JP2002113834A - Decorative sheet and a decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which is excellent in folding processability and thermoforming properties, can be laminated on a base material in a complex three-dimensional shape, and can produce a decorative material excellent in various surface properties such as solvent resistance, fouling resistance, surface hardness, and scratch resistance and the decorative material using the decorative sheet. SOLUTION: In the decorative sheet, a transparent or translucent surface sheet 2 of a crystalline polyester resin in an amorphous state is laminated on a base material sheet 1 of an amorphous polyester resin. The decorative sheet, while being molded along the surface of the base material for the decorative material in a three-dimensional shape by a vacuum forming method, is laminated/bonded, and simultaneously the crystalline polyester resin of the surface sheet 2 is crystallized by heat during the molding, so that decoration is applied to follow the three-dimensional shape of the surface of the base material for the decorative material, and the decorative material having good surface physical properties can be obtained easily.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to interior and exterior materials and construction materials for buildings such as houses, construction materials such as fittings, furniture and fixtures, and cosmetics used for surface makeup of household equipment and home appliances. The present invention relates to a sheet, particularly to a decorative sheet suitable for use by laminating by a vacuum forming method on a surface of a decorative material substrate having a three-dimensional three-dimensional shape composed of a wooden substrate, an inorganic board, a metal plate, and the like. Further, the decorative sheet also includes a decorative material in which the decorative sheet is laminated on a surface of a substrate.

[0002]

2. Description of the Related Art Conventionally, in the production of a cosmetic material having a complicated three-dimensional three-dimensional shape, such as a kitchen door or a member for a schoolchild desk, for example, a three-dimensional three-dimensional shape of a target cosmetic material is previously formed. On the surface of a decorative material base such as a wood base,
The decorative sheet made of thermoplastic resin is stretched while being softened by heating.
By applying pressure to the space on the side of the decorative material substrate of the decorative sheet and pressurizing the space on the opposite side, the decorative sheet is adhered while being formed along the three-dimensional shape of the surface of the decorative material substrate. Lamination, a so-called vacuum forming method, is widely adopted.

The above-mentioned vacuum forming method involves heating a decorative sheet and reducing the pressure of the decorative sheet against the surface of the decorative material substrate due to the pressure difference between the space on the decorative material substrate side and the space on the opposite side. The imposition is performed through a flexible and elastic membrane rubber such as a silicone rubber film stretched on the side opposite to the decorative material base of the decorative sheet, that is, a so-called membrane press method, and without using the membrane rubber. There is a so-called membraneless press method in which the decorative sheet is directly heated and the decorative sheet itself is used as a pressing force impressing medium.
In Japan, vacuum presses of the membrane press method have been mainly used in the past.However, vacuum presses of the membraneless press method have become the mainstream overseas, and in Japan, their formability and productivity are high. Therefore, the adoption of the membraneless press method is increasing in some cases.

As described above, as a decorative sheet used for forming into a three-dimensional three-dimensional shape by a vacuum forming method, conventionally, it has a unique excellent thermoformability, and also has a surface hardness, abrasion resistance, and chemical resistance. A decorative sheet made of a polyvinyl chloride resin, which has widely well-balanced properties such as various surface physical properties such as weather resistance and secondary workability, has been most widely used. However, in recent years, polyvinyl chloride resin is suspected of having an endocrine disrupting action (so-called environmental hormone action) in additives such as a plasticizer used in the polyvinyl chloride resin, or remains in an unreacted state. Suspected of causing carcinogenicity of vinyl chloride monomer, and generating harmful substances such as hydrogen chloride and dioxin during combustion, etc., are regarded as problems, and do not contain chlorine that does not have such a problem The substitution with resin has been strongly demanded by society.

To meet such demands, for example, a decorative sheet using a thermoplastic polyolefin resin has already been proposed (see JP-A-6-16832), and the replacement with a decorative sheet made of polyvinyl chloride resin has rapidly progressed. I am doing it. However, as this polyolefin resin,
For example, decorative sheets and the like using ordinary general-purpose polypropylene resin have sufficiently excellent performance for laminating on a flat plate, but lack flexibility for bending or vacuum forming, Whitening, cracks, fractures,
Molding defects such as necking, and pattern elongation due to locally uneven expansion are apt to occur, and it has been difficult to use them for applications such as forming into the above-described three-dimensional three-dimensional shape.

On the other hand, resins such as polypropylene
Various attempts have been made to impart flexibility by copolymerization with a soft monomer, blending of a soft component such as an elastomer, and the like.
For cosmetic sheets, there is a problem that heat resistance and surface scratch resistance are poor. As a result, as a result, a decorative sheet made of a polyolefin resin has not been able to satisfy all the necessary physical properties.

One of the causes of the problems in the above-mentioned decorative sheet made of polyolefin resin is that the polyolefin resin is essentially a crystalline polymer, and crystallized portions are scattered in an amorphous matrix. It is considered that the resin has a non-uniform structure. Therefore, in order to fundamentally solve the above problem, it is considered preferable to use a resin having a uniform structure, for example, an essentially amorphous resin. As one type of decorative sheet using such an amorphous resin, there has already been proposed a decorative sheet made of an amorphous polyester resin (see JP-A-7-24979).

However, the decorative sheet made of the amorphous polyester resin has not always been satisfactory. The main reasons are that amorphous polyester resin is significantly inferior in solvent resistance and chemical resistance compared to olefin resin, etc., and that the surface hardness and scratch resistance as a decorative sheet are not always sufficient. Is mentioned. To some extent, this problem can be solved by providing a thick top coat layer made of a hard curable resin having excellent solvent resistance and chemical resistance on the surface, but sufficient surface properties are imparted. If an attempt is made to provide an excessively thick top coat layer, the flexibility and thermoformability of the decorative sheet will be reduced as a result,
Following a complicated three-dimensional three-dimensional shape becomes difficult.

As one solution to the above problem, a thermoplastic resin layer having excellent solvent resistance, for example, a layer made of a polyolefin resin or a crystalline polyester resin is provided on the surface of the amorphous polyester resin layer. It is also conceivable to provide them.
However, when the crystalline resin layer is present on the surface of the decorative sheet in this manner, the flexibility and thermoformability of the decorative sheet as a whole are reduced, or the crystalline resin on the surface during molding is reduced. There has been a problem that a layer of the layer may be whitened or cracked, making it impossible to obtain a good product.

[0010]

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems in the prior art, and it is an object of the present invention to provide excellent bending workability and thermoformability. Production of cosmetic materials that can be sufficiently laminated on substrates with complex three-dimensional shapes, and that also have excellent surface properties such as solvent resistance, chemical resistance, surface hardness, and scratch resistance. And a decorative material using the decorative sheet.

[0011]

According to the present invention, a transparent or translucent top sheet made of an amorphous crystalline polyester resin is laminated on a base sheet made of an amorphous polyester resin. It is a decorative sheet characterized by the following.

Further, the present invention is characterized in that the decorative sheet is laminated on the surface of a base material for decorative material and the amorphous crystalline polyester resin constituting the surface sheet is crystallized. It is a cosmetic material.

The present invention also provides the decorative material, wherein the decorative material base has a three-dimensional three-dimensional shape on a surface, and the decorative sheet is laminated on the surface by a vacuum forming method. Further, the present invention is a decorative material, characterized in that crystallization of the amorphous crystalline polyester resin constituting the topsheet is performed simultaneously with lamination by the vacuum forming method.

[0014]

BEST MODE FOR CARRYING OUT THE INVENTION As shown in FIG. 1, a decorative sheet according to the present invention has a transparent or translucent amorphous polyester resin on a base sheet 1 made of at least an amorphous polyester resin. Are laminated. This decorative sheet is usually provided with a pattern layer 3 for the purpose of giving a design pattern by printing or the like. Further, if necessary, a surface protective layer 4 such as a top coat layer is provided on the top sheet 2, or an adhesive layer 5 for bonding to a base material for a decorative material is provided on the back surface. (Fig. 2).

When the decorative sheet of the present invention is required to have sufficient concealing properties against undesired colors and defects on the surface of the base material for decorative material, the decorative sheet is used together with the picture layer 3 on the back side thereof. If the concealing layer 6 is provided (FIG. 3), or the picture layer 3 is sandwiched between the base sheet 1 as a concealed colored sheet and the transparent or translucent top sheet 2 (FIG. 4). good.

Conversely, in order to obtain a decorative material utilizing the texture of a base material for a decorative material such as a wooden base material, the decorative sheet must have a transparent base material as a whole. Therefore, both the base sheet 1 and the top sheet 2 are made transparent or translucent, and the pattern layer 3 is not provided, or a transparent ink is used or a printing layer having many dots such as halftone dots is used. Therefore, it is necessary to provide transparency or transparency. At that time, the pattern layer 3 is
(See FIG. 4).
However, when the design layer 3 is provided on the back surface side of the base material sheet 1 (FIG. 3), the thickness of the transparent layer on the design layer 3 is increased, and a decorative material excellent in painting feeling and depth feeling is obtained. This is advantageous.

In addition to the above, the decorative sheet of the present invention may be embossed on the surface on the side of the top sheet 2 if necessary.
By filling the embossed concave portion with a coloring agent, a three-dimensional design feeling can be further improved. The shape of the embossing is arbitrary as desired, for example, an arbitrary pattern such as a wood grain conduit groove shape, a satin texture, a grain shape, a hairline shape, a parallel linear shape or a parallel curved shape, or a combination thereof. In addition, when embossing is provided on the surface, as shown in FIGS. 1 to 3, it is preferable that the pattern layer 3 is provided on the back side of the transparent or translucent base material sheet 1. This is advantageous because the thickness of the upper transparent layer is increased, and the formation of a deep emboss having an excellent three-dimensional design feeling is facilitated.

In the decorative sheet of the present invention, the non-crystalline polyester resin constituting the base sheet 1 is a thermoplastic polyester resin having a crystallization rate that is so low that it hardly crystallizes under ordinary resin molding conditions. If it is,
Specifically, in the condensation polymerization reaction of a dicarboxylic acid such as terephthalic acid or an ester thereof with a diol such as ethylene glycol, for example, as a dicarboxylic acid, for example, sebacic acid, eicoic acid, dodecandioic acid, dimer acid, cyclohexanedicarboxylic acid, or the like. Introducing long-chain aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids, and / or
Examples of the diol component include a copolymerized polyester resin obtained by introducing a polyether diol such as polyethylene glycol, polytetraethylene glycol, and cyclohexane dimethanol and / or an alicyclic diol.

Among them, the most typical one is a so-called PET-
G is a commercially available 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin,
Specific examples of the sheet made of the resin include those commercially available as “NAGASEA-PET” manufactured by Nagase & Co., Ltd. and “Revester” manufactured by Riken Vinyl Industry Co., Ltd.

The amorphous crystalline polyester resin constituting the topsheet 2 is, for example, a crystalline polyester resin which is originally crystalline, such as a polyethylene terephthalate resin, a polybutylene terephthalate resin, and a polyethylene naphthalate. Preferably 5% crystallinity
Hereinafter, it is molded into a sheet under molding conditions.

The most commonly used amorphous polyester resin sheet in the amorphous state is a pure or almost pure polyethylene terephthalate resin commercially available as a so-called A-PET resin. Teijin Tetron sheet (A-PE)
T) ”, Toyobo Co., Ltd.“ Toyobo PETMAX Sheet A Series ”, Kanebo Co., Ltd.“ Kanebo A-PET ”
Sheets and the like that are commercially available can be used.

In the initial amorphous state, the surface sheet 2 made of an amorphous crystalline polyester resin has excellent flexibility and thermoformability, which can be bent and three-dimensionally formed. And partially undergoes crystallization through a heating step such as vacuum forming or heat lamination (depending on heating conditions, etc., usually has a crystallinity of 30 to 60).
%), Excellent surface hardness, scratch resistance, solvent resistance, chemical resistance, and the like are exhibited, thereby contributing to the realization of various decorative materials having various surface physical properties.

As described above, the decorative sheet of the present invention hardly crystallizes under heating conditions in ordinary processing such as vacuum forming and heat lamination, and has excellent flexibility, bendability, thermoformability and transparency. Mainly, a base sheet 1 made of an amorphous polyester resin, which maintains the property, and has sufficient flexibility and moldability on its surface because it is in an amorphous state before a heating step. By laminating a surface sheet 2 made of an amorphous crystalline polyester resin, which is crystallized through the process and exhibits excellent various surface physical properties, flexibility and bending workability peculiar to the amorphous polyester resin are obtained. In addition, it is possible to easily obtain a cosmetic material having various surface physical properties while sufficiently utilizing thermoformability, transparency, and the like.

When the decorative sheet of the present invention is used for vacuum forming, the amorphous polyester resin constituting the base sheet 1 and the amorphous crystalline polyester resin constituting the topsheet 2 are formed by glass transition. Temperature 65-85
When a material having a temperature of ° C. is selected, the molding operation can be performed efficiently under substantially the same molding conditions as in the case of a decorative sheet made of a conventional polyvinyl chloride resin. For example, the aforementioned 1,4-
The glass transition temperature of the cyclohexane dimethanol copolymerized polyester resin is 80 ° C, showing good thermoformability in combination with its excellent flexibility, and a decorative sheet with excellent followability to complicated three-dimensional three-dimensional shapes. Obtainable.

If necessary, the base sheet 1 and the top sheet 2 may be, for example, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a filler, a flame retardant, a gloss regulator, an antistatic agent,
One or more selected from various additives such as a dew condensation inhibitor, a lubricant, an antibacterial agent, and a fungicide may be added. In addition to providing the concealing property, the coloring agent such as the dye or the pigment may be used as long as the picture layer 3 and / or the base material for the decorative material can be seen even if transparency is required. It may be added and colored.

The thicknesses of the base sheet 1 and the topsheet 2 are not particularly limited. However, if the topsheet 2 is too thin, its surface hardness, scratch resistance, solvent resistance, chemical resistance, etc., even after molding and crystallization. At least 1 μm
m or more, usually 5 μm or more. On the other hand, if the thickness is too large, the design may be impaired due to the decrease in transparency (increase in haze) due to crystallization after the heating step. Therefore, the thickness is usually preferably 50 μm or less.

The thickness of the base sheet 1 may be appropriately designed in consideration of the total thickness of the decorative sheet (usually about 50 to 300 μm) and the thickness required for the top sheet 2 described above. If the thickness of the base sheet 1 is too small in comparison with the thickness of the top sheet 2, the bending workability and the thermoformability are inferior. Therefore, the thickness ratio of the base sheet 1 to the top sheet 2 is 95%. : 5 to 60:40.

The method of laminating the base sheet 1 and the topsheet 2 is not particularly limited, and includes, for example, a dry lamination method or a wet lamination method with an adhesive, a heat lamination method with or without an adhesive, and a melt extrusion method. Lamination method,
Any conventionally known laminating method such as a co-extrusion method can be appropriately employed.

The picture layer 3 represents a picture of a desired design by printing or the like, and there are no restrictions on the kind of the picture, constituent materials, forming method and the like. In general, the pattern is, for example, a wood pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometric pattern, a character or a symbol, or a combination thereof. Absent. As a constituent material, for example, a printing ink or a paint in which a urethane-based resin, an acrylic resin, a vinyl-based resin, a polyester-based resin, a cellulose derivative, or the like is used as a vehicle and a coloring agent such as a dye or a pigment is dispersed therein. Can be used.

The pattern layer 3 may be formed by a known printing method such as a gravure printing method, an offset printing method, a gravure offset printing method, a screen printing method, a flexographic printing method, a relief printing method, an ink jet printing method, or the like. In the case of a state, for example, gravure coating method, microgravure coating method, roll coating method, knife coating method, air knife coating method, die coating method, lip coating method, comma coating method, dip coating method, flow coating method, spray coating method And other known coating methods.

Before printing the pattern layer 3, the surface to be printed is preliminarily subjected to an easy adhesion treatment such as a corona discharge treatment, a plasma treatment, a flame treatment, an ionizing radiation treatment, an anchor treatment or a primer treatment to improve the adhesiveness. This can also be arbitrarily performed as needed.

Although the material of the surface protective layer 4 is not particularly limited, it is desirable to use a curable resin from the viewpoint of various surface properties. Specifically, for example, a urethane resin, an amino alkyd resin, a melamine resin, an epoxy resin, an unsaturated polyester resin, a urea resin, a thermosetting resin such as a phenol resin, an unsaturated polyester resin, An ionizing radiation curable resin such as an acrylate resin or a methacrylate resin can be used.

Among them, a two-component curable urethane resin excellent in balance between surface physical properties such as surface hardness and abrasion resistance and flexibility suitable for bending and three-dimensional molding, that is, acrylic polyol or acrylic A thermosetting resin or the like, which is mainly composed of polyether and is crosslinked and cured by adding an isocyanate curing agent, is most suitable for the purpose of the present invention. Although the thickness of the surface protective layer 4 is not particularly limited in the present invention, it is usually appropriate to set it to about 3 to 20 μm.

If necessary, the surface protective layer 4 may be, for example, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a gloss adjusting agent, a lubricant, an antistatic agent, a dew condensation preventing agent, an antibacterial agent, a fungicide, or an antifriction agent. One or more additives selected from various additives such as agents, coloring agents, and fillers may be added. The surface protective layer 4 is made of the same or different
It may be composed of a plurality of layers. For example, a second layer containing no such particles is provided on a first layer containing high-hardness abrasion-resistant particles such as silica, alumina, and silicon carbide. To achieve both abrasion resistance and scratch resistance and surface gloss and surface smoothness, and to provide a second layer having a different gloss state on the first layer provided on the entire surface in an arbitrary pattern. Thus, applications such as expressing a visual three-dimensional effect due to a gloss change are also possible.

As mentioned above, the decorative sheet of the present invention is used by bonding and laminating on the surface of various kinds of base materials for decorative materials with an appropriate adhesive or the like. At the time of the adhesion lamination,
The adhesive may be applied to the surface of the decorative material base material in advance, or may be applied to the back surface of the decorative sheet immediately before the laminating step. In the case of bonding and laminating on the surface of the base material for decorative material by a vacuum or vacuum forming method, 80 to 1
An adhesive layer 5 made of a solid adhesive at room temperature, that is, a hot-melt adhesive (or a heat-sensitive adhesive), which has a property of exhibiting adhesiveness by being melted or softened by heat of about 40 ° C.
Is provided, the step of applying the adhesive before the laminating step becomes unnecessary, and furthermore, the adhesiveness is developed by heating during the laminating step so that the adhesive is excellently bonded, so that there is an advantage that the workability is excellent.

The type of the adhesive used for the adhesive layer 5 is not particularly limited.
From a conventionally known hot melt adhesive such as a vinyl acetate copolymer resin-based, polyamide-based, polyester-based, or polyolefin-based adhesive, a material suitable for a material of a decorative sheet or a base material for a decorative material may be appropriately selected and used. . Above all, when a reaction-curable hot-melt adhesive such as a moisture-curable polyurethane-based adhesive containing an isocyanate group is employed, there is an advantage that the heat-resistant adhesiveness after the adhesive curing is excellent.

The thickness of the adhesive layer 5 depends on the material and surface condition of the base material for a decorative material, but is generally in the range of about 5 to 50 μm, and especially about 10 to 40 μm. Most preferred. Examples of the coating method of the adhesive layer 5 include a roll coating method, a comma coating method, a gravure coating method, a microgravure coating method, a rod coating method, a flow coating method, a knife coating method, an air knife coating method,
The method can be arbitrarily selected from various conventionally known coating methods such as a die coating method, a lip coating method, a spray coating method, and an applicator method.

The material, shape, dimensions, and the like of the decorative material substrate in the decorative material of the present invention are exactly the same as those of the same type of conventional decorative material, and are not particularly limited in the present invention. Specifically, for example, solid wood and veneer of natural wood,
Plywood, laminated wood, medium-density fiberboard, hard fiberboard, particleboard, oriented board, laminated wood, and other metal-based materials such as steel plates, brass plates, stainless steel plates, aluminum plates, and duralumin plates Inorganic base materials such as base materials, natural stone materials, glass, ceramics, plaster boards, slag gypsum boards, calcium silicate boards, slate boards, wool cement boards, asbestos cement boards, glass fiber reinforced concrete boards, lightweight cellular concrete boards, etc. Olefin resin, acrylic resin, styrene resin, ABS resin, polycarbonate resin, polyester resin, synthetic resin base material such as FRP, etc., or a base composed of a mixture, laminate, composite, etc. of two or more selected from these. Materials can be used.

The method of laminating the decorative sheet of the present invention with the base material for decorative material is not particularly limited. For example, a flat press method, a roll laminating method, a soft wrapping method, a vacuum forming method (membrane press method, membraneless method) Pressing method is also possible), and the method can be appropriately selected from various conventionally known laminating methods according to the surface shape of the decorative material base material. In this laminating method, if a laminating method involving heating of the decorative sheet is employed at the time of laminating, the amorphous polyester resin in the amorphous state of the surface sheet is simultaneously formed and adhered to the surface of the decorative material substrate. There is an advantage that the layer can be crystallized and excellent surface properties can be obtained.

However, after the decorative sheet of the present invention is laminated and adhered to the surface of, for example, a flat-shaped decorative material substrate, it is subjected to groove processing such as V-cut from the back side of the decorative material substrate to be bent. When used in the case, the surface sheet may be poorly suited for bending if the surface sheet is crystallized and hardened before bending, so in such a case, the step of heating and crystallizing the surface sheet may include: It is desirable to perform the process after bending the cosmetic material (for example, simultaneously with curing of the adhesive for fixing the bent portion).

[0041]

EXAMPLES Hereinafter, the present invention will be described in more detail by showing specific examples and comparative examples of the present invention.

Example 1 An amorphous polyethylene terephthalate resin layer (crystalline polyester resin layer) having a thickness of 20 μm and a thickness of 80 μm
A non-crystalline 1,4-cyclohexane dimethanol copolymerized polyethylene terephthalate resin layer (non-crystalline polyester resin layer) is laminated on a non-crystalline polyester resin layer side of a transparent co-extruded film. A wood grain pattern is printed by a gravure printing method using a printing ink, and an ethylene-vinyl acetate copolymer resin-based hot melt adhesive having a softening point of 100 ° C. is formed on the printing surface by a gravure coating method. It was applied to 30 μm to obtain a decorative sheet of the present invention.

Comparative Example 1 A wood pattern was printed on the back surface of a transparent polyvinyl chloride resin film having a thickness of 90 μm by a gravure printing method using a urethane resin-based printing ink.
An ethylene-vinyl acetate copolymer resin-based hot melt adhesive at 0 ° C. was applied to a thickness of 30 μm by a gravure coating method to obtain a decorative sheet.

Comparative Example 2 A wood grain pattern was printed on the back surface of a transparent amorphous 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin film having a thickness of 80 μm by a gravure printing method using a urethane resin-based printing ink. On the printing surface, an ethylene-vinyl acetate copolymer resin-based hot melt adhesive having a softening point of 100 ° C. is applied to a thickness of 3 by a gravure coating method.
It was applied to 0 μm to obtain a decorative sheet.

Comparative Example 3 A wood grain pattern was printed on the back surface of a transparent polypropylene resin film having a thickness of 70 μm by a gravure printing method using a urethane resin printing ink.
An ethylene-vinyl acetate copolymer resin-based hot melt adhesive at 00 ° C. was applied to a thickness of 30 μm by a gravure coating method to obtain a decorative sheet.

Comparative Example 4 A wood grain pattern was printed on the surface of a colored polypropylene resin film having a thickness of 100 μm by a gravure printing method using a urethane resin printing ink. Through urethane resin-based dry laminating adhesive,
A decorative sheet was obtained by laminating a transparent polypropylene resin film having a thickness of 100 μm.

Vacuum Forming Test Using the decorative sheets of Example 1 and Comparative Examples 1 to 3, vacuum forming was performed on the surface of a laminated wood substrate cut and formed into a kitchen door having a three-dimensional uneven shape. Vacuum forming and laminating were performed by a machine under a forming condition of a hot platen temperature of 150 ° C. and a thermocompression bonding time of 120 seconds to produce a desired decorative material (kitchen door).
When the molding state and the like of the obtained decorative material were evaluated, they were as shown in the following table.

Performance Comparison Example 1 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Unnecessary Unnecessary Unnecessary Necessary Pre-application of Adhesive Vacuum Formability of Adhesive Good Good Good Bad Bad Corner Elongation None No No Yes Yes Yes Corner whitening No No No Yes Yes Adhesive strength Good Good Good Good Good Surface hardness 2B or more 2B or more 6B 6B 6B Solvent resistance Good Good Bad Good Good (Lacquer thinner) Hydrogen chloride when burning No Yes No No No Occurrence of

As described above, the decorative material obtained by using the decorative sheet of the present invention is an environmentally friendly product that does not generate harmful substances such as hydrogen chloride when burned. The decorative sheet was formed by sufficiently following the three-dimensional uneven shape of the surface of the material base material, and had excellent appearance quality without forming defects such as pattern elongation, whitening, and cracks of the decorative sheet, and In terms of surface physical properties such as surface hardness and solvent resistance, it was confirmed that the cosmetic material had sufficient performance as various cosmetic materials.

[0050]

The decorative sheet of the present invention is obtained by laminating a transparent or translucent top sheet made of an amorphous crystalline polyester resin on a base sheet made of an amorphous polyester resin. Before the treatment, both the base sheet and the topsheet are made of amorphous polyester resin with a uniform structure, so that the decorative sheet as a whole has flexibility and thermoformability comparable to those of conventional polyvinyl chloride resin decorative sheets. It is not only suitable for bending, but also used for laminating on the surface of a three-dimensional three-dimensional base material for cosmetics by vacuum forming method, whitening and cracking, breaking, necking,
The shaping can be performed in a manner that faithfully follows the three-dimensional three-dimensional shape of the surface of the base material for a cosmetic material without locally causing uneven elongation or the like. Moreover, by applying a heat treatment after or at the same time as the lamination to the base material for the decorative material, the amorphous polyester resin in the amorphous state of the topsheet is crystallized, so that surface hardness, abrasion resistance, and scratch resistance are provided. It has a remarkable advantage that a cosmetic material having excellent properties, solvent resistance, chemical resistance, stain resistance and the like can be easily obtained.

Particularly, the decorative material obtained by laminating and adhering the decorative sheet to the surface of the base material for decorative material while forming it by the vacuum forming method is a crystalline polyester in an amorphous state of the surface sheet by heating at the time of vacuum forming. Since the resin is crystallized, the forming and laminating step and the heat crystallization step can be performed at the same time, and in addition to being excellent in production efficiency, the decorative sheet is crystallized while being stretched at the time of vacuum forming, so that the crystal is formed. Since there is little increase in the haze of the surface sheet and the decrease in surface gloss due to the surface treatment, there is a remarkable advantage that a decorative material excellent in design in addition to various surface physical properties can be easily obtained.

[Brief description of the drawings]

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

FIG. 2 is a schematic sectional view showing an embodiment of the decorative sheet of the present invention.

FIG. 3 is a schematic sectional view showing an embodiment of the decorative sheet of the present invention.

FIG. 4 is a schematic sectional view showing an embodiment of the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Base sheet 2 ... Surface sheet 3 ... Picture layer 4 ... Surface protective layer 5 ... Adhesive layer 6 ... Concealment layer

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B29L 31:10 B29L 31:10 31:44 31:44 31:58 31:58 (72) Inventor Hiroshi Shibata 1-5-1, Taito, Taito-ku, Tokyo Letterpress Printing Co., Ltd. F-term (reference) 4F100 AK41A AK41B BA02 BA10A BA10B BA16 GB07 GB48 GB81 HB31 JA11B JA12A JA12B JB01 JK09 JK12 JK14 JL01 JL09 JN01B 4F208 AAH37 MA01 MB01 MB22 MG04

Claims (3)

[Claims] 1. A decorative sheet comprising a transparent or translucent surface sheet made of an amorphous crystalline polyester resin laminated on a base sheet made of an amorphous polyester resin. 2. A decorative sheet according to claim 1, wherein the decorative sheet is laminated on a surface of a base material for decorative material, and the amorphous crystalline polyester resin constituting the surface sheet is crystallized. And cosmetic materials. 3. The decorative material base material has a three-dimensional three-dimensional shape on the surface, and the decorative sheet according to claim 1 is laminated on the surface by a vacuum forming method, and the surface sheet is laminated. 3. The decorative material according to claim 2, wherein crystallization of the amorphous crystalline polyester resin constituting (b) is performed simultaneously with lamination by the vacuum forming method. 4.