoint of the viscosity of (F), ease of production, and economic efficiency, it is preferable that the amount of (E) added be 1.0 to 200.0% (mass ratio) of the total amount of alcohol compound (A) and isocyanate compound (B).

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

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.

The amount of thermal polymerization inhibitor to be added may be appropriately set depending on the type of unsaturated group, the unsaturated group equivalent, etc., but from the standpoint of polymerization inhibition effect, ease of production, and economic efficiency, it is usually preferably 0.001 to 5.0% by mass, and more preferably 0.01 to 1.0% by mass, based on the obtained unsaturated urethane compound (F).

The molecular weight of the unsaturated urethane compound (F) obtained by the manufacturing method of the present invention is not particularly limited, but the number average molecular weight is preferably 250 to 1,000,000. (F) is used as a raw material for a curable resin composition, and since it is possible to easily impart various properties such as flexibility, bendability, softness, toughness, solvent resistance, and abrasion resistance to the cured product obtained by curing this, it is widely used in various fields such as adhesives, coatings, and inks. In order to be suitable for these applications, the number average molecular weight is preferably 250 or more, and from the viewpoint of maintaining 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.

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 molecule of (F) has one or more unsaturated groups, and it can be used as a raw material for polymerizable or curable resins. When the unsaturated group equivalent is 500,000 or less, even the high molecular weight unsaturated urethane compound (F) has two or more unsaturated groups in the molecule, so the cured product obtained using it has flexibility and pliability, and in particular, the cured product using urethane (meth)acrylamide having a (meth)acrylamide group as the unsaturated group has good toughness, solvent resistance, and abrasion resistance, so it is preferable. Also, it is more preferable that the unsaturated group equivalent is 400 to 50,000.

The unsaturated urethane compound (F) can be mixed with other unsaturated monomers or unsaturated oligomers 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 according to 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, the molecular weight, etc.

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

The curable resin composition can be used for a variety of applications. Specific applications include 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, sealing materials, abrasives, etc.; transparent adhesive sheets, adhesives and pressure-sensitive adhesives such as UV-curable tackifiers and adhesives, sealing materials and sealants, dental hygiene materials, optical materials, photo-modeling materials, materials for reinforced plastics, and resin compositions for three-dimensional photo-modeling, but the applications are not necessarily limited to these.

The present invention will be explained 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 weight unless otherwise specified.

Unsaturated urethane compounds (F-1) to (F-23) of the examples and urethane compounds (I-1) to (I-7) of the comparative examples
Example 1 Synthesis of unsaturated urethane compound (F-1) 50.0 parts by mass of diethylene glycol diethyl ether (D-1), 53.5 parts by mass of N-(2-hydroxyethyl)acrylamide (a1-1), 46.5 parts by mass of 2,4,4-trimethylhexamethylene diisocyanate (b2-1), 5.0 parts by mass of diisopropoxybis(ethylacetoacetate)titanium (Orgatics TC-750, Matsumoto Fine Chemical Co., Ltd.) (C-1) as a catalyst, 0.01 parts by mass of methoxyhydroquinone (H-1) as a polymerization inhibitor, and stirred at 60 ° C. After 15 hours, analysis was performed by infrared absorption (IR) spectroscopy, and the disappearance of the absorption specific to the isocyanate group derived from b2-1 (near 2260 cm ^-1 ) was confirmed, and a D-1 solution of unsaturated urethane compound (F-1) was obtained.

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.

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) spectrum analysis showed that the absorption characteristic of isocyanate groups (near 2260 cm ^-1 ) had hardly decreased, confirming that the urethanization reaction had hardly progressed.

Comparative Examples 2 and 3: Synthesis of urethane compounds (I-2) and (I-3) Using the compositions shown in Table 1, the same operations as in Example 1 were 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.

Example 10 Synthesis of unsaturated urethane compound (F-10) 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 were placed in a separable flask and stirred at 60 ° C. IR analysis was performed to confirm the end of the decrease (24 hours after the start of the reaction) of the absorption (near 2260 cm ⁻¹ ) specific to the isocyanate group derived from b2-2, and the first-stage reaction was terminated. 16.2 parts by mass of hydroxyethyl acrylate (a1-7) was added to the resulting reaction solution, and the second-stage reaction was initiated by stirring at 60 ° C. 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).

Example 16 Synthesis of unsaturated urethane compound (F-16) In a separable flask, 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 were placed and stirred for 6 hours at 60 ° C. Similarly, the end of the reaction was confirmed by IR analysis, and a D-6 solution of unsaturated urethane compound (F-16) was obtained.

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

Comparative Example 4 Synthesis of Urethane Compound (I-4) Using the composition and reaction conditions shown in Table 2, the same operation as in Example 10 was carried out to synthesize urethane compound (I-4) corresponding to Comparative Example 4. However, the results of infrared absorption (IR) spectrum analysis after 48 hours showed that the absorption characteristic of the isocyanate group (near 2260 cm ⁻¹ ) had hardly changed from the initial state, indicating that the first-step reaction had hardly progressed.

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.

Comparative Examples 6 and 7 Synthesis of Urethane Compounds (I-6) and (I-7) Using the compositions shown in Table 2, the same operation 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 are shown in Table 2.

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)

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

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

(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)

(Catalysts (C) and (G))
C-1: Diisopropoxybis(ethylacetoacetate)titanium (Orgatics 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 (manufactured by 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-ethylhexanoic acid) (FUJIFILM Wako Pure Chemical Industries, Ltd.)
C-6: Tris(acetylacetonate)iron(III) (FUJIFILM Wako Pure Chemical Industries, Ltd.)
C-7: Tetrakis(acetylacetonate)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.)

(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

(Other Components (E))
E-1: Isobornyl acrylate E-2: Ethyl acetate

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

Measurement of molecular weight and calculation of unsaturated group equivalent of products of Examples 1 to 9 and Comparative Examples 1 to 3 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, so the molecular weight was measured by mass spectrometry using an infusion method (acetonitrile/0.1% acetic acid aqueous solution = 9/1 (mass ratio) as eluent) using a TSQ Quantum Access MAX (manufactured by Thermo Science) and an ESI probe (H-ESI2, positive measurement). In addition, the unsaturated group equivalent (molecular weight per unsaturated group) was calculated (unsaturated group equivalent = molecular weight/number of unsaturated groups). In addition, in Comparative Example 1, the urethane reaction hardly proceeded, so the molecular weight measurement was not performed. These results are shown in Table 3.

Measurement of molecular weight and calculation of unsaturated group equivalent of products in 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 are polymers with molecular weight distribution, and were measured by high performance liquid chromatography (using LC10A manufactured by Shimadzu Corporation, a Shodex GPC KF-806L column (exclusion limit molecular weight: 2×10 ⁷ , separation range: 100 to 2×10 ⁷ , theoretical plate number: 10,000 plates/unit), and tetrahydrofuran was used as the eluent.) and the number average molecular weight was calculated in terms of the molecular weight of standard polystyrene. 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 urethane reaction hardly proceeded, so the molecular weight was not measured. These results are shown in Table 4.

(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 the urethane compound (I) obtained in each Example and Comparative Example, or the viscosity of a solution of the unsaturated urethane compound (F) and the urethane compound (I) was measured at 60°C in accordance with JIS K5600-2-3. In Comparative Examples 1 and 4, the urethane reaction hardly proceeded, so no measurement was performed. The results of the viscosity measurement are shown in Tables 3 and 4.

(Hue)
The hue of the unsaturated urethane compound (F) and the urethane compound (I) obtained in each Example and Comparative Example, or the hue of the solution of the unsaturated urethane compound (F) and the urethane compound (I), was measured as the Hazen color number (APHA) 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 measurement are shown in Tables 3 and 4.
◎: APHA is 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.

(Stability)
The hue of the unsaturated urethane compound (F) and the urethane compound (I) obtained in each Example and Comparative Example, or the solution of the unsaturated urethane compound (F) and the urethane compound (I) was stored at 60°C for one week, and the viscosity was measured after storage, 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 ±10% or more but less than ±20% △: Viscosity change is ±20% or more but less than ±100% ×: Viscosity change is ±100% or more

The results of the production and evaluation of unsaturated urethane compounds with molecular weights of less than 1000 are shown in Tables 1 and 3. As is clear from these results, the unsaturated urethane compounds (F-1) to (F-9) can be produced at relatively low temperatures in a short time by the method of the present invention, and the resulting compounds (F-1) to (F-9) had good hue and thermal stability. On the other hand, in Comparative Example 1 where no catalyst was added, the reaction was not completed, and in Comparative Example 2 where a tertiary amine was used as a catalyst, a high temperature and long reaction time was required, and the resulting urethane compound (I-2) was brownish-brown and had a poor hue. In addition, it was prone to Michael addition of the amine and the unsaturated bond, and had low stability. In Comparative Example 3 where zinc bis(neodecanoic acid) derived from a group 12 element was used as a catalyst, the catalytic activity was low, a long reaction time was required, the resulting product (I-3) had a poor hue, was also low in stability, and the production of insoluble matter was confirmed.

The results of the production and evaluation of high molecular weight unsaturated urethane compounds having a molecular weight of 1000 or more obtained by using a polyol (a2) having two or more hydroxyl groups and a polyisocyanate (b2) having two or more isocyanate groups in combination are shown in Tables 2 and 4. As is clear from these results, the method of the present invention shows good reactivity even when (a2) and (b2) are reacted with (a1) (multi-step reaction) as in Example 10, and when (a1), (a2), and (b2) are charged at once and reacted as in Example 16, it was found that the reaction is completed at a relatively low temperature and in a short time. In addition, it is possible to produce a variety of unsaturated urethane compounds ranging from high molecular weight and high viscosity to low molecular weight and low viscosity, and the obtained unsaturated urethane compounds (F-10) to (F-23) were excellent in hue and thermal stability. In Examples 11 and 12, which contain an amide bond in the reaction system, the reactivity was improved, and in Examples 13 to 23, which contain both an ether bond and an amide bond in the reaction system, the reactivity was further improved, the hue of the obtained unsaturated urethane compound was lower, and the thermal stability was further improved. On the other hand, in Comparative Example 4, which does not contain a catalyst even though it contains both an ether bond and an amide bond as in Example 14, the reaction was not completed. In Comparative Example 5, which uses a tertiary amine as a catalyst, the required reaction temperature was high, the reaction time was long, and the hue and thermal stability of the obtained urethane compound (I-5) were poor. In addition, Comparative Examples 6 and 7, which use acryloylmorpholine (D-6) containing both an ether bond and an amide bond as a diluent monomer with reference to Example 2 and Comparative Example 1 described in Patent Document 4 (JP Patent Publication 2010-215774 A), showed relatively good reactivity, but Comparative Example 6, which uses a zinc-based catalyst, was severely colored, and Comparative Example 7, which uses a tin-based catalyst, was slightly colored, and at the same time, the viscosity was reduced by about 30%.

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 1 to 3 transition elements and the group 13 to 15 elements (excluding tin) as a catalyst. Since the unsaturated urethane compound can be efficiently obtained at a low temperature in a short time, it is possible to reduce costs and improve the color and quality. In addition, the unsaturated urethane compound obtained does not use a toxic tin-based catalyst, and is highly safe and can be suitably used as a raw material for curable resin compositions. It can be used in various fields such as paints for automobiles, electrical appliances, furniture, etc., coating materials, buffer materials, packings, vibration-proof materials, sound-absorbing materials, printing plates, sealants, abrasives, transparent adhesive sheets, UV-curable adhesives and pressure-sensitive adhesives, sealing materials, sealants, dental hygiene materials, optical materials, photo-modeling materials, materials for reinforced plastics, and resin compositions for three-dimensional photo-modeling.

Claims (8)

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 compound (D) having an ether bond and a catalyst (C) which is an organic salt or complex of at least one metal element selected from the group consisting of titanium, aluminum, hafnium, zirconium, bismuth and iron ,
D is alkylene (having 1 to 4 carbon atoms, the same applies below) glycol dialkyl (having 1 to 18 carbon atoms, the same applies below) ether, dialkylene glycol dialkyl ether, trialkylene glycol dialkyl ether, polyalkylene glycol dialkyl ether, alkylene glycol alkyl ether acetate, dialkylene glycol alkyl ether acetate, trialkylene glycol alkyl ether acetate, polyalkylene glycol alkyl ether acetate, alkylene glycol diaryl ether, dialkylene glycol diaryl ether, trialkylene glycol diaryl ether, polyalkylene glycol diaryl ether, alkylene glycol aryl ether acetate, dialkylene glycol aryl ether a method for producing an unsaturated urethane compound, which is an unsaturated urethane compound selected from the group consisting of aryl ether acetate, trialkylene glycol aryl ether acetate, polyalkylene glycol aryl ether acetate, 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, cyclic ethers, and cyclic ether group-introduced (meth)acrylates . The method for producing an unsaturated urethane compound according to claim 1, 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. The method for producing an unsaturated urethane compound according to claim 1 or 2, characterized in that the unsaturated bond is one or more unsaturated bonds selected from the group consisting of (meth)acrylate groups, (meth)acrylamide groups, vinyl groups, vinyl ether groups, methyl vinyl ether groups, allyl groups, (meth)allyl ether groups and maleimide groups. The method for producing an unsaturated urethane compound according to any one of claims 1 to 3 , 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. The method for producing an unsaturated urethane compound according to any one of claims 1 to 4 , characterized in that the compound (D) is a compound further having an amide bond. The method for producing an unsaturated urethane compound according to any one of claims 1 to 5 , characterized in that the compound (D) is an aliphatic, alicyclic, or aromatic compound having no active hydrogen. The method for producing an unsaturated urethane compound according to any one of claims 1 to 6 , characterized in that the amount of the catalyst (C) is 0.001 to 5.0% (mass ratio) based on the total amount of the alcohol compound (A) and the isocyanate compound (B). The method for producing an unsaturated urethane compound according to any one of claims 1 to 7 , characterized in that the blending amount of the compound (D) is 1 to 200% (mass ratio) based on the total amount of the alcohol compound (A) and the isocyanate compound (B).