KR20150135243A - Active-energy-ray-curable coating composition - Google Patents

Abstract

The active energy ray-curable coating composition of the present invention contains the following components (A) to (C) in a specific ratio. (A2) 0.3 to 1.8 mols of a silicon compound (a2) represented by SiY ₄ (Y is a siloxane bond-forming group), based on 1 mol of the (meth) acryloyl group- containing silicon compound (a1) represented by the general formula (1) (B) an organosilicon compound derived from at least three aliphatic polyhydric alcohols and having at least two (meth) acryloyl groups and at least one (meth) acryloyl group having at least one (meth) acryloyl group, (Meth) acrylate composed of a urethane adduct compound (b1) obtained by the addition reaction of a polyisocyanate with a polyisocyanate and a (meth) acrylate (b2) having at least three (meth) acryloyl groups and no hydroxyl group (C): a radically polymerizable unsaturated compound having a nitrogen atom in a molecule.

Description

ACTIVE-ENERGY-RAY-CURABLE COATING COMPOSITION [0002]

TECHNICAL FIELD The present invention relates to an active energy ray-curable coating composition, and is in the technical field of an active energy ray-curable composition and a coating composition.

In recent years, glass has been used for displays such as touch panels and smart phones, which are rapidly spreading. However, substitution of plastics for the purpose of lightening and preventing scattering of glass during breakage has been studied.

In general, a plastic substrate is lightweight, has excellent impact resistance and inequality formation, but has a defect that the surface thereof is easily scratched and the hardness is low, and therefore, when used as it is, the appearance is remarkably damaged. Therefore, in many cases, the surface of the plastic substrate is coated with a coating composition and subjected to a so-called hard coating treatment to impart abrasion resistance and scratch resistance.

The conventional coating composition is a coating composition obtained by dissolving a resin in a solvent and then coating the base material and then drying to form a resin film. However, for the purpose of improving productivity, etc., the photocurable composition and the thermosetting composition Are being reviewed.

As the hard coating agent for the plastic substrate, an acrylic hard coating agent of an ultraviolet curing type, a silicone hard coating agent of a thermosetting type, and the like have been proposed.

The thermosetting silicone based hard coating agent is superior in abrasion resistance and scratch resistance, but has a problem that the productivity is low due to a long curing time and that the base is deformed due to high temperature at the time of curing. On the other hand, the ultraviolet curable acrylic hard coating agent generally has low abrasion resistance and scratch resistance but has a short curing time and therefore is excellent in productivity.

As described above, the ultraviolet curing type acrylic hard coating agent is excellent in terms of productivity and energy saving for the thermosetting composition as described above, and studies have been made to improve the abrasion resistance and scratch resistance of the cured film which has insufficient performance in order to utilize this characteristic.

For example, there is known a method of blending colloidal silica or a silane compound having a (meth) acryloyloxy group in a composition.

Specifically, there is disclosed an ultraviolet curable coating composition comprising colloidal silica, an alkoxysilane having (meth) acryloyloxy group and acrylate (Patent Document 1), an isocyanate-containing alkoxysilane, a hydroxyl group in the molecule and three or more acryloyl groups (Patent Document 2) including a reaction product of a polyfunctional acrylate having at least three acryloyl groups, a polyfunctional acrylate having at least three acryloyl groups, and colloidal silica is known.

However, these coating compositions are superior in abrasion resistance and scratch resistance of the cured film as compared with conventional ultraviolet ray curable coating compositions, but both of the abrasion resistance and scratch resistance can not be satisfied at the same time, nor have satisfactory performance in practical use. In addition, depending on the substrate used, the adhesion may be insufficient.

On the other hand, the applicant has proposed a photocurable coating composition containing a specific organosilicon compound as a hard coating agent having excellent abrasion resistance, scratch resistance and adhesion to a base material (Patent Document 3).

Japanese Patent Publication No. 57-500984 Japanese Patent Publication No. 5-287215 Japanese Patent Application Laid-Open No. 2011-88996

However, the photocurable coating composition described in Patent Document 3 requires an organic solvent in order to adjust the viscosity of the composition and to impart coating applicability. For this reason, for example, in the case of coating with a thick film, it takes time to remove solvent distillation, and there is room for improvement.

Generally, when the viscosity of the composition is adjusted by adding a reactive monomer or the like in place of the organic solvent, the hardness and scratch resistance of the cured product are lowered, so that the obtained cured film is not sufficiently satisfied as a hard coat. As a result, there has been a demand for a coating composition which is a solventless type, satisfies hardness and scratch resistance, and can be cured by active energy rays such as electron beams and ultraviolet rays.

Further, in general, by compounding an unsaturated compound having a long-chain segment in the molecule in the curable composition, the Tg of the cured product is reduced and the impact resistance is improved. However, such a cured film has a tendency that hardness and scratch resistance are lowered because the crosslinking density is lowered. As a result, there has been a demand for a curable composition which satisfies the hardness and scratch resistance and also has a cured film excellent in impact resistance.

The present invention relates to an active energy ray-curable coating composition which does not contain an organic solvent and which has sufficiently reduced viscosity to a degree of coating, and when applied to a substrate such as a plastic, the cured film thereof has a sufficient hardness and scratch- It is an object of the present invention to provide a coating composition.

It is another object of the present invention to provide an actinic energy ray curable coating composition which has sufficiently reduced viscosity to a degree of coating and exhibits sufficient hardness and scratch resistance when applied to a base material such as plastic and also excellent in impact resistance We will do it.

The present inventors have intensively studied to solve the above problems and found that by using a composition containing a compound having a nitrogen atom and a radically polymerizable unsaturated group, the composition can be adjusted to a sufficiently coatable level without using an organic solvent, And a cured product excellent in scratch resistance can be obtained. Further, the present inventors have found that a cured film having high hardness and excellent scratch resistance and impact resistance can be obtained by using a composition containing an isocyanuric ring and a compound having a radically polymerizable unsaturated group, and thus accomplished the present invention.

The present invention is as follows.

(1) A method for producing a silicon compound (a) which comprises reacting a silicon compound (a1) represented by the following general formula (1) and a silicon compound (a2) represented by the following general formula (2) An organosilicon compound obtained by hydrolytic condensation-condensation in a proportion of 0.3 to 1.8 mol of the silicon compound (a2)

(In the general formula (1), R ¹ is an organic group having an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ² is a divalent saturated R ³ is a hydrogen atom or a methyl group, X is a hydrolysable group, plural Xs may be the same or different and n is 0 or 1)

(In the general formula (2), Y is a siloxane bond generating group, and a plurality of Ys may be the same or different)

(Meth) acrylate derived from a (B) trivalent or higher aliphatic polyhydric alcohol and having at least two (meth) acryloyl groups and having at least one hydroxyl group, with an addition reaction of a polyisocyanate (Meth) acrylate derived from a trivalent or higher aliphatic polyhydric alcohol and having at least three (meth) acryloyl groups and (meth) acrylate (b2) having no hydroxyl group (Meth) acrylate mixture, and

(C) a radically polymerizable unsaturated compound having a nitrogen atom in a molecule and containing a compound other than the above-mentioned component (A) and the above-mentioned component (B)

The content of the component (A), the component (B) and the component (C) is preferably 5 to 50 parts by weight, the content of the component (B) is 30 to 100 parts by weight, 90 parts by weight, and the component (C) is 5 to 35 parts by weight.

[2] The compound (a1) is a compound wherein X in the general formula (1) is an alkoxy group and n is 0,

The active energy ray-curable coating composition according to [1], wherein the compound (a2) in the general formula (2) is an alkoxy group.

[3] The composition according to [1] or [2], wherein the component (C) comprises at least one compound (C1) selected from a morpholinyl group-containing monomer, an amide group- Coating composition.

[4] The compound according to the above [3], wherein the compound (C1) is at least one selected from acryloylmorpholine, N-vinylformamide, N-vinylacetamide and N-vinyl-epsilon -caprolactam. Curable coating composition.

[5] The composition according to any one of [1] to [4], wherein the component (C) comprises a compound (C2) having an isocyanuric ring and the content of the compound (C2) is 5 to 30 parts by weight Active energy ray curable coating composition.

[6] The active energy ray-curable coating composition according to [5], wherein the compound (C2) is a radically polymerizable unsaturated compound modified with an alkylene oxide or caprolactone.

(C) is 10 to 35 parts by weight based on 100 parts by weight of the total of the component (A), the component (B) and the component (C) Comprises at least one compound (C1) selected from a morpholinyl group-containing monomer, an amide group-containing monomer and a lactam compound, and a compound (C2) having an isocyanuric ring, the sum of both being 10 to 35 parts by weight The active energy ray according to any one of the above [1] to [6], wherein the content of the compound (C1) is 5 to 30 parts by weight and the content of the compound (C2) is 5 to 30 parts by weight, Curable coating composition.

The composition of one form of the present invention can be a composition that does not contain an organic solvent, and it is possible to form a cured film having high hardness and excellent scratch resistance for various substrates such as plastics.

Further, according to the composition of another form of the present invention, it becomes possible to form a cured film having high hardness and excellent in scratch resistance and impact resistance to various substrates such as plastics.

The active energy ray-curable coating composition of the present invention contains the components (A), (B) and (C) in a total amount of 100 parts by weight thereof,

5 to 50 parts by weight of the component (A)

30 to 90 parts by weight of the component (B)

And 5 to 35 parts by weight of the component (C).

Hereinafter, details of each component and composition will be described.

In the present specification, an acryloyl group or a methacryloyl group is referred to as a "(meth) acryloyl group", and an acrylate or methacrylate is referred to as "(meth) acrylate".

1. Component (A)

The component (A) according to the present invention is obtained by reacting a silicon compound (a1) (hereinafter referred to as a " compound (a1) ") represented by the following general formula (1) Is an organosilicon compound obtained by hydrolyzing and condensing a silicon compound (a2) (hereinafter referred to as "compound (a2)") expressed in a ratio of 0.3 to 1.8 moles of the compound (a2) to 1 mole of the compound (a1) .

(In the general formula (1), R ¹ is an organic group having an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ² is a divalent saturated R ³ is a hydrogen atom or a methyl group, X is a hydrolysable group, plural Xs may be the same or different and n is 0 or 1)

(In the general formula (2), Y is a siloxane bond generating group, and a plurality of Ys may be the same or different)

In the general formula (1) representing the compound (a1), R ¹ is an organic group having an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, or an aryl group having 6 to 10 carbon atoms.

Among them, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable because a cured film of the resulting composition is excellent in abrasion resistance.

R ² is a divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and an alkylene group is preferable. As the alkylene group, the cured film of the obtained composition is excellent in abrasion resistance, and in view of raw material cost, a trimethylene group is more preferable. R ³ is a hydrogen atom or a methyl group.

X is a hydrolyzable group, plural Xs may be the same or different. As the hydrolyzable group, various groups are possible as long as the group has hydrolytic ability. Specific examples thereof include a hydrogen atom, an alkoxy group, a cycloalkoxy group, an aryloxy group and an arylalkoxy group. Of these, an alkoxy group is preferable, and an alkoxy group having 1 to 6 carbon atoms is more preferable. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group and a hexyloxy group.

Further, n is 0 or 1, and preferably 0 because the cured film of the resulting composition is excellent in abrasion resistance.

Specific examples of the compound represented by the general formula (1) in which n is 0 and X is an alkoxy group include 2- (meth) acryloyloxyethyltriethoxysilane, 3- (meth) acryloyloxypropyl tri Methoxysilane, and 3- (meth) acryloyloxypropylethyltriethoxysilane.

In the general formula (2) representing the compound (a2), Y is a siloxane bond generating group, and plural siloxane bond generators in one molecule may be mutually the same or different.

As the siloxane bond generator, an alkoxy group is preferable. Preferable examples of the alkoxy group include an alkoxy group having 1 to 4 carbon atoms such as methoxy, ethoxy, n-propoxy, iso-propoxy, n-butoxy and sec-butoxy groups.

Preferred examples of the compound (a2) are n-propoxysilane such as tetra-n-propoxysilane, trimethoxy-n-propoxysilane, dimethoxydi-n-propoxysilane, methoxytri- -Propoxy group. ≪ / RTI >

The n-propoxy group-containing alkoxysilane compound may be a single compound or a mixture of compounds having an n-propoxy group and another alkoxy group.

The mixture of the n-propoxy group-containing alkoxysilane compound may be a mixture of plural kinds of components, but the mixture prepared by alcohol exchange may be used as it is. For example, it can be obtained by subjecting a compound represented by the above general formula (2) to a alcohol exchange reaction with a compound having no n-propoxy group (for example, tetramethoxysilane) in 1-propanol. The reaction product obtained by this reaction may be used as it is.

The component (A) is obtained by hydrolyzing and condensing the compound (a1) and the compound (a2) in a ratio of 0.3 to 1.8 moles of the compound (a2) to 1 mole of the compound (a1) ). The reaction conditions for the hydrolytic condensation are not particularly limited, but are preferably alkaline conditions. Hereinafter, the first step under alkaline conditions will be explained.

The reaction ratio of the compound (a1) to the compound (a2) is 0.3 to 1.8 moles, preferably the ratio of the compound (a2) is 0.8 to 1.6 moles relative to 1 mole of the compound (a1) Is 1 to 1.4 moles of the compound (a2). By reacting in this ratio, component (A) can be efficiently produced without causing gelation during and after the reaction.

Gelation after the reaction can be prevented by proceeding the first step under alkaline conditions, and component (A) can be produced with high yield.

Specifically, the pH of the reaction system is more than 7, preferably 8 or more, more preferably 9 or more. The upper limit is usually pH 13. By setting the reaction system to the above-mentioned pH, component (A) having excellent storage stability can be produced with high yield.

Organosilicon compounds obtained by hydrolytic condensation under acidic conditions (pH lower than 7) may be inferior in storage stability.

In addition, under a neutral condition (near pH 7), the hydrolytic condensation reaction may be difficult to proceed.

In the first step, the condensation ratio of the compound (a1) and the compound (a2) may be 92% or more, more preferably 95% or more, and even more preferably 98% or more. It is most preferable that all the siloxane bond generators (including the hydrolyzable group) are substantially condensed, but the upper limit of the condensation ratio in the first step is usually 99.9%.

Conventionally, a method of producing an organosilicon compound by an acidic condition is known, but it is difficult to uniformly react both the compound (a1) and the compound (a2), which are the starting compounds, and the gel is easily generated. As a result, there has been known a method of avoiding gelation by acting as a terminal sealing agent, such as trimethylalkoxysilane or hexamethyldisiloxane, with a silicon compound having only one siloxane bond generator (hereinafter referred to as "M monomer").

However, even if gelation can be avoided by concurrently using a predetermined amount or more of the M monomers, the inorganic properties of the resulting organosilicon compound tend to be lowered.

On the other hand, according to the production method by an alkaline condition, the effect that the compound (a1) and the compound (a2) can be subjected to air condensation without gelation, and thereafter, the inorganic property of the obtained cured product is not lowered.

The component (A) is produced by making the first process essentially as described above, but the production method of the component (A) may further include the following steps, if necessary.

(Second step) A step of neutralizing the reaction solution obtained in the first step with an acid.

(Third step) A step of removing volatile components from the neutralized liquid obtained in the second step.

(Fourth Step) A step of mixing and bringing the concentrate obtained in the third step and an organic solvent for cleaning to dissolve at least the component (A) in the organic solvent for cleaning.

(Step 5) A step of washing the organic solution obtained in the fourth step with water, and then obtaining an organic solution containing the component (A).

(Step 6) A step of removing volatile components from the organic solution obtained in the fifth step.

The method for producing the component (A) preferably includes the first step, the second step and the fifth step.

In the production of the component (A), the reaction system of the first step, the reaction solution containing the component (A) after the first step, the neutralization solution after the second step, the organic solution after the fourth step and the organic solution after the fifth step For at least one, a polymerization inhibitor which inhibits the polymerization of the (meth) acryloyl group may be added.

The content of the component (A) in the composition of the present invention is 5 to 50 parts by weight, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total of the components (A), (B) and (C) More preferably 10 to 35 parts by weight.

By making the content ratio of the component (A) 5 to 50 parts by weight, a composition giving a cured film excellent in hardness and scratch resistance can be obtained.

2. Component (B)

Component (B) according to the present invention is a (meth) acrylate derived from a tri- or higher-valent aliphatic polyhydric alcohol and includes (meth) acryloyl groups having two or more (meth) acryloyl groups and having at least one hydroxyl group The urethane adduct compound (b1) (hereinafter referred to as "component (b1)") obtained by the addition reaction of a polyisocyanate and the (meth) acryloyl group derived from a trivalent or higher aliphatic polyhydric alcohol (Meth) acrylate (hereinafter referred to as " component (b2) ") having at least three (meth) acrylates and no hydroxyl group.

The raw material compound of the component (b1) is a (meth) acrylate derived from a tri- or higher-valent aliphatic polyhydric alcohol, and a (meth) acrylate having two or more (meth) acryloyl groups and having at least one hydroxyl group Quot; hydroxyl group-containing polyfunctional (meth) acrylate ").

As the tri- or higher-valent aliphatic polyhydric alcohol which is the raw material compound of the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used, and trimethylolpropane, pentaerythritol, ditrimethylolpropane and dipentaerythritol .

As the hydroxyl group-containing polyfunctional (meth) acrylate, various compounds can be used. Specific examples thereof include trimethylolpropane di (meth) acrylate, di or tri (meth) acrylate of pentaerythritol, ditrimethylolpropane Di (meth) acrylate of di (meth) acrylate and di (tri), tetra or penta (meth) acrylate of dipentaerythritol.

Among these, compounds having three or more (meth) acryloyl groups and one hydroxyl group are preferable because the cured film is excellent in hardness and scratch resistance, and specific examples thereof include pentaerythritol tri (meth) acrylate, Ditrimethylolpropane tri (meth) acrylate and dipentaerythritol penta (meth) acrylate.

As the polyisocyanate which is the other synthetic raw material for the other component (b1), various compounds can be used.

Examples of preferred polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornadiisocyanate, 2,4-tolylene diisocyanate, .

The component (b1) is synthesized by the addition reaction of a hydroxyl group-containing polyfunctional (meth) acrylate and a polyisocyanate. This addition reaction can be carried out without a catalyst, but in order to proceed the reaction efficiently, the reaction is carried out in the presence of a catalyst such as a tin compound such as dibutyltin dilaurate or an amine compound such as triethylamine .

Component (b2) is a (meth) acrylate derived from a trivalent or higher aliphatic polyhydric alcohol.

As the trivalent or higher aliphatic polyhydric alcohol which is the raw material compound of the component (b2), the same ones as exemplified above can be used.

Specific examples of the component (b2) include trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate and dipentaerythritol hexa .

Among them, a compound having at least 4 (meth) acryloyl groups is preferable because the cured film is excellent in abrasion resistance and scratch resistance. Specific examples thereof include pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra (Meth) acrylate and dipentaerythritol hexa (meth) acrylate.

Component (B) according to the invention is a mixture of components (b1) and (b2).

The ratio of the components (b1) and (b2) may be properly set according to the purpose. The component (B) is preferably a mixture comprising a weight ratio of (b1) :( b2) = 10:90 to 75:25, more preferably a mixture of (b1) :( b2) = 30: 70 to 70 : 30 by weight.

By setting the weight ratio of the components (b1) and (b2) within this range, a composition that gives a cured film excellent in hardness and scratch resistance can be obtained.

The content of the component (B) in the composition of the present invention is 30 to 90 parts by weight, preferably 40 to 90 parts by weight per 100 parts by weight of the total of the components (A), (B) and (C) And more preferably 50 to 85 parts by weight.

By making the content ratio of the component (B) 30 to 90 parts by weight, a composition giving a cured film excellent in hardness and scratch resistance can be obtained.

3. Component (C)

Component (C) according to the present invention is a radically polymerizable unsaturated compound having a nitrogen atom in the molecule (hereinafter also referred to as "unsaturated compound (C)") and is a compound other than the component (A) .

By using the unsaturated compound (C), it becomes possible to provide an active energy ray curable coating composition which gives a cured film excellent in hardness and scratch resistance. When the specific compound (C1) to be described later is contained, a composition having a sufficiently low viscosity can be obtained. When the specific compound (C2) to be described later is contained, the cured film can be obtained without decreasing the hardness and scratch resistance The impact resistance can be improved.

In the present invention, the number of the radically polymerizable unsaturated group of the unsaturated compound (C) is not particularly limited, but when the viscosity of the composition is relatively low, a compound having one radically polymerizable unsaturated group, that is, a monofunctional unsaturated compound is preferable Do.

Specific examples of such monofunctional unsaturated compounds include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-methylol (Meth) acrylamide, N, N-dimethylaminopropylacrylamide, N-vinylformamide, N-vinyl (meth) acrylamide, Amide group-containing monomers such as acetamide and diacetone (meth) acrylamide; Amino group-containing monomers such as dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, and t-butylaminoethyl (meth) acrylate; N-vinylpyrrolidone; Lactam compounds such as N-vinyl-epsilon -caprolactam; (Meth) acryloylmorpholine, and the like; (Meth) acrylonitrile, N-cyclohexylmaleimide, and N-phenylmaleimide. These compounds may be used alone or in combination of two or more.

Of these, amide group-containing monomers, lactam compounds and morpholinyl group-containing monomers (hereinafter collectively referred to as "compound (C1)") are preferable because of the high Tg of the homopolymer and good hardness and scratch resistance of the resulting cured film. desirable. As the compound (C1), dimethyl (meth) acrylamide, N-vinylformamide, N-vinylacetamide and (meth) acryloylmorpholine are more preferable. Among them, N-vinylformamide and N-vinylacetamide, which are amide group-containing monomers, are preferable because they have a high effect of reducing the viscosity of the composition as well as the performance of the cured product.

The unsaturated compound (C) is also a preferable component in combination with the compound (C1), either alone or in the form of a radical polymerizable unsaturated compound having an isocyanuric ring in the molecule (hereinafter also referred to as "compound (C2)"). Examples of the compound (C2) include isocyanuric acid EO-modified di (meth) acrylate and isocyanuric acid EO-modified tri (meth) acrylate, and mixtures thereof (specific trade names include, for example, Alkylene oxide modification (such as "Aronix M-313" and "Aronix M-315" manufactured by Hitachi Chemical Co., Ltd., "Pancryl FA-731A" manufactured by Hitachi Chemical Industry Co., Ltd., and "NK Ester A-9300" manufactured by Shin Nakamura Kagaku Kogyo Co., Meth) acrylates; (Aronix M-327 manufactured by Doagosei Co., Ltd., NK Ester A-1 manufactured by Shin Nakamura Kagaku Kogyo Co., Ltd.), and tris [2- (meth) acryloxyethyl] isocyanurate 9300-1CL ") and the like;? -Caprolactone modified (meth) acrylates; Hexamethylene diisocyanate, isophorone diisocyanate and isophorone diisocyanate, and reaction products such as hydroxyl group-containing (meth) acrylate (specific trade names include "Art Resin UN-905" manufactured by Negami Kogyo Co., Ltd.) Esters of 1,3-bis (2-carboxyethyl) isocyanurate and 2-hydroxyethyl (meth) acrylate, tri (meth) acrylate esters of tris (2-hydroxyethyl) isocyanurate, Other isocyanuric acid derivatives (specific trade names such as "MA-DGIC", "DA-MGIC", "MeDAIC", "AcDGIC" manufactured by Shikoku Chemicals Corporation) can be mentioned. These compounds may be used alone or in combination of two or more.

As the compound (C2), alkylene oxide-modified (meth) acrylates and? -Caprolactone modified (meth) acrylates are more preferable because the resulting cured film has better impact resistance.

The number of radically polymerizable unsaturated groups of the compound (C2) is not particularly limited and may be one or two or more. In the present invention, a compound having two or more radically polymerizable unsaturated groups is preferable in that a cured film having high hardness and good scratch resistance is easily obtained.

The content of the unsaturated compound (C) in the composition of the present invention is 5 to 35 parts by weight, preferably 5 to 30 parts by weight, based on 100 parts by weight of the total of the components (A), (B) 30 parts by weight, and more preferably 8 to 25 parts by weight.

By containing 5 to 35 parts by weight of the unsaturated compound (C), a cured film excellent in hardness and scratch resistance can be obtained.

In the present invention, when the unsaturated compound (C) contains only the compound (C1), the viscosity of the composition is reduced to such an extent that it can be applied even without containing an organic solvent. C is preferably from 5 to 35 parts by weight, more preferably from 5 to 30 parts by weight, and still more preferably from 8 to 25 parts by weight, based on 100 parts by weight of the total amount.

When the unsaturated compound (C) contains only the compound (C2), a cured film having better impact resistance is obtained. Therefore, the content of the unsaturated compound (C) Preferably 5 to 30 parts by weight, more preferably 8 to 30 parts by weight, still more preferably 10 to 25 parts by weight.

Further, when the unsaturated compound (C) contains the compounds (C1) and (C2), a cured film excellent in both hardness, scratch resistance and impact resistance is obtained. The content of the compound (C1) is preferably 5 to 30 parts by weight, more preferably 5 to 25 parts by weight, still more preferably 8 to 25 parts by weight, based on 10 to 35 parts by weight of the total of both , And the content of the compound (C2) is preferably 5 to 30 parts by weight, more preferably 8 to 30 parts by weight, still more preferably 10 to 25 parts by weight. By setting the content ratio of the compound (C1) to 5 to 30 parts by weight, the viscosity of the composition is reduced to such an extent that coating is possible without using an organic solvent, and a cured film excellent in hardness, scratch resistance and impact resistance can be obtained.

4. Active energy ray curable coating composition

The active energy ray-curable coating composition of the present invention may be a composition containing an organic solvent and a composition containing no organic solvent, or may be a composition containing an organic solvent depending on the kind of the component (C). For example, when the component (C) contains the compound (C1), a composition containing no organic solvent can be used. When the component (C) contains the compound (C2) or contains both the compounds (C1) and (C2), it is preferable to contain the organic solvent. The usable organic solvent will be described later.

The composition of the present invention comprises the components (A), (B) and (C) as essential components, but may be a photopolymerization initiator, a pigment, a dye, a surface modifier, an ultraviolet absorber, a light stabilizer such as HALS, , (B), and (C), and an organic polymer may be further blended.

As the photopolymerization initiator, various compounds can be used. Specific examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexyl- Methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy- (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, (2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} and 2-hydroxy- 2-methylpropionyl) benzyl] phenyl} -2-methyl-propan-1-one; Benzophenone compounds such as benzophenone, 4-phenylbenzophenone, 2,4,6-trimethylbenzophenone and 4-benzoyl-4'-methyl-diphenylsulfide; Methyl esters such as methyl benzoyl formate, 2- (2-oxo-2-phenylacetoxyethoxy) ethyl ester of oxyphenylacetic acid and 2- (2-hydroxyethoxy) ethyl ester of oxyphenylacetic acid compound; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, bis (2,6-dimethoxybenzoyl) Phosphine oxide compounds such as pin oxide and the like; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether and benzoin isobutyl ether; Titanocene compounds; Acetophenone / benzophenone hybrid photoinitiators such as 1- [4- (4-benzoylphenylsulfanyl) 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; And camphorquinone.

The preferred blending amount of the photopolymerization initiator is 0.1 to 10 parts by weight, more preferably 0.5 to 7 parts by weight, particularly preferably 1 to 10 parts by weight, based on 100 parts by weight of the total of the components (A), (B) To 5 parts by weight.

When the blending amount of the photopolymerization initiator is 0.1 to 10 parts by weight, the composition is excellent in curability and can be a composition which gives a cured film excellent in hardness and scratch resistance.

The surface modifier has an effect of enhancing the leveling property when the composition of the present invention is applied and an effect of improving the antifouling property and sliding property of the cured coating film. As the surface conditioner, a silicon surface conditioner and a fluoric surface conditioner are suitable. Specific examples thereof include a silicone polymer having a silicone chain and a polyalkylene oxide chain, a fluoropolymer having a perfluoroalkyl group and a polyalkylene oxide chain, and a fluoropolymer having a perfluoroalkylether chain and a polyalkylene oxide chain. .

The preferable amount of the surface modifier is 0.01 to 3 parts by weight, more preferably 0.02 to 0.5 parts by weight, based on 100 parts by weight of the total of the components (A), (B) and (C). By setting the blending amount to 0.01 part by weight or more, the surface smoothness of the coating film can be enhanced and the occurrence of bubbles during coating can be suppressed.

The compound having another radically polymerizable unsaturated group is not particularly limited so long as it is a compound having at least one radically polymerizable unsaturated group in one molecule.

Specific examples of the compound having one radically polymerizable unsaturated group in one molecule include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (Meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl (meth) acrylate, 2-hydroxyethyl (Meth) acrylate of an alkylene oxide adduct of an alkylphenol, a (meth) acrylate of an alkylene oxide adduct of an alkylphenol, an alkylene oxide adduct of an alkylene oxide adduct of a phenol, And the like.

Further, a compound having two or more radically polymerizable unsaturated groups in one molecule (hereinafter referred to as " another polyfunctional unsaturated compound ") can improve adhesion to a substrate, hardness and scratch resistance.

The number of radically polymerizable unsaturated groups in the other polyunsaturated unsaturated compound is preferably 3 to 20 in one molecule from the viewpoint of not lowering hardness and scratch resistance.

As the other polyfunctional unsaturated compound, a compound having two or more (meth) acryloyl groups in one molecule is preferable.

Specific examples thereof include di (meth) acrylates of alkylene oxide adducts of bisphenol A, di (meth) acrylates of alkylene oxide adducts of bisphenol F, di (meth) acrylates of alkylene oxide adducts of bisphenol Z, bisphenol S Di (meth) acrylates of alkylene oxide adducts of thiobisphenol, di (meth) acrylates of bisphenol A, di (meth) acrylates of bisphenol F, bisphenol Z Di (meth) acrylate of bisphenol S, di (meth) acrylate of thiobisphenol, tricyclodecane dimethylol (meth) acrylate, ethylene glycol di (meth) acrylate, polyethylene glycol Di (meth) acrylate, propylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, neopentyl glycol di Di (meth) acrylate of an alkylene oxide adduct of 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, glycerin di (meth) Tri (meth) acrylates of alkylene oxide adducts of trimellitic acid diol (meth) acrylate, cyclohexanedimethylol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane, pentaerythritol tri And tetraacrylate, tri- and tetraacrylates of alkylene oxide adducts of pentaerythritol, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa and pentaacrylates, polyester (meth) acrylates, epoxy (Meth) acrylate, urethane (meth) acrylate, and silicone resins having a (meth) acryloyl group at the terminal.

Among them, examples of the polyester (meth) acrylate include a dehydration condensation product of a polyester polyol and (meth) acrylic acid. Examples of the polyester polyol include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol and trimethylolpropane, Or a reaction product obtained by using an acid component such as a dibasic acid such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or an anhydride thereof and a polyol component such as an alkylene oxide adduct of these, And dehydration condensates of polyol and (meth) acrylic acid.

Examples of the epoxy (meth) acrylate include a (meth) acrylic acid adduct of a bisphenol A type epoxy resin, a (meth) acrylic acid adduct of a hydrogenated bisphenol A type epoxy resin, a (meth) acrylic acid adduct of a phenol or cresol novolak type epoxy resin Water, diglycidyl ether (meth) acrylic acid adduct of a polyether such as a (meth) acrylic acid adduct of a biphenyl type epoxy resin, polytetramethylene glycol and the like, a (meth) acrylic acid adduct of a diglycidyl ether of a polybutadiene (Meth) acrylic acid adduct of a polybutadiene internal epoxy compound, a (meth) acrylic acid adduct of a silicone resin having an epoxy group, a (meth) acrylic acid adduct of limonene dioxide, 3,4-epoxycyclohexylmethyl- (Meth) acrylic acid adduct of 4-epoxycyclohexanecarboxylate, and the like.

As the urethane (meth) acrylate, a compound obtained by addition reaction of an organic polyisocyanate and a hydroxyl group-containing (meth) acrylate or a compound obtained by addition reaction of an organic polyisocyanate, a polyol and a hydroxyl group- .

Examples of the polyol include a low molecular weight polyol, a polyether polyol, a polyester polyol and a polycarbonate polyol.

Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, neopentyl glycol, cyclohexanedimethanol, 3-methyl-1,5-pentanediol and glycerin.

Examples of the polyether polyol include polypropylene glycol and polytetramethylene glycol.

Examples of polyester polyols include reaction products of these low molecular weight polyols and / or polyether polyols with acid components such as dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid or anhydrides thereof.

Examples of the organic polyisocyanate include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, And phonon diisocyanate.

Examples of the hydroxyl group-containing (meth) acrylate include hydroxyalkyls such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) (Meth) acrylate of a hydroxyl group of an acrylate.

The organic polymer has an effect of reducing warpage during curing while maintaining transparency. Suitable organic polymers are (meth) acrylic polymers, and suitable monomeric monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic acid, glycidyl (meth) acrylate, N- (Meth) acryloxyethyl) tetrahydrophthalimide, and the like. In the case of a polymer obtained by copolymerizing (meth) acrylic acid, a (meth) acryloyl group may be introduced into the polymer chain by adding glycidyl (meth) acrylate.

The composition of the present invention may be excellent in coating properties and handling properties even if it does not contain an organic solvent. However, an organic solvent may be used for the purpose of further improving the performance of the composition or adjusting the viscosity of the composition. As the organic solvent, it is preferable to dissolve the components (A), (B) and (C).

Specific examples of the preferable organic solvent include alcohols such as ethanol and isopropanol; Alkylene glycol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; Acetone alcohols such as diacetone alcohol; Aromatic compounds such as toluene and xylene; Ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate and butyl acetate; Ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; Ethers such as dibutyl ether; N-methylpyrrolidone and the like.

The preferable blending amount of the organic solvent is 10 to 1000 parts by weight, more preferably 50 to 500 parts by weight, still more preferably 50 to 500 parts by weight, based on 100 parts by weight of the total of the components (A), (B) and (C) To 300 parts by weight.

(Barcoat, rollcoat, spincoat, dipcoat, gravurecoat, diecoat, flowcoat, spraycoat, and the like) can be obtained because the viscosity of the curable composition is sufficiently reduced by blending the organic solvent in an amount of 10 to 1000 parts by weight, It is easy to prepare the coating composition corresponding to the coating composition.

The viscosity (25 ° C) of the active energy ray-curable coating composition of the present invention measured by an E-type viscometer is preferably 20,000 mPa · s or less, more preferably 15,000 mPa · s or less, Is 10,000 mPa 占 퐏 or less. The lower limit is usually 100 mPa · s.

The process for producing the active energy ray-curable coating composition of the present invention can be carried out according to a conventional method and can be carried out by mixing the component (A), the component (B), the component (C) And the like.

5. Painting method

The active energy ray-curable coating composition of the present invention is suitable for forming a coating film having high adhesion to a substrate.

The composition of the present invention can be applied to a substrate comprising various materials. Examples of preferred substrates include wood, metal, inorganic materials and plastics.

Examples of the inorganic material include mortar, concrete and glass.

Specific examples of the plastic include an acrylic resin such as polymethyl methacrylate, a polyester resin such as polyethylene terephthalate, a polyvinyl chloride, a polycarbonate resin, an epoxy resin and a polyurethane resin.

The method of applying the composition of the present invention to a substrate is not particularly limited and may be carried out by a conventional method. For example, bar coats, roll coats, spin coats, dip coats, gravure coats, flow coats, spray coats and the like can be applied.

Specific examples of the method for forming a cured film include a method of applying a composition to a substrate and then irradiating the coating film with an active energy ray. Further, if necessary, the coating film may be subjected to a drying step or a preliminary heating step before irradiation with an active energy ray.

The coating film and the film thickness after drying may be suitably set according to the purpose, but are generally about 5 to 300 mu m.

The drying temperature or the preliminary heating temperature is not particularly limited as long as it is a temperature at which the substrate to be applied does not cause problems such as deformation.

Examples of the active energy ray for curing the coating film containing the composition of the present invention include electron beam, ultraviolet ray, visible ray and X-ray, but ultraviolet ray is preferable because an inexpensive apparatus can be used.

Examples of the ultraviolet irradiator include a high-pressure mercury lamp, a metal halide lamp, a UV non-electrode lamp, and an LED.

For example, in the case of using a high-pressure mercury lamp, the irradiation energy is preferably 100 to 5,000 mJ / cm 2, more preferably 200 to 5000 mJ / cm 2 as the irradiation energy of the UV-A region, More preferably 1,000 mJ / cm 2.

In the case of curing by electron beam, various devices can be used as the electron beam (EB) irradiating device which can be used. Examples of the electron beam (EB) irradiating device include a Cocrosston type, a Vandegraph type and a resonant transformer type device. It is preferable to apply energy of 50 to 1,000 eV, more preferably 100 to 300 eV.

The cured film obtained by using the composition of the present invention is excellent in hardness and scratch resistance. For example, the pencil hardness measured according to JIS K 5600-5-4 is usually 8H or more, and occurrence of scratches due to contact with a metal member or the like is suppressed. The material having the cured film can be used for various purposes by taking advantage of these properties.

For example, a front plate for a display panel, a construction material application, a lighting device, a display or a housing such as a mobile phone and a smart phone, a housing of a household appliance, and various lenses such as glasses can be mentioned.

Specific examples of the front panel for the display panel include an electric bulletin board, a display, a signboard, an advertisement, and a cover.

Examples of using wood as the base material include woodwork products such as stairs, floors and furniture. Examples of the metal used as the base material include metal kitchen articles such as kitchen panels and stainless steel sinks.

Example

Hereinafter, the present invention will be described in detail based on examples. The present invention is not limited to these examples.

In the following, " part " means weight part and "% " means weight%.

1. Preparation of component (A)

Production Example 1 (Production of MAC-TQ)

150 g of 1-propanol for alcohol exchange reaction and 36.53 g (0.24 mol) of tetramethoxysilane (hereinafter referred to as " TMOS ") were charged into a reactor equipped with a stirrer and a thermometer, 4.37 g of a tetramethylammonium methanol solution (0.1 mol of methanol, 12 mmol of tetramethylammonium hydroxide) was slowly added and the mixture was reacted at 25 DEG C and pH 9 for 6 hours. Thereafter, the inner temperature was adjusted to 60 캜, and the mixture was further reacted for 1 hour while stirring. Here, when the reaction solution was analyzed by gas chromatography (TCD detector), it was confirmed that each compound of 1, 2, 3, or 4 substituents in which 1 to 4 of methoxy groups contained in TMOS were substituted with n-propoxy groups, The TMOS of the reaction was detected. Only trace amounts of TMOS were detected. Of these, the ratio of the n-propoxy group-containing compound (n-propoxy group-containing alkoxy silane) was about 100% in total. Based on the peak area of the product in the gas chromatogram, the number of substitution of 1-propanol (number average of n-propoxy groups per one molecule of n-propoxy group) was found to be 2.7.

Then, 59.62 g (0.24 mol) of 3-methacryloxypropyltrimethoxysilane was added to the reaction solution, and 30.2 g of water was further added. Then, 7.88 g of a 25% tetramethylammonium hydroxide solution in methanol (0.18 mol of methanol, 21.6 mmol of tetramethylammonium hydroxide) was added and reacted at 25 ° C. and pH 9 for 24 hours with stirring. Thereafter, 22.2 g (35.3 mmol) of 10% nitric acid aqueous solution was added to neutralize. Subsequently, this neutralized liquid was added to a mixed solution of 120 g of diisopropyl ether and 180 g of water and extraction was carried out. The diisopropyl ether layer was washed with water to remove salts and excess acid. Thereafter, an N-nitrosophenylhydroxylamic acid aluminum salt " Q-1301 " (trade name) manufactured by Wako Pure Chemical Industries, Lt; / RTI > From the obtained diisopropyl ether solution, the organic solvent was distilled off under reduced pressure to obtain a colorless transparent solid organic silicon compound (hereinafter referred to as "MAC-TQ"). The yield was 57.72 g.

¹ H-NMR analysis of MAC-TQ revealed that 3-methacryloxypropyltrimethoxysilane used as the compound (a1) and the n-propoxy group-containing alkoxysilane used as the compound (a2) were stoichiometrically reacted It was confirmed that it was an air condensation product obtained.

The content of the alkoxy group (n-propoxy group bonded to the silicon atom) calculated from the ¹ H-NMR chart of MAC-TQ was 2.5% with respect to the total alkoxy groups contained in the starting material.

Further, the average molecular weight of MAC-TQ was measured by gel permeation chromatography (GPC), and the Mn in terms of standard polystyrene was 9,600.

2. Preparation of component (B)

Production Example 2 (Preparation of HDI-M305)

A mixture of pentaerythritol triacrylate (hereinafter referred to as "PETri") and pentaerythritol tetraacrylate (hereinafter referred to as "PETet") was added to a 0.5 L separable flask equipped with a stirrer and an air suction pipe 159.2 g of Aronix M-305 (trade name, hereinafter referred to as "M-305") manufactured by Doi Kosei Co., Ltd., which contains 0.3 mol of PETri and 0.2 mol of PETet, 2,6-di- (Hereinafter referred to as " BHT ") and 0.055 g of dibutyltin dilaurate (hereinafter referred to as " DBTL ") were charged, and the solution temperature was adjusted to 70 to 75 캜. 25.2 g (0.15 mol) of hexamethylene diisocyanate (hereinafter referred to as " HDI ") was added dropwise and reacted.

After completion of dropwise addition of the HDI, the reaction was further continued at an internal temperature of 80 캜 and stirred for 3 hours. Then, IR (infrared absorption) analysis of the reaction product confirmed that the isocyanate group was lost, and the reaction was terminated. Hereinafter, this reaction product is referred to as " HDI-M305 ".

HDI-M305 contains a urethane adduct compound (b1) which is a reaction product of PETri and HDI and a PETet (corresponding to compound (b2)) which does not react with HDI and has a weight ratio of b1 :( b2) = 6: 4 .

3. Preparation and evaluation of active energy ray-curable coating compositions

Using the MAC-TQ and HDI-M305 obtained above and the components shown in Table 1, an active energy ray-curable coating composition was prepared and provided for various evaluations.

Examples 1-1 to 1-4 and Comparative Examples 1-1 to 1-4

Each raw material was used in a ratio shown in Table 2 and stirred and mixed at room temperature according to a conventional method to prepare an active energy ray curable coating composition.

Thereafter, the viscosity of each composition thus obtained at 25 캜 was measured by an E-type viscometer, and the obtained values were shown in the respective tables.

Thereafter, each composition was passed over the surface of one side of a 7 cm x 15 cm x 50 m polyethylene terephthalate film, and a 50 m-thick release film containing polyethylene terephthalate and transmitting ultraviolet rays was put thereon . Subsequently, the film was passed through a laminate roll so that the film thickness after curing was about 50 μm, and the thickness of the coating film was adjusted. A coating film was formed on the other side of the polyethylene terephthalate film in the same manner. Then, ultraviolet rays were irradiated through the release film under the following conditions to prepare a cured film on both sides of the polyethylene terephthalate film.

The ultraviolet ray irradiation was carried out using an ultraviolet ray irradiator (high-pressure mercury lamp) manufactured by Eye Graphics Co., Ltd. with a lamp height of 19 cm and a conveyor speed of 2.3 m / min. The irradiation energy per pass was measured by a photometer "UV POWER PUCK" manufactured by EIT, and found to be 900 mJ / cm 2 in the UV-A region. The peak illuminance was 170 mW / cm < 2 > in the UV-A region.

With respect to the obtained cured film, pencil hardness, scratch resistance and adhesion were evaluated by the following methods. The evaluation results are shown in Table 2.

(1) Pencil Hardness

The pencil hardness was measured according to JIS K 5600-5-4.

(2) Scratch resistance

On the surface of the cured film, the number of scratches when rubbing 400 reciprocations while applying a load of 1200 g / 4 cm2 was measured in the state that a steel wool "BONSTAR # 0000" made by Nippon Steel Wool Co., Ltd. was placed. The number of scratches was used to evaluate scratch resistance based on the following criteria. Here, evaluation " A " or " B "

A: There were no scratches.

B: There were 1 to 9 scratches.

C: There were more than 10 scratches.

Each of the compositions of Examples 1 to 5 exhibited a viscosity of 10,850 mPa 占 퐏 or less although the organic solvent was not used, and the viscosity was sufficiently reduced to such an extent that it could be applied. Further, it was confirmed that the cured film thereof exhibited excellent pencil hardness of 8H to 10H, and was excellent in abrasion resistance and scratch resistance. Among them, in Examples 3 to 5 using N-vinylformamide (NVF) as the component (C), the viscosity of the composition was further reduced, which was advantageous in coating properties during various coatings.

On the other hand, Comparative Example 1 does not contain the component (C) according to the present invention, and therefore the composition has a viscosity as high as 34,400 mPa · s and needs to be diluted with an organic solvent or the like during handling and coating. Further, in Comparative Example 2 using 1,6-hexanediol diacrylate (HDDA), which is an unsaturated compound containing no nitrogen atom, both the pencil hardness and scratch resistance of the cured film were reduced.

Comparative Examples 3 and 4 are experimental examples in which the content of the component (C) according to the present invention is out of the range specified in the present invention. In Comparative Example 3 in which the content of the component (C) was too small, the viscosity of the composition could not be sufficiently reduced. On the contrary, in Comparative Example 4 in which the content of the component (C) was excessively large, the cured film had low pencil hardness and scratch resistance .

Examples 6 to 11 and Comparative Example 5

Each raw material and each raw material shown in Table 3 were used in a ratio shown in Table 3 and stirred and mixed at room temperature according to a conventional method to prepare an active energy ray curable coating composition. The composition of Comparative Example 5 is the same as that of Comparative Example 1. The viscosity of each composition was measured, and the applicability of the coating was determined based on the following criteria. The results are shown in Table 3.

A: Viscosity was 100 mPa 占 퐏 or more and 10,000 mPa 占 퐏 or less

B: Viscosity was more than 10,000 mPa · s and less than 15,000 mPa · s

C: Viscosity was more than 15,000 mPa · s and less than 20,000 mPa · s

D: viscosity exceeded 20,000 mPa 占 퐏

Thereafter, in the same manner as in Example 1, a cured film was formed on both sides of the polyethylene terephthalate film. Then, in addition to (1) hardness and (2) scratch resistance, the following (3) impact resistance evaluation was carried out. The evaluation results are shown in Table 3.

(3) Impact resistance (fall test)

On the surface of the cured film, 25 g of iron balls according to JIS B 1501 were dropped from a height of 10 cm. When cracks and cracks did not occur in the cured film, the operation of raising the height by 5 cm and dropping the iron ball was repeated to record the maximum height at which cracks and cracks did not occur. This test was carried out on five cured products to evaluate the impact resistance by calculating the average value of the highest value at which cracks and cracks did not occur.

The test was also conducted under constant temperature and humidity conditions of 23 캜 and 50% RH.

Each of the compositions of Examples 6 to 11 was also sufficiently reduced in viscosity to the extent that it could be applied. Further, it was confirmed that all of the cured films obtained exhibited a good pencil hardness of 8H to 10H and were excellent in scratch resistance and impact resistance (fall test). In particular, in Examples 9 to 11 using two kinds of NVF as component (C), the viscosity of the composition was low and the coating work was easy.

On the other hand, Comparative Example 5 is an example of a composition which does not contain the component (C) according to the present invention, but its viscosity is high and the hardened film obtained is excellent in hardness and scratch resistance. However, the value of the fall test is as low as 15 cm The impact was poor.

The active energy ray-curable coating composition of the present invention can be suitably used for coating various substrates such as wood, metal, inorganic materials and plastics.

Claims (7)

(A1) a silicone compound (a1) represented by the following general formula (1) and a silicon compound (a2) represented by the following general formula (2) An organosilicon compound obtained by hydrolysis-condensation of the silicon compound (a2) in a proportion of 0.3 to 1.8 mol,

(In the general formula (1), R ¹ is an organic group having an alkyl group having 1 to 6 carbon atoms, an aralkyl group having 7 to 10 carbon atoms or an aryl group having 6 to 10 carbon atoms, R ² is a divalent saturated R ³ is a hydrogen atom or a methyl group, X is a hydrolysable group, plural Xs may be the same or different and n is 0 or 1)

(In the general formula (2), Y is a siloxane bond generating group, and a plurality of Ys may be the same or different)
(Meth) acrylate derived from a (B) trivalent or higher aliphatic polyhydric alcohol, a (meth) acrylate having at least two (meth) acryloyl groups and at least one (Meth) acrylate (b2) having at least three (meth) acryloyl groups and no hydroxyl group as the (meth) acrylate derived from the trivalent or higher aliphatic polyhydric alcohol as the urethane adduct compound (b1) (Meth) acrylate mixture consisting of
(C) a radically polymerizable unsaturated compound having a nitrogen atom in a molecule and containing a compound other than the above-mentioned component (A) and the above-mentioned component (B)
The content of the component (A), the component (B) and the component (C) is 5 to 50 parts by weight and the content of the component (B) is 30 to 30 parts by weight, To 90 parts by weight, and the component (C) is 5 to 35 parts by weight. The compound according to claim 1, wherein the compound (a1) is a compound wherein X in the general formula (1) is an alkoxy group and n is 0,
Wherein the compound (a2) is an alkoxy group in the general formula (2). The active energy ray-curable coating composition according to claim 1 or 2, wherein the component (C) comprises at least one compound (C1) selected from a morpholinyl group-containing monomer, an amide group-containing monomer and a lactam compound. The active energy ray-curable coating composition according to claim 3, wherein the compound (C1) is at least one selected from acryloylmorpholine, N-vinylformamide, N-vinylacetamide and N-vinyl-epsilon -caprolactam . The positive active material according to any one of claims 1 to 4, wherein the component (C) comprises a compound (C2) having an isocyanuric ring and the content of the compound (C2) is 5 to 30 parts by weight. Curable coating composition. The active energy ray-curable coating composition according to claim 5, wherein the compound (C2) is a radically polymerizable unsaturated compound modified with an alkylene oxide or caprolactone. The positive resist composition according to any one of claims 1 to 6, wherein the content of the component (C) is 10 to 100 parts by weight based on 100 parts by weight of the total of the component (A), the component (B) 35 parts by weight,
Wherein the component (C) comprises at least one compound (C1) selected from a morpholinyl group-containing monomer, an amide group-containing monomer and a lactam compound, and a compound (C2) having an isocyanuric ring, Wherein the content of the compound (C1) is 5 to 30 parts by weight and the content of the compound (C2) is 5 to 30 parts by weight in the case of 10 to 35 parts by weight.