JP2000280418A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a decorative sheet having thermoformability, weatherability, transparency and easy adhesiveness with an adherend equal to those of a decorative sheet using a polyvinyl chloride resin. SOLUTION: A transparent soft polypropylene film having a composite three- dimensional structure comprising a mixed system of isotatic polypropylene and atactic polypropylene is used as a surface film and a pattern layer 12 is formed on this transparent PO film 13 by printing and this printed film and a colored acrylic resin film 11 are thermally fused by using an embossing plate and, at the same time, an embossed pattern is formed on the surface of the transparent PO film 13 and the embossed recessed parts 17 of the embossed pattern are filled with color ink 18 by wiping processing and, further, a transparent OP layer 19 is formed thereon and a primer layer 14 is formed on the rear surface of the acrylic resin film to produce a decorative sheet.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet for imparting a design to a surface used for interior decoration of buildings, surface decoration of fittings, interior decoration of vehicles, and the like. In particular, even when the surface of a molded article is decorated by vacuum molding using a decorative sheet, the moldability is improved so that a good surface decoration can be achieved.

[0002]

2. Description of the Related Art Conventionally, as a decorative sheet used as a surface decoration material for interiors such as walls and ceilings of buildings, furniture, cabinets and the like, a polyvinyl chloride sheet is often used as a base sheet. For example, there are a sheet in which a grain pattern or the like is printed on a polyvinyl chloride sheet and a transparent polyvinyl chloride sheet is laminated on the sheet pattern, and a sheet in which a transparent polyvinyl chloride sheet is embossed. As a substitute for the polyvinyl chloride sheet, a decorative sheet using a polyolefin resin sheet such as polyethylene or polypropylene has been proposed (see Japanese Patent Application Laid-Open No. Sho 54-62255).

Further, as a decorative sheet using an acrylic resin sheet, an acrylic resin sheet is used as a base sheet,
A decorative sheet using a polyolefin resin sheet on the surface or a polyvinyl chloride sheet on the base sheet and an acrylic resin sheet on the surface is also used.

[0004]

However, decorative sheets using polyvinyl chloride sheets are said to have a risk of generating hydrochloric acid gas and dioxin when discarded and incinerated. There is a problem with later disposal.
There are also problems such as insufficient heat resistance and contamination of the surface by bleed-out of the plasticizer. In addition, since a decorative sheet using a polyolefin resin sheet such as polyethylene and polypropylene does not have a polar group,
In the case of forming a picture layer, it was necessary to provide an easy-adhesion layer such as a corona discharge treatment or a method of forming a primer layer on the surface of the olefin-based resin sheet in order to improve the adhesive strength with the printing ink. Furthermore, a decorative sheet using a polyolefin-based resin sheet has a problem that, when decorating the surface of a molded product by vacuum forming, the suitability for vacuum forming is inferior to a decorative sheet using polyvinyl chloride.

[0005] Further, when a decorative sheet using an acrylic resin film on the surface is used for surface decoration of a three-dimensional molded article having an irregular shape, the decorative sheet formed by vacuum forming may return due to application of heat. Or a change in surface gloss. Further, when an acrylic resin film is used as the base film, the acrylic resin film has poor solvent resistance, and thus has poor printability. For example, 3 after solid printing
When color printing is performed, registration is difficult due to swelling of the film. Furthermore, when an acrylic resin film is used for the base film and a polyolefin resin film is used for the surface film, the elongation is poor, and when performing surface decoration of a three-dimensional molded product by vacuum forming, it is difficult to form a complicated molded product. .

As described above, the conventional decorative sheet has advantages and disadvantages and is not always satisfactory. Ordinarily, decorative sheets used as interior decoration materials such as interior walls such as walls and ceilings of buildings, furniture and cabinets are required to have the following functions. (1) Thermoforming suitability equivalent to a decorative sheet using polyvinyl chloride. In particular, the change in elongation under a constant load due to temperature changes should be as slow and continuous as that of polyvinyl chloride. In addition, physical properties should not be deteriorated even by repeated temperature changes from heating to cooling to heating. (2) creep deformation resistance. Exterior and interior materials are often subjected to a fixed load by fittings and furniture for a long time, and when creep deformation occurs, the loaded portion is turned up or peeled off. Therefore, it is required that the material does not cause creep deformation as much as possible. (3) Cold bending strength. Folding such as V-cut processing in cold regions (when a decorative material laminated with decorative sheets is bent, a V-shaped groove is formed in the decorative material and the bending process is performed, hereinafter simply referred to as V-cut processing). If the stress relaxation is insufficient during the processing, whitening, cracking, breakage, etc. occur in the bent portion.

(4) Organic solvent resistance. When bonding the decorative sheet and the adherend, the decorative sheet is prevented from swelling and deforming due to the solvent in the adhesive. The same applies to a decorative sheet having a multilayer structure. (5) Elongation at break, impact resistance. In order to prevent cracks in the bent part during V-cut processing,
This property is required. (6) It has an appropriate flexural modulus. This is necessary because the followability of the decorative sheet in the bent portion is sufficient. (7) Good transparency. (8) Whitening and turbidity due to recrystallization do not occur even by heating and cooling during embossing or the like. (9) Easy adhesion. (10) Excellent weather resistance.

The present invention has been intensively studied with the aim of solving the problems of the conventional decorative sheet using a polyolefin resin and an acrylic resin. It has been found that a decorative sheet having the same thermoformability, weather resistance, transparency, and easy adhesion to an adherend as a decorative sheet using a vinyl chloride resin can be obtained,
The present invention has been made.

[0009]

Means for Solving the Problems In order to solve the above problems, the configuration of the decorative sheet is as follows. A decorative sheet was obtained by laminating a transparent polyolefin-based resin film, a pattern layer, and a colored acrylic resin film in this order. And, for the transparent polyolefin resin film, a colorless or colored transparent soft polypropylene resin having a complex three-dimensional structure composed of a mixed system of isotactic polypropylene and atactic polypropylene is used, and the transparent polyolefin resin film is used. The colored acrylic resin film was used as a decorative sheet laminated by heat fusion or dry lamination. Further, an embossed pattern is formed on the surface of the decorative sheet, wiping is performed on the embossed pattern, an overprint layer is formed thereon, and on the back surface of the decorative sheet,
A decorative sheet having a primer layer was formed. Further, the acrylic resin film used for the decorative sheet has a shrinkage ratio of 0 to 20% in the vertical direction and −10 to +1 in the horizontal direction when heated at 100 ° C. for 30 minutes.
It was a decorative sheet characterized by being 0%.

That is, the decorative sheet of the present invention uses, as a surface film, a colorless or colored transparent soft polypropylene resin film having a composite three-dimensional structure composed of a mixture of isotactic polypropylene and atactic polypropylene, Using a colored acrylic resin film as a film, providing a pattern layer by printing or the like between the surface film and the base film, and laminating both films by a heat fusion method or a dry lamination method. Things. Further, as the colored acrylic resin film, the shrinkage by heating at 100 ° C. for 30 minutes is 0 to 20% in the vertical direction and −1 in the horizontal direction.
It is characterized in that a film of 0 to + 10% is used. The decorative sheet having the above-described configuration improves the vacuum forming aptitude, and is a decorative sheet having the same thermoformability as a decorative sheet using a conventional polyvinyl chloride film. Further, the decorative sheet has an embossing process and a wiping process on the surface in order to enhance the design, and a primer layer is formed on the back surface in order to improve the adhesiveness with the adherend. .

[0011]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the drawings. FIG. 1 is a schematic sectional view showing an example of the decorative sheet of the present invention. FIG. 2 shows another embodiment of the decorative sheet of the present invention, in which a transparent polyolefin resin film (hereinafter referred to as a PO film) and a colored acrylic resin film (hereinafter referred to as a colored acrylic film) are laminated with an adhesive, and a transparent PO film on the surface is provided. FIG. 2 is a schematic cross-sectional view when embossing and wiping are performed on a back surface to form a primer layer on the back surface. FIG. 3 shows still another embodiment of the decorative sheet according to the present invention, in which a transparent PO film and a colored acrylic film are laminated by a heat fusion method, a transparent PO film on the front surface is embossed and wiped, and a primer on the back surface. FIG. 4 is a schematic sectional view when a layer is formed. FIG. 4 is an explanatory diagram when the decorative sheet of the present invention is produced using an adhesive. FIG. 5 is an explanatory view when the decorative sheet of the present invention is produced by heat fusion. FIG. 6 is an explanatory diagram when a decorative sheet having a surface subjected to embossing and wiping is produced by heat fusion. FIG. 7 is an explanatory view when a decorative sheet having a surface subjected to embossing and wiping is produced using an adhesive. FIG. 8 is an explanatory diagram when the decorative sheet of the present invention is manufactured according to Example 1.
FIG. 9 is an explanatory diagram when a decorative sheet of the present invention is manufactured according to Example 2. FIG. 10 is an explanatory diagram when the quality of a decorative sheet is determined by a vacuum forming suitability test. FIG.
FIG. 4 is an explanatory diagram when a V-cut processing suitability test of a decorative sheet is performed.

As shown in FIG. 1, the decorative sheet 1 of the present invention is basically provided with a pattern layer 12 by printing or the like on a transparent PO film 13 and heat-sealing the printed film and the colored acrylic film 11. (Or an adhesive). As another mode of the decorative sheet 1, FIG.
As shown in the figure, a pattern layer 12 and an adhesive layer 15 are formed on a transparent PO film 13, and the printed film and the colored acrylic film are laminated by a dry lamination method with the adhesive layer 15 interposed therebetween. Transparent PO
The film 13 is embossed, and the embossed concave portion 17 is filled with the coloring ink 18 by wiping,
A transparent overprinting layer 19 (hereinafter, referred to as a transparent OP layer) is formed thereon as a surface protective layer, and a primer layer 14 is further formed on the back surface of the laminated sheet to improve adhesiveness to an adherend. It was done. Further, as another embodiment of the decorative sheet, as shown in FIG. 3, a transparent PO film 13 on which a picture layer 12 is formed and a colored acrylic film 11 are laminated by heat fusion, and the laminated sheet is formed in the same manner as described above. The decorative sheet 1 may be formed by forming the embossed concave portions 17, the coloring ink 19, and the transparent OP layer 19 on the PO film on the front surface, and forming the primer layer 14 on the back surface of the laminated sheet.

The transparent P used in the decorative sheet of the present invention
As the O film, a film of a soft polypropylene resin having a complex three-dimensional structure composed of a mixed system of isotactic polypropylene and atactic polypropylene is used, and a colorless or colored transparent film is used. As this soft polypropylene resin, a soft polypropylene comprising (A) 10 to 90% by weight of atactic polypropylene and (B) 90 to 10% by weight of isotactic polypropylene is used.

The atactic polypropylene of the component (A) includes (a) a solid catalyst component containing magnesium, titanium, a halogen atom and an electron donor as essential components, (b) an organoaluminum compound, and (c) the following: It is obtained by polymerizing propylene in the presence of a catalyst comprising a combination of an alkoxy group-containing aromatic compound represented by the general formula [Chemical formula 1], and has a number average molecular weight (Mn) of 25,000 or more, And the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight (Mn)
Is 7 or less, and polypropylene soluble in boiling heptane is used.

[0015]

Embedded image Wherein R ¹ in the formula is an alkyl group having ¹ to 20 carbon atoms, R ²
Is a hydrocarbon group, a hydroxyl group or a nitroso group having 1 to 10 carbon atoms, m is an integer of 1 to 6, n is 0 or an integer of 1 to (6-m).

The isotactic polypropylene as the component (B) has a melt index of 0.1 to 4
g / 10 minutes, polypropylene insoluble in boiling heptane is used.

The above soft polypropylene resin (blended resin of atactic polypropylene and isotactic polypropylene) has an elongation at break (T _b ) of 400% or more,
The residual elongation (PS _1oo ) after elongation is preferably from 500 to 700%, and 100%, and preferably from 50 to 75.
%, And at break stress (M _B) and at yield stress (M _Y) ratio of (M _B / M _Y) is 1.0 or more, preferably l. 5-
It is desirable to be in the range of 3.5.

In the above soft polypropylene resin,
The atactic polypropylene (A) is soluble in boiling heptane and has a number average molecular weight (Mn) of 25,
000 or more, preferably in the range of 30,000 to 60,000, and the ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is 7 or less, preferably in the range of 2 to 6. Is used. This Mn is 2
Intended ones and the Mw / Mn ratio of less than 5,000 is more than 7, the contribution effect of the mechanical properties of the atactic polypropylene in the resulting resin is not sufficiently exhibited, at break stress of the obtained resin (M _B ) And the stress at yield (M _Y ) are 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 have a propylene unit content of 40% by weight or less, preferably 30% by weight or less, of other α-olefins having 2 to 30 carbon atoms. It may be a propylene copolymer containing an olefin unit. Also, this atactic polypropylene may be used alone or in combination of two or more. The atactic polypropylene of the component (A) is prepared by a known method (Japanese Patent Publication No.
No. 23278).

The isotactic polypropylene of the component (B) in the soft polypropylene resin has a melt index (MI) of 0.1 to 4 g / 10 min.
Crystalline isotactic polypropylene insoluble in boiling heptane is used. Melt index is 0.1g
If it is less than / 10 minutes, the melting property is low, and sheet forming becomes difficult. If it exceeds 4 g / 10 minutes, the mechanical strength becomes insufficient and V-cut processing may not be performed well.

As the isotactic polypropylene of the component (B), a propylene homopolymer having isotactic stereoregularity may be used, or propylene having the stereoregularity and another α-olefin may be used. May be used. As the α-olefin used in this copolymer, those having 2 to 8 carbon atoms, for example, ethylene, butene-1, pentene-1, heptene-1, octene-1 and the like are preferable, and among them, ethylene and butene-
1 is preferred. As the copolymer, a block copolymer or a random copolymer containing the other α-olefin unit usually at most 40% by weight, preferably at most 30% by weight is used.

Preferred examples of the isotactic polypropylene as the component (B) include a propylene homopolymer and 1 to 30% by weight of ethylene units, preferably 3 to 30% by weight.
A random copolymer or a block copolymer of propylene and ethylene containing 25% by weight is exemplified. There is no particular limitation on the production of such isotactic polypropylene, and any method can be selected and used from the production of conventional crystalline polypropylene.
In the soft polypropylene resin, the isotactic polypropylene of the component (B) may be used alone or in combination of two or more.

In the above soft polypropylene resin,
The content of the atactic polypropylene of the component (A) is 10 to 90% by weight, preferably 25 to 80% by weight.
The content of the isotactic polypropylene of the component (B) is 90 to 10% by weight, preferably 75 to 20% by weight.

[0024] (A) The content of the component is less than 10 wt%, and the yield stress at the resin (M _Y) is too large, the ratio of the breaking stress at the (M _B) and at yield stress (M _Y) M _B / M
_Y is less than 1.0, and the residual elongation (PS ₁₀₀ ) after 100% elongation is also larger than 80%, so that the object of the present invention cannot be achieved. On the other hand, when the content of the component (A) is 90
And at break stress (M _B) is too small to exceed wt%, the M _B / M _Y ratio is less than 1.0, and the mechanical strength there is a possibility to decrease. Further, 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.

In order to reinforce the function required as a surface layer of the decorative sheet, various additives, reinforcing materials, and fillers such as an ultraviolet absorber, a light stabilizer, Heat stabilizers, antioxidants, antistatic agents, flame retardants, lubricants and the like are added. The UV absorber and the light stabilizer are for imparting good weather resistance (light resistance) to the resin, and the amount of the UV absorber and the light stabilizer is usually 0.5 to 10% by weight for both the UV absorber and the light stabilizer. %. Generally, it is preferable to use an ultraviolet absorber and a light stabilizer together.

Organic substances such as benzotriazole, benzophenone, salicylate, etc.
Alternatively, an inorganic substance such as zinc oxide, cerium oxide, and titanium oxide having a particle size of 0.2 μm or less can be used. As the light stabilizer, bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (N
-Methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate, a hindered amine radical scavenger, a piperidyl radical scavenger, and the like.

In order to prevent deterioration due to ultraviolet rays and further improve weather resistance, it is preferable to add a radical scavenger as another light stabilizer. Examples of the radical scavenger include bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (N-methyl-2,
(2,6,6-tetramethyl-4-piperidinyl) sebacate and, for example, a hindered amine radical scavenger such as a compound disclosed in Japanese Patent Publication No. 4-82625 and a piperidyl radical scavenger are used. .

The soft polypropylene resin film used in the present invention is the above-mentioned isotactic polypropylene,
A film obtained by blending atactic polypropylene and other additives is formed into a colorless or colored transparent film by calendering or the like. The film obtained as described above satisfies various conditions as the surface film of the decorative sheet of the present invention. The thickness of the film is used in the range of 50 to 200 μm, preferably about 100 μm.

As the colored acrylic film used for the substrate sheet of the present invention, a film obtained by adding a coloring agent to the following acrylic resin and forming a film to a predetermined thickness by a calendar method or the like is used. The thickness of the colored acrylic film is 2
0-100 μm is preferred. As acrylic resin,
Methyl poly (meth) acrylate, ethyl poly (meth) acrylate, propyl poly (meth) acrylate, butyl poly (meth) acrylate, methyl (meth) acrylate
(Meth) butyl acrylate copolymer, ethyl (meth) acrylate-butyl (meth) acrylate copolymer, ethylene-methyl (meth) acrylate copolymer, styrene-
An acrylic resin comprising a homo- or copolymer containing a (meth) acrylate such as a methyl (meth) acrylate copolymer is used. (However, here, (meth) acryl means acryl or methacryl, and will be used in the same meaning hereinafter.)

The coloring agent added to the acrylic resin gives the base sheet a necessary color as a decorative sheet. If necessary, a coloring agent composed of a pigment or a dye is used. The coloring of the acrylic film, transparent coloring, opaque coloring is used depending on the application, but in general,
It is necessary to cover the surface of the adherend, and colored opaque is preferable. As coloring agents, titanium white, zinc white, red petals,
Inorganic pigments such as vermilion, ultramarine, cobalt blue, titanium yellow, carbon black, etc., organic pigments or dyes such as isoindolinone, banza yellow A, quinacridone, permanent red 4R, phthalocyanine blue, metal pigments such as aluminum and pearls, titanium dioxide Pearlescent pigments made of foil powder of coated mica, basic zinc carbonate and the like are used. If necessary, an inorganic filler may be added, and calcium carbonate, barium sulfate, clay, talc,
Silica (silicon dioxide), alumina (aluminum oxide)
And the like.

Hereinafter, the method for producing the decorative sheet of the present invention will be described. First, using a soft polypropylene made of the above-mentioned isotactic polypropylene and atactic polypropylene, if necessary, an ultraviolet absorber or a light stabilizer is added to form a blend, and the blend is prepared by a calendar method or the like. Then, a transparent film having a thickness of 3 mm is produced to form a transparent PO film 13 as shown in FIG. In addition, the transparent PO film 13 is subjected to an easy-adhesion treatment such as a corona discharge treatment, a plasma treatment, or the formation of an easy-adhesion layer, as necessary, in order to increase the adhesion with a printing ink or a colored acrylic film. There are cases.

As the easily adhesive layer (also called a primer layer or an anchor layer), acrylic resin, urethane resin, vinyl chloride-vinyl acetate copolymer resin, polyester resin, polyurethane resin, chlorinated polyethylene, chlorinated polypropylene, etc. A coating solution in which a resin is dissolved in a solvent is used, and a polyurethane resin is particularly desirable. By applying a coating solution obtained by dissolving the above resin in a solvent by a known method and drying to form an easily adhesive layer, the adhesive strength between the transparent PO film and the picture layer or the colored acrylic film can be enhanced. .

Examples of the acrylic resin include poly (methyl meth) acrylate, poly (meth) ethyl acrylate, poly (meth) acrylate, butyl poly (meth) acrylate, and methyl (meth) acrylate / (meth) acrylate. ) Butyl acrylate copolymer, ethyl (meth) acrylate / butyl (meth) acrylate copolymer, ethylene / methyl (meth) acrylate copolymer, styrene / methyl (meth) acrylate copolymer, etc. An acrylic resin comprising a homo- or copolymer containing a (meth) acrylic ester (however, (meth) acryl means acryl or methacryl, and the same hereinafter) is used.

Polyurethane is mainly composed of a polyol (polyhydric alcohol) and isocyanate as a crosslinking agent (curing agent).
Polyurethane. The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, and polyether polyol. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, 2,4 tolylene diisocyanate, xylene diisocyanate, 4,4
Aromatic isocyanates such as diphenylmethane diisocyanate, or aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used.

As shown in FIG.
As shown in (b), the picture layer 12 and the adhesive layer 15 are formed. Picture layer, gravure printing, offset printing,
It is formed using a known printing method such as silk screen printing or transfer printing from a transfer sheet. Examples of the pattern of the picture layer include a wood grain pattern, a stone grain pattern, a leather pattern, a geometric figure, a character, a symbol, and a solid printing on the entire surface. The picture layer may be provided on either the transparent PO film 13 or the colored acrylic film 11, but the acrylic film is excellent in solvent resistance because a problem may occur depending on the type of ink in terms of solvent resistance. It is preferable to form a transparent PO film. Therefore, in the present invention, the transparent PO
A pattern layer was provided on the film.

As the printing ink for providing the picture layer, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyesters, polyurethanes, acryl, vinyl acetate, vinyl chloride-vinyl acetate copolymers, cellulose resins, Or a mixture of two or more of these, to which known pigments, dyes, fillers, and other additives are added. When printing directly on the transparent PO film 13, a chlorinated polyolefin, polyurethane, acrylic, or the like is preferable as a binder in terms of adhesiveness. However, as described above, if an easily adhesive primer layer is appropriately selected and formed. Even if other binders are used, sufficient adhesiveness can be obtained. As the colorant for the ink, those mentioned above as the colorant for the acrylic film can be used.

On the other hand, a film is formed by a known method using the acrylic resin and the coloring agent, and a colored acrylic film 11 is formed as shown in FIG. Next, the transparent PO film provided with the picture layer 12 and the adhesive layer 15 (hereinafter, the transparent PO film provided with the picture layer or the picture layer and the adhesive layer is referred to as a print film 2) and the colored acrylic film 11 are dried. Laminating is performed by a lamination method to produce a decorative sheet 1 as shown in FIG.

The adhesive layer 15 is provided for laminating the printed film 2 (a transparent PO film provided with a picture layer) and a colored acrylic film by a dry lamination method or the like. Mold polyurethane resin, polyester resin, etc. are used. However, when the printed film 2 and the colored acrylic film 11 are laminated without the adhesive layer, the adhesive layer can be omitted. For example, when the printing film 2 and the colored acrylic film 11 are heat-sealed by hot pressing, the adhesive layer 15 need not be provided.

That is, as shown in FIGS. 5 (a) and 5 (b), the printed film 2 and the colored acrylic film 11 produced as described above are laminated by heat fusion using a hot press or a hot roll. Then, a decorative sheet 1 as shown in FIG. 5 (c) can be obtained. Further, when an embossing pattern is formed on the surface of the decorative sheet using an embossing roll or an embossing plate, the printing film 2 is formed simultaneously with the embossing process.
And the colored acrylic film 11 are thermally fused to form a decorative sheet 1.
Can also be prepared. In addition, as a method of laminating without an adhesive layer, a transparent PO film 13 provided with a picture layer 12 and a colored acrylic film 11 can be laminated by a sandwich lamination method using an adhesive resin. Also, a colored acrylic film 1 provided with a picture layer
The above-mentioned soft polypropylene can be melt-extruded on the laminate 1 by extrusion and laminated.

Next, as another embodiment of the decorative sheet of the present invention, a decorative sheet having a surface embossed and wiped will be described. As shown in FIGS. 6A and 6B, the print film 2 and the colored acrylic film 11 were prepared as described above, and the pattern layer 12 of the print film 2 was colored as shown in FIG. 6C. The printed film 2 and the colored acrylic film 11 are overlapped so as to be in contact with the acrylic film 11, and the transparent PO film 13 is embossed by a doubling embossing method using an embossing roll or an embossing plate as shown in FIG. Simultaneously with the formation of the pattern 16, the printed film 2 and the colored acrylic film 11 are heat-sealed to produce the embossed laminated sheet 4.

Next, as shown in FIG. 6E, the embossed concave portion 17 of the embossed pattern 16 is filled with a coloring ink 18 by wiping, and a transparent overprint layer 19 (hereinafter referred to as a transparent OP layer 19) is further filled thereon. Is formed, and a primer layer 14 is formed on the colored acrylic film 11 on the back surface in order to improve the adhesiveness with the adherend, and the decorative sheet 1 as shown in FIG.

In the embossing, a transparent PO film is heated and softened, pressurized and shaped with an embossing plate, and fixed by cooling to form a concavo-convex pattern. A known sheet-fed or rotary embossing machine is used. Used. Embossed pattern (uneven shape)
Wood grain board conduit groove, stone board surface unevenness (Hananan rock open face etc.), cloth surface texture, satin, sand grain, hair line,
There is a linear groove. Further, the concave portion of the embossed pattern is filled with a coloring ink by a known wiping method. The colored ink is coated on the concave part of the decorative sheet surface with a roll coat or knife coat, and then scraped off with a doctor blade or wiping paper to remove the colored ink other than the concave part on the decorative sheet surface and color only the concave part. Allow ink to remain. The color tone of the colored ink is preferably the same or similar to a conduit in the case of a wood pattern, for example, and is preferably the same or similar to a crack in the case of a stone pattern.

To impart abrasion resistance, chemical resistance and the like to the surface of the decorative sheet, and to adjust the gloss of the surface, a surface protective layer, that is, an OP layer is provided. Acrylic resin,
Polyurethane resins, epoxy resins, chlorinated polyolefins, ionizing radiation-curable resins and the like are used, but chlorinated polyolefins, two-part curable polyurethanes, and ionizing radiation-curable resins are preferred. As a method for forming the OP layer, a gravure code, a method such as roll coating, knife coating, or an air knife can be used.

As the ionizing radiation-curable resin used in the present invention, a prepolymer having a polymerizable unsaturated bond or a cationic polymerizable functional group in a molecule (including a so-called oligomer) and / or a composition obtained by appropriately mixing a monomer. And those curable by ionizing radiation are used. Here, the ionizing radiation means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or cross-linking a molecule, and usually, an electron beam or an ultraviolet ray is used.

As the ionizing radiation-curable resin, specifically, a radical polymerizable unsaturated group such as a (meth) acryloyl group or a (meth) acryloyloxy group, a cationic polymerizable functional group such as an epoxy group, or the like in a molecule. It consists of monomers, prepolymers and oligomers having two or more thiols. These monomers or prepolymers may be used alone or as a mixture of several types. Here, the (meth) acryloyl group is used in the meaning of an acryloyl group or a methacryloyl group, and the following (meth) is used in the same meaning.

Examples of the prepolymers and oligomers include unsaturated polyesters such as condensates of unsaturated dicarboxylic acids and polyhydric alcohols, polyester methacrylates, and the like.
Examples include methacrylates such as polyether methacrylate, polyol methacrylate, and melamine methacrylate, acrylates such as polyester acrylate, epoxy acrylate, urethane acrylate, polyether acrylate, polyol acrylate, and melamine acrylate, and cationic polymerization type epoxy compounds. A molecular weight of about 250 to 10,000 is usually used. As the polymer having a radical polymerizable unsaturated group, the degree of polymerization of the polymer is 10,000.
Those having a degree or higher are used.

Examples of the prepolymer having a cationically polymerizable functional group include prepolymers of epoxy resins such as bisphenol epoxy resins and novolak epoxy resins, and vinyl ether resins such as aliphatic vinyl ethers and aromatic vinyl ethers. No.

As examples of the monomer having a cationically polymerizable functional group, the above-mentioned prepolymeric monomer having a cationically polymerizable functional group can be used. Examples of the monomer having a thiol group include trimethylolpropane trithioglycolate, trimethylolpropane trithiopropylate, dipentaerythritol tetrathioglycolate, and the like.

Examples of the prepolymer having a radical polymerizable unsaturated group include polyester (meth) acrylate, urethane (meth) acrylate, epoxy (meth)
Acrylate, melamine (meth) acrylate, triazine (meth) acrylate, silicone (meth) acrylate and the like can be used. The molecular weight is 250 to 10
The one of about 000 is used.

Examples of the monofunctional monomer having a radical polymerizable unsaturated group include monofunctional monomers of a (meth) acrylate compound, for example, methyl (meth) acrylate,
Ethylhexyl (meth) acrylate, phenoxyethyl (meth) acrylate and the like can be mentioned.

Examples of the polyfunctional monomer having a radical polymerizable unsaturated group include diethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and trimethylolpropane ethylene oxide. Tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, and the like.

When the resin is cured by ultraviolet light or visible light as the ionizing radiation-curable resin, a photopolymerization initiator is added to the ionizing radiation-curable resin. In the case of a resin having a radical polymerizable unsaturated group, acetophenones, benzophenones, thioxanthones, benzoin, benzoin methyl ether and the like can be used alone or in combination as a photopolymerization initiator. In the case of a resin system having a cationically polymerizable functional group, an aromatic diazonium salt, an aromatic sulfonium salt, an aromatic iodonium salt, a metaceron compound, a benzoin sulfonic acid ester, or the like is used alone or as a mixture as a photopolymerization initiator. be able to.
The addition amount of these photopolymerization initiators is about 0.1 to 10 parts by weight based on 100 parts by weight of the ionizing radiation-curable resin.

Various additives may be added to the ionizing radiation-curable resin as required. As these additives, for example, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, acrylic resin, thermoplastic resin such as cellulose resin, calcium carbonate, barium sulfate, silica,
There are extenders (fillers) composed of fine powders such as alumina, doses, and coloring agents such as pigments.

The coating method of the ionizing radiation curable resin includes gravure coat, gravure reverse coat, gravure offset coat, spinner coat, roll coat, reverse roll coat, kiss coat, dip coat, solid coat by silk screen coat, wire bar coat, Comma coat, spray coat, float coat, pouring coat, brush coating, spray coat, and the like can be used. Among them, a gravure coat is preferable.

As the ionizing radiation irradiating device for curing the ionizing radiation curable resin, an ultraviolet irradiating device or an electron beam irradiating device is used. As the ultraviolet irradiation device, for example, a light source such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, and a metal halide lamp is used. The wavelength of the ultraviolet light is usually 19
The wavelength range from 0 to 380 nm is mainly used. As the electron beam irradiator, various electron beam accelerators such as a Cockloft-Wald type, a Bande graph type, a resonance transformer type, an insulating core transformer type or a linear type, a dynamitron type, and a high frequency type are used.

When irradiating with an electron beam, the acceleration voltage is 100 to 1000 KeV, preferably 100 to 300 KV.
Irradiation at eV, the absorbed dose is usually 1 to 300 k
It is about Gy (kilo gray). If the absorbed dose is less than 1 kGy, curing of the coating film will be insufficient, and
If it exceeds 0 kGy, the cured coating film and substrate will turn yellow or be damaged. In the case of ultraviolet irradiation, the irradiation amount is preferably in the range of 50 to 1000 mJ / cm ² .
When the irradiation amount of ultraviolet rays is less than 50 mJ / cm ² , the curing of the coating film becomes insufficient, and the irradiation amount is 1000 mJ / cm ^2.
If it exceeds 300, the cured coating film will turn yellow. In addition, as a method of irradiating ionizing radiation, first, an ultraviolet ray is irradiated to cure the ionizing radiation-curable resin so that at least the surface is dry to the touch, and thereafter, the coating film is completely cured by irradiating with an electron beam. There is also a way to do this.

Further, as another embodiment of the decorative sheet of the present invention, a decorative sheet whose surface is embossed and wiped can be produced as follows. That is, as shown in FIGS. 7A and 7B, as described above, the printed film 2 in which the picture layer 12 and the adhesive layer 15 are formed on the transparent PO film 13, and the colored acrylic film 11
Then, the printed film 2 and the colored acrylic film 11 are laminated via the adhesive layer 15 of the printed film 2 by a dry lamination method or the like, and a laminated sheet 3 is prepared as shown in FIG. 7C. .

Next, using an embossing roll or embossing plate, heating and pressing are performed so that the transparent PO film 13 of the laminated sheet 4 is in contact with the embossing roll or embossing plate.
As shown in FIG. 7D, an embossed pattern 16 is formed on a transparent PO film 13 to produce an embossed laminated sheet 4. Next, as described above, the embossed concave portion 17 of the embossed pattern 16 is filled with the coloring ink 18 by wiping, and a transparent OP layer 19 is further formed thereon. 7 is formed to improve the adhesiveness of
A decorative sheet 1 as shown in FIG.

The decorative sheet of the present invention can be used for various applications by laminating on various adherends and subjecting it to a predetermined molding process. For example, interior decoration of buildings such as walls, ceilings and floors, surface decoration of fittings such as window frames, doors, and handrails, furniture or light electricity / O
It can be used for surface decoration of cabinets of equipment A, interior of vehicles such as automobiles and trains, interior of aircraft, makeup of window glass, and the like. Therefore, when the decorative sheet cannot be directly bonded to a material or the like, the decorative sheet is bonded to an adherend via an appropriate easy-adhesion layer or an adhesive layer. However, when the decorative sheet can be bonded to the adherend by heat fusion or the like, the easy-adhesion layer or the adhesive layer may be omitted.

The object to be adhered is a plate material such as a flat plate or a curved plate of various materials, a sheet (or film), or various three-dimensionally shaped articles (molded articles). For example, the decorative sheet of the present invention can be bonded to a molded product having a curved surface such as an injection molded product. When a three-dimensional molded product is used as the adherend, a vacuum forming method is often used, but the decorative sheet of the present invention has good adhesiveness to the R portion or the reverse R portion of the three-dimensional molded product, and has a good adhesion. It is possible to perform various surface makeup. Further, even on a surface having irregularities, the concave portion is narrowed down and the narrowed portion does not return due to heating, so that a more excellent irregular surface can be formed on the decorative sheet.

As a material to be used as an adherend, either a plate material or a sheet (film), a wood veneer,
Wood plywood, particle board, medium density fiberboard (MD
F), such as wood board, woody board such as wood fiber board, metal such as iron and aluminum, acrylic, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate, polyester, polystyrene, polyolefin, ABS,
Phenolic resin, polyvinyl chloride, cellulosic resin,
Resins such as rubber are exemplified.

As a method of laminating these various adherends,
For example, the following methods can be mentioned. That is, a method of laminating a plate-shaped substrate by pressing with a pressure roller via an adhesive layer therebetween, Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27.
No. 488, etc., a decorative sheet is inserted between the male and female molds for injection molding, the molds are closed, the molten resin is injected and filled from the male gate, and then cooled and the resin is cooled. A so-called simultaneous injection molding laminating method in which a decorative sheet is adhered and laminated on the surface of a molded article at the same time as molding, Japanese Patent Publication No. 56-45768, Japanese Patent Publication No. 60-58.
No. 014, etc., a decorative sheet is placed on the surface of a molded article facing or opposite to the molded article via an adhesive, and the decorative sheet is placed on the surface of the molded article by a pressure difference due to vacuum suction from the molded article side. Lamination, so-called vacuum press lamination method, JP-B-61-5895, JP-B-3-2666
As described in Japanese Patent Application Publication No. 2000-205, the columnar base material such as a cylinder, a polygonal column, and the like, while supplying a decorative sheet through an adhesive layer between the column, a plurality of rollers having different directions, the columnar body. A so-called lapping method in which decorative sheets are sequentially adhered to a plurality of side surfaces constituting the sheet by laminating under pressure, a so-called lapping method, Japanese Utility Model Publication No. 15-31122, Japanese Unexamined Patent Publication No. 48-47.
No. 972, etc., a decorative sheet is first laminated on a plate-like base material via an adhesive layer, and then the decorative sheet and the plate-like material are placed on the surface of the plate-like base material opposite to the decorative sheet. Cut a V-shaped or U-shaped groove reaching the interface with the base material, then apply an adhesive in the groove, and then bend the groove to form a box or columnar body A so-called V-cut or U-cut processing method may be used.

In particular, as a method of bonding the decorative sheet of the present invention to a three-dimensional object having irregularities, a lapping method, a V-cut method, a simultaneous injection molding laminating method, a vacuum press laminating method and the like are preferable. .

[0064]

The present invention will be described below in more detail with reference to examples. (Example 1) A resin prepared by blending isotactic polypropylene and atactic polypropylene in a ratio of 1: 1 was mixed with a benzotriazole-based ultraviolet absorber at 3000 p.
pm, using a blend resin (manufactured by Mitsubishi Chemical Corporation) to which 5000 ppm of a hindered amine-based radical scavenger is added as a light stabilizer, using a calender method to have a thickness of 100 μm.
m transparent soft polypropylene film (hereinafter referred to as soft PP
Film 13a) was produced. A gravure ink (manufactured by Showa Ink Industry Co., Ltd.) using an acrylic urethane resin as a binder on the back surface of the soft PP film 13a.
The gravure printing of the wood pattern was carried out by using, and a pattern layer 12 was formed as shown in FIG. In addition, a thickness 80 of polymethyl methacrylate
A μm opaque colored acrylic film (manufactured by Kyowa Leather Co., Ltd.) was prepared and used as a colored acrylic film 11 as shown in FIG. The colored acrylic film used had a shrinkage ratio during heating shown below of 18% in the vertical direction and -5% in the horizontal direction.

(Shrinkage Test During Heating) A colored acrylic film was cut into a size of 120 mm × 120 mm, and a mark of 100 mm in length was written in the center of the test piece by a ballpoint pen so as to be perpendicular. This test piece was placed on a mount, heated in an oven at 100 ° C. for 30 minutes, taken out and allowed to stand at room temperature. After the test piece cooled to room temperature, the length of the marked line was measured, and the following equation was obtained. Was calculated according to the following equation. S = (L1−L2) / L1 × 100 S: Shrinkage rate (%) L1: Length of marked line before heating (mm) L2: Length of marked line after heating (mm) That is, −5% above Indicates that elongation was 5% by heating.

Next, as shown in FIG. 8C, the printing film 2 and the colored acrylic film 11 are overlapped,
The printing film 2 and the colored acrylic film 11 are heated and pressurized and heat-sealed by a doubling embossing method using an embossing plate, and an embossed pattern 16 is formed on a transparent soft PP film. As shown, an embossed laminated sheet 4 was produced. Next, a two-part curable wiping ink (manufactured by Showa Ink Industries, Ltd.) is applied to the transparent soft PP film 13a on which the embossed pattern 16 is formed by wiping, and the embossed pattern is formed as shown in FIG. The concave portion 17 is filled with a coloring ink 18, and a two-part curing type transparent paint is further coated thereon to form a transparent OP layer 19, and a urethane-based primer (Showa Ink Kogyo Co., Ltd. stock)
8) to form a primer layer 14,
A decorative sheet 1 as shown in (e) was produced.

(Example 2) Using the same blended resin of isotactic polypropylene and atactic polypropylene as in Example 1, a thickness of 60 μm was obtained by a calender method.
To produce a transparent soft PP film 13a of
On the back surface of the P film 13a, as shown in FIG.
After applying a urethane-based primer solution (manufactured by Showa Ink Industry Co., Ltd.) to form a primer layer 14, similarly to Example 1, a wood pattern is gravure-printed to form a picture layer 12, and further thereon, An adhesive layer 15 was formed using a primer layer 14 and a two-component curable urethane-based adhesive to produce a printed film 2. In addition, as in Example 1, the thickness was 80 μm.
An opaque colored acrylic film (manufactured by Kyowa Leather Co., Ltd.) was prepared to form a colored acrylic film 11 as shown in FIG. 9B. The shrinkage ratio of the colored acrylic film used during heating was 17% in the vertical direction and 5% in the horizontal direction.

Next, the printed film 2 and the colored acrylic film 11 were laminated by a dry lamination method to produce a laminated sheet 3 as shown in FIG. 9C. Next, an embossed pattern 1 was formed on the transparent soft PP film 13a of the laminated sheet 3 using an embossing roll.
6 to form an embossed laminated sheet 4. Furthermore,
In the same manner as in Example 1, the embossed concave portion 17 of the embossed laminated sheet 4 is filled with the coloring ink 18 by wiping, a transparent OP layer 19 is formed thereon, and the primer layer 14 is formed on the colored acrylic film 11 on the back surface. The decorative sheet 1 was formed as shown in FIG.

Comparative Example 1 As a surface film, a transparent biaxially stretched isotactic polypropylene film (thickness: 100 μm) having a draw ratio of 3 times, and a base film,
A decorative sheet was prepared in the same manner as in Example 1 using a colored opaque biaxially stretched isotactic polypropylene film (thickness: 80 μm) having a stretch ratio of 3 times. The shrinkage of the base film during heating was 30% in the vertical direction and 20% in the horizontal direction. Comparative Example 2 A decorative sheet was produced in the same manner as in Example 2, except that the same film as in Comparative Example 1 was used as the surface film and the base film. The shrinkage ratio of the base film during heating was 25% in the vertical direction and 15% in the horizontal direction.

(Performance Test) Examples 1 and 2 and Comparative Example 1,
The following tests were performed on the decorative sheets prepared in 2, and their performances were compared.

(Vacuum forming suitability test) As shown in FIG. 10 (a), the size was 100 mm × 100 mm and the thickness was 30 mm.
A groove having a depth of 5 mm and an angle of 90 ° is formed on the central surface of the rawan plywood, and a decorative sheet 1 coated with an adhesive is placed on the plywood 20 having the groove formed thereon, and the decorative sheet 1 is formed by vacuum forming. Was adhered to the plywood 20. The plywood to which the decorative sheet was adhered was taken out, and the surface and cross section were visually observed.
As shown in FIG. 10B, it was determined that the decorative sheet was neatly inserted into the groove of the plywood as を, and as shown in FIG. 10C, the decorative sheet was floating from the groove as X.

(Cold Heat Repeat Test) A plywood bonded with a decorative sheet prepared by the above vacuum forming method was used as a sample, and this sample was placed in an oven at 80 ± 3 ° C. for 2 hours, and then -20 ± 3.
2 hours in a freezer at 80 ° C. and 2 hours again in an oven at 80 ± 3 ° C. After repeating this 10 times,
The surface and cross section of the sample were visually observed, and FIG.
As shown in FIG. 10, it was determined that the decorative sheet was inserted into the groove as ○, and as shown in FIG. 10C, the decorative sheet was floating from the groove as x.

(V-cut processing suitability test) After the decorative sheet was bonded to a 10 mm-thick Lauan plywood using an adhesive,
As shown in FIG. 11 (a), a V-shaped groove 21 is cut into the rawan plywood 20 on the opposite side of the decorative sheet so as to reach the interface between the rawan plywood and the adhesive layer. After the adhesive is applied to the groove, as shown in FIG. 11B, the plywood is bent and bonded in an L-shape (cross section) so as to close the groove, and the bent portion is whitened, cracked, etc. Was visually observed. The ambient temperature during processing was set at 10 ° C.

Table 1 shows the results of the above performance tests of the decorative sheets prepared in Examples 1 and 2 and Comparative Examples 1 and 2.

[0075]

[Table 1]

As can be seen from the results in Table 1, Example 1,
The base film (colored acrylic film) used for the decorative sheet prepared in Step 2 has little shrinkage during heating,
0-20% in vertical direction, -10+ in horizontal direction
It was in the range of 10%. On the other hand, in the case of the base film used in Comparative Example 1, the length was 30% and the width was 20%, and in the case of the base film used in Comparative Example 2, it was 25% and the width was 1%.
5%, and the shrinkage rate was large in each case.

As described above, in the case of the comparative example, since the heat shrinkage was large, the decorative sheet was lifted in the repeated cold test, and was not satisfactory as a decorative sheet. On the other hand, the decorative sheets produced in Examples 1 and 2 did not float even in the repeated cold / hot test, and were satisfactory as decorative sheets. Also in the vacuum forming test, it can be expected that the groove can be sufficiently inserted into the groove and that it can be used for surface decoration of a three-dimensional molded article having an uneven shape. Further, good results were obtained in the V-cut processing suitability test, and it can be expected that the composition can be used in cold regions.

[0078]

The decorative sheet of the present invention uses an acrylic resin for the base sheet and a soft polypropylene mixed with isotactic polypropylene and atactic polypropylene as the surface layer. Even in the case of treatment, there is no risk of generating harmful gases such as hydrochloric acid gas and dioxin. Further, the decorative sheet of the present invention uses an acrylic resin film having a low heat shrinkage rate as a base sheet, and a soft polypropylene of a mixed system of isotactic polypropylene and atactic polypropylene as a surface film. When used for surface decoration of a three-dimensional molded product having an irregular shape by vacuum molding, it has excellent moldability, and it can easily enter recesses and can provide excellent surface decoration.

Further, since the decorative sheet of the present invention has a small heat shrinkage upon heating, when used for surface decoration of a three-dimensional molded article having a concave-convex shape, even if heating and cooling are repeated, the concave part of the three-dimensional molded article remains. No floating phenomenon of the entered decorative sheet is observed, and no return is observed in the surface irregularities. That is, the decorative sheet of the present invention has excellent weather resistance. Also,
The decorative sheet of the present invention has good suitability for V-cut processing, and the decorative sheet may be cracked even when bent.
Since whitening does not occur, it is excellent in workability. Further, since the decorative sheet of the present invention can be subjected to embossing and wiping, it is possible to impart design properties equivalent to those of a decorative sheet using a conventional polyvinyl chloride resin.

[Brief description of the drawings]

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

FIG. 2 shows another embodiment of the decorative sheet according to the present invention, wherein the transparent PO
It is a schematic cross-sectional view when a film and a colored acrylic film are laminated with an adhesive, a transparent PO film on the front surface is embossed and wiped, and a primer layer is formed on the back surface.

FIG. 3 shows still another embodiment of the decorative sheet of the present invention, wherein transparent P
It is a schematic cross-sectional view when an O film and a colored acrylic film are laminated by a heat fusion method, a transparent PO film on the front surface is embossed and wiped, and a primer layer is formed on the back surface.

FIG. 4 is an explanatory diagram when a decorative sheet of the present invention is produced by heat fusion.

FIG. 5 is an explanatory view when the decorative sheet of the present invention is produced using an adhesive.

FIG. 6 is an explanatory diagram when a decorative sheet having a surface subjected to embossing and wiping is produced by heat fusion.

FIG. 7 is an explanatory diagram when a decorative sheet having a surface subjected to embossing and wiping is produced using an adhesive.

FIG. 8 is an explanatory diagram when a decorative sheet of the present invention is manufactured according to Example 1.

FIG. 9 is an explanatory diagram when a decorative sheet of the present invention is produced according to Example 2.

FIG. 10 is an explanatory diagram when judging the quality of a decorative sheet by a vacuum forming suitability test.

FIG. 11 is an explanatory diagram when a V-cut processing suitability test of a decorative sheet is performed.

[Description of Signs] 1 decorative sheet 2 printed film 3 laminated sheet 4 embossed laminated sheet 11 colored acrylic film 12 picture layer 13 transparent PO film 13a soft PP film 14 primer layer 15 adhesive layer 16 embossed pattern 17 embossed recess 18 colored ink 19 Transparent OP layer 20 Plywood 21 V-shaped groove

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 4F100 AH03H AK03A AK07A AK07K AK25C AK51 AL05A AR00D BA03 BA04 BA07 BA10A BA10C BA10D CA05 CA07 CA13C DD20D EC03 EC18 EJ39A EJ65C EK06 GB08 GB31 J01 J33 JB01L YY00C

Claims (6)

[Claims] 1. A transparent polyolefin resin film,
A decorative sheet comprising a pattern layer and a colored acrylic resin film laminated in this order. 2. The transparent polyolefin resin film according to claim 1, wherein the transparent polyolefin resin film is a colorless or colored transparent soft polypropylene resin having a composite three-dimensional structure composed of a mixture of isotactic polypropylene and atactic polypropylene. A decorative sheet according to claim 1. 3. The decorative sheet according to claim 1, wherein the transparent polyolefin resin film and the colored acrylic resin film are laminated by a heat fusion method or a dry lamination method. 4. The embossed pattern is formed on the surface of the decorative sheet, a wiping process is performed on the embossed pattern, and an overprint layer is formed thereon. A decorative sheet according to any of the claims. 5. The decorative sheet according to claim 1, wherein a primer layer is formed on a back surface of the decorative sheet. 6. The shrinkage ratio of the acrylic resin film of the decorative sheet by heating at 100 ° C. for 30 minutes is 0 to 20% in the vertical direction and −10 to + 10% in the horizontal direction. The decorative sheet according to any one of claims 1 to 5.