JP2000281807A - Polyolefin-based ornamental sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyolefin-based ornamental sheet having reduced adhesive property on the surface of the ornamental sheet and excellent in transparency when it is used at 40-100 deg.C without causing cracks and whitening on a folded surface. SOLUTION: This polyolefin-based ornamental sheet comprises one or more of structural layers and brings the layer consisting of a resin composition comprising 20-90 wt.% of an amorphous polyolefin containing >=50 wt.% of propylene and/or butene-1 and <=60 wt.% of an insoluble portion in boiling n-heptane and 10-80 wt.% of a crystalline polyolefin to the one layer of the constitutional layer. A laminate, which consists of a layer comprising a resin composition containing an amorphous polyolefin and a crystalline polyolefin and a layer containing a crystalline polyolefin, is brought to be one layer of the constitutional layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to building materials, home electric appliances,
The present invention relates to a polyolefin-based decorative sheet used for surface decoration and surface protection of interior and exterior materials of vehicles and the like. More specifically, the present invention relates to a polyolefin-based decorative sheet which contains a specific amorphous polyolefin as a component of a constituent layer, and has characteristics such that cracks and whitening hardly occur on a folded surface when folded and excellent transparency.

[0002]

2. Description of the Related Art Conventionally, a polyvinyl chloride film containing a plasticizer has been mainly used as a decorative sheet used for surface decoration and surface protection of building materials, home electric appliances, vehicle interior materials and exterior materials. . Polyvinyl chloride film containing a plasticizer is excellent in thermoforming processability.When folded, it is hard to crack or whiten on the bent surface, has good transparency, has low surface tackiness, etc. Has suitable properties. However, polyvinyl chloride films generate harmful gases when incinerated, and the plasticizers contained in them have problems such as adversely affecting the environment and the human body.
There is a need for a material that replaces the polyvinyl chloride film. At present, as a substitute for the polyvinyl chloride film, development is being promoted centering on a polyolefin-based material which does not generate harmful gas when incinerated. For example, Japanese Patent Application Laid-Open No. 6-198830 discloses a decorative sheet having a polypropylene-based film as a main constituent layer.
No. 832 proposes a decorative sheet having an olefin-based thermoplastic elastomer as a main constituent layer.

[0003]

However, the proposed decorative sheet mainly comprising a polyolefin-based film has several problems as compared with a polyvinyl chloride film. For example, in the case of a decorative sheet having a polypropylene film as a constituent layer proposed in JP-A-6-198830, the crystallinity and melting point of polypropylene are high.
There are problems such as inferior flexibility, high forming temperature, narrow allowable range of processing conditions, and the possibility of cracking or whitening of the bent surface when bent. In the case of a decorative sheet comprising an olefin-based thermoplastic elastomer proposed in JP-A-6-16832 as a constituent layer, the decorative sheet is excellent in flexibility and hardly causes cracks or whitening on the folded surface, but has insufficient transparency and mechanical strength. And other problems. Japanese Patent Application Laid-Open No. 5-77371 discloses a laminated film of a layer containing a specific amorphous polyolefin as one component and a layer made of crystalline polypropylene. This laminated film has properties suitable for a decorative sheet, but has a use temperature of 40 ° C. or higher, for example, 40 to 1
When used at 00 ° C., low molecular weight substances and the like in the amorphous polyolefin may ooze out on the decorative sheet surface, the decorative sheet surface becomes sticky, the surface becomes sticky, or bleeding is deposited. And there were restrictions on use.

[0004] The present invention has solved the problems as in the prior art, that is, when the bent surface is almost free from cracks and whitening, and when used at a temperature of 40 to 100 ° C, It is an object of the present invention to provide a polyolefin-based decorative sheet that has little adhesiveness on the surface of the decorative sheet and is excellent in transparency.

[0005]

In order to solve the problems of the present invention, as a result of studying various polyolefin-based materials as constituent layers of a decorative sheet, specific amorphous polyolefin and crystalline polypropylene were specified as constituent layers. The decorative sheet using the layer composed of the resin composition containing the resin composition has almost no cracks or whitening on the bent surface, and the surface of the decorative sheet is almost sticky even when the temperature during use is as high as 40 ° C. or higher. The present invention was found to show no properties and to have good transparency, and reached the present invention.

[0006] That is, the present invention relates to a decorative sheet comprising one or more constituent layers, which comprises propylene and / or butene.
20 to 90% by weight of an amorphous polyolefin and a crystalline polypropylene 1 having a content of 50% by weight or more and a boiling n-heptane insoluble content of 60% by weight or less.
A polyolefin-based decorative sheet having a layer composed of a resin composition containing 0 to 80% by weight as a constituent layer. or,
A polyolefin-based decorative sheet comprising, as one of the constituent layers, a laminate comprising a layer comprising the above resin composition and a layer comprising a crystalline polyolefin.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail. The polyolefin-based decorative sheet of the present invention has a layer composed of a resin composition containing 20 to 90% by weight of a specific amorphous polyolefin and 10 to 80% by weight of a crystalline polypropylene as an essential component. The specific amorphous polyolefin used in the present invention has a propylene and / or butene-1 content of 50% by weight or more, and contains, as a component other than propylene and butene-1, an α-olefin having 2 to 8 carbon atoms. It can be used and has a boiling n-heptane insoluble content of 60% by weight or less, preferably 50% by weight or less. Examples of the usable α-olefin having 2 to 8 carbon atoms include ethylene, pentene-1,4-methyl-1
-Pentene, hexene-1, heptene-1, octene-
1 and the like. These α-olefins can be used alone or in appropriate combination of two or more kinds. The content of propylene and / or butene-1 in the amorphous polyolefin may be 50% by weight or more, and the total amount of propylene and / or butene-1 or both may be 100% by weight. When the content of propylene and / or butene-1 is less than 50% by weight, the mechanical strength is reduced, so that it is difficult to form a sheet-like molded article by itself or the decorative sheet surface exhibits adhesiveness. May be.

When the amount of the boiling n-heptane-insoluble content of the amorphous polyolefin used in the present invention is more than 60% by weight, the flexibility of the obtained decorative sheet is reduced, and the folded surface is cracked or white. And may be changed. According to the present invention, the flexibility in which the amount of boiling n-heptane insolubles is reduced is improved, and the bent surface is less likely to crack or whiten, and the amount of boiling n-heptane insolubles may be omitted.

The boiling n-heptane insoluble content is measured by using a double-tube Soxhlet extractor, wherein n is 50 to 200 times the weight of the amorphous polyolefin to be measured.
Using heptane for several hours, usually 5 to 24 hours,
After boiling and refluxing to dissolve the components soluble in boiling n-heptane, the insoluble matter is separated by filtration and calculated from the weight of the sample before boiling n-heptane extraction and the weight of the remaining insoluble matter. The amorphous polyolefin used in the present invention refers to a polyolefin that behaves substantially similar to amorphous, and has a crystallinity of 30% or less, and usually a crystallinity of 0.
Means 1-20% low crystalline polyolefin. The density of the amorphous polyolefin used is 0.885 g / c.
m ³ or less, usually 0.855 to 0.885 g / cm ³ . Based on the density measured by the density gradient tube method of JIS K 7112, the degree of crystallinity was determined to be 0.936 g / cm ³ for the 100% crystal density of polypropylene and 0.855 for the amorphous density.
It is a value calculated as g / cm ³ . The sample used for density measurement was obtained by sandwiching amorphous polyolefin pellets between metal plates coated with Teflon (registered trademark),
The sheet is formed by heating and compressing at 23 ° C. to form a sheet, and then allowed to cool at 23 ° C.

Specific examples of the amorphous polyolefin include:
Propylene homopolymer having a boiling n-heptane insoluble content of 60% by weight or less, propylene / butene-1 copolymer, propylene / ethylene copolymer having a propylene component and / or butene-1 component content of 50% by weight or more Terpolymer of propylene / butene-1 / ethylene, terpolymer of propylene / hexene-1 / octene-1 and terpolymer of propylene / hexene-1 / 4-methylpentene-1 Butene-1 homopolymer, butene-1 · ethylene copolymer, butene-1 · hexene-1 · octene-1 terpolymer, butene-1 · hexene-1 ・ 4-methylpentene-1 Ternary copolymers and the like can be mentioned. When the amorphous polyolefin is a propylene / ethylene copolymer,
Those having an ethylene component content of 0.01 to 30% by weight, preferably 1 to 20% by weight are desirable. When the content of the ethylene component is more than 30% by weight, the mechanical strength decreases. In the present invention, the amorphous polyolefin can be used alone or in combination of two or more.

The amorphous polyolefin used in the present invention can be produced by a known polyolefin production method. For example, a known polymerization catalyst such as a catalyst system comprising a titanium-supported catalyst and triethylaluminum in which a raw material monomer comprising propylene and / or butene-1 and, if necessary, an α-olefin as a copolymerization component is supported on magnesium chloride. It is produced by polymerizing using a system in the presence or absence of hydrogen. In addition, it is a commercial product,
An amorphous polyolefin having the same composition and characteristics as the present invention can be used. As a commercial product, for example,
Lexene of the United States (Rexene) Lexutakku (RE
XTAC) and Ube Tex by Ube Lexen.

Crystalline polypropylene, which is another component of the resin composition used in the present invention, is a polypropylene having an isotactic structure which is mostly insoluble in boiling n-heptane, and is used for extrusion molding, injection molding, and blow molding. Commercially available crystalline polypropylene can be used. This crystalline polypropylene may be a propylene homopolymer or a copolymer of propylene and another α-olefin, and usually has a density of 0.890 g / cm ³ or more. As the α-olefin used for the copolymerization, α-olefins having 2 to 8 carbon atoms, excluding propylene, for example, ethylene, butene-1, pentene-
Examples thereof include 1,4-methyl-1-pentene, hexene-1, heptene-1, and octene-1. Of these, ethylene and butene-1 are preferred.

Specific examples of the crystalline polypropylene include a propylene homopolymer, a random or block copolymer of propylene / ethylene containing 30% by weight or less, preferably 1 to 25% by weight of an ethylene component, 1
Propylene-butene-1 random copolymer or block copolymer, propylene-ethylene-butene ternary random copolymer or ternary block copolymer containing 20% by weight or less.

The production of crystalline polypropylene is not particularly limited, and it can be produced by a known method for producing crystalline polypropylene. For example, using a catalyst system in which a solid catalyst component comprising magnesium, titanium, a halogen atom and an electron donor, an organoaluminum compound, an alkoxy group-containing aromatic compound and, if necessary, an electron donating compound, a gas-phase one-stage It is produced by a method such as a synthesizing method, a slurry one-stage polymerization method, a gas-phase multi-stage polymerization method, and a slurry multi-stage polymerization method.

Further, the above-mentioned amorphous polyolefin and crystalline polypropylene are prepared from unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid and / or their esters, acid anhydrides and metal salts. Such as derivatives, unsaturated amides, amino compounds, glycidyl methacrylate, hydroxy methacrylate, etc.
Those modified by a known method using a twin-screw kneader or the like may be used. Among these modified ones, those modified with maleic anhydride or itaconic anhydride are preferably used.

The resin composition constituting the decorative sheet of the present invention comprises 20 to 90% by weight, preferably 25 to 80% by weight of an amorphous polyolefin, and 10 to 90% by weight of a crystalline polypropylene.
It is composed of 80% by weight, preferably 20 to 75% by weight. When the proportion of the amorphous polyolefin is less than 20% by weight, the flexibility is reduced, and the bent surface may be cracked, whitened, or the transparency may be reduced. on the other hand,
If the content is more than 90% by weight, the decorative sheet surface becomes tacky. Amorphous polyolefin contributes to the flexibility of the decorative sheet and cracks on the bent surface and prevention of whitening, while crystalline polypropylene contributes to mechanical strength such as heat resistance and tensile modulus.
Contributes to tackiness prevention. By setting the above mixing ratio, the flexibility and bending workability of the decorative sheet are good,
A decorative sheet having almost no surface tackiness can be obtained.

The resin composition containing the amorphous polyolefin and the crystalline polypropylene is produced by a known method. For example, a kneader such as a kneader, a Banbury mixer, or a roll, or a single-screw or twin-screw extruder may be used. It is manufactured by a method in which a polyolefin and a crystalline polypropylene are kneaded by heating.

A resin composition containing an amorphous polyolefin and a crystalline polypropylene is a preferred constituent layer for achieving the object of the decorative sheet of the present invention. Further, a laminate composed of a layer comprising the resin composition and a layer comprising the crystalline polyolefin is also a preferred constitutional layer. Usually, this laminate is
The crystalline polyolefin is laminated on both outer layers or one outer layer, and the amorphous polyolefin is laminated on the inner layer or one outer layer. The number of layers may be two or more,
Usually, there are three layers. This laminate is applied to uses requiring mechanical strength, heat resistance, and the like, as compared with the case where the resin composition is used alone.

The crystalline polyolefin used for the outer layer of the laminate includes a crystalline propylene homopolymer, a crystalline random copolymer of propylene and an α-olefin or a crystalline block copolymer, Examples thereof include a mixture of a random copolymer or a block copolymer and a crystalline propylene homopolymer. Specific examples of the α-olefin include ethylene, butene-1, pentene-1, hexene-1, 4-methyl-1-pentene,
Heptene-1, octene-1, nonene-1, decene-1
And the like. Specific examples of the crystalline copolymer of propylene and α-olefin include propylene 70 to 99
wt%, α-olefins other than propylene 1-30 wt%
% Propylene / ethylene random copolymer or block copolymer, propylene / butene-1 random copolymer / block copolymer, propylene / ethylene / butene-1 ternary random copolymer or ternary copolymer And block copolymers.

The decorative sheet of the present invention may be composed of a surface layer, an adhesive layer, a printing layer, a base layer and the like, similarly to a normal decorative sheet. In this case, the decorative sheet has a configuration in which the printing layer is formed on the base layer and the surface layer is formed on the printing layer, and the adhesive layer is formed of the base layer and the printing layer, and the printing layer and the surface layer as necessary. Used in between. However, the decorative sheet of the present invention does not need to have all of these constituent layers, and it is also possible to use the base layer alone as a decorative sheet.

Usually, the surface layer of the decorative sheet is a layer made of crystalline polypropylene, a crystalline copolymer of propylene and α-olefin, a layer or a laminate made of the resin composition containing the amorphous polyolefin of the present invention. And the like are used. The thickness of this surface layer is usually 2 to 150 μm. The print layer has, for example, patterns such as wood grain, stone grain, cloth grain, and abstract pattern printed thereon, and is made of soft crystalline polypropylene, a random copolymer of propylene and α-olefin, a block copolymer, or the like. You. The thickness of the printing layer is usually 1 to 30 μm. As the base layer, a layer composed of a resin composition containing the amorphous polyolefin of the present invention and crystalline polypropylene or a layer composed of a laminate containing the resin composition and the crystalline polyolefin can be used. The thickness of the substrate layer is usually 10 to 200 μm.

The adhesive layer may be in the form of a liquid, semi-molten, film or sheet. For example, polyurethane resin, epoxy resin, acrylic resin, vinyl resin, vinyl acetate resin, polyester resin Examples thereof include known adhesives containing a resin, an ethylene-vinyl acetate copolymer, a polyamide resin, an ionomer resin as a main component, and a polyolefin modified with an acid anhydride or acrylic acid.

As described above, the layer composed of the resin composition containing the amorphous polyolefin and the crystalline polypropylene of the present invention and the layer composed of the laminate containing the resin composition and the crystalline polyolefin are formed on the surface layer of the decorative sheet, Used for base layer. Further, the decorative sheet may be composed of only a layer composed of a resin composition containing an amorphous polyolefin and crystalline polypropylene, or a layer composed of a laminate containing this resin composition and a crystalline polyolefin.

Known additives may be added to the layer comprising the resin composition containing the amorphous polyolefin and the crystalline polypropylene and the laminate comprising the resin composition and the crystalline polyolefin.
Antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, dispersants, chlorine scavengers, flame retardants, crystallization nucleating agents, antiblocking agents, slip agents, antifogging agents, release agents, Pigments, organic fillers, inorganic fillers, neutralizers, lubricants, decomposers, metal deactivators, antifouling agents, antibacterial agents and other resins, thermoplastic elastomers, etc. within the range where the effects of the present invention are not impaired Can be added.

Examples of these additives include phenolic antioxidants such as 2,6-di-t-butyl-4-methylphenol and 2,6-dicyclohexyl-4-ethylphenol. There are organic phosphite antioxidants such as trioctyl phosphite and tristridecyl phosphite, and sulfur antioxidants such as dilauryl thiodipropionate and pentaerythritol tetralauryl thiopropionate. As a light stabilizer, bis (2,2,6,6-tetramethyl-4-piperidine) sebacate, tetrakis (2,2,6,6-tetramethyl-4-piperidine) -1,2,3,4- There are hindered amine stabilizers such as butanetetracarboxylate. Examples of the ultraviolet absorber include benzophenone-based ultraviolet absorbers such as 2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone, and 2,2 ′
-Methylene-bis [4- (1,1,3,3-tetramethylbutyl) -6-[(2H-benzotriazole-2-
Yl) phenol]], and benzotriazole-based ultraviolet absorbers such as 2- (3-t-butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole.

Examples of the antistatic agent include nonionic antistatic agents such as poly (oxyethylene) alkylamine and poly (oxyethylene) alkylamide; cationic antistatic agents such as quaternary ammonium chloride and quaternary ammonium sulfate; There are anionic antistatic agents such as alkylsulfonates and alkylbenzenesulfonates. Ethylene bisoleic acid amide as a dispersant,
There are bisamide-based dispersants such as ethylenebisstearic acid amide, wax-based dispersants such as microcrystalline wax, and organic metal salt-based dispersants such as barium stearate, calcium stearate, and zinc stearate.

Examples of the flame retardant include phosphate flame retardants such as tricresyl phosphate and ammonium phosphate, antimony trioxide, magnesium hydroxide, aluminum hydroxide, red phosphorus and the like. Examples of the antiblocking agent include fine particles of silica, natural zeolite, synthetic zeolite, kaolin, talc, silicone resin, silicone rubber, fused silica, melamine resin, acrylic resin, and hydrotalcite. As the slip agent, any higher fatty acid amide such as lauric amide and oleic amide is suitable. Diglycine monooleate or the like is added as an antifogging agent. Other resins that can be added include high-density polyethylene, low-density polyethylene, polyethylene obtained with a metallocene catalyst, ethylene-ethyl acrylate copolymer, ethylene-methyl methacrylate copolymer, ethylene-vinyl acetate copolymer, polyethylene Examples include waxes, petroleum resins, terpene resins, cumarone-indene resins, rosin-based resins, and hydrogenated derivatives thereof. As a thermoplastic elastomer,
Styrene-butadiene-styrene block copolymer, styrene-isoprene-styrene block copolymer, and hydrogenated styrene-ethylene-butylene-styrene block copolymer, styrene-ethylene-propylene-styrene block copolymer There are coalescence.

The layer comprising the resin composition containing the amorphous polyolefin and the crystalline polypropylene of the present invention is usually used after being formed into a film or sheet. Films and sheets made of this resin composition can be produced by a known film or sheet production method, for example, a T-die method using a melt extruder,
Inflation method, tubular method, calendar method,
It is manufactured by a method such as a solvent casting method or a hot pressing method. The obtained film is stretched by a known uniaxial or biaxial stretching method, if necessary. In the case of stretching, the surface stretching ratio is preferably from 1.1 to 30 times.

A laminate composed of a layer composed of a resin composition containing an amorphous polyolefin and a crystalline polypropylene and a layer composed of a layer containing a crystalline polyolefin are usually used in the form of a laminated film or a laminated sheet. The laminated film and the laminated sheet are produced by a known production method, for example, a coextrusion lamination method, a lamination method, a dry lamination method, or the like. Among these methods, a coextrusion lamination method that can be melt-bonded is preferable. To specifically explain the method for producing a laminated film by the co-extrusion lamination method, melt extrusion is performed using a number of extruders corresponding to the number of laminations, and after laminating in a molten state by a method such as a T-die method or an inflation method, By cooling with a cooling roll, a method such as water cooling or air cooling, a laminated film is obtained. The thickness and ratio of each layer constituting the laminated film is not particularly limited,
Although it can be arbitrarily selected, the thickness of the film made of the resin composition containing the amorphous polyolefin should be 20 to 9 times the thickness of the laminated film in order not to cause cracks or whitening on the bent surface.
It is preferably 9%, more preferably 30 to 90%.
Further, the obtained laminated film is stretched by a known uniaxial or biaxial stretching method, if necessary. In the case of stretching, the surface stretching ratio is preferably from 1.1 to 30 times.

The resin composition containing the amorphous polyolefin and the crystalline polypropylene and the laminate containing the resin composition and the crystalline polyolefin may be colored, and the coloring agent may be titanium oxide, carbon black, black oxide or the like. Iron, quinacridone, diketopyrrolopyrrole, isoindolinone, nickel titanium yellow, chromium titanium yellow, yellow iron oxide, cyanine green, cyanine blue,
Organic or inorganic colorants containing ultramarine blue, red iron oxide or the like as a main component are appropriately used as long as the effects of the present invention are not impaired. In addition, the printed layer may be omitted from the decorative sheet as necessary. When the printing layer is omitted, a layer composed of a resin composition containing an amorphous polyolefin and a crystalline polypropylene or a layer composed of a laminate containing the resin composition and a crystalline polyolefin is wood grain, stone grain, cloth grain, etc. Pattern may be printed. In this case, in order to improve the printability, a surface treatment such as a corona discharge treatment, a plasma treatment, a flame treatment, and an acid treatment is performed on the film or sheet made of the resin composition or the laminate. Films and sheets made of the resin composition or laminate subjected to these treatments are usually
Printing is performed with an ink using polyurethane or methacrylic resin as a binder.

In the present invention, a known method can be used as a method for preparing a decorative sheet using the film or sheet comprising the above resin composition or laminate. For example, a printing layer or a surface layer is laminated as necessary on a substrate layer composed of a film or sheet composed of a resin composition or a laminate. The lamination method is performed by a method such as hot lamination or dry lamination using an adhesive. The surface layer is subjected to embossing if necessary.

At this time, the adhesive used is one which can be securely bonded without impairing the appearance of the decorative sheet, and
Any adhesive may be used as long as it does not impair the effects of the present invention. Specific examples of the adhesive include thermosetting resin adhesives such as epoxy resin and silicone resin, polyvinyl ether, acrylic resin, vinyl acetate-ethylene copolymer, polyamide resin-based hot melt adhesives, and rubber-based adhesives such as nitrile rubber. An adhesive and the like can be mentioned.

Furthermore, a wiping coating can be applied in which the colored ink is inserted into the embossed portion and wiped off. In addition, the decorative sheet of the present invention may be coated with a transparent protective layer such as urethane or various thermosetting or light-curing emulsions for the purpose of protecting the surface and imparting functionality, or may be made of nylon, polyester, ethylene-vinyl acetate copolymer. Coalescing,
A layer made of an ethylene-vinyl alcohol copolymer or the like may be laminated.

[0034] The decorative sheet obtained as described above is a plywood,
Inorganic boards such as steel plates, aluminum plates, particle boards, and plaster, concrete walls, resin boards, foams, heat insulators, and composites of these can be attached with adhesives to form decorative boards.

Examples of the method of attaching to various materials such as plywood and steel plate include flat attachment, lapping, V-cutting, and vacuum forming. The flat bonding includes a manual bonding, a press bonding, a roller bonding, a bonding method using a roller press, and the like, and there is no problem even if the bonding is performed using other methods.

The adhesive used when affixing to the decorative sheet and various materials is not particularly limited. For example, a thermosetting adhesive such as an epoxy resin or a silicone resin,
Thermoplastic adhesives such as polyvinyl ether, acrylic resin, vinyl acetate-ethylene copolymer, polyamide resin,
A rubber-based adhesive such as nitrile rubber can be used.

The use of the decorative board obtained is not particularly limited, but home appliances such as a TV cabinet, a stereo speaker box and a video cabinet, various storage furniture,
Furniture products such as unit furniture, housing materials such as doors, door frames, window frames, rims, skirting boards, opening frames, kitchen and storage furniture door and other furniture materials, flooring materials, ceiling materials, wallpaper materials, etc. It can be suitably used for automotive interior and exterior materials, home appliances, office equipment, office supplies and the like.

[0038]

The present invention will be described below in detail with reference to examples and comparative examples. The characteristics described in the examples and comparative examples were measured by the following methods.

1) Measurement of boiling n-heptane insoluble content in amorphous polyolefin About 2 g of amorphous polyolefin was put into a dry cylindrical filter paper, and the weight was measured. set. 150 g of n-heptane is placed in this Soxhlet container, heated and boiled under reflux for 10 hours,
Extract the dissolved components in the amorphous polyolefin. Thereafter, the tubular filter paper having the boiling n-heptane insoluble content remaining is taken out, dried under reduced pressure until a constant weight is obtained, and its weight is measured.
The boiling n-heptane insoluble content is calculated from the weight ratio before and after the extraction with boiling n-heptane according to equation (1).

## EQU00001 ## Boiling n-heptane insoluble matter (% by weight) = (MN) /S.times.100 (1) (where, in the formula, M is the difference between the n-heptane insoluble matter after drying under reduced pressure and the cylindrical filter paper). Weight, N is the weight of dry tubular filter paper, S
Is the weight of the amorphous polyolefin before boiling n-heptane extraction. The unit of weight is g. )

2) Evaluation of folded surface The decorative sheet having the resin composition or the laminate of the present invention as a constituent layer was bent at 180 degrees, and sandwiched in a heating press machine in this state, at 80 ° C and a surface pressure of 5 MPa for 5 minutes. Held. Thereafter, the folded decorative sheet was taken out, the folded portion was spread, and the presence or absence of cracks and whitening was visually observed.

3) Evaluation of Adhesion A decorative sheet having a resin composition or a laminate of the present invention as a constituent layer was placed in an oven at 80 ° C. and kept for 10 days.
Take out the decorative sheet. After cooling, the surface of the decorative sheet was touched with a finger and evaluated by touch. Based on the tactile sensation of the surface before this test, those with almost no difference were regarded as having no tackiness, and those having tackiness with stickiness or having bleeding were regarded as having tackiness.

4) Measurement of Transparency A haze was measured according to ASTM D1003 using a decorative sheet having the resin composition or the laminate of the present invention as a constituent layer as a sample.

Example 1 A copolymer having a propylene content of 65% by weight and a butene-1 content of 35% by weight and having a boiling n-heptane insoluble content of 5% by weight.
Amorphous polyolefin (manufactured by Ube Industries, Ltd., trade name Ubetakku UT2780, density 0.86 g / cm ³⁾ and the density 0.91 g / cm ³ of the crystalline polypropylene (Inc. Grand Polymer Co., Ltd., trade name: F226D) And 50 /
50 parts by weight, and 0.1 part by weight of glycerin monostearate and 0.05 part by weight of calcium stearate were added to 100 parts by weight of this mixture.
The mixture was melted and kneaded at ℃ to prepare pellets. The pellets were supplied to an extruder connected to a T-die, melt-extruded at 190 ° C., and passed through a casting roll at 20 ° C. to form a film having a thickness of about 100 μm. After performing a printing process on this film, an adhesive containing a vinyl acetate-ethylene copolymer as a component is applied to a thickness of about 3 μm on the surface subjected to the printing process, and a melt index of 1.5 g / 10 min and an ethylene content of 10 wt. % Of a propylene-ethylene random copolymer, to give a decorative sheet.
The folded surface and the adhesiveness of this decorative sheet were evaluated, and the results are shown in Table 1.

Comparative Example 1 A decorative sheet was obtained in the same manner as in Example 1 except that the mixing ratio of the amorphous polyolefin and the crystalline polypropylene used in Example 1 was changed to 10/90 by weight. . The folded surface and the adhesiveness of this decorative sheet were evaluated, and the results are shown in Table 1.

Comparative Example 2 A decorative sheet was obtained in the same manner as in Example 1 except that the mixing ratio of the amorphous polyolefin and the crystalline polypropylene used in Example 1 was changed to 95/5 by weight. Was. The folded surface and the adhesiveness of this decorative sheet were evaluated, and the results are shown in Table 1.

Comparative Example 3 A propylene content of 85 was used instead of the amorphous polyolefin.
A decorative sheet was obtained in the same manner as in Example 1 except that a polyolefin having a boiling n-heptane-insoluble content of 80% by weight was used as a copolymer having a butene-1 content of 15% by weight. Was. The folded surface and the adhesiveness of this decorative sheet were evaluated, and the results are shown in Table 1.

Example 2 Amorphous polyolefin having a propylene content of 85% by weight and an ethylene content of 15% by weight and having a boiling n-heptane insoluble content of 0.7% by weight (trade name, manufactured by Ube Industries, Ltd.) Ube Tack UT2585), a crystalline polypropylene having a density of 0.91 g / cm ³ and a melt flow rate of 9 g / 10 min (manufactured by Grand Polymer Co., Ltd., trade name: F219)
And D) at a weight ratio of 30/70.
0.1 parts by weight of glycerin monostearate and 0.05 parts by weight of calcium stearate were added to 0 parts by weight, and the mixture was melt-kneaded at a temperature of 200 ° C. to obtain pellets, which were used as raw material A. On the other hand, a crystalline polypropylene having a density of 0.91 g / cm ³ and a melt flow rate of 6 g / 10 min (manufactured by Grand Polymer Co., Ltd., trade name: F-226)
D) was used as raw material B. The raw material A is used as an inner layer and the raw material B is used as a raw material for both outer layers. Using an extruder in which three independent T dies are set at a temperature of 200 ° C. and a total thickness of 100 μm by coextrusion lamination, Specifically, a three-layer laminated film in which both outer layers each had a thickness of 30 μm and the inner layer had a thickness of 40 μm was formed into a decorative sheet. The folded surface, adhesiveness and transparency of this decorative sheet were evaluated. The results are shown in Table 1.

Comparative Example 3 The procedure of Example 2 was repeated except that the amorphous polyolefin used in Example 2 was replaced by an ethylene propylene copolymer having a propylene content of 10% by weight and an ethylene content of 90% by weight. And a decorative sheet was obtained. The folded surface, adhesiveness and transparency of this decorative sheet were evaluated. Table 1 shows the results
It was shown to.

Example 3 Instead of the amorphous polyolefin of Example 2, a copolymer having a propylene content of 65% by weight and a butene-1 content of 35% by weight and having a boiling n-heptane-insoluble content of 46% by weight was used. Amorphous polyolefin (manufactured by Ube Industries, Ltd., density 0.88 g /
cm ³ ) using this amorphous polyolefin and crystalline polypropylene (manufactured by Grand Polymer Co., Ltd.)
The decorative sheet was obtained in the same manner as in Example 2, except that the weight ratio to F219D) was 70/30. The folded surface, adhesiveness and transparency of this decorative sheet were evaluated. The results are shown in Table 1.

[0050]

[Table 1]

[0051]

The polyolefin-based decorative sheet comprising the resin composition of the present invention as a constituent layer does not generate harmful gases when burned, hardly causes cracks or whitening on the bent surface, and has a high surface even when used at high temperatures. It has features such as low tackiness and excellent transparency.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08L 23/02 C08L 23/02 23/12 23/12 F term (Reference) 3D023 AA01 AD06 BA01 BE05 4F071 AA15 AA15A AA20 AA21 AA28A AA31A AA42A AA43A AA53A AA54A AA78A AA89 AH03 BA01 BB02 BB03 BB04 BB06 BB07 BB08 BB09 BC01 CA01 CB01 CB06 CD06 4F100 AK03A AK03B AK07A AK09A AK64 AK67 AK68G AL01A AL05A BA02 EC18 EC182 EH17 EH172 GB07 GB08 GB32 GB33 JA11A JA11B JA12A JB11A JK14 JL00 JN01 YY00A 4J002 BB12W BB12X BB14W BB15W BB17W FD070 FD100 FD130 GL01

Claims (2)

[Claims] 1. A decorative sheet comprising one or more constituent layers, wherein the content of propylene and / or butene-1 is 5
Amorphous polyolefin 20 to 20% by weight or more, and the amount of boiling n-heptane insolubles is 60% by weight or less.
90% by weight and 10 to 80% by weight of crystalline polypropylene
A polyolefin-based decorative sheet, characterized in that a layer made of a resin composition containing 2. A layer comprising a layer comprising a resin composition comprising the amorphous polyolefin according to claim 1 and crystalline polypropylene and a layer comprising a crystalline polyolefin as one of the constituent layers. The polyolefin-based decorative sheet according to claim 1.