JP2021017492A - Curable composition - Google Patents

Abstract

To provide a curable composition in which the cured product of the composition has a low surface resistivity, an excellent anti-static ability, and an excellent hardness, and preferably an active energy ray-curable composition.SOLUTION: Provided is a curable composition containing a (meth)acrylate of an alkyleneoxide adduct of (A) component: alditol (excluding glycerol) and having a surface resistivity of the cured product of less than 1×1013 Ω. The curable composition can preferably be used as an active ray-curable composition, and can more preferably be used as an active energy ray-curable coating agent composition.SELECTED DRAWING: None

Description

The present invention relates to a curable composition, preferably an active energy ray-curable composition, more preferably an active energy ray-curable coating composition, and belongs to these technical fields.
In the present specification, "acryloyl group and / or methacryloyl group" is referred to as "(meth) acryloyl group", "acrylate and / or methacrylate" is referred to as "(meth) acrylate", and "acrylic acid and / or methacrylic acid". "Acid" is expressed as "(meth) acrylic acid".
Further, a compound having an ethylenically unsaturated group is referred to as a "curable component" in the composition, and other components are referred to as a "non-curable component".

Lens sheets such as prism sheets, antireflection films (so-called moth-eye films) having a microconcavo-convex structure with a period equal to or less than the wavelength of visible light on the surface, antiglare films, light extraction films for organic EL / LEDs, light for solar cells Molded films such as confinement films and heat ray retroreflective films are usually produced by the following methods.
That is, an active energy ray-curable composition is filled between a stamper having an inverted structure having a fine concavo-convex structure on its surface and a transparent substrate, cured by irradiation with active energy rays, and then the stamper is released. A method of transferring a fine concavo-convex structure to a cured product, or an active energy ray-curable composition is filled between the stamper and a transparent substrate, and then the stamper is released to obtain an active energy ray-curable composition. A method is used in which the fine concavo-convex structure is transferred and then the active energy ray-curable composition is cured by irradiation with active energy rays.

As such a curable composition for a shaped material, an active energy ray-curable composition containing a polyfunctional (meth) acrylate such as trimethylolpropane triacrylate (hereinafter referred to as "TMPTA") has been conventionally known. (Patent Document 1).
However, since the composition has a high surface resistivity, it is easily charged, and there is a problem that foreign matter adheres to the parts and deteriorates the product quality.

Further, not only the curable composition for a shaping material but also the surface of plastic, glass or the like used in an optical material or an electronic material is required to be antistatic.
For example, if the surface of plastic or glass is charged, dust or the like may adhere to the surface and cause stains, or the IC or LSI may be destroyed or defective due to a high voltage of static electricity. There is a problem caused by static electricity such as malfunction of electronic devices due to electromagnetic noise.
Therefore, antistatic coatings are applied to the surfaces of plastics, glass, and the like used in optical materials and electronic materials.

As a coating agent for improving antistatic properties, an active energy ray-curable composition containing polyethylene glycol di (meth) acrylate is known (Patent Document 2).
However, although the composition has a low surface resistivity of the cured film and is excellent in antistatic performance, it has a problem that the hardness is low and it is easily scratched.

Japanese Unexamined Patent Publication No. 2000-071290 Japanese Patent No. 3083916

The present inventors consider that the cured product of the composition is a curable composition having a low surface resistivity, excellent antistatic ability, and excellent hardness, preferably an active energy ray-curable composition, and more preferably an active energy ray-cured composition. Diligent studies were conducted to find a mold coating composition.

In order to solve the above problems, the present inventors have a composition containing a (meth) acrylate produced from a plant-derived alcohol and containing a polyfunctional (meth) acrylate having both a hydroxyl group and an ether group in the molecule. The present invention has been completed by finding that the cured product has a low surface resistance, excellent hardness, and excellent adhesion to various plastic substrates.
Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, the cured product has a low surface resistivity and can exhibit sufficient antistatic ability. Further, the cured product of the composition has excellent hardness.
Therefore, the composition of the present invention can be preferably used for an active energy ray-curable composition, and more preferably for an active energy ray-curable coating composition.

The present invention relates to a curable composition containing (A) component: (meth) acrylate as an alkylene oxide adduct of alditol (excluding glycerol) and having a cured product having a surface resistivity of less than 1 × 10 ¹³ Ω. ..
In the following, the description of "alditol (excluding glycerol)" may be simply referred to as "alditol".
Hereinafter, the component (A), its manufacturing method, and its use will be described.

1. 1. Component (A) Component (A) is a (meth) acrylate of an alkylene oxide adduct of alditol (excluding glycerol).
In the present invention, an alkylene oxide adduct of alditol (hereinafter referred to as "AZ-RO") is used as the raw material compound of the component (A). However, in the present invention, glycerol is excluded as alditol.

1-1. AZ-RO
As the alditol which is a raw material compound of AZ-RO, various compounds can be used.
Specific examples of alditol include erythritol, threitol, ribitol, arabitol, xylitol, aritol, sorbitol, mannitol, iditol, galactitol, and taritol, and it is preferable to use an easily available D-form.
Among these compounds, erythritol, xylitol, sorbitol (D-glycitol), and mannitol are preferable and easily available because they are industrially easily available and the desired (meth) acrylate can be easily produced. It is preferable to use the D form.
These compounds are derived from plants and have a low environmental load.
As alditol, these compounds may be used alone, or two or more kinds thereof may be used in combination.
Among these compounds, sorbitol is preferable as alditol.

Examples of the alkylene oxide unit in AZ-RO include ethylene oxide, propylene oxide, tetramethylene oxide, and a mixed unit of these alkylene oxides, and among these, the obtained (meth) acrylate has excellent curability. In that respect, ethylene oxide is preferred.
As the number of moles of alkylene oxide added in AZ-RO, a compound having a large number of moles of alkylene oxide is generally preferable because it is easy to handle and can reduce the inhibition of radical polymerization in the presence of oxygen.
The number of moles of alkylene oxide added in AZ-RO is preferably 1 to 20, and more preferably 2 to 15.
By setting the number of moles of alkylene oxide added to 1 or more, it dissolves only in a hydrophilic solvent such as water or alcohol, and becomes difficult to dissolve in a compound having one (meth) acryloyl group or an organic solvent in a transesterification reaction. Therefore, it is possible to prevent the transesterification reaction from becoming difficult to proceed, and to prevent the compatibility with other components from being significantly reduced when the obtained (meth) acrylate is used as a curable composition. On the other hand, when the number of moles of alkylene oxide added is 20 or less, the hardness of the cured product can be increased when the obtained (meth) acrylate is used as a curable composition.

The component (A) is produced by (meth) acrylate-forming AZ-RO.
As a method for producing the component (A), a transesterification reaction of a compound having AZ-RO and one (meth) acryloyl group [hereinafter referred to as “monofunctional (meth) acrylate”] in the presence of a transesterification catalyst. Examples thereof include a method of causing AZ-RO and (meth) acrylic acid to undergo a dehydration esterification reaction in the presence of an acid catalyst, and a transesterification reaction is preferable.

1-2. Preferred Form of Component (A) Component (A) is preferably a mixture of reaction products containing (meth) acrylate obtained by transesterification of AZ-RO and monofunctional (meth) acrylate. The component (A) is a mixture of a (meth) acrylate having a different number of (meth) acryloyl groups and a side reaction product.

Examples of the alkylene oxide unit in the component (A) include ethylene oxide, propylene oxide, tetramethylene oxide, and a mixed unit of these alkylene oxides, and ethylene oxide is preferable in terms of excellent curability.
As the number of moles of alkylene oxide added in the component (A), a compound having a large number of moles of addition is generally preferable because it is easy to handle and can reduce the inhibition of radical polymerization in the presence of oxygen.
The number of moles of alkylene oxide added in the component (A) is preferably 1 to 20, and more preferably 2 to 15.
When the number of moles of alkylene oxide added is 1 or more, it dissolves only in a hydrophilic solvent such as water or alcohol, and it becomes difficult to dissolve in a monofunctional (meth) acrylate or an organic solvent in the transesterification reaction. Can be prevented from becoming difficult to proceed, and when the obtained (meth) acrylate is used as a curable composition, it is possible to prevent the compatibility with other components from being significantly reduced. On the other hand, when the number of moles of alkylene oxide added is 20 or less, the hardness of the cured product can be increased when the obtained (meth) acrylate is used as a curable composition.

As the component (A), a compound having hydrophilicity is preferable, and a compound having water solubility is more preferable.
As for the component (A) which is hydrophilic or water-soluble, the curable composition becomes hydrophilic or water-soluble, and the obtained cured product also becomes hydrophilic or water-soluble. Utilizing this property, the curable composition containing the component (A) can be used for various purposes, for example, an antistatic coating agent, a self-coating agent, and a hydrophobic coating agent can be made hydrophilic. It can be used as a primer for coating on a base material.
In the present invention, hydrophilicity or water solubility means a case where the solubility of distilled water with respect to the component (A) is 10% or more at a temperature of 22 ° C.
The solubility is defined by the following formula, and means a uniform liquid state in which no turbidity or layer separation is confirmed in the mixed solution after the distilled water and the component (A) are mixed and allowed to stand.
(A) Solubility of distilled water with respect to the component (%)
= Weight part of distilled water / (Weight part of distilled water + Weight part of component (A)) x 100
In the present invention, the hydroxyl group of AZ-RO, which is the raw material compound of the component (A), is transesterified to obtain the component (A) having a (meth) acryloyl group, and the (meth) acrylate conversion rate of the hydroxyl group is 50%. By keeping the amount to less than or leaving the hydroxyl group, the component (A) can be made to exhibit extremely high solubility in water.

Further, as the component (A), a mixture having a saponification value of 150 to 300 mgKOH / g is preferable, and a saponification value of 200 to 280 mgKOH / g is more preferable. By setting the saponification value to 150 mgKOH / g or more, the cured product of the composition containing the component (A) can be made to have high hardness, and by setting the saponification value to 300 mgKOH / g or less, the component (A) can be obtained. Can be excellent in hydrophilicity or water solubility.
The saponification value in the present invention means that an ethanol solution of potassium hydroxide is added to a sample, heat-treated in a warm bath at 75 ° C. for 30 minutes, allowed to cool, and then based with an aqueous hydrochloric acid solution using a phenolphthalein solution as an indicator. Means the value obtained by titrating.

Further, as the component (A), a mixture having a hydroxyl value of 100 mgKOH / g or more is preferable, more preferably 150 mgKOH / g, and a preferable upper limit is 600 mgKOH / g.
By setting the hydroxyl value to 100 mgKOH / g or more, the component (A) can be made excellent in hydrophilicity or water solubility.
The hydroxyl value in the present invention means that a mixed solution of acetic anhydride and pyridine is added to a sample and heat-treated in a warm bath at 92 ° C for 1 hour, and then a small amount of water is added in a warm bath at 92 ° C. It means a value obtained by heat-treating for 10 minutes, allowing to cool, and then titrating an acid with an ethanol solution of potassium hydroxide using a phenolphthalein solution as an indicator.

As the component (A), a compound represented by the following general formula (5) is preferable.

[In the formula (5), R ^{14 to} R ¹⁶ each independently represent a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms, and when there are a plurality of each of R ^{14 to} R ^16. It may be the same or different. X ^{1 to} X ³ independently represent a hydrogen atom or a (meth) acryloyl group. Each of a, b, and c represents a positive number, and all of them do not become 0 at the same time, satisfying 0 <(a + nb + c) ≦ 80. n represents an integer of 2-4. ]

R ^{14 to} R ¹⁶ are divalent aliphatic hydrocarbon groups having 2 to 4 carbon atoms. Examples of the aliphatic hydrocarbon group include a linear aliphatic hydrocarbon group and a branched aliphatic hydrocarbon group.
Specific examples of the linear aliphatic hydrocarbon group include an ethylene group, a 1,3-propylene group (trimethylene group), a 1,4-butylene group (tetramethylene group) and the like.
Specific examples of the branched aliphatic hydrocarbon group include a 1,2-propylene group (isopropylene group) and a 1,1-dimethylethylene group (isobutylene group).
Among these functional groups, an ethylene group is preferable as R ^{14 to} R ¹⁶ .

In formula (5), n, which means the structure of the alditol skeleton, is 2-4.
a, b and c mean the number of moles of oxyalkylene units present in the hydroxyl group of alditol. Each of a, b and c represents a positive number, and not all of them become 0 at the same time.
a + nb + c means the total number of moles of oxyalkylene units present in the molecule of alditol (the average number of moles of alkylene oxide added to the whole alditol). a + nb + c satisfies the following equation.
0 <(a + nb + c) ≤80
The lower limit of a + nb + c is preferably 1 or more. As a + nb + c, 2 ≦ (a + nb + c) ≦ 10 is more preferable. Within this range, synthesis is facilitated, which is advantageous in terms of economy, and compatibility with other components is improved, so that the degree of freedom in compounding design is increased, and a composition having excellent curability can be obtained. be able to.

The (meth) acrylate is preferably an acrylate from the viewpoint of reactivity during the transesterification reaction and quick curing of the component (A).

1-3. The production method of the production method (A) component of the component (A), as described above, in the presence of a transesterification catalyst, AZ-RO and a monofunctional (meth) acrylate a method of transesterification reaction is preferred.
Further, as a method for producing the component (A), a production method in which AZ-RO and a monofunctional (meth) acrylate are transesterified in the presence of the following catalysts X and Y is preferable.
Catalyst X: A type selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or salts or complexes thereof, amidin or salts thereof or complexes thereof, compounds having a pyridine ring or salts or complexes thereof, and phosphine or salts or complexes thereof. The above compounds.
Catalyst Y: A compound containing zinc.
Hereinafter, a preferable method for producing the component (A) will be described.

1-3-1. AZ-RO
AZ-RO is as described in detail above.

1-3-2. 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 represented by, for example, the following general formula (1). Compounds are mentioned.

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 carbons such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a 2-ethylhexyl group. Alkyl alkyl groups of number 1-8, 2-methoxyethyl group, 2-ethoxyethyl group, 2-methoxybutyl group, etc., as well as N, N-dimethylaminoethyl group, N, N-diethylaminoethyl group, N , N-Dimethylaminopropyl group and dialkylamino groups such as N, N-diethylaminopropyl group and the like.
Specific examples of R ² in the general formula (1) include the functional groups mentioned in JP-A-2017-39916, JP-A-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, carbons such as methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate and 2-ethylhexyl (meth) acrylate Alkyl (meth) acrylates having an alkyl group of several 1 to 8, alkoxyalkyl (meth) acrylates such as 2-methoxyethyl acrylate, or N, N-dimethylaminoethyl (meth) acrylates are preferable, and AZ-RO in particular On the other hand, a (meth) acrylate having an alkyl group having 1 to 4 carbon atoms or an alkoxyalkyl (meth) acrylate having an alkyl group having 1 to 2 carbon atoms, which shows good reactivity and is easily available, is preferable.
Further, an alkoxyalkyl (meth) acrylate having an alkyl group having 1 to 2 carbon atoms, which promotes the dissolution of AZ-RO and exhibits extremely good reactivity, is more preferable, and 2-methoxyethyl (meth) acrylate is particularly preferable.
Furthermore, as the monofunctional (meth) acrylate, acrylate is particularly preferable because it has excellent reactivity.

The ratio of AZ-RO and monofunctional (meth) acrylate used in the method for producing the component (A) is not particularly limited, but 0.4 to 10 monofunctional (meth) acrylate is used for 1 mol of hydroxyl groups of AZ-RO. It is preferably 0.0 mol, more preferably 0.6 to 5.0 mol. Side reactions can be suppressed by increasing 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 the component (A) produced can be increased and the productivity can be improved.

1-3-3. As the transesterification reaction catalyst in the method for producing the catalyst (A) component, the following catalysts X and Y are used in combination as catalysts because (meth) acrylate can be produced in a high yield.
Catalyst X: Cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof (hereinafter referred to as "azabicyclo compound"), amidin or a salt or complex thereof (hereinafter referred to as "amidine compound"), a compound having a pyridine ring or One or more compounds selected from the group consisting of the salt or complex (hereinafter referred to as "pyridine compound") and phosphine or a salt or complex thereof (hereinafter referred to as "phosphine compound").
Catalyst Y: A compound containing zinc.
Hereinafter, the catalyst X and the catalyst Y will be described.

1-3-3-3-1. Catalyst X
The catalyst X in the method for producing the component (A) is one or more compounds selected from the group consisting of azabicyclo-based compounds, amidine-based compounds, pyridine-based compounds, and phosphine-based compounds.
As the catalyst X, one or more compounds selected from the group consisting of azabicyclo-based compounds, amidine-based compounds and pyridine-based compounds are preferable among the above-mentioned compound groups. These compounds have excellent catalytic activity and can preferably produce the component (A). In addition, they form a complex with the catalyst Y described later during and after the reaction, and the complex is a reaction solution after the reaction is completed by a simple method such as adsorption. Can be easily removed from. In particular, the azacyclo compound can be more easily removed by filtration, adsorption or the like because the complex with the catalyst Y becomes poorly soluble in the reaction solution.
On the other hand, although the phosphine compound has excellent catalytic activity, it is difficult to form a complex with the catalyst Y, or when a complex is formed, it is easily soluble in the reaction solution, and the phosphine compound is contained 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 a simple method such as filtration and adsorption. For this reason, the phosphine-based catalyst remains in the final product, which causes turbidity and catalyst precipitation during storage of the product, and thickening or gelation over time, resulting in storage stability. May cause problems.

Specific examples of the azabicyclo-based compound include a cyclic tertiary amine having an azabicyclo structure, a salt of the amine, and various compounds as long as they satisfy the complex of the amine, and preferred compounds include quinuclidine and 3. -Hydroxyquinuclidine, 3-quinucridinone, 1-azabicyclo [2.2.2] octane-3-carboxylic acid, and triethylenediamine (also known as 1,4-diazabicyclo [2.2.2] octane. DABCO ") and the like.
Specific examples of the azabicyclo-based compound include the compounds mentioned in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732.

Specific examples of the amidine-based compound include imidazole, N-methylimidazole, N-ethylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-vinyl imidazole, 1-allyl imidazole, 1 , 8-diazabicyclo [5.4.0] undec-7-ene (hereinafter referred to as "DBU"), 1,5-diazabicyclo [4.3.0] nona-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 and the like.

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

Examples of the phosphine-based compound include compounds containing a structure represented by the following general formula (2).

[In the formula (2), R ³ , R ⁴ and R ⁵ 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, and 6 carbon atoms. It means an aryl group of ~ 24 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, and tris (4-methoxy-3,5-dimethylphenyl). ) Phosphine, tricyclohexylphosphine and the like.
Specific examples of the phosphine-based compound include the compounds mentioned in JP-A-2017-39916, JP-A-2017-39917, and International Publication No. 2017/033732, in addition to the above.

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 preferable, and they show good reactivity with most polyhydric alcohols. 3-Hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP are particularly preferred because of their availability.

The ratio of the catalyst X used in the method for producing the component (A) is not particularly limited, but it is preferable to use 0.0001 to 0.5 mol of the catalyst X with respect to 1 mol of the hydroxyl group of AZ-RO, which is more preferable. Is 0.0005 to 0.2 mol. By using 0.0001 mol or more of catalyst X, the yield of the reaction product containing the target (meth) acrylate can be increased, and by using 0.5 mol or less, the production and reaction of by-products can be increased. Coloring of the liquid can be suppressed, and the purification step after completion of the reaction can be simplified.

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

[In the formula (3), R ⁶ and R ⁷ have a linear or branched alkyl group having 1 to 20 carbon atoms, a linear or branched alkenyl group having 1 to 20 carbon atoms, and 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. ]
As the compound of the formula (3), a compound in which R ⁶ and R ⁷ are linear or branched alkyl groups or alkenyl groups having 1 to 20 carbon atoms is preferable. 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 having no halogen atom such as fluorine and chlorine, and the catalyst Y having the functional group is It is preferable because the reaction product containing the desired (meth) acrylate can be produced in high yield.

Examples of the zinc diketone enolate 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 having 1 to 20 carbon atoms. 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, and the like. Examples thereof include zinc stearate, zinc cyclohexane butyrate, zinc 2-ethylhexanate, zinc benzoate, zinc t-butyl benzoate, zinc salicylate, zinc naphthenate, zinc acrylate, and zinc methacrylate.
If a complex with the hydrate, solvate, or catalyst X of these zinc-containing compounds is present, the complex with the hydrate, solvate, and catalyst X is also a component (A). Can be used as the catalyst Y in the production method of.

Specific examples of the zinc-containing compound represented by the above general formula (4) include zinc acetylacetonate, zinc acetylacetonate hydrate, bis (2,6-dimethyl-3,5-heptandionat) zinc, and bis. Examples thereof include (2,2,6,6-tetramethyl-3,5-heptandionat) zinc and bis (5,5-dimethyl-2,4-hexanedionat) zinc. If a complex with the hydrate, solvate, or catalyst X of these zinc-containing compounds is present, the complex with the hydrate, solvate, and catalyst X is also a component (A). Can be used as the catalyst Y in the production method of.

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

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 preferable, and in particular, they show good reactivity with most polyhydric alcohols and are easily available. Zinc acetate, zinc acrylate and zinc acetylacetonate are preferred.

The ratio of the catalyst Y used in the method for producing the component (A) is not particularly limited, but it is preferable to use 0.0001 to 0.5 mol of the catalyst Y with respect to 1 mol of the total hydroxyl groups of AZ-RO. It is preferably 0.0005 to 0.2 mol. By using 0.0001 mol or more of the catalyst Y, the yield of the reaction product containing the target (meth) acrylate can be increased, and by using 0.5 mol or less, the production and reaction of the by-product can be increased. Coloring of the liquid can be suppressed, and the purification step after completion of the reaction can be simplified.

1-3-4. Preferred Production Method of Component (A) Component (A) is produced by transesterifying AZ-RO with a monofunctional (meth) acrylate in the presence of the catalysts X and Y.
The (meth) acrylate of AZ-RO was a compound that was difficult to produce by a conventional dehydration esterification reaction or transesterification reaction. On the other hand, according to the production method used in the present invention, the (meth) acrylate of AZ-RO can be produced without any problem, and the obtained (meth) acrylate has almost no coloring and has a high molecular weight. The proportion of the body is small.
The ratio of the catalyst X and the catalyst Y used in the method for producing the component (A) is not particularly limited, but it is preferable to use 0.005 to 10.0 mol of the catalyst X with respect to 1 mol of the catalyst Y. It is preferably 0.05 to 5.0 mol. By using 0.005 mol or more, the yield of the reaction product containing the target (meth) acrylate can be increased, and by using 10.0 mol or less, by-product formation and coloring of the reaction solution can be achieved. Can be suppressed, and the purification step after the reaction is completed can be simplified.

As the combination of the catalyst X and the catalyst Y used in combination in the present invention, it is preferable that the catalyst X is an azabicyclo-based compound, the catalyst Y is a compound represented by the general formula (3), and the azabicyclo-based compound is DABCO. A combination in which the compound represented by the general formula (3) is zinc acetate and / or zinc acrylate is particularly preferable.
In addition to obtaining a reaction product containing (meth) acrylate in good yield, this combination has an excellent color tone (small yellowness) after the reaction is completed, so that colorless transparency is important for coating applications and the like. Can be suitably used for. Furthermore, since it is a catalyst that can be obtained at a relatively low cost, it is an economically advantageous production method.

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

The reaction temperature in the method for producing the 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 is suppressed, and the reaction solution is colored. Can be suppressed, and the purification step after the reaction is completed can be simplified.

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

In the method for producing the component (A), a monohydric alcohol derived from a monofunctional (meth) acrylate is by-produced as the transesterification reaction progresses.
When a part of the hydroxyl group (for example, about 50 mol%) of AZ-RO is (meth) acrylated, the monohydric alcohol is allowed to coexist in the reaction system to bring it into an equilibrium state, and after the catalyst is adsorbed and removed or deactivated. By distilling off the monohydric alcohol and the monofunctional (meth) acrylate as a raw material, a product having a controlled acrylate conversion rate can be stably produced.
On the other hand, when the hydroxyl group of AZ-RO is positively (meth) acrylated, 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 the component (A), the reaction can be carried out without using a solvent, but a solvent may be used if necessary.
Specific examples of the solvent 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, diethyl acetal, dihexyl acetal , T-Butyl methyl ether, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, trioxane, dioxane, anisole, diphenyl ether, dimethyl cellosolve, diglyme, triglyme and tetraglyme and other ethers; 18-crown-6 and other crown ethers; benzo Ethers 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 and the like. Compounds; Sulfons such as sulfolanes; Sulfoxides such as dimethyl sulfoxide; Ureas or derivatives thereof; Phosphine oxides such as tributylphosphine oxide, ionic liquids such as imidazolium salt, piperidinium salt and pyridinium salt; Silicon oil and; Examples include water.
Among these solvents, at least one solvent selected from the group consisting of hydrocarbons, ethers, carbonate compounds and ionic liquids is preferable.
These solvents may be used alone, or two or more kinds may be arbitrarily combined and used as a mixed solvent.

In the method for producing the component (A), an inert gas such as argon, helium, nitrogen or carbon dioxide may be introduced into the system for the purpose of maintaining a good color tone of the reaction solution, but the (meth) acryloyl group An oxygen-containing gas may be introduced into the system for the purpose of preventing the polymerization of. 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. As a method for introducing the oxygen-containing gas, there is a method of dissolving it in the reaction solution or blowing it into the reaction solution (so-called bubbling).

In the method for producing the component (A), it is preferable to add a polymerization inhibitor to the reaction solution for the purpose of preventing the polymerization of the (meth) acryloyl group.
Specific examples of the polymerization inhibitor 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-phenylhydroxylamineammonium, 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. Polymerization inhibitors can be mentioned.
The polymerization inhibitor may be added alone or in combination of two or more, may be added from the beginning of the present invention, or may be added in the middle. Further, the desired amount to be used may be added all at once, or may be added in divided portions. Alternatively, it may be added continuously via a rectification tower.
The addition ratio of the polymerization inhibitor is preferably 5 to 30,000 wtppm, more preferably 25 to 10,000 wtppm in the reaction solution. By setting this ratio to 5 wtppm or more, the polymerization inhibitory effect can be sufficiently exhibited, and by setting it to 30,000 wtppm or less, coloring of the reaction solution can be suppressed, and the purification step after the reaction is completed can be simplified. It is possible to prevent a decrease in the curing rate of the obtained component (A).

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

The method for producing the component (A) can be carried out by any of a batch method, a semi-batch method and a continuous method. As an example of the batch type, AZ-RO, a monofunctional (meth) acrylate, a catalyst and a polymerization inhibitor are charged in a reactor, and oxygen-containing gas is bubbling in the reaction solution and stirred at a predetermined temperature. After that, the monohydric alcohol produced as a by-product with the progress of the transesterification reaction can be extracted from the reactor at a predetermined pressure to produce the desired component (A).

For the reaction product obtained by the method for producing the component (A), it is preferable to obtain a reaction product containing (meth) acrylate for which the purpose is to carry out a separation / purification operation with high purity.
Examples of the separation / purification operation include an adsorption operation, a crystallization operation, a filtration operation, a distillation operation, an extraction operation, and the like, and it is preferable to combine these operations. Examples of the adsorption operation include adsorption of a catalyst by an adsorbent, and examples of the adsorbent include aluminum silicate. Examples of the crystallization operation include cooling crystallization and concentrated crystallization. Examples of the filtration operation include pressure filtration, suction filtration, centrifugal filtration and the like. Examples of the distillation operation include single distillation, fractional distillation, molecular distillation, steam distillation and the like. Examples of the extraction operation include solid-liquid extraction and liquid-liquid extraction.
A solvent may be used in the separation and purification operation. In addition, a neutralizing agent for neutralizing the catalyst and / or polymerization inhibitor used in the present invention, an acid and / or alkali for decomposing or removing by-products, activated carbon for improving color tone, and filtration. Diatomaceous earth or the like may be used to improve efficiency and filtration rate.

2. 2. Curable Composition The present invention relates to a curable composition containing the component (A).
As a method for producing the composition, a mixture of reaction products containing (meth) acrylate obtained by transesterifying AZ-RO and monofunctional (meth) acrylate in the presence of the catalysts X and Y (? A manufacturing method including a step of manufacturing A) is preferable.
According to the production method, the component (A) can be obtained in a high yield, so that the cost and productivity are excellent. Further, the component (A) obtained by the production method is preferable because it has a low viscosity and is easy to handle because there are few side reaction high molecular weight substances, and it is excellent in quick curing property, hardness of cured product and antistatic property.
As the step, the method for producing the component (A) described above may be followed.
Further, when the other components described later are blended, the component (A) and the other components may be stirred and mixed.

When the components are mixed, they may be heated and stirred as necessary. The temperature at the time of heating, stirring and mixing is preferably in the range of 40 to 90 ° C. However, when the thermal polymerization initiator described later is blended, it is preferably carried out at 30 ° C. or lower in order to prevent polymerization during the production of the composition.

The viscosity of the composition may be appropriately set according to the intended use and purpose.
The viscosity is preferably 5 to 30,000 mPa · s, more preferably 10 to 25,000 mPa · s. When the viscosity is high, it is difficult to obtain a cured film having excellent surface smoothness as a thin film. Therefore, the viscosity may be appropriately adjusted with a solvent.
In the present invention, the viscosity means a value measured at 25 ° C. with an E-type viscometer (cone plate type viscometer).
When the component (A) is used for a preferable purpose such as a coating agent, an ink and a pattern formation, it may be appropriately set according to the purpose, preferably 1 to 100,000 mPa · s, and more preferably 5 to 50. It is 000 mPa · s. By setting the viscosity in the range, the leveling property of the composition at the time of coating is excellent, and the appearance of the cured product can be excellent.

The composition of the present invention requires the surface resistivity of the cured product to be less than 1 × 10 ¹³ Ω. Thereby, the charge on the surface of the cured product can be suppressed, and problems such as foreign matter such as dust adhering to the surface of the cured product can be solved.
More preferred values of the volume resistivity is less than 1 × 10 ¹² Ω, the lower limit is 10 ¹ Omega.
In the present invention, the surface resistivity means the value measured by the double ring electrode method.

The composition of the present invention can be used as an active energy ray-curable composition or a thermosetting composition, but can be preferably used as an active energy ray-curable composition.
Further, the composition of the present invention can be used in any form of a solvent-free composition containing no organic solvent, a solvent-type composition containing an organic solvent, and an aqueous composition in which the component (A) is dissolved or dispersed in water. can do. In the aqueous composition in which the component (A) is dispersed in water, an emulsifier usually used or a reactive emulsifier described later can be used as the dispersant.

When the composition of the present invention is used for the above-mentioned applications such as coating agents, inks and pattern formation, when the component (A) is used as a main component, the content ratio of the component (A) in the composition is From the viewpoint of excellent quick-curing property, hardness and antistatic property, it is preferably 20 to 100% by weight, more preferably 30 to 100% by weight, based on 100% by weight of the total amount of the curable components.
The "curable component" is a group of compounds having an ethylenically unsaturated group, which means a component (A), and is a compound having an ethylenically unsaturated group other than the component (A) described later [(D). Ingredients] means component (A) and component (D).

The composition of the present invention contains the component (A) as an essential component, but various components can be blended depending on the purpose.
Specific preferred examples of the other components include a photopolymerization initiator [hereinafter referred to as "(B) component"], a thermal polymerization initiator [hereinafter referred to as "(C) component"], and the component (A). Examples thereof include compounds having an ethylenically unsaturated group other than the above [hereinafter referred to as “component (D)”], ionic organic compounds [hereinafter referred to as “component (E)”], and the like.
Hereinafter, these components will be described.
As the other components described later, only one of the illustrated compounds may be used, or two or more of them may be used in combination.

2-1. (B) Component When the composition of the present invention is used as an active energy ray-curable composition and further used as an electron beam-curable composition, the component (B) (photopolymerization initiator) is not contained and electrons are not contained. It is also possible to cure with a wire.
When the composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays and visible rays are used as the active energy rays, the component (B) is further added from the viewpoint of easiness of curing and cost. It is preferable to contain it.
When used as an electron beam-curable composition, the component (B) does not necessarily have to be contained, but a small amount may be added as needed to improve the curability.

As the component (B) in the present invention, various known photopolymerization initiators can be used. The component (B) is preferably a photoradical polymerization initiator.
Specific examples of the component (B) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenylpropan-1-one. , 1- [4- (2-Hydroxyethoxy) phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopro Pan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) butane-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1- [4- (4-( Acetphenone compounds such as 1-methylvinyl) phenyl] propanone} and 2-hydroxy-1- {4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one ;
Benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyldiphenylsulfide;
Α-ketoester compounds such as methylbenzoylformate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid;
2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide Phenyloxide compounds such as;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; titanosen compounds; 1- [4- (4-benzoylphenyl sulfanyl) phenyl] -2-methyl-2- (4) -Acetophenone / benzophenone hybrid photoinitiators such as -methylphenylsulfinyl) propan-1-one;
Oxime ester-based photopolymerization initiators such as 2- (O-benzoyloxime) -1- [4- (phenylthio)] -1,2-octanedione; and camphorquinone and the like can be mentioned.

Among these, acetophenone-based compounds, benzophenone-based compounds, and phosphine oxide-based compounds are preferably mentioned, and good curability in air can be easily obtained even when the cured film is coated with a thin film of several μm or less. Acetophenone-based compounds are particularly preferable because they can be used.

The content ratio of the component (B) is preferably 0.01 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, based on 100 parts by weight of the total amount of the curable components. It is particularly preferably ~ 5 parts by weight. Within the above range, the curability of the composition is excellent, and the scratch resistance of the obtained cured film is excellent.

2-2. Component (C) Component (C) is a thermosetting initiator, and when the composition is used as a thermosetting composition, the component (C) can be blended.
The composition of the present invention can also be heat-cured by blending a thermal polymerization initiator.
As the thermal polymerization initiator, various compounds can be used, and organic peroxides and azo-based initiators are preferable.

Specific examples of the organic peroxide include 1,1-bis (t-butylperoxy) 2-methylcyclohexane, 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, and 1 , 1-bis (t-hexyl peroxy) 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-toluoleperoxy) hexane, t-butylper Oxyisopropyl monocarbonate, t-butylperoxy2-ethylhexylmonocarbonate, 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-menthan hydroperoxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexin-3, diisopropylbenzenehydroperoxide, t-butyltrimethylsilyl peroxide, 1,1,3 , 3-Tetramethylbutylhydroperoxide, cumenehydroperoxide, t-hexylhydroperoxide, t-butylhydroperoxide and the like.

Specific examples of azo compounds include 1,1'-azobis (cyclohexane-1-carbonitrile), 2- (carbamoylazo) isobutyronitrile, 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. In addition, the organic peroxide can be combined with a reducing agent to cause a redox reaction.

The content ratio of the component (C) is preferably 10 parts by weight or less with respect to 100 parts by weight of the total amount of the curable component.
When the thermal polymerization initiator is used alone, it may be carried out according to the usual means of radical thermal polymerization, and in some cases, it may be used in combination with the component (B) (photopolymerization initiator), and after being photocured, the reaction rate is further increased. It is also possible to carry out thermosetting for the purpose of improving.

2-3. Component (D) Component (D) is a compound having an ethylenically unsaturated group other than the component (A).
As the ethylenically unsaturated group of the component (D), a (meth) acryloyl group is preferable, and an acryloyl group is more preferable, because the composition is excellent in curability.

As the component (D), a compound having one (meth) acryloyl group in the molecule (hereinafter referred to as "bifunctional (meth) acrylate") and a compound having two (meth) acryloyl groups (hereinafter, "" Bifunctional (meth) acrylate ”), compounds having three or more (meth) acryloyl groups (hereinafter referred to as“ trifunctional or higher (meth) acrylate ”), and the like can be mentioned.
Specific examples of monofunctional (meth) acrylates include
Methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, lauryl ( Alkyl (meth) acrylates such as meta) acrylates and stearyl (meth) acrylates;
Hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate;
Mono (meth) of polyols such as trimethylolpropane mono (meth) acrylate, glycerin mono (meth) acrylate, mono (meth) acrylate of pentaerythritol, ditrimethylolpropane mono (meth) acrylate and dipentaerythritol mono (meth) acrylate. Acrylate:
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, etc. Monofunctional (meth) acrylate having an alicyclic group of
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolane) Monofunctional (meth) acrylate having a cyclic ether group such as -4-yl) methyl (meth) acrylate, 3-ethyl-3-oxetanylmethyl (meth) acrylate;
Aromatic monofunctional (meth) acrylates such as benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, o-phenylphenoxy (meth) acrylate and p-cumylphenol ethylene (meth) acrylate;
(Meta) Monofunctional (meth) acrylate having a maleimide group such as acryloryloxyethyl hexahydrophthalimide;
(Meta) acryloyl morpholine; and monofunctional (meth) acrylates having an alkoxyalkyl group such as alkylcarbitol (meth) acrylates such as ethylcarbitol (meth) acrylate and 2-ethylhexylcarbitol (meth) acrylate. Can be done.

Specific examples of the monofunctional (meth) acrylamide include N-methyl (meth) acrylamide, N-n-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, and N-n-butyl (meth) acrylamide. N-alkyl (meth) acrylamide such as N-sec-butyl (meth) acrylamide, Nt-butyl (meth) acrylamide, Nn-hexyl (meth) acrylamide; N such as N-hydroxyethyl (meth) acrylamide -Hydroxyalkyl (meth) acrylamide; as well as N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) ) Acrylamide, N, N-di-n-propyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide and N, N-dihexyl (meth) acrylamide N, N-dialkyl (meth) acrylamide and the like.

Specific examples of the bifunctional (meth) acrylate include aliphatic diol di (meth) acrylates such as butane diol di (meth) acrylate, hexane diol di (meth) acrylate and nonane diol di (meth) acrylate;
Di (meth) acrylates of trivalent or higher polyols such as glycerin di (meth) acrylate, trimethylolpropane di (meth) acrylate, trimethylolpropane di (meth) acrylate, and dipentaerythritol di (meth) acrylate;
Di (meth) acrylates of these polyol alkylene oxide adducts; di (meth) acrylates of alkylene oxide adducts of bisphenol A, di (meth) acrylates of bisphenol alkylene oxide adducts such as bisphenol F, and the like can be mentioned. ..
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide. In addition, (meth) acrylic oligomers such as epoxy (meth) acrylate and urethane (meth) acrylate can also be used depending on the purpose. Since many of these (meth) acrylic oligomers generally have a high viscosity, when the composition of the present invention is diluted with a solvent and applied, the composition is prevented from repelling in the drying step, which is good. The appearance of the coating film can be obtained.

Specific examples of the trifunctional or higher functional (meth) acrylate include glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane tri or tetra (meth) acrylate, and dipentaerythritol tri. Poly (meth) acrylates of polyols such as tetra, penta or hexa (meth) acrylates; and di (meth) acrylates of these polyol alkylene oxide adducts can be mentioned.
In this case, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide, and tetramethylene oxide.

As these compounds exemplified as the component (D), any compound can be used depending on the purpose.
When the composition is used as a coating agent, preferably for hard coating applications, polyfunctional (meth) acrylates such as pentaerythritol (meth) acrylate and dipentaerythritol (meth) acrylate, and polyfunctional (meth) acrylates thereof. Examples thereof include polyfunctional urethane (meth) acrylate in which the residual hydroxyl group is urethaneized with polyisocyanate.
In addition, glycerin tri (meth) acrylate is preferable when it is desired to reduce the viscosity while maintaining the hardness of the cured product of the composition.
When imparting antistatic properties to the cured film, it has a glycerindi (meth) acrylate, pentaerythritol di (meth) acrylate, pentaerythritol tri (meth) acrylate, and an isocyanurate ring, and has a (meth) acryloyl group. A compound having two or / and a compound having three (meth) acryloyl groups [(meth) acrylate having an isocyanurate skeleton] is preferable.
Specific examples of the (meth) acrylate having an isocyanuric acid skeleton include di (meth) acrylate of the isocyanuric acid alkylene oxide adduct, tri (meth) acrylate of the isocyanuric acid alkylene oxide adduct, and ε- for the isocyanuric acid alkylene oxide adduct. Examples thereof include di (meth) acrylate of the caprolactone adduct and tri (meth) acrylate of the ε-caprolactone adduct with respect to the isocyanuric acid alkylene oxide adduct.
Here, examples of the alkylene oxide in the alkylene oxide adduct include ethylene oxide, propylene oxide and tetramethylene oxide, and ethylene oxide is preferable. The number of moles of alkylene oxide added is preferably 1 to 3 moles per molecule.
The number of moles of ε-caprolactone added is preferably 1 to 3 mol in one molecule.

As the component (D), only one of the above-mentioned compounds may be used, or two or more of them may be used in combination.

(Meta) acrylates having an isocyanuric acid skeleton are commercially available, and examples thereof include the following products.
-Di and triacrylate mixture of 3 mol of ethylene oxide isocyanuric acid adduct (hydroxyl value: 130 mgKOH / g): Aronix M-215 manufactured by Toagosei Co., Ltd.
-Di and triacrylate mixture of 3 mol of ethylene oxide isocyanuric acid adduct (hydroxyl value: 50 mgKOH / g), Aronix M-313 manufactured by Toagosei Co., Ltd.
・ Di and triacrylate mixture of 3 mol adduct of ethylene oxide ethylene oxide (hydroxyl value: 130 mgKOH / g), Aronix MT-2513 manufactured by Toa Synthetic Co., Ltd. (transesterified product, low solvent grade)
-Triacrylate of 3 mol of ethylene oxide isocyanuric acid adduct: A-9300 manufactured by Shin Nakamura Chemical Industry Co., Ltd., Funkrill FA-731A manufactured by Hitachi Kasei Co., Ltd.
-Mixture of di and tri (meth) acrylate adduct of ethylene oxide 3 mol of isocyanuric acid: Aronix M-313 and M-315 manufactured by Toagosei Co., Ltd.
-Triacrylate of 1 mol adduct of ε-caprolactone with respect to 3 mol adduct of ethylene oxide isocyanuric acid: A-9300-1CL manufactured by Shin Nakamura Chemical Industry Co., Ltd. and the like can be mentioned.
-Triacrylate of ε-caprolactone 3 mol adduct with respect to isocyanuric acid ethylene oxide 3 mol adduct: Aronix M-327 manufactured by Toa Synthetic Co., Ltd.
These compounds have relatively high hydrophilicity among trifunctional or higher (meth) acrylates, and are preferable in that the coating film hardness and curability can be improved by blending these components without adversely affecting the antistatic property.

The content ratio of the component (D) may be appropriately set according to the purpose.
When the composition of the present invention is used for the above-mentioned coating agents, inks, pattern formation, etc., when the component (A) is used as the main component, 80% by weight or less in the total 100% by weight of the curable components. It is preferably contained in, more preferably 70% by weight or less. Further, the preferable lower limit is 20% by weight or more in 100% by weight of the total curable components.
By containing 20% by weight or more of the component (D), the hardness of the cured film and the adhesion to various substrates can be adjusted, and by setting it to 80% by weight or less, the cured film has good water resistance. Can be given.

In the present invention, these (meth) acrylates can be used alone or in any combination of two or more.

2-4. Component (E) Component (E) is an ionic organic compound.
The cured product of the composition of the present invention has a low surface resistivity, but the component (E) is added for the purpose and application of further reducing the surface resistivity.

Examples of the component (E) include an ionic liquid and an alkali metal salt.
Examples of the ionic liquid include nitrogen-containing onium salt (pyridinium salt, imidazolium salt), sulfur-containing onium salt, and phosphorus-containing onium salt.

As the alkali metal salt, an anionic metal salt having an (E-1) fluoro group and a sulfonyl group is preferable.
Antistatic agents other than the component (E-1), such as quaternary ammonium salts, phosphite esters, and polyether compounds, have a problem of low antistatic ability in low humidity conditions, and are conductive. In the case of a sex powder, the optical properties are deteriorated.

In the component (E-1), the trifluoromethanesulfonyl group is preferable as the anion having a fluoro group and a sulfonyl group.
In the component (E-1), as the metal forming the metal salt, an alkali metal, a group 2A element, a transition metal and an amphoteric metal are preferable, and an alkali metal is more preferable. Further, as the alkali metal salt, a lithylium salt is preferable.
As the component (E-1), a compound in which the anion having a fluoro group and a sulfonyl group is a trifluoromethanesulfonyl group and the metal is an alkali metal is more preferable, and the anion having a fluoro group and a sulfonyl group is a trifluoromethanesulfonyl. A compound which is a group and the metal is a lithium metal is particularly preferable.
The compound is a compound that can reduce the surface resistivity by adding it to the composition, thereby exhibiting a high antistatic ability even in a low humidity state and not deteriorating the optical properties.

As the specific compound of the component (E-1), a metal salt of bis (trifluoromethanesulfonyl) imide, an alkali metal salt of tris (trifluoromethanesulfonyl) methide, and an alkali metal salt of trifluoromethanesulfonic acid ion are preferable.
That is, any one of the compounds represented by the following general formulas (E-1-1) to (E-1-3) is preferable.
M (CF ₃ SO ₂ ) ₂ N ・ ・ ・ ・ ・ ・ (E-1-1)
M (CF ₃ SO ₂ ) ³ C ・ ・ ・ ・ ・ ・ (E-1-2)
M (CF ₃ SO ₃ ) ・ ・ ・ ・ ・ ・ (E-1-3)
In the general formulas (E-1-1) to (E-1-3), M means an alkali metal.
As the alkali metal salt, lithium, sodium and potassium are preferable, and lithium is more preferable.

Specific examples of the component (E-1) include bis (fluoroalkylsulfonyl) imide ion, tris (fluoroalkylsulfonyl) methide ion, and fluoroalkylsulfonic acid ion, and specifically, bis (trifluoromethanesulfonyl) imidelithium [ Li (CF ₃ SO ₂ ) ₂ N], bis (trifluoromethanesulfonyl) imidolipotassium [K (CF ₃ SO ₂ ) ₂ N], bis (trifluoromethanesulfonyl) imide sodium [Na (CF ₃ SO ₂ ) ₂ N] ], Tris (trifluoromethanesulfonyl) methidolithium [Li (CF ₃ SO ₂ ) ³ C], Tris (trifluoromethanesulfonyl) methidopotassium [K (CF ₃ SO ₂ ) ₃ C], Tris (trifluoromethanesulfonyl) methidosodium [ Na (CF ₃ SO ₂ ) ₃ C, lithium trifluoromethanesulfonate [Li (CF ₃ SO ₃ )], potassium trifluoromethanesulfonate [K (CF ₃ SO ₃ )], sodium trifluoromethanesulfonate [Na (CF ₃₎ SO ₃ )] and the like.
Among these compounds, bis (trifluoromethanesulfonyl) imide lithium, tris (trifluoromethanesulfonyl) methidolithium and lithium trifluoromethanesulfonate are preferable, and bis (trifluoromethanesulfonyl) imide lithium and lithium trifluoromethanesulfonate are particularly preferable.

As the component (E), a component diluted in an organic solvent in advance may be used for the purpose of improving workability and reducing the surface resistivity. As the organic solvent, the component (F) described later can be used. The mixing ratio of the organic solvent is preferably 10 to 90 parts by weight, more preferably 20 to 80 parts by weight, based on 100 parts by weight of the solid content of the component (E).

The mixing ratio of the component (E) is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of the solid content in the composition.
By setting the blending ratio of the component (E) to 0.1 parts by weight or more, the effect of reducing the surface resistivity is exhibited, while by setting it to 20 parts by weight or less, the water resistance of the cured product is excellent. can do.

The content ratio of the component (E) may be appropriately set according to the purpose, and is preferably 1 to 30% by weight, more preferably 3 to 20% by weight, in 100% by weight of the total curable component.
When the proportion of the component (E) is 1% by weight or more, the surface resistance value of the cured film is low and the antistatic property is excellent, and when it is 30% by weight or less, it is sufficient to impart antistatic property. It is a cured film that has both hydrophilicity and water resistance that does not swell and peel off due to water absorption even when exposed to high temperature and high humidity for a long time.
As described above, the component (A), the component (E) or / and the component (D), which is a group of compounds having an ethylenically unsaturated group, is referred to as a "curable component".

2-5. Other components other than the above As the other components other than the above, known additives can be used. For example, organic solvents, water, antifogging modifiers, UV absorbers, light stabilizers, acidic substances, antioxidants, surface modifiers, hydrophilic polymers, fillers, silane coupling agents, acid generators, pigments. , Dyes, tackifiers, polymerization inhibitors and the like.
Among these other components, organic solvents, water, antifogging modifiers, ultraviolet absorbers, light stabilizers, acidic substances, antioxidants, surface modifiers, hydrophilic polymers, and fillers will be described below. ..

<Organic solvent and water>
The composition of the present invention can be used without a solvent, but various organic solvents can be used for the purpose of adjusting the coating viscosity and the film thickness.
Any organic solvent can be used, specifically, aromatic compounds such as benzene, toluene and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; acetone, methyl ethyl ketone and methyl. Ketone compounds such as isobutyl ketone; ether compounds such as dibutyl ether; and N-methylpyrrolidone and the like can be mentioned.
When the curable composition contains the component (A) as a main component, it is compatible with water at an arbitrary ratio, so that water can be used instead of the organic solvent. Further, when the component (D) used as needed is water-soluble, it can be diluted with water.

The content ratio of the organic solvent and / or water is preferably 0.01 to 200 parts by weight, more preferably 10 to 150 parts by weight, based on 100 parts by weight of the total amount of the curable component. It is more preferably 20 to 100 parts by weight.

<Antistatic aid>
In the composition of the present invention, the cured film is excellent in antistatic property, but an antistatic auxiliary agent can be added for the purpose of further improving the initial antistatic property.
Examples of the antistatic auxiliary agent include an ionic surfactant having no ethylenically unsaturated group.
As the ionic surfactant having no ethylenically unsaturated group, known ones can be used, and examples thereof include anionic surfactants, cationic surfactants and amphoteric ionic surfactants. ..

Anionic surfactants include dialkyl sulfosuccinates such as di (2-ethylhexyl) sulfosuccinate and ammonium di (2-ethylhexyl) sulfosuccinate; fatty acid salts such as sodium oleate and potassium oleate; lauryl. Higher alcohol sulfate esters such as sodium sulfate and ammonium lauryl sulfate; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; alkylnaphthalene sulfonates of sodium alkylnaphthalene sulfonate; sodium naphthalene sulfonate formalin condensates; dialkyl phosphate salts; and polyoxy Polyoxyethylene sulfate salts such as ethylene alkylphenyl ether sodium sulfate are used.
Among these compounds, dialkylsulfosuccinate is preferable because it is superior in initial antistatic property.
Dialkyl sulfosuccinates are commercially available and commercially available products can be used. As the sodium sulfosuccinate (2-ethylhexyl) salt, Ricasurf P-10 (solution of the same compound), M-30 (solution of the same compound) and G-30 (propylene glycol of the same compound) manufactured by Shin Nihon Rika Co., Ltd. / Water mixed solution), and Lapizol A30, A70, A80, and A90 manufactured by Nichiyu Co., Ltd. can be mentioned. Examples of the di (2-ethylhexyl) ammonium sulfosuccinate salt include Ricasurf G-600 manufactured by Shin Nihon Rika Co., Ltd. [propylene glycol / water mixed solution of the same compound] and the like.

Examples of cationic surfactants include amine salts such as ethanolamines, laurylamine acetate, triethanolamine monoatelate, and stearamide ethyldiethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and dilauryldimethylammonium chloride. , Quaternary ammonium salts such as distearyldimethylammonium chloride, lauryldimethylbenzylammonium chloride and stearyldimethylbenzylammonium chloride.

Examples of the zwitterionic surfactant include fatty acid type zwitterionic surfactants such as dimethylalkyllaurylbetaine and dimethylalkylstearylbetaine, sulfonic acid type zwitterionic surfactants such as dimethylalkylsulfobetaine, and alkylglycine. Can be mentioned.

Among these ionic surfactants having no ethylenically unsaturated group, anionic surfactants are preferable in that they are more excellent in initial antistatic properties, and dialkylsulfosuccinate is more preferable as described above.

The content ratio of the antistatic auxiliary agent is preferably 0.1 to 10% by weight in 100% by weight of the total amount of the composition of the present invention. When the content ratio of the antistatic auxiliary agent is in the above range, the initial antistatic property can be excellent without impairing the durability of the antistatic property of the cured film.

<UV absorber>
Specific examples of the ultraviolet absorber include 2- [4-[(2-hydroxy-3-dodecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl)-. 1,3,5-triazine, 2- [4-[(2-hydroxy-3-tridecyloxypropyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1, 3,5-Triazine, 2- [4-[(2-Hydroxy-3- (2-ethylhexyloxy) propyl) oxy] -2-hydroxyphenyl] -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine, 2,4-bis (2-hydroxy-4-butyloxyphenyl) -6- (2,4-bisbutyroxyphenyl) -1,3,5-triazine, 2-( Triazine-based UV absorbers such as 2-hydroxy-4- [1-octyloxycarbonylethoxy] phenyl) -4,6-bis (4-phenylphenyl) -1,3,5-triazine; 2- (2H-benzo) Triazole-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2-hydroxy-5-tert-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy -5- (2- (Meta) acryloyloxyethyl) phenyl] -2H-Benzotriazole-based ultraviolet absorbers such as benzotriazole; benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone Agents, cyanoacrylate-based ultraviolet absorbers such as ethyl-2-cyano-3,3-diphenylacrylate, octyl-2-cyano-3,3-diphenylacrylate, ultraviolet rays such as titanium oxide particles, zinc oxide particles, and tin oxide particles. Examples include inorganic particles that absorb phenyl group.
Among the compounds, a benzotriazole-based ultraviolet absorber is particularly preferable.

Ultraviolet absorbers are used for the purpose of suppressing discoloration of plastic substrates that are prone to yellowing due to irradiation with active energy rays, and when an article with a cured coating film is used outdoors, the article is exposed to sunlight. Used for the purpose of preventing deterioration.
The content ratio of the ultraviolet absorber is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total amount of the curable components. It is more preferably 1 to 2 parts by weight.

<Light stabilizer>
As the light stabilizer, a known light stabilizer can be used, and among them, a hindered amine-based light stabilizer (HALS) is preferably mentioned.
Specific examples of the hindered amine-based light stabilizer include bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate. , 2,4-Bis [N-butyl-N- (1-cyclohexyloxy-2,2,6,6-tetramethylpiperidin-4-yl) amino] -6- (2-hydroxyethylamine) -1,3 , 5-Triazine, bisdecanoic acid (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and the like.
Commercially available products of the hindered amine-based light stabilizer include TINUVIN 111FDL, TINUVIN123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 manufactured by BASF.

The content ratio of the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, based on 100 parts by weight of the total amount of the curable components. It is more preferably 1 to 1 part by weight.

<Acid substances>
The composition of the present invention is excellent as an adhesive material to a base material such as plastic, but the adhesiveness can be further improved by adding an acidic substance.
Examples of the acidic substance include a photoacid generator that generates an acid by irradiation with active energy rays, an inorganic acid, and an organic acid. Examples of the inorganic acid include sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and the like. Examples of the organic acid include p-toluenesulfonic acid and organic sulfonic acid compounds such as methanesulfonic acid.
Among these, an inorganic acid or an organic acid is preferable, an organic sulfonic acid compound which is an organic acid is more preferable, an aromatic sulfonic acid compound is further preferable, and p-toluenesulfonic acid is particularly preferable.
The content ratio of the acidic substance is preferably 0.0001 to 5 parts by weight, more preferably 0.0001 to 1 part by weight, and 0.0005 with respect to 100 parts by weight of the total amount of the curable components. It is more preferably ~ 0.5 parts by weight. When the content ratio of the acidic substance is in the above range, the cured film is more excellent in adhesion to the base material, and problems such as corrosion of the base material and decomposition of other components can be prevented.

<Antioxidant>
The composition of the present invention may further contain an antioxidant for the purpose of improving the heat resistance and weather resistance of the cured film.
Examples of the antioxidant used in the present invention include phenolic antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants and the like.
As the phenolic antioxidant, for example, hindered phenols such as dit-butylhydroxytoluene can be preferably mentioned. Examples of commercially available products include AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, and AO-80 manufactured by ADEKA CORPORATION.
Preferred examples of the phosphorus-based antioxidant include phosphines such as trialkylphosphine and triarylphosphine, and trialkyl phosphite and triaryl phosphite. Commercially available products of these derivatives include, for example, ADEKA CORPORATION PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. And so on.
Examples of the sulfur-based antioxidant include thioether-based compounds, and examples of commercially available products include AO-23, AO-212S, and AO-503A manufactured by ADEKA CORPORATION.

The content ratio of the antioxidant is preferably 0.01 to 5% by weight, more preferably 0.1 to 1% by weight, in 100% by weight of the total amount of the composition of the present invention. When the content of the antioxidant is within the above range, the stability of the composition is excellent, and the curability and adhesive strength are good.

<Surface modifier>
In the composition of the present invention, a surface modifier may be added for the purpose of enhancing the leveling property at the time of application, increasing the slipperiness of the cured film and enhancing the scratch resistance, and the like.
Examples of the surface modifier include a surface conditioner, a surfactant other than the above, a leveling agent, a defoaming agent, a slipperiness imparting agent, an antifouling property imparting agent, and the like, and a known surface modifier should be used. Can be done.
Among them, a silicone-based surface modifier and a fluorine-based surface modifier are preferably mentioned. Specific examples include a silicone-based polymer and oligomer having a silicone chain and a polyalkylene oxide chain, a silicone-based polymer and an oligomer having a silicone chain and a polyester chain, and a fluoropolymer having a perfluoroalkyl group and a polyalkylene oxide chain. And oligomers, and fluoropolymers and oligomers having a perfluoroalkyl ether chain and a polyalkylene oxide chain.
Further, a surface modifier having an ethylenically unsaturated group, preferably a (meth) acryloyl group in the molecule may be used for the purpose of enhancing the sustainability of slipperiness.

The content ratio of the surface modifier is preferably 0.01 to 1.0% by weight in 100% by weight of the total amount of the composition of the present invention. When the content ratio of the surface modifier is in the above range, the surface smoothness of the cured film is excellent.

<Hydrophilic polymer>
When the curable composition of the present invention is applied to a base material, cissing or the like may occur in the coating film after the composition is applied to the base material and dried depending on the type of the base material to be applied and the coating method. , The finally obtained cured film may have a poor appearance.
In this case, it is preferable to add a hydrophilic polymer to the curable composition for the purpose of preventing repelling of the coating film.

Examples of the hydrophilic polymer include a polymer having a hydrophilic group.
Examples of the hydrophilic group include an acidic group and a hydroxyl group, and an acidic group is preferable. Examples of the acidic group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group, and a carboxyl group or a sulfonic acid group is preferable, and a carboxyl group is more preferable.
As the polymer in which the hydrophilic polymer has an acidic group (hereinafter, referred to as “acid group-containing polymer”), a neutralized salt in which a part or all of the acidic groups are neutralized is preferable. As a method for producing a neutralized salt of the acidic group-containing polymer, a method for producing a neutralized salt as a raw material vinyl-based monomer and a method for producing an acidic group-containing polymer and then neutralizing the polymer Examples thereof include a manufacturing method.

As the hydrophilic polymer, a polymer having a vinyl-based monomer having a hydrophilic group as an essential constituent monomer unit is preferable. Examples of the vinyl-based monomer having a hydrophilic group include a vinyl-based monomer having an acidic group and a vinyl-based monomer having a hydroxyl group.

Examples of the vinyl-based monomer having an acidic group include an ethylenically unsaturated compound having a carboxyl group, an ethylenically unsaturated compound having a sulfonic acid group, and an ethylenically unsaturated compound having a phosphoric acid group.
Examples of the ethylenically unsaturated compound having a carboxyl group include (meth) acrylic acid, maleic acid, itaconic acid, crotonic acid, and salts of these compounds. Examples of the ethylenically unsaturated compound having a sulfonic acid group include acrylamide2-methylpropanesulfonic acid, styrenesulfonic acid, and (meth) allylsulfonic acid. Examples of the ethylenically unsaturated compound having a phosphoric acid group include a phosphoric acid group-containing (meth) acrylate such as an esterified product of phosphoric acid and (meth) acrylic acid.
When the acidic group-containing polymer is a neutralized salt in which a part or all of the acidic groups are neutralized, it is preferable to use the neutralized salt as the vinyl-based monomer having an acidic group.
Examples of the alkaline compound for forming the neutralizing salt of the vinyl-based monomer having an acidic group include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide; ammonia; and triethylamine and triethanol. Examples thereof include amine compounds such as amine.

Examples of the vinyl-based monomer having a hydroxyl group include hydroxyalkyl (meth) acrylates such as hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate and hydroxybutyl (meth) acrylate.

The hydrophilic polymer may be a copolymer of a vinyl-based monomer other than the vinyl-based monomer having a hydrophilic group (hereinafter, referred to as “other monomer”).
Other monomers include alkyl (meth) acrylate, alkylaminoalkyl (meth) acrylate, styrene, alkyl vinyl ether, vinylidene chloride, (meth) acrylamide, N-vinylformamide, N-vinylacetamide, vinyl acetate, vinylpyrrolidone, etc. Examples thereof include (meth) acrylic nitrile and (meth) acryloyl morpholine.
Alkyl (meth) acrylates include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, octyl (meth) acrylate, and nonyl (meth) acrylate. ) Acrylate, decyl (meth) acrylate and the like can be mentioned.
Examples of the dialkylaminoalkyl (meth) acrylate include dimethylaminoethyl (meth) acrylate and diethylaminoethyl (meth) acrylate.

The Mw of the hydrophilic polymer is preferably 5,000 to 100,000, more preferably 7,000 to 30,000.
In the present invention, Mw of the hydrophilic polymer means a value obtained by GPC using standard polystyrene as a calibration curve, and is a value measured before neutralizing an acidic group such as carboxylic acid as an acid component. is there. In addition, since GPC measurement cannot be performed when an amine-based monomer is contained as another monomer, ordinary alkyl (meth) acrylate is used instead of these components, and the same polymerization temperature, initiator concentration, and monomer are used. It means a value obtained by using the GPC measurement result of the polymer polymerized under the conditions such as concentration and solvent concentration as an estimated value.

As the hydrophilic polymer, one produced by using the above-mentioned monomer according to the usual polymerization can be used.
For example, a radical polymerization method, a living anion polymerization method, a living radical polymerization method and the like can be mentioned.
Moreover, as a form of polymerization, for example, a solution polymerization method, an emulsion polymerization method, a suspension polymerization method, a bulk polymerization method and the like can be mentioned.
In order to produce the above-mentioned low molecular weight polymer by a usual polymerization method, it is usually necessary to increase the amount of chain transfer agent and polymerization initiator. When a polymer using a large amount of chain transfer agent is used, the cured film is easily colored by irradiation with active energy rays, and when a polymer using a large amount of a polymerization initiator is used, the storage stability of the composition is stable. Is likely to decrease.
Therefore, a polymer produced by high-temperature polymerization that does not require a large amount of chain transfer agent or polymerization initiator is preferable.
The temperature of the high temperature polymerization is preferably 160 to 350 ° C, more preferably 180 to 300 ° C.

The form of the hydrophilic polymer may be selected according to the intended purpose, and examples thereof include a solution of the hydrophilic polymer, a dispersion liquid of the hydrophilic polymer, and a powder.
Specific examples thereof include an organic solvent solution of a hydrophilic polymer, an aqueous solution or an aqueous dispersion of a hydrophilic polymer, a mixed solution or water powder of an organic solvent and water of a hydrophilic polymer, and a powder. Among these, an aqueous solution or an aqueous dispersion of a hydrophilic polymer, an organic solvent solution, a mixed solution of an organic solvent and water of a hydrophilic polymer, or a water spray is preferable because of its excellent solubility in a composition.
The solid content of the hydrophilic polymer solution and the dispersion is preferably 3 to 70% by weight.
The viscosity of the hydrophilic polymer solution and the dispersion is preferably 5 to 20,000 mPa · s.

The content ratio of the hydrophilic polymer is preferably 0.5 to 50 parts by weight with respect to 100 parts by weight of the total amount of the composition based on the solid content in either the aqueous solution or the aqueous dispersion. , More preferably 2 to 30 parts by weight.
By setting the content ratio of the hydrophilic polymer to 0.5 parts by weight or more, it is possible to prevent repelling of the cured film, improve the adhesion to various substrates, and make it a thin substrate such as a film. It is possible to prevent deformation and warpage of the base material when the composition of the present invention is applied and cured, and when the composition is 50 parts by weight or less, the appearance of the cured film such as cloudiness, uneven streaks, and loose skin can be prevented. Can be prevented.

<Filler>
When the composition of the present invention contains an organic solvent and either the component (A) or the component (D) to be blended as necessary has a low viscosity, the composition is spray-coated or spin-coated. In the subsequent drying step, when the organic solvent volatilizes, the composition may repel on the substrate, resulting in a poor appearance of the coating film.
When the coating method as described above is carried out using a composition containing an organic solvent, it is preferable to add a filler to the composition to thicken the composition because it can prevent cissing after drying.
As the filler, either an inorganic filler or an organic filler can be used, and an organic filler is preferable.
Examples of the inorganic filler include inorganic compounds such as silica and alumina.
Examples of the organic filler include hydrophobic polymers, such as polyurethane, poly (meth) acrylate, polyamide, polyurea, nylon, polystyrene, polyethylene and polypropylene, with poly (meth) acrylate being preferred.
As the hydrophobic polymer, a polymer having a high average molecular weight is preferable because the number of additional parts required for thickening can be reduced and the antistatic property of the composition can be prevented from being lowered. However, the molecular weight is preferably high as long as the compatibility with the composition is not impaired, and the weight average molecular weight is preferably 10,000 to 5,000,000, more preferably 100,000 to 2,000,000.
The filler is preferably in the form of particles, and the average particle size thereof is preferably 1 to 15 μm, more preferably 4 to 12 μm.
The average particle size in the present invention means a value measured at a wavelength of 680 nm by a laser diffraction method.
Regarding the content ratio of the filler, it is preferable that the thickening can be performed with a smaller amount of addition in consideration of the influence on the antistatic property, and 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the composition excluding the organic solvent. Is preferable, and 0.5 to 5 parts by weight is more preferable.

3. 3. Method of use As a method of using the composition of the present invention, a conventional method may be followed.
For example, a method in which the composition is applied to the applied substrate by a usual coating method and then irradiated with active energy rays or heated to cure.
As the method of irradiating the active energy rays, a general method known as a conventional curing method may be adopted.
Further, the composition is adhered to the substrate by using the component (B) (photopolymerization initiator) and the component (C) (thermal polymerization initiator) in combination, irradiating them with active energy rays, and then heat-curing them. A method of improving the sex can also be adopted.

When the curable composition is an active energy ray-curable composition, when there is a heating step after irradiation with active energy rays, the antistatic property may decrease when heated for a long time.
In this case, a method of supplying an inert gas such as nitrogen gas, irradiating the active energy rays in an atmosphere of the inert gas, and then heating is preferable because the deterioration of the antistatic property can be prevented.

Examples of the base material to which the composition of the present invention can be applied include wood, inorganic materials, plastics, paper and the like, which can be applied to various materials.
Examples of the inorganic material include glass, metal, mortar, concrete and stone, and examples of the metal include steel plates, metals such as aluminum and chromium, and metal oxides such as zinc oxide (ZnO) and indium tin oxide (ITO). Can be mentioned.
Specific examples of the plastic include polyolefins such as polyethylene and polypropylene, ABS resin, polyvinyl alcohol, cellulose acetate resins such as triacetyl cellulose and diacetyl cellulose, acrylic resin, polyethylene terephthalate, polycarbonate, polyarylate, polyether sulfone, norbornene and the like. Examples thereof include cyclic polyolefin resins, polyvinyl chlorides, epoxy resins and polyurethane resins using the cyclic olefins of the above as monomers.

Among these base materials, the composition of the present invention has excellent adhesion to plastics and wood, and therefore can be preferably applied to plastics and wood. Further, the inorganic material can be preferably applied to glass and metal, and the plastic can be preferably applied to polyethylene terephthalate, polycarbonate, poly (methyl) methacrylate and a copolymer containing the same as a main component.

The method for applying the composition of the present invention to the substrate may be appropriately set according to the intended purpose, and is a bar coater, an applicator, a doctor blade, a dip coater, a roll coater, a spin coater, a flow coater, a knife coater, and a comma. Examples thereof include a method of coating with a coater, a reverse roll coater, a die coater, a lip coater, a spray coater, a gravure coater, a micro gravure coater and the like.

The film thickness of the composition cured film with respect to the base material may be appropriately set according to the intended purpose. The thickness of the cured film may be selected depending on the use of the substrate to be used and the application of the produced substrate having the cured film, but is preferably 1 to 100 μm, more preferably 2 to 40 μm. ..

When the composition contains an organic solvent, it is preferable that the base material is coated and then heated and dried to evaporate the organic solvent.
The drying temperature is not particularly limited as long as the applied base material is at a temperature or lower that does not cause problems such as deformation. The preferred heating temperature is 40 to 100 ° C. The drying time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 20 minutes.

When the composition of the present invention is used as an active energy ray-curable composition, examples of the active energy ray for curing include electron beams, ultraviolet rays and visible rays, but ultraviolet rays or visible rays are preferable, and ultraviolet rays are preferable. Especially preferable. 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 should be appropriately set according to the type of active energy ray and the compounding composition. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 50 to 8,000 mJ /. cm ² is preferable, and 100 to 3,000 mJ / cm ² is more preferable.

When the composition of the present invention is used as a thermosetting composition, the cured film can be obtained by allowing the cured film to stand in a heatable dryer or the like.
The heating temperature may be appropriately set according to the substrate to be used and the purpose, and is preferably 40 to 180 ° C. When the base material is plastic, the temperature is preferably 120 ° C. or lower because the base material may be deformed if the temperature is too high.
The heating time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 60 minutes.

4. Applications The curable composition of the present invention can be used for various purposes, such as coating agents, excipients, molding agents, inks, pattern forming agents, adhesives, fillers and sealing agents. It can be used for various purposes.

The composition of the present invention can be preferably used as a coating agent.
Specific examples of the coating agent include top coats and primers for woodworking paints, antistatic coating agents for glass and plastics, and the like.
Specific examples of applications of electrical and electronic materials include liquid crystal protective films, liquid crystal substrates, antistatic tapes for semiconductor processes, IC carrier tapes, and the like.
Further, when used for building materials, antistatic agents for floors of factories and business establishments that require static electricity control can be mentioned. Specific examples include clean rooms, electronics factories, IC and C electronic component factories, computer rooms, medical facilities, research facilities and the like.
In addition to the above, various packaging materials and plastic molded products can be mentioned.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. The present invention is not limited to these examples.
Further, in the following, unless otherwise specified, "part" means a part by weight, and "%" means% by weight.
The abbreviations in the examples mean the following.
-MCA: 2-Methoxyethyl acrylate-MEL: 2-Methoxyethanol-DABCO: Triethylenediamine-MEHQ: Hydroquinone monomethyl ether-TEMPOL: 4-Hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl-DEHA : N, N-diethylhydroxylamine

1. 1. (A) Manufacture of ingredients
1) Production Example 1 [ Production of 38 mol% acrylated product of 6 mol adduct of ethylene oxide of sorbitol (hydroxyl value 734)]
An ethylene oxide adduct of sorbitol [manufactured by Aoki Yushi Kogyo Co., Ltd., hydroxyl value 734 mgKOH / g (13.1 meq /)) in a 3 liter flask equipped with a stirrer, thermometer, gas introduction pipe, rectification tower and cooling pipe. g), average ethylene oxide addition number 6.28, peroxide concentration 0.7 wtppm] 200 g (2.6 mol as hydroxyl group), 613 g (4.7 mol) of MCA, 0.88 g DABCO as catalyst X (g) 0.0078 mol), 3.26 g (0.0157 mol) of zinc acrylate as catalyst Y, 0.25 g of MEHQ, 0.05 g of TEMPOL, oxygen-containing gas (5% by volume of oxygen, 95 volumes of nitrogen) %) Was bubbling in the liquid, and the ester exchange reaction was carried out by heating and stirring at an internal temperature of 125 ° C. to 130 ° C. for 10 hours. During this time, MCA containing MEHQ and TEMPOL was added to the reaction solution at any time via the rectification column.

The acrylate conversion rate of the hydroxyl group by the transesterification reaction was determined from the amount of MEL produced by liquid chromatography (hereinafter referred to as "liquid chromatography") and found to be 37 mol%.
The quantification of MEL was performed by a high performance liquid chromatograph equipped with a differential refractometer (column: Atlantis (Part No. 186003748, column inner diameter 4.6 mm, column length 250 mm) manufactured by Japan Waters Co., Ltd.), solvent: pure. Water or 10% by volume isopropanol aqueous solution) was used, and the procedure was carried out by the internal standard method.
Acrylation rate (mol%) = number of moles of MEL produced as a by-product with the progress of transesterification reaction / (number of moles of alcohol used as raw material x number of alcoholic hydroxyl groups of alcohol molecule used as raw material) x 100

After cooling the reaction solution to room temperature, the solid matter was separated by pressure filtration. Aluminum silicate in the filtrate [Kyoward 700SEN-S (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.). Hereinafter, it is referred to as "K700". ] Was added and stirred for 1 hour in an internal temperature range of 95 ° C. to 100 ° C. to adsorb the catalyst dissolved in the filtrate. Then, the reaction solution was cooled to an internal temperature of 40 ° C. or lower, 3.2 g of calcium hydroxide was added, and the mixture was further stirred at room temperature for 3 hours, and then the solid matter was separated by pressure filtration.
The obtained filtrate is placed in a flask to which a stirrer, a thermometer, a gas introduction tube, a cooling tube for distillation, and a tube for depressurization are connected, and the internal temperature is 90 to 100 ° C. and the pressure is in the range of 0.01 to 200 mmHg. , The dry air was stirred for 13 hours while bubbling, and the unreacted MCA and the by-product MEL were distilled off.
The kettle solution in the flask was cooled to room temperature, 0.076 parts (0.0008 mol) of DEHA was added, and the mixture was stirred at an internal temperature of 75 ° C. to 85 ° C. under normal pressure for 1 hour. Then, pressure filtration was performed, and 239 g of a filtrate was obtained. The acrylate mixture obtained in Production Example 1 is hereinafter referred to as Sb-EOA-1.

As a result of ESI-MS analysis of Sb-EOA-1, it was confirmed that the acrylated product of the ethylene oxide adduct of sorbitol was contained as a main component.
The residual amount of MCA in Sb-EOA-1 was 200 ppm or less as a result of gas chromatography (hereinafter referred to as "gas chromatographic") measurement, and no odor was felt.
Further, the viscosity of Sb-EOA-1, the solubility in water, the hydroxyl value, APHA, Mw, and the saponification value were measured according to the methods shown below. The results are shown below.
Viscosity (25 ° C): 10.93 Pa · s, solubility in water: 75% or more, hydroxyl value: 276 mgKOH / g, APHA: 92, Mw: 1,206, saponification value: 222 mgKOH / g, addition number of acryloyl groups q : 2.3, acrylicization rate 38 mol%
The addition number q of the acryloyl group was calculated according to the method described in JP-A-4-136041.

◆ Peroxide Concentration Measurement Conditions・ Isopropyl alcohol, glacial acetic acid, and potassium iodide aqueous solution were added to the sorbitol alkylene oxide adduct, and the mixture was heated in a hot water bath at 85 ° C. for 3 minutes to generate iodine. Then, the treatment liquid was taken out from the hot water bath, and iodine was titrated with sodium thiosulfate before the temperature of the treatment liquid became 40 ° C. or lower. The concentration of active oxygen was calculated from the titration amount and used as the peroxide concentration.

◆ ESI-MS measurement conditions・ Measurement method: Flow injection method ・ Sample pretreatment: Prepare 500 μg / mL solution with acetonitrile ・ Equipment: Quattro Premier (made by Waters) + AcQuity UPLC (made by Waters)
・ Injection amount: 2 μL
-Eluent flow rate: 0.3 mL / min
-Eluent composition: 10 mM NH4 acetate / acetonitrile = 50/50 (solution ratio, 0 min → 1 min)
・ Capillary voltage: 3.0kV
・ Cone voltage: 10V
・ Source temperature: 120 ℃
-Solvent removal temperature: 400 ° C
-Amount of desolvent gas: 800 L / h
・ Amount of cone gas: 50 L / h
-Mass spectrometry range: m / z = 180 to 1200 (SCAN mode)
・ Ionization mode: ESI +

◆ Gas chromatography measurement conditions / equipment: GC-17A manufactured by Shimadzu Corporation
-Detector: FID detector-Carrier gas: Helium-Column: Inert Cap (film thickness 0.5 μm, 0.32 mm ID x 60 m)
・ Injection temperature: 200 ℃
・ FID temperature: 250 ° C
-Column temperature: After holding at 120 ° C. for 5 minutes, raise the temperature to 240 ° C. at a rate of 10 ° C./min, and then hold for 25 minutes.
・ Injection amount: 0.2 μL
-The content of MEL was determined by weight% by the internal standard method.

◆ Viscosity measurement conditions The viscosity at 25 ° C. was measured using an E-type viscometer.

◆ Measurement of solubility At a temperature of 22 ° C, the obtained component (A) and distilled water were placed in a screw tube at a mixing ratio of 5%, 10%, 15%, 20%, 25%, 50% and 75% and mixed. After mixing with a rotor for 2 hours, the mixture was allowed to stand for 24 hours. The mixed solution after standing was carefully visually observed, and the presence or absence of turbidity or layer separation and uniformity were observed.
The mixing ratio (%) was defined by the following formula, and the mixing ratio (%) that maintained a uniform liquid without turbidity or layer separation after standing for 24 hours was regarded as the solubility (%).

Mixing ratio (%) = parts by weight of distilled water / (parts by weight of distilled water + parts by weight of component (A)) x 100

◆ Hydroxylity value measurement conditions A mixed solution of acetic anhydride and pyridine is added to a sample and heat-treated in a warm bath at 92 ° C. for 1 hour. Then, a small amount of water is added and heat treatment is performed in a warm bath at 92 ° C. for 10 minutes. After allowing to cool, the acid was titrated with an ethanol solution of potassium hydroxide using a phenolphthalein solution as an indicator to determine the hydroxyl value.

◆ APHA
APHA was measured using a color difference meter (Petroleum product color tester OME-2000 manufactured by Nippon Denshoku Kogyo Co., Ltd.).

◆ GPC measurement conditions / equipment: Waters Co., Ltd. GPC system name 1515 2414 717P RI
-Detector: RI detector-Column: Guard column Showa Denko Co., Ltd. Shodex KFG (8 μm 4.6 x 10 mm), 2 types of this column Waters Co., Ltd. stylel HR 4E THF (7.8 x 300 mm) + stylel HR 1 THF (7.8 x 300 mm)
-Column temperature: 40 ° C
-Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL / min-calibration curve: Calibration curve was created using standard polystyrene.
The weight average molecular weight was calculated by regarding the detected peaks having a molecular weight of 400 or more as one peak without dividing them.

◆ Measurement conditions for saponification value Add an ethanol solution of potassium hydroxide to the sample and heat-treat it in a warm bath at 75 ° C for 30 minutes. After allowing to cool, the base was titrated with an aqueous hydrochloric acid solution using a phenolphthalein solution as an indicator to determine the saponification value.

2. 2. Example 1 and Comparative Examples 1 to 3 (active energy ray-curable composition)
1) Preparation of composition Using the component (A) obtained in Production Example 1 and the component shown by the abbreviation below, the composition was obtained by stirring and mixing at 40 ° C. at the ratio shown in Table 1.
The viscosity of the obtained composition was measured at 25 ° C. with an E-type viscometer.
Component (A) -Sb-EOA: Acrylate obtained in Production Example 1
(D) Ingredients -M-305: Mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, hydroxyl value: 100 mgKOH / g) [manufactured by Toa Synthetic Co., Ltd., trade name: Aronix M-305]
-M-240: Polyethylene glycol (average number of moles added 4) diacrylate, hydroxyl value: 2 mgKOH / g) [manufactured by Toa Synthetic Co., Ltd., trade name: Aronix M-240]
4EG-A: Polyethylene glycol (average number of moles added 14) diacrylate, hydroxyl value: 3 mgKOH / g) [manufactured by Kyoeisha Chemical Co., Ltd., trade name: light acrylate 4EG-A]
(B) Ingredients -Om907: 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one [Omnirad 907D manufactured by IGM Resins]

2) Evaluation of composition Using the obtained compositions of Example 1 and Comparative Examples 1 to 3, the easily adhesive PET film (Cosmo Shine A4300, film thickness) manufactured by Toyobo Co., Ltd. was cut using a bar coater. : 100 μm) was coated so that the film thickness was 5 μm to prepare a test piece.
Using a test piece, using a high-pressure mercury lamp equipped with a conveyor [H06-L41 manufactured by Eye Graphics Co., Ltd.], UV-A lamp output illuminance 60 W / cm, irradiation intensity 500 mW / cm ² per pass The test piece was irradiated with ultraviolet rays under the condition that the irradiation energy was 800 mJ / cm ² .
The obtained cured film was used and evaluated according to the following method. The results are shown in Table 2.

(1) Surface resistivity The obtained cured film is adjusted for 12 hours or more under the conditions of 25 ° C. and 50% RH, and then the coating film before ultraviolet irradiation is applied according to JIS K6271-2008 (double ring electrode method). The volume resistivity of the cured product after irradiation with ultraviolet rays was measured.
Based on the obtained results, the antistatic property was evaluated on the following three levels.
○: 10 ¹² Ω or less, △: 10 ¹² to 10 ¹⁴ Ω, ×: 10 ¹⁴ Ω exceeded
(2) Hardness Using the obtained cured film, the pencil hardness was evaluated according to JIS K5600.
In addition, using the obtained cured film, using a surface film physical property tester [Fisherscope H-100C manufactured by Fisher Instruments Co., Ltd.], Martens hardness under the conditions of a pushing depth of 2 μm and a pushing load of 10 mN. Evaluated.

(3) Evaluation Results As is clear from the results of Example 1 in Table 2, the composition of the present invention has a low surface resistivity of 6.3 × 10 ¹¹ Ω and exhibits sufficient antistatic properties. .. The pencil hardness was B, which was about the same as the composition of Comparative Example 2 and significantly higher than that of the composition of Comparative Example 3.
On the other hand, the compositions of Comparative Examples 1 and 2 containing no component (A) were excellent in pencil hardness and Martens hardness, but had a surface resistivity as high as 4 orders of magnitude and a low antistatic property. On the other hand, in the composition of Comparative Example 3, the surface resistivity of the cured product was lower than that of Example 1, but both the pencil hardness and the Martens hardness were lower than those of the composition of Example 1, and the cured film. The performance was inferior.

The curable composition of the present invention can be used in various applications such as coating agents, molding agents, inks, pattern forming agents, adhesives, fillers and sealants.
Further, the curable composition of the present invention can be preferably used as an active energy ray-curable composition, and more preferably as an active energy ray-curable coating agent composition.

Claims (23)

Component (A): A curable composition containing (meth) acrylate as an alkylene oxide adduct of alditol (excluding glycerol) and having a surface resistivity of a cured product of less than 1 × 10 ¹³ Ω. The curable composition according to claim 1, wherein the component (A) is a compound represented by the following general formula (5).

[In the formula (5), R ^{14 to} R ¹⁶ each independently represent a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms, and when there are a plurality of each of R ^{14 to} R ^16. It may be the same or different. X ^{1 to} X ³ independently represent a hydrogen atom or a (meth) acryloyl group. Each of a, b, and c represents a positive number, and all of them do not become 0 at the same time, satisfying 0 <(a + nb + c) ≦ 80. n represents an integer of 2-4. ] The component (A) is obtained by transesterifying a compound having one (meth) acryloyl group with an alkylene oxide adduct of alditol (excluding glycerol) in the presence of the following catalysts X and Y. The curable composition according to claim 1 or 2, which is a mixture (A) of a compound having an (meth) acryloyl group.
Catalyst X: A type selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or salts or complexes thereof, amidin or salts thereof or complexes thereof, compounds having a pyridine ring or salts or complexes thereof, and phosphine or salts or complexes thereof. The above compounds.
Catalyst Y: A compound containing zinc. The curable composition according to any one of claims 1 to 3, wherein the component (A) is a di (meth) acrylate of an alkylene oxide adduct of sorbitol. The curable composition according to claim 1 to claim 4, wherein the component (A) has a solubility in distilled water at a temperature of 22 ° C. of 10% or more. The curable composition according to any one of claims 1 to 5, wherein the component (A) has a saponification value of 150 to 300 mgKOH / g. The curable composition according to any one of claims 3 to 6, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, amidin or a salt thereof or a complex thereof, and a compound having a pyridine ring or a salt or complex thereof. The curable composition according to any one of claims 3 to 7. The curable composition according to any one of claims 3 to 8, wherein the catalyst Y is zinc organic acid and / or zinc diketone enolate. The curable composition according to any one of claims 1 to 9, further comprising a component (B): a photopolymerization initiator in addition to the component (A). The curable composition according to any one of claims 1 to 10, further comprising a component (C): a thermal polymerization initiator in addition to the component (A). The curable composition according to any one of claims 1 to 11, wherein the component (A) further contains a compound (D): a compound having an ethylenically unsaturated group other than the component (A). The curable composition according to any one of claims 1 to 12, further comprising water and / or an organic solvent in the component (A). The curable composition according to any one of claims 1 to 13, further comprising the component (E): an ionic organic compound in addition to the component (A). The curable composition according to claim 14, wherein the component (E) is a component (E-1): a metal salt of an anion having a fluoro group and a sulfonyl group. An active energy ray-curable coating agent composition comprising the composition according to any one of claims 1 to 15. A mixture of an alkylene oxide adduct of alditol (excluding glycerol) and a compound having a (meth) acryloyl group in which a compound having one (meth) acryloyl group is transesterified in the presence of the following catalysts X and Y. Including the step of manufacturing (A)
A method for producing a curable composition, wherein the surface resistivity of the cured product is less than 1 × 10 ¹³ Ω.
Catalyst X: A type selected from the group consisting of cyclic tertiary amines having an azabicyclo structure or salts or complexes thereof, amidin or salts thereof or complexes thereof, compounds having a pyridine ring or salts or complexes thereof, and phosphine or salts or complexes thereof. The above compounds.
Catalyst Y: A compound containing zinc. The method for producing a curable composition according to claim 17, wherein the component (A) is a compound represented by the following general formula (5).

[In the formula (5), R ^{14 to} R ¹⁶ each independently represent a divalent aliphatic hydrocarbon group having 2 to 4 carbon atoms, and when there are a plurality of each of R ^{14 to} R ^16. It may be the same or different. X ^{1 to} X ³ independently represent a hydrogen atom or a (meth) acryloyl group. Each of a, b, and c represents a positive number, and all of them do not become 0 at the same time, satisfying 0 <(a + nb + c) ≦ 80. n represents an integer of 2-4. ] The method for producing a curable composition according to claim 17 or 18, wherein the component (A) has a solubility in distilled water at a temperature of 22 ° C. of 10% or more. The method for producing a curable composition according to any one of claims 17 to 19, wherein the component (A) has a saponification value of 150 to 300 mgKOH / g. The method for producing a curable composition according to any one of claims 17 to 20, wherein the compound having one (meth) acryloyl group is an alkoxyalkyl (meth) acrylate. The catalyst X is one or more compounds selected from the group consisting of a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, amidin or a salt thereof or a complex thereof, and a compound having a pyridine ring or a salt or complex thereof. The method for producing a curable composition according to any one of claims 17 to 21. The method for producing a curable composition according to any one of claims 17 to 22, wherein the catalyst Y is zinc organic acid and / or zinc diketone enolate.