JP4090048B2 - Laminated decorative sheet - Google Patents

Description

  The present invention relates to a laminated decorative sheet. More specifically, the present invention is difficult to whiten during embossing and heat bonding, and has excellent moldability, low-temperature impact properties, surface smoothness, colorless transparency, and the like. The present invention relates to a laminated decorative sheet having various physical properties that are practically sufficient. The laminated decorative sheet of the present invention is particularly suitable for vacuum press molding, pressure press molding and membrane press molding.

  Conventionally, laminated decorative sheets have been widely used by being bonded to metal or wood-based materials such as furniture, cabinets, joinery, desks, and cupboards. In addition, the laminated decorative sheet is subjected to membrane press molding on an adherend having a complicated curved surface, and the laminated decorative sheet is adhered to the contour faithfully.

Examples of such a laminated decorative sheet include a sheet described in Patent Document 1 below. This is obtained by using a polyvinyl chloride sheet as a base material layer and laminating a transfer film thereon using a so-called doubling embossing system. The sheet is said to have stain resistance, scratch resistance, and high gloss.
Apart from this, for example, a sheet described in Patent Document 2 below can be cited. This is a laminated decorative sheet comprising a base layer of an opaque polyolefin resin film and an amorphous polyethylene terephthalate resin film. In addition, the amorphous film used for the sheet | seat described in this patent document 2 has some crystallinity. According to this prior art, it is said that a laminated decorative sheet that is excellent in moldability, excellent in transparency, weather resistance, stain resistance, etc., but good is obtained.

Japanese Patent Publication No. 7-39170 Japanese Patent Laid-Open No. 7-24979

However, when the above laminated decorative sheet is used for membrane press molding, vacuum, and pressure press molding, there is a problem that whitening occurs during embossing and heat bonding.
Membrane press molding is a process in which a thermoplastic decorative sheet having a desired thickness or a desired color printed on a surface is heated to the vicinity of its softening point, and this is applied to an adherend of a predetermined shape, for example, the shape of a door of a kitchen set. Cover an adherend with a complicated curved surface, and then apply a stretchable membrane (film-like material), such as a rubber film, on top of this to apply the pressure of air or liquid, and faithfully follow its contour. A laminated decorative sheet is attached. The basic principle of vacuum press molding and compressed air press molding is the same as membrane press molding, but the former is a method of molding by vacuum pressure without using membrane rubber, and the latter is molding using air pressurization. Is the method.
In addition, the laminated decorative sheet is generally manufactured by a calender rolling method, but at this time, unevenness due to uneven flow of resin, which is called a so-called bank mark, is generated partially. Although there is no practical problem, the smoothness of the surface is deteriorated and as a result, the appearance is impaired. Furthermore, if the line speed is increased during doubling embossing, this bank mark becomes more conspicuous, resulting in poor productivity.
Furthermore, the laminated decorative sheet tends to break easily at low temperatures, and rarely cracks may occur during handling in winter.
Furthermore, the sheet using the polyvinyl chloride sheet described in Patent Document 1 as the base material layer is initially colored due to thermal deterioration, and cannot be said to be a particularly excellent material.

  The object of the present invention is that it is difficult to whiten during embossing and heat bonding, has excellent moldability, low-temperature impact properties, surface smoothness, colorless transparency, and other various physical properties are practically sufficient, especially in vacuum. It is to provide a laminated decorative sheet particularly suitable for press molding, compressed air press molding and membrane press molding.

As a result of intensive studies, the present inventors have been able to solve the conventional problems as described above.
The invention according to claim 1 is (A) a completely amorphous polyester in which the dicarboxylic acid component is terephthalic acid and the diol component is 60 to 80 mol% ethylene glycol and 20 to 40 mol% 1,4-cyclohexanedimethanol. system resin layer, and (B) a base layer consisting of a acrylonitrile-butadiene-styrene resin or acrylonitrile-styrene-acrylic acid ester-based resin material, a laminated decorative sheet, characterized in that layered in this order is there.
The invention of claim 2 is the laminated decorative sheet according to claim 1, wherein the transfer foil is provided on the (A) completely amorphous polyester resin layer.
The invention of claim 3 is a laminated sheet for membrane press molding comprising the laminated decorative sheet according to any one of claims 1 to 2.

  According to the present invention, a laminated decorative sheet that does not easily whiten during embossing and heat bonding, is excellent in moldability, low-temperature impact properties, surface smoothness, colorless transparency, and has various other physical properties that are practically sufficient. Is provided. The laminated decorative sheet of the present invention is particularly suitable for vacuum press molding, pressure press molding and membrane press molding.

Hereinafter, the present invention will be described in more detail.
(B) Base material layer The base material layer in the present invention comprises a polyolefin resin, a polyvinyl chloride resin, an acrylonitrile / butadiene / styrene resin, an acrylonitrile / styrene / acrylic ester resin, an acrylonitrile / ethylene propylene / styrene resin. It is made of a material such as methyl methacrylate / butadiene / styrene resin, polyethylene terephthalate or completely amorphous polyester resin.

As the polyolefin resin, a polypropylene resin, a polyethylene resin, and a copolymer thereof (for example, ethylene-vinyl acetate copolymer) can be used.
MFR (measurement conditions of polypropylene: JIS K7210, 230 ° C., 2.16 kgf, measurement conditions of polyethylene: JIS K7210, 190 ° C., 2.16 kgf) of these resins is preferably 0.3 to 30 g / 10 minutes. More preferably, 0.3-10 g / 10min is good. In addition, when using ethylene-vinyl acetate copolymer, 70 to 95 weight% of ethylene content is suitable, and a saponification thing can also be used.

The polyvinyl chloride resin preferably has a polymerization degree of 400-1500. More preferably, it is 700-1300. A copolymer may be used in addition to the polyvinyl chloride resin homopolymer.
A plasticizer, a stabilizer, a lubricant, and a filler can be blended with the polyvinyl chloride resin as necessary.
Plasticizers include phthalate ester compounds, adipic acid ester compounds, sebacic acid ester compounds, azelaic acid ester compounds, trimellitic acid ester compounds, phosphate ester compounds, polyester compounds, epoxy compounds, Examples include chlorinated paraffin, aromatic hydrocarbon compounds, petroleum hydrocarbon compounds, and the like.
As stabilizers, metal soap (calcium soap, barium soap, zinc soap, cadmium soap, lead soap, lead salt stabilizer), metal liquid stabilizer (branched fatty acid (2-ethylhexoic acid, indecanoic acid, etc.), unsaturated fat Group (oleic acid, ricinoleic acid, linoleic acid, etc.), aromatic acid (barium, calcium, zinc, tin, magnesium, sodium or potassium metal salts of carboxylic acid, benzoic acid, salicylic acid and their derivatives), organic tin stable Agents and the like.
Examples of the lubricant include hydrocarbon lubricants, fatty acid lubricants, aliphatic alcohol lubricants, aliphatic amide lubricants, aliphatic ester lubricants, fatty acid metal soap lubricants, and the like.
Examples of the filler include calcium carbonate, aluminum hydroxide, kaolin clay, talc, wollastonite, mica, silica, whisker and the like.

  The acrylonitrile / butadiene / styrene resin preferably has a butadiene content of 5 to 70% by weight. More preferably, it is 10 to 30% by weight. Moreover, 90: 10-50: 50 (weight ratio) is good for styrene: acrylonitrile. The weight average molecular weight is preferably 50,000 to 300,000.

  As the acrylonitrile / styrene / acrylic acid ester resin, those having an acrylic rubber content of 5 to 70% by weight are preferable. More preferably, it is 10 to 30% by weight. Moreover, 90: 10-50: 50 (weight ratio) is good for styrene: acrylonitrile. The weight average molecular weight is preferably 50,000 to 200,000.

  As the acrylonitrile / ethylene propylene / styrene resin, those having 5 to 70% by weight of ethylene propylene are preferable. More preferably, it is 10 to 30% by weight. Moreover, 90: 10-50: 50 (weight ratio) is good for styrene: acrylonitrile. The weight average molecular weight is preferably 50,000 to 200,000.

  The methyl methacrylate / butadiene / styrene resin preferably has a butadiene content of 5 to 80% by weight. More preferably, it is 20 to 70% by weight. Styrene: methyl methacrylate is preferably 30:70 to 70:30 (weight ratio).

  Polyethylene terephthalate (PET) having an IV value of 0.6 to 0.8 is preferable. Copolymer PET can also be used.

  In the present invention, (A) a completely amorphous polyester resin described below can also be used as the (B) substrate layer.

  (B) Although the thickness of a base material layer is suitably determined according to a use, it is 0.1-2 mm, for example, Preferably 0.3-1.0 mm is good.

(A) Completely amorphous polyester-based resin (A) The completely amorphous polyester-based resin in the present invention does not cause deterioration in physical properties due to recrystallization even when heat treatment is performed again, and has no crystalline component at all. Is. The crystallinity referred to in the present invention is measured in accordance with JIS K7121 (DSC method).

  As the completely amorphous polyester resin, for example, a resin produced by a polycondensation reaction through an esterification reaction containing terephthalic acid or dimethyl terephthalic acid and ethylene glycol as main components is preferably used.

  The fully amorphous polyester resin may be a copolymer type fully amorphous polyester obtained by copolymerizing a third component in addition to the two components used in the above completely amorphous polyester. This type is preferred. As the third component, 1,4-cyclohexanedimethanol or isophthalic acid is suitable, and more preferably, the diol component is composed of two or more types, and optimally the dicarboxylic acid component Is terephthalic acid, and the diol component is preferably 50 to 99 mol% ethylene glycol and 1 to 50 mol% 1,4-cyclohexanedimethanol. In particular, those having 60 to 80 mol% of ethylene glycol and 20 to 40 mol% of 1,4-cyclohexanedimethanol are preferable.

  A method for producing a completely amorphous polyester resin is already widely known in the art, and is disclosed, for example, in US Pat. No. 5,340,907.

  Here, in the present invention, when (B) a polyolefin resin is selected for the base material layer, the completely amorphous polyester resin of (A) is of a copolymer type containing the above third component. preferable. By this combination, the whitening phenomenon is suppressed during embossing and heat bonding.

  (A) Although the thickness of a completely amorphous polyester-type resin layer is suitably determined according to a use, it is 0.1-2.0 mm, for example, Preferably it is 0.1-1.0 mm.

(B) The base material layer and (A) the completely amorphous polyester resin layer are usually subjected to corona treatment (for example, 20 to 200 W / m ² / min) on the adhesive surface of the base material layer as necessary. It can be laminated with an adhesive.
The corona discharge treatment can be performed using a known corona discharge treatment apparatus such as a vacuum tube method or a thyristor method.

  In the present invention, (A) a completely amorphous polyester-based resin layer can faithfully represent a print color without affecting the print color when printing is performed on the (B) substrate layer, Furthermore, a feeling of depth can be imparted.

Moreover, the laminated decorative sheet of this invention can provide a transfer foil on the (A) completely amorphous polyester-type resin layer as needed. This transfer foil can contain a printing layer, a transparent protective film for protecting this printing layer, a topcoat layer, etc., in order to improve designability like the conventional technology. When the transfer foil is not used, embossing can be applied to the upper part of the completely amorphous polyester resin layer, and ink can be introduced into the recesses of the emboss. Furthermore, a top coat layer can be provided on the upper portion by a gravure method.
Apart from this, also when a completely amorphous polyester-based resin is used as the (B) substrate layer, a transfer foil can be provided directly on the (B) substrate layer. According to this aspect, even if the transfer foils are laminated, a laminated decorative sheet can be obtained with a simple two-layer structure while maintaining the effects of the present invention, which is advantageous in terms of manufacturing and cost.
It is also possible to emboss an upper part of the completely amorphous polyester resin layer and provide a top coat layer directly on the upper part by a gravure method.

  The total thickness of the laminated decorative sheet of the present invention is not particularly limited, but is preferably about 0.15 to 2.0 mm, and preferably 0.2 to 1.0 mm.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
Example 1
(B) 0.1 mm thick polyvinyl chloride (trade name: R type, polymerization degree: 800, including plasticizer and stabilizer as other additives) as a base material layer ( A) A non-crystalline polyethylene terephthalate having a thickness of 0.3 mm (trade name: Novapex A TEST, diol component: ethylene glycol, dicarboxylic acid component: terephthalic acid, crystal as a completely amorphous polyester-based resin layer Ingredient 0%), transfer foil for polyethylene terephthalate having a thickness of 12 μm (trade name CL-AP, manufactured by Keihan Oike Transfer Co., Ltd.), and in the order of (B) layer- (A) layer-transfer foil These were heat-bonded with an embossing roll at 150 ° C. to 160 ° C. for 40 seconds (nip pressure: 2.0 kg / cm).

(Comparative Example 1)
In Example 1, (A) a completely amorphous polyester-based resin layer was converted to a 0.3 mm thick polyvinyl chloride layer (manufactured by Riken Vinyl Industry Co., Ltd., trade name: S1916 FC039, degree of polymerization: 700, other additives). In addition, the transfer foil was changed to a 12 μm-thick polyvinyl chloride transfer foil (trade name CL-03B, manufactured by Keihan Oike Transfer Co., Ltd.). Repeated.

The laminated decorative sheets obtained in Example 1 and Comparative Example 1 were measured for the DuPont impact test, surface roughness, and transparency. The results are shown in Table 1.
The DuPont impact test was conducted as follows.
After the laminated decorative sheet is left at a temperature of 23 ° C., it is placed between a striker having a tip diameter of 1/2 inch and a cradle having a dent corresponding to the diameter, and the heavyweight is dropped from a predetermined height. Observe for surface cracks.
The maximum value at which cracks do not occur is obtained by changing the height at which heavyweight is dropped and the weight of heavyweight, and the impact value is obtained from the following formula.

The surface roughness was measured according to JIS B0601.
The measuring apparatus used was Tokyo Seimitsu Co., Ltd., trade name Handy Surf E-30A. In Table 1, Ra represents center line average roughness, and Rz represents ten-point average roughness.

  For the evaluation of transparency, a base material is prepared, the chromaticity of this base material is measured, the laminated decorative sheet of the present invention is subsequently attached to the base material, the chromaticity is measured, and the former This was performed by obtaining the color difference ΔE when the latter chromaticity was subtracted from the chromaticity. As a color difference meter, a product name CM2002 manufactured by Minolta Co., Ltd. was used.

  From Table 1, it can be seen that the laminated decorative sheet of Example 1 is superior to Comparative Example 1 in impact resistance at low temperatures, surface roughness, and transparency.

(Example 2)
(B) Polypropylene with a thickness of 0.1 mm (trade name: # 041 OW 9039 type, MFR: 6 to 7 g / 10 min), (A) completely amorphous polyester, as a base material layer As the resin layer, an amorphous polyethylene terephthalate having a thickness of 0.3 mm (manufactured by Mitsubishi Chemical Co., Ltd., trade name: Novapex A TEST, diol component: ethylene glycol, dicarboxylic acid component: terephthalic acid, crystal component 0%) is used ( Between the A) layer and the (B) layer, a weight ratio of 5 to 6 μm thick adhesive (polyester adhesive Byron 63SS manufactured by Toyobo Co., Ltd. and isocyanate-based curing agent Coronate HX manufactured by Nippon Polyurethane Co., Ltd .: 100: 3) was applied, and dry lamination was performed in the order of (A) layer-adhesive- (B) layer. These were embossed for 40 seconds with an embossing roll at 150 ° C. to 160 ° C. (nip pressure: 2.0 kg / cm). After that, (B) corona treatment (for example, 20 to 200 W / m ² / min) is performed on the back surface of the base material layer (opposite side of the A layer) to form a primer layer (H. B. Fuller) having a thickness of 2 to 3 μm. (Trade name: L1135 / 43, manufactured by Nippon Polyurethane Co., Ltd., trade name: Coronate HX mixed at a weight ratio of 100: 3).

(Example 3)
(A) A non-crystalline polyethylene terephthalate having a thickness of 0.3 mm (made by Eastman Chemical Co., trade name: KODAR PETG 6763, copolymer type, diol component: 70% by weight of ethylene glycol) And Example 2 was repeated except that it was changed to 1,4-cyclohexanedimethanol 30% by weight, dicarboxylic acid component: terephthalic acid, crystal component 0%).

(Comparative Example 2)
(A) A completely amorphous polyester resin layer having a thickness of 0.3 mm of amorphous polyethylene terephthalate (manufactured by Osaka Resin Processing Co., Ltd., trade name: PET-1S, homotype, diol component: ethylene glycol, dicarboxylic acid component: Example 2 was repeated except that it was changed to terephthalic acid, partly having a crystal component.

(Comparative Example 3)
(A) A completely amorphous polyester resin layer having a thickness of 0.3 mm of amorphous polyethylene terephthalate (manufactured by Idemitsu Petrochemical Co., Ltd., trade name: Crystalline, diol component: ethylene glycol, dicarboxylic acid component: terephthalic acid, Example 2 was repeated except that it was changed to (partially having a crystal component).

  The laminated decorative sheets obtained in Examples 2 to 3 and Comparative Examples 2 to 3 were subjected to a DuPont impact test, a tensile test, an appearance after embossing (visual observation), and a membrane press test. The results are shown in Table 2. Each test method is shown below.

Tensile test Tensile test, tensile strength, elongation, breaking point were measured according to JIS K6734 of laminated decorative sheets.
In various tests, the laminated decorative sheet before embossing roll processing was displayed as untreated, and the laminated decorative sheet after embossing roll processing was displayed as processed.

Membrane press test The laminated decorative sheet is placed in a predetermined place of a membrane press (model name: KT-M-139, manufacturer name: Ben Honner), and the bonding conditions (temperature: 130 to 140 ° C., time: 60 seconds) , Pressure: 4 kg / cm ² ), and the moldability was evaluated.
The adherend (MDF) is a plywood obtained by finely cutting a wood chip such as a conifer or lauan wood and pressing it to harden it. The adherend was cut into a door shape incorporated in a system kitchen or the like (size of about 400 mm × 600 mm, thickness of about 18 to 40 mm), and further subjected to curved surface processing (about 3R to 10R). In addition, a decorative groove was carved on the top.
In membrane press molding, on the door-shaped MDF surface, a 1-30 μm-thick urethane adhesive (Henmytin's adhesive, product name: 34333, the company's curing agent, product name: Hardener D, (Mixed at a weight ratio of 100: 5).

  From Table 2, the moldability of the laminated decorative sheet of the present invention was good and no whitening was seen after embossing, whereas the laminated decorative sheets of Comparative Examples 2 and 3 had difficulty in moldability due to insufficient film elongation. There was also a whitening phenomenon.

Example 4
(B) Polypropylene with a thickness of 0.1 mm (trade name: # 041 OW 9039 type, MFR: 6 to 7 g / 10 min), (A) completely amorphous polyester, as a base material layer As the resin layer, an amorphous polyethylene terephthalate having a thickness of 0.3 mm (manufactured by Mitsubishi Chemical Co., Ltd., trade name: Novapex A TEST, diol component: ethylene glycol, dicarboxylic acid component: terephthalic acid, crystal component 0%) is used ( Between the A) layer and the (B) layer, as the resin ink, a urethane resin (trade name: Lamister, manufactured by Toyo Ink Co., Ltd.) is applied, and these are in the order of (A) layer-resin ink- (B) layer. Using a heat bonding embossing machine, bonding was performed under conditions of a bonding temperature of 130 ° C. to 140 ° C., a bonding time of 40 seconds, and a bonding pressure of 2.0 kg / cm.

(Example 5)
(A) A non-crystalline polyethylene terephthalate having a thickness of 0.3 mm (made by Eastman Chemical Co., trade name: KODAR PETG 6763, copolymer type, diol component: 70% by weight of ethylene glycol) And Example 4 was repeated except that 1,4-cyclohexanedimethanol 30% by weight, crystal component 0%).

(Comparative Example 4)
(A) A completely amorphous polyester resin layer having a thickness of 0.3 mm of amorphous polyethylene terephthalate (manufactured by Osaka Resin Processing Co., Ltd., trade name: PET-1S, homotype, diol component: ethylene glycol, dicarboxylic acid component: Example 4 was repeated except that the resin ink was changed to a urethane resin (trade name: Lamister, manufactured by Toyo Ink Co., Ltd.).

(Comparative Example 5)
(A) A completely amorphous polyester resin layer having a thickness of 0.3 mm of amorphous polyethylene terephthalate (manufactured by Idemitsu Petrochemical Co., Ltd., trade name: Crystalline, diol component: ethylene glycol, dicarboxylic acid component: terephthalic acid, Comparative Example 4 was repeated, except that the crystal component was changed to (having some crystal components).

  The appearance properties of the laminated decorative sheets obtained in Examples 4 to 5 and Comparative Examples 4 to 5 were evaluated. The results are shown in Table 3. The test method is shown below.

Appearance The appearance of the laminated decorative sheet after heat bonding was visually evaluated.

  From Table 3, it can be seen that the appearance of the laminated decorative sheet of the present invention is better than that of the comparative example.

(Example 6)
(B) Polypropylene with a thickness of 0.1 mm (trade name: # 041 OW 9039 type, MFR: 6 to 7 g / 10 min), (A) completely amorphous polyester, as a base material layer As the resin layer, an amorphous polyethylene terephthalate having a thickness of 0.3 mm (manufactured by Mitsubishi Chemical Co., Ltd., trade name: Novapex A TEST, diol component: ethylene glycol, dicarboxylic acid component: terephthalic acid, crystal component 0%) is used ( Between the layers A) and (B), a vinyl chloride-vinyl acetate copolymer resin (trade name: ALFA, manufactured by The Intec Co., Ltd.) is applied as an adhesive, and as a transfer foil, for polyethylene terephthalate having a thickness of 19 μm Using a transfer foil (trade name CL-AP, manufactured by Keihan Oike Transfer Co., Ltd.), these were 150 ° C. to 160 ° C. in the order of (B) layer-adhesive- (A) layer-transfer foil. It was stuck 40 seconds heat at the embossing roll (nip pressure: 2.0kg / cm).
The peel strength of the obtained laminated decorative sheet was measured and found to be 3.5 kg / inch. The measuring method of peeling strength is shown below. Moreover, the pencil hardness of JIS K5400 and a 200-g load is F, and was practically sufficient. Further, no whitening phenomenon was observed.

Peeling strength (B) After peeling off the base material layer and (A) completely amorphous polyester resin layer, fix (A) and (B) to the tensile tester in a state where they are peeled in the opposite directions by 180 degrees, The tensile load was measured while peeling.
Test conditions: Temperature 23 ± 2 ° C., Test piece size: Width 25 mm, Length 150 mm, Tensile speed 100 mm / min

(Example 7)
(B) As a base material layer, amorphous polyethylene terephthalate having a thickness of 0.3 mm (manufactured by Eastman Chemical Co., Ltd., trade name: KODAR PETG 6763, copolymer type, diol component: 70% by weight of ethylene glycol and 1,4- Cyclohexanedimethanol 30% by weight, dicarboxylic acid component: terephthalic acid, crystal component 0%), and a transfer foil for polyethylene terephthalate having a thickness of 12 μm (trade name CL-AP, manufactured by Keihan Oike Transfer Co., Ltd.) The layer (B) and the transfer foil were heat bonded with a dielectric roll at 150 ° C. to 160 ° C. (nip pressure: 2.0 kg / cm, roll speed 1 m / min).
The laminated decorative sheet of the present invention thus obtained was subjected to DuPont impact test and surface roughness measurement. These results are shown in Table 4.

(Comparative Example 6)
In Example 7, (A) a completely amorphous polyester-based resin layer was converted into a 0.3 mm-thick polyvinyl chloride layer (manufactured by Riken Vinyl Industry Co., Ltd., trade name: S1916 FC039, degree of polymerization: 700, other additives) Example 7 was changed by changing the transfer foil to a 12 μm-thick polyvinyl chloride transfer foil (trade name CL-03B, manufactured by Keihan Oike Transfer Co., Ltd.). Repeated.

  According to the present invention, a laminated decorative sheet that does not easily whiten during embossing and heat bonding, is excellent in moldability, low-temperature impact properties, surface smoothness, colorless transparency, and has various other physical properties that are practically sufficient. Is provided. The laminated decorative sheet of the present invention is particularly suitable for vacuum press molding, pressure press molding and membrane press molding.

Claims (3)

(A) a completely amorphous polyester resin layer in which the dicarboxylic acid component is terephthalic acid and the diol component is 60 to 80 mol% ethylene glycol and 20 to 40 mol% 1,4-cyclohexanedimethanol; the base layer consists of) a acrylonitrile-butadiene-styrene resin or acrylonitrile-styrene-acrylate resin material,
A laminated decorative sheet characterized by being laminated in this order.   The laminated decorative sheet according to claim 1, wherein the transfer foil is provided on the (A) completely amorphous polyester resin layer.   A laminated sheet for membrane press molding comprising the laminated decorative sheet according to any one of claims 1 to 2.