JP2000351182A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in stain resistance and weatherability and having lasting antistatic effect. SOLUTION: A decorative sheet has layered constitution wherein a conductive layer 3 is interposed between a thermoplastic resin substrate layer 1 and a surface layer 2 comprising a thermoplastic fluoropolymer resin or the conductive layer 3 is interposed between the thermoplastic resin substrate layer 1 lined with a fibrous base material layer and the surface layer 2 comprising the thermoplastic fluoropolymer resin. Charge becomes hard to accumulate by the static electricity shielding effect developed by the conductive layer and the adhesion of dust can be suppressed. By providing the conductive layer between the substrate layer and the surface layer, the surface of the conductive layer is protected by a film and antistatic effect lasts for a long time.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet used for surface decoration of a wall or the like in a building, and more particularly to a decorative sheet improved in stain resistance by laminating a film.

[0002]

2. Description of the Related Art Conventionally, as this kind of decorative sheet,
A decorative sheet provided with stain resistance and weather resistance by laminating a fluororesin film on the surface has been proposed. For example, in the case of a wallpaper type, the surface of aluminum hydroxide powder mixed paper or flame retardant paper is coated with a PVC sol, and a pattern printed or the like is applied to a fluororesin film having good stain resistance, which is subjected to an easy adhesion treatment. Is known.

[0003]

However, the decorative sheet described above has a drawback that the fluororesin film to be laminated has a high volume resistivity and is easily charged, so that dust or the like in the air adheres and is easily stained. Therefore, antistatic treatment is also performed by kneading a surfactant into the fluororesin film.However, the antistatic effect of the surfactant is affected by the humidity in the atmosphere. There is a problem that the conductive effect is difficult to appear. Also, a surfactant is applied to the surface of the fluororesin film. However, in addition to the same problem as in the case of kneading, although the surfactant has an antistatic effect in the short term, the surfactant is not used. Since the bleeding occurs on the surface, there is a problem in that the bleeding is lost with time and the effect is reduced, and the effect does not last for a long time.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a decorative sheet which is excellent in stain resistance and weather resistance and has a sustained antistatic effect. Is to do.

[0005]

In order to solve the above problems, a first type of decorative sheet according to the present invention comprises a thermoplastic resin base layer, a carboxyl group and a quaternary ammonium base in the molecule. It has a layer structure in which a conductive layer formed by epoxy cross-linking of a cross-linkable copolymer having the same and a surface layer formed of a fluorine-based thermoplastic resin are laminated in this order.

A second type of decorative sheet according to the present invention comprises a fibrous base material layer, a thermoplastic resin base material layer, and a cross-linkable polymer having a carboxyl group and a quaternary ammonium group in the molecule. It has a layer configuration in which a conductive layer formed by crosslinking and a surface layer made of a fluorine-based thermoplastic resin are laminated in this order.

[0007]

FIG. 1 is a cross-sectional view for explaining a first type of decorative sheet according to the present invention. The first type of decorative sheet comprises a thermoplastic resin base material layer 1 and a fluorine-based material. It has a layer configuration in which a conductive layer 3 is interposed between surface layers 2 made of a thermoplastic resin.

FIG. 2 is a sectional view for explaining a second type of decorative sheet according to the present invention. The second type of decorative sheet is made of a thermoplastic resin base material lined with a fibrous base material layer 4. It has a layer configuration in which a conductive layer 3 is interposed between a layer 1 and a surface layer 2 made of a fluorine-based thermoplastic resin.

The thermoplastic resin base material layer has a thickness of 20 to 300.
It is a film having a thickness of about μm, and is made of polyethylene, polypropylene, polybutene, an ethylene-propylene-butene copolymer, a polyolefin resin such as an olefin-based thermoplastic elastomer, a poly (methyl) acrylate, a poly (meth) acrylate. Butyl, methyl (meth) acrylate-butyl (meth) acrylate copolymer, methyl (meth) acrylate-butyl (meth) acrylate-
Acrylic resins such as (meth) acrylic acid 2-hydroxyethyl copolymer and (meth) acrylic acid methyl-styrene copolymer (however, (meth) acryl means acrylic or methacrylic), polyethylene terephthalate, polybutylene terephthalate, etc. Examples include polyester resin, polyvinyl chloride, polystyrene, and ABS resin.

The resin constituting the conductive layer can be obtained by subjecting a crosslinkable copolymer having a carboxyl group and a quaternary ammonium base in the molecule to epoxy crosslinking using an epoxy ring-opening reaction catalyst.

Specific examples of such a monomer of the crosslinkable copolymer include (meth) acrylic acid, acrylyloxyethyl succinic acid, and -COOH (carboxyl group) -terminated monomers. Examples include phthalic acid and (meth) hexahydrophthalic acid. Examples of the monomer having a quaternary ammonium base include dimethylaminoethyl acrylate quaternary compounds (including anions such as chloride, sulfate, sulfonate, and alkyl sulfonate as counter ions)
Is mentioned. Further, the conductive layer is formed by two liquids or one liquid (moisture).
A surface layer via an adhesive layer made of a curable urethane resin,
Alternatively, in the case of laminating with a thermoplastic resin base material layer, it is preferable to copolymerize a monomer having a hydroxyl group (-OH) together. Examples of the monomer having a hydroxyl group include bifunctional monomer glycerin diglycidyl ether. Epoxy derivatives such as trimethylolpropane triglycidyl ether of trifunctional monomers and ethyleneimine derivatives such as trimethylolpropane triaziridinyl ether are exemplified. In addition, examples of the polymerizable monomer include (meth) alkyl acrylate, styrene, vinyl acetate, vinyl halide, and vinyl derivatives such as olefin.

2-methylimidazole, 2-methylimidazole, 2-methylimidazole,
Epoxy ring-opening reaction catalysts of imidazole derivatives such as -ethyl and 4-methylimidazole and other amines can be used as additives. The composition ratio of each monomer can be changed within a wide range. Among them, a monomer having a quaternary ammonium base is 15 to 40 mol based on all monomers of the copolymer.
The composition in the range of 1% is preferable, and the amount of the monomer having a terminal -COOH group is preferably 3 to 13 mol% based on all monomers. Other constituent monomers are 63.5 to 79.5 mol.
% Of the copolymer. When the monomer having a quaternary ammonium base is 15 mol% or less, the effect of preventing electrostatic induction is small, and when it exceeds 40 mol%, the hydrophilicity of the monomer becomes too high. Further, the amount of the monomer having a hydroxy group is preferably 0.5 to 1.5 mol% based on all monomers.

The conductive layer is formed by applying the above resin to a thermoplastic resin base material layer or a surface layer using a roll coater, a gravure coater or the like. The coating thickness is about 1 to 10 μm. The surface layer and the base layer are thermocompression-bonded via the coated conductive layer. Alternatively, the surface layer and the thermoplastic resin base material layer are dry-laminated via an adhesive layer such as a two-component curable urethane resin. Alternatively, polyvinyl chloride, vinyl chloride
The surface layer and the thermoplastic resin base material layer are thermocompression-bonded via a primer layer such as a vinyl acetate copolymer or an ethylene-vinyl acetate copolymer.

The electrostatic shielding effect of the conductive layer is a function completely different from the conventional charge dissipation phenomenon due to the low surface resistance of the antistatic agent, and is a function of preventing static induction (dielectric). That is, the conductive layer in the decorative sheet of the present invention has a high dielectric constant and conductivity, and is dielectrically polarized by the charge on the surface of the decorative sheet. Since the counter charge of the dielectrically polarized conductive layer is neutralized between the layers, the polarized charge disappears in a very short relaxation time. In addition, the lines of electric force due to the charges of the conductive layer are always inward,
There are no lines of electric force outside the decorative sheet surface, and no electrostatic induction occurs in the space surrounding the decorative sheet surface. Therefore, no dielectric charges are generated on the surrounding minute dust, and no dust adheres to the surface of the decorative sheet. Thus, this effect is exhibited as an antistatic effect of the decorative sheet. As a result, even if the conductive layer is inserted between the two resin layers, which are insulators, instead of the surface, the antistatic effect can be obtained.

The surface layer made of a fluorine-based thermoplastic resin is
It is a film having a thickness of about 5 to 50 μm, and is made of polytetrafluoroethylene, polyvinylidene fluoride, polyvinyl fluoride, ethylene-tetrafluoroethylene copolymer, ethylene-chlorotrifluoroethylene copolymer, or the like. Is mentioned. If necessary, known colorants such as dyes and pigments, and additives such as ultraviolet absorbers and antibacterial agents may be added to the surface layer.

As the fibrous base material layer, paper such as backing paper for wallpaper, high quality paper, kraft paper, Japanese paper, linter paper, or a woven or non-woven fabric made of fibers such as vinylon, polyester resin, glass, and asbestos is used. And rice basis weight 50-120g /
m ² . It is laminated on the back surface of the thermoplastic resin base material layer to reinforce the mechanical strength or to improve the adhesion to the adherend.

The picture layer is formed by a known printing method (gravure, offset, silk screen, etc.) as necessary. Normally, as shown in FIG. 3, it is formed on the surface side of the thermoplastic resin base material layer 1 with the printing ink 5. The patterns include wood grain, stone grain, cloth grain, geometric pattern, sand grain, and solid surface.

If necessary, as shown in FIG. 4, an uneven pattern 6 may be formed on the front side of the surface layer 2 by known embossing, hairline processing, or the like. Examples of the shape of the recess include a grain conduit, a grain, and a hairline.

The decorative sheet of the present invention can be used as a surface decorative material for building interiors such as walls, floors and ceilings, window frames, doors, etc.
It is used as a surface decorative material for construction members such as skirting boards, and a surface decorative material for home electric appliances.

[0020]

EXAMPLES (Example 1) (1) A fibrous base material layer having a thickness of 150 g as a thermoplastic resin base material layer on a 90 g / m ² paper backing paper for wallpaper.
Prepare a laminate consisting of a μm acrylic resin layer,
Using an ink obtained by adding a pigment composed of titanium white, carbon black, quinacridone, isoindolinone and phthalocyanine blue to a binder of a 1: 1 weight ratio mixture of an acrylic resin and a vinyl chloride-vinyl acetate copolymer. Gravure printing was used to print the wood pattern of cedar planks. Then, a PVC (polyvinyl chloride) -based primer (“KV-631” manufactured by Konishi) was solid-printed in-line by a gravure method so as to be 5 g / m ² .

(2) 1 g of the following adjustment liquid 1 was applied to the corona-discharge treated surface of a surface layer made of a 12 μm-thick ETFE (ethylene-tetrafluoroethylene copolymer) film which had been previously subjected to a corona discharge treatment on one side. / M ² by solid printing (gravure coating) by a gravure method to form a conductive layer.

<Preparation liquid 1> MMA / EA / AA / DMA
The monomer of Q was copolymerized at a weight ratio of 50/10/5/35 in a mixed solution of isopropanol / water (mixing ratio 1/1) to obtain a transparent solution having a solid content of 30%. here,
MMA: methyl methacrylate, EA: ethyl acrylate, AA: acrylic acid, DMAQ: dimethylaminoethyl methacrylate quaternary chloride. Further, 10% of an epoxy monomer is added to this solution as a crosslinking agent based on the solid content of the solution, and 2-methylimidazole is added as a catalyst at 5% of the amount of the epoxy monomer. Is adjusted.

(3) Using a vertical embossing machine, the films produced in (1) and (2) are thermocompression-bonded and, at the same time, the embossed pattern of the wood channel groove is embossed on the surface of the surface layer. A sheet was prepared.

Example 2 (1) 20 μm-thick ET subjected to corona discharge treatment on both sides
The above adjustment solution 1 was solid-printed on the corona discharge-treated surface of the surface layer made of an FE (ethylene-tetrafluoroethylene copolymer) film by a gravure method so as to be 0.5 g / m ² . (2) The film prepared in (1) and an inorganic first-grade wallpaper base material (“MIG coloring” manufactured by Nippon Wavelock) are bonded to a two-component curable urethane resin adhesive (“UB-5” manufactured by Seiko Chemical Co., Ltd.).
20 "). Thereby, a decorative sheet as shown in FIG. 3 was obtained.

Comparative Example 1 A decorative sheet was prepared in the same manner as in Example 1 except that the conductive layer was omitted.

Comparative Example 2 The procedure of Comparative Example 1 was repeated except that the surface layer was a 12 μm-thick ETFE (ethylene-tetrafluoroethylene copolymer) film in which 3% of an anionic surfactant was kneaded. A decorative sheet was produced.

The decorative sheets obtained in Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to an ash adhesion test. In particular,
A 10-cm square test specimen was rubbed 230 times with a cloth, approached to tobacco ash, and observed for ash adhesion at a height of 1 mm to the ash. As a result, ash adhered to the decorative sheets of Comparative Examples 1 and 2, but no ash was observed to the decorative sheets of Examples 1 and 2.

[0028]

As described above, the decorative sheet of the present invention makes it difficult for electric charges to accumulate due to the electrostatic shielding effect, and can suppress the adhesion of dust. Further, by providing the conductive layer between the base layer and the surface layer, the surface of the conductive layer is protected by the film, and the antistatic effect is maintained for a long time.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view illustrating a first type of decorative sheet according to the present invention.

FIG. 2 is a sectional view illustrating a second type of decorative sheet according to the present invention.

FIG. 3 is a cross-sectional view showing an example in which a pattern layer is provided on the decorative sheet of FIG.

4 is a cross-sectional view showing an example in which a concave portion is provided in the decorative sheet of FIG. 1 by embossing or hairline processing.

FIG. 5 is a cross-sectional view for explaining the decorative sheet produced in Example 1.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Thermoplastic resin base material layer 2 Surface layer 3 Conductive layer 4 Fibrous base material 5 Printing ink 6 Uneven pattern

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AK01A AK01B AK01J AK17C AK25A AK25B AK25J AL01B BA03 BA04 BA07 BA10A BA10C BA10D BA13 CA02B CC00 DG10D DG12D DG15D EJ55C HB00 HB01 JB16JJL

Claims (2)

[Claims] 1. A thermoplastic resin base material layer, a conductive layer formed by epoxy-crosslinking a crosslinkable copolymer having a carboxyl group and a quaternary ammonium base in a molecule, and a surface layer formed of a fluorine-based thermoplastic resin. A decorative sheet having a layer structure laminated in this order. 2. A fibrous base material layer, a thermoplastic resin base material layer, a conductive layer formed by epoxy-crosslinking a crosslinkable polymer having a carboxyl group and a quaternary ammonium group in a molecule, and a fluorine-based thermoplastic resin. A decorative sheet, characterized in that the surface layer comprises a layer structure laminated in this order.