JPH10286927A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which does not use a vinyl chloride resin and is highly weatherable. SOLUTION: This decorative sheet is of such a construction that a printing ink layer 2 of an arbitrary pictorial pattern is formed on a base material sheet 1 made of an opaque olefin thermoplastic elastomer, then a molten transparent olefin thermoplastic elastomer resin, extruded from a T die extruder, is laminated on the printing ink layer 2 as a top sheet 3 and the laminate is embossed. In addition, 'a copolymer obtained by causing a chemical reaction between a reaction-type ultraviolet absorber and a reactive resin' is added to the transparent olefin thermoplastic elastomer resin as the top sheet 3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

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

[0002]

Conventionally, this type of decorative sheet has been mainly made of a PVC resin. However, in recent years, as an alternative resin, an olefin resin or an olefin elastomer resin has been used. A method has been proposed in which a molten transparent resin is extruded onto a base sheet that has been subjected to extrusion, laminated as a top sheet, and simultaneously embossed to produce a decorative sheet. There is also a statement that additives can be added. However, when the conventional ultraviolet absorber is used, there are the following problems. Among these problems, those showing that the added ultraviolet absorber tends to decrease with time are cosmetics. It means a decrease in the weather resistance of the sheet.

<Problem> Poor compatibility with resin, and reduction in the number of added parts due to bleed-out. Loss due to transpiration during heat processing. Limitation on the number of parts to be added due to solubility problem of ultraviolet absorber. Decrease in transparency due to compatibility with resin. Elution into hot water, acids, alkalis, alcohols and oils.

[0004] The present invention has been made in view of the above problems, and an object of the present invention is to provide a decorative sheet which does not use a PVC resin and has good weather resistance. Is to do.

[0005]

In order to achieve the above object, the present invention provides a printing ink layer of an arbitrary pattern on a base sheet made of an opaque olefin-based thermoplastic elastomer resin, and melts the printing ink layer on the printing ink layer. The transparent olefin-based thermoplastic elastomer resin extruded by a T-die extruder and laminated as a top sheet, and at the same time, in the embossed decorative sheet, the reactive olefin-based thermoplastic elastomer resin contained in the top sheet was "reactive UV-absorbing". And a copolymer obtained by reacting an agent with a resin that reacts with the agent.

[0006] Then, two or more transparent olefin-based thermoplastic elastomer resin layers of the top sheet are provided by co-extrusion, and at least one of the layers is provided with a "reactive ultraviolet absorber and a copolymer obtained by reacting a resin reactive therewith". You may make it add.

[0007]

FIG. 1 shows one embodiment of a decorative sheet according to the present invention. This decorative sheet is a base sheet 1 made of a colored opaque olefin-based thermoplastic elastomer resin.
Is provided with a printing ink layer 2 on which a transparent olefin-based thermoplastic elastomer resin is extruded from above by a T-die extruder to be laminated as a top sheet 3 and simultaneously embossed. Then, a “reactive-type ultraviolet absorber and a copolymer obtained by reacting a resin that reacts with the reactive ultraviolet absorber” are added to the transparent olefin-based thermoplastic elastomer resin of the top sheet 3.

FIG. 2 shows another embodiment of the decorative sheet according to the present invention. In this decorative sheet, three transparent olefin-based thermoplastic elastomer resin layers of the top sheet 3 are formed.
a, 3b, 3c) are provided by co-extrusion, and a “copolymer obtained by reacting a reactive ultraviolet absorber and a resin that reacts with the reactive ultraviolet absorber” is added to the middle layer 3b.

The olefin-based thermoplastic elastomers are the following three types of composite thermoplastic elastomers composed of an elastomer and an olefin-based resin. That is,
A simple blend of an elastomer as the soft segment and an olefin-based resin as the hard segment, a cross-linked type in which the elastomer and the olefin-based resin are partially cross-linked to form a complex, and an olefin-based resin that is cross-linked with the olefin-based elastomer And the following five types are specifically mentioned.

[0010] A simple blend of (A) an elastomer as a soft segment and (B) an olefin resin as a hard segment. Specifically, as the olefin resin, polyethylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, polypropylene, propylene / butene-1 copolymer, polybutene-
1, butene-1, propylene, ethylene, terpolymers, butene-1, hexene-1, octene-1, terpolymers, and polymethylpentene resins alone or as a mixture of two or more resins. Can be Examples of the elastomer include various rubbers. Examples of the rubber include a diene rubber, a hydrogenated diene rubber, and an olefin elastomer. Among them, a hydrogenated diene rubber is preferable.

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

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

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

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

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

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

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

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

Further, a coloring agent, a heat stabilizer, an antioxidant, an antistatic agent, a flame retardant, a foaming agent, etc. are added to these olefinic thermoplastic elastomers, if desired.

Examples of the coloring agent include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine blue, cobalt blue, titanium yellow, carbon black, isoindoline, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue and the like. Organic pigments, dyes, metal pigments such as aluminum and brass, pearlescent pigments made of titanium dioxide-coated mica, and foil powders such as basic zinc carbonate. Also, an inorganic filler may be added as necessary,
Examples of the inorganic filler include powders such as calcium carbonate, barium sulfate, clay, talc, silica (silicon dioxide), and alumina (aluminum oxide). The coloring of the base sheet may be colored transparent or colored opaque (concealing property) depending on the application. Generally, colored opaque is preferred because the surface of the adherend can be concealed.

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

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

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

As the high-density polyethylene, it is more preferable to use a polyethylene having a specific gravity of 0.94 to 0.96 and having a high degree of crystallinity obtained by a low-pressure method and having a small number of branched structures. . Examples of the thermoplastic elastomer include a diene rubber, a hydrogenated diene rubber, and an olefin elastomer, and the same as those described above are used. The addition amount of the thermoplastic elastomer is 10 to 60% by weight, preferably about 30% by weight in the base sheet. If the amount is less than 10% by weight, the change in elongation at a constant load becomes too sharp, and the elongation at break and the impact resistance decrease. If the amount is more than 60% by weight, the transparency, weather resistance and creep resistance are reduced. A drop occurs. As the inorganic filler, the same one as described above is used, and about 5 to 60% by weight, preferably 3 to
About 0% by weight is added. If the addition amount is less than 5% by weight, the creep deformation resistance and the easy adhesion decrease, and if it is more than 60% by weight, the elongation at break and the impact resistance decrease. As the colorant, the same one as described above is used.

Preferred examples of the transparent olefin-based thermoplastic elastomer provided on the surface include those described in the description of the above-mentioned olefin-based thermoplastic elastomer.
It is a sheet made of a colorless or colored transparent soft polypropylene-based resin having a composite three-dimensional structure, comprising a mixed system of isotactic polypropylene and atactic polypropylene. According to the sheet made of the soft polypropylene resin having the above composite three-dimensional structure, the performance required as a decorative sheet, namely, creep deformation resistance, organic solvent resistance, elongation at break, impact strength, moderate flexural modulus And good transparency and weather resistance (no whitening or turbidity due to recrystallization even when heating and cooling accompanying embossing or the like are applied). Specific examples of the soft polypropylene resin include (A) (a) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donor as essential components, (b) an organoaluminum compound, and (c) a general aluminum compound. Formula 1

Embedded image (Wherein R ¹ is an alkyl group having 1 to 20 carbon atoms, R ² is a hydrocarbon group having 1 to 10 carbon atoms, a hydroxyl group or a nitroso group, m
Is an integer of 1 to 6, and n is an integer of 0 or 1 to (6-m)), and is obtained by polymerizing propylene in the presence of a catalyst comprising a combination of alkoxy group-containing aromatic compounds. , The number average molecular weight (Mn) is 25,000
Boiling heptane-soluble polypropylene (atactic polypropylene) having a weight average molecular weight (Mw) of 0 or more and a ratio (Mw / Mn) of number average molecular weight (Mn) of 7 or less
10 to 90% by weight and (B) the melt index is 0.1%.
90 to 10% by weight of boiling heptane-insoluble polypropylene (isotactic polypropylene) of 1 to 4 g / 10 minutes
And a soft polypropylene resin composition comprising:

The above soft polypropylene resin composition has an elongation at break (T _b ) of 400% or more, preferably 500 to 7%.
Residual elongation (PS ₁₀₀ ) after 100% and 100% elongation is 80
%, Preferably 50 to 75%, and the stress at break (M
_B ) and the stress at yield (M _Y ) (M _B / M _Y ) are 1.
It is desirably 0 or more, preferably in the range of 1.5 to 3.5.

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

The atactic polypropylene of the component (A) may be a homopolymer of propylene, or may contain other propylene units having a carbon number of not more than 40% by weight, preferably not more than 30% by weight, and other α-olefins having 2 to 30 carbon atoms. It may be a propylene copolymer containing an olefin unit. Further, this atactic polypropylene may be used alone or in combination of two or more. The atactic polypropylene of the component (A) can be produced by a known method (Japanese Patent Publication No. 23278/1994).

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

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

In the above soft polypropylene resin composition, the isotactic polypropylene of the component (B) may be used alone or in combination of two or more. The atactic polypropylene of the component (A) and the isotactic polypropylene of the component (B) have a content of the component (A) of 10 to 90% by weight, preferably 25 to 80% by weight, and the component (B) Content of 90 to
It is used in such a proportion that it becomes 10% by weight, preferably 75 to 20% by weight. The content of the component (A) is 10% by weight.
If it is less than 1, the stress at yield (M _Y ) of the resin becomes too large, and the ratio M of stress at break (M _B ) to stress at yield (M _Y ) is M.
_{The B} / _MY ratio is less than 1.0, and the residual elongation (PS ₁₀₀ ) after 100% elongation is also larger than 80%. On the other hand, if the content exceeds 90% by weight, the stress at break (M
_B) is too small, the M _B / M _Y ratio is less than 1.0, and the mechanical strength there is a possibility to decrease. Also,
By increasing the ratio of the component (B), the Young's modulus of the obtained soft polypropylene increases. A particularly preferred ratio of the component (A) to the component (B) is 1: 1.

Further, the two-layer structure of the base sheet and the top sheet laminated thereon is made of a base sheet made of the above-described high-density polyethylene resin, a thermoplastic elastomer, a coloring agent, and an inorganic filler. By making a sheet made of a colorless or colored transparent soft polypropylene-based resin composed of a mixture of the above-mentioned isotactic polypropylene and atactic polypropylene, each sheet shares various conditions required for the decorative sheet described above. Thus, a highly practical decorative sheet of the present invention can be obtained.

As a copolymer to be added to the transparent olefin-based thermoplastic elastomer resin constituting the top sheet, 2- (2'-hydroxy-5'-methacryloxyethylphenyl) -2H-benzo which is a reactive ultraviolet absorber is used. A copolymer (average molecular weight: 10,000) of 30% by weight of triazole and 70% by weight of methyl methacrylate or styrene is used. Here, benzotriazoles include 2 (2′-hydroxy-5-methylphenyl) benzotriazole, substituted benzotriazoles, substituted benzotriazoles, and other benzphenones.
There are acrylate type, salicylate type, and Ni-bisoctylphenyl sulfide [2,2'-thiobis (4-t-octylphenolato)]-n-butylamine Ni, but none of them are reactive. That is, these are addition type ultraviolet absorbers. On the other hand, the above-mentioned reactive ultraviolet absorber easily forms a copolymer with methyl methacrylate, styrene or the like by radical polymerization at a methacryloyl group. Therefore, by making the UV absorber a copolymer, it is difficult for the UV absorber to decrease over time due to bleed-out or to be reduced due to evaporation during heat processing. As a result, the UV absorber is absorbed over a long period of time. By maintaining the effect of the agent, the weather resistance of the decorative sheet is improved.

The transparent olefin-based thermoplastic elastomer having good adhesion properties is the same as the transparent olefin-based thermoplastic elastomer described above, except that olefin-based elastomer and olefin-based resin such as polyethylene, ethylene-α-olefin copolymer, polypropylene, polybutene, and polyisobutylene are used. And polydiolefins such as polybutadiene and polyisoprene or copolymers thereof, for example, carboxylic acids, carboxylate salts, carboxylic anhydrides, carboxylic acid esters, carboxylic acid amides to imides, aldehydes, ketones Ethylene such as a copolymer with one or more ethylenically unsaturated monomers having a carbonyl group based on the like alone or in combination with a cyano group, a hydroxy group, an ether group, an oxirane ring group, etc. With unsaturated monomers And copolymers. Generally, it is sufficient if the thickness is about 10 μm.

Examples of the ethylenically unsaturated monomer having a polar group include: Ethylenically unsaturated carboxylic acids: acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, 5-norbornene-2.3-dicarboxylic acid and the like. B. Ethylenically unsaturated carboxylic anhydride: maleic anhydride, citraconic anhydride, 5-norbornene-2.3-dicarboxylic anhydride, tetrahydrophthalic anhydride and the like. C. Ethylenically unsaturated esters: ethyl acrylate, methyl methacrylate, 2-ethylhexyl acrylate, mono or diethyl maleate, vinyl acetate, vinyl propionate, propyl γ-hydroxy methacrylate, β-
Ethyl hydroxyacrylate, glycidyl acrylate, glycidyl methacrylate, β-N-ethylaminoethyl acrylate, and the like. D. Ethylenically unsaturated amide to imide: acrylamide, methacrylamide, maleimide and the like. E. FIG. Ethylenically unsaturated aldehydes or ketones: acrolein, methacrolein, vinyl methyl ketone, vinyl butyl ketone and the like. Is mentioned.

Preferred as the easily-adhesive thermoplastic elastomer are homo-chlorine-modified polyolefins and random-polymerized non-chlorine polyolefins. The following metal ions are used as the carboxylate. Na ⁺ , K ⁺ , Li ⁺ , C as monovalent metal ions
There are s ⁺ , Ag ⁺ , Hg ⁺ , and Cu ⁺ , and as divalent metal ions, Be ⁺⁺ , Mg ⁺⁺ , Ca ⁺⁺ , Ba ⁺⁺ , Cu ⁺⁺ , C
d ⁺⁺ , Hg ⁺⁺ , Sn ⁺⁺ , Pb ⁺⁺ , Fe ⁺⁺ , Co ⁺⁺ , Ni
⁺⁺ , Zn ⁺⁺ , and trivalent metal ions include Al ⁺⁺⁺ , Sc
⁺⁺⁺ , Fe ⁺⁺⁺ , and Yt ⁺⁺⁺ . The degree of neutralization is determined by MI after neutralizing the copolymer carboxylic acid with metal ions.
Is in the range of about 2 to 20.

An anchor coat layer may be provided for thermally bonding the easily adhesive olefin-based thermoplastic elastomer layer of the top sheet to the printing ink layer on the base sheet.
A reactive hot melt adhesive is used for the anchor coat layer. In addition, although the adhesion strength decreases, isocyanate-based anchor coating agents (for example, tolylene diisocyanate,
Compounds such as hexamethylene diisocyanate) can also be used. Ordinary thermoplastic inks can also be used.

As the ink used in the printing ink layer, when the above-mentioned heat-adhesive anchor layer is used, chlorinated olefin-based inks such as chlorinated polyethylene and chlorinated polypropylene, amide-based inks, urethane-based inks, vinyl acetate, A general olefin ink such as a vinyl / vinyl acetate copolymer or a cellulose resin is used. When the heat-adhesive anchor layer is not used, a urethane-based high-temperature reaction type (150 to 250 ° C.) ink is preferable.

As the pattern of the printing ink layer, a wood grain pattern,
Stone patterns, cloth patterns, leather crests, geometric figures, characters, symbols, line drawings, various abstract patterns, and the like may be used.

By providing a primer layer between the base sheet and the printing ink layer for improving ink adhesion, the range of vehicles for printing ink can be widened. The same can be said for the portion between the printing ink layer and the anchor coat layer or between the printing ink layer and the top sheet. However, since the number of steps increases, it is determined in consideration of the required adhesion strength. As the resin for the primer layer, acryl, vinyl chloride / vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene, chlorinated polyethylene and the like are used, and polyurethane is particularly preferable.

[0041]

【Example】

Example 1 A 100 μm-thick base sheet (“Soft Rex” manufactured by Nippon Petrochemical) made of an olefin-based thermoplastic elastomer resin was used with a vinyl chloride-based resin ink (“Chemical X” manufactured by Showa Ink Industries, Ltd.). A straight-grain pattern printing was performed to obtain a printed sheet.

The transparent olefin-based thermoplastic elastomer resin melted from above the printing surface of the printing sheet is
The sheet was extruded by a die extruder, laminated as a top sheet, and simultaneously embossed. In this example, a product containing 0.5% by weight of Otsuka Chemical's "PUVA-30M" as a copolymer in "E-2600" manufactured by Idemitsu Petrochemical Industries, Ltd. was used and extruded at a thickness of 100 [mu] m.

(Example 2) A two-component curable polyester resin ink ("AFS" manufactured by Showa Ink Kogyo Co., Ltd.) was applied to the same base sheet as in Example 1 to form a primer layer, and two-component curing was performed from above. -Colored acrylic urethane resin ink ("UE" manufactured by Showa Ink Industries Co., Ltd.), and then printed with straight-grain pattern printing using a vinyl chloride resin ink ("Ka X" manufactured by Showa Ink Industries Co., Ltd.) And

A two-component curable polyurethane resin ink ("ALF" manufactured by Showa Ink Industry Co., Ltd.)
A)) to form a primer layer, and further, a heat-sensitive adhesive anchor coat layer was formed using a vinyl chloride vinyl acetate / acrylic resin-based ink (“UNISTOL P-805” manufactured by Mitsui Petrochemical). The same transparent olefin-based thermoplastic elastomer resin as in No. 1 was extruded by a T-die extruder, laminated as a top sheet, and simultaneously embossed.

Further, a decorative sheet having excellent design properties was obtained by performing a wiping treatment and providing a surface resin coat layer. Specifically, after performing corona treatment on the embossed surface, an acrylic urethane-based resin (“W-14 manufactured by Showa Ink Industries, Ltd.”
1)), and a surface resin coat layer was formed using a urethane resin (“OP, No. 80” manufactured by Showa Ink Industries, Ltd.).

(Example 3) A heat-sensitive adhesive anchor coat layer was formed on the printing surface of the same printing sheet as in Example 1 by using polyvinyl chloride / acrylic resin-based ink ("UNISTOL P-805" manufactured by Mitsui Petrochemical). Then, the molten transparent olefin-based thermoplastic elastomer resin was extruded in three layers by a T-die extruder, laminated as a top sheet, and simultaneously embossed. In this example, "E-2600" manufactured by Idemitsu Petrochemical Industry Co., Ltd. was used for the outermost layer, and "PUVA-30" manufactured by Otsuka Chemical Co. was used as a copolymer for the intermediate layer.
M "containing 1.8% by weight, and having a composition comprising 50 parts by weight of" Polytack "manufactured by Idemitsu Petrochemical Co. and 50 parts by weight of" E-2600 "manufactured by Idemitsu Petrochemical Co., Ltd. Using 70 μm, 20 μm, and 10 μm, respectively.
Extruded at the thickness of.

Example 4 A two-component curable polyurethane resin ink (“ALFA” manufactured by Showa Ink Kogyo Co., Ltd.) was applied on the printing surface of the same printing sheet as in Example 2 to form a primer layer. Example 3 After forming a heat-sensitive adhesive anchor coat layer with vinyl acetate / acrylic resin-based ink (“UNISTOL P-805” manufactured by Mitsui Petrochemical),
The same transparent olefin thermoplastic elastomer resin as T
It was extruded in three layers by a die extruder, laminated as a top sheet, and simultaneously embossed.

Further, the decorative sheet was subjected to wiping treatment and provided with a surface resin coat layer to obtain a decorative sheet excellent in design. Specifically, after performing corona treatment on the embossed surface, an acrylic urethane-based resin (“W-14 manufactured by Showa Ink Industries, Ltd.”
1)), and a surface resin coat layer was formed using a urethane resin (“OP, No. 80” manufactured by Showa Ink Industries, Ltd.).

For the decorative sheets obtained in Examples 1 to 4, the sunshine carbon arc W.P. O. M. At 100
When treated for 0 hour, almost no decrease in the interlayer strength between the printing ink layer and the top sheet was observed.

[0050]

As described above, according to the present invention, a printing ink layer having an arbitrary pattern is provided on a base sheet made of an opaque olefin-based thermoplastic elastomer resin, and a transparent olefin-based thermoplastic resin melted from above is provided. The elastomer resin is extruded with a T-die extruder and laminated as a top sheet, and at the same time, in the embossed decorative sheet, the transparent olefin-based thermoplastic elastomer resin of the top sheet contains a "reactive ultraviolet absorber and reacts therewith. The addition of the `` copolymer reacted resin '' makes it difficult to reduce the amount of the ultraviolet absorber in the top sheet, so it is possible to obtain a decorative sheet that does not use a PVC resin and has good weather resistance. it can.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view showing one embodiment of a decorative sheet according to the present invention.

FIG. 2 is a cross-sectional view showing another form of the decorative sheet according to the present invention.

[Explanation of symbols]

 1 base sheet 2 printing ink layer 3 top sheet

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[Procedure amendment]

[Submission date] May 19, 1997

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

The olefin-based thermoplastic elastomers are the following three types of composite thermoplastic elastomers composed of an elastomer and an olefin-based resin. That is,
Elastomer and simplicity blended type olefinic resin as a hard segment as a soft segment, elastomer and the olefin resin and partially to crosslink the in composite, crosslinked type, it by crosslinking the error elastomer olefin resin There are three types of dispersion, specifically, the following five types.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0034

[Correction method] Change

[Correction contents]

The top sheet is made of a transparent olefin thermoplastic.
When two or more layers of elastomer resin are co-extruded
If the layer on the side that matches the printing surface of the base sheet
Consisting of a transparent olefin-based thermoplastic elastomer
Adhesive transparent olefin-based thermoplastic elastomer as a layer
-Layer, the base sheet and top sheet
Adhesive strength can be obtained. Highly adhesive transparent olefinic thermoplastic elastomer, in the above-mentioned transparent olefin thermoplastic elastomer, if example embodiment, polyethylene, ethylene -α- olefin copolymer, polypropylene, polybutene, polyisobutylene, such as poly α-
Olefin and polydiolefins such as polybutadiene and polyisoprene or copolymers thereof, and carbonyl groups based on, for example, carboxylic acids, carboxylate salts, carboxylic anhydrides, carboxylic esters, carboxylic amides or imides, aldehydes, ketones, etc. , Alone or in combination with one or more ethylenically unsaturated monomers having a cyano group, a hydroxy group, an ether group, an oxirane ring group or the like . It is composed of a copolymer with a monomer and the like . Generally, it is sufficient if the film is formed to a thickness of about 10 μm.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI B32B 27/32 B32B 27/32 E // B29L 9:00

Claims (2)

[Claims] 1. A printing ink layer having an arbitrary pattern is provided on a base sheet made of an opaque olefin-based thermoplastic elastomer resin, and a molten transparent olefin-based thermoplastic elastomer resin is extruded from above by a T-die extruder. In a decorative sheet laminated as a top sheet and embossed at the same time, a `` copolymer obtained by reacting a reactive ultraviolet absorber and a resin reacting therewith '' was added to the transparent olefin-based thermoplastic elastomer resin of the top sheet. A decorative sheet, characterized in that: 2. A transparent olefin-based thermoplastic elastomer resin layer of a top sheet is provided by co-extrusion of two or more layers, and at least one of the layers is formed by reacting a reactive ultraviolet absorber with a resin which reacts therewith. The decorative sheet according to claim 1, wherein the decorative sheet is added.