JP2001232727A - Decorative material having surface coating film layer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative material having a surface coating film layer excellent in scratch resistance, capable of being suppressed to a practical range in cost by the use of inexpensive inorganic particles, enabling the stable coating of the surface coating film layer, stable in quality and possible to produce with good workability. SOLUTION: The decorative material 1 is constituted by providing the coating film layer 3, which is formed from a composition consisting to inorganic fine particles (A) with a Wadell practical spherical degree of 0.70-0.99 and a Knoop hardness of 1,300-8,000 kg/mm2, reaction cured matter of an active energy beam reactive resin (B1) and a dispersant (C) and containing 5-35 mass% of (A) based on the sum total mass of (A)-(C), 45-95 mass% of (B1) and 0.2-10 mass% of (C), on the surface of a base material 2.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a decorative material having a surface coating layer having excellent scratch resistance.

[0002]

2. Description of the Related Art Conventionally, a decorative material having a surface coating layer provided for the purpose of surface protection or the like on a substrate such as paper or plastic film (especially, when the substrate is a sheet (film), a decorative sheet). Is also known. As a coating agent for forming the surface coating layer, a reactive resin such as an active energy ray reactive resin is used. As this coating agent, in order to improve the abrasion resistance of the surface coating layer and to protect it from friction and scratches, hard spherical particles made of α-alumina or the like are hardened into an active energy ray-reactive resin. There has been proposed a cosmetic material using a material added to a product (for example, see Japanese Patent Application Laid-Open No. Hei 8-1).
83147).

[0003]

However, as a result of continuing the trial evaluation, a cosmetic material using a coating agent obtained by adding the above-described conventional hard spherical particles to an active energy ray-curable resin has been conventionally used. Many of the spherical particles had incomplete sphericity, and it was found that the abrasion resistance originally intended by the present invention could not be obtained. Of course, hard spherical particles can increase the precision of processing and manufacturing of the particles themselves, making it possible to bring the sphericity closer to perfection. With that, the price of the spherical particles rises, and the cost of the cosmetic material itself rises. Because
However, there was a problem that it was not possible to rely on increasing the degree of sphere without limit.

When a coating composition is prepared by diluting hard spherical particles added to a reactive resin with a solvent, the hard spherical particles are liable to settle, making it difficult to perform stable coating. There was a problem.

SUMMARY OF THE INVENTION The present invention is intended to solve the above-mentioned drawbacks of the prior art. In a cosmetic material having a surface coating layer having excellent scratch resistance, the cost of the cosmetic material can be reduced by using inexpensive inorganic fine particles. Can be suppressed to a typical range,
It is an object of the present invention to provide a cosmetic material capable of performing stable coating of a surface coating layer and capable of producing stable quality with good workability.

[0006]

Means for Solving the Problems The present invention provides (1) reactive
Wadell practical spheres in the resin cured product (B)
The degree is 0.70 to 0.99 and the Knoop hardness is 1300
~ 8000kg / mm ^TwoSpherical inorganic fine particles (A)
Is 5 to 35 mass based on the total mass of (A) and (B).
% Is provided on the surface of the substrate
A cosmetic material having a surface coating layer, characterized by (2) Wad
Practical sphericity of the cell is 0.70 to 0.99 and Knoop
Hardness is 1300-8000kg / mm^TwoInorganic fine particles
(A), a reaction cured product of an active energy ray-reactive resin (B
1) and a dispersant (C), and the sum of (A) to (C)
(A) is 5 to 35% by mass and (B1) is 4 based on the mass.
Composition containing 5 to 95% by mass and 0.2 to 10% by mass of (C)
The surface coating layer formed from the product is provided on the surface of the substrate
A cosmetic material having a surface coating layer, characterized in that:
(3) The average particle diameter of the inorganic fine particles (A) is 3 to 50 μm.
Having a surface coating layer according to the above (1) or (2)
Material, (4) the inorganic fine particles (A) are alumina-based fine particles
Surface coating layer according to any one of the above (1) to (3)
(5) The dispersant (C) has an active energy of
Any of the above (2) to (4), which have
A cosmetic material having the surface coating layer according to any one of (1) to (6).
The powder (C) is a compound having a quaternary ammonium base as a counter cation.
Any of (2) to (4) above,
A cosmetic material having a surface coating layer according to claim 1, (7) a base material
Liquid repellent pattern layer is partially formed between the film and the surface coating layer
Directly above the liquid-repellent pattern layer,
The above-mentioned surface coating layer is more concave than its surroundings.
It has the surface coating layer according to any one of (1) to (6).
(8) Penetration between base material and surface coating layer
A pattern layer partially formed, and the permeable pattern
Immediately above the layer, the surface coating layer is more concave than the surroundings.
As described in any one of (1) to (6) above,
A cosmetic material having a surface coating layer of
You.

[0007]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings. FIG. 1 is a sectional view showing an example of the decorative material of the present invention. As shown in FIG. 1, a decorative material 1 according to the present invention is configured such that a surface coating layer 3 is provided on a surface side of a substrate 2 such as a substrate sheet. In the decorative material of the embodiment shown in FIG.
Is provided with a solid layer 5 and a picture layer 6 via a sealer layer 4, and a surface coating layer 3 is provided on both layers.

As the material of the base material 2 for the decorative material, paper, plastic, metal, wood, non-metallic ceramic materials and the like are used, and the shape is, for example, a sheet such as paper, plastic sheet, non-woven fabric, metal foil and the like. Or a plate-shaped material such as a metal plate, a wood plate, and a plastic plate. A sheet-like material having flexibility as a substrate has an advantage that a roll of a sheet-like material can be used as a substrate in a manufacturing process to enable continuous production of a decorative material. When a sheet-like substrate is used, a substrate having a thickness of 5 to 200 μm is preferably used. Further, as the substrate, a substrate having irregularities on the surface, a substrate having a three-dimensional shape, or the like can be used.

Specific examples of the paper used as the base material 2 include thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, and so-called vinyl wallpaper in which polyvinyl chloride resin is sol-coated or dry-laminated on paper. Raw paper, high quality paper,
Examples include coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, Japanese paper, and the like. Further, a paper-like sheet can also be used as the base material. The above-mentioned paper-like sheet includes glass fiber, asbestos, potassium titanate fiber,
Inorganic fiber such as alumina fiber, silica fiber, carbon fiber,
A woven or non-woven fabric using an organic resin such as polyester or vinylon is exemplified. Further, a resin-impregnated paper obtained by impregnating the above paper or paper-like sheet with a resin such as an acrylic resin, a urethane resin, or a rubber can be used.

The plastic sheet used as the base material 2 includes polyolefin resins such as polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, olefin thermoplastic elastomer, polyvinyl chloride, polyvinylidene chloride, Vinyl-vinyl acetate copolymer, ethylene-vinyl acetate copolymer, vinyl-based resin such as ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polybutylene terephthalate, ethylene-ralephthalate-isophthalate copolymer, polyarylate, Polyester resin such as polyester thermoplastic elastomer, poly (meth)
Acrylic resins such as methyl acrylate, poly (meth) ethyl acrylate, poly (meth) butyl acrylate (where "(meth) acrylic acid" means acrylic acid or methacrylic acid), nylon 6, nylon 66 Or a cellulose resin such as cellulose triacetate, cellophane, etc .; a synthetic resin film such as polystyrene or polycarbonate; or a monolayer of sheets or a laminate of two or more layers of different materials selected from the above. . Examples of the metal used as the metal foil include aluminum, stainless steel, iron, and copper.

The plate used as the substrate 2 is as follows. (1) wood board; cedar, cypress, oak, pine, oak, zelkova, lauan, teak,
Wood veneer, wood plywood, particle board, MDF (medium density fiberboard), laminated wood, etc. made of trees such as melapie. (2) Non-metallic ceramic material plates; gypsum plates, gypsum-based plates such as gypsum slag plates, calcium silicate plates, asbestos slate plates, lightweight foam concrete plates, cement plates such as hollow extruded cement plates,
Fiber cement board such as pulp cement board, asbestos cement board, wood chip cement board, pottery, porcelain, stoneware, earthenware, glass,
Ceramic plate such as enamel. (3) Metal plate; iron plate, galvanized steel plate, polyvinyl chloride sol coated steel plate, aluminum plate, copper plate, etc. (4) Plastic plate; thermoplastic resin plate such as polyrefin resin plate, acrylic resin plate, ABS resin plate, polycarbonate plate, phenol resin plate, urea resin plate, unsaturated polyester resin plate, polyurethane resin plate, epoxy resin plate, melamine Thermosetting resin plate such as resin plate, phenolic resin, urea resin, unsaturated polyester resin, polyurethane resin,
A resin plate such as a so-called FRP plate formed by impregnating and curing a resin such as an epoxy resin, a melamine resin, and a diallyl phthalate resin into a glass fiber nonwoven fabric, a cloth, paper, and various other fibrous base materials.

The base material 2 may be a composite base material obtained by laminating two or more of the above various base materials by a known means such as an adhesive or heat fusion.

In the decorative material shown in FIG.
Is composed of inorganic fine particles 3A and a reaction cured product 3B of a reactive resin. The surface coating layer 3 can be formed by applying a coating composition obtained by adding inorganic fine particles to a reactive resin by an appropriate method and curing the reactive resin to obtain a reaction cured product.

The surface coating layer 3 is more preferably added with a coating composition to which a dispersant (C) is added in order to prevent sedimentation of the inorganic fine particles (A). , Reactive cured product of reactive resin (B) and dispersant (C)
May be used.

The inorganic fine particles (A) used in the coating composition constituting the surface coating layer 3 include aluminas (aluminum oxide, aluminum hydroxide, alumina white), zirconia (zirconium oxide), tungsten carbide, titanium carbide, Examples include those selected from the group consisting of silicon carbide, boron carbide, and diamond. They are,
One or more of them may be used in combination. The alumina-based fine particles include, in addition to alumina, silica-alumina and alumina whose surface is coated with a resin. Of these, aluminas and zirconia are preferred, and aluminas are particularly preferred.

The practical spherical degree of Wadell of the inorganic fine particles (A) is usually 0.70 to 0.99, preferably 0.80.
To 0.98, particularly preferably 0.90 to 0.97. If the practical spherical degree of Wadell is less than 0.70, the scratch resistance of the surface of the surface coating layer becomes insufficient.
If it exceeds 99, the production cost increases, the market rationality of the composition is lost, and the cost exceeds the practical cost range as a cosmetic material. The above-mentioned practical sphericity does not need to be in the above range for all of the inorganic particles, but may be in the above range as an average value. Note that Wadell's practical sphericity is
It is a value represented by [diameter of circle having the same projected area of particle] / [diameter of minimum circle circumscribing the projected image of particle], and can be measured by observing the particle with an electron microscope. When the inorganic fine particles are perfectly spherical, Wadell's sphericity is 1.00.

The Knoop hardness of the inorganic fine particles (A) is usually 1
300-8000 kg / mm ² , preferably 15
00 to 7000 kg / mm ² , particularly preferably 1
It is 700 to 6000 kg / mm ² . Knoop hardness of 1
If it is less than 300 kg / mm ² , the surface of the surface coating layer will have insufficient scratch resistance. The Knoop hardness is 8000kg /
Those exceeding mm ² do not exist in nature. Knoop hardness is a small indentation hardness measured using a Knoop indenter, and the load when a diamond-shaped indentation is applied to the test piece is the projected area of the dent calculated from the length of the longer diagonal line of the permanent dent. This is the value represented by the quotient. This test method is based on ASTM
This is performed based on C-849.

The average particle diameter (Nassenstein diameter) of the inorganic fine particles is usually 3 to 50 μm, preferably 8 to 40 μm.
It is. When the average particle diameter of the inorganic fine particles is in the range of 3 to 50 μm, the transparency, scratch resistance, surface smoothness, and coating suitability of the coating are improved. The particle size of the inorganic fine particles having an average particle size of 1 to 100 µm is 90% or more by mass, preferably 95% or more. The average particle size is measured using an SK laser particle size distribution analyzer (manufactured by Seishin Enterprise Co., Ltd.), adding 50 to 100 mg of a test sample of a dispersion medium, applying ultrasonic waves for 60 seconds, and then using the SK laser particle size distribution analyzer. And measure.

In the present invention, the reactive resin constituting the reaction cured product (B) of the surface coating layer 2 comprises a monomer, a prepolymer (including the concept of an oligomer), a polymer, or a mixture thereof. It refers to a resin that has a high molecular weight and is cured by a chemical reaction such as a crosslinking reaction, an addition polymerization reaction, a polycondensation reaction, or a polyaddition reaction by the action of energy rays, heat, or the like.

Particularly preferred as the reaction cured product (B) of the surface coating layer is a reaction cured product (B1) of an active energy ray-reactive resin. The active energy ray-reactive resin refers to a resin which is cured by irradiation with an active energy ray such as an ultraviolet ray or an electron beam. Preferably, the form of the reactive curing is a three-dimensional crosslinking reaction. As such a resin, a compound having 1 to 5 or more reactive groups such as a radical polymerizable double bond or an epoxy bond in a molecular structure is used. In particular, in the case of crosslinking reaction curing, the number of reactive groups is 2 or more on average per molecule of the compound. The radical polymerizable double bond equivalent contained in the resin is 0.5 to 1
5 meq / g, preferably 1 to 8 meq / g. Radical polymerizable double bond equivalent is 0.5 to 15 me
If it is q / g, the curability is good, the curing shrinkage is small, and it can be used as a coating composition without any problem.

As the active energy ray-reactive resin, a known resin can be used and is not particularly limited. Preferably, a resin containing an ethylenically unsaturated group is used.
000 or less monomers and number average molecular weight 1
Oligomers or prepolymers of more than 30,000 or more are listed.

Specific examples of the above-mentioned monomers include the following nonionic ones. (1) 2-3 carbon atoms
0 to 1 to 6 functional aliphatic alcohols, or 2 to 2 carbon atoms
(Meth) acrylate of 1 to 30 mol adduct of alkylene oxide 4 (where "(meth) acrylate" means acrylate or methacrylate) a) (Meth) acrylate lauryl (meth) containing no hydroxyl group Acrylate, stearyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, propylene oxide of 1,6 hexylene glycol (hereinafter abbreviated as PO) 6 Molar adduct, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, polyethylene glycol di (meth) acrylate (molecular weight 1000 or less), polypropylene glyco Distearate (meth) acrylate (molecular weight 1,000 or less), trimethylolpropane P
O 10 mol adduct tri (meth) acrylate, sorbitol PO 15 mol adduct hexa (meth) acrylate, etc .; b) hydroxyl group-containing (meth) acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, neopentyl Glycol mono (meth) acrylate, trimethylolpropane di (meth) acrylate, pentaerythritol di (meth) acrylate, polyethylene glycol monomethacrylate (molecular weight 1000 or less), polypropylene glycol mono (meth) acrylate (molecular weight 100
0 or less);

(2) Alkylene oxides having 1 to 6 carbon atoms having 1 to 6 functional groups having 6 to 50 carbon atoms.
Mono (meth) acrylates such as a 0 mol adduct (meth) acrylate, a phenol ethylene oxide (hereinafter abbreviated as EO), a 4 mol adduct (meth) acrylate, and a 8 mol nonylphenol EO adduct (meth) acrylate; Di (meth) acrylates such as EO 4 mole adduct di (meth) acrylate and bisphenol A PO 20 mole adduct di (meth) acrylate;

(3) 1 to 30 moles of an alicyclic alcohol having 3 to 6 or more rings and having 6 to 50 or more carbon atoms or an alkylene oxide having 2 to 4 carbon atoms. Hexafunctional (meth) acrylate cyclobutane (meth) acrolate, dimethylol cyclobutane di (meth) acrylate, dimethylol cyclobutane EO 8 mol adduct di (meth) acrylate, cyclohexane (meth) acrylate, cyclohexanethio (meth) acrylate, isobonyl (Meth) acrylate, cyclohexanediol di (meth) acrylate,
Dimethylol tricyclodecane di (meth) acrylate, hydrogenated bisphenol A di (meth) acrylate,
PO (20) mole adduct of hydrogenated bisphenol A di (meth) acrylate, 3,3 ′, 5,5′-tetrahydroxyl hydrogenated bisphenol A tetra (meth) acrylate, 1,4-cyclododecanedi (meth) acrylate;

(4) Amide group-containing ethylenically unsaturated compound (meth) acrylamide, N-alkyl (having 1 to 1 carbon atoms)
8) (meth) acrylamide [for example, N-methylacrylamide and the like], N, N-dialkyl (having 1 to 1 carbon atoms)
8) acrylamide [for example, N, N-dimethylacrylamide, N, N-di-n- or i-propylacrylamide and the like], N-hydroxyalkyl (having 1 to 1 carbon atoms)
8) (meth) acrylamide [for example, N-methylol (meth) acrylamide, N-hydroxyethyl (meth) acrylamide, etc.]; N, N-dihydroxyalkyl (1 to 8 carbon atoms) (meth) acrylamide [for example, N, N-dihydroxyethyl (meth) acrylamide, etc.], vinyl lactams [eg, N-vinylpyrrolidone, etc.];

(5) Amino group-containing ethylenically unsaturated compound dialkyl (C1-8) aminoalkyl (C2
-10) esters, dihydroxyalkyls (1 to 10 carbon atoms)
8) aminoalkyl (2 to 10 carbon atoms) ester, morpholinoalkyl (1 to 8 carbon atoms) ester and the like [for example,
Dimethylaminoethyl (meth) acrylate, diethylamino (meth) acrylate, morpholinoethyl (meth) acrylate, dimethylaminoethyl fumarate, etc.], heterocyclic vinyl compounds [for example, 2-vinylpyridine, 4-vinylpyridine N-vinylpyridine Vinylpyridines, N-vinylimidazole, etc.] and the like;

(6) Halogen atom-containing compound (meth) acrylate Tribromophenyl (meth) acrylate, tribromobenzyl (meth) acrylate, tribromophenyloxyethyl (meth) acrylate, (meth) acryl of dibromophenylglycidylethyl ether Acid ester, polyethoxydi (meth) acrylate of tetrabromobisphenol A, and the like;

(7) Other ethylenically unsaturated compounds: glycidyl (meth) acrylate, styrenes (eg, styrene, vinyltoluene, etc.), allyl compounds (eg, diallyl phthalate, etc.);

Specific examples of the oligomers include the following. (8) Urethane (meth) acrylate A polyol having 2 to 6 functional groups (eg, ethylene glycol, 1,4-butanediol, neopentyl glycol, polyether polyol, polycaprolactone polyol, polyester polyol, polycarbonate polyol, polytetramethylene glycol, etc.) ), An organic polyisocyanate (for example, tolylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, etc.) and a hydroxyl group-containing ethylenically unsaturated compound [for example, the hydroxyl group-containing (meth) acrylate of the above (1) b)] A urethane (meth) acrylate having a number average molecular weight of 30,000 or less, which is a reaction product of

(9) Polyester (meth) acrylate Polybasic acid (for example, isophthalic acid, terephthalic acid, fumaric acid, maleic acid, adipic acid, etc.), polyhydric alcohol having 2 to 6 functional groups [for example, as described in (8) above) Polyesters (meth) acrylates having a plurality of ester bonds and a plurality of ethylenically unsaturated groups obtained by esterification from acrylic acid and acrylic acid;

(10) Epoxy (meth) acrylate bisphenol A type epoxy resin, bisphenol F type epoxy resin, organic polyisocyanate (for example,
Epoxy resins such as 4-tolylene diisocyanate, 2,6-tolylene diisocyanate), modified bisphenol A type epoxy resin, terminal glycidyl ether of bisphenol A type propylene oxide adduct and (meth)
Epoxy (meth) acrylate, which is a reaction product of acrylic acid;

(11) butadiene polymer having an ethylenically unsaturated group in the main chain and side chain (for example, polybutadiene);

(12) A siloxane polymer having an ethylenically unsaturated group in the main chain and side chain of dimethylpolysiloxane [for example, dimethylsiloxane di (meth) acrylate or the like]; one or more of these can be used. Of these, preferred are acrylates, and particularly preferred are acrylate monomers (1) to (3),
(9) The acrylate oligomer according to (11).

The dispersant (C) prevents the inorganic fine particles (A) in the coating composition from separating and settling during storage of the composition or during application. However,
When the influence of separation and sedimentation can be ignored by controlling the conditions of storage and coating, the addition of the separating agent can be omitted. Such a dispersant (C) is not particularly limited as long as it is commonly used in paints and inks. As specific examples, a non-reactive high molecular organic dispersant, a non-reactive low molecular organic dispersant,
Examples thereof include ionic and reactive low-molecular-weight organic dispersants and non-reactive inorganic dispersants.

Examples of the non-reactive high molecular organic dispersant include a formalin condensate of naphthalene sulfonate, polystyrene sulfonate, carboxymethyl cellulose, polycarboxylate (such as polyacrylate), and polyvinyl alcohol. . These have a weight average molecular weight of 200
0-500000, preferably 3000-200000
It is.

Examples of the non-reactive low molecular weight organic dispersant include those having a weight average molecular weight of less than 20,000 shown below. (I) a polyalkylene glycol type; an alkylene (C2-4) oxide (1-30 mol) adduct of an aliphatic alcohol having 4 to 3 carbon atoms, an alkylene (C2 to C2) of an alkylphenol having 4 to 30 carbon atoms 4) Oxide (1 to 30 mol) adduct, alkylene (2 to 4 carbon) oxide (1 to 30 carbon atoms) of an aliphatic amine having 4 to 30 carbon atoms
Mol) adduct, alkylene (2-4 carbon) oxide (1-30 mol) adduct of an aliphatic amide having 4 to 30 carbon atoms, and the like;

(Ii) Polyhydric alcohol type; having 4 to 3 carbon atoms
0 monoester compound of fatty acid and glycerin, monoester compound of fatty acid having 4 to 30 carbon atoms and pentaerythritol, monoester compound of fatty acid having 4 to 30 carbon atoms and sorbit, monoester compound of fatty acid having 4 to 30 carbon atoms and sorbitan Ester compounds and the like;

(Iii) Carboxylate type; having 4 to 3 carbon atoms
Alkali metal of fatty acid 0 (sodium, potassium, etc.)
Salts, ammonium salts and quaternary ammonium salts and the like;

(Iv) Sulfate ester type; having 4 to 30 carbon atoms
Of aliphatic alcohol sulfates of 4 to 30 carbon atoms, sulfates of alkylene (2 to 4 carbon atoms) oxide (1 to 30 mol) adducts of aliphatic alcohols of 4 to 30 carbon atoms Alkali metal (sodium, potassium, etc.) salts, ammonium salts and quaternary ammonium salts;

(V) Sulfonate type: Alkali metal (sodium, potassium, etc.) salts, ammonium salts and quaternary salts of alkylphenol sulfonic acids having 4 to 30 carbon atoms, alkylphenol sulfonic acids having 4 to 30 carbon atoms, and the like. Ammonium salts and the like;

(Vi) Phosphate ester type; having 4 to 3 carbon atoms
Aliphatic alcohol phosphate monoester of 0, having 4 to 4 carbon atoms
30 aliphatic alcohol phosphoric acid diester, having 4 to 4 carbon atoms
Alkali metal (sodium, potassium, etc.) salts, ammonium salts, quaternary ammonium salts, etc., such as aliphatic alcohol phosphate monoesters of No. 30;

(Vii) Primary to tertiary amine salt type: inorganic (primary to tertiary) amines having 4 to 30 carbon atoms, inorganic monoesters of triethanolamine and fatty acids having 4 to 30 carbon atoms Acid (such as hydrochloric acid) salts, organic acids (such as carboxylic acids having 1 to 4 carbon atoms) and the like;

(Viii) quaternary ammonium salts; quaternary ammonium salts of fatty acids having 4 to 30 carbon atoms, etc.

Examples of the ionic and reactive low molecular weight organic dispersant include those having a weight average molecular weight of less than 2,000. (I) Sulfate ester type anionic dispersant of (meth) acryloyloxy group-containing alcohol; (meth) acryloyloxy group-containing aliphatic alcohol sulfate having 4 to 30 carbon atoms, (meth) acryloyloxy group-containing fat having 4 to 30 carbon atoms Alkali metal (sodium, potassium, etc.) salts, ammonium salts, quaternary ammonium salts, etc. of sulfates such as alkylene (2-4 carbon atoms) oxide (1-30 mol) adducts of group 4 alcohols; ) Phosphate ester type anionic dispersants of acryloyloxy group-containing alcohols; (meth) acryloyloxy group-containing aliphatic alcohol phosphate monoester having 4 to 30 carbon atoms, (meth) acryloyloxy group-containing aliphatic alcohol having 4 to 30 carbon atoms Phosphoric diester, (meth) acryloyloxy having 4 to 30 carbon atoms Alkali metal (sodium, potassium, etc.) salts, ammonium salts, quaternary ammonium salts, etc., such as group-containing aliphatic alcohol phosphate monoesters; and (iii) cationic dispersants containing (meth) acryloyloxy groups, for example, (meth) acryloyl. Roxyalkyl (2-6 carbon atoms) trialkyl (4-30 carbon atoms) ammonium salt (counter anion is halogen anion, sulfate anion,
Carbonate anion), alkylene (C2-4) oxide adduct of methyl (meth) acrylate and dialkyl (C4-30) aminoethanol (1-100 mol)
And the like obtained by reacting an ester exchange reaction product with an alkylating agent such as an alkyl (C1-30) halide or dialkyl sulfate [for example, (meth) acryloyloxyethyl dimethyl lauryl ammonium chloride,
(Meth) acryloyloxypropyldiethylhexylammonium methosulfate etc.]; etc.

Examples of the inorganic dispersant include phosphates such as polyphosphate and phosphoric acid.

Of these, preferred are ionic and reactive low molecular weight organic dispersants, and more preferred are sulfate ester type anionic dispersants of (meth) acryloyloxy group-containing alcohols, and (meth) ) Phosphate ester type anionic dispersants for acryloyloxy group-containing alcohols. Preferred as a counter ion of the (meth) acryloyloxy group-containing anionic dispersant is a quaternary trialkylammonium base. The alkyl group has, for example, 1 to 6 carbon atoms, which may be the same or different.

Specific examples of the anionic dispersant having a quaternary ammonium base as a counter cation include methyltriethylammonium salt of hydroxyethyl methacrylate monophosphate, methyltriethylammonium salt of hydroxyethyl acrylate monophosphate, and hydroxyethyl methacrylate. Examples include triethylammonium salt of monophosphate ester of butyl acrylate, methyltriethylammonium salt of sulfate of hydroxyethyl methacrylate, and methyltriethylammonium salt of sulfate of hydroxyethyl acrylate. Of these, quaternary ammonium salts of monoethyl phosphate of hydroxyethyl methacrylate are preferred.

As a method for producing the quaternary ammonium salt of the sulfate ester and the quaternary ammonium salt of the phosphoric acid ester, for example, a method obtained through the following (i) to (iii) is exemplified. (I) (meth) acrylic acid and alkylene (2 to 3 carbon atoms)
0) Monotellation reaction with diol or polyalkylene (2-4 carbon atoms) glycol (number average molecular weight 3000 or less) is performed. This is represented by the general formula (1).

[0049]

Embedded image [Wherein, R ¹ represents H or CH ₃ , and R ² represents an alkylene group (carbon number: 2 to 30) or polyalkylene glycol (molecular weight: 3000 or less)]

This reaction is carried out in the presence of (a) an excess of alcohol (for example, an excess of 1.1 to 10 mol per mol of acrylic acid), and after completion of the reaction, unreacted substances are removed by distillation under reduced pressure. (B) Next, the compound obtained in the above a (containing one hydroxyl group)
And a acid (sulfuric anhydride, phosphoric anhydride, etc.) to perform a monoesterification reaction. This is represented by general formulas (2) to (4).

[0051]

Embedded image Wherein R ¹ and R ² are the same as above. ]

When reacted with phosphoric anhydride, some diester compounds are obtained as replicas, but most of the reactants are phosphoric monoester compounds. (C) A neutralization reaction of the compound obtained in the above (b) with a base (sodium hydroxide, potassium hydroxide, quaternary ammonium salt, etc.) is performed. This is represented by general formulas (5) to (8).

[0053]

Embedded image Wherein R ¹ and R ² are the same as above. R ^{3 to} R ⁶ represent an alkyl group (carbon number; 1 to 6). X is Cl ^-, B
_{^{r -, CH 3 SO 4 -}} , C 2 H 5 SO 4 -, CH 3 OCO 2 - represents a]

In the reaction (c), it is not necessary to completely neutralize the sulfated monoester compound and the phosphoric acid monoester compound obtained in the reaction (b) with a base. It may be used in the composition of the present invention. The acid value of the obtained dispersant is usually 0 to 500 mgKOH / g.
And preferably 20 to 300 mgKOH / g.

Inorganic fine particles (A) in the coating composition
Is usually 5 to 35 mass with respect to the total mass of the inorganic fine particles (A) and the cured product of the reactive resin (B), or the total mass of (A), (B) and the dispersant (C). %, Preferably 10 to 25% by mass. When the content of the inorganic fine particles (A) in the composition is less than 5% by mass, the scratch resistance of the cured surface coating layer becomes poor, and when the content exceeds 35% by mass, the surface coating layer is formed. In this case, the sedimentation stability of the inorganic fine particles (A) in the coating composition is deteriorated, and the inorganic fine particles (A) are not suitable as a coating composition.

The content of the active energy ray-reactive resin (B1) in the coating composition is usually from 45 to 95% by mass, preferably from 70 to 95% by mass, based on the total mass of (A) to (C). 92% by mass. If the amount is less than 45% by mass, the curability of the coating composition will be poor, and if it exceeds 95% by mass, the design properties required for the coating composition cannot be achieved (the gloss of the coating film cannot be reduced).

The content of the dispersant (C) in the coating composition is usually 0.2% based on the total mass of (A) to (C).
10 to 10% by mass, and preferably 1 to 8% by mass. If it is less than 0.2% by mass, the sedimentation stability of the fine particles (A) in the coating composition is poor, and if it exceeds 10% by mass, the curability of the coating composition is poor, and it is not suitable as a coating composition.

Other fine particles (D) can be further blended into the coating composition of the surface coating layer.
Examples of (D) include inorganic fine particles other than (A).
There are no particular restrictions on the shape, particle size, etc., but the average particle size is usually 0.1.
01 to 50 μm can be used, and 0.05 to 30 μm
Is preferable, and there is no problem as long as it can be used as a matting agent, a filler, and a pigment. For example, silicas (fine silica, hydrous silica, diatomaceous earth, colloidal silica, etc.), carbonates (precipitable (active, dry, heavy or light) calcium carbonate, silicates (fine magnesium silicate, talc, Soap stone, stearite, calcium silicate, magnesium aluminosilicate, sodium aluminosilicate, etc., carbon blacks (channel black, furnace black, thermal black, acetylene black, etc.), chalk, cold water clay, chalk, chalk, magnesium carbonate Etc.), clays (kaolin clay, sericite clay, pyrophyllite clay,
Montmorillonite clay, bentonite, acid clay, etc.), aluminum sulfates (sulfate band, sulfated alumina, satin white, etc.), barium sulfates (barite powder, precipitated barium sulfate, lithobon, etc.), gypsum (anhydrous,
Hemihydrate, etc.), lead white, mica powder, zinc white, titanium oxide, activated calcium fluoride, zeolite, cement, lime, calcium sulfite, molybdenum disulfide, asbestos, glass fiber, rock fiber, microballoon and the like. Two or more of these may be used in combination, or two or more of these may be combined. Of these, silicas and carbonates are preferred. The compounding amount is 50% by mass or less, preferably 30% by mass or less based on the total mass.

The coating composition may further contain a photopolymerization initiator, an antifoaming agent, a leveling agent, a silane coupling agent, a thixotropic agent (thickening agent), a slip agent, an antioxidant, and an ultraviolet ray, if necessary. Additives usually added to paints and inks, such as absorbents, can be arbitrarily compounded. Usually, the amount is 20% by mass or less, preferably 6% by mass or less, based on the total mass of the composition.

Benzophenone, a photopolymerization initiator,
Methyl orthobenzoyl benzoate, 4-benzoyl-
4'-methyldiphenyl sulfide, isopropylthioxanthone, diethylthioxanthone, ethyl-4-
Hydrogen abstraction type photopolymerization initiator such as (diethylamino) benzoate; benzoin alkyl ether, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one , Alkylphenylglyoxylate, diethoxyacetophenone and the like.

Examples of the antifoaming agent include lower alcohol-based antifoaming agents such as methanol and butanol; higher alcohol-based antifoaming agents such as octyl alcohol and hexadecyl alcohol; fatty acid-based antifoaming agents such as oleic acid and stearic acid; Fatty acid ester defoamers such as monolaurate; phosphate ester defoamers such as tributyl phosphate; metal soap defoamers such as calcium stearate and aluminum stearate; other mineral oil defoamers; polyethylene glycol And polyether-based antifoaming agents such as polypropylene glycol and polypropylene glycol, and silicone-based antifoaming agents such as dimethyl silicone oil, alkyl-modified silicone oil and fluorosilicone oil.

Examples of the leveling agent include polyethylene glycol type nonionic surfactants such as nonylphenol ethylene oxide adduct and ethylene oxide stearic acid adduct; sorbitan palmitate monoester, sorbitan stearate monoester, and sorbitan stearic acid triester. Polyhydric alcohol type nonionic surfactants such as esters; fluorinated surfactants such as perfluoroalkylethylene oxide adducts, perfluoroalkylcarboxylates and perfluoroalkylbetaines; alkyl-modified silicone oils, polyether-modified silicones And modified silicone oils such as oils.

Examples of the silane coupling agent include amino silane coupling agents such as γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, γ-phenylaminopropyltrimethoxysilane; ureidopropyltriethoxysilane and the like. Urea-based silane coupling agent; vinyl silane coupling agent such as vinylethoxysilane, vinylmethoxysilane, vinyltris (β-methoxyethoxy) silane; γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane A methacrylate-based silane coupling agent; an epoxy-based silane coupling agent such as γ-glycidoxypropyltrimethoxysilane;
isocyanate-based silane coupling agents such as γ-isocyanatepropyltriethoxysilane; polymer-type silane coupling agents such as polyethoxydimethylsiloxane and polyethoxydimethylsiloxane; N- (N-benzyl-β-aminoethyl) -γ-amino Cationic silane coupling agents such as propyltrimethoxysilane hydrochloride and the like can be mentioned.

Examples of the thixotropic agent (thickener) include inorganic thixotropic agents (thickeners) such as bentonite, organic treated bentonite, and ultrafine surface-treated calcium carbonate; hydrogenated castor oil wax, calcium stearate, Organic thixotropic agents (thickeners) such as aluminum oleate and polymerized linseed oil are exemplified.

As slip agents, higher fatty acid esters such as butyl stearate; higher fatty acid amides such as ethylene bisstearic acid amide and oleic acid amide; metal soaps such as calcium stearate and aluminum oleate; High molecular weight hydrocarbons; polyethylene wax, polypropylene wax,
Polyolefin waxes such as carboxyl group-containing polyethylene wax; silicones such as dimethyl silicone oil, alkyl-modified silicone oil, and fluorosilicone oil.

As the antioxidant, triethylene glycol-bis- [3- (3-tert-butyl-5-methyl-4)
-Hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], and cutadecyl 3- (3,5-di-t -Butyl-4-hydroxyphenylpropionate, 3,5-di-t-butyl-4
Hindered phenol-based antioxidants such as -hydroxybenzylphosphonate diethyl ester; amine-based antioxidants such as n-butylamine, triethylamine and diethylaminomethyl methacrylate.

As the ultraviolet absorber, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (5-methyl-2-hydroxyphenyl) benzotriazole,
(3,5-di-t-butyl-2-hydroxyphenyl)
Benzotriazole, 2- (3,5-di-t-butyl-
Benzotriazole-based ultraviolet absorbers such as 2-hydroxyphenyl) -5-chlorobenzotriazole and 2- (3,5-di-t-amyl-2-hydroxyphenyl) benzotriazole; 2- (4,6-diphenyl- 1,3,3
Triazine-based ultraviolet absorbers such as 5-triazin-2-yl) -5-[(hexyl) oxy] -phenol;
Benzophenone-based ultraviolet absorbers such as hydroxy-4-n-octyloxybenzophenone; 2-ethoxy-2 '
-Ethyl oxalate anilide UV absorbers such as bisanilide oxalic acid.

The coating composition of the surface coating layer is obtained by uniformly mixing the above two (A) and (B) (or B1). More preferably, (A), (B) (or B
1) and (C) are uniformly blended. If necessary, the above-mentioned other components are uniformly mixed with these basic components. As a method of mixing, for example, (A), (B) (or B1), (C) a method of mixing two of the three and then mixing the remaining one, a method of simultaneously mixing the three, and the like There is no particular limitation. The temperature at the time of mixing is usually 0 to 60 ° C, preferably 5 to 40 ° C.
° C, particularly preferably 15 to 30 ° C. In order to remove bubbles generated during mixing, it is preferable to perform mixing under reduced pressure (40 mmHg or less). The mixing apparatus is a universal mixer capable of depressurizing the inside of the kettle, and a planetary mixer.

When the coating composition is applied to the surface of the substrate 2, it may be diluted with one or more solvents as necessary to adjust the viscosity to a level suitable for application. The solvent content in the paint is preferably 50% by mass or less, more preferably 40% by mass or less from the viewpoint of suitability for coating. When the solvent content in the paint is 50% or less, drying takes no time, so that the coating can be performed without lowering the production speed.

The solvent is not particularly limited as long as it dissolves the resin composition (excluding inorganic fine particles). Specifically, for example, aromatic hydrocarbon solvents such as toluene, xylene and ethylbenzene; ester or ester ether solvents such as ethyl acetate, butyl acetate and methoxybutyl acetate; diethyl ether, tetrahydrofuran, ethylene glycol monoethyl ether;
Ether solvents such as ethylene glycol monobutyl ether, propylene glycol monomethyl ether and diethylene glycol monoethyl ether; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, di-n-butyl ketone and cyclohexanone; methanol, ethanol and n-propanol Alcohol solvents such as, isopropanol, n-butanol, isobutanol, t-butanol, 2-ethylhexyl alcohol and benzyl alcohol; amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone; dimethyl sulfoxide and the like Water, and a mixed solvent of two or more of these.

Among these solvents, preferred are ester solvents and alcohol solvents having a boiling point of about 70 to 100 ° C., and particularly preferred are ethyl acetate, isopropyl alcohol and mixtures thereof. The viscosity of the paint (at 25 ° C.) is usually 200 to 5000 mPa ·
S, preferably 400 to 3000 mPa · S. When the viscosity is within this range, there is no problem such as uneven permeation and deterioration of the leveling property of the paint, and the coating can be performed stably.

When applying the coating composition, a coating machine such as a roll coater (size press, gate roll coater, etc.), a bar coater, a gravure coater, an air knife coater, a blade coater and the like can be used. The coating amount is usually 1 to 50 g / m ² as a mass after drying,
Preferably, it is 3 to 30 g / m ² . Drying is performed by heating with hot air or the like. The drying temperature varies depending on the type of dryer, but the temperature inside the dryer is usually 50
To 200 ° C, preferably 100 to 150 ° C. When the composition of the present invention is applied using these coating machines, the thickness of the coating varies depending on the coating machine, but is usually 3 to 50 μm, and preferably 5 to 30 μm.

Between the (average) particle size d of the inorganic fine particles (A) and the thickness t of the surface coating layer 3, 0.3t ≦ d ≦ 2.0t,
More preferably, 0.5t ≦ d ≦ 1.0t is preferable in terms of abrasion resistance, surface smoothness, and prevention of abrasion of contact articles. When 0.3t> d, the abrasion resistance becomes insufficient, and when d> 2.0t, the surface becomes rough, and it is easy to wear other articles (furniture, shoes, socks) in contact therewith. .

As shown in FIG. 1, all of the inorganic fine particles 3B may be buried in the surface coating layer and may not protrude (in this case, d <t), or
As shown in FIGS. 4A and 4B, at least some of the particles may protrude from the surface of the surface coating layer 3. When the inorganic fine particles (A) protrude, as shown in FIG.
The surface of c may be coated with a resin of a surface coating layer,
Alternatively, as shown in FIG. 4A, the surface of the protruding particles 3e may be exposed to the outside without being covered with the resin of the resin layer.

As the active energy ray for irradiating the coating composition applied to the surface of the substrate 2, ultraviolet rays and electron beams are typical and practical.
X-rays, α-rays and the like are also included. When curing with UV light,
A known ultraviolet irradiation device equipped with a high-pressure mercury lamp, a low-pressure mercury lamp, a metal halide lamp, or the like can be used. The irradiation amount of ultraviolet rays at the time of curing is preferably 50 to 200.
0 mJ / cm ² . If the irradiation amount is less than 50 mJ / cm ² , the curing is insufficient, and if it exceeds 2000 mJ / cm ² , the cured coating film may be yellowed and deteriorated.
In the case of curing with an electron beam, a known electron beam irradiation device can be used. The irradiation amount of the electron beam is preferably 1-1.
0 Mrad. If the irradiation amount is less than 1 Mrad, the curing is insufficient. If the irradiation amount exceeds 10 Mrad, the cured coating film or substrate (paper, film, etc.) may be damaged and deteriorated. The acceleration energy of the electron beam is
Although it depends on the thickness of the surface coating layer, usually 100 to 1000
It is about keV.

Evaluation of scratch resistance is based on JIS K-6902.
In accordance with the above, a Taber abrasion test is performed for evaluation. The scratch resistance test method is as follows. (1) A cured film is formed on a substrate sheet by applying the coating composition to the substrate sheet and irradiating the substrate sheet with active energy rays. (2) Paste this on an adhesive-treated cardboard, and
Cut out to a size of cm × 10 cm. This is used as a test sample. (3) A Taber abrasion test is performed according to JIS K-6902. The amount of wear after 500 rotations with a 1 kg load is measured. Before the test, the mass of the test sample is measured to the order of mg, the mass of the test sample after the test is measured, and the abrasion loss of the coating is calculated as the difference in weight (loss) between before and after the test. The amount of wear of the coating of the present invention in a cosmetic material is usually 50
mg or less, preferably 40 mg or less.

The sealer layer 4 provided on the surface of the substrate 2 fills and smooths (stops) the fine irregularities when the surface of the substrate is rough (fine irregularities), or forms the substrate on paper, non-woven fabric, In the case of permeable materials such as wood, etc., the permeability is sealed (prevention of penetration). Has a function of preventing the leaching of alkali from the base material when it is alkaline such as cement. Such a sealer layer 4 is
Vinyl chloride-vinyl acetate copolymer, acrylic resin, polyester resin, butyral (polyvinyl butyral) resin, polyurethane resin (two-component curing type comprising isocyanate curing agent and various polyols), chlorinated polypropylene, chlorinated polyethylene, etc. It can be formed by applying a solution of a kind or a mixture of two or more kinds. When a polyolefin-based thermoplastic elastomer is used as the base sheet, it is preferable to use a two-part curable polyurethane resin and add an isocyanate curing agent to form the base sheet.

In addition to the above resin, the sealer layer 4 may contain additives such as a filler such as silica fine powder and a light stabilizer. The sealer layer coats these compositions,
It is formed by drying and curing as needed. Specifically, it is formed by applying the sealer composition by a method such as gravure roll coating or roll coating and drying (curing). The coating amount of the sealer layer 4 is preferably 1 to ²⁰ g / m ² (when dry), and more preferably 1 to 5 g / m ² (when dry).

The solid layer 5 is formed by solid printing with a colored ink having concealing properties. The picture layer 6 includes a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather crest pattern, a brickwork pattern,
Tile patterns, geometric figures, characters, symbols, line drawings, and various abstract patterns are printed and formed. These printing layers may be composed of the pattern layer 6 alone, of the solid layer 5 alone, or of both the pattern layer and the solid layer.

The solid layer 5 and the picture layer 6 can be formed by printing or coating with a general picture printing ink. The ink comprises a binder resin and a colorant. For example, as the binder resin, chlorinated polyolefin such as chlorinated polyethylene, chlorinated polypropylene, polyester resin, polyurethane resin (two-component curable urethane resin, or thermoplastic urethane resin) ), An acrylic resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate copolymer, a cellulose resin, a butyral resin, a melamine resin, an alkyd resin, or the like, or a mixture of two or more thereof. Examples of the coloring agent include pigments or dyes such as titanium white, carbon black, red iron oxide, graphite, ultramarine blue, phthalocyanine blue, quinacridone red, and isoindolinone yellow; metal pigments such as aluminum and brass; One or a mixture of two or more brilliant pigments composed of foil powder such as titanium-coated mica is exemplified.

When a polyolefin resin sheet is used as the substrate 2, it is preferable to use a urethane resin ink or a chlorinated polyolefin resin ink as the ink for the picture layer or solid layer. Further, as a picture layer or a solid layer, a metal thin film may be used instead of printing. For example, using a metal such as aluminum, chromium, gold, silver, or copper, a metal thin film is formed by a method such as vacuum deposition or sputtering. This metal thin film may be formed in a pattern such as a solid pattern, a partial pattern, or a pattern, or may be combined with the pattern layer and the solid layer.

As another form of makeup, as shown in FIGS. 2 and 3, by devising the pattern layer, the surface coating layer immediately above the pattern layer is made into a concave portion, and In some cases, irregularities synchronized with the coating layer are formed simultaneously with coating. The decorative material in the form of FIG.
A sealer layer 4, a solid layer 5, a liquid-repellent pattern layer 6rep, and a surface coating layer 3 are formed. Here, the lyophobic picture layer 6
The rep is constituted by using a liquid-repellent resin as a binder resin of the ink constituting the picture, adding a liquid-repellent to the binder resin, or using both of them.

Examples of the liquid-repellent resin constituting the binder resin include a silicon-based resin such as polysiloxane, a fluorocarbon polymer such as polyvinylidene fluoride, and a fluorine-containing urethane (a fluorocarbon-based polyol is crosslinked with isocyanate). ) And the like. Examples of the liquid repellent include waxes such as wood wax, montan wax and paraffin wax, fluorine resins such as fluorocarbon polymers, and silicon-based resins such as silicone. The addition amount of the liquid repellent is usually about 1 to 10% by mass based on the binder resin.

Representative examples of the pattern of the lyophobic pattern layer 6rep include wood conduit ducts, siding boards, tiled or brick-laid joints, cloth texture (texture), and the like.

After a sealer layer 4, a solid layer 5, and a lyophobic pattern layer 6rep are sequentially formed on the base material 2, a surface coating layer 3 is further applied over the entire surface to obtain a lyophobic pattern. Layer 6re
As a result of the liquid repellency of p, the surface coating layer in the uncured flow state is repelled and removed, and as a result, the surface coating layer immediately above the liquid-repellent pattern layer 6rep becomes a concave portion 7. Such a method of forming the concave portion itself is a known method already disclosed in JP-A-51-88616 and JP-B-52-2641.

The decorative material shown in FIG. 3 has a sealer layer 4, a solid layer 5, and a permeable pattern layer 6
pen, the surface coating layer 3 is formed. Here, the penetrating picture layer 6pen can be made porous by adding a filler to the binder resin of the ink constituting the picture, or can be made porous by adding a foaming agent, or foamed. It is constituted by using these in combination.

As the filler, calcium carbonate,
Particles such as barium sulfate, silica (silicon oxide), glass, kaolinite, diatomaceous earth, terra alba, sepiolite, kaolinite, tobermorite, and zeolite are added in an amount of about 10 to 50% by mass. Among the fillers, porous ones such as zeolite and diatomaceous earth are particularly preferable.

Examples of the foaming agent include pyrolytic foaming agents such as sodium hydrogencarbonate, sodium boron hydride, azodicarbonamide, oxybisbenzenesulfonyl hydrazide, and volatile substances such as pentane and hexane.
A microcapsule type foaming agent encapsulated in a hollow spherical shell of a thermoplastic resin such as polyacrylonitrile or polyvinylidene chloride is added to the binder resin in an amount of 1 to 10% by mass.

After printing the ink to which the foaming agent has been added in a desired pattern, the foaming agent is foamed by heating, whereby the picture layer is made porous.

The penetrating picture layer 6pen thus obtained
When the surface coating layer 3 is coated on the surface, the permeable pattern layer 6pe
As a result of the penetration of the surface coating layer immediately above n into the pattern layer 6pen, the surface coating layer immediately above the pattern layer 6pen becomes a recess 7. Such a method for forming the concave portion itself has already been disclosed in
This is a method known from, for example, JP-A-41364.

When a decorative material of the form shown in FIGS. 2 and 3 is provided on a permeable (absorbent) base material such as paper, nonwoven fabric, wood, etc., the sealer layer 4 is formed. Is preferred. That is, by providing the sealer layer 4 on the base material 2, the portion other than the concave portion of the surface coating layer 3 penetrates into the base material 2, and the unevenness between the concave portion 7 and the concave portion (relatively the convex portion) This is because it is possible to prevent a disadvantage that the step is reduced.

The decorative material 1 thus formed can be applied to various other base materials via an adhesive layer or the like to form a decorative plate, and can be used as various building materials. In order to impart antibacterial properties to the decorative material 1, the antibacterial agent such as zeolite carrying silver ions or the like such as 10,10'-oxybisphenoxyarsine is added to a base material, a surface coating layer, or another resin layer. A fungicide or the like may be added.

The material of the above-mentioned adhesive layer is appropriately selected according to another substrate (hereinafter, referred to as an adherend) on which the decorative material is to be applied. For example, when the adherend is a wooden material, a vinyl chloride-vinyl acetate copolymer based on a hydroxyl group and a urethane-based adhesive are preferable. When the adherend is a plastic material, a hot melt adhesive, an adhesive for dry lamination, or the like can be used. The hot melt adhesive can use preheating or post-heating when forming the adherend. In addition,
When the decorative material itself can be bonded to the adherend by means such as heat fusion, the adhesive layer may be omitted.

[0094]

Embodiments of the present invention will be described below. The present invention is not limited to this. [Production Example of Dispersant] In a glass reactor equipped with a dropping funnel, a thermometer and a stirring rod, 1000 parts by mass of a phosphoric acid monoester of hydroxyethyl methacrylate was charged, and 2
Adjust the temperature to 5 ° C. Under stirring, 435 parts of monomethyltriethylammonium methyl carbonate are added dropwise over 60 minutes. As monomethyltriethylammonium methyl carbonate is added dropwise, carbon dioxide gas starts to be generated. Therefore, the addition is continued while being careful not to cause the reaction to run away. After the dropping was completed, stirring was continued for 90 minutes, and the pressure was reduced to 20 mmHg or less for 20 minutes. This is referred to as Dispersant 1. The acid value of this dispersant was 270 mgKOH / g.

Example 1 The following coating composition for a surface coating layer was uniformly mixed with a planetary mixer to obtain a coating composition. This is impregnated paper for building materials (solid basis 60 g / m2, impregnated with acrylic resin) printed with solid layer and picture layer
Was coated to a dry thickness of 25 μm and cured by irradiating an electron beam at 5 Mrad to obtain a decorative sheet (decorative material). The coating uses a roll coater. The coating was performed under two conditions: a case where the composition was circulated between the ink pan and the ink tank, and coating was performed while stirring the inside of the ink tank; and a case where neither circulation nor stirring was performed. The amount of wear of this cosmetic material in the aforementioned Taber abrasion test was 35 mg. The picture layer is made by using a mixture of nitrified cotton and alkyd resin as a binder resin, and using a gravure printing method to print a grain pattern using an ink obtained by adding a pigment consisting mainly of a red stem and carbon black. The solid layer is formed by gravure printing using an ink obtained by adding a mixture of nitrified cotton and an acrylic resin as a binder resin, and adding a pigment mainly composed of titanium white, graphite, and red iron oxide. It was formed by a method.

[Coating agent composition for surface coating layer (unit is parts by mass)] Neomer BA-641 [manufactured by Sanyo Chemical Industries, Ltd .: bisphenol A (EO) 4 diaacrylate] 64.0 parts Neomer TA- 401 [manufactured by Sanyo Chemical Industries, Ltd .: trimethylolpropane (EO) 3 triacrylate] 20.0 parts ・ Halimic AX-116 [manufactured by Micron: average particle diameter 25 μm, Knoop hardness 2800, practical spherical degree of Wadell 0.97 15.0 parts ・ Aerosil 200 [manufactured by Nippon Aerosil Co., Ltd .: thixotropic agent] 1.0 part ・ Ethyl acetate 30.0 parts ・ Dispersant 1 1.0 part

Examples 2 to 6, Comparative Examples 1 to 4 Using the coating compositions shown in Table 1, a surface coating layer was formed on the surface of impregnated paper for building materials (60 g / m ² ) in the same manner as in Example 1. To form a cosmetic material.

[0098]

[Table 1] * 4: Harimic C100-32 is a fused alumina manufactured by Micron with an average particle size of 6 μm, a Knoop hardness of 2800, and a Wadell practical sphericity of 0.96. * 5: Sumicorundum AA18 is a Sumitomo Chemical Co., Ltd. average particle size of 18 μm, Knoop hardness of 2800, Wadell.
Is an alumina having a practical sphericity of 0.80. * 6: Alumina X is an average particle size of 15μ manufactured by Micron.
It is a crushed alumina having a m, Knoop hardness of 2800, and Wadell having a practical sphericity of 0.65.

The decorative materials of Examples 1 to 6 and Comparative Examples 1 to 4 were subjected to a wear resistance test, and the surface condition was observed. Table 2 shows the results.

[0100]

[Table 2] * 7: The abrasion amount was evaluated as x when the substrate was scraped off. * 8: When visually observed, there was no problem with no unevenness or streaks, and the result was evaluated as ○, and when there was unevenness or streaks, the result was evaluated as x.

[0101]

According to the present invention, the reactive hardened product (B) of a reactive resin has a Wadell having a practical sphericity of 0.70 to 0.70.
0.99 and Knoop hardness of 1300-8000kg
/ Mm ² , a surface coating layer containing 5-35% by mass based on the total mass of (A) and (B), wherein the surface coating layer is provided on the surface of the substrate. By adopting the configuration described above, it is possible to use inexpensive inorganic fine particles in a cosmetic material having a surface coating layer having excellent scratch resistance, and to keep the cost of the cosmetic material within a practical range. it can.

In particular, when a dispersant is added, inorganic fine particles having better sedimentation stability than hard spherical particles can be used, so that the composition is not circulated or stirred during coating. Even in this case, it is possible to perform a stable coating without unevenness or streak of the surface coating layer, and it is possible to manufacture a cosmetic material of stable quality with good workability.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one example of a decorative material having a surface coating layer of the present invention.

FIG. 2 is a cross-sectional view showing one example of a decorative material having a surface coating layer of the present invention.

FIG. 3 is a cross-sectional view showing one example of a decorative material having a surface coating layer of the present invention.

FIG. 4 is a cross-sectional view for explaining an embodiment in which inorganic fine particles protrude from a surface coating layer in the decorative material of the present invention, and (a) shows a state where inorganic fine particles are exposed from the surface coating layer; (B) shows a state in which the inorganic fine particles are covered with the resin of the surface coating layer.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cosmetic material which has a surface coating layer 2 Base material 3 Surface coating layer 3A Inorganic fine particles 3B Reaction hardened material of reactive resin

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 33/00 B32B 33/00 C09D 4/00 C09D 4/00 5/00 5/00 Z 7/12 7 / 12 201/00 201/00 F-term (reference) 4D075 CA02 CB11 DA04 DB18 DB31 DC31 EA21 EC02 EC24 4F100 AA01A AA19A AK01A AT00B BA02 BA03 BA10A BA10B CA30A CC00A DD01A DE04A DG10 EH46A EJ08A J07 GB08B12B00 J00 4J038 DF012 FA011 FA091 FA121 FA131 FA141 FA151 FA161 FA221 FA241 FA251 FA261 FA281 GA03 GA12 HA216 JA20 JA21 JA43 JC09 JC14 JC20 KA03 KA06 KA08 KA09 KA20 NA11 PA17 PC02 PC04 PC06 PC08 PC10

Claims (8)

[Claims] 1. A method according to claim 1, wherein W is contained in the reactive cured product (B) of the reactive resin.
Adell has a practical sphericity of 0.70 to 0.99 and a Knoop hardness of 1300 to 8000 kg / mm ^{2. The} spherical inorganic fine particles (A) are 5 based on the total mass of (A) and (B). A decorative material having a surface coating layer, wherein a surface coating layer containing up to 35% by mass is provided on the surface of the substrate. 2. Wadell has a practical sphericity of 0.70 to 0.70.
0.99 and Knoop hardness of 1300-8000 kg /
mm ² of inorganic fine particles (A), a reactive cured product of an active energy ray reactive resin (B1) and a dispersant (C),
(A) is 5 to 35 based on the total mass of (A) to (C).
Mass%, (B1) is 45 to 95 mass%, and (C) is 0.2
A surface coating layer formed from a composition containing 10 to 10% by mass,
A decorative material having a surface coating layer, which is provided on a surface of a substrate. 3. The inorganic fine particles (A) have an average particle size of 3 to 50.
The decorative material having a surface coating layer according to claim 1 or 2, which has a thickness of µm. 4. The decorative material having a surface coating layer according to claim 1, wherein the inorganic fine particles (A) are alumina-based fine particles. 5. The decorative material having a surface coating layer according to claim 2, wherein the dispersant (C) has an active energy ray reactivity. 6. The dispersant (C) is an anionic dispersant having a quaternary ammonium base as a counter cation.
A decorative material having the surface coating layer according to any one of Items 1 to 4. 7. A liquid-repellent pattern layer is partially formed between a substrate and a surface-coating layer, and the surface-coating layer is formed immediately above the liquid-repellent pattern layer. The decorative material having a surface coating layer according to any one of claims 1 to 6, wherein the decorative material has a concave portion than the surroundings. 8. A permeable pattern layer is partially formed between the substrate and the surface coating layer, and the surface coating layer is formed directly above the permeable pattern layer. A decorative material having a surface coating layer according to any one of claims 1 to 6, wherein the decorative material is more concave.