JPH11170448A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To manufacture a decorative sheet of high stain resistance, high interlaminar bonding strength and strength sufficient as a building material. SOLUTION: A printed pattern layer 2 is formed on a base sheet 1 composed of olefin thermoplastic elastomer, on which a top sheet 3 composed of transparent acrylic resin is laminated, and further a top coat layer 4 composed of acryl- fluorine copolymer resin is formed on the laminate. Firm bonding is provided between both layers by laminating the acryl-fluorine copolymer resin on acrylic resin, and the effect is maintained for a long period of time. Also the effect of superior solvent resistance such as resistance to alcohol is provided. Also in the case an antibacterial agent is contained in the top coat layer 4, the antibacterial effect is not lowered as the stain resistance is provided in the top coat layer itself.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet used by being bonded to the surface of a wooden board / bar, metal plate or the like.

[0002]

Heretofore, many decorative sheets of this type which mainly use vinyl chloride have been used. Vinyl chloride is excellent in printability and embossability, and is easy to process into decorative sheets.
It has excellent post-processing properties such as cutting and wrapping, and has the advantage of being inexpensive. However, this type of decorative sheet has drawbacks such as insufficient heat resistance and poor stain resistance. Therefore, coating is carried out for the purpose of preventing contamination, but there is a problem that the adhesion of the coating agent is poor due to bleeding (exuding) of the plasticizer.

[0003] Here, examples of the coating agent for preventing contamination include those which exhibit a stain-proofing property by adding a fluorine-based surfactant having a perfluoroalkyl group to a resin to be bonded to urethane, and those comprising an acrylic silicone resin. However, those using a fluorine-based surfactant cannot maintain its performance for a long period of time due to weak bonding force with urethane resin or small molecular weight, and acrylic silicone resin has alcohol resistance. There is a problem that there is no solvent resistance.

On the other hand, as a coating agent exhibiting antibacterial properties, there is a coating agent in which an inorganic or organic antibacterial agent is dispersed in a urethane-bonded resin. However, urethane-bonded resins have poorer stain resistance than fluorine-based resins,
Contaminated areas have reduced antimicrobial performance.

The present invention has been made in view of the above-mentioned problems, and an object of the present invention is to provide a decorative sheet having high stain resistance, high interlayer adhesion strength, and sufficient strength for use as a building material. Is to provide.

[0006]

Means for Solving the Problems To achieve the above object, the decorative sheet of the present invention comprises a printed pattern layer formed on a base sheet made of an olefin-based thermoplastic elastomer,
A top sheet made of a transparent acrylic resin is laminated thereon, and a top coat layer made of an acrylic-fluoro copolymer resin is further provided thereon. Further, an antibacterial agent may be contained in the top coat layer.

[0007]

FIG. 1 shows one embodiment of a decorative sheet according to the present invention. In this decorative sheet, a printed pattern layer 2 is formed on a base sheet 1 and a transparent top sheet 3 is formed thereon.
Are laminated, and a top coat layer 4 is further provided thereon. In this example, irregularities are formed on the top sheet 3, and the concave portions are filled with the coloring agent 5.

[0008] The base sheet is composed of an olefin-based thermoplastic elastomer. The olefin-based thermoplastic elastomer is a composite thermoplastic elastomer composed of an elastomer and an olefin-based resin, and is classified into the following three types. That is, a type in which an elastomer as a soft segment and an olefin-based resin as a hard segment are simply blended, a cross-linked type in which an elastomer and an olefin-based resin are partially cross-linked to form a complex, and an elastomer which is cross-linked to form an olefin-based resin And the following five types are specifically mentioned.

A simple blend of (A) an elastomer as a soft segment and (B) an olefin resin as a hard segment. Specifically, as the olefin resin, polyethylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, polypropylene, propylene / butene-1 copolymer, polybutene-
1, butene-1, propylene, ethylene, terpolymers, butene-1, hexene-1, octene-1, terpolymers, and polymethylpentene resins alone or as a mixture of two or more resins. Can be Examples of the elastomer include various rubbers. Examples of the rubber include a diene rubber, a hydrogenated diene rubber, and an olefin elastomer. Among them, a hydrogenated diene rubber is preferable.

[0010] The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule, and suppresses crystallization of the polyolefin resin.
It plays a role in improving flexibility and transparency. Also, generally, when a diene rubber is added to a polyolefin resin, the double bond of the diene rubber causes the weather resistance and heat resistance to be lower than those of the polyolefin resin without the diene rubber.
In the present invention, since the double bond of the diene rubber is saturated with hydrogen, the polyolefin resin has good weather resistance and heat resistance without deterioration. 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. For the purpose of the present invention, styrene-butadiene rubber is particularly preferred.

The olefin elastomer may be of two types or three types.
An elastic copolymer obtained by adding at least one kind of polyene copolymerizable with at least one kind of olefin. As the olefin, ethylene, propylene, α-olefin or the like is used. As the polyene, 1,4 hexadiene, cyclic diene , Norbornene and the like are used. Preferred olefin copolymer rubbers include, for example, elastic copolymers containing an olefin as a main component, such as ethylene-propylene copolymer rubber, ethylene-propylene non-conjugated diene rubber, and ethylene-butadiene copolymer rubber.

The rubber is added in an amount of about 1 to 90 parts by weight based on 100 parts by weight of the olefin resin.
If the amount is less than 1 part by weight, the elasticity, elongation, and impact resistance due to the addition of rubber are insufficient, and cracks and cracks are likely to occur during bending such as V-cutting and drawing. On the other hand, if it exceeds 90 parts by weight, the elasticity and elongation become too large, and the registration during printing becomes poor, which is not preferable.

Further, the elastomer will be described later.
And the like.

(A) The number average molecular weight Mn is 25,000 or more, and the ratio Mw / Mn of the weight average molecular weight Mw to the number average molecular weight Mn as described in JP-B-6-23278.
From a mixture of 10 to 90% by weight of a boiling heptane-soluble polypropylene of ≦ 7 (soft segment) and (B) 90 to 10% by weight of a boiling heptane-insoluble polypropylene (hard segment) having a melt index of 0.1 to 4 g / 10 min. Becomes soft polypropylene.

As described in JP-B-53-21021, (A) an olefin polymer (crystalline polymer) such as polyethylene, polypropylene or polymethylpentene is used as a hard segment, and (B) a partially crosslinked ethylene An olefin elastomer obtained by using a mono-olefin copolymer rubber such as a propylene copolymer rubber or an unsaturated ethylene / propylene non-conjugated diene terpolymer rubber as a soft segment, and uniformly blending and mixing these. (B) /
(A) = 50/50 to 90/10 (weight ratio).

As described in JP-B-53-34210, (A) an uncrosslinked monoolefin copolymer rubber (soft segment), (B) an olefin copolymer (crystalline, hard segment) and a crosslinking agent are mixed. An olefin elastomer obtained by heating and applying a shear stress to dynamically partially crosslink. (A) / (B) = 60 / 40-80 / 20
(Weight ratio).

As described in JP-B-56-15575, etc., (A) mixed with a peroxide such as isotactic polypropylene, propylene / ethylene copolymer or propylene / butene-1 copolymer, and the molecular weight is reduced by heating. By mixing and heating a peroxide-decomposable olefin polymer (hard segment) that increases fluidity and a peroxide such as (B) ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene terpolymer rubber, Mixing with peroxides such as peroxide-crosslinked monoolefin copolymer rubber (soft segment) whose flowability is reduced by crosslinking, (C) polyisobutylene, butyl rubber, etc.
Peroxide non-crosslinked hydrocarbon rubber (soft segment and fluidity-modifying component) that does not crosslink even when heated and does not change its flowability, and (D) mineral oil softening such as paraffinic, naphthenic, aromatic, etc. An olefin-based elastomer obtained by mixing the agent and an agent and dynamically heat-treating the mixture in the presence of an organic peroxide. (A) is 90 to 40 parts by weight, (B) is 10 to 60 parts by weight, and (C) and (D) are 5 to 100 parts by weight.

These olefinic thermoplastic elastomers may optionally contain a colorant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, an antioxidant, an antistatic agent, a flame retardant,
A foaming agent or the like is added.

Titanium white, zinc white, red stalks,
Vermilion, ultramarine, cobalt blue, titanium yellow, inorganic pigments such as carbon black, isoindoline, Hansa Yellow A,
Organic pigments such as quinacridone, permanent red 4R, and phthalocyanine blue; metal pigments such as aluminum and brass; pearl luster pigments made of foil powder such as titanium dioxide-coated mica and basic zinc carbonate are used. As the filler, those generally used as plastic fillers, for example, calcium carbonate, calcium sulfate, talc, clay, diatomaceous earth, silica, titanium oxide and the like are used.

The UV absorber and the light stabilizer are for imparting good weather resistance (light resistance) to the resin, and the amount of the UV absorber and the light stabilizer is usually 0.01 to 0.01.
It is about 0.15% by weight. Generally, it is preferable to use an ultraviolet absorber and a light stabilizer in combination. As the ultraviolet absorber, an organic substance such as benzotriazole, benzophenone, and salicylate, or an inorganic substance such as zinc oxide, cerium oxide, and titanium oxide in the form of fine particles having a diameter of 0.2 μm or less can be used. As a light stabilizer, bis- (2,
Hindered amine radical scavengers such as (2,6,6-tetramethyl-4-piperidinyl) sebacate and radical scavengers such as piperidine radical scavengers can be used.

Known heat stabilizers such as phenol, sulfite, phenylalkane, phosphite, and amine are used, and they are more effective in preventing deterioration such as thermal discoloration during thermal processing. Improve.

As the flame retardant, powders such as aluminum hydroxide and magnesium hydroxide are used, and these are added when it is necessary to impart flame retardancy.

Further, as a preferable base sheet for use in the present invention, a sheet comprising a high-density polyethylene resin, a thermoplastic elastomer, a coloring agent and an inorganic filler can be mentioned. According to the sheet, the performance required as a decorative sheet, that is, thermoformability similar to polyvinyl chloride, creep deformation resistance, cold bending resistance, organic solvent resistance, elongation at break, impact strength, moderate A material that satisfies a high flexural modulus and easy adhesion is obtained.

As the high-density polyethylene, it is more preferable to use a polyethylene having a specific gravity of 0.94 to 0.96 and having a high degree of crystallinity obtained by a low-pressure method and having a small number of branched structures. . Examples of the thermoplastic elastomer include a diene rubber, a hydrogenated diene rubber, and an olefin elastomer, and the same as those described above are used. The addition amount of the thermoplastic elastomer 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 sharp, and the elongation at break and the impact resistance decrease. If the amount is more than 60% by weight, transparency, weather resistance and creep resistance are reduced. A drop occurs. As the inorganic filler, the same one as described above is used, and about 5 to 60% by weight, preferably 3 to
About 0% by weight is added. If the addition amount is less than 5% by weight, the creep deformation resistance and the easy adhesion decrease, and if it is more than 60% by weight, the elongation at break and the impact resistance decrease. As the colorant, the same one as described above is used.

As the ink used for forming the print pattern layer, a urethane-based high temperature reaction type ink (150 to 250 ° C.) is preferable. In addition, as the pattern of the print pattern layer, a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather crest pattern, a geometric figure,
Examples include letters, symbols, line drawings, various abstract patterns, and the like.

The top sheet is made of a transparent acrylic thermoplastic resin. The transparent acrylic thermoplastic resin is a random copolymer of ethylene and methacrylic acid, a resin in which carboxyl groups randomly present in a molecular chain are cross-linked between molecular chains by hydrogen bonding, and methyl acrylate and ethylene. A copolymer with an ionomer resin,
Use one of Further, acrylic rubber may be added to these transparent acrylic thermoplastic resins.

Since the adhesive strength between the base sheet and the top sheet deteriorates with time due to ultraviolet rays, it is not sufficient to secure the initial adhesive strength as a decorative sheet during production. (Plaque panel 63 ° C.) In order to provide sufficient adhesion strength as a decorative sheet even after irradiation, an ultraviolet absorber may be added to the top sheet. As a result of various studies, it is preferable to add a benzotriazole-based UV absorber at 0.1% by weight or more or a hindered amine-based UV absorber at 0.1% by weight or more as a result of various studies.

As the acrylic rubber to be added to the transparent acrylic thermoplastic resin, there may be mentioned a rubber-like elastic material obtained by polymerization of an acrylate or copolymerization of the acrylate. Examples of the acrylate include ethyl acrylate and butyl acrylate, and the monomers to be copolymerized include 2-chloroethyl vinyl ether, methyl vinyl ketone, acrylic acid, acrylonitrile, and butadiene. An amine such as ethyltetramine and tetraethylenepentamine and sulfur are used for flowing the copolymer.

The top sheet needs to be thinner than the base sheet in consideration of the suitability for V processing and lapping.
The total thickness of the decorative sheet is preferably from 100 to 200 μm.
A method of attaching an acrylic film to the base sheet with doubling embossing is also conceivable, but the processing speed is low due to the problem of reproducibility of embossing, and the occurrence of curl is large, so the melt extrusion simultaneous embossing method of the present invention wins I have. The embossing plate to be used is, for example, one obtained by copying the state of unevenness such as the surface of wood by electroforming to form an embossed pattern of the conduit, or by copying the state of unevenness such as the surface of wood by photoengraving. It is preferable to form an embossed pattern of a conduit by a photoetching method using the prepared master. Further, for example, in the case of a stone pattern, the state of unevenness of the stone material surface including a crack or the like can be similarly copied. By using such an embossing plate, it is subjected to heat and pressure molding to form a concave pattern.

The top sheet surface may be filled with a coloring agent in the recesses of the recessed pattern. Examples of the coloring agent include natural resins such as shellac, corval, dammar, rosin, and rosin esters or modified resins thereof, and nitro resins. Cellulose, acetylcellulose, ethylcellulose, cellulose derivatives such as benzylcellulose, phenolic resins, urea resins, phthalic resins, maleic resins,
Melamine resin, polyvinyl acetate resin, polyvinyl chloride resin, acrylic resin, polyvinyl alcohol, polyvinyl butyral, epoxy resin, silicone resin,
Polyester resin, polyamide resin, polyurethane resin, other synthetic resins, and other rubber derivatives such as chlorinated rubber, cyclized rubber, and synthetic rubber are used as vehicle constituent materials, and coloring agents, precipitated barium sulfate, etc. are contained in the vehicle. A paint or ink obtained by adding an extender, a plasticizer, or the like is used.

This colored paint or ink is coated on the concave portion of the sheet surface with a roll coat or knife coat, and then scraped off with a doctor blade or wiping paper to remove the colored paint or ink coated on the convex portion of the sheet. Then, only the concave portion is filled with the colored paint or ink. Here, the viscosity of the paint or the ink composition, the number of rotations of the roll, the angle of the blade of the doctor, the thickness, the sheet speed, the speed of the wiping paper, the hardness of the rubber roll, and the like are set so that the paint or the ink composition remains only in the concave portion. It needs to be adjusted. For example, the color tone of the colored paint or ink is preferably the same or similar to a conduit in the case of a wood pattern, and is preferably the same or similar to a crack in the case of a stone pattern.

The top coat layer is composed of an acrylic-fluoro copolymer resin. Strong adhesion can be obtained by coating and laminating on a top sheet made of an acrylic resin.
Since this resin is obtained by copolymerizing an acrylic resin and fluorine, contamination resistance is exhibited. In addition, the effect lasts for a long time because of chemical bonding. Further, since the acrylic resin is bonded by urethane, the resin is excellent in alcohol resistance. Further, since the top coat has an antifouling property as described above, even if an antibacterial agent is contained, its antibacterial effect does not decrease.

As the antibacterial agent to be contained in the top coat layer, the following commercially available products can be used.

Antibacterial Ag ⁺ , Cu ²⁺ , Zn ²⁺ , Hg
⁺ , Ni ²⁺ , Cd ^2+, etc. (especially because Ag ⁺ is harmless to the human body and has a long lasting effect, which is desirable from the viewpoint of safety and performance). Zeolite, apatite, glass, silica gel, An ion exchanger such as a phosphate or zirconium phosphate (especially, zeolite and zirconium phosphate, which have a high track record and high reliability) are supported ion-exchangeably (JP-B-63-54013, JP-A-4-300).
975, and Japanese Patent No. 2529574). Metal ion content is 0.1 to 15 in the case of Ag ⁺
%, And in the case of Cu2 ⁺ or Zn2 ⁺ , 0.1 to 8% by weight is preferable.

In the above, an antibacterial ion obtained by further adding an ammonium ion to a metal ion (disclosed in Japanese Patent Publication No. 4-28646, Japanese Patent No. 2529574, etc.).

Organic compounds having antibacterial properties, for example, P-
Aminobenzenesulfonamide, sulfathiazole,
Sulfa agents such as sulfapyridine and sulfadiazine; dithiocarbamates such as dimethyldithiocarbamate and ethylenebisdithiocarbamate; 2- (2-furyl) -3- (5-nitro-2furyl) acrylamide;

Antibacterial trimethoxysilylpropyloctadecyl ammonium chloride, 10,1
0'-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) -phthalimide, N- (fluorodichloromethylthio) florimide, griseofulvin,
Tricomycin, amphotericin B and the like.

Antibiotics, for example, penicillins such as phenoxymethyl penicillin and dicloxacillin, cephalosporins such as cephalotin and cefazolin, streptomycins such as streptomycin sulfate and paromomycin (sulfate), erythromycins such as erythromycin and josamycin, tetracycline, loritetracycline nitrate and the like. Of tetracycline, chloramphenicol,
Chloramphenicol such as thiamphenicol / aminoacetic acid ester hydrochloride;

Fine particles of anatase-type titanium dioxide or those obtained by supporting the same on an inorganic porous material such as zeolite or silicagen. These are excited by light to generate oxygen radicals and hydroxyl radicals from surrounding water molecules and oxygen molecules, and decompose molds and bacteria by the reaction of these radicals.

In addition, amino acid metal soaps, metal phosphates and the like can also be used. In addition, as natural antibacterial and antifungal agents, chitin and chitosan, components of crab shell, hinokitiol, components of cypress and hiba, and bamboo components, and tea leaves (mainly catechin) are used. Stuff, wasabi,
Those using ingredients of mustard and the like can be mentioned.

As the adherend of the decorative sheet of the present invention, flat materials of various materials, plate materials such as curved plates, and articles of various shapes such as sheets (or films) are applicable. Materials used for both plate materials and sheets (films) include:
Wood veneer, wood plywood, particle board, wood board such as medium density fiber board (MDF), wood board such as wood fiber board, iron,
Metal such as aluminum, acrylic, polycarbonate,
Ethylene vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin,
Materials such as ABS, phenolic resin, polyvinyl chloride, cellulosic resin, rubber, etc., and materials exclusively used as plate materials or three-dimensionally shaped articles include ceramics such as glass and ceramics, cement such as ALC (foamed lightweight concrete), calcium silicate , Non-cement ceramic materials such as gypsum,
Materials used exclusively as a sheet (or film) include paper such as high-quality paper and Japanese paper, and nonwoven fabric or woven fabric made of fibers such as carbon, asbestos, potassium titanate, glass, and synthetic resin.

As a method of laminating these various adherends,
For example, as described in Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488, and the like, a decorative sheet is a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive layer therebetween. Is inserted between the male and female molds for injection molding, the molds are closed, and molten resin is injected and filled from the male mold gate. Adhesive lamination, so-called simultaneous injection molding laminating method, JP-B-56-45768 and JP-B-60
As described in JP-A-58014 or the like, a decorative sheet is opposed or placed on the surface of a molded article via an adhesive layer therebetween, and the decorative sheet is formed by a pressure difference due to vacuum suction from the molded article side. So-called vacuum press laminating method for laminating on the surface, Japanese Patent Publication No. 61-5895, Japanese Patent Publication No. 3-266
No. 6, as described in JP-A No. 6-203, while a decorative sheet is supplied in the longitudinal direction of a columnar base material such as a columnar column and a polygonal column via an adhesive layer between the columns, a plurality of rollers having different directions are used to form the columnar substrate. A so-called lapping method or the like, in which decorative sheets are sequentially adhered to a plurality of side surfaces constituting the body by pressure bonding and laminated, may be used.

The decorative sheet of the present invention can be used as a surface decoration material for various uses. For example, interior materials of buildings such as walls, floors and ceilings, furniture such as partitions, furniture, interior materials of vehicles such as automobiles and trains, housing equipment such as kitchens, bathtubs, bathrooms, and surfaces of containers such as bags and boxes. It is used by being laminated on.

[0044]

EXAMPLES (Example 1) First, a wood grain pattern was formed on a base sheet made of a colored polyethylene resin by a gravure printing method to obtain a printed film. Then, thickness 30μ
m acrylic resin film as a top sheet,
It was double-embossed with an embossing plate having a conduit pattern together with the above-mentioned printing film. Subsequently, after the conduit portion formed on the acrylic resin film was wiped with an acrylic urethane-based ink, a composition having the following formulation A was laminated as a top coat layer by a gravure printing method to produce a decorative sheet.

[Formulation A] Acrylic-fluorine copolymer 100 parts by weight Polyisocyanate 5 parts by weight Slip agent 3 parts by weight Silver antibacterial agent 3 parts by weight

Example 2 First, a wood grain pattern was formed on a base material sheet made of a colored polypropylene resin by a gravure printing method to obtain a printed film. Next, an acrylic resin was extruded onto the pattern of the printed film with a T-die extruder to a thickness of about 50 μm and laminated as a top sheet, and at the same time, a conduit was embossed. Subsequently, after the conduit portion formed on the acrylic resin layer was wiped with an acrylic urethane-based ink, a composition having the following formulation B was laminated as a top coat layer by a gravure printing method to produce a decorative sheet.

[Formulation B] Acrylic-fluorine copolymer 100 parts by weight Polyisocyanate 5 parts by weight Slip agent 3 parts by weight Organic antibacterial agent 3 parts by weight

Comparative Example 1 A decorative sheet was prepared in the same manner as in Example 1 except that the top coat layer was formed of a urethane resin to which an activator was added.

Comparative Example 2 A decorative sheet was prepared in the same manner as in Example 2 except that the top coat layer was formed of an acrylic silicone resin.

The decorative sheets obtained in Examples 1 and 2 had stronger adhesion of the top coat layer than the decorative sheets of Comparative Examples 1 and 2, and did not peel off even after V-cutting or lapping. In addition, the antibacterial effect of the decorative sheet of the comparative example gradually decreased, but the antibacterial effect of the decorative sheet of the example did not decrease over a long period of time.

[0051]

According to the decorative sheet of the present invention, an acrylic-fluoro copolymer resin is laminated as a top coat layer on a top sheet made of an acrylic resin. It can be used enough for many building materials. In addition, there is an effect that the stain resistance is good and the effect is maintained for a long time,
Further, there is also an effect that the solvent resistance such as alcohol resistance is excellent. When the topcoat layer contains an antibacterial agent, the topcoat layer itself has an antifouling property, so that an antibacterial effect is not reduced.

[Brief description of the drawings]

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

[Explanation of symbols]

 Reference Signs List 1 base sheet 2 printed picture layer 3 top sheet 4 top coat layer 5 colorant

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 33/00 B32B 33/00

Claims (2)

[Claims] 1. A printed pattern layer is formed on a base sheet made of an olefin-based thermoplastic elastomer, a top sheet made of a transparent acrylic resin is laminated thereon, and an acrylic-fluoro copolymer resin is further formed thereon. A decorative sheet provided with a top coat layer. 2. The decorative sheet according to claim 1, wherein the topcoat layer contains an antibacterial agent.