JP7044104B2 - Curable composition - Google Patents

Description

The present invention relates to a curable composition, preferably an active energy ray curable composition. The cured composition of the present invention is preferably used as a coating agent because the cured film has excellent adhesion to a base material, particularly to a plastic base material, and has excellent anti-fog property and anti-adhesion performance such as dust. Can belong 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. It is expressed as.

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 since it has high productivity, it is widely used as an ink and a coating agent for various substrates. It is used.
The surface of a plastic base material such as a plastic plate and a plastic film is protected by a hard coat agent for the purpose of preventing scratches on the surface, and an active energy ray-curable composition is also used for this purpose.

Since the plastic base material is highly transparent, it is used for protective glasses, goggles, inner walls of bathrooms, head lamp covers and rear lamp covers for automobiles and motorcycles, etc. When used in a large place, dew condensation may occur on the surface, resulting in cloudiness and loss of transparency.
In order to solve these problems, a method of applying an anti-fog composition composed of a non-reactive surfactant to the surface of a substrate has been conventionally adopted, 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 anti-fog composition composed of a hydrophilic polymer diluted with an organic solvent to the surface of the base material, but the coating film hardness is insufficient and the solvent resistance is insufficient. In addition, the anti-fog property was not satisfactory.

In order to solve the above problems, anti-fog compositions that are cured by active energy rays such as ultraviolet rays and electron beams have been proposed in recent years. Specifically, an antifogging agent composed of a hydrophilic group-containing photocurable ethylenically unsaturated compound, a hydrophilic group-free photocurable ethylenically unsaturated compound, and a photocuring initiator (Patent Document 1), and (1) a) a copolymer of 2-hydroxyalkyl (meth) acrylate and b) dialkylaminoalkyl (meth) acrylate, (2) di (meth) acrylate having a polyalkylene oxide chain, (3) glycerin diepoxide. A photocurable coating composition containing (meth) acrylic acid adduct, (4) hydroxyalkyl (meth) acrylate, and a photopolymerization initiator has been proposed (Patent Document 2).

Further, an anti-fog coating composition comprising a hydrophilic monomer and a surfactant has also been proposed (Patent Document 3).

Further, a visible light or active energy ray-curable anti-fog composition containing (meth) acrylate and a reactive surfactant has been proposed, which has excellent surface hardness and anti-fog durability. (Patent Document 4).

Japanese Unexamined Patent Publication No. 55-6678 Japanese Unexamined Patent Publication No. 3-31369 Japanese Unexamined Patent Publication No. 3-215589 Japanese Unexamined Patent Publication No. 11-140109

However, the anti-fog agent of Patent Document 1 and the photocurable coating composition of Patent Document 2 have a problem that anti-fog property is not exhibited in an environment under high humidity.
Further, the anti-fog coating composition of Patent Document 3 lacks anti-fog sustainability because the anti-fog property is lowered when the surface of the cured film is wiped.
Further, since the (meth) acrylate used in the visible light or active energy ray-curable antifogging composition of Patent Document 4 is an oligomer having a relatively large molecular weight, the molar fraction of the (meth) acryloyl group occupies the entire molecule. Due to the relatively low rate, the surface hardness was inadequate.
Moreover, since the hydrophilicity of the (meth) acrylate constituting the composition is also insufficient, the antifog property is also insufficient. Therefore, in order to obtain good anti-fog properties by using the composition, it is necessary to increase the blending amount of the surfactant, and in this case, the hard coat property that the cured film is excellent in physical properties such as hardness is obtained. It deteriorated, and it was difficult to achieve both anti-fog property and hard coat property.
In addition, the hard coat agent obtained from the conventional active energy ray-curable composition has a problem that the cured film is charged and dust is easily attached.

In view of the above problems, the present invention has excellent adhesion to the substrate, particularly adhesion to the plastic substrate, has good surface hardness, and can be preferably used as a hard coating agent even under high humidity. It is an object of the present invention to provide a curable composition having good anti-fog property, which has sufficient anti-fog property even when the surface of the cured film is wiped off, and which is also excellent in dust adhesion prevention performance.

According to the present invention, the obtained cured film has excellent adhesion to a base material, particularly to a plastic base material, has good surface hardness, can be preferably used as a hard coat agent, and is also good even under high humidity. A specific (meth) acrylate mixture with an ethylenically unsaturated group and an ionic group, which have antifogging properties, and which have sufficient antifogging properties even when the surface of the cured film is wiped off and have excellent dust adhesion prevention performance. A curable composition comprising a compound having the above is provided.

The cured film formed by using the curable composition of the present invention has good adhesion to a plastic substrate, high surface hardness, exhibits good anti-fog durability, and is also excellent in dust adhesion prevention performance. ..
Therefore, the curable composition of the present invention can be preferably used as a coating agent, and is used for coating agents such as protective eyeglasses and goggles, which require anti-fog properties for the cured film, and head lamps and rear lamp covers for automobiles and motorcycles. It can be preferably applied to a coating agent or the like.

The present invention includes the following components (A) and (B).
When the total amount of the cured composition is 100% by weight, the component (A) is contained in an amount of 30 to 99% by weight.
The component (B) is contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the component (A).
It relates to a curable composition (hereinafter, may be simply referred to as "composition").
(A) Component: A mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and polyglycerin (meth) acrylate, and having a hydroxyl value of 80 to 380 mgKOH / g or more (B). ) Component: A compound having an ethylenically unsaturated group and an ionic group and containing the following (B-1) component and / or the following (B-2) component.
(B-1) Component: A compound consisting of a cation having an ethylenically unsaturated group in one molecule and an anion.
(B-2) Component: A compound consisting of an anion having an ethylenically unsaturated group in one molecule and a cation.

Hereinafter, the component (A), the component (B), other components, the method of use, and the like will be described.

1. 1. Component (A ) Component (A) is a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and polyglycerin (meth) acrylate, and has a hydroxyl value of 80 mgKOH / g or more. Is.
The component (A) is a component for imparting good hardness and adhesion to a plastic to the cured film of the composition, and has good hydrophilicity, so that the compatibility with the component (B) is good. Moreover, it is excellent in reactivity with the component (B).
As the component (A), in the case of a mixture of glycerin (meth) acrylate, a compound having at least one hydroxyl group and two (meth) acryloyl groups as a main component is preferable, and polyglycerin (meth) is preferable. ) In the case of a mixture of acrylates, those containing a compound having at least one hydroxyl group and two or more (meth) acryloyl groups as a main component are preferable.
When the component (A) is a mixture of polyglycerin (meth) acrylate, the number of repetitions of the structural unit derived from glycerin in the raw material polyglycerin is preferably 2 to 10, and more preferably 2 to 5. By setting the number of repetitions of the structural unit derived from glycerin to 10 or less, shrinkage during curing can be suppressed and adhesion to the substrate can be improved, and good antifogging property even if the component (B) is added. Can be expressed. Further, it is possible to improve the surface hardness of the cured film and prevent the cured film from swelling and peeling from the substrate due to water absorption due to the hydrophilicity of the cured film becoming too high.

The component (A) can be obtained by a transesterification reaction between glycerin and / or polyglycerin (hereinafter collectively referred to as “(poly) glycerin”) and a monofunctional (meth) acrylate. The component (A) can also be obtained by a dehydration esterification reaction of (poly) glycerin and (meth) acrylic acid.
When glycerin is used as a raw material, the component (A) is a mixture of mono (meth) acrylate, di (meth) acrylate, and tri (meth) acrylate of glycerin. When polyglycerin is used as a raw material, the component (A) is a mono (meth) acrylate of polyglycerin and a poly such as di (meth) acrylate, tri (meth) acrylate, and tetra (meth) acrylate of polyglycerin. It is a mixture of (meth) acrylate.
The component (A) is a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and polyglycerin (meth) acrylate, and has a hydroxyl value of 80 mgKOH / g or more. The hydroxyl value of the component (A) is preferably 80 to 380 mgKOH / g, more preferably 150 to 300 mgKOH / g.
If the hydroxyl value of the component (A) is less than 80 mgKOH / g, the anti-fog property of the cured film of the composition is lowered. Further, by setting the hydroxyl value to 380 mgKOH / g or less, the hardness of the cured film of the composition can be further improved.
In the present invention, the hydroxyl value means the number of mg of potassium hydroxide equivalent to the hydroxyl group in 1 g of the sample.

(A) The component may be one kind or a combination of two or more kinds.

1) Preferred component (A) The component (A) is a mixture of glycerin (meth) acrylate among a mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and polyglycerin (meth) acrylate. However, it is preferable because the cured film of the composition has excellent hardness, excellent adhesion to plastic, and excellent antifogging property.

Further, as the mixture of glycerin (meth) acrylate, a mixture containing glycerin di (meth) acrylate (hereinafter, also referred to as “GLY-DA”) is more preferable.
GLY-DA is a compound represented by the following formula (1) or formula (2).

[In the above formula (1), R ¹ and R ² independently represent a hydrogen atom or a methyl group, respectively. ]

[In the above formula (2), R ³ and R ⁴ independently represent a hydrogen atom or a methyl group, respectively. ]

Since GLY-DA is obtained as a mixture of the compound represented by the formula (1) and the compound represented by the formula (2) at the time of production unless it is specially purified, these may be used as they are, and in particular, the formula ( There is no restriction on the mixing ratio of the compound represented by 1) and the compound represented by the formula (2), and there is no problem even if it is used in any ratio.

The purity of GLY-DA contained in the component (A) is preferably 30% or more, more preferably 40% or more, still more preferably 50%, when determined using the following formula (3). That is all. By setting the purity of GLY-DA to 30% or more, the curing rate of the composition containing the component (A) is excellent, and the hardness or anti-fog property of the cured film can be excellent.

GLY-DA purity (%)
= [(D × 1.27) / (M × 1.74 + D × 1.27 + T)] × 100… Equation (3)
D, M, and T in the calculation formula (3) are obtained by analyzing the component (A) using a high performance liquid chromatograph (hereinafter, also referred to as “HPLC”) equipped with an ultraviolet (UV) detector. Means the value of.
-D: Peak area of GLY-DA at 210 nm-M: Peak area of glycerin mono (meth) acrylate at 210 nm-T: Peak area of glycerin tri (meth) acrylate at 210 nm The peak area by HPLC is measured under the following conditions. Means the value that was set.
-Detector: UV detector, detection wavelength 210nm
Column type: Column filled with silica gel modified with an alkyl group having 18 carbon atoms Specifically, ACQUITY UPLC BEH C18 (Part No. 186002350, column inner diameter 2.1 mm, column length 50 mm) manufactured by Waters Corp. )
-Column temperature: 40 ° C
-Eluent composition: 0.03 wt% trifluoroacetic acid aqueous solution and methanol mixed solution-Eluent flow rate: 0.3 mL / min

2) Production method (A) As the component, those obtained by various production methods can be used.
For example, one obtained by a transesterification reaction between (poly) glycerin and a compound having one (meth) acryloyl group (hereinafter referred to as "monofunctional (meth) acrylate") in the presence of a transesterification catalyst, or Examples thereof include those obtained by dehydration transesterification of (poly) glycerin and (meth) acrylic acid in the presence of an acidic catalyst.

When the component (A) is a mixture of polyglycerin (meth) acrylate, the polyglycerin used as a raw material for the component (A) is, for example, a polyether polyol having a structure in which glycerin or glycidol is polymerized.
The number of repetitions of the structural unit derived from glycerin in polyglycerin is preferably 2 to 10.
The hydroxyl value, which means the average degree of polymerization of polyglycerin, is 700 to 1,200 mgKOH / g, preferably 800 to 1,150 mgKOH / g, more preferably 850 to 1,100 mgKOH / g, and even more preferably. It is 900 to 1,050 mgKOH / g.
When the hydroxyl value of polyglycerin is 1,200 mgKOH / g or less, curling of the cured product of the composition can be suppressed, and when the hydroxyl value is 700 mgKOH / g or more, production is easy, and handling is possible with low viscosity. It's easy.
The hydroxyl value of polyglycerin is related to the average degree of polymerization, and for example, at an average degree of polymerization of 6, it is approximately 970 mgKOH / g.

As the component (A), among the above-mentioned production methods, those obtained by the transesterification reaction between (poly) glycerin and monofunctional (meth) acrylate have few impurities and obtain the desired (meth) acrylate. It is preferable because it can be used.

Further, as the transesterification reaction, an ester exchange reaction between (poly) glycerin and a monofunctional (meth) acrylate in the presence of the following catalysts X and Y is preferable.
Catalyst X: Cyclic tertiary amine having an azabicyclo structure or a salt or complex thereof (hereinafter, also referred to as “azabicyclo compound”), amidin or a salt or complex thereof (hereinafter, also referred to as “amidine compound”), and a pyridine ring. One or more compounds selected from the group consisting of a compound or a salt or complex thereof (hereinafter, also referred to as "pyridine compound") and phosphine or a salt or complex thereof (hereinafter, also referred to as "phosphin compound").
Catalyst Y: A compound containing zinc.

As the monofunctional (meth) acrylate, an alkoxyalkyl (meth) acrylate having an alkyl group having 1 to 2 carbon atoms, which promotes the dissolution of (poly) glycerin and exhibits extremely good reactivity, is preferable, and 2-methoxyethyl (2-methoxyethyl) ( Meta) acrylate is more preferred.
Further, as the monofunctional (meth) acrylate, acrylate is particularly preferable because it has excellent reactivity.

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 after the reaction is completed, and the complex can be easily obtained from the reaction solution after the reaction by a simple method such as adsorption. Can be removed. In particular, since the complex with the catalyst Y is sparingly soluble in the reaction solution, the azabicyclo-based compound can be more easily removed by filtration, adsorption or the like.

Examples of the catalyst X include quinuclidine, 3-quinucridinone, 3-hydroxyquinuclidine, and triethylenediamine (also known as 1,4-diazabicyclo [2.2.2] octane, which are examples of azabicyclo compounds. Hereinafter, "DABCO". Also referred to as), N-methylimidazole, 1,8-diazabicyclo [5.4.0] undec-7-ene (hereinafter also referred to as "DBU"), and 1,5-diazabicyclo [4.3.0] nona. -5-ene (hereinafter, also referred to as "DBN") and N, N-dimethyl-4-aminopyridine (hereinafter, also referred to as "DMAP"), which is an example of an amidin compound, are preferable.
Of these, 3-hydroxyquinuclidine, DABCO, N-methylimidazole, DBU and DMAP, which show good reactivity with most polyhydric alcohols and are easily available, are more preferable.

As the catalyst Y, various compounds can be used as long as they are compounds containing zinc, but zinc organic acid and zinc diketone enolate are preferable because of their excellent reactivity.
As the catalyst Y, zinc acetate, zinc propionate, zinc acrylate and zinc methacrylate, which are examples of organic zinc acid, are preferable, and zinc acetylacetonate, which is an example of zinc diketone enolate, is preferable.
Among them, as the catalyst Y, zinc acetate, zinc acrylate, and zinc acetylacetonate, which show good reactivity with most polyhydric alcohols and are easily available, are particularly preferable.

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, and it is 0. It is more preferable to use 0.05 to 5.0 mol. By using 0.005 mol or more of the catalyst X with respect to 1 mol of the catalyst Y, the amount of the desired polyfunctional (meth) acrylate produced can be increased, and by setting the amount to 10.0 mol or less, the subordinate It is possible to suppress the formation of a product and the coloring of the reaction solution, and simplify the purification step after the reaction is completed.

As a combination of the catalyst X and the catalyst Y, a combination in which the catalyst X is an azabicyclo compound and the catalyst Y is zinc organic acid is preferable, the azabicyclo compound is DABCO, and the zinc organic acid is zinc acetate and / or acrylic acid. A combination that is zinc is particularly preferred.
In addition to obtaining (poly) glycerin poly (meth) acrylate in good yield, this combination has excellent color tone after completion of the reaction (for example, low yellowness), so that it is colorless and transparent such as clear varnish and hard coat. Can be suitably used for applications where is important. Further, since the above-mentioned catalyst is available at a relatively low cost, it is an economically advantageous manufacturing method.

The reaction temperature in the method for producing the component (A) is preferably 40 to 180 ° C, more preferably 60 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 may be produced as a by-product as the transesterification reaction progresses.
When a part of the hydroxyl group (for example, about 50 mol%) of (poly) glycerin is (meth) acrylated, the monohydric alcohol is allowed to coexist in the reaction system to bring it into an equilibrium state, and the catalyst is adsorbed and removed or deactivated. After that, by distilling off the monohydric alcohol and the monofunctional (meth) acrylate of the raw material, a product having a controlled acrylate conversion rate can be stably produced.

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 hydrocarbons, ethers, crown ethers, esters, ketones, carbonate compounds, sulfones, sulfoxides, ureas or derivatives thereof, phosphine oxides, ionic liquids, silicon oil and water. And so on.
Among these solvents, hydrocarbons, ethers, carbonate compounds and ionic liquids are preferred.
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 (meth) acryloyl may be introduced. An oxygen-containing gas may be introduced into the system for the purpose of preventing the polymerization of the group. 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.
Examples of the polymerization inhibitor include organic polymerization inhibitors, inorganic polymerization inhibitors and organic salt polymerization inhibitors.
Specific examples of the organic polymerization inhibitor include hydroquinone, tert-butylhydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-4-methylphenol, 2,4,6-tri-tert-butylphenol and 4 -Phenolic compounds such as tert-butylcatechol, quinone compounds such as benzoquinone, phenothiazine, N-nitroso-N-phenylhydroxylamineammonium, N-oxyl compounds and the like can be mentioned.
Examples of the N-oxyl compound include 2,2,6,6-tetramethylpiperidine-1-oxyl, 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl, 4-oxo-2,2. , 6,6-Tetramethylpiperidine-1-oxyl and 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl and the like.
Among the above-mentioned compounds, it is preferable to use an N-oxyl compound as the polymerization inhibitor. As the N-oxyl compound, the above-mentioned compound is preferable.
Further, as the polymerization inhibitor, it is preferable to use an N-oxyl compound and other polymerization inhibitors in combination. In that case, as the polymerization inhibitor other than the N-oxyl compound, a phenol-based compound and phenothiazine are preferable, and a phenol-based compound is more preferable.
The polymerization inhibitor may be added alone or in combination of two or more, or may be added from the beginning of the method for producing the component (A), or may be added from the middle. May be good. Further, the desired amount to be used may be added all at once or may be added in divided portions. Further, it may be continuously added via the rectification tower.
The addition ratio of the polymerization inhibitor is preferably 5 to 30,000 wtppm, more preferably 25 to 10,000 wtppm with respect to the total weight of the reaction solution. By setting the addition ratio of the polymerization inhibitor to 5 wtppm or more, the polymerization prohibition effect can be exhibited, and by setting it to 30,000 wtppm or less, the coloring of the reaction solution can be suppressed, and the purification step after the reaction is completed can be simplified. In addition, it is possible to suppress a decrease in the curing rate of the obtained component (A).

3) The content ratio or less, the component (A), or the component (A) and the component (C) are collectively referred to as a curable component. The content ratio of the curable component in the curable composition is preferably 30 to 99% by weight, more preferably 40 to 80% by weight, when the total amount of the curable composition is 100% by weight.
By setting the ratio of the curable component in the curable composition to 30% by weight or more, the hardcourt property of the cured film of the curable composition can be sufficiently obtained, the surface resistance can be sufficiently reduced, and 99. By weight% or less, sufficient antifogging property can be imparted to the cured film of the curable composition, and the curability when irradiated with active energy rays can be excellent.

2. 2. Component (B) The component (B) is a compound having an ethylenically unsaturated group and an ionic group.
The component (B) is a component that imparts good anti-fog property and low surface resistance necessary for preventing dust adhesion to the cured film by curing the curable composition. The component (B) can maintain excellent antifogging properties even if the surface of the cured film is wetted or wiped by reacting with an ethylenically unsaturated group and chemically bonding in the cured film. , It can be repeatedly made excellent in antifogging property.

The content ratio of the component (B) is preferably 0.01 to 20 parts by weight, more preferably 1 to 15 parts by weight, based on 100 parts by weight of the total amount of the curable component.
By setting the ratio of the component (B) to 0.01 weight or more, the anti-fog property and low surface resistance of the cured film of the composition can be improved, and by setting it to 20 parts by weight or less, the cured film can be improved. It can be excellent in hard coat property and adhesion to a base material.

As the component (B), 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 (B), the (meth) acryloyl group is preferable because the reactivity with the component (A) and the component (C) described later is good and the curability is excellent. Groups are more preferred.

Since the component (B) has an ionic group, anti-fog property and low surface resistance can be obtained 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 (B), examples of the ionic group include salts of strong acids, specifically, sulfonates such as ammonium sulfonate, sodium sulfonate and potassium sulfonate, ammonium alkyl sulphate, sodium alkyl sulphate and potassium alkyl sulphate and the like. Alkyl sulfate, and carboxylates such as ammonium carboxylate, sodium carboxylate and potassium carboxylate can be mentioned.

As the ionic group, an alkyl sulfate or a sulfonic acid base is preferable because a desired effect can be obtained even when the content ratio of the component (B) 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.
Among these, it is more preferable that methylethanolamine, ethylethanolamine, dimethylethanolamine, diethylethanolamine, or lauryldiethanolamine are protonated ions, and methylethanolamine, ethylethanolamine, or lauryldiethanolamine is each. It is more preferably a protonated ion, further preferably a protonated ion of methylethanolamine, dimethylethanolamine or ethylethanolamine, respectively, and a protonated ion of ethylethanolamine. Especially preferable.

The ionic group of the component (B) 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 (B) include the following components (B-1) and (B-2), both of which can be used.
Component (B-1): Compound consisting of a cation having an ethylenically unsaturated group in one molecule and an anion (B-2) Component: An anion having an ethylenically unsaturated group in one molecule and a cation Compound consisting of

The component (B-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 species selected from the group can be exemplified.

Specific examples of cations having an ethylenically unsaturated group in one molecule include ethylammonium dimethylmono (meth) acrylate (that is, quaternary ammonium ion of dimethylaminoethyl (meth) acrylate) and diethylmono (meth). ) Dialkyl mono (meth) alkylammonium acrylate ions such as ethylammonium acrylate ion (ie, quaternary ammonium ion of diethylaminoethyl (meth) acrylate), as well as 1,2,2,6,6-pentamethyl-4-(. Meta) Acrylate piperidinium ion and the like can be mentioned as suitable ones.
In the above 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 (B-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 alkoxypolyethylene glycol sulfonic acid, an anion of an alkyl group-containing aromatic sulfonic acid such as isopropylbenzene sulfonic acid, and the like.

The component (B-1) is preferably a compound composed of an alkylammonium ion of dialkylmono (meth) acrylate and an anion of a sulfonic acid having a polyoxyalkylene unit.

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

The component (B-2) is a compound composed of an anion having an ethylenically unsaturated group in one molecule and a cation.
Specific examples of the component (B-2) include the following examples as examples in which the anionic group is a sulfonic acid ion.
That is, polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt, polyoxyethylene nonylpropenylphenyl ether sulfate ammonium salt, α-sulfo-ω- (1- (alkoxy) methyl, in which the cation is ammonium ion. -2- (2-Propenyloxy) ethoxy) -poly (oxy-1,2-ethandyl) ammonium salt, and bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate ester ammonium salt, and
2-Sodium sulfoethyl methacrylate, alkylallyl sulfosuccinate sodium salt, (meth) chryloyl polyoxyalkylene sodium sulfate, and bis (polyoxyethylene polycyclic phenyl ether) methacrylate sulfate sodium salt, the cations are sodium ions,
And so on.

As the component (B-2), a commercially available product can be used.
For example, as polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt, trade names "Aqualon KH-10", "Aqualon KH-1025", and "Aqualon KH" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. -05 ";
As the polyoxyethylene nonylpropenylphenyl ether ammonium sulfate ammonium salt, the trade names "Aqualon HS-10", "Aqualon HS-1025", "Aqualon BC-0515", "Aqualon BC-10" manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd. , "Aquaron BC-1025" and "Aquaron BC-20" and "Aquaron BC-2020";
The α-sulfo-ω- (1- (alkoxy) methyl-2- (2-propenyloxy) ethoxy) -poly (oxy-1,2-ethandyl) ammonium salt is a trade name manufactured by ADEKA CORPORATION. "Adecaria 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 Emulsium Co., Ltd.;
As the alkylallyl succinate sulfonic acid sodium salt, the trade name "Antox SAD" manufactured by Nippon Emulsorium Co., Ltd .;
As 2-sodium sulfoethyl methacrylate, the trade name "Antox MS-2N" manufactured by Nippon Emulsor Co., Ltd .;
As the sodium alkylallyl sulfosuccinate salt, the trade name "Eleminol JS-20" manufactured by Sanyo Chemical Industries, Ltd .; and as the sodium methacryloylpolyoxyalkylene sulfate, the trade name "Eleminol" manufactured by Sanyo Chemical Industries, Ltd. RS-3000 ",
And so on.

As the component (B), the component (B-1) is preferable because it is more excellent in anti-fog durability than the component (B-2).
The details of the reason why the component (B-1) is superior to the antifogging durability are unknown, but the cation as a counterion (for example, ammonium ion) probably constituting the component (B-2) is more compatible with water. On the other hand, the anions as counterions (for example, alkyl sulfonic acid ion, alkyl benzene sulfonic acid ion, alkyl naphthalene sulfonic acid ion, and polyoxyethylene alkyl sulfate ion) constituting the component (B-1) are slightly hydrophobic. It is presumed that due to its properties, the elution of the surface of the cured film due to moisture is reduced.

3. 3. Curable Composition The present invention is a curable composition containing the components (A) and (B).
As a method for producing the curable composition of the present invention, the components (A) and (B) and, if necessary, other components described later may be stirred and mixed.
When the components (A) and (B) and other components described later are mixed as necessary, they may be heated and stirred as necessary. The temperature in the case of heating, stirring and mixing is preferably in the range of 40 to 90 ° C. However, when the thermal polymerization initiator described later is blended, it is preferably carried out at 30 ° C. or lower in order to prevent polymerization during the production of the curable composition.

The viscosity of the curable composition may be appropriately set according to the intended use and purpose. The viscosity of the cured composition is preferably 5 to 10,000 mPa · s, more preferably 10 to 1,000 mPa · s. When the viscosity becomes high, it is difficult to obtain a cured film having excellent surface smoothness as a thin film, and therefore the desired viscosity may be appropriately adjusted with a solvent.
In the present invention, the viscosity means a value measured at 25 ° C. with an E-type viscometer.

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

1) Component (C) The component (C) is a compound having an ethylenically unsaturated group other than the components (A) and (B).
The component (C) is an arbitrary component used for adjusting the viscosity and other physical characteristics of the composition, and various components can be used.
As the component (C), a compound having one ethylenically unsaturated group (hereinafter, also referred to as "monofunctional unsaturated compound") and a compound having two or more ethylenically unsaturated groups (hereinafter, "many"). It is called a "functional unsaturated compound").

(1) Monofunctional unsaturated compound As an example of the monofunctional unsaturated compound, a (meth) acrylate having one (meth) acryloyl group (hereinafter, also referred to as “monofunctional (meth) acrylate”) and one. (Meta) acrylamide compound having a (meth) acryloyl group (hereinafter, also referred to as “monofunctional (meth) acrylamide”) 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;
Cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, and dicyclopentenyloxyethyl (meth) acrylate Monofunctional (meth) acrylate having an alicyclic group such as;
Glycidyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl (meth) acrylate, cyclohexanespiro-2- (1,3-dioxolan) Monofunctional (meth) acrylates with cyclic ether groups such as -4-yl) methyl (meth) acrylates and 3-ethyl-3-oxetanylmethyl (meth) acrylates;
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;
Monofunctional (meth) acrylates having an alkoxyalkyl group such as ethyl carbitol (meth) acrylates and alkyl carbitol (meth) acrylates such as 2-ethylhexyl carbitol (meth) acrylates,
And so on.

Specifically, as monofunctional (meth) acrylamide,
N-methyl (meth) acrylamide, Nn-propyl (meth) acrylamide, N-isopropyl (meth) acrylamide, Nn-butyl (meth) acrylamide, N-sec-butyl (meth) acrylamide, Nt- N-alkyl (meth) acrylamide such as butyl (meth) acrylamide and Nn-hexyl (meth) acrylamide;
N-hydroxyalkyl (meth) acrylamide such as N-hydroxyethyl (meth) acrylamide;
N, N-dimethylaminoethyl (meth) acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N, N-di- N, N-dialkyl (N, N-dialkyl such as n-propyl (meth) acrylamide, N, N-diisopropyl (meth) acrylamide, N, N-di-n-butyl (meth) acrylamide, and N, N-dihexyl (meth) acrylamide. Meta) acrylamide,
And so on.

(2) Polyfunctional unsaturated compound As an example of the polyfunctional unsaturated compound, a (meth) acrylate having two (meth) acryloyl groups (hereinafter, also referred to as “bifunctional (meth) acrylate”) and two. Examples thereof include (meth) acrylates having the above (meth) acryloyl groups (hereinafter, also referred to as “trifunctional or higher (meth) acrylates”).
Specifically, as the bifunctional (meth) acrylate,
Di (meth) acrylate of alkylene oxide adduct of bisphenol A, di (meth) acrylate of alkylene oxide adduct of bisphenol F, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, and nonanediol di (meth). ) Didiole (meth) acrylates such as acrylates;
Di (meth) acrylate of polyols such as di (meth) acrylate of dipentaerythritol;
Di (meth) acrylates of these polyol alkylene oxide adducts;
Di (meth) acrylate of isocyanuric acid;
Di (meth) acrylate of isocyanuric acid alkylene oxide adduct, etc.
Can be mentioned.
Examples of the alkylene oxide in the alkylene oxide adduct in this case include ethylene oxide, propylene oxide, and tetramethylene oxide.

Specifically, as a trifunctional or higher (meth) acrylate,
Glycerintri (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dimethylolpropane tri (meth) acrylate, trimethylolpropane tetra (meth) acrylate, Polypoly (meth) acrylates of polyols such as dipentaerythritol tetra (meth) acrylates, dipentaerythritol penta (meth) acrylates, and dipentaerythritol hexa (meth) acrylates;
Di (meth) acrylates of these polyol alkylene oxide adducts;
Tris (2- (meth) acryloyloxyethyl) isocyanurate, etc .;
Tri (meth) acrylate of isocyanuric acid alkylene oxide adduct,
And so on.
Examples of the alkylene oxide in the alkylene oxide adduct in this case include ethylene oxide, propylene oxide, and tetramethylene oxide.

The content ratio of the component (C) is preferably 1 to 30 parts by weight, more preferably 5 to 25 parts by weight, and 10 to 20 parts by weight with respect to 100 parts by weight of the total amount of the curable component. Is more preferable. When the content ratio of the component (C) is in the above range, the physical properties can be adjusted without impairing the excellent substrate adhesion characteristic of the composition of the present invention.

2) Component (D) When the curable 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 (D) (that is, a photopolymerization initiator) is used. It is also possible to cure with an electron beam without containing.
When the curable composition of the present invention is used as an active energy ray-curable composition, particularly when ultraviolet rays or visible light are used as the active energy ray, the component (D) is considered from the viewpoint of ease of curing and cost. It is preferable to further contain.
When used as an electron beam curable composition, it is not always necessary to contain the component (D), but a small amount may be added as needed in order to improve the curability.

As the component (D) in the present invention, various known photopolymerization initiators can be used.
Further, the component (D) is preferably a photoradical polymerization initiator.
As a specific example of the component (D),
2,2-Dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropane-1-one, 1-[4- (2-hydroxy) Ethoxy) Phenyl] -2-hydroxy-2-methyl-1-propane-1-one, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1-one, 2-benzyl- 2-Dimethylamino-1- (4-morpholinophenyl) butane-1-one, diethoxyacetophenone, oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone}, And 2-hydroxy-1-{4- [4- (2-hydroxy-2-methylpropionyl) benzyl] phenyl} -2-methylpropan-1-one and other acetophenone compounds;
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) phenylphosphin oxide, and bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine Phosphine oxide compounds such as oxide;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether;
Titanocene compound;
Acetophenone / benzophenone hybrid photoinitiators such as 1- [4- (4-benzoylphenyl sulfanyl) phenyl] -2-methyl-2- (4-methylphenylsulfinyl) propan-1-one;
Oxime ester-based photopolymerization initiators such as 2- (O-benzoyloxime) -1- [4- (phenylthio)] -1,2-octanedione;
Camphorquinone,
And so on.

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. Therefore, an acetophenone-based compound is particularly preferable.

The content ratio of the component (D) 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 component. It is particularly preferable that the amount is up to 5 parts by weight. When the content ratio of the component (D) is in the above range, the curability of the composition is excellent, and the scratch resistance of the obtained cured film is excellent.

3) Component (E) The component (E) is a thermosetting initiator, and when the curable composition is used as the thermosetting composition, the component (E) can be blended.
The curable 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 and 1,1-bis (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1 , 1-bis (t-hexylperoxy) cyclohexane, 1,1-bis (t-butylperoxy) -3,3,5-trimethylcyclohexane, 1,1-bis (t-butylperoxy) cyclohexane, 2, , 2-bis (4,4-di-butylperoxycyclohexyl) propane, 1,1-bis (t-butylperoxy) cyclododecane, t-hexylperoxyisopropylmonocarbonate, t-butylperoxymaleic acid, t-Butylperoxy-3,5,5-trimethylhexanoate, t-butylperoxylaurate, 2,5-dimethyl-2,5-di (m-toroil peroxy) 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 the azo compound 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.
The organic peroxide and the azo compound may be used alone or in combination of two or more. Further, the organic peroxide can be subjected to a redox reaction by combining with a reducing agent.

The content ratio of the component (E) 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 a known means of radical thermal polymerization, and in some cases, it may be used in combination with the component (D) (that is, a photopolymerization initiator) and further reacted after being photocured. Thermosetting can also be performed for the purpose of improving the rate.

4) Other components other than the above As the other components other than the above, known additives can be used, and for example, organic solvents, ultraviolet absorbers, light stabilizers, acidic substances, inorganic particles, and antioxidants can be used. , Silane coupling agents, surface modifiers, polymers, acid generators, pigments, dyes, tackifiers, polymerization inhibitors and the like.

<Organic solvent>
The composition of the present invention can be used without containing an organic solvent, but various organic solvents can be used for the purpose of adjusting the coating viscosity and the film thickness. Specifically, alcohol compounds such as methanol, ethanol, isopropanol, and butanol; alkylene glycol monoether compounds such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; benzene, toluene, xylene and the like. Aromatic compounds; 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. Be done.

The content ratio of the organic solvent is preferably 0.01 to 200 parts by weight, more preferably 10 to 150 parts by weight, and 20 to 100 parts by weight with respect to 100 parts by weight of the total amount of the composition. It is more preferable to have.

<Anti-fog modifier>
In the cured composition of the present invention, the cured film has excellent anti-fog properties, but especially when it is used as an active energy ray-curable composition, when the irradiation condition of the active energy ray is a high irradiation amount. In some cases, the anti-fog performance was insufficient. Further, in the curable composition of the present invention, the cured film is repeatedly excellent in anti-fog property, but it may be necessary to further improve the initial anti-fog property depending on the intended use. For these purposes, an anti-fog modifier can be added to the extent that it does not adversely affect the other performance of the present invention.
Examples of the anti-fog 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 dialkylsulfosuccinates such as di (2-ethylhexyl) sulfosuccinate and di (2-ethylhexyl) ammonium 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; naphthalenesulfonate 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 anti-fog property.
Dialkyl sulfosuccinates are commercially available and commercially available products can be used. The sodium salts of di (2-ethylhexyl) sulfosuccinate include Ricasurf P-10 (solution of the same compound), M-30 (solution of the same compound) and G-30 (propylene glycol of the same compound) manufactured by Shin Nihon Rika Co., Ltd. / Water mixed solution), and Lapizol A30, A70, A80, and A90 manufactured by Nichiyu Co., Ltd. can be mentioned. Examples of the di (2-ethylhexyl) ammonium salt sulfosuccinate include Ricasurf G-600 [propylene glycol / water mixed solution of the same compound] manufactured by New Japan Pro-Wrestling Corporation.

Examples of the cationic surfactant include amine salts such as ethanolamines, laurylamine acetate, triethanolamine monoaterate, and stearamide ethyldiethylamine acetate, lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and dilauryldimethylammonium chloride. , A quaternary ammonium salt such as distealyldimethylammonium 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 anti-fog property, and dialkyl sulfosuccinate is more preferable as described above.

The content ratio of the anti-fog modifier is preferably 0.1 to 10% by weight in 100% by weight of the total amount of the composition of the present invention. Within the above range, the initial anti-fog property can be excellent without impairing the repeated anti-fog property of the cured film.

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

The above-mentioned ultraviolet absorber is used for the purpose of suppressing discoloration of a plastic base material that tends to yellow due to irradiation with active energy rays, and when an article having a cured film formed is used outdoors, it is an article due to sunlight. It is used for the purpose of preventing deterioration of.
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 photostabilizer 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-tetramethylpiperidine-4-yl) amino] -6- (2-hydroxyethylamine) -1,3 , 5-Triazine, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester and the like.
Examples of commercially available products of the hindered amine-based light stabilizer include TINUVIN 111FDL, TINUVIN123, TINUVIN 144, TINUVIN 152, TINUVIN 292, and TINUVIN 5100 manufactured by BASF.

The content ratio of the light stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 2 parts by weight, and 0. It is more preferably 1 to 1 part by weight.

<Acid substance>
The composition of the present invention is excellent as an adhesive material to a substrate 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.
Among these, inorganic acids or organic acids are preferable. As the inorganic acid, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid and the like are more preferable. As the organic acid, an organic sulfonic acid compound such as p-toluene sulfonic acid or methane sulfonic acid is more preferable, an aromatic sulfonic acid compound is further preferable, and p-toluene sulfonic 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 component. It is more preferably to 0.5 parts by weight. When the content ratio of the acidic substance is in the above range, the adhesion of the composition to the base material is excellent, 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, trialkyl phosphite, and triaryl phosphite. Commercially available products of these derivatives include, for example, ADEKA CORPORATION PEP-4C, PEP-8, PEP-24G, PEP-36, HP-10, 260, 522A, 329K, 1178, 1500, 135A, 3010. And so on.
Examples of the sulfur-based antioxidant include thioether-based compounds, and examples of commercially available products include AO-23, AO-412S, and AO-503A manufactured by ADEKA CORPORATION.

The content ratio of the antioxidant is preferably 0.01 to 5 parts by weight, more preferably 0.1 to 1 part by weight, based on 100 parts by weight of the total amount of the composition of the present invention. When the content ratio of the antioxidant is in the above range, the stability of the composition is excellent, and the curability and the 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 coating and the purpose of increasing the slipperiness of the cured film to enhance the scratch resistance.
Examples of the surface modifier include a surface conditioner, a surfactant, a leveling agent, a defoaming agent, a slipperiness-imparting agent, an antifouling agent, and the like, and these known surface modifiers can be used. can.
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, as well as 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 parts by weight with respect to 100 parts 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 on 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 sulfone group, a phosphine group and the like, and a carboxyl group and a sulfone group are preferable, and a carboxyl group is more preferable.
As the polymer in which the hydrophilic polymer has an acidic group (hereinafter, referred to as “acidic group-containing polymer”), a neutralized salt in which a part or all of the acidic group is neutralized is preferable. As a method for producing a neutralized salt of the acidic group-containing polymer, a method for producing a neutralized salt as a raw material vinyl-based monomer and a method for producing the acidic group-containing polymer and then neutralizing the polymer are performed. 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 sulfone 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 sulfone group include acrylamide 2-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.
The alkaline compounds for forming the neutralizing salt of the vinyl-based monomer having an acidic group include hydroxides of alkali metals such as sodium hydroxide, potassium hydroxide and lithium hydroxide; ammonia; and triethylamine and triethanol. Examples thereof include amine compounds such as amine.

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

The hydrophilic polymer may be a copolymer of a vinyl-based monomer (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, alkylvinyl ether, vinylidene chloride, (meth) acrylamide, N-vinylformamide, N-vinylacetamide, vinyl acetate, vinylpyrrolidone, etc. Examples thereof include (meth) acrylic nitrile and (meth) acryloylmorpholine.
Examples of the alkyl (meth) acrylate 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 weight average molecular weight (hereinafter referred to as “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 gel permeation chromatography (hereinafter referred to as “GPC”) using standard polystyrene as a calibration curve, and carboxylic acid or the like as an acid component. It is a value measured before neutralizing the acidic group of. 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 of a hydrophilic polymer and water, 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. Can be prevented.

4. Method of Use As a method of using the curable composition of the present invention, a known method may be followed.
For example, a method of applying the composition to the applied substrate by a usual coating method and then irradiating it with active energy rays or heating it to cure it can be mentioned.
As the method of irradiating the active energy rays, a general method known as a conventional curing method may be adopted.
Further, the composition is adhered to the substrate by using the component (D) (photopolymerization initiator) and the component (E) (thermal polymerization initiator) in combination, irradiating them with active energy rays, and then heating and curing them. A method of improving sex can also be adopted.

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

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

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 cured film of the cured composition may be appropriately set according to the 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 curable composition contains an organic solvent, it is preferable to apply it to a substrate and then heat and dry it to evaporate the organic solvent.
The drying temperature is not particularly limited as long as the applied base material is at a temperature or lower that does not cause problems such as deformation. The preferred heating temperature is 40 to 100 ° C. The drying time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 3 minutes.

When the curable 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 light and visible light, but ultraviolet light or visible light is preferable. Ultraviolet light is particularly preferred. Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, an ultraviolet (UV) electrodeless lamp, and a light emitting diode (LED).
The irradiation energy should be appropriately set according to the type of active energy ray and the composition of the compound. For example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is 100 to 8,000 mJ /. cm ² is preferable, and 200 to 3,000 mJ / cm ² is more preferable. When the irradiation energy is 1,000 mJ / cm ² or more, the anti-fog performance of the cured film may be insufficient. In this case, it is preferable to add the anti-fog modifier described above.

When the curable composition of the present invention is thermally cured, the cured film can be obtained by allowing the cured film to stand in a heatable dryer or the like. The drying time may be appropriately set depending on the substrate to be applied and the heating temperature, and is preferably 0.5 to 60 minutes.

5. Applications The curable composition of the present invention can be used for various purposes, can be used as a coating agent, an ink, or the like, and can be preferably used as a coating agent.

Specific examples of the coating agent include an anti-fog coating agent and a dust adhesion prevention coating agent.
Examples of applications of the anti-fog coating agent include protective glasses, goggles, inner walls of bathrooms, members around kitchens, and glass and plastic used in head lamp covers and rear lamp covers of automobiles and motorcycles. Examples of the application of the dust adhesion prevention coating agent include a plastic base material and a floor surface.

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.

1. 1. Manufacturing example
1-1) Production Example 1 [Production of acrylate containing component (A)]
Glycerin (refined glycerin manufactured by Sakamoto Yakuhin Kogyo Co., Ltd. (trade name); hereinafter also referred to as "GLY") is placed in a 3-liter flask equipped with a stirrer, a thermometer, a gas introduction tube, a rectification tower and a cooling tube. 302.75 parts (3.29 mol), 2-methoxyethyl acrylate (hereinafter, also referred to as “MCA”) 2312.84 parts (17.77 mol), and DABCO 6.51 parts (0. 06 mol), 24.07 parts (0.12 mol) of zinc acrylate as catalyst Y, 1.19 part (0.01 mol) of hydroquinone monomethyl ether (hereinafter, also referred to as “MEHQ”), and 0. Twenty-one parts (0.002 mol) were charged, and an oxygen-containing gas (5% by volume of oxygen and 95% by volume of nitrogen) was bubbled into the liquid.
The pressure in the reaction system was adjusted in the range of 110 to 760 mmHg while heating and stirring in the reaction solution temperature range of 100 to 130 ° C., and 2-methoxyethanol produced as a by-product with the progress of the transesterification reaction with MCA (hereinafter, "" The mixed solution with "MEL") was withdrawn from the reaction system via a rectification column and a cooling tube. In addition, MCA of the same weight as the withdrawal liquid was added to the reaction system at any time. Eighteen hours after the start of heating and stirring, the pressure in the reaction system was returned to normal pressure to complete the extraction.
As a result of determining the acrylateration rate of the hydroxyl group of GLY from the amount of MEL produced, it was 58 mol%.
After cooling the reaction solution to room temperature and filtering and separating the precipitate, aluminum silicate (Kyoward 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.) is used to adsorb and remove the catalyst X and the catalyst Y contained in the filtrate. Was added in 58.7 parts and stirred, and further heated and stirred in the range of 70 to 100 ° C. for 1 hour. After the aluminum silicate after the adsorption treatment is filtered and separated, the filtrate is placed in a flask connected to a stirrer, a thermometer, a gas introduction tube, a cooling tube for distillation, and a tube for decompression, and the temperature is 70 to 100 ° C. Distillation was carried out under reduced pressure for 10 hours while bubbling dry air in the range of 0.001 to 100 mmHg, and the distillate containing unreacted MCA was separated. 5.0 parts of diatomaceous earth (Radiolite (trade name) manufactured by Showa Chemical Industry Co., Ltd.) was added to the kettle liquid and subjected to pressure filtration, and the obtained filtrate was used as the component (A). The yield of the component (A) was 651 parts. Hereinafter, this is referred to as A-1.
The yield when all of the charged GLY 302.75 parts are converted to glycerin diacrylate (hereinafter, also referred to as "GLY-DA") is 658 parts, but the yield of A-1 calculated based on this is 658 parts. It was 99%.
As a result of calculating the purity of each component contained in A-1 by the following formula (3) using HPLC equipped with a UV detector, GLY-DA was 62%, and glycerin triacrylate (hereinafter, "GLY-"). (Also referred to as "TA") was 33%, and glycerin monoacrylate (hereinafter, also referred to as "GLY-MA") was 5%.
The obtained component (A) had a viscosity of 43 mPa · s (25 ° C.) and a hydroxyl value of 238 mgKOH / g. The Mw (Molecular weight) measured by GPC (Gel Permeation Chromatography) was 314.

The HPLC, viscosity, hydroxyl value, GPC and GC (Gas Chromatography) were measured under the following conditions.
◆ HPLC measurement conditions / equipment: ACQUITY UPLC manufactured by Waters Corp.
・ Detector: UV detector ・ Detection wavelength: 210nm
-Column: ACQUITY UPLC BEH C18 (Part No. 186002350, column inner diameter 2.1 mm, column length 50 mm) manufactured by Waters Corp.
-Column temperature: 40 ° C
-Eluent composition: 0.03 wt% trifluoroacetic acid aqueous solution and methanol mixed solution-Eluent flow rate: 0.3 mL / min

◆ (A) Purity calculation method of GLY-DA contained in the component GLY-DA purity (%)
= [(D × 1.27) / (M × 1.74 + D × 1.27 + T)] × 100… Equation (3)
D, M, and T in the calculation formula (3) mean the following values obtained by analyzing the component (A) using HPLC equipped with an ultraviolet (UV) detector.
-D: Peak area of GLY-DA at 210 nm-M: Peak area of GLY-MA at 210 nm-T: Peak area of GLY-TA at 210 nm

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

◆ Hydroxylity value measurement conditions Add an acetylation reagent to the sample and heat-treat it in a warm bath at 92 ° C for 1 hour. After allowing to cool, a small amount of water is added and heat-treated in a warm bath at 92 ° C. for 10 minutes. After allowing to cool, the acid was titrated with a potassium hydroxide ethanol solution using a phenolphthalein solution as an indicator to determine the hydroxyl value.

◆ 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) and stylel HR 1 THF (7.8 x 300 mm)
-Column temperature: 40 ° C
-Eluent composition: THF (containing 0.03% sulfur as an internal standard), flow rate 0.75 mL / min-calibration curve: Calibration curve was created using standard polystyrene.
-Of the detection peaks derived from the component (A), the detection peaks derived from monofunctional (meth) acrylate, the solvent, and the peaks having a slower retention time than the peaks derived from water are not considered in the calculation of Mw. , And other multiple detected peaks were regarded as one peak, and Mw was calculated.

1-2) Production Example 2 [Production of acrylates other than component (A)]
302.71 parts (3.29 mol) of GLY and 2312.76 parts (17.77 mol) of MCA in a 3 liter flask equipped with a stirrer, thermometer, gas introduction tube, rectification tower and cooling tube. As catalyst X, DABCO is 9.76 parts (0.087 mol), catalyst Y is zinc acrylate 36.10 parts (0.17 mol), MEHQ is 1.60 parts, 4-hydroxy-2,2. 0.074 parts of 6,6-tetramethylpiperidin-1-oxyl (hereinafter, also referred to as "TEMPOL") and 5.00 parts (0.28 mol) of pure water were charged, and oxygen-containing gas (5% by volume of oxygen) was charged. , 95% by volume of nitrogen) was bubbled into the liquid. The pressure in the reaction system was adjusted in the range of 150 to 760 mmHg while heating and stirring in the reaction solution temperature range of 105 to 130 ° C., and the mixed solution of MCA and MEL produced as a by-product with the progress of the transesterification reaction was rectified. It was withdrawn from the reaction system via a column and a cooling tube. In addition, MCA of the same weight as the withdrawal liquid was added to the reaction system at any time. In addition, MCA containing MEHQ and TEMPOL was added to the reaction system at any time via a rectification column. Forty hours after the start of heating and stirring, the pressure in the reaction system was returned to normal pressure to complete the extraction.
As a result of determining the acrylateration rate of the hydroxyl group of GLY from the amount of MEL produced, it was 91 mol%.
The obtained reaction product was cooled to room temperature, and the precipitate was separated by pressure filtration.
14 parts of aluminum silicate (Kyoward 700 (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.) was added to the filtrate, heated and stirred under normal pressure for 1 hour at an internal temperature of 80 to 105 ° C., and then contacted inside. 27 parts of calcium hydroxide was added in a temperature range of 20 to 40 ° C., and the mixture was stirred under normal pressure for 1 hour.
After separating the insoluble material by pressure filtration, vacuum distillation is performed for 16 hours at a temperature of 70 to 98 ° C. and a pressure of 0.001 to 100 mmHg while bubbling dry air in the filtrate, and unreacted MCA is contained. The distillate was separated.
The obtained kettle solution was cooled to room temperature, 0.16 part (0.0018 mol) of N, N-diethylhydroxylamine was added, and the mixture was stirred under normal pressure for 1 hour. Then, 8.0 parts of activated carbon (Taiko S (trade name) manufactured by Futamura Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour for contact treatment, and then the solid matter containing activated carbon was separated by pressure filtration to obtain a filtrate. rice field. Hereinafter, this filtrate is referred to as A'-1.
As a result of calculating the purity of each component contained in A'-1 from the above formula (3) using HPLC equipped with a UV detector, GLY-DA was 8% and GLY-TA was 92%. rice field.
The obtained component (A) had a viscosity of 26 mPa · s (25 ° C.) and a hydroxyl value of 16 mgKOH / g. The Mw measured by GPC was 338.

2. 2. Examples 1 to 11 and Comparative Examples 1 to 5 (preparation of curable composition)
Each component shown in Tables 1 to 3 below was stirred and mixed at 40 ° C. to obtain a curable composition.
The viscosity of the obtained cured composition was measured at 25 ° C. with an E-type viscometer. The curable composition of Example 7 was obtained by stirring and mixing the components other than the component (E) at 40 ° C., cooling to 30 ° C., and then dissolving the component (E).

3. 3. Evaluation of Plastic Substrate A Polycarbonate manufactured by Mitsubishi Engineering Plastics Co., Ltd., Iupiron NF2000 (150 mm × 70 mm × 1 mm) obtained by cutting the obtained curable compositions of Examples 1 to 11 and Comparative Examples 1 to 5 using a bar coater. A test piece was prepared by coating the material with a thickness of 10 μm.
The compositions of Examples 10 and 11 were applied to the substrate and then dried at 80 ° C. for 90 seconds.
Next, using a high-pressure mercury lamp equipped with a conveyor (H06-L 41 manufactured by Eye Graphics Co., Ltd.), a UV-A lamp output illuminance of 80 W / cm and an irradiation intensity of 250 mW / cm ² per pass (pass). The test piece was irradiated with ultraviolet rays under the condition that the irradiation energy was 400 mJ / cm ² . As an index of active energy ray curability, the number of passes until the tack on the surface of the cured film disappeared was evaluated. The smaller the number of passes, the better the curability.
The curable composition of Example 7 was heated for 60 minutes in a dryer at 80 ° C. with nitrogen flowing at 5 mL / min.
The obtained cured film was used and evaluated according to the following method. The results are shown in Tables 4 to 6.

1) Adhesion In the cured film obtained, cuts with a cutter knife at intervals of 1 mm in length and width are made to form 100 squares with a size of 1 mm x 1 mm, and Nichiban Co., Ltd. # 405 is formed on this grid. After applying the cellophane tape, it was strongly peeled off. The number of residual films after exfoliation was evaluated. The larger the number of residual films, the better the adhesion.

2) Pencil hardness The obtained cured film was measured for pencil hardness under a load of 750 g according to JIS K5600-5-4.

3) The anti-fog persistent cured film was exposed to steam at 80 ° C. for 1 minute, and evaluated by whether or not the cured film became cloudy. Further, the anti-fog 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 after the evaluation. In addition, A, B, and C in Tables 3 and 4 represent the following meanings.
A: Not cloudy, B: Slightly cloudy, C: Cloudy

4) Surface resistivity The surface resistivity of the cured film formed on a PET film (A-4300 manufactured by Toyobo Co., Ltd.) with a film thickness of 188 μm under the above coating and curing conditions is measured by the surface resistivity meter (Dia Instruments Co., Ltd., Lorester GP). It was measured by MCP-T600) and used as the surface resistivity immediately after patterning. These results are shown in Table 1. (Ω / □): Ohm / square is a unit of surface resistivity, and the smaller this value is, the smaller the surface resistivity is.
The measurement was carried out in two ways: the cured film immediately after curing and the cured film after the anti-fog durability test was performed.

The abbreviations in Tables 1 to 3 mean the following. The numerical values in parentheses in Tables 1 to 3 mean the number of copies of each component, and "-" means that they are not contained.
(A) Ingredient
A-1: Glycerin acrylate mixture obtained in Production Example 1 (hydroxyl value: 238 mgKOH / g)
(A)'Ingredient
A'-1: Glycerin acrylate mixture obtained in Production Example 2 (hydroxyl value: 16 mgKOH / g)
(B) Ingredient
-JI-62C01: Propylene glycol monomethyl ether 50% solution of a compound having a cation having an acryloyl group and an ammonium ion and an anion (JI-62C01 manufactured by Nippon Embroidery Co., Ltd.).
-IL-MA2: A compound having a cation having a methacryloyl group and an ammonium ion and an anion (IL-MA2 manufactured by Koei Chemical Industry Co., Ltd.).
RS-3000: Sodium methacryloyl polyoxyalkylene sulfate (Eleminol RS-3000 manufactured by Sanyo Chemical Industries, Ltd.)
KH-10: Polyoxyethylene-1- (allyloxymethyl) alkyl ether sulfate ammonium salt (Aqualon KH-10 manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.)
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 Adecaria] Thorpe SR-10]
(B)'Component
2F-30: 30% aqueous solution of sodium lauryl sulfate (Emar 2F-30 manufactured by Kao Corporation)
(C) Ingredient
-M-240: Polyethylene glycol diacrylate (average number of moles of ethylene oxide added 4) (Aronix M-240 manufactured by Toagosei Co., Ltd.)
-M-305: Mixture product of pentaerythritol triacrylate and pentaerythritol tetraacrylate (Aronix M-305 manufactured by Toagosei Co., Ltd.)
DMAA: Dimethylacrylamide (DMAA manufactured by KJ Chemicals Co., Ltd.)
-M-402: Mixture product of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate (Aronix M-402 manufactured by Toagosei Co., Ltd.)
M-313: A mixture product of di and triacrylate of isocyanuric acid ethylene oxide adduct (Aronix M-313 manufactured by Toagosei Co., Ltd.)
(D) component
-HCPK: 1-Hydroxy-cyclohexyl-phenyl-ketone (IRGACURE 184 manufactured by BASF)
-TPO: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (DAROCUR TPO manufactured by BASF)
(E) Ingredient
-Perbutyl O: t-butyl peroxy-2-ethylhexanoate (Perbutyl O manufactured by NOF CORPORATION)
Other ingredients
G-30: Propylene glycol / water mixed solution of di (2-ethylhexyl) sulfosuccinate, Rikasurf G-30 manufactured by Shin Nihon Rika Co., Ltd.
AT-210: Aqueous solution of acidic group-containing polymer, AT-210 manufactured by Toa Synthetic Co., Ltd. (Aqueous solution containing neutralizing salt of carboxyl group-containing polymer, solid content: 30%, viscosity: 9,000 mPa · s, pH = 8, Mw: 10,000)
ET-410: Aqueous dispersion of acidic group-containing polymer, ET-410 manufactured by Toagosei Co., Ltd. (Aqueous dispersion containing neutralizing salt of carboxyl group-containing polymer, solid content: 30%, viscosity: 40 mPa. s, pH = 8, Mw: 10,000)
-PGM: Propylene glycol monomethyl ether

4. Evaluation Results As is clear from the results of Examples 1 to 11 in Tables 4 and 6, the curable composition of the present invention has adhesion to a plastic substrate, surface hardness, and anti-fog property on the surface of the cured film. It was excellent in its sustainability. Further, the surface resistivity of the obtained cured film was low.
On the other hand, as is clear from the results in Table 5, the curable composition of Comparative Example 1 has a hydroxyl value of the glycerin acrylate mixture to be blended, which is less than the lower limit of 80 mgKOH / g of the component (A). Although it is an acrylate having the above as a skeleton, sufficient hydrophilicity could not be obtained, and anti-fog property could not be obtained even when the component (B) was added.
Further, even when an acrylate having a structure different from that of the component (A), which is considered to have high hydrophilicity as shown in Comparative Examples 2 and 3, was used, anti-fog property was not obtained in the same manner.
The curable composition of Comparative Example 4 was a curable composition containing no component (B), but had no anti-fog property at all.
The cured composition of Comparative Example 5 uses a surfactant having no ethylenically unsaturated group instead of the component (B), and this cured composition also obtains good anti-fog properties. I couldn't.
For the compositions of Examples 1 to 11, a cured film was formed by the same method as described above except that the test piece was irradiated with ultraviolet rays under the condition of irradiation energy of 1000 mJ / cm ² , and antifogging was performed in the same manner as described above. Sustainability was evaluated. As a result, in the compositions of Examples 1 to 7, the antifogging durability of the cured film was lowered, but in the compositions of Examples 8 to 11 including G-30, the antifogging of the cured film was reduced. There was no change in sustainability and it was excellent.

The curable composition of the present invention can be preferably used as an active energy ray-curable composition, and the obtained cured film has excellent adhesion to various substrates, excellent scratch resistance, and antifogging property. It is also excellent in dust adhesion prevention performance.
The curable composition of the present invention can be preferably used as a coating agent, and more specifically, protective glasses, goggles, inner walls of bathrooms, head lamp covers and rear lamp covers for automobiles and motorcycles, and protection for security camera lenses and the like. It can be preferably used as a fogging coating agent or a dust adhesion prevention coating agent for plastic substrates.

Claims (16)

Contains the following components (A) and (B)
When the total amount of the cured composition is 100% by weight, the component (A) is contained in an amount of 30 to 99% by weight.
The component (B) is contained in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the component (A).
Curable composition.
(A) Component: A mixture of at least one compound selected from the group consisting of glycerin (meth) acrylate and polyglycerin (meth) acrylate, and having a hydroxyl value of 80 to 380 mgKOH / g or more (B). ) Component: A compound having an ethylenically unsaturated group and an ionic group and containing the following (B-1) component and / or the following (B-2) component.
(B-1) Component: A compound consisting of a cation having an ethylenically unsaturated group in one molecule and an anion.
(B-2) Component: A compound consisting of an anion having an ethylenically unsaturated group in one molecule and a cation. The curable composition according to claim 1, wherein the component (A) is a mixture of glycerin (meth) acrylate. Claimed that the component (A) is a mixture containing 30% or more of glycerin di (meth) acrylate as a value calculated from a peak area obtained by analysis using a high performance liquid chromatograph equipped with an ultraviolet detector. 2. The curable composition according to 2. The curable composition according to any one of claims 1 to 3 , wherein the component (B) is a compound having a (meth) acryloyl group as the ethylenically unsaturated group. Further containing the following component ( C)
When the total amount of the cured composition is 100% by weight, the component (A) and the component (C) are contained in an amount of 30 to 99% by weight.
The curable composition according to any one of claims 1 to 4 .
Component (C): A compound having an ethylenically unsaturated group other than the components (A) and (B). The curable composition according to claim 5 , which contains 0.01 to 20 parts by weight of the component (B) with respect to a total of 100 parts by weight of the components (A) and (C). The curable composition according to any one of claims 1 to 6 , further comprising an ionic surfactant having no ethylenically unsaturated group. The curable composition according to any one of claims 1 to 7 , further comprising a photopolymerization initiator (D). The curable composition according to claim 8 , which is an active energy ray - curable coating agent composition. The curable composition according to claim 8 , which is an active energy ray-curable anti - fog coating agent composition. The curable composition according to any one of claims 1 to 7 , further comprising a thermal polymerization initiator (E). The curable composition according to claim 11 , which is a thermosetting coating agent composition. The curable composition according to claim 11 , which is a thermosetting anti - fog coating agent composition. The curable composition according to any one of claims 1 to 7 , further comprising a photopolymerization initiator (D) and a thermal polymerization initiator (E). The curable composition according to claim 14 , which is an active energy ray-curable type and a thermosetting type coating agent composition. The curable composition according to claim 14, which is an active energy ray-curable type and a thermosetting type anti-fog coating agent composition.