JPH10109392A - Decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To stably coat in the case of coating with a top coating layer by reducing a load to an apparatus at the time of coating in the case of coating with the layer with excellent wear resistance by using abrasion-proofing agent- containing resin bead for the layer. SOLUTION: Abrasion-proofing agent-containing resin bead 5 used for a top coating layer of the decorative material is resin bead formed in particle-like state by incorporating particles having higher hardness than that of binder resin 52 as abrasion-proofing agent 51 in the resin 52. The dispersed state of the agent 51 in the bead 5 may be such that the agent 51 exists at least on a surface of the bead 5. Accordingly, a decorative plate having low load of an apparatus at the time of coating and satisfactory wear resistance is obtained. The layer has satisfactory drape with the resin of the layer. Property of precipitating the bead 5 of coating composition is small. As a result, management of quality of the layer is easy.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a wear-resistant decorative material used as a decorative sheet or decorative plate.

[0002]

2. Related Background Art Hitherto, as a wear-resistant decorative material, a decorative material having a top coat layer made of a wear-resistant resin on the surface of the decorative material has been known. As the resin of the top coat layer, a hard resin such as a thermosetting resin or an ionizing radiation-curable resin is used. In order to improve abrasion resistance, the layer is formed to be thick. However, when the top coat layer is formed thick, there is a problem that curling or cracking is apt to occur when a flexible material or thin paper is used as the base material.

In order to improve the abrasion resistance of the top coat layer, the top coat layer is formed by using resin beads formed from a polycarbonate resin or a composition obtained by adding an inorganic filler such as silica to a binder resin. Are known. However, these decorative materials have improved abrasion resistance, but the degree of the improvement is slight, and further excellent abrasion resistance has been demanded.

[0004] In order to improve the above drawbacks, the present applicant has
A cosmetic material containing a spherical alumina in the top coat layer has been previously proposed (Japanese Patent Application No. 7-158591).
This cosmetic material had an effect that the wear resistance of the top coat layer was remarkably improved and the top coat layer did not need to be formed thick, but the following problems were found.

[0005]

When a top coat layer is applied, a heavy load is imposed on a coating apparatus. That is, the alumina particles of the coating composition will wear the plate, doctor, pump and the like of the coating apparatus. Also,
In the coating composition of the top coat, there is a problem that the alumina particles are liable to settle, are separated in the coating liquid and become non-uniform, and the quality control of the top coat layer is troublesome.

Further, in order to adjust the abrasion resistance of the above-mentioned decorative material, the amount of the anti-wear agent (alumina) in the coating composition, the viscosity, the particle size, the film thickness, etc. of the coating solution are arbitrarily set. However, since the viscosity of the coating liquid changes during coating, there is a problem that it takes time and effort to obtain a cosmetic material of a constant quality.

The present invention has been made to solve the above-mentioned drawbacks, has excellent abrasion resistance, has a small load on a device at the time of coating the top coat layer, and has a small load on the top coat layer. An object of the present invention is to provide a cosmetic material capable of performing stable coating.

[0008]

The present invention provides (1) a decorative material having a wear-resistant top coat layer provided on the surface side of a base material, wherein the top coat layer comprises a resin bead containing an anti-wear agent. (2) The cosmetic material according to the above (1), wherein spherical alumina is used as an anti-wear agent for the anti-wear resin beads, and the resin beads have an average particle size of 10 to 100 μm. 3) The cosmetic material according to the above (1) or (2), wherein the resin of the resin beads containing an anti-wear agent is an acrylic resin.
It is the gist.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings. As shown in FIG. 1, the decorative material 1 of the present invention is a decorative material in which a top coat layer 3 is provided on the surface side of a base material 2, wherein the top coat layer 3 uses resin beads 5 containing an abrasive. is there. In addition, a printing layer 4 can be provided between the base material 2 and the top coat layer 3.

As shown in FIG. 3, the resin beads 5 containing an anti-wear agent used in the present invention are formed into particles by adding particles having higher hardness than the above-mentioned binder resin to the binder resin 52 in the binder resin 52. Resin beads.
As shown in FIG. 3, the state of dispersion of the lubricant in the resin beads containing the lubricant is as follows.
May be uniformly dispersed in the resin 52, or may be in a state where it adheres only to the surface side of the resin beads 5 and the anti-wear agent 51 does not exist inside the resin beads 5 as shown in FIG. . It is sufficient that the anti-wear agent is present at least on the surface of the anti-wear resin beads.

The above-mentioned anti-friction agent is not particularly limited as long as it is particles having a hardness higher than that of the binder resin, but usually, inorganic particles are used. The anti-wear agent 51 is specifically alumina,
Silica, calcium carbonate and the like can be used. Alumina is preferably used because of its good hardness. The content of the anti-wear agent 51 in the anti-wear resin beads 5 is preferably in the range of 0.1 to 70% by weight, particularly preferably 30 to 50% by weight, based on the whole resin beads. Also,
As the binder resin, acrylic, urethane, polyester, urea resin and the like are used. The binder resin is preferably an acrylic resin from the viewpoint of abrasion resistance.

The average particle size of the resin beads 5 containing the anti-wear agent is preferably 10 to 100 μm, and more preferably 10 to 30 μm. Further, the particle size of the anti-wear agent 51 is preferably 2 μm or more, and particularly preferably 3 to
5 μm.

The thickness of the top coat layer 3 may be smaller than the particle size of the resin beads 5 containing the abrasive as shown in FIG.
Alternatively, as shown in FIG. 2, the resin beads 5 may be formed to be thicker than the particle diameter of the resin beads 5 containing the anti-wear agent.

In the resin beads 5 containing an anti-wear agent, the relation between the anti-wear agent 51 and the particle size of the resin beads 5 is determined by the ratio A: B = the ratio of the particle size (A) of the anti-wear agent to the particle size (B) of the resin beads. 1: 3
A range of １ ： 1: 100 is preferred. If the above B is less than 3, it does not hold as particles. On the other hand, if B exceeds 100, sufficient properties cannot be exhibited with abrasion resistance. More preferred A: B
Is 1: 4 to 1:20.

In the top coat layer 3, the addition amount of the resin beads 5 containing the anti-wear agent (% by weight based on the binder resin)
Is preferably in the range of 5 to 50% by weight based on the binder resin. If the amount of the resin beads containing the anti-wear agent is less than 5% by weight, sufficient abrasion resistance cannot be obtained. If the amount exceeds 50% by weight, the resin becomes a paste and cannot be used. A more preferable addition amount of the resin beads containing the anti-wear agent to the top coat layer 3 is 1
0 to 30% by weight.

The following means is used to form the top coat layer 3 in the decorative material of the present invention. The resin composition is cured by applying a coating composition in which resin beads containing an anti-wear agent are mixed into the composition of the top coat layer. After applying the resin composition containing no anti-wear agent, the anti-wear agent-containing resin beads are adhered to the surface of the coated surface in a state where the resin is in an uncured state, and then cured.

When the resin beads containing the anti-wear agent are adhered to the uncured resin coated surface as in the above-mentioned means, since the anti-wear agent of the resin beads containing the anti-wear agent is exposed on the surface of the resin beads, the binder is used. The biting of the resin to the coated surface is good. In addition, when applying the anti-wear agent to the surface after applying the resin of the top coat layer in this way, it is possible to impart abrasion resistance to the top coat layer and, at the same time, to make the surface of the top coat layer matte. Yes, the gloss of the surface of the top tart layer can be arbitrarily adjusted.

The binder resin of the top coat layer 3 is an ionizing radiation curable resin such as an electron beam curable resin or an ultraviolet curable resin, or a thermosetting resin (including a room temperature curable resin and a two-component reaction curable resin). Resins used for a top coat layer of a conventionally known decorative material such as the above can be used.

The ionizing radiation-curable resin is, specifically, a composition which is appropriately mixed with a prepolymer, an oligomer and / or a monomer having a polymerizable unsaturated bond or an epoxy group in a molecule and which can be cured by ionizing radiation. Object is used. 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 is usually an ultraviolet ray or an electron beam.

The above prepolymer and oligomer include:
Unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, polyester methacrylate, polyether methacrylate, polyol methacrylate,
Examples include methacrylates such as melamine methacrylate, acrylates such as polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds.

Examples of the monomer include styrene monomers such as styrene and α-methylstyrene, methyl acrylate, 2-ethylhexyl acrylate, methoxyethyl acrylate, butoxyethyl acrylate, butyl acrylate, methoxybutyl acrylate, and acryl acrylate. Acrylates such as phenyl acrylate, methacrylates such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, methoxyethyl methacrylate, ethoxymethyl methacrylate, phenyl methacrylate, lauryl methacrylate, acrylic acid-2- (N, N-diethylamino) ethyl, 2- (N, N-dimethylamino) ethyl memethacrylate, 2- (N, N-dibenzylamino) methyl acrylate, 2- (N, N -Diethylamino) propi Substituted amino alcohol esters such as acrylamide, methacrylamide, etc., unsaturated carboxylic acid amides such as acrylamide, methacrylamide, etc., ethylene glycol diacrylate, propylene glycol diacrylate, propylene glycol diacrylate, neopentyl glycol diacrylate, 1,6 hexane Compounds such as diol diacrylate and triethylene glycol diacrylate, polyfunctional compounds such as dipropylene glycol diacrylate, ethylene glycol diacrylate, propylene glycol dimethacrylate, diethylene glycol dimethacrylate, and / or two or more compounds in a molecule Polythiol compounds having thiol groups, such as trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, Pentaerythritol tetrathioglycol and the like.

When curing by irradiation with ultraviolet rays, acetophenones, benzophenones, Michler benzoyl benzoate, α-aminoxime ester, tetramethylthiuram monosulfide,
Thioxanthones, aromatic diazonium salts, aromatic sulfonium salts, metallocenes, and photopolymerization accelerators (sensitizers)
N-butylamine, triethylamine, tri-n
-Butylphosphine and the like are added.

The thermosetting resin used as the binder resin for the top coat layer is a phenol resin, a urea resin, a diallyl phthalate resin, a melamine resin, a guanamine resin,
Examples include unsaturated polyester resins, polyurethane resins (including two-pack polyurethanes), epoxy resins, amino alkyd resins, melamine-urea co-condensation resins, silicon resins, polysiloxane resins, 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, divalent or higher aliphatic or aromatic isocyanate can be used, but aliphatic isocyanate is preferable from the viewpoint of prevention of thermal discoloration and weather resistance.
Specific isocyanates include tolylene diisocyanate, xylylene diisocyanate, 4,4'-diphenylmethane diisocyanate, hexamethylene diisocyanate, lysine diisocyanate and the like.

As the two-pack type polyurethane, a first liquid consisting of a polyol compound having an average of two or more hydroxyl groups in its molecular structure and a second liquid consisting of a polyisocyanate compound are prepared by mixing a hydroxyl group and an isocyanate group. What was blended so that equivalent ratio might be set to 0.7-1.5 is mentioned.

The epoxy resin includes 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 top coat layer 3 may contain additives other than the above-mentioned resin and resin beads containing an anti-wear agent. For example, in order to improve cellophane tape resistance and stain resistance, a silicone-based or fluorine-based additive can be added in a range of 0.1 to 10% by weight.

The substrate 2 is made of paper, plastic, metal, wood, or the like, and may be in any of a sheet shape, a plate shape, a shape having irregularities on the surface, and a shape having a three-dimensional shape.
The base material 2 has a thickness of 5 to 5 when a sheet-like material is used.
Those having a thickness of 200 μm are preferably used.

The paper used for the base material 2 is thin paper, kraft paper, titanium paper, linter paper, paperboard, gypsum board paper, or a so-called vinyl wallpaper raw material obtained by sol-coating or dry-laminating a polyvinyl chloride resin on paper, high-quality paper. , Coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, Japanese paper, and paper-like sheets such as glass fiber, asbestos,
Woven or nonwoven fabrics using inorganic fibers such as potassium titanate fiber, alumina fiber, silica fiber, carbon fiber and the like, organic resins such as polyester and vinylon, and the like can be given.

The plastic sheet used for the substrate 2 is made of polyolefin resin such as polyethylene, polypropylene, 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,
Monolayers or laminates of polyamides such as nylon 6 and nylon 66, cellulose resins such as cellulose triacetate and cellophane, synthetic resin films such as polystyrene, polycarbonate, polyarylate, and polyimide, or sheets. Examples of the metal used as the metal foil include aluminum, stainless steel, iron, and copper.

The board used for 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, asbestos slate Board, lightweight foam concrete board, cement board such as hollow extruded cement board, pulp cement board,
Fiber cement board such as asbestos cement board, wood chip cement board,
Ceramic plates such as pottery, magnetism, pottery, earthenware, glass, enamel, etc., iron plates, galvanized steel plates, polyvinyl chloride sol coated steel plates, aluminum plates, metal plates such as copper plates, polyolefin resin plates, acrylic resin plates, ABS plates, Thermoplastic resin plate such as polycarbonate plate, phenol resin plate, urea resin plate, unsaturated polyester resin plate, polyurethane resin plate,
Thermosetting resin plates such as epoxy resin plates and melamine resin plates,
Phenolic resin, urea resin, unsaturated polyester resin,
A resin plate such as a so-called FRP plate obtained by impregnating and curing a resin such as a polyurethane resin, 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 to form a composite. .

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

The decorative material of the present invention is used as a decorative sheet, a decorative plate, a decorative steel plate, etc., for example, as a surface decoration material for interiors such as floors, walls and ceilings of buildings, furniture and various cabinets. It can be optimally used for applications requiring wear resistance.

[0034]

【Example】

Example 1 A solid layer and a pattern layer were successively gravure-printed on the surface of impregnated paper (manufactured by Kojin: GF-606) using HAT ink (manufactured by Inktec) to obtain a printing paper. A top coat layer composition in which 20% by weight of the following anti-wear resin beads are dispersed in a polyether-based electron beam-curable resin (manufactured by Sanyo Chemical Industries),
The printing surface of the printing paper is coated by a gravure reverse method (coating amount: 20 g / m ² ), and an electron beam (175 KV, 5 Mr) is applied.
ad) was irradiated and cured to obtain a decorative paper. [Rubber-resistant resin beads (average particle size: 25 μm)] ・ Acrylic resin 70% by weight ・ Alumina (average particle size 5 μm) 30% by weight The obtained decorative paper is according to JIS K-6902.
Table 1 shows the results of the abrasion resistance test performed on the polishing paper S-42.

Example 2 A printed sheet was obtained by gravure printing a pattern on the surface of a 0.1 mm thick polyvinyl chloride resin sheet (manufactured by Riken Vinyl: 23 phr) using Chemical X (manufactured by Showa Ink). On the printing surface of the printing sheet, a composition obtained by dispersing 20% by weight of the resin beads containing the anti-wear agent used in Example 1 in a polyester-based ultraviolet curable resin (manufactured by Inktec) by a gravure reverse method ( Coating amount 20 g / m ² ) The composition was cured by ultraviolet irradiation to obtain a decorative sheet. Table 1 shows the results of the abrasion resistance and scratch resistance tests performed on the decorative sheet obtained in the same manner as in Example 1.

Example 3 A composition obtained by gravure printing a pattern on a steel plate and dispersing the resin beads used in Example 1 in a polyether-based electron beam-curable resin (manufactured by Sanyo Chemical Industries) on the printed surface. Was applied by a silk printing method (coating amount: 20 g / m ² ) and cured by irradiating an electron beam to obtain a wear-resistant steel sheet usable for interior of a tunnel or the like.

Example 4 An electron beam curable resin was gravure coated on a printed steel plate (coating amount: 20 g / m ² ), and the resin beads used in Example 1 were sprayed on the coated surface by an air spray method. After being applied and attached, it was irradiated with an electron beam and cured to obtain a decorative material. The obtained decorative material had a matte surface. .

Example 5 A solid printing layer using HAT ink (manufactured by Inktec) and a picture printing layer using HA ink (manufactured by Inktec) were provided on the surface of thin paper (manufactured by Sanko: FIX-30). A two-pack reaction type DA using isocyanate
A composition in which 20% by weight of the same resin beads (average particle size: 15 μm) as in Example 1 was dispersed in an ISEC ink was applied by a gravure method (application amount: 12 g / m), cured at 70 ° C. for 72 hours, and cured. Then, a cosmetic material was obtained.

Comparative Example 1 A picture layer was formed by gravure printing on a surface of a polyvinyl chloride resin having a thickness of 0.1 mm using Chemical X (manufactured by Showa Ink).
UV curable resin (manufactured by Inktec) from above the pattern layer
Was applied with a composition in which about 20% by weight of silica having an average particle size of 20 μm was dispersed (application amount: 15 g / m ² ), and cured by irradiation with ultraviolet rays to obtain a decorative sheet. Table 1 shows the results of a test conducted in the same manner as in Example 2 for the abrasion resistance and scratch resistance of the obtained decorative sheet.

[0040]

[Table 1] [Scratch resistance test method]-Hoffman scratch tester (BYK Garder
Inc. 25g from 25g
The test was performed up to 500 g in steps, and the load immediately before the load at which the print layer was shaved was determined as the end point.

[0041]

As described above, the decorative material of the present invention uses the resin beads containing an anti-wear agent for the top coat layer, and therefore, compared with the conventional top coat layer directly added with an inorganic filler such as alumina. A cosmetic material having a small load on the apparatus during coating and having good wear resistance can be obtained. Also,
The resin beads containing the anti-wear agent have better conformity to the resin in the top coat layer than the inorganic filler, and the resin beads of the coating composition have much lower sedimentation properties than the inorganic filler. As a result, there is no possibility that the composition in the top coat layer coating material changes during coating and the quality becomes unstable,
Since the coating composition is uniform, it is easy to control the quality of the top coat layer.

The wear-resistant resin beads can have any desired abrasion resistance by changing the content of the lubricant. Therefore, conventionally, the wear resistance was controlled by changing the addition amount of the inorganic filler in the composition of the top coat layer or by changing the thickness of the top coat layer by a complicated operation. Abrasion resistance can be changed with the resin bead content of the top coat layer and the thickness of the top coat layer kept constant, and it is easy to manufacture decorative materials having various abrasion resistances depending on the application. it can.

The resin beads containing an anti-wear agent used for the top coat layer have an effect of improving abrasion resistance without increasing the hardness of the coating film when added to the resin coating film, as compared with an alumina filler or the like. . Therefore, a decorative sheet or the like having excellent workability can be easily obtained. Also, since the resin beads containing the anti-wear agent have protrusions of the anti-wear agent on the surface and are firmly held against the coating film, the abrasion-resistant resin beads are compared with the case where spherical alumina particles are directly added to the top coat layer. The content of the agent can be reduced.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of an essential part showing an example of a decorative material of the present invention.

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

FIG. 3 is a cross-sectional view showing one example of resin beads containing an anti-wear agent.

FIG. 4 is a cross-sectional view showing another example of the resin beads containing an anti-wear agent.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cosmetic material 2 Base material 3 Top coat layer 5 Resin beads containing an anti-wear agent

Claims (3)

[Claims] 1. A decorative material provided with a wear-resistant top coat layer on the surface side of a substrate, wherein the top coat layer is made of resin beads containing an anti-wear agent. 2. A method according to claim 1, wherein spherical alumina is used as an anti-wear agent for the anti-wear resin beads, and said resin beads have an average particle size of 10 to 1
The decorative material according to claim 1, which has a thickness of 00 µm. 3. The decorative material according to claim 1, wherein the resin of the resin beads containing an anti-wear agent is an acrylic resin.