JPH10157026A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To prevent mildew and various germs from growing and propagation on the surface of a sheet and therearound by forming the sheet base material of olefinic resin formed by blending a thermoplastic elastomer and inorganic filling agent in high density polyethylene, and gibing an antibacterial treatment on at least the uppermost surface side. SOLUTION: The decorative laminated sheet 1 is composed by laminating an acrylic resin protection sheet 3 on the sheet base material 2 of an olefinic resin. In this instance, the sheet base material 2 comprises olifinic resin formed by blending a thermoplastic elastomer and inorganic filling agent in high density polyethylene, and an antibacterial treatment is given on at least the uppermost surface thereof.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a building interior,
The present invention relates to a decorative sheet used for the purpose of imparting a design property to these surfaces and protecting the surfaces, such as for surface decoration of fittings and vehicle interiors.

[0002]

2. Description of the Related Art Conventionally, the following three types of decorative sheets have been known as decorative sheets used for such purposes.

(1) A polyvinyl chloride sheet decorated with printing or embossing (Japanese Patent Publication No. 28-5036)
No., JP-B-58-14312). (2) A sheet using a polyolefin sheet such as polyethylene or polypropylene instead of polyvinyl chloride (JP-A-54-62255).

(3) An olefin-based thermoplastic elastomer is mixed with a polyolefin-based resin obtained by graft-polymerizing a polar functional group (Japanese Unexamined Patent Publication No. Hei 6-210808, Japanese Unexamined Patent Publication No. Hei 4-210808).
JP-A-504384), a polyurethane resin is mixed with a polyolefin resin using a compatibilizing agent,
-26038), the disadvantage of the decorative sheet of (1) and the following of the decorative sheet of (2):
What tried to solve the disadvantages of. And so on.

[0005]

In the decorative sheet using a polyvinyl chloride sheet as described in (1), the heat resistance is insufficient, or the bleeding of the plasticizer causes the surface to be stain resistant. There was a problem that was bad.

In the case of the conventional decorative sheet as described in (2), the drawback of the decorative sheet using the polyvinyl chloride film can be improved, but the transparency is insufficient.
Insufficient heat resistance. Poor weather resistance. Inflexible. Insufficient adhesion to ink, adhesive, etc. during printing and lamination. After forming a groove having a V-shaped cross section on the back surface of the decorative material having a weak impact resistance and a decorative sheet laminated on the surface,
When the decorative material is bent (the process of forming the V-shaped groove and bending the decorative material is hereinafter simply referred to as V-cut processing), the decorative sheet cracks and breaks. In particular, crystallization progresses due to the heat history at the time of embossing from heating softening to embossing plate pressing to cooling, the sheet becomes brittle, and this tendency is strengthened. Furthermore, embossing conditions are very narrow because of high crystallinity. And so on. Further, even with the decorative sheet as in (3), it was still difficult to say that the disadvantage of the sheet in (2) has been solved.

In order to solve the above problems, the present inventors have studied a decorative sheet having a structure in which a protective sheet of an acrylic resin is laminated on a sheet base of an olefin resin. However, in the case of a decorative sheet in which an acrylic resin protective sheet is simply laminated on an olefin resin sheet base, if the decorative material in which the sheet is laminated is subjected to V-cut processing, cracks are formed in the acrylic resin protective sheet. Or the protective sheet is whitened.
Furthermore, the above-mentioned conventional decorative sheet has a problem that mold is grown on the sheet surface or its periphery due to the adsorbed water on the surface, and various germs are easily propagated.

The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, in a decorative sheet in which an acrylic resin protective sheet is laminated on an olefin resin sheet base, the olefin resin constituting the sheet base is used as a decorative sheet. By using an olefin resin obtained by blending a thermoplastic elastomer and an inorganic filler in high-density polyethylene, it has been found that cracks and whitening can be prevented from occurring in the protective sheet during V-cut processing, The present inventors have found that by performing antibacterial treatment on the outermost surface side, it is possible to prevent the growth of mold and the propagation of various bacteria on and around the sheet surface due to the water adsorbed on the decorative sheet surface, and have completed the present invention.

[0009]

That is, the decorative sheet of the present invention is a decorative sheet obtained by laminating a protective sheet of an acrylic resin on a sheet substrate of an olefin resin. It is made of an olefin resin containing a plastic elastomer and an inorganic filler, and at least the outermost surface has been subjected to an antibacterial treatment.

[0010]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 shows an embodiment of a decorative sheet 1 of the present invention. In the figure, reference numeral 2 denotes a polyolefin-based resin sheet base, and 3 denotes a protective sheet.

In the decorative sheet 1 of the present invention, the sheet substrate 2 is made of an olefin resin in which a high-density polyethylene is mixed with a thermoplastic elastomer and an inorganic filler. High density polyethylene has a specific gravity of 0.94 to 0.9
Polyethylene No. 6 is a polyethylene having a high crystallinity obtained by a low-pressure method and having a small number of branched molecules.
The compounding amount of the high-density polyethylene is preferably 30% by weight or more and 85% by weight or less with respect to the olefin resin obtained by mixing the thermoplastic elastomer and the inorganic filler with the high-density polyethylene.

In the present invention, as the thermoplastic elastomer, for example, the number average molecular weight: Mn is 2500
0 or more, weight average molecular weight: Mw and number average molecular weight: Mn
A mixture of 10 to 90% by weight of a boiling heptane-soluble polypropylene having a ratio of Mw / Mn ≦ 7 and 90 to 10% by weight of a boiling heptane-insoluble polypropylene having a melt index of 0.1 to 4 g / 10 minutes (particularly, Fairness 6-2327
No. 8 soft polyethylene), polyethylene, polypropylene, olefin polymers such as polymethylpentene (crystalline polymer) as a hard segment,
A monoolefin copolymer rubber such as an ethylene / propylene / non-conjugated diene terpolymer rubber partially crosslinked is used as a soft segment, and the soft segment / hard segment = 50/50 to 90/10 in weight ratio. An olefin elastomer (olefin elastomer described in JP-B-53-21021), a non-crosslinked monoolefin copolymer rubber (soft segment), and an olefin copolymer (crystalline) And a soft segment / hard segment = 60/40 to 80/20 in weight ratio, mixed with a crosslinking agent, heated and dynamically partially crosslinked while applying shear stress. Olefin-based elastomer (an olefin-based elastomer described in JP-B-53-34210) Peroxide decomposable olefin-based polymers having the property of decreasing the molecular weight by mixing and heating with a peroxide, such as isotactic polypropylene, propylene / ethylene copolymer, propylene / butene-1 copolymer, etc. Hard segment) 90 to 40 parts by weight, peroxide crosslinking such as ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated gen terpolymer rubber, etc., which are crosslinked by heating and mixed to reduce fluidity 10 to 60 parts by weight of a monoolefin copolymer rubber (soft segment) and a peroxide non-crosslinked hydrocarbon rubber (soft segment) such as polyisobutylene, butyl rubber, etc. 5-100 parts by weight, and a paraffin-based component Naphthenic, olefinic elastomers by mixing the mineral oil softening agent 5-100 parts by weight of aromatic, obtained by dynamic heat treatment in the presence of an organic peroxide (JP-B-56-15741
Olefin-based elastomer described in Japanese Patent Application Laid-Open No. H08-139232, and an olefin-based elastomer comprising an ethylene / styrene / butylene copolymer (olefin-based elastomer described in JP-A-2-139232).

As the thermoplastic elastomer, a diene rubber, a hydrogenated diene rubber and the like can be used, and among them, a hydrogenated diene rubber is preferable. The hydrogenated diene-based rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene-based rubber molecule, and has a role of suppressing crystallization of high-density polyethylene and increasing flexibility and transparency. In general, when a diene rubber is added to a polyolefin resin, a double bond of the diene rubber occurs,
Weather resistance and heat resistance are lower than those of polyolefin resins without the addition of diene rubber, but saturating the double bonds of the diene rubber with hydrogen may reduce the weather resistance and heat resistance of the polyolefin resin. Disappears.

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.

On the other hand, the inorganic filler contained in the sheet substrate 2 includes calcium carbonate, barium sulfate, clay,
Powder such as talc is used. The olefin-based resin constituting the sheet base 2 contains 10 thermoplastic elastomers.
It is preferable that the content of the inorganic filler is 5 to 60% by weight, and the total content of both is 70% by weight or less. 10 content of thermoplastic elastomer
Less than 5% by weight or the content of inorganic filler is 5% by weight
If it is less than 3, the elasticity, elongation, and impact resistance of the sheet substrate 2 are insufficient, and when the decorative material is subjected to bending such as V-cutting or drawing, the protective sheet 3 may be cracked or cracked. It is easy to occur. When the content of the thermoplastic elastomer is 6
When the content exceeds 0% by weight or when the content of the inorganic filler exceeds 60% by weight, the elasticity and elongation of the sheet base material 2 become too large, and the decoration described later by printing or the like on the sheet base material 2. When forming the layer 4, it is difficult to position the position where the decorative layer 4 is formed, which is not preferable.

Further, there is a correlation between the thermal dimensional shrinkage of the sheet substrate 2 and the crack and rupture resistance of the decorative sheet 1 at the time of V-cut processing of the decorative material. The dimensional shrinkage after heating (based on before heating)
Preferably, the thickness is in the range of -2 to + 7% in the sheet longitudinal direction (longitudinal direction of a long extruded sheet) and in the range of -7 to + 2% in the sheet width direction (direction perpendicular to the longitudinal direction). If the dimensional shrinkage ratio deviates from this range, cracks are likely to occur during V-cut processing. The reason why the allowable value of the heating dimensional shrinkage ratio is different in the sheet longitudinal direction and the sheet width direction is that the material mechanical history of the sheet at the time of sheet production and the manner of applying the impact force at the time of sheet processing are determined by the longitudinal direction And in the width direction. The dimensional shrinkage upon heating largely correlates mainly with the stretching of the sheet substrate 2. If it is not stretched, the dimensional heat shrinkage of the sheet substrate 2 falls within the above range, and if it is stretched three times or more, it generally falls outside the above range. Therefore, in the case of stretching, it is preferable to suppress the stretching ratio so that the heating dimensional shrinkage falls within the above range.

In the present invention, the acrylic resin constituting the protective sheet 3 includes poly (methyl meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, and butyl poly (meth) acrylate. , Methyl (meth) acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer,
Homogenous or copolymer containing (meth) acrylic acid ester of styrene / methyl (meth) acrylate (herein, (meth) acryl means acryl or methacryl, and the same applies hereinafter). ) And the like. The thickness of the acrylic resin protective sheet 2 is 20 to
It is preferably about 100 μm.

The method of laminating the sheet substrate 2 and the protective sheet 3 includes melt extrusion coating (extrusion coating), fusion by hot press, or adhesive such as two-component curable polyurethane resin or polyester resin. The used dry laminating etc. are mentioned.

A decorative layer 4 to be described later can be directly formed on the surface of the sheet substrate 2 by printing, or an adhesive for bonding the protective sheet 3 can be directly applied.
If it is necessary to make the adhesive strength between the printing ink or adhesive forming the sheet and the sheet substrate 2 stronger, the surface of the sheet substrate 2 should be subjected to an easy adhesion treatment such as a corona discharge treatment or a plasma treatment. Or an easy adhesion layer (primer layer, or
(Also referred to as an anchor layer). Figure 1
In the example shown in FIG. 3, an easy-adhesion layer 5 is provided on the back surface side of the sheet substrate 2. Although not particularly shown, the decorative sheet 1 shown in FIGS. 1 and 2 may be further provided with a surface protective layer 8 on the surface of the protective sheet 3 like the decorative sheet 1 shown in FIG. Details will be described later.)

For forming the easy-adhesion layer 5, acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester,
Polyurethane, chlorinated polypropylene, chlorinated polyethylene and the like are used, and chlorinated polypropylene is particularly desirable.

The acrylic resin for forming the easy-adhesion layer 5 includes poly (methyl meth) acrylate, poly (ethyl meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and the like. Methyl (meth) acrylate / butyl (meth) acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer,
Acrylic resins comprising a homo- or copolymer containing a (meth) acrylate such as styrene-methyl (meth) acrylate are exemplified.

Polyurethane is a polymer obtained by using a polyol (polyhydric alcohol) as a main component, an isocyanate compound as a crosslinking agent (curing agent), and reacting both. As the polyol, those having two or more hydroxyl groups in the molecule, basically, a monomer diol, a triol or the like, and a polymer diol containing a chain of alkylene repeating units mainly contributing to the molecular weight thereof, Contains triol. Typical polymer polyols consist essentially of either linear or branched chains of the above repeating units terminated with hydroxy groups, preferably monomeric polyols having 2, 3, 4 or more hydroxy groups including. For example, ethylene glycol, propylene glycol,
Glycerin, trimethylolpropane, 1,2,6-hexanetriol, butenediol, sucrose,
Including glucose, sorbitol, pentaerythritol, mannitol, triethanolamine, n-methyldimethanolamine, and cyclic aromatic and aliphatic and triols. In addition, polyethylene glycol,
Polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used.

On the other hand, as the isocyanate compound, a polyvalent isocyanate compound having two or more isocyanate groups in a molecule is used. For example, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, crude MD
A polyphenylmethane polyisocyanate designated I,
Xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, aliphatic or alicyclic or aromatic di- or triisocyanate compounds such as triphenylmethane triisocyanate, hydrogenated tolylene diisocyanate, Isocyanate terminals obtained by reacting hydrogenated diphenylmethane diisocyanate or a polyisocyanate compound with a low molecular weight glycol or triol, for example, dipropylene glycol, 1,6-hexanediol, 1,2,6-hexanetriol, trimethylolpropane Low molecular weight adducts and the like can be used.

As a method of decorating the decorative sheet 1 of the present invention, a method of adding a dye or a pigment to the sheet base 2 to impart a transparent or opaque color may be employed. Pigments added to the sheet substrate 2 include titanium white, zinc white, red stalks,
Inorganic pigments such as vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black and the like, and organic pigments such as isoindolinone, Hansa yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indaslen blue RS, aniline black and the like (or Dyes), metal pigments such as aluminum and brass, pearlescent pigments made of foil powder such as titanium dioxide-coated mica, and basic lead carbonate, and the like. These can be added and dispersed in the resin constituting the sheet base material 2 as powder or scaly foil pieces.

As another method of decorating the decorative sheet 1 of the present invention, there is a method of providing a decorative layer 4 between the sheet substrate 2 and the protective sheet 3 as shown in FIG. The decorative layer 4 can be formed by printing or laminating a metal thin film. As a printing method, gravure printing, intaglio printing, offset printing, letterpress printing, flexographic printing, silk screen printing, electrostatic printing, inkjet printing, etc., or separately forming a pattern on a release sheet once A transfer sheet is prepared, and a transfer printing method using the transfer sheet is exemplified.

When the decorative layer 4 is formed by printing, various inks for printing can be used, and a composition comprising a coloring agent, an extender pigment, a binder, a curing agent, an additive, a solvent, and the like. Can be used. The binder is not particularly limited, and is chlorinated polyethylene, chlorinated polypropylene, vinyl acetate, a vinyl chloride-vinyl acetate copolymer, a thermoplastic resin such as a cellulosic resin, or a room temperature or thermosetting polyurethane. Ordinary resins such as a conductive resin or an ionizing radiation curable resin such as an acrylic resin can be used. In the case of printing directly on the sheet substrate 2, it is preferable to use chlorinated polyolefin polyurethane or the like as a binder from the viewpoint of adhesiveness.
If a suitable binder is selected, a sufficient adhesiveness can be obtained even if another binder is used.

In the case where the decorative layer 4 is formed of a metal thin film, a method of laminating the metal thin film on the entire surface or partially in a pattern may be used. This metal thin film can be formed by using a metal such as aluminum, chromium, gold, silver, or copper by a method such as vacuum evaporation or sputtering, and can be formed into a partially patterned metal thin film by an etching method or the like.

The patterns of the decoration layer 4 include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric figure, a character, a symbol,
Examples include line drawings and various abstract patterns, but decorations such as solid printing on the entire surface may also be used. The decorative layer 4 is not limited to being provided between the sheet base 2 and the protective sheet 3 as shown in FIG. 1, and may be provided on the back side of the sheet base 2 when the sheet base 2 is transparent. 1 (in the example shown in FIG. 1, the upper surface of the easy adhesion layer 5). As shown in FIG. 2, the sheet base 2 may be composed of two (or more) olefin-based resin sheets 2a, 2b, and the decorative layer 4 may be provided between the sheets 2a, 2b.

As still another method of decorating the decorative sheet 1 of the present invention, there is a method of forming an uneven pattern 6 on the surface of the protective sheet 3 as shown in FIG. In order to form the concavo-convex pattern 6, for example, there is an embossing method by heating and pressing. In this embossing method, the surface of the protective sheet 3 is heated and softened, and the surface is pressed with an embossing plate to form the concavo-convex pattern on the embossing plate. Is formed, cooled, and fixed, and a known single-wafer or rotary embossing machine can be used. Also, the uneven pattern 6 can be formed by hairline processing.

Examples of the concavo-convex pattern 6 include a wood grain board conduit groove, a stone board surface irregularity (granite cleavage face, etc.), a cloth surface texture, a matte finish, a grain, a hairline, a linear groove, and the like.

Further, an ink layer 7 may be formed in the recessed portion of the above-mentioned uneven pattern 6 by a wiping method or the like. As the wiping method, the ink is applied to the entire surface including the concave portion by the doctor blade coating method or the knife coating method, and then the ink is removed from the surface other than the concave portion to form the ink layer 7 only on the concave portion. Can be used. As the ink for forming the ink layer 7, a colored ink is usually used, but a transparent or translucent ink can also be used. Examples of the coloring ink include an ink composed of an organic pigment, an inorganic pigment, a bright pigment and the like, a binder resin such as a thermoplastic resin, a thermosetting resin, and an ionizing radiation-curable resin, and an ink including a vehicle. Water-based ink can be used.

The surface of the protective sheet 3 on which the irregular pattern 6 has been formed can be covered with a surface protective layer 8 if necessary. The surface protective layer 8 is made of a two-component curable polyurethane, an unsaturated polyester, a thermosetting resin such as an epoxy resin, a melamine resin, an acrylic resin, a vinyl acetate resin, a vinyl chloride resin.
It is preferable to use a thermoplastic resin such as a vinyl acetate copolymer, a cellulose resin, a thermoplastic polyester, or a chlorinated polyolefin, or an ionizing radiation-curable resin.

The ionizing radiation-curable resin is specifically curable by ionizing radiation by appropriately mixing a prepolymer, polymer and / or monomer having a polymerizable unsaturated bond or a cationically polymerizable functional group in a molecule. A suitable composition is preferably used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually an ultraviolet ray (UV) or an electron beam (EB) is used.

The ionizing radiation-curable resin forming the cured coating film is more specifically a (meth) acryloyl group in the molecule.
It comprises a radically polymerizable unsaturated group such as (meth) acryloyloxy, a cationic polymerizable functional group such as an epoxy group, or a monomer having two or more thiol groups, a prepolymer or a polymer. These monomers, prepolymers or polymers may be used alone or as a mixture of two or more. Here, for example, a (meth) acryloyl group is used to mean an acryloyl group or a methacryloyl group.

Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth)
Acrylate, melamine (meth) acrylate, triazine (meth) acrylate and the like can be used, and those having a molecular weight of about 250 to 10,000 are usually used. As the polymer having a radical polymerizable unsaturated group, a polymer having a degree of polymerization of the above prepolymer of about 10,000 or more is used.

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers such as epoxy resins such as bisphenol epoxy resins and novolak epoxy resins, and vinyl ether resins such as aliphatic vinyl ethers and aromatic vinyl ethers. Is mentioned.

Examples of the monomer having a radical polymerizable unsaturated group include monofunctional monomers such as (meth) acrylate compounds, for example, methyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and phenoxyethyl (meth) acrylate. A) acrylates and polyfunctional monomers such as diethylene glycol di (meth) acrylate, propylene glycol (meth) acrylate, trimethylolpropane tri (meth) acrylate, trimethylolpropane ethylene oxide tri (meth) acrylate, dipentaerythritol penta (Meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

As the monomer having a cationically polymerizable functional group, the above-mentioned prepolymeric monomer having a cationically polymerizable functional group can be used. Examples of the monomer having a thiol group include trimethylolpropane trithioglycolate and pentaerythritol tetrathioglycolate.

When curing with ultraviolet light or visible light, a photopolymerization initiator is added to the ionizing radiation-curable resin. In the case of a resin system having a radical polymerizable unsaturated group,
As the photopolymerization initiator, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like can be used alone or as a mixture. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metaceron compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to. The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin.

When the surface protective layer 8 is matted, a matting agent (light diffusing agent) is added. As a matting agent,
Calcium carbonate, silica, alumina, barium sulfate, urethane resin beads, polycarbonate resin beads, etc.
Fine particles having a particle size of about 1 to 30 μm are effective. The thickness of the surface protective layer 8 is preferably about 1 to 100 μm.

In the present invention, each of the above-described methods of imparting decoration can be employed not only in one kind but also in an appropriate combination of two or more kinds.

The decorative sheet 1 of the present invention has an antibacterial treatment on the outermost surface. In order to perform the antibacterial treatment, in the case of the decorative sheet shown in FIG. 1, a method of incorporating the antibacterial agent into the protective sheet 3 of the acrylic resin by kneading the antibacterial agent or the like may be used. In the case of a decorative sheet provided with a surface protective layer 8 on the surface of the protective sheet 3 made of an acrylic resin (this decorative sheet is not particularly shown), the surface protective layer 8 or the antibacterial agent in the surface protective layer 8 and the protective sheet 3 Is included. Further, in the case of the decorative sheet 1 shown in FIG. 3, an antibacterial agent is contained in the surface protective layer 8 or the surface protective layer 8 and the ink layer 7, or the surface protective layer 8, the ink layer 7 and the protective sheet 3 are added to each other. A method of containing an antibacterial agent is employed.

The following antibacterial agents can be used. JP-B-63-54013, JP-A-4-300975
No., as described in Japanese Patent No. 2529574, etc., antimicrobial ^{Ag +, Cu 2+, Zn 2+} , Hg +, N
Metal ions such as i ²⁺ and Cd ²⁺ (in particular, Ag ⁺ is harmless to the human body and has a long lasting effect, and is therefore preferred in terms of safety and performance). Zeolite, apatite, glass, silica gel, phosphate , ion exchangers such as zirconium phosphate (among others zeolite, zirconium phosphate has a higher performance and reliability.) to those obtained by ion replaceably supported (metal ion content is 0.1 when the Ag ⁺ 15% by weight, and 0.1 to 8% by weight in the case of Cu ²⁺ .)

Japanese Patent Publication No. Hei 4-28646 and Japanese Patent No. 252
As described in, for example, No. 9574 and the like, antibacterial ions of the above antibacterial agents obtained by further adding ammonium ions to metal ions.

Organic compounds having antibacterial properties, for example, p-
Aminobenzenesulfonamide, sulfathiazole, sulfapyridine, sulfa agent such as sulfadiazine,
Dithiocarbamates such as dimethyldithiocarbamate and ethylenebisdithiocarbamate; 2- (2-furyl) -3- (5-nitro-2-furyl) acrylamide;

Compounds having antibacterial and antifungal properties, for example, 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) -phthalimide, N- (fluorodichloromethylthio) florimide, griseofulvin, tricomycin, amphotericin B and the like.

Antibiotics, for example, penicillins such as phenoxymethylpenicillin and cycloxacillin, cephalosporins such as cephalotin and cefazolin, streptomycins such as streptomycin sulfate and paromomycin (sulfate), erythromycins such as erythromycin and josamycin, tetracycline, lolinitrate nitrate Tetracycline such as tetracycline, chloramphenicol,
Chloramphenicol such as thiamphenicol / aminoacetic acid ester hydrochloride;

In the decorative sheet 1 of the present invention, in order to impart better weather resistance (light) to the resin, an ultraviolet absorber and a light stabilizer may be added to the sheet base 2 and the protective sheet 3 as necessary. Can be added.

Organic substances such as benzotriazole, benzophenone, salicylate, etc.
Alternatively, inorganic substances such as zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used.
As a light stabilizer, bis- (2,2,6,6-tetramethyl-4-
Hindered amine radical scavengers such as piperidinyl) sebacate and radical scavengers such as piperidine radical scavengers can be used. Both the ultraviolet absorber and the light stabilizer are usually added so as to be about 0.5 to 10% by weight, but it is generally preferable to use the ultraviolet absorber and the light stabilizer together.

Further, in order to impart flame retardancy to the decorative sheet 1, a flame retardant can be added to the sheet substrate 2 or the protective sheet 3. Powders such as aluminum hydroxide and magnesium hydroxide are used as the flame retardant. The addition amount of the flame retardant is preferably about 10 to 150 parts by weight based on 100 parts by weight of the total of the high-density polyethylene and the thermoplastic elastomer.

Further, a cellular (sponge-like) foam may be used as the sheet substrate 2. In this case, a foaming agent is added to the resin constituting the sheet substrate 2, and the foaming agent is heated. Foam. Examples of the foaming agent include azodicarbonamide, azobisisobutyronitrile, N-N'-dinitrosopentamethylenetetramine, oxybisbenzenesulfonylhydrazide, pyrolysis type such as sodium hydrogen carbonate, potassium hydrogen carbonate, and acrylonitrile. A microcapsule type in which a heat-expandable gas such as hexane or isobutane is sealed in a resin spherical shell of the above. The addition amount of the foaming agent is about 1 to 10 parts by weight based on 100 parts by weight of the base resin (the total amount of the high-density polyethylene and the thermoplastic elastomer) constituting the sheet base.

The decorative sheet 1 of the present invention can be used by being laminated on another adherend (backing material). FIG. 4 shows a case where the adherend is a three-dimensional article 9, and FIG. 5 shows a case where the adherend is a flat or curved plate 10. The lamination of the decorative sheet 1 and the adherend can be performed without using an adhesive if the decorative sheet 1 itself can be bonded to the adherend (by heat fusion or the like). If does not adhere to the adherend,
Laminate using a suitable adhesive. The decorative sheet 1 of the present invention
May be a final product such as a decorative material by being laminated on an adherend, or may be laminated on an adherend in order to reinforce the mechanical strength of the decorative sheet 1 or to impart concealment. .

The object to be adhered is a molded article having a three-dimensional shape as shown in FIG. 4, a plate material having a flat or curved shape as shown in FIG. 5, or an article having various shapes such as a sheet (or film). Become. Materials used for any of plate materials, three-dimensionally shaped articles, and sheets (films) include wood veneers,
Wood plywood, particle board, medium density fiberboard (MD
F) or other wood board, wood fiber board such as wood fiber board, metal such as iron or aluminum, acrylic, polyester, polystyrene, polyolefin, ABS, phenol resin, polyvinyl chloride, cellulose resin, rubber or other resin, exclusively board material Materials used as three-dimensional articles include ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, and materials exclusively used as sheets (or films) include paper such as high-quality paper and Japanese paper. And nonwoven fabrics or woven fabrics made of fibers of carbon, asbestos, potassium titanate, glass, synthetic resin and the like.

The method of laminating these various adherends is as follows.
For example, as described in Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488, and the like, a method of laminating a plate-like base material by pressing with a pressure roller with an adhesive therebetween, Insert between the male and female molds of injection molding,
Close both molds, inject and inject molten resin from the male mold gate, cool, and simultaneously mold and mold a resin molded product. No. 45768, Japanese Patent Publication No. 60-
As described in Japanese Patent No. 58014, etc., a decorative sheet is opposed to or placed on the surface of a molded article with an adhesive therebetween.
A so-called vacuum press lamination method in which a decorative sheet is laminated on the surface of a molded product by a pressure difference caused by vacuum suction from the molded product side,
As described in JP-B-61-5895, JP-B-3-2666, etc., a decorative sheet is supplied in the longitudinal direction of a columnar substrate such as a column or a polygonal column via an adhesive layer therebetween. In addition, a so-called lapping method or the like is used in which decorative sheets are successively pressed and laminated on a plurality of side surfaces constituting a columnar body by a plurality of rollers having different directions. In order to obtain a three-dimensional article having the decorative sheet 1 of the present invention as a surface decorative layer, the above-mentioned lapping method, simultaneous injection molding laminating method, vacuum forming simultaneous laminating method and the like are preferable.

Further, the decorative sheet 1 is laminated on the plate material 10 via an adhesive, and then on the surface of the plate material 10 opposite to the surface on which the decorative sheet 1 is laminated, at the interface between the decorative sheet 1 and the plate-like base material. The resulting groove 11 having a V-shaped or U-shaped cross section is cut, an adhesive is applied to the groove 11, and the box 11 is bent by the groove 11 as shown in FIG. An irregular three-dimensional article having the decorative sheet 1 of the present invention as a surface decorative layer can also be obtained by a so-called V-cut processing (or U-cut processing) method or the like formed in a columnar body. In the decorative sheet 1 of the present invention, even when the V-cut processing (or the U-cut processing) shown in FIG. 6 is performed, there is no fear that the protective sheet 3 is cracked or whitened.

The decorative sheet 1 of the present invention can be laminated on various adherends, subjected to a predetermined forming process, and used for various decorative purposes. For example, interior decoration of buildings such as walls, ceilings, floors, window frames, doors, surface decoration of fittings such as handrails, partitions, kitchen, bathtubs / bathrooms, etc., household equipment such as furniture, containers such as bags, boxes, etc. Applications include surface cosmetics, surface cosmetics for cabinets of light electric / OA equipment, vehicle interiors such as automobiles and trains, aircraft interiors, and window glass cosmetics. In particular, since the decorative sheet of the present invention has antibacterial properties, it is suitable for use in hospitals, cafeterias, bathroom interiors, food-related containers, kitchens, bathtubs, and the like.

[0057]

Embodiments of the present invention will be described below in detail.

Example 1 Thickness 0.1 mm made of an olefin resin having the following composition
Gravure coating with the ink (NH medium) manufactured by The Inktec Co., Ltd. on the surface of the beige sheet base material, and gravure the grain pattern with the ink (Chem. X1) manufactured by The Inktec Co., Ltd. Printed. Olefin resin sheet composition High density polyethylene 60 parts by weight Styrene-butadiene rubber 30 parts by weight Calcium carbonate 10 parts by weight

Further, an acrylic resin sheet (Acryprene HBS-027) manufactured by Mitsubishi Rayon Co., Ltd. having a thickness of 0.03 mm was laminated on the printed layer by thermal lamination and simultaneously embossed. Next, the embossed concave portion of the obtained embossed sheet was subjected to a wiping process with a urethane resin-based ink (GM-A12) manufactured by Showa Ink Co., Ltd. to form a colored layer.

A two-part curable urethane resin binder comprising acrylic polyol and hexamethylene diisocyanate was coated on the surface of this sheet with an antibacterial agent having a particle size distribution of 2 to 5 μm, a silver content of 2.5% by weight, and a zinc content. Quantity 1
5% by weight of 4.5% by weight of a silver ion type zeolite antibacterial agent, an average primary particle size of 16 nm, and a specific surface area of 110 m ^2.
/ G of microsilica (enrichment pigment) was applied by a gravure coating method to a dry thickness of 3 μm, and dried to form a surface protective layer to obtain a decorative sheet. Table 1 shows the physical properties of this decorative sheet.

[0061]

[Table 1]

The breaking strength and breaking elongation are measured in accordance with JIS K-
According to 6734 6.3, pulling speed 20mm
/ Min. Lapping aptitude, using an ethylene-vinyl acetate copolymer emulsion-based adhesive, wrapping with a normal lapping laminating machine so that the base sheet side of the decorative sheet and the R surface and L90 surface of the irregular cross section are bonded together. Processing and evaluation were performed. In addition, the V-cut processing suitability is as follows. The base sheet side of the decorative sheet is 10 m thick using an ethylene-vinyl acetate copolymer emulsion adhesive.
After laminating and bonding to the Rawan plywood of m, the V-shaped cross-section groove reaching the interface between the plywood and the adhesive layer is cut on the side opposite to the decorative sheet side of the plywood, and into the groove. After applying the ethylene-vinyl acetate copolymer emulsion-based adhesive, the plywood was bent into an L-shape (cross section) so as to close the groove, and the test was carried out (atmospheric temperature during processing was 10 ° C).

Example 2 A wood grain pattern was gravure-printed on the surface of the same sheet substrate as in Example 1 in the same manner as in Example 1, and a primer layer made of a two-component curable resin was provided thereon. Acrylic resin (Mitsubishi Rayon Co., Ltd .: Acryprene HBS-02)
7.) The silver content is 2.5% by weight and the zinc content is 14.
5% by weight of a silver ion type zeolite antibacterial agent (particle size distribution 2
To 5 μm) were mixed and dispersed so as to have a content of 5% by weight, and sheets formed to a thickness of 30 μm were laminated to form a protective sheet of an acrylic resin to obtain a decorative sheet. The protective sheet made of acrylic resin containing an antibacterial agent is brought into contact with the heating drum of a rotary-type hot press, and is heated and softened by an infrared heater. Press and crimp with
Subsequently, it was wound around a water-cooled drum, cooled to room temperature, and laminated. Table 1 shows the physical properties of the obtained decorative sheet.

Comparative Example 1 An olefin resin sheet base having the following composition was used in place of the olefin resin sheet base as the sheet base in Example 1, and the surface protective layer contained no antibacterial agent. Except for the above, the same processing as in Example 1 was performed to obtain a decorative sheet. Table 1 shows the physical properties of the obtained decorative sheet. Olefin resin sheet composition High density polyethylene 70 parts by weight Calcium carbonate 30 parts by weight

Comparative Example 2 A decorative sheet was obtained in the same manner as in Example 2 except that a surface protective layer was formed using an acrylic resin sheet containing no antibacterial agent. Table 1 shows the physical properties of the obtained decorative sheet.

The bacteria-controlling effects of the decorative sheets of Examples 1 and 2 and Comparative Examples 1 and 2 were tested as follows.
Table 2 shows the results. (1) Test strain Escherichia coli IFO 3301
(Escherichia coli, hereinafter referred to as "E. coli".) Methicillin Resistant Staphylococcus aureus
us) (Meticillin-resistant Staphylococcus aureus;
A ". (2) Preparation of test bacterial solution 35 ° C, 1 in normal broth medium (manufactured by Eiken Chemical Co., Ltd.)
A culture solution of the test bacteria cultured with shaking for 6 to 20 hours was diluted 20,000-fold with a sterile phosphate buffer to obtain a bacterial solution.
The number of viable bacteria in the bacterial solution was measured by the method described below. (3) Antibacterial test 1 ml of the above-mentioned bacterial solution was dropped on the surface of the sample decorative sheet (the surface sheet or the protective sheet side), and after storing at 25 ° C for 24 hours, the number of bacteria was measured to determine the antibacterial property of the decorative sheet. As a control, 1 ml of the above bacterial solution was dropped on a Petri dish, and the number of bacteria after storage was measured in the same manner. (4) Measurement of Number of Bacteria The number of viable bacteria in the bacterial solution was measured by a pour plate method (cultured at 35 ° C. for 2 days) using a standard agar medium (manufactured by Eiken Chemical Co., Ltd.). For the sample cosmetic sheet and the control stored for 24 hours by the method (3), Nippon Pharmaceutical Co., Ltd. SCDLP (Soy Casein Digest Lecithin Polys)
orbate) medium was washed out with 10 ml of the medium, and the number of viable bacteria in the wash was measured by a pour plate method (cultured at 35 ° C. for 2 days) using a standard agar medium (manufactured by Eiken Chemical Co., Ltd.).

[0067]

[Table 2]

As shown in Table 2 above, in the decorative sheets of Examples 1 and 2, the initial number of bacteria in E. coli was 1.2 × 10 ⁵ , but after 24 hours, the number was 30 in E. coli (Examples 2 and 3). 1) and 80 cells (Example 2), and the initial number of bacteria was 1.7 × 10 ⁵ in MRSA, but after 24 hours, 10 cells or less (Example 1) and 30 cells (Example 2) 2), and the sterilization rate of the decorative sheet of the present invention against E. coli and MRSA was 99.99% or more. On the other hand, in the decorative sheets of Comparative Examples 1 and 2, E. Coli and MR
In both SAs, there was almost no change in the number of bacteria even after 24 hours, indicating that the antibacterial effect was insufficient.

[0069]

As described above, the decorative sheet of the present invention is a decorative sheet having a structure in which a protective sheet of an acrylic resin is laminated on an olefin resin sheet base material. By forming the sheet base with an olefin resin blended with a filler, the decorative sheet of the present invention can eliminate the drawbacks of the conventional decorative sheet and apply a V-cut to the decorative material laminated with the decorative sheet. However, there is no fear that the protective sheet of the decorative sheet of the present invention may be cracked or whitened.
Also, the cosmetic sheet of the present invention exhibits excellent antibacterial properties,
The adsorbed water on the sheet surface has effects such as preventing the growth of mold and the propagation of various bacteria on and around the sheet surface.

[Brief description of the drawings]

FIG. 1 is a longitudinal sectional view of one embodiment of a decorative sheet of the present invention.

FIG. 2 is a longitudinal sectional view of another embodiment of the decorative sheet of the present invention.

FIG. 3 is a longitudinal sectional view of still another embodiment of the decorative sheet of the present invention.

FIG. 4 is a longitudinal sectional view of a three-dimensional article in which the decorative sheet of the present invention is laminated on an adherend.

FIG. 5 is a longitudinal sectional view of a plate-like body in which the decorative sheet of the present invention is laminated on an adherend.

6 is a longitudinal sectional view showing a state where the plate-shaped body of FIG. 5 is bent.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Decorative sheet 2 Sheet base material 3 Protective sheet 4 Decorative layer 5 Easy adhesion layer 6 Uneven pattern 7 Coloring layer 8 Surface protective layer

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 33/00 B32B 33/00 C08K 3/00 C08K 3/00 C08L 23/00 C08L 23/00 23/06 23/06 E04F 13 / 00 E04F 13/00 13/18 13/18 A

Claims (13)

[Claims] 1. A decorative sheet comprising an acrylic resin protective sheet laminated on an olefin resin sheet base, wherein the sheet base is a high density polyethylene blended with a thermoplastic elastomer and an inorganic filler. A decorative sheet comprising an antibacterial treatment at least on the outermost surface side. 2. The decorative sheet according to claim 1, wherein the acrylic resin protective sheet contains an antibacterial agent. 3. The decorative sheet according to claim 1, further comprising a surface protective layer on the surface of the acrylic resin protective sheet. 4. The decorative sheet according to claim 3, wherein the surface protective layer or the surface protective layer and the acrylic resin protective sheet contain an antimicrobial agent. 5. The decorative sheet according to claim 1, wherein a surface side of the protective sheet is embossed. 6. The decorative sheet according to claim 5, wherein a surface protective layer is further provided on the surface of the embossed protective sheet. 7. The decorative sheet according to claim 6, wherein the surface protective layer contains an antibacterial agent. 8. The decorative sheet according to claim 6, wherein an ink layer is provided in the embossed concave portion. 9. The decorative sheet according to claim 8, wherein an antimicrobial agent is contained in the surface protective layer or the surface protective layer and the ink layer provided in the embossed concave portions. 10. The decorative sheet according to claim 8, wherein an antimicrobial agent is contained in the surface protective layer, the ink layer provided in the embossed concave portion, and the acrylic resin protective sheet. 11. A thermoplastic elastomer in an amount of 10 to 60% by weight, based on an olefin resin constituting a sheet substrate.
The decorative sheet according to any one of claims 1 to 10, wherein the decorative sheet contains 5 to 60% by weight of an inorganic filler, and a total of the thermoplastic elastomer and the inorganic filler is 70% by weight or less. 12. The method according to claim 1, wherein a decorative layer is provided between the sheet substrate and the acrylic resin protective sheet.
12. The decorative sheet according to any one of claims 11 to 11. 13. The decorative sheet according to claim 1, wherein an easy adhesion treatment is applied to the back surface of the sheet substrate.