KR102158660B1 - 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)-(C) in a specific ratio. (A): 0.3 to 1.8 moles of silicon compound (a2) represented by SiY ₄ (Y is a siloxane bond generator) with respect to 1 mole of the (meth)acryloyl group-containing silicon compound (a1) represented by the general formula (1) Organosilicon compound obtained by hydrolysis cocondensation at a ratio of, (B): (meth)acrylic each derived from trihydric or higher aliphatic polyhydric alcohols, having two or more (meth)acryloyl groups, and having one or more hydroxyl groups (Meth)acrylate consisting of a urethane adduct compound (b1) obtained by addition reaction of a rate and a polyisocyanate, and a (meth)acrylate (b2) having three or more (meth)acryloyl groups and not having a hydroxyl group Mixture, (C): a radically polymerizable unsaturated compound having a nitrogen atom in its molecule.

Description

Active energy ray-curable coating composition {ACTIVE-ENERGY-RAY-CURABLE COATING COMPOSITION}

The present invention relates to an active energy ray-curable coating composition, and belongs to the technical field of an active energy ray-curable composition and a coating material.

In recent years, although glass is used in displays such as touch panels and smartphones, which are rapidly spreading, studies are being conducted to replace them with plastics for the purpose of reducing weight or preventing glass scattering when damaged.

In general, plastic substrates are lightweight, have excellent impact resistance and moldability, but have a drawback in that the surface is easily scratched and has low hardness, so that if used as it is, the appearance is remarkably damaged. For this reason, in many cases, the surface of a plastic substrate is coated with a paint composition and a so-called hard coating treatment is performed to impart abrasion resistance and scratch resistance.

Conventional paint compositions are to form a resin film by drying after coating a substrate using a paint composition in which a resin is dissolved in a solvent, but for the purpose of improving productivity, photocurable compositions or thermosetting compositions are also used. It is being reviewed.

Here, as a hard coating agent for a plastic substrate, an ultraviolet curable acrylic hard coating agent, a thermosetting silicone type hard coating agent, and the like have been proposed.

The thermosetting silicone-based hard coating agent is excellent in abrasion resistance and scratch resistance, but there are problems in that the curing time is long, resulting in poor productivity, and the substrate may be deformed because it requires a high temperature during curing. In contrast, the UV-curable acrylic hard coating agent generally has poor abrasion resistance and scratch resistance, but has a short curing time and excellent productivity.

As described above, the ultraviolet curable acrylic hard coating agent is excellent in terms of productivity and energy saving with respect to the thermosetting composition, and in order to take advantage of this characteristic, studies to improve the abrasion resistance and scratch resistance of the cured film, which were insufficient performance, are being conducted.

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

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

However, these coating compositions are superior in abrasion resistance and scratch resistance of the cured film compared to conventional ultraviolet curable coating compositions, but cannot simultaneously satisfy both abrasion resistance and abrasion resistance, or have no satisfactory performance in practical use. Further, depending on the substrate to be used, the adhesiveness may be insufficient.

In contrast, 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 substrate (Patent Document 3).

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

However, the photocurable coating composition described in Patent Literature 3 required an organic solvent in order to adjust the viscosity of the composition and impart coating suitability. For this reason, for example, in the case of applying a thick film or the like, it may take time for solvent distillation and removal, and there is room for improvement.

In general, when the viscosity of the composition is adjusted by mixing a reactive monomer or the like in place of an organic solvent, the hardness and scratch resistance of the cured product are lowered, and thus the obtained cured film is not sufficiently satisfied as a hard coat. For this reason, there has been a demand for a coating composition that is solvent-free, satisfies hardness and scratch resistance, and can be cured by active energy rays such as electron beams and ultraviolet rays.

Further, in general, by blending an unsaturated compound having a long chain segment in the molecule into the curable composition, the Tg of the cured product is reduced and the impact resistance is improved. However, since the crosslinking density of such a cured film is lowered, the hardness and scratch resistance tend to decrease. For this reason, a curable composition which satisfies hardness and abrasion resistance and obtains a cured film excellent in impact resistance has been desired.

The present invention is an active energy ray-curable coating composition that does not contain an organic solvent, the viscosity is sufficiently reduced to the extent that it can be applied, and when applied to a substrate such as plastic, the cured film thereof exhibits sufficient hardness and scratch resistance. It is an object to provide a coating composition.

In addition, the present invention is to provide an active energy ray-curable coating composition having a sufficiently reduced viscosity to the extent that coating is possible, and when applied to a substrate such as plastic, the cured film thereof exhibits sufficient hardness and scratch resistance, and is also excellent in impact resistance. Make it an assignment.

The inventors of the present invention have studied intensively in order to solve the above problems, and 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 viscosity without using an organic solvent, and hardness And it was discovered that a cured product excellent in scratch resistance was obtained. In addition, the present inventors found that by using a composition containing an isocyanuric ring and a compound having a radically polymerizable unsaturated group, a cured film having high hardness and excellent abrasion resistance and impact resistance can be obtained, thereby completing the present invention.

The present invention is as follows.

[1] (A) A (meth)acryloyl group-containing silicon compound (a1) represented by the following general formula (1) and a silicon compound (a2) represented by the following general formula (2), the silicon compound (a1) An organosilicon compound obtained by hydrolysis cocondensation in a ratio of 0.3 to 1.8 moles of the silicon compound (a2) per 1 mole,

(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, and R ² is a divalent saturated group having 1 to 6 carbon atoms A hydrocarbon group, R ³ is a hydrogen atom or a methyl group, X is a hydrolyzable group, a plurality of Xs may be the same or different, and n is 0 or 1)

(In the general formula (2), Y is a siloxane bond generator, and a plurality of Ys may be the same or different from each other)

(B) It is a (meth)acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, and the addition reaction of a (meth)acrylate having two or more (meth)acryloyl groups and one or more hydroxyl groups, and a polyisocyanate It is a (meth)acrylate derived from the resulting urethane adduct compound (b1) and a trihydric or higher aliphatic polyhydric alcohol, and has three or more (meth)acryloyl groups, and a (meth)acrylate (b2) having no hydroxyl group. Consisting of (meth)acrylate mixture, and

(C) a radically polymerizable unsaturated compound having a nitrogen atom in the molecule, and contains compounds other than the above component (A) and the above component (B),

The content of the component (A), the component (B) and the component (C) is 5 to 50 parts by weight of the component (A), and 30 to 50 parts by weight of the component (B) when the sum of them is 100 parts by weight. 90 parts by weight, the component (C) is 5 to 35 parts by weight of the active energy ray-curable coating composition.

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

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

[3] The active energy ray-curable type according to [1] or [2], wherein the component (C) contains at least one compound (C1) selected from a morpholinyl group-containing monomer, an amide group-containing monomer, and a lactam compound. Paint composition.

[4] The active energy ray according to [3], wherein the compound (C1) is at least one selected from acryloylmorpholine, N-vinylformamide, N-vinylacetamide and N-vinyl-ε-caprolactam. Curable paint composition.

[5] According to any one of [1] to [4], wherein the component (C) contains 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 alkylene oxide or caprolactone.

[7] The content of the component (C) is 10 to 35 parts by weight when the total of the component (A), the component (B) and the component (C) is 100 parts by weight, and the component (C) A, 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 isocyanur ring, the total of both being 10 to 35 parts by weight In one case, the active energy ray according to any one of [1] to [6], wherein the content ratio of the compound (C1) is 5 to 30 parts by weight, and the content ratio of the compound (C2) is 5 to 30 parts by weight. Curable paint composition.

The composition of one embodiment of the present invention can be made into a composition that does not contain an organic solvent, has high hardness with respect to various substrates such as plastics, and becomes possible to form a cured film excellent in scratch resistance.

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

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

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

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

It contains 5 to 35 parts by weight of component (C).

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

In addition, in this specification, an acryloyl group or a methacryloyl group is represented by "(meth)acryloyl group", and an acrylate or methacrylate is represented by "(meth)acrylate".

1. Ingredient (A)

The component (A) according to the present invention is a (meth)acryloyl group-containing silicon compound (a1) represented by the following general formula (1) (hereinafter referred to as ``compound (a1)'') and the following general formula (2). It is an organosilicon compound obtained by hydrolysis cocondensation of the expressed silicon compound (a2) (hereinafter referred to as ``compound (a2)'') in a ratio of 0.3 to 1.8 moles of compound (a2) with respect to 1 mole of 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, and R ² is a divalent saturated group having 1 to 6 carbon atoms A hydrocarbon group, R ³ is a hydrogen atom or a methyl group, X is a hydrolyzable group, a plurality of Xs may be the same or different, and n is 0 or 1)

(In the general formula (2), Y is a siloxane bond generator, and a plurality of Ys may be the same or different from each other)

In General Formula (1) representing 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 these, an alkyl group having 1 to 6 carbon atoms is preferable, and a methyl group is more preferable because the cured film of the resulting composition is excellent in abrasion resistance.

R ² is a C 1 to C 6 divalent saturated hydrocarbon group, preferably an alkylene group. As the alkylene group, the cured film of the resulting composition becomes excellent in abrasion resistance, and from the viewpoint 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, and a plurality of Xs may be the same or different. As the hydrolyzable group, various groups are possible as long as it is a group having hydrolysability. Specifically, a hydrogen atom, an alkoxy group, a cycloalkoxy group, an aryloxy group, and an arylalkoxy group are mentioned. Among 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.

In addition, n is 0 or 1, and since the cured film of the obtained composition is excellent in abrasion resistance, it is preferably 0.

In the general formula (1), as a specific example of a compound in which n is 0 and X is an alkoxy group, which is a preferred compound, 2-(meth)acryloyloxyethyltriethoxysilane, 3-(meth)acryloyloxypropyltri Methoxysilane and 3-(meth)acryloyloxypropylethyltriethoxysilane.

In the general formula (2) representing the compound (a2), Y is a siloxane bond generator, and a plurality of siloxane bond generator groups in one molecule may be the same or different.

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

Preferred specific examples of the compound (a2) include n such as tetra-n-propoxysilane, trimethoxy-n-propoxysilane, dimethoxydi-n-propoxysilane, and methoxytri-n-propoxysilane. -It is an alkoxysilane compound having a propoxy group.

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

The mixture of the n-propoxy group-containing alkoxysilane compound may be used by mixing a plurality of components, but those prepared by alcohol exchange may be used as they are. For example, a silicon compound represented by the general formula (2), and a compound having no n-propoxy group (for example, tetramethoxysilane) can be obtained by alcohol exchange reaction in 1-propanol. Moreover, the reaction product obtained by this reaction can also be used as it is.

Component (A) hydrolyzes and copolymerizes compound (a1) and compound (a2) in a ratio of 0.3 to 1.8 moles of compound (a2) with respect to 1 mole of compound (a1) (hereinafter referred to as ``first step''). Ha) is obtained. In addition, the reaction conditions for hydrolysis cocondensation are not particularly limited, but are preferably alkaline conditions, and the first step under alkaline conditions will be described below.

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

By proceeding the first step under alkaline conditions, gelation after the reaction can be prevented, and component (A) can be prepared in high yield.

Alkaline conditions are, specifically, a value in which the pH of the reaction system exceeds 7, preferably the pH is 8 or more, and more preferably the pH is 9 or more. In addition, the upper limit is usually pH 13. By setting the reaction system to the above pH, the component (A) excellent in storage stability can be produced in high yield.

The organosilicon compound obtained by hydrolysis cocondensation under acidic conditions (pH less than 7) may have poor storage stability.

Further, under neutral conditions (near pH 7), the hydrolysis cocondensation reaction may be difficult to proceed.

In the first step, the condensation rate of the compound (a1) and the compound (a2) can be set to 92% or more, more preferably 95% or more, and still more preferably 98% or more. It is most preferable that substantially all of the siloxane bond generating groups (including hydrolyzable groups) are condensed, but the upper limit of the condensation rate in the first step is usually 99.9%.

Conventionally, a method of producing an organosilicon compound under acidic conditions is known, but it is difficult to uniformly react both the compound (a1) and the compound (a2) as the raw material compounds, and it is easy to generate a gel. For this reason, a method of avoiding gelation by using a silicon compound (hereinafter referred to as "M monomer") having only one siloxane bond generating group, such as trimethylalkoxysilane or hexamethyldisiloxane, as an end sealant, is known.

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

On the other hand, according to the production method under alkaline conditions, the compound (a1) and the compound (a2) can be copolymerized without gelling, and thereafter, the resulting cured product has an effect that the inorganic properties of the resulting cured product are not reduced.

Component (A) is produced by making the first step essential, but the method for producing component (A) may further include the following steps as necessary.

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

(3rd process) A process of removing a volatile component from the neutralization liquid obtained in a 2nd process.

(Fourth step) A step of mixing and contacting the concentrate obtained in the third step with an organic solvent for washing, and dissolving at least the component (A) in the organic solvent for washing.

(Fifth step) A step of obtaining an organic solution containing the component (A) after washing the organic liquid obtained in the fourth step with water.

(6th process) A process of removing a volatile component from the organic solution obtained in a 5th process.

It is preferable that the manufacturing method of component (A) includes a 1st process, a 2nd process, and a 5th process.

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

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

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

2. Ingredient (B)

Component (B) according to the present invention is a (meth)acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, which has two or more (meth)acryloyl groups, and a (meth)acrylate having one or more hydroxyl groups, and As a (meth)acrylate derived from a urethane adduct compound (b1) (hereinafter referred to as ``component (b1)'') obtained by addition reaction of a polyisocyanate, and a trihydric or higher aliphatic polyhydric alcohol, a (meth)acryloyl group It is a (meth)acrylate mixture composed of (meth)acrylate (b2) (hereinafter referred to as "component (b2)") which has 3 or more and does not have a hydroxyl group.

The raw material compound of component (b1) is a (meth)acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, which has two or more (meth)acryloyl groups, and a (meth)acrylate having one or more hydroxyl groups (hereinafter, It is referred to as a hydroxyl-containing polyfunctional (meth)acrylate").

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

Various compounds can be used as the hydroxyl group-containing polyfunctional (meth)acrylate, specifically, trimethylolpropane di(meth)acrylate, di or tri(meth)acrylate of pentaerythritol, and ditrimethylolpropane. Di, tri, tetra, or penta (meth) acrylate of di or tri(meth)acrylate and dipentaerythritol.

Among these, since the cured film is excellent in hardness and scratch resistance, a compound having three or more (meth)acryloyl groups and one hydroxyl group is preferable, and specifically, pentaerythritol tri(meth)acrylate, Ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and the like.

Various compounds can be used as the polyisocyanate which is the other synthetic raw material for component (b1).

Examples of preferred polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 2,4-tolylene diisocyanate, and nurate-type trimers thereof. Can be lifted.

Component (b1) is synthesized by an addition reaction of a polyfunctional (meth)acrylate containing a hydroxyl group and a polyisocyanate. This addition reaction can be carried out without a catalyst, but in order to efficiently proceed the reaction, 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. Also works.

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

As the trihydric or higher aliphatic polyhydric alcohol as the raw material compound for 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, dipentaerythritol hexa(meth)acrylate, etc. Can be mentioned.

Among these, since the cured film is excellent in abrasion resistance and abrasion resistance, compounds having four or more (meth)acryloyl groups are preferred, and specifically, pentaerythritol tetra (meth) acrylate, ditrimethylolpropane tetra ( And 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 appropriately set according to the purpose. The component (B) is preferably a mixture containing in a weight ratio of (b1):(b2)=10:90 to 75:25, more preferably (b1):(b2)=30:70 to 70 It is a mixture containing in a weight ratio of :30.

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

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

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

3. Ingredient (C)

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

By using the said unsaturated compound (C), it becomes possible to set it as an active energy ray-curable coating composition which gives a cured film excellent in hardness and abrasion resistance. In addition, when it contains a specific compound (C1) described later, a composition having a sufficiently low viscosity can be obtained, and when a specific compound (C2) described later is included, the hardness and scratch resistance are not reduced, and the resistance of the cured film is Impact properties can be improved.

In the present invention, the number of radically polymerizable unsaturated groups in 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, a so-called monofunctional unsaturated compound, is preferred. 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, and N -Methoxymethyl(meth)acrylamide, N-butoxymethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, N,N-dimethylaminopropylacrylamide, N-vinylformamide, N-vinyl 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-ε-caprolactam; Morpholinyl group-containing monomers such as (meth)acryloylmorpholine; (Meth)acrylonitrile, N-cyclohexyl maleimide, N-phenyl maleimide, etc. are mentioned. These compounds may be used alone or in combination of two or more.

Among these, since the Tg of the homopolymer is high and the hardness and scratch resistance of the resulting cured film are good, an amide group-containing monomer, a lactam compound, and a morpholinyl group-containing monomer (hereinafter, these are collectively referred to as ``compound (C1)'') desirable. As this 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 more preferable because not only the performance of the cured product but also the effect of reducing the viscosity of the composition is high.

Further, the unsaturated compound (C) is a radically polymerizable unsaturated compound having an isocyanuric ring in its molecule (hereinafter, also referred to as "compound (C2)") alone or in combination with the compound (C1). And, as this compound (C2), isocyanuric acid EO-modified di(meth)acrylate and isocyanuric acid EO-modified tri(meth)acrylate, and mixtures thereof (as a specific brand name, for example, manufactured by Toa Kosei Co., Ltd. Alkylene oxide modification (such as ``Aronix M-313'' and ``Aronix M-315'', ``Pancryl FA-731A'' by Hitachi Kasei, and ``NK Ester A-9300'' by Shinnakamura Chemical Co., Ltd.) Meth)acrylates; ε-caprolactone-modified tris[2-(meth)acryloxyethyl]isocyanurate (as a specific brand name, for example, "Aronix M-327" manufactured by Toa Kosei Co., Ltd., "NK Ester A-" manufactured by Shinnakamura Chemical Industry Co., Ltd. [Epsilon]-caprolactone-modified (meth)acrylates such as "9300-1CL" and the like; A reactant such as a trimer of a difunctional isocyanate such as hexamethylene diisocyanate and isophorone diisocyanate and a hydroxyl group-containing (meth)acrylate (as a specific brand name, for example, ``Atresin UN-905'' manufactured by Negami Kogyo, etc.), Ester product of 1,3-bis(2-carboxyethyl)isocyanurate and 2-hydroxyethyl(meth)acrylate, tri(meth)acrylic acid ester of tris(2-hydroxyethyl)isocyanurate, Other isocyanuric acid derivatives (specific brand names include "MA-DGIC", "DA-MGIC", "MeDAIC", "AcDGIC", etc. manufactured by Shikoku Chemicals. These compounds may be used alone or in combination of two or more.

As the compound (C2), alkylene oxide-modified (meth)acrylates and ε-caprolactone-modified (meth)acrylates are more preferable from the viewpoint of more favorable impact resistance of the resulting cured film.

In addition, the number of radically polymerizable unsaturated groups in 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 because a cured film having high hardness and good scratch resistance can be easily obtained.

The content ratio of the unsaturated compound (C) in the composition of the present invention is 5 to 35 parts by weight, and preferably 5 to 35 parts by weight, when the total of components (A), (B) and (C) is 100 parts by weight. It is 30 parts by weight, 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 compound (C1), the viscosity of the composition is reduced to the extent that coating is possible even without containing an organic solvent, so the content ratio thereof is the components (A), (B) and ( When the total of C) is 100 parts by weight, it is preferably 5 to 35 parts by weight, more preferably 5 to 30 parts by weight, and still more preferably 8 to 25 parts by weight.

When the unsaturated compound (C) contains only compound (C2), a cured film having better impact resistance is obtained, so the content ratio thereof is when the total of components (A), (B) and (C) is 100 parts by weight. , Preferably it is 5 to 30 parts by weight, more preferably 8 to 30 parts by weight, still more preferably 10 to 25 parts by weight.

In addition, when the unsaturated compound (C) contains compounds (C1) and (C2), a cured film excellent in all of hardness, scratch resistance, and impact resistance is obtained, and therefore the preferred content ratio of these compounds is shown below. In the case where the total of both is 10 to 35 parts by weight, the content ratio of the compound (C1) is preferably 5 to 30 parts by weight, more preferably 5 to 25 parts by weight, even more preferably 8 to 25 parts by weight. And, the content ratio of the compound (C2) is preferably 5 to 30 parts by weight, more preferably 8 to 30 parts by weight, and 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 the extent that coating is possible even without using an organic solvent, and a cured film excellent in hardness, abrasion 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 any of a composition containing an organic solvent and a composition not containing an organic solvent, or a composition containing an organic solvent depending on the type of component (C). For example, when component (C) contains compound (C1), it can be set as a composition which does not contain an organic solvent. In addition, when component (C) contains compound (C2) or contains both compounds (C1) and (C2), it is preferable to contain an organic solvent. The organic solvent that can be used will be described later.

The composition of the present invention contains components (A), (B) and (C) as essential, but depending on the purpose, photopolymerization initiators, pigments, dyes, surface modifiers, ultraviolet absorbers, light stabilizers such as HALS, component (A) , (B) and (C) other than the compound having a radically polymerizable unsaturated group and various components such as an organic polymer may be further blended.

Various compounds can be used as the photoinitiator, and specific examples thereof include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxycyclohexyl-phenyl-ketone, and 2-hydroxy-2 -Methyl-1-phenyl-propan-1-one, 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one, 2-methyl -1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, Diethoxyacetophenone, oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone} and 2-hydroxy-1-{4-[4-(2-hydroxy) Acetophenone compounds such as oxy-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-diphenyl sulfide; Α-keto esters such as methylbenzoyl 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)-2,4,4-trimethylpentylphosphine Phosphine oxide compounds such as pin oxide; 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 photoinitiators such as 2-(O-benzoyloxime)-1-[4-(phenylthio)]-1,2-octanedione; And campoquinone.

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, when the total of components (A), (B) and (C) is 100 parts by weight. To 5 parts by weight.

By setting the blending amount of the photopolymerization initiator to 0.1 to 10 parts by weight, the composition becomes excellent in curability, and a composition that provides a cured film excellent in hardness and scratch resistance can be obtained.

The surface modifier has an effect of enhancing the leveling property when the composition of the present invention is applied, and an action of increasing the stain resistance and slipperiness of the cured coating film. As the surface modifier, a silicone-based surface modifier or a fluorine-based surface modifier is suitable. Specific examples include a silicone polymer having a silicone chain and a polyalkylene oxide chain, a fluorine polymer having a perfluoroalkyl group and a polyalkylene oxide chain, and a fluorine polymer having a perfluoroalkylether chain and a polyalkylene oxide chain. I can.

A preferable blending amount of the surface modifier is 0.01 to 3 parts by weight, more preferably 0.02 to 0.5 parts by weight, when the total of the components (A), (B) and (C) is 100 parts by weight. When the blending amount is 0.01 parts by weight or more, the surface smoothness of the coating film can be increased, and generation of air bubbles during application can be suppressed.

The compound having another radically polymerizable unsaturated group is not particularly limited as 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, and cyclohexyl ( Meth)acrylate, isobornyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate , Styrene, 2-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, (meth)acrylate of alkylene oxide adduct of phenol, (meth)acrylic of alkylene oxide adduct of alkylphenol Rate, etc. are mentioned.

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

The number of radically polymerizable unsaturated groups in other polyfunctional unsaturated compounds is preferably 3 to 20 per molecule from the viewpoint of not reducing hardness and scratch resistance.

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

Specific examples include di(meth)acrylate of an alkylene oxide adduct of bisphenol A, di(meth)acrylate of an alkylene oxide adduct of bisphenol F, di(meth)acrylate of an alkylene oxide adduct of bisphenol Z, bisphenol S Di(meth)acrylate of alkylene oxide adduct of thiobisphenol, di(meth)acrylate of alkylene oxide adduct of thiobisphenol, di(meth)acrylate of bisphenol A, di(meth)acrylate of bisphenol F, bisphenol Z Di(meth)acrylate, bisphenol S di(meth)acrylate, thiobisphenol di(meth)acrylate, tricyclodecanedimethyloldi(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(meth)acrylate, 1,6-hexanedioldi(meth)acrylate, 1 ,9-nonanedioldi(meth)acrylate, glycerindi(meth)acrylate, di(meth)acrylate of the alkylene oxide adduct of glycerin, dimer acid dioldi(meth)acrylate, cyclohexanedimethyloldi(meth) Tri(meth)acrylate of acrylate, trimethylolpropane tri(meth)acrylate, alkylene oxide adduct of trimethylolpropane, tree and tetraacrylate of pentaerythritol, tree of alkylene oxide adduct of pentaerythritol, and Tetraacrylate, ditrimethylolpropanetetra(meth)acrylate, dipentaerythritol hexa and pentaacrylate, polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, at the end ( And silicone resins having a meth)acryloyl group.

Among these, as polyester (meth)acrylate, a dehydration condensation product of a polyester polyol and (meth)acrylic acid is mentioned. Examples of polyester polyols include low molecular weight polyols such as ethylene glycol, polyethylene glycol, cyclohexanedimethylol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, 1,6-hexanediol and trimethylolpropane, Or reaction products obtained by using polyol components such as alkylene oxide adducts thereof, dibasic acids such as adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid and terephthalic acid, or acid components such as anhydrides thereof, and various dendrimer types The dehydration condensate of polyol and (meth)acrylic acid, etc. are mentioned.

As epoxy (meth)acrylate, (meth)acrylic acid adduct of bisphenol A type epoxy resin, (meth)acrylic acid adduct of hydrogenated bisphenol A type epoxy resin, and (meth)acrylic acid addition of phenol or cresol novolak type epoxy resin Water, (meth)acrylic acid adduct of biphenyl type epoxy resin, diglycidyl ether (meth)acrylic acid adduct of polyether such as polytetramethylene glycol, and (meth)acrylic acid addition of diglycidyl ether of polybutadiene Water, (meth)acrylic acid adduct of polybutadiene internal epoxidation, (meth)acrylic acid adduct of silicone resin having an epoxy group, (meth)acrylic acid adduct of limonenedioxide, 3,4-epoxycyclohexylmethyl-3, (Meth)acrylic acid adduct of 4-epoxycyclohexane carboxylate, etc. are mentioned.

Examples of urethane (meth)acrylates include compounds obtained by addition reaction of organic polyisocyanate and hydroxyl group-containing (meth)acrylate, and compounds obtained by addition reaction of organic polyisocyanate and polyol and hydroxyl group-containing (meth)acrylate. I can.

Here, as a polyol, a low molecular weight polyol, a polyether polyol, a polyester polyol, a polycarbonate polyol, etc. are mentioned.

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

As polyether polyol, polypropylene glycol, polytetramethylene glycol, etc. are mentioned.

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 organic polyisocyanates include tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, and iso. Foron diisocyanate, etc. are mentioned.

Examples of the hydroxyl group-containing (meth)acrylate include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate. ) A hydroxyl group-containing (meth)acrylate of an acrylate, etc. are mentioned.

The organic polymer has an effect of reducing warpage during curing while maintaining transparency. Suitable organic polymers are (meth)acrylic polymers, and suitable constituent monomers include methyl (meth)acrylate, cyclohexyl (meth)acrylate, (meth)acrylic acid, glycidyl (meth)acrylate, N-(2- (Meth)acryloxyethyl)tetrahydrophthalimide, etc. are mentioned. In the case of a polymer copolymerized with (meth)acrylic acid, glycidyl (meth)acrylate may be added to introduce a (meth)acryloyl group into the polymer chain.

Even if the composition of the present invention does not contain an organic solvent, coating properties and handling properties may be excellent in some cases, but an organic solvent can be used for the purpose of further improving these performances or for adjusting the viscosity of the composition. As an organic solvent, it is preferable to dissolve components (A), (B) and (C).

Specific examples of a preferred 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, etc. are mentioned.

The preferred 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 when the total of components (A), (B) and (C) is 100 parts by weight. To 300 parts by weight.

Known coating methods (bar coat, roll coat, spin coat, dip coat, gravure coat, die coat, flow coat, spray coat, etc.) since the viscosity of the curable composition is sufficiently reduced by setting the blending amount of the organic solvent to 10 to 1000 parts by weight. It is easy to prepare a coating composition corresponding to.

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

The method for preparing the active energy ray-curable coating composition of the present invention can be carried out according to a conventional method, such as stirring and mixing component (A), component (B), component (C), and other components used as necessary. It can be set as the manufacturing method provided with a process.

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 including various materials. And, as a preferable base material, wood, metal, inorganic materials, plastics, etc. are mentioned.

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

Specific examples of plastics include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride, polycarbonate resins, epoxy resins, and polyurethane resins.

The method of coating the composition of the present invention on a substrate is not particularly limited, and a conventional method may be used. For example, bar coat, roll coat, spin coat, dip coat, gravure coat, flow coat, spray coat, and the like can be applied.

In addition, as a specific method of forming a cured film, a method of irradiating the coating film with active energy rays after applying the composition to the substrate may be mentioned. Further, if necessary, before irradiation with active energy rays, a drying step or a preheating step of the coating film may be performed.

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

The drying temperature or preheating temperature is not particularly limited as long as the substrate to be applied is below a temperature that does not cause problems such as deformation.

Examples of active energy rays for curing the coating film containing the composition of the present invention include electron beams, ultraviolet rays, visible rays, and X rays, but since an inexpensive device can be used, ultraviolet rays are preferable.

Examples of the ultraviolet irradiation device include a high-pressure mercury lamp, a metal halide lamp, a UV electrodeless lamp, and an LED.

The irradiation energy should be appropriately set according to the type or composition of the active energy ray, but for example, when a high-pressure mercury lamp is used, the irradiation energy in the UV-A region is preferably 100 to 5,000 mJ/cm 2, and 200 to 1,000 mJ/cm 2 is more preferable.

In the case of curing with an electron beam, various devices can be used as the electron beam (EB) irradiation device that can be used, for example, a Cocroft Walton type, a Vander graph type, and a resonance transformer type device, and the like. It is preferable to impart an 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 the occurrence of scratches due to contact with a metal member or the like is also suppressed. The material having the cured film can be used for various purposes by taking advantage of this property.

For example, a front plate for a display panel, a building material application, a lighting fixture, a display or housing such as a mobile phone and a smart phone, a housing for a home appliance, and various lenses such as glasses may be mentioned.

As a specific example of the front plate for a display panel, an electric bulletin board, a display, a signboard, an advertisement, a sign, etc. are mentioned.

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

Example

Hereinafter, the present invention will be described in detail based on examples. In addition, the present invention is not limited by these examples.

In addition, below, "part" means a weight part, and "%" means weight%.

1. Preparation of component (A)

Preparation Example 1 (Preparation of MAC-TQ)

To a reactor equipped with a stirrer and a thermometer, 150 g of 1-propanol for alcohol exchange reaction and 36.53 g (0.24 mol) of tetramethoxysilane (hereinafter referred to as "TMOS") were added, and then 25% hydroxylated while stirring them. 4.37 g of a tetramethylammonium methanol solution (0.1 mol of methanol, 12 mmol of tetramethylammonium hydroxide) was gradually added, and the mixture was reacted at a temperature of 25°C and a pH of 9 for 6 hours. After that, the internal temperature was set to 60° C. and reacted for 1 hour while stirring. Here, as a result of gas chromatographic analysis (TCD detector) of the reaction solution, 1 to 4 of the methoxy groups included in the TMOS were substituted with n-propoxy groups, and each compound and non-substituent of mono-, di-, tri- or tetra-substituted The TMOS of the reaction was detected. Only trace amounts were detected in TMOS. Among these, the proportion of the n-propoxy group-containing compound (n-propoxy group-containing alkoxysilane) was approximately 100% in total. Based on the peak area of the product in the gas chromatogram, the number of substitutions of 1-propanol (average of the number of n-propoxy groups per molecule of the n-propoxy group-containing compound) was determined and found to be 2.7.

Next, to the reaction solution, 59.62 g (0.24 mol) of 3-methacryloxypropyltrimethoxysilane was added, and 30.2 g of water was further added. Then, 7.88 g of a 25% tetramethylammonium hydroxide methanol solution (0.18 moles of methanol, 21.6 mmol of tetramethylammonium hydroxide) was added, followed by reaction at a temperature of 25°C and pH 9 for 24 hours while stirring. Then, 22.2 g (35.3 mmol) of 10% nitric acid aqueous solution was added to neutralize. Subsequently, this neutralized solution was added to a mixed solution of 120 g of diisopropyl ether and 180 g of water, followed by extraction. The diisopropyl ether layer is washed with water to remove salts and excess acid, and then, as a polymerization inhibitor, 11.5 N-nitrosophenylhydroxyamicaluminum salt "Q-1301" (brand name) manufactured by Wako Junyaku Kogyo Co., Ltd. Mg was added. The organic solvent was distilled off from the obtained diisopropyl ether solution under reduced pressure to obtain a colorless and transparent solid organosilicon compound (hereinafter referred to as "MAC-TQ"). Its yield was 57.72 g.

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

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

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

2. Preparation of component (B)

Preparation Example 2 (Preparation of HDI-M305)

A mixture of pentaerythritol triacrylate (hereinafter referred to as ``PETri'') and pentaerythritol tetraacrylate (hereinafter referred to as ``PETet'') in a 0.5 L separable flask equipped with a stirring device and an air intake pipe ( (Contains 0.3 moles of PETri and 0.2 moles of PETet) 159.2g, 2,6-di-tert-butyl-4 manufactured by Doa Kosei Co., Ltd., "Aronix M-305" (brand name, hereinafter referred to as "M-305") -0.092 g of methylphenol (hereinafter referred to as "BHT") and 0.055 g of dibutyltin dilaurate (hereinafter referred to as "DBTL") were added, and the liquid temperature was set to 70 to 75°C, while stirring these, 25.2 g (0.15 mol) of hexamethylene diisocyanate (hereinafter, referred to as "HDI") was added dropwise and reacted.

After completion of the dropping of HDI, the reaction was further continued with the internal temperature set to 80°C, followed by stirring for 3 hours. Then, IR (infrared absorption) analysis of the reaction product confirmed that the isocyanate group had disappeared, 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 PETet (equivalent to compound (b2)) that does not react with HDI, and the weight ratio is (b1):(b2)=6:4 It is a mixture containing as.

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

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 subjected to various evaluations.

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

Each raw material was used in the 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.

Then, the viscosity at 25 degreeC of each obtained composition was measured with the E-type viscometer, and the obtained value was put together in each table.

Thereafter, each composition was poured onto the surface of one side of a 7 cm x 15 cm x 50 µm polyethylene terephthalate film, and a 50 µm thick release film containing polyethylene terephthalate and transmitting ultraviolet rays was covered thereon. . Subsequently, the thickness of the coating film was adjusted by passing it through a laminate roll so that the film thickness after curing became about 50 µm. A coating film was formed on the other side of the polyethylene terephthalate film by the same method. Then, through the release film, ultraviolet irradiation was performed under the following conditions, and the cured film was created on both surfaces of a polyethylene terephthalate film.

Ultraviolet irradiation was performed using an ultraviolet 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 with a photometer "UV POWER PUCK" manufactured by EIT, and it was 900 mJ/cm 2 in the UV-A region. In addition, the peak illuminance was 170 mW/cm 2 in the UV-A region.

About the obtained cured film, pencil hardness, abrasion resistance, and adhesiveness were evaluated by the method shown below. Table 2 shows the evaluation results.

(1) pencil hardness

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 rubbed 400 reciprocating was measured while applying a load of 1200 g/4 cm 2, in a state where the Nippon Steel Wool Company made steel wool "Bonstar #0000" was disposed. Using the number of scratches, the scratch resistance was evaluated based on the following criteria. Here, evaluation "A" or "B" was made into good abrasion resistance.

A: There were no scratches.

B: There were 1 to 9 scratches.

C: There were 10 or more scratches.

Each of the compositions of Examples 1 to 5 exhibited a viscosity of 10,850 mPa·s or less even though an organic solvent was not used, and the viscosity was sufficiently reduced to the extent that coating was possible. Further, it was confirmed that the cured film exhibited good pencil hardness of 8H to 10H, was excellent in abrasion resistance, and was also excellent in scratch resistance. Among them, Examples 3 to 5 in which N-vinylformamide (NVF) was used as the component (C) further reduced the viscosity of the composition, and were advantageous in coating properties during various coatings.

In contrast, Comparative Example 1 did not contain the component (C) according to the present invention, so the composition had a very high viscosity of 34,400 mPa·s, and the necessity of dilution with an organic solvent or the like was high during handling and coating. In addition, in Comparative Example 2 using 1,6-hexanediol diacrylate (HDDA), which is an unsaturated compound containing no nitrogen atom, both the pencil hardness and the scratch resistance of the cured film were reduced.

Comparative Examples 3 and 4 are experimental examples when 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. Conversely, in Comparative Example 4 in which the content of the component (C) was too large, the pencil hardness and scratch resistance of the cured film were low. .

Examples 6 to 11 and Comparative Example 5

Each raw material and each raw material shown in Table 3 were used in the ratios shown in Table 3, and stirred and mixed at room temperature according to an ordinary method to prepare an active energy ray-curable coating composition. In addition, the composition of Comparative Example 5 is the same as the composition of Comparative Example 1. The viscosity of each composition was measured, and coating suitability was determined based on the criteria classified as follows. The results are listed in Table 3.

A: The viscosity was 100 mPa·s or more and 10,000 mPa·s or less

B: The viscosity exceeded 10,000 mPa·s and was 15,000 mPas or less

C: The viscosity exceeded 15,000 mPa·s and was 20,000 mPas or less

D: The viscosity exceeded 20,000 mPa·s

Then, in the same manner as in Example 1, a cured film was formed on both surfaces of the polyethylene terephthalate film. And in addition to the said (1) hardness and (2) abrasion resistance, the following (3) impact resistance was evaluated. Table 3 shows these evaluation results.

(3) Impact resistance (falling ball test)

With respect to the surface of the cured film, 25 g of iron balls in accordance with JIS B 1501 were dropped from a height of 10 cm. When no cracks or cracks occurred in the cured film, the height was increased by 5 cm, and the operation of dropping the iron balls was repeated, and the highest value of the height at which cracks or cracks did not occur was recorded. Impact resistance was evaluated by performing this test on five hardened products and calculating the average value of the highest value at which no cracks or cracks occurred.

In addition, the test was conducted under constant temperature and humidity conditions of 23°C and 50% RH.

The viscosity of each composition of Examples 6 to 11 was also sufficiently reduced to the extent that coating was possible. In addition, it was confirmed that all of the obtained cured films showed good pencil hardness of 8H to 10H, and were also excellent in scratch resistance and impact resistance (falling ball test). Particularly, in Examples 9 to 11 in which two types containing NVF were used as the component (C), the viscosity of the composition was low, and the coating operation was easy.

On the other hand, Comparative Example 5 is an experimental example of a composition not containing the component (C) according to the present invention, but its viscosity is high, and the obtained cured film is excellent in hardness and scratch resistance, but the value of the falling ball test is low to 15 cm. It was less impactful.

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 (8)

(A) A (meth)acryloyl group-containing silicon compound (a1) represented by the following general formula (1) and a silicon compound (a2) represented by the following general formula (2) were added to 1 mole of the silicon compound (a1). An organosilicon compound obtained by hydrolysis copolymerization in a ratio 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, and R ² is a divalent saturated group having 1 to 6 carbon atoms A hydrocarbon group, R ³ is a hydrogen atom or a methyl group, X is a hydrolyzable group, a plurality of Xs may be the same or different, and n is 0 or 1)

(In general formula (2), Y is a siloxane bond generator, and a plurality of Ys may be the same or different from each other)
(B) As a (meth)acrylate derived from a trihydric or higher aliphatic polyhydric alcohol, by addition reaction of a (meth)acrylate having two or more (meth)acryloyl groups and one or more hydroxyl groups, and a polyisocyanate (Meth)acrylate derived from the resulting urethane adduct compound (b1) and trihydric or higher aliphatic polyhydric alcohol, which has three or more (meth)acryloyl groups and no hydroxyl group (meth)acrylate (b2) (Meth)acrylate mixture consisting of, and
(C) a radically polymerizable unsaturated compound having a nitrogen atom in the molecule, and contains compounds other than the above component (A) and the above component (B),
The content of the component (A), the component (B) and the component (C) is 5 to 50 parts by weight of the component (A), and 30 parts by weight of the component (B) when the total is 100 parts by weight. To 90 parts by weight, the component (C) is 5 to 35 parts by weight of an active energy ray-curable coating composition. The compound according to claim 1, wherein the compound (a1) is a compound in which X in the general formula (1) is an alkoxy group and n is 0,
The active energy ray-curable coating composition in which the compound (a2) is an alkoxy group in which Y in the general formula (2) is. The active energy ray-curable coating composition according to claim 1 or 2, wherein the component (C) contains 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-ε-caprolactam. . The active energy ray-curable coating composition according to claim 4, wherein the component (C1) contains at least N-vinylformamide. The active energy ray-curable coating composition according to claim 1 or 2, wherein the component (C) contains a compound (C2) having an isocyanuric ring, and the content of the compound (C2) is 5 to 30 parts by weight. The active energy ray-curable coating composition according to claim 6, wherein the compound (C2) is a radically polymerizable unsaturated compound modified with alkylene oxide or caprolactone. The content of the component (C) according to claim 1 or 2, when the sum of the component (A), the component (B) and the component (C) is 100 parts by weight, and is 10 to 35 parts by weight. ,
The component (C) contains 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 isocyanur ring, and the sum of both When the content is 10 to 35 parts by weight, the content ratio of the compound (C1) is 5 to 30 parts by weight, and the content ratio of the compound (C2) is 5 to 30 parts by weight.