JP2020189833A - Method for producing unsaturated urethane compound - Google Patents

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

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 having unsaturated bonds between carbon atoms (unsaturated urethane compounds) have various skeleton structures of unsaturated groups between carbon atoms and urethane compounds, and thus can be used as a raw material for curable resin compositions. It is widely used, and by using it in a photocurable resin composition, it is easy to impart various performances such as flexibility, flexibility, flexibility, toughness, solvent resistance, and abrasion resistance to the cured product. It is possible to use it and is widely used in various fields such as adhesives, coatings, and inks.

Such unsaturated urethane compounds usually react a polyol with a polyisocyanate to give a polyurethane having hydroxyl groups or isocyanate groups at both ends, after which each further comprises a hydroxyl group-containing unsaturated compound or an isocyanate group-containing unsaturated compound. It is synthesized by reacting (Patent Documents 1 to 3).

Organic tin compounds such as dibutyltin dilaurate and tertiary amines are often used as catalysts in the urethanization reaction between isocyanate groups and hydroxyl groups. However, in the multi-step reaction often used for the synthesis of unsaturated urethane compounds, tertiary amines are not suitable because they have low catalytic activity, and organotin compounds show good catalytic activity, but are endocrine. It has been regarded as a problem as a disturbing substance, and its use has been regulated in recent years.

Therefore, as an alternative to the organotin compound, various organometallic compounds are newly studied as urethanization catalysts. For example, in a curable composition composed of urethane acrylate obtained by synthesizing urethane acrylate in the presence of a zinc compound and a hydroxyl group-containing acrylate, the inclusion of the zinc compound reduces the composition generated by the tin catalyst. The problem of stickiness (decrease in viscosity over time) could be suppressed (Patent Document 4). Further, in order to produce polyurethane, a zinc complex or a salt thereof has been proposed as a novel catalyst that is tin-free (Patent Document 5). However, these zinc catalysts have lower activity than conventional tin catalysts, the reaction progresses extremely slowly under normal conditions, and the urethanization reaction is not completed even if the amount of catalyst added is increased up to 3 times. Moreover, there is a problem that the product of the reaction is colored.

JP-A-2010-267703 WO2015 / 141537 WO2017 / 047615 JP-A-2010-215774 Special Table 2012-511506

An object of the present invention is to provide a method for producing an unsaturated urethane compound under normal reaction conditions (reaction temperature, catalyst addition amount, etc.) using a catalyst having excellent reaction activity without using an organotin catalyst. And. Another object of the present invention is to provide a method for producing an unsaturated urethane compound having a good hue and quality without causing troubles in temperature control by using the catalyst.

As a result of intensive studies to solve the above problems, the present inventors have made the first to third transition elements and the first as a catalyst when producing an unsaturated urethane compound by reacting an alcohol compound with an isocyanate compound. The present invention has been found that an unsaturated urethane compound of good quality can be efficiently produced by using an organic salt or complex of at least one metal element selected from Group 13 to 15 elements (excluding tin). Has been completed.

That is, the present invention is (1) a method for producing an unsaturated urethane compound having an unsaturated bond between carbon atoms, wherein the alcohol compound (A) and the isocyanate compound (B) are used as a catalyst (C). Production of unsaturated urethane compounds characterized by reaction in the presence of an organic salt or complex of at least one metal element selected from ~ 3 transition elements and Group 13 ~ 15 elements (excluding tin). Method,
(2) 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, and the isocyanate compound (B) is unsaturated between carbon atoms. The molar ratio of the isocyanate compound (b1) having a bond and / or the polyisocyanate (b2) having two or more isocyanate groups, and the hydroxyl group (OH) to the isocyanate group (NCO) is 0.9 to 1.1. The method for producing an unsaturated urethane compound according to (1) above, wherein the method is characterized by the above.
(3) The unsaturated bond is 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 group1 The method for producing an unsaturated urethane compound according to (1) or (2) above, which has an unsaturated bond of more than one species.
(4) The catalyst (C) is scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, ytterbium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, lantern, cerium, praseodymium, neodymium, At least selected from Samalium, Europium, Gadolinium, Terbium, Dysprosium, Holmium, Elbium, Thulium, Ytterbium, Hafnium, Tantal, Tungsten, Renium, Osmium, Iridium, Platinum, Gold, Aluminum, Gallium, Indium, Tallium, Lead, Bismus The method for producing an unsaturated urethane compound according to any one of (1) to (3) above, which is an organic salt or a complex of one kind of metal element.
(5) The above-mentioned (1) to (4), wherein any one or more 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 the above.
(6) The method for producing an unsaturated urethane compound according to any one of (1) to (5) above, which further contains a compound (D) having an ether bond and / or an amide bond.
(7) The unsaturated urethane according to any one of (1) to (6) above, wherein the compound (D) is an aliphatic, alicyclic, or aromatic compound having no active hydrogen. Method of producing compounds,
(8) The compounding amount of the catalyst (C) is 0.001 to 5.0% (mass ratio) with respect to the total of the alcohol compound (A) and the isocyanate compound (B). ) To the method for producing an unsaturated urethane compound according to any one of (7).
(9) The compounding amount of the compound (D) is 1 to 200% (mass ratio) with respect to the total of the alcohol compound (A) and the isocyanate compound (B). ), The method for producing an unsaturated urethane compound according to any one of the above.
Is to provide.

According to the present invention, when an unsaturated urethane compound having an unsaturated bond between carbon atoms is produced by reacting an alcohol compound and an isocyanate compound, the 1st to 3rd transition elements and the 13th to 15th group elements (tin) are produced. By using an organic salt or complex of at least one metal element selected from (excluding) as a catalyst, an unsaturated urethane compound under normal reaction conditions can be efficiently produced without using an organic tin catalyst. it can. Further, by using a novel catalyst, the reaction temperature can be easily controlled, and an unsaturated urethane compound having good hue and quality can be obtained.

The present invention will be described in detail below. In the method for producing an unsaturated urethane compound of the present invention, an alcohol compound (A) and an isocyanate compound (B) are mixed with the catalysts (C) of the 1st to 3rd transition elements and the 13th to 15th group elements (excluding tin). It is characterized by reacting in the presence of an organic salt or complex of at least one metal element selected from the above. Hereinafter, each configuration in the manufacturing method of the present invention will be described.

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. The alcohol compound (a1) is 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. More preferably, it contains one or more unsaturated bonds.

Examples of (a1) include hydroxyalkyl (meth) acrylates having linear, branched, or cyclic alkylene groups having 1 to 20 carbon atoms introduced, hydroxyalkyl (meth) acrylamides, hydroxyalkyl vinyl ethers, hydroxyalkyl (methyl) vinyl ethers, and hydroxys. Polyalkylene glycol (meth) acrylate, polyalkylene glycol (meth) acrylamide, and polyalkylene having an alkyl (meth) allyl ether, hydroxyalkyl maleimide, and alkylene glycol having 1 to 9 carbon atoms and 1 to 23 repeating units of the alkylene glycol. Glycolvinyl ether, polyalkylene glycol (methyl) vinyl ether, polyalkylene glycol (meth) allyl ether, polyalkylene glycol maleimide, linear, branched or cyclic alkyl having 1 to 8 carbon atoms on the nitrogen atom of the (meth) acrylamide-based monomer. Hydroxyphenyl (meth) such as N-alkyl (hydroxyalkyl) (meth) acrylamide introduced with groups and alkylene groups, N-alkyl (polyalkylene glycol) (meth) acrylamide, N-alkyl (hydroxyphenyl) (meth) acrylamide, etc. Examples thereof include acrylate, hydroxyphenyl (meth) acrylamide, hydroxyphenyl vinyl ether, hydroxyphenyl (methyl) vinyl ether, hydroxyphenyl (meth) allyl ether, and hydroxyphenyl maleimide. Among them, hydroxyalkyl (meth) acrylate and hydroxyalkyl (meth). It is preferable to use acrylamide because the polymerizable urethane compound improves the polymerizable property. These (a1) can be used individually by 1 type or in combination of 2 or more types.

Reference numeral (a2) is a polyol having two or more hydroxyl groups in the molecule, an alkylene polyol, a polyether polyol, a polyester polyol, a polycarbonate polyol, a hydrogenated polyalkaziene polyol, a polyalkaziene polyol, and a silicone skeleton. It is preferable, and among them, a polyol having two hydroxyl groups in the molecule, an alkylene diol, a polyether diol, a polyester diol, a polycarbonate diol, a hydrogenated polyalkaziene diol, a poly alkaziene diol, and a silicone skeleton. Is more preferable. These (a2) can be used individually by 1 type or in combination of 2 or more types.

Examples of the alkylene polyol include linear, branched and cyclic alkylene diols having 2 to 18 carbon atoms, alkylene triol and alkylene tetraol, and specific examples thereof include ethylene glycol, 1,2-propylene glycol and 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- Examples thereof include decanediol, 1,18-octadecanediol, glycerin, trimethylolpropane, pentaerythritol and the like.

Examples of the polyether polyol include linear, branched, and cyclic polyalkylene glycols having 2 to 18 carbon atoms, and specific examples thereof include polyethylene glycol, glycerin tri (polyoxyethylene) ether, and trimethyl propantri (polyoxyethylene). ) Ether, pentaerythritol tetra (polyoxyethylene) ether, poly (oxy-1,3-propylene) glycol, glycerintri (polyoxy-1,3-propylene) ether, trimethyl propantri (polyoxy-1,3-propylene) ) Ether, pentaerythritol tetra (polyoxy-1,3-propylene) ether, poly (oxy-1,2-propylene) glycol, glycerintri (polyoxy-1,2-propylene) ether, trimethyl propantri (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) Examples thereof include alkylene glycols such as −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 terminal. 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, and 1,4-cyclohexanedicarboxylic acid. Acids, succinic acid, maleic acid, phthalic acid, adipic acid, azelaic acid, sebacic acid, dodecanedioic acid, 1,2,4-butanetricarboxylic acid, hemimelitoic acid, trimellitic acid, trimesic acid, cyclohexanetricarboxylic acid, pyromerit Examples thereof include acids, cyclohexanetetracarboxylic acids, and the like, and examples of the polyol component include the alkylene polyols according to the above item [0015].

Examples of the polycarbonate polyol include those composed of a carbonyl component and a polyol, having a carbonate skeleton in the molecule, and having a hydroxyl group at the terminal. Examples of the carbonyl component include phosgene, chloroformate, dialkyl carbonate, diaryl carbonate, alkylene carbonate and the like, and examples of the polyol component include the alkylene polyols according to the above item [0015].

Examples of the hydrogenated polyalkaziene polyol include 1,2-hydrogenated polybutadienediol, 1,4-hydrogenated polybutadienediol, and hydrogenated polyisoprene polyol. Examples of the polyalkaziene polyol include 1,2-polybutadienediol. , 1,4-Polybutadienediol, polyisoprene polyol and the like.

The polyol having a silicone skeleton includes a siloxane bond in the molecule in the main examiner skeleton and has two or more hydroxyl groups at both ends or side chains, and is a side chain introduction type carbinol-modified silicone, both ends introduced. Examples include type carbinol-modified silicone, side chain and double-ended introduction type carbinol-modified silicone.

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. The isocyanate compound (b1) is 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 group1 It is more preferable to contain unsaturated bonds of more than one species.

Examples of (b1) include isocyanatoalkyl (meth) acrylate, isocyanatoalkyl (meth) acrylamide, isocyanatoalkyl vinyl ether, and isocyanatoalkyl (methyl) introduced with a linear, branched, or cyclic alkylene group having 1 to 18 carbon atoms. ) Vinyl ether, isocyanatoalkyl (meth) allyl ether, isocyanatoalkyl maleimide, isocyanatoalkoxyalkyl (meth) acrylate, isocyanatoalkoxyalkyl (meth) acrylamide, isocyanatoalkoxyalkyl vinyl ether, isocyanatoalkoxyalkyl (methyl) vinyl ether, N- in which a linear, branched or cyclic alkyl group or alkylene group having 1 to 8 carbon atoms is introduced into the nitrogen atom of isocyanatoalkoxyalkyl (meth) allyl ether, isocyanatoalkoxyalkyl maleimide, or the (meth) acrylamide-based monomer. Alkyl (isocyanatoalkyl) (meth) acrylamide, N-alkyl (isocyanatoalkoxyalkyl) (meth) acrylamide, N-alkyl (isocyanatophenyl) (meth) acrylamide, etc. Isocyanatophenyl (meth) acrylate, isocyanatophenyl (Meta) acrylamide, isocyanatophenyl vinyl ether, isocyanatophenyl (methyl) vinyl ether, isocyanatophenyl (meth) allyl ether, isocyanatophenyl maleimide, among which isocyanatoalkyl (meth) acrylate, isocyanatoalkyl ( It is preferable to use meta) acrylamide because the polymerizable property of the unsaturated urethane compound becomes good. These (b1) can be used individually by 1 type or in combination of 2 or more types.

Examples of (b2) include trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, 1,2-propylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, and 1,3. -Alidiisocyanates such as butylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, 2,4- Aromatic diisocyanates such as tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 2,4-diphenylmethane diisocyanate, xylylene diisocyanate, cyclopentylene diisocyanate, cycloheximethylene diisocyanate, isophorone diisocyanate, 4 , 4'-Dicyclohexylmethane diisocyanate, methylcyclohexamethylene diisocyanate, 2,5-norbornan diisocyanate, 2,6-norbornan diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane and other alicyclic diisocyanates, or adducts thereof Examples include type, isocyanurate type, and bullet type. These can be used individually by 1 type or in combination of 2 or more types.

In obtaining the unsaturated urethane compound by the production method of the present invention, the combination of the alcohol compound (A) and the isocyanate compound (B) is arbitrary, but the unsaturated urethane compound contains an unsaturated bond between carbon atoms. In addition, 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. Further, when the polyol (a2) having two or more hydroxyl groups and the polyisocyanate (b2) having two or more isocyanate groups are contained, the unsaturated urethane compound obtained by the ratio of (a2) and (b2) It is preferable because the molecular weight can be adjusted arbitrarily.

The combination of the alcohol compound (A) and the isocyanate compound (B) is arbitrary, but the total number of hydroxyl groups contained in the alcohol compound (a1) having an unsaturated bond and / or the polyol (a2) having two or more hydroxyl groups ( The molar ratio calculated from the total (mol) of isocyanate groups contained in (molar) and the isocyanate compound (b1) having an unsaturated bond and / or polyisocyanate (b2) having two or more isocyanate groups is a hydroxyl group (molar). OH) / isocyanate group (NCO) = 0.9 to 1.1, and if an isocyanate group remains in the obtained unsaturated urethane compound, it may react with moisture in the air and cause instability. Since it becomes a factor, it is more preferable that the hydroxyl group (OH) / isocyanate group (NCO) = 1.0 to 1.1, which is more than the isocyanate group.

The catalyst (C) used in the present invention is 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). Specifically, scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, ittrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, lantern, cerium, praseodymium, neodymium, samarium, europium. , Gadolinium, terbium, dysprosium, holmium, erbium, thulium, itterbium, hafnium, tantalum, tungsten, renium, osmium, iridium, platinum, gold, aluminum, gallium, indium, tarium, lead, bismuth It is preferably an organic salt or complex of a metal element. Of these, titanium, iron, zirconium, hafnium, aluminum, and bismuth are more preferable, and iron, zirconium, and bismuth are particularly preferable.

As the organic salt of the metal element, an organic acid and a metal salt, an organic acid and a metal oxide salt, an organic acid and an alkyl metal salt, an organic acid and an alkoxy metal salt and the like are preferable, and the organic acid has a carbon number of carbon atoms. 1-18 linear, branched, cyclic alkylcarboxylic acids, formic acids, dodecylbenzenesulfonic acids, maleic acids, fumaric acids, lactic acids, oxalic acids, naphthenic acids, tartaric acids, citric acids, oleic acids, (meth) acrylic acids, Examples thereof include pyridine-2-carboxylic acid, trifluoroacetic acid and trifluoromethanesulfonic acid. Organic salts of titanium, iron, zirconium, and bismas are preferable from the viewpoint of showing good catalytic activity, and bis (acetate) iron (II), tris (2-ethylhexanoic acid) iron (III), and bis (stearate) iron ( II), Tris (stearic acid) iron (III), bis (dodecylbenzenesulfonic acid) diisopropoxytitanium, zirconium tetrakis (2-ethylhexanoic acid), zirconium tetrakis (stearic acid), bismastris (2-ethylhexanoic acid) ), Bismastris (neodecansanoic acid), etc., and because of their low colorability, tris (stearic acid) iron, bismastris (2-ethylhexanoic acid), bismastris (neodecansanoic acid), zirconium tetrakis (2) -Ethylhexanoic acid) and zirconium tetrakis (stearic acid) are more preferable.

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 and the like, and specifically, an acetylacetonet complex and an ethylacetate. Acetate complex, dimethoxyethane complex, tetrahydrofuran complex, 2,2,6,6-tetramethyl-3,5-heptandionat complex, trifluoroacetylacetonetate complex, hexafluoroacetylacetonate complex, cyclopentadienyl complex, pentafluoro A cyclopentadienyl complex or the like is preferable, and a complex with titanium, iron, zirconium, hafnium, aluminum or bismuth is preferable from the viewpoint of exhibiting good catalytic activity, and diisopropoxybis (ethylacetone acetate) titanium and tetrakis (acetylacetonate) are preferable. ) Titanium, bis (cyclopentadienyl) iron, iron (II) bis (acetylacetoneate), iron (III) tris (acetylacetoneate), zirconium monoacetylacetonate, zirconium tetrakis (acetylacetonate) zirconium, zirconium More preferably, ethylacetacetate, tetrakis (acetylacetonate) hafnium, tris (acetylacetonate) aluminum, tris (2,2,6,6, -tetramethyl-3,5-heptandionat) bismuth, and colorability. It is more preferable to use zirconium monoacetylacetonate, tetrakis (acetylacetonate) zirconium, zirconium ethylacetone acetate, or tetrachlorobis (tetrachloride) zirconium because of its low value.

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 with respect to the total of the alcohol compound (A) and the isocyanate compound (B). Use of 0.001% or more is preferable because the urethanization reaction can proceed rapidly, and use of 5.0% or less is preferable because coloring by a catalyst can be suppressed. Further, it is more preferably 0.01 to 1.0%.

The method for producing an 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, but the reaction system When a compound having an ether bond and / or an amide bond is contained therein, the rate of the urethanization reaction is improved, so that the unsaturated urethane compound can be produced at a low temperature or in a short time, and the obtained unsaturated urethane compound can be produced. It is preferable because it has good hue and quality and can reduce the manufacturing cost by low temperature and short time reaction.

As a method for incorporating the compound having an ether bond and / or an amide bond in the reaction system, (1) the bond to the alcohol compound (A), the isocyanate compound (B), and the catalyst (C) used in the present invention. (2) A method of adding the compound (D) having the bond can be mentioned.

Specific examples of the compound having an ether bond in the method (1) include polyalkylene glycol (meth) acrylate, polyalkylene glycol (meth) acrylamide, and polyether polyol as the alcohol compound (A). Examples of the isocyanate compound (B) include 2- (2-isocyanatoethoxy) ethyl (meth) acrylate, and examples of the catalyst (C) include tetrachlorobis (tetrahydrofuran) zirconium. Of these, a polyether polyol capable of introducing a larger amount of ether structure into the reaction system is preferable.

In the method (1) above, as the compound having an amide bond, specifically, as the alcohol compound (A), hydroxyalkyl (1 to 18 carbon atoms) (meth) acrylamide and alkylene glycol have 2 to 6 carbon atoms. A linear, branched or cyclic alkyl group or alkylene group having 1 to 8 carbon atoms is introduced into the nitrogen atom of the polyalkylene glycol (meth) acrylamide in which the repeating unit of the alkylene glycol is 1 to 23 and the (meth) acrylamide-based monomer. N-alkyl (hydroxyalkyl (1 to 18 carbon atoms)) (meth) acrylamide, polyalkylene glycol-N-alkyl (meth) having 2 to 6 carbon atoms of alkylene glycol and 1 to 23 repeating units of alkylene glycol. ) Acrylamide, (hydroxyphenyl) -N-alkyl (meth) acrylamide and the like. Of these, hydroxyalkyl (1 to 18 carbon atoms) (meth) acrylamide is more preferable, and N- (2-hydroxyethyl) acrylamide is particularly preferable because PII = 0.0, which is low in skin irritation and high in safety.

In the method (1), by having an ether bond in any one or more of the compounds (A), (B) and (C), the catalytic activity can be improved, and the catalytic activity can be improved at a low temperature in a short time. It is preferable because the reaction can be carried out and the problem of easy coloring due to the unsaturated bond of the unsaturated urethane compound according to the present invention can be solved. Further, by having an amide bond in any one or more of the compounds (A), (B) and (C), the reactivity between the hydroxyl group and the isocyanate group is improved, and as a result, in the production of the unsaturated urethane compound, This is preferable because troubles such as polymerization and thickening that tend to occur in the manufacturing process can be suppressed. Furthermore, when an ether bond and an amide bond are simultaneously present in the reaction system using (A), (B) and (C), an unsaturated urethane compound can be stably produced, and coloring of the obtained unsaturated urethane compound is prevented. It is more preferable because it can be possible. It is speculated by the present inventors that when an intramolecular or intermolecular ether bond and an amide bond approach each other, their interaction increases the specific effect of each and at the same time further improves the rate of the urethanization reaction. 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 has an ether bond and / or an amide bond, but does not react with (A), (B) or (C) (activity). If it does not have hydrogen), it can be preferably used. The ether bond and / or amide bond of compound (D) has the same effect as described above, and one or both of the ether bond and amide bond in the reaction system using (A), (B) and (C). When the compound (D) having one or both of the ether bond and the amide bond is contained, the ether bond and the amide bond are simultaneously contained in the reaction system, and the synergistic effect due to the interaction between them is similarly contained. Is more preferable because it can be provided. Further, it is particularly preferable to use the compound (D) having an ether bond and an amide bond at the same time, because a high effect can be expected even if a small amount is added.

Examples of the compound (D) include aliphatic, alicyclic, and aromatic compounds containing an ether bond and / or an amide bond and having no active hydrogen, and specific examples thereof include alkylene glycols having 1 to 4 carbon atoms. Alkylene glycol dialkyl ether, dialkylene glycol dialkyl ether, trialkylene glycol dialkyl ether, polyalkylene glycol dialkyl ether, alkylene glycol alkyl ether acetate, which are composed of linear, branched, cyclic alkyl or aryl groups having 1 to 18 carbon atoms. 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, Glycols such as dialkylene glycol aryl ether acetate, trialkylene glycol aryl ether acetate, polyalkylene glycol aryl ether acetate, amides such as dialkylformamide, dialkylacetamide, dialkylpropionamide, morpholinacetamide, morpholinpropanamide, alkoxy-N, Amido ethers such as N-dialkylacetamide, alkoxy-N, N-dialkylpropanamide, cyclic ethers such as tetrahydrofuran and 1,4-dioxane, alkylene glycol alkyl ether (meth) acrylate, dialkylene glycol alkyl ether (meth) Acrylic, trialkylene glycol alkyl ether (meth) acrylate, polyalkylene glycol alkyl ether (meth) acrylate, arylalkylene glycol (meth) acrylate, aryldialkylene glycol (meth) acrylate, aryltrialkylene glycol (meth) acrylate, arylpoly Glycol (meth) acrylates such as alkylene glycol (meth) acrylate, alkylene glycol alkyl ether (meth) acrylamide, dialkylene glycol alkyl ether (meth) acrylamide, trialkylene glycol alkyl ether (meth) acrylamide, polyal Glycols such as gillene glycol alkyl ether (meth) acrylamide, alkylene glycol aryl ether (meth) acrylamide, dialkylene glycol aryl ether (meth) acrylamide, trialkylene glycol aryl ether (meth) acrylamide, polyalkylene glycol aryl ether (meth) acrylamide Substituted (meth) acrylamides such as (meth) acrylamides, dialkyl (meth) acrylamides, and diacetone acrylamides, introduction of cyclic ether groups such as tetrahirodoflufuryl (meth) acrylates and cyclic trimethylolpropaneformal (meth) acrylates ( Examples thereof include cyclic ether group-introduced (meth) acrylamides such as meta) acrylates, tetrahirodoflufuryl (meth) acrylamide, cyclic trimethylolpropaneformal (meth) acrylamide, and (meth) acryloylmorpholin. These can be used individually by 1 type or in combination of 2 or more types.

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 urethanization reaction becomes better. Therefore, morpholinacetamide and methoxy-N, N-dimethylpropaneamide It is more preferable to use amide ethers such as, and cyclic ether group-introduced (meth) acrylamides such as acryloylmorpholine.

The blending amount of the compound (D) is preferably 1.0 to 200.0% (mass ratio) with respect to the total of the alcohol compound (A) and the isocyanate compound (B). When it is 1.0% or more, the rate of the urethanization reaction is improved and the hue of the obtained unsaturated urethane compound is low, which is preferable. When it is 200.0% or less, the reaction promoting effect of the compound (D) and the decrease in the reaction rate due to the decrease in the concentration of the alcohol compound (A) and the isocyanate compound (B) in the reaction system are balanced and the reaction is carried out. It is preferable because the speed is easy to control.

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 rapidly, and if the temperature is 100 ° C. or lower, coloring, thickening, etc. can be suppressed due to production, which is preferable. Further, the reaction temperature is more preferably 30 to 80 ° C.

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 may be carried out collectively or may be carried out in several steps. Further, the production method of the present invention can be carried out without a solvent, but if necessary, the compound (D) and other components (E) having no ether bond or / or amide bond are diluted with an organic solvent or reactive. It can be used as an agent.

Among the other components (E), examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, aprotonic polar solvents such as dimethylformamide, dimethylacetamide and dimethylsulfoxide, ethyl acetate and acetic acid. Examples thereof include ester solvents such as butyl, 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.

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

The amount of (E) added may be appropriately set according to the unsaturated urethane compound (F), but from the viewpoint of the viscosity of (F), ease of production, and economy, the amount of the alcohol compound (A) is higher than that of the alcohol compound (A). It is preferably 1.0 to 200.0% (mass ratio) with respect to the total of the isocyanate compounds (B).

In the production method of the present invention, various additives can be appropriately used as needed. Additives include UV sensitizers, thermal polymerization inhibitors, anti-aging agents, antioxidants, preservatives, phosphate ester and other flame retardants, surfactants, wet dispersants, antistatic agents, colorants. , Plasticizers, Surfactants, Leveling Agents, Softeners, Thickeners, Pigments, Organic Fillers, Inorganic Fillers, etc. In particular, thermal polymerization is prohibited to prevent the polymerization of unsaturated bonds between carbon atoms. It is preferable to add an agent.

Examples of the thermal polymerization inhibitor include quinone-based polymerization inhibitors such as hydroquinone, methoxyhydroquinone, benzoquinone, and p-tert-butylcatechol; 2,6-di-tert-butylphenol, 2,4-di-tert-butylphenol, and the like. Alkylphenolic polymerization inhibitors such as 2-tert-butyl 4,6-dimethylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol; alkylated diphenylamine, Amine-based polymerization inhibitors such as N, N'-diphenyl-p-phenylenediamine, phenothiazine, N-oxyls such as 4-hydroxy-2,2,6,6-tetramethylpiperidin-N-oxyl; dimethyldithiocarbamic acid Examples thereof include copper-based dithiocarbamate polymerization inhibitors such as copper, copper diethyldithiocarbamate, and copper dibutyldithiocarbamate. These may be used alone or in combination of two or more.

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

The molecular weight of the unsaturated urethane compound (F) obtained in the production method of the present invention is not particularly limited, but is preferably a number average molecular weight of 250 to 1,000,000. (F) is used as a raw material for a curable resin composition, and the cured product obtained by curing the cured product can be easily subjected to various performances such as flexibility, flexibility, flexibility, toughness, solvent resistance, and abrasion resistance. Since it can be applied to, it is widely used in various fields such as adhesives, coatings, and inks. The number average molecular weight is preferably 250 or more for suitable use in these applications, and the number average molecular weight is maintained from the viewpoint of maintaining good compatibility with polymerizable monomers and organic solvents and maintaining a viscosity suitable for operability. Is preferably 1,000,000 or less, and more preferably a number average molecular weight of 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 (F) has one or more unsaturated groups and can be used as a raw material for a polymerizable or curable resin. Further, 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, and thus a cured product obtained by using the unsaturated group. Is flexible and flexible, and in particular, a cured product using urethane (meth) acrylamide having a (meth) acrylamide group as an unsaturated group is also excellent in toughness, solvent resistance and abrasion resistance. Therefore, it is preferable. Further, 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, unsaturated oligomers, etc. to prepare a polymerizable curable resin composition. As a method of adjusting the curability of the resin composition and the physical property values such as the strength and elongation of the obtained cured product according to the intended use, the type and amount of the unsaturated monomer or unsaturated oligomer to be added are adjusted. Examples thereof include a method and a method of adjusting according to the type of the urethane skeleton of (F), the number of unsaturated bonds between carbon atoms, the molecular weight, and the like.

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

The curable resin composition can be used for various purposes. Specifically, it is used as a coating material used for paints and coating materials for automobiles, electrical appliances, furniture, etc., and as a buffer material, packing, vibration isolator, sound absorbing material, printing plate, sealing material, abrasive, etc. Materials for elastomers, transparent adhesive sheets, adhesives and adhesives such as UV curable adhesives, sealing materials and encapsulants, dental hygiene materials, optical materials, optical molding materials, materials for reinforced plastics, Examples thereof include resin compositions for three-dimensional optical modeling, but the applications are not necessarily limited to these.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In the following, "parts" and "%" are all based on mass unless otherwise specified.

Unsaturated urethane compounds (F-1) to (F-23) of Examples and urethane compounds (I-1) to (I-7) for Comparative Examples)
Example 1 Synthesis of unsaturated urethane compound (F-1) 50.0 parts by mass of diethylene glycol diethyl ether (D-1) and 53.5 parts by mass of N- (2-hydroxyethyl) acrylamide (a1-1) in a separable flask. Part, 2,4,4-trimethylhexamethylene diisocyanate (b2-1) 46.5 parts by mass, diisopropoxybis (ethylacetacetate) titanium as a catalyst (manufactured by Organix TC-750 Matsumoto Fine Chemical Co., Ltd.) (C- 1) 5.0 parts by mass and 0.01 part by mass of methoxyhydroquinone (H-1) as a polymerization inhibitor were added, and the mixture was stirred at 60 ° C. After 15 hours, analysis was performed by infrared absorption (IR) spectrum, and disappearance of absorption (around 2260 cm ^-1 ) peculiar to the isocyanate group derived from b2-1 was confirmed, and D of the unsaturated urethane compound (F-1) was confirmed. -1 Solution was obtained.

Synthesis of Examples 2-9 Unsaturated Urethane Compounds (F-2) to (F-9) Unsaturated Urethane Corresponding to Examples 2-9 by performing the same operation as in Example 1 with the composition shown in Table 1. Solutions of compounds (F-2) to (F-9) were obtained. Table 1 shows their reaction temperatures and reaction times.

Comparative Example 1
The same reaction as in Example 1 was carried out except that the catalyst C-1 was removed, and infrared absorption (IR) spectrum analysis after 48 hours showed that the absorption peculiar to the isocyanate group (around 2260 cm ^-1 ) was hardly reduced. It was confirmed that the urethanization reaction hardly proceeded.

Comparative Examples 2 and 3 Synthesis of Urethane Compounds (I-2) and (I-3) The urethane compounds (I-) corresponding to Comparative Examples 2 and 3 were subjected to the same operations as in Example 1 with the compositions shown in Table 1. The solution of 2) and the solution of (I-3) were obtained. Table 1 shows their reaction temperature and reaction time (time required to complete the reaction).

Example 10 Synthesis of unsaturated urethane compound (F-10) In a separable flask, Clare polyol P-1012 (manufactured by Kurare Co., Ltd.) (a2-3) 58.0 parts by mass, isophorone diisocyanate (b2-2) 25.8. 0.1 part by mass of tetrakis (acetylacetonate) zirconium (C-6) as a catalyst and 0.01 part by mass of methoxyhydroquinone (H-1) as a polymerization inhibitor were added by mass and stirred at 60 ° C. IR analysis was performed to confirm that the absorption (around 2260 cm ^-1 ) peculiar to the isocyanate group derived from b2-2 stopped decreasing (24 hours after the start of the reaction), and the first-stage reaction was completed. 16.2 parts by mass of hydroxyethyl acrylate (a1-7) was added to the obtained reaction solution, and the mixture was stirred at 60 ° C. to start 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 completed 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), Clare polyol P-2010 (a2-6) 74. 5 parts by mass, 16.8 parts by mass of isophorone diisocyanate (b2-2), 100 parts by mass of N-acrylamide morpholine (D-6), 0.05 parts by mass of bismastris (2-ethylhexanoic acid) (C-5) as a catalyst. , 0.05 part by mass of 2,6-di-tert-butylphenol (H-2) as a polymerization inhibitor was added, and the mixture was stirred at 60 ° C. for 6 hours. Similarly, the completion of the reaction was confirmed by IR analysis to obtain a D-6 solution of the unsaturated urethane compound (F-16).

Examples 11-15, 17-23 Synthesis of unsaturated urethane compounds (F-11) to (F-15), (F-17) to (F-23) The composition shown in Table 2 is the same as that of Example 10. Examples 11 to 15 and 17 to 23 were carried out by the above-mentioned operation to obtain unsaturated urethane compounds (F-11) to (F-15) and (F-17) to (F-23). Table 2 shows the reaction temperature and reaction time of the first-stage reaction and the second-stage reaction.

Comparative Example 4 Synthesis of Urethane Compound (I-4) The urethane compound (I-4) corresponding to Comparative Example 4 was synthesized by performing the same operation as in Example 10 under the composition and reaction conditions shown in Table 2. However, from the infrared absorption (IR) spectrum analysis results after 48 hours, it was found that the absorption peculiar to the isocyanate group (around 2260 cm ^-1 ) hardly changed from the initial state, and the first stage reaction hardly proceeded. ..

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

Comparative Examples 6 and 7 Synthesis of Urethane Compounds (I-6) and (I-7) The urethane compounds (I-) corresponding to Comparative Examples 6 and 7 were subjected to the same operations as in Example 16 with the compositions shown in Table 2. The solution of 6) and the solution of (I-7) were obtained. Table 2 shows the respective reaction temperatures and reaction times.

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

(Polyxe having two or more hydroxyl groups (a2))
a2-1: Polytetramethylene glycol having a number average molecular weight of 650 (PTMG650, manufactured by Mitsubishi Chemical Corporation)
a2-2: Number average molecular weight 300 Polypropylene glycol, triol type (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
a2-3: Polyester diol with 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 with a number average molecular weight of 2,000 (condensation of 3-methyl-1,5-pentanediol / 1,6-hexanediol / diethyl carbonate) (Kuraray polyol C-2090, manufactured by Kuraray Co., Ltd.)
a2-5: Polyester polyol (3-methyl-1,5-pentanediol / adipic acid) having 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-butadiene diol with a number average molecular weight of 1,000 (GI-1000, manufactured by Nippon Soda Corporation)
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 with a number average molecular weight of 1,000 (condensation 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 (manufactured by Karenz AOI Showa Denko KK)

(Polyisocyanate having two or more isocyanate groups (b2))
b2-1: 2,4,4-trimethylhexamethylene diisocyanate (TMHDI)
b2-2: Isophorone diisocyanate (IPDI)
b2-3: Isocyanurate form 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 (ethylacetacetate) titanium (manufactured by Organix TC-750 Matsumoto Fine Chemical Co., Ltd.)
C-2: Tris (acetylacetonate) aluminum (manufactured by Organix AL-3100 Matsumoto Fine Chemical Co., Ltd.)
C-3: Tetrakis (acetylacetonate) hafnium (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)
C-4: Zirconium tetrakis (2-ethylhexanoic acid) (manufactured by Organix ZC-200 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 (Organix ZC-150 manufactured by Matsumoto Fine Chemical Co., Ltd.)
C-8: Tris (iron stearate) (III) (manufactured by Tokyo Chemical Industry Co., Ltd.)
G-1: N, N, N, N-Tetramethylethylenediamine G-2: Zinc bis (neodecanic acid) (Borchi Kat22 manufactured by Matsuo Industry Co., Ltd.)
G-3: Bis (acetylacetone) Zinc (manufactured by Tokyo Chemical Industry Co., Ltd.)
G-4: Dibutyl tin dilaurate (manufactured by Tokyo Chemical Industry Co., Ltd.)

(Compound (D))
D-1: Diethylene glycol diethyl ether D-2: Tetrahydrofurfuryl acrylate D-3: Tetrahydrofuran D-4: Morpholine acetamide D-5: methoxy-N, N-dimethylpropanamide (registered trademark "KJCMPA", KJ Chemicals, Inc. Made)
D-6: N-acryloyl morpholine (registered trademark "ACMO", registered trademark "Kohsylmer", manufactured by KJ Chemicals Co., Ltd.)
D-7: N, N-diethylacrylamide (registered trademark "DEAA", registered trademark "Kohsylmer", manufactured by KJ Chemicals Co., Ltd.)
D-8: Diacetone Acrylamide (registered trademark "Kohsylmer", manufactured by KJ Chemicals Co., Ltd.)
D-9: N, N-dimethylacetamide

(Other component (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-tetramethylpiperidin-N-oxyl

Molecular weight measurement and unsaturated group equivalent calculation of products of Examples 1 to 9 and Comparative Examples 1 to 9 Unsaturated urethane compounds (F-1) to (F-9) obtained in Examples 1 to 9, Comparative Examples. Since the urethane compounds (I-2) and (I-3) obtained in 2 and 3 are obtained as a single compound, TSQ Quantum Acetonitrile MAX (manufactured by Thermo Science), ESI probe (H-ESI2, positive measurement) ) Was used as an infusion method (acetonitrile / 0.1% acetic acid aqueous solution as eluent = 9/1 (mass ratio)) to measure the molecular weight by mass spectrum. In addition, the unsaturated group equivalent (molecular weight per unsaturated group) was calculated (unsaturated group equivalent = molecular weight / number of unsaturated groups). Further, in Comparative Example 1, since the urethanization reaction hardly proceeded, the molecular weight was not measured. These results are shown in Table 3.

Molecular weight measurement and unsaturated group equivalent calculation of products of Examples 10 to 21 and Comparative Examples 4 to 7 Unsaturated urethane compounds (F-10) to (F-21) obtained in Examples 10 to 21 and Comparative Examples. The urethane compounds (I-5) to (I-7) obtained in 5 to 7 are polymers having a molecular weight distribution, and high performance liquid chromatography (LC10A manufactured by Shimadzu Corporation is used, and the column is Shodex GPC). KF-806L. of (exclusion limit molecular weight: 2 × 10 ^7, separation range: one hundred to two × 10 ^7, theoretical plate number: 10,000 steps / present), was used tetrahydrofuran as eluent) to measure the standard polystyrene molecular weight The number average molecular weight was calculated by conversion. Further, the unsaturated group equivalent (molecular weight per unsaturated group) was calculated (unsaturated group equivalent = number average molecular weight / number of unsaturated groups). Further, in Comparative Example 4, since the urethanization reaction hardly proceeded, the molecular weight was not measured. These results are shown in Table 4.

(Viscosity measurement)
Obtained in each Example and Comparative Example at 60 ° C. using a Brookfeedle type viscometer (device name: digital viscometer LV DV2T manufactured by Hidehiro Seiki Co., Ltd.) according to JIS K5600-2-3. The viscosity of the unsaturated urethane compound (F) and the urethane compound (I), or the viscosity of the solution of the unsaturated urethane compound (F) and the urethane compound (I) was measured. Further, in Comparative Examples 1 and 4, since the urethanization reaction hardly proceeded, the measurement was not performed. The results of the viscosity measurement are shown in Tables 3 and 4.

(Hue)
The number of Hazen colors (APHA) as 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 with a dedicated device for transparent color measurement (Nippon Deniro TZ6000), and the following evaluation was performed from the APHA value. Further, in Comparative Examples 1 and 4, since the urethanization reaction hardly proceeded, the measurement was not performed. The results of hue measurement are shown in Tables 3 and 4.
⊚: APHA is less than 50 ○: APHA is 50 or more and less than 100 Δ: APHA is 100 or more and less than 200 ×: APHA is 200 or more

(Stability)
The hues 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) is stored at 60 ° C. for 1 week. Then, the viscosity was measured after storage, and the stability was evaluated from the change in viscosity. Further, Comparative Examples 1 and 4 were not evaluated because the urethanization reaction hardly proceeded. 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 and less than ± 20% Δ: Viscosity change is ± 20% or more and less than ± 100% ×: Viscosity change is ± 100% or more

Tables 1 and 3 show the results of production and evaluation of unsaturated urethane compounds having a molecular weight of less than 1000. As is clear from these results, unsaturated urethane compounds (F-1) to (F-9) can be produced at a relatively low temperature in a short time by the method of the present invention, and obtained (F). -1) The hues and thermal stability of (F-9) were good. On the other hand, in Comparative Example 1 in which no catalyst was added, the reaction was not completed, and in Comparative Example 2 using a tertiary amine as a catalyst, a high temperature and long-term reaction was required, and the obtained urethane compound (I-2) was brown. And the hue was bad. In addition, Michael addition of an unsaturated bond with amine was likely to occur, and the stability was low. In Comparative Example 3 using zinc bis (neodecanic acid) derived from a group 12 element as a catalyst, the catalytic activity is low, a long-term reaction is required, the hue of the obtained product (I-3) is poor, and the color is more stable. The property was low, and the formation of insoluble matter was confirmed.

Production and evaluation of a high molecular weight type unsaturated urethane compound having a molecular weight of 1000 or more, which is obtained by using a polyol (a2) having two or more hydroxyl groups and a polyisocyanate (b2) having two or more isocyanate groups in combination. The results are shown in Tables 2 and 4. As is clear from these results, even when the method of the present invention causes the reaction of (a2) and (b2) and then the reaction of (a1) as in Example 10 (multi-step reaction), Examples It was found that even when (a1), (a2), and (b2) were collectively charged and reacted as in No. 16, good reactivity was exhibited and the reaction was completed at a relatively low temperature and in a short time. Further, various unsaturated urethane compounds can be produced 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) have hue and heat. It was excellent in stability. In Examples 11 and 12 in which the amide bond is contained in the reaction system, the reactivity is further improved, and in Examples 13 to 23 in which both the ether bond and the amide bond are contained in the reaction system, the reactivity is further improved. However, the hue of the obtained unsaturated urethane compound became lower, and the thermal stability was further improved. On the other hand, even if both an ether bond and an amide bond were contained as in Example 14, the reaction was not completed in Comparative Example 4 in which no catalyst was added. In Comparative Example 5 using 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. Further, with reference to Example 2 and Comparative Example 1 described in Patent Document 4 (Japanese Unexamined Patent Publication No. 2010-215774), the diluting monomer was changed to acryloyl morpholine (D-6) containing both an ether bond and an amide bond. Comparative Examples 6 and 7 showed relatively good reactivity, but the zinc-based catalyst Comparative Example 6 was heavily colored, and the tin-based catalyst Comparative Example 7 was slightly colored at the same time. The viscosity decreased by about 30%.

As described above, in the method for producing an unsaturated urethane compound of the present invention, at least one or more metals selected from the 1st to 3rd transition elements and the 13th to 15th group elements (excluding tin) as a catalyst. It is characterized by using an organic salt or complex of an element. Since unsaturated urethane compounds can be efficiently obtained at low temperature and in a short time, it is possible to reduce costs and improve hue and quality. In addition, the obtained unsaturated urethane compound is highly safe without using a toxic tin-based catalyst, and can be suitably used as a raw material for a curable resin composition, and can be used for automobiles, electrical appliances, furniture, etc. Paints, coating materials, cushioning materials, packings, vibration isolators, sound absorbing materials, printing plates, sealing materials, abrasives, transparent adhesive sheets, UV curable adhesives / adhesives, sealing materials, sealing materials, dental hygiene materials , Optical materials, optical modeling materials, reinforced plastic materials, resin compositions for three-dimensional optical modeling, etc. can be used in various fields.

Claims (9)

A method for producing an unsaturated urethane compound having an unsaturated bond between carbon atoms, in which an alcohol compound (A) and an isocyanate compound (B) are used as catalysts (C), the first to third transition elements, and the thirteenth to thirteenth. A method for producing an unsaturated urethane compound, which comprises reacting in the presence of an organic salt or a complex of at least one metal element selected from Group 15 elements (excluding tin). The alcohol compound (A) has an unsaturated bond between carbon atoms (a1) and / or a polyol (a2) having two or more hydroxyl groups, and the isocyanate compound (B) has an unsaturated bond between carbon atoms. It is characterized by having an isocyanate compound (b1) and / or a polyisocyanate (b2) having two or more isocyanate groups, and a molar ratio of a hydroxyl group (OH) to an isocyanate group (NCO) of 0.9 to 1.1. The method for producing an unsaturated urethane compound according to claim 1. The unsaturated bond is one or more 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. The method for producing an unsaturated urethane compound according to claim 1 or 2, which comprises an unsaturated bond. The catalyst (C) is scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, ittrium, zirconium, niobium, molybdenum, ruthenium, rhodium, palladium, silver, lantern, cerium, praseodymium, neodymium, samarium, uropyum. , Gadolinium, terbium, dysprosium, holmium, erbium, thulium, itterbium, hafnium, tantalum, tungsten, renium, osmium, iridium, platinum, gold, aluminum, gallium, indium, thulium, lead, bismuth The method for producing an unsaturated urethane compound according to any one of claims 1 to 3, which is an organic salt or a complex of a metal element. Any one of claims 1 to 4, wherein the compound of any one or more 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. The method for producing an unsaturated urethane compound according to any one of claims 1 to 5, further containing a compound (D) having an ether bond and / or an amide bond. The method for producing an unsaturated urethane compound according to any one of claims 1 to 6, wherein the compound (D) is an aliphatic, alicyclic, or aromatic compound having no active hydrogen. The compounding amount of the catalyst (C) is 0.001 to 5.0% (mass ratio) with respect to the total of the alcohol compound (A) and the isocyanate compound (B), according to claims 1 to 7. The method for producing an unsaturated urethane compound according to any one of the above. Any one of claims 1 to 8, wherein the compounding amount of the compound (D) is 1 to 200% (mass ratio) with respect to the total of the alcohol compound (A) and the isocyanate compound (B). The method for producing an unsaturated urethane compound according to.