JPH09314755A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To apply decoration processing to at least one of laminated sheets wherein a polyolefin resin sheet is laminated on a surface of an ethylene-vinyl alcohol copolymer resin sheet, improve resistances to heat and staining on a surface, a rate of elongation, resistance to tear transmission, etc., and make incineration disposal possible at the time of making the laminated sheets to waste. SOLUTION: A polyolefin resin sheet 1 is laminated on a surface of an ethylene-vinyl alcohol copolymer resin sheet 9, and at least one of the sheets thus laminated is subjected to decoration processing. In this decoration processing, powder of a pigment 2 or scaly foils are added to and dispersed in the ethylene-vinyl alcohol copolymer resin sheet 9 to color the same. Or, the polyolefin resin sheet 1 is decorated with patterns 5 and recess and protrusion patterns 7 by embossing processing, hairline processing, etc. Accordingly, the laminated sheet has a rate of elongation, a tear resistance and softness, which make V-cut processing possible, and is also good in a heat resistance and adhesiveness. Further, a design effect can be improved by printing, a chemical resistance and a solvent resistance can be imparted to the laminated sheet, and, to make the same to waste, incineration disposal can be performed.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention can be used as a surface decorative sheet used for interior decoration of buildings, surface makeup of fittings, interior decoration of vehicles, and the like.

[0002]

2. Description of the Related Art The following three types of decorative sheets are mainly used as conventional decorative sheets for such purposes.

(1) There is a two-layer tabling decorative sheet which is printed on a polyvinyl chloride film and decorated by embossing or the like. (Special Publication 28-
(2) There was a decorative sheet obtained by doubling a normal polyolefin film formed by stretching a film of polyethylene, polypropylene or the like at a stretching ratio of 3 to 5 times.
(JP-A-54-62255) (3) There is a decorative sheet obtained by doubling an acrylic resin film on the surface of a normal polyolefin film obtained by stretching a film of polyethylene, polypropylene or the like at a stretching ratio of 3 to 5 times. It was (JP-A-6-262729
(Japanese Patent Laid-Open No. 54-123166)

[0004]

The decorative sheet using the polyvinyl chloride film as described in (1) has insufficient heat resistance or cannot be incinerated for disposal (hydrogen chloride gas is generated during combustion). Therefore, there is a problem that the stain resistance of the surface is poor due to bleeding (exudation) of the plasticizer.

[0005] In the conventional decorative sheet as described in (2), although the above-mentioned drawbacks of polyvinyl chloride can be improved, it is not flexible, and it has poor ink and adhesive properties during printing and laminating. Insufficient adhesive strength with agents. It has low elongation and tear propagation resistance, and cracks during V-cut processing. In particular, crystallization progresses due to the heat history at the time of embossing from heating softening to embossing plate pressing to cooling, the sheet becomes brittle, and this tendency is strengthened. There was a problem. Further, in the conventional decorative sheet as described in (3), although the above-mentioned drawbacks can be improved, the above-mentioned problems cannot be solved and the chemical resistance and solvent resistance are inferior. There was a new problem.

[0006]

In order to solve the above problems, in the present invention, at least a laminated sheet obtained by laminating a polyolefin resin sheet on the surface of an ethylene / vinyl alcohol copolymer resin sheet, We have developed a decorative sheet that is decorative on one sheet. And, in such a decorative sheet, particularly preferably,
The dimensional shrinkage after heating for 30 minutes in an atmosphere with a heating dimensional shrinkage of 100 ° C. (based on before heating) is −2 to + 7% in the long sheet longitudinal direction and −7 to +2 in the sheet width direction.
%, The dimensional shrinkage after heating for 30 minutes in an atmosphere with a heating dimensional shrinkage of 100 ° C. (based on before heating) is a long sheet. It has been found that it is effective to use a polyolefin resin sheet having a longitudinal direction of −2 to + 7% and a sheet width direction of −7 to + 2%.

[0007]

Embodiments of the present invention will be described below in detail with reference to the drawings. FIG. 1 is a sectional view showing an example of a decorative sheet according to the present invention. FIG. 2 is a sectional view showing an application example of the decorative sheet according to the present invention.

In the decorative sheet of the present invention, the surface sheet is a polyolefin resin sheet. And
Examples of such polyolefin resin include polyethylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, polypropylene, propylene / butene-
1 copolymer, polybutene-1, butene-1, propylene, ethylene, terpolymer, butene-1, hexene-1
Octene-1 terpolymer, polymethylpentene,
Alternatively, olefin elastomers described in JP-A-6-16832 and the like are used. These polyolefin resins may be used alone or in combination of two or more. The thickness is about 50 to 500 μm.

These polyolefin resins can be used by themselves, but various rubbers are preferably added in order to impart flexibility, impact resistance and easy adhesion to the polyolefin resin. 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 is used as a modifier for the polyolefin resin in the present invention. It has the role of suppressing crystallization of the polyolefin resin and improving flexibility and transparency. In general, when a diene rubber is added to a polyolefin resin, the weather resistance and heat resistance are lower than those of the diene rubber-free polyolefin resin due to the double bond of the diene rubber. Since the double bond is saturated with hydrogen, weatherability and heat resistance of the polyolefin-based resin are not deteriorated and the polyolefin resin becomes good.

As the diene rubber, isoprene rubber,
Examples include 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 preferable. The addition amount is about 1 to 90 parts by weight with respect to 100 parts by weight of the polyolefin resin.

If the amount is less than 1 part by weight, elasticity due to rubber addition,
Elongation rate and impact resistance are insufficient, and cracks and cracks are likely to occur during bending such as V-cutting and drawing. Also 90
If it is more than weight part, elasticity and elongation become too large,
Registration during printing becomes poor, which is not preferable.

There is a correlation between the heating dimensional shrinkage and the cracking / breaking resistance during bending such as V-cutting, and the "polyolefin resin sheet" and "polyolefin resin sheet" used in the present invention (particularly claim 3 and claim 2). "Ethylene / vinyl alcohol copolymer resin sheet" means a dimensional shrinkage ratio (based on before heating) after heating in an atmosphere of 100 ° C for 30 minutes, that is, [(dimension after heating)-(before heating). Dimensions)] x 100 /
(Dimension before heating) = Shrinkage rate of heating dimension (%) In the case of a long belt-shaped sheet, the sheet longitudinal direction is -2 to +
7% and the sheet width direction is in the range of -7 to + 2%. If the dimensional shrinkage ratio deviates from this range, the elongation ratio and the tear propagation resistance are significantly reduced with respect to the impact strength, and the sheet is subjected to impactal bending,
It is not preferable because cracks are easily generated during V-cut processing.

The reason why the allowable value of the heating dimensional shrinkage ratio is different between the longitudinal direction and the width direction of the sheet is that the mechanical history of the sheet at the time of manufacturing the sheet and the method of applying the impact force at the time of processing the sheet. This is because the length direction differs from the width direction.

The dimensional shrinkage upon heating has a large correlation mainly with the stretching of the polyolefin resin sheet. The lower the draw ratio, the closer the heating dimensional shrinkage is to 0. In the case of polypropylene, the draw ratio in the longitudinal direction of the sheet is 0 times or more and less than 3 times,
When the stretching ratio in the sheet width direction is 0 times or more and less than 3 times,
Generally, the heating dimensional shrinkage falls within this range. However, generally, when the draw ratio is increased, the transparency and tensile strength of the sheet are improved. Therefore, the stretching ratio is set to an appropriate value in the above range according to the required degree of transparency and tensile strength. When the draw ratio exceeds 3 times, the heating dimensional shrinkage ratio deviates from this range. The dimensional shrinkage upon heating is also correlated with the presence or absence of side chains (branches) of the molecule and the stereoregularity (symmetry) of the molecule. The smaller the number of side chains (branches) of the molecule, the lower the dimensional shrinkage upon heating. In the case of polyethylene, the low-pressure polyethylene has less side chains than the high-pressure polyethylene, and therefore the shrinkage rate upon heating is small and good. Regarding the steric regularity of the molecule, the higher the regularity, the lower the dimensional shrinkage upon heating. Hydrocarbon skeleton (main chain) like polypropylene
In the case of a molecular structure having a functional group such as methyl group, isotactic or syndiotactic has a smaller dimensional shrinkage upon heating and is better than atactic.

If desired, pigments, dyes, fillers, flame retardants, ultraviolet absorbers, etc. are added to the polyolefin resin sheet or the ethylene / vinyl alcohol copolymer resin sheet.

Although it is possible to directly print a pattern or apply an adhesive agent on the ethylene / vinyl alcohol copolymer resin sheet itself, which is the polyolefin resin sheet or the base material sheet, ink or adhesive agent and each of the above resins can be applied. If it is necessary to make the adhesive force with the sheet stronger, it is advisable to apply an easy-adhesion layer, corona discharge treatment, plasma treatment, or other easy-adhesion treatment to the surface of each resin sheet.

In the decorative sheet of the present invention, acrylic, vinyl chloride-vinyl acetate copolymer, polyester, polyurethane, chlorinated polypropylene and chlorinated polyethylene are used as the easily adhesive layer (also referred to as primer layer or anchor layer). However, chlorinated polypropylene is particularly preferable. FIG. 2A shows an example in which the easy-adhesion layer is formed, in which the easy-adhesion layer 4 is provided between the ethylene-vinyl alcohol copolymer resin sheet 9 and the adhesive layer 30 on the adherend side.

As the acrylic, methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate / (meth) acrylic Butyl acid copolymer, ethyl (meth) acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, styrene / methyl (meth) acrylate copolymer ) An acrylic resin composed of a homopolymer or a copolymer containing an acrylic ester (provided that (meth) acrylic means acrylic or methacrylic, and the same applies hereinafter).

Polyurethane is mainly composed of polyol (polyhydric alcohol) and isocyanate as a crosslinking agent (curing agent).
And polyurethane.

The polyol has 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, 2 in the molecule is used.
A polyvalent isocyanate having one or more isocyanate groups is used. For example, aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate and 4-4 diphenylmethane diisocyanate, or aliphatic (or alicyclic) such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate and hydrogenated diphenylmethane diisocyanate. Group) isocyanates are used.

The decoration processing means coloring (transparent or opaque coloring) by adding a pigment as shown in FIGS. 1A and 1B, printing of a pattern as shown in FIGS. 1 (A)
And embossing (heating press), hairline processing and the like to form a concavo-convex pattern.

As pigments, titanium white, zinc white, red iron oxide,
Inorganic pigments such as vermilion, ultramarine blue, cobalt blue, titanium yellow, graphite, carbon black, etc .; Dyes), metal pigments such as aluminum, brass, etc., pearlescent (pearl) pigments composed of foil powder such as titanium dioxide-coated mica, basic lead carbonate, etc., depending on the application, transparent coloring pigments or opaque colorings Choose one of the pigments.

These are added and dispersed as powder or scale-like foil pieces.

As the pattern printing, a pattern is formed by ink (or paint) using a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet.

As the pattern, there are a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometrical figure, a character, a symbol, or a solid surface. The pattern is on the front, back, both sides of the sheet,
Alternatively, it is provided between layers.

As the ink (or) paint, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane, acrylic, vinyl acetate, vinyl chloride / vinyl acetate copolymer, cellulose resin, etc. are used as binders. And used alone or in combination of two or more. A material obtained by adding known pigments as described above to this is used.

When printing directly on a polyolefin resin sheet or an ethylene / vinyl alcohol copolymer resin sheet, a chlorinated polyolefin, polyurethane or the like is preferable as a binder in terms of adhesiveness, but an easily adhesive primer is appropriately selected to form a layer. Once formed, it provides sufficient adhesion even with other binders.

The embossing is carried out by heating and softening the polyolefin resin, pressing and shaping it with an embossing plate, cooling and fixing, and a known sheet-fed or rotary embossing machine is used.

Examples of the uneven shape include a wood grain board conduit groove, a stone board surface unevenness (granite cleavage plane, etc.), a cloth surface texture, a satin finish, a grain, a hairline, a linear groove, and the like.

Further, if necessary, the concave portions of the concavo-convex pattern can be filled with a coloring ink by a known wiping method (see Japanese Patent Publication No. 58-14312). The same thing as the above can be used for the coloring ink. However, from the viewpoint of abrasion resistance, a material using a two-component curable urethane resin as a binder is preferable.

The metal thin film is made of aluminum, chromium, gold,
A film is formed by a method such as vacuum evaporation and sputtering using a metal such as silver or copper. Alternatively, a combination of these may be used.
The metal thin film may be provided on the entire surface or partially in a pattern.

Next, an ethylene / vinyl alcohol copolymer resin sheet to be a base sheet (that is, an adherend side) will be described. The base sheet is laminated by hot melting,
Or a two-component curing type urethane resin, melt extrusion (extrusion) by an adhesive such as coated polyethylene, is formed by laminating an ethylene vinyl alcohol copolymer sheet on the polyolefin resin layer to be a surface sheet, The thickness is preferably 10 to 100 μm, more preferably 12 to 25 μm. As the sheet, a sheet obtained by molding a random copolymer of ethylene and vinyl alcohol into a film is generally used.

The ethylene / vinyl alcohol copolymer resin sheet may be either a stretched sheet or an unstretched sheet. However, the unstretched sheet is suitable for flexibility, bending workability, embossability and the like. It is preferably used.

The ethylene / vinyl alcohol copolymer resin sheet is prepared by changing the ratio of the copolymer components to obtain the thermoplasticity and water resistance of ethylene and the rigidity, oil resistance, solvent resistance, and chargeability of vinyl alcohol. Although the magnitude of the performance of easy adhesion can be arbitrarily adjusted, the ethylene component is preferably 30 to 45 mol% in order to obtain a film having both characteristics as much as possible and having excellent workability. If it is less than 30 mol%, thermoplasticity, heat processing suitability, and water resistance are poor, and if it exceeds 45%, rigidity, oil resistance, solvent resistance, non-charging properties, and easy adhesion are unfavorably deteriorated.

The dimensional shrinkage upon heating has a great correlation with the stretching of the ethylene / vinyl alcohol copolymer resin sheet. The lower the draw ratio, the closer the heating dimension shrinkage becomes to 0. In the case of ethylene / vinyl alcohol copolymer resin, the draw ratio in the longitudinal direction of the sheet is 0 times or more and less than 3 times, and the draw ratio in the sheet width direction is 0 times or more. If it is less than 3 times, generally the dimensional shrinkage upon heating falls within this range. However, generally, when the draw ratio is increased, the transparency and tensile strength of the sheet are improved. Therefore, the stretching ratio is set to an appropriate value in the above range according to the required degree of transparency and tensile strength. When the draw ratio exceeds 3 times, the heating dimensional shrinkage ratio deviates from this range.

The dimensional shrinkage upon heating is determined by the side chain (branch) of the molecule.
And the stereoregularity (symmetry) of the molecule.
The smaller the number of side chains (branches) of the molecule, the lower the dimensional shrinkage upon heating. Regarding the steric regularity of the molecule, the higher the regularity, the lower the dimensional shrinkage upon heating. In the case of a molecular structure in which a functional group such as a hydroxyl group is emitted from a hydrocarbon skeleton (main chain), such as an ethylene-vinyl alcohol copolymer resin, isotactic or syndiotactic is more effective than atactic. Good dimensional shrinkage due to heating.

[Ultraviolet Absorber / Light Stabilizer] An ultraviolet absorber and / or a light stabilizer can be added in order to impart better weather resistance (light resistance) to the resin. Both the absorber and the light stabilizer are usually about 0.5 to 10% by weight, but it is generally preferable to use the ultraviolet absorber and the light stabilizer together.

Organic substances such as benzotriazole, benzophenone, salicylate, etc.
Alternatively, inorganic substances such as zinc oxide, cerium oxide, and titanium oxide having a diameter of 0.2 μm or less can be used. As the light stabilizer, a hindered amine radical scavenger such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and a radical scavenger such as a piperidine radical scavenger can be used. The above ultraviolet absorbers and light stabilizers are common to ethylene / vinyl alcohol copolymer and polyolefin.

As the filler, powders such as calcium carbonate, barium sulfate, clay and talc are used. Add an appropriate amount as needed. 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. The addition amount is about 10 to 150 parts by weight with respect to 100 parts by weight of the polyolefin resin or the ethylene / vinyl alcohol copolymer resin.

The decorative sheet may be a laminate of two layers of an ethylene / vinyl alcohol copolymer resin sheet and a polyolefin resin sheet (FIG. 1) or a laminate of three or more layers (not shown).

The decorative sheet of the present invention can be laminated on another adherend (backing material). In the case of lamination, the adhesive layer may be omitted if the decorative sheet itself can be adhered to the adherend (by a thermal melting point or the like) (FIG. 2 (B)), and the decorative sheet itself adheres to the adherend. If not, the layers are laminated via an appropriate easy-adhesion layer and an adhesive layer (FIG. 2A).

The adherend is a final product, and a decorative sheet may be laminated for the surface decoration. If necessary, the decorative sheet may be used to reinforce the mechanical strength of the decorative sheet or to provide concealment. An adherend may be laminated on the back surface.

As the adherend, plate materials such as flat plates and curved plates of various materials [FIG. 2 (A)], three-dimensional shaped articles [molded products, FIG.
(B)], a sheet (or a film) and other various shaped articles are targeted. As a material used for any of a plate material, a three-dimensional article, and a sheet (film), wood veneer such as wood veneer, wood plywood, particle board, medium density fiber board (MDF), wood fiber board such as wood fiber board , Metals such as iron and aluminum, acrylic, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, A
Materials such as BS, phenol resin, polyvinyl chloride, cellulosic resin, rubber and the like, materials exclusively used for plate materials or three-dimensional articles include ceramics such as glass and ceramics, cement such as ALC (foam lightweight concrete), Non-cement ceramic materials such as calcium silicate, gypsum,
Materials used exclusively as sheets (or films) include papers such as high-quality paper and Japanese paper, non-woven fabrics or woven fabrics made of fibers such as carbon, asbestos, potassium titanate, glass, and synthetic resin.

As a method for laminating these various adherends,
For example, as described in JP-B-50-19132, JP-B-43-27488, and the like, a decorative sheet is a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive layer therebetween. Between the male and female molds for injection molding,
The two molds are closed, the molten resin is injected and filled from the male mold gate, and then cooled, and a decorative sheet is adhered and laminated on the surface of the molded resin simultaneously with the molding of the molded resin. No. 45768, Japanese Patent Publication No. 60-
As described in JP-A-58014, etc., a decorative sheet is placed on the surface of a molded product so as to face or be placed with an adhesive layer in between.
A so-called vacuum press lamination method in which a decorative sheet is laminated on the surface of a molded product by a pressure difference caused by vacuum suction from the molded product side,
As described in Japanese Examined Patent Publication No. 61-5895, Japanese Examined Patent Publication No. 3-2666, etc., a decorative sheet is supplied in the major axis direction of a columnar substrate such as a column or a polygonal column with an adhesive layer interposed therebetween. On the other hand, a decorative sheet is sequentially pressure-bonded and laminated on a plurality of side faces forming a columnar body by a plurality of rollers having different orientations, a so-called lapping method, actual size 15-31.
No. 122, JP-A-48-47972, etc., a decorative sheet is first laminated on a plate-shaped substrate with an adhesive layer interposed therebetween, and then the plate-shaped substrate opposite to the decorative sheet. A groove having a V-shaped or U-shaped cross section, which reaches the interface between the decorative sheet and the plate-shaped base material, is cut on the surface of, and then an adhesive is applied to the groove, and then the groove is bent. There is a so-called V-cut or U-cut processing method for forming a box body or a columnar body.

In particular, as a method of bonding the decorative sheet of the present invention to a three-dimensional object having irregularities, of the above methods, (a) a lapping method, (b) a V-cut method, (c) a simultaneous lamination method of injection molding, d) A vacuum forming simultaneous lamination method or the like is preferable.

The decorative sheet of the present invention is laminated on various adherends, subjected to predetermined molding and the like and used for various 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 such as automobiles and trains, aircraft interiors, windows Glass makeup.

[0049]

EXAMPLES Examples of the present invention will be described in detail below.

Example 1 Based on 100 parts by weight of polypropylene, 10 parts by weight of hydrogenated styrene-butadiene rubber, 3 parts by weight of a hindered amine radical scavenger, and 2 parts by weight of a benzotriazole ultraviolet absorber were added to give a thickness of 80 μm. Corona treatment is applied to the surface of the transparent unstretched sheet (top sheet) of, and hexamethylene diisocyanate is used as a curing agent, and a urethane-based two-component curable resin containing acrylic polyol as a main component is used as a binder. The keyaki board pattern was subjected to gravure printing, and a chlorinated polypropylene primer was further used to provide an easily adhesive primer layer having a thickness of 3 μm by the gravure coating method.

The decorative sheet obtained above was placed on an unstretched ethylene-vinyl alcohol copolymer resin sheet so that the primer face was on the base sheet side, and as a filler,
The sheet was superimposed on a base sheet having a thickness of 80 μm to which a red iron oxide and carbon black were added as a coloring pigment also using calcium carbonate, and both sheets were laminated and bonded using a rotary hot press embossing machine. At this time, of the laminate (nip) roll, the roll coming to the top sheet side is a metal roll, and the decorative sheet and the adherend substrate are laminated as an embossing roll having a surface formed with irregularities of the zelkova wood channel groove. At the same time as bonding, an embossed pattern was formed on the surface of the decorative sheet. The embossing conditions were as follows: Emboss sheet heating temperature: 165 ° C (heating drum temperature) Sheet feed speed: 15 m / min Emboss plate surface temperature: 40 ° C

Comparative Example 1 A filler and a pigment were used as the base sheet of Example 1 in Example 1.
An 80 μm thick sheet of biaxially stretched polypropylene having a draw ratio of 3 times added in the same manner as in Example 1 was used. Others were the same as Example 1.

Comparative Example 2 A 50 μm-thick transparent acrylic resin sheet made of polymethyl methacrylate to which a benzotriazole-based ultraviolet absorber was added at 2% by weight was used as the surface sheet of Example 1. A 50-μm-thick biaxially-stretched polypropylene sheet with a draw ratio of 3 was used. Others were the same as Example 1.

[Performance Evaluation Test] Table 1 shows the results obtained by comparing the decorative sheet of Example 1 and the decorative sheets of Comparative Examples 1 and 2 in various physical properties.

[Test Method] Transparency The haze value is measured with a direct-reading haze meter manufactured by Toyo Seiki Co., Ltd. It is measured with a single surface sheet layer without decoration treatment. 2. Irradiation up to 3000 hours with a carbon arc lamp type sunshine weatherometer, stop at a place where visual changes such as cracks, whitening, discoloration, etc. become significant (visual judgment). Black panel temperature 63 ° C. The sample after irradiation is visually evaluated. 3. Heat resistance Heat in an 80 ° C atmosphere for 3 minutes, and visually check the discolored state before and after the heating. 4. Sheet break / crack during V-cut The base sheet side of the decorative sheet is bonded and laminated to a 10mm-thick Rawan plywood using an ethylene-vinyl acetate copolymer emulsion adhesive, and the decorative sheet side of the plywood is On the other side, a V-shaped groove extending to the interface between the plywood and the adhesive layer is cut, and an adhesive of an ethylene / vinyl acetate copolymer emulsion is applied to the groove, and the groove is formed. The plywood was bent in a closed manner so that the plywood was bent into an L-shape (cross section). The ambient temperature during processing was 10 ° C. 5. Reproduction of uneven pattern Evaluation was made visually. 6. Adhesive strength A sample obtained by cutting a laminate obtained by laminating a base sheet side of a decorative sheet and a 3 mm thick Rawan plywood as an adherend with an adhesive of an ethylene-vinyl acetate copolymer system emulsion to a width of 1 cm is used. A tensile test was performed in a direction perpendicular to the direction at a tensile speed of 50 mm / min and an ambient temperature of 20 ° C. so that the tensile directions of both samples were 180 ° to each other, and the tension at the time of peeling of the interlayer interface was measured. 7. Heating dimensional shrinkage ratio The decorative sheet is heated in an atmosphere of 100 ° C. for 30 minutes, and [(dimension after heating) − (dimension before heating)] × 100 /
(Dimension before heating) = Shrinkage ratio of heating dimension (%) was determined for each of the longitudinal direction (MD) and the width direction (TD).

[0056]

[Table 1]

[0057]

Industrial Applicability The decorative sheet of the present invention has a V-cut elongation rate, tear resistance, and flexibility, good heat resistance and good adhesiveness, and has a good design by printing. It has the effect of being up. Has excellent chemical resistance and solvent resistance. When the decorative sheet is burned, there is an effect that harmful chlorine-based gas is not generated unlike the conventional polyvinyl chloride.

[Brief description of drawings]

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

FIG. 2 is a sectional view showing an application example of a decorative sheet according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Polyolefin resin sheet 2 Pigment 4 Easy-adhesion layer (primer layer) 5 Pattern 7 Uneven pattern 9 Ethylene / vinyl alcohol copolymer resin sheet 21 Decorative sheet 22 Decorative sheet 23 Decorative sheet 30 Adhesive layer 31 Adherent (flat plate) 33 Adherend

Claims (3)

[Claims] 1. A decorative sheet, characterized in that, in a laminated sheet obtained by laminating a polyolefin resin sheet on the surface of an ethylene / vinyl alcohol copolymer resin sheet, at least one of the sheets is subjected to a decorative treatment. 2. The dimensional shrinkage after heating in an atmosphere having a heating dimensional shrinkage of 100 ° C. for 30 minutes (based on before heating) is −2 to + 7% in the longitudinal direction of the long sheet and in the sheet width direction. The decorative sheet according to claim 1, wherein an ethylene / vinyl alcohol copolymer resin sheet having a range of -7 to + 2% is used. 3. The dimensional shrinkage after heating for 30 minutes in an atmosphere having a heating dimensional shrinkage of 100 ° C. (based on before heating) is −2 to + 7% in the longitudinal direction of the long sheet and in the sheet width direction. The decorative sheet according to claim 2, wherein a polyolefin resin sheet having a range of -7 to + 2% is used.