JPH09314793A - Makeup sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a decorative sheet with high surface physical properties and design properties without affecting working environment adversely during the manufacture of the decorative sheet by laminating a surface protecting layer consisting of a reactive hot melt composition on a base material. SOLUTION: A surface protecting layer comprising a reactive hot melt composition is laminated on a base material and is thermally method, and further, the applied coating film is cured by a chemical reaction. The base material is such papers as tissue and titanium paper, or a polyolefin resin. In addition, the reactive holt met composition is such as containing a polyol, polyisocyanate or thermoplastic resin. The preferable polyol to be used is a polyester polyol or epoxy polyol. The method for forming a surface protecting layer by lamination uses an application device and a film forming device such as a gravure roll, a transfer roll, a doctor knife coater or a die method.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet for a building material, which is provided for the purpose of imparting a design and protecting the surface of furniture, wall surfaces, floor surfaces and the like.

[0002]

2. Description of the Related Art Conventionally, various compositions have been used as a surface protective layer of a decorative sheet for building materials. For example, coating composition in which the composition of the surface protective layer is dissolved in a solvent, that is, when formed by coating a solvent-based coating on a substrate, there is an advantage of excellent coating suitability, the solvent in the coating after coating There is a drawback that a step of removing is required. In particular, in the case of water-based paint, the storage stability of the paint is poor, and the water resistance and heat resistance of the coating film are poor. Further, the organic solvent paint has a problem in safety of working environment.

On the other hand, in the case of using a solventless paint which does not use a solvent, such as a paint containing an ionizing radiation curable resin or a hot melt resin as a component, the problem of skin irritation of the paint itself and the odor of a monomer is caused. There is a problem of deterioration of the substrate due to irradiation with ionizing radiation. In addition, the hot-melt type resin has the advantage that a coating film can be formed only by heating and melting and applying it, and a drying device is not necessary, but the formed coating film softens at high temperature and has chemical resistance. It has inferior drawbacks.

[0004]

The problem to be solved by the present invention is to solve the drawbacks described in the prior art of the present invention and to have good workability such as not adversely affecting the work environment during manufacturing. The present invention provides a decorative sheet having excellent surface properties and design.

[0005]

In order to solve the above-mentioned problems, the inventors of the present invention laminated a surface protective layer made of a reactive hot melt composition on a substrate, and heat-melted it. The present inventors have found a decorative sheet that is excellent in workability during production, surface protection, and designability by the reaction curing of the applied coating film. Further, the present invention has been completed by finding a decorative sheet having a three-dimensional design property by forming a concave pattern in the surface protection property and further forming a colored layer in the concave part.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The substrate of the present invention includes paper such as thin paper and titanium paper, plastic film or sheet such as polyolefin resin, polyester resin, vinyl resin, wood-based, ceramic-based, metal-based It is also possible to use the above-mentioned plate and a composite base material obtained by laminating two or more of the above-mentioned various base materials by a known means such as an adhesive or heat fusion. Further, a colorant, a filler, or the like may be dispersed in the plastic film or sheet to form a base material having colorability and hiding power.

As the above-mentioned polyolefin resin,
Polyethylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, polypropylene, propylene / butene-1 copolymer, polybutene-1, butene-1.
Propylene / ethylene / terpolymer, butene-1, hexene-1, octene-1, terpolymer, polymethylpentene, or olefin elastomers described in JP-A-6-16832 are used. To be done. Thickness is 5
Either a stretched sheet or an unstretched sheet can be used with a thickness of about 0 to 500 μm, but the unstretched sheet is better in terms of moldability such as V-cut processing.

Examples of the colorant (pigment) include inorganic pigments such as titanium white, zinc white, petal, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, carbon black, isoindolinone, Hansa Yellow A, quinacridone, Permanent red 4R, phthalocyanine blue, induslenbly RS, aniline black and other organic pigments (or dyes), aluminum, brass and other metal pigments, titanium dioxide coated mica, pearls made of foil powder such as basic lead carbonate Examples include luster (pearl) pigments.

As the filler, powders of calcium carbonate, barium sulfate, clay, talc and the like are used. Add an appropriate amount as needed.

The reactive hot melt composition of the present invention has a viscosity capable of forming a coating film by heating and melting, and has a surface physical property such as coating film hardness and chemical resistance, which is cured after the coating film is formed. Can be used. For example, a composition in which a hot-melt resin is mixed with a curable resin can be used.

As the reactive hot melt composition of the present invention, a composition containing a polyol, a polyisocyanate and a thermoplastic resin can be used.

In the present invention, the preferred polyol is
Polyester polyol, polyether polyol, acrylic polyol, epoxy polyol, polyethylene glycol, polypropylene glycol and the like can be used.

Examples of the polyisocyanate of the present invention include 2,4 tolylene diisocyanate, 2,6 tolylene diisocyanate and diphenylmethane-4,4'-.
Diisocyanate, polyphenylmethane polyisocyanate called crude MDI, xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4 '
An aliphatic, alicyclic or aromatic di- or triisocyanate compound such as diisocyanate or triphenylmethane triisocyanate, or a polyisocyanate compound and a low molecular weight glycol or triol, for example, dipropylene glycol, 1,6-hexanediol, Isocyanate-terminated low molecular weight adducts obtained by reacting with 1,2,6-hexanetriol or trimethylolpropane can be used.

The molar equivalent ratio A of NCO groups to OH groups in the composition containing the polyol and polyisocyanate is 1 <A ≦ 10, preferably 1.2 ≦ A ≦ 5.0.
It is what becomes.

The reaction between the above-mentioned polyol and polyisocyanate comprises a urethane prepolymer having a terminal isocyanate group obtained by reacting the polyol with an excess of polyisocyanate, and the prepolymer reacts with moisture to give a three-dimensional crosslinked structure. Take In this, first, the NCO group reacts with water to bond with urea to extend the chain, and the active hydrogen of the urethane bond of the prepolymer component and the NCO group react with each other to form a three-dimensional crosslinked structure.

The above polyester polyol is obtained by reacting a polyol with a polyfunctional carboxylic acid compound.

The above-mentioned polyol has a molecular weight of 50.
The thing of 0-10000 can be used. Basically, polyols include monomeric diols, triols, and the like, as well as polymeric diols, triols that include chains of alkylene repeating units that contribute primarily to their molecular weight. Typical polymer polyols consist essentially of either linear or branched chains of the above repeating units terminated with hydroxy groups, preferably monomeric polyols having 2, 3, 4 or more hydroxy groups including. For example, ethylene glycol, propylene glycol, glycerin, trimethylolpropane, 1,2,6-hexanetriol,
Includes butenediol, sucrose, glucose, sorbitol, pentaerythritol, dipentaerythritol, mannitol, triethanolamine, n-methyldimethanolamine, and cyclic aromatic and aliphatic and triols.

Examples of the above polyfunctional carboxylic acid include 1,6-hexanedioic acid, dodecanedioic acid, azelaic acid, sebacic acid, 1,18-octadecanedioic acid, phthalic acid, phthalic anhydride, and amber. Acids, higher alkyl or alkenyl substituted succinic anhydrides such as dodecenyl succinic anhydride, octadecyl succinic anhydride and others, dimer acid made from maleic acid, fumaric acid, mono-, di- or tri-substituted fatty acids, acid wax, acid anhydride graft wax , Or other suitable polycarboxylic acid reactive compounds can be used.

The thermoplastic resin contained in the reactive hot melt composition of the present invention includes ethylene-vinyl acetate copolymer, low molecular weight polyethylene, modified olefin, atactic polypropylene, linear polyester resin, ethylene-acrylic acid copolymer. Examples thereof include polymers. Among them, the ethylene-vinyl acetate copolymer is preferably a copolymer containing a copolymer having a melt index of about 0.2 to 1000 because it has good compatibility with the urethane prepolymer and imparts hot melt characteristics. .

Further, the reactive hot melt composition of the present invention includes a filler, the above-mentioned pigment, dye, plasticizer, the above-mentioned filler, a viscosity modifier, a leveling agent, an ultraviolet absorber,
A light stabilizer, a matting agent, an antiblocking agent, and other usual additives can be used.

As the filler, those in the form of particles or fibers having a composition such as ceramic, glass, silica, quartz, mica, treated clay, titanium dioxide, graphite, carbon black, glass fiber, asbestos fiber, metal powder and the like are used.

[Ultraviolet Absorber / Light Stabilizer] In order to impart better weather resistance (light resistance) to the resin, an ultraviolet absorber and / or a light stabilizer can be added. The amount of both the absorber and the light stabilizer is usually about 0.5 to 10% by weight, but it is generally preferable to use the ultraviolet absorber and the light stabilizer together. As the ultraviolet absorber, an organic substance such as benzotriazole, benzophenone, and salicylate, or an inorganic substance such as zinc oxide, cerium oxide, and titanium oxide in the form of fine particles having a diameter of 0.2 μm or less can be used. As a light stabilizer, bis- (2,2,6,
Radical scavengers such as hindered amine radical scavengers such as 6-tetramethyl-4-piperidinyl) sebacate and piperidine radical scavengers can be used.

As the method for forming the surface protective layer by laminating the reactive hot melt composition of the present invention on a substrate, a usual coating device and film such as a gravure roll, a transfer roll, a doctor knife coater and a die system are used. A forming device can be used.

The coating thickness of the surface protective layer is 10 to 1
00 μm, preferably 40 to 80 μm is used.

A pattern layer may be provided on the substrate of the present invention before forming the surface protective layer. In this case, the pattern can be printed by gravure printing, intaglio printing, offset printing, letterpress printing. Flexographic printing, silk screen printing,
Examples include electrostatic printing and inkjet printing. Alternatively, a pattern may be once formed on a release sheet, a transfer sheet may be prepared, and the transfer sheet may be formed by transfer printing using the obtained transfer sheet.

Various kinds of ink can be used as the ink for the picture layer, and the composition comprising the above-mentioned colorant (pigment), extender pigment, binder, curing agent, additive, solvent and the like is used. can do. The binder is not particularly limited, and a usual one such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation curable resin can be used.

For example, as an ink (or) paint when the base material is a polyolefin resin, as a binder, a chlorinated polyolefin such as chlorinated polyethylene or chlorinated polypropylene, polyester, polyurethane,
Acrylic, vinyl acetate, vinyl chloride / vinyl acetate copolymer, cellulosic resin, etc. are used, and one kind or a mixture of two or more kinds is used. A material obtained by adding known pigments as described above to this is used.

When printing directly on the base material polyolefin resin, chlorinated polyolefin, polyurethane or the like is preferable as a binder in terms of adhesiveness,
If an easily-adhesive primer is appropriately selected to form a layer, sufficient adhesion can be provided even if another binder is used.

Here, as the picture pattern, a natural pattern such as wood grain, stone grain, cloth grain, leather grain, etc., characters, symbols, drawings with line drawing or solid printing, various abstract patterns, etc. are appropriately selected. . The pattern is provided on the front surface, the back surface, both the front and back surfaces of the substrate, or between the layers.

Further, in order to form a concave pattern on the front side of the surface protective layer of the present invention, there is an embossing method by heating and pressing as a method, and this embossing method uses an embossing roll-shaped sheet having a convex pattern. The method of using the mold is used.

The concave pattern is not particularly limited,
For example, wood grain, stone grain, grain, cloth, satin, hairline, woven fabric, leather, paper surface, patterns, letters, symbols, various abstract patterns, line patterns, various matte surfaces, etc. .

As a method for producing a decorative sheet having a concave pattern by laminating a surface protective layer made of a reactive hot melt composition on the substrate of the present invention, for example, a thermoplastic sheet as the substrate is used. A printed layer is formed on the coated layer, and a reactive hot-melt composition heated and melted thereon is formed into a coating film by a hot-melt coater, and at the same time, an embossing roll is brought into contact with the coating film and peeled after being pressurized, A method of curing the coating film is used.

Alternatively, a hot-melted reactive hot melt composition is applied onto a printed substrate by using a shaping sheet on which a convex pattern corresponding to a concave pattern is previously formed, and at the same time, the above-mentioned shaping sheet. Is used to polymerize and pressurize, the release sheet is peeled off, and then the coating film is cured.

Furthermore, a wiping method (Japanese Examined Patent Publication No. 58-14) is used for the concave portion of the concave pattern provided by the embossing method.
The colored layer can be formed by the method described in Japanese Patent Publication No. 312). As the wiping method, by applying a colorant ink to the entire surface including the recessed portion by a doctor blade coating method or a knife coating method and removing the colorant ink from the surface other than the recessed portion, the colorant is applied to the recessed portion. A filling method can be used. The colorant ink for forming the colored layer, the organic pigment and the inorganic pigment described above,
A pigment containing a coloring pigment such as a bright pigment and a binder resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation curable resin can be used.

[0035]

EXAMPLES Next, examples of the decorative sheet according to the present invention will be specifically described.

(Example 1) A wood grain pattern was printed on a thin paper (made by Tenma Paper Co., Ltd.) having a basis weight of 30 g by three-color gravure printing with a urethane gravure ink (trade name UE manufactured by The Inktech Co., Ltd.).

Next, the following reactive hot melt composition was applied to the entire printing surface side and a silicon roll at 130 ° C.
While being heated, the solution was applied with a hot melt coater (Matsushita Industry Co., Ltd.). The film was cured at 20 ° C., 60% RH for 4 days to obtain a decorative sheet having a surface protective layer with a coating film thickness of 40 μm. Reactive hot melt composition Polyester polyol 30 parts by weight Polyisocyanate 60 parts by weight (NCO / OH molar equivalent ratio = 2) Ethylene-vinyl acetate copolymer 10 parts by weight

Example 2 A surface of a polyvinyl chloride film having a thickness of 200 μm (manufactured by Bando Kagaku) was coated with urethane-based gravure ink (Showa Ink, trade name AFS).
An abstract pattern was printed by color gravure printing.

Next, the following reactive hot melt composition was applied to the entire surface of the printing surface, and a silicon roll was placed at 130 ° C.
In the state of being heated to 100 ° C., it was applied with a hot melt coater (manufactured by Matsushita Industry Co., Ltd.) under the temperature condition of 100 ° C. to 120 ° C.
The film was cured at 20 ° C., 60% RH for 4 days to obtain a decorative sheet having a surface protective layer with a coating film thickness of 40 μm. Reactive hot melt composition Polyester polyol 20 parts by weight Polyisocyanate 80 parts by weight (NCO / OH molar equivalent ratio = 4)

[0040]

The present invention is carried out in the form described above, and has the following effects.

By using the reactive hot melt composition as the surface protective layer of the decorative sheet, a drying device is not required at the time of production, there is no cause of deteriorating the working environment such as solvent exhaust gas and the like, which is excellent in environmental aspects and is a coating film. It is possible to obtain a decorative sheet having excellent surface physical properties and design.

By forming a concave pattern on the surface protective layer and further forming a colored layer on the concave portion, a decorative sheet having a three-dimensional and deep design can be obtained.

Further, as the reactive hot melt composition,
By using a material containing a polyol, a polyisocyanate and a thermoplastic resin, it is possible to obtain a decorative sheet with excellent abrasion resistance of the surface protective layer.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Office reference number FI technical display location E04F 13/08 0231-2E E04F 13/08 A

Claims (4)

[Claims] 1. A decorative sheet comprising a base material and a surface protective layer made of a reactive hot melt composition laminated on the base material. 2. A decorative sheet, wherein the reactive hot melt composition according to claim 1 contains a polyol, a polyisocyanate and a thermoplastic resin. 3. A decorative sheet, characterized in that a concave pattern is formed on the front side of the surface protective layer according to claim 1. 4. A decorative sheet, wherein a colored layer is formed in the concave portion of the concave pattern according to claim 3.