JPH10175270A - Interior decorative sheet - Google Patents

Abstract

(57) [Summary] [Problem] A conventional interior decorative sheet having a layer structure in which a polyvinyl chloride resin layer is formed on a backing substrate, which is suitable for handling such as winding and application to a wall surface and embossing. It also has excellent surface contamination resistance, abrasion resistance, weather resistance (light resistance), and also has excellent anti-dust and anti-contamination properties, fungus adhesion and anti-bacterial properties. Provide interior decorative sheets. An acrylic resin emulsion is applied to the surface of a backing substrate (2) and then dried and solidified to form an acrylic resin layer (3), and an antistatic agent and / or an antibacterial agent is further formed on the acrylic resin layer (3). The fluororesin layer 4 is formed.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an interior decorative sheet used for wallpaper and the like.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet for an interior used as wallpaper or the like which is attached to a wall of a building or the like, for example, a sol-like polyvinyl chloride resin is used on a backing substrate. It is known that after heating, it is gelled by heating to form a solid film, or a polyvinyl chloride sheet is laminated or the like, and the surface is subjected to design processing such as printing or embossing.

However, in such interior decorative sheets, polyvinyl chloride resin has printability and embossability, but the addition of a plasticizer is indispensable to impart flexibility. Soil components dissolve into the plasticizer added to the plastic, and the plasticizer bleeds
In addition, there is a problem that the surface is easily stained due to stickiness and the like, and the scratch resistance is poor, so that the surface is not only easily scratched by rubbing or the like, but also poor in weather resistance (light resistance).

[0004] Further, by providing a polyvinyl chloride paste layer on the backing substrate and further laminating a fluororesin film via an adhesive thereon, a polyvinyl chloride decorative sheet provided with stain resistance and scratch resistance is provided. Although it is also known (Japanese Patent Publication No. 64-11752 and Japanese Patent Application Laid-Open No. HEI 8-118553), such a decorative sheet is coated with a fluororesin film by a plasticizer bleeding (leaching) from a polyvinyl chloride resin. Has been lost, and the film has been peeled off with time.

Therefore, it has been proposed that the resin layer to be laminated on the backing substrate is changed to an acrylic resin emulsion without bleeding (leaching) of a plasticizer, and that the surface of the resin layer is separated from the fluororesin film with time. (JP-A-2-5933)
No. 8, Japanese Patent No. 2512003).

However, when such a wallpaper was actually used, it was found that there were still insufficient points.
That is, fluorocarbon resin has a small critical surface tension and a large contact angle with various liquids (high lyophobic property), it is difficult for dirt to adhere, and once it is adhered, it is easy to wipe off. Fluororesin also has a characteristic that it is easily charged because of its large volume resistivity. For this reason, dust and aerosols in the atmosphere are absorbed by electrostatic attraction, and the surface is eventually stained. Of course, it can be easily removed by wiping, but it takes time for wiping. I found that there was. In addition, spores of bacteria and fungi are often attached to dust, and the attachment of dust also means contamination by fungi and the like. Even if only dust is wiped off, molds may remain, and the fluororesin itself does not have an antibacterial and antifungal effect. Therefore, there has been a problem that the conventional product has no effect of preventing fungi from contamination.

In view of the above-mentioned problems of the prior art, the present inventors have found that the surface is more excellent in stain resistance and abrasion resistance than a conventional fluororesin alone having a surface layer. As a result of intensive studies to provide an interior decorative sheet having excellent antibacterial and antifungal properties, the present invention has been completed.

[0008]

That is, the decorative sheet for interior use of the present invention comprises a backing substrate, a layer obtained by drying and solidifying an acrylic resin emulsion, and a fluororesin containing an antistatic agent and / or an antibacterial agent. The layers are stacked in this order.

[0009]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a sectional view showing an example of the decorative sheet for interior of the present invention.

The interior decorative sheet 1 of the present invention comprises a backing substrate 2, an acrylic resin layer 3 and a fluororesin layer 4 sequentially laminated on the backing substrate 2.

As the backing base material 2 constituting the interior decorative sheet 1 of the present invention, high-quality paper having a basis weight of about 50 to 120 g / m ² , paper such as kraft paper, Japanese paper, cloth, and nonwoven fabric are used. Its thickness is preferably about 50 to 200 μm.

The material of the backing substrate 2 includes cellulose pulp, hemp, cotton, nylon, polyester, vinylon,
Organic fibers such as acrylics and inorganic fibers such as asbestos, glass, quartz, carbon, potassium titanate and the like are included. In particular, when flame retardancy or non-flammability is required, aluminum hydroxide powder mixed paper or asbestos Fabrics or nonwoven fabrics made of inorganic fibers such as glass fibers, alumina fibers, silica fibers, and potassium titanate fibers are preferably used. Also,
If the material itself is not flame-retardant or non-flammable,
Flame retardant treatment can also be performed by mixing aluminum hydroxide powder, antimony trioxide powder or a phosphoric acid compound such as aziridinyl phosphine oxide as a flame retardant.

In the interior decorative sheet 1 of the present invention,
An acrylic resin layer 3 is formed on such a backing substrate 2.

The base resin for forming the acrylic resin layer 3 includes poly (methyl meth) acrylate, poly (ethyl meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate- (meth) acrylate. Poly (meth) acrylate based polymers such as butyl acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate, (meth) acrylate-styrene copolymer, polyacrylonitrile (Meth) acrylic polyol resins comprising a resin or a copolymer of these resins with a monomer having a hydroxyl group such as vinyl alcohol or hydroxyalkyl vinyl ether; and the like. These may be used alone or in combination of two or more. It can also be used. In addition, (meth) acrylic acid shall mean "acrylic acid or methacrylic acid".

The acrylic resin layer 3 of the interior decorative sheet 1 of the present invention comprises an acrylic resin emulsion obtained by emulsion-polymerizing the above-mentioned base resin and dispersing it in a dispersion medium such as water, using a roll coater, a doctor knife coater, a wire, or the like. Rod coater,
It is formed by applying to the surface of the backing substrate 2 by an appropriate coating means such as coating with a comma coater, impregnation, spraying or the like, and then drying the dispersion medium and solidifying the acrylic resin emulsion. The thickness of the acrylic resin layer 3 obtained by drying and solidifying the acrylic resin emulsion is 5
It is preferably about 0 to 200 μm.

In order to impart flame retardancy to the acrylic resin layer 3, the acrylic resin emulsion forming the acrylic resin layer 3 includes a phosphoric ester-based organic flame retardant containing a phosphoric acid ester, System, antimony trioxide, zinc borate, barium metaborate, magnesium hydroxide, aluminum hydroxide, etc.
About 150 parts by weight, and if necessary, calcium carbonate powder, clay, mica, diatomaceous earth,
Fillers such as silica and talc, organotin-based, inorganic chlorine-based,
Metal soap-based heat stabilizers such as lead, cadmium, barium, and calcium can be added.

In the present invention, the acrylic resin layer 3 can be a cellular foam layer as required. By using the acrylic resin layer 3 as a cellular foam layer, it is possible to increase the thickness of the acrylic resin layer 3 to impart embossing suitability and enhance cushioning, sound insulation, heat insulation, and the like. There are advantages.

To make the acrylic resin layer 3 a foam layer,
For example, adding a foaming agent to an acrylic resin emulsion,
It is mechanically foamed by stirring with a stirrer such as a planetary mixer, or an azo compound such as azodicarbonamide, azobisisobutyronitrile, or a sulfonyl hydrazide compound such as paratoluenesulfonyl hydrazide or oxybisbenzenesulfonyl hydrazide. , N, N'-dinitrosopentamethylenetetramine and other nitroso compounds, ammonium carbonate, sodium boron hydride,
Microcapsules in which a thermally decomposable blowing agent such as potassium bicarbonate or sodium bicarbonate, or a resin shell made of acrylonitrile, methyl (meth) acrylate, etc., contains a heat-expandable gas such as hexane, pentane, butane, or air A method in which a foaming agent alone or a mixture of two or more kinds is added in an amount of about 1 to 5 parts by weight based on 100 parts by weight of the base resin, and the foaming agent is thermally decomposed and foamed.

Acrylic resin layer 3 using a pyrolytic foaming agent
In the case where is a foam layer, a foaming accelerator can be added together with the foaming agent, if necessary.

As the foaming accelerator, a substance which promotes the thermal decomposition and gas generation reaction of the thermal decomposition type foaming agent to be used is used. For example, when an azo compound such as azodicarbonamide is used as a foaming agent, dibasic lead sulfate, tribasic lead sulfate, tribasic lead maleate, dibasic lead phthalate, Lead stearate, zinc white, urea, oxalic acid, ethanolamine and the like can be used alone or in combination of two or more. When N, N'-dinitrosopentamethylenetetramine is used as a foaming agent, oxalic acid, salicylic acid, phthalic anhydride, urea, ethylene glycol, boric acid, benzoic acid, etc. may be used alone or as a foaming accelerator. A mixture of more than one species can be used.

In the decorative sheet 1 for an interior of the present invention, a fluororesin layer 4 containing one or both of an antistatic agent and an antibacterial agent is further formed on the acrylic resin layer 3. The base resin for forming the fluororesin layer 4 includes polyvinyl fluoride, polyvinylidene fluoride, polychloroethylene trifluoride, polytetrafluoroethylene, and tetrafluoroethylene.
Hexafluoropropylene copolymer, ethylene-trichloroethylene copolymer, ethylene tetrafluoride-perfluoroalkyl vinyl ether copolymer, ethylene-tetrafluoroethylene copolymer, etc., and various types containing a hydroxyl group or a carboxyl group Of a fluororesin.

Representative examples of the fluororesin containing a hydroxyl group or a carboxyl group are as follows.

(1) A copolymer containing fluoroolefin, cyclohexyl vinyl ether, alkyl vinyl ether and hydroxyalkyl vinyl ether as essential components. Typical of the fluoroolefins are perhaloolefins such as chlorotrifluoroethylene and tetrafluoroethylene. The molar ratio of the copolymer is as follows: fluoroolefin 40 to 60%, cyclohexyl vinyl ether 5 to 45%, alkyl vinyl ether 5 to 45%.
%, And 3 to 15% of hydroxyalkyl vinyl ether (JP-A-57-34107).

(2) Perfluoroolefin, vinylidene fluoride, and vinyl ester are essential components,
The molar ratio of these is from 20 to 80 perfluoroolefin.
%, Vinylidene fluoride 5 to 80%, vinyl ester 3 to
Hydroxyl group-containing fluoropolymer obtained by hydrolyzing 45% of a copolymer (JP-A-56-174657).

(3) A fluoropolymer obtained by reacting the hydroxyl group-containing fluoropolymer described in the above (1) or (2) with a dibasic acid anhydride to form an ester to convert at least a part of the hydroxyl group into a carboxyl group. (JP-A-58-136605)
No.).

(4) Unit (a) CH ₂ ＣＦCF ₂ , Unit (b) CH ₂ ＣＨCH—O— (CH ₂ ) _n —OH (provided that
n is an integer), unit (c) CFX = CFX [where X is hydrogen, chlorine, or fluorine, Y is fluorine, a lower fluoroalkyl group, or-(OCF ₂ CF (CF ₃ )) _m -OC]
₃ F ₇ (where, m is an integer of 0 to 3) copolymer obtained by copolymerizing].

If necessary, these hydroxyl or carboxyl group-containing fluororesins may be further cross-linked with a cross-linking agent such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated toluene diisocyanate, melamine resin or polybasic acid. You may let it.

Further, for example, JP-A-57-34108, JP-A-59-219372, and JP-A-59-1
No. 89108, JP-A-60-67517, JP-A-60-67518, JP-A-60-14741
For example, a fluorine resin described in Japanese Patent Publication No. 5 and the like can be used.

The fluororesin layer 4 may be composed of only the fluororesin as described above. In particular, in order to further enhance the adhesive strength with the acrylic resin layer 3, the base resin on which the fluororesin layer 4 is to be formed is formed. It is preferable to mix an acrylic resin.
The mixing ratio in this case is such that when the total amount of the fluororesin and the acrylic resin is 100 parts by weight, the fluororesins 45 to 8
It is preferable to use 55 to 15 parts by weight of the acrylic resin for 5 parts by weight.

As the acrylic resin to be mixed with the fluororesin, the same resins as those exemplified above as the base resin for forming the acrylic resin layer 3 can be used.

The fluororesin layer 4 is formed on the acrylic resin layer 3 by coating means such as a roll coater, a comma coater, a melt-extrusion (extrusion) coater, a flow coater or the like, or is formed in a sheet form in advance. The film is laminated by hot melting, or a fluororesin film is laminated on the acrylic resin layer 3 by an adhesive such as a two-component curable urethane resin or a melt-extruded (extrusion) coated polyethylene. Can be formed. The thickness of the fluororesin layer is preferably about 5 to 100 μm.

The acrylic resin and the fluororesin originally have some weather resistance (light resistance), but the acrylic resin layer 3 and the fluororesin layer 4 provide better weather resistance (light resistance).
In order to provide the layer, an ultraviolet absorber or a light stabilizer can be added to these layers. The addition amount of the ultraviolet absorber and the light stabilizer is usually about 0.5 to 10% by weight, but it is generally preferable to use the ultraviolet absorber and the light stabilizer together.

Examples of the ultraviolet absorber include organic compounds such as benzotriazole, benzophenone and salicylic acid ester, zinc oxide in the form of fine particles of 0.2 μm or less,
An inorganic compound such as cerium oxide can be used.
As the light stabilizer, for example, a hindered amine radical scavenger such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and a radical scavenger such as a piperidine radical scavenger can be used.

In the present invention, the pattern layer 5 may be formed on at least one of the backing substrate 2, the acrylic resin layer 3, and the fluororesin layer 4 in order to impart decorativeness. On which surface the pattern layer 5 is formed is appropriately selected according to the design to be applied to the interior decorative sheet 1. FIG. 2 shows an interior decorative sheet 1 of the present invention in which a pattern layer 5 is formed on an acrylic resin layer 3.

The pattern layer 5 may be a layer formed in an arbitrary pattern such as a wood pattern, a cloth pattern, a stone pattern, a geometric figure, a character, a symbol, or the like, or a layer formed entirely on the entire surface. In addition, the pattern layer 5 can be formed as a printing layer formed by printing with a printing ink or a metal layer by a metal vapor deposition method or the like. If necessary, the printing layer and the metal layer can be combined.

When the pattern layer 5 is formed as a printing layer, the printing ink does not necessarily need to contain a coloring agent.
When a coloring agent is incorporated into a printing ink to form a printed layer having high designability by coloring, a coloring agent excellent in weather resistance, for example, isoindolinone (40 yellow), quinacridone (15 red), perylene (100 Organic pigments such as red), phthalocyanine blue (blue), aniline black (black), condensed azo / quinacridone (weather-resistant red), graphite (yellow), titanium yellow (yellow), red petal (red), cadmium red ( Red), cobalt blue (blue), ultramarine (blue),
By using an inorganic pigment composed of carbon (black), titanium white (white), etc., the weather resistance of the printing layer can be increased. However, the above-mentioned ultraviolet absorber or light stabilizer is mixed into the printing ink. It is also effective.

As the binder for the printing ink, a urethane resin, an acrylic resin, a polyamide resin, a polyester resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer, or the like, or a mixture of two or more kinds is used. be able to. In addition, extenders such as calcium carbonate and microsilica may be added to the printing ink as necessary.

As a printing method, a normal printing method such as gravure printing, offset printing, letterpress printing, silk screen printing, etc. can be used, but drawing may be used. In addition, a print layer on a peelable support sheet, and a transfer sheet having an adhesive layer formed thereon, if necessary, are prepared in advance, and the print layer formed on the transfer sheet is pressurized or pressed. A so-called transfer printing method in which the pattern is transferred to the surface on which the pattern layer 5 (printing layer) is formed by heating can also be used.

In order to form the pattern layer 5 as a metal layer, a metal such as aluminum or chromium is formed by means such as vacuum evaporation and sputtering. Such a metal layer may be formed on the entire surface or may be formed in a pattern so as to obtain the above-described pattern. Is formed in a desired pattern, a metal is vapor-deposited on the entire surface, and then a known method is used, such as washing with water to remove the metal layer immediately above the removal layer together with the removal layer. However, when a material having poor water resistance such as paper is used for the backing base material 2 or when the heat resistance of the acrylic resin layer 3 is insufficient and vacuum deposition processing is difficult, a transfer printing method is used to form a transfer sheet in advance. The metal layer that has been set may be transferred to the surface on which the pattern layer 5 (metal layer) is formed.

In the present invention, whether or not the acrylic resin layer 3 and the fluororesin layer 4 are transparent is not particularly limited, and the acrylic resin layer 3 and the fluororesin layer 4 can be colored to any color by a commonly used pigment or dye. In the case where the pattern layer 5 is provided below the layers 3 and 4, it is required that the pattern layer 5 be at least transparent enough to be seen. In addition, when it is necessary to conceal the appearance and color tone of an adherend to be described later to which the interior decorative sheet 1 of the present invention is bonded, the concealing property of the base sheet 2 alone is often insufficient. Has a resin layer 3
Or a concealing pigment such as titanium dioxide in the fluororesin layer 4
It is preferable to add about 20 parts by weight to form an opaque layer, and to impart hiding properties to the layers 3 and 4.

In the present invention, as shown in FIG. 3, the surface of the fluororesin layer 4 can be embossed to form embossed irregularities. The embossing can be performed by any known embossing method. For example, the surface of the layer 4 can be made uneven by using a normal hot press type sheet-fed or rotary embossing machine.

The depth of the concave portion 6 of the embossed irregularities slightly varies depending on the pattern expressed thereby, the thickness of the acrylic resin layer 3 and the thickness of the fluororesin layer 4 and the like. 50-20 to bring
It is preferably about 0 μm.

As the embossed irregularities formed by embossing, those expressing wood grain conduit grooves, wood grain texture, stone surface unevenness, surface tex chair of fabric, satin finish, grain, hairline, etc., or a combination thereof are used. No.

The concave portion 6 of the embossed surface may be filled with a coloring ink 7 by wiping as required. As the coloring ink, a urethane resin, an acrylic resin, a polyester resin, or a commonly used vehicle to which a pigment or a dye is added is selected and used, and a two-pack curing type having good adhesion and solvent resistance is preferable. Wiping may be performed by any of conventionally used wiping methods such as a doctor blade method and a roll coating method.

The interior decorative sheet 1 of the present invention includes:
An antistatic treatment can be performed by including an antistatic agent in the fluororesin layer 4, and as the antistatic agent,
The following a) to d) can be used.

A) Surfactants. For this, various types such as anionic, cationic, nonionic and amphoteric can be used. The amount of addition is usually about 0.5 to 3% by weight. As the substance to be used, specifically, a polyoxyethylene alkyl phosphate ester-based surfactant, particularly a grade such as an inorganic powder for dispersion in water, an emulsifier for food, and a foaming thickener for cosmetics is useful. In addition, naphthalene sulfonic acid formalin condensate, special polycarboxylic acid type polymer surfactant, polyoxyethylene derivative, oxyethylene-oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine , Alkyl alkanolamides, quaternary ammonium salts, pyridium salts, aminosulfuric esters and the like.

B) Metal. Specifically, a good electric conductor with low volume resistivity such as gold, silver, copper, palladium, nickel, and aluminum is used. The shape is powder, scaly foil,
Or a short fiber. Average particle size or average fiber length is 0.1 ~
It is about 30 μm. The amount of addition is usually about 1 to 10% by weight.

C) Graphite (graphite). Its shape is powder or scaly foil, and the amount of addition is usually 1 to 10% by weight.
It is about.

D) ITO (indium tin oxide). Its shape is powder or scaly foil, the amount of addition is usually 1 to 10
% By weight.

E) A mixture of two or more selected from the above groups a) to d).

However, when the fluororesin layer needs to be colorless and transparent, it is preferable to use a surfactant or ITO. In order to obtain the effect of preventing adhesion of dust and aerosol, the surface resistance of the fluororesin layer according to JIS K 6900 is preferably 10 ¹² Ω or less, more preferably 10 ¹² Ω or less.
The type, amount and dispersion method of the antistatic agent are adjusted so as to be ¹⁰ Ω or less.

The interior decorative sheet 1 of the present invention includes:
An antimicrobial treatment can also be performed by incorporating an antimicrobial agent into the fluororesin layer 4.

The term "antimicrobial agent" of the present invention is used to include both an antimicrobial agent in a narrow sense that kills bacteria and suppresses growth and an antifungal agent in a narrow sense that kills and suppresses growth of fungi. I do. Specific examples of such antibacterial agents include the following.

Japanese Patent Publication No. 63-54013,
-300975, Patent No. 2529574, etc., antibacterial Ag ⁺ , Cu ²⁺ , Zn ²⁺ , H
Metal ions such as g ⁺ , Ni ²⁺ , and Cd ²⁺ (preferably from the viewpoint of safety and performance because Ag ⁺ is harmless to the human body and has a long lasting effect) can be used for zeolite, apatite, glass,
An ion exchanger such as silica gel, phosphate, zirconium phosphate, etc. (particularly, zeolite and zirconium phosphate have high track record and high reliability) supported ion-exchangeably (metal ion content is Ag ⁺ Case 0.1-1
5% by weight, and in the case of Cu ²⁺ , 0.1 to 8% by weight is preferable. ). The particle size is usually about 1 to 10 μm.

Japanese Patent Publication No. Hei 4-28646 and Japanese Patent No. 25
As described in, for example, Japanese Patent No. 29574 and the like, a metal ion to which an ammonium ion is further added as an antibacterial ion of the above antibacterial agent.

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-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 cephalothin and cefazolin, streptomycins such as streptomycin sulfate and paromomycin (sulfate), erythromycins such as erythromycin and josamycin, tetracycline, and lolinitrate Tetracycline such as tetracycline; chloramphenicol; chloramphenicol such as thiamphenicol aminoacetic acid ester hydrochloride;

Anatase-type titanium dioxide powder or a photocatalyst type in which anatase-type titanium dioxide is supported on inorganic porous particles such as silica gel, zeolite, and apatite. These usually have a particle size of 1 to 10 μm.
m is used.

In the present invention, both of these antistatic agents and antibacterial agents can be added. In this case, a synergistic effect between the dust adhesion preventing effect and the antibacterial effect is imparted to the surface of the fluororesin layer, which is preferable.

The decorative sheet for interior 1 of the present invention can be laminated on various adherends and subjected to a predetermined molding process to be used for various decorative purposes. For example, interior decoration of buildings such as walls, ceilings, floors, window frames, doors, surface decorations of fittings such as handrails, partitions, kitchens, housing equipment such as bathtubs and bathrooms, furniture 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, when the cosmetic sheet of the present invention is subjected to antibacterial treatment, it is suitable for use in hospitals, cafeterias, bathroom interiors, food-related containers, kitchens, bathtubs, and the like. The interior decorative sheet 1 of the present invention can be directly bonded to an adherend or bonded in advance to a component member of the adherend, and then cut into predetermined dimensions, V-cut, or the like. It can also be in the form of a product.

[0062]

The present invention will be described below in more detail with reference to specific examples.

Example 1 An acrylic resin emulsion composition having the following composition was applied to a flame-retardant backing paper for wallpaper having a basis weight of 90 g / m ² using a comma coater, and dried and solidified with hot air to form an acrylic resin layer. . The thickness of the acrylic resin layer was 180 μm.

[Acrylic Resin Emulsion Composition] Resin: 42 parts by weight of methyl methacrylate, 42 parts by weight of 2-ethylhexyl acrylate, 10 parts by weight of acrylonitrile, 1 part by weight of N-methylolacrylamide, 5 parts by weight of acrylic acid Water-dispersed resin formed by turbid polymerization 100 parts by weight Pigment: titanium dioxide powder 5 parts by weight Filler: calcium carbonate 15 parts by weight Difficult Flame retardant: antimony trioxide 3 parts by weight Thickener: Na salt of carboxymethyl cellulose 0.15 parts by weight Defoaming agent 0.06 parts by weight

Next, a fluororesin paint prepared by adding 9 parts by weight of an isocyanate compound as a cross-linking agent to 100 parts by weight of a fluoroolefin having a hydroxyl group in the molecule [trade name "Lumiflon" manufactured by Asahi Glass Co., Ltd.] 3 parts by weight of a quaternary ammonium salt type anionic surfactant as an antistatic agent, an average particle size of 5 μm as an antibacterial agent, a silver content of 2.5% by weight, and a zinc content of A coating obtained by adding 5 parts by weight of 14.5% by weight of a silver ion type zeolite antibacterial agent and microsilica having an average particle diameter (primary) of 16 nm and a specific surface area of 110 m ² / g as an extender pigment was coated on the surface of an acrylic resin layer. Was coated with a gravure roll coater and cured and cured in a 40 ° C. atmosphere for 5 days to form a 5 μm-thick fluororesin layer to obtain a decorative sheet for interior use.

Comparative Example 1 An interior decorative sheet was obtained in the same manner as in Example 1 except that the antistatic agent and the antibacterial agent were not added to the fluororesin paint.

The interior decorative sheets obtained in Example 1 and Comparative Example 1 were evaluated for the following two types of properties having a correlation with the effect of preventing dust adhesion due to charging. Table 1 shows the results.
Shown in The atmosphere at the time of measurement was 25 ° C. and 60% RH, the applied potential at the time of measurement was −10 kV, and the application time was 30.
Seconds. (1) Surface resistance value The surface resistance [Ω] of each fluororesin layer of Example 1 and Comparative Example 1 was measured in accordance with JIS K 6900. (2) Saturation potential and half-life of potential Using a static honest meter (manufactured by Shishido Shokai),
The saturation potential [V] and the half-life of the potential [second] during charging were measured for each of Example 1 and Comparative Example 1.

[0068]

[Table 1]

Next, the interior ash sheets obtained in Example 1 and Comparative Example 1 were subjected to the following ash adhesion test.

[Ash Adhesion Test] Each decorative sheet of Example 1 and Comparative Example 1 was cut into a length × width = 5 cm × 5 cm to obtain a test piece. On the other hand, a sheet of cigarette ash spread all over a glass plate was prepared. Next, the fluororesin layer of each test piece was rubbed back and forth with paper (trade name: “JK Wiper (trademark)”, manufactured by Cressia Corp.) for 10 times, and immediately afterwards, the fluororesin layer was turned on the glass plate to direct fluorine Distance between resin layer and ash is 5
The ash was gradually approached from 0 cm to 0 cm, and the state of adhesion of the ash to the fluororesin layer was visually observed. The test was conducted at 20 ° C and 55%
Performed in an atmosphere of RH.

In Example 1, even when the distance between the fluororesin layer and the ash became 0 cm, no ash adhered to the fluororesin layer. On the other hand, in Comparative Example 1, the distance between the fluororesin layer and the ash was 10 cm, and the ash adhered to the entire surface of the fluororesin layer (however, it could be completely removed by wiping with a wet cloth).

Further, with respect to the decorative sheets of Example 1 and Comparative Example 1, the bacteria suppressing effect was 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 specimen decorative sheet (the fluororesin layer side of the surface), 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.).

[0074]

[Table 2]

As shown in Table 2 above, in the decorative sheet of Example 1, the initial number of bacteria in E. coli was 1.2 × 10 ⁵ , but after 24 hours the number was reduced to 30. The number of bacteria was 1.7 × 10 ⁵ but decreased to 10 or less after 24 hours, and the bactericidal 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 sheet of Comparative Example 1, E. Col.
Both i and MRSA showed almost no change in the number of bacteria even after 24 hours, indicating that the antibacterial effect was insufficient.

[0076]

The interior decorative sheet of the present invention is suitable for handling such as winding and application to a wall surface and embossing suitability. It has a layer structure in which a polyvinyl chloride resin layer is formed on a backing substrate. While it is equivalent to an interior decorative sheet, it has excellent durability such as scratch resistance and weather resistance (light resistance) on the surface.

The acrylic resin layer obtained by drying and solidifying the acrylic resin emulsion has sufficient flexibility, so that it is not particularly necessary to add a plasticizer, and the fluorinated resin layer is formed by bleeding of the plasticizer. There is no danger of peeling, and in addition to this, especially by adding an antistatic agent to the fluororesin layer, dust and aerosol (smoke, etc.) are less likely to be trapped and adhered by electrostatic attraction of the charged electric charge, thus preventing contamination. Even if contaminants adhere, they can be easily wiped and washed due to the poor adhesion of fluorocarbon resin, and it is difficult for fungi that survive in dust etc. to adhere. Therefore, it has an unprecedented effect that it is also excellent in the prevention of fungal contamination.

In particular, when both the antistatic agent and the antibacterial agent are contained in the fluororesin layer, the fungi are hardly adhered due to the poor adhesion of the fluororesin, and in addition to the fungi on the surface. Even if it adheres, the fungi adhered can be killed by the action of the antibacterial agent, and a hygienic surface can be maintained.

[Brief description of the drawings]

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

FIG. 2 is a sectional view showing another example of the interior decorative sheet of the present invention.

FIG. 3 is a cross-sectional view showing another example of the decorative sheet for interior according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Interior decorative sheet 2 Backing base material 3 Acrylic resin layer 4 Fluororesin layer 5 Pattern layer

Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/30 B32B 27/30 A D E04F 13/18 E04F 13/18 A

Claims (1)

[Claims] (1) A layer obtained by drying and solidifying an acrylic resin emulsion and a fluororesin layer containing an antistatic agent and / or an antibacterial agent are laminated on a backing substrate in this order. Interior decorative sheet.