JP2022059451A - Active energy ray-curable resin composition and base material with cured coated film - Google Patents

Abstract

To provide an active energy ray-curable resin composition which enables formation of a cured coated film having low glossiness, and excellent stain resistance, especially, excellent resistance against a hair dye solution, and has low viscosity and good workability.SOLUTION: An active energy ray-curable resin composition contains (A) an active energy ray-curable resin, (B) a (meth)acrylate monomer, (C) silica particles, and (D) a matting agent, in which (B) the (meth)acrylate monomer contains tricyclodecan dimethanol diacrylate, a content of (C) the silica particles is less than 1 mass% based on 100 mass% in terms of a solid content of the active energy ray-curable resin composition, and viscosity at 25°C of the active energy ray-curable resin composition is less than 120 KU.SELECTED DRAWING: None

Description

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

Conventionally, a cured film has been provided on the surface of a base material such as a floor material of a house or a store or an interior wall. The performance required for this cured film includes stain resistance and designability. Regarding stain resistance, it is required that it is difficult to adhere to dirt. In particular, since a commercially available hair dyeing solution has a high dyeing power, it is very difficult to remove it when it adheres to a floor or the like.

To solve the above problems, for example, Patent Document 1 contains an organic polyisocyanate (A), a polycarbonate polyol (B) having an alicyclic structure, and one or more hydroxyl groups in the molecule (meth). ) It has been proposed to form a cured coating film using an energy ray-curable resin composition containing a urethane acrylate obtained by reacting with an acrylate (C). Further, in Patent Document 2, it is a urethane (meth) acrylate having a cyclic structure in the molecule, and the total weight of carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms constituting the ring of the cyclic structure is urethane (? Cured using an active energy ray-curable resin composition containing urethane (meth) acrylate having an average number of functional groups of 3.5 to 4.5 and 10% by weight or more based on the meta) acrylate (100% by weight). It has been proposed to form a layer.

Further, in recent years, it has been desired to reduce the gloss of the surface of the base material in terms of design. Therefore, it is being considered to add a matte material to the cured film.

Japanese Unexamined Patent Publication No. 2009-227915 International Publication No. 2014/174861

Therefore, the present invention has low viscosity and good workability, and is capable of forming a cured film having low gloss and excellent stain resistance, particularly stain resistance to a hair dye that is difficult to remove. It is an object of the present invention to provide a mold resin composition.

As a result of diligent studies, the present inventors have added (A) an active energy ray-curable resin to the active energy ray-curable resin composition and tricyclodecanedimethanol di (meth) acrylate as the (B) (meth) acrylate monomer. By containing (C) silica particles and (D) a matting agent, and adjusting the content of (C) silica particles and the viscosity of the active energy ray-curable resin composition within a specific range. It is possible to obtain an active energy ray-curable resin composition having low gloss and excellent workability, capable of forming a cured film having excellent stain resistance, particularly stain resistance to a hair dye that is difficult to remove. I found out. The present invention has been completed based on such findings.

That is, according to the present invention, the following invention is provided.
[1] An active energy ray-curable resin composition containing (A) an active energy ray-curable resin, (B) (meth) acrylate monomer, (C) silica particles, and (D) a matting agent. hand,
(B) The (meth) acrylate monomer contains tricyclodecanedimethanol di (meth) acrylate.
(C) The content of the silica particles is less than 1% by mass based on 100% by mass in terms of solid content of the active energy ray-curable resin composition.
An active energy ray-curable resin composition having a viscosity of the active energy ray-curable resin composition at 25 ° C. of less than 120 KU.
[2] The active energy ray-curable resin composition according to [1], wherein the (A) active energy ray-curable resin 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 (a1) a bifunctional urethane (meth) acrylate oligomer having two unsaturated double bonds. thing.
[5] The content of the tricyclodecanedimethanol di (meth) acrylate is 10% by mass or more and 70% by mass or less based on 100% by mass in terms of solid content of the active energy ray-curable resin composition [1]. ] To [4]. The active energy ray-curable resin composition according to any one of.
[6] The active energy ray-curable resin composition according to any one of [1] to [5], wherein the matting agent is urethane particles.
[7] The active energy ray-curable resin composition according to any one of [1] to [6], further comprising (E) a photopolymerization initiator.
[8] The active energy ray-curable resin composition according to any one of [1] to [7], which is used for flooring materials.
[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 having a low viscosity and good workability, which can form a cured film having low gloss and excellent stain resistance. Further, according to the present invention, it is possible to provide a substrate with a cured coating having low gloss and excellent stain resistance. In particular, the cured film according to the present invention has excellent stain resistance (hereinafter referred to as hair dyeing liquid resistance) to a hair dyeing liquid that is difficult to remove.

Hereinafter, the present invention will be described in more detail.
In addition, in this specification, "(meth) acrylate" represents acrylate and methacrylate, and "(meth) acryloyl" represents acryloyl and methacryloyl.
The "active energy ray" means an ultraviolet ray, a visible 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 constituting a cured film when cured.

<Active energy ray-curable resin composition>
The active energy ray-curable resin composition according to the present invention comprises at least (A) an active energy ray-curable resin, (B) (meth) acrylate monomer, (C) silica particles, and (D) a matting agent. Is included. The active energy ray-curable resin composition according to the present invention may further contain (E) a photopolymerization initiator and other components.

The active energy ray-curable resin composition according to the present invention has a low viscosity and is excellent in workability. The active energy ray-curable resin composition conforms to JIS K 5600-2-2 and has a viscosity measured by a Stormer viscometer at 25 ° C., preferably less than 120 KU, more preferably less than 100 KU, and also. It is preferably 50 KU or more, and more preferably 70 KU or more. When the viscosity of the active energy ray-curable resin composition is within the above numerical range, it is suitable as a paint because it is excellent in workability.

In the active energy ray-curable resin composition according to the present invention, it is preferable that the 60-degree mirror gloss of the cured film having a thickness of 10 to 15 μm formed by coating on a wooden flooring flooring is 30 or less. When the 60-degree mirror surface gloss of the cured film formed on the wood flooring floor material is less than 30, it is suitable as a paint for the floor material for which low gloss is desired. The 60-degree mirror glossiness can be measured using a commercially available glossiness meter.

The cured film formed from the active energy ray-curable resin composition according to the present invention has low gloss and is excellent in stain resistance, particularly hair dyeing liquid resistance. Therefore, the active energy ray-curable resin composition according to the present invention can be suitably used for a base material having excellent stain resistance, particularly for an interior material such as a floor material, or an outdoor or semi-outdoor floor material. Hereinafter, each component of the active energy ray-curable resin composition according to the present invention will be described in detail.

((A) Active energy ray-curable resin)
The (A) active energy ray-curable resin (hereinafter, also referred to as the component (A)) is at least one selected from oligomers and polymers having at least one unsaturated double bond. The component (A) 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 (A) include urethane (meth) acrylate oligomers, epoxy (meth) acrylate oligomers, polyester (meth) acrylate oligomers, polyether (meth) acrylate oligomers, acrylic (meth) acrylate oligomers, and the like. It is not limited to these. Among these, urethane (meth) acrylate oligomers are preferable from the viewpoint of stain resistance of the cured film. Such a component (A) 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 diisocyanates, and hydrogenated diphenylmethanes. Isocyanate group-containing cyclic hydrocarbons such as diisocyanate, hydrogenated xylenediocyanate, hydrogenated toluene diisocyanate, p-phenylenediisocyanate, 3,3'-dimethyldiphenyl-4,4'-diisocyanate, 1,3-xylene diisocyanate, dianisidine diisocyanate. , Tetramethylxylenediocyanate, 1,5-naphthalenediocyanate, tolylene diisocyanate, 4,4-diphenylmethane diisocyanate and other diisocyanate group-containing aromatic hydrocarbons, but the present invention is 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 hydroxyl groups, 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. In addition, an ether bond (COC 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, alkylene diols, etc. not. Such polyols may be used alone or in combination of two or more.

The weight average molecular weight of the gel permeation chromatography of the (A) active energy ray-curable resin is usually 500 to 100,000, preferably 600 to 50,000, and more preferably 1,000 to 30,000. In the present specification, the weight average molecular weight is a value in terms of standard polystyrene measured by the (GPC) method.

(A) The content of the active energy ray-curable resin is usually 3% by mass or more and 40% by mass or less, preferably 5% by mass or more and 35, 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 10% by mass or more and 30% by mass or less. When the content of the active energy ray-curable resin is within the above range, the cured film formed from the active energy ray-curable resin composition is considered to be superior in stain resistance to various stains such as oil and chemicals. Become.

((A1) 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 (a1)) as the (A) active energy ray-curable resin. .) Is preferably used. The cured film formed from the active energy ray-curable resin composition containing the component (a1) is more excellent in stain resistance.

(A1) 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. As commercially available products, specifically, EBECRYL210, EBECRYL230, EBECRYL270, EBECRYL280, EBECRYL284, EBECRYL4858, EBECRYL8402, EBECRYL8402, EBECRYL9270, (trade name, manufactured by Daicel Ornex UV-3210 6630B, Shikou UV-6640B (trade name, manufactured by Mitsubishi 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 Examples thereof include Resin UN-261, Art Resin UN-701, and Art Resin UN-9000PEP (trade name, manufactured by Negami Kogyo Co., Ltd.). Such a bifunctional urethane (meth) acrylate oligomer (a1) may be used alone or in combination of two or more.

(A1) The weight average molecular weight of the bifunctional urethane (meth) acrylate oligomer is usually 500 to 50,000, preferably 600 to 20,000, and more preferably 1,000 to 15,000.

((A2) 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 (A) an active energy ray-curable resin, together with a bifunctional urethane (meth) acrylate oligomer (a1), or a bifunctional urethane (meth) acrylate oligomer (a1). Alternatively, it may contain a trifunctional or higher functional urethane (meth) acrylate oligomer (a2) having three or more unsaturated double bonds (hereinafter, also referred to as a component (a2)). The cured film formed from the active energy ray-curable resin composition of the present invention using the component (a2) has improved surface hardness, which makes it more difficult for stains to adhere and improves stain resistance. When the component (a1) and the component (a2) are used in combination, the obtained cured film becomes more excellent in stain resistance.

(A2) As the trifunctional or higher functional urethane (meth) acrylate oligomer, urethane obtained by reacting with 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 EBECRYL 4738, EBECRYL 4740, and EBECRYL 8254 (trade name, manufactured by Daicel Ornex Co., Ltd.). Such a trifunctional or higher functional urethane (meth) acrylate oligomer (a2) may be used alone or in combination of two or more.

(A2) The weight average molecular weight of the trifunctional or higher functional urethane (meth) acrylate oligomer is usually 500 to 50,000, preferably 600 to 20,000, and more preferably 1,000 to 15,000.

((B) (meth) acrylate monomer)
The active energy ray-curable resin composition of the present invention contains a (meth) acrylate monomer (hereinafter, also referred to as a component (B)). The (B) (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 (A) the active energy ray-curable resin.

In the present invention, the (B) (meth) acrylate monomer contains at least tricyclodecanedimethanol di (meth) acrylate in order to improve the stain resistance of the cured film, particularly the hair dyeing liquid resistance. As the (meth) acrylate monomer, in addition to tricyclodecanedimethanol di (meth) acrylate, acryloylmorpholine, dicyclopentenyloxyethyl (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, and tripropylene glycol di (Meta) acrylate, methoxytriethylene glycol (meth) acrylate, 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, Trimethylol Propanetri (meth) Acrylate, Pentaerythritol Tri (meth) Acrylate, Pentaerythritol Tetra (Meta) Acrylate, Neopentyl glycol Di (meth) Acrylate, Dipentaerythritol Penta (Meta) Acrylate, Dipentaerythritol Penta (meth) Acrylate Examples thereof include, but are not limited to, pentaerythritol hexa (meth) acrylate and trimethylpropane (ethoxylate) triacrylate. Further, such a (meth) acrylate-based monomer may be a lactone-modified form such as (meth) acrylate of ε-caprolactone-modified dipentaerythritol. These (meth) acrylate monomers can be used alone or in combination of two or more in addition to the tricyclodecanedimethanol di (meth) acrylate.

The content of (B) tricyclodecanedimethanol di (meth) acrylate is preferably 10% by mass or more and 70% by mass or less based on 100% by mass in terms of solid content of the active energy ray-curable resin composition. It is preferably 20% by mass or more and 65% by mass or less, and more preferably 25% by mass or more and 60% by mass or less. Further, the total content of (B) (meth) acrylate monomer (total content of tricyclodecanedimethanol di (meth) acrylate and other (meth) acrylate monomers) is the solid of the active energy ray-curable resin composition. Based on 100% by mass in terms of minutes, it is preferably 40% by mass or more and 75% by mass or less, and more preferably 45% by mass or more and 65% by mass or less.

((C) Silica particles)
The active energy ray-curable resin composition according to the present invention contains a small amount of silica particles in order to suppress unevenness on the surface of the cured film. The silica particles are not particularly limited, and conventionally known silica particles can be used. The shape of the silica particles is not particularly limited and may be spherical, plate-shaped, or flaky. The silica particles may be either amorphous silica or crystalline silica, or a mixture thereof. Commercially available products can also be used as the silica particles.

The volume average particle diameter of the silica particles is not particularly limited, but is preferably 0.1 μm or more and 50 μm or less, more preferably 0.2 μm or more and 30 μm or less, still more preferably 0.5 μm or more and 20 μm or less, and further. More preferably, it is 1 μm or more and 15 μm or less.

The content of the silica particles (C) is less than 1% by mass, preferably 0.01% by mass or more and 0.9% by mass or less, based on 100% by mass in terms of solid content of the active energy ray-curable resin composition. Yes, more preferably 0.1% by mass or more and 0.8% by mass or less. When the content of the silica particles is as low as described above, the surface of the cured film formed from the active energy ray-curable resin composition is not uneven, and a stable and good appearance is obtained.

((D) Matte)
The active energy ray-curable resin composition of the present invention contains a matting agent. As the matting agent, for example, at least one selected from the group consisting of inorganic fine powder (excluding the above silica particles) and organic fine powder is used. As the inorganic fine powder, salts such as glass, mica, zeolite, diatomaceous earth, graphite, clay, talc, calcium carbonate, metal, metal oxide and the like can also be used. Urethane particles (beads) are preferably used as the organic fine powder, and various resin particles (beads) 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 having a diameter of 0.1 to 30 μm is preferable.

The content of the (D) matting agent is usually more than 0 and 30% by mass or less, preferably 5% by mass or more and 20% by mass or less, based on 100% by mass in terms of solid content of the active energy ray-curable resin composition. be. When the content of the matting agent is within the above range, the cured film formed from the active energy ray-curable resin composition can be made low in gloss.

((E) 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 (E)) is used. When polymerizing and curing with an electron beam, it is not usually used.

(E) Specific examples of the 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-methylpropane-1-one, 1- (4-dodecylphenyl) -2-hydroxy-2-methylpropane-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'- Phenylphenone-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 the like; thioxanthone-based photopolymerization initiator; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphin oxide and the like acyl Examples thereof include a phosphinoxide-based photopolymerization initiator. Of these, a benzophenone-based photopolymerization initiator is preferable, and benzophenone is more preferable. Such (D) photopolymerization initiator may be used alone or in combination of two or more.

(E) When a 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, a polymerization inhibitor, a non-reactive diluent, a defoaming agent, an antistatic agent, a leveling agent, and a dispersion are further required. Agent, heat stabilizer, UV absorber, light stabilizer, antifouling agent, substrate adhesion improver, photosensitizer, antistatic agent, scratch resistant agent, antifungal agent, silane coupling agent, plasticizer Etc. can be used as long as the object of the present invention is not impaired.

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, and a stirrer. Examples of such an apparatus include a mixing / dispersing mill, a mortar mixer, a roll, a paint shaker, a homogenizer, and the like.

[Base material with hardened 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 film when it is provided on a part of the film is not particularly limited, and any mode such as a sea-island-like sea portion or an 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. The interior material is a member used inside a building, a 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 require stain resistance are preferable, and floor materials are more preferable. Examples of the base material include a base material made of a synthetic resin. Examples of the synthetic resin 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 flooring materials made of synthetic resin, thermoplastic resins are preferable, and vinyl chloride-based resins are more preferable, from the viewpoints of workability and ease of construction as flooring materials. The thickness of the base material is not particularly limited, but is preferably 0.2 to 10 mm, more preferably 1 to 5 mm.

(Hardened 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 stain resistance. 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 coating 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, the 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 wear resistance and stain resistance.

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 or the like). 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, and 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 ultraviolet rays or the like, a photopolymerization initiator is used. On the other hand, when curing with the above 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 , 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 oligomer (viscosity (25 ° C) 7,000 to 13000 mPa · s)
Ester acrylate oligomer (viscosity (25 ° C) 7000 to 12000 mPa · s)
Epoxy acrylate oligomer (viscosity (25 ° C) 250-400 dPa · s)
-Bifunctional acrylate monomer (tricyclodecanedimethanol diacrylate, manufactured by Dycel Ornex Co., Ltd., trade name: EBECRYL 130)
-Monofunctional acrylate (acryloyl morpholine, Beijing RBL Chemicals Co., Ltd., trade name: RBL-ACMO)
Trifunctional acrylate monomer 1 (trimethylpropane (ethoxylate) triacrylate, KPX Green Chemical Co., Ltd., trade name: KOMERATE-T033)
-Trifunctional acrylate monomer 2 (pentaerythritol triacrylate, KPX Green Chemical Co., Ltd., trade name: KOMERATE-T001)
-Silica particles (volume average particle size: 6 μm, manufactured by Mizusawa Industrial Chemicals, Inc., trade name: Mizukasil P-801)
・ Matter (urethane beads, average particle size: 10.0 ± 2.0 μm)
-Photopolymerization initiator (1-hydroxycyclohexylphenyl ketone, manufactured by BASF Japan Ltd., trade name: Omnirad 184)

[Examples 1 to 9, Comparative Examples 1 to 3]
<Preparation of active energy ray-curable resin composition>
According to the formulation shown in Table 1, the components (A) to (D) and other components were mixed and stirred using a homodisper to obtain an active energy ray-curable resin composition.

<Evaluation>
(Viscosity of active energy ray-curable resin composition)
The viscosity of the active energy ray-curable resin composition prepared above was measured with a Stormer viscometer at 25 ° C. according to JIS K 5600-2-2. In addition, the viscosity was evaluated according to the following criteria. The lower the viscosity of the composition, the better the workability as a paint. The measured values and evaluation results are shown in Table 2.
[Evaluation criteria]
⊚: The viscosity of the composition was less than 100 KU.
◯: The viscosity of the composition was 100 KU or more and less than 120 KU.
X: The viscosity of the composition was 120 KU or more.

(Mirror gloss)
The active energy ray-curable resin composition prepared above was applied to a wood flooring flooring having a thickness of 12 mm using a roll coater so that the thickness of the film after curing was 10 to 15 μm. Subsequently, with a high-pressure mercury lamp (manufactured by Eye Graphics Co., Ltd.), ultraviolet rays were irradiated with an integrated light amount of 250 mJ / cm ² and cured to obtain a substrate with a cured film. Next, the 60-degree mirror glossiness of the obtained substrate with a cured film was measured using a glossiness meter (manufactured by HORIBA, Ltd., model number: IG-320). Further, the 60-degree mirror gloss (%) was evaluated according to the following criteria. The measured values and evaluation results are shown in Table 2.
[Evaluation criteria]
◯: The 60-degree mirror gloss was 30 or less.
X: The mirror surface gloss of 60 degrees was more than 30.

(Stain resistance)
After the substrate with the cured film obtained above was placed horizontally, a line having a width of 10 mm was drawn on the surface of the cured film with an oil-based ink (black) and a general commercial blue ink for office use. Subsequently, after allowing to stand at 25 ° C. for 4 hours, each ink was blown off with a paper waste containing a solvent (butyl acetate or ethyl acetate), and the contamination state was evaluated according to the following criteria. The evaluation results are shown in Table 2.
[Evaluation criteria]
〇: No color remained on the surface of the cured film.
X: Color remained on the surface of the cured film.

(Hair dyeing liquid resistance)
After the substrate with the cured film obtained above was placed horizontally, a hair dye solution (Hair Dymen's Bigen / Cream 7G, manufactured by Hoyu Co., Ltd.) was applied to the surface of the cured film and spread in a circle with a diameter of about 3 cm. .. Then, after allowing to stand at 25 ° C. for 30 minutes, the hair dye solution was blown off with a paper waste containing a solvent (butyl acetate or ethyl acetate), and the contamination state was evaluated according to the following criteria. The evaluation results of ◎ and ○ were accepted. The evaluation results are shown in Table 2.
[Evaluation criteria]
⊚: No trace was found.
◯: Traces were slightly observed, but there was no problem in practical use.
X: Traces were clearly recognized.

(Appearance evaluation)
The surface of the cured film of the substrate with the cured film obtained above was visually evaluated according to the following criteria.
[Evaluation criteria]
◯: The surface of the cured film was not uneven, and the appearance was stable and good.
X: Unevenness was generated on the surface of the cured film.

Claims (10)

An active energy ray-curable resin composition comprising (A) an active energy ray-curable resin, (B) (meth) acrylate monomer, (C) silica particles, and (D) a matting agent.
(B) The (meth) acrylate monomer contains tricyclodecanedimethanol di (meth) acrylate.
(C) The content of the silica particles is less than 1% by mass based on 100% by mass in terms of solid content of the active energy ray-curable resin composition.
An active energy ray-curable resin composition having a viscosity of the active energy ray-curable resin composition at 25 ° C. of less than 120 KU. The active energy ray-curable resin composition according to claim 1, wherein the (A) 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 (a1) a bifunctional urethane (meth) acrylate oligomer having two unsaturated double bonds. Claims 1 to 4 in which the content of the tricyclodecanedimethanol di (meth) acrylate is 10% by mass or more and 70% by mass or less based on 100% by mass in terms of solid content of the active energy ray-curable resin composition. The active energy ray-curable resin composition according to any one of the above. (D) The active energy ray-curable resin composition according to any one of claims 1 to 5, wherein the matting agent is urethane particles. (E) The active energy ray-curable resin composition according to any one of claims 1 to 6, further comprising a photopolymerization initiator. 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.