JPH1067081A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a decorative sheet with high fabricability in terms of bending and application to a complicated shape by providing a polyolefin film with specific physical properties as a forming layer. SOLUTION: This decorative sheet consists of a base material film layer 1, a printed layer 2 and a transparent coated film layer 3. These base material film layer 1 and/or transparent coated film layer 3 is formed of polyolefin film which shows a tensile modulus of 300-2000MPa in the film flow direction (MD direction) and an orthogonal direction (TD direction) to the film flow direction (MD direction) and a tensile break elongation of 30-500% in both MD and TD directions, and further, having no yield point at least in one direction.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a novel decorative sheet containing a specific polyolefin film as a constituent layer. Specifically, the decorative sheet is excellent in secondary workability.

[0002]

2. Description of the Related Art Conventionally, decorative sheets have been widely used as interior building components. Because the films that make up these decorative sheets require weather resistance and stain resistance,
Polyvinyl chloride films have been mainly used.

However, in recent years, it has been pointed out that various organic substances such as a plasticizer contained in a polyvinyl chloride film, and substances such as hydrogen chloride gas generated when the film is incinerated have an adverse effect on the environment. . Therefore, Japanese Patent Application Laid-Open Nos. Hei 6-16832 and Hei 8-34105 disclose a novel decorative sheet replacing the decorative sheet having the polyvinyl chloride film as a constituent layer. There has been proposed a decorative sheet in place of a base resin.

[0004] However, the decorative sheet having a polyolefin-based film as a constituent layer proposed in the above publication cannot sufficiently satisfy the properties as a decorative sheet. For example, a decorative sheet using a polyolefin-based film described in JP-A-8-34105 as a constituent layer can be used by being stretched when pasting on a support such as wood, or subjected to secondary molding such as vacuum forming. When processing, the stress decreases near the yield point,
Necking is likely to occur and the appearance is likely to be poor, and there has been a problem particularly in the ease of secondary processing into a complicated shape. Further, a film using a film using a low-crystalline elastomer or the like described in JP-A-6-16832 as a constituent layer,
Even if the occurrence of necking can be reduced, the film becomes soft, so that there is a problem that poor appearance is likely to occur during secondary processing.

[0005]

SUMMARY OF THE INVENTION Accordingly, it is an object of the present invention to provide a decorative sheet having good secondary workability such as bending and attaching to a complicated shape.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above problems, and as a result, the above object has been achieved by a decorative sheet having a polyolefin film having specific physical properties as a constituent layer. The inventors have found that the present invention can be performed, and have completed the present invention.

That is, according to the present invention, the tensile modulus is 300 to 2000 MPa in both the film flow direction (hereinafter referred to as MD direction) and the direction perpendicular to the film flow direction (hereinafter referred to as TD direction). , Tensile elongation at break is M
A decorative sheet comprising, as a constituent layer, a polyolefin-based film having a yield point of at least one direction in 30 to 500% in both the D direction and the TD direction.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION As a raw material for a polyolefin film used in the decorative sheet of the present invention, a known polyolefin can be used without any particular limitation. Among them, a crystalline polyolefin is preferable, and a crystalline polyolefin having a crystallinity of 5% or more, more preferably 20% or more, and still more preferably 30% or more is suitable. When the crystallinity of the polyolefin is lower than 5%, the modulus of elasticity of the film becomes low and the obtained decorative sheet becomes too soft. Is likely to occur, which is not preferable. Examples of the polyolefin include α-olefin homopolymers such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 4-methyl-1-pentene, and random or block copolymers of the α-olefins. And a copolymer of an α-olefin with a monomer other than the α-olefin copolymerizable with the α-olefin, or a mixture of these polymers. Among them, considering the above crystallinity, propylene homopolymer, propylene-ethylene random copolymer having a monomer unit based on ethylene of 20 mol% or less, polypropylene component and propylene-ethylene random copolymer component are used. Block copolymers containing less than 40 mol% of monomer units based on ethylene are preferred.

Here, examples of the monomer other than the α-olefin include vinyl acetate, maleic acid, vinyl alcohol, methacrylic acid, methyl methacrylate, and ethyl methacrylate. Further, in the polyolefin, the proportion of monomers other than α-olefin is as follows:
In consideration of the effects of the present invention, the content is preferably 10 mol% or less.

As the method for producing the above-mentioned polyolefin, any known method can be used without any limitation. For example, the above-mentioned monomer can be produced using a known polymerization catalyst for polyolefin such as TiCl ₃ , supported TiCl ₃ , and a metallocene catalyst. Is polymerized. Further, a method of decomposing with a peroxide or the like after polymerization using the above catalyst may be performed.

The above-mentioned polyolefin includes known additives, antioxidants, heat stabilizers, light stabilizers, ultraviolet absorbers, antistatic agents, dispersants, chlorine scavengers, flame retardants, crystallization nucleating agents, Anti-blocking agents, slip agents, release agents, pigments, organic fillers, inorganic fillers, neutralizers, lubricants, decomposers, metal deactivators, antifouling agents, antibacterial agents, etc., do not impair the effects of the invention. It can be added in a range. Examples of these additives include phenol-based antioxidants, organic phosphorus-based organic phosphites and phosphites, thioethers and the like, hindered amine-based heat stabilizers, and benzophenone-based ultraviolet absorbers. , Benzotriazole, benzoate, etc., nonionic, cationic, anionic, etc. as an antistatic agent, bisamide, wax, organic metal salt, etc. as a dispersing agent,
Examples of the chlorine scavenger include alkaline earth metal salts and carboxylate salts, and examples of the flame retardant include phosphoric acid, antimony trioxide, magnesium hydroxide, and red phosphorus. As the crystallization nucleating agent, aluminum benzoate, potassium benzoate, sodium benzoate, lithium benzoate, Al-p
Carboxylic acid metal salt compounds such as -butylbenzoate, sodium β-naphthoate, sodium cyclohexanecarboxylate and sodium cyclopentanecarboxylate; sodium bis (4-t-butylphenyl) phosphate, bis (4-t-butyl) Phenyl) lithium phosphate, aluminum bis (4-t-butylphenyl) phosphate, calcium bis (4-t-butylphenyl) phosphate, magnesium bis (4-t-butylphenyl) phosphate,
Sodium 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, lithium 2,2′-methylene-bis (4,6-di-t-butylphenyl) phosphate, Aluminum 2,2'-methylene-bis (4,6-di-t-butylphenyl) phosphate, calcium 2,2'-methylidene-bis (4,6-di-t-butylphenyl) phosphate, 2, 2'-methylidene-bis (4,6-
Di-t-butylphenyl) phosphate magnesium salt, 2,
Sodium 2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, lithium 2,2'-ethylidene-bis (4,6-di-t-butylphenyl) phosphate, 2, 2'-ethylidene-bis (4,6-di-t-butylphenyl) aluminum phosphate, bis- (4-t
-Butylphenyl) phosphate calcium salt, bis- (4-
metal salts of aromatic phosphates such as t-butylphenyl) magnesium phosphate; dibenzylidene sorbitol;
1.3,2.4-di (methylbenzylidene) sorbitol, 1.3,2.4-di (ethylbenzylidene) sorbitol, 1.3,2.4-di (butylbenzylidene) sorbitol, 1.3,2 Di-, such as .4-di (methoxybenzylidene) sorbitol, 1.3,2.4-di (ethoxybenzylidene) sorbitol, 1.3-chlorobenzylidene, 2.4-methylbenzylidenesorbitol, mono (methyl) dibenzylidenesorbitol, etc. Benzylidene sorbitol compounds; inorganic compounds such as silica, titanium dioxide, carbon black, talc, mica, alum, pigments and the like. Among them, Al-p-butylbenzoate, 2,2'-methylene-bis (4,6
-Di-t-butylphenyl) phosphate metal salt, 1.3,
2.4-Di (methylbenzylidene) sorbitol is most preferred. Examples of the antiblocking agent include silica, natural zeolite, synthetic zeolite, kaolin, talc, silicone resin, silicone rubber, fused silica, melamine resin, acrylic resin, fine particles such as hadtaltalcite, among which softer than the above polyolefin Rubber-based materials are preferred. The shape of the anti-blocking agent is preferably spherical. As the slipping agent, a higher fatty acid amide is preferable, but it is not preferable to add a large amount of the slipping agent because the film may be whitened and the transparency may be reduced. Further, it is preferable to add an appropriate amount of an antistatic agent because generation of static electricity can be suppressed.

The decorative sheet of the present invention can provide a decorative sheet having good secondary workability by using a polyolefin film having the following characteristics as a constituent layer. That is, the tensile elastic modulus of the polyolefin-based film is 300 to 2000 M in both the MD and TD directions.
It is necessary to be Pa, and 500 to 1500 MPa
Is more preferable. Tensile modulus is 300MPa
If the size is smaller than that, the resulting decorative sheet becomes too soft, and it is not preferable because the appearance is likely to be poor due to generation of wrinkles or the like when affixed to a support. On the other hand, when the tensile elastic modulus is more than 2000 MPa, the decorative sheet is insufficient in flexibility, and is likely to cause poor appearance such as wrinkles due to reduced adhesion to the support, which is not preferable. In the present invention, the tensile modulus refers to JIS-K
It is a value calculated from a tensile stress-strain curve measured at a tensile speed of 20 mm / min according to 7113.

The tensile elongation at break of the polyolefin film must be 30 to 500% in both the MD and TD directions, preferably 100 to 500%, and more preferably 150 to 500%. When the tensile elongation at break is less than 30%, the tensile elongation at break of the obtained decorative sheet is also insufficient, and the sheet hardly stretches along the shape of the support at the time of secondary processing such as attaching to a support. This is not preferable because the film is easily broken or poor adhesion to the support is likely to occur. If the tensile elongation at break is more than 500%, the sheet is locally stretched when the resulting decorative sheet is attached to a support, and this is not preferable because the appearance tends to be poor. In the present invention, the tensile elongation at break refers to a tensile speed of 300 mm / according to JIS-K7113.
It is the value of elongation at break measured in min.

Further, a polyolefin-based film is
When a tensile test according to S-K7113 is performed, it is necessary that the material does not have a yield point in at least one direction.
More preferably, neither the D direction nor the TD direction has a yield point. A decorative sheet using a film having a yield point in both directions is not preferable because the sheet is likely to neck when a bending process such as a V-cut process is performed, thereby causing poor appearance. In the present invention, the presence or absence of a yield point is determined according to JIS-K7113 by a tensile speed of 300 mm /
It is measured from the tensile stress-strain curve measured in min.

The polyolefin-based film used in the present invention is not limited to a single-layer film, but may be a laminated film in which two or more layers are laminated. In this case, as long as the effects of the present invention are not impaired, resins having different properties may be combined according to the required performance. For example, a layer of a block copolymer containing a polypropylene component having excellent flexibility and a propylene-ethylene random copolymer component, or a layer of a mixture of this block copolymer and polypropylene, and polypropylene alone having excellent mechanical performance A laminated film composed of a polymer or a layer of a propylene-ethylene random copolymer is exemplified.

In the present invention, the above-mentioned film may be produced by a method which satisfies the above-mentioned properties, but a typical method is exemplified by a method of melt-extruding a polyolefin and a method of stretching after melt-extrusion. And the like. In order to satisfy the above characteristics,
A method of stretching after melt extrusion is preferred. Examples of the stretching method include a vertical or horizontal uniaxial stretching method, a vertical and horizontal sequential biaxial stretching method, a simultaneous biaxial stretching method, a rolling method, a method of continuously stretching a sheet formed by calendering in at least one direction, and the like. However, in consideration of the balance of physical properties in the MD direction and the TD direction, and the accuracy of thickness and thickness, a longitudinal and horizontal sequential biaxial stretching method is preferable.

In the case where the above-mentioned film is a laminated film, the method of producing the laminated film is a method of co-extrusion of the resin constituting each layer and thereafter uniaxially or biaxially stretching, or a method of melt-extruding one layer of the resin and uniaxially stretching. A method in which the resin of the other layer is melt-extruded and stretched in a direction substantially perpendicular to the direction of the uniaxial stretching.

Further, it is preferable to relax the film after the stretching at a temperature slightly higher than the stretching temperature, since low heat shrinkage can be imparted.

As the stretching conditions in the above stretching method, the area stretching ratio is preferably 1.1 to 30 times. Especially,
In order to impart appropriate rigidity, flexibility and elongation, stretching at an area stretching ratio of 4 to 25 times is more preferred. When the area stretching ratio is lower than 1.1, the decorative sheet obtained has a low tensile modulus, and even if necking occurs or necking does not occur, the decorative sheet becomes too soft. It stretches and is not preferred for this application. When the area stretching ratio exceeds 30 times, the tensile strength of the obtained decorative sheet increases, and the tensile elongation decreases, so that when performing secondary processing, the sheet is likely to have poor appearance such as tearing. Not preferred.

The stretching ratio in each of the MD and TD directions is appropriately selected in the range of 1.1 to 10 times so that there is no yield point in at least one direction. Among them, in particular, in order to balance physical properties in the MD and TD directions, impart flexibility and elasticity, and further impart elongation, MD
In both the TD and TD directions, stretching by 2 to 6 times is preferable, and 3 to 5 times is more preferable.

The structure of the decorative sheet of the present invention is not particularly limited as long as the structure contains the polyolefin film as a constituent layer.

In general, a decorative sheet generally has, for example, a structure including a base film layer and a printing layer, and a structure including a base film layer 1, a printing layer 2, and a transparent covering film layer 3 as shown in FIG. It is a target.

In the decorative sheet of the present invention, the polyolefin-based film is suitably used as the base film layer and / or the transparent coating film layer having the above-mentioned structure.

As shown in FIG. 1, in the decorative sheet of the present invention, in addition to the above basic structure, other known structures are employed without any particular limitation. For example, a wiping coating 4 and a surface protection layer 5 can be provided.

A typical example of such a wiping coating method is as follows. A transparent coating film layer is bonded to the printed layer of a base film layer having a printed layer such as woodgrain by hot lamination or dry lamination. Performing a conduit embossing on the surface of the transparent coating film layer,
After inserting the coloring ink into the conduit portion, a method of wiping it off may be used. The transparent protective layer is formed by coating a transparent member such as urethane or polyolefin by a known method.

In the present invention, the thicknesses of the substrate film layer and the transparent covering film layer are not particularly limited, but are preferably 50 to 200 μm.

In the present invention, the polyolefin-based film constituting the base film layer may be colored, and pigments used in this case may be appropriately used as long as the effects of the present invention are not impaired, such as organic and inorganic pigments. it can.

The decorative sheet of the present invention generally has a printed layer on the substrate film layer, but the printed layer can be omitted if necessary.

The polyolefin film constituting the transparent coating film layer can be appropriately colored, and a printing layer can be further formed on the surface of the transparent coating film layer.

Further, the polyolefin-based film constituting the base film layer and / or the transparent coating film layer is
Because printing and / or adhesive may be applied,
The surface may be subjected to a corona treatment, a plasma treatment, a primer treatment, or the like as long as the effect of the invention is not impaired, or an adhesive resin may be present on the surface layer by lamination or coextrusion. The primers described above are not particularly limited, and for example, chlorinated polyolefins and the like can be used.

In the present invention, any method for forming a decorative sheet using a polyolefin film may be used. To give an example, after performing printing such as woodgrain on the unstretched polyolefin-based film constituting the base film layer, laminating the base film layer and the transparent covering film layer composed of the polyolefin-based film of the present invention under heat Alternatively, there is a method in which the surfaces of the transparent coating film layer are embossed with a conduit by laminating by a method such as dry lamination with an adhesive.

The adhesive used at this time can be any adhesive as long as it does not impair the appearance of the base film layer and the transparent covering film layer and can be securely bonded, and further does not impair the effects of the present invention. There is no problem with using. Examples of the adhesive include thermosetting resin adhesives such as epoxy resin and silicone resin, polyvinyl ether,
Examples include thermoplastic resin adhesives such as acrylic resins, vinyl acetate-ethylene copolymers, and polyamide resins, rubber-based adhesives such as nitrile rubber, and hot melt agents.

Further, a wiping coating may be applied in which the colored ink is inserted into the embossed conduit and wiped off, and a transparent protective layer such as urethane or various thermosetting or photo-curing emulsions may be applied on the surface. In the method of coating, the method of laminating olefin-based films by thermal bonding, the method of extrusion laminating polyolefin, etc.
A surface protective layer may be provided.

The decorative sheet thus formed is
It can be used for known applications without any particular limitation. For example, plywood,
For steel plate, aluminum plate, particle board, MDF (medium fiber board), inorganic board (gypsum board, etc.), concrete wall, resin board, foam, heat insulator, and support for these hybrids and mixtures The decorative sheet can be attached to the decorative sheet via an adhesive to form a decorative plate.

Examples of the method of sticking to the support include flat sticking, lapping, V-cutting, vacuum forming, and the like. The flat sticking includes hand sticking, press sticking, roller sticking, and roller sticking. Lamination by press and the like can be mentioned. Also, there is no problem even if it is stuck to the support using other methods.

The adhesive used when attaching the decorative sheet and the support is not particularly limited,
For example, thermosetting resin adhesives such as epoxy resin and silicone resin, thermoplastic resin adhesives such as polyvinyl ether, acrylic resin, vinyl acetate-ethylene copolymer and polyamide resin, rubber adhesives such as nitrile rubber, hot And a melt agent.

The application of the decorative board obtained in this manner is not particularly limited, but includes a TV cabinet, a stereo speaker box, a video cabinet, various storage furniture,
Home appliances and furniture products such as unit furniture, doors, door frames,
Housing materials such as window frames, rims, baseboards, opening frames, etc., furniture materials such as kitchens, storage furniture doors, flooring materials, ceiling materials, wallpaper and other building materials, automotive interior materials, home appliances, stationery, office supplies It can be suitably used for such purposes.

[0038]

The decorative sheet of the present invention has no necking, moderate flexibility and tensile elongation by using a specific polyolefin film as a constituent layer such as a base film layer and / or a transparent covering film layer. Gives a polyolefin-based decorative sheet excellent in secondary workability.

[0039]

EXAMPLES The present invention will be described below with reference to examples and comparative examples, but the present invention is not limited to these examples. The physical properties of the films in the following examples and comparative examples were measured by the following methods.

(1) Crystallinity A powder or pellet resin is heated at 230 ° C. for 5 minutes, pressed between glass plates having an interval of 1 mm and a thickness of 1 mm, and pressed into a sheet. The sheet was left in the environment for 48 hours to obtain a sheet. Next, the obtained sheet was cut into a size of 20 mm in length × 20 mm in width to prepare a test piece for measurement.

In the measurement, the test piece was mounted on a rotating sample table in a transmission method, and while being rotated at a high speed about an axis perpendicular to the sheet surface, X-rays were incident from a direction perpendicular to the sheet surface to reduce the diffraction intensity. It was measured.

The degree of crystallinity was determined by separating the obtained X-ray diffraction intensity curve into an amorphous peak and each crystalline peak, and from the peak area of each peak by the following formula. The peak separation was performed by a general peak separation method using a Gaussian function and a Lorentz function after removing a background due to air scattering or the like in a diffraction angle (2θ) range of 9 to 31 °.

[0043] The crystallinity was measured using an X-ray diffractometer JDX-3500 manufactured by JEOL Ltd. under the following conditions.

Target: copper (Cu-Kα ray) Tube voltage-tube voltage: 40 Kv-400 mA X-ray incidence method: vertical beam transmission method Monochromatization: graphite monochromator Coloring slit: 0.2 mm Light receiving slit: 0.4 mm Detector : Scintillation counter Measurement angle range: 9.0 to 31.0 ° Step angle: 0.04 ° Counting time: 4.0 seconds Sample rotation speed: 120 rotations / min (2) Tensile modulus According to JIS-K7113 Was measured by the following method.

10 mm wide and 100 mm long from the film
Was cut out, and both ends of the sample were fixed with chucks of a tensile strength measuring machine (Autograph: manufactured by Shimadzu Corporation). In this case, the chuck gap in the longitudinal direction of the sample is 2
It was adjusted to be 0 mm. Tensile speed 20mm / mi
n, a tensile test was performed to create a tensile stress-strain curve.

The tensile modulus was calculated by the following equation using the first straight part of the tensile stress-strain curve.

Em = Δδ / Δε Em: Tensile modulus Δδ: Stress difference due to the original average cross-sectional area between two points on the straight line Δε: Difference in strain between the same two points It was measured.

(3) Tensile elongation at break Measured by the following method according to JIS-K7113.

10 mm wide and 100 mm long from film
Was cut out, and both ends of the sample were fixed with chucks of a tensile strength measuring machine (Autograph; manufactured by Shimadzu Corporation). In this case, the chuck gap in the longitudinal direction of the sample is 2
It was adjusted to be 0 mm. Tension speed 300mm / m
The tensile test was performed in, and the distance between the chucks at the time of breaking was calculated by the following equation.

L = ((L−L ₀ ) / L ₀ ) × 100 1: tensile elongation at break L: distance between chucks at break L ₀ : distance between original chucks (4) Yield point According to JIS-K7113 Was measured by the following method.

From the film, width 10 mm, length 100 mm
Was cut out, and both ends of the sample were fixed with chucks of a tensile strength measuring machine (Autograph; manufactured by Shimadzu Corporation). In this case, the chuck gap in the longitudinal direction of the sample is 2
It was adjusted to be 0 mm. Tension speed 300mm / m
The tensile test was performed in, and a tensile stress-strain curve was created. The presence or absence of a yield point was confirmed from the change in the tensile stress in the vicinity after the elastic deformation.

(5) Secondary workability Necking The obtained decorative sheet is 100 mm wide and 200 mm long.
The sample was cut out and affixed to the surface of the wooden substrate shown in FIG. 2A with a double-sided tape, and then the substrate was bent at a right angle under an atmosphere of 23 ° C. Thereafter, the decorative sheet was peeled off from the base, and the film thickness t of the folded portion and the thickness t ₀ of the decorative sheet of the unfolded portion were measured.
The ratio of t ₀ was calculated.

Wrinkles and cracks The resulting decorative sheet was attached to a 500 μm thick polypropylene sheet, and the sheet was 160 mm × 100 m thick.
Perform vacuum pressure air molding with a dish-shaped mold of mx 30 mm in depth,
Evaluation was made as to whether wrinkles or cracks occurred in the attached film.

Examples 1 to 4 Ethylene content 2.2% by weight, melt index 2.
To 100 parts by weight of an ethylene-propylene copolymer having a crystallinity of 54% and 2 g / 10 min, tetrakis [methylene (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] methane is used as an antioxidant. 2 parts by weight, 0.1 part by weight of glycerin monostearate and 0.1% by weight of N, N'-bis (2-hydroxyethyl) stearylamine as antistatic agents, erucamide: 0.0
1 part by weight, calcium stearate: 0.04 part by weight,
Raw material A was prepared by adding and melting and kneading 0.1 parts by weight of PMMA particles having an average particle diameter of 0.2 μm. On the other hand, a block copolymer containing a polypropylene component and a propylene-ethylene random copolymer component, wherein the polypropylene component is 10% by weight, the ethylene content is 15%, and the propylene-ethylene random copolymer component having an ethylene content is 90% by weight; Melt index 1.5g / 10min, Crystallinity 31%
A raw material B was obtained by adding the above additives to the propylene-ethylene block copolymer and melt-kneading the mixture. The raw material A was used as the raw material for both outer layers, and the raw material A and the raw material B were mixed at the mixing ratio shown in Table 1 as the raw material for the middle layer, and were melt-extruded at 260 ° C. using a three-layer T-die extruder. 0.9 mm on a 40 ° C. casting roll. This sheet was preheated by a heating roll at 125 ° C. and stretched 3.0 times in the machine direction. Next, the film was stretched 3.0 times in the transverse direction in a transverse stretching machine heated to 145 ° C., and then relaxed 10% in the transverse direction at 150 ° C. in the heat setting zone. The thickness of the obtained polyolefin-based film was 100 μm, and the breakdown was 80 μm for the middle layer and 10 μm for both outer layers. Table 1 shows the tensile elongation, tensile modulus, and yield point of the polyolefin-based film thus obtained.

Next, the polyolefin-based film is subjected to a printing treatment to form a printing layer, and a printing layer is formed on the printing layer side through an adhesive layer having a thickness of 5 μm made of an adhesive containing a vinyl acetate-ethylene copolymer as a component. A decorative sheet was formed by providing a transparent covering layer made of a similar polyolefin-based film.
The secondary workability of the obtained decorative sheet, such as necking, wrinkles, and cracks, was evaluated and is shown in Table 1.

Example 5 The raw material A was used as the raw material for both outer layers.
30 wt% as a raw material for the middle layer, and melt-extruded at 260 ° C. using a three-layer T-die extruder;
A 0.4 mm sheet was formed on a casting roll at 40 ° C. This sheet was preheated by a heating roll at 125 ° C. and stretched 2.0 times in the machine direction. Next, the film was stretched 2.0 times in the transverse direction in a transverse stretching machine heated to 145 ° C., and relaxed 10% in the transverse direction at 150 ° C. in the heat setting zone. The thickness of the obtained film was 100 μm, which was 80 μm for the middle layer and 10 μm for both outer layers.

Table 1 shows the tensile elongation, tensile modulus and yield point of the polyolefin-based film thus obtained. Further, a decorative sheet was formed in the same manner as in Example 1 using the obtained polyolefin-based film. The secondary workability of the obtained decorative sheet, such as necking, wrinkles, and cracks, was evaluated and is shown in Table 1.

Example 6 The raw material A was used as the raw material for both outer layers.
The mixture obtained by mixing 30% by weight was melt-extruded at 260 ° C. using a three-layer T-die extruder as a middle layer raw material.
A 1.6 mm sheet was formed on a 0 ° C. casting roll. This sheet is preheated with a heating roll at 125 ° C.
The film was stretched 4.0 times in the machine direction. Next, the film was stretched 4.0 times in the transverse direction in a transverse stretching machine heated to 145 ° C., and then relaxed 10% in the heat setting zone at 150 ° C. in the transverse direction. The thickness of the obtained film was 100 μm, which was 80 μm for the middle layer and 10 μm for both outer layers.

Table 1 shows the tensile elongation, tensile modulus and yield point of the polyolefin-based film thus obtained. Further, a decorative sheet was formed in the same manner as in Example 1 using the obtained polyolefin-based film. The secondary workability of the obtained decorative sheet, such as necking, wrinkles, and cracks, was evaluated and is shown in Table 1.

Example 7 A decorative sheet was formed in the same manner as in Example 2 except that the film on which the printed layer was formed was changed to a random non-stretched polypropylene film, and secondary workability such as necking, wrinkles, and cracks was evaluated. The results are shown in Table 1.

Example 8 A mixture of 70% by weight of the raw material A and 30% by weight of the raw material B was melt-extruded at 260 ° C. using a T-die type extruder and 0.9 m on a 40 ° C. casting roll.
m sheet. This sheet was preheated by a heating roll at 125 ° C. and stretched 3.0 times in the machine direction. Then 1
After stretching 3.0 times in the transverse direction in a transverse stretching machine heated to 45 ° C, the film was relaxed 10% in the transverse direction at 150 ° C in the heat setting zone. The thickness of the obtained film was 100 μm.

Table 1 shows the tensile elongation, tensile modulus and yield point of the polyolefin-based film thus obtained. Further, a decorative sheet was formed in the same manner as in Example 1 using the obtained polyolefin-based film. The secondary workability of the obtained decorative sheet, such as necking, wrinkles, and cracks, was evaluated and is shown in Table 1.

Example 9 A mixture of 60% by weight of the raw material A and 40% by weight of the raw material B was melt-extruded at 260 ° C. using a T-die extruder, and 0.9 m was cast on a 40 ° C. casting roll.
m sheet. This sheet was preheated by a heating roll at 125 ° C. and stretched 3.0 times in the machine direction. Then 1
After stretching 3.0 times in the transverse direction in a transverse stretching machine heated to 45 ° C, the film was relaxed 10% in the transverse direction at 150 ° C in the heat setting zone. The thickness of the obtained film was 100 μm.

Table 1 shows the tensile elongation, tensile modulus and yield point of the polyolefin film thus obtained. Further, a decorative sheet was formed in the same manner as in Example 1 using the obtained polyolefin-based film. The secondary workability of the obtained decorative sheet, such as necking, wrinkles, and cracks, was evaluated and is shown in Table 1.

Example 10 The raw material A was used as the raw material for both outer layers, and the raw material A and the raw material B
30 wt% as a raw material for the middle layer, and melt-extruded at 260 ° C. using a three-layer T-die extruder;
A 0.3 mm sheet was formed on a 40 ° C. casting roll. This sheet was preheated by a heating roll at 125 ° C. and stretched 3.0 times in the machine direction. The thickness of the obtained film was 100 μm, which was 80 μm for the middle layer and 10 μm for both outer layers. Table 1 shows the tensile elongation, tensile modulus, and yield point of the polyolefin-based film thus obtained. Further, a decorative sheet was formed in the same manner as in Example 1 using the obtained polyolefin-based film. The secondary workability of the obtained decorative sheet, such as necking, wrinkles, and cracks, was evaluated and is shown in Table 1.

Example 11 Example 2 was repeated except that the resin composition was the same as that of Example 2, and the outer layer was changed to 5 μm and the middle layer was changed to 90 μm.
A film was formed under the same conditions as described above to obtain a polyolefin-based film. The thickness of the obtained film was 100 μm.

Table 1 shows the tensile elongation, tensile modulus and yield point of the polyolefin-based film thus obtained. Further, a decorative sheet was formed in the same manner as in Example 1 using the obtained polyolefin-based film. The secondary workability of the obtained decorative sheet, such as necking, wrinkles, and cracks, was evaluated and is shown in Table 1.

Example 12 A film was formed under the same conditions as in Example 2 except that the resin composition was the same as that of Example 2 and the layer structure was changed to a two-layer structure of one outer layer and an intermediate layer. I got The thickness of the obtained film was 100 μm, which was 80 μm in the middle layer and 20 μm in the outer layer.

Table 1 shows the tensile elongation, tensile modulus and yield point of the polyolefin-based film thus obtained. Further, a decorative sheet was formed in the same manner as in Example 1 using the obtained polyolefin-based film. The secondary workability of the obtained decorative sheet, such as necking, wrinkles, and cracks, was evaluated and is shown in Table 1.

Comparative Example 1 The raw material A was used as the raw material for both outer layers, and further, the raw material A was 70% by weight.
And 30% by weight of the raw material B as a middle layer raw material, are melt-extruded at 260 ° C. using a three-layer T-die extruder, and are 3.2 mm on a 40 ° C. casting roll.
Sheet. This sheet was preheated by a heating roll at 125 ° C. and stretched 4.0 times in the machine direction. Then, 14
After stretching 8.0 times in the transverse direction in a transverse stretching machine heated to 5 ° C, the film was relaxed 10% in the transverse direction at 150 ° C in the heat setting zone. The thickness of the obtained film is 100 μm, and the breakdown is that the middle layer is 80 μm and both outer layers are 10 μm
Met.

Table 1 shows the tensile elongation, tensile modulus, and yield point of the polyolefin film thus obtained. Further, a decorative sheet was formed in the same manner as in Example 1 using the obtained polyolefin-based film. The secondary workability of the obtained decorative sheet, such as necking, wrinkles, and cracks, was evaluated and is shown in Table 1.

Comparative Example 2 Raw material A was used as the raw material for both outer layers, and a mixture of 70% by weight of raw material A and 30% by weight of raw material B was used as the raw material for the middle layer.
Using a three-layer T-die extruder, the mixture was melt-extruded at 260 ° C., and a 100 μm film was formed on a 40 ° C. casting roll. The thickness of the obtained film is 100μ
m, of which the middle layer is 80 μm and both outer layers are 10 μm each.
m.

Table 1 shows the tensile elongation, tensile modulus and yield point of the polyolefin film thus obtained. Further, a decorative sheet was formed in the same manner as in Example 1 using the obtained polyolefin-based film. The secondary workability of the obtained decorative sheet, such as necking, wrinkles, and cracks, was evaluated and is shown in Table 1.

[0074]

[Table 1]

[Brief description of the drawings]

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

FIG. 2 is a side view showing an instrument used for a necking test.

Claims (3)

[Claims] 1. A film having a tensile modulus of elasticity of 300 in both the film flow direction and the direction perpendicular to the film flow direction.
A polyolefin having a tensile elongation at break of 30 to 500% in both the flow direction of the film and the direction perpendicular to the flow direction of the film, and further having no yield point in at least one direction. A decorative sheet containing a base film as a constituent layer. 2. A decorative sheet comprising a base film layer and a printed layer, wherein the base film layer is composed of the polyolefin-based film of claim 1. 3. A decorative sheet comprising a base film layer, a printing layer and a transparent covering film layer, wherein said base film layer and / or
Or a decorative sheet comprising a transparent covering film made of the polyolefin-based film of claim 1.