JP2021046485A - Curable composition - Google Patents

Abstract

To provide a curable composition in which a resulting cured film is excellent in adhesion to a substrate, particularly the adhesion to a plastic substrate, excellent in antifogging properties, and is also excellent in adhesion to a poorly adhesive plastic substrate, and also excellent in antifogging persistence (repeating antifogging properties) under severe conditions of high temperature and long time.SOLUTION: A curable composition contains the following (A) component and (B) component. The (A) component: a (meth)acrylate of an alkylene oxide adduct of alditol (excluding glycerol). The (B) component: a thermosetting agent.SELECTED DRAWING: None

Description

The present invention relates to a curable composition, preferably an active energy ray-curable composition. The cured film of the composition of the present invention has excellent curability and permeability to a porous base material such as wood, and can be used as a primer layer having good adhesion, and also has excellent adhesion to a plastic base material, and is made of plastic. It can be preferably used as a surface anti-fog (anti-fog coating agent) or a coating agent for the purpose of preventing dust and the like from adhering to plastics, and belongs to these technical fields.
In the present specification, acrylate and / or methacrylate are referred to as (meth) acrylate, acryloyl group and / or methacrylic acid group is referred to as (meth) acryloyl group, and acrylic acid and / or methacrylic acid is referred to as (meth) acrylic acid. The allyl group and / or the methacrylic group is referred to as a (meth) allyl group.
Further, the polyfunctional (meth) acrylate means a compound having two or more (meth) acryloyl groups.

The active energy ray-curable composition can be cured by irradiating it with active energy rays such as ultraviolet rays, visible rays, and electron beams for a very short time, and is widely used as an ink and coating for various substrates because of its high productivity. Has been done.
The surface of plastic substrates such as plastic plates and plastic films is protected by a hard coating agent for the purpose of preventing surface scratches, etc., but active energy ray-curable compositions are also used for this purpose. There is.
Also, for porous substrates such as wood, topcoats are applied for the purpose of preventing surface scratches and imparting design, and primers are applied for the purpose of improving adhesion with other paints. As an active energy ray-curable composition is used.

Since the plastic base material is highly transparent, it is used for protective glasses, goggles, inner walls of bathrooms, and headlamp covers and rear lamp covers for automobiles and motorcycles. When used in place, it may become cloudy and lose its transparency due to condensation on its surface.
In order to solve these problems, a method of applying an antifogging composition composed of a non-reactive surfactant to the surface of a base material has been conventionally performed, but this method is used after coating. In the initial stage, the anti-fog effect was exhibited, but once the treated surface was wiped, the anti-fog property was lowered, that is, the anti-fog sustainability was lacking.
There is also a method of applying an antifogging composition composed of a hydrophilic polymer diluted with an organic solvent to the surface of the base material, but the hardness of the cured film is insufficient and the solvent resistance is insufficient. In addition, the anti-fog property was not satisfactory.

In order to solve the above problems, an antifogging composition that is cured by active energy rays such as ultraviolet rays and electron beams has been proposed in recent years. Specifically, an ultraviolet curable antifogging coating composition composed of a hydrophilic group-containing unsaturated compound and a hydrophilic group-free unsaturated compound (Patent Document 1), a hydrophilic polymer and various hydrophilic (meth). A photocurable antifogging coating composition made of acrylate has been proposed (Patent Document 2).
However, these compositions have a problem that anti-fog property is not exhibited in an environment under high humidity.

Further, an antifogging coating composition composed of a hydrophilic monomer and a non-reactive surfactant has also been proposed (Patent Documents 3 and 4), but the composition has antifogging property when the surface of the cured film is wiped. It decreased and lacked anti-fog sustainability.

On the other hand, the active energy ray-curable composition is required to have fast curing property regardless of the use as a coating agent for plastics and wood.
As (meth) acrylates having excellent fast-curing properties, (meth) acrylates having a hydroxyl group in the molecule and (meth) acrylates having an ether bond have been reported (Non-Patent Documents 1 and 2), but in one molecule. Mono (meth) acrylates and di (meth) acrylates, which have a low concentration of (meth) acryloyl groups, are susceptible to curing inhibition by oxygen in the air when coated with a thin film, and the desired curability may not be obtained. is there.
In addition, many (meth) acrylates having pentaerythritol or dipentaerythritol as a skeleton have excellent curability even in a thin film. However, these (meth) acrylates have a large shrinkage during curing and may not provide sufficient adhesion, and when a coating is applied to a base material having a thin film thickness, the base material may not be sufficiently adhered. Warpage and deformation could be a problem.

Furthermore, in recent years, there has been a movement to use plant-derived raw materials for the purpose of using environmentally friendly materials as raw materials used for applications such as inks and coating agents, and they are used in curable compositions. The use of plant-derived raw materials for curable components is also being considered.
Further, in the curable composition, an organic solvent is used for the purpose of adjusting the viscosity and the like. However, the use of organic solvents may be restricted due to problems such as environmental pollution. When using a curable composition using an organic solvent, it is necessary to carry out the coating and curing steps using a closed device in order to prevent the organic solvent from scattering into the atmosphere. There are problems that the process becomes complicated and the equipment becomes expensive.
Water is a viscosity modifier other than an organic solvent and has no problem of environmental pollution. However, since many conventional (meth) acrylates are hydrophobic compounds, they are separated when water is used as a viscosity modifier and cannot be used.
Further, since the curable composition containing water has excellent permeability to a porous base material such as wood, it has been desired as a coating agent used for a porous base material such as wood.

JP-A-55-69678 Japanese Unexamined Patent Publication No. 3-31369 Japanese Unexamined Patent Publication No. 3-215589 Japanese Unexamined Patent Publication No. 11-140109 T. Y. Lee et al. (T.Y. Lee et al.), Macromolecules, 2004, Vol. 37, pp. 3659-3665. T. Y. Lee et al. (T.Y. Lee et al.), Polymer, 2004, Vol. 45, pp. 6155-6162

The present inventors have excellent curability, preferably can contain water that does not have an impact on the environment, and the obtained cured film has excellent adhesion to a base material, particularly to a plastic base material and wood. In particular, in order to find a curable composition that can be preferably used as a coating agent and has excellent antifogging properties, a diligent study was conducted.
As a result, the present inventors, as a composition capable of solving the above-mentioned problems, are (meth) acrylates produced from plant-derived alcohols, and polyfunctional (meth) acrylates having both a hydroxyl group and an ether group in the molecule. A composition comprising the above has been found (Japanese Patent Application No. 2019-082327).

The composition developed by the present inventors was excellent in adhesion to a base material, particularly to a plastic base material, and also excellent in antifogging property.
However, depending on the type of plastic base material, the adhesion of the obtained cured film may be insufficient. Further, regarding the antifogging property of the cured film, the antifogging durability (repeated antifogging property) under the harsh conditions of high temperature and long time may be insufficient.

In order to solve the above problems, the present inventors use a (meth) acrylate produced from a plant-derived alcohol and thermoset with a polyfunctional (meth) acrylate having both a hydroxyl group and an ether group in the molecule. The composition containing the agent has excellent curability, and the obtained cured film has excellent adhesion to the plastic base material, excellent adhesion to the poorly adhesive plastic base material, and further, antifogging property. The present invention has been completed by finding that it is excellent in antifogging durability under harsh conditions such as high temperature and long time.
Hereinafter, the present invention will be described in detail.

According to the composition of the present invention, water having excellent curability and preferably having no burden on the environment can be contained. Further, the cured film formed from the composition of the present invention has good adhesion to a base material such as plastic or wood, and also has excellent adhesion to a plastic base material which is considered to be difficult to adhere. Further, since the cured film is excellent in hydrophilicity, it exhibits good antifogging property and is also excellent in antifogging durability under harsh conditions such as high temperature and long time.
Therefore, the composition of the present invention comprises a coating agent for various substrates, a primer, a coating for protective eyeglasses and goggles that require antifogging performance for a cured film, and a coating for headlamps and rear lamp covers of automobiles and motorcycles. It can be preferably applied to agents and the like.

The present invention relates to a curable composition containing the following components (A) and (B).
Component (A): (Meta) acrylate (B) component of alkylene oxide adduct of alditol (excluding glycerol): Thermosetting agent In the following, the description of "alditol (excluding glycerol)" is given. , May simply be described 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, 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, 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. Therefore, 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 antifogging 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 a cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof, amidin or a salt thereof or a complex thereof, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex thereof. The above compounds.
Catalyst Y: A compound containing zinc.
Hereinafter, a preferred 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). Examples include compounds that are used.

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 and other alkoxyalkyl groups, 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 is particularly preferable. 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 the hydroxyl group 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 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 the catalyst 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.

1-3-3-1. 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), and 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 sparingly soluble in the reaction solution.
On the other hand, although the phosphine-based 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-based 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, in addition to the above.

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.

Major specific 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 contain 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 are linear or branched alkyl groups having 1 to 20 carbon atoms, linear or branched alkenyl groups 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-hexanezonato) 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 the (meth) acryloyl group in the raw material or product 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 produced as a by-product as the transesterification reaction progresses.
When a part of the hydroxyl groups (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, 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. Moreover, you may add 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 exerted, 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).

The reaction product obtained by the method for producing the component (A) is preferable because a reaction product containing (meth) acrylate, which is intended to be separated and purified, can be obtained 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 and the like. 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. Component (B) Component (B) is a thermosetting agent.
The thermosetting agent is a component to be blended for the purpose of imparting excellent substrate adhesion and water resistance to the cured film by reacting with the hydroxyl group derived from the component (A).

Examples of the component (B) include isocyanate compounds such as polyisocyanates and blocked polyisocyanates, amino resins such as melamine resins, urea resins, and benzoguanamine resins, and phenol resins.

As the polyisocyanate in the isocyanate-based compound, various compounds can be used as long as it is a compound having two or more isocyanate groups.
For example, aromatic diisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate and naphthalene diisocyanate; aliphatic diisocyanates such as tetramethylene diisocyanate, hexamethylene diisocyanate, dimerate diisocyanate and lysine diisocyanate; methylenebis (cyclohexyl isocyanate), isophorone diisocyanate, Alicyclic diisocyanates such as methylcyclohexane diisocyanate, cyclohexane diisocyanate and cyclopentane diisocyanate; veulet type adducts and isocyanul ring type adducts of the polyisocyanates; Examples thereof include a free isocyanate group-containing prepolymer obtained by reacting a polyol, a polyester polyol, a polyether polyol, etc.) with an excess of isocyanate groups.

Further, as the isocyanate-based compound, the free isocyanate group of the polyisocyanate is used as a phenol compound, an oxime compound, an active methylene compound, a lactam compound, an alcohol compound, a mercaptan compound, an acid amide compound, an imide compound, an amine compound, or an imidazole compound. Blocked polyisocyanates sealed with a blocking agent such as a compound, a urea-based compound, a carbamate-based compound, and an imine-based compound can also be used.

The amino resin is a resin obtained by addition-condensing formaldehyde or alcohol to an amino compound such as melamine, urea and benzoguanamine.

As the melamine resin, a part or all of the methylol groups of methylolated melamine may be a monohydric alcohol having 1 to 8 carbon atoms, for example, methyl alcohol, ethyl alcohol, n-propyl alcohol, i-propyl alcohol, n-butyl alcohol, etc. Examples thereof include partially etherified or fully etherified melamine resins etherified with i-butyl alcohol, 2-ethylbutanol, 2-ethylhexanol and the like.

The urea resin is obtained by a condensation reaction of urea and formaldehyde, and can be dissolved or dispersed in a solvent or water.

Examples of the benzoguanamine resin include methylolated benzoguanamine resin obtained by reacting benzoguanamine with an aldehyde.
Examples of the aldehyde include formaldehyde, paraformaldehyde, acetaldehyde, benzaldehyde and the like.
The benzoguanamine resin also includes a methylolated benzoguanamine resin etherified with one or more alcohols.
Examples of the alcohol used for etherification include monohydric alcohols such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, 2-ethylbutanol and 2-ethylhexanol. ..
Among these, a benzoguanamine resin obtained by etherifying at least a part of the methylol groups of the methylolated benzoguanamine resin with a monohydric alcohol having 1 to 4 carbon atoms is preferable.

Examples of the phenol resin include a resol-type phenol resin in which phenols and formaldehydes are heated in the presence of a reaction catalyst and subjected to a condensation reaction to introduce a methylol group.

Examples of phenols used in the production of phenolic resins include bifunctional phenols such as o-cresol, p-cresol, p-tert-butylphenol, p-ethylphenol, 2,3-xylenol, and 2,5-xylenol; phenols. , M-cresol, m-ethylphenol, 3,5-xylenol, m-methoxyphenol and other trifunctional phenols; bis (4-hydroxyphenyl) -2,2-propane [bisphenol A], bis (4-hydroxy) Examples thereof include tetrafunctional phenols such as phenyl) methane [bisphenol F], and these can be used alone or in combination of two or more.

Examples of formaldehydes used in the production of phenolic resins include formaldehyde, paraformaldehyde, trioxane and the like, and these can be used alone or in combination of two or more. Further, as the phenol resin, a methylolated phenol resin in which a part of the methylol group is alkyl etherized can also be used. As the alcohol used for alkyl etherification, a monohydric alcohol having 1 to 8 carbon atoms, preferably 1 to 4 carbon atoms is suitable, and examples thereof include methanol, ethanol, n-butanol, isobutanol and the like. it can.

As the component (B), among the above-mentioned compounds, isocyanate compounds and melamine resins are preferable.

The content ratio of the component (B) may be appropriately set according to the types of the components (A) and (B) to be used, the purpose of use of the composition, and the like.
The content ratio of the component (B) is preferably 0.1 to 100 parts by weight, more preferably 1 to 60 parts by weight, based on 100 parts by weight of the total component (A).
When an isocyanate compound is used as the component (B), the molar ratio (OH / NCO) of the component (B) to the hydroxyl value (mgKOH / g) of the component (A) is 0.1. ~ 1.2 is preferable, and more preferably 0.4 to 1.05.

A curing accelerator can be used in combination with the component (B).
When an isocyanate compound is used as the component (B), it is preferable to use a curing accelerator in combination.
As the curing accelerator for the isocyanate-based compound, a compound used as a catalyst for the urethanization reaction can be used. Examples of curing accelerators include organic tin compounds such as dibutyltin dilaurate, metal alkoxides such as tetrabutoxytitanium, amine compounds such as triethylamine, and metal complexes such as tris (acetylacetonate) iron and zirconium tetraacetylacetonate. And so on.
Examples of the curing accelerator when a melamine resin is used as the component (B) include strong acids such as dinonylnaphthalenesulfonic acid, dodecylbenzenesulfonic acid, and p-toluenesulfonic acid.
The content ratio of the curing accelerator is preferably 0.001 to 2 parts by weight with respect to 100 parts by weight of the component (B).

3. 3. Curable Composition The present invention relates to a curable composition containing the components (A) and (B).
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 also excellent in quick curing property, hardness of cured product and antifogging property.
As the step, the method for producing the component (A) described above may be followed.
Further, the component (A) and the component (B) are stirred and mixed to produce a composition. When other components described later are blended, the components (A), (B) and other components may be stirred and mixed.
When a heat-unstable compound such as an isocyanate compound is used as the component (B), it is preferable to stir and mix the component (A) and the component (B) immediately before use to produce a composition. ..
When a compound in which the component (B) is heat-stable is used, the composition can be produced and stored by stirring and mixing the component (A) and the component (B).

When the components are mixed, they may be heated and stirred as necessary. The temperature when heated, stirred and mixed is preferably in the range of 40 to 90 ° C.
However, when a heat-unstable compound such as an isocyanate-based compound is used as the component (B) or when a thermal polymerization initiator described later is blended, the temperature is 30 ° C. or lower to prevent polymerization during the production of the composition. Is preferable.
Further, when a heat-unstable compound such as an isocyanate compound is used as the component (B), it is preferable to mix the component excluding the component (B) and carry out the above heating.

The viscosity of the composition may be appropriately set according to the intended use and purpose.
The preferred viscosity is one that is easy to handle during coating.

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.

In the composition of the present invention, the cured film has excellent adhesion even to a plastic which is considered to have poor adhesion. For example, it is possible to form a cured film having excellent adhesion to Takiron [manufactured by Takiron Co., Ltd.], which is known as poorly adhesive as polycarbonate.
Moreover, the cured film is excellent in anti-fog property and also excellent in anti-fog durability. Specifically, even if the cured film is exposed to steam, the moisture is wiped off, and then the cured film is exposed to steam again, the antifogging property is excellent.
In addition, even if the cured film is exposed to steam, the water is wiped off, and then the cured film is exposed to steam again, there is no trace of water dripping.

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 quick-curing property, hardness and antifogging 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 [(E). Ingredients] or / and a compound having an ethylenically unsaturated group and an ionic group [component (G)] means a component (A) and a component (E) or / and a component (G).

On the other hand, when the composition of the present invention is used for the above-mentioned coating agents and the like, flexibility can be imparted to the cured film by using the component (A) as an additive. When used as the additive, the content ratio of the component (A) is preferably 5 to 50% by weight with respect to 100% by weight of the total amount of the curable components.
The content ratio of the component (A) required to impart flexibility may be adjusted according to the type of the component (E) to be combined, the intended use and physical properties. For example, as the component (E), trifunctional or higher (meth) such as pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, and dipentaerythritol hexa (meth) acrylate. When acrylates are used, these (meth) acrylates have high hardness of the cured product and are completely inflexible. When such a component (E) is used, it is preferable to add 10% by weight or more of the component (A) with respect to 100% by weight of the total amount of the curable component. On the other hand, when a component (E) having a slight toughness in the cured product is used, such as urethane (meth) acrylate having about 2 to 4 (meth) acryloyl groups in the molecule, the curable component is used. Since the desired effect can be obtained by blending the component (A) in an amount of about 5% by weight with respect to 100% by weight of the total amount, 5% by weight or more is preferable.

The composition of the present invention contains the above-mentioned component (A) and component (B) as essential components, 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 “(C) component”], a thermal polymerization initiator [hereinafter referred to as “(D) component”], and the component (A). Compounds having ethylenically unsaturated groups other than [hereinafter referred to as "component (E)"], organic solvents and / or water [hereinafter referred to as "component (F)"], and ethylenically unsaturated groups and ionicity. Examples thereof include compounds having a group [hereinafter, referred to as “component (G)”] 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.

3-1. Component (C) 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 (C) (photopolymerization initiator) is not contained and electrons are not contained. It can also be cured by 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 (C) 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, it is not always necessary to contain the component (C), but a small amount may be added if necessary in order to improve the curability.

As the component (C) in the present invention, various known photopolymerization initiators can be used. The component (C) is preferably a photoradical polymerization initiator.
Specific examples of the component (C) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, and 2-hydroxy-2-methyl-1-phenylpropane-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) -Acetphenone / Benzoin 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 (C) 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 preferable that the amount is ~ 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.

3-2. Component (D) Component (D) is a thermosetting initiator, and when the composition is used as a thermosetting composition, the component (D) 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, and 2-phenylazo-4-methoxy-2,4-dimethylvaleronitrile. , Azodi-t-octane, azodi-t-butane and the like.
These may be used alone or in combination of two or more. In addition, the organic peroxide can be combined with a reducing agent to cause a redox reaction.

The content ratio of the component (D) 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 (C) (photopolymerization initiator), and after photocuring, the reaction rate is further increased. It is also possible to carry out thermosetting for the purpose of improving the above.

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

As the component (E), 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 ”) and 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-dioxolane-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 butanediol di (meth) acrylate, hexanediol di (meth) acrylate and nonanediol 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 (E), any compound can be used depending on the purpose.
When the composition is used for hard coating, polyfunctional (meth) acrylates such as pentaerythritol (meth) acrylate and dipentaerythritol (meth) acrylate, and residual hydroxyl groups of these polyfunctional (meth) acrylates are treated with polyisocyanate. Examples thereof include urethanized polyfunctional urethane (meth) acrylate.
Further, 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 antifogging property to the cured film, it has a glycerin di (meth) acrylate, a pentaerythritol di (meth) acrylate, a 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 isocyanuric acid 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 (E), only one kind of the above-mentioned compound may be used, or two or more kinds thereof 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 adduct of ethylene isocyanuric acid (hydroxyl value: 130 mgKOH / g): Aronix M-215 manufactured by Toagosei Co., Ltd.
-Di and triacrylate mixture of 3 mol adduct of ethylene isocyanuric acid (hydroxyl value: 50 mgKOH / g), Aronix M-313 manufactured by Toagosei Co., Ltd.
・ Di and triacrylate mixture of 3 mol adduct of ethylene isocyanuric acid (hydroxyl value: 130 mgKOH / g), Aronix MT-2513 manufactured by Toa Synthetic Co., Ltd. (transesterification method, low solvent grade)
-Triacrylate of 3 mol of ethylene oxide of isocyanuric acid: 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 of 3 mol adduct of ethylene 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 of 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 antifogging property.

The content ratio of the component (E) 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 (E), 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.
On the other hand, when the component (A) is used as an additive for the purpose of imparting flexibility to the cured film, the content ratio of the component (E) is based on 100% by weight of the total amount of the curable components. It is preferably 50 to 95% by weight.

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

When used for the purpose of imparting antifogging performance to the cured film, a compound having a hydroxyl group as the component (E) is obtained because a uniform water film is formed on the surface of the cured film and good antifogging property is obtained. Is preferable.
Specifically, a compound having a hydroxyl value of 20 to 160 mgKOH / g is preferable.

3-4. Component (F) The composition of the present invention can be used without a solvent, but the component (F) (organic solvent and / or water) can be used for the purpose of adjusting the coating viscosity and the film thickness. ..
Various compounds can be used as the organic solvent in the component (F). Specifically, aromatic compounds such as benzene, toluene and xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; ketone compounds such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ether compounds such as dibutyl ether. ; And N-methylpyrrolidone and the like.
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 (E) used as needed is water-soluble, it can be diluted with water.

The content ratio of the component (F) is preferably 0.01 to 200 parts by weight, more preferably 10 to 150 parts by weight, and 20 parts by weight, based on 100 parts by weight of the total amount of the curable component. It is more preferably ~ 100 parts by weight.

3-5. Component (G) Component (G) is a compound having an ethylenically unsaturated group and an ionic group.
The component (G) is a component that imparts good antifogging property and low surface resistance necessary for preventing dust adhesion to the cured film by curing the composition.
The component (G) maintains excellent antifogging properties even when the surface of the cured film is wetted or wiped by chemically bonding ionic groups in the cured film by the reaction of ethylenically unsaturated groups. It can be made to be excellent in anti-fog durability (repeated anti-fog property).
As the component (G), various compounds can be used as long as they are compounds having an ethylenically unsaturated group and an ionic group.
Examples of the ethylenically unsaturated group include a (meth) acryloyl group, a (meth) allyl group, a vinyl group, and a styryl group.
As the ethylenically unsaturated group of the component (G), (meth) acryloyl is excellent because it has good reactivity with the component (A) or the component (E) to be blended as needed and has excellent curability. Groups are preferred, and acryloyl groups are more preferred.

Since the component (G) has an ionic group, it is possible to obtain antifogging property and low surface resistance without impairing the hard coat property inherent in the cured film of the composition, and the content ratio is smaller. However, the effect can be achieved.
In the component (G), examples of the ionic group include salts of strong acids, specifically, sulfonates such as ammonium sulfonate, sodium sulfonate and potassium sulfonate, ammonium alkylsulfate, sodium alkylsulfate and potassium alkylsulfate and the like. Alkyl sulfate, and carboxylates such as ammonium carboxylate, sodium carboxylate and potassium carboxylate can be mentioned.

As the ionic group of the component (G), a salt of a sulfonic acid group and a salt of an alkyl sulfate group are preferable because a desired effect can be obtained even when the content ratio of the component (G) is made smaller. ..
Further, examples of the counter cation constituting the sulfonate include a secondary ammonium ion, a tertiary ammonium ion and a quaternary ammonium ion.
Specifically, the secondary ammonium ions include dimethylamine, diethylamine, di-1-propylamine, di-2-propylamine, di-n-butylamine, di-2-butylamine, and di-1-pentylamine. , Di-2-pentylamine, di-3-pentylamine, dineopentylamine, dicyclopentylamine, di-1-hexylamine, di-2-hexylamine, di-3-hexylamine, dicyclohexylamine, methylethanol Examples thereof include ions in which amines and ethylethanolamines are protonated, respectively.
Examples of the tertiary ammonium ion include trimethylamine, triethylamine, tri-1-propylamine, tri-2-propylamine, tri-n-butylamine, tri-2-butylamine, tri-1-pentylamine, and tri-2-pentyl. Amine, tri-3-pentylamine, trineopentylamine, tricyclopentylamine, tri-1-hexylamine, tri-2-hexylamine, tri-3-hexylamine, tricyclohexylamine, dimethylethanolamine, ethylmethylethanol Examples thereof include ions in which amines, diethylethanolamines, lauryldiethanolamines and bis (2-methoxyethyl) methylamines are protonated, respectively.
Among these, methylethanolamine, ethylethanolamine, dimethylethanolamine, diethylethanolamine, or lauryldiethanolamine are preferably protonated ions, and methylethanolamine, ethylethanolamine, or lauryldiethanolamine is each protonated. It is more preferably a protonated ion, more preferably a protonated ion of methylethanolamine, dimethylethanolamine or ethylethanolamine, respectively, and particularly preferably an ion in which ethylethanolamine is protonated. preferable.

The ionic group of the component (G) is preferably bonded to an ethylenically unsaturated group via an alkyl group, an alkylbenzene group, an alkylene oxide group or the like.

Examples of the component (G) include the following components (G-1) and (G-2), both of which can be used.
Component (G-1): A compound consisting of a cation having an ethylenically unsaturated group in one molecule and an anion (G-2) Component: From an anion having an ethylenically unsaturated group in one molecule and a cation Compound

The component (G-1) is a compound composed of a cation having an ethylenically unsaturated group in one molecule and an anion.
Examples of the cationic group in the cation having an ethylenically unsaturated group in one molecule include ammonium ion, imidazolium ion, pyridinium ion, pyrrolidinium ion, pyrrolinium ion, piperidinium ion, pyrazinium ion and pyrimidinium ion. , Triazolium ion, triazinium ion, quinolinium ion, isoquinolinium ion, indolinium ion, quinoxalinium ion, piperazinium ion, oxazolinium ion, thiazolinium ion, and morpholinium ion At least one selected from the group can be exemplified.

Specific examples of cations having an ethylenically unsaturated group in one molecule include ethylammonium dimethylmono (meth) acrylate [quaternary ammonium ion of dimethylaminoethyl (meth) acrylate] and diethylmono (meth) acrylic. Dialkyl mono (meth) alkylammonium acrylate ions such as ethylammonium acid acid [quaternary ammonium ion of diethylaminoethyl (meth) acrylate], and 1,2,2,6,6-pentamethyl-4- (meth) acrylate pipette. Lidinium ions and the like can be mentioned as suitable ones.
In the above-mentioned ammonium ion, the description of "N-", "N, N-" and the like indicating that it is a substituent on the nitrogen atom is omitted.

Examples of the anion constituting the component (G-1) include a sulfonic acid derivative, a halogen-based anion such as bromide ion and triflate, a boron-based anion such as tetraphenylborate, and a phosphorus-based anion such as hexafluorophosphate.
As the anion, a sulfonic acid derivative is preferable. Specific examples of the sulfonic acid derivative include an anion of a sulfonic acid having a polyoxyalkylene unit such as an anion of alkoxypolyethylene glycol sulfonic acid, an anion of an alkyl group-containing aromatic sulfonic acid such as an anion of isopropylbenzenesulfonic acid, and the like. Be done.

The component (G-1) is preferably a compound composed of an alkylammonium ion of dialkylmono (meth) acrylate and an anion of sulfonic acid. Further, as the sulfonic acid anion, a sulfonic acid anion having a polyoxyalkylene unit is preferable.
As the compound, a compound represented by the following formula (6) is preferable.

In the above formula (6), R ^a represents a hydrogen atom or a methyl group, R ^b represents an alkylene group having 1 to 12 carbon atoms which may be branched, and R ^c and R ^d are independent of each other. It represents an alkyl group having 1 to 10 carbon atoms which may be branched, and X ^- is an alkyl sulfate ion, a polyoxyalkylene alkyl ether sulfate ion, a polyoxyalkylene alkyl phenyl ether sulfate ion, an alkyl sulfonic acid ion or Represents an alkylbenzene sulfonate ion.

R ^b is an alkylene group having 1 to 12 carbon atoms which may be branched. Specific examples thereof include a methylene group, an ethylene group, a propylene group, a butylene group and the like.
R ^c and R ^d are alkyl groups having 1 to 10 carbon atoms which may be branched independently of each other. Specific examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group and the like.

X ^- is an alkyl sulfate ion, a polyoxyalkylene alkyl ether sulfate ion, a polyoxyalkylene alkyl phenyl ether sulfate ion, an alkyl sulfonic acid ion, or an alkyl benzene sulfonic acid ion.
In order to exhibit good antifogging property, the component (G) needs to be present near the surface of the cured film, but in general, the component having strong hydrophobicity is oriented on the surface of the coating film after the composition is applied. It's easy to do. Therefore, as the alkyl group in these groups, an alkyl group having 6 or more carbon atoms is preferable so as to have high hydrophobicity, and an alkyl group having 6 to 20 carbon atoms is preferable.
Examples of the polyoxyalkylene unit in these groups include a polyoxyethylene unit, a polyoxypropylene unit, a polyoxytetramethylene unit, and the like.

As the component (G-1), a commercially available product can be used.
For example, as a compound having a cation containing a (meth) acryloyl group and an ammonium ion in the molecule and an anion, the trade names "IL-MA1", "IL-MA2" and "IL-" manufactured by Koei Chemical Industry Co., Ltd. MA3 ";
Examples of the compound having an anion and a cation containing an acryloyl group and an ammonium ion include trade names "JI-62C01" and "JI-63F01" manufactured by Nippon Emulsifier Co., Ltd .; and a cation containing a methacryloyl group and an ammonium ion and an anion. Examples of the compound having alkylsulfuric acid as an example include the trade name "JNA-04006" manufactured by Nippon Emulsifier Co., Ltd.

The component (G-2) is a compound composed of an anion having an ethylenically unsaturated group in one molecule and a cation.
Specific examples of the component (G-2) include the following examples as examples in which the anionic group is a sulfonic acid ion.
That is, the cation is an example of ammonium ion, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt, polyoxyethylene nonylpropenylphenyl ether ammonium sulfate, α-sulfo-ω- (1- (alkoxy). ) Methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt, bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate ammonium salt,
2-Sodium sulfoethyl methacrylate, alkylallyl sulfosuccinate sodium salt, (meth) chryloyl polyoxyalkylene sulfate sodium salt, bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate sodium salt, etc. Can be mentioned.

As the component (G-2), a commercially available product can be used.
Specific examples thereof include polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salts, which are trade names "Aquaron KH-10" and "Aqualon KH-1025" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. , "Aqualon KH-05";
As ammonium polyoxyethylene nonylpropenylphenyl ether sulfate, trade names "Aquaron HS-10", "Aqualon HS-1025", "Aqualon BC-0515", "Aqualon BC-10" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. , "Aqualon BC-1025" and "Aqualon BC-20" and "Aqualon BC-2020";
As the α-sulfo-ω- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethanediyl) ammonium salt, the trade name "ADEKA" manufactured by ADEKA Corporation "Rear Soap SR-10", "Adecaria Soap SR-20", "Adecaria Soap SR-1025" and "Adecaria Soap SR-3025";
As the bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate ester salt, the trade name "Antox MS-60" manufactured by Nippon Emulsifier Co., Ltd.;
As the sodium alkyl-allyl succinate sulfonic acid salt, the trade name "Antox SAD" manufactured by Nippon Emulsifier Co., Ltd.
As 2-sodium sulfoethyl methacrylate, the trade name "Antox MS-2N" manufactured by Nippon Emulsifier Co., Ltd .;
As the sodium alkylallyl sulfosuccinate salt, the trade name "Eleminol JS-20" manufactured by Sanyo Kasei Kogyo Co., Ltd .; and as the sodium methacryloyl polyoxyalkylene sulfate, the trade name "Ereminol RS" manufactured by Sanyo Kasei Kogyo Co., Ltd. -3000 "and the like.

In the component (G), the components (G-1) and (G-2) may be selected according to the purpose.
As the component (G), the component (G-1) is preferable because it is more excellent in anti-fog durability than the component (G-2).
The details of the reason why the component (G-1) is superior in antifogging persistence are unknown, but it is probably hydrophilic when the counterion cation constituting the component (E-2) is a metal cation such as sodium and potassium. It is considered that these are easily eluted from the cured film when they come into contact with water because of their extremely high properties, and it is difficult to maintain the antifogging property. If a non-metal cation such as ammonium ion is used as the cation, the hydrophilicity is slightly lowered and anti-fog durability is expected to be improved, but generally available compounds are limited to those having a relatively low molecular weight. It is considered that elution over time cannot be sufficiently prevented and the antifogging sustainability becomes insufficient.
On the other hand, anions (for example, alkyl sulfonic acid ion, alkyl benzene sulfonic acid ion, alkyl naphthalene sulfonic acid ion, and polyoxyethylene alkyl sulfate ion), which are counter ions constituting the component (G-1), are slightly hydrophobic. Therefore, it is presumed that the elution of the surface of the cured film due to moisture is reduced. Further, when these anions have a polyoxyalkylene ether structure, a chemical bond is formed with the cured film by the action of radicals generated on the ether group in the radical polymerization process, so that the antifogging durability is further improved. Conceivable.
Further, when the ultraviolet irradiation amount is increased, it is preferable to use the components (G-1) and (E-2) in combination from the viewpoint of antifogging property. This suppresses the increase in the crosslink density on the surface of the cured film as the ultraviolet irradiation amount increases, maintains the motility of the component exhibiting the antifogging performance appropriately, and is more excellent in the antifogging performance. In order to exhibit stable anti-fog properties, the copolymerization property is significantly different from the component (A) or the component (E) to be blended as needed, and the design is such that the concentration of the component (G) is locally increased. Specifically, this object can be achieved by using the component (G-1) and the component (G-2) in combination.

The component (G) is often solid at room temperature, and is preferably diluted with an organic solvent or a reactive diluent from the viewpoint of handling problems such as ease of blending into the composition.
As the organic solvent, it is preferable to use a compound having a hydroxyl group and other than a compound having no ethylenically unsaturated group, a ketone solvent such as methyl ethyl ketone and methyl isobutyl ketone, ethyl acetate, butyl acetate and the like. Examples include the ester solvent of.

The content ratio of the component (G) may be appropriately set according to the intended 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 (G) is 1% by weight or more, the antifogging property of the cured film becomes excellent, and when it is 30% by weight or less, the hydrophilicity is sufficient to impart the antifogging property and the length is long. It is a cured film that has both water resistance without swelling and peeling 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 (G), which is a group of compounds having an ethylenically unsaturated group, is referred to as a "curable component".

3-6. Other components other than the above As the other components other than the above, known additives can be used. For example, anti-fog modifiers, UV absorbers, light stabilizers, acidic substances, antioxidants, surface modifiers, hydrophilic polymers, fillers, silane coupling agents, acid generators, pigments, dyes, adhesive Examples include an imparting agent and a polymerization inhibitor.
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. ..

<Anti-fog modifier>
In the composition of the present invention, the cured film has excellent anti-fog durability (repeated anti-fog property), but the anti-fog durability of the present invention is not adversely affected for the purpose of further improving the initial anti-fog property. An anti-fog modifier can be added within the range.
Examples of the antifogging modifier 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 more excellent in initial antifogging property.
Dialkyl sulfosuccinates are commercially available and commercially available products can be used. As the sodium sulfosuccinate (2-ethylhexyl) salt, Rikasurf 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 [propylene glycol / water mixed solution of the same compound] manufactured by New Japan Chemical Co., Ltd.

Cationic surfactants include amine salts such as ethanolamines, laurylamine acetate, triethanolamine monoatelate, stearamide ethyldiethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and dilauryldimethylammonium chloride. , Teruary 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 antifogging property, and dialkylsulfosuccinate is more preferable as described above.

The content ratio of the antifogging modifier 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 antifogging modifier is in the above range, the initial antifogging property can be excellent without impairing the antifogging durability 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-Benzophenone-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, and 0. 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.
Examples of commercially available hindered amine-based light stabilizers 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, and 0. 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 a phenol-based antioxidant, a phosphorus-based antioxidant, a sulfur-based antioxidant, 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 phosphine. 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, an antifoaming 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 polymer and oligomer having a silicone chain and a polyalkylene oxide chain, a silicone 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 polymers 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, a phosphoric acid group and the like, 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 using 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 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 polymer (hereinafter, referred to as “other monomer”) other than the vinyl-based monomer having a hydrophilic group.
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 a 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, a polymer produced by using the above-mentioned monomer according to a conventional polymerization method 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 based on the solid content in either the aqueous solution or the aqueous dispersion with respect to 100 parts by weight of the total amount of the composition. , 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 white turbidity, uneven streaks, and loose skin can be prevented. Can be prevented.

<Filler>
When the composition of the present invention contains an organic solvent, if either the component (A) or the component (E) to be blended if 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, one having a high average molecular weight is preferable because the number of additional parts required for thickening can be reduced and the deterioration of the antifogging property of the composition can be prevented. 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 antifogging 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.

4. Method of use As a method of using the composition of the present invention, a conventional method may be followed.
When the curable composition is an active energy ray-curable composition, for example, the composition is applied to the applied substrate by a usual coating method, irradiated with active energy rays, and then the component (B) is applied. A method of further heating for the purpose of curing can be mentioned.
As the method of irradiating the active energy rays, a general method known as a conventional curing method may be adopted.
When the curable composition is a thermosetting composition, for example, the composition is applied to an applied base material by a usual coating method, heated, and then the component (B) is cured for the purpose of curing the component (B). Further, a method of heating at a temperature higher than the heating temperature can be mentioned.
Hereinafter, heating performed for the purpose of curing the component (B) is referred to as "post-heating".

When the curable composition is an active energy ray-curable composition, when there is a heating step after irradiation with active energy rays, the antifogging 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 inert gas atmosphere, and then heating is preferable because the deterioration of the antifogging property can be prevented.

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.

The composition of the present invention can be preferably used as a method for producing an article with a cured film in which the following steps 1 to 3 are sequentially carried out.
-Step 1: A step of applying the above-mentioned composition to the base material-Step 2: A step of irradiating the coated surface of the composition obtained in Step 1 with active energy rays to form a cured film-Step 3: Step of heating the base material with a cured film obtained in Step 2 The production method will be described below.

4-1. Process 1
Step 1 is a step of applying the above-mentioned composition to the base material.
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. 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 plastics 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.
Further, in the composition of the present invention, the cured film has excellent adhesion to plastics which are considered to have poor adhesion. For example, as polycarbonate, Takiron [manufactured by Takiron Co., Ltd.] is said to have poor adhesion, but the composition of the present invention can form a cured film having excellent adhesion.

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 or below a temperature at which problems such as deformation do not occur. 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.

4-2. Step 2
Step 2 is a step of irradiating the coated surface of the composition obtained in Step 1 with active energy rays to form a cured film.
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 beam, ultraviolet ray and visible light, but ultraviolet ray or visible light ray is preferable, and ultraviolet ray is 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 and composition of the active energy rays. 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 irradiation energy is 1,000 mJ / cm ² or more, it is preferable to add the above-mentioned antifogging modifier from the viewpoint of the antifogging performance of the cured film.

4-3. Process 3
Step 3 is a step of heating (post-heating) the substrate with a cured film obtained in Step 2.
Step 3 is post-heating performed for the purpose of curing the component (B), and the heating temperature and the heating time may be appropriately set according to the type and purpose of the component (B) to be used.
For example, when an isocyanate compound is used as the component (B), the temperature is preferably 60 to 120 ° C. and the heating time is preferably 10 minutes to 10 hours.
When a melamine resin is used as the component (B), the temperature is preferably 80 to 160 ° C. and the heating time is preferably 3 to 60 minutes.

5. Applications The curable composition of the present invention can be used for various purposes, for example, for various applications such as coating agents, molding agents, inks, pattern forming agents, adhesives, fillers and sealants. It is possible.

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, antifogging coating agents for plastic films, and dust adhesion prevention coating agents for plastic substrates and floors. Further, when used for building materials, the cured film of the composition of the present invention does not repel water and has excellent wettability on the entire surface, so that dirt adhering to the surface of the coating film can be easily washed away, and antifouling properties are also imparted. can do.
More preferable specific examples of the coating agent are protective glasses, goggles, coating of building / construction materials, bathroom inner walls, members around the kitchen, head lamp covers for automobiles and motorcycles, rear lamp covers, and other glass and plastic antifogging coatings. Examples thereof include agents, plastic base materials, dust adhesion prevention coating agents for preventing dust adhesion on the floor surface, and the like.

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)]
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, and 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 is 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 [Kyowa Chemical Industry Co., Ltd. Kyoward 700SEN-S (trade name). Hereinafter, it is referred to as "K700". ] Was added and stirred, and the mixture was stirred at an internal temperature of 95 ° C. to 100 ° C. for 1 hour 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 connected with a stirrer, a thermometer, a gas introduction tube, a distilling cooling tube, and a depressurizing tube, and the internal temperature is 90 to 100 ° C. and the pressure is 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, and Mw were measured according to the methods shown below. The results are shown below.
Viscosity (25 ° C.): 4.13 Pa · s, Solubility in water: 75% or more, Hydroxyl value: 300 mgKOH / g, APHA: 45, Mw: 760, Acrylate rate 33 mol%

◆ Peroxide Concentration Measurement Conditions・ Isopropyl alcohol, glacial acetic acid, and potassium iodide aqueous solution were added to the alkylene oxide adduct of sorbitol, 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 a 500 μg / mL solution with acetonitrile ・ Equipment: Quattro Premier (manufactured by Waters) + AcQuity UPLC (manufactured 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, the temperature was raised to 240 ° C. at a rate of 10 ° C./min, and then held 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 (%) for maintaining a uniform liquid was regarded as the solubility (%) without turbidity or layer separation being confirmed after standing for 24 hours.

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 prepared 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.

2. Examples 1 to 4 and Comparative Example 1 (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.
Component (A) -Sb-EOA-1: Acrylate obtained in Production Example 1
(B) Ingredients ◆ TPA-100: Hexamethylene diisocyanate trimer (isocyanurate type): Duranate TPA-100 manufactured by Asahi Kasei Corporation (NCO% = 23.1% by weight in the product)
(C) Ingredient ◆ HCPK: 1-Hydroxy-cyclohexyl-phenyl-ketone (Omnirad 184 manufactured by IGM Resins)
Ingredients (E) and (G) ◆ JI-64C02: A solution containing 50% of G-1-1 below and 50% of E-1 below [JI-64C01 manufactured by Nippon Emulsifier].
* A solution in which the entire amount of propylene glycol monomethyl ether (hereinafter referred to as "PGME") of JI-62C01 below is replaced with E-1.
JI-62C01: A 50% PGME solution of a compound consisting of an acryloyl group and ammonium ions and having a counterion (hereinafter referred to as "G-1-1") [JI-62C01 manufactured by Nippon Emulsifier].
E-1: Glycerin diacrylate (GLY-DA) 62%, glycerin triacrylate (hereinafter referred to as "GLY-TA") 33%, glycerin monoacrylate obtained based on Production Example 1 of International Publication WO2018 / 207828. 5% mixture (hereinafter referred to as "GLY-MA")
(F) Ingredient ◆ Vinegar Echi: Ethyl acetate
(G) Component ◆ SR-10: Polyethylene glycol (additional number of moles 10) _{A compound having 4 SO 3} NH groups (anionic) at one end and an alkyl group and an allyl group at the other end [ADEKA Corporation. ) Made Adecaria Soap SR-10]
Other Ingredients ◆ DBTL: 1% vinegar ethi solution of dibutyltin dilaurate. In Table 1 below, the solid content and the component (F) (vinegar ethic) are listed separately.
◆ G-30: Propylene glycol of di (2-ethylhexyl) sulfosuccinate (hereinafter referred to as "PG") / water mixed solution (solid content: 70%, PG: 15%, water: 15%), New Japan Chemical Rika Surf G-30 manufactured by Rika Surf Co., Ltd. In Table 1 below, the solid content and the component (F) (PG and water) are listed separately.

The numbers in the table 1 formulation column mean the number of copies of each component, and the blanks mean that they are not included.
In the column of composition in Table 1, the solid content [(B) component] and (F) component (organic solvent) contained in TPA-100 used as a raw material are described separately and included in JI-64C02. The component (E) [(E-1)] and the component (G) [(G-1-1)] are described separately, and the solid content contained in DBTL and the component (F) (organic solvent) are separately described. It is described.

2) Evaluation of composition The obtained compositions of Examples 1 to 4 and Comparative Example 1 were cut using a bar coater, and Mitsubishi Engineering Plastics Co., Ltd. polycarbonate, Iupiron NF2000 (150 mm × 70 mm × 1 mm) ( (Hereinafter, referred to as "engineering plastic") was coated so that the film thickness was 10 μm, and this was heated in a dryer at 80 ° C. for 1 minute to volatilize the solvent.
Next, using a high-pressure mercury lamp equipped with a conveyor [H06-L 41 manufactured by Eye Graphics Co., Ltd.], 5 passes under the condition ^{that the UV-A illuminance is 80 W / cm and the irradiation energy per pass is 200 mJ / cm 2.} The test piece was irradiated with ultraviolet rays and cured. The obtained test piece was further heated at 80 ° C. for 1 hour.
The obtained cured film was used and evaluated according to the following method. The results are shown in Table 2.

(1) Anti-fog by sighing The cured film was blown with sigh and visually observed to confirm the presence or absence of fogging on the surface of the cured film, and evaluated on the following two levels.
○: No cloudiness ×: Cloudy

(2) Adhesion The cured film was cut with a cutter knife at 1 mm intervals to form 25 squares with a size of 1 mm x 1 mm, and Nichiban Co., Ltd. # 405 was formed on this grid. After sticking the cellophane tape, it was strongly peeled off. The number of residual films after peeling was evaluated (adhesion test 1 in Table 2). The larger the number of residual films, the better the adhesion.
Further, as the base material, UV irradiation is performed in the same manner as described above using Takiron Co., Ltd. polycarbonate, Takiron PC1600 150 mm × 70 mm × 2 mm (hereinafter referred to as “Takiron”) which has been changed to the above-mentioned Iupilon and cut. In addition, the adhesion was evaluated in the same manner for those cured by heating (adhesion test 1 in Table 2).
Furthermore, the adhesion of the cured film after the following anti-fog durability test was evaluated according to the same method as described above (adhesion test 2 in Table 2).

(3) The anti-fog persistent cured film was allowed to stand in a dryer at 80 ° C. for 14 days, and then the cured film was taken out and visually evaluated whether or not the cured film was fogged. Further, the antifogging persistence was evaluated by repeating the operation of wiping off the moisture adhering to the surface of the cured film with paper and then exposing the cured film to steam at 80 ° C. for 1 minute, a total of 5 times. In addition, ◯, Δ, and × in Table 2 have the following meanings.
○: Not cloudy, △: Slightly cloudy, ×: Cloudy

(3) Evaluation Results As is clear from the results of Examples 1 to 4 in Table 2, the composition of the present invention has excellent breathing and antifogging properties, and also has excellent adhesion to various plastic substrates, and is antifogging. Adhesion did not decrease even after the sustainability test. Furthermore, it was also excellent in anti-fog durability.
On the other hand, the composition of Comparative Example 1 containing no component (B) is excellent in antifogging property for breathing, but the adhesion to Iupilon, which is a plastic base material, is insufficient with respect to the composition of Example. , Adhesion to Takiron has decreased significantly. Furthermore, under harsh conditions, the anti-fog sustainability was insufficient.
In addition, in the compositions of Examples 1 to 4, even if the cured film was exposed to steam, the water content was wiped off, and then the cured film was exposed to steam again, no trace of water dripping was formed. On the other hand, the composition of Comparative Example 1 had a trace of water dripping when the same operation was performed.

The curable composition of the present invention can be used for various purposes, for example, for various purposes such as coating agents, molding agents, inks, pattern forming agents, adhesives, fillers and sealants. Is.
In particular, the composition of the present invention has excellent curability, the cured film formed has good adhesion, the permeability to the porous substrate can be adjusted, and the hydrophilicity is excellent, so that the composition has good antifogging properties. Is expressed.
Therefore, the composition of the present invention comprises a coating agent for various substrates, a primer, a coating for protective eyeglasses and goggles that require antifogging performance for a cured film, and a coating for headlamps and rear lamp covers of automobiles and motorcycles. It can be preferably applied to agents and the like.

Claims (27)

A curable composition containing the following components (A) and (B).
Component (A): (Meta) acrylate (B) component of alkylene oxide adduct of alditol (excluding glycerol): Thermosetting agent 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 of compounds having an (meth) acryloyl group.
Catalyst X: A type 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, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex 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) 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 4, wherein the component (A) has a hydroxyl value of 100 mgKOH / g or more. The curable composition according to any one of claims 3 to 5, 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 6. The curable composition according to any one of claims 3 to 7, wherein the catalyst Y is zinc organic acid and / or zinc diketone enolate. The curable composition according to any one of claims 1 to 8, wherein the component (B) contains an isocyanate compound. The curable composition according to any one of claims 1 to 9, further comprising a component (C): 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 (D): a thermal polymerization initiator in addition to the component (A). The curable composition according to any one of claims 1 to 11, further comprising a compound having an ethylenically unsaturated group other than the component (E): component (A) in addition to the component (A). The curable composition according to any one of claims 1 to 12, wherein the component (A) further contains a component (F): water and / or an organic solvent. Claims 1 to 1, wherein the component (A) further contains a component (G): a compound having an ethylenically unsaturated group and an ionic group, and the component (G) further contains the following component (G-1). The cured product according to any one of claims 13.
Component (G-1): A compound consisting of a cation having an ethylenically unsaturated group in one molecule and an anion. The cured product according to claim 14, wherein the component (G-1) contains a compound represented by the following formula (6).

[In the above formula (6), R ^a represents a hydrogen atom or a methyl group, R ^b represents an alkylene group having 1 to 12 carbon atoms which may be branched, and R ^c and R ^d are respectively. Independently, it represents an alkyl group having 1 to 10 carbon atoms which may be branched, and X ^- is an alkyl sulfate ion, a polyoxyalkylene alkyl ether sulfate ion, a polyoxyalkylene alkyl phenyl ether sulfate ion, and an alkyl sulfonic acid ion. Alternatively, it represents an alkylbenzene sulfonate ion. ] The curable composition according to claim 14 or 15, wherein the component (G) contains the component (G-1) and the component (G-2) below.
Component (G-2): A compound consisting of an anionic group having an ethylenically unsaturated group in one molecule and a cation. The curable composition according to any one of claims 1 to 16, further comprising an ionic surfactant having no ethylenically unsaturated group. An active energy ray-curable coating composition comprising the composition according to any one of claims 1 to 17. An active energy ray-curable antifogging coating composition comprising the composition according to claim 1 to 18. A method for producing an article with a cured film, in which the following steps 1 to 3 are sequentially carried out.
-Step 1: The composition according to any one of claims 1 to 19 is applied to the base material.-Step 2: Active energy rays are applied to the coated surface of the composition obtained in Step 1. Step of irradiating and forming a cured film-Step 3: Step of heating the substrate with a cured film obtained in Step 2. 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. A method for producing a curable composition, which comprises a step of producing the component (A) and a step of mixing the component (B): a heat-curing agent.
Catalyst X: A type 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, a compound having a pyridine ring or a salt or complex thereof, and phosphine or a salt or complex thereof. The above compounds.
Catalyst Y: A compound containing zinc. The method for producing a curable composition according to claim 21, 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 21, 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 21 to 23, wherein the component (A) has a hydroxyl value of 100 mgKOH / g or more. The method for producing a curable composition according to any one of claims 21 to 24, 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 21 to 25. The method for producing a curable composition according to any one of claims 21 to 26, wherein the catalyst Y is zinc organic acid and / or zinc diketone enolate.