JP2000301682A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in sharpness and secondary processability and able to produce simply and inexpensively. SOLUTION: A decorative sheet is constituted by successively laminating a printing layer 2, a transparent thermoplastic resin intermediate layer 4 and a transparent thermoplastic polyester resin layer 7 on a thermoplastic resin substrate sheet 1. The transparent thermoplastic polyester resin layer 7 is desirably harder than the transparent thermoplastic resin intermediate layer 4. The thermoplastic resin substrate sheet 1 is desirably constituted of a polyolefinic resin or a polyester resin and the transparent thermoplastic resin intermediate layer 4 is desirably constituted of a polyolefinic resin.

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 for buildings such as houses, construction materials, building materials such as fittings, furniture and fixtures, and the like.
The present invention relates to a decorative sheet for use in surface makeup of household equipment and home electric appliances. More specifically, the present invention relates to a decorative sheet particularly suitable for applications requiring high designability, mainly high definition, such as kitchen doors and bathroom interiors.

[0002]

2. Description of the Related Art Conventionally, decorative sheets for such applications include:
Films obtained by printing an appropriate pattern on a polyvinyl chloride resin film were mainly used. In recent years, in addition to this, in consideration of environmental issues, a decorative sheet using a non-chlorine-based resin film such as a polyolefin-based resin, which is free from the risk of generating harmful substances such as hydrogen chloride or dioxin during combustion. Have also been developed and are becoming widely used.

[0003] By the way, in applications such as the above kitchen doors and bathroom interiors, much superior high image clarity is required as compared with other ordinary applications, and the above-mentioned polyvinyl chloride resin film and polyolefin are required. A resin film cannot be used. This is due to the fact that the polyvinyl chloride resin film is soft and has poor thickness accuracy and surface smoothness, and that the polyolefin resin has high crystallinity and thus has a high surface haze, and that both have weak scratch resistance. .

[0004] Therefore, as a decorative sheet for applications requiring high definition, a decorative sheet having a structure in which a polyester resin film excellent in transparency, surface smoothness, scratch resistance and the like is disposed on the surface has conventionally been used. Sheets are mainly used (JP-A-57-165259, JP-A-4-238).
026, JP-A-10-258488, etc.).
Specifically, a transparent polyester resin having an appropriate pattern printed on its back surface in advance through an adhesive on the surface of a concealable base sheet made of a colored polyvinyl chloride resin film or a colored polyolefin resin film It is made by laminating a film.

[0005] However, the printing of the pattern on the decorative sheet is generally performed by multi-color printing with a plurality of color printing inks for the purpose of expressing various colors close to natural colors. Although there are fine irregularities due to the presence or absence of the printing ink layer of each color, the decorative sheet of the above configuration has a pattern printing sandwiched between the opaque base sheet and the transparent polyester resin film. Because of the configuration, the fine irregularities on the surface of the pattern printing layer are easily reflected on the surface of the transparent polyester resin film, and as a result, the fine irregularities occur on the surface of the decorative sheet, and the smoothness is lost. Therefore, there is a problem that it is difficult to obtain satisfactory high definition.

In order to address this problem, the thickness of the polyester resin film is increased, or a decorative sheet (or a decorative material in which the decorative sheet is adhered to an appropriate substrate) is heated using a mirror surface plate. There is also a method such as applying a pressure press process,
In the former case, the decorative sheet becomes thicker as a whole, and secondary workability such as bending is deteriorated, and it is uneconomical. In the latter case, the process is complicated, the versatility is poor, and the cost is disadvantageous. There was a point.

[0007]

SUMMARY OF THE INVENTION The present invention has been made for the purpose of solving the above-mentioned problems in the prior art, and is excellent in high definition and secondary workability. Another object of the present invention is to provide a decorative sheet that can be easily and inexpensively manufactured.

[0008]

Means for Solving the Problems The decorative sheet of the present invention comprises:
A pattern printing layer, a transparent thermoplastic resin intermediate layer, and a transparent thermoplastic polyester resin layer are sequentially laminated on a thermoplastic resin base sheet.

The decorative sheet of the present invention is characterized in that the transparent thermoplastic polyester resin layer is harder than the transparent thermoplastic resin intermediate layer.

The decorative sheet of the present invention is characterized in that the thermoplastic resin base sheet is made of a polyolefin resin or a polyester resin, and the transparent thermoplastic resin intermediate layer is made of a polyolefin resin. .

[0011]

Embodiments of the present invention will be described below in detail with reference to the drawings. 1 and 2 are side sectional views showing an embodiment of the decorative sheet of the present invention.

As shown in FIG. 1, the decorative sheet of the present invention comprises a thermoplastic resin base sheet 1, a pattern print layer 2,
The transparent thermoplastic resin intermediate layer 4 and the transparent thermoplastic polyester-based resin layer 7 are sequentially laminated.

The type of thermoplastic resin constituting the thermoplastic resin base sheet 1 is not particularly limited, and any thermoplastic resin conventionally used as a base sheet material for decorative sheets may be used. Can be. Specifically, for example, polyethylene, polypropylene, polybutene, polyolefin resins such as polymethylpentene, ethylene-
Polyvinyl-based copolymers or saponified products thereof, polyolefin-based copolymers such as ethylene- (meth) acrylic acid (ester) copolymer, and polyester-based polymers such as polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, polyarylate, and polycarbonate Resins, acrylic resins such as polymethyl methacrylate, styrene resins such as polystyrene, AS resin and ABS resin, cellulose derivatives such as cellulose acetate and nitrocellulose, chlorine resins such as polyvinyl chloride and polyvinylidene chloride, and polyfluorination Vinyl, polyvinylidene fluoride,
Fluorinated resins such as polytetrafluoroethylene and ethylene-tetrafluoroethylene copolymer, or two or more copolymers, mixtures, composites, and laminates selected from these can be used.

However, considering the response to environmental problems that have been rapidly gaining public interest in recent years, the use of chlorine-based resins and fluorine-based resins among the above-mentioned various thermoplastic resins is very preferable. It is preferable to use a non-halogen thermoplastic resin containing no halogen elements such as chlorine and fluorine. Above all, it is possible to use a polyolefin-based resin or polyester-based resin in view of various aspects such as a balance between moderate flexibility and strength for a decorative sheet, workability such as bending, cutting, and cutting, and weather resistance. Most desirable.

As the above-mentioned polyolefin resin, various homopolymers and copolymers including the above-mentioned ones are known. Among them, a polypropylene resin, ie, a polypropylene resin, is most preferable as a material for a base sheet for a decorative sheet. Or a copolymer having as a main component. Specifically, for example, a homopolypropylene resin, a random polypropylene resin, a block polypropylene resin, and an α-olefin having 2 to 20 carbon atoms other than propylene having a polypropylene crystal part, preferably ethylene, butene-1,4 Examples thereof include propylene-α-olefin copolymers containing 15 mol% or more of a comonomer of -methylpentene-1, hexene-1 or octene-1. It is also possible to add modifiers such as ethylene-α-olefin copolymer, ethylene-propylene copolymer rubber, ethylene-propylene-non-conjugated diene copolymer rubber which are usually used for softening a polypropylene resin. .

In addition to the above-mentioned various homopolymers as the above-mentioned polyester-based resins, copolymerized polyester-based resins or polyester-based resins to which various copolymerized or modified components are added for the purpose of softening the resin or the like. A resin called a thermoplastic elastomer or the like can also be used. Specifically, for example, terephthalic acid, aromatic dicarboxylic acid or dicarboxylic acid ester such as naphthalenedicarboxylic acid, and ethylene glycol, in the condensation polymerization reaction with an aliphatic diol such as 1,4-butanediol, as a dicarboxylic acid component, Long-chain aliphatic dicarboxylic acids and / or alicyclic dicarboxylic acids such as sebacic acid, eicoic acid, dodecandioic acid, dimer acid, and cyclohexanedicarboxylic acid are introduced, and / or polyethylene glycol or polytetramethylene as a diol component Examples thereof include those in which a polyether-based diol having a hydroxyl group at both terminals such as glycol is introduced.

Of course, the kind of polyolefin resin or polyester resin constituting the thermoplastic resin base sheet 1 is not limited to these. Further, a laminate of a plurality of layers made of the same or different polyolefin-based resin or polyester-based resin may be used.

The thickness of the thermoplastic resin base sheet 1 is not particularly limited, and a thickness similar to that of a conventional decorative sheet base sheet can be used. Specifically, roughly 2
It is generally selected from the range of about 0 to 500 μm, and the range of about 50 to 200 μm is most desirable.

The thermoplastic resin base sheet 1 may be provided with a coloring agent, a filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, a lubricant, an antistatic agent, if necessary.
One or more of various additives such as a flame retardant can be added.

In particular, when the intended decorative sheet is required to have a concealing property with respect to the surface of the base material to be adhered, a coloring agent is added to the resin constituting the thermoplastic resin base sheet 1 and colored. It is desirable to have concealment. As the colorant, for example, an organic or inorganic dye or pigment may be mentioned, but from the viewpoint of hiding power, it is desirable to use at least an inorganic pigment.

Specifically, for example, white inorganic pigments such as titanium oxide, zinc oxide and basic lead carbonate;
Colored inorganic pigments such as yellow iron oxide and iron black), chromium oxide, cobalt blue and carbon black; metal powder pigments such as aluminum powder and bronze powder; pearlescent pigments such as titanium oxide-coated mica and bismuth oxide chloride. Can be.
Needless to say, for the purpose of adjusting the color, an organic pigment having excellent weather resistance such as a phthalocyanine pigment may be used in combination. If necessary, extender pigments such as silicon oxide, calcium carbonate, barium sulfate and the like can be used in combination.

Other additives include antioxidants such as phenols, sulfur and phosphorus, and ultraviolet absorbers such as benzophenone, benzotriazole, salicylate, cyanoacrylate, formamidine and oxanilide. Such as hindered amine type, nickel complex type, etc., as the light stabilizer, hindered phenol type, sulfur type, hydrazine type, etc., as the heat stabilizer, and phthalic acid ester type as the plasticizer,
Phosphate ester type, fatty acid ester type, aliphatic dibasic acid ester type, oxybenzoic acid ester type, epoxy type,
For example, polyester-based lubricants such as fatty acid ester-based, fatty acid-based, metal soap-based, aliphatic amide-based, higher alcohol-based, paraffin-based, and silicone-based anti-static agents, such as cationic, anionic, and nonionic,
Examples of flame retardants such as zwitterionics are bromine-based, phosphorus-based,
Chlorine-based, nitrogen-based, aluminum-based, antimony-based, magnesium-based, boron-based, and zirconium-based fillers such as calcium carbonate, barium sulfate, talc, rubble,
It is used in one kind or a mixture of two or more kinds selected from kaolin and the like.

The pattern printing layer 2 is provided for the purpose of imparting a decorative sheet with a desired appropriate design. There is no particular limitation on the type of the pattern. For example, a wood pattern, a stone pattern, a cloth pattern, an abstract pattern, a geometric pattern, or the like, or a simple color or color, including a wood grain pattern widely used in the field of decorative sheets according to the related art. For the purpose of adjustment, a single-color solid color may be used. In short, any desired pattern can be adopted according to the intended use of the decorative sheet.

There are no particular restrictions on the constituent materials and the forming method of the pattern printing layer 2. For example, a coloring agent such as a dye or a pigment similar to that conventionally applied to the pattern printing layer of a decorative sheet may be used. A printing ink or a coating agent dissolved or dispersed in an appropriate solvent can be used together with a suitable binder resin.

Examples of the coloring agent include inorganic pigments such as carbon black, titanium white, zinc white, red iron oxide, navy blue and cadmium red, azo pigments, lake pigments, anthraquinone pigments, quinacridone pigments, phthalocyanine pigments, and isoindolinone pigments. Pigments, organic pigments such as dioxazine pigments,
Metal powder pigments such as aluminum powders and bronze powders, mica coated with titanium oxide, pearlescent pigments such as bismuth oxychloride, fluorescent pigments, luminous pigments, and the like, or a mixture of two or more selected from these can be used.

As the binder resin, for example, acrylic resin, styrene resin, polyester resin,
Urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin And various synthetic resins such as cellulose derivatives, rubber resins, or a mixture of two or more thereof.

Examples of the solvent include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane and methylcyclohexane, and ethyl acetate, butyl acetate and acetic acid-2.
-Ethyl organic solvents such as -methoxyethyl, acetic acid-2-ethoxyethyl, etc., alcoholic organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol, acetone, methyl ethyl ketone, methyl Ketone organic solvents such as isobutyl ketone and cyclohexanone; ether organic solvents such as diethyl ether, dioxane and tetrahydrofuran; various organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene and other organic solvents; and inorganic materials such as water. A solvent or a mixture of two or more thereof can be used.

In addition, various types of additives such as extenders, plasticizers, dispersants, surfactants, tackifiers, adhesion aids, desiccants, stabilizers, curing agents, curing accelerators or retarders, if necessary. Can be appropriately added.

The method of forming the picture printing layer 2 is not particularly limited, and various conventionally known printing methods such as a gravure printing method, an offset printing method, a screen printing method, a flexographic printing method, an electrostatic printing method and an ink jet printing method are used. A method can be used. In addition, for example, when the entire surface is solid, in addition to the various printing methods described above, for example, a roll coating method, a knife coating method, an air knife coating method, a die coating method, a lip coating method, a comma coating method, a kiss coating method, a flow coating method And various coating methods such as a dip coating method. In addition, for example, a hand-drawing method, a sinking method, a photographic method, a transfer method, a laser beam or electron beam drawing method, a partial vapor deposition method of metal or the like, an etching method, or the like, or an appropriate combination of two or more kinds selected from these various methods. It is of course possible to do so.

Prior to the formation of the picture print layer 2, if necessary, the surface to be printed of the thermoplastic resin base sheet 1 may be subjected to, for example, corona treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, or the like. By performing a surface treatment such as an anchor or primer treatment, the adhesion between the thermoplastic resin base sheet 1 and the picture printing layer 2 can be improved.

The pattern printing layer 2 may be provided on the back surface of the transparent thermoplastic resin intermediate layer 4 instead of being provided on the surface of the thermoplastic resin base sheet 1 as described above.

When the intended decorative sheet needs concealing properties, and when the thermoplastic resin base sheet 1 is transparent or lacks concealing properties, it is attached on the back side together with the pattern printing layer 2. A hiding layer can also be provided. The material and method for forming the concealing layer are the same as in the case of the pattern printing layer 2 described above, but in order to obtain a good concealing property, at least a concealing inorganic pigment such as a titanium oxide pigment or an iron oxide pigment is used. It is preferred to use. In addition, by coloring in an appropriate color, the function as the background color of the pattern printing layer 2 can be also provided.

The transparent thermoplastic resin intermediate layer 4 is provided as a kind of buffer layer so that the unevenness caused by the pattern printing layer 2 does not reach the surface of the transparent polyester resin layer 7. At the same time, the thickness (distance) between the pattern printing layer 2 and the surface of the decorative sheet is sufficiently secured, and the decorative sheet has an effect of giving an excellent feeling of painting and depth.

The kind of the thermoplastic resin constituting the transparent thermoplastic resin intermediate layer 4 is not particularly limited, and for example, those exemplified as the thermoplastic resins constituting the thermoplastic resin base sheet 1 described above are used. be able to. However, it is desirable to employ a thermoplastic resin having excellent flexibility in order to absorb irregularities on the surface of the pattern printing layer 2 and to maintain sufficient flexibility in handling or bending the decorative sheet.
In addition, it is most preferable to employ a polyolefin resin in consideration of processing suitability, price, non-halogen resin, and the like.

Examples of the type of polyolefin resin to be used as the constituent material of the transparent thermoplastic resin intermediate layer 4 include, for example, the various polyolefin resins listed as the constituent materials of the thermoplastic resin base sheet 1 described above. Can be appropriately selected from the polyolefin resins described above. However, in consideration of the above-mentioned flexibility, it is desirable to employ a material obtained by mixing or copolymerizing a non-crystalline or low-crystalline component or a rubber component. Specifically, for example, a polypropylene-based resin softened by blending an amorphous atactic polypropylene with a highly crystalline isotactic polypropylene, or an olefin-based elastomer as a soft segment with an olefin-based resin as a hard segment. Graft copolymerization, block copolymerization, partially crosslinked, or simply blended olefinic thermoplastic elastomer resins can be exemplified.

Of course, the kind of the polyolefin resin constituting the transparent thermoplastic resin intermediate layer 4 is not limited to these. Also, a laminate of a plurality of layers made of the same or different polyolefin-based resins may be used.

Further, various kinds of additives similar to those of the thermoplastic resin base sheet 1 described above are appropriately added to the resin constituting the transparent thermoplastic resin intermediate layer 4 as long as the transparency is maintained. can do. In addition, “transparent” of the transparent thermoplastic resin intermediate layer 4 does not necessarily mean complete colorless and transparent, and may be translucent or colored and transparent as long as the picture print layer 2 can be seen through. . Within that range, the transparent thermoplastic resin intermediate layer 4 may contain a colorant or a filler.

As long as the transparent thermoplastic resin intermediate layer 4 has transparency or transparency as described above, it does not contain any coloring agent or filler at all or contains only a very small amount. Sufficient flexibility is maintained without becoming brittle and brittle, thereby easily absorbing irregularities on the surface of the pattern printing layer 2 on the thermoplastic resin base material sheet 1 and making the transparent thermoplastic polyester resin layer 7 The effect can be prevented from being exerted on the surface.

The thickness of the transparent thermoplastic resin intermediate layer 4 is not particularly limited, but is preferably at least 10 μm or more in order to sufficiently absorb the unevenness on the surface of the picture printing layer 2. The upper limit is handleability (flexibility) as a decorative sheet
It is about 900 μm from the viewpoint of workability, cost and the like. The most preferable range is generally about 50 to 200 μm.

The method for forming the transparent thermoplastic resin intermediate layer 4 is not particularly limited. For example, a dry lamination method or a wet lamination method with the adhesive layer 3 interposed therebetween, or a heat lamination method with or without the interposition of the adhesive layer 3. Specification and use of the desired decorative sheet, such as extrusion lamination, sand lamination (a method of extruding and laminating a molten resin between the thermoplastic resin base sheet 1 and the transparent thermoplastic polyester-based resin layer 7 in layers) and the like. A method that matches the characteristics of the resin to be used may be appropriately selected.

Prior to lamination by the above-mentioned various laminating methods, the laminating surface of the thermoplastic resin base sheet 1 and / or the transparent thermoplastic resin intermediate layer 4 is, for example, corona-coated to improve interlayer adhesion. An appropriate adhesion treatment such as treatment, ozone treatment, plasma treatment, ionizing radiation treatment, dichromic acid treatment, anchor or primer treatment may be performed. In the extrusion laminating method and the sand laminating method, for example, a method of co-extruding and laminating such that an adhesive resin layer made of a carboxylic acid-modified olefin-based resin or the like is interposed therebetween may be employed.

The transparent thermoplastic polyester resin layer 7 comprises:
It is provided for the purpose of imparting high clarity due to its excellent surface smoothness and transparency to the decorative sheet, but at the same time it has various surface properties such as excellent surface hardness, abrasion resistance and solvent resistance. Can also be given.

The kind of the polyester resin constituting the transparent thermoplastic polyester resin layer 7 is not particularly limited.
For example, it can be appropriately selected from the various polyester resins listed as the types of polyester resins that can be used as the constituent material of the thermoplastic resin base sheet 1 described above.

More specifically, for applications where bending workability is not so strictly required, for example, for steel plate applications, a biaxially stretched polyester film made of polyethylene terephthalate resin or polyethylene naphthalate resin can be used. This is because the biaxially stretched polyester film has excellent transparency and surface smoothness among various thermoplastic resin films, and is most advantageous for achieving the high sharpness which is the object of the decorative sheet of the present invention. is there. Also, among various thermoplastic polyester resin films, there is an advantage that the surface hardness, abrasion resistance, abrasion resistance, solvent resistance and the like are particularly excellent.

However, the above-mentioned biaxially stretched polyester film is relatively hard as a thermoplastic resin film and is hardly stretched, so that it is not very suitable for applications requiring strict bending workability such as sharp angle V-cut processing. . Therefore, for such applications, it is desirable to employ a polyester resin having better flexibility. Specifically, it is desirable to employ, for example, a non-stretched polyester film, an amorphous polyester resin, a so-called copolymerized polyester resin obtained by copolymerizing or adding a flexible component, or a polyester thermoplastic elastomer resin.

In particular, when used for laminating by a vacuum forming method or the like along the surface of a three-dimensional three-dimensional base material, it is necessary to pay attention to the thermoforming characteristics. Specifically, as the thermoforming characteristics, it is desirable that the glass transition temperature is 60 ° C. or more and 85 ° C. or less in order to conform to general vacuum forming conditions of a decorative material. If the glass transition temperature exceeds 85 ° C, it is necessary to set the heating temperature during vacuum molding higher than usual, which is disadvantageous in terms of heat energy efficiency and molding cycle time, and in terms of moldability because the resin becomes hard. But it is disadvantageous. On the other hand, when the temperature is lower than 60 ° C., the sheet is inferior in heat resistance, so that molding defects such as drawdown are likely to occur, and the produced decorative material is disadvantageous in terms of heat resistance and durability.

For the above applications, a cold crystallization temperature of 12
It is desirable to use a polyester resin at 0 ° C. or higher. If the cold crystallization temperature is less than 120 ° C., the crystallization of the resin proceeds by heating during vacuum forming, the resin loses flexibility and the moldability is reduced, and the sea-island structure of the crystalline phase and the amorphous phase is reduced. This is because molding defects such as necking and pattern distortion due to a difference in deformation characteristics between the two and whitening due to a difference in refractive index between the two tend to occur.

For the above applications, the tensile modulus is 100%.
It is desirable to employ kgf / mm ² or more 300 kgf / mm ² or less of a polyester resin. Tensile modulus is 1
If it is less than 00 kgf / mm ² , the resin is too soft and easily damaged, and its stiffness is weak. It is likely to cause wrinkles and scratches during lamination, drawdown, and poor molding for picking up irregularities on the surface of the base material. On the other hand, if it exceeds 300 kgf / mm ² ,
Poor processability due to insufficient flexibility of the resin, inability to completely follow the three-dimensional three-dimensional shape of the surface of the base material, causes molding failure, cracks, whitening, peeling over time due to residual stress after molding, etc. It is because it is easy to become.

The method for laminating the transparent thermoplastic polyester-based resin layer 7 is not particularly limited. For example, the method for laminating the transparent thermoplastic resin intermediate layer 4 on the thermoplastic resin base sheet 1 may be any of the various methods already listed. It can be selected and implemented as appropriate. In this case, it is needless to say that the laminated surface of the transparent thermoplastic resin intermediate layer 4 and / or the transparent thermoplastic polyester-based resin layer 7 may be subjected to various easy adhesion treatments, or the adhesive resin layer may be sandwiched. No.

If the transparent thermoplastic polyester-based resin layer 7 is softer than the transparent thermoplastic resin intermediate layer 4, the unevenness of the surface of the pattern printing layer 2 in the laminating step of the transparent thermoplastic resin-based intermediate layer 4 is reduced. 4 does not absorb the resin completely and appears on the surface of the thermoplastic polyester resin layer 7, or after laminating, the unevenness is generated over time due to the residual stress in the transparent thermoplastic resin intermediate layer 4. In some cases, sufficient high definition cannot be achieved due to the appearance of the surface. In order to avoid such a situation, it is desirable that the transparent thermoplastic polyester-based resin layer 7 is harder than the transparent thermoplastic resin intermediate layer 4.

The thickness of the transparent thermoplastic polyester-based resin layer 7 is not particularly limited, but if it is too thin, the surface smoothness and, consequently, the high sharpness cannot be sufficiently obtained.
It is desirable that the thickness be at least μm. The upper limit is determined from the handleability (flexibility) as a decorative sheet, processability, economy, and the like, and is desirably approximately 500 μm or less. Generally, it depends on the kind of the polyester resin, the constitution of the other layers, the intended use of the decorative sheet, etc.
The range of about 0 μm is most preferable.

The total thickness of the decorative sheet of the present invention including the above-mentioned transparent thermoplastic polyester resin layer, the thermoplastic resin base sheet 1, the transparent thermoplastic resin intermediate layer 4, and other layers is particularly limited. Although it is not a thing, as in the case of a conventional general decorative sheet, the range is preferably about 100 to 1000 µm, and most preferably about 150 to 500 µm.

The surface of the transparent thermoplastic polyester-based resin layer 7 may be appropriately subjected to a known surface treatment which has been performed on a conventional decorative sheet of the same kind. For example, for the purpose of imparting more excellent surface properties to the surface of the decorative sheet,
A surface protection layer 8 can be provided. The surface protection layer 8
In addition to having to have at least transparency so that the underlayer can be seen, the curable resin must have a surface property such as abrasion resistance, abrasion resistance, solvent resistance, and stain resistance required by the use of the decorative sheet. It is preferable to use a resin-based material.

Specific examples of the constituent material of the surface protective layer 8 include a melamine resin, a phenol resin, a urea resin, an epoxy resin, an aminoalkyd resin, a urethane resin, a polyester resin, and a silicone resin. And the like, and an ionizing radiation-curable resin such as a (meth) acrylate-based resin can be suitably used. If necessary, various additives such as a gloss adjusting agent, a lubricant, an antistatic agent, an anti-condensation agent, an antibacterial agent, and a fungicide can be appropriately added.

By providing the surface protective layer 8 with at least a low surface tension component such as a silicone resin or a fluorine resin, the surface of the decorative sheet can have excellent antifouling properties. In addition, the surface protection layer 8
By using a plurality of types of resin compositions having different gloss states, by forming part or all of the resin composition in an arbitrary pattern,
The surface of the decorative sheet can be provided with a visual three-dimensional sense of design due to a change in the gloss state.

The method for forming the surface protective layer 8 is not particularly limited. When the surface protective layer 8 is formed uniformly over the entire surface, for example, a gravure coating method, a roll coating method, a dip coating method, an air knife coating method, a knife coating method, a comma coating method Method, die coating method, lip coating method, kiss coating method, rod coating method, spray coating method, conventionally known arbitrary coating method such as flow coating method, etc., when forming in a pattern, for example, gravure printing method, offset printing method An appropriate printing method such as a screen printing method and a flexographic printing method can be adopted.

When the adhesiveness between the transparent thermoplastic polyester resin layer 7 and the surface protective layer 8 is insufficient, the transparent thermoplastic polyester resin is coated before the surface protective layer 8 is formed. By subjecting the surface of the layer 7 to an appropriate easy adhesion treatment, the adhesion between the two can be improved.

In addition, by embossing the surface of the transparent thermoplastic polyester resin layer 7 with a concavo-convex pattern or filling a concave portion of the concavity and convexity with a coloring agent by a wiping method or the like, as is conventionally known. A decorative sheet excellent in design can also be obtained.

As described above, the decorative sheet of the present invention is used by pasting (laminating) it on the surface of various base materials such as a wooden base material and an inorganic base material, like the conventional decorative sheet. Generally, an appropriate adhesive such as a urethane-based or vinyl acetate-based adhesive is used for the attachment. However, depending on the type of the adhesive, the adhesiveness to the thermoplastic resin base sheet 1 may be insufficient. In preparation for such a case, it is desirable to provide a primer resin layer 9 made of a resin having excellent adhesiveness with a general-purpose laminating adhesive on the back surface of the thermoplastic resin base sheet 1.

As the primer resin layer 9, for example, various primers such as urethane, acrylic, ethylene-vinyl acetate copolymer and vinyl chloride-vinyl acetate copolymer are known. A material that matches the resin constituting the plastic resin base sheet 1 is selected and used. If powder such as silica, alumina, calcium carbonate, barium sulfate, or the like is added to the primer resin layer 9, the surface of the primer resin layer 9 is roughened, thereby blocking the decorative sheet during winding and preservation. In addition to preventing the adhesion, it is possible to improve the adhesion to the laminating adhesive by the anchor effect.

In the decorative sheet of the present invention, the transparent thermoplastic resin intermediate layer 4 and the transparent thermoplastic polyester resin layer 7 are provided between the transparent thermoplastic resin intermediate layer 4 and the transparent thermoplastic polyester resin layer 7 in order to realize the high sharpness by maintaining the above-mentioned surface smoothness. Although it is most desirable not to provide a pattern printing layer, the pattern printing layer 2 on the thermoplastic resin base sheet 1
In addition, it is acceptable to adopt a configuration in which the transparent pattern printing layer 5 having a low coating amount enough to allow the transparent thermoplastic resin layer 4 to be provided between the transparent thermoplastic resin layer 4 and the transparent thermoplastic polyester-based resin layer 7. No (Fig. 2).

If the structure is used in combination with the pattern printing layer 2 on the thermoplastic resin substrate sheet 1, the transparent thermoplastic resin intermediate layer 4
The transparent pattern printing layer 5 provided between the transparent thermoplastic polyester-based resin layer 7 and the transparent thermoplastic polyester-based resin layer 7 has a very small coating amount compared with the case where the transparent pattern printing layer 5 is provided alone. Pattern printing layer 2 with sufficient coating amount on material sheet 1
And the pattern is visually observed at a density sufficient for design. Therefore, since the transparent pattern printing layer 5 requires only a small amount of coating, the surface irregularities are extremely small, and the transparent thermoplastic resin intermediate layer 4 sufficiently absorbs the irregularities, and the transparent thermoplastic polyester resin layer 7 This is because it is possible to prevent the influence on the surface.

As described above, in combination with the pattern printing layer 2 on the thermoplastic resin base sheet 1, the transparent pattern printing layer is provided between the transparent thermoplastic resin intermediate layer 4 and the transparent thermoplastic polyester resin layer 7. With the configuration provided with 5, the positional relationship between the two changes slightly depending on the viewing angle, and a decorative sheet excellent in three-dimensional effect and depth can be obtained.

[0064]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to specific examples of the decorative sheet of the present invention.

Example 1 A wood grain base was formed on a surface of a colored polypropylene resin film having a thickness of 120 μm by a gravure printing method using a urethane resin-based gravure printing ink for building materials (trade name “Ramister”, manufactured by Toyo Ink Mfg. Co., Ltd.). A pattern is printed, and a urethane-based easy-adhesion primer resin (trade name “V180” manufactured by Toyo Ink Mfg. Co., Ltd.) to which silica powder has been added is coated on the back surface of the film at a coating amount of 1 g / m ² after drying. Thus, a printed polypropylene single-layer film was obtained.

A transparent polyolefin-based thermoplastic elastomer resin (trade name “H4900N”, manufactured by Nippon Synthetic Rubber Co., Ltd.) having a thickness of 150 μm was coated on the printing surface of the printing film.
Extrusion lamination on m to form a transparent thermoplastic resin intermediate layer, and on its surface a gravure printing method using a urethane resin gravure printing ink for building materials (trade name "Lamister" manufactured by Toyo Ink Mfg. Co., Ltd.) To print a transparent woodgrain pattern to obtain a printed polypropylene laminated film.

An isocyanate-curable polyurethane resin (Toyo Ink Manufacturing Co., Ltd.) obtained by adding a silicone compound to the surface of a 100 μm-thick transparent polyethylene terephthalate (PET) resin film (trade name “T600” manufactured by Mitsubishi Chemical Polyester Co., Ltd.) Product name "YL3
41)) was applied to a coating amount of 5 g / m ² after drying, and dried and cured to obtain an antifouling-coated PET film.

Thereafter, the surface of the printed polypropylene laminated film and the antifouling-coated PET film were
The decorative sheet of the present invention was prepared by bonding by a dry lamination method via a urethane resin-based dry laminating adhesive (trade name “A-540” manufactured by Takeda Pharmaceutical Co., Ltd.).

Example 2 A transparent polyolefin was placed between the printing surface of the printed polypropylene single-layer film as the intermediate product of Example 1 and the uncoated surface of the antifouling-coated PET film also as the intermediate product of Example 1. -Based thermoplastic elastomer resin (trade name "H4900N" manufactured by Nippon Synthetic Rubber Co., Ltd.) with a thickness of 150
It was extruded to a thickness of μm and subjected to sand lamination to produce a decorative sheet of the present invention.

[0070]

As described in detail above, the decorative sheet of the present invention comprises, on a thermoplastic resin base sheet, a printing layer, a transparent thermoplastic resin intermediate layer, and a transparent thermoplastic polyester-based resin layer sequentially laminated. By being constituted, the transparent thermoplastic resin intermediate layer contains no coloring agent or filler or contains only a very small amount, so that it is rich in flexibility, so that the printing layer on the thermoplastic resin base sheet is used. Since the irregularities can be easily absorbed, the irregularities do not reach the surface of the transparent thermoplastic polyester-based resin layer, so that the surface of the transparent thermoplastic polyester-based resin layer maintains a high degree of smoothness and is extremely excellent. High sharpness can be easily obtained.

In particular, by making the transparent thermoplastic polyester resin layer harder than the transparent thermoplastic resin intermediate layer, unevenness due to the printing layer on the thermoplastic resin base sheet is reduced.
The decorative sheet which is easily absorbed by the soft transparent thermoplastic resin intermediate layer and which is more excellent in the above-described effects can be easily obtained.

In particular, since the thermoplastic resin base sheet is composed of a polyolefin resin or a polyester resin, and the transparent thermoplastic resin intermediate layer is composed of a polyolefin resin, no polyvinyl chloride resin is used. Naturally, it is an environmentally friendly decorative sheet, and it is possible to easily obtain a decorative sheet that is inexpensive, easy to manufacture, and excellent in various secondary processing properties.

[Brief description of the drawings]

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

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Thermoplastic resin base sheet 2 Picture printing layer 3 Adhesive layer 4 Transparent thermoplastic resin intermediate layer 5 Transparent picture printing layer 6 Adhesive layer 7 Transparent thermoplastic polyester resin layer 8 Surface protection layer 9 Primer resin layer

Continued on front page F-term (reference) 4F100 AA20 AK01A AK01C AK03A AK03C AK07 AK41A AK41D AK41G AK42 AK51 AR00B BA04 BA07 BA10A BA10D CB02 GB07 GB08 HB00 HB31B JB16A JB16C JB16K JD01

Claims (3)

[Claims] 1. A decorative sheet comprising a thermoplastic resin base sheet, a pattern printing layer, a transparent thermoplastic resin intermediate layer, and a transparent thermoplastic polyester resin layer sequentially laminated. 2. The decorative sheet according to claim 1, wherein the transparent thermoplastic polyester resin layer is harder than the transparent thermoplastic resin intermediate layer. 3. The cosmetic according to claim 1, wherein the thermoplastic resin base sheet is made of a polyolefin resin or a polyester resin, and the transparent thermoplastic resin intermediate layer is made of a polyolefin resin. Sheet.