JP7363036B2 - (Meth)acrylate manufacturing method - Google Patents

Description

The present invention relates to a method for producing (meth)acrylate, and more specifically to a method for producing a compound having two or more (meth)acryloyl groups obtained by transesterifying a high molecular weight polyol and a monofunctional (meth)acrylate. Regarding the manufacturing method, preferably regarding the manufacturing method of a compound having two (meth)acryloyl groups obtained by transesterifying a high molecular weight diol and a monofunctional (meth)acrylate, manufacturing and using the (meth)acrylate. Belongs to the technical field.
In this specification, an acryloyl group and/or a methacryloyl group will be referred to as a (meth)acryloyl group, an acrylate and/or a methacrylate will be referred to as a (meth)acrylate, and an acrylic acid and/or a methacrylic acid will be referred to as a (meth)acrylic acid. Expressed as
In addition, in this specification, "monofunctional" means a compound having one ethylenically unsaturated group such as a (meth)acryloyl group, and a compound having two or more (meth)acryloyl groups is referred to as a polyfunctional compound. Sometimes referred to as (meth)acrylate.

(Meth)acrylate oligomers such as polycarbonate di(meth)acrylate and polyester di(meth)acrylate are useful compounds. (Meth)acrylate oligomers are cured by irradiation with active energy rays such as ultraviolet rays or electron beams, or by heating, so they are used in coating agents such as paints, inks, adhesives, optical lenses, fillers, and molding materials. used as a crosslinking component or as a reactive diluent component in formulations of

(Meth)acrylate oligomers are usually produced by dehydrating and esterifying diols and (meth)acrylic acid in the presence of an acid catalyst, and transesterifying diols and (meth)acrylates in the presence of a catalyst. There is a production method that involves transesterification, but it may have problems depending on the purpose and use.

As a specific example of a method for producing polycarbonate di(meth)acrylate, for example, a method for producing polycarbonate di(meth)acrylate includes dehydrating polycarbonate diol and acrylic acid in the presence of a protonic acid catalyst such as p-toluenesulfonic acid. A production method involving chemical reaction is known (Patent Document 1).
As a method for producing polyester di(meth)acrylate, for example, a production method in which polyester diol and (meth)acrylic acid are directly subjected to a dehydration reaction is known (Patent Document 2).
However, these dehydration esterification methods have a problem in that the di(meth)acrylate obtained is colored, and in the case of polycarbonate diol di(meth)acrylate, there is a problem in that it is colored brown. Ta.

As a specific example of a production method using a transesterification reaction, for example, a production method using a transesterification reaction is known in which polycarbonate diol and (meth)acrylate are reacted in the presence of an organometallic catalyst while extracting the alcohol produced (patented). Reference 3). However, in this manufacturing method, an aromatic solvent such as toluene is used as an organic solvent, and in recent years, awareness of the harmful effects of environmentally hazardous substances has been increasing, so the use of aromatic solvents is not preferable.
Furthermore, according to the study results of the present inventors, depending on the type of the transesterification reaction catalyst, there were cases in which the molecular weight of the resulting di(meth)acrylate decreased or the resulting di(meth)acrylate was colored.

In addition to the methods described above, a manufacturing method is known in which polyester diol and methacrylic anhydride are reacted in the presence of a metal catalyst (Patent Document 4).
However, this production method requires the use of an unstable and expensive acid anhydride, and has the problem of generating a large amount of waste water because it is extracted and washed after the reaction is completed.

Japanese Unexamined Patent Publication No. 4-208251 Japanese Patent Application Publication No. 2000-311516 Japanese Patent Application Publication No. 2001-151730 Japanese Patent Application Publication No. 2013-116933

The present invention has been made in view of the above-mentioned current situation, and provides a manufacturing method capable of obtaining high-quality (meth)acrylate oligomers with high molecular weight and little coloring, preferably polycarbonate di(meth)acrylate and polyester. An object of the present invention is to provide a manufacturing method capable of obtaining di(meth)acrylate.

In order to solve the above problem, the present inventors used a specific basic catalyst or a phosphine-based catalyst, and a zinc-based catalyst in combination, and a polyol with a specific number average molecular weight (hereinafter referred to as "Mn") and a monomer. The present invention was completed based on the discovery that polyfunctional (meth)acrylates with high molecular weight and little coloring can be obtained by transesterification with functional (meth)acrylates.
The present invention will be explained in detail below.

According to the present invention, the obtained polyfunctional (meth)acrylate has a high molecular weight and can be made into a high-quality product with little coloring.

In the present invention, in the presence of the following catalyst The present invention relates to a method for producing a mixture (A) of a compound having two (meth)acryloyl groups, in which a polyester diol and a monofunctional (meth)acrylate are transesterified.
Catalyst X: cyclic tertiary amine having an azabicyclo structure, or a salt or complex thereof.
Catalyst Y: Compound containing zinc.
Hereinafter, polyols, monofunctional (meth)acrylates, catalysts, manufacturing methods, and uses will be explained.

1. Production method
1-1. Polyol In the present invention, a polyol having an Mn of 500 to 10,000 is used as a raw material for component (A). The Mn of the polyol is preferably 1,000 to 6,000.
In the present invention, Mn refers to the number average molecular weight measured by gel permeation chromatography (hereinafter referred to as "GPC") in terms of polystyrene.

As the polyol in the present invention, various polyols can be used as long as they satisfy the above Mn.
The present invention can be preferably applied to a production method using a diol as a polyol.

The production method of the present invention can be preferably applied to a production method using a polyol having a carbonate skeleton or an ester skeleton as the polyol, and more preferably to a production method using a diol having a carbonate skeleton or an ester skeleton.
When producing (meth)acrylate using a polyol having a carbonate skeleton or ester skeleton, there is a problem that the resulting (meth)acrylate tends to have a low molecular weight, probably because the bonds of the carbonate skeleton or ester skeleton are broken. However, the present invention does not have such a problem.
Hereinafter, polyols having a carbonate skeleton and polyols having an ester skeleton will be explained.

1-1-1. Polyol having a carbonate skeleton As the polyol having a carbonate skeleton, those manufactured by a known method can be used.
Examples include transesterification reaction between a polyol and a carbonate ester, ring-opening polymerization of a cyclic carbonate ester having an alkylene group, and reaction between a polyol and a chloroformate or phosgene. Preferably, those manufactured by

Diols are preferred as polyols. Examples of the diol include aliphatic diols, alicyclic diols, and diols in which a carbon atom of an alkylene group is substituted with an oxygen atom.

Examples of aliphatic diols include diols in which the alkylene group is a trimethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, and the like.
Examples of diols whose alkylene group is trimethylene group include 2-methyl-1,3-propanediol, 1,3-butanediol, 2,4-heptanediol, 2,2-diethyl-1,3-propanediol, -Methyl-2-propyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2-methyl-2,4-pentanediol, 2,2,4-trimethyl-1,3-pentanediol , and 2-butyl-2-ethyl-1,3-propanediol.
Examples of diols whose alkylene group is a pentamethylene group include 1,5-pentanediol, 3-methyl-1,5-pentanediol, and 1,5-hexanediol.
Examples of diols whose alkylene group is a hexamethylene group include 1,6-hexanediol and 2-ethyl-1,6-hexanediol.
Examples of diols whose alkylene group is a heptamethylene group include 1,7-heptanediol and the like.
Examples of diols whose alkylene group is an octamethylene group include 1,8-octanediol and 2-methyl-1,8-octanediol.
In addition to these, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, 1,20-eicosandiol and the like can be mentioned.

Examples of alicyclic diols include 1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexane-1,4-dimethanol, cyclohexane-1,4-diethanol, and 2,2-bis(4-hydroxycyclohexyl)propane. and 2,7-norbornanediol.

Examples of diols in which a carbon atom of an alkylene group is substituted with an oxygen atom include polyalkylene glycol.
Specific examples of polyalkylene glycol include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.
Examples of compounds other than the above include 2,5-tetrahydrofurandimethanol, 1,4-bis(hydroxyethoxy)cyclohexane, etc. in which the carbon atom of the alkylene group is substituted with an oxygen atom and an aliphatic ring is formed. Examples include compounds such as

The diol is preferably an aliphatic diol having 2 to 30 carbon atoms, more preferably an aliphatic diol having 3 to 12 carbon atoms. Further, the aliphatic diol is preferably a linear aliphatic diol having 2 to 30 carbon atoms, more preferably a linear aliphatic diol having 3 to 12 carbon atoms, and particularly preferably 1,10 -Decanediol.

Examples of carbonate esters include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, and diphenyl carbonate.

Examples of the diol having a carbonate skeleton include a compound represented by the following formula (5).

[In formula (5), R ¹⁵ and R ¹⁶ mean a divalent hydrocarbon group having 2 to 30 carbon atoms. R ¹⁵ and R ¹⁶ may be the same or different. n represents the average degree of polymerization and is a number from 1 to 50. ]

R ¹⁵ and R ¹⁶ mean a divalent hydrocarbon group having 2 to 30 carbon atoms.
Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
Examples of the aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.
Furthermore, the hydrocarbon group may contain at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur in the carbon skeleton.

Specific examples of linear aliphatic hydrocarbon groups include ethylene group, 1,3-propylene group (trimethylene group), 1,4-butylene group (tetramethylene group), 1,5-pentylene group (pentamethylene group) ), 1,6-hexylene group (hexamethylene group), 1,8-octylene group (octamethylene group), 1,9-nonylene group, and 1,10-decanylene group.
Specific examples of branched aliphatic hydrocarbon groups include 1,2-propylene group (isopropylene group),
Examples include 1,1-dimethylethylene group (isobutylene group), ethylethylene group, isopentene group, 3-methylpentene group, and 2,4-diethyl-1,5-pentene group.

The cycloaliphatic hydrocarbon group is preferably a cycloalkylene group (cycloalkanediyl group) having 3 to 12 carbon atoms, such as a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, or a cycloheptylene group. , and a cyclooctylene group.

Among those mentioned above, R ¹⁵ and R ¹⁶ are preferably divalent linear aliphatic hydrocarbon groups having 2 to 30 carbon atoms, more preferably divalent linear aliphatic hydrocarbon groups having 3 to 12 carbon atoms. It is an aliphatic hydrocarbon group, particularly preferably a 1,10-decanylene group.

1-1-2. Polyol having an ester skeleton Examples of the polyol having an ester skeleton include polyester polyols which are reaction products of polyols and organic polybasic acids.

Polyols include low molecular weight polyols, polyether polyols and polycarbonate polyols.
Examples of the low molecular weight polyol include polyols having a molecular weight of about 50 to 300, with low molecular weight diols being preferred.
Examples of low molecular weight diols include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 2-methyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol, and 1,5-pentane. Diol, neopentyl glycol (2,2-dimethyl-1,3-propanediol), 1,6-hexanediol, 3-methyl-1,5-pentanediol and 2,4-diethyl-1,5-pentanediol Aliphatic diols such as;
Hydrogenated bisphenol A, 1,2-cyclohexane glycol, 1,3-cyclohexane glycol, 1,4-cyclohexane glycol, 1,4-cyclohexanedimethanol, bicyclohexyl-4,4'-diol, 2,6-decalin glycol and alicyclic diols such as 2,7-decalin glycol; and aromatic diols such as paraxylene glycol.
Among these compounds, aliphatic diols are preferred as diols, and furthermore, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol and 2, 4-diethyl-1,5-pentanediol is more preferred.

Examples of polyether polyols include polyalkylene glycols having three or more oxyalkylene units. Specific examples include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, and the like.

Examples of the polycarbonate polyol include the compounds listed above.

Examples of the organic polybasic acid include polybasic acids and polybasic acid anhydrides, with dibasic acids and dibasic acid anhydrides being preferred.
Examples of dibasic acids or dibasic acid anhydrides include succinic acid, glutaric acid, adipic acid, sebacic acid, fumaric acid, maleic acid, itaconic acid, citraconic acid, mesaconic acid, phthalic acid, tetrahydrophthalic acid, hexahydroanhydride. Examples include phthalic acid, terephthalic acid, azelaic acid, hymic acid and endohet acid, and anhydrides of these compounds.
Among these compounds, succinic acid, glutaric acid, adipic acid and sebacic acid are preferred as the dibasic acid or dibasic acid anhydride.

As the polyester polyol, polyester diol is preferred.
Examples of polyester diols include polyester diols obtained by reacting diols with dibasic acids or dibasic acid anhydrides.
In the compound, the diol is exemplified by the compounds mentioned above, and the dibasic acid or dibasic acid anhydride is exemplified by the compounds mentioned above.

Furthermore, as the polyester diol, a polyester diol which is a reaction product of 2,4-diethyl-1,5-pentanediol and succinic acid or sebacic acid is more preferable.

As the diol having an ester skeleton, a compound represented by the following formula (6) is preferable.

[In formula (6), R ¹⁷ , R ¹⁸ and R ¹⁹ mean a divalent hydrocarbon group having 2 to 30 carbon atoms. R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different. n represents the average degree of polymerization and is a number from 1 to 50. ]

R ¹⁷ , R ¹⁸ and R ¹⁹ each mean a divalent hydrocarbon group having 2 to 30 carbon atoms.
Examples of the hydrocarbon group include an aliphatic hydrocarbon group and an aromatic hydrocarbon group.
Examples of the aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group, a branched aliphatic hydrocarbon group, and a cyclic aliphatic hydrocarbon group.
Furthermore, the hydrocarbon group may contain at least one atom selected from the group consisting of oxygen, nitrogen, and sulfur in the carbon skeleton.

Specific examples of R ¹⁷ , R ¹⁸ and R ¹⁹ include the same functional groups as the divalent hydrocarbon groups exemplified above as specific examples of R ¹⁵ and R ¹⁶ .

Furthermore, preferred examples of R ¹⁷ , R ¹⁸ and R ¹⁹ in formula (6) will be explained.
R ¹⁷ and R ¹⁸ include 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 3-methyl-1,5-pentylene group and 2,4-diethyl-1,5- Preferred are groups selected from the group consisting of pentylene groups.
These functional groups are derived from the raw material compounds 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol and 2,4-diethyl-1, Each group is derived from 5-pentanediol.
R ¹⁹ is preferably a group selected from the group consisting of ethylene, trimethylene, tetramethylene and 1,8-octylene.
These functional groups are groups derived from the raw material compounds succinic acid, glutaric acid, adipic acid, and sebacic acid, respectively.

Furthermore, as a preferable combination of R ¹⁷ , R ¹⁸ and R ¹⁹ in formula (6), R ¹⁷ and R ¹⁸ are 2,4-diethyl-1,5-pentylene groups, and R ¹⁹ is an ethylene group or 1,8-octylene group is preferred.
That is, polyester diol which is a reaction product of 2,4-diethyl-1,5-pentanediol and succinic acid or sebacic acid is preferred.

1-2. The monofunctional (meth)acrylate used as a raw material for the monofunctional (meth)acrylate (A) component is a compound having one (meth)acryloyl group in the molecule, and is, for example, represented by the following general formula (1). Compounds that can be mentioned include:

In formula (1), R ¹ represents a hydrogen atom or a methyl group. R ² represents an organic group having 1 to 50 carbon atoms.

Preferred specific examples of R ² in the above general formula (1) include carbon atoms such as methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, and 2-ethylhexyl group. Alkyl groups of numbers 1 to 8, alkoxyalkyl groups such as 2-methoxyethyl group, 2-ethoxyethyl group and 2-methoxybutyl group, and N,N-dimethylaminoethyl group, N,N-diethylaminoethyl group, N , N-dimethylaminopropyl group, and dialkylamino groups such as N,N-diethylaminopropyl group.
Specific examples of R ² in the above general formula (1) include, in addition to the above, the functional groups listed in JP-A No. 2017-39916, JP-A No. 2017-39917, and International Publication No. 2017/033732. .

In the present invention, these monofunctional (meth)acrylates can be used alone or in any combination of two or more.
Among these monofunctional (meth)acrylates, carbonaceous compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, i-butyl (meth)acrylate, and 2-ethylhexyl (meth)acrylate Preferred are alkyl (meth)acrylates having 1 to 8 alkyl groups, alkoxyalkyl (meth)acrylates such as 2-methoxyethyl acrylate, or N,N-dimethylaminoethyl (meth)acrylate, particularly for polyols. Preferred are (meth)acrylates having an alkyl group having 1 to 4 carbon atoms or alkoxyalkyl (meth)acrylates having an alkyl group having 1 to 2 carbon atoms, which exhibit good reactivity and are easily available.
Furthermore, alkoxyalkyl (meth)acrylates having an alkyl group having 1 to 2 carbon atoms that promote dissolution of polyol and exhibit extremely good reactivity are more preferred, and 2-methoxyethyl (meth)acrylate is particularly preferred.
Furthermore, as the monofunctional (meth)acrylate, acrylate is particularly preferred since it has excellent reactivity.

There is no particular restriction on the ratio of polyol and monofunctional (meth)acrylate used in the method for producing component (A), but 0.4 to 10.0 mol of monofunctional (meth)acrylate is used per 1 mol of hydroxyl group of polyol. Preferably, it is more preferably 0.6 to 5.0 mol. Side reactions can be suppressed by controlling the amount of monofunctional (meth)acrylate to 0.4 mol or more. Further, by setting the amount to 10.0 mol or less, the amount of component (A) produced can be increased, and productivity can be improved.

1-3. As the transesterification catalyst in the method for producing the catalyst (A) component, the following catalysts X and Y are used in combination because they can produce a reaction product containing di(meth)acrylate in high yield.
Catalyst One or more compounds selected from the group consisting of salts or complexes thereof (hereinafter referred to as "pyridine compounds"), and phosphine or salts or complexes thereof (hereinafter referred to as "phosphine compounds").
Catalyst Y: Compound containing zinc.
Catalyst X and catalyst Y will be explained below.

1-3-1. Catalyst X
Catalyst X in the method for producing component (A) is one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, pyridine compounds, and phosphine compounds.
Among the above-mentioned compound groups, the catalyst X is preferably one or more compounds selected from the group consisting of azabicyclo compounds, amidine compounds, and pyridine compounds. These compounds have excellent catalytic activity and can preferably produce component (A), and also form a complex with catalyst Y, which will be described later, during and after the reaction, and the complex can be added to the reaction solution after the reaction by a simple method such as adsorption. can be easily removed from In particular, the azabicyclo compound can be more easily removed by filtration, adsorption, etc., since the complex with the catalyst Y is hardly soluble in the reaction solution.
On the other hand, although phosphine-based compounds have excellent catalytic activity, they are difficult to form a complex with catalyst Y, or if they form a complex, they are easily soluble in the reaction solution, and phosphine-based compounds are included in the reaction solution after the reaction is completed. Since most of the compound or complex remains dissolved, it is difficult to remove it from the reaction solution by simple methods such as filtration and adsorption. As a result, the phosphine-based catalyst remains in the final product, resulting in turbidity and catalyst precipitation during product storage, as well as increased viscosity or gelation over time, resulting in poor storage stability. This may cause problems.

Specific examples of azabicyclo-based compounds include various compounds as long as they satisfy the requirements of a cyclic tertiary amine having an azabicyclo structure, a salt of the amine, or a complex of the amine. Preferred compounds include quinuclidine, 3 -Hydroxyquinuclidine, 3-quinuclidinone, 1-azabicyclo[2.2.2]octane-3-carboxylic acid, and triethylenediamine (also known as 1,4-diazabicyclo[2.2.2]octane. Hereinafter, "``DABCO'').
Specific examples of azabicyclo-based compounds include, in addition to the above, compounds listed in JP-A No. 2017-39916, JP-A No. 2017-39917, and International Publication No. 2017/033732.

Specific examples of amidine compounds include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinylimidazole, 1-allylimidazole, 1 , 8-diazabicyclo[5.4.0]undec-7-ene (hereinafter referred to as "DBU"), 1,5-diazabicyclo[4.3.0]non-5-ene (hereinafter referred to as "DBN") , N-methylimidazole hydrochloride, DBU hydrochloride, DBN hydrochloride, N-methylimidazole acetate, DBU acetate, DBN acetate, N-methylimidazole acrylate, DBU acrylate, DBN acrylate, and Examples include phthalimide DBU.

Main specific examples of pyridine compounds include pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-ethylpyridine, 3-ethylpyridine, 4-ethylpyridine, and N,N-dimethylpyridine. Examples include 4-aminopyridine (hereinafter referred to as "DMAP").
Specific examples of pyridine-based compounds include, in addition to the above, compounds listed in JP-A No. 2017-39916, JP-A No. 2017-39917, and International Publication No. 2017/033732.

Examples of the phosphine compounds include compounds having a structure represented by the following general formula (2).

[In formula (2), R ³ , R ⁴ and R ⁵ are a straight chain or branched alkyl group having 1 to 20 carbon atoms, a straight chain or branched alkenyl group having 1 to 20 carbon atoms, or a straight chain or branched alkenyl group having 6 carbon atoms. -24 aryl group or a cycloalkyl group having 5 to 20 carbon atoms. R ³ , R ⁴ and R ⁵ may be the same or different. ]

Specific examples of phosphine compounds include triphenylphosphine, tris(4-methoxyphenyl)phosphine, tri(p-tolyl)phosphine, tri(m-tolyl)phosphine, tris(4-methoxy-3,5-dimethylphenyl) ) phosphine, tricyclohexylphosphine, and the like.
Specific examples of phosphine-based compounds include, in addition to the above, compounds listed in JP-A No. 2017-39916, JP-A No. 2017-39917, and International Publication No. 2017/033732.

In the present invention, these catalysts X can be used alone or in any combination of two or more. Among these catalysts X, quinuclidine, 3-quinuclidinone, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU, DBN and DMAP are preferred, and they have particularly good reactivity with most polyhydric alcohols. Preferred are 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP, which are readily available.

There is no particular restriction on the proportion of catalyst 0.0005 to 0.2 mol. By using 0.0001 mol or more of catalyst Coloration of the reaction solution can be suppressed, and the purification process after the reaction is completed can be simplified.

1-3-2. Catalyst Y
Catalyst Y is a compound containing zinc.
As the catalyst Y, various compounds can be used as long as they contain zinc, but organic acid zinc and zinc diketone enolate are preferred because of their excellent reactivity.
Examples of the organic acid zinc include dibasic zinc acids such as zinc oxalate, and compounds represented by the following general formula (3).

[In formula (3), R ⁶ and R ⁷ are a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, or a linear or branched alkenyl group having 6 to 24 carbon atoms. It means an aryl group or a cycloalkyl group having 5 to 20 carbon atoms. R ⁶ and R ⁷ may be the same or different. ]
The compound of formula (3) is preferably a compound in which R ⁶ and R ⁷ are a linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms. In R ⁶ and R ⁷ , the linear or branched alkyl group or alkenyl group having 1 to 20 carbon atoms is a functional group that does not have a halogen atom such as fluorine or chlorine, and the catalyst Y having the functional group is This method is preferable because a reaction product containing the target di(meth)acrylate can be produced in high yield.

Examples of zinc diketone enolates include compounds represented by the following general formula (4).

[In formula (4), R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ are hydrogen atoms, linear or branched alkyl groups having 1 to 20 carbon atoms, and It means a linear or branched alkenyl group, an aryl group having 6 to 24 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms. R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² and R ¹³ may be the same or different. ]

Specific examples of the zinc-containing compound represented by the above general formula (3) include zinc acetate, zinc acetate dihydrate, zinc propionate, zinc octylate, zinc neodecanoate, zinc laurate, zinc myristate, Examples include zinc stearate, zinc cyclohexanebutyrate, zinc 2-ethylhexanoate, zinc benzoate, zinc t-butylbenzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.
In addition, regarding these zinc-containing compounds, if their hydrates or solvates or complexes with catalyst X exist, the hydrates and solvates and complexes with catalyst X are also included in component (A). It can be used as catalyst Y in the production method.

Specific examples of zinc-containing compounds represented by the above general formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, bis(2,6-dimethyl-3,5-heptanedionato)zinc, bis Examples include (2,2,6,6-tetramethyl-3,5-heptanedionato)zinc and bis(5,5-dimethyl-2,4-hexanedionato)zinc. In addition, regarding these zinc-containing compounds, if their hydrates or solvates or complexes with catalyst X exist, the hydrates and solvates and complexes with catalyst X are also included in component (A). It can be used as catalyst Y in the production method.

As the organic acid zinc and zinc diketone enolate in catalyst Y, the above-mentioned compounds can be used directly, but these compounds can also be generated and used in the reaction system.
For example, zinc compounds such as metal zinc, zinc oxide, zinc hydroxide, zinc chloride, and zinc nitrate (hereinafter referred to as "raw material zinc compounds") are used as raw materials, and in the case of organic acid zinc, raw material zinc compounds and organic acids are used as raw materials. In the case of zinc diketone enolate, examples include a method of reacting a raw material zinc compound with 1,3-diketone.

In the present invention, these catalysts Y can be used alone or in any combination of two or more. Among these catalysts Y, zinc acetate, zinc propionate, zinc acrylate, zinc methacrylate, and zinc acetylacetonate are preferred, and catalysts that exhibit particularly good reactivity with most polyhydric alcohols and are easily available. Zinc acetate, zinc acrylate, and zinc acetylacetonate are preferred.

The proportion of catalyst Y used in the method for producing component (A) is not particularly limited, but it is preferable to use 0.0001 to 0.5 mole of catalyst Y, more preferably The amount is 0.0005 to 0.2 mol. By using 0.0001 mol or more of catalyst Y, the yield of the reaction product containing the target di(meth)acrylate can be increased, and by using 0.5 mol or less, the production of by-products and Coloration of the reaction solution can be suppressed, and the purification process after the reaction is completed can be simplified.

1-4. Production method The present invention is a production method in which a polyol and a monofunctional (meth)acrylate are transesterified in the presence of the catalysts X and Y.
There is no particular restriction on the proportion of catalyst X and catalyst Y used in the method for producing component (A), but it is preferable that catalyst Preferably it is 0.05 to 5.0 mol. By using 0.005 mol or more, the yield of the reaction product containing the target di(meth)acrylate can be increased, and by using 10.0 mol or less, the formation of by-products and the reaction solution Coloring can be suppressed and the purification process after the reaction completed can be simplified.

The combination of catalysts X and catalysts Y used together in the present invention is preferably a combination in which catalyst A combination in which the compound represented by the general formula (3) is zinc acetate and/or zinc acrylate is particularly preferred.
In addition to being able to obtain a reaction product containing di(meth)acrylate in a high yield, this combination has excellent color tone (less yellowish tinge) after the reaction is completed, so it is used in coating applications where colorless transparency is important. It can be suitably used for etc. Furthermore, since the catalyst is available at a relatively low cost, it is an economically advantageous production method.

Catalyst X and catalyst Y used in the present invention may be added from the beginning of the above reaction or may be added during the reaction. Further, the desired amount may be added all at once, or may be added in portions.

The reaction temperature in the method for producing component (A) is preferably 40°C to 180°C, more preferably 60°C to 160°C. By setting the reaction temperature to 40°C or higher, the reaction rate can be increased, and by setting the reaction temperature to 180°C or lower, thermal polymerization of (meth)acryloyl groups in raw materials and products can be suppressed, and coloring of the reaction solution can be increased. can be suppressed, and the purification process after the reaction is completed can be simplified.

The reaction pressure in the method for producing component (A) is not particularly limited as long as a predetermined reaction temperature can be maintained, and the reaction may be carried out under reduced pressure or under increased pressure. The reaction pressure is preferably 0.000001 to 10 MPa (absolute pressure).

In the method for producing component (A), monohydric alcohol derived from monofunctional (meth)acrylate is produced as a by-product as the transesterification reaction progresses.
When converting a part (for example, about 50 mol%) of the hydroxyl groups of a polyol into (meth)acrylate, the monohydric alcohol is allowed to coexist in the reaction system to create an equilibrium state, and after the catalyst is removed by adsorption or deactivated, the monohydric alcohol is By distilling off the monohydric alcohol and the monofunctional (meth)acrylate as a raw material, a product with a controlled acrylation rate can be stably produced.
On the other hand, when actively converting the hydroxyl group of the polyol into (meth)acrylate, it is preferable to discharge the monohydric alcohol out of the reaction system to further promote the progress of the transesterification reaction.

In the method for producing component (A), the reaction can be carried out without using a solvent, but a solvent may be used if necessary.
Specific examples of solvents include n-hexane, cyclohexane, methylcyclohexane, n-heptane, n-octane, n-nonane, n-decane, benzene, toluene, xylene, ethylbenzene, diethylbenzene, isopropylbenzene, amylbenzene, and diamyl. Hydrocarbons such as benzene, triamylbenzene, dodecylbenzene, didodecylbenzene, amyltoluene, isopropyltoluene, decalin and tetralin; diethyl ether, dipropyl ether, diisopropyl ether, dibutyl ether, diamyl ether, diethylacetal, dihexyl acetal , t-butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether, dimethyl cellosolve, diglyme, triglyme, tetraglyme and other ethers; crown ethers such as 18-crown-6; benzoin Esters such as methyl acid and γ-butyrolactone; Ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, acetophenone, and benzophenone; Carbonates such as dimethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, 1,2-butylene carbonate, etc. Compounds; sulfones such as sulfolane; sulfoxides such as dimethyl sulfoxide; ureas or derivatives thereof; phosphine oxides such as tributylphosphine oxide; ionic liquids such as imidazolium salts, piperidinium salts, and pyridinium salts; silicone oil; Examples include water.
Among these solvents, at least one solvent selected from the group consisting of hydrocarbons, ethers, carbonate compounds, and ionic liquids is preferred.
These solvents may be used alone, or two or more of them may be used in any combination as a mixed solvent.

In the method for producing component (A), inert gases such as argon, helium, nitrogen, and carbon dioxide gas may be introduced into the system in order to maintain a good color tone of the reaction solution, but (meth)acryloyl group An oxygen-containing gas may be introduced into the system for the purpose of preventing polymerization. Specific examples of the oxygen-containing gas include air, a mixed gas of oxygen and nitrogen, a mixed gas of oxygen and helium, and the like. The oxygen-containing gas can be introduced by dissolving it in the reaction solution or by blowing it into the reaction solution (so-called bubbling).

In the method for producing component (A), it is preferable to add a polymerization inhibitor to the reaction solution for the purpose of preventing polymerization of the (meth)acryloyl group.
Specific examples of polymerization inhibitors include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol, 4-tert -Butylcatechol, benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamine ammonium, 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine - Organic polymerization inhibitors such as 1-oxyl, inorganic polymerization inhibitors such as copper chloride, copper sulfate, and iron sulfate, and organic salts such as copper dibutyldithiocarbamate and N-nitroso-N-phenylhydroxylamine aluminum salt. Examples include polymerization inhibitors.
The polymerization inhibitors may be added singly or in any combination of two or more, and may be added from the beginning or during the process of the present invention. Further, the desired amount may be added all at once, or may be added in portions. Alternatively, it may be added continuously via a rectification column.
The addition ratio of the polymerization inhibitor to the reaction solution is preferably 5 to 30,000 wtppm, more preferably 25 to 10,000 wtppm. By setting this ratio to 5 wtppm or more, the polymerization inhibition effect can be sufficiently exhibited, and by setting this ratio to 30,000 wtppm or less, coloring of the reaction solution can be suppressed and the purification process after the reaction is completed can be simplified. It is also possible to prevent a decrease in the curing speed of the resulting component (A).

The reaction time in the method for producing component (A) varies depending on the type and amount of catalyst used, reaction temperature, reaction pressure, etc., but is preferably 0.1 to 150 hours, more preferably 0.5 to 80 hours.

The method for producing component (A) can be carried out by any of a batch method, a semi-batch method, and a continuous method. As an example of a batch method, a polyol, a monofunctional (meth)acrylate, a catalyst, and a polymerization inhibitor are charged into a reactor, and the reaction solution is stirred at a predetermined temperature while bubbling oxygen-containing gas into the reaction solution. Thereafter, the desired component (A) can be produced by extracting monohydric alcohol by-produced as a result of the transesterification reaction from the reactor at a predetermined pressure.

For the reaction product obtained by the method for producing component (A), it is preferable to carry out separation and purification operations because the reaction product containing the target di(meth)acrylate can be obtained with high purity.
Separation/purification operations include adsorption operations, crystallization operations, filtration operations, distillation operations, extraction operations, etc., and a combination of these operations is preferred. The adsorption operation includes adsorption of the catalyst by an adsorbent, and examples of the adsorbent include aluminum silicate. Examples of crystallization operations include cooling crystallization and concentration crystallization. Examples of the filtration operation include pressure filtration, suction filtration, and centrifugal filtration. Examples of distillation operations include simple distillation, fractional distillation, molecular distillation, and steam distillation. Extraction operations include solid-liquid extraction, liquid-liquid extraction, and the like.
A solvent may be used in the separation and purification operation. In addition, neutralizing agents to neutralize the catalyst and/or polymerization inhibitor used in the present invention, acids and/or alkalis to decompose or remove byproducts, activated carbon to improve color tone, and filtration. Diatomaceous earth and the like may be used to increase efficiency and filtration rate.

1-5. Component (A) Component (A ), which is a mixture of polyfunctional (meth)acrylates having a polyol skeleton having an Mn of 500 to 10,000 as a raw material, can be obtained by the above-described production method.
The Mn of component (A) is preferably 500 to 10,000, more preferably 1,000 to 6,000. Polyfunctional (meth)acrylates with Mn in the range of 500 to 10,000 are preferred because they have low viscosity and facilitate the separation and purification operations.
As component (A), a compound having two (meth)acryloyl groups is preferable.

2. Applications The component (A) obtained by the production method of the present invention can be used for various purposes.
For example, it can be used as a heat or active energy ray-curable compound, a crosslinking agent, etc., and it can also be used as a raw material for other resins.
Furthermore, the composition containing component (A) can be used in various applications such as coating agents such as inks and paints, adhesives, fillers, sealants, and pattern forming agents.
Among these uses, the component (A) obtained by the production method of the present invention is preferably used as a component of a curable composition.
The curable composition will be explained below.

3. The curable composition (A) component is preferably used as a component of the curable composition.
The viscosity of the composition may be appropriately set depending on the purpose.
When component (A) is used for preferred purposes such as coating agents, inks, and pattern formation, it may be set appropriately depending on the purpose, and is preferably 1 to 100,000 mPa・s, more preferably 5 to 50,000 mPa・s. 000mPa・s. By setting the viscosity within this range, the composition can have excellent leveling properties during coating, and the cured product can have an excellent appearance.
Note that the viscosity in the present invention means a value measured at 25° C. using an E-type viscometer.

Although the composition of the present invention can be used as both an active energy ray-curable composition and a thermosetting composition, active energy ray-curable compositions are preferred.
Although the composition of the present invention has the above (A) as an essential component, various components can be added depending on the purpose.
Other components include, specifically, a photopolymerization initiator [hereinafter referred to as "component (B)"], a thermal polymerization initiator [hereinafter referred to as "component (C)"], and ethylene other than the component (A). Examples include compounds having a sexually unsaturated group [hereinafter referred to as "component (D)"] and organic solvents [hereinafter referred to as "component (E)"].
These components will be explained below.
In addition, as for the other components to be described later, only one type of the exemplified compounds may be used, or two or more types may be used in combination.

3-1. (B) Component When using the composition of the present invention as an active energy ray-curable composition and further as an electron beam curable composition, it is preferable that the composition of the present invention not contain component (B) (photopolymerization initiator) and Curing by wire is also possible.
When using the composition of the present invention as an active energy ray-curable composition, especially when ultraviolet rays and visible rays are used as the active energy rays, component (B) may be further added from the viewpoint of ease of curing and cost. It is preferable to contain.
When using an electron beam as the active energy ray, it is not necessarily required to be blended, but a small amount can be blended as necessary to improve curability.

Specific examples of component (B) include benzyl dimethyl ketal, benzyl, benzoin, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropane. 1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy-2-methyl-1-propan-1-one, oligo[2-hydroxy-2-methyl-1-[4-1 -(methylvinyl)phenyl]propanone, 2-hydroxy-1-[4-[4-(2-hydroxy-2-methyl-propionyl)benzyl]phenyl]-2-methylpropan-1-one, 2-methyl- 1-[4-(Methylthio)]phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino -2-(4-methylbenzyl)-1-(4-morpholin-4-yl-phenyl)butan-1-one, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-n- Aromatic ketone compounds such as octylcarbazole, methyl phenylglyoxylate, ethyl anthraquinone and phenanthrenequinone;
Benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4-phenylbenzophenone, 4-(methylphenylthio)phenylphenylmethane, methyl-2-benzophenone, 1- [4-(4-Benzoylphenylsulfanyl)phenyl]-2-methyl-2-(4-methylphenylsulfonyl)propan-1-one, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis Benzophenone compounds such as (diethylamino)benzophenone and 4-methoxy-4'-dimethylaminobenzophenone;
Bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl(2,4,6-trimethylbenzoyl)phenylphosphine and bis(2,6- Acyl phosphine oxide compounds such as dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide;
Thioxanthone, 2-chlorothioxanthone, 2,4-diethylthioxanthone, isopropylthioxanthone, 1-chloro-4-propylthioxanthone, 3-[3,4-dimethyl-9-oxo-9H-thioxanthon-2-yl-oxy]- Examples include thioxanthone compounds such as 2-hydroxypropyl-N,N,N-trimethylammonium chloride and fluorothioxanthone.

Among these compounds, α-hydroxyphenylketones are preferable because they have good surface hardening properties even in thin film coatings in the atmosphere, and specifically, 1-hydroxycyclohexylphenylketone and 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one is more preferred.
In addition, when it is necessary to increase the thickness of the cured film, for example, when it is necessary to increase the thickness to 50 μm or more, it is necessary to increase the thickness of the cured film for the purpose of improving the curability inside the cured film, or when using UV absorbers and pigments together. (2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, ethyl-(2,4,6-trimethylbenzoyl)phenylphosphine and bis(2,6 Acyl phosphine oxide compounds such as -dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, 2-methyl-1-[4-(methylthio)]phenyl]-2-morpholinopropan-1-one, 2-Benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholin-4-yl- It is preferable to use phenyl)-butan-1-one or the like in combination.

The content of component (B) is preferably 0.1 to 10 parts by weight, more preferably 0.5 to 8 parts by weight, based on 100 parts by weight of the total amount of curable components. By setting the proportion of component (B) to 0.1 parts by weight or more, the photocurability of the composition can be improved and the adhesion can be made excellent. By setting the proportion of component (B) to 10 parts by weight or less, the cured film can be It is possible to improve the internal curability of the material, and the adhesion to the base material can be improved.
In the present invention, the "curable component" is a component that is cured by heat or active energy rays, and means component (A), and when combining component (D), which will be described later, (A) and ( D) means an ingredient.

3-2. Component (C) When the composition of the present invention is used as a thermosetting composition, a thermal polymerization initiator can be added.
Various compounds can be used as the thermal polymerization initiator, and organic peroxides and azo initiators are preferred.
Specific examples of organic peroxides include 1,1-bis(t-butylperoxy)2-methylcyclohexane, 1,1-bis(t-hexylperoxy)-3,3,5-trimethylcyclohexane, 1 , 1-bis(t-hexylperoxy)cyclohexane, 1,1-bis(t-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, 2 , 2-bis(4,4-di-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)cyclododecane, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di(m-toluoylperoxy)hexane, t-butylperoxy Oxyisopropyl monocarbonate, t-butylperoxy 2-ethylhexyl monocarbonate, t-hexylperoxybenzoate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane, t-butylperoxyacetate, 2, 2-bis(t-butylperoxy)butane, t-butylperoxybenzoate, n-butyl-4,4-bis(t-butylperoxy)valerate, di-t-butylperoxyisophthalate, α, α '-Bis(t-butylperoxy)diisopropylbenzene, dicumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, t-butylcumyl peroxide, di-t-butyl Peroxide, p-menthane hydroperoxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3, diisopropylbenzene hydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 , 3-tetramethylbutyl hydroperoxide, cumene hydroperoxide, t-hexyl hydroperoxide, t-butyl hydroperoxide and the like.
Specific examples of azo compounds include 1,1'-azobis(cyclohexane-1-carbonitrile), 2-(carbamoylazo)isobutyronitrile, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. , azodi-t-octane, azodi-t-butane, and the like.
These may be used alone or in combination of two or more. Moreover, an organic peroxide can also be combined with a reducing agent to cause a redox reaction.

The amount of these thermal polymerization initiators used is preferably 10 parts by weight or less based on 100 parts by weight of the total amount of curable components.
When using a thermal polymerization initiator alone, it can be carried out according to the conventional method of normal radical thermal polymerization. Heat curing can also be performed for the purpose of improving.

3-3. Component (D) Component (D) is an ethylenically unsaturated compound other than the component (A), and is blended for the purpose of imparting various physical properties to the cured product of the composition.
Examples of the ethylenically unsaturated group in component (D) include a (meth)acryloyl group, a (meth)acrylamide group, a vinyl group, and a (meth)allyl group, with a (meth)acryloyl group being preferred.
In addition, in the following, "monofunctional" means a compound having one ethylenically unsaturated group, "○ functional" means a compound having ○ ethylenically unsaturated groups, and "polyfunctional" means a compound having ○ ethylenically unsaturated groups. means a compound having two or more ethylenically unsaturated groups.

In component (D), specific examples of the monofunctional ethylenically unsaturated compound include compounds similar to the above-mentioned monofunctional (meth)acrylates, such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, ) acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate and tert-butylcyclohexyl (meth)acrylate and 2-methoxyethyl acrylate are preferred.
Compounds other than the monofunctional (meth)acrylates mentioned above include (meth)acrylic acid, Michael addition type dimer of acrylic acid, ω-carboxy-polycaprolactone mono(meth)acrylate, and monohydroxyethyl phthalate (meth)acrylate. , ethyl carbitol (meth)acrylate, butyl carbitol (meth)acrylate, 2-ethylhexyl carbitol (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, (meth)acrylate of alkylene oxide adduct of phenol , (meth)acrylate of alkylene oxide adduct of alkylphenol, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl acrylate, (meth)acrylate of alkylene oxide adduct of paracumylphenol , orthophenylphenol (meth)acrylate, (meth)acrylate of alkylene oxide adduct of orthophenylphenol, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, tricyclodecanemethylol (meth)acrylate, 2-hydroxy- 3-phenoxypropyl (meth)acrylate, N-(2-(meth)acryloxyethyl)hexahydrophthalimide, N-(2-(meth)acryloxyethyl)tetrahydrophthalimide, N,N-dimethylacrylamide, acryloylmorpholine, Examples include N-vinylpyrrolidone and N-vinylcaprolactam.

Specifically, the bifunctional (meth)acrylate compound includes polyethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, and tetramethylene glycol. Di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, di(meth)acrylate of alkylene oxide adduct of bisphenol A, di(meth)acrylate of alkylene oxide adduct of bisphenol F, butanediol di(meth)acrylate Examples include acrylate, hexanediol di(meth)acrylate, and nonanediol di(meth)acrylate. In addition, epoxy (meth)acrylates having a bisphenol skeleton, polyether skeleton, or polyalkylene skeleton, urethane (meth)acrylates having a polyester skeleton, polyether skeleton, or polycarbonate skeleton, and polyester (meth)acrylates may also be used. Can be done.

Examples of trifunctional or higher-functional (meth)acrylate compounds include various compounds having three or more (meth)acryloyl groups, such as trimethylolpropane tri(meth)acrylate, pentaerythritol tri- or tetra- Polyol poly(meth)acrylates such as (meth)acrylates, tri- or tetra(meth)acrylates of ditrimethylolpropane and tri-, tetra-, penta- or hexa(meth)acrylates of dipentaerythritol;
Tri- or tetra(meth)acrylates of pentaerythritol alkylene oxide adducts, tri- or tetra(meth)acrylates of ditrimethylolpropane alkylene oxide adducts, tri-, tetra-, penta- or hexa(meth)acrylates of dipentaerythritol alkylene oxide adducts Poly(meth)acrylates of polyol alkylene oxide adducts such as;
Compounds with hydroxyl groups and three or more (meth)acryloyl groups, such as isocyanuric acid alkylene oxide adduct tri(meth)acrylate; and pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and organic Examples include urethane (meth)acrylate, which is a reaction product with polyisocyanate.
Examples of the alkylene oxide adducts mentioned above include ethylene oxide adducts, propylene oxide adducts, and ethylene oxide and propylene oxide adducts.
Further, the organic polyisocyanate includes hexamethylene diisocyanate, tetramethylene diisocyanate, trimethylhexamethylene diisocyanate, lysine diisocyanate, isophorone diisocyanate, norbornane diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, and hydrogenated xylene diisocyanate. Examples include trimers of diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hexamethylene diisocyanate.

The content of component (D) is preferably 0 to 60% by weight, more preferably 0 to 30% by weight in 100 parts by weight of the total amount of curable components.
By setting the content of component (D) to 60% by weight or less, it is possible to prevent the cured film from becoming brittle, especially when component (D) is a polyfunctional ethylenically unsaturated compound.

3-4. Component (E) The composition of the present invention may contain an organic solvent as component (E) for the purpose of improving coatability on a substrate.

Specific examples of component (E) include alcohol compounds such as methanol, ethanol, isopropanol, and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohol such as diacetone alcohol; benzene, toluene and aromatic compounds such as xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone, and methyl isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone, etc. Can be mentioned.
Among these, alkylene glycol monoether compounds and ketone compounds are preferred, and alkylene glycol monoether compounds are more preferred.

The content ratio of component (E) is preferably 10 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, and more preferably 50 to 300 parts by weight, based on 100 parts by weight of the total amount of curable components. Parts by weight are more preferred. Within the above range, the composition can have a viscosity suitable for coating, and can be easily coated by a known coating method described later.

3-5. Applications of curable composition The composition of the present invention can be used for various applications.
Examples of specific uses include coating compositions, molding material compositions, ink compositions, pattern forming compositions, adhesives, fillers, and sealants. , ink compositions and pattern-forming compositions are preferred.
Preferred applications will be explained below.

3-5-1. Coating Composition The composition of the present invention has excellent thin film curability and high hardness of the cured product, so it can be preferably used as a coating composition, and component (A) has a low viscosity, so it is a solvent-free type. It can be more preferably used as a coating composition.

The coating composition can be preferably used as a hard coat, more preferably as a solvent-free hard coat agent, and can be used as a base material such as plastic films used in polarizer protective films and antireflection films, and home appliances. Examples include resin molded products used for products and automobile interior and exterior parts.

Although the coating composition has the above-mentioned (A) as an essential component, various components can be added depending on the purpose.
Other components include, specifically, the above-mentioned components (B), (C), (D), and (E), as well as antioxidants, ultraviolet absorbers, pigments/dyes, silane coupling agents, and surface modifiers. Examples include polymers, polymers, polymerization inhibitors, and the like.
Specific examples of antioxidants, ultraviolet absorbers, pigments/dyes, silane coupling agents, surface modifiers, polymers, and polymerization inhibitors include paragraph numbers [0086] to [0094] of International Publication WO 2017/002964 pamphlet. Compounds similar to those mentioned above can be mentioned.
As for these other components, only one of the exemplified compounds may be used, or two or more thereof may be used in combination.

As another use of the coating composition, it can be preferably used as a coating agent for metal substrates.
Thereby, a metal base material having a cured film of the curable composition formed on the surface of the metal base material can be manufactured.
The method for producing a metal substrate having a cured film using the composition of the present invention includes a step of coating a curable composition on a part or all of the metal substrate, and It is preferable to include a step of curing by irradiating active energy rays or heating.
The metal substrate having a cured film obtained from the composition of the present invention has excellent followability to deformation of metal substrates, especially film-like metal substrates, and solvent resistance, so it can be used for PDP (plasma display panel). It can be suitably used as an electrode protection material, a board circuit protection material for electric bicycles, an electrode protection coating agent used for lithium ion batteries, etc.

3-5-2. Composition for Molding Materials The composition of the present invention has a low viscosity and a high hardness of the cured product, so it can be preferably used as a composition for molding materials used in mold transfer, nanoimprinting, and the like. In the present invention, microfabrication applications such as nanoimprinting are also referred to as molding materials for convenience.

Although the composition for molding material has the above-mentioned (A) as an essential component, various components can be blended depending on the purpose.
Other components include, specifically, the above-mentioned components (B), (C), (D), and (E), as well as antioxidants, ultraviolet absorbers, pigments/dyes, silane coupling agents, and surface modifiers. Examples include polymers, polymers, polymerization inhibitors, and the like.

3-5-3. Composition for Ink The composition of the present invention has excellent thin film curability, so it can be used as a transparent overprint varnish ink that is further printed on a printing machine after monochrome or multicolor printing, and for color printing such as yellow, red, indigo, and black. It can be preferably used for ink.

Printing methods include offset printing (regular planography that uses dampening water and waterless planography that does not use dampening water), letterpress printing (flat pressure letterpress, letterpress semi-rotary press, rotary press, intermittent rotary press, flexo), and intaglio printing. (gravure printing), stencil printing (screen printing), inkjet printing, and other printing methods, and since it has excellent emulsion stability, it can be preferably used for offset printing using dampening water. Furthermore, since it has a low viscosity, it can be preferably used for inkjet printing.

Although the ink composition contains the above (A) as an essential component, various components can be added depending on the purpose.
The method for producing the ink composition may be according to the conventional method for producing the ink composition, including component (A), component (B) (when the active energy ray is ultraviolet rays), component (F), and component (G). ), a polymerization inhibitor, wax, and other additives are blended, a pigment is added, and the mixture is dispersed using a dispersing machine such as a three-roll mill or a bead mill.

Other components include, in addition to the components (B), (C), and (D) described above, a binder [hereinafter referred to as "component (F)"], and a pigment [hereinafter referred to as "component (G)"]. , plasticizers, antifriction agents, and the like.
Specific examples of component (F), component (G), plasticizer, and antifriction agent include compounds similar to those listed in paragraph numbers [0101] to [0107] of International Publication WO2017/002964 pamphlet. .
As for these other components, only one of the exemplified compounds may be used, or two or more thereof may be used in combination.

3-5-4. Pattern-forming composition The composition of the present invention has high exposure sensitivity, excellent developability, and can form precise and accurate patterns, so it can be preferably used as a pattern-forming composition.

Although the pattern forming composition has the above (A) as an essential component, various components can be added depending on the purpose.
Other components include, specifically, the above-mentioned components (B), (D), and (E), antioxidants, ultraviolet absorbers, silane coupling agents, surface modifiers, and polymerization inhibitors, as well as alkali Examples include soluble resins [hereinafter referred to as "component (H)"].
Specific examples of the component (H) include compounds similar to those listed in paragraph numbers [0110] to [0122] of International Publication WO 2017/002964 pamphlet.
As for these other components, only one of the exemplified compounds may be used, or two or more thereof may be used in combination.

3-6. how to use
3-6-1. Method of using the coating composition The composition of the present invention may be used in accordance with conventional methods.
For example, a method may be used in which the composition is applied to a base material and then cured by irradiation with active energy rays or heating.
Specifically, after applying the composition to the substrate to be applied by a normal coating method, in the case of an active energy ray-curable composition, the composition is cured by irradiation with active energy rays, or a thermosetting composition is In the case of a material, methods such as heating and curing may be mentioned.
As the active energy ray irradiation method and the heating method, a general method known as a conventional curing method may be used.
In addition, by using component (C) (photopolymerization initiator) and component (D) (thermal polymerization initiator) together in the composition, irradiating the composition with active energy rays, and then heating and curing it, adhesiveness to the substrate can be improved. Methods to improve sexual performance can also be adopted.

The composition of the present invention can be applied to various materials, including plastics, wood, metals, inorganic materials, and paper.
Specific examples of plastics include polyvinyl alcohol, cellulose acetate resins such as triacetylcellulose and diacetylcellulose, acrylic resins, polyethylene terephthalate, polycarbonate, polyarylate, polyethersulfone, and cyclic polyolefin resins containing cyclic olefins such as norbornene as monomers. , polyvinyl chloride, epoxy resin and polyurethane resin.
Examples of the wood include natural wood and synthetic wood.
Examples of metals include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO).
Examples of inorganic materials include glass, mortar, concrete, and stone.
Among these, plastic base materials are particularly preferred.

The thickness of the cured composition film relative to the substrate may be appropriately set depending on the purpose. The thickness of the cured film may be selected depending on the substrate used and the purpose of the substrate having the produced cured film, but it is preferably 1 to 500 μm, more preferably 5 to 200 μm. .

The method for applying the composition of the present invention to the substrate may be appropriately set depending on the purpose, and can be applied using a bar coater, applicator, doctor blade, dip coater, roll coater, spin coater, flow coater, knife coater, comma coater, etc. Examples include coating methods using a coater, reverse roll coater, die coater, lip coater, gravure coater, microgravure coater, inkjet, and the like.

Examples of active energy rays for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, but ultraviolet rays are preferred.
Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).
The irradiation energy may be set appropriately depending on the type of active energy ray and the composition. For example, when using a high-pressure mercury lamp, the irradiation energy in the UV-A range is 100 to 5,000 mJ/cm ² is preferable, and 200 to 1,000 mJ/cm ² is more preferable.

3-6-2. Method of using the composition for molding materials When using the composition of the present invention for molding materials, conventional methods may be followed.
Specifically, the composition is applied to a mold called a stamper having the desired shape, laminated with a film or sheet base material (hereinafter collectively referred to as "film base material"), and then active energy is applied to the composition. A method of curing by irradiating the composition with radiation, a method of injecting the composition into a predetermined mold, and a method of curing by irradiating the composition with active energy rays in the case of an active energy ray-curable composition, and a method of curing by irradiating the composition with active energy rays in the case of a thermosetting composition. In such cases, a method of curing by heating may be used.

Film base materials that can be used in the present invention include polymethyl methacrylate, polymethyl methacrylate-styrene copolymer film, polyethylene terephthalate, polyethylene naphthalate, polyarylate, polyacrylonitrile, polycarbonate, polysulfone, polyether sulfone, and polyetherimide. , polyetherketone, polyimide, polymethylpentene, etc., are preferred, and if necessary, a glass base material can be used.

The film base material is preferably transparent or translucent (for example, milky white). The thickness of the film base material is preferably 20 to 500 μm.

Examples of active energy rays for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, but ultraviolet rays are preferred.
Examples of the ultraviolet irradiation device include devices similar to those described above.
The irradiation energy may be appropriately set depending on the type and composition of the active energy ray, and examples thereof include the same irradiation energy as described above.

An example of manufacturing a lens sheet using the composition of the present invention will be described.
When manufacturing a relatively thin lens sheet, the composition of the present invention is applied to a transparent substrate, and then a mold called a stamper having the shape of the desired lens is brought into close contact with the transparent substrate.
Next, active energy rays are irradiated from the transparent substrate side to cure the composition, and then it is peeled off from the mold.

On the other hand, when manufacturing a relatively thick lens sheet, the composition of the present invention is poured between a mold having the shape of the desired lens and a transparent substrate.
Next, the composition is cured by irradiating active energy rays from the side of the transparent substrate, and then the mold is removed.

The material of the mold is not particularly limited, and examples thereof include metals such as brass and nickel, and resins such as epoxy resin. It is preferable to use metal because the mold has a long life.

When using the composition of the present invention for nanoimprint purposes, conventional methods may be followed.
For example, after applying the composition to a base material, a transparent mold having a microfabricated pattern is pressed.
Next, a method can be used in which the composition is cured by irradiating active energy rays from above the transparent mold, and then the mold is removed.

3-6-3. Method of using ink composition The printing base material used in the printed matter of the present invention is not particularly limited, and examples thereof include paper such as high-quality paper, coated paper, art paper, imitation paper, thin paper, and cardboard, various synthetic papers, Polyester resin, acrylic resin, vinyl chloride resin, vinylidene chloride resin, polyvinyl alcohol, polyethylene, polypropylene, polyacrylonitrile, ethylene vinyl acetate copolymer, ethylene vinyl alcohol copolymer, ethylene methacrylic acid copolymer, nylon, polylactic acid, Examples include films or sheets such as polycarbonate, cellophane, aluminum foil, and other various substrates conventionally used as printing substrates.
Among these, paper base materials are particularly preferred.

The thickness of the cured composition film relative to the substrate may be appropriately set depending on the purpose. The thickness of the cured film may be selected depending on the substrate used and the purpose of the substrate having the produced cured film, but it is preferably 1 to 20 μm, more preferably 1 to 10 μm. .

When the composition of the present invention is used as an offset ink, an offset printing machine that continuously supplies water onto the printing plate can be suitably used as a method for coating the substrate. Further, it can be suitably used in both sheet-fed offset printing machines using sheet-shaped printing paper and offset rotary printing machines using reel-shaped printing paper, both paper supply systems.

When the composition of the present invention is used as an inkjet ink, it can be suitably applied to a substrate using a known inkjet recording device that forms an image by discharging it using an inkjet method. .

In the inkjet method, the viscosity of the composition should be 7 mPa·s to 30 mPa·s at the temperature at the time of ejection (for example, 40°C to 80°C, preferably 25°C to 30°C), considering the ejection property. preferable. More preferably it is 7 mPa·s to 20 mPa·s.

Examples of active energy rays for curing the composition of the present invention include ultraviolet rays, visible rays, and electron beams, but ultraviolet rays are preferred.
Examples of the ultraviolet irradiation device include devices similar to those described above.
The irradiation energy may be appropriately set depending on the type and composition of the active energy ray, and examples thereof include the same irradiation energy as described above.

3-6-4. How to use pattern-forming compositions Pattern-forming compositions can be used to form photosensitive lithographic printing plates, resists such as etching resists and solder resists, columnar spacers in the manufacture of liquid crystal panels, pixels and black matrices in color filters, etc. Coloring compositions for color filters, color filter protective films, etc.

Among these uses, the composition of the present invention can be more preferably used for columnar spacers, coloring compositions for color filters, and protective films for color filters in the production of liquid crystal panels.
When used as a columnar spacer or color filter protective film, a nonionic surfactant such as polyoxyethylene lauryl ether or a fluorine surfactant may be added to the composition to improve coating properties and developability. It can also be added. Furthermore, adhesion aids, storage stabilizers, antifoaming agents, and the like may be added as appropriate.

EXAMPLES Below, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
In the following, "parts" means parts by weight, "%" means "% by weight", and "ppm" means "ppm by weight".

1. Various definitions
1) Abbreviations Abbreviations in the Examples have the following meanings.
・MCA: 2-methoxyethyl acrylate ・MEL: 2-methoxyethanol ・DABCO: triethylenediamine ・MEHQ: hydroquinone monomethyl ether ・TEMPOL: 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl ・DEHA :N,N-diethylhydroxylamine

2) Reaction yield The reaction yield of the transesterification in Examples 1 and 2 and Comparative Examples 1 to 4 is based on MEL [derived from MCA used as a raw material] produced as a by-product as the transesterification progresses. It was quantified and calculated using the following formula (1).
The determination of MEL was carried out using a high-performance liquid chromatograph equipped with a differential refractive index detector (column: Atlantis manufactured by Nippon Waters Co., Ltd. (Part No. 186003748, column inner diameter 4.6 mm, column length 250 mm), solvent: pure Water or a 10% by volume isopropanol aqueous solution) was used, and the internal standard method was used.

Reaction yield (mol%) = Number of moles of MEL by-produced as the transesterification reaction progresses/(Number of moles of diol used as raw material x 2 (number of alcoholic hydroxyl groups possessed by diol used as raw material)) x 100 ...(1)

3) Measurement of number average molecular weight (Mn) GPC system manufactured by Nippon Waters Co., Ltd.: Detector = RI, Waters 2414, column: STYRAGEL HR1 manufactured by Nippon Waters Co., Ltd. (column inner diameter 7.8 mm, column length 300 mm, THF The number average molecular weight was calculated using a polystyrene standard sample as a reference.

4) Measurement of color tone The APHA and a1 values were measured using a color difference meter (Nippon Denshoku Kogyo Petroleum Product Color Tester OME-2000).

2. Examples and comparative examples
1) Example 1
Polycarbonate diol [Product name: NL3010DB, manufactured by Mitsubishi Chemical Corporation, Mn: 3,542, hydroxyl value 38] was placed in a 3-liter flask equipped with a stirrer, thermometer, gas inlet tube, rectification column, and cooling tube. .3mgKOH/g], 240.00 g (0.082 mol) of MCA, 665.17 g (5.11 mol) of MCA, 0.19 g (0.0017 mol) of DABCO as catalyst X, and zinc acrylate as catalyst Y. 0.68 g (0.0033 mol), 0.15 g of MEHQ (239 ppm relative to the total weight of the charged raw materials), 0.050 g of TEMPOL (55 ppm relative to the total weight of the charged raw materials), oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid.
While heating and stirring the reaction solution temperature in the range of 125 to 130°C, the pressure in the reaction system was adjusted in the range of 30.7 × 10 ^-3 to 32.0 × 10 ^-3 MPa (230 to 240 mmHg), and transesterification was carried out. A mixed liquid of MEL and MCA, which was produced as a by-product as the reaction progressed, was extracted from the reaction system through a rectification column and a cooling pipe.
Further, MCA of the same weight as the extracted liquid was added to the reaction system at any time. Further, MCA containing MEHQ and TEMPOL was added to the reaction system from time to time via a rectification column. As a result of quantifying MEL contained in the liquid extracted from the reaction system, the reaction yield reached 93% 12 hours after the start of heating and stirring, so the heating of the reaction liquid was stopped and the pressure inside the reaction system was constantly maintained. The pressure was returned to complete extraction.
Incidentally, 0.00055 g of MEHQ and 0.00061 g of TEMPOL were used with respect to a total of 100 g of the reaction solution.

11.5 parts of aluminum silicate [Kyoward 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.] as an adsorbent was added to the filtrate, and the mixture was heated and stirred for 1 hour under normal pressure at an internal temperature of 80 to 105°C to bring the mixture into contact. After the treatment, 0.23 parts of calcium hydroxide was added while the internal temperature was in the range of 20 to 40°C, and the mixture was stirred for 1 hour under normal pressure.
After separating insoluble matter by pressure filtration, vacuum distillation is performed for 16 hours at a temperature of 70 to 98°C and a pressure of 0.001 to 100 mmHg while bubbling dry air to the filtrate to remove unreacted MCA. The distillate was separated.
The obtained pot solution was cooled to room temperature, 0.081 part of DEHA (350 ppm based on the obtained pot solution) was added, and the mixture was stirred at an internal temperature of 80° C. under normal pressure for 3 hours. Thereafter, solid matter was separated by pressure filtration.
As a result of performing a composition analysis of the filtrate after pressure filtration using ¹ H NMR, it was confirmed that it contained polycarbonate diacrylate as a main component. The purification yield calculated by considering the filtrate as a purified product was 93%.

2) Comparative Examples 1 and 2
A transesterification reaction was carried out in the same manner as in Example 1, except that the type of catalyst was changed as shown in Table 1 below, to obtain a purified product containing the desired acrylate.

3) Example 2
In the same flask as in Example 1, 240.00 g (0.082 mol) of polyester diol [trade name: HS 2N-220S, manufactured by Toyokuni Oil Co., Ltd., Mn: 2,461, hydroxyl value 56.2 mgKOH/g] was added. ), 650.70 g (5.00 mol) of MCA, 0.24 g (0.0021 mol) of DABCO as catalyst 15g (241ppm based on the total weight of the raw materials charged), 0.18g TEMPOL (202ppm based on the total weight of the raw materials charged), and oxygen-containing gas (oxygen 5% by volume, nitrogen 95% by volume). bubbling into the liquid.
While heating and stirring the reaction solution temperature in the range of 125 to 130°C, the pressure in the reaction system was adjusted in the range of 31.2 × 10 ^-3 to 32.1 × 10 ^-3 MPa (237 to 244 mmHg), and transesterification was carried out. A mixed liquid of MEL and MCA, which was produced as a by-product as the reaction progressed, was extracted from the reaction system through a rectification column and a cooling pipe.
Further, MCA of the same weight as the extracted liquid was added to the reaction system at any time. Further, MCA containing MEHQ and TEMPOL was added to the reaction system from time to time via a rectification column. As a result of quantifying MEL contained in the liquid extracted from the reaction system, the reaction yield reached 91% 16 hours after the start of heating and stirring, so the heating of the reaction liquid was stopped and the pressure inside the reaction system was constantly maintained. The pressure was returned to complete extraction.
Incidentally, 0.00055 g of MEHQ and 0.00061 g of TEMPOL were used with respect to a total of 100 g of the reaction solution.

Add 14 parts of aluminum silicate (Kyoward 700) as an adsorbent to the filtrate, heat and stir for 1 hour under normal pressure at an internal temperature of 80 to 105°C for contact treatment, and then heat and stir at an internal temperature of 20 to 40°C. 0.36 parts of calcium hydroxide was added, and the mixture was stirred for 1 hour under normal pressure.
After separating insoluble matter by pressure filtration, vacuum distillation is performed for 16 hours at a temperature of 70 to 98°C and a pressure of 0.001 to 100 mmHg while bubbling dry air to the filtrate to remove unreacted MCA. The distillate was separated.
The obtained pot solution was cooled to room temperature, 0.19 parts of DEHA (850 ppm based on the obtained pot solution) was added, and the mixture was stirred at an internal temperature of 80° C. under normal pressure for 3 hours. Thereafter, solid matter was separated by pressure filtration.
As a result of performing a composition analysis of the filtrate after pressure filtration using ¹ H NMR, it was confirmed that it contained polyester diacrylate as a main component. The purification yield calculated by considering the filtrate as a purified product was 91%.

4) Comparative Examples 3 and 4
A transesterification reaction was carried out in the same manner as in Example 2, except that the type of catalyst was changed as shown in Table 2 below, to obtain a purified product containing the desired acrylate.

3. Summary As is clear from the results of Examples 1 and 2, according to the production method of the present invention, the obtained diacrylate can suppress lowering of the molecular weight, and there is no problem of coloring.
On the other hand, in the production methods of Comparative Examples 1 and 3 in which a tin-based catalyst was used as a catalyst, the resulting diacrylates had a reduced molecular weight and were colored.
In addition, in the production methods of Comparative Examples 2 and 4 in which titanium-based catalysts were used as catalysts, the obtained diacrylates had high molecular weights, but were significantly colored.

The manufacturing method of the present invention can be used for manufacturing (meth)acrylate.
Furthermore, the (meth)acrylate obtained by the production method of the present invention can be used in various applications such as coating agents, molding agents, inks, pattern forming agents, adhesives, fillers, and sealants.

Claims (8)

In the presence of the following catalyst A method for producing a mixture ( A) of a compound having two (meth)acryloyl groups, which comprises performing a transesterification reaction with an alkyl (meth)acrylate.

[In formula (6), R ¹⁷ , R ¹⁸ and R ¹⁹ mean a divalent hydrocarbon group having 2 to 30 carbon atoms. R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different. n represents the average degree of polymerization and is a number from 1 to 50. ]
Catalyst X: cyclic tertiary amine having an azabicyclo structure, or a salt or complex thereof.
Catalyst Y: Compound containing zinc. 2. The two polyester diols according to claim 1, wherein in the polyester diol represented by formula (6), R ¹⁹ is a group selected from the group consisting of an ethylene group, a trimethylene group, a tetramethylene group, and a 1,8-octylene group. A method for producing a mixture (A) of compounds having a (meth)acryloyl group. In the polyester diol represented by formula (6), R ¹⁷ and R ¹⁸ are 1,4-butylene group, 1,5-pentylene group, 1,6-hexylene group, 3-methyl-1,5-pentylene group and 2,4-diethyl-1,5-pentylene group of the mixture (A) of compounds having two (meth)acryloyl groups according to claim 1 or 2. Production method. In the polyester diol represented by formula (6), R ¹⁷ and R ¹⁸ are 2,4-diethyl-1,5-pentylene groups, and R ¹⁹ is a tetramethylene group or 1,8-octylene group. A method for producing a mixture (A) of compounds having two (meth)acryloyl groups according to any one of claims 1 to 3 . 2 according to any one of claims 1 to 4 , wherein the mixture (A) of compounds having two (meth)acryloyl groups obtained by the transesterification reaction has an Mn of 500 to 10,000. A method for producing a mixture (A) of compounds having (meth)acryloyl groups. The method for producing a mixture (A) of compounds having two (meth)acryloyl groups according to any one of claims 1 to 5, wherein the catalyst Y is an organic acid zinc and/or a zinc diketone enolate. . In the presence of the following catalyst A curable composition comprising a mixture (A) of compounds having two (meth)acryloyl groups obtained by

[In formula (6), R ¹⁷ , R ¹⁸ and R ¹⁹ mean a divalent hydrocarbon group having 2 to 30 carbon atoms. R ¹⁷ , R ¹⁸ and R ¹⁹ may be the same or different. n represents the average degree of polymerization and is a number from 1 to 50. ]
Catalyst X: cyclic tertiary amine having an azabicyclo structure, or a salt or complex thereof.
Catalyst Y: Compound containing zinc. The curable composition according to claim 7 , wherein the catalyst Y is an organic acid zinc or/and a zinc diketone enolate.