JPH10119197A - Decorative sheet with antibacterial performance - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve problems by manufacturing a decorative sheet by using polyolefin sheet, forming an ultrathin protective layer by using a resin composition containing antibacterial agent on its uppermost surface, and charging wiping ink containing the agent in embossed recesses of its surface though a decorative sheet having antibacterial performance used for electric product or various implements at a place needing a sanitary environment of an indoor water section of a kitchen, hospital or the others frequently uses a polyvinyl chloride sheet but generates hydrogen chloride gas at the time of incinerating it to cause an environmental contamination. SOLUTION: The antibacterial decorative sheet 1 is manufactured by forming a print layer 12 of woodgrain design or the like on a thermoplastic resin sheet 11 made of polyolefin resin, laminating a transparent unoriented EVOH film formed with an adhesive layer 13 thereon to form a laminated sheet, coating the surface of the EVOH film of the laminated sheet with resin composition containing antibacterial agent 16, drying it, and forming a protective layer 15 containing 1 to 10wt.% of the agent 16 with a thickness of 2 to 10gm.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a plastic,
The present invention relates to a decorative sheet used for imparting antibacterial performance to any substrate such as paper, wood, metal plate, and inorganic material.

[0002]

2. Description of the Related Art Conventionally, various equipment (electrical appliances, various appliances, etc.) in indoor water-related areas (kitchens, bathrooms, washrooms, etc.), in hot and humid places, and in hospitals and other places requiring a sanitary environment. As for, there is a demand for a product that can prevent the generation of mold and bacteria. Therefore, as a method for imparting antifungal or antibacterial properties to decorative paper or decorative boards used in these, a method of kneading a fungicide or antibacterial agent into the relevant material,
Alternatively, a method of applying a paint containing an antibacterial agent in a post-process has been performed (disclosed in Japanese Patent Publication Nos. 63-54013 and 4-28646). Also, attempts have been made to impart antibacterial properties to the above-mentioned fixtures and the like by using wallpaper and decorative sheets having antifungal and antibacterial properties (disclosed in JP-A-1-313533).

[0003]

However, when a fungicide or an antibacterial agent is kneaded into a molded plastic product, problems such as an increase in the production process and costs and a decrease in productivity are likely to occur. It is the antibacterial agent present on the surface of the product that shows the antibacterial effect of the product to which the antibacterial agent is added, but most of the antibacterial agent is kneaded into the resin when kneading it into the molding resin or paint resin. Since the antibacterial agent is present in the molded article and cannot exert an antibacterial effect, it is a great economical problem as a method of using an antibacterial agent.

[0004] Conventionally, interiors such as walls and ceilings of buildings,
As a decorative sheet used as a surface decoration material for furniture, cabinets, and the like, a polyvinyl chloride sheet is often used for the sheet. For example, there is a pattern in which a wood grain pattern is printed on a polyvinyl chloride sheet and a transparent polyvinyl chloride sheet is laminated on the pattern, and another sheet in which a transparent polyvinyl chloride sheet is embossed is used. A decorative sheet using a polyolefin sheet instead of the sheet has been proposed. However, when the decorative sheet is adhered to an adherend and subjected to V-cutting or lapping, there is a problem in the suitability of the decorative sheet for processing.

According to the present invention, a decorative sheet is prepared using a polyolefin sheet instead of polyvinyl chloride, and an extremely thin protective layer is formed on the outermost surface using a resin composition containing an antibacterial agent. The above problem could be solved by filling the embossed concave portions on the surface with wiping ink containing an antibacterial agent.

[0006]

Means for Solving the Problems In order to solve the above problems, the configuration of the decorative sheet is as follows. In a decorative sheet in which a printing layer, an adhesive layer, an unstretched ethylene-vinyl alcohol copolymer film and a protective layer are sequentially laminated on a thermoplastic resin sheet base material, the protective layer is formed of a composition to which an antimicrobial agent is added. This is a decorative sheet having antibacterial performance. And the protective layer to which the antimicrobial agent was added contained an antimicrobial agent in an amount of 1 to 10% by weight, and the thickness was 2 to 10 μm.

[0007] In addition, the printed sheet, the adhesive layer, and the unstretched ethylene-vinyl alcohol copolymer film are sequentially laminated on the thermoplastic resin sheet base, and the unstretched ethylene-vinyl alcohol copolymer film surface of the laminate sheet has irregularities. A decorative sheet having an antibacterial property, wherein the decorative sheet comprises a pattern, and the wiping ink comprises an ink containing 1 to 10% by weight of an antibacterial agent. did. Furthermore, an uneven pattern is formed on the unstretched ethylene-vinyl alcohol copolymer film surface of the laminated sheet in which a printing layer, an adhesive layer, and an unstretched ethylene-vinyl alcohol copolymer film are sequentially laminated on a thermoplastic resin sheet base material. Then, in a decorative sheet in which a concave portion of the concave and convex pattern is filled with a wiping ink and a protective layer is formed thereon, the protective layer contains 1 to 10% by weight of an antibacterial agent and has a thickness of 2 to 10 μm. A decorative sheet having an antibacterial performance characterized by the following.

The decorative sheet is a decorative sheet having antibacterial properties, which is a decorative sheet obtained by laminating a thermoplastic resin sheet and an undrawn ethylene-vinyl alcohol copolymer film by heat fusion. Further, the decorative sheet is a decorative sheet in which the antibacterial agent is an antibacterial zeolite in which part or all of ion-exchangeable ions of zeolite are replaced with ions of silver, copper, zinc, tin, lead, mercury, ammonium and the like.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of a decorative sheet having antibacterial performance of the present invention. FIG. 2 is a schematic cross-sectional view of another embodiment of the decorative sheet having antibacterial performance of the present invention, in which embossed concave portions are filled with ink containing an antibacterial agent to impart antibacterial properties. FIG. 3 is a schematic cross-sectional view of another embodiment of the decorative sheet having antibacterial performance according to the present invention, in which a protective layer to which an antibacterial agent is added is formed on an embossed pattern to impart antibacterial properties. FIG. 4 is an explanatory view when a decorative sheet having antibacterial performance is prepared by adding an antibacterial agent to the protective layer. FIG. 5 is an explanatory diagram for producing a decorative sheet having antibacterial performance by adding an antibacterial agent to the wiping ink. FIG. 6 is an explanatory diagram when the decorative sheet of the present invention is manufactured according to Example 1. FIG. 7 is an explanatory diagram when a decorative sheet of the present invention is manufactured according to Example 2. FIG. 8 is an explanatory diagram when a decorative sheet of the present invention is manufactured according to Example 3. FIG. 9 is an explanatory diagram when a decorative sheet of the present invention is produced according to Example 4.

As shown in FIG. 1, a decorative sheet having an antibacterial property (hereinafter simply referred to as an antibacterial decorative sheet) of the present invention comprises a thermoplastic resin sheet 11, a printing layer 12, and an adhesive layer 1.
3. An ethylene-vinyl alcohol copolymer film (hereinafter referred to as an EVOH film) and a protective layer 15 containing an antibacterial agent 16.

As shown in FIG. 2, an embossed pattern was formed on the laminated sheet composed of the thermoplastic resin sheet 11, the printed layer 12, the adhesive layer 13, and the EVOH film 14 by embossing the surface of the EVOH film 14. Then, the embossed concave portions are filled with a wiping ink 17 to which an antibacterial agent has been added to impart antibacterial performance to the decorative sheet surface.

Further, as shown in FIG. 3, after the laminating sheet having the embossed pattern formed thereon as described above is filled with wiping ink 17a which does not contain an antibacterial agent in the recesses of the embossed pattern by wiping processing, in addition,
The protective layer 15 containing the antibacterial agent 16 is formed to form the antibacterial decorative sheet 1.

Further, the antibacterial cosmetic sheet of the present invention is manufactured as follows. First, as shown in FIG. 4A, a wood grain pattern or the like is printed on a thermoplastic resin sheet 11 such as polyethylene (hereinafter, referred to as PE) or polypropylene (hereinafter, referred to as PP) to form a print layer 12. On the other hand, as shown in FIG. 4B, an adhesive is applied to the unstretched EVOH film 14 to form an adhesive layer 14.

Next, the thermoplastic resin sheet 11 provided with the printing layer and the unstretched EVOH film 14 provided with the adhesive layer 13 are bonded together by a dry lamination method or the like, and a laminated sheet as shown in FIG. 2 is produced.
On the surface of the unstretched EVOH film 14 of the laminated sheet 2,
As shown in FIG. 4D, a resin composition to which an antibacterial agent such as an antibacterial zeolite is added is applied and dried, and the protective layer 15 containing 1 to 10% by weight of the antibacterial agent 16 in the dry resin solid content.
Is formed in a thickness of 2 to 10 μm to form an antibacterial decorative sheet 1
Is prepared.

The antibacterial cosmetic sheet of another embodiment of the present invention is produced as follows. As shown in FIGS. 5A and 5B, similarly to the above, a woodgrain pattern or the like is printed on the thermoplastic resin sheet 11 to form the print layer 12, and the unstretched E
An adhesive is applied to the VOH film 13 to form an adhesive layer 14. Next, the thermoplastic resin sheet 11 and the unstretched EVOH film 13 are overlapped, and the thermoplastic resin sheet 11 and the unstretched EVOH film 13 are laminated by heating and pressing using an embossing roll having an embossed pattern. At the same time, as shown in FIG. 5C, an embossed pattern 18 is formed on the unstretched EVOH film surface.

The antimicrobial agent 1 is formed in the embossed concave portion 19 of the laminated sheet having the embossed pattern by wiping.
5 is filled with the wiping ink 17 to which
As shown in (d), an antibacterial property was imparted to the embossed surface to obtain an antibacterial decorative sheet 1. The content of the antibacterial agent in the wiping ink should be 1 to 10% by weight as a dry matter. Further, the embossed pattern is formed by applying heat and pressure so that the EVOH film of the laminated sheet is in contact with the embossing roll, using an embossing roll obtained by cutting a wood grain conduit or the like by engraving. 8
It was set to 0 μm.

Further, as another embodiment of the present invention, similarly to the above, after forming an embossed pattern on the laminated sheet and filling the concave portion of the embossed portion with an ink using a wiping ink to which a normal antibacterial agent is not added, As shown in FIG. 3, a protective layer 15 containing an antibacterial agent may be formed thereon to form the antibacterial decorative sheet 1. Of course, a protective layer 15 containing an antibacterial agent can be further formed on the embossed surface of the antibacterial decorative sheet as shown in FIG. 2 to obtain an antibacterial decorative sheet. In this case, the layer having antibacterial performance is doubled,
The antimicrobial agent added to the wiping ink cannot exhibit the antimicrobial effect sufficiently, and there is a problem as a method for effectively using the antimicrobial agent.

Examples of the thermoplastic resin sheet used in the present invention include polyolefin resins. Polyolefin resins include polyethylene (PE), polypropylene (PP), ethylene / propylene copolymer, ethylene / butene-1 copolymer, propylene / butene-1
Copolymer, polybutene-1, butene-1, propylene
Ethylene tricopolymer, butene-1, hexene-1, octene-1 tricopolymer, polymethylpentene, olefin elastomers described in JP-A-6-16832 and the like are used. These resins may be used alone or in combination of two or more. And the thickness of the film used is in the range of 50 to 500 μm, and any of a stretched film and an unstretched film can be used,
An unstretched film is better in terms of workability such as V-cut processing. These polyolefin-based resins can be used as such, but preferably a thermoplastic elastomer is added to impart flexibility, impact resistance and easy adhesion to the polyolefin-based resin.

As the thermoplastic elastomer, diene rubber, hydrogenated diene rubber, olefin elastomer and the like are used. Hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule.In the present invention, the hydrogenated diene rubber is used as a modifier for a polyolefin resin. It works to suppress, improve flexibility and transparency.
In general, when a diene rubber is added to a polyolefin resin, weather resistance and heat resistance are lower than those of a polyolefin resin to which a diene rubber is not added because of a double bond of the diene rubber. Is saturated with a hydrogen atom, so that a decrease in the weather resistance and heat resistance of the polyolefin resin is prevented and the polyolefin resin becomes favorable.

Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene / butadiene rubber. The olefin elastomer is an elastic copolymer obtained by adding at least one polyene that can be copolymerized with two or three or more olefins. As the olefin, ethylene, propylene, α-olefin, or the like is used. 1,4 hexadiene, cyclic dienes, norbornene and the like are used. Preferred olefin copolymer rubbers include, for example, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene rubber,
Elastic copolymers containing an olefin as a main component, such as ethylene butadiene copolymer rubber, may be used.

If necessary, pigments, dyes, fillers, foaming agents, flame retardants, ultraviolet absorbers and the like are added to the polyolefin resin. Powders such as calcium carbonate, barium sulfate, clay, and talc are used as the inorganic filler. Add an appropriate amount as needed.

The pigment is used to give the base sheet the necessary color as a decorative sheet. Inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, carbon black, etc. Linone, Hansa Yellow A: Organic pigments or dyes such as quinacridone, permanent red 4R, and phthalocyanine blue; metal pigments such as aluminum and brass; pearlescent pigments such as titanium dioxide-coated mica and foil powders such as basic zinc carbonate are used. Can be The coloring may be either transparent coloring or opaque (concealing) coloring, but opaque coloring is generally preferred in order to cover the adherend.

A more preferred substrate sheet is a colored substrate sheet produced using a material whose main raw materials include a high-density polyethylene, a thermoplastic elastomer, a coloring agent composed of pigments and dyes, and an inorganic filler. The high-density polyethylene constituting the colored base sheet of the decorative sheet of the present invention is preferably polyethylene having a specific gravity of 0.94 to 0.95, which has a high degree of crystallinity obtained by a low-pressure method and is branched into molecules. High-density polyethylene, which is a polymer having a small structure, is used.

The thermoplastic elastomer used in the present invention is the same as described above. The amount of the thermoplastic elastomer added is 10 to 60% by weight, preferably about 30% by weight in the base sheet. If the amount is less than 10% by weight, the change in elongation at a constant load becomes too steep, and the elongation at break and impact resistance decrease. If the amount is more than 60% by weight, transparency, weather resistance and creep resistance decrease. Occurs.

The filler in the present invention is the same as described above. The amount of addition is 5-6 in the base sheet.
It is about 0% by weight, preferably about 30% by weight. 5% by weight
If the amount is less than the above, the creep deformation resistance and the easy adhesion decrease. If the amount is more than 60% by weight, the elongation at break and the impact resistance decrease.

The thermoplastic resin sheet can be colored to any color with an organic or inorganic coloring pigment or dye. Further, the thermoplastic resin sheet may be opaque or transparent. Depending on the coloring of the material to which the decorative sheet is to be attached (for example, the plate material forming the walls of the building), the heat applied to the decorative sheet may be appropriately determined in consideration of the effect on the design of the decorative sheet, the depth of the decorative sheet, the feeling of painting, and the like. The transparency of the plastic resin sheet is selected.

The thickness of the thermoplastic resin sheet is usually from 50 to
In the range of 500 μm, it is appropriately selected according to the application,
The range of 80 to 100 μm is preferred. As the thermoplastic resin sheet used in the present invention, a single sheet is often used, but a sheet in which the same or different thermoplastic resin sheets are laminated can also be used. When it is difficult to satisfy desired physical properties such as mechanical properties and easy adhesion with the same kind of single-layer sheet, it is possible to obtain desired physical properties by laminating different kinds of thermoplastic resin sheets having different physical properties. Can be.

On the other hand, the unstretched ethylene-vinyl alcohol copolymer film used in the present invention is usually a random copolymer of ethylene and vinyl alcohol in the form of a film, which is unstretched. Its thickness is 1
Used at 0-100 μm, preferably 20-30 μm
Range.

The ethylene-vinyl alcohol copolymer film has the thermoplastic and water resistance of ethylene and the rigidity, oil resistance, and solvent resistance of vinyl alcohol by changing the ratio of the ethylene / vinyl alcohol copolymer component. It is possible to arbitrarily adjust the non-charging performance. However, in order to obtain a film having both characteristics of ethylene and vinyl alcohol and excellent in processability, the ethylene component is contained in an amount of 30 to 45 mol%. It is preferred that
If the ethylene component is less than 30 mol%, thermoplasticity, suitability for heat processing and water resistance are inferior, and if it exceeds 45 mol%, rigidity, oil resistance, solvent resistance and non-charging properties are inferior, which is not preferable.

When the decorative sheet is used in an environment where the sheet is exposed to sunlight, the ethylene-vinyl alcohol copolymer may be used in combination with an ultraviolet absorber such as benzotriazole and finely divided zinc oxide, and a hindered amine radical scavenger. It is preferable to add a light stabilizer to improve the weather resistance.

In the present invention, the EVOH film is used in an unstretched state for the following reasons. The ethylene-vinyl alcohol copolymer is a crystalline polymer, and tends to be brittle due to crystallization by stretching. As a result, cracking and whitening due to micro-cracks occur due to bending processing such as V-cut processing and lapping processing. Also, the temperature range in which appropriate fluidity and plasticity are exhibited is narrow, and slight fluctuations in heating conditions during embossing are performed. Therefore, there arises a problem that the work is hindered in the post-processing such as a change in embossing. In contrast, unstretched EVOH
The film had good bending workability, good embossing suitability, and the like, and could solve the above problems.

The printing layer in the present invention is usually provided on either the front surface of the thermoplastic resin sheet or the back surface of the EVOH film, or may be provided on both sheets and the film. However, the printing layer needs to be provided between the thermoplastic resin sheet and the EVOH film. Examples of the pattern pattern of the printing layer include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a squeezed pattern, a geometric figure, characters, symbols, various abstract patterns, and a solid printing on the entire surface. Further, after forming the concealing layer of solid printing on the entire surface, a picture printing layer may be formed thereon.

The ink used to form the printing layer varies depending on the material and form of the printing substrate (thermoplastic resin sheet or EVOH film). In general, nitrified cotton, cellulose acetate, vinyl chloride and vinyl acetate are commonly used. Polymer, polyvinyl butyral, urethane resin, acrylic resin, a homopolymer such as a polyester resin, or a polymer with other monomers as a vehicle, and this and ordinary pigments, coloring agents such as dyes, extender pigments, curing agents, An ink composed of additives, solvents and the like is used. In particular, for the decorative sheet of the present invention, an ink having excellent heat resistance and weather resistance is appropriately selected depending on the application.

As a method for forming the printing layer, a usual printing method such as gravure printing, intaglio printing, offset printing, letterpress printing, flexographic printing, silk screen printing, electrostatic printing, and ink jet printing can be used. Alternatively, a picture pattern may be formed once on a release sheet to prepare a transfer sheet, and a picture print layer may be transferred by a transfer printing method from the obtained transfer sheet to provide a picture layer. Also,
Instead of the printing layer, a metal thin film of aluminum, chromium, or the like may be formed on the entire surface or a part of the sheet or the film to form a decoration layer.

When a polyolefin resin sheet is used as the thermoplastic resin sheet and printing is performed directly on the sheet, chlorinated polyolefin, polyurethane or the like is preferable as the binder in terms of adhesiveness. If a corona discharge treatment, a plasma treatment, or an easy-adhesion layer (also referred to as a primer layer or an anchor coat layer) is appropriately selected and formed on the resin sheet surface, a sufficient adhesive force can be obtained even if other binders are used. be able to.

As the primer layer, an acrylic resin,
Using an ink in which a resin such as urethane resin, vinyl chloride-vinyl acetate copolymer resin, polyester resin, polyurethane resin, chlorinated polyethylene, or chlorinated polypropylene is dissolved in a solvent, apply by a known method, dry and easily adhere. Layers. It is possible to print a pattern or apply an adhesive directly to the polyolefin resin sheet itself, but by providing an easy-adhesion layer, it is possible to bond the pattern printing layer or adhesive with the polyolefin resin sheet. Power can be strong.

The above-mentioned thermoplastic resin sheet and EVOH film are generally laminated by an adhesive by a dry lamination method. As a typical adhesive by a dry lamination method, a two-component curable urethane resin using isocyanate as a curing agent is used, but a rubber-based resin or a polyester resin is also used. Alternatively, extrusion lamination can be performed using polyethylene as an adhesive layer as a polysand lamination method.
When the print layer is provided on the thermoplastic resin sheet, it is necessary to see the pattern of the print layer through the adhesive layer from the unstretched EVOH film side of the surface, and the adhesive layer is required to have transparency. However, when the printing layer is provided on the back surface of the unstretched EVOH film, the adhesive layer may be transparent or opaque.

Printed thermoplastic resin sheet and unstretched EV
A laminated sheet obtained by laminating an OH film by a dry lamination method, etc. is to emboss the unstretched EVOH film on the surface and fill the embossed recesses with the coloring ink by wiping to obtain a decorative sheet with high designability. There is. As the embossing, all conventionally known embossing methods can be used. For example, irregularities can be formed on the surface of the decorative sheet using a normal hot press type sheet-fed or rotary embossing machine. In addition, when the printed thermoplastic resin sheet and the unstretched EVOH film are thermally laminated, the unevenness can be formed by a so-called doubling embossing method in which the unstretched EVOH film on the surface is simultaneously embossed using an embossing plate. . The depth of the embossed concave portion varies depending on the pattern or the like expressed by the embossing, but is preferably about 30 to 80 μm in order to express a good feeling of unevenness on the surface of the decorative sheet.

The embossed pattern is a representation of the texture of the wood surface, such as a conduit groove of a grain of wood, the unevenness of the annual ring of a floating wood grain board, a glossy state of a painted board, or a combination thereof, and a hairline, a sandy ground. For example, a satin pattern, an abstract pattern, a stone pattern expressing the texture of the surface of a stone plate such as a granite plate, a texture pattern expressing the surface texture of a cloth, a skin drawing pattern expressing the texture of a leather surface, or the like can be used.

The coloring ink used as the wiping ink to be filled in the embossed concave portion is a urethane resin,
Acrylic resin, polyester resin, and other common ink vehicles, ordinary pigments, coloring agents such as dyes, extenders, curing agents, additives, solvents, etc.
Although selected according to the application, a two-part curable ink is preferred in terms of adhesion and solvent resistance. The wiping method is
Any of the conventionally known wiping methods such as a doctor blade method and a roll coating method may be used.

In the present invention, a protective layer having an antibacterial property is further provided on the wiped decorative sheet to impart antibacterial property to the decorative sheet. The protective layer having antibacterial performance is formed as follows. A protective layer having antimicrobial performance (hereinafter simply referred to as an antimicrobial protective layer) is formed by using a resin composition to which an antimicrobial agent is added, and by using a known coating method, an antimicrobial resin having a thickness of 2 to 10 μm. A layer is formed. It is necessary that the resin used for the protective layer does not contain a substance that adversely affects the antibacterial agent.
Those that discolor by light, ionizing radiation, etc. cannot be used. Particularly, an acid catalyst used for curing the thermosetting resin or a compound having a property of reducing a metal ion of an antibacterial agent is not added.

Examples of the thermoplastic resin satisfying the above conditions include vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, vinyl resin such as polyvinyl chloride, poly (methyl (meth) acrylate) and poly (ethyl (meth) acrylate). And acrylic resins such as homo- or copolymers of (meth) acrylates such as butyl poly (meth) acrylate and the like, cellulose resins, thermoplastic polyesters, chlorinated polyolefins and the like. However, the above-mentioned poly (methyl meth) acrylate means poly (methyl methacrylate) or poly (methyl methacrylate), and (meth) will be used in the same meaning hereinafter.

Examples of the thermosetting resin include two-component curing type polyurethane resin, unsaturated polyester resin type, epoxy resin type, amino alkyd resin type, melamine resin, guanamine resin, urea resin, thermosetting acrylic resin and the like. .

Examples of the ionizing radiation-curable resin include monomers and / or prepolymers containing a polymerizable unsaturated group such as a (meth) acryloyl group or a (meth) acryloyloxy group, an epoxy group, a thiol group, or the like in the molecule. Is cured by polymerizing (crosslinking reaction, addition reaction, etc.) with ionizing radiation, and electron beams, ultraviolet rays, etc. are used as ionizing radiation. Examples of these prepolymers include (meth) acrylates such as urethane (meth) acrylate, polyester (meth) acrylate, and epoxy (meth) acrylate, and unsaturated polyesters. Examples of the monomer include styrene monomers such as styrene and α-methylstyrene, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol pentane (Meth) acrylate, trimethylolpropane tri (meth) acrylate, and the like.

As the antibacterial agent to be added to the antibacterial protective layer and the wiping ink, generally available industrial antibacterial agents can be used. Antibacterial agents include organic antibacterial agents and inorganic antibacterial agents, and the following antibacterial agents can be used. Examples of inorganic antibacterial agents include JP-B-63-54013, JP-A-4-300975, and Patent No. 25295.
No. 74, zeolite, apatite, glass, silica gel, phosphate, part or all of ion-exchangeable ions such as zirconium phosphate, silver,
There are ion exchangers substituted with ions of copper, zinc, tin, lead, mercury, cobalt, ammonium and the like. Among them, zeolite and zirconium phosphate, in which some of the ion-exchangeable ions are replaced with silver ions, are preferable from the viewpoint of safety and actual product. The content of the metal ion supported on zeolite and zirconium phosphate is 0.1 in the case of silver ion.
1 to 15% by weight, 0.1 to 8 for copper or zinc ions
% By weight is preferred. There is also an ion exchanger substituted with the above-mentioned metal ion, which is further substituted with an ammonium ion. (Japanese Patent Publication No. 4-28646, Patent No. 2529)
No. 574, etc.)

Organic compounds having antibacterial properties include
sulfa agents such as p-aminobenzenesulfonamide, sulfathiazole, sulfapyridine and sulfapidiazine; dithiocarbamates such as dimethyldithiocarbamate and ethylenebisthiocarbamate; 2- (2
-Furyl) -3- (5-nitro-2-furyl) acrylamide and the like.

Compounds having antibacterial and antifungal properties include trimethoxysilylpropyloctadecyl ammonium chloride, 10,10′-oxybisphenoxyarsine, 2- (4-thiazolyl) -benzimidazole, bis (2-pyridylthio- 1-oxide) zinc,
2-N-octyl-4-isothiazolin-3-one,
2,3,5,6--cytochloro-4- (methylthio)-
Examples include phthalimide, N- (fluorodichloromethylthio) fluorimide, griseofulvin, tricomycin, amphotericin B and the like.

Examples of the antibiotic include penicillins such as phenoxymethylpenicillin and dicloxacillin, cephalostins such as cephalothin and cefazolin, streptomycins such as streptomycin sulfate and paromomycin (sulfate), erythromycins such as erythromycin and josamycin, tetracycline, and loritetracycline nitrate. And chloramphenicol such as thiamphenicolamine acetate hydrochloride.

The particle size of the inorganic antibacterial agent is 1 to 10% by weight and the coating thickness (as dry matter) is 2%.
For 10 to 10 μm, it is preferable to use one having an appropriate particle size distribution in the range of 0.1 to 10 μm in order to give the maximum antibacterial action with the minimum addition amount. In particular, the particle size is preferably 2 to 5 μm. In the resin composition to which the antibacterial agent is added, it is necessary to remove components that have an adverse effect on the antibacterial agent. When the resin composition forms a coating film, it is generally desired that the resin composition be transparent. Therefore, when an inorganic antibacterial agent that does not dissolve in a solvent is added, the amount of addition is limited. Further, metals such as silver and nickel often cause discoloration, deterioration, and deterioration of organic compounds, and excessive addition is not preferable from this point as well.

In the case of the above antibacterial agent, the content of the antibacterial zeolite is desirably in the range of 1 to 10% by weight as the dry matter when the resin composition forms a coating film, and the antibacterial effect and transparency are emphasized. In this case, 2 to 5% by weight is suitable. When the content of the antibacterial zeolite exceeds 10% by weight, the above problems cannot be ignored, and when the content is less than 1% by weight, a sufficient antibacterial action cannot be obtained.

As a method for forming a protective layer using a resin composition to which an antibacterial agent is added, gravure coating, roll coating, air knife coating, kiss coating, spray coating, wheeler coating, curtain flow coating, brush coating, or gravure printing , Gravure offset printing, intaglio printing, silk screen printing, or the like.

Since the antimicrobial resin layer exerts the maximum antimicrobial effect with a minimum amount of addition, it is necessary that a part of the antimicrobial agent particles be exposed on the surface of the coating film. %, The thickness of the coating film is about 2 to 10 μm, and the antibacterial agent particles are preferably about 2 to 5 μm. If the amount of coating is not enough due to the coating method, use one coat to 2
In some cases, overprinting of about 1 to 3 coats is performed. However, when the particle size of the antibacterial agent is large or the amount of the antibacterial agent is increased, the antibacterial effect can be exhibited even if the thickness of the coating film exceeds 10 μm, but transparency is not desired. In addition, it is enclosed inside the coating film,
The proportion of substances that do not directly contribute to the antibacterial action increases. 2 coatings
If it is less than μm, the coating film will have insufficient durability and insufficient bonding strength to adhere the inorganic antibacterial agent of the above-mentioned particle size and amount to the coating film.

[0053]

The present invention will be described below in more detail with reference to examples. (Example 1) As shown in FIG. 6A, an opaque polyethylene resin sheet 11a having an opaque thickness of 100 μm and colored in beige by adding a pigment (“TUFPER TKP beige” manufactured by Tatsuno Chemical Co., Ltd.) A printing layer 12 was formed on the surface of a colored PE sheet (hereinafter referred to as a colored PE sheet) by gravure printing a wood grain pattern using a polyurethane-based gravure ink. In addition, the said coloring PE sheet contained 25 weight% of calcium carbonate particles with an average particle diameter of 10 micrometers, and performed the whitening prevention process. At this time, in order to improve the familiarity between the calcium carbonate particles and the resin, the particles were subjected to a rosin treatment and a surfactant treatment.

Further, as shown in FIG.
A two-part curable adhesive using isocyanate as a curing agent is applied to the back surface of a transparent EVOH film 14 having a thickness of 5 μm (“EF-E” manufactured by Kuraray Co., Ltd.) and dried to form an adhesive layer 13 having a thickness of 5 μm. Was formed. Next, as shown in FIG.
Immediately by the dry lamination method, the laminated surface was laminated on the printed surface of the colored PE sheet.

Next, as shown in FIG. 6 (d), the surface of the EVOH film 14 of the laminated sheet 2 was coated with a paint using a two-part curable urethane resin composed of acrylic polyol and hexamethylene diisocyanate as a binder. 5% by weight of a silver ion type zeolite antibacterial agent having a particle size distribution of 2 to 5 μm, a silver content of 2.5% by weight and a zinc content of 14.5% by weight, and an average primary particle size as an extender A protective layer 15 having a thickness of 3 μm after curing is formed by a gravure roll coating method using an antibacterial paint to which 5% by weight of microsilica having a specific surface area of 16 nm and a specific surface area of 110 m ² / g is added. 1 was produced.

Example 2 As shown in FIG. 7A, a laminated sheet 2 was produced in the same manner as in Example 1. Next, FIG.
As shown in (b), the embossed pattern 18 of the wood channel was formed on the surface of the EVOH film 14 of the laminated sheet 2 using a hot press embossing machine. Furthermore,
As shown in FIG. 7C, the antibacterial agent 16 used in Example 1 was used.
The embossed concave portion 19 is filled with a wiping ink 17 using a urethane resin wiping ink (“W-1411” manufactured by Showa Ink Industries, Ltd.) to which 5% by weight of Produced.

(Example 3) Using the same colored PE sheet as in Example 1, the surface of this colored PE sheet 11 was
As shown in (a), the wood pattern is printed by gravure printing using a two-pack curable urethane resin ink (“NL-ALFA” manufactured by The Inktech Co., Ltd.) using isocyanate as a curing agent. Layer 12 was provided. Next, as shown in FIG. 8B, the printing surface of the colored PE sheet 11
The same EVOH film 14 as above was overlaid and thermally laminated by heat and pressure to produce a laminated sheet 2.

Next, as shown in FIG. 8 (c), the embossed pattern 1 of the wood channel groove was formed on the surface of the EVOH film 14 of the laminated sheet 2 using a hot press type embossing machine.
After the formation of No. 8, as shown in FIG. 8 (d), the embossed concave portions are formed using a urethane-based resin wiping ink 17a ("W-1411" manufactured by Showa Ink Industries, Ltd.) to which no antimicrobial agent is added. The wiping ink 17a was filled.

Further, as shown in FIG.
In the same manner as in Example 1, a protective layer 15 having a thickness of 3 μm was formed by a gravure roll coating method using an antibacterial paint, thereby producing an antibacterial decorative sheet 1.

Example 4 As shown in FIG. 9A, an opaque polypropylene resin sheet 11b having a thickness of 100 μm and colored sepia by adding a pigment (“SA-3025” manufactured by Riken Vinyl Industry Co., Ltd.) ") (Hereinafter referred to as a colored PP sheet), a primer layer 20 having a thickness of 3 µm was formed by gravure coating using a primer solution for polyolefin (" AFS "manufactured by Showa Ink Industries, Ltd.). Next, on the primer layer of the colored PP sheet, a two-part curable urethane resin ink (“NL-ALFA” manufactured by The Inktech Co., Ltd.) using isocyanate as a curing agent.
)), The gravure printing of the wood pattern is performed, and the printing layer 12 is formed.
Was provided. Further, on the printing layer 12, a polyamide-based paint ("P-933" manufactured by Honey Chemical Co., Ltd.) was used as shown in FIG.
As shown in the figure, 5μm thick by gravure coating
Was formed.

Next, using the same EVOH film as in Example 1, the EVOH film is superimposed on the adhesive layer of the colored PP sheet 11b on which the printing layer and the adhesive layer are formed, and both are laminated by doubling embossing. As shown in FIG.
On the surface of the VOH film 14, an embossed pattern 18 of wood grain conduit grooves was formed.

Next, as shown in FIG. 9C, a wiping ink 17a of a urethane resin to which no antibacterial agent is added.
The embossed concave portion 19 was filled with the wiping ink 17a using (W-1411 manufactured by Showa Ink Industries, Ltd.). Further, as shown in FIG.
Similarly to the above, the protective layer 15 having a thickness of 3 μm was formed by the gravure roll coating method using the antibacterial paint, and the antibacterial decorative sheet 1 was produced.

A decorative sheet to which no antibacterial agent was added was prepared in the same manner as in the example, and the following comparative examples 1, 2, 3, and 4 were prepared.
A cosmetic sheet having no antibacterial performance was obtained. (Comparative Example 1) A decorative sheet was prepared as Comparative Example 1 in the same manner as in Example 1 except that no antibacterial agent was added to the protective layer. (Comparative Example 2) A decorative sheet was prepared as Comparative Example 2 in the same manner as in Example 2 except that no antibacterial agent was added to the wiping ink. (Comparative Example 3) A decorative sheet was prepared as Comparative Example 3 in the same manner as in Example 3 except that no antibacterial agent was added to the protective layer. (Comparative Example 4) A decorative sheet was prepared as Comparative Example 4 in the same manner as in Example 4 except that no antibacterial agent was added to the protective layer.

(Antibacterial test) Examples 1, 2, 3, 4
Antibacterial cosmetic sheet and Comparative Examples 1, 2, 3, 4
The decorative sheet prepared in the above was tested for its inhibitory effect on bacteria by the following method. Test strainEscherichia coli IFO 3301
(Escherichia coli, hereafter referred to as E.coli) ・ Methicillin Resistant Staphylococcus aurus (Methicillin Resistant Staphylococcus aurus)
eus) (Methicillin-resistant Staphylococcus aureus; hereinafter referred to as MRSA) Preparation of test bacterial solution In a normal broth medium (manufactured by Eiken Chemical Co., Ltd.) at 35 ° C and 16 ° C.
The culture solution of the test bacterium cultured with shaking for ２０20 hours was diluted 20,000-fold with a sterile phosphate buffer to obtain a bacterial solution. The number of viable bacteria was separately measured for the bacterial solution. Antibacterial test 1 ml of a bacterial solution was dropped on the surface of the antibacterial resin layer of the specimen (antibacterial decorative sheet and decorative sheet), and after storing at 25 ° C for 24 hours, the number of bacteria was measured to determine the antibacterial performance of the specimen. In addition, 1 ml of a bacterial solution was dropped on a petri dish as a control sample, and the same test was performed. Measurement of viable cell count Samples and control samples stored for 24 hours were subjected to SCDLP (Soy
Casein Digest Lecithin Polysorbate) Washed out with 10 ml of medium (manufactured by Nippon Pharmaceutical Co., Ltd.). The viable cell count is measured by
The number of bacteria per specimen and control sample was calculated.

The test results are shown in Table 1. All the samples prepared in the examples had excellent bactericidal effects, and the antibacterial performance of the decorative sheet having the antibacterial performance of the present invention was demonstrated. That is, the antibacterial cosmetic sheet prepared in Examples 1, 2, 3, and 4 gave E. coli after 24 hours. In E. coli, the initial number of bacteria is reduced from 1.2 × 10 ⁵ to 30. In MRSA,
The initial number of bacteria decreased from 2.4 × 10 ⁵ to 10 or less. The sterilization rate of the antibacterial cosmetic sheet against E. coli and MRSA is 99.99% or more. On the contrary,
In Comparative Examples 1, 2, 3, and 4 in which no antimicrobial agent was added, E. coli c
oli and residual number of bacteria after 24 hours of MRSA is only reduced to about one order of magnitude at most, still, even it remained 10 ⁴ to 10 ^5. Therefore, the antibacterial cosmetic sheet of the present invention has an excellent bactericidal effect and can be an effective means for preventing bacterial contamination if used for various equipment in hospitals and other places requiring a sanitary environment. Can be expected.

[0066]

[Table 1] * E.coli: Escherichia coli IFO 3301 * MRSA: Methicillin Resistant Staphylococcus aureus

[0067]

The antibacterial decorative sheet of the present invention can impart antibacterial properties to its surface by being attached to any substrate such as plastic, paper, wood, metal plate, inorganic material, etc. Very effective in imparting antibacterial performance to various equipment (electric appliances, cabinets, various appliances, etc.) used in indoor water-related areas, places with high temperature and high humidity, hospitals and other places requiring a sanitary environment Means. For example, when a decorative steel sheet is manufactured using the decorative sheet having the antibacterial performance of the present invention, and this decorative steel sheet is used for a hospital partition, a screen, a handrail, etc., it exhibits a bactericidal action against attached bacteria. In addition, the room can be kept clean and hospital infections of various bacteria can be prevented. In addition, since the antibacterial performance of the present invention can be imparted by sticking the decorative sheet having antibacterial performance to existing electric appliances, cabinets, various appliances, etc., the economic burden on preventing bacterial contamination is reduced. I'm done. Furthermore, since the decorative sheet having antibacterial performance of the present invention has an antibacterial agent added to a very thin layer on the surface, it can have an antibacterial effect in a small amount and can be kneaded into a conventional resin. In comparison, it is economically advantageous.

[Brief description of the drawings]

FIG. 1 is a schematic sectional view showing an example of a decorative sheet having antibacterial performance according to the present invention.

FIG. 2 is a schematic cross-sectional view of a decorative sheet provided with antibacterial performance by filling an embossed concave portion with an ink containing an antibacterial agent.

FIG. 3 is a schematic cross-sectional view of a decorative sheet provided with an antibacterial property by forming a protective layer to which an antibacterial agent is added on an embossed pattern.

FIG. 4 is an explanatory diagram for producing a decorative sheet having antibacterial performance according to the present invention.

FIG. 5 is an explanatory view when a decorative sheet having antibacterial performance is prepared by filling an embossed concave portion with ink containing an antibacterial agent.

FIG. 6 is an explanatory diagram for producing an antibacterial decorative sheet according to Example 1.

FIG. 7 is an explanatory diagram for producing an antibacterial decorative sheet according to Example 2.

FIG. 8 is an explanatory diagram for producing an antibacterial decorative sheet according to Example 3.

FIG. 9 is an explanatory diagram for producing an antibacterial decorative sheet according to Example 4.

[Explanation of symbols]

 Reference Signs List 1 antibacterial decorative sheet 2 laminated sheet 11 thermoplastic resin sheet 11a colored PE sheet 11b colored PP sheet 12 printed layer 13 adhesive layer 14 EVOH film 15 protective layer 16 antibacterial agent 17 wiping ink 17a wiping ink without antibacterial agent 18 embossed pattern 19 Embossed recess 20 Primer layer

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/00 B32B 27/00 E 27/18 27/18 F // A61L 2/16 A61L 2/16 A

Claims (7)

[Claims] 1. A decorative sheet in which a printing layer, an adhesive layer, an unstretched ethylene-vinyl alcohol copolymer film and a protective layer are sequentially laminated on a thermoplastic resin sheet substrate, wherein the protective layer contains an antimicrobial agent. A decorative sheet having antibacterial performance, which is formed of a resin composition. 2. The antibacterial agent according to claim 1, wherein the protective layer to which the antibacterial agent is added contains 1 to 10% by weight of the antibacterial agent and has a thickness of 2 to 10 μm. Makeup sheet. 3. A laminated sheet in which a printing layer, an adhesive layer, and an unstretched ethylene-vinyl alcohol copolymer film are sequentially laminated on a thermoplastic resin sheet base material, wherein the unstretched ethylene-vinyl alcohol copolymer film comprises: A decorative sheet having antibacterial performance, comprising 1 to 10% by weight of an antibacterial agent. 4. An unstretched ethylene-vinyl alcohol copolymer film surface of a thermoplastic resin sheet base material in which a printing layer, an adhesive layer, and an unstretched ethylene-vinyl alcohol copolymer film are sequentially laminated. In a decorative sheet in which a pattern is formed and a concave portion of the concavo-convex pattern is filled with a coloring ink, the coloring ink contains 1 to 10% by weight of an antibacterial agent.
A decorative sheet having antibacterial performance, characterized by comprising an ink to be contained. 5. A laminated sheet in which a printing layer, an adhesive layer, and an unstretched ethylene-vinyl alcohol copolymer film are sequentially laminated on a thermoplastic resin sheet substrate, and the surface of the unstretched ethylene-vinyl alcohol copolymer film has irregularities. In a decorative sheet in which a pattern is formed, a concave portion of the concave-convex pattern is filled with a coloring ink, and a protective layer is formed thereon, the protective layer comprises a resin composition containing 1 to 10% by weight of an antibacterial agent; A decorative sheet having antibacterial performance, the thickness of which is 2 to 10 μm. 6. The decorative sheet according to claim 1, wherein the decorative sheet is a decorative sheet obtained by laminating a thermoplastic resin sheet and an undrawn ethylene-vinyl alcohol copolymer film by heat fusion. Decorative sheet with antibacterial performance. 7. The antimicrobial agent is an antimicrobial zeolite in which part or all of ion-exchangeable ions of zeolite are replaced with ions of silver, copper, zinc, tin, lead, mercury, ammonium and the like. The decorative sheet having antibacterial performance according to claim 1.