JPH08323920A - Surface protecting decorative sheet - Google Patents

Abstract

PURPOSE: To provide a decorative sheet decorating the wall surface of the entrance and exit, passage, kitchen or bathroom of a house and the surface of furniture or the like to protect the same from the contamination from the outside, water, humidity, heat, fungi or the like and the sheet constitution capable of being superposed on the surface of the decorative sheet to be laminated thereto. CONSTITUTION: A surface protecting decorative sheet 1 is constituted by providing a tetrafluoroethylene resin film layer 2 composed of an ethylene/ tetrafluoroethylene copolymer, a tetrafluoroethylene/perfluoroalkylvinyl ether copolymer and a tetrafluoroethylene/hexafluoropropylene copolymer on the surface of a sheet base material 4 and successively laminating a metal foil layer 6 and a self-adhesive layer 7 having good adhesiveness to the tetrafluoroethylene resin to the other surface thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION The present invention applies makeup to entrances and exits of houses, corridors, walls of kitchens and bathrooms, surfaces of furniture, etc. to prevent external pollution, water, moisture, heat, mold, etc. The present invention relates to a decorative sheet which is used by being attached to protect the surface of the sheet, and which can be overlaid on the surface of the decorative sheet.

[0002]

2. Description of the Related Art Generally, a decorative sheet is usually used by attaching a pressure-sensitive adhesive layer to a laminate of a soft polyvinyl chloride sheet printed on the back surface or another printed plastic sheet and fixing it to a wall surface or the like. As one means for protecting the surface of such a sheet from moisture, heat, dirt, etc., a plastic film layer having a small surface energy such as vinyl fluoride resin or vinylidene fluoride resin has been provided on the surface. It was

On the other hand, as a surface protection around water such as in kitchens and bathrooms, a metal foil such as an aluminum foil is provided with a pressure-sensitive adhesive layer to be fixed and used. However, the metal surface is exposed on the surface and remarkably. Since it impairs aesthetics, it can only be used as a sealing material.

[0004]

A composite sheet in which a vinyl fluoride resin or vinylidene fluoride resin is provided on the surface of a decorative sheet is more waterproof than ordinary decorative sheets such as vinyl chloride resin and acrylonitrile-butadiene (ABS) resin. Although it is quite excellent in terms of performance, it is not sufficiently satisfactory in terms of antifouling property, heat resistance, and long-term durability, and the above-mentioned performance improvement was required. Further, the fluororesin film has a high electrification property, and has a defect that dust is conspicuously attached.

[0005] The tetrafluoroethylene resin (perfluoroethylene resin) is the most excellent in such performance and is used by being molded into a chemically resistant container, packing, various electronic equipment parts, etc. Since the viscosity is extremely high, it cannot be formed into a film by extrusion molding, and there is no choice but to rely on the skiving method of forming and cutting a round bar, and the obtained tetrafluoroethylene resin film is opaque. At present, it is difficult to use it as a laminated material for the surface of a decorative sheet, and there is no preferable adhesive for adhering this well.

Further, although the metal foil such as the aluminum foil with adhesive has good heat resistance and waterproofness, it cannot be said that the antifouling property is good, and rather the surface is oxidized over time so that stains are not generated. Conspicuous and surface stains due to oxidation cannot be removed by general means such as wiping with detergent or organic solvent.

Further, the surface of the metal foil is smooth, and the softness and the hardness of the metal foil are too good to follow the underlying material and pick up the unevenness of the underlying material so that it becomes a shadow and the unevenness of the surface is emphasized more than necessary. It also has the drawback that it is done. Before that, a surface material having a bare metal foil surface was not very preferable in terms of aesthetics, and in general, it was used only in unavoidable areas such as prevention of water leakage rather than surface makeup.

[0008]

Means for Solving the Problems As a result of investigations by the present inventors, on the surface of a sheet base material, an ethylene-4fluoroethylene copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, a tetrafluoride were obtained. It is characterized in that a tetrafluoroethylene-based resin film layer selected from any of ethylene-6-fluoropropylene copolymer is provided, and a metal foil layer and an adhesive layer are sequentially laminated on the other surface. It has been found that the above-mentioned problems can be solved by a constituent material composed of a surface protective decorative sheet.

Further, an acrylic ester copolymer obtained by adding or mixing a compound having an alkoxysilyl group to the pressure-sensitive adhesive of the decorative sheet, a composition containing a liquid tackifier as an essential component, and the pressure-sensitive adhesive being acrylic acid. Ester polymer (A) and vinylidene fluoride copolymer (B)
And a silicone pressure-sensitive adhesive (C) having a dimethylpolysiloxane skeleton are mixed to give adhesiveness to the surface of the tetrafluoroethylene-based resin film.

The present invention is a decorative sheet having an aesthetic appearance, in which various properties such as waterproofness, heat resistance, antifouling property and antifungal property of a conventional surface material are provided with a tetrafluoroethylene resin layer. It is possible to remarkably improve, and by providing a metal foil layer, moisture resistance, antistatic property, flame retardancy and sheet rigidity are improved, and it is also possible to give followability to the base material if necessary. Becomes

[0011]

The present invention will be described below with reference to the drawings. FIG.
FIG. 1 is a schematic cross-sectional view showing an embodiment of a surface protective decorative sheet according to the present invention. As shown in FIG. 1, the surface protective decorative sheet 1 according to the present invention has an ethylene-4 fluoroethylene copolymer, a tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and an adhesive 3 on one side of a sheet substrate 4. ,
A tetrafluoroethylene-based resin film layer 2 selected from any one of a tetrafluoroethylene-6-fluoropropylene copolymer is provided, and an adhesive 5 is provided on the other surface of the sheet base material 4 The metal foil layer 6 and the pressure-sensitive adhesive layer 7 are sequentially laminated. The pressure-sensitive adhesive layer 7 (the lower surface in the figure) of the surface-protective decorative sheet 1 is usually coated with a release paper 8 that is removed during use.

Next, a detailed description will be given according to each constituent element of the surface protective decorative sheet according to the present invention. In addition, a part in a sentence means a weight part. First, the sheet base material may be one that can impart a design property as a base material for a decorative sheet, and is generally polyvinyl chloride, polyethylene terephthalate, polybutylene terephthalate, polypropylene,
Polycarbonate, polystyrene, acrylonitrile-
Sheets of plastics such as butadiene-styrene and acrylic, fiber base materials such as woven fabrics, knitted fabrics and non-woven fabrics of various structures, and wood materials such as printed paper and wood board can also be used according to the application.

Such a sheet base material is often used by printing, printing, painting, etc., but in the case of a plastic material, if it is not even a single color depending on the part to be used,
Coloring by kneading pigments is also possible.

Next, the tetrafluoroethylene-based resin provided on the surface of the above-mentioned substrate sheet must have excellent workability which is difficult to put into practical use with perfluoroethylene resin (PTFE). It is selected from tetrafluoroethylene copolymer (ETFE), tetrafluoroethylene-perfluoroalkylvinylether copolymer (PFA), and tetrafluoroethylene-6-fluoropropylene copolymer (FEP). Thus, these resins can be melted at a high temperature of 360 ° C. or higher and extruded into a film. The tetrafluoroethylene resin has good stretchability,
It is also possible to use it after biaxial stretching.

The film thus obtained has a thickness of 20 to 100 μm.
It is characterized by having a thickness of about m, high transparency, and almost no pinholes. Lamination of the film and the sheet substrate surface, corona treatment is applied to the film,
It is possible to apply a special adhesive using a high molecular weight polyester resin having a low glass transition temperature to the corona-treated surface of the sheet base material or film, and heat laminate.

A monofluoride or difluoride resin such as vinyl fluoride resin or vinylidene fluoride resin can be laminated without any problem by using a general adhesive. For the system resin, it is necessary to take the above-mentioned method while paying attention to the surface treatment and heating conditions of the film.

Next, the metal foil is a general metal foil obtained by rolling, and aluminum, copper, iron, stainless steel or the like can be used. These can be used either soft or hard, but in this application, the thickness is 20
It is preferably in the range of ˜100 μm. 20 thickness
If the thickness is less than μm, the strength is too weak as a building material and pinholes are easily generated, and the effect of adapting to the base is poor, and if the thickness exceeds 100 μm, the entire sheet becomes too hard, making it difficult to apply as a decorative sheet. Becomes

The metal foil and the sheet base material can be adhered by so-called general laminating adhesion, and solvent type or emulsion type rubber adhesives, vinyl acetate adhesives, polyester adhesives, acrylic adhesives, A polyamide-based adhesive or the like can be arbitrarily selected, and in some cases, a rubber-based or acrylic-based adhesive or a hot-melt adhesive such as ethylene vinyl acetate copolymer can be used.
There is no problem in applying the adhesive to any of a sheet base material and a metal foil, and any laminating method such as solution application or dry lamination can be applied.
When using a wood base material, a wet laminating method is also possible.

An adhesive layer is provided on the back surface of the metal foil. At this time, there is no problem even if a thin layer of thermoplastic resin such as polyolefin is provided on the adhesive-coated surface of the metal foil. Since the metal foil does not stretch, in most cases such as food packaging, a polyolefin resin is provided by extrusion lamination on at least one side, which is performed for the purpose of reinforcing the foil and improving processability.

Examples of the adhesive provided on the metal foil surface include various types such as natural rubber type, butyl rubber type, polyisobutylene type, styrene block polymer type, acrylic ester polymer and polyorganosiloxane type.

[0021] The surface-protective decorative sheet has a low energy surface which makes it difficult for the pressure-sensitive adhesive to adhere to it, and generally cannot be laminated. Due to its nature, the product of the present invention used for surface-protection makeup is applied by being attached to a site that is easily susceptible to contamination, scratches, etc., and thus may require repair. Alternatively, as a terminal treatment of the present decorative sheet, the decorative sheets may be spliced to each other, and it is preferable to use an adhesive that can be pasted on the surface.

An acrylic ester polymer system containing a compound having an alkoxysilyl group and a liquid adhesion-imparting agent is effective as a pressure-sensitive adhesive having good adhesion to the surface of tetrafluoroethylene resin. Examples of the compound having an alkoxysilyl group include vinylsilane, aminosilane, mercaptosilane, and silane coupling agents such as epoxysilane, which are graft-polymerized in a solution of an acrylic acid ester copolymer synthesized by a conventional method, Alternatively, mix and disperse. The adhesive containing an alkoxysilyl group is
Since it cures when it reacts with water, it is necessary to perform sufficient dehydration during graft polymerization and mixing.

Liquid tackifiers mixed and added to the pressure-sensitive adhesive include rosin-based resins, terpene-based resins, xylene-based resins,
A low softening point resin such as isoprene resin or petroleum resin having a softening point of 30 ° C. or lower and a molecular weight of 500 to 3000. The adhesion-imparting resin which is liquid at room temperature is an essential component for obtaining the initial wettability with the tetrafluoroethylene-based resin having a low energy surface, and when its softening point exceeds 30 ° C. and its molecular weight is 3000 or less. When it is large, the effect of imparting wettability cannot be obtained, and when the molecular weight is smaller than 500, there arises a problem that the cohesive force of the pressure-sensitive adhesive composition is significantly reduced.

A liquid pressure-sensitive adhesive resin is dissolved and mixed in an acrylic acid ester pressure-sensitive adhesive solution containing an alkoxysilyl group to obtain a desired pressure-sensitive adhesive composition. Agents, cross-linking agents, pigments, flame retardants and the like can be optionally added. The cross-linking agent is preferably added to obtain a stable cohesive force of the pressure-sensitive adhesive.

The vinylidene fluoride copolymer mixed with the acrylic ester polymer is a generally known comonomer such as trifluoroethylene, hexafluoropropylene or chlorotrifluoroethylene, and a comonomer such as hexafluoroacetone and fluorine. A copolymer with vinylidene fluoride having a vinylidene fluoride content of 60 to 95 mol% is preferable.

When the content of vinylidene fluoride is less than 60 mol%, the adhesive force to the surface of low energy tetrafluoroethylene resin is low, and when it exceeds 95 mol%, the crystallinity of the resin becomes too high and the pressure sensitive adhesive is used. The compatibility with is significantly deteriorated.
The mixing ratio of the vinylidene fluoride copolymer resin is 5 with respect to 100 parts of the acrylic ester polymer of the adhesive.
-40 parts is preferable. If it exceeds 40 parts, the compatibility and dispersibility with the pressure-sensitive adhesive will deteriorate, and if it is less than 5 parts, the adhesiveness will decrease.

The silicone adhesive having a dimethylpolysiloxane skeleton is 2 to 2 parts per 100 parts of the mixture of vinylidene fluoride copolymer and acrylic ester polymer.
A range of 20 parts is preferred.

This is because if the silicone adhesive is less than 2 parts, sufficient adhesiveness cannot be obtained, and if it exceeds 20 parts, the compatibility also deteriorates. Further, the acrylic ester polymer of the present pressure-sensitive adhesive is preferably cross-linked with a cross-linking agent such as polyisocyanate, epoxy resin, melamine resin and metal chelate compound. The silicone adhesive may not be crosslinked.

The thickness of the pressure-sensitive adhesive is generally in the range of 30 to 90 μm. When it is thinner than 30 μm, the adhesive force becomes too low, and when it is thicker than 90 μm, the adhesive force becomes too high and workability tends to be impaired.

The pressure-sensitive adhesive is used in various forms such as a solvent system dissolved in an organic solvent, an emulsion using water as a medium, or a hot-melt type or a solventless UV-curing type. Alternatively, the pressure-sensitive adhesive film is formed by solidifying after cooling or curing. Such a pressure-sensitive adhesive may be applied directly to the metal foil side, or may be applied onto a release-treated release paper and transferred onto the metal foil surface.

[0031]

EXAMPLES Next, the contents of the present invention will be described with reference to actual examples.

(Production Example 1) Cylinder diameter 100 mmφ,
Cylinder length is 2000mm, crosshead and adapter are attached to the tip of the cylinder, T-die is attached to the extruder, hopper is 200 ℃, tip is 400
Grab a temperature gradient of ℃ and use 4 crossheads and 4 T-die
It is heated to 00 ° C., the raw material PFA pellets are charged from the hopper, the raw material is heated, and the inside of the cylinder is agitated, kneaded and melted, passed through the slit of the T die and discharged from the film-shaped tip, and flowed downward. While cooling with a cooling roll, to form a film of 40 μm,
It was wound up after the corona discharge treatment.

(Production Example 2) The tip of the extruder was heated to 360 ° C. and the crosshead T die was heated to 360 ° C., and ETFE having a thickness of 40 μm was used in the same manner as in Production Example 1 using the raw ETFE pellets.
A film was formed.

(Production Example 3) Raw material F at a processing temperature of 360 ° C.
EP pellets were molded under the same conditions as in Production Example 2,
An 80 μm thick FEP film was obtained.

(Production Example 4) 600 parts of ethyl acetate, 50 parts of 2-ethylhexyl acrylate, 220 parts of butyl acrylate
Parts, ethyl acrylate 60 parts, vinyl acetate 20 parts, acrylic acid 15 parts, 2-hydroxyethyl acrylate 0.5
Part was placed in a separable flask, tert-butyl peroxide was added dropwise to the mixture while heating to 85 ° C. and stirring.
Reflux at 85 ° C for a period of time to carry out polymerization to stop the reaction,
An adhesive solution (A-1) was obtained. The obtained adhesive solution had a nonvolatile content of 38% and a viscosity of 3500 cps / 25 ° C.
To the adhesive solution (A-1), 30 parts of vinylsilane (silane coupling agent, A1100, manufactured by Shin-Etsu Chemical Co., Ltd.) was charged, benzoyl peroxide was added dropwise, and the mixture was stirred at 50 ° C. for 2 hours for graft polymerization. Completed. After the reaction was stopped, the obtained pressure-sensitive adhesive (A-2) had a nonvolatile content of 40%,
The viscosity was 5400 cps / 25 ° C. Xylene resin (trade name Nikanol H80, manufactured by Mitsubishi Chemical Co., Ltd.) as a liquid tackifying resin for 100 parts of the adhesive solution A-2.
10 parts were added and mixed to obtain an adhesive (A-3).

(Production Example 5) 600 parts of ethyl acetate, 200 parts of 2-ethylhexyl acrylate, 12 parts of butyl acrylate
0 parts, 30 parts of vinyl acetate, 15 parts of acrylic acid, and 0.5 parts of 2-hydroxyethyl acrylate were charged in a separable flask, and tert-butyl peroxide was added dropwise while heating to 85 ° C. and stirring for 9 hours 85. Polymerization was carried out by maintaining the temperature at ℃ and reflux. After stopping the reaction, the obtained adhesive solution (A-
4) is non-volatile content 40%, viscosity 7000cps / 25 ° C
Met.

(Production Example 6) 300 parts of vinylidene fluoride,
Hexafluoropropylene (40 parts), hexafluoroacetone (30 parts) and ethyl acetate (300 parts) were charged into a pressure-resistant autoclave, and cumene peroxide was added thereto, followed by polymerization at 70 ° C. for 18 hours. The obtained solution (B-1) had a nonvolatile content of 55% and a viscosity of 460 cps / 25 ° C.

(Production Example 7) A rosin resin (trade name: Harcoline D, manufactured by Rika Hercules Co., Ltd.) 5 as a liquid tackifying resin was added to 100 parts of the adhesive solution of the adhesive (A-2) obtained in Production Example 4. Parts were added and mixed to give a pressure-sensitive adhesive (A-5).

(Production Example 8) A liquid isoprene resin (trade name: Claprene LI as a liquid tackifying resin) was added to 100 parts of the adhesive solution of the adhesive (A-2) obtained in Production Example 4.
R290, Kuraray Co., Ltd.) 10 parts were added and mixed, and further 10 parts of a rosin-based resin (trade name Super Ester A115, Arakawa Chemical Co., Ltd.) as a solid adhesion imparting agent was added and mixed to obtain an adhesive (A-6). And

Example 1 On the corona discharge treated surface of the PFA film obtained in Production Example 1,
100 parts of polyester adhesive (trade name: Hibon 7040, manufactured by Hitachi Chemical Polymer Co., Ltd.) and 4 parts of crosslinking agent for isocyanate compound (trade name: Desmodule RE, manufactured by Sumitomo Bayer Urethane Co., Ltd., hereinafter also simply referred to as D-RE) Was added and mixed with a gravure roll, and after drying, it was laminated and adhered to a soft vinyl chloride sheet having a thickness of 0.2 mm and a plasticizer content of 18% as a sheet base by a hot roll at 90 ° C. Furthermore, the thickness is 0.05mm
80 parts of a soft aluminum (Al) foil prepared by mixing 100 parts of a polyester adhesive (trade name: Hibon 7663, manufactured by Hitachi Chemical Polymer Co., Ltd.) with 3 parts of a cross-linking agent D-RE (described above). / M ² was directly applied, and after drying, the back surface of the soft vinyl chloride sheet was laminated with a hot roll at 90 ° C. and adhered. To 100 parts of the adhesive A-3 obtained in Production Example 4, 2.0 parts of Coronate L (polyisocyanate, manufactured by Nippon Polyurethane Co., Ltd.) was added and mixed, and a release paper EKR78 (Lintech Co., Ltd.) and then dry at 90 ° C for 2 minutes to 50
An adhesive coating having a thickness of μm was obtained. This was transferred to the aluminum foil surface of the three-layer laminated product of PFA / soft vinyl chloride sheet / soft aluminum foil to obtain a surface protective decorative sheet. The following sheet base material and the tetrafluoroethylene resin film laminate adhesion method and the sheet base material and metal foil laminate adhesion method were all performed in the same manner.

Example 2 The ETFE film obtained in Production Example 2 was laminated and adhered to a soft vinyl chloride sheet substrate in the same manner as in Example 1. This was laminated and adhered to a soft aluminum foil having a thickness of 0.02 mm which was extrusion-laminated with 0.3 mm of polyethylene in the same manner as in Example 1. On the other hand, to 100 parts of the acrylic pressure-sensitive adhesive solution (A-4) obtained in Production Example 5, 10 parts of the vinylidene fluoride resin solution obtained in Production Example 6 was added and mixed, and further silicone adhesive X40-3018 (Shin-Etsu 20 parts of a solution manufactured by Kagaku Co., Ltd. was added and mixed. Add 1.0 part of Coronate L (above) as a cross-linking agent, stir well, apply this to release paper EKR78 and dry to obtain a film thickness of 70 μm.
m adhesive layer was formed. By transferring this pressure-sensitive adhesive layer to the aluminum foil surface, a surface protective decorative sheet was obtained.

Example 3 The FEP film obtained in Production Example 2 and an ABS having a thickness of 0.3 mm produced by calendering as a sheet substrate.
The resin sheets were laminated and bonded in the same manner as in Example 1. This is a soft aluminum foil with a thickness of 0.05 mm,
Lamination adhesion was performed in the same manner as in Example 1. On the other hand, Production Example 7
To 100 parts of the acrylic adhesive solution (A-6) obtained in
As a cross-linking agent, 1.5 parts of Coronate L (described above) was added and well stirred, and this was coated on release paper EKR78 and dried to form a pressure-sensitive adhesive layer having a film thickness of 60 μm. By transferring this pressure-sensitive adhesive layer to the aluminum foil surface, a surface protective decorative sheet was obtained.

Examples 4 to 8 In the same manner as in Examples 1 to 3, the sheet base materials shown in Table 1 and 4
A fluorinated ethylene resin film was laminated and adhered, and the other surface of the sheet substrate and the metal foil shown in Table 1 were laminated and adhered. Similarly, each pressure-sensitive adhesive was coated and dried so that the dry coating thickness was 50 μm, and a pressure-sensitive adhesive layer was formed and transferred onto the metal foil surface to obtain a surface-protective decorative sheet. However, in Examples 4 and 8, 100 parts of the acrylic adhesive A-6 obtained in Production Example 8 was used as the adhesive in Coronate L (above) 1.
5 was added and mixed, and in Example 5, 100 parts of A-4 obtained in Production Example 5 was added and mixed with 1.0 part of Coronate L (described above). Further, for Examples 6 and 7, the adhesive was the vinylidene fluoride resin solution (B-
1) Add and mix 20 parts, silicone adhesive X40-30
A solution of 04 (manufactured by Shin-Etsu Chemical Co., Ltd.) and 2.0 parts of Coronate L were added and mixed. Table 1
In the table, the non-woven fabric / Teijin Unicell is used as the sheet substrate, and it is a polyester non-woven fabric (trade name: Unicel) manufactured by Teijin Limited with a basis weight of 80 g / m ² . The acrylic resin-impregnated paper is a reinforced paper having a basis weight of 90 g / m ² impregnated with an acrylic resin binder to 150 g / m ² .

Comparative Example 1 The soft vinyl chloride sheet of Example 1 and a polyvinylidene chloride film having a thickness of 0.04 mm were adhered by the same method.
A pressure-sensitive adhesive A-1 obtained in Production Example 4 was obtained by laminating and bonding a 0.05 mm thick aluminum foil in the same manner as in Example 1.
Release paper EKR78 obtained by adding and mixing 1.0 part of Coronate L (previously mentioned) to 100 parts of
(Manufactured by Lintec Co., Ltd.) and then dried at 90 ° C. for 2 minutes to obtain a 50 μm thick adhesive coating film. This was transferred to an aluminum foil surface to obtain a surface protective decorative sheet.

Comparative Example 2 On the ABS resin sheet of Example 3, the tetrafluoroethylene resin film and the metal foil were used as they were without being laminated and bonded. On 100 parts of the pressure-sensitive adhesive A-1 obtained in Production Example 4, 1.0 part of Coronate L (described above) was added and mixed, and a release paper EKR78 (manufactured by Lintec Co.) coated with a silicone mold release agent was applied. Was applied to the surface of the resin composition and dried at 90 ° C. for 2 minutes to obtain a pressure-sensitive adhesive coating having a thickness of 50 μm.

Comparative Example 3 In the same manner as in Example 5 except that the metal foil layer was not provided, the ETFE film and the impregnated paper were laminated and adhered to 100 parts of the pressure-sensitive adhesive A-1 obtained in Production Example 4, 1.0 part of Coronate L (described above) was added and mixed, and coated on a release paper EKR78 (manufactured by Lintec Co., Ltd.) coated with a silicone release agent, dried at 90 ° C. for 2 minutes, and adhered to a thickness of 50 μm. An agent coating film was obtained. This was transferred to an aluminum foil surface to obtain a surface protective decorative sheet.

Table 1 shows the constituents of Examples 1 to 8 and Comparative Examples 1 to 3 and the evaluation results. Each evaluation method is as follows. (Evaluation Method) Surface Contamination: 150 mm x 1 for each surface protective decorative sheet
A 50 mm x 1.0 mm aluminum plate was adhered and irradiated with a sunshine weather meter for 1000 hours to conduct a weather resistance test. After taking out, the surface was cleaned with methyl alcohol, and the stainability was evaluated by visual comparison with an unirradiated test body. Moisture resistance: It was performed according to the moisture permeability test method of JIS Z 0208. However, the measurement temperature was 30 ° C., and the pressure-sensitive adhesive surface was fixed to the cup side. The unit of results shown in Table 1 is
g / m ² · 24 hrs 90%. Antistatic property: Rubbing the surface of each sheet with a cotton cloth several times to measure the electrostatic voltage on the surface with an electrostatic voltage measuring device (Statilon TH,
It was measured by Shishido Electrostatic Co., Ltd.). The resulting values in Table 1 are KV. Edgeability: Each sheet was attached to a kitchen system kitchen door made of an MDF board having a thickness of 30 mm, and the sharpness of the parting line at the corner was evaluated. Overlap adhesion: Each sheet is 25 mm x 150 mm 2
The pieces were cut one by one, and one adhesive surface was adhered to the other tetrafluoroethylene resin film surface. After 24 hours at 20 ° C., T peeling was performed at a speed of 200 mm / min to measure the adhesive strength. However, for Comparative Examples 1 and 2, the adhesion of the sheet of Example 1 to the PFA film surface was tested. The unit of adhesive force is kgf / 25 mm. (Evaluation of) ◎: Remarkably excellent ○: Good Δ: Normal ×: Inferior

[0048]

[Table 1]

[0049]

EFFECTS OF THE INVENTION The decorative sheet according to the present invention can be made to conform to the base material by carefully venting air from the wall surface and performing the attaching work. For example, even when it is attached to a product with many corners such as furniture, if it is strongly pressed with a scraper or the like, the metal foil is deformed so that the base can be fitted along the corner. In the case where the base has a defective portion, the flexibility of the sheet base material does not strongly pick up the base as when the aluminum foil or the like is attached alone unless strong pressure bonding is applied.

Further, after being attached as a decorative sheet, high waterproofness, antifouling property, heat resistance and antifungal property can be obtained by the effect of the tetrafluoroethylene resin layer, so that the appearance should be maintained for a long time. Is possible. Furthermore, due to the synergistic effect with the metal foil, moisture resistance and antistatic property can be imparted, gas barrier property and flame retardancy can be obtained, and excellent effect for surface protection is exhibited.

[Brief description of drawings]

FIG. 1 shows a schematic sectional view of a surface protective decorative sheet according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Surface protection decorative sheet, 2 ... 4 fluorinated ethylene resin film, 3 ... Adhesive agent, 4 ... Sheet base material, 5 ... Adhesive agent, 6 ... Metal foil, 7 ... Adhesive agent, 8 ... Release paper.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location B32B 33/00 B32B 33/00 (72) Inventor Shinji Sakazaki 200 Nakazato, Noda-shi, Chiba Hitachi Chemical Poly Mar Co., Ltd. Noda Factory (72) Inventor Hirotaka Takahashi 1-13-7 Kanda, Chiyoda-ku, Tokyo Inside Nitatsu Kasei Polymer Co., Ltd. (72) Inventor Norio Asagono 3-7 Nishi-Shinjuku, Shinjuku-ku, Tokyo No. 1 Tokyo Gas Fluoro Material Co., Ltd. (72) Inventor Kazuo Hatasegawa 1-15-7 Kameguro, Meguro-ku, Tokyo Tominai Co., Ltd.

Claims (3)

[Claims] 1. A surface of a sheet substrate is made of any one of ethylene-4fluoroethylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer and tetrafluoroethylene-6fluoropropylene copolymer. A surface-protection decorative sheet comprising a selected tetrafluoroethylene-based resin film layer and a metal foil layer and an adhesive layer sequentially laminated on the other surface. 2. The adhesive is a composition comprising an acrylic acid ester copolymer obtained by adding or mixing a compound having an alkoxysilyl group and a liquid tackifier as essential components. 1. The surface protective decorative sheet according to 1. 3. A pressure-sensitive adhesive, an acrylic ester polymer (A), a vinylidene fluoride copolymer (B), and a silicone pressure-sensitive adhesive (C) having a dimethylpolysiloxane skeleton.
The surface protective decorative sheet according to claim 1, which is a composition obtained by mixing and.