JPH08216347A - Antibacterial decorative sheet and manufacture thereof - Google Patents

Abstract

PURPOSE: To maintain soft touch and stable antibacterial effect by applying a thermoplastic elastomer having a silver zeolite powder of an antibacterial agent to a surface of a decorative paper or fusing a film of the elastomer to it. CONSTITUTION: A thermoplastic resin elastomer having a silver zeolite powder as an antibacterial agent is melted with heat and applied to a surface of a decorative paper, or a film of the thermoplastic resin elastomer is fused with heat to the surface of the decorative paper so as to form a surface of a decorative sheet. For the antibacterial agent, 0.05-10 pts.wt. of the silver zeolite having an average grain diameter of 40μm or less and a silver content of 0.1-15wt.% is added in 100 pts.wt. of the thermoplastic resin elastomer, so that preferable antibacterial property can be obtained. As the thermoplastic resin elastomer which is forming the decorative sheet is of a thermoplastic polyester resin and the thermoplastic resin elastomer has a thickness of 20-200μm, antibacterial property, excellent appearance and elasticity, other physical property and workability can be obtained.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an antibacterial decorative sheet used as a surface material for interior building materials, furniture, furniture, etc., and a method for producing the same. The antibacterial decorative sheet of the present invention has a relatively wide range of uses as an antibacterial cosmetic material because it is relatively thin, tough and flexible, has a soft surface texture and soft touch, and has excellent physical properties such as abrasion resistance. Suitable for

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet having flexibility, a pattern is printed on an opaque vinyl chloride sheet in which a pigment is kneaded, and a transparent vinyl chloride film is further heat-bonded thereon, if necessary. A so-called loose vinyl chloride decorative sheet obtained by pressing the surface with a roll having irregularities and embossing, or a thermoplastic resin decorative sheet using various thermoplastic films instead of the vinyl chloride resin.

A thin-leaf decorative sheet obtained by applying colored solid printing to thin paper having a basis weight of about 30 g / m ² , printing a pattern on the thin solid paper, and finishing coating with aminoalkyd resin paint or polyurethane resin paint.

Decorative paper having a basis weight of 55 to 200 g / m ² impregnated with a thermosetting resin such as melamine resin, diallyl phthalate resin or polyester resin is used as a base material such as kraft paper impregnated with the same thermosetting resin. There was a thermosetting resin decorative sheet having a thickness of 0.3 to 0.7 mm obtained by stacking on a sheet and thermoforming using a multi-stage hot pressing machine or a continuous molding press machine.

As a method for producing an antibacterial decorative board, Japanese Patent Laid-Open No.
As described in No. 198607, an antibacterial agent is added to a paint or a solution such as a melamine resin and mixed, and then applied to a plate material or a decorative paper-coated plate material, or after impregnating and drying the decorative paper, the base It was intended to produce a decorative plate having antibacterial properties by stacking it on a material and heating and pressing.

[0006]

However, although each of the above decorative sheets has unique characteristics depending on the material and manufacturing method, it does not necessarily have general versatility in terms of appearance, physical properties, processability, and the like. In particular, it was not satisfactory in terms of soft touch with elasticity.

Further, these decorative sheets do not have antibacterial properties and are not effective for the recent problem of preventing hospital infection due to drug-resistant Staphylococcus aureus (MRSA).

In the method of adding the antibacterial agent to the paint or the impregnating resin liquid and mixing them, the added antibacterial agent precipitates from the mixing to the coating or the impregnation, so that the antibacterial agent is uniformly mixed. It was difficult to maintain the liquid composition, and as a result, stable antibacterial properties could not be obtained. In addition, it was not possible to obtain a soft tactile sensation even with these decorative boards.

[0009]

According to the present invention, an elastomer made of a thermoplastic resin containing an antibacterial agent made of silver zeolite is heat-melted and applied on the surface of a decorative paper, or a film of the elastomer is heated. While being fused,
If necessary, isocyanate is impregnated from the back side to strengthen the space between the sheets, resulting in a soft touch like suede due to the elasticity of the resin layer on the front side, and less stretching, scratch resistance, abrasion resistance, weather resistance It has excellent properties, has good affinity with adhesives, can be bent to complicated shapes such as wrapping and acute angles, and does not cause compositional variations due to precipitation of antibacterial agents in the manufacturing process.
The purpose is to obtain an antibacterial decorative sheet having a stable antibacterial effect.

According to the present invention, a thermoplastic resin elastomer containing silver zeolite powder as an antibacterial agent is heat-melted and applied on the surface of a decorative paper, or a film of the thermoplastic resin elastomer is heat-sealed. An antibacterial decorative sheet having a surface of a decorative sheet and a method for producing the same, wherein the antibacterial agent has an average particle size of 40 μm or less and a silver content of 0.1 to 15% by weight. Is a thermoplastic resin elastomer 1
A preferable antibacterial property is obtained by containing 0.05 to 10 parts by weight with respect to 00 parts by weight. In particular, the antibacterial agent made of silver zeolite powder contained in the thermoplastic resin elastomer forming the surface of the decorative sheet has some or all of the ion-exchangeable ions in the zeolite replaced with silver ions and ammonium ions. Antibacterial effect is enhanced, and the thermoplastic resin elastomer forming the surface of the decorative sheet is a thermoplastic polyester resin, and the thickness of the thermoplastic resin elastomer is 20 to 200 μm In addition, it has excellent appearance, elasticity, other physical properties, and processability.

In the present invention, the basis weight is 20 to 200 g / m ^2.
Decorative paper is used, and if necessary, such as appearance and design,
Those with various patterns by coloring or printing are used. In particular, a decorative paper for a melamine decorative board, a diallyl phthalate resin decorative board, a polyester decorative board, and excellent designability can be obtained by using a general-purpose decorative paper mixed with titanium oxide and other color pigments.

The thermoplastic resin elastomer forming a decorative layer on the surface of the decorative paper is composed of a flexible component having rubber elasticity and a hard component for preventing plastic deformation, and the molecular constraining component which is the hard component is plasticized by heating. Also, when cooled, it rehardens. Examples of the thermoplastic resin elastomer used in the present invention include polyester-based, polyurethane-based, polyolefin-based, polystyrene-based, polyamide-based, etc., but especially from the viewpoint of weather resistance, flex resistance, abrasion resistance, heat resistance, etc. Thermoplastic polyester resin elastomers are suitable.

In the present invention, the silver zeolite-based antibacterial agent added to and contained in the thermoplastic resin elastomer is a powder having an average particle size of 40 μm or less. The silver zeolite-based antibacterial agent is a zeolite containing silver ions and ammonium ions. It is a compound in which silver ions are stabilized inside the three-dimensional skeleton structure of the zeolite by being bound to, and the antibacterial property is imparted without losing the original properties of the zeolite. By binding ammonium ion, it is possible to prevent discoloration of silver zeolite (Jikkou 6-068844). The content of silver with respect to zeolite is 0.1
Good antibacterial properties can be obtained at -15% by weight. Further, it is desirable that the ammonium ion is contained in the range of 0.5 to 3.0% by weight with respect to the silver zeolite. The silver zeolite-based antibacterial agent is a white powder, and when it is used as a fine powder having an average particle size of 40 μm or less, preferably 0.6 to 10 μm, the influence on the color tone is small, and the above-mentioned addition amount causes a trouble in appearance. No change in color tone is seen.

Further, the content of the zeolite powder with respect to the thermoplastic resin elastomer is preferably 0.05 to 10% by weight, and when the content is 0.05% or less, the antibacterial property is not sufficient. Further, if it is 10% or more, it is not advantageous in terms of price and the transparency of the coating film is lowered.

The silver zeolite antibacterial agent and the thermoplastic resin elastomer are mixed by mixing the silver zeolite antibacterial agent and the thermoplastic resin elastomer particles in a desired ratio and then heating or powdering the antibacterial agent. Is kneaded with a small amount of elastomer by heating to previously prepare a so-called master batch which is formed into particles or pellets, and this master batch is blended with the raw material elastomer.

A method of forming a decorative layer of a thermoplastic resin elastomer on the surface of a decorative paper is as follows:
A die is installed, the thermoplastic resin elastomer is extruded in a molten state into a film, cast on the surface of the decorative paper, cooled by pressure, rolled into a film with a calendar and pressed onto the surface of the decorative paper, or melted. There is a method of roll coating in the state. It is also possible to make a film in advance and stack it on the decorative paper surface with a heating roll, heating belt or the like to fuse them. The layer thickness of the thermoplastic resin elastomer is preferably 20 to 2
With a thickness of 00 μm, the appearance and physical properties required for a decorative sheet can be economically obtained. When the thickness of the coating film is 20 μm or less, a scaly appearance is likely to occur and it is difficult to obtain sufficient surface properties such as abrasion resistance.

Prior to forming the surface layer of the elastomer made of a thermoplastic resin on the decorative paper, it is heated and dried in advance by using a dryer such as a heating drum to remove water, thereby preventing the generation of bubbles and improving the adhesiveness. Therefore, it becomes possible to form a coating film uniformly.

After forming the coating film, if necessary, the coating film surface can be pressed with an embossing roll having irregularities of a desired design, the irregularities can be transfer-shaped, and embossing can be performed. By this embossing, the soft and soft touch like suede is emphasized, a unique texture is obtained, and scratch resistance and the like are improved.

The decorative paper used in the present invention is 20 to 200.
It is g / m ² , and by impregnating it with a polyisocyanate solution and drying it as necessary, the paper quality is strengthened and peeling between papers can be prevented.

The coating treatment with the polyisocyanate solution is carried out before or after the step of forming the thermoplastic elastomer coating film on the surface of the decorative paper.

[0021]

EXAMPLES Parts and% shown below represent parts by weight and% by weight, respectively. Example 1 As the thermoplastic resin elastomer, ELA4300 (manufactured by Teijin), which is a thermoplastic polyester resin elastomer in which the soft component is polytetramethylene ether glycol and the hard component is polybutylene naphthalate is used.

The antibacterial agent composed of silver zeolite is A
-Type zeolite obtained by ion-exchange of silver ion and ammonium ion, wherein the silver ion in the silver zeolite is 2.5% and the ammonium ion is 1.5%.
% Silver zeolite powder having an average particle diameter of 0.8 μm, and zinc oxide-coated silver zeolite powder coated with zinc oxide in an amount of 20% based on the silver zeolite powder.

The antibacterial agent may be added to the thermoplastic resin elastomer by adding 0.2 part of the zinc oxide-coated silver zeolite powder to 100 parts of the thermoplastic polyester resin elastomer and heating to 100 ° C. with a ribbon blender. However, the antibacterial elastomer was obtained by stirring and mixing so as to uniformly disperse.

A decorative paper obtained by gravure-printing a wood grain pattern on titanium paper having a basis weight of 80 g / m ² is dried with a heating drum, and the antibacterial elastomer is thickened with an extruder having a T-die on the surface of the decorative paper. It was extruded at 200 ° C. so as to have a thickness of 80 μm, cast and applied, and the applied surface was brought into contact with a cooling drum having a matte surface to cool it.

Next, using a roll coater, as a polyisocyanate solution, Coronate HX (made by Nippon Polyurethane), which is a trimer of hexamethylated isocyanate
Was dissolved in toluene to a concentration of 20%, applied from the back side of the decorative paper to impregnate it, then passed through a dryer and dried with hot air at 120 ° C for 1 minute, suitable for curved surface attachment processing. I got a makeup sheet. The amount of coronate HX attached to the decorative paper of this decorative sheet was 18% in terms of nonvolatile content. The decorative sheet thus obtained had a soft hand and was excellent in design.

Comparative Example 1 A decorative sheet was obtained in the same manner as in Example 1 except that the zinc oxide-coated silver zeolite powder, which was an antibacterial agent, was not added to the thermoplastic polyester resin elastomer. Table 1 shows the results of the antibacterial test of Example 1 and Comparative Example 1.

Test Method A test piece of 50 mm × 50 mm was cut from each sample, washed with ethanol, and then Staphyococcus, aureus ATCC, 6538P was applied to the decorative surface.
1 ml of the bacterial solution was added dropwise and the cells were cultured at 37 ° C. for 24 hours. Thereafter, the surviving bacteria on the test piece were washed out with a sterilized phosphate buffer solution. With respect to the washed-out solution, the number of surviving cells was measured by a pour plate culture method using a medium for measuring the number of cells, and converted into the number of viable cells per one test piece. The culture conditions are 37
C. and 24 hours. As a control, a test using only the bacterial solution was also performed at the same time.

[0028]

[Table 1]

[0029]

EFFECTS OF THE INVENTION The antibacterial decorative sheet of the present invention provides a soft touch which is not found in conventional decorative sheets due to the elasticity of the thermoplastic resin elastomer on the surface, and has a complicated curved surface lapping process or V-cut bending process. It is also suitable for and does not easily expand or deform due to heat. In addition, the antibacterial agent in the elastomer that constitutes the surface of the decorative sheet provides excellent antibacterial properties due to the bactericidal action of silver ions, and since the elution of silver ions is minute, there is no change in appearance or harm to the human body. There is no effect, and the antibacterial effect does not decrease even after long-term use.

The antibacterial zeolite is a white fine powder, and addition of a small amount thereof does not impair the transparency of the coating film. Furthermore, by binding ammonium ions, discoloration is prevented, so even when compared with a normal thermosetting resin decorative board, the appearance such as the expression of colors and patterns is hardly impaired.

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Claims (5)

[Claims] 1. A decorative sheet is produced by heating and melting a thermoplastic resin elastomer containing silver zeolite powder as an antibacterial agent on the surface of a decorative paper, or by heat-sealing a film of the thermoplastic resin elastomer. An antibacterial decorative sheet, characterized in that the surface of the sheet is formed. 2. As an antibacterial agent, a silver zeolite having an average particle size of 40 μm or less and a silver content of 0.1 to 15% by weight is used in an amount of 0.05 to 100 parts by weight of a thermoplastic resin elastomer. The antibacterial decorative sheet according to claim 1, wherein the antibacterial decorative sheet is contained in an amount of 10 parts by weight. 3. An antibacterial agent comprising silver zeolite powder contained in a thermoplastic resin elastomer for forming a surface of a decorative paper, wherein a part or all of ion-exchangeable ions in zeolite are silver ions and ammonium ions. The antibacterial decorative sheet according to claim 1 or 2, which is substituted. 4. The decorative sheet according to claim 1, wherein the thermoplastic resin elastomer forming the surface of the decorative paper is a thermoplastic polyester resin, and the thickness of the thermoplastic resin elastomer is 20 to 200 μm. 5. As an antibacterial agent, silver zeolite having an average particle size of 40 μm or less and a silver content of 0.1 to 15% by weight is used in an amount of 0.05 to 10 with respect to 100 parts by weight of the thermoplastic resin elastomer. Production of an antibacterial decorative sheet, characterized in that, after containing by weight, the thermoplastic resin elastomer is heated and melted and applied to the surface of the decorative paper, or a film made of the thermoplastic resin elastomer is heat-sealed. Method.