JP2021020994A - Active energy ray-curable resin composition - Google Patents

Abstract

To provide an active energy ray-curable resin composition that can form a cured coat having excellent contamination prevention properties to various stains of oil, drugs and the like.MEANS: An active energy ray-curable resin composition contains (A) urethane acrylate particles, and (B) an active energy ray-curable resin, and the content of the (A) urethane acrylate particles is 1 mass% or more and 60 mass% or less relative to 100 mass% of the composition in terms of solid content.SELECTED DRAWING: None

Description

The present invention relates to an active energy ray-curable resin composition. The present invention also relates to a member with a cured coating, wherein at least one surface of the substrate is coated with a cured coating formed from an active energy ray-curable resin composition.

Conventionally, synthetic resin materials such as polyvinyl chloride have been used for the interiors of various buildings such as large commercial facilities, public facilities, offices, and vehicles such as railways and buses, especially for the floor surface. Interior materials are required to have anti-contamination functions against various stains, and materials having various anti-contamination functions against oil, chemicals and the like have been developed. For example, synthetic resin materials tend to have stains such as soles on the surface, and in order to maintain their aesthetic appearance, antifouling treatment (wax maintenance) with wax or the like is required on a regular basis, resulting in high maintenance costs. There was a problem. Therefore, in order to eliminate the need for wax maintenance, a synthetic resin flooring material having improved antifouling property is provided by forming a cured film with an active energy ray-curable resin composition on the surface to improve the surface hardness. Are known.

For example, in Patent Document 1, an active energy ray-curable resin composition for a floor material containing polyhedral-shaped inorganic particles (A) and an active energy ray-curable resin (B) having an average particle diameter in the range of 2 to 25 μm. Has been proposed.

Japanese Unexamined Patent Publication No. 2018-141041

However, base materials such as interior materials are required to have antifouling properties against various stains such as oil and chemicals, and there is still room for further improvement in antifouling properties.

Therefore, an object of the present invention is to provide an active energy ray-curable resin composition capable of forming a cured film having excellent antifouling property against various stains such as oil and chemicals.

As a result of diligent studies in order to solve the above problems, the present inventors have added (A) urethane acrylate particles and (B) active energy ray-curable resin to the active energy ray-curable resin composition. A) It was found that the above problems can be solved by adjusting the content of urethane acrylate particles within a specific range. The present invention has been completed based on such findings.

That is, according to the present invention, the following invention is provided.
[1] Contains (A) urethane acrylate particles and (B) active energy ray-curable resin.
(A) An active energy ray-curable resin composition in which the content of urethane acrylate particles is 1% by mass or more and 60% by mass or less based on 100% by mass in terms of solid content of the composition.
[2] The active energy ray-curable resin composition according to [1], wherein the active energy ray-curable resin (B) contains a urethane (meth) acrylate oligomer.
[3] The active energy ray-curable resin composition according to [2], wherein the urethane (meth) acrylate oligomer contains a polyfunctional urethane (meth) acrylate oligomer having two or more unsaturated double bonds.
[4] The active energy ray-curable resin composition according to [3], wherein the polyfunctional urethane (meth) acrylate oligomer contains (b1) a bifunctional urethane (meth) acrylate oligomer having two unsaturated double bonds. Stuff.
[5] The active energy ray-curable resin composition according to any one of [1] to [4], further comprising (C) (meth) acrylate monomer.
[6] The active energy ray-curable resin composition according to any one of [1] to [5], further comprising (D) a photopolymerization initiator.
[7] The active energy ray-curable resin composition according to any one of [1] to [6], wherein the weight average molecular weight of the active energy ray-curable resin (B) is in the range of 500 or more and 100,000 or less. Stuff.
[8] The active energy ray-curable resin composition according to any one of [1] to [7], which is used for an interior material or an outdoor or semi-outdoor floor material.
[9] A substrate with a cured film, wherein at least one surface of the substrate is coated with a cured film formed from the active energy ray-curable resin composition according to any one of [1] to [8].
[10] The base material with a cured coating according to [9], wherein the base material is for an interior material or an outdoor or semi-outdoor floor material.

According to the present invention, it is possible to provide an active energy ray-curable resin composition capable of forming a cured film having excellent antifouling property against various stains such as oil and chemicals. Further, according to the present invention, it is possible to provide a substrate with a cured film having excellent antifouling property against various stains such as oil and chemicals.

Hereinafter, the present invention will be described in more detail.
In the present specification, "(meth) acrylate" represents acrylate and methacrylate, "(meth) acrylic" represents acrylic and methacrylic, and "(meth) acryloyl" represents acryloyl and methacryloyl.
The "active energy ray" means an ultraviolet ray, an infrared ray, an electron beam, an X-ray, a γ-ray, a proton ray, a neutron ray, and the like.
The "solid content" is an active energy ray-curable resin composition obtained by removing volatile components such as an organic solvent, and indicates a component that constitutes a cured film when cured.

<Active energy ray-curable resin composition>
The active energy ray-curable resin composition according to the present invention contains at least (A) urethane acrylate particles and (B) active energy ray-curable resin. The active energy ray-curable resin composition according to the present invention may further contain (C) (meth) acrylate monomer and (D) photopolymerization initiator. The cured film formed from such an active energy ray-curable resin composition is excellent in antifouling property against various stains such as oil and chemicals. Therefore, the active energy ray-curable resin composition according to the present invention can be suitably used as a base material for various stains such as oil and chemicals, particularly for interior materials such as flooring materials, or outdoor or semi-outdoor flooring materials. .. Hereinafter, each component of the active energy ray-curable resin composition according to the present invention will be described in detail.

((A) Urethane acrylate particles)
The urethane acrylate particles (hereinafter, also referred to as the component (A)) are resin particles obtained from a resin composition containing a urethane component, a (meth) acrylate component, and / or urethane acrylate. Such urethane acrylate particles can be produced by a conventionally known method. For example, a polyisocyanate prepolymer as a urethane component may be reacted with a (meth) acrylate monomer as a (meth) acrylate component, or urethane. It can also be obtained by polymerizing a (meth) acrylate oligomer.

As the polyisocyanate prepolymer contained in the urethane component, a compound obtained by using isocyanate and having two or more isocyanate groups at the terminal, or a bifunctional or higher functional isocyanate is used. Examples of the compound obtained by using isocyanate and having two or more isocyanate groups at the terminal include hydroxyl groups of polyols such as ethylene glycol, propylene glycol, 1,4-butylene glycol, polyalkylene glycol, trimethylolpropane, and hexanetriol. On the other hand, an additive obtained by reacting an isocyanate compound in an excessive amount of isocyanate groups; a compound obtained by adding isocyanate to the end of a polyol; a uretdione-type polyisocyanate of an isocyanate compound, an isocyanurate-type polyisocyanate of isocyanate, etc. Can be mentioned.

As the isocyanate compound, for example, a diisocyanate compound such as an aliphatic diisocyanate compound, an alicyclic diisocyanate compound, or an aromatic diisocyanate compound is used. Specifically, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, xylylene diisocyanate, xylene diisocyanate, lysine diisocyanate, 4,4'-methylenebis (cyclohexyl isocyanate), methylcyclohexane-2,4 (or 2,6). − Diisocyanis, 1,3- (isocyanismethyl) cyclohexane, isophorone diisocyanis, trimethylhexamethylene diisocyanate, dimersate diisocyanate, dianisidine diisocyanate, phenyldiisocyanis, halogenated phenyldiisocyanate, methylene diisocyanate, ethylene diisocyanis, butylene diisocyanate, propylene diisocyanate, octa Decisylene diisocyanis, 1,5-naphthalene diisocyanate, polymethylene polyphenylene diisocyanate, naphthalene diisocyanate, tolylene diisocyanate polymer, diphenylmethane diisocyanate polymer, hexamethylene diisocyanate polymer, 3-phenyl-2-ethylene diisocyanis, cumen-2 , 4-Diisocyanis, 4-methoxy-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylenediisocyanate, 2,4'-diisocyanide diphenyl ether, 5,6-dimethyl-1,3-phenylenediisocyanate, 4, 4'-diisocyanide diphenyl ether, benzidine diisocianate, 9,10-anthracen diisocyanate, 4,4'-diisocyanide benzyl, 3,3'-dimethyl-4,4'-diisocyanide diphenylmethane, 2,6-dimethyl-4, 4'-diisocyanide diphenyl, 3,3'-dimethoxy-4,4'-diisocyanide diphenyl, 1,4-anthracene diisocyanate, phenylenediisocyanate, 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1, Examples thereof include 10-decamethylene diisocyanate, 1,3-cyclohexamethylene diisocyanate, and 4,4'-methylene-bis (cyclohexyl isocyanate).

Examples of the bifunctional or higher functional isocyanate include triphenylmethane-4,4', 4 "-triisocyanate, 1,3,5-triisocyanatobenzene, and the like trifunctional or higher functional isocyanate, in addition to the diisocyanate compound. 2,4,6-triisocyanatotoluene, 2,4,4'-triisocyanate diphenyl ether, 4,4'-dimethyldiphenylmethane-2,2', 5,5'-tetraisocyanate and the like can be used.

Among isocyanates, non-yellowing type isocyanates such as aliphatic and alicyclic isocyanates are preferable because urethane resins having higher flexibility than those using aromatic isocyanates can be obtained.

A polyol may be further used as the urethane component. As the polyol, for example, polyester polyol, polyether polyol, polycarbonate polyol, polybutadiene polyol, acrylic polyol and the like are used. The polyol is appropriately selected according to the purpose and application. For example, when a highly flexible urethane resin is obtained, it is preferable to use a polyether polyol. When a urethane resin having high elasticity is obtained, it is preferable to use a polyester polyol. When a urethane resin having high hydrolysis resistance is obtained, it is preferable to use a polycarbonate polyol. When a urethane resin having high heat resistance is obtained, it is preferable to use a polybutadiene polyol or an acrylic polyol.

Moreover, it is preferable to use trifunctional or higher as any of the polyols. If a polyol having trifunctionality or higher is used, a crosslinked structure can be obtained, and the contamination prevention property of the obtained urethane acrylate particles can be improved. As the polyol, one type may be used alone, or two or more types may be used in combination.

Further, it is preferable to use trifunctional or higher functional isocyanate or polyol which constitutes the polyisocyanate prepolymer. If a polyisocyanate prepolymer composed of trifunctional or higher functional substances is used for either isocyanate or polyol, a crosslinked structure can be obtained, and the contamination prevention property of the obtained urethane acrylate particles can be improved. One type of polyisocyanate prepolymer may be used alone, or two or more types may be used in combination.

The (meth) acrylate monomer contained in the acrylate component is an alkyl esterified product of (meth) acrylic acid or a nitrile derivative. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, t-butyl (meth) acrylate, amyl (meth). ) Acrylate, hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, n-octyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, 2-ethoxyethyl (meth) acrylate, benzyl (Meta) acrylate, 2-hydroxyethyl (meth) acrylate, glycidyl (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, polyethylene glycol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, ethylene oxide-modified bisphenol A di (meth) acrylate, propionoxide-modified bisphenol A di (meth) acrylate, trimethyl propantri ( Meta) acrylate, ethylene oxide-modified trimethylolpropane (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, allyl (meth) acrylate, and (meth) Acrylate and the like can be mentioned. Among these (meth) acrylate monomers, methyl (meth) acrylate is preferable.

Further, it is preferable to use a (meth) acrylate monomer having trifunctionality or higher. If a trifunctional or higher functional (meth) acrylate monomer is used, a crosslinked structure can be obtained, and the contamination prevention property of the obtained urethane acrylate particles can be improved.
One type of (meth) acrylate monomer may be used alone, or two or more types may be used in combination.

Further, the raw material of the urethane acrylate particles may contain other vinyl-based monomers capable of reacting with the (meth) acrylate monomer, if necessary. Examples of other vinyl-based monomers include styrene, acrylonitrile, vinyl acetate, vinyl chloride, (meth) acrylamide, phenylmaleimide, cyclohexylmaleimide and the like.
One type of other vinyl-based monomer may be used alone, or two or more types may be used in combination.

At the time of the reaction, the ratio (A / B) of the mass A of the urethane component and the mass B of the vinyl-based monomer component is set to, for example, 70/30 to 5/95, preferably 67/33 to 17 /. Set to 83.

At the time of the reaction, it is preferable to add a radical polymerization initiator and a urethanization catalyst in order to accelerate the reaction.

Examples of the radical polymerization initiator include benzoyl peroxide, t-butyl benzoate, lauroyl peroxide, m-toluyl peroxide, diisopropyl peroxydicarbonate, t-butyl peroxypivalate, and cumyl peroxyneodecanoate. Organic peroxides such as t-butylperoxy2 ethylhexanoate, octanoyl peroxide, decanoyle peroxide, t-butylperoxy2 ethylhexanoate, t-butylperoxyisopropylcarbonate, cumylperoxyoctaate, etc. Examples thereof include azo compounds such as 2,2-azobisisobutyronitrile, 2,2-azobis (2,4-dimethylvaleronitrile), and 1,1-azobis (cyclohexane-1-carbonitrile).

Examples of the urethanization catalyst include a metal catalyst such as dibutyl tin laurate and an amine catalyst such as triethylamine.

The content of the urethane acrylate particles (A) is 1% by mass or more and 60% by mass or less, preferably 5% by mass or more and 50% by mass or less, based on 100% by mass in terms of solid content of the active energy ray-curable resin composition. It is more preferably 5% by mass or more and 40% by mass or less, and further preferably 10% by mass or more and 30% by mass or less. When the content of the urethane acrylate particles (A) is within the above range, the cured film formed from the active energy ray-curable resin composition is excellent in antifouling property against various stains such as oil and chemicals. Become.

The volume average particle diameter of the urethane acrylate particles (A) is not particularly limited, but is preferably 1 to 100 μm, more preferably 2 to 20 μm, and further preferably 5 to 10 μm. The volume average particle size can be measured using a commercially available particle size distribution measuring machine.

((B) Active energy ray-curable resin)
The (B) active energy ray-curable resin (hereinafter, also referred to as the component (B)) is at least one selected from oligomers and polymers having at least one unsaturated double bond. The component (B) forms a cured film (cured product) by polymerizing unsaturated double bonds when irradiated with energy. Examples of the functional group having an unsaturated double bond include (meth) acryloyl group, vinyl group, allyl group, styryl group and the like, and (meth) acryloyl from the viewpoint of reactivity at the time of irradiation with active energy rays. Groups are preferred.

Examples of the component (B) include urethane (meth) acrylate oligomer, epoxy (meth) acrylate oligomer, polyester (meth) acrylate oligomer, polyether (meth) acrylate oligomer, acrylic (meth) acrylate oligomer, and the like. It is not limited to this. Among these, urethane (meth) acrylate oligomers are preferable from the viewpoint of preventing contamination of the cured film. Such a component (B) can be produced by a conventionally known method.

The urethane (meth) acrylate oligomer is obtained by reacting a polyisocyanate with a hydroxyl group-containing (meth) acrylate and, if necessary, a polyol other than the hydroxyl group-containing (meth) acrylate, and acryloyl as a functional group in the molecule. It has a group (CH ₂ = CHCO−) and / or a methacryloyl group (CH ₂ = C (CH ₃ ) −CO−) and a urethane bond (-NH · COO−).

The polyisocyanate does not limit the number of carbon atoms as long as the effect of the present invention is not impaired, but for example, it contains a linear or branched isocyanate group having a total carbon number of 4 to 20, preferably 6 to 15. Hydrocarbons, isocyanate group-containing cyclic hydrocarbons, and isocyanate group-containing aromatic hydrocarbons can be used.

Specifically, isocyanate group-containing linear hydrocarbons such as tetramethylene diisocyanate and hexamethylene diisocyanate, isocyanate group-containing branched chain hydrocarbons such as 2,2,4-trimethylhexamethylene diisocyanate, isophorone diisocyanate, and hydrogenated diphenylmethane. Isocyanate group-containing cyclic hydrocarbons such as diisocyanate, hydrogenated xylene diisocyanate, hydrogenated toluene diisocyanate, p-phenylenediocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 1,3-xylene diisocyanate, dianisidine diisocyanate. , Tetramethylximethylene diisocyanate, 1,5-naphthalenediocyanate, tolylene diisocyanate, diisocyanate group-containing aromatic hydrocarbons such as 4,4-diphenylmethane diisocyanate, etc., but are not limited to these examples.

The polyisocyanate may be modified with isocyanurate or the like, and examples of the isocyanurate-modified one include isocyanurate-modified toluene diisocyanate and the like. Further, as the polyisocyanate other than the above, a polyfunctional isocyanate such as dimethyltriphenylmethanetetraisocyanate, triphenylmethanetriisocyanate, or isocyanate group-containing acrylate may be used. Such polyisocyanates may be used alone or in combination of two or more.

As the hydroxyl group-containing (meth) acrylate, a (meth) acrylate having at least one or more, preferably 1 to 5 hydroxyl groups can be used. Further, such a hydroxyl group-containing (meth) acrylate does not limit the number of carbon atoms as long as the effect of the present invention is not impaired, but it is preferable that the hydroxyl group-containing (meth) acrylate has a hydrocarbon moiety having 2 to 20 carbon atoms. Here, the hydrocarbon moiety refers to an organic group having a linear or branched aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group, and is an aliphatic hydrocarbon group or an alicyclic. The formula hydrocarbon group may be saturated or unsaturated. An ether bond (C—O—C bond) may be contained in a part of the hydrocarbon moiety.

Specifically, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-Hydroxybutyl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, hydroxyhexyl (meth) acrylate, 3-hydroxy-3-chloropropyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, Polypropylene glycol mono (meth) acrylate, glycidol di (meth) acrylate, pentaerythritol tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol tri (meth) acrylate, Examples thereof include dipentaerythritol di (meth) acrylate, but the present invention is not limited to these examples. In addition to the above, a modified product such as polycaprolactone-modified 2-hydroxyethyl (meth) acrylate may be used. Such a hydroxyl group-containing (meth) acrylate may be used alone or in combination of two or more.

As the polyol other than the hydroxyl group-containing (meth) acrylate used as needed, known polyols such as polyether polyols, polyester-based polyols, and polyolefin-based polyols can be used, and specifically, polyoxyethylene. Examples thereof include glycols, polyoxypropylene glycols, polyoxytetramethylene glycols, ethylene oxide adducts of bisphenol A, propylene oxide adducts of bisphenol A, polycaprolactone polyols, and alkylene diols, but the examples are not limited to these examples. Absent. Such polyols may be used alone or in combination of two or more.

The weight average molecular weight of the active energy ray-curable resin (B) for gel permeation chromatography is usually 500 to 100,000, preferably 600 to 50,000, and more preferably 1,000 to 10,000. In the present specification, the weight average molecular weight is a standard polystyrene-equivalent value measured by the (GPC) method.

The content of the active energy ray-curable resin (B) is usually 10% by mass or more and 99% by mass or less, preferably 10% by mass or more and 90% based on 100% by mass in terms of solid content of the active energy ray-curable resin composition. It is mass% or less, more preferably 20 mass% or more and 70 mass% or less. When the content of the active energy ray-curable resin (B) is within the above range, the cured film formed from the active energy ray-curable resin composition is more excellent in preventing contamination against various stains such as oil and chemicals. It will be the one.

((B1) Bifunctional urethane (meth) acrylate oligomer having two unsaturated double bonds)
The active energy ray-curable resin composition of the present invention is a bifunctional urethane (meth) acrylate oligomer having two unsaturated double bonds (hereinafter, also referred to as a component (b1)) as the (B) active energy ray-curable resin. .) Is preferably used. The cured film formed from the active energy ray-curable resin composition containing the component (b1) is more excellent in antifouling property.

(B1) As the bifunctional urethane (meth) acrylate oligomer, urethane (meth) obtained by reacting with a polyol other than the above-mentioned polyisocyanate, hydroxyl group-containing (meth) acrylate and, if necessary, hydroxyl group-containing (meth) acrylate. Of the acrylate oligomers, bifunctional ones can be appropriately selected and used. Specific examples of commercially available products include UV-841, UV-71, UV-72, UV-73, UV-820, UV-822, and UV-831 (trade name, above, Akira Otake Shinkagaku). EBECRYL210, EBECRYL215, EBECRYL230, EBECRYL244, EBECRYL245, EBECRYL270, EBECRYL284, EBECRYL285, EBECRYL8402, EBECRYL8402, EBECRYL8402, EBECRYL8402, EBECRYL8402, EBECRYL8402 -6640B (trade name, manufactured by Nippon Synthetic Chemical Industry Co., Ltd.), UA-122P, U-200PA, UA-4200 (trade name, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.), Art Resin UN-333, Art Resin UN -2600, Art Resin UN-2700, Art Resin UN-9000PEP (trade name, manufactured by Negami Kogyo Co., Ltd.) and the like. Such a bifunctional urethane (meth) acrylate oligomer (b1) may be used alone or in combination of two or more.

(B1) The weight average molecular weight of the bifunctional urethane (meth) acrylate oligomer is usually 500 to 20,000, preferably 600 to 10,000, and more preferably 1,000 to 7,000.

((B2) Trifunctional or higher functional urethane (meth) acrylate oligomer having three or more unsaturated double bonds)
The active energy ray-curable resin composition of the present invention comprises, as the (B) active energy ray-curable resin, a bifunctional urethane (meth) acrylate oligomer (b1) or a bifunctional urethane (meth) acrylate oligomer (b1). Alternatively, it may contain a trifunctional or higher functional urethane (meth) acrylate oligomer (b2) having three or more unsaturated double bonds (hereinafter, also referred to as a component (b2)). The cured film formed from the active energy ray-curable resin composition of the present invention using the component (b2) has improved surface hardness, which makes it more difficult for stains to adhere and improves contamination prevention. When the component (b1) and the component (b2) are used in combination, the obtained cured film is more excellent in antifouling property.

(B2) As the trifunctional or higher functional urethane (meth) acrylate oligomer, urethane obtained by reacting the above-mentioned polyisocyanate, hydroxyl group-containing (meth) acrylate and, if necessary, a polyol other than the hydroxyl group-containing (meth) acrylate. Among the (meth) acrylate oligomers, trifunctional or higher functional ones can be appropriately selected and used. Specific examples of commercially available products include UV-55 (trade name, manufactured by Meijishingai Otake Co., Ltd.), EBECRYL 4738, EBECRYL 4740, EBECRYL 8254 (trade name, manufactured by Daicel Ornex Co., Ltd.) and the like. Be done. Such a trifunctional or higher functional urethane (meth) acrylate oligomer (b2) may be used alone or in combination of two or more.

(B2) The weight average molecular weight of the trifunctional or higher functional urethane (meth) acrylate oligomer is usually 500 to 20,000, preferably 600 to 10,000, and more preferably 1,000 to 7,000.

((C) (meth) acrylate monomer)
The active energy ray-curable resin composition of the present invention may contain a (meth) acrylate monomer (hereinafter, also referred to as a component (C)). The (C) (meth) acrylate monomer is a monomer having at least one (meth) acryloyl group, and has a role as a reactive diluent for adjusting the viscosity of the active energy ray-curable resin composition. When the resin composition is irradiated with active energy rays, a cured film is formed together with (B) the active energy ray-curable resin.

Examples of the (meth) acrylate monomer include phenoxypolyethylene glycol (meth) acrylate, tripropylene glycol di (meth) acrylate, methoxytriethylene glycol (meth) acrylate, and methoxytetraethylene glycol (meth) acrylate, 1, 6-Hexanediol ethoxylate di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, 1,9-nonanediol di (meth) acrylate, Neopentyl glycol di (meth) acrylate, 2- (2-ethoxyethoxy) ethyl (meth) acrylate, bisphenol A ethoxylate di (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, Diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, trimethylpropanthry (meth) acrylate, pentaerythritol tetra (meth) acrylate, neopentyl hydroxypivalate Glycoldi (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate and the like can be mentioned, but the present invention is not limited thereto. Further, such a (meth) acrylate-based monomer may be a lactone-modified product such as (meth) acrylate of ε-caprolactone-modified dipentaerythritol.

Among the above, phenoxypolyethylene glycol acrylate, methoxytriethylene glycol acrylate, tripropylene glycol diacrylate, and 1,6-hexane from the viewpoint of adjusting the viscosity of the active energy ray-curable resin composition and adjusting the hardness of the cured film. Diol ethoxylate diacrylate is preferred. When phenoxypolyethylene glycol acrylate or methoxytriethylene glycol acrylate is used, it is easy to adjust the viscosity of the active energy ray-curable resin composition. Further, when tripropylene glycol diacrylate or 1,6-hexanediol ethoxylate diacrylate is used, the hardness of the cured film can be easily adjusted. In particular, when phenoxypolyethylene glycol acrylate and tripropylene glycol diacrylate are used in combination, the wear resistance is excellent. Such (meth) acrylate monomers can be used alone or in combination of two or more.

When the (C) (meth) acrylate monomer is used, it is usually contained in the active energy ray-curable resin composition in an amount of 90% by mass or less based on 100% by mass in terms of solid content of the composition, preferably. It is contained in a proportion of 10 to 90% by mass, more preferably 20 to 60% by mass. The weight ratio of the (C) (meth) acrylate monomer to the (B) active energy ray-curable resin is such that the component (B): component (C) is usually 100: 0 to 10:90, preferably 80: The ratio is preferably 20 to 20:80, more preferably 70:30 to 30:70.

((D) Photopolymerization Initiator)
When the active energy ray-curable resin composition of the present invention is polymerized and cured by light such as ultraviolet rays, a photopolymerization initiator (hereinafter, also referred to as component (D)) is used. When polymerizing and curing with an electron beam, it is not usually used.

Specific examples of the (D) photopolymerization initiator include benzoin-based photopolymerization initiators such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzyl dimethyl ketal (also known as 2,2). -Dimethoxy-2-phenylacetophenone), diethoxyacetophenone, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, 4-t-butyl-trichloroacetophenone, 2-hydroxy-2-methyl-1-phenylpropane- 1-on, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropan-1-one, 4- (2-Hydroxyethoxy) -phenyl (2-hydroxy-2-propyl) ketone, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropane-1, methylbenzoyl Acetphenone-based photopolymerization initiators such as formates; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylicized benzophenone, 4-benzoyl-4'-methyldiphenylsulfide, 3,3'- Benzophenone-based photopolymerization initiators such as dimethyl-4-methoxybenzophenone; thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, isopropylthioxanthone, 2,4-dichlorothioxanthone, 2,4-diethylthioxanthone. , 2,4-Diisopropylthioxanthone and other thioxanthone-based photopolymerization initiators; acyls such as 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide and the like. Examples thereof include a phenyl oxide-based photopolymerization initiator. Among them, a benzophenone-based photopolymerization initiator is preferable, and benzophenone is more preferable. Such a photopolymerization initiator (D) may be used alone or in combination of two or more.

When the (D) photopolymerization initiator is used, it is usually 1 to 10% by mass, preferably 3 to 7% by mass, based on 100% by mass in terms of solid content of the composition in the active energy ray-curable resin composition. It is desirable to use in the ratio of.

(Other ingredients)
In the active energy ray-curable resin composition according to the present invention, in addition to the above components, if necessary, epoxy acrylate, polyester acrylate, acrylic oligomer, silicone acrylate, silicone-modified urethane acrylate, fluorine-modified acrylate, etc. Acrylate other than the above components, polymerization inhibitor, non-reactive diluent, matting agent, defoaming agent, anti-settling agent, leveling agent, dispersant, heat stabilizer, ultraviolet absorber, light stabilizer, antifouling property Use an improver, a substrate adhesion improver, a photosensitizer, an antioxidant, an antibacterial agent, an antifungal agent, an antiviral agent, a silane coupling agent, a plasticizer, etc. within a range that does not impair the object of the present invention. be able to.

In the present invention, it is preferable to use a matting agent, and specifically, at least one selected from the group consisting of inorganic fine powder and organic fine powder is used. As the inorganic fine powder, silica is preferably used, and salts such as glass, mica, zeolite, diatomaceous earth, graphite, clay, talc and calcium carbonate, metals, metal oxides and the like can also be used. Polyurethane beads are preferably used as the organic fine powder, and various resins such as acrylic resin and polyamide, silicone rubber, pulp, cellulose and the like can also be used. Two or more of these fine powders may be used in combination. The matting agent is preferably spherical, and the average particle size is not particularly limited, and a matting agent of 0.1 to 30 μm is preferable.

When a matting agent is used, the amount is usually more than 0 and 50% by mass or less, preferably 1 to 50% by mass, in the active energy ray-curable resin composition based on 100% by mass in terms of solid content of the composition. It is desirable that it is contained in the amount of.

The active energy ray-curable resin composition according to the present embodiment does not need to be diluted with a solvent-type resin composition diluted with an organic solvent (non-reactive diluent) such as thinner or alcohol, or with an organic solvent. Either solvent-free resin composition may be used. However, since there is no residual volatile organic compound (VOC), the solvent-free resin composition is preferable because it has no effect on the human body and is excellent in environmental friendliness.

(Method for preparing active energy ray-curable resin composition)
The active energy ray-curable resin composition according to the present invention can be obtained by mixing and stirring the above-mentioned components using a conventionally known device such as a mixer, a disperser, or a stirrer. Examples of such a device include a mixing / dispersing mill, a mortar mixer, a roll, a paint shaker, a homogenizer, and the like.
The viscosity of the composition of the present invention at 25 ° C. is usually 10 to 20,000 mPa · s, preferably 100 to 10,000 mPa · s. A B-type viscometer is used to measure the viscosity.

[Base material with cured film]
At least one side of the substrate with a cured film according to the present invention is coated with a cured film formed from the above-mentioned active energy ray-curable resin composition. The cured film may be provided on the entire surface of one side of the base material, may be provided only on a part of one side, or may be provided on both sides of the base material. The mode of the cured coating when it is provided on a part is not particularly limited, and any mode such as a sea-island-like sea portion or island portion, a lattice-like shape, or a mosaic-like shape can be adopted without particular limitation.

(Base material)
In the present invention, the base material can be used as an interior material. Interior material refers to a member used inside a building, vehicle, or the like. For example, windows, walls, ceilings, floors, roofs, fittings, wallpaper and the like. The base material can also be used as an outdoor or semi-outdoor flooring material. In particular, floor materials and wall materials that are required to have antifouling properties are preferable, and floor materials are more preferable. Examples of the base material include a base material made of a synthetic resin. Examples of synthetic resins include thermoplastic resins and thermosetting resins. Specific examples of the thermoplastic resin include polyvinyl chloride resin, polyolefin resin, polystyrene resin, polyester resin, acrylic resin and the like. Specific examples of the thermosetting resin include phenol-based resins, epoxy-based resins, urethane-based resins, urea-based resins, and melamine-based resins. Among them, when used for a floor material made of synthetic resin, a thermoplastic resin is preferable, and a vinyl chloride resin is more preferable, from the viewpoint of workability and ease of construction as a floor material. The thickness of the base material is preferably 0.2 to 10 mm, more preferably 1 to 5 mm.

(Curing film)
The cured film is formed from the above-mentioned active energy ray-curable resin composition. The film thickness of the cured film is not particularly limited, but is usually 1 to 100 μm, preferably 3 to 70 μm, and more preferably 5 to 50 μm from the viewpoint of long-term maintenance of antifouling property. The film thickness in the present invention refers to the thickness of the cured film when the cross section of the cured film is observed with an optical microscope, a scanning electron microscope (SEM), or the like. When forming a film having such a film thickness, a film having a desired thickness may be formed by one coating, or a film having a desired thickness may be formed by a plurality of coatings.

<Manufacturing method of base material with cured film>
The substrate with a cured film according to the present invention comprises a step of applying the above-mentioned active energy ray-curable resin composition to at least one surface of the substrate (coating step) and irradiating the coated surface with active energy rays. It includes a step of curing the composition (curing step).

(Applying process)
The coating step is a step of coating the above-mentioned active energy ray-curable resin composition on at least one surface of the base material by a conventionally known method. For coating, for example, a coating machine such as a bar coater, a gravure coater, a roll coater (natural roll coater, reverse roll coater, etc.), an air knife coater, a spin coater, a blade coater, etc. can be used. Among these, a coating method using a roll coater is preferable from the viewpoint of workability and productivity.

The coating film thickness is preferably 1 to 100 μm as the film thickness after curing and drying. A more preferable upper limit is 100 μm from the viewpoint of dryness and curability, and a further preferable lower limit is 1 μm from the viewpoint of abrasion resistance and stain prevention.

When the active energy ray-curable resin composition is diluted with a solvent and used, it is preferable to dry it after coating. Examples of the drying method include hot air drying (dryer, etc.). The drying temperature is preferably 10 to 200 ° C., a more preferable upper limit is 150 ° C. from the viewpoint of smoothness and appearance of the coating film, and a further preferable lower limit is 30 ° C. from the viewpoint of drying speed.

(Curing process)
The curing step is a step of irradiating the coated surface of the base material with active energy rays to cure the applied active energy ray-curable resin composition to form a cured film. Examples of the active energy ray include an electron beam and the like in addition to ultraviolet rays (far ultraviolet rays, near ultraviolet rays, etc.) and infrared rays. Among them, in terms of curing speed, availability of an irradiation device, price, etc. , Ultraviolet rays are preferable.

When the active energy ray-curable resin composition according to the present invention is cured by the above-mentioned light rays such as ultraviolet rays, a photopolymerization initiator is used. On the other hand, when it is cured by the above-mentioned electron beam or the like, it is usually not necessary to use a photopolymerization initiator.

Examples of the method of curing with ultraviolet rays include a method of irradiating ultraviolet rays using a high-pressure mercury lamp, a metal halide lamp, a xenon lamp, a chemical lamp, a UV-LED, or the like that emits light in the wavelength range of 200 to 500 nm. The irradiation amount of ultraviolet rays is preferably 100 to 3,000 mJ / cm ² , and more preferably 200 to 2,000 mJ / cm, from the viewpoint of curability of the active energy ray-curable resin composition and flexibility of the cured product. It is cm ² .

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to the following Examples.

<Preparation of active energy ray-curable resin composition>
First, the following raw materials were prepared for the preparation of the active energy ray-curable resin composition.
-Urethane acrylate particles (manufactured by Negami Kogyo Co., Ltd., trade name: Artpearl UA-806T, volume average particle diameter: 6 μm)
-Urethane particles 1 (manufactured by Negami Kogyo Co., Ltd., trade name: Art Pearl AK-800TR, volume average particle diameter: 6 μm)
-Urethane particles 2 (manufactured by Negami Kogyo Co., Ltd., trade name: Art Pearl CE-800T, volume average particle diameter: 6 μm)
-Acrylic particles (manufactured by Aika Kogyo Co., Ltd., trade name: Ganzpearl GM-1001, volume average particle diameter: 10 μm)
-Silica 1 (manufactured by Mizusawa Industrial Chemicals Co., Ltd., trade name: Mizukasil P-802Y, volume average particle size: 5 μm)
-Silica 2 (manufactured by Evonik Japan Co., Ltd., trade name: ACEMATT OK-607, volume average particle size: 4.4 μm)
・ Bifunctional urethane acrylate (manufactured by Meijishingai Otake Co., Ltd., product name: UV-841)
・ 6-functional urethane acrylate (manufactured by Mitsubishi Chemical Corporation, trade name: Shikou UV-7600B)
-Monofunctional acrylate (manufactured by Kyoeisha Chemical Co., Ltd., trade name: light acrylate P-200A)
-Bifunctional acrylate 1 (Miwon Specialy Chemical, trade name: Miramer M-220)
Bifunctional acrylate 2 (manufactured by Miwon Specialy Chemical, trade name: Miramer M-202)
-Photopolymerization initiator 1 (manufactured by ChemFine International, trade name: HYCURE BENZOPHENONE)
-Photopolymerization initiator 2 (manufactured by IGM Resin, trade name: Omnirad MBF)
-Photopolymerization initiator 3 (manufactured by IGM Resin, trade name: Omnirad 184)
・ Polymerization inhibitor (Hydroquinone manufactured by Ube Industries, Ltd.)
Dispersant (manufactured by Big Chemie Co., Ltd., trade name: Disperbyk-2164)
・ Leveling agent (manufactured by Toray Dow Corning Co., Ltd., product name: DC 57 ADDITIVE (Paintad 57))
・ Defoamer (manufactured by Big Chemie Co., Ltd., product name: BYK-1790)

[Examples 1 to 3 and Comparative Examples 1 to 8]
<Preparation of active energy ray-curable resin composition>
According to the formulation shown in Table 1, particles other than the component (A) or the component (A), the component (B), the component (C), the component (D), and other components are mixed and stirred using a homodisper. Then, an active energy ray-curable resin composition was obtained. The "total solid content of the composition" in Table 1 refers to the value obtained by removing the amount of the solvent contained in the dispersant from the "total" value of each component.

<Manufacturing of base material with cured film>
The active energy ray-curable resin composition prepared in Examples 1 to 3 and Comparative Examples 1 to 8 is cured with a roll coater on a soft vinyl chloride sheet having a thickness of 2 mm, and the thickness of the film becomes 15 μm. With a high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays were irradiated at an integrated light intensity of 700 mJ / cm ² and cured to obtain a substrate with a cured film.

<Evaluation>
(Pollution prevention 1)
A simple black pollutant, which was a mixture of black carbon and calcium carbonate at a ratio of 2: 8, was rubbed and adhered to the surface of the substrate with a cured film with a Kim towel (manufactured by Nippon Paper Crecia Co., Ltd.). Then, the contaminants adhering to the surface of the substrate were wiped off with a new Kim towel, and the degree of removeability of the contaminants was observed. Evaluation was made according to the following criteria, and the evaluation results are shown in Table 1. Those with an evaluation of "○" or higher were regarded as acceptable.
[Evaluation criteria]
◯: Most of the pollutants were removed.
Δ: More than half of the pollutants were removed.
X: Almost no pollutants were removed.

(Pollution prevention 2)
0.1 g of Isodine mouthwash (manufactured by Shionogi Pharmaceutical Co., Ltd.) was added dropwise to the surface of the substrate with a cured film. After 6 hours, it was washed with water and the degree of coloring was observed. Evaluation was made according to the following criteria, and the evaluation results are shown in Table 1. Those with an evaluation of "○" or higher were regarded as acceptable.
[Evaluation criteria]
◯: No coloring or light coloring.
X: Deeply colored.

(Pollution prevention 3)
A line having a width of 3 cm was drawn on the surface of the substrate with a cured film with McKee ultrafine (manufactured by Zebra Co., Ltd.), and after 1 minute, it was wiped off with a Kim towel (manufactured by Nippon Paper Crecia Co., Ltd.). Evaluation was made according to the following criteria, and the evaluation results are shown in Table 1. Those with an evaluation of "○" or higher were regarded as acceptable.
[Evaluation criteria]
◯: The line was wiped off.
Δ: A slight trace of the line remained.
X: Traces of lines remained.

Claims (10)

It contains (A) urethane acrylate particles and (B) active energy ray-curable resin.
(A) An active energy ray-curable resin composition in which the content of urethane acrylate particles is 1% by mass or more and 60% by mass or less based on 100% by mass in terms of solid content of the composition. (B) The active energy ray-curable resin composition according to claim 1, wherein the active energy ray-curable resin contains a urethane (meth) acrylate oligomer. The active energy ray-curable resin composition according to claim 2, wherein the urethane (meth) acrylate oligomer contains a polyfunctional urethane (meth) acrylate oligomer having two or more unsaturated double bonds. The active energy ray-curable resin composition according to claim 3, wherein the polyfunctional urethane (meth) acrylate oligomer contains (b1) a bifunctional urethane (meth) acrylate oligomer having two unsaturated double bonds. (C) The active energy ray-curable resin composition according to any one of claims 1 to 4, further comprising a (meth) acrylate monomer. (D) The active energy ray-curable resin composition according to any one of claims 1 to 5, further comprising a photopolymerization initiator. (B) The active energy ray-curable resin composition according to any one of claims 1 to 6, wherein the weight average molecular weight of the active energy ray-curable resin is in the range of 500 or more and 100,000 or less. The active energy ray-curable resin composition according to any one of claims 1 to 7, which is used for an interior material or an outdoor or semi-outdoor floor material. A substrate with a cured film, wherein at least one side of the substrate is coated with a cured film formed from the active energy ray-curable resin composition according to any one of claims 1 to 8. The base material with a cured coating according to claim 9, wherein the base material is for an interior material or an outdoor or semi-outdoor floor material.