TWI617630B - Active energy ray hardening coating composition - Google Patents

Abstract

The active energy ray-curable coating composition of the present invention contains a specific ratio: an organosilicon compound, which is a silicon compound (a1) containing a (meth) acrylfluorenyl group represented by general formula (1), and The silicon compound (a2) represented by SiY ₄ (Y is a siloxane bond generating group) is hydrolyzed at a ratio of 0.3 to 1.8 moles of silicon compound (a2) to 1 mole of silicon compound (a1). Copolymerization and condensation; (meth) acrylic acid ester mixture, which is derived from: (meth) acrylic acid esters derived from aliphatic polyhydric alcohols of three or more valences; (Meth) acrylic acid ester having one or more hydroxyl groups, an urethane addition compound (b1) obtained by addition reaction with polyisocyanate, and a derivative derived from an aliphatic polyhydric alcohol having a valence of 3 or more ( (Meth) acrylic acid esters, and (meth) acrylic acid esters (b2) having three or more (meth) acrylfluorenyl groups and having no hydroxyl groups; Saturated compounds.

Description

Active energy ray hardening coating composition

The invention relates to an active energy ray-curable coating composition, and belongs to the field of active energy ray-curable coatings and coatings.

In recent years, glass has been used as a display for touch panels or smart phones, which have been rapidly gaining popularity. However, for the purpose of reducing weight or preventing scattering of glass when broken, a method of replacing it with plastic has been gradually explored.

Generally speaking, plastic substrates are lightweight and have excellent impact resistance and formability. However, since the surface is easily damaged and the hardness is low, when used directly, it has the disadvantage of significantly damaging the appearance. Therefore, the surface of a plastic substrate is often coated with a coating composition, that is, a so-called hard coating film treatment is performed to impart abrasion resistance and abrasion resistance.

Conventional coating compositions are coating compositions in which a resin is dissolved in a solvent, and are dried after coating on a substrate to form a resin film. However, for the purpose of improving productivity, the photocurable composition or The heat-curable composition is examined.

Here, the hard coating agent formed on the plastic substrate was proposed by UV Linear curing type acrylic hard coating agent, and thermosetting silicone hard coating agent, etc.

Heat-curable polysiloxane-based hard coating agent has excellent abrasion resistance and abrasion resistance, but it has a long curing time, which deteriorates productivity, and requires high temperatures during curing, which may cause deformation of the substrate. And other issues. On the other hand, in general, a UV-curable acrylic hard coating agent has poor abrasion resistance and abrasion resistance, but has a short curing time and excellent productivity.

As mentioned above, the UV-curable acrylic hard coating agent is superior to the thermosetting composition from the viewpoint of productivity and energy saving. In order to take advantage of this feature, some people are exploring the improvement of its insufficient performance. The abrasion resistance and scratch resistance of the hardened film.

For example, a method is known in which a colloidal silicon dioxide or a silane compound having a (meth) acryloxy group is formulated into a composition.

Specifically, a UV-curable coating composition containing colloidal silicon dioxide, an alkoxysilane having a (meth) acryloxy group, and an acrylate is known (Japanese Patent Publication No. 57-500984), And a reactant comprising an isocyanate-containing alkoxysilane and a polyfunctional acrylate having a hydroxyl group and three or more acrylfluorene groups in the molecule, and a polyfunctional acrylate having three or more acrylfluorene groups and colloidal silica UV-curable coating composition (Japanese Patent No. 5-287215).

However, compared with conventional UV-curable coating compositions, these coating compositions have excellent abrasion resistance and abrasion resistance, but cannot satisfy both abrasion resistance and abrasion resistance at the same time. Has practically satisfying performance. In addition, depending on the substrate used, it may be tight Will be insufficient.

In contrast, the present applicant has proposed a light-curable coating composition containing a specific organic silicon compound as a hard coating agent excellent in abrasion resistance, abrasion resistance, and tightness to a substrate (Japanese Patent Laid-Open) 2011-88996).

However, the photocurable coating composition described in Patent Document 3 must use an organic solvent in order to adjust the viscosity of the composition to impart coating suitability. Therefore, for example, in the case of thick film coating, there is still room for improvement in the case where solvent distillation takes time.

Generally, when a reactive monomer or the like is blended instead of an organic solvent to adjust the viscosity of a composition, the hardness or abrasion resistance of a cured product is reduced, so that the resulting cured film cannot sufficiently satisfy a hard coating film. Therefore, there is a need for a solvent-free coating composition that can satisfy hardness or abrasion resistance and can be hardened by active energy rays such as electron beams and ultraviolet rays.

In addition, in general, by blending an unsaturated compound having a long chain segment in a molecule with a hardenable composition, the Tg of the hardened material can be reduced, and impact resistance can be improved. However, such a cured film tends to have reduced hardness and abrasion resistance because its cross-linking density decreases. Therefore, there is a need for a hardenable composition that can obtain a hardened film that can satisfy hardness or scratch resistance and is also excellent in impact resistance.

The object of the present invention is to provide an active energy ray hardening Type coating composition, which is an active energy ray hardening type coating composition that does not contain organic solvents, can sufficiently reduce the viscosity to the extent that it can be applied, and when applied to substrates such as plastics, the cured film can appear Out of full hardness and scratch resistance.

In addition, an object of the present invention is to provide an active energy ray-curable coating composition, which can sufficiently reduce the viscosity to a coatable level, and when applied to a substrate such as plastic, the cured film can be sufficiently developed. Hardness and scratch resistance, and excellent impact resistance.

The present inventors have conducted intensive studies in order to solve the above problems, and as a result, have found that by using a composition containing a compound having a nitrogen atom and a radical polymerizable unsaturated group, the composition can be adjusted without using an organic solvent. In order to obtain sufficient coating viscosity, a hardened product having excellent hardness and scratch resistance is obtained. In addition, the present inventors have also found that by using a composition containing a compound having an isocyanuric acid ring and a radically polymerizable unsaturated group, hardening with high hardness and excellent scratch resistance and impact resistance can be obtained. Film, thus completing the present invention.

The present invention is as follows.

[1] An active energy ray-curable coating composition containing: (A) an organosilicon compound comprising a (meth) acrylfluorene-containing silicon compound (a1) represented by the following general formula (1) ), And a silicon compound (a2) represented by the following general formula (2), hydrolyzed and copolymerized at a ratio of 0.3 to 1.8 mol of the silicon compound (a2) relative to 1 mol of the silicon compound (a1). Derived from condensation

(In 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 an organic group having 1 to 6 carbon atoms. A divalent saturated hydrocarbon group of 6, R ³ is a hydrogen atom or a methyl group, X is a hydrolyzable group, and a plurality of X may be the same or different from each other, and n is 0 or 1)

SiY ₄ ‧‧‧ (2)

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

(B) (meth) acrylate mixture, which is a (meth) acrylate derived from an aliphatic polyhydric alcohol having a valence of 3 or more, and is composed of a (meth) acrylic acid fluorenyl group having 2 or more A (meth) acrylate having one or more hydroxyl groups, an urethane addition compound (b1) obtained by an addition reaction with a polyisocyanate, and a (methyl group derived from an aliphatic polyhydric alcohol having a valence of three or more. ) Acrylate, and is composed of (meth) acrylate (b2) having 3 or more (meth) acrylfluorenyl groups and having no hydroxyl group; and (C) A radically polymerizable unsaturated compound having a nitrogen atom in the molecule, and a modification other than the above-mentioned component (A) and the above-mentioned component (B) When the content of the component (A), the component (B), and the component (C) is 100 parts by weight, the component (A) is 5 to 50 parts by weight, and the component (B ) Is 30 to 90 parts by weight, and the component (C) is 5 to 35 parts by weight.

[2] The active energy ray-curable coating composition according to the above [1], wherein the compound (a1) is a compound in which X is an alkoxy group and n is 0 in the general formula (1), In the compound (a2), Y in the general formula (2) is an alkoxy group.

[3] The active energy ray-curable coating composition according to the above [1], wherein the component (C) is selected from the group consisting of a monomer containing a morpholino group, a monomer containing an amidino group, and a lactam compound At least one compound (C1).

[4] The active energy ray-curable coating composition according to the above [3], wherein the compound (C1) is selected from the group consisting of acrylamidomorpholine, N-vinylformamide, N-vinylacetamide, and N -At least one kind of vinyl-ε-caprolactone.

[5] The active energy ray-curable coating composition according to the above [1], 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.

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

[7] The active energy ray-curable coating composition according to the above [1], wherein the content of the component (C) is based on the component (A) and the component When the total of (B) and the aforementioned component (C) is 100 parts by weight, it is 10 to 35 parts by weight. The aforementioned component (C) is selected from the group consisting of a monomer containing a morpholino group, a monomer containing an amidino group, When the compound (C1) is at least one compound selected from the group consisting of lactam compounds and the compound (C2) having an isocyanuric acid ring, when the total of the two is 10 to 35 parts by weight, The content ratio is 5 to 30 parts by weight, and the content ratio of the compound (C2) is 5 to 30 parts by weight.

The composition of one form of the present invention can be a composition that does not contain an organic solvent, and can form a hardened film having high hardness and excellent abrasion resistance to various substrates such as plastic.

In addition, according to the composition of another type of the present invention, a hardened film having high hardness and excellent scratch resistance and impact resistance can be formed on various substrates such as plastic.

The active-energy-ray-curable coating composition of the present invention contains 5 to 50 parts by weight of the component (A) with respect to 100 parts by weight of the total of the components (A), (B), and (C), and (B) The component is 30 to 90 parts by weight, and the (C) component is 5 to 35 parts by weight.

The details of each component and composition are described below.

In this specification, "(meth) acrylfluorenyl" means acrylfluorenyl or methacrylfluorenyl, and "(meth) acrylate" means an acrylate or methacrylate.

1. Ingredient (A)

The component (A) of the present invention is a silicon compound (a1) containing a (meth) acrylfluorenyl group represented by the following general formula (1) (hereinafter referred to as "compound (a1)") and the following general The silicon compound (a2) (hereinafter referred to as "compound (a2)") represented by formula (2) is hydrolyzed at a ratio of 0.3 to 1.8 moles of compound (a2) to 1 mole of compound (a1). An organosilicon compound obtained by copolymerization and condensation.

(In 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 an organic group having 1 to 6 carbon atoms. A divalent saturated hydrocarbon group of 6, R ³ is a hydrogen atom or a methyl group, X is a hydrolyzable group, and a plurality of X may be the same or different from each other, and n is 0 or 1).

SiY ₄ ‧‧‧ (2)

(In general formula (2), Y is a siloxane bond generating group, and a plurality of Y Can be the same or different from each other).

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 these, an alkyl group having 1 to 6 carbon atoms is preferred, and from the viewpoint of excellent abrasion resistance of a cured film of the obtained composition, a methyl group is more preferred.

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

X is a hydrolyzable group, and a plurality of X may be the same or different from each other. The hydrolyzable group may be any hydrolyzable group, and may be various groups. Specific examples include a hydrogen atom, an alkoxy group, a cycloalkoxy group, an aryloxy group, and an aralkoxy group. 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 methoxy, ethoxy, propoxy, butoxy, pentoxy, and hexyloxy.

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

In the general formula (1), specific examples of a compound in which n is 0 and X is an alkoxy group include 2- (meth) acryloxyethyltriethoxysilane, 3- ( (Meth) acryloxypropyltrimethoxysilane and 3- (meth) acryloxypropylethyltriethoxysilane.

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

The siloxane bond forming group is preferably an alkoxy group. Preferred examples of alkoxy include alkoxy having 1 to 4 carbon atoms, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, and secondary butoxy. base.

Preferred specific examples of the compound (a2) include n-propyl groups such as tetra-n-propoxysilane, trimethoxy-n-propoxysilane, dimethoxydi-n-propoxysilane, and methoxytri-n-propoxysilane. Alkoxysilane compounds.

The alkoxysilane compound having n-propoxy group may be one kind of compound or a mixture of compounds having n-propoxy group and other alkoxy groups.

A mixture of an alkoxysilane compound having n-propoxy group can be used by mixing a plurality of components, but it can also be used directly by an alcohol exchange manufacturer. For example, a silicon compound represented by the above general formula (2) and a compound having no n-propoxy group (for example, tetramethoxysilane) can be obtained by performing an alcohol exchange reaction in 1-propanol. Moreover, the reaction product obtained by this reaction can also be used as it is.

The component (A) is subjected to hydrolysis copolymerization and condensation at a ratio of the compound (a1) and the compound (a2) to the compound (a1) 1 mole and the compound (a2) is 0.3 to 1.8 moles (hereinafter referred to as "the first 1 step "). The reaction conditions for the hydrolysis copolymerization condensation are not particularly limited, but are preferably basic conditions. The first step under basic conditions will be described below.

The reaction ratio of the compound (a1) to the compound (a2) is 0.3 to 1.8 for the compound (a1) 1 mole. Moore, the compound (a2) is preferably 0.8 to 1.6 moles, and the compound (a2) is more preferably 1 to 1.4 moles. By performing the reaction at this ratio, gelation does not occur during and after the reaction, and the component (A) can be efficiently produced.

By performing the above-mentioned first step under alkaline conditions, the gelation after the reaction can be prevented, and the component (A) can be produced in a high yield.

The alkaline condition is specifically a value in which the pH of the reaction system exceeds 7, the pH is preferably 8 or more, and the pH is more preferably 9 or more. The upper limit is usually pH13. By constituting the reaction system at the above-mentioned pH, the component (A) having excellent storage stability can be produced in a high yield.

The organosilicon compound obtained by hydrolytic copolymerization and condensation under acidic conditions (less than pH 7) may have poor storage stability.

In addition, under neutral conditions (near pH 7), it may be difficult to perform a hydrolysis copolymerization condensation reaction.

In the first step, the condensation ratio of the compound (a1) and the compound (a2) may be set to 92% or more, preferably 95% or more, and more preferably 98% or more. The siloxane bond-forming group (including the hydrolyzable group) is preferably substantially all condensed, but the upper limit of the condensation rate in the first step is usually 99.9%.

Conventionally, there are known methods for producing an organosilicon compound under acidic conditions, but it is difficult to uniformly react both the compound (a1) and the compound (a2) as a raw material compound, and it is easy to generate a gel. Therefore, a silicon compound (hereinafter referred to as "M monomer") having only one siloxane bond generating group such as trimethylalkoxy-based alkane or hexamethyldisilaxane is used as a terminal blocking agent to Avoid gelation.

However, if M monomers having a predetermined amount or more are used in combination, even if gelation can be avoided, the inorganic properties of the obtained organosilicon compound tend to decrease.

On the other hand, according to the production method under basic conditions, the compound (a1) and the compound (a2) can be copolymerized and condensed without causing gelation, and the effect of reducing the inorganic properties of the obtained cured product can be exhibited .

The component (A) is produced by using the above-mentioned first step as a necessary step, but the method for producing the 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.

(Third step) A step of removing volatile components from the neutralization solution obtained in the second step.

(Step 4) A step of mixing and contacting the concentrate obtained in the step 3 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.

(Step 6) A step of removing volatile components from the organic solution obtained in Step 5.

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 liquid containing the component (A) after the first step, the neutralization liquid after the second step, the organic liquid after the fourth step, and Organic solvent after step 5 At least one kind of liquid is added with a polymerization inhibitor which inhibits the polymerization of (meth) acrylfluorenyl group.

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

By setting the content ratio of the component (A) to 5 to 50 parts by weight, it is possible to constitute a composition that imparts a cured film excellent in hardness and scratch resistance.

2. Ingredient (B)

The component (B) of the present invention is a (meth) acrylic acid ester derived from an aliphatic polyhydric alcohol having a valence of 3 or more, and has (meth) acrylfluorenyl groups of 2 or more, and has 1 The urethane addition compound (b1) (hereinafter referred to as "component (b1)") obtained by the addition reaction of the above-mentioned hydroxyl (meth) acrylate and polyisocyanate, Alcohol-derived (meth) acrylic acid esters (meth) acrylic acid esters (b2) having three or more (meth) acrylfluorenyl groups and having no hydroxyl groups (hereinafter referred to as "ingredient (b2)" ).

The raw material compound of the component (b1) is a (meth) acrylate derived from an aliphatic polyhydric alcohol having a valence of three or more, and is composed of two or more (meth) acrylfluorenyl groups and one or more Hydroxyl (meth) acrylate (hereinafter referred to as "hydroxy-containing polyfunctional (meth) acrylate").

As the trivalent or higher aliphatic polyhydric alcohol of the hydroxyl-containing polyfunctional (meth) acrylate raw material compound, various compounds can be used, and examples thereof include trimethylolpropane, neopentyl tetraol, and bis (trimethylol). Propane) and dinepentaerythritol.

Various compounds can be used as the hydroxyl-containing polyfunctional (meth) acrylate. Specific examples include trimethylolpropane di (meth) acrylate, neopentyl tetrakis (tri) methacrylate, Or di (trimethylolpropane) tris (meth) acrylate and dineopentaerythritol di, tri, tetra or penta (meth) acrylate, and the like.

Among these, from the viewpoint of excellent hardness and scratch resistance of the cured film, a compound having three or more (meth) acrylfluorenyl groups and one or more hydroxyl groups is preferable, and specifically, three Neopentaerythritol (meth) acrylate, bis (trimethylolpropane) tris (meth) acrylate, dinepentaerythritol penta (meth) acrylate, and the like.

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

Examples of preferred polyisocyanates include isophorone diisocyanate, hexamethylene diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, norbornane diisocyanate, 2,4-toluene diisocyanate, and the like Etc. cyanurate type trimer and so on.

The component (b1) is synthesized by an addition reaction of a polyfunctional (meth) acrylate containing a hydroxyl group and a polyisocyanate. This addition reaction may be catalyst-free, but for efficient reaction, a tin-based compound such as dibutyltin dilaurate or an amine-based compound such as triethylamine may be used. The reaction may be performed in the presence of a catalyst.

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

As the trivalent or higher aliphatic polyhydric alcohol as a raw material compound of the component (b2), the same as those listed above can be used.

Specific examples of the component (b2) include trimethylolpropane tri (meth) acrylate, neopentyl tetrakis (meth) acrylate, and bis (trimethylolpropane) tetra (meth) acrylate. ) Esters and dipentaerythritol hexa (meth) acrylate.

Among these, from the viewpoint of excellent abrasion resistance and abrasion resistance of the cured film, a compound having four or more (meth) acrylfluorenyl groups is preferred, and tetra (meth) acrylic acid is specifically exemplified. Neopentaerythritol ester, bis (trimethylolpropane) tetra (meth) acrylate, and dinepentaerythritol hexa (meth) acrylate.

The component (B) of the present invention is a mixture of the components (b1) and (b2).

The ratio of the components (b1) and (b2) can be appropriately set according to the purpose. The above component (B) is preferably a mixture contained in a weight ratio of (b1) :( b2) = 10: 90 ~ 75: 25, and more preferably (b1) :( b2) = 30: 70 ~ 70 : The mixture contained in a weight ratio of 30.

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

The content ratio of the component (B) of the composition of the present invention is 100 parts by weight with respect to the total of the components (A), (B), and (C), and is 30 to 90 parts by weight, preferably 40 to 90 parts by weight, 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, it is possible to constitute a composition that imparts a cured film excellent in hardness and scratch resistance.

3. Ingredient (C)

The component (C) of the present invention is a radically polymerizable unsaturated compound having a nitrogen atom in the molecule (hereinafter referred to as "unsaturated compound (C)"), and is the above-mentioned component (A) and the above-mentioned component (B) Other compounds.

By using the said unsaturated compound (C), the active-energy-ray-curable coating composition which provides the hardened film excellent in hardness and abrasion resistance can be comprised. In addition, when the specific compound (C1) described later is contained, a composition having a sufficiently low viscosity can be formed. When the specific compound (C2) described later is contained, the hardness of the cured film can be improved without reducing the hardness and abrasion resistance. Impact.

In the present invention, the number of the radically polymerizable unsaturated groups of the unsaturated compound (C) is not particularly limited. When the viscosity of the composition is reduced to a relatively low level, it is preferable to have one radically polymerizable property. Unsaturated compounds, also known as monofunctional unsaturated compounds.

Specific examples of such a monofunctional unsaturated compound include (meth) acrylamide, N, N-dimethyl (meth) acrylamide, and N, N-diethyl (meth) acrylamide Amine, N-methylol (meth) acrylamide, N-methoxymethyl (meth) acrylamine, N-butoxymethyl (meth) acrylamine Amine, N-isopropyl (meth) acrylamide, N, N-dimethylaminopropylacrylamide, N-vinylformamide, N-vinylacetamide, diacetone (methyl ) Amine-containing monomers such as acrylamide; dimethylamine ethyl (meth) acrylate, diethylamine ethyl (meth) acrylate, tertiary butylamine ethyl (meth) acrylate Ethylamine-containing monomers; N-vinylpyrrolidone; N-vinyl-ε-caprolactam and other lactam compounds; (meth) acrylfluorenyl morpholine and other morpholinyl groups Monomers; (meth) acrylonitrile, N-cyclohexyl maleimide diimide, N-phenyl maleimide diimide and the like. These compounds can be used alone or in combination of two or more.

Among these, from the viewpoints that the Tg of the homopolymer is high and the hardness and scratch resistance of the resulting cured film are good, monomers containing amidino group, lactam compounds, and monomers containing morpholino group are preferred. (Hereinafter collectively referred to as "compound (C1)"). This compound (C1) is more preferably dimethyl (meth) acrylamide, N-vinylformamidine, N-vinylacetamidine, (meth) acrylfluorenylmorpholine. Among them, N-vinylformamide and N-vinylacetamide, which are monomers containing amidino group, are not only high in the properties of the above-mentioned hardened material, but also have a high effect of reducing the viscosity of the composition, so they are more preferable.

In addition, the unsaturated compound (C), a radically polymerizable unsaturated compound having an isotricyanic acid ring in the molecule (hereinafter also referred to as "compound (C2)") is also used alone or in combination with compound (C1 ) A better combination of ingredients. Examples of the compound (C2) include di (meth) acrylate modified with EO isocyanurate, tri (meth) acrylate modified with EO isocyanurate, and mixtures thereof (specifically Trade name (For example, there are "Aronix M-313" and "Aronix M-315" manufactured by Toa Synthesis Corporation, "Fancryl FA-731A" manufactured by Hitachi Chemical Co., Ltd., and "NK Ester A-9300" manufactured by Shin Nakamura Chemical Industry Co., Ltd., etc.) (Meth) acrylates modified by alkylene oxide; tris [2- (meth) acryloyloxyethyl] isocyanate modified by ε-caprolactone (specific trade names, such as Ε-caprolactone modified (meth) acrylic acid esters such as "Aronix M-327" manufactured by Toa Synthesis Corporation, "NK Ester A-9300-1CL" manufactured by Shin Nakamura Chemical Industry Co., Ltd .; hexamethylene dioxane Terpolymers of bifunctional isocyanates such as isocyanate and isophorone diisocyanate, and reactants (such as (meth) acrylates containing hydroxyl groups) (specific product names, such as "Art Resin UN-905" manufactured by Negami Industries, Ltd.) Etc.), Esters of 1,3-bis (2-carboxyethyl) isocyanurate and 2-hydroxyethyl (meth) acrylate, Tris (2-hydroxyethyl) isocyanurate Tris (meth) acrylate, other isotricyanic acid derivatives (specific product names, for example, "Shikoku Kasei Corporation" MA-DGIC "," DA-MGIC "," MeDAIC "," Ac DGIC ", etc.). These compounds can be used alone or in combination of two or more.

As the compound (C2), from the viewpoint of better impact resistance of the obtained cured film, alkylene oxide-modified (meth) acrylates and ε-caprolactone-modified (methyl) ) Acrylates.

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 radical polymerizable unsaturated groups is preferred from the viewpoint of easily obtaining a cured film having high hardness and good abrasion resistance.

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

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

In the present invention, when the unsaturated compound (C) is composed of only the compound (C1), the viscosity of the composition can be reduced to the extent that it can be applied even if it does not contain an organic solvent. Therefore, the content ratio is based on the component ( When the total of A), (B), and (C) is 100 parts by weight, it is preferably 5 to 35 parts by weight, more preferably 5 to 30 parts by weight, and even more preferably 8 to 25 parts by weight.

When the unsaturated compound (C) is composed of only the compound (C2), in order to obtain a hardened film having more excellent impact resistance, the total content of the components (A), (B), and (C) is set as the content ratio. When it is 100 parts by weight, it is preferably 5 to 30 parts by weight, preferably 8 to 30 parts by weight, and more preferably 10 to 25 parts by weight.

Furthermore, when the unsaturated compound (C) is composed of the compound (C1) and the compound (C2), in order to obtain a cured film excellent in hardness, abrasion resistance, and impact resistance, the preferable content ratio of these compounds is Shown below. When the total of the two is 10 to 35 parts by weight, the content ratio of the compound (C1) is preferably 5 to 30 parts by weight, preferably 5 to 25 parts by weight, and more preferably 8 to 25 parts by weight. The compound (C2) The content ratio of) is preferably 5 to 30 parts by weight, preferably 8 to 30 parts by weight, and more preferably 10 to 25 parts by weight. Serving. By constituting the content ratio of the compound (C1) to 5 to 30 parts by weight, the composition can be adjusted to a degree that it can be sufficiently coated without using an organic solvent to reduce the viscosity of the composition, thereby obtaining hardness and scratch resistance. Hardened film with excellent properties and impact resistance.

4. Active energy ray hardening coating composition

The active energy ray-curable coating composition of the present invention may be any one of a composition containing an organic solvent and a composition not containing an organic solvent, and may be configured to contain an organic solvent according to the type of the component (C).组合 物。 Composition. For example, when the component (C) contains the compound (C1), it can be constituted as a composition containing no organic solvent. When the component (C) contains the compound (C2) or both the compound (C1) and the compound (C2), it is preferable to contain an organic solvent. Organic solvents that can be used are described below.

The composition of the present invention includes the components (A), (B), and (C) as essential components, and according to the purpose, a photopolymerization initiator, pigment, dye, surface conditioner, ultraviolet absorber, and HALS can be further formulated. Various components such as light stabilizers, components (A), (B), and (C) and other compounds having a radical polymerizable unsaturated group and organic polymers.

As the photopolymerization initiator, various compounds can be used. Specific examples thereof include 2,2-dimethoxy-1,2-diphenylethane-1-one, 1-hydroxycyclohexylbenzophenone, and 2 -Hydroxy-2-methyl-1-phenylpropane-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propane-1 -Ketone, 2- Methyl-1- [4- (methylthio)] phenyl] -2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinyl) ) -Butane-1-one, diethoxyacetophenone, oligomeric {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] acetone} and 2- Acetophenone-based compounds such as hydroxy-1- {4- [4- (2-hydroxy-2-methylpropanyl) benzyl] phenyl} -2-methylpropane-1-one; diphenyl Diphenyl ketones such as ketones, 4-phenyldiphenyl ketones, 2,4,6-trimethyldiphenyl ketones, and 4-benzylidene-4'-methyl-diphenyl sulfides Compounds; methylbenzyl formate, 2- (2- pendant oxygen-2-phenylethylfluorenyloxyethoxy) ethyl oxyphenylacetate, and 2- (2- Α-ketoester-based compounds such as hydroxyethoxy) ethyl ester; 2,4,6-trimethylbenzylidene diphenylphosphine oxide, bis (2,4,6-trimethylbenzidine) Phosphine oxide compounds such as phenylphosphine oxide, bis (2,6-dimethoxybenzylidene) -2,4,4-trimethylpentylphosphine oxide; benzoin, benzoin Ether, benzoin ether, benzoin isopropyl ether and benzoin isobutyl ether, etc .; benzoin-based compounds; titanocene-based compounds; 1- [4- (4-benzidine Phenylsulfonyl) phenyl] -2-methyl-2- (4-methylphenylsulfinamilide) propane-1-one-1-one and other acetophenone / diphenylketone mixed systems Photoinitiators; 2- (O-benzylidene oxime ester) -1- [4- (phenylthio)]-1,2-octanedione, and other oxime ester-based photopolymerization initiators; and camphor Quinone and so on.

The optimum blending amount of the photopolymerization initiator is 0.1 to 10 parts by weight when the total of the components (A), (B) and (C) is 100 parts by weight, preferably 0.5 to 7 parts by weight, and more preferably It is 1 to 5 parts by weight.

By setting the blending amount of the photopolymerization initiator to 0.1 to 10 parts by weight, the composition is excellent in hardenability, and can be configured to impart hardness and scratch resistance. Composition of hardened film.

The surface conditioner has the effect of improving the homogeneity when applying the composition of the present invention, and the effect of improving the antifouling property or smoothness of the cured coating film. As the surface conditioner, a polysiloxane surface conditioner and a fluorine surface conditioner are more suitable. Specific examples include a polysiloxane polymer having a polysiloxane chain and a polyalkylene oxide chain, a fluoropolymer having a perfluoroalkyl group and a polyalkylene oxide chain, and a perfluoroalkyl ether chain. Fluorine polymer with polyalkylene oxide chain.

The preferable blending amount of the surface modifier is 0.01 to 3 parts by weight, and 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. By setting the blending amount to 0.01 parts by weight or more, the surface smoothness of the coating film can be improved, and the generation of air bubbles during coating can be suppressed.

Other compounds having a radically polymerizable unsaturated group are not particularly limited as long as they are compounds 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, and (meth) ) 2-ethylhexyl acrylate, cyclohexyl (meth) acrylate, isoamyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentyl (meth) acrylate, (formyl) 2-hydroxyethyl acrylate, benzyl (meth) acrylate, styrene, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, alkylene oxide adducts of phenol (Meth) acrylate, alkylphenol ring (Meth) acrylates of oxane adducts and the like.

In addition, a compound having two or more radically polymerizable unsaturated groups in one molecule (hereinafter referred to as "other polyfunctional unsaturated compound") can improve the tightness, hardness, and scratch resistance with respect to the substrate.

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

The other polyfunctional unsaturated compound is preferably a compound having two or more (meth) acrylfluorenyl groups in one molecule.

Specific examples include di (meth) acrylates of alkylene oxide adducts of bisphenol A, di (meth) acrylates of alkylene oxide adducts of bisphenol F, and epoxy of bisphenol Z. Di (meth) acrylates of alkyl adducts, di (meth) acrylates of alkylene oxide adducts of bisphenol S, di (meth) acrylic acid of alkylene oxide adducts of thiobisphenols Esters, di (meth) acrylates of bisphenol A, di (meth) acrylates of bisphenol F, di (meth) acrylates of bisphenol Z, di (meth) acrylates of bisphenol S, Di (meth) acrylate of thiobisphenol, tricyclodecane dimethylol di (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-hexanediol di (meth) acrylate, bis (methyl) Base) 1,9-nonanediol acrylic acid, glyceryl di (meth) acrylate, di (meth) acrylate of glycerol alkylene oxide adduct, di (meth) acrylic acid dimer acid dimer Alcohol esters, cyclohexanedimethylol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, tri (meth) acrylates of alkylene oxide adducts of trimethylolpropane , Neo-pentaerythritol tri- and tetra-acrylate, tri- and tetra-acrylates of alkylene oxide adducts of neo-pentaerythritol, bis (trimethylolpropane) tetra (meth) acrylate, hexa-pentaacrylate Neopentaerythritol ester, polyester (meth) acrylate, epoxy (meth) acrylate, urethane (meth) acrylate, silicone resin having a (meth) acrylfluorene group at the end, and the like.

Among these, polyester (meth) acrylates include dehydrated condensates of polyester polyols and (meth) acrylic acid. Examples of the polyester polyol include ethylene glycol, polyethylene glycol, cyclohexane dimethylol, 3-methyl-1,5-pentanediol, propylene glycol, polypropylene glycol, and hexamethylene dioxane. Low molecular weight polyols such as alcohols and trimethylolpropane, or polyol components such as the alkylene oxide adduct, and adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and p-benzene A reaction product obtained from a diprotic acid such as dicarboxylic acid or an acid component thereof such as an anhydride, and further, dehydration condensates of various dendritic polymer polyols and (meth) acrylic acid.

Examples of the (meth) acrylic epoxy ester include (meth) acrylic adducts of bisphenol A epoxy resin, (meth) acrylic adducts of hydrogenated bisphenol A epoxy resin, phenol, or (Meth) acrylic adducts of cresol-phenolic epoxy resins, (meth) acrylic adducts of biphenyl epoxy resins, diglycidyl ethers of polyethers such as polytetramethylene glycol (Meth) acrylic acid adduct, polybutadiene diglycidyl ether (meth) acrylic acid adduct, polybutadiene diglycidyl ether internal epoxidation (Meth) acrylic acid adducts of products, (meth) acrylic acid adducts of polysiloxane resins having epoxy groups, (meth) acrylic acid adducts of lemon olein, 3,4-ring (Meth) acrylic acid adducts of oxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate and the like.

Examples of the (meth) acrylic acid urethane include a compound that reacts an organic polyisocyanate with a hydroxyl group-containing (meth) acrylate, or an organic polyisocyanate and a polyol with a hydroxyl group-containing (methyl group). ) A compound that undergoes an addition reaction of an acrylate.

Here, examples of the polyol include low molecular weight polyols, polyether polyols, polyester polyols, and polycarbonate polyols.

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

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

Examples of the polyester polyol include such low molecular weight polyols and / or polyether polyols, and adipic acid, succinic acid, phthalic acid, hexahydrophthalic acid, and terephthalic acid. Reactant of acid component such as proton acid or its anhydride.

Examples of the organic polyisocyanate include toluene diisocyanate, xylene diisocyanate, tetramethylxylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, and hexamethylene. Methyl diisocyanate and isophorone diisocyanate.

Examples of the (meth) acrylate containing a hydroxyl group include (methyl) 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, and the like. Hydroxyalkyl acrylate (Meth) acrylates and the like.

Organic polymers have the effect of reducing warpage during curing while maintaining transparency. The preferred organic polymer is a (meth) acrylic polymer. Examples of preferred constituent monomers include methyl (meth) acrylate, cyclohexyl (meth) acrylate, and (meth) acrylic acid. , Glycidyl (meth) acrylate, N- (2- (meth) acryloxyethyl) tetrahydrophthalimide and the like. In order to copolymerize a (meth) acrylic polymer, glycidyl (meth) acrylate may be added to introduce a (meth) acryl group into the polymer chain.

The composition of the present invention may be excellent in coatability and handleability even if it does not contain an organic solvent. However, for the purpose of further improving these properties or for adjusting the viscosity of the composition, organic compounds may be used. Solvent. As an organic solvent, the soluble components (A), (B), and (C) are preferable.

Specific examples of preferred organic solvents include alcohols such as ethanol and isopropanol; alkanediol monoethers such as ethylene glycol monomethyl ether and propylene glycol monomethyl ether; acetone alcohols such as diacetone alcohol; toluene and Aromatic compounds such as xylene; ester compounds such as propylene glycol monomethyl ether acetate, ethyl acetate, butyl acetate; ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone; ethers such as dibutyl ether ; N-methylpyrrolidone and the like.

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

By setting the blending amount of the organic solvent to 10 to 1,000 parts by weight, it can be charged. Reduce the viscosity of the hardenable composition separately, and easily prepare a coating method (rod coating, roll coating, spin coating, dip coating, gravure coating, lamination coating, flow coating) that is commonly known. Cloth, spray coating, etc.).

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, and more preferably 15,000 mPa from the viewpoint of coating properties. ‧S or less, more preferably 10,000mPa s or less The lower limit is usually 100mPa‧s.

The method for producing an active energy ray-curable coating composition of the present invention can be configured to follow a method generally used, that is, it is configured to include component (A), component (B), component (C), and if necessary A manufacturing method of stirring and mixing other components used.

5. Painting method

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

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

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

Specific examples of the plastic include acrylic resins such as polymethyl methacrylate, polyester resins such as polyethylene terephthalate, polyvinyl chloride, polycarbonate resins, epoxy resins, and polyurethanes. Ester resin, etc.

The method for applying the composition of the present invention to a substrate is not particularly limited, and it may follow a commonly used method. For example, bar coating, roll coating, spin coating, dip coating, gravure coating, flow coating, spray coating, and the like can be applied.

Moreover, the specific method of forming a cured film includes the method of apply | coating a composition to a base material, and irradiating an active energy ray to a coating film. In addition, if necessary, a drying step or a preliminary heating step of the coating film may be performed before irradiating the active energy rays.

The thickness of the coating film and the film after drying can be appropriately set according to the purpose, and is generally about 5 to 300 μm.

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

Examples of the active energy rays used to harden the coating film composed of the composition of the present invention include electron beams, ultraviolet rays, visible light, and X-rays. Since inexpensive devices can be used, ultraviolet rays are preferred.

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 must be appropriately set according to the type of active energy rays or the composition of the formulation. When using a high-pressure mercury lamp as an example, the irradiation energy meter in the UV-A region is preferably 100 to 5,000 mJ / cm ² , more preferably It is 200 to 1,000 mJ / cm ² .

When the electron beam is used for curing, various electron beam (EB) irradiation devices can be used. For example, Cockcroft-Walton type, Van der Graf type, de The Graaf) type and resonance transformer type devices are preferably those having 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 abrasion resistance. For example, pencil hardness measured according to JIS K 5600-5-4 is usually 8H or more, and damage caused by contact with metal members and the like can also be suppressed. The material having the above-mentioned cured film can be used in various applications by utilizing this characteristic.

For example, various lenses such as a front panel for a display panel, a display for a building material, a display for a lighting device, a mobile phone, a smartphone, or the like, a housing for a home electric appliance, and glasses are listed.

Specific examples of the front panel for a display panel include electronic bulletin boards, displays, signboards, advertisements, and signs.

Examples of the use of wood as the base material include woodwork products such as steps, floors, and furniture. Examples of the use of metal as the base material include metal products such as stainless steel panels for kitchens and stainless steel fluidizers.

[Example]

The following specifically describes the present invention based on examples. However, the present invention is not limited to these embodiments.

In the following description, "parts" means parts by weight, and "%" means% by weight.

1. Manufacture of ingredient (A) Manufacturing example 1 (manufacturing 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, and then slowly added while stirring these A solution of 4.37 g of a 25% tetramethylammonium hydroxide methanol solution (0.1 mol of methanol and 12 mmol of tetramethylammonium hydroxide) was reacted at a temperature of 25 ° C and pH 9 for 6 hours. Then, the internal temperature was raised to 60 ° C, and the reaction was further performed for 1 hour while stirring. Here, gas chromatography (TCD detector) was performed on the reaction solution to detect that 1 to 4 of the methoxy groups contained in the TMOS were substituted with a 1-substituent, 2-substituent, 3 Substitute and 4-substitute compounds and unreacted TMOS. TMOS only detects the amount of traces. The ratio of these compounds containing n-propoxy groups (alkoxysilanes containing n-propoxy groups) is almost 100% in total. The number of 1-propanol substitutions (average of the number of n-propoxy groups per molecule of the n-propoxy-containing compound) was calculated from the peak area of the product in gas chromatography, and the result was 2.7.

Next, 59.62 g (0.24 mole) of 3-methacryloxypropyltrimethoxysilane was added to the above reaction solution, and 30.2 g of water was further added. Next, 7.88 g of a 25% tetramethylammonium hydroxide methanol solution (0.18 mol of methanol and 21.6 mmol of tetramethylammonium hydroxide) was added, and the reaction was carried out at 25 ° C and pH 9 for 24 hours while stirring. Then, 22.2 g (35.3 mmol) of a 10% nitric acid aqueous solution was added for neutralization. This neutralized solution was then added to a mixed solution of 120 g of diisopropyl ether and 180 g of water to perform extraction. This diisopropyl ether layer was washed with water to remove salts and excess acid, and then 11.5 mg of N-nitrosophenylhydroxylamine aluminum salt "Q-1301" (trade name) manufactured by Wako Pure Chemical Industries, Ltd. was added as polymerization. Prohibition. Diisopropyl In an ether solution, the organic solvent was distilled off under reduced pressure to obtain a colorless and transparent solid organic silicon compound (hereinafter referred to as "MAC-TQ"). The yield was 57.72 g.

The ¹ H-NMR analysis of MAC-TQ confirmed that it was 3-methacryloxypropyltrimethoxysilane used as the compound (a1) and n-propoxy-containing alkane used as the compound (a2). Copolymer condensate obtained from a stoichiometric reaction of oxysilane.

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

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

2. Manufacture of ingredient (B) Manufacturing example 2 (manufacturing of HDI-M305)

East Asia, which contains a mixture of neopentaerythritol triacrylate (hereinafter referred to as "PETri") and neopentaerythritol tetraacrylate (hereinafter referred to as "PETet") (containing 0.3 moles of PETri and 0.2 moles of PETet) 159.2 g of "Aronix M-305" (trade name, hereinafter referred to as "M-305") manufactured by Synthetic Corporation, 2,6-bis (tributyl) -4-methylphenol (hereinafter referred to as "BHT") 0.092 g and 0.055 g of dibutyltin dilaurate (hereinafter referred to as "DBTL") are put into a 0.5 L separable flask equipped with a stirring device and an air blowing tube, and the liquid temperature is 70 to 75 ° C While stirring these, hexamethylene diisocyanate (hereinafter referred to as "HDI") was added dropwise. 25.2 g (0.15 mol) was used for the reaction.

After the dripping of HDI was completed, the internal temperature was further increased to 80 ° C. and the reaction was continued, followed by stirring for 3 hours. Then, by IR (infrared absorption) analysis of the reaction product, it was confirmed that the isocyanate group disappeared and the reaction was completed. This reaction product is hereinafter referred to as "HDI-M305".

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

3. Manufacturing and evaluation of active energy ray hardening coating composition

Using the obtained MAC-TQ and HDI-M305 and the components shown in Table 1, an active energy ray-curable coating composition was produced and provided to each evaluation.

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

Each of the raw materials was used at the ratios shown in Table 2. The active energy ray-curable coating composition was prepared by stirring and mixing at room temperature according to a common method.

Then, the viscosity of each obtained composition at 25 ° C. was measured using an E-type viscometer, and the obtained values are shown in each table together.

Then, each composition is dropped on the surface of one side of a polyethylene terephthalate film of 7 cm × 15 cm × 50 μm, and the cover is made of polyethylene terephthalate, and UV rays can be transmitted through it. A release film having a thickness of 50 μm. Next, the thickness of the coating film was adjusted by passing it through a laminating roll so that the thickness of the cured film became about 50 μm. In the same manner, a coating film was formed on the other side of the polyethylene terephthalate film. Then, the cured film was formed on both sides of the polyethylene terephthalate film by irradiating ultraviolet rays under the following conditions between the release film.

For ultraviolet irradiation, an ultraviolet irradiation machine (high-pressure mercury lamp) manufactured by Eye Graphics was used, the lamp height was set to 19 cm, and each side was irradiated once at a conveyor speed of 2.3 m / min. The irradiation dose per pass was measured with a photometer "UV POWER PUCK" manufactured by EIT, and was 900 mJ / cm ² in the UV-A region. The peak illuminance was 170 mW / cm ² in the UV-A region.

About the obtained cured film, pencil hardness, abrasion resistance, and tightness were evaluated by the methods shown below. The results of these evaluations are shown in Table 2.

(1) Pencil hardness

The pencil hardness was measured in accordance with JIS K 5600-5-4.

(2) Scratch resistance

The steel wool "BON STAR # 0000" manufactured by Nippon Steel Wool was placed on the surface of the cured film, and was wiped back and forth 400 times while applying a load of 1200 g / 4 cm ² , and the number of damage at this time was measured. The number of this damage was used and the abrasion resistance was evaluated according to the following criteria. Here, the evaluation "A" or "B" is set to be excellent in abrasion resistance.

A: No damage at all.

B: There are 1 to 9 lesions.

C: The damage is 10 or more.

Each of the compositions of Examples 1 to 5 exhibited a viscosity of 10,850 mPa · s or less even when no organic solvent was used, and the viscosity was sufficiently reduced to the extent that it can be coated. In addition, the cured film exhibited a good pencil hardness of 8H to 10H, and it was confirmed that it was excellent in abrasion resistance and excellent in abrasion resistance. Among them, Examples 3 to 5 in which N-vinylformamide (NVF) is used as the component (C) can further reduce the viscosity of the composition, which is beneficial to the applicability during various coatings.

In contrast, Comparative Example 1 does not contain the component (C) of the present invention, so the composition has an extremely high viscosity of 34,400 mPa · s, and it is necessary to dilute it with an organic solvent during processing or coating. High sex. In Comparative Example 2 in which 1,6-hexanediol diacrylate (HDDA) containing an unsaturated compound containing no nitrogen atom was used, the pencil hardness and scratch resistance of the cured film were reduced.

Comparative Examples 3 and 4 are experimental examples when the content of the component (C) of the present invention deviates from the range specified by 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 lowered. In contrast, 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

The raw materials shown in Table 3 are used at the ratios shown in Table 3, and are stirred and mixed at room temperature according to a common method to prepare an active energy ray-curable coating composition. The composition of Comparative Example 5 is the same as the composition of Comparative Example 1. The viscosity of each composition was measured, and To determine the applicability of the coating on a point basis. The results are shown in Table 3 together.

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

B: The viscosity exceeds 10,000 mPa‧s and is 15,000 mPa‧s or less.

C: The viscosity exceeds 15,000 mPa‧s and is 20,000 mPa‧s or less.

D: Viscosity exceeds 20,000 mPa‧s.

Then, as in Example 1, a cured film was formed on both sides of the polyethylene terephthalate film. Then, in addition to the above (1) hardness and (2) abrasion resistance, the following (3) impact resistance was evaluated. The results of these evaluations are shown in Table 3.

(3) Impact resistance (drop ball test)

From a height of 10 cm, 25 g of iron balls according to JIS B 1501 were dropped onto the surface of the cured film. When the hardened film is not damaged or cracked, the operation of increasing the height by 5 cm and dropping the iron ball is repeated once, and the highest value of the height where no damage or cracking occurs is recorded. This test was performed on five hardened pieces, and the highest value was averaged to evaluate the impact resistance.

The test was carried out 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 it can be coated. In addition, all the obtained cured films showed good pencil hardness of 8H to 10H, and it was confirmed that the abrasion resistance and impact resistance (ball drop test) were also excellent. In particular, in Examples 9 to 11 in which two types of 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) of the present invention. Its viscosity is high. Although the obtained hardened film has excellent hardness and abrasion resistance, the value of the falling ball test is lower 15cm, and the impact resistance is poor.

[Industrial applicability]

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 (9)

An active energy ray-curable coating composition comprising: (A) an organic silicon compound that is a silicon compound (a1) containing a (meth) acrylfluorenyl group represented by the following general formula (1), and The silicon compound (a2) represented by the following general formula (2) is obtained by hydrolytic copolymerization and condensation at a ratio of 0.3 to 1.8 moles of the silicon compound (a2) relative to 1 mole of the silicon compound (a1). ; (In 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 an organic group having 1 to 6 carbon atoms. A bivalent saturated hydrocarbon group of 6, R ³ is a hydrogen atom or a methyl group, X is a hydrolyzable group, and a plurality of X may be the same or different from each other, and n is 0 or 1) SiY ₄ ‧‧‧ (2) (general formula In (2), Y is a siloxane bond forming group, and a plurality of Y may be the same or different from each other) (B) (meth) acrylate mixture, which is composed of a trivalent or higher aliphatic polyol Derived (meth) acrylate, and is an amine obtained by addition reaction of (meth) acrylate having two or more (meth) acrylfluorenyl groups and having one or more hydroxyl groups, and polyisocyanate An ethyl formate addition compound (b1) and a (meth) acrylate derived from an aliphatic polyhydric alcohol having a valence of 3 or more, and having a (meth) acrylfluorenyl group of 3 or more and having no hydroxyl group ( It is composed of a meth) acrylate (b2); and (C) a radically polymerizable unsaturated compound having a nitrogen atom in the molecule, and is a compound other than the aforementioned component (A) and the aforementioned component (B); the aforementioned component ( A), the aforementioned component (B) When the content of the component (C) is 100 parts by weight in total, the component (A) is 5 to 50 parts by weight, the component (B) is 30 to 90 parts by weight, and the component (C) It is 5 to 35 parts by weight. The active energy ray-curable coating composition according to claim 1, wherein the aforementioned compound (a1) is a compound in which X is an alkoxy group and n is 0 in the general formula (1), and the aforementioned compound (a2) is a general formula Y in (2) is an alkoxy group. The active energy ray-curable coating composition according to claim 1 or 2, wherein the aforementioned component (C) comprises at least 1 selected from the group consisting of a morpholine group-containing monomer, a fluorenamine group-containing monomer, and a lactam compound Compound (C1). The active energy ray-curable coating composition according to claim 3, wherein the compound (C1) is selected from the group consisting of acrylamidomorpholine, N-vinylformamide, N-vinylacetamide, and N-vinyl- At least one of ε-caprolactam. The active energy ray-curable coating composition according to claim 4, wherein the aforementioned compound (C1) contains at least N-vinylformamide. The active energy ray-curable coating composition according to claim 1 or 2, wherein the aforementioned component (C) contains a compound (C2) having an isotricyanic acid 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 radical polymerizable unsaturated compound modified by alkylene oxide or caprolactone. The active energy ray-curable coating composition according to claim 1 or 2, wherein the content of the aforementioned component (C) is when the total of the aforementioned component (A), the aforementioned component (B), and the aforementioned component (C) is 100 parts by weight 10 to 35 parts by weight, the aforementioned component (C) is a compound (C1) consisting of at least one selected from the group consisting of a morpholino-containing monomer, a fluorenamine-containing monomer, and a lactam compound, and having The isocyanuric acid ring compound (C2) is composed of 10 to 35 parts by weight, the content ratio of the compound (C1) is 5 to 30 parts by weight, and the content of the compound (C2) is The ratio is 5 to 30 parts by weight. A cured film obtained from the active energy ray-curable coating composition according to any one of claims 1 to 8.