TWI499605B - Method of producing urethane compound and urethane compound obtained by the method - Google Patents

Description

Method for producing ethyl urethane compound and urethane compound prepared by the same

The present invention relates to a method for producing an ethyl urethane compound and a urethane compound produced by the method of production, and more particularly to ethyl urethane (meth) acrylate or poly A method for producing a urethane compound such as urethane or the like and a urethane compound produced by the production method.

In the past, a catalyst used in the ethylation of ethyl amide has gradually been made of a tin-based catalyst such as dibutyltin dilaurate.

However, in recent years, some people have pointed out the toxicity problem of tin-based catalysts and are seeking alternative catalysts.

For example, in the liquid curable resin composition for optical fiber coating of Patent Document 1, it has been described that a zirconium-based catalyst such as zirconium tetraethyl phthalate or zirconium acetonate is used. Dibutyltin dilaurate is subjected to an ethyl carbamate reaction in the presence thereof to produce ethyl urethane (meth) acrylate.

Further, in the curable composition of Patent Document 2, similarly, it has been described in the presence of a zirconium-based catalyst such as zirconium tetraacetate or the like, and an ethyl carbamate reaction is carried out to produce ethyl urethane ( Methyl) acrylate.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-327637

[Patent Document 2] International Publication No. 2009/063912

However, the zirconium catalyst such as zirconium tetraacetate pyruvate used in the techniques disclosed in Patent Document 1 and Patent Document 2 is a urethane raw material for an isocyanate compound, various polyols, various monomers, solvents, and the like. Insoluble. When the ethyl carbamate reaction is carried out in a state where the zirconium catalyst is insoluble, the concentration of the catalyst is not uniform, and the ureidoformation reaction also proceeds unevenly to produce an aminocarboxylic acid. The tendency of by-products other than ethyl ester compounds (insoluble compounds formed by abnormal reactions).

Accordingly, the present invention has an object to provide a method for producing a urethane compound capable of uniformly performing a ureidoformation reaction and capable of suppressing the generation of by-products, and a method for producing the same. The ethyl urethane compound.

The inventors of the present invention have continuously studied in view of such facts, and as a result, it has been found that when a urethane reaction is carried out, a zirconium compound and a zinc compound are used as a catalyst and the two are mixed due to the concentration of the catalyst in the reaction system. Since it is uniform, the ethyl carbamate reaction proceeds uniformly, and the generation of by-products can be suppressed, and the present invention has been completed.

That is, the gist of the present invention relates to a method for producing an ethyl urethane compound, which is a method for producing a urethane compound by reacting a hydroxyl group-containing component with an isocyanate component, characterized in that an amine group is used. In the ethyl formate reaction, a zirconium compound and a zinc compound are used as a catalyst, and a metal urethane compound is produced by a production method using the above-described urethane reaction.

The method for producing the ethyl urethane compound of the present invention is to use a zirconium compound and a zinc compound as a catalyst user in the case of performing an ethyl carbamate reaction. In this manner, by mixing the zirconium compound and the zinc compound, since the concentration of the catalyst in the reaction system becomes uniform, the reaction of the ethyl amide is uniformly performed, and the generation of by-products can be suppressed.

(Best form of implementing the invention)

Hereinafter, the present invention will be described in detail, but these examples show an example of a preferred embodiment.

Further, in the present invention, the ethyl urethane compound means a urethane-containing compound which is obtained by reacting a hydroxyl group-containing component with an isocyanate component.

Further, (meth)acrylic means acrylic or methacrylic, and (meth)acrylate means acrylate or methacrylate.

The method for producing the ethyl urethane compound of the present invention is a method for producing a urethane compound by reacting a hydroxyl group-containing component with an isocyanate component, and a zirconium compound and a zinc compound when performing a hydroxyethylation reaction Used as a catalyst.

The zirconium compound may be used as a function of a urethane-based catalyst, and examples thereof include a metal monomer (zirconium monomer), inorganic zirconium, and organic zirconium.

In addition, one type or a combination of two or more types can be used.

Examples of the inorganic zirconium include zirconium oxide, zirconium hydroxide, zirconium inorganic salt, zirconium mineral acid salt, and the like.

The zirconium oxide can be, for example, zirconia.

The zirconium hydroxide can be, for example, zirconium hydroxide.

Examples of the zirconium inorganic salt include calcium zirconate, magnesium zirconate, sodium zirconate, potassium zirconate and the like.

The zirconium mineral acid salt can be, for example, zirconium chloride, zirconium sulfate or the like.

On the other hand, the organic zirconium is a compound composed of zirconium and an organic atom group, and examples thereof include an organic acid salt of zirconium, an alkoxy zirconium compound, an amine zirconium compound, a β-diketone zirconium compound, and a cyclopentane. Alkenyl zirconium compound and the like. Among these, a β-diketone zirconium compound is preferred from the viewpoint of strong catalytic activity at the initial stage of the ureidoformation reaction and superior workability.

Examples of the organic acid salt of zirconium include zirconium formate, zirconium acetate, zirconium propionate, zirconium butyrate, zirconium isobutyrate, zirconium valerate, zirconium hexanoate, zirconium octoate, zirconium 2-ethylhexanoate, ruthenium. Zirconium acid, zirconium neodecanoate, zirconium rosinate, zirconium naphthenate, and the like.

The above alkoxy zirconium compound may, for example, be cerium (methoxy) zirconium, cerium (ethoxy) zirconium, cerium (propoxy) zirconium, cerium (isopropoxy) zirconium, cerium (butoxy). Zirconium, cerium (isobutoxy) zirconium, cerium (tertiary butoxy) zirconium, cerium (pentyloxy) zirconium, cerium (tertiary pentyloxy) zirconium, tetra [2-(2-methoxy) Ethyl]zirconium, tetrakis[2-(1-methyl-2-methoxy)propoxy]zirconium, tetrakis[2-(2-methoxy)propoxy]zirconium, tetra [2- (dimethylamino)ethoxy]zirconium, tetrakis[2-(2-dimethylamino-1-methyl)propoxy]zirconium, tetrakis[2-(2-dimethylamino)propoxy Zirconium, bis(2-propoxy)bis[2-(2-dimethylamino-1-methyl)propoxy]zirconium, bis(tertiary butoxy)bis[2-(2-di) Methylamino-1-methyl)propoxy]zirconium, bis(tertiary butoxy)bis[2-(2-dimethylamino)propoxy]zirconium, (tertiary butoxy)tri[ 2-(2-Dimethylamino-1-methyl)propoxy]zirconium, ginseng (tertiary butoxy)[2-(2-dimethylamino-1-methyl)propoxy]zirconium Wait.

Examples of the aminozirconium compound include zirconium (dimethylamino) zirconium, cerium (diethylamino) zirconium, cerium (ethyl methylamino) zirconium, cerium (dipropyl) zirconium, and cerium (dibutyl). Azide, zirconium, bis(dimethylamino)bis(diethylamino)zirconium, bis(diethylamino)bis(ethylmethylamino)zirconium, (diethylamino) ginseng (ethylmethylamine) Zirconium or the like; or bis(methoxy)bis(dimethylamino)zirconium, bis(methoxy)bis(diethylamino)zirconium, bis(methoxy)bis(ethylmethylamino) Zirconium, bis(ethoxy)bis(dimethylamino)zirconium, bis(ethoxy)bis(diethylamino)zirconium, bis(ethoxy)bis(ethylmethylamino)zirconium, double 2-propoxy)bis(diethylamino)zirconium, bis(tributyl)bis(diethylamino)zirconium, bis(tertiary butyl)bis(ethylmethylamino)zirconium, (three Butyl butyl) ginseng (ethylmethylamino) zirconium and the like.

The β-diketone zirconium compound can be, for example, zirconium acetonide, zirconium acetophenium acetonide, zirconium hexane-2,4-diketide zirconium, cerium-5-methylhexane-2, Zirconium 4-ketoate, zirconium heptane-2,4-dione, zirconium-2-methylheptane-3,5-diketonate, 肆-5-methylheptane-2,4 Zirconium diketonate, zirconium-6-methylheptane-2,4-dione, zirconium-2,2-dimethylheptane-3,5-diketonate, cesium-2,6 - zirconium dimethyl heptane-3,5-diketonate, zirconium 2,2,6-trimethylheptane-3,5-diketonate, bismuth-2,2,6,6-tetramethyl Zirconium-3,5-diketonate, zirconium octane-2,4-diketide, zirconium-2,2,6-trimethyloctane-3,5-diketonate, ruthenium -2,6-Dimethyloctane-3,5-diketonate zirconium, cerium-2-methyl-6-ethyldecane-3,5-diketonate zirconium, cerium-2,2-di a substituted alkyl group of methyl-6-ethylnonane-3,5-diketonate, etc.; β-diketone zirconium; 肆-1,1,1-trifluoropentane-2,4- Zirconium diketone, cerium-1,1,1-trifluoro-5,5-dimethylhexane-2,4-diketonic acid zirconium, cerium-1,1,1,5,5,5-six a fluorine-substituted alkyl β-diketone zirconium such as fluoropentane-2,4-diketonic acid zirconium, ruthenium-1,3-diperfluorohexylpropane-1,3-diketide zirconate or the like; 1,1,5,5-tetramethyl-1- Oxygen hexane-2,4-diketonic acid zirconium, cerium-2,2,6,6-tetramethyl-1-methoxyheptane-3,5-diketonic acid zirconium, cerium-2,2, An ether-substituted β-diketone zirconium such as 6,6-tetramethyl-1-(2-methoxyethoxy)heptane-3,5-diketonate or the like.

Among these β-diketone zirconium compounds, a β-diketone zirconium which is preferably a substituted alkyl group is particularly preferred from the viewpoint of catalytic activity and workability in the initial reaction of the ethyl carbamate reaction. Ethylene acetonide zirconium.

For example, ruthenium cyclopentadienyl zirconium, fluorenylmethylcyclopentadienyl zirconium, iridium ethylcyclopentadienyl zirconium, perylene pentamethylcyclopentadienyl zirconium or the like can be used as the cyclopentadiene. Zirconium compound.

In addition, as long as it is a function of the urethane-based catalyst, for example, an organic acid salt of zinc or the like can be used as the zinc compound.

The zinc organic acid salt can be exemplified by a carboxylate having a carbon number of preferably from 1 to 30, particularly preferably from 1 to 18, still more preferably from 6 to 18. Among these, from the viewpoint of superior reactivity of the ureidoformation reaction, zinc carboxylate is preferred, and zinc hexanoate is particularly preferred.

Further, from the viewpoint of superior solubility of the zirconium compound, the zinc compound is preferably liquid at 25 °C.

Here, the term "dissolved" means that the zirconium compound is dissolved in a zinc compound at a normal temperature (25 ° C), and the two are integrated into a liquid material, and do not include a simple dispersion. Such a liquid state also includes a process until it becomes such a state.

The amount of the zirconium compound of the present invention is preferably 0.00001 to 1% by weight (in atom%), particularly preferably 0.0001 to 0.5% by weight (in terms of Zr atom), based on the total amount of the hydroxyl group-containing component and the isocyanate component. Further, it is more preferably 0.001 to 0.1% by weight (calculated as Zr atom). When the amount of the zirconium compound is too large, side reactions tend to occur, and it is economically inefficient. When the amount is too small, the effect of adding the catalyst tends not to be obtained.

The amount of the zinc compound of the present invention is preferably 0.00001 to 5% by weight (in terms of Zn atom), particularly preferably 0.0001 to 1% by weight, based on the total amount of the hydroxyl group-containing component and the isocyanate component (in terms of Zn atom). Further, it is more preferably 0.001 to 0.1% by weight (calculated as Zn atom). When the amount of the zinc compound is too large, side reactions tend to occur, and the economy tends to be inefficient. When the amount is too small, the effect of adding the catalyst tends not to be obtained.

Further, the use ratio of the zirconium compound to the zinc compound is preferably a zirconium compound: zinc compound = 1.00: 0.99 to 1.00: 19.85 (metal-to-weight ratio), particularly preferably zirconium compound: zinc compound = 1.00: 0.99 to 1.00: 14.73 ( Further, a zirconium compound: zinc compound = 1.00: 0.99 to 1.00: 9.93 (metal-to-weight ratio) is preferable. When the proportion of the zinc compound used is too large, the reaction rate tends to decrease. When the proportion of the zinc compound used is too small, the zirconium compound becomes insoluble, and the reaction system becomes uneven, and the tendency of by-products is observed.

In the present invention, the above-mentioned method of using the zirconium compound and the zinc compound as a catalyst may be: (1) mixing the two catalysts before being mixed in the reaction system, and introducing the zirconium compound in a state of dissolving the zirconium compound in the zinc compound. a method of performing a urethane reaction in a reaction system; or (2) after performing a part of the ureidoformation reaction in a state in which one of the catalysts is mixed in the reaction system, Next, a method in which another catalyst is mixed in a reaction system to carry out a ureidoformation reaction, particularly a viewpoint of suppressing generation of by-products, is preferably a method (1).

Further, in the case of (2), a method of adding a zirconium compound first, followed by adding a zinc compound is preferred.

In the method of the above (1), the method of mixing the zirconium compound and the zinc compound is, for example, after adding the two catalysts to the reaction vessel, and mixing at a temperature of 60 to 120 ° C for 0.5 to 6 hours while stirring.

Usually, the supply of the catalyst is carried out by mixing the catalyst with a hydroxyl group-containing component and pouring it into the system.

Further, the mixture of the catalysts may be fed together or may be poured in several steps. For example, a method in which the catalyst is dropped or fractionated into a component containing a hydroxyl group may be exemplified.

Further, in the case where the reaction rate is insufficient, only the feed catalyst may be added.

The catalyst is blended by the above method, and the reaction temperature is usually from 30 to 90 ° C, preferably from 40 to 80 ° C, and the reaction time is usually from 2 to 10 hours, preferably from 3 to 8 hours, for the ethyl carbamate reaction. Just fine.

The urethane compound to be produced by the present invention is a urethane-bond-containing compound prepared by reacting a hydroxyl group-containing component with an isocyanate component, and examples thereof include a polyvalent isocyanate compound and a plurality of compounds. The reaction product of an alcohol compound, a hydroxyl group-containing (meth) acrylate compound, or a reaction product of a polyvalent isocyanate compound or a hydroxyl group-containing (meth) acrylate compound, that is, ethyl urethane (methyl) The acrylate (A); or a reaction product of a polyisocyanate compound and a polyol compound, that is, a polyurethane (B) or the like.

Hereinafter, a method for producing ethyl urethane (meth) acrylate (A) will be described first.

The ethyl urethane (meth) acrylate (A) is preferably a hydroxyl group-containing (methyl) in the presence of a zirconium compound and a zinc compound, preferably a catalyst for dissolving the zirconium compound in the zinc compound. The acrylate-based compound (a1), the polyvalent isocyanate-based compound (a2), and, if necessary, further reacted with the polyol-based compound (a3).

The hydroxyl group-containing (meth) acrylate type compound (a1) can be exemplified by, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, or (meth)acrylic acid-2. - Hydroxybutyl methacrylate, 4-hydroxybutyl (meth) acrylate, hydroxyalkyl (meth) acrylate such as 6-hydroxyhexyl (meth) acrylate; 2-hydroxyethyl acrylate phthalate 2-(meth)acryloyloxyethyl-2-hydroxypropyl phthalate, caprolactone (meth)acrylic acid modified 2-hydroxyethyl ester, (meth)acrylic acid dipropylene glycol ester, fatty acid modification Glycidyl (meth)acrylate, polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, 2-hydroxy-3-(methyl)acrylic acid (meth)acrylate Oxypropyl propyl ester, glyceryl di(meth) acrylate, 2-hydroxy-3-propenyl propyl methacrylate, pentaerythritol (meth) acrylate, caprolactone modified ginseng (meth) acrylate Pentaerythritol ester, ethylene oxide modified pentaerythritol (meth)acrylate, dipentaerythritol penta(meth)acrylate, pentaerythritol penta(meth)acrylate, ethylene oxide modified penta Base) dipentaerythritol acrylate or the like.

Among these, a hydroxy (meth) acrylate having one hydroxyl group is preferred, and in view of superior reactivity and versatility, it is particularly preferred to use 2-hydroxyethyl (meth)acrylate. Pentaerythritol (meth)acrylate, dipentaerythritol penta(meth)acrylate.

In addition, one type or a combination of two or more types can be used.

The polyisocyanate compound (a2) can be, for example, toluene diisocyanate, diphenylmethane diisocyanate, polyphenylmethane polyisocyanate, modified diphenylmethane diisocyanate, xylene diisocyanate, tetramethyl xylene An aromatic polyisocyanate such as isocyanate, phenyl diisocyanate or naphthalene diisocyanate; fat such as hexamethylene diisocyanate, trimethyl hexamethylene diisocyanate, diazonic acid diisocyanate or isocyanuric acid triisocyanate; Polyisocyanate; hydrogenated diphenylmethane diisocyanate, hydrogenated xylyl diisocyanate, isophorone diisocyanate, decene diisocyanate, 1,3-bis(isocyanate methyl)cyclohexane, etc. Isocyanate, or a trimer or multimer compound of such polyisocyanate; allophanate type polyisocyanate, biuret type polyisocyanate, water-dispersible polyisocyanate (for example, manufactured by Japan Polyurethane Industrial Co., Ltd.) "Aquanate 100", "Aquanate 110", "Aquanate 200", "Aquanate 210", etc.)

Among these, an alicyclic polyisocyanate compound is preferably used, and in particular, isophorone diisocyanate, hydrogenated diphenylmethane diisocyanate, or hydrogenated xylylene diisocyanate is more preferably used.

Examples of the polyol compound (a3) include propylene glycol, dipropylene glycol, tripropylene glycol, 2,4-pentanediol, 1,3-butylene glycol, 1,2-butanediol, and 2,3-butane. Alcohol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, 1,4-cyclohexanediol, 2-ethyl-1,3-hexanediol, glycerin, diglycerin, 1,2 , lower polyhydric alcohols such as 6-hexanetriol, sorbitol, triisopropanolamine, phenyldiisopropanolamine, N,N'-bis(2-hydroxypropyl)aniline, polyether polyols A polyester-based polyol, a polycarbonate-based polyol, a polyolefin-based polyol, a polybutadiene-based polyol, a (meth)acrylic polyol, a polyoxyalkylene-based polyol, or the like.

Among these, a polyester-based polyol or a polyether-based polyol is preferable, and a polyester-based polyol is particularly preferable from the viewpoint of mechanical properties such as superior flexibility at the time of curing.

The weight average molecular weight of the polyol compound (a3) is preferably from 500 to 8,000, particularly preferably from 550 to 5,000, still more preferably from 600 to 3,000. When the weight average molecular weight of the polyol compound (a3) is too large, the mechanical properties such as the hardness of the coating film during curing tend to be lowered, and when it is too small, the curing shrinkage tends to be large and the stability tends to be lowered.

The method for producing the ethyl urethane (meth) acrylate (A) is not particularly limited, and for example, it can be exemplified:

(a) feeding together a polyvalent isocyanate compound (a2), a hydroxyl group-containing (meth)acrylate compound (a1), an optional polyol compound (a3), and a zirconium compound dissolved in a zinc compound Catalyst, a method of reacting;

(b) a fraction of a mixture of a hydroxyl group-containing (meth) acrylate-based compound (a1), an optional polyol-based compound (a3), and a catalyst for dissolving a zirconium compound in a zinc compound a method of sub-addition to the polyisocyanate compound (a2);

(c) the fractional addition of the polyisocyanate compound (a2) to the hydroxyl group-containing (meth)acrylate compound (a1), the optional polyol compound (a3), and the dissolution of the zirconium compound to zinc A method in a mixture of catalysts in a compound. Among these, the viewpoint of the stability of the reaction control is preferably the method of (b).

In the reaction of the polyol compound (a3) with the polyvalent isocyanate compound (a2), for example, by the isocyanate group in the polyisocyanate compound (a2): the hydroxyl group in the polyol compound (a3) The ear ratio is usually 2n:(2n-2) (n is an integer of 2 or more), and after obtaining a terminal isocyanate group-containing ethyl urethane (meth) acrylate having an residual isocyanate group, it can be carried out with a hydroxyl group. The addition reaction of the (meth) acrylate compound (a1).

The addition reaction of the reaction product prepared by reacting the above polyol compound (a3) with the polyvalent isocyanate compound (a2) and the hydroxyl group-containing (meth)acrylate compound (a1) can also be used. The means of reaction.

The reaction molar ratio of the reaction product to the hydroxyl group-containing (meth) acrylate-based compound (a1), for example, the isocyanate group in the polyisocyanate compound (a2) is two and the hydroxyl group-containing (meth) acrylate system When the hydroxyl group of the compound (a1) is one, the reaction product: the hydroxyl group-containing (meth)acrylate compound (a1) is about 1:2; and the polyisocyanate compound (a2) has three isocyanate groups. When the hydroxyl group-containing (meth)acrylate compound (a1) has one hydroxyl group, the reaction product: hydroxyl group-containing (meth)acrylate compound (a1) is about 1:3.

In the addition reaction of the reaction product with the hydroxyl group-containing (meth) acrylate-based compound (a1), when the residual isocyanate group content in the reaction system is 0.5% by weight or less, the reaction is completed. Ethyl urethane (meth) acrylate (A).

Further, in the present invention, an organic solvent which does not have a functional group reactive with an isocyanate group can be used, and for example, an ester of ethyl acetate, butyl acetate or the like can be used; methyl ethyl ketone or methyl isobutyl A ketone such as a ketone or an organic solvent such as an aromatic compound such as toluene or xylene.

Further, in the production of ethyl urethane (meth) acrylate (A), a polymerization inhibitor such as 2,6-di(tributyl)-4-methylphenol (BHT) can also be used.

The reaction temperature in the production of ethyl urethane (meth) acrylate (A) is usually from 30 to 90 ° C, preferably from 40 to 80 ° C; the reaction time is usually from 2 to 10 hours, preferably from 3 to 8 hours.

Further, from the viewpoint of easy reaction control, it is preferred that i) is reacted at 30 to 50 ° C for 0.5 to 2 hours, and then ii) at 40 to 90 ° C for 2 to 8 hours.

Further, the ethyl urethane (meth) acrylate (A) preferably has two or more ethylenically unsaturated groups, and particularly preferably has three hardnesses in the case of hard coating or the like requiring high hardness. The above ethylenically unsaturated group is further preferably one having four or more ethylenically unsaturated groups.

Further, the upper limit of the ethylenically unsaturated group contained in the ethyl urethane (meth) acrylate (A) is usually 50, preferably 20 or less, and particularly preferably 10 or less.

The weight average molecular weight of the ethyl urethane (meth) acrylate (A) produced is preferably from 500 to 50,000, more preferably from 1,000 to 30,000. When the weight average molecular weight is too small, the cured coating film tends to become brittle; if it is too large, it tends to be highly viscous and difficult to handle.

In addition, the weight average molecular weight is a weight average molecular weight obtained by conversion of a standard polystyrene molecular weight, and is used in a high-speed liquid chromatography ("Shodex GPC system type 11" manufactured by Showa Denko Co., Ltd.). Column: Shodex GPC KF-806L (exclusion limit molecular weight: 2 × 10 ⁷ , separation range: 100 to 2 × 10 ⁷ , theoretical number of plates: 10,000 plates / column, filler material: styrene-divinylbenzene copolymerization The particle size of the material and the filler was 10 μm.

The urethane (meth) acrylate (A) preferably has a viscosity at 60 ° C of 500 to 150,000 mPa ‧ , particularly preferably 500 to 120,000 mPa ‧ , more preferably 1,000 to 100,000 mPa‧s. When the viscosity is outside the above range, the coating property tends to be lowered.

Also, the viscosity measurement method is based on an E-type viscometer.

In the present invention, the ethyl urethane (meth) acrylate (A) is preferably an urethane (meth) acrylate (A1) having a structure represented by the following formula (1).

[In the formula, the urethane bond residue of the R ¹ -based polyisocyanate compound, the urethane bond residue of the R ² -based hydroxyl group-containing (meth) acrylate compound, and the a system 2 To an integer of 50].

The a in the above formula (1) may be an integer of 2 to 50, preferably 2 to 20, particularly preferably 2 to 10.

The urethane (meth) acrylate represented by the above formula (1) is obtained by reacting a polyvalent isocyanate compound with a hydroxyl group-containing (meth) acrylate compound.

The polyvalent isocyanate compound may be exemplified by reacting the above polyvalent isocyanate compound (a2) or the polyisocyanate compound (a2) with a polyol compound (a3); and the hydroxyl group-containing (meth) acrylate The compound can be exemplified by the above-mentioned hydroxyl group-containing (meth) acrylate compound (a1).

The urethane (meth) acrylate (A) can be a hydroxyl group-containing (meth) acrylate compound (a1) or a polyvalent isocyanate compound (a2) in the presence of a zirconium compound and a zinc compound. It is prepared by further reacting with the polyol compound (a3) as needed.

It can be used as an active energy ray-curable resin composition by containing an ethylenically unsaturated compound, a photopolymerization initiator, or the like in the ethyl urethane (meth) acrylate (A) produced in this manner. . The active energy ray-curable resin composition is used as a coating, an adhesive, an adhesive, an adhesive, an ink, a protective coating agent, a tackifying coating agent, a magnetic powder coating adhesive, a coating for sand blasting, a plate material, etc. Various coating film forming materials, among which there are very many coating agents for using metal as a substrate.

Next, a method for producing the polyurethane (B) will be described.

The polyurethane (B) is preferably a polyisocyanate compound (b1) and a polyol in the presence of a zirconium compound and a zinc compound, preferably in the presence of a catalyst for dissolving the zirconium compound in the zinc compound. The compound (b2) is produced by a reaction.

The polyvalent isocyanate compound (b1) may be the same as the above-mentioned polyvalent isocyanate compound (a2), and the polyol compound (b2) may be the same as the above polyol compound (a3).

The production method of the polyurethane (B) can be, for example, an example:

(a) a method of uniformly reacting a polyvalent isocyanate compound (b1), a polyol compound (b2), and a catalyst for dissolving a zirconium compound in a zinc compound;

(b) a method of adding a mixed liquid of the mixed polyol compound (b2) and a catalyst for dissolving the zirconium compound in the zinc compound to the polyvalent isocyanate compound (b1) in portions;

(C) A method in which a polyisocyanate compound (b1) is added in portions to a mixed liquid of a mixed polyol compound (b2) and a catalyst for dissolving a zirconium compound in a zinc compound. Among the viewpoints of the stability of the reaction control, among these, the method of (b) is preferred.

In the reaction molar ratio, for example, when the polyisocyanate compound (b1) has two isocyanate groups and the polyol compound (b2) has two hydroxyl groups, the polyisocyanate compound (b1): a polyol compound (b2) ) is about 1:1. In the addition reaction, when the residual isocyanate group content of the reaction system is 0.5% by weight or less, the reaction is completed to obtain ethyl urethane (B).

Further, in the present invention, an organic solvent which does not have a functional group reactive with an isocyanate group can be used, and for example, an ester of ethyl acetate, butyl acetate or the like can be used; methyl ethyl ketone or methyl isobutyl A ketone such as a ketone or an organic solvent such as an aromatic compound such as toluene or xylene.

The reaction temperature in the production of the polyurethane (B) is usually from 30 to 90 ° C, preferably from 40 to 80 ° C; and the reaction time is usually from 2 to 10 hours, preferably from 3 to 8 hours. Further, from the viewpoint of easy reaction control, it is preferred that i) is reacted at 30 to 50 ° C for 0.5 to 2 hours, and then ii) at 40 to 90 ° C for 2 to 8 hours.

The weight average molecular weight of the produced polyurethane (B) is preferably from 5,000 to 500,000, further preferably from 10,000 to 100,000. When the weight average molecular weight is too small, the cured coating film tends to become brittle; if it is too large, it tends to be highly viscous and difficult to handle.

Further, the measurement of the weight average molecular weight was carried out in the same manner as described above.

Example

Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not to be construed as limited to the details. Also, in the examples, "parts" and "%" mean the basis of weight.

In the examples and comparative examples, the zirconium compound used as a catalyst is referred to as a "zirconium catalyst", and the zinc compound used as a catalyst is referred to as a "zinc catalyst". Further, the expression "liquid" means a state at 25 °C.

First, in order to evaluate the dissolution state of the zirconium-based catalyst, various catalysts were synthesized as follows.

[Synthesis Example 1]

In a 300 ml reaction vessel equipped with a stirrer, a zirconium-based catalyst of 40 g of zirconium pyruvate, a liquid zinc-based catalyst of zinc hexanoate (Zn: 15%) of mineral eucalyptus solution (mineral) Emu oil: 35%) 160 g, and the mixed solution was stirred while heating the liquid temperature until it became 60 ° C to prepare a mixed solution.

Further, the mineral eucalyptus oil is ethylbenzene, 1,3,5-trimethylbenzene, xylene (isomer mixture), and mineral spirits (hydrogen treatment of petroleum distillation components in the presence of a catalyst) A hydrocarbon mixture obtained consisting essentially of a hydrocarbon having a carbon number ranging from C9 to C16 and having a boiling range of from about 150 ° C to 280 ° C.

[Synthesis Example 2]

The same procedure as in Synthesis Example 1 was carried out, except that zirconium pyridinium pyruvate (4 g) was used as 4 g and zinc hexanoate (Zn: 15%) mineral eucalyptus oil solution (mineral eucalyptus oil: 35%) was set to 196 g. The mixed solution was prepared.

[Synthesis Example 3]

The mineral eucalyptus solution of zinc hexanoate which is a liquid zinc-based catalyst of Synthesis Example 1 was replaced with zinc hexanoate containing no mineral eucalyptus oil solution. That is, in a 300 ml reaction vessel equipped with a stirrer, 6 g of zirconium acetylate pyruvate, which is a zirconium catalyst, and 194 g of zinc hexanoate (Zn: 15%), which is a liquid zinc-based catalyst, are fed. Stir the mixture while stirring the liquid

The mixture was heated until it became 60 ° C to prepare a mixed solution.

[Comparative Synthesis Example 1]

A mixed solution was prepared in the same manner as in Synthesis Example 1, except that 160 g of an ethyl acetonate of an organic solvent was used instead of 160 g of a mineral eucalyptus oil solution (mineral eucalyptus oil: 35%) of zinc hexanoate (Zn: 15%).

[Comparative Synthesis Example 2]

A mixed solution was prepared in the same manner as in Synthesis Example 1 except that 160 g of an organic solvent ethyl acetate (160 g) was used instead of the mineral eucalyptus oil solution (mineral eucalyptus oil: 35%) of zinc hexanoate (Zn: 15%).

[Comparative Synthesis Example 3]

In addition to the mineral eucalyptus oil solution (mineral eucalyptus oil: 45%) 160 g of zirconium hexanoate (Zr: 12%) which is a liquid zirconium-based catalyst, a mineral eucalyptus solution which replaces zinc hexanoate (Zn: 15%) (Mineral eucalyptus oil: 35%) Other than 160 g, the mixed solution was prepared in the same manner as in Synthesis Example 1.

[Comparative Synthesis Example 4]

A mineral eucalyptus solution of zinc hexanoate which is a liquid zinc-based catalyst of Synthesis Example 1 was used instead of zirconium hexanoate which is a mineral zirconium-free catalyst. In a 300 ml reaction vessel equipped with a stirrer, 7 g of zirconium acetylate pyruvate, which is a zirconium catalyst, and 193 g of Zirconium hexanoate (Zr: 12%), which is a liquid zirconium catalyst, are fed. The mixed solution was stirred while heating the liquid until it reached 60 ° C to prepare a mixed solution.

The dissolved state of the zirconium pyruvate (zirconium-based catalyst) in the mixed solution of the synthesis example and the comparative synthesis example prepared in this manner was visually confirmed. The results are shown in Table 1 below.

<evaluation>

○...Zirconium catalyst is completely dissolved

×...Zirconium catalyst is insoluble or completely insoluble

[Table 1]

From the results of Table 1 above, in Synthesis Example 1 and Synthesis Example 2 using zinc hexanoate which is a liquid zinc-based catalyst, the zirconium-based catalyst was completely dissolved. Further, in the same manner as in Synthesis Example 3 in which the mineral eucalyptus oil solution was not contained, the zirconium-based catalyst was completely dissolved.

On the other hand, in Comparative Example 1 and Comparative Synthesis Example 2, the zirconium-based catalyst was insoluble in the use of the organic solvent instead of the liquid zinc-based catalyst.

Further, in Comparative Example 3 in which a liquid zirconium catalyst was used instead of the liquid zinc-based catalyst, the zirconium catalyst was completely insoluble. Further, Comparative Synthesis Example 4 containing no mineral eucalyptus oil was also insoluble in the same manner.

Next, ethyl urethane (meth) acrylate (A) and ethyl urethane (B) were synthesized using the catalyst and other catalysts produced in Synthesis Examples 1 to 3.

[Example 1] Production Example 1 of ethyl urethane (meth) acrylate (A)

In a 500 ml reaction vessel equipped with a stirrer, 0.3 g of a catalyst (active ingredient: 480 ppm) produced in Synthesis Example 1 and 2,6-di(tri-butyl)-4-methyl as a polymerization inhibitor were fed. A mixture of 0.2 g of phenol (BHT), pentaerythritol triacrylate and pentaerythritol tetraacrylate (OH valence of 120 mg KOH/g) of 245 g was heated while stirring until the liquid temperature became 40 °C.

55 g of isophorone diisocyanate was slowly added to the reaction solution, and after reacting for 1 hour, the temperature was raised to 70 ° C over 1 hour. Thereafter, the reaction was continued at 70 ° C for one hour, and after 8 hours, the free NCO % was continuously measured every 2 hours. Further, the appearance of the reaction solution was visually evaluated.

<evaluation>

Good...no impurities, the color is colorless and transparent

Impurity... impurity generator

Coloring...the color has changed

[Example 2] Production Example 2 of ethyl urethane (meth) acrylate (A)

The amine group was synthesized in the same manner as in Example 1 except that 0.3 g (active ingredient: 360 ppm) of the catalyst produced in Synthesis Example 2 was used instead of 0.3 g (active ingredient: 480 ppm) of the catalyst produced in Synthesis Example 1. Ethyl formate (meth) acrylate (A). Then, the free NCO% was measured in the same manner as in Example 1, and the appearance of the reaction solution was also evaluated.

[Example 3] Production Example 3 of ethyl urethane (meth) acrylate (A)

In a 500 ml reaction vessel equipped with a stirrer, a mixture of 0.06 g (200 ppm) of zirconium pyruvate as a catalyst, 0.2 g of BHT as a polymerization inhibitor, pentaerythritol triacrylate and pentaerythritol tetraacrylate ( The OH value was 120 mg KOH/g) 245 g, and the side was heated while stirring until the liquid temperature became 40 °C.

55 g of isophorone diisocyanate was slowly added to the reaction solution, and after reacting for 1 hour, the temperature was raised to 70 ° C over 1 hour.

Thereafter, a mineral eucalyptus oil solution (mineral eucalyptus oil: 35%) of 0.20 g (active ingredient: 280 ppm) of zinc hexanoate (Zn: 15%) was added, and the reaction was continued at 70 ° C for one hour until every two hours after 8 hours. The free NCO% was continuously measured. Further, the appearance of the reaction solution was evaluated in the same manner as in Example 1.

[Example 4] Production Example 4 of ethyl urethane (meth) acrylate (A)

The amine group was synthesized in the same manner as in Example 1 except that 0.1 g (active ingredient: 180 ppm) of the catalyst produced in Synthesis Example 3 was used instead of 0.3 g (active ingredient: 480 ppm) of the catalyst produced in Synthesis Example 1. Ethyl formate (meth) acrylate (A). Then, the free NCO% was measured in the same manner as in Example 1, and the appearance of the reaction solution was also evaluated.

[Example 5] Production Example 1 of Polyurethane (B)

In a 500 ml reaction vessel equipped with a stirrer, 0.3 g of the catalyst produced in Synthesis Example 1 (active ingredient: 480 ppm), polycarbonate diol 85 g (OH valence: 140 mg KOH/g), 1, 4 were fed. 10 g of butanediol and 150 g of methyl ethyl ketone of the solvent were heated while stirring until the liquid temperature became 50 °C.

55 g of hydrogenated diphenylmethane diisocyanate was slowly added to the reaction solution, and after reacting for 1 hour, the temperature was raised to 80 ° C over 1 hour. Thereafter, the reaction was continued at 80 ° C for one hour, and after 8 hours, the free NCO % was continuously measured every 2 hours. Further, the appearance of the reaction solution was visually evaluated.

[Example 6] Production Example 2 of Polyurethane (B)

The polyamine was synthesized in the same manner as in Example 5 except that 0.3 g of the catalyst produced in Synthesis Example 2 (360 ppm of active ingredient) was used instead of 0.3 g (active ingredient: 480 ppm) of the catalyst produced in Synthesis Example 1. Ethyl carbamate (B). Then, the free NCO% was measured in the same manner as in Example 5, and the appearance of the reaction solution was also evaluated.

[Example 7] Production Example 3 of Polyurethane (B)

The polyamine was synthesized in the same manner as in Example 5, except that 0.1 g (active ingredient: 180 ppm) of the catalyst produced in Synthesis Example 3 was used instead of 0.3 g (active ingredient: 480 ppm) of the catalyst produced in Synthesis Example 1. Ethyl carbamate (B). Then, the free NCO% was measured in the same manner as in Example 5, and the appearance of the reaction solution was also evaluated.

[Comparative Example 1]

In addition to the catalyst system, a zirconium-based catalyst of zirconium pyruvate zirconium 0.03 g (100 ppm) was used alone to replace the zirconium-ceramic acid zirconium pyruvate, and the liquid zinc-based catalyst zinc hexanoate. The urethane (meth) acrylate (A) was synthesized in the same manner as in Example 1 except for the catalyst of Synthesis Example 1. Then, the free NCO% was measured in the same manner as in Example 1, and the appearance of the reaction solution was also evaluated.

[Comparative Example 2]

In addition to the catalyst system, a liquid zinc-based catalyst of zinc hexanoate (Zn: 15%) is used as a mineral eucalyptus oil solution (mineral eucalyptus oil: 35%) 0.3 g (active ingredient 350 ppm) instead of zirconium The urethane (meth) acrylate (A) was synthesized in the same manner as in Example 1 except that the catalyst of the synthesis example 1 of zirconium pyruvate and zinc hexanoate of the liquid zinc-based catalyst was used. ). Then, the free NCO% was measured in the same manner as in Example 1, and the appearance of the reaction solution was also evaluated.

[Comparative Example 3]

In addition to the catalyst system, a zirconium-based catalyst of zirconium pyruvate zirconium 0.03 g (100 ppm) was used alone to replace the zirconium-based catalyst, zirconium pyruvate, and the liquid zinc-based catalyst. The polyurethane (B) was synthesized in the same manner as in Example 5 except for the catalyst of Synthesis Example 1. Then, the free NCO% was measured in the same manner as in Example 5, and the appearance of the reaction solution was also evaluated.

[Comparative Example 4]

In addition to the catalyst system, a zinc hexanoate (Zn: 15%) mineral eucalyptus solution (mineral eucalyptus oil: 35%) 0.3 g (active ingredient 350 ppm) was used as a liquid zinc-based catalyst alone to replace the zirconium system. Polyurethane (B) was synthesized in the same manner as in Example 5 except that the catalyst of the catalyst of Synthesis Example 1 of zirconium pyruvate and zinc hexate as the liquid zinc catalyst was used. Then, the free NCO% was measured in the same manner as in Example 5, and the appearance of the reaction solution was also evaluated.

For the ethyl urethane (meth) acrylate (A) and the ethyl urethane (B) of the examples and the comparative examples, the urethane (meth) acrylate was determined for the free NCO%. The case of (A) is after the temperature is raised to 70 ° C; the case of the ethyl polyurethane (B) is 0 hours, 2 hours, 4 hours, 6 hours, 8 hours after the temperature is raised to 100 ° C, and the reaction solution The evaluation results of the appearance are shown in Table 2 below.

From the results of Table 2, Synthesis Examples 1 to 3 were prepared by using zirconium pyruvate, which was initially mixed into a zirconium catalyst, zinc hexanoate with a liquid zinc catalyst, and dissolving a zirconium catalyst. In the examples 1, 2, 4 and 7 of the catalyst, the ethyl carbamate reaction was uniform and the value of the free NCO% was small, and the ethyl carbamate reaction was carried out in a short time, and the appearance of the reaction solution was also good. .

Further, in Example 3 in which a liquid zinc-based catalyst was added to a solution which was heated up to 70 ° C, the same procedure as in Examples 1 and 2 was carried out, and the ethyl carbamate reaction was uniform and free NCO%. The value was small, and the reaction of the ethyl carbamate was carried out in a short time, and the appearance of the reaction solution was also good.

On the other hand, in Comparative Examples 1 and 3 in which zirconium ruthenate zirconium pyruvate which is a zirconium-based catalyst was used alone, since the catalyst was insoluble, the ethyl carbamate reaction became uneven, and impurities were generated in the reaction solution.

Further, in Comparative Examples 2 and 4, the reaction solution was colored by using zinc hexanoate which is a liquid zinc-based catalyst alone.

Further, in the above embodiments, the present invention has been described with respect to the specific embodiments of the present invention, but the above-described embodiments are merely illustrative examples and are not to be construed as limiting. Further, all modifications belonging to the scope of the claims are within the scope of the invention.

(industrial use)

A urethane compound such as ethyl urethane (meth) acrylate or poly urethane prepared by the production method of the present invention is used as a coating, an adhesive, an adhesive, an adhesive, and an ink. It is useful as a main component of various coating film forming materials such as a protective coating agent, a tackifier coating agent, a magnetic powder coating adhesive, a coating film for sand blasting, and a plate material, and it is useful as a main component of a coating agent for a metal substrate. .

Claims (9)

A method for producing an ethyl urethane compound, which is a method for producing a urethane compound by reacting a hydroxyl group-containing component with an isocyanate component, characterized in that zirconium is used in the ethyl urethane reaction The compound and the zinc compound are used as a catalyst, and the ratio of use of the zirconium compound to the zinc compound is zirconium compound: zinc compound = 1.00: 0.99 to 1.00: 19.85 in terms of metal-to-weight ratio. A method for producing an ethyl urethane compound according to claim 1, wherein the zirconium compound contains a β-diketone zirconium compound. A method for producing an ethyl urethane compound according to claim 1, wherein the zinc compound is liquid at 25 °C. A method for producing an ethyl urethane compound according to claim 1, wherein the zinc compound contains zinc carboxylate. The method for producing a urethane compound according to the first aspect of the invention, wherein the zirconium compound is used in an amount of 0.00001 to 1% by weight based on the total amount of the hydroxyl group-containing component and the isocyanate component in terms of Zr atom. . The method for producing a urethane compound according to the first aspect of the invention, wherein the amount of the zinc compound is 0.00001 to 5% by weight based on the total amount of the hydroxyl group-containing component and the isocyanate component in terms of Zn atom . A method for producing an ethyl urethane compound according to claim 1, wherein the urethane compound is ethyl urethane (meth) acrylate. A method for producing an ethyl urethane compound according to the first aspect of the invention, wherein the ethyl urethane compound is a polyurethane. The method for producing an urethane compound according to any one of claims 1 to 8, wherein a solution in which a zirconium compound is dissolved in a zinc compound is used as a catalyst.