JP2002113833A - Decorative sheet and 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 of a complex three-dimensional shape, and can produce a decorative material excellent in various surface physical properties including solvent resistance, chemical resistance, surface hardness, and scratch resistance and the decorative material using the sheet. SOLUTION: In the decorative sheet, a transparent or translucent amorphous polyester resin layer 12 and a transparent or translucent amorphous crystalline polyester resin layer 13 are laminated in turn on a base material sheet 11 of a polyolefin resin or a thermoplastic resin such as an amorphous polyester resin. The decorative material is obtained by laminating the decorative sheet on the three-dimensional base material preferably by a vacuum forming method.

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 using an amorphous polyester resin (Japanese Patent Laid-Open No. 7-24979).
Reference).

[0008] However, decorative sheets using this amorphous polyester resin have not always been fully satisfactory. The main reason is that amorphous polyester resins are inferior to various surface properties such as solvent resistance, chemical resistance, surface hardness, and scratch resistance as compared with olefin resins and the like. In particular, in order to improve the bending processability and vacuum forming suitability, when the amorphous polyester resin is softened by copolymerization of the third component or the like, the various surface properties described above tend to decrease, and the flexibility and It is difficult to achieve both moldability and various surface properties. 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 the top coat layer is provided with an excessively large thickness, the flexibility and thermoformability of the decorative sheet are reduced, and it is difficult to follow a complicated three-dimensional three-dimensional shape.

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 amorphous polyester resin layer and a transparent or translucent amorphous crystalline polyester resin are provided on a base sheet made of a thermoplastic resin. And a decorative sheet formed by sequentially laminating layers.

Further, the present invention provides the above decorative sheet,
The decorative sheet is characterized in that the thermoplastic resin forming the base sheet is a polyolefin resin.

Further, the present invention provides the decorative sheet,
The decorative sheet is characterized in that the thermoplastic resin forming the base sheet is an amorphous polyester resin.

[0014] The present invention is also a decorative material characterized in that any one of the decorative sheets described above is laminated on the surface of a decorative material base material by a vacuum forming method.

[0015] The present invention also provides the decorative material, wherein the amorphous polyester resin layer is partially crystallized at the same time as the decorative sheet is laminated on the decorative material base by a vacuum forming method. A decorative material characterized by comprising:

[0016]

BEST MODE FOR CARRYING OUT THE INVENTION As shown in FIG. 1, a decorative sheet 1 of the present invention is provided on a base sheet 11 made of a thermoplastic resin.
A transparent or translucent amorphous polyester resin layer 12,
A transparent or translucent amorphous crystalline polyester resin layer 13 is sequentially laminated. The decorative sheet 1 is generally provided with a pattern layer 14 for the purpose of giving a desired design pattern by printing or the like. Also, if necessary, the surface of the amorphous crystalline polyester resin layer 13 on the side of the amorphous state is provided with a concavo-convex pattern by embossing 15, or the concave portion of the concavo-convex pattern is filled with a coloring agent by a wiping method or the like, A surface protective layer 16 such as a top coat layer may be provided on the front surface, or a primer layer 17 for facilitating adhesion to the base material for decorative material 2 may be provided on the back surface.

The decorative sheet 1 of the present invention is provided with a decorative material substrate 2
When it is necessary to impart sufficient concealing properties to undesired colors and defects on the surface of the base sheet 11, an opaque pigment is added to the thermoplastic resin constituting the base sheet 11 to obtain a concealing colored sheet. In addition, a hiding layer (not shown) made of a printing ink or a paint containing a large amount of an opaque pigment may be provided on the back side of the picture layer 14.
Conversely, when trying to obtain a decorative material utilizing the texture of the decorative material base material 2, the transparent or translucent base material sheet 11 is used and the picture layer 14 is not provided, or Transparency or see-through may be provided by using a transparent ink for the picture layer 14 or by providing the picture layer 14 in a pattern with many holes such as halftone dots.

In the decorative sheet of the present invention, the kind of the thermoplastic resin constituting the base sheet 11 is not particularly limited, and examples thereof include polyolefin resins such as polyethylene, polypropylene, polybutene-1, and poly-4-methylpentene; Olefins such as ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, ethylene- (meth) acrylic acid (ester) copolymer, and ethylene-unsaturated carboxylic acid copolymer metal hydrate (so-called ionomer) -Based copolymer resin, polyethylene terephthalate, polybutylene terephthalate, polyethylene terephthalate
Isophthalate copolymer, polyethylene naphthalate,
Polyarylate, polyester resins such as polycarbonate, polyacrylonitrile, polymethacrylonitrile, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polymethyl acrylate,
Acrylic resins such as polyethyl acrylate and polybutyl acrylate, styrene resins such as polystyrene, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, 6-nylon, 6 , 6-Nylon, 6,10-
Polyamide resins such as nylon, vinyl resins such as polyvinyl acetate, polyvinyl alcohol, polyvinyl acetal and polyvinyl butyral; cellulose derivatives such as acetylcellulose and nitrocellulose;
Films or sheets comprising a mixture of more than one kind, copolymers, laminates, composites and the like can be used.

However, in consideration of adaptation to environmental problems, which are rapidly becoming a social problem in recent years, the use of a resin containing a halogen element such as chlorine or fluorine, such as a polyvinyl chloride resin or a polyvinyl fluoride resin, is not considered. Undesirably, it is desirable to use a non-halogen resin. Among them, the price and distribution volume in the market, the ease of procurement, the balance of moderate flexibility and strength as a base sheet for decorative sheets, the suitability for bending, cutting / cutting, thermoforming, etc. It is most preferable to employ a polyolefin-based resin or a polyester resin from various aspects such as surface physical properties such as abrasion resistance and solvent resistance and weather resistance.

As the above-mentioned polyolefin resin, various homopolymers and copolymers are known, including the above-mentioned ones. Among them, polypropylene resin is most preferable as a base sheet material for decorative sheet. That is, a homopolymer or a copolymer containing polypropylene as a main component, specifically, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and
Having a polypropylene crystal part, and an α-olefin having 2 to 20 carbon atoms other than propylene, preferably ethylene,
A propylene-α-olefin copolymer containing at least 15 mol% of a comonomer of butene-1, 4-methylpentene-1, hexene-1 or octene-1 can be exemplified. Further, modifiers such as ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber, atactic polypropylene and the like which are usually used for softening a polypropylene resin are used. It can also be added.

In addition to the polypropylene-based resin, polyolefin-based resins which can be suitably used for the base sheet 1 include high-density polyethylene having excellent balance between flexibility, moldability, strength and stiffness, and crystalline polyolefin components. Olefin-based thermoplastic elastomer resin (TPO) made of a simple blend, block copolymer or cross-linked product of styrene and an amorphous elastomer component and having both properties as a thermoplastic resin and properties as an elastomer. it can.

The polyester resin may be a general-purpose crystalline polyester resin such as the polyethylene terephthalate, polybutylene terephthalate, or polyethylene naphthalate described above. It is a non-crystalline polyester resin with excellent properties and thermoformability. The non-crystalline polyester resin is a polyester resin having a crystallization rate reduced to a level that hardly causes crystallization under ordinary molding conditions, and specifically, for example, aromatic resins such as terephthalic acid and naphthalenedicarboxylic acid. In the condensation polymerization reaction of a dicarboxylic acid or an ester thereof with an aliphatic diol such as ethylene glycol or 1,4-butanediol, for example, sebacic acid, eicoic acid, dodecanedioic acid, dimer acid, cyclohexanedicarboxylic acid, or the like as a dicarboxylic acid component Polyether-based diols having hydroxyl groups at both ends, such as polyethylene glycol, polytetramethylene glycol, cyclohexane dimethanol, etc., into which long-chain aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids are introduced. And / or an alicyclic diol It is equal to copolymerized polyester resin prepared to enter.

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 base sheet 11 is selected from various additives such as an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, a flame retardant, and a filler, if necessary. One or more kinds may be added. The base sheet 11 may be transparent or translucent, or may be colored transparent or colored opaque by the addition of a coloring agent. In the case where opacity against undesired colors and defects on the surface is required, the base sheet 11 is made opaque by adding an opaque pigment such as a titanium oxide pigment, an iron oxide pigment or carbon black. Is desirable.

The thickness of the base sheet 11 is not particularly limited. The total thickness of the desired decorative sheet 1 and the surface side selected from the viewpoints of bending workability, thermoformability, embossing suitability, surface physical properties, and the like. The thickness of the transparent or translucent non-crystalline polyester resin layer 12 and the transparent or translucent non-crystalline crystalline polyester resin layer 13 and the workability and economics of the base sheet 11 itself are comprehensively considered. And may be determined appropriately. Generally, the total thickness of the decorative sheet 1 is 10
About 0 to 500 μm, especially 200 to 400 μm
The degree is most preferred. The ratio of the base sheet 11 to the total thickness of the decorative sheet 1 is usually preferably about 30 to 60% from the viewpoint of moldability, and the thickness of the base sheet 11 is 30 to 3%.
It is about 00 μm, and most preferably about 50 to 200 μm.

The non-crystalline polyester resin layer 12 is intended to provide the decorative sheet 1 of the present invention with excellent flexibility and thermoformability which can sufficiently cope with not only bending but also three-dimensional forming. It is provided in. The non-crystalline polyester resin has extremely uniform moldability due to its uniform amorphous structure, and molding defects such as necking, breakage, whitening, and pattern elongation due to uneven stretching during bending and thermoforming. Is hardly generated. Moreover, since there is no light scattering due to the difference in the refractive index between the crystalline part and the non-crystalline part in the crystalline resin, the decorative sheet 1 having excellent transparency (low haze property) and excellent design can be obtained. There are advantages too.

The non-crystalline polyester resin used for the non-crystalline polyester resin layer 12 is the same non-crystalline thermoplastic polyester resin as that described above as the non-crystalline polyester resin usable for the base sheet 11. Can be used. Above all, the 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin is flexible and excellent in moldability, and of course can sufficiently follow the three-dimensional three-dimensional cosmetic base material 2. Since the glass transition temperature is about 80 ° C., there is an advantage that, in thermoforming such as vacuum forming, it can be satisfactorily molded under the same molding conditions as in the case of a conventional polyvinyl chloride resin decorative sheet.

On the other hand, the crystalline polyester resin layer 13 in the amorphous state can provide the decorative sheet 1 of the present invention with good chemical resistance (particularly alkali resistance) and solvent resistance without impairing flexibility and thermoformability. It is provided for the purpose of imparting surface properties such as properties, surface hardness, and scratch resistance. That is, the crystalline polyester resin in the amorphous state, for example, polyethylene terephthalate, polyethylene terephthalate-isophthalate copolymer, polybutylene terephthalate, polyethylene naphthalate, and the like, a normal thermoplastic polyester resin that is crystalline, The film is formed into a sheet under the molding conditions that are not to be formed (preferably, the crystallinity is 5% or less). Since the film is hardly contained, the crystal part is hardly formed even by deformation during bending or thermoforming. It is unlikely to cause a phase shift with the non-crystalline part, and although relatively inferior to the non-crystalline polyester resin, relatively uniform moldability is obtained, and it is difficult to cause molding defects such as necking, breakage, whitening, pattern elongation. In addition to non-crystalline polyester resin, it has better chemical resistance (especially alkali resistance), solvent resistance, surface hardness, etc. This is because are excellent.

As the amorphous crystalline polyester resin, one having a glass transition temperature of 65 to 85 ° C. (depending not only on the kind of resin but also on film forming conditions) is used in thermoforming such as vacuum forming. There is an advantage that molding can be performed well under the same molding conditions as in the case of a decorative sheet made of a conventional polyvinyl chloride resin. Thus, for this purpose, homopolyethylene terephthalate or polyethylene terephthalate-
A polyethylene terephthalate polyester resin such as an isophthalate copolymer is most suitable.

The most common amorphous polyester resin in the amorphous state is a pure or nearly pure polyethylene terephthalate resin which is commercially available as a so-called A-PET resin. Examples include commercially available “Teijin Tetron sheet (A-PET)” manufactured by the company, “Toyobo PETMAX sheet A series” manufactured by Toyobo Co., Ltd., and “Kanebo A-PET sheet” manufactured by Kanebo Co., Ltd. .

The amorphous crystalline polyester resin layer 13 is heated by heat treatment at the time of sticking to the base material 2 for the decorative material, at the time of bending after the sticking, or at any time after the bending. When partially crystallized (generally about 30 to 60% depending on heating conditions), various surface properties such as surface hardness, scratch resistance, solvent resistance, and chemical resistance can be further improved. In particular, in the case of performing the thermoforming by the vacuum forming method along the surface of the base material 2 for a cosmetic material having a three-dimensional three-dimensional shape and simultaneously laminating and adhering, the heat at the time of the thermoforming, and at the time of the thermoforming, When stretched, by the effects of heat and stretching, it can be crystallized at the same time as forming and laminating and can exhibit excellent surface physical properties,
There is an advantage that a cosmetic material having various surface properties can be produced with the highest workability.

The thickness of the non-crystalline polyester resin layer 12 and the non-crystalline crystalline polyester resin layer 13 is not particularly limited, and the total thickness of the decorative sheet 1 and the thickness of the base sheet 1 described above. In view of this, the design may be appropriately made in consideration of the bending workability, moldability, designability, and the like. Generally, the total thickness of both is 50 to 200 μm
It is preferable to set the degree.

Regarding the composition ratio of the amorphous polyester resin layer 12 and the amorphous crystalline polyester resin layer 13, when comparing the two, the amorphous polyester resin layer 1
No. 2 is superior in bending workability and formability, and the surface physical properties such as solvent resistance, chemical resistance, surface hardness, and scratch resistance are better in the amorphous crystalline polyester resin layer 13. Therefore, the thickness ratio between the amorphous polyester resin layer 12 and the amorphous crystalline polyester resin layer 13 is 9
It is desirable to be in the range of about 5: 5 to 60:40.

However, if the thickness of the amorphous crystalline polyester resin layer 13 is extremely thin, various surface properties become unsatisfactory. Therefore, it is preferable that the thickness is at least 1 μm, usually 5 μm or more. On the other hand, if it is too thick, the excellent flexibility and moldability of the amorphous polyester resin layer 12 cannot be fully utilized, and especially the amorphous polyester resin layer 1 in the amorphous state
When crystallizing 3 at the time of adhering or after adhering to the base material 2 for decorative material, the crystallinity may decrease the transparency, increase the haze, and impair the design, so that it is usually 50 μm.
It is desirable to make the following.

The non-crystalline polyester resin layer 12 and the non-crystalline crystalline polyester resin layer 13 may include, for example, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer,
Filler, flame retardant, gloss control agent, antistatic agent, anti-condensation agent,
1 selected from various additives such as lubricants, antibacterial agents and fungicides
Seeds or more may be added. The base sheet 11
A picture layer 14 between the non-crystalline polyester resin layer 12 and
Is provided, a colorant such as a dye or a pigment may be added and colored as long as the picture layer 14 can be seen through at least.

A base sheet 11, an amorphous polyester resin layer 12, and an amorphous crystalline polyester resin layer 13
There are no particular limitations on the method of lamination between them, for example, a dry lamination method or a wet lamination method using an adhesive, a heat lamination method with or without an adhesive (heat sealant), a melt extrusion lamination method, Any conventionally known laminating method such as an extrusion film forming method can be appropriately employed. Of course, the lamination method of the base material sheet 11 and the non-crystalline polyester resin layer 12 and the lamination method of the non-crystalline polyester resin layer 12 and the non-crystalline crystalline polyester resin layer 13 are the same. Good and may be different. In addition, the order of lamination is not particularly limited. Even if the crystalline polyester resin layer 13 in the amorphous state is laminated after the lamination of the base sheet 11 and the amorphous polyester resin layer 12, the non-crystalline polyester resin layer 12 After laminating with the crystalline polyester resin layer 13 in the amorphous state, the lamination with the base sheet 11 may be performed, or three layers may be laminated simultaneously.

When a picture layer 14 is provided between the base sheet 11 and the non-crystalline polyester resin layer 12, the picture layer 14 is first provided on the surface of the base sheet 11 by a printing method or the like. The surface of the non-crystalline polyester resin layer 12 of the co-extruded film of the non-crystalline polyester resin layer 12 and the non-crystalline crystalline polyester resin layer 13 prepared separately is coated on the surface of the layer 14 by dry lamination or heat A method of laminating by a lamination method or the like, or, while forming a film by a non-crystalline polyester resin and a crystalline polyester resin by a melt co-extrusion method under conditions that do not crystallize the latter, the surface of the non-crystalline polyester resin side Are laminated toward the pattern layer 14 side of the base sheet 11 on which the pattern layer 14 is provided in advance, so that the amorphous polyester resin layer 12 and the amorphous Crystalline state polyester resin layer 13
Is most preferable because the decorative sheet 1 of the present invention can be efficiently manufactured by simple steps.

The picture layer 14 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 the constituent material, it is common to use a printing ink or a paint in which a coloring agent such as a dye or a pigment is dispersed in a vehicle such as a synthetic resin. However, in the present invention, a bending process or a vacuum forming process is used. It is necessary to have flexibility that can follow the elongation of the sheet at the time of use, for example, use a printing ink or paint using a urethane resin, an acrylic resin, a vinyl resin, a cellulose derivative, etc. as a color developing agent It is desirable to do.

The pattern layer 14 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, a transfer printing method, and the like. Method, or in the case of solid, 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 A known coating method such as a spray coating method or the like can be used.

Before printing the pattern layer 14, the surface to be printed is preliminarily subjected to an easy adhesion treatment such as corona discharge treatment, plasma treatment, flame treatment, ionizing radiation treatment, acid treatment, alkali treatment, anchor treatment or primer treatment. Thereby, the adhesiveness can be arbitrarily improved as needed.

The decorative sheet 1 of the present invention can be given a three-dimensional design feeling by embossing 15 on the surface as required. There is no particular limitation on the type of the pattern of the emboss 15. For example, various patterns such as a wood pattern (particularly a conduit groove pattern), a stone pattern, a cloth pattern, a Japanese paper pattern, and a geometric pattern may be used. Or, for example, it may be a matte shape such as a grain shape or a satin shape, a suede shape, a leather shape, a hairline shape, a group of parallel straight lines, a group of parallel straight lines, or a combination thereof. The design of the embossment 15 can be synchronized with the design of the picture layer 14 to further improve the design. However, if it is not necessary, the design may be out of synchronization. It is also possible to provide a pattern-shaped emboss 15 including both a pattern synchronized with the pattern of the above and a pattern not synchronized with the pattern. In addition, emboss 1
5 may be filled with a coloring agent by a technique such as a wiping method, if necessary.
And a decorative sheet 1 having a color pattern synchronized with the concave and convex pattern of the present invention and having excellent design properties.

Although the material of the surface protective layer 16 is not particularly limited in the present invention, it is desirable to use a curable resin from the viewpoint of various surface properties. In particular,
For example, urethane resin, amino alkyd resin, melamine resin, epoxy resin, unsaturated polyester resin, urea resin, thermosetting resin such as phenolic resin, unsaturated polyester resin, acrylate resin,
An ionizing radiation curable resin such as a methacrylate resin can be used.

Above all, a two-part 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, etc., that is, acrylic polyol Alternatively, a thermosetting resin which is mainly composed of acrylic 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 16 is not particularly limited in the present invention, it is usually appropriate to be about 3 to 20 μm in consideration of physical properties and flexibility.

If necessary, the surface protective layer 16 may include, for example, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a gloss adjusting agent, a lubricant,
One or more selected from various additives such as an antistatic agent, an anti-condensation agent, an antibacterial agent, an antifungal agent, a lubricant, a coloring agent, and a filler may be added. The surface protective layer 16 may be composed of two or more layers of the same type or different types. For example, the first layer containing high-hardness abrasion-resistant particles such as silica, alumina, and silicon carbide may be used.
A second layer not containing the particles is provided on the layer of
To achieve both abrasion resistance and scratch resistance, surface gloss and surface smoothness, and to form a second layer having a different gloss state on the first layer provided on the entire surface in an arbitrary pattern. It is also possible to apply such as providing a visual three-dimensional effect by a gloss change.

As described above, the decorative sheet 1 of the present invention
As shown in FIG. 2, it is used as a decorative material by sticking and laminating on the surface of various types of decorative material base materials 2. At the time of the adhesion and lamination, an appropriate adhesive such as an isocyanate-curable urethane resin system or a modified vinyl acetate resin emulsion system is usually used, but depending on the material of the base sheet 11,
In some cases, the adhesion to such a general-purpose laminating adhesive is insufficient. In preparation for such a case, a primer layer 17 made of a resin composition having excellent adhesion to the above-mentioned general-purpose laminating adhesive may be provided on the back surface of the base sheet 11.

As the primer layer 17, for example, a urethane type, an acrylic type, an ethylene-vinyl acetate copolymer type,
Vinyl chloride-vinyl acetate copolymer system, polyester system,
Various types of primer coating agents such as polyamides are known, and a material suitable for the material of the base sheet 11 and the type of adhesive for laminating is selected from these and used. For example, when the base sheet 11 is made of a polyolefin-based resin or a polyester-based resin and a modified vinyl acetate resin emulsion-based adhesive is used as the laminating adhesive,
Good adhesion can be obtained with a urethane primer. When the inorganic fine powder such as silica is added to the primer layer 17, the surface of the primer layer 17 is roughened, so that the decorative sheet 1 can be prevented from blocking during winding and preservation, and can be anchored. Can improve the adhesiveness with the laminating adhesive.

The material, shape, dimensions and the like of the decorative material base 2 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, wood-based materials such as solid wood and veneer of natural wood, veneer, plywood, laminated wood, medium-density fiberboard, hard fiberboard, particle board, oriented board, laminated veneer, steel plate, brass Plate, stainless plate, aluminum plate,
Metal substrate such as duralumin board, natural stone, glass, ceramics, gypsum board, slag gypsum board, calcium silicate board, slate board, wool cement board, asbestos cement board, glass fiber reinforced concrete board, lightweight foam concrete board, etc. Inorganic base material, olefin resin, acrylic resin, styrene resin, ABS resin, polycarbonate resin, polyester resin, synthetic resin base material such as FRP, or a mixture of two or more selected from these, a laminate, A substrate composed of a composite or the like can be used.

The method of laminating the decorative sheet 1 with the decorative material substrate 2 is not particularly limited.
Appropriately selected from various conventionally known laminating methods such as a roll laminating method, a soft wrapping method, and a vacuum forming method (a membrane pressing method and a membraneless pressing method are also applicable) according to the surface shape of the base material 2 for a decorative material. Can be implemented. In this lamination method, if a lamination method involving heating of the decorative sheet 1 at the time of lamination, for example, a heat laminating method or a vacuum forming method, is adopted, the decorative sheet 1 is laminated and adhered to the surface of the decorative material base material 2. At the same time, the crystalline polyester resin layer 13 in the amorphous state is partially crystallized to provide a cosmetic material having excellent surface properties such as surface hardness, scratch resistance, abrasion resistance, chemical resistance, and solvent resistance. There are advantages that can be obtained.
In particular, the vacuum forming method is a processing method that makes full use of the excellent thermoformability of the decorative sheet 1 of the present invention into a three-dimensional three-dimensional shape. I can say that there is.

However, after the decorative sheet 1 of the present invention is laminated and adhered to the surface of, for example, a flat-shaped decorative material base material 2, groove processing such as V-cut is performed from the back side of the decorative material base material 2. In the case of application for bending and application, if the crystalline polyester resin layer 13 in an amorphous state is crystallized and hardened before bending, it may be inferior in bending processability. In addition, the step of heat crystallization of the amorphous crystalline polyester resin layer 13 is performed simultaneously with or after the bending of the decorative material (for example, simultaneously with the curing of the adhesive for fixing the bent portion). It is desirable.

[0050]

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

Example 1 A transparent amorphous 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate (PET) resin having a thickness of 80 μm was formed on a printed surface of a colored high-density polyethylene resin film having a thickness of 100 μm on which a wood grain pattern was printed. -G) PET-G of a 120-μm-thick transparent amorphous polyester resin film formed by co-extrusion of a layer and a 40-μm-thick amorphous transparent crystalline polyethylene terephthalate resin (A-PET) layer. The decorative sheet of the present invention was obtained by laminating the layer side as an adhesive surface.

Example 2 A transparent amorphous 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin (PET-G) having a thickness of 180 μm was formed on a printed surface of a colored polypropylene resin film having a thickness of 70 μm on which a wood grain pattern was printed. ) Layer and thickness 2
A 200 μm thick transparent amorphous polyester resin film formed by co-extrusion with a 0 μm amorphous transparent crystalline polyethylene terephthalate resin (A-PET) layer
The decorative sheet of the present invention was obtained by laminating the ET-G layer side as an adhesive surface.

Example 3 A 120 μm-thick colored non-crystalline 1, having a wood grain pattern printed thereon
4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin (PET-G)
The same transparent amorphous polyester resin film having a thickness of 120 μm as that used in Example 1 was laminated with the PET-G layer side as an adhesive surface to obtain a decorative sheet of the present invention.

Comparative Example 1 A 120 μm thick transparent polypropylene resin film was adhered and laminated on the printed surface of a 100 μm thick colored high density polyethylene resin film on which a wood pattern was printed to obtain a decorative sheet.

Comparative Example 2 A 200 μm-thick transparent polypropylene-based resin film was adhered and laminated on the printed surface of a 70 μm-thick colored polypropylene-based resin film on which a grain pattern was printed to obtain a decorative sheet.

Comparative Example 3 Colored non-crystalline 1, having a thickness of 120 μm on which a wood grain pattern was printed
4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin (PET-G)
A 120 μm thick transparent amorphous 1,4-cyclohexanedimethanol copolymerized polyethylene terephthalate resin (PET-G) film was bonded and laminated to obtain a decorative sheet.

Molding test Using the decorative sheets of Examples 1 to 3 and Comparative Examples 1 to 3, a modified vinyl acetate resin emulsion-based adhesive (“CVC555” manufactured by Konishi Co., Ltd.) was previously applied to the surface after drying. A wooden base material (500 mm long × 500 mm wide × thickness 18) spray-coated to an amount of 30 g / m ² and dried, and processed into a three-dimensional three-dimensional shape having a radius of curvature of 4R × 4R as shown in FIG.
mm), vacuum forming and laminating with a vacuum forming machine under hot plate temperature of 150 ° C. and thermocompression bonding time of 120 seconds.
A cosmetic material was produced. When the molded state of the obtained decorative material (elongation and whitening of the corner portion), pencil hardness of the surface, solvent resistance (lacquer thinner) and chemical resistance (2% sodium carbonate) were evaluated, the following table was obtained. Met. In addition, vacuum molding was performed by two methods, a membrane press molding method and a membraneless press molding method, but there was no difference due to the molding method except a part.

Test Result Pattern Elongation Whitening Pencil Hardness Solvent Resistance Chemical Resistance Example 1 None None 2B Good Good Example 2 None None 2B Good Good Example 3 None None 2B Good Good Comparative Example 1 Yes * 6B Good Good Comparative Example 2 Yes Yes 6B Good Good Comparative Example 3 No No 6B Poor Poor * Membrane press method → Yes, Membraneless press method → Some Yes

As described above, if the decorative sheet of the present invention is used, the decorative sheet can be formed along the three-dimensional three-dimensional shape of the surface of the base material for decorative material without causing molding defects such as elongation of the corners and whitening. It can be molded, and has surface hardness, solvent resistance,
It was confirmed that a cosmetic material having excellent surface properties such as chemical resistance can be easily produced.

[0060]

As described in detail above, the decorative sheet of the present invention comprises a transparent or translucent amorphous polyester resin layer and a transparent or translucent amorphous By laminating the crystalline polyester resin layer in a state sequentially, bending processing such as V-cut processing and lapping processing, as well as vacuum forming lamination to a complex three-dimensional three-dimensional base material for decorative material Even when used for processing, it has excellent flexibility and thermoformability that can sufficiently cope without forming defects such as necking, breakage, cracking, whitening, and pattern elongation due to local elongation. In addition, since it has a highly transparent and low haze non-crystalline polyester resin layer, it has excellent transparency, depth and coating, and has an amorphous crystalline polyester resin layer on its surface, so that it has a surface hardness. It has a remarkable practical effect that various cosmetic materials having excellent various surface properties such as scratch resistance, abrasion resistance, solvent resistance, and chemical resistance can be easily produced. .

[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 material of the present invention.

[Explanation of symbols]

 1 decorative sheet 11 base material sheet 12 non-crystalline polyester resin layer 13 amorphous crystalline polyester resin layer 14 picture layer 15 emboss 16 surface protective layer 17 ‥ Primer layer 2 ‥‥‥ Cosmetic base material

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B29K 67:00 B29K 67:00 B29L 31:10 B29L 31:10 31:44 31:44 31:58 31: 58 (72) Inventor Yumiko Tsuruta 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. F-term (reference) 4F100 AK01A AK03A AK05A AK41A AK41B AK41C AK42B AK42C AK42J BA01B BA03 BA10A BA15 BA16 EH20 GB24 GB24 GB HB31 JA11C JA12A JA12B JB01 JB16A JL01 JN01B JN01C 4F208 AA03 AA24 AG03 AH42 AH47 AH48 AH51 MA01 MB01 MB22 MG04

Claims (5)

[Claims] 1. A transparent or translucent amorphous polyester resin layer and a transparent or translucent amorphous crystalline polyester resin layer on a base sheet made of a thermoplastic resin.
A decorative sheet characterized by being sequentially laminated. 2. The decorative sheet according to claim 1, wherein the thermoplastic resin forming the base sheet is a polyolefin resin. 3. The decorative sheet according to claim 1, wherein the thermoplastic resin forming the base sheet is a non-crystalline polyester resin. 4. A decorative material obtained by laminating the decorative sheet according to any one of claims 1 to 3 on a surface of a decorative material base material by a vacuum forming method. 5. The amorphous polyester resin layer is partially crystallized simultaneously with laminating the decorative sheet on the decorative material base material by a vacuum forming method. Item 5. The cosmetic material according to Item 4.