JPH11262980A - Decorative sheet and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a mildew resistant/antifungal decorative sheet and its manufacturing method, wherein deteriorating of an effect of an anti-fungus agent in a heating process and dissipating of the anti-fungus agent at the time of embossing are not generated, and sufficient antifungal effect is developed by a small amount of the anti-fungus agent. SOLUTION: A printed layer 2 is formed on a base sheet 1 composed of a thermoplastic elastomer, and an adhesive layer 3 is formed thereon. And thereafter, two or more surface sheet 4a and 4b are formed simultaneously by multi-layer extrusion of a molten olefin resin. The surface sheet 4b, which is formed on an uppermost layer of the surface sheet 4a and 4b, is contained a mildew resistant/antifungal agent before the extruding, and embossing is applied on the surface sheet 4b during cooling immediately after extruding. A protective layer 5 is formed on an upper layer of the surface sheet 4b by using a two-pack curable acrylic urethane resin containing the mildew resistant/ antifungal agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a building material such as an interior material,
In particular, the present invention relates to a decorative sheet containing a fungicide / antibacterial agent and a method for producing the same, which can be used in kitchens and bathrooms where mold and bacteria are easily generated.

[0002]

2. Description of the Related Art Decorative sheets used for building materials such as interior materials are often required to have antifungal properties and antibacterial properties. In particular, a kitchen sheet and a bathroom, which are likely to be in a high-temperature and high-humidity environment and are liable to generate mold and bacteria, and a living room where the temperature difference is large and dew condensation is likely to occur, requires a decorative sheet having a high antibacterial activity for a long time. Therefore, various antifungal / antibacterial decorative sheets have been manufactured.

[0003] As a main material of these antifungal and antibacterial decorative sheets, vinyl chloride resins which have high affinity with plasticizers and coloring agents and are easy to process and color have been widely used. Antibacterial decorative sheets mainly made of vinyl chloride resin are generally
Heating in a manufacturing process such as embossing has the disadvantage that a dehydrochlorination reaction accompanied by discoloration of the resin occurs, and that the antifungal and antibacterial agents easily bleed (elut) on the resin surface.

[0004] To solve the above problem, for example, Japanese Patent Laid-Open No.
No. 0833 discloses a method in which a metal chelator and a plasticizer having a large polarity are added, and N-fluorodichloromethyl-phthalimide is selected as an antibacterial agent, thereby removing hydrochloric acid from a vinyl chloride resin and producing an antibacterial agent. A decorative sheet in which bleed is suppressed is disclosed.

[0005] Japanese Patent Application Laid-Open No. 9-262942 discloses a decorative sheet in which the amount of an antibacterial agent added is reduced. In general, the antibacterial effect of an antibacterial decorative sheet depends on the density of the antibacterial agent near the surface of the sheet. Therefore, by forming two coat layers made of a thermosetting resin on the upper layer of a base material made of a thermoplastic resin such as vinyl chloride, and including only the upper coat layer with an antibacterial agent, In the decorative sheet described in JP-A-262942, excessive addition of an antibacterial agent is not required.

[0006]

However, among the conventional mold- and antibacterial decorative sheets, the above-mentioned Japanese Patent Application Laid-Open No.
Decorative sheets mainly made of vinyl chloride resin, such as the decorative sheet described in JP-A-833, have low heat resistance of vinyl chloride resin. Release. In particular, a large amount of hydrogen chloride is generated during incineration. Further, since vinyl chloride resin is thermally decomposed at a high temperature, recycling of resin waste material is relatively difficult.

[0007] For these reasons, the main material of the decorative sheet has been replaced by an olefin resin from a vinyl chloride resin, but in that case, a new problem occurs. Olefin-based resin has lower adhesiveness than vinyl chloride resin, so if olefin-based resin is used as the main material, in addition to the usual manufacturing process of bonding between layers, a process of easily bonding the bonding surface, In many cases, a step of providing an easy-adhesion layer is required.
Although these steps involve heating, it is necessary to reduce the number of heating steps as much as possible in order to avoid decomposition or deterioration of the antibacterial agent due to heating, particularly in the case of a fungicide / antibacterial sheet.

In addition to the above-mentioned problem, there is also a problem in the case where embossing is performed on the surface of a mold / antibacterial decorative sheet. The antifungal / decorative sheet described in Japanese Patent Application Laid-Open No. 9-262942 discloses that the antibacterial coat layer on the surface is made of a thermosetting resin such as a phenol resin, a melamine resin, an epoxy resin, a polyester resin, or a urethane resin. Is difficult to emboss.

Even when a thermoplastic olefin resin is used as the main material of the decorative sheet, after the olefin resin layer containing the antibacterial agent is formed, the surface is reheated to soften the resin, thereby embossing. It has been confirmed that when processing is performed, the antibacterial agent contained in the embossed portion flows around and the antibacterial property of the embossed portion is easily lost.

[0010] Originally, the embossed concave portion is a portion to which dirt easily adheres. Therefore, the antifungal / antibacterial decorative sheet in which the antibacterial property of the embossed portion is insufficient does not sufficiently fulfill the antibacterial function.

The present invention has been made in view of the above problems, and does not reduce the effectiveness of the antibacterial agent in the heating step or dissipate the antibacterial agent during embossing.
An object of the present invention is to provide a fungicide / antibacterial cosmetic sheet having a sufficient antibacterial activity while keeping the amount of an antibacterial agent low, and a method for producing the same.

[0012]

Means for Solving the Problems In order to achieve the above object, a decorative sheet according to the present invention is a decorative sheet having a surface sheet comprising a laminate of two or more layers on a base sheet. The top layer is characterized by containing a fungicide / antibacterial agent.

According to the present invention, even when the amount of the antibacterial agent used is small, the decorative sheet can have sufficient antibacterial properties. In general, the antibacterial effect of an antibacterial decorative sheet depends on the density of the antibacterial agent near the sheet surface. Is shown. Therefore, if the surface sheet laminated on the base material sheet is a laminate composed of two or more layers, and the antifungal / antibacterial agent is added only to the uppermost layer of the laminate, the decorative sheet can be added without excessively adding the antibacterial agent. Can have sufficient antibacterial activity.

[0014] The decorative sheet of the present invention is preferably characterized in that the topsheet is embossed. By forming the decorative sheet of the present invention to have a structure having a surface sheet composed of a laminate of two or more layers as described above, it is possible to form a surface sheet of the outermost layer containing a fungicide / antibacterial agent by multilayer extrusion. Almost simultaneously, it becomes possible to perform embossing on the outermost surface sheet. Therefore, in the decorative sheet of the present invention, unlike the case where embossing is performed by reheating the laminated decorative sheet,
The antibacterial agent in the embossed portion is prevented from flowing and dissipating around. As a result, a decorative sheet provided with antifungal and antibacterial properties even on the embossed portion can be obtained.

Further, the decorative sheet of the present invention is preferably characterized in that a protective layer containing a fungicide / antibacterial agent is preferably provided on the topsheet. By providing such a protective layer, it is possible to improve the abrasion resistance of the surface of the decorative sheet while maintaining the antifungal and antibacterial properties of the surface of the decorative sheet. The light resistance of the decorative sheet of the present invention can be improved by including an ultraviolet absorber in the protective layer.

The decorative sheet of the present invention is preferably characterized in that the base sheet and the topsheet are made of a thermoplastic resin. The main material of the base sheet and the surface sheet of the decorative sheet of the present invention is a thermoplastic resin, particularly, by using an olefin-based thermoplastic elastomer, compared with a conventional decorative sheet mainly containing a vinyl chloride resin. In addition, generation of hydrogen chloride at the time of incineration is suppressed, and recycling of resin waste material becomes easy.

In order to achieve the above object, a method for producing a decorative sheet according to the present invention comprises a step of forming a base sheet mainly composed of a thermoplastic resin and a step of forming a thermoplastic resin on the base sheet in a multilayered manner. By extruding, a method of manufacturing a decorative sheet having at least a step of forming a surface sheet composed of a laminate of two or more layers and a step of embossing the surface of the surface sheet; Is characterized by adding a fungicide / antibacterial agent. The method for producing a decorative sheet according to the present invention preferably includes a step of forming a protective layer containing a fungicide / antibacterial agent on the topsheet.

As a result, even when the antibacterial layer is formed thin, the antibacterial agent density can be appropriately adjusted to increase the antibacterial activity of the antifungal / antibacterial decorative sheet. Further, by adding the antibacterial agent only to the uppermost layer of the topsheet, the amount of the antibacterial agent used can be reduced. Furthermore, this can prevent excessive antibacterial agent from being mixed into the surface sheet other than near the surface, so that the transparency of the surface sheet can be increased, and the anti-fungal / antibacterial agent can coagulate in the surface sheet or bleed. Can also be prevented.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the decorative sheet of the present invention will be described in detail. As the base sheet constituting the decorative sheet of the present invention, any one selected from olefin-based resins, acrylic resins, ethylene-vinyl alcohol copolymer resins, and thermoplastic polyester resins can be used.

Of the above resins, olefin resins are preferably used from the viewpoint of moldability and the like. Examples of the olefin resin include polyethylene (low density or high density), polypropylene, polymethylpentene,
Examples thereof include highly crystalline non-elastomeric olefin resins such as polybutene, ethylene-propylene copolymer and propylene-butene copolymer, and various olefin thermoplastic elastomers.

As the olefin-based thermoplastic elastomer, for example, the following can be used. (1) As the soft segment described in JP-B-6-23278, the number average molecular weight Mn is 25,000 or more, and the weight average molecular weight Mw and the number average molecular weight M
n is Mw / Mn ≦ 7, and 10 to 90% by weight of atactic polypropylene soluble in boiling heptane
And (B) 90 to 10% by weight of a heptane-insoluble isotactic polypropylene having a melt index of 0.1 to 4 g / 10 minutes as a hard segment.

In particular, when molding into various shapes by heating and pressurizing, it is preferable to use a mixture of isotactic polypropylene and atactic polypropylene, wherein the weight ratio of atactic polypropylene is 10 to 50% by weight. .

In the case of a polypropylene-based olefin-based thermoplastic elastomer used for applications such as packaging containers,
Since the strength is emphasized, the weight ratio of the atactic polypropylene as the soft segment is often less than 5% by weight. However, when an olefin resin is used for a decorative sheet as in the present invention, flexibility and processability are required. Therefore, the weight ratio of atactic polypropylene is 10% by weight or more, preferably 20% by weight. % Or more.

On the other hand, if the weight ratio of the atactic polypropylene is excessive, the sheet itself is likely to be deformed, and when the sheet is passed through a printing machine, the sheet is deformed and the pattern is distorted. (Registers) may not be matched. Further, it is not preferable because the sheet is easily broken at the time of forming the sheet.

With respect to the upper limit of the weight ratio of the atactic polypropylene, a printing layer is formed using a usual rotary printing machine such as rotary gravure printing, and embossing of the base sheet is performed.
When performing vacuum forming or the like, 50% by weight or less, preferably 4% by weight or less.
0% by weight or less.

(2) A thermoplastic elastomer comprising an ethylene-propylene-butene copolymer, wherein the butene contains one or more of three structural isomers of 1-butene, 2-butene and isobutylene. The copolymer is a random copolymer and partially includes an amorphous portion.

Preferred specific examples of the ethylene-propylene-butene copolymer include the following (A) to (C). (A) Ethylene-described in JP-A No. 9-111055.
It is a random copolymer of a propylene-butene terpolymer, preferably having a monomer component weight ratio of 90% by weight or more and a melt flow rate of 230%.
1 ° C., 50 g / 10 min at 23.16 kg. With respect to 100 parts by weight of the ternary random copolymer as described above, 0.01 to 50 parts by weight of a transparent nucleating agent containing a phosphate aryl ester compound as a main component and 12 to 22 carbon atoms.
A fatty acid amide obtained by melting and kneading 0.003 to 0.3 parts by weight.

(B) An ethylene-propylene-butene terpolymer described in JP-A-5-77371, comprising 20 to 100% by weight of an amorphous polymer having a propylene content of 50% by weight or more. And 8 pieces of crystalline polypropylene
What is added by 0 to 0% by weight.

(C) Those described in JP-A-7-316358. 20 to 100% by weight of a low crystalline polymer having a propylene and / or 1-butene content of 50% by weight or more based on an ethylene-propylene-butene terpolymer, An oil gelling agent such as an N-acylamino acid amine salt or an N-acylamino acid ester is added in an amount of 0.5% by weight to 100 parts by weight of a composition in which 80 to 0% by weight of a functional polyolefin is mixed.

The above-mentioned ethylene-propylene-butene copolymer resin may be used alone, or may be used by mixing the above-mentioned resins (A) to (C) with another olefin resin if necessary. You may.

(3) An olefin polymer (crystalline polymer) such as polyethylene, polypropylene or polymethylpentene described in JP-B-53-21021 was used as a hard segment, and this was partially crosslinked. An olefin elastomer obtained by forming a soft segment of a monoolefin copolymer rubber such as an ethylene-propylene copolymer rubber or an unsaturated ethylene-propylene-non-conjugated diene terpolymer rubber, and uniformly mixing and mixing these. In addition,
Monoolefin rubber / olefin polymer = 50 / 50-
Mix at a ratio of 90/10 (weight ratio).

(4) Uncrosslinked monoolefin copolymer rubber (soft segment) and (A) olefin copolymer (crystalline, hard segment) described in JP-B-53-34210. An olefin-based elastomer obtained by mixing with an agent, heating and applying shear stress to dynamically partially cross-link. (B) Monoolefin rubber /
(A) Olefin-based copolymer = 60/40 to 80/20
(Weight ratio).

(5) Mixing and heating with a peroxide such as (A) isotactic polypropylene, propylene-ethylene copolymer or propylene-butene-1 copolymer described in JP-B-56-15741 reduces the molecular weight. ,
By mixing and heating a peroxide-decomposable olefin polymer (hard segment) which increases fluidity and a peroxide such as (B) ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene terpolymer rubber, etc. Mixing with peroxides such as peroxide-crosslinked monoolefin copolymer rubber (soft segment) which crosslinks and reduces fluidity, (C) peroxides such as polyisobutylene and butyl rubber
Peroxide non-crosslinked hydrocarbon rubber (soft segment and fluidity-modifying component) that does not crosslink and remains fluid even when heated, and (D) mineral oils such as paraffinic, naphthenic and aromatic An olefin-based elastomer obtained by mixing a softener and dynamically heat-treating the mixture in the presence of an organic peroxide. (A) is 90 to 40 parts by weight, (B) is 1
(A) + (B) = 100 parts by weight, and (C) and / or (D) are 5-100 parts by weight.
A compounding ratio of parts by weight.

(6) An olefin-based thermoplastic elastomer comprising an ethylene-styrene-butylene copolymer described in JP-A-2-139232. (7) The olefin-based thermoplastic elastomer according to the above (1) to (6), having a hydroxyl group or a carboxyl group.
For example, an olefin-based thermoplastic elastomer in which a hydroxyl group is introduced by graft polymerization of an ethylene-vinyl alcohol copolymer or the like and a carboxyl group is introduced by a copolymer of maleic acid, fumaric acid, itaconic acid or the like is used. Either a hydroxyl group or a carboxyl group may be introduced, or both may be used in combination. These groups, printing layer, adhesive layer, etc.
It has the function of improving the adhesion to other layers.

The olefin resin as described above can be formed into a sheet by a film forming method such as a calender method, an inflation method, and a T-die extrusion method. As a base sheet made of an olefin resin, a stretched sheet,
Any unstretched sheet can be used, but the unstretched sheet is more suitable for molding such as V-cutting and embossing.

As the base sheet, a thermoplastic elastomer other than the olefin resin can be used. For example, as an acrylic resin, poly (meth) acrylate, poly (meth) acrylate, poly (meth) acrylate, butyl (meth) acrylate,
Methyl (meth) acrylate-butyl (meth) acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, styrene- (meth) Acrylic resins comprising a homo- or copolymer containing a (meth) acrylate such as a methyl acrylate copolymer.

When an ethylene-vinyl alcohol copolymer resin is used for the base sheet, a random copolymer of ethylene and vinyl alcohol is formed into a film. This ethylene-vinyl alcohol copolymer resin film,
Either a stretched film or an unstretched film may be used, but it is preferable to use an unstretched film from the viewpoint of bending properties of the film.

The ethylene-vinyl alcohol copolymer film can arbitrarily change the thermoplastic and water resistance of ethylene and the rigidity, oil resistance and solvent resistance of vinyl alcohol by changing the ratio of the copolymer components. Although it can be adjusted, in order to obtain a film having both characteristics and excellent workability, the ethylene component should be 30 to 45 mol%.
It is preferred that If less than 30 mol%, thermoplasticity,
Heat processing suitability and water resistance are inferior, and if it exceeds 45%, rigidity, oil resistance, and solvent resistance are inferior, which is not preferable.

The thermoplastic polyester resin which can be used for the base sheet is represented by polyethylene terephthalate, ethylene-terephthalate-isophthalate copolymer and the like. As the acid component, terephthalic acid, isophthalic acid, naphthalene Copolymers obtained as esters of both aromatic dicarboxylic acids such as dicarboxylic acids and aliphatic diols such as ethylene glycol, diethylene glycol, butanediol and hexanediol as alcohol components are exemplified.

Various additives such as a filler, a foaming agent, a flame retardant, a lubricant, an antioxidant, a heat stabilizer, an ultraviolet absorber, and a light stabilizer may be added to the base sheet made of each of the above resins, if necessary. Is added. Known heat stabilizers such as phenol-based, sulfide-based, phenylalkane-based, phosphite-based, and amine-based stabilizers can be used, and have a function of preventing deterioration such as thermal discoloration that occurs during thermal processing. Examples of the flame retardant include powders such as aluminum hydroxide and magnesium hydroxide.

For example, when an olefin resin is used for the base sheet, talc or aluminum benzoate may be added as a transparent nucleating agent in addition to the above-mentioned aryl phosphate compound. When particularly high transparency is required, a sorbitol-based transparent nucleating agent may be added. Further, in order to improve the dispersibility of the transparent nucleating agent in the resin, at least one selected from the group consisting of alkali metal salts of organic carboxylic acids, alkali metal salts of β-diketonates and alkali metal salts of β-ketoacetic esters. Seed dispersants may be added.

When one or both of the ultraviolet absorber and the light stabilizer are added to the base sheet, the amount of the ultraviolet absorber and the light stabilizer is usually 0.1 to 10% by weight.
It is generally preferable to use an ultraviolet absorber and a light stabilizer in combination.

In the present invention, an organic compound having a hydroxyl group in the molecule can be preferably used as the ultraviolet absorber. For example, a benzotriazole-based ultraviolet absorber,
In particular, 2- (2'-hydroxy-3 ', 5'-di-te
rt-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 '-Tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-3'-isobutyl-
2'-hydroxyphenylbenzotriazole-based ultraviolet absorbers such as 5'-propylphenyl) -5-chlorobenzotriazole.

Examples of the benzophenone-based ultraviolet absorbers include 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, and 2,2 ', 4,4. Examples include 2,2'-dihydroxybenzophenone-based ultraviolet absorbers such as' -tetrahydroxybenzophenone, and 2-hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone and 2,4-dihydroxybenzophenone.

In addition, an ultraviolet absorber having an acryloyl group or a methacryloyl group introduced into a benzotriazole skeleton, or an inorganic substance such as zinc oxide, cerium oxide, or titanium oxide in the form of fine particles having a diameter of 0.2 μm or less can also be used. Examples of the filler (extending pigment) include calcium carbonate, silica (silicon dioxide), alumina (aluminum oxide), and barium sulfate.

The thickness of the base sheet is usually set to 50 to 200 μm in consideration of the strength of the decorative sheet molded article and the like. From the viewpoint of the flexibility and workability of the decorative sheet, preferably 50 to 1
It is 50 μm.

One or both surfaces of the resin film used as the base sheet may be subjected to a surface treatment for improving the laminating property (easy adhesion property) and the adhesive applicability of the film. Examples of the surface treatment method include a corona discharge treatment, a plasma treatment, a flame treatment, an ozone treatment, and an acid treatment. In the present invention, any of these methods can be used.

Among these methods, a plasma treatment, a flame treatment, and a corona discharge treatment are preferable because they can be continuously processed and can be easily carried out before the winding step in the film production process. From the viewpoint, corona discharge treatment is particularly preferred.

The upper layer of the base sheet may be subjected to a decorative treatment in order to improve the decorativeness of the decorative sheet. Examples of the method of the decoration treatment include a method of coloring a base sheet by adding a pigment, and a method of forming a printed layer by printing a pattern such as a picture on the base sheet with ink or paint.

The printing layer may be formed directly on a base sheet made of an olefin resin film previously colored with a pigment or a dye, or a primer layer made of a two-component curable polyurethane resin may be formed on the base sheet. Forming
A printing layer may be formed on the upper layer, or any of them may be used. As the resin for the primer layer, an acrylic resin, a vinyl chloride-vinyl acetate copolymer, a polyester resin, a chlorinated polypropylene resin, a chlorinated polyethylene resin, or the like can be used in addition to the urethane resin.

The printing layer may have a laminate structure composed of two layers, the lower layer being a solid printing layer (underlying concealed printing layer) and the upper layer being a picture printing layer. Printing of patterns etc. is gravure printing,
The printing can be performed by a known printing method such as offset printing, silk screen printing, and transfer printing from a transfer sheet.

Examples of pigments or dyes used for forming a printing layer or coloring a base sheet include inorganic pigments such as titanium white, zinc white, cobalt blue, titanium yellow and carbon black, isoindolinone, Hansa Yellow A, quinacridone, and the like. Permanent red 4R, phthalocyanine blue,
Organic dyes such as aniline black; pearlescent (pearl) pigments made of foil powder such as titanium dioxide-coated mica;

An adhesive layer is provided for bonding the printing layer and the top sheet formed on the upper layer. As the binder resin for the adhesive layer, an acrylic resin, a vinyl chloride-vinyl acetate copolymer, a polyester resin, a urethane resin, a polyethylene chloride resin, a chlorine chloride polypropylene resin, or the like is used. The thickness of the adhesive layer is 1 to 20 μm, preferably 3 to 5 μm.

As the acrylic resin, poly (meth)
Methyl acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate-butyl (meth) acrylate copolymer, (meth) acrylic acid Homo- or copolymers containing (meth) acrylates such as ethyl-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, and styrene-methyl (meth) acrylate copolymer An acrylic resin consisting of Here, (meth) acryl refers to acryl or methacryl.

The urethane resin is a urethane resin having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent). The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, and polyether polyol. The isocyanate is
A polyvalent isocyanate having two or more isocyanate groups in the molecule is used. For example, 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4-
Aromatic isocyanates such as diphenylmethane diisocyanate, or aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used.

The topsheet is formed by multilayer extrusion of resin. Extrusion coating is performed by extruding the molten resin onto or without the adhesive layer or the primer layer on the printing layer.
ng; hereinafter, EC coating) method. The thickness of the topsheet is 10 to 500 μm
About 30 to 120 μm.

As the resin of the surface sheet, a resin selected from olefin resins, acrylic resins, ethylene-vinyl alcohol copolymer resins, and thermoplastic polyester resins can be used as in the case of the base sheet.
Among the above resins, an olefin resin, preferably an olefin thermoplastic elastomer, is used in terms of moldability and the like.

The preferred olefin-based thermoplastic elastomer used for the topsheet is a colorless or colored transparent soft polypropylene-based resin having a composite three-dimensional structure, which is a mixed system of isotactic polypropylene and atactic polypropylene. Resins. This polypropylene resin is, specifically,
(A) (a) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donor as essential components,
(B) an organoaluminum compound, and (c) a general formula

[0059]

Embedded image

(Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitroso group, m is an integer of 1 to 6, n is 0 or 1) ~ (6
-M) is a number average molecular weight (M) obtained by polymerizing propylene in the presence of a catalyst comprising a combination of an alkoxy group-containing aromatic compound represented by the following formula:
n) is 25,000 or more and the weight average molecular weight (M
w) and the number average molecular weight (Mn) ratio (Mw / Mn) is 7
From 10 to 90% by weight of the following boiling heptane-soluble polypropylene (atactic polypropylene) and (B) 90 to 10% by weight of a boiling heptane-insoluble polypropylene (isotactic polypropylene) having a melt index of 0.1 to 4 g / 10 min. Flexible polypropylene resin composition.

The above soft polypropylene resin composition has an elongation at break (T _b ) of 400% or more, preferably 500 to 7%.
Residual elongation (PS ₁₀₀ ) after 100% and 100% elongation is 80
% Or less, preferably 50 to 75%, and at break stress (M _B) and at yield stress (M _Y) ratio of (M _B / M _Y) is 1.0 or more, preferably 1.5 to 3. It is desirably in the range of 5.

In the above soft polypropylene resin composition, the atactic polypropylene as the component (A) is soluble in boiling heptane and has a number average molecular weight (M
n) is 25,000 or more, preferably 30,000 to 6
Weight average molecular weight (Mw) in the range of 000
And a number average molecular weight (Mn) having a ratio Mw / Mn of 7 or less, preferably 2 to 6. This M
If the n is less than 25,000 or the Mw / Mn ratio exceeds 7, the effect of contributing to the mechanical properties of the atactic polypropylene in the obtained resin is not sufficiently exhibited, and the stress at break of the obtained resin ( M _B) and may become the ratio of the yield stress at _{(M Y) (M B /} M Y) is less than 1.0, the residual elongation after 100% elongation (PS ₁₀₀₎ is or exceeds 80% Not desirable.

The atactic polypropylene of the above component (A) may be a propylene homopolymer, or may contain a propylene unit and 40% by weight or less, preferably 30% by weight or less of other α-alkyl having 2 to 30 carbon atoms. It may be a propylene copolymer containing an olefin unit. Also, this atactic polypropylene may be used alone or in combination of two or more. The atactic polypropylene of the component (A) can be prepared by a known method (Japanese Patent Application Laid-Open No.
For example, the method described in JP-A-3-243106).

In the above soft polypropylene resin composition, as the component (B), a melt index (MI)
However, boiling heptane-insoluble crystalline isotactic polypropylene of 0.1 to 4 g / 10 min is used. If the melt index is less than 0.1 / 10 minutes, the melting properties are low, and sheet molding becomes difficult. If the melt index exceeds 4 g / 10 minutes, the mechanical strength becomes insufficient and V-cut processing may not be performed well. is there. The isotactic polypropylene of the component (B) may be a propylene homopolymer having isotactic stereoregularity or a copolymer of propylene having the stereoregularity and another α-olefin. It may be. As the α-olefin, those having 2 to 8 carbon atoms, for example, ethylene, butene-1, pentene-1, heptene-1, octene-1 and the like are preferable, and ethylene and butene-1 are particularly preferable. As the copolymer, a block copolymer or a random copolymer containing the other α-olefin unit in an amount of usually 40% by weight or less, preferably 30% by weight or less is used.

Preferred as the isotactic polypropylene as the component (B) are propylene homopolymer and 1 to 30% by weight of ethylene units, preferably 3 to 30% by weight.
A random copolymer or block copolymer of propylene and ethylene containing up to 25% by weight. The production of such an isotactic polypropylene can be performed in the same manner as the production of a conventional crystalline polypropylene.

In the above soft polypropylene resin composition, the isotactic polypropylene of the component (B) may be used alone or in combination of two or more. Further, the atactic polypropylene of the component (A) and the isotactic polypropylene of the component (B)
When the content of the component (A) is 10 to 90% by weight, preferably 2%
It is used in such a ratio that the content of the component (B) is 5 to 80% by weight, and 90 to 10% by weight, preferably 75 to 20% by weight. The In content of the component (A) is less than 10 wt%, and the yield stress at the resin (M _Y) is too large, the ratio of the breaking stress at the (M _B) and at yield stress (M _Y) (M _B /
M _Y ) is less than 1.0, and the residual elongation (PS ₁₀₀ ) after 100% elongation is also greater than 80%. on the other hand,
(A) and the content of the component exceeds 90 wt% at break stress (M _B) is too small, M _B / M _Y is less than 1.0, and the mechanical strength may be decreased. Also,
By increasing the ratio of the component (B), the Young's modulus of the obtained soft polypropylene increases. A particularly preferred ratio of the component (A) to the component (B) is 1: 1.

In the decorative sheet of the present invention, the uppermost layer of the topsheet contains a resin such as an olefin-based thermoplastic elastomer and an antifungal and antibacterial agent. Commercially available industrial antibacterial agents can be used as the fungicide / antibacterial agent. Usually, commercially available industrial antibacterial agents are roughly classified into inorganic antibacterial agents and organic antibacterial agents, and any of the antibacterial agents can be used for the decorative sheet of the present invention.

Examples of the inorganic antibacterial agent include A having antibacterial properties.
Metal ions such as g ⁺ , Cu ²⁺ , Zn ²⁺ , Hg ⁺ , Ni ²⁺ , and Cd ²⁺ (in particular, Ag ⁺ is widely used for its long-lasting effect and safety) are replaced with inorganic ions. What is held on the body is used. As the inorganic ion exchanger, for example,
In addition to inorganic adsorbents such as activated carbon, activated alumina, and silica gel, zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, hydrated bismuth, hydrated zirconium, and the like are used. The above-mentioned inorganic ion exchanger may be further exchanged with an ammonium ion (an antibacterial agent described in Japanese Patent Publication No. 4-28646).

Among the above-mentioned inorganic antibacterial agents, in particular, ions in zeolite can be reduced to about 0.1% by using silver nitrate, silver sulfate or the like.
Antibacterial zeolite substituted with 0.1 to 8% of copper ions and 0.1 to 8% of zinc ions in addition to the above-mentioned ions (for example, Japanese Patent Application Laid-Open No. Antimicrobial agents described in -78789 are frequently used and are preferably used.

The particle size of the above-mentioned inorganic antibacterial agent is 0.1 to 10% by weight, and when the film thickness (when dried) of the surface sheet containing the fungicide / antibacterial agent is 2 to 10 μm, it is 0.1% by weight. ~ 1
0 μm, preferably 2 to 5 μm. Since it is usually desired that the topsheet is transparent, when an inorganic antibacterial agent having low solubility in a solvent is added, the amount added is limited to the solubility. Furthermore, since metals such as silver and nickel often have adverse effects such as discoloration, deterioration, and deterioration on organic compounds such as resins forming each layer, avoid excessive addition of these inorganic antibacterial agents. I do.

As the organic antibacterial agent, for example, JP-A-3
In addition to N-fluorodichloromethyl-phthalimide described in JP-A-10-10833 and 10,10'-oxybisphenoxyarsine described in JP-A-9-227844,
-(Fluorodichloromethylthio) phthalimide, 2-
(4-thiazoyl) benzimidazole, p-aminobenzenesulfonamide, sulfathiazole, sulfapyridine, sulfadiazine, dimethyldithiocarbamate, ethylenebisdithiocarbamate, 2- (2-
Furyl) -3- (5-nitro-2furyl) acrylamide, trimethoxysilylpropyloctadecyl ammonium chloride, bis (2-pyridylthio-1-oxide) zinc, 2-N-octyl-4-isothiazoline-3
-One, 2,3,5,6-cytochloro-4- (methylthio) -phthalimide, N- (fluorodichloromethylthio) florimide, and other antibacterial agents can be used. The addition amount of these organic antibacterial agents is usually 0.1 to 10% by weight.

In the decorative sheet of the present invention, deterioration of each layer due to ultraviolet rays is prevented on the uppermost layer of the topsheet,
In order to improve the weather resistance, the same ultraviolet absorber as that which can be added to the above-mentioned base sheet can be added, and further, a light stabilizer composed of a radical scavenger can be added.

As the radical scavenger, bis- (2,2
2,6,6-tetramethyl-4-piperidinyl) sepagate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sepagate, and others, for example, Japanese Patent Publication No. 4-82625 Hindered amine radical scavengers such as the compounds described above, piperidyl radical scavengers, and the like can be used.

When a light stabilizer comprising a hindered amine radical scavenger is added to the olefin resin, not only the olefin resin but also an adhesive layer and a printing layer adjacent to the olefin resin may be used. It is preferable to use a resin containing no chlorine atom in the molecule, such as a urethane resin, an olefin-based resin, and a polyamide resin.

When a resin containing a chlorine atom in a molecule, such as a vinyl chloride-vinyl acetate copolymer, is used for the olefin resin or a layer adjacent to the olefin resin, these resins are acted upon by the action of ultraviolet light or heat. Generates hydrogen chloride by a dechlorination reaction, which reacts with the hindered amine radical scavenger to deactivate and inhibit the action as a light stabilizer, so that the hindered amine radical scavenger does not contribute to the improvement of weather resistance.

On the surface of the topsheet, a pattern having an uneven shape can be formed by embossing. When embossing is performed on the topsheet of the present invention, immediately after forming the topsheet by multilayer extrusion of the resin, the decorative sheet is placed on a stainless steel belt containing two or more horizontal cooling rolls that serve as stable supports. Then, a decorative sheet is introduced directly under an uneven endless stainless belt having two or more cooling rolls.

As a result, the surface of the decorative sheet is embossed at a high speed while the decorative sheet is cooled with high cooling efficiency. When embossing is performed while cooling by multilayer melt extrusion at a high temperature, the molding resin is reheated and softened, and the embossing reproducibility is generally higher than when embossing is performed. Examples of the shape of the concavo-convex pattern formed by embossing include a wood grain conduit groove, a wood grain wood grain, a slab surface, a cloth grain, a satin finish, a grain grain, a line shape, or a combination thereof.

In the decorative sheet of the present invention, a protective layer containing a fungicide / antibacterial agent may be preferably formed on the top layer of the topsheet. The protective layer is provided to improve the scratch resistance of the surface of the decorative sheet.
To about 10 μm. As the resin used for the protective layer, for example, urethane resin, fluorine resin, silicon resin,
There are polyfunctional acrylates and the like which are cured by ultraviolet rays or electron beams. Preferred examples include a two-component curable polyurethane resin containing a polyol as a main component and an isocyanate as a crosslinking agent (curing agent).

As the fungicide / antibacterial agent contained in the protective layer, the same fungicide / antibacterial agent added to the above-mentioned topsheet is used at the same concentration (0.1 to 10% by weight). be able to. For example, the protective layer is made of a two-part curable urethane-based resin composed of acrylic polyol and hexamethylene diisocyanate, and has a particle size distribution of 2 to 5 μm as an antibacterial agent.
m, 5% by weight of a silver ion type zeolite antibacterial agent having a silver content of 2.5% by weight and a zinc content of 14.5% by weight,
A coating obtained by adding microsilica having an average primary particle size of 16 nm and a specific surface area of 110 m ² / g as an extender is coated on the top sheet by a gravure roll coating method so that the coating has a thickness of about 3 μm (when dried). It can be formed by coating.

In a decorative sheet mainly composed of an olefin-based resin, if a layer composed of a vinyl chloride-vinyl acetate copolymer is contained, the adhesiveness between layers and the light-proof adhesiveness tend to decrease. For this reason, the above-mentioned two-component curable polyurethane resin having a polyol as a main component and an isocyanate as a cross-linking agent (curing agent) without using a vinyl chloride-vinyl acetate copolymer as a main material of the protective layer is used. Such a decrease in interlayer adhesion can be prevented. As the two-component curable urethane resin, a two-component curable polyurethane resin composed of the same polyol and isocyanate as used for the adhesive layer can be used.

In the case of the two-part curable urethane resin, more preferably, the number (mol number) of isocyanate groups in the isocyanate compound is made to be larger than the number (mol number) of hydroxyl groups in the polyol which reacts with the isocyanate compound, so that urethane bonds are formed. Even after the generation, a large amount of excess isocyanate groups may remain. In that case, the number of isocyanate groups / the number of hydroxyl groups is at most about 1.4.

The skeleton structure of the molecular chain of the prepolymer having an isocyanate group at the molecular terminal is arbitrary, and specific examples include a polyurethane skeleton having a urethane bond, a polyester skeleton having an ester bond, and a polybutadiene skeleton. As appropriate, one or more of these skeletal structures are employed. When a urethane bond is present in the molecular chain, the terminal isocyanate group also reacts with the urethane bond to generate an allophanate bond, which also causes a cross-linking reaction.

The protective layer may contain an ultraviolet absorber for the purpose of improving the light resistance of the decorative sheet. As the ultraviolet absorber, the same ones that can be contained in the base sheet or top sheet can be used. In particular, when an organic compound having a hydroxyl group in the molecule is used as the ultraviolet absorber, the protective layer is preferably formed using a resin having an isocyanate group.

In such a combination, when the ultraviolet absorbent bleeds (elutions) and enters the protective layer, the hydroxyl group of the ultraviolet absorbent reacts with the isocyanate group in the protective layer to form a urethane bond. To be trapped in the protective layer. Therefore, bleeding of the ultraviolet absorber over time is prevented. The bleed prevention method described above is
In particular, it is effective in the case where the organic ultraviolet absorber is an olefin resin which is easily bleed.

The above-mentioned base sheet, printing layer, adhesive layer and surface sheet constitute the basic constitution of the decorative sheet of the present invention, and further, the above-mentioned protective layer is provided if necessary.
Various modifications can be made to the above basic sheet configuration. For example, the topsheet may have a multilayer structure in which three or more topsheets are stacked. However, it is assumed that the topsheet is formed into multiple layers at the same time by melt extrusion using a multilayer coextrusion machine.

The decorative sheet of the present invention can be used by being laminated on various adherends. If the adherend is the final product and a decorative sheet is laminated for its surface makeup,
Alternatively, when the mechanical strength of the decorative sheet is reinforced or concealment is imparted as necessary, the back surface of the decorative sheet is laminated on the adherend.

When the decorative sheet itself can be laminated on the adherend by heat fusion or the like due to the adhesiveness of the decorative sheet itself, it is not necessary to provide an adhesive layer on the back surface of the decorative sheet. If the decorative sheet itself does not adhere to the adherend, the decorative sheet is laminated using an appropriate adhesive.

Among the adherend materials, various materials such as flat and curved plates, three-dimensionally shaped articles, and sheets (or films) include wood veneer,
Wood plywood, particle board, medium density fiberboard (MD
F) and other wood materials, metals such as iron and aluminum, polycarbonate resins, ethylene-vinyl acetate copolymers, ethylene vinyl acetate copolymers, polyester resins, polystyrene resins, acrylic resins, olefin resins, AB
There are resins such as S resin, phenol resin, polyvinyl chloride resin, cellulose resin, and rubber.

Among the adherend materials, the material used exclusively as a plate material or a three-dimensionally shaped article includes glass, ceramics such as porcelain, cement such as ALC (foamed lightweight concrete), and non-cement such as calcium silicate and gypsum. There are ceramic materials. Materials used exclusively as sheets (or films) include high quality paper,
Paper such as Japanese paper, or carbon, asbestos, potassium titanate,
There is a nonwoven fabric or a woven fabric made of fibers such as glass and synthetic resin.

As a method of laminating these various adherends,
For example, (1) a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive,
No. 2, JP-B-43-27488, etc., insert the decorative sheet into both male and female molds for injection molding, close both molds, and inject molten resin from the male gate. After cooling, a decorative sheet is adhered and laminated on the surface of the resin molded article simultaneously with the molding of the resin molded article, so-called simultaneous lamination method of injection molding. (3) JP-B-56-45768 and JP-B-60-58014. As described in, etc., a decorative sheet is opposed to or placed on the surface of the molded article via an adhesive layer therebetween, and the decorative sheet is laminated on the surface of the molded article by a pressure difference due to vacuum suction from the molded article. So-called vacuum press laminating method, (4) JP-B-61-5895.
Japanese Patent Publication No. JP-B-3-2666, etc.
While supplying the decorative sheet in the long axis direction of the columnar base material such as a polygonal column through an adhesive layer therebetween, the decorative sheets are sequentially applied to a plurality of side surfaces constituting the columnar body by a plurality of rollers having different directions. A so-called lapping method of laminating by pressure bonding. (5) First, a decorative sheet is bonded to a plate-like base material as described in Japanese Utility Model Publication No. 15-31122, JP-A-48-47972, and the like. Laminating through the layers, and then reaching the interface between the decorative sheet and the plate-shaped substrate on the surface of the plate-shaped substrate opposite to the decorative sheet, forming a V-shaped or U-shaped groove in cross section. After cutting, and then applying an adhesive in the groove, the groove is bent to form a box or a columnar body.
There is a cutting or U-cut processing method.

The method of bonding the decorative sheet of the present invention to a three-dimensional object having irregularities includes (4) a lapping method, (5) a V-cut method, (2) a simultaneous injection molding laminating method, (3) A vacuum press lamination method or the like is preferable.

The decorative sheet of the present invention can be used for various purposes by laminating it on various adherends as required and subjecting it to a predetermined molding process. Applications of the decorative sheet of the present invention include, for example, interior decoration of buildings such as walls, ceilings and floors, window frames, doors, surface decoration of fittings such as handrails, furniture or home appliances,
Surface makeup for OA equipment cabinets, vehicle interiors such as automobiles and trains, aircraft interiors, window glass makeup, and the like.

Since the decorative sheet of the present invention has fungicidal and antibacterial properties, it is used especially for interior materials used in places where mold and bacteria easily propagate, such as kitchens and bathrooms, and for hospitals where antibacterial properties are required. It can be suitably used for various materials.

[0094]

(Embodiment 1) FIG. 1 is a sectional view of a decorative sheet according to this embodiment. The decorative sheet according to the present embodiment includes a base sheet 1
It has a structure in which a printing layer 2 is formed on the upper layer, and two surface sheets 4a and 4b are laminated on the printing layer 2 with an adhesive layer 3 interposed therebetween.

As the base sheet 1, a high-density polyethylene-based film having a thickness of 100 μm and opaque yellow-brown coloring with titanium white, carbon black and yellow lead is used. As a high-density polyethylene film,
A composition obtained by adding 10 parts by weight of styrene-butadiene rubber and 10 parts by weight of calcium carbonate as an inorganic filler to 60 parts by weight of high-density polyethylene is used. A hindered amine antioxidant is added to the high-density polyethylene film of the base sheet 1 in addition to the above additives.

In order to make the above-mentioned high-density polyethylene film easy to adhere, a corona discharge treatment is applied to the film surface. The critical surface tension of the olefin-based resin is usually about 30 (dyne / cm) at room temperature.
(Dyne / cm).

A wood pattern is printed on the base sheet 1 by gravure printing to form a print layer 2. An adhesive for two-component curable polyester urethane dry lamination is applied to the upper layer of the printing layer 2 at a rate of 2 g / m ² (dry) by a gravure method to form an adhesive layer 3.

Top sheet 4 formed on adhesive layer 3
As the resins (a) and (4b), an elastomer based on a polypropylene resin composed of a soft segment and a hard segment in which isotactic polypropylene and atactic polypropylene are mixed is used.

Using a multilayer extruder, two layers of a transparent polypropylene resin in a molten state were extruded onto the adhesive layer 3, and the resin surface was immediately subjected to corona discharge treatment, and then cooled to a wood grain conduit shape. It is introduced into a roll to cool and solidify the topsheets 4a, 4b.

Regarding the thickness of the surface sheet, the lower surface sheet 4a is 40 μm, and the upper surface sheet 4b is
Is 10 μm. The upper surface sheet 4b is a known antibacterial zeolite in which ions in the zeolite are replaced with silver ions of about 0.1 to 15% using silver nitrate, silver sulfate or the like as a fungicide / antibacterial agent in an amount of 3% by weight. %Added. Further, for the purpose of improving the weather resistance, the surface sheets 4a, 4b
0.4% by weight of an antioxidant and 0.8% by weight of an ultraviolet absorber are added to each layer. As a result, a decorative sheet according to the present embodiment whose sectional view is shown in FIG. 1 is obtained.

Example 2 FIG. 2 is a sectional view of a decorative sheet according to this example. In the decorative sheet of the present embodiment, a printed layer 2 is formed on an upper layer of a base sheet 1, and two surface sheets 4 a and 4 b are laminated on the upper layer via an adhesive layer 3,
It has a structure in which a protective layer 5 is formed on the uppermost layer.

As the base sheet 1, a high-density polyethylene film having a thickness of 100 μm, which is opaque yellow-brown colored with titanium white, carbon black and graphite, is used. As a high-density polyethylene film,
A composition obtained by adding 10 parts by weight of styrene-butadiene rubber and 10 parts by weight of calcium carbonate as an inorganic filler to 60 parts by weight of high-density polyethylene is used. A hindered amine antioxidant is added to the high-density polyethylene film of the base sheet 1 in addition to the above additives.

In order to make the above-mentioned high-density polyethylene film easy to adhere, a corona discharge treatment is applied to the film surface. The critical surface tension of the olefin-based resin is usually about 30 (dyne / cm) at room temperature.
(Dyne / cm).

A wood pattern is printed on the base sheet 1 by gravure printing to form a print layer 2. An adhesive for two-component curable polyester urethane dry lamination is applied to the upper layer of the printing layer 2 at a rate of 2 g / m ² (dry) by a gravure method to form an adhesive layer 3.

Top sheet 4 formed on adhesive layer 3
As the resins (a) and (4b), an elastomer based on a polypropylene resin composed of a soft segment and a hard segment in which isotactic polypropylene and atactic polypropylene are mixed is used.

Using a multilayer extruder, two layers of a transparent polypropylene resin in a molten state were extruded onto the adhesive layer 3, and the resin surface was immediately subjected to corona discharge treatment, and then cooled to a wood grain conduit shape. It is introduced into a roll to cool and solidify the topsheets 4a, 4b.

Regarding the thickness of the surface sheet, the lower surface sheet 4a is 40 μm, and the upper surface sheet 4b is
Is 10 μm. 0.3% by weight of N-fluorodichloromethyl-phthalimide is added to the upper surface sheet 4b as a fungicide / antibacterial agent. For the purpose of improving the weather resistance, 0.4% by weight of an antioxidant and 0.8% by weight of an ultraviolet absorber are added to each layer of the topsheets 4a and 4b.

Further, as an antibacterial and antifungal agent, an acrylic urethane-based resin to which 3% by weight of antibacterial zeolite in which ions in zeolite are replaced by silver ions of about 0.1 to 15% is applied, is applied. The protection layer 5 is formed.
The resin of the protective layer 5 has a phase transition temperature of 90 ° C. and a molecular weight of 8
Acrylic polyol of 3,000 as a solid resin is 23% by weight, ethyl acetate as a solvent is 50% by weight, and in addition, hexamethylene diisocyanate as an isocyanate component, and trace amounts (less than 1% by weight) of an antifoaming agent and wax are contained. A two-component curable resin having such a composition is used. As a result, a decorative sheet according to the present embodiment whose sectional view is shown in FIG. 2 is obtained.

[0109]

According to the decorative sheet of the present invention and the method for producing the same, the effectiveness of the antibacterial agent in the heating step is not reduced, and the antibacterial agent is not dissipated during embossing.
A decorative sheet having a sufficient antibacterial activity while keeping the amount of the antibacterial agent low can be obtained.

[Brief description of the drawings]

FIG. 1 is a sectional view of a decorative sheet according to Example 1 of the present invention.

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

[Explanation of symbols]

DESCRIPTION OF SYMBOLS 1 ... Substrate sheet, 2 ... Printing layer, 3 ... Adhesive layer, 4a ... Surface sheet, 4b ... Surface sheet containing a fungicide / antibacterial agent, 5 ... Protective layer.

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[Procedure amendment]

[Submission date] March 19, 1998

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0059

[Correction method] Change

[Correction contents]

[0059]

Embedded image

Claims (6)

[Claims] 1. A decorative sheet having a surface sheet comprising a laminate of two or more layers on a base material sheet, wherein an antifungal / antibacterial agent is compounded in the uppermost layer of the surface sheet. To make a decorative sheet. 2. The decorative sheet according to claim 1, wherein an embossing process is performed on the topsheet. 3. The decorative sheet according to claim 1, further comprising a protective layer containing a fungicide / antibacterial agent on the topsheet. 4. The base sheet and the top sheet,
The decorative sheet according to any one of claims 1 to 3, comprising a thermoplastic resin. 5. A step of forming a base sheet mainly composed of a thermoplastic resin, and extruding a plurality of thermoplastic resins on the base sheet to form a surface sheet composed of a laminate of two or more layers. Forming, and a method of manufacturing a decorative sheet having at least a step of embossing the surface of the topsheet, wherein the top layer of the topsheet is added with a fungicide / antibacterial agent, Manufacturing method of decorative sheet. 6. The method for producing a decorative sheet according to claim 5, further comprising a step of forming a protective layer containing a fungicide / antibacterial agent on the topsheet.