JP2000006325A - Decorative material having abrasion resistance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative material having excellent abrasion resistance, not abrading the roll or detector knife of a coating apparatus at the time of production, capable of being formed from a flexible base material, hardly abrading other matter and excellent in matte surface design properties. SOLUTION: A decorative material 1 is formed by providing an abrasion- resistant resin layer 3 formed from a coating compsn. containing a binder 4 comprising a crosslinkable resin, spherical particles 5 having hardness higher than that of the crosslinkable resin and amorphous particles 6 on the surface of a base material 2. When the average film thickness of the abrasion-resistant resin layer 3 is set to t (μm), the average particle size of spherical particles 5 is set to dl (μm) and the average particle size of the amorphous particles 6 is set to d2 (μm), formula 1:0.3t<=dl<=2.0t and formula 2:d2<d1 are satisfied.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to floors, walls,
The present invention relates to a decorative material used as a surface decoration material for interiors such as ceilings, furniture, various cabinets, and the like, and particularly to a decorative material used for applications requiring surface abrasion resistance.

[0002]

2. Description of the Related Art Various decorative materials such as melamine veneer, dup veneer, polyester veneer, printed plywood, and vinyl chloride veneer have been used as materials for decorating the interior of buildings, furniture, cabinets, and other surfaces. Is used. Various attempts have been made to improve the wear resistance of the surface of such a decorative material.

[0003] The applicant of the present invention has excellent abrasion resistance, does not wear the rolls and doctor knives of the coating apparatus when forming the surface resin layer, and further has a soft resin base material. Cosmetic materials with improved abrasion resistance can also be formed, and as a cosmetic material that has abrasion resistance but is less likely to wear, as a binder made of a crosslinkable resin and spherical particles of higher hardness than the crosslinkable resin. (Japanese Patent Publication No. 2740948) has been proposed.

[0004]

However, although the cosmetic material described in the above patent publication has excellent abrasion resistance, the gloss of the surface can be changed only by adding spherical particles to the abrasion-resistant resin layer on the surface. And the design is monotonous. In addition, if a conventionally known matting agent is added to the surface resin layer, a matte surface can be obtained.However, since the matting agent is generally amorphous inorganic particles, simply adding it will cause other There is a possibility that the article may be worn or the properties such as abrasion resistance may be adversely affected.

The present invention has been made to solve the above-mentioned drawbacks of the prior art, and has a more excellent wear resistance.
When forming the surface resin layer, the rolls and doctor knives of the coating device can be made of a flexible substrate without abrasion, and the surface gloss can be reduced without deteriorating properties such as abrasion resistance. It is an object of the present invention to provide a cosmetic material which can be adjusted and has excellent design properties.

[0006]

The present invention provides a coating composition comprising (1) a binder comprising a crosslinkable resin, at least spherical particles having a higher hardness than the crosslinkable resin, and irregular particles. The formed wear-resistant resin layer is provided on the surface of the substrate, the average thickness of the wear-resistant resin layer is t (μm), the average particle size of the spherical particles is d1 (μm), and the irregular particles are When the average particle size d2 (μm) is satisfied, the following formulas (1) and (2) are satisfied;

[Formula 3] 0.3t ≦ d1 ≦ 2.0t (1)

D2 <d1 (2) (2) (1) wherein the spherical particles are spherical α-alumina
(3) The cosmetic material having abrasion resistance according to the above (1) or (2), wherein the binder made of a crosslinkable resin is made of an ionizing radiation-curable resin.
(4) A wear-resistant decorative material according to any one of (1) to (3) above, wherein the surface of the wear-resistant resin layer has releasability.

[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 longitudinal sectional view showing one example of a wear-resistant decorative material of the present invention. As shown in FIG. 1, a wear-resistant decorative material 1 of the present invention (hereinafter, may be simply abbreviated as a decorative material) 1 has a structure in which a wear-resistant resin layer 3 is provided on a surface of a base material 2. Is done. The abrasion-resistant resin layer 3 is located on the outermost surface of the decorative material 1 and is provided for protecting the surface and imparting abrasion resistance to the decorative material 1 and adjusting the gloss of the surface.
As shown in FIG. 1, the decorative material 1 has a solid printing layer 7a on the entire surface of the base material 2 and a pattern printing layer 7b formed on the solid printing layer 7a. It may be configured by providing a wear-resistant resin layer 3 thereon. Although not particularly shown, it may be constituted only by the base material 2 and the wear-resistant resin layer 3 provided on the surface of the base material.

In the present invention, the abrasion-resistant resin layer 3 is a coating composition containing a binder 4 composed of a crosslinkable resin, at least spherical particles 5 having a higher hardness than the crosslinkable resin, and irregular particles 6. Is formed from. The spherical particles 5 are added to impart wear resistance to the wear-resistant resin layer 3,
The irregular shaped particles 6 are added to adjust the gloss of the surface of the layer.

The spherical particles 5 only need to be surrounded by a smooth curved surface such as a true sphere, an elliptical sphere obtained by flattening a sphere, and a shape close to the true sphere or the elliptical sphere.
The spherical particles 5 are preferably spherical without any protrusions or corners on the particle surface, that is, without a so-called cutting edge. Spherical particles greatly improve the abrasion resistance of the surface resin layer itself compared to amorphous particles of the same material, and do not wear the coating device, and other objects that come into contact with the coating film after curing. And the transparency of the coating film is also increased, and the effect is particularly large when there is no cutting edge.

The amount of the spherical particles 5 contained in the abrasion-resistant resin layer 3 depends on the amount of the binder component 1 comprising the crosslinked resin after curing.
It is preferable to adjust the coating composition so as to be 5 to 20 parts by weight with respect to 00 parts by weight. When the addition amount of the spherical particles 5 is small, the effect of the addition of the spherical particles such as improvement of abrasion resistance may not be sufficiently exerted. On the other hand, when the addition amount of the spherical particles 5 is too large, the binder of the crosslinkable resin may be insufficient. As a result, adverse effects such as the possibility that the flexibility of the coating film is reduced and the workability of the coating composition is reduced may occur.

The material of the spherical particles 5 only needs to be higher in hardness than the crosslinkable resin, and either inorganic particles or organic resin particles can be used. The difference in hardness between the spherical particles 5 and the crosslinkable resin is measured by a method such as Mohs hardness or Vickers hardness, and is preferably 1 or more when expressed in Mohs hardness, for example. The spherical particles 5 have a Knoop hardness of 1
It is preferably at least 300 kg / mm ^2, more preferably
Knoop hardness is 1800 kg / mm ² or more.

The Knoop hardness referred to herein is a minute indentation hardness measured using a Knoop indenter. The load when a diamond-shaped indentation is formed before the test is defined as the length of the longer diagonal line of the permanent dent. It is a value represented by a quotient divided by the projected area of the dent determined from the above. This test method is based on ASTM C-849.
It is described in.

The material of the spherical particles 5 is specifically α-alumina, silica, chromium oxide, iron oxide, diamond,
Examples include inorganic particles such as graphite, and organic resin particles such as synthetic resin beads such as cross-linked acryl. Examples of the α-alumina include fused alumina, Bayer method alumina, and the like, and examples of the inorganic particles other than the above include zirconia, titania, and a eutectic mixture of these with molten alumina, Bayer method alumina, and the like. As a method of making the shape of these inorganic particles spherical, the above-mentioned inorganic compound of a pulverized amorphous shape is charged into a high-temperature furnace having a melting point or higher and melted,
Examples of the method include a method of forming a sphere using surface tension, and a method of blowing the above-mentioned inorganic substance at a temperature higher than its melting point into a mist to form a sphere.

Particularly preferred spherical particles 5 include spherical α-alumina because they have very high hardness and a large effect on abrasion resistance, and spherical particles are relatively easily obtained. . As described in JP-A-2-55269, spherical α-alumina is obtained by adding a mineralizing agent or a crystallizing agent such as alumina hydrate, a halogen compound or a boron compound to a fused alumina or a sintered alumina. By adding a small amount to the pulverized product and subjecting it to a heat treatment at a temperature of 1400 ° C. or more for 2 hours or more, a cutting edge in alumina is reduced and, at the same time, a spherical shape can be obtained. Such a spherical alumina is available from Showa Denko KK as "Spherical Alumina A".
S-10, AS-20, AS-30, AS-40, AS
Various types of particles having an average particle size of "-50" are commercially available.

The spherical particles 5 can be treated on the surface of the particles. For example, treatment with a fatty acid such as stearic acid improves dispersibility. In addition, by treating the surface with a silane coupling agent, the adhesion to the crosslinkable resin used as a binder and the dispersibility of the particles in the coating composition are improved. Examples of the silane coupling agent include an alkoxysilane having a radically polymerizable unsaturated bond such as vinyl and methacryl in the molecule and an alkoxysilane having a functional group such as epoxy, amino and mercapto in the molecule. Depending on the type of the crosslinkable resin used together with the spherical particles, the silane coupling agent may be, for example, an ionizing radiation-curable resin such as (meth) acrylate or the like, using an alkoxysilane having a radical polymerizable unsaturated bond, In the case of a two-part curable urethane resin, it is preferable to select the type of radically polymerizable unsaturated bond or functional group, such as using an alkoxysilane having an epoxy group or an amino group. Specific examples of the alkoxysilane having a radical polymerizable unsaturated bond include γ-methacryloxypropyltrimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyldimethylmethoxysilane, and γ-methacryloxypropyldimethylethoxy. Silane, γ-acryloxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyldimethylmethoxysilane, γ-acryloxypropyltriethoxysilane, γ
-Acryloxypropylmethyldiethoxysilane, γ-
Examples include alkoxysilane having a radical polymerizable unsaturated bond in a molecule such as acryloxypropyldimethylethoxysilane and vinyltriethoxysilane, and alkoxysilane having a functional group such as epoxy, amino, and mercapto in a molecule.

The method of treating the surface of the spherical particles 5 with a silane coupling agent is not particularly limited, and a known method can be used. For example, a method in which a predetermined amount of a silane coupling agent is sprayed while vigorously stirring spherical particles as a dry method, or a method in which a predetermined amount of a silane coupling agent is dispersed after dispersing spherical particles in a solvent such as toluene as a wet method. A method of adding and reacting is given. The processing amount (required amount) of the silane coupling agent for the spherical particles is preferably such that the minimum coating area of the silane coupling agent is 10 or more with respect to the specific surface area of the spherical particles of 100. The minimum coverage area of the spherical particles is 10 per 100 of the specific surface area of the spherical particles.
Less than that is not very effective.

The particle diameter of the spherical particles 5 is usually 5 to 100 μm.
m (average particle diameter) can be preferably used. If the average particle size of the spherical particles 5 is less than 5 μm, the coating may be opaque, while if the average particle size exceeds 100 μm, the surface smoothness of the coating may be reduced. As the particle diameter of the spherical particles 5 decreases, the wear resistance decreases. On the other hand, when the particle diameter of the spherical particles 5 is large, the abrasion resistance is improved. However, when the particle diameter is too large, uniform coating at the time of coating becomes difficult. The relationship between the thickness of the wear-resistant resin layer 3 and the particle diameter of the spherical particles 5 is as follows.

The average thickness of the wear-resistant resin layer 3 is t (mm)
When the average particle diameter of the spherical particles 5 is d1 (mm), the spherical particles are selected so as to satisfy the following expression (1). When the average particle diameter d1 of the spherical particles 5 exceeds 2.0 t,
There is a possibility that the spherical particles 5 protrude largely from the surface of the wear-resistant resin layer 3 and the appearance of the layer is deteriorated. On the other hand, spherical particles 5
If the average particle size d (mm) is less than 0.3 t, sufficient abrasion resistance may not be obtained.

0.3t ≦ d1 ≦ 2.0t (1)

The irregular particles 6 are added to adjust the surface gloss. The addition of the irregular shaped particles 6 makes it possible to easily obtain a matte surface and to obtain a decorative material having high design properties. The irregular particles 6 need to have a smaller particle diameter (average particle diameter) than the spherical particles 5 so as to satisfy the following expression (2). When the diameter of the irregular-shaped particles 6 is larger than that of the spherical particles, there is a possibility that a coating device such as a gravure roll or a doctor blade may be worn when applying the coating composition for the wear-resistant resin layer. In addition, when a cosmetic material is used, the feel of the abrasion-resistant resin layer on the surface becomes rough and other articles in contact with the cosmetic material are worn.

D2 <d1 (2) The irregular particles 6 have an average particle diameter of preferably 0.1 to 50 μm, more preferably 0.5 to 25 μm. If the average particle size of the irregular shaped particles 6 is less than 0.1 μm, there is no matting effect, and if it exceeds 50 μm, the roughness of the surface may be large.

As the material of the irregular shaped particles 6, inorganic particles having Moh's hardness of 1 or more are used. Specifically, the materials exemplified as the above-mentioned spherical particles may be mentioned, and inorganic particles formed into an irregular shape may be used. A preferred amorphous particle is silica. The addition amount of the irregular particles 6 can be appropriately included according to the desired luster of the wear-resistant resin layer 3. A preferable addition amount is 3 to 3 as a content in the wear-resistant resin layer 3. Preferably, it is 30% by weight.

A release agent can be added to the abrasion-resistant resin layer 3 so that the surface has releasability. Examples of the release agent include silicone, fluorine-based resin, polyethylene, polypropylene, and wax.In particular, when an ionizing radiation-curable resin is used as a binder resin for the abrasion-resistant resin layer, for example, methacrylate-modified silicone or the like is used. Those having introduced a functional group which reacts with the ionizing radiation-curable resin by irradiation with ionizing radiation are preferably used. Also,
The amount of the release agent added is preferably 0.1% by weight to 10% by weight. When a release agent is added to the abrasion-resistant resin layer 3 to impart releasability, dirt on the surface is less likely to adhere, and the durability is further improved.

As the material of the substrate 2 used in the present invention, paper, plastic, metal foil, plate, etc. are used.
As the shape, for example, any of a sheet shape such as paper, a plastic sheet, a nonwoven fabric, or a plate shape such as a metal plate, a wood plate, and a plastic plate can be used. It is preferable to use a sheet material in the manufacturing process because a roll of a sheet-like material can be used as a base material to enable continuous production of a decorative material. Usually, when the base material 2 is used in the form of a sheet, it has a thickness of 5 to 2 mm.
Those having a size of 00 μm are preferably used. Further, as the substrate 2, a substrate having irregularities on its surface, a substrate having a three-dimensional shape, or the like can be used.

The paper used as the substrate 2 is specifically a so-called vinyl wallpaper obtained by sol-coating or dry-laminating a polyvinyl chloride resin on paper, such as tissue paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board 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.

The plastic sheet used as the base material 2 includes polyolefin resins such as polyethylene, polypropylene and polymethylpentene, polyvinyl chloride, polyvinylidene chloride, polyvinyl alcohol, vinyl chloride-vinyl acetate copolymer, ethylene-vinyl acetate. Copolymer, ethylene-vinyl alcohol copolymer, vinyl resin such as vinylon, polyester resin such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate-isophthalate copolymer, polymethyl methacrylate, polymethacrylic acid Acrylic resins such as ethyl, polyethyl acrylate, and polybutyl acrylate; polyamides such as nylon 6 and nylon 66; cellulose resins such as cellulose triacetate and cellophane; polystyrene; Sulfonates, polyarylate, synthetic resin films such as polyimide, or a single layer body or a laminated body of the sheets. Examples of the metal used as the metal foil include aluminum, stainless steel, iron, and copper.

The board used as the base material 2 is wood veneer, wood plywood, particle board, wood board such as MDF (medium density fiber board), gypsum board, gypsum board such as gypsum slag board, calcium silicate board, etc. , Asbestos slate board, lightweight foam concrete board, hollow extruded cement board etc., cement board, pulp cement board, asbestos cement board, wood cement board etc. fiber cement board, pottery, magnetism, stoneware, earthenware, glass, enamel etc. Ceramic plate, iron plate, galvanized steel plate, polyvinyl chloride sol coated steel plate, aluminum plate, metal plate such as copper plate, polyolefin resin plate, acrylic resin plate, ABS
Thermosetting resin plate such as a thermoplastic resin plate such as a plate, a polycarbonate plate, a phenol resin plate, a urea resin plate, an unsaturated polyester resin plate, a polyurethane resin plate, an epoxy resin plate, a melamine resin plate, a phenol resin, a urea resin, Unsaturated polyester resin, polyurethane resin, epoxy resin,
A resin plate such as a so-called FRP plate or the like obtained by impregnating and curing a resin such as a melamine resin or a diallyl phthalate resin into a glass fiber nonwoven fabric, a cloth, paper, or other various fibrous base materials to form a composite.

The substrate 2 may be a composite substrate obtained by laminating two or more of the above-mentioned various substrates by a known means such as an adhesive or heat fusion.

In the present invention, the crosslinkable resin 4 used as a binder for forming the abrasion-resistant resin layer 3 on the surface of the substrate 2 is an ionizing radiation-curable resin or a thermosetting resin (room temperature-curable resin, Resin used as a crosslinkable resin of a conventionally known cosmetic material (including a liquid reaction curable resin) can be used. As a cross-linkable resin, ionizing radiation-curable resin has a high curing speed and good workability, and it is easy to adjust physical properties of the resin such as flexibility and hardness. This is preferable because a sheet-like decorative material can be efficiently and continuously produced. Further, the selection of the above-mentioned crosslinkable resin can be appropriately selected according to the use of the decorative material.
The crosslinkable resin is applied by dispersing spherical particles in an uncrosslinked state, then crosslinked and cured to complete the coating film.

The higher the crosslink density of the crosslinkable resin, the higher the abrasion resistance, but the lower the flexibility. Therefore, the cross-linking density of the cross-linkable resin, depending on the wear resistance and flexibility depending on the use of the cosmetic material, etc., appropriately in accordance with the type of the base material,
It is preferable to select one. The crosslink density can be represented by, for example, the average molecular weight between crosslinks shown in the following formula (3). The average molecular weight between crosslinks can be used in the range of 100 to 1000, preferably 100 to 700, and more preferably 300 to 700 from the viewpoint of flexibility.

[0029]

## EQU00007 ## Average molecular weight between crosslinks = total molecular weight / number of crosslink points (3) where the total molecular weight is Σ (the number of moles of each component × the molecular weight of each component). The number of points is {[{(the number of functional groups of each component −1) × 2} × the number of moles of each component].

The ionizing radiation-curable resin used as the crosslinkable resin is, specifically, an ionizing radiation curable resin obtained by appropriately mixing a prepolymer, oligomer, and / or monomer having a polymerizable unsaturated bond or an epoxy group in a molecule. The composition which can be cured by the above is used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually an ultraviolet ray or an electron beam is used.

Examples of the above prepolymers and oligomers include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, methacrylates such as polyester methacrylate, polyether methacrylate, polyol methacrylate and melamine methacrylate, polyester acrylates, and the like. Examples include acrylates such as epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds.

The urethane acrylate includes, for example, a polyether-based urethane (meth) acrylate represented by the following general formula [1], which is obtained by reacting a polyether diol with a diisocyanate.

## STR1 ## ^{_{CH 2 = C (R 1)}} -COOCH 2 CH 2 -O
CONH-X-NHCOO - ^{[- CH (R 2) - (} CH
_{2) n} -O-] _{m -CONH-X-NHCOO-CH} 2
CH ₂ OCOC (R ¹ ) = CH ₂ (wherein R ¹ and R ² are each hydrogen or a methyl group, X is a diisocyanate residue, n is an integer of 1 to 3, m
Is an integer of 6 to 60. )

Examples of the diisocyanate used in the above polyether urethane (meth) acrylate include isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, and tolylene diisocyanate. Examples of the polyether diol include polyoxypropylene glycol, polyoxyethylene glycol, and polyoxytetramethylene glycol having a molecular weight of 500 to 3,000.

Hereinafter, a production example of urethane acrylate will be described. In a glass reaction vessel equipped with a dropping funnel, a thermometer, a reflux condenser, and a stirring rod, 1,000 parts of polytetrameralene glycol having a molecular weight of 1,000 and 444 parts of isophorone diisocyanate were charged and reacted at 120 ° C. for 3 hours. Thereafter, the mixture was cooled to 80 ° C. or lower, 232 parts by weight of 2-hydroxyethyl acrylate was added, and the reaction was carried out at 80 ° C. until the isocyanate group disappeared to obtain a urethane acrylate.

Examples of monomers used for the ionizing radiation-curable resin include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, and acrylic acid. Acrylates such as butyl, methoxybutyl acrylate and phenyl acrylate, methacrylic acid such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate and lauryl methacrylate Esters, 2- (N, N-diethylamino) ethyl acrylate, 2- (N, N-dimethylamino) ethyl memethacrylate, 2- (N, N-dibenzylamino) methyl acrylate, acrylic Acid-2- (N Substituted amino alcohol esters of unsaturated acids such as N-diethylamino) propyl, unsaturated carboxylic acid amides such as acrylamide and methacrylamide, ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate ,
Compounds such as 1,6 hexanediol diacrylate and triethylene glycol diacrylate; polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, and diethylene glycol dimethacrylate; and / or Polythiol compounds having two or more thiol groups, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, and pentaerythritol tetrathioglycol.

Usually, one or more of the above compounds may be used as a mixture, if necessary. In order to impart ordinary coating suitability to the ionizing radiation-curable resin, the prepolymer or polythiol is used in combination with 5 or more. It is preferable that the content of the monomer and / or polythiol be not more than 95% by weight.

In selecting the monomer, when the flexibility of the cured product is required, the amount of the monomer may be reduced as long as the coatability is not impaired, or a monofunctional or bifunctional acrylate monomer may be used. The structure has a relatively low crosslink density. In the case where the abrasion resistance, heat resistance, solvent resistance, etc. of the cured product are required, increase the amount of the monomer within a range that does not hinder coating suitability, or use a trifunctional or higher acrylate monomer. And a structure having a high crosslinking density can be obtained. In addition, a monofunctional monomer and a trifunctional or higher functional monomer may be mixed to adjust coating aptitude and physical properties of a cured product.

The above-mentioned monofunctional acrylate monomers include 2-hydroxyacrylate, 2-hexyl acrylate, phenoxyethyl acrylate and the like. Examples of the bifunctional acrylate include ethylene glycol diacrylate and 1,6-hexanediol diacrylate, and examples of the trifunctional or higher acrylate include trimethylolpropane triacrylate, pentaerythritol tri (tetra) acrylate, and dipentaerythritol hexaacrylate. Acrylate and the like.

Further, a non-ionizing radiation curable resin for adjusting physical properties such as flexibility and surface hardness of the cured product can be added to the ionizing radiation curable resin. As the ionizing radiation non-curable resin, thermoplastic resins such as urethane-based, cellulose-based, polyester-based, acrylic-based, butyral-based, polyvinyl chloride, and polyvinyl acetate are used. Particularly, cellulose-based and urethane-based resins are used. Butyral is preferred from the viewpoint of flexibility.

When irradiating ultraviolet rays to cure the ionizing radiation-curable resin having the above composition, acetophenones, benzophenones, Michler benzoyl benzoate, α-aminoxime ester may be used as a photopolymerization initiator. , Tetramethylthiuram monosulfide,
Thioxanthones, aromatic diazonium salts, aromatic sulfonium salts, metallocenes, and photopolymerization accelerators (sensitizers)
N-butylamine, triethylamine, tri-n
-Butylphosphine and the like can be further mixed and used.

Specific examples of the thermosetting resin used as the crosslinkable resin include a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin, an unsaturated polyester resin, and a polyurethane resin (two-pack polyurethane resin). ), An epoxy resin, an amino alkyd resin, a melamine-urea co-condensation resin, a silicon resin, a polysiloxane resin, and the like. If necessary, a crosslinking agent, a curing agent such as a polymerization initiator, a polymerization accelerator, etc. may be added and used.
As the above curing agent, isocyanates or organic sulfonates are usually used in unsaturated polyester resins or polyurethane resins, amines are used in epoxy resins, peroxides such as methyl ethyl ketone peroxide and radical initiators such as azoisobutyl nitrile are used. Often used for saturated polyesters.

As the above isocyanate, a divalent or higher aliphatic or aromatic isocyanate can be used, but an aliphatic isocyanate is desirable from the viewpoint of preventing thermal discoloration and weather resistance. Specific isocyanates include tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like.

The two-pack type polyurethane includes a first solution comprising a polyol compound having an average of two or more hydroxyl groups in its molecular structure, and a second solution comprising a polyisocyanate compound. What was blended so that equivalent ratio might be set to 0.7-1.5 is mentioned.

Examples of the epoxy resin include an epoxy resin having an average of two or more epoxy groups in its molecular structure and a mono- or poly-amine having three or more active hydrogens which react with the epoxy group in one molecule. Examples include those blended such that the ratio of the epoxy equivalent of the epoxy resin to the active hydrogen equivalent of the mono or polyamine is 0.7 to 1.5.

The coating composition for the abrasion-resistant resin layer 3 contains, as components other than the binder resin, the spherical particles and the irregular particles, coloring agents such as dyes and pigments, and other components such as CaCO ₃ and Ba.
Additives usually added to paints and inks such as fillers such as SO ₄ and nylon resin beads, defoamers, leveling agents, and thixotropic agents can be added.

The coating composition for the abrasion-resistant resin layer 3 can dissolve the components of the crosslinkable resin in order to adjust the viscosity, and has a boiling point at normal pressure of 70 ° C. to 150 ° C. Solvents can be used in the composition in a range of 30% by weight or less. When the amount of the solvent added is in the range of 30% by weight or less, drying is smooth, and there is no significant decrease in production speed.

As the above-mentioned solvent, those usually used for paints, inks and the like can be used. Specific examples thereof include aromatic hydrocarbons such as toluene and xylene, ketones such as acetone, methyl ethyl ketone methyl isobutyl ketone and cyclohexanone. Acetic acid esters such as ethyl acetate, isopropyl acetate and amyl acetate; alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol; ethers such as dioxane, tetrahydrofuran and diisopropyl ether; and mixtures of two or more of these.

Next, a method of forming the wear-resistant resin layer 3 on the surface of the substrate 2 using the above-mentioned coating composition will be described. The wear-resistant resin layer 3 is formed by directly coating the coating composition on the surface of the base material 2, or after forming the wear-resistant resin layer on the surface of the peelable base material in advance, A transfer coating method of transferring to the surface of the substrate 2 is used. Generally, as the material of the base material 2, any of the above and any of the above may be used when a material that does not penetrate the coating composition is used. Substrate with irregularities on the surface, and, if the uniformity of the coating film thickness is to be obtained, if the intensity of ionizing radiation is to be uniform to form uniform abrasion resistance, the above-mentioned transfer coating method is preferably used. .

The above direct coating methods include gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, wheeler coat, dip coat, solid coat by silk screen, wire bar coat, flow coat , A comma coat, a pouring coat, a brush coat, a spray coat and the like can be used, and a gravure coat is preferable.

The transfer coating method includes the following (a) to
(D) is a method of forming a coating film on a thin sheet (film) substrate once, crosslinking and curing the coating film, and then coating the coating on the surface of the substrate. A lamination method (a, b) for adhering to a product, a transfer sheet formed by forming a coating film and, if necessary, an adhesive layer on a release support sheet, and crosslinking and curing the coating film, Can be used, such as a transfer method (c) in which only the support sheet is peeled off after bonding to the three-dimensional object. In addition, on a thin sheet substrate,
As the method for forming the wear-resistant resin layer, the same various coating means as used in the direct coating method described above can be used. (A) JP-B-2-42080, JP-B-4-199
No. 24, etc., simultaneous injection molding transfer method.
Alternatively, an injection molding simultaneous lamination method as disclosed in Japanese Patent Publication No. 50-19132. (B) JP-A-4-288214, JP-A-5-57
No. 786, a vacuum forming simultaneous transfer method.
Alternatively, a vacuum forming simultaneous lamination method as disclosed in JP-B-56-45768. (C) JP-B-59-51900, JP-B-61-5
No. 895, JP-B-3-2666, etc., a lapping simultaneous transfer method or a lapping simultaneous lamination method. (D) V-cut simultaneous lamination method disclosed in Japanese Utility Model Publication No. 15-31122 or Japanese Patent Publication No. 56-31122.
V-cut simultaneous transfer method disclosed in JP 7866 and the like.

As one of the above transfer coating methods, for example, when an ionizing radiation-curable resin is used as the crosslinkable resin, a method in which the following steps (A) to (D) are sequentially performed may be used. (Described in JP-A-2-26673). (A) A step of applying an uncured liquid ionizing radiation-curable resin composition to a non-absorbable and releasable synthetic resin sheet. (B) a step of laminating so that the application surface of the ionizing radiation-curable resin composition is in contact with a substrate. (C) a step of irradiating the coating film of the ionizing radiation-curable resin composition with ionizing radiation to crosslink and cure. (D) a step of peeling and removing the synthetic resin sheet. In the above step, when a resin diluted with a solvent is used as the ionizing radiation-curable resin, a step of drying the solvent is performed between steps (A) and (B). According to the above method, even when the base material is a highly permeable material such as paper, the resin is reliably prevented from leaking to the back side of the base material, so-called "uneven", and the surface of the base material is reliably prevented. A good wear-resistant resin layer can be easily formed.

When an ionizing radiation-curable resin is used as the crosslinkable resin, the ionizing radiation irradiator used for curing the resin may be an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, A light source such as an arc, a black light lamp, or a metal halide lamp is used. When irradiating an electron beam, a Cockloft-Walton type, a bandeograph type, a resonance transformer type, an insulating core transformer type, or a linear type or a dynamic type is used. Various electron beam accelerators such as a tron type and a high frequency type are used.

The irradiation amount of the electron beam is usually 100 to 1000
Electrons having an energy of keV, preferably 100 to 300 keV, are irradiated at a dose of about 0.1 to 30 Mrad. When the irradiation amount is less than 0.1 Mrad, curing may be insufficient, and when the irradiation amount exceeds 30 Mrad, the cured coating film or the base material may be damaged. In addition, the irradiation amount when curing with ultraviolet light is
Preferably it is 50 to 1000 mJ / cm ² . If the irradiation amount of ultraviolet rays is less than 50 mJ / cm, curing may be insufficient, and if the irradiation amount exceeds 1000 mJ / cm ² , the cured coating film may turn yellow.

When a thermosetting resin is used as the crosslinkable resin, the coating composition may be heated after coating in order to accelerate the curing reaction of the thermosetting resin. The heating time is, for example, usually 40 to 60 in the case of an isocyanate-curable unsaturated polyester resin or a polyurethane resin.
C. for about 1 to 5 days, and in the case of a polysiloxane resin, usually about 80 to 150 ° C. for about 1 to 300 minutes.

The pattern layers 7 such as the solid printing layer 7a and the pattern printing layer 7b may be formed of known coloring agents such as pigments and dyes, extenders, solvents, stabilizers, plasticizers, catalysts, Printing is carried out using a printing ink obtained by appropriately mixing agents and the like.

As the above-mentioned vehicle, use is made of a thermoplastic resin, a thermosetting resin, an ionizing radiation-curable resin, or the like, which is appropriately selected according to necessary physical properties, printing suitability and the like.
Further, as the pigment, a commonly used organic or inorganic pigment can be used. As the diluting solvent, a liquid solvent which has a dissolving and dispersing ability for a vehicle resin, a coloring agent such as a pigment, and other additives and has an appropriate drying property is used. Generally, it is preferable from the viewpoint of solubility to select a liquid solvent whose solubility parameter is close to that of the vehicle.

The pattern printing layer 7b is provided in a pattern (for example, a pattern such as wood grain, cloth grain, figure, character, etc.), and may be provided on the entire surface of the base material 2 or may be provided partially. The pattern printing layer 7b is partially provided, for example, when it is desired to particularly emphasize a part of a picture (for example, a shining part of a wood grain pattern). Further, the solid printed layer 7a can be provided, for example, in a case where a solid pearl pattern or an interference appearance is entirely exhibited in a solid pattern.

FIG. 2 is a longitudinal sectional view showing another embodiment of the decorative material of the present invention. As shown in FIG. 2, in the decorative material 1 of the present invention, a surface resin layer 8 is provided on the surface of the base material 2, and a pattern-shaped concave portion is formed on the surface. To form a wiping ink layer 9 and form a wear-resistant resin layer 3 on the outermost surface. Although not shown, a concave portion and a wiping ink layer may be provided directly and partially on the surface of the substrate 2.

The embodiment shown in FIG. 2 is an example in which a coating composition for forming a wear-resistant resin layer is used as a surface protective layer of a wiping ink. The following method is used to form the wiping ink layer 9 of the coloring ink filled with wiping in the decorative material 1 shown in FIG. A coating composition containing a coloring ink is applied to the entire surface of the base material 2 having the pattern irregularities provided on the surface resin layer 8 by a known embossing method, and then the coated surface of the coating product is coated. The colored ink resin layer is formed only in the concave portions by removing the coating composition of the convex portions by wiping the resin layer 8 with a roller or the like having a doctor blade, an air knife, a sponge, or the like as a surface material. In the wiping process, by using a colored coating composition, it is possible to synchronize the pattern and the concave portion with the pattern as a grain, and to reproduce the appearance of the conduit portion of the grain satisfactorily. In this case, the surface resin layer 8 uses a transparent resin.

The abrasion-resistant cosmetic material of the present invention is suitable for various uses, for example, buildings, vehicle ships, furniture, musical instruments,
It is useful for decoration of cabinets and other surfaces and decoration of packaging materials. In particular, the cosmetic material of the present invention is most suitable for fields requiring abrasion resistance. In the case where the decorative material of the present invention is used for the above-mentioned purpose, the surface of the above-mentioned various decorations is described in (a) to (a) to the explanation part of the transfer coating method.
Lamination can be performed by using various means (d).

[0061]

EXAMPLE 1 Acrylic resin latex-impregnated paper (60 g / m
² ) A colored solid layer (acrylic nitrified cotton mixed ink) and a picture layer (nitrified cotton alkyd mixed ink) are sequentially printed on the surface of ( ² ) using a gravure printing machine to form a gravure coater. The following paint is applied using (coating amount: 25 g / m ² dry), and an electron beam is irradiated (175 kv, 5 Mrad) using an electron beam irradiation device to crosslink the coating film.
After curing, a wear-resistant surface resin layer was provided to obtain a decorative material.

[Abrasion-resistant resin layer coating composition] Bisphenol A ethylene oxide-modified diacrylate 50 parts by weight Trimethylolpropane ethylene oxide-modified triacrylate 20 parts by weight Spherical alumina (average particle size 25 μm) 20 parts by weight 8 parts by weight amorphous silica (average particle size: 1.8 μm) 1 part by weight fine powder silica (average particle size: 0.1 μm) 1 part by weight methacrylate-modified silicone at both ends

Comparative Example 1 Cosmetic was conducted in the same manner as in Example 1 except that the coating composition of Example 1 except for the amorphous silica and the silicone modified at both ends with methacrylate was used. Wood was obtained.

The gloss of the surface of the decorative materials obtained in Example 1 and Comparative Example 1 was observed, and a cellophane tape peeling resistance test (10 times peeling test) and an abrasion resistance test were performed. Table 1 shows the results. As shown in Table 1, the decorative material of Example 1 has the same abrasion resistance and the like as compared with the decorative material of Comparative Example 1, has a good result of the cellophane tape peeling resistance test, and has a matte state. It was good.

[0065]

[Table 1]

[0066]

As described above, the present invention provides a coating composition comprising a binder comprising a crosslinkable resin, at least spherical particles having a higher hardness than the crosslinkable resin, and irregular particles. A wear-resistant resin layer is provided on the surface of the substrate, the average thickness of the wear-resistant resin layer is t (mm),
When the average particle diameter of the spherical particles is d1 (μm) and the average particle diameter of the irregular particles is d2, by adopting a configuration satisfying the following equations (1) and (2),

[Expression 8] 0.3t ≦ d1 ≦ 2.0t (1)

D2 <d1 (2) While having a matte design, it has excellent abrasion resistance and wears a gravure roll, a doctor blade, etc. of a coating apparatus during the production of a cosmetic material. Also, when a cosmetic material is used, other articles that come into contact with the cosmetic material are not worn or the touch feeling is not reduced.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view showing one embodiment of a decorative material of the present invention.

FIG. 2 is a longitudinal sectional view showing another embodiment of the decorative material of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Abrasion resistant decorative material 2 Base material 3 Abrasion resistant resin layer 4 Binder made of crosslinkable resin 5 Spherical particles 6 Irregular particles

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification code FI Theme coat ゛ (Reference) C09D 5/32 C09D 5/32 E04F 13/18 E04F 13/18 A F term (Reference) 2E110 AA47 AB03 AB04 AB05 BA02 BA11 BB04 GA13X GA23W GA24X GA32X GA33X GA42X GA43W GB02X GB05W GB06X GB07X GB12X GB16X GB17X GB19X GB23X GB28X GB32X GB35W GB35X GB43X GB44W GB44X GB45X GB46X GB47X GB48X GB52EB02 DB32CA02 DB32 DB02 4F100 AB10A AK01A AK25 AR00C AS00A AT00B BA02 BA03 BA07 BA10B BA10C CC00A DE01A DG10 EJ05A EJ53 EJ82 GB07 GB81 HB00 HB31 JB14A JK09A JK12A JK15 JL14C JM01 YY00A 4J021 BF05 CC1 BG051 EN116 EP016 EV066 FA087 FB107 FB137 FB147 FB157 FD013 FD017 FD018 FD142 FD146 GH02 4J038 DB371 DD191 EA011 FA251 FA261 FA271 FA281 HA216 KA20 NA11 PA17

Claims (4)

[Claims] An abrasion-resistant resin layer formed from a coating composition containing a binder composed of a crosslinkable resin, at least spherical particles having a higher hardness than the crosslinkable resin, and irregular particles, comprises a base material. The average thickness of the abrasion-resistant resin layer provided on the surface of the material is t (μm), and the average particle size of the spherical particles is d1 (μm).
m), and when the average particle diameter d2 (μm) of the irregular shaped particles is satisfied, the following formulas (1) and (2) are satisfied. 0.3t ≦ d1 ≦ 2.0t (1) d2 <d1 (2) 2. The abrasion-resistant decorative material according to claim 1, wherein the spherical particles are spherical α-alumina. 3. The abrasion-resistant decorative material according to claim 1, wherein the binder made of a crosslinkable resin is made of an ionizing radiation-curable resin. 4. The wear-resistant decorative material according to claim 1, wherein the surface of the wear-resistant resin layer has releasability.