JPH11334021A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To maintain an excellent weather resistance even in the case of being brought into contact with a warm water, chemicals, oil or the like by incorporating an ionizing radiation reaction type weather resistance additive into an ionizing radiation curable resin. SOLUTION: A design layer 2 constituted of a solid pattern layer 21, a design layer 22 and the like is provided on one side surface of a base material sheet 1 using a highly crystalline non-elastomer polyolefin resin such as a polyethylene, polypropylene polymethylpentene or the like, and a protective layer 3 is provided on the layer 2. The layer 3 is constituted of an ionizing radiation curable resin composition obtained by adding an ionizing radiation reaction type weather resistance additive 4 to be reacted with an ionizing radiation to an ionizing radiation curable resin. Thus, a decrease in a weather resistance according to a postprocessing or the like and a decrease in a transparency of the layer 3 or the like are eliminated. Even in the case of bringing it into contact with a warm water, chemicals, oil or the like, the weather resistance can be maintained good.

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 for interior decoration of buildings, surface decoration of fittings, interior decoration of vehicles, etc., and used for the purpose of giving a design to these surfaces or protecting the surfaces.

[0002]

2. Description of the Related Art Heretofore, in order to impart weatherability to a decorative sheet, a sheet obtained by adding an ultraviolet absorber, a light stabilizer and the like to a surface protective layer is known. The surface protective layer is usually formed so transparent that the design of the lower picture layer can be seen.

[0003]

In the above-mentioned conventional decorative sheet, since the ultraviolet absorber and the light stabilizer have a poor compatibility with the resin of the protective layer and the ink resin of the picture, the decorative sheet migrates to the surface by bleed-out. In addition, there has been a problem that the concentration in the layer decreases with time, and the weather resistance decreases.

[0004] When the decorative sheet is subjected to post-processing involving heating, bleed-out of an ultraviolet absorber, a light stabilizer and the like is further promoted, and the transpiration of these materials is increased, and the weather resistance is further reduced.

Further, conventionally used ultraviolet absorbers, light stabilizers and the like have a low solubility in a binder resin such as a protective layer to be added and the like, so that the number of added parts is limited.
In particular, when the ultraviolet absorber or the light stabilizer has low solubility in the binder resin, the transparency of the resin layer to which these are added is reduced, and the lower layer pattern becomes difficult to see and the design property is deteriorated. Will occur.

When a decorative sheet is used, hot water,
When it comes into contact with acids, alkalis, alcohols, oils, etc., there is also a problem that ultraviolet absorbers, light stabilizers and the like are eluted into them, the concentration in the layer is reduced, and the weather resistance is reduced.

The present invention has been made in view of the above-mentioned drawbacks of the prior art, and is excellent in weather resistance and can maintain high weather resistance for a long period of time. There is no decrease in properties, warm water, chemicals,
An object of the present invention is to provide a decorative sheet capable of maintaining excellent weather resistance even when it comes into contact with oil or the like.

[0008]

SUMMARY OF THE INVENTION The present invention relates to a decorative sheet having a pattern layer provided on at least one surface of a base sheet and a protective layer made of an ionizing radiation-curable resin on the surface. The gist of the present invention is a decorative sheet characterized in that the resin contains an ionizing radiation-reactive weather-resistant additive.

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to the drawings. In the decorative sheet of the present invention, as shown in FIG. 1, a pattern layer 2 composed of a solid pattern layer 21 and a pattern layer 22 is provided on at least one surface of a base sheet 1,
In a decorative sheet provided with a protective layer 3 made of an ionizing radiation-curable resin, the protective layer 3 is formed by adding an ionizing radiation-responsive weatherable additive 4 that reacts with ionizing radiation to the ionizing radiation-curable resin. It is composed of a radiation-curable resin composition.

The base sheet 1 may be any one that is used as a base material of a normal decorative sheet, but it is preferable to use a polyolefin resin. Examples of the polyolefin resin include highly crystalline non-elastomeric polyolefin resins such as polyethylene (low density or high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, and various types of polyolefin resins. An olefin-based thermoplastic elastomer is used.

The olefin-based thermoplastic elastomer is
The main raw material is made of either high-density polyethylene or polypropylene which is a hard segment, to which an elastomer and an inorganic filler as a soft segment are added, and the hard segment described in JP-B-6-23278. A mixture comprising an isotactic polypropylene and an atactic polypropylene as a soft segment;
JP, JP-A-5-77371, JP-A-7-31
The ethylene-propylene-butene copolymer described in JP-B-6358 and the like are typical. If necessary, a coloring agent may be added to this. The details are described below.

The high-density polyethylene used in the present invention is preferably a polyethylene having a specific gravity of 0.94 to 0.96, and a polymer having a high degree of crystallinity and a small number of branched structures obtained by a low-pressure method. High density polyethylene is used. Further, as the polypropylene, preferably, isotactic polypropylene is used.

As the elastomer in the present invention, a diene rubber, a hydrogenated diene rubber, an olefin elastomer and the like are used. 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 the crystallization of the polyolefin resin (high-density polyethylene or polypropylene in the present invention). Increase flexibility. Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene butadiene rubber. The olefin elastomer is an elastic copolymer to which at least one polyene copolymerizable with two or three or more olefins is added, and the olefin is ethylene, propylene, α
An olefin or the like is used;
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-nonconjugated diene rubber, and ethylene-butadiene copolymer rubber. In addition, these elastomers may be appropriately cross-linked by using a cross-linking agent such as an organic peroxide or sulfur, if necessary.

The amount of these elastomers is 1
It is about 0 to 60% by weight, preferably about 30% by weight. 1
If the amount is less than 0% by weight, the change in elongation at a constant load becomes too steep, and the elongation at break, impact resistance and easy adhesion are reduced. The creep property decreases.

As the inorganic filler in the present invention, powder having an average particle size of about 0.1 to 10 μm, such as calcium carbonate, barium sulfate, clay, and talc, is used. The amount of addition is about 1 to 60% by weight, preferably about 5 to 30% by weight. If the amount is less than 1% by weight, the creep deformation resistance and the adhesion will decrease. If the amount is more than 60% by weight, the elongation at break and the impact resistance will decrease.

Japanese Patent Publication No. Hei 6-23278 discloses
(A) As a soft segment, the number average molecular weight Mn is 2
(B) 10 to 90% by weight of atactic polypropylene soluble in boiling heptane having a ratio of weight average molecular weight Mw to number average molecular weight Mn of 5,000 or more, Mw / Mn ≦ 7;
As a hard segment, the melt index is 0.1
Soft polypropylene consisting of a mixture of ４4 g / 10 min boiling heptane-insoluble isotactic polypropylene 90-10 wt%. Among this kind of olefin-based thermoplastic elastomers, so-called "necking" is unlikely to occur, and as a material having good suitability for molding or embossing using heat and pressure, isotactic polypropylene and It is made of a mixture with atactic polypropylene, and the weight ratio of the atactic polypropylene is 5% by weight or more and 50% by weight or less. The polypropylene-based olefin-based thermoplastic elastomer itself is already known, but when used in a conventionally known application such as a packaging container, the weight ratio of the atactic polypropylene as a soft segment is 5 to emphasize strength. Less than% by weight was exclusively used. However, when the present invention is applied to a novel use such as forming into a three-dimensional shape or uneven shape as intended in the present invention or embossing, necking occurs as described above, and good processing is impossible. Therefore, as a result of various studies, the present inventor contradicts the conventional composition design by setting the weight ratio of the atactic polypropylene to 5% by weight or more in the polypropylene-based olefin-based thermoplastic elastomer. It has been found that non-uniform sheet deformation due to necking when embossing or molding into a three-dimensional or irregularly shaped article, and the resulting defects such as wrinkles and picture distortions are eliminated. Particularly, the case where the weight ratio of the atactic polypropylene is 20% by weight or more is preferable. On the other hand, if the weight ratio of the atactic polypropylene increases too much, the sheet itself is deformed, the pattern is distorted,
In the case of multicolor printing, defects such as misregistration are likely to occur. Further, it is not preferable because it is easily broken during molding. As the upper limit of the weight ratio of atactic polypropylene, the pattern layer is printed using a normal rotary printing machine such as rotary gravure printing, and embossing of a sheet, vacuum forming, V-cut processing, simultaneous lamination of injection molding, etc. When employed, it is at most 50% by weight, more preferably at most 40% by weight.

A thermoplastic elastomer comprising an ethylene / propylene / butene copolymer resin. Here, as the butene, any one of the three structural isomers of 1-butene, 2-butene and isobutylene can be used. The copolymer is a random copolymer and partially includes an amorphous portion. Preferred specific examples of the ethylene / propylene / butene copolymer include the following (i) to (iii). (i) Those described in JP-A-9-1111055. This is a random copolymer of a terpolymer of ethylene, propylene and butene. The weight ratio of the monomer components is 90% by weight or more of propylene. Melt flow rate is
It is preferable that the temperature is 230 ° C. and 2.16 kg for 1 to 50 g / 10 minutes. Then, based on 100 parts by weight of such a ternary random copolymer, 0.01 to 50 parts by weight of a transparent nucleating agent containing a phosphoric acid aryl ester compound as a main component, and 0.1 to 0.2 parts by weight of a fatty acid amide having 12 to 22 carbon atoms. 003 to 0.3 parts by weight are melt-kneaded. (ii) Those described in JP-A-5-77371. this is,
A terpolymer of ethylene, propylene and 1-butene, in which 20 to 100% by weight of an amorphous polymer having a propylene content of 50% by weight or more,
0 to 0% by weight is added. (iii) Those described in JP-A-7-316358. This is an ethylene-propylene / 1-butene terpolymer, in which the content of propylene and / or 1-butene is 50% by weight or more and the low crystalline polymer is 20 to 100% by weight.
A composition obtained by adding 5% by weight of an oil gelling agent such as an N-acylamino acid amine salt or an N-acylamino acid ester to 100 parts by weight of a composition mixed with 80 to 0% by weight of a crystalline polyolefin such as isotactic polypropylene. It is. The ethylene / propylene / butene copolymer resin may be used alone, or may be used by mixing other polyolefin resins as required in the above (i) to (iii).

A coloring agent may be added to the base sheet.
The coloring agent is for giving the base sheet the necessary color as a decorative sheet, and includes titanium white, zinc white, red stalks,
Inorganic pigments such as vermilion, ultramarine, cobalt blue, titanium yellow, graphite, and carbon black; organic pigments or dyes such as isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, and phthalocyanine blue; and foil powders such as aluminum and brass Pigments, titanium dioxide-coated mica, pearlescent pigments made of foil powder such as basic zinc carbonate, and the like. The coloring may be either transparent coloring or opaque (concealing) coloring, but opaque coloring is generally preferred for covering the adherend.

Further, if necessary, a heat stabilizer, a flame retardant, a radical scavenger and the like are added. The heat stabilizer is a known one such as a phenol type, a sulfite type, a phenylalkane type, a phosphite type, and an amine type, and is used for further improving the prevention of deterioration such as thermal discoloration during thermal processing. 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.

A blend of these materials is formed into a film by a conventional method such as a calendering method to obtain an opaque colored base sheet. The thickness of the base sheet is about 50 to 200 μm, preferably about 100 μm.

The surface of the base sheet is preferably subjected to an easy-adhesion treatment such as application of an easy-adhesion layer, corona discharge treatment, plasma treatment, and ozone treatment. Acrylic resin, vinyl chloride-vinyl acetate copolymer, polyester resin, urethane resin, chlorinated polypropylene, and chlorinated polyethylene are used as the easy-adhesion layer (also referred to as a primer layer or an anchor layer). Is desirable.

Examples of the acrylic resin include poly (methyl meth) acrylate, poly (ethyl meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate / (meth) acrylate. Such as butyl acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate, ethylene / methyl (meth) acrylate, and styrene / methyl (meth) acrylate An acrylic resin composed of a homo- or copolymer containing (meth) acrylic acid ester (here, (meth) acryl means acryl or methacryl) is used.

The urethane resin is a polyurethane having a polyol (polyhydric alcohol) as a main component and an isocyanate as a crosslinking agent (curing agent). As a polyol,
Those having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol and the like are used. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, 2,4 tolylene diisocyanate, xylene diisocyanate, 4,
Aromatic isocyanates such as 4-diphenylmethane diisocyanate or aliphatic (or alicyclic) isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used. Alternatively, adducts or multimers of these isocyanates can also be used.

As the base sheet, any of a stretched sheet and an unstretched sheet can be used, and if necessary, a foaming agent, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, a light-stable Various additives such as agents are added. The thickness of the base sheet 1 depends on the use and the like, but is 20 to 300 μm.
The degree is preferred.

The picture layer 2 is a pattern layer 21 such as a wood grain pattern, a stone grain pattern, a cloth grain pattern, a squeezed pattern, a geometric figure, a character, a symbol, a line drawing, various abstract patterns, or a solid layer 22 such as a solid printing.
Etc. Even if the picture layer 2 is composed of only the pattern layer 21,
It may be composed of only the solid layer 22 or may be composed of both the pattern layer 21 and the solid layer 22 as shown in FIG.

The picture layer 2 can be formed by printing and applying using a general picture printing ink. Examples of inks include, as binders, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyesters, polyurethanes (two-component curable urethane resins or thermoplastic urethane resins), acrylics, vinyl acetate, vinyl chloride and vinyl acetate copolymers. Coalescence, cellulosic resin, etc.,
One type or a mixture of two or more types may be mentioned.

Although not shown, the picture layer 2 can be applied to the back side of the base sheet 1. In addition, 2
It may be composed of (or more) sheets, and a picture layer may be provided between the sheets.

As shown in FIG. 1, the protective layer 3 is provided on the front side of the base sheet 1 where the picture layer is provided (not shown, but the front side of the base sheet 1 when the picture layer is provided on the back side). It is formed by coating and curing an ionizing radiation-curable resin composition.
The ionizing radiation-curable resin composition contains at least an ionizing radiation-curable resin serving as a binder and an ionizing radiation-reactive weather-resistant additive, and is further added with other additives as necessary. The thickness of the protective layer 3 is preferably formed such that the thickness when dried is about 1 to 100 μm.

The ionizing radiation-curable resin of the protective layer 3 is specifically prepared by appropriately mixing a prepolymer, a polymer and / or a monomer having a polymerizable unsaturated bond or a cation polymerizable functional group in a molecule. A composition curable by radiation 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 is more specifically a radical polymerizable unsaturated group such as (meth) acryloyl group or (meth) acryloyloxy, a cationic polymerizable functional group such as epoxy group, or a thiol group in the molecule. Consisting of a monomer, prepolymer or polymer having two or more These monomers, prepolymers or polymers may be used alone or as a mixture of two or more. Here, for example, (meta)
An acryloyl group means 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. ) 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.

The ionizing radiation-responsive weathering additive is an ionizing radiation-responsive ultraviolet absorber obtained by introducing a reactive group which reacts with ionizing radiation into a compound having a basic structure of an ultraviolet absorber or a light stabilizer. Alternatively, an ionizing radiation responsive light stabilizer is used. Reactive groups that react with ionizing radiation include:
Examples include an acryloyl group, a methacryloyl group, an allyl group, and a vinyl group. Preferred reactive groups are an acryloyl group and a methacryloyl group from the viewpoint of a high reaction rate.

Examples of the ultraviolet absorber having a basic structure of the weathering additive include benzotriazoles, benzophenones such as 2-hydroxybenzophenone, salicylates such as phenyl salicylate and 4-t-butyl-phenyl-salicylate, and acrylonitrile. And metal complex salts. Examples of the light stabilizer serving as the basic structure of the weather resistance additive include hindered amine-based and piberidine-based radical scavengers.

The amount of the weather-resistant additive comprising an ionizing radiation-responsive ultraviolet absorber or an ionizing radiation-responsive light stabilizer is preferably 0.5 to 20% by weight, more preferably 0.1 to 10% by weight. %. When the ultraviolet absorber and the light stabilizer are used in combination, the total amount is preferably within the above range. If the amount of the weathering additive is less than 0.5% by weight, the effect of improving the weatherability may not be sufficiently obtained, and if it exceeds 20% by weight, the compatibility with the ionizing radiation-curable resin may be insufficient. This can be a problem. The addition of only one of the ionizing radiation-responsive ultraviolet absorber and the ionizing radiation-responsive light stabilizer can provide the effect of improving the weather resistance, but it is more preferable to use both together.

Further, in order to further prevent deterioration of the decorative sheet due to ultraviolet rays and improve weather resistance, a base sheet,
It is preferable to add an ultraviolet absorber or a light stabilizer to the picture layer and the protective layer. The ultraviolet absorber and the light stabilizer may be added alone or in combination. The amount of these ultraviolet absorbers or light stabilizers is usually about 0.1 to 10% by weight. UV absorbers and light stabilizers include benzophenone UV absorbers such as 2-hydroxybenzophenone, salicylate UV absorbers such as phenyl salicylate and 4-t-butyl-phenyl-salicylate, benzotriazole UV absorbers, bis − (2,
2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and others, for example, in Japanese Patent Publication No. 4-82625. Hindered amine radical scavengers such as the disclosed compounds, piperidinyl radical scavengers and the like can be mentioned. Further, the above-mentioned ionizing radiation-responsive ultraviolet absorber and light stabilizer used for the protective layer may be added to the base sheet or the picture layer.

When a light stabilizer comprising a hindered amine radical scavenger is added to the decorative sheet, a polyurethane resin may be added to the base sheet, the picture layer and the protective layer.
Use of a resin containing no chlorine atom in the molecule, such as a polyolefin resin or a polyamide resin, is more favorable in terms of weather resistance. When a resin containing a chlorine atom in a molecule such as a vinyl chloride-vinyl acetate copolymer or chlorinated polyethylene is used, hydrogen chloride is generated from these resins by the action of ultraviolet light or heat by a dechlorination reaction, and this is a trapping of a hindered amine radical. Since it reacts with the agent to deactivate or inhibit its action, the weather resistance is not sufficiently improved.

When the ionizing radiation-curable resin of the protective layer 3 is cured by ultraviolet light or visible light, a photopolymerization initiator is added to the composition of the ionizing radiation-curable resin. In the case of a resin system having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like can be used alone or as a mixture as a photopolymerization initiator. 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 metallocene compound, a benzoinsulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to. Incidentally, the addition amount of these photopolymerization initiators, per 100 parts by weight of the ionizing radiation-curable resin,
It is about 0.1 to 10 parts by weight.

Other additives to be added to the ionizing radiation-curable resin composition include, for example, a matting agent (light diffusing agent) for matting the protective layer 3. The matting agent is
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.

As a method of applying the ionizing radiation-curable resin composition, a method such as a gravy coat, a roll coat, a knife coat, and an air knife is used.

As another method of decorating a decorative sheet,
A method of forming an uneven pattern such as a wood grain board conduit groove, a stone board surface unevenness (granite cleavage plane or the like), a cloth surface texture, a matte finish, a grain, a hairline, a parallel groove on the surface of the protective layer 3 is exemplified. In order to form the concavo-convex pattern, for example, there are an embossing method by heating and pressing, a hairline processing method, and a shaping film method. The embossing method heats and softens the surface of the protective layer, presses the surface with an embossing plate to shape the concavo-convex pattern of the embossing plate, and cools and fixes it. Embossing machine or the like is used.

Further, a colored layer may be formed in the concave portion of the above-mentioned uneven pattern by a wiping method. As a wiping method, after applying the colorant ink to the entire surface including the concave portion by the doctor blade coating method or the knife coat method, the colorant ink is removed from the surface other than the concave portion, so that only the concave portion is colored. Form a layer. The colorant ink that forms the colored layer is composed of an organic pigment, an inorganic pigment, a coloring pigment such as a brilliant pigment, a binder resin such as a thermoplastic resin, a thermosetting resin, and an ionizing radiation-curable resin, and a vehicle. And an aqueous ink of an emulsion type can be used.

Further, in order to impart flame retardancy to the decorative sheet, a powder such as aluminum hydroxide or magnesium hydroxide may be added to the base sheet 1 or the protective layer 3 as a flame retardant.

In order to impart antibacterial properties to the decorative sheet, an antibacterial agent (including an antifungal agent) may be added to the base sheet, the protective layer and the like. Examples of the antibacterial agent include the following compounds. Antibacterial Ag ⁺ , Cu ²⁺ , Zn ²⁺ , Hg ⁺ , Ni ²⁺ ,
And metal ions such as Cd ²⁺ (in particular, Ag ⁺ is harmless to the human body and has a long lasting antibacterial effect, which is desirable from the viewpoint of safety and performance). Zeolite, apatite, glass, silica gel, phosphoric acid Inorganic ones which are ion-exchangeably supported on salts and ion exchangers such as zirconium phosphate (especially, zeolite and zirconium phosphate have high track record and reliability). The metal ion content is 0.1 to 15% by weight in the case of Ag ⁺ ,
In the case of u ²⁺ or Zn ^2+, the content is preferably 0.1% by weight to 8% by weight. In the above, as antibacterial ion,
A product obtained by adding ammonium ions to metal ions.
Organic compounds having antibacterial properties, for example, sulfa agents such as P-aminobenzenesulfonamide, sulfathiazole, sulfapyridine, and sulfadiazine; dithiocarbamates such as dimethyldithiocarbamate and ethylenebisdithiocarbamate; -(2-furyl)-
3- (5-nitro-2-furyl) -acrylamide and the like.
Trimethoxysilylpropyl octadecyl ammonium chloride having antibacterial and antifungal properties, 10, 10 '
-Oxybisphenoxyarsine (trademark Vinadin),
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 such as phenoxymethyl penicillin, penicillins such as dicloxacillin, cephalothin,
And cephalosporins such as cefazolin; streptomycin sulfate and streptomycin such as paromomycin (sulfate); erythromycin such as erythromycin and josamycin; tetracycline such as tetracycline and lolitetracycline nitrate; chloramphenicol; Chloramphenicol such as ester hydrochloride. Among the above antibacterial agents, it is preferable to use an inorganic material because the antibacterial and antifungal properties can be maintained for a long period of time.

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 and floors, surface decoration of fittings such as window frames, doors, handrails, surface decoration of cabinets of furniture or light electric / OA equipment, vehicle interiors of automobiles and trains, aircraft interiors, windows Uses such as glass cosmetics can be mentioned.

[0048]

Examples 1 to 5 and Comparative Examples 1 to 3 An 80 μm thick polypropylene sheet (75 parts by weight of a polypropylene resin mainly composed of isotactic polypropylene as a hard segment and hydrogen as a soft segment 25 parts by weight of the added styrene-butadiene rubber are mixed, 5 parts by weight of calcium carbonate powder as an inorganic filler, and 7 parts by weight of a mixed pigment of titanium white, red iron oxide, carbon black, and isoindolinone as a coloring agent. After adding corona discharge treatment to both the front and back surfaces of the sheet, the binder is mainly made of acrylic-urethane copolymer resin, and the coloring agent is mainly made of red iron oxide and carbon black. using ink wood grain pattern layer provided by a gravure printing in the order of solid and handle (coated amount 5 g / m ² As a surface protective layer on the surface of the 該絵 pattern layer, a material obtained by adding the ultraviolet absorber shown in Table 1 to a composition essentially below (Example 1, Comparative Example 1,
2) Roll-coated with an ultraviolet absorber and a light stabilizer (Examples 2 to 5) (coating amount 20
g / m) and irradiation with ionizing radiation (200 kV, 5 Mra)
d, line speed 50 m / min) to form a protective layer. Further, the sheet is embossed from above the protective layer (emboss drum temperature: 120 ° C., emboss plate temperature: 50 ° C.).
(° C, embossing speed: 20 m / min) to obtain a decorative sheet. Table 1 shows the results of the weather resistance test of the obtained decorative sheet.

[Ionizing radiation-curable resin layer composition of surface protective layer] Bifunctional urethane acrylate oligomer 80 parts by weight 2-hydroxyethyl acrylate 10 parts by weight 1,6-hexanediol diacrylate 10 parts by weight Matting agent (Silica) 10 parts by weight ・ 1 part by weight of silicone acrylate ・ 4 parts by weight of ultraviolet absorber When adding a light stabilizer, a composition obtained by adding 2 parts by weight of a light stabilizer to the above composition was used.

[0050]

[Table 1]

* 1

[Outside 1] * 2

[Outside 2]

[Outside 3]

* 3: Weather resistance test method The decorative sheet was exposed using a sunshine weatherometer and was subjected to 250 until peeling occurred in a cellophane adhesion test.
A cellotape adhesion test was performed every hour. A sample having good adhesion was evaluated as ○, and a sample having peeled was evaluated as ×.

[0053]

As described above, the decorative sheet of the present invention is provided with a pattern layer on at least one surface of the base sheet,
In a decorative sheet provided with a protective layer made of an ionizing radiation-curable resin on the surface, a conventional ionizing radiation-responsive type weather-resistant additive is incorporated into the ionizing radiation-curable resin to achieve the conventional ionization. Compared to a decorative sheet that has a protective layer consisting of an ionizing radiation-curable resin layer to which an ultraviolet absorber and a light stabilizer that do not react with radiation are added, the ionizing radiation-curable resin reacts with the weatherable additive in the protective layer. The weather-resistant additive bleeds and migrates to the surface, preventing it from evaporating.The weather-resistant additive is retained in the protective layer for a long time, and the protective layer is weather-resistant. It has excellent weather resistance and can maintain high weather resistance for a long period of time.Furthermore, there is no decrease in weather resistance due to post-processing, etc., no decrease in the transparency of the transparent protective layer, etc. But It has such an effect it is not possible to lower.

[Brief description of the drawings]

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base sheet 2 Picture layer 3 Protective layer 4 Ionizing radiation-responsive weathering additive

Claims (1)

[Claims] 1. A decorative sheet provided with a pattern layer on at least one surface of a base sheet and a protective layer made of an ionizing radiation-curable resin on the surface, wherein the ionizing radiation-curable resin is contained in the ionizing radiation-curable resin. A decorative sheet comprising a weather-resistant additive.