JP2002036461A - Decorative sheet - Google Patents

Abstract

(57) [Summary] [Problem] Of course, three-dimensional forming such as V-cutting, lapping on irregular substrate, vacuum forming, etc. is also possible. An environmentally friendly decorative sheet that does not generate harmful substances such as hydrogen gas.
Provided is a decorative sheet that does not limit the range of expressible design patterns, that can provide sufficient concealment properties to an adhered substrate, and that can easily produce various decorative materials with high design. . A decorative sheet is formed by sequentially laminating a picture layer (3) and a transparent thermoplastic olefin resin layer (4) on a base sheet (1) made of an amorphous polyester resin via an adhesive layer (2). is there. The pattern layer 3 is formed by printing on the back surface of the transparent thermoplastic olefin-based resin layer 4 to prevent a solvent attack on the base sheet 1 made of an amorphous polyester-based resin having poor solvent resistance. High concealment can be provided.

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, sticking to a flat base material is of course possible, and three-dimensional forming processes such as V-cutting, lapping to uneven substrates, and vacuum forming are also possible. The present invention relates to an environment-friendly decorative sheet that does not generate substances.

[0002]

2. Description of the Related Art In recent years, with the sophistication and diversification of consumer preferences, demands for various complicated three-dimensional decorative members have been increasing. As such a three-dimensional decorative material, for example, plywood, particle board, medium density fiberboard (MDF)
On a decorative board obtained by sticking a decorative sheet on the surface of a substrate such as
Examples include a sheet that has been subjected to bending processing such as V-cut processing and a sheet that has been subjected to lapping processing, in which a decorative sheet is wound and adhered along the surface of a columnar substrate having an uneven surface.

However, according to these techniques, the range of the three-dimensional shape that can be manufactured is limited to a shape that can be developed in a plane, and it is not possible to cope with a more complicated three-dimensional shape. Therefore, a decorative sheet made of a thermoplastic resin with excellent thermoformability is applied to the surface of various base materials molded into a complicated three-dimensional three-dimensional shape by vacuum forming (including air-pressure forming and vacuum-pressure forming). The technique of attaching at the same time as three-dimensional molding,
It has already been widely adopted. In addition, with the recent sophistication and diversification of consumer preferences, the demand for more and more complicated three-dimensional three-dimensional decorative members is increasing, and the development of decorative sheets that can withstand more severe molding conditions is increasing. It is increasingly required.

Heretofore, as a thermoplastic resin constituting a decorative sheet made of a general thermoplastic resin, a polyvinyl chloride resin which is inexpensive and has excellent workability and various physical properties has been most often used. However, in recent years, in response to growing public interest in environmental issues, polyvinyl chloride resins that may generate harmful substances such as hydrogen chloride gas and dioxin during combustion have been shunned. There is a strong demand for a decorative sheet using a non-chlorine-based resin that has little adverse effect on the environment.

[0005] In response to this, decorative sheets using, for example, a thermoplastic olefin resin have been developed as a substitute material for the polyvinyl chloride resin and have been put into practical use (for example, Japanese Patent Application Laid-Open No. 6-16832). . However,
For example, a decorative sheet using a general-purpose polypropylene resin as a thermoplastic olefin resin is insufficient in flexibility, and causes whitening, cracks, breakage, necking, etc. when bending or vacuum forming is performed. There was a problem that it was easy to do.

[0006] On the other hand, various attempts have been made to impart flexibility by copolymerizing a resin such as polypropylene with a soft monomer or blending a soft component such as an elastomer with the resin. There was a problem with poor properties. As a result, as a result, a decorative sheet using only a thermoplastic olefin resin has not been able to obtain a sheet satisfying all necessary physical properties.

Therefore, the present inventors have already proposed a decorative sheet having a structure in which a transparent thermoplastic resin layer is laminated on a thermoplastic base sheet, in order to solve the above-mentioned problems in the decorative sheet made of a thermoplastic olefin resin. Has proposed a decorative sheet using an amorphous polyester resin instead of a thermoplastic olefin resin for the base sheet and using a thermoplastic olefin resin for the transparent resin layer (Japanese Patent Application No. 11-112402). .

The decorative sheet is folded by the excellent thermoforming properties of the amorphous polyester resin used for the base sheet and the excellent surface properties of the thermoplastic olefin resin used for the transparent resin layer on the surface. A decorative sheet that satisfies both processing suitability and vacuum forming suitability (prevention of whitening, cracking, breakage, necking, etc.) and surface properties (scratch resistance, abrasion resistance, solvent resistance, heat resistance, etc.) can be easily realized. It has excellent advantages that can be done.

However, the decorative sheet has a low solvent resistance and a low heat resistance of the amorphous polyester resin used for the base sheet.
When printing over a relatively thick solvent-based printing ink,
The base sheet is affected by the solvent in the printing ink, causing uneven gloss and color tone on the surface, or the solvent in the printing ink penetrates into the base sheet and swells, resulting in a normal state. Under drying conditions that do not deform (dimension change, warp, wavy, etc.) the base sheet in the printing machine, the solvent content that has penetrated into the base sheet cannot be sufficiently removed, causing blocking during winding. In addition, there is a problem that bubbles may be generated due to vaporization of the solvent during or after lamination with the transparent resin layer.

[0010] For this reason, in the decorative sheet, the type of printable printing ink and the amount of inking are limited, the range of the design of the pattern that can be expressed by printing is restricted, and the concealing solid ink layer has a sufficient concealing property. Cannot be applied, the hiding power of the decorative sheet is insufficient, and when applied to the surface of a substrate such as plywood, the color tone and defects on the surface of the substrate can be seen through. In some cases, this may cause a deterioration in design properties such as stability or a defect in a picture.

As a method of avoiding the above problem, a method of printing a picture or the like with a printing ink using only a solvent that does not attack the amorphous polyester resin of the base sheet may be considered. However, solvents that do not attack the amorphous polyester resin are limited to solvents having relatively low dissolving power for various resins, and therefore, do not reduce the types of resins that can be used as vehicles for printing inks and printability. The solid content concentration of the printing ink and the concentration of the pigment that can be added within the range will also be restricted, and as a result, the range of the design of the pattern that can be printed and expressed will still be restricted, and it will be necessary as a decorative sheet. It is still extremely difficult to sufficiently satisfy the weather resistance of a simple pattern, the concealing property on the surface of the adhered substrate, and the like.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems in the prior art,
The problem is, of course, sticking to a flat base material is also possible, and three-dimensional forming processes such as V-cutting, lapping to uneven substrates, and vacuum forming are also possible. It is an environmentally friendly decorative sheet that does not generate harmful substances such as harmful substances. It is an object of the present invention to provide a decorative sheet capable of easily producing various types of decorative materials having different properties.

[0013]

In order to solve the above-mentioned problems, the present invention relates to a method of manufacturing a base material sheet made of an amorphous polyester resin, comprising a pattern layer, an adhesive layer, and a transparent thermoplastic resin. Provided is a decorative sheet characterized by being sequentially laminated with an olefin-based resin layer.

Further, the present invention provides the decorative sheet described above, wherein the pattern layer is formed by printing on the back surface of a transparent thermoplastic olefin resin layer.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION As shown in FIG. 1, a decorative sheet according to the present invention is provided on a base sheet 1 made of an amorphous polyester resin, with an image layer 3 and an adhesive layer 2 interposed therebetween. The thermoplastic olefin-based resin layer 4 is formed by laminating the thermoplastic olefin-based resin layer 4. If necessary, the surface of the transparent thermoplastic olefin-based resin layer 4 may be provided with an uneven pattern 5 by embossing or the like. The concave portion 5 may be filled with the coloring agent 6 by a wiping method or the like, or the top coat layer 7 may be applied to the surface thereof.

The amorphous polyester resin sheet used for the base sheet 1 is formed by extruding a general-purpose crystalline polyester resin such as a polyethylene terephthalate resin into a sheet under molding conditions that do not cause crystallization (so-called A). -PET sheet) and a sheet formed of a resin obtained by copolymerizing various copolymerization components for suppressing crystallization in the basic skeleton of the above-mentioned crystalline polyester-based resin (so-called copolymerized polyester-based resin). Any of them can be used for the purpose of the present invention.

When the decorative sheet of the present invention is adhered to the surface of various substrates to be adhered by using an adhesive method involving heating, such as a heat laminating method or a vacuum forming laminating method, the former method is used. A-PET sheet has the property of being crystallized by heating to increase its hardness, and is therefore particularly suitable for applications where surface hardness and scratch resistance are particularly strictly required. Since flexibility and transparency are reduced, a bending process such as a V-cut process is performed after application to the substrate to be adhered, or a transparent decorative sheet for utilizing the texture of the surface of the substrate to be adhered. In some cases, it is somewhat unsuitable.

On the other hand, the latter copolymerized polyester resin sheet has a property of maintaining flexibility and transparency without being crystallized even when subjected to a heat treatment.
Even when attached to the surface of the substrate to be attached by an attaching method involving heating,
Although no improvement in surface hardness or scratch resistance can be expected, it should be used without any problem in cases such as when bending is performed after the application or when it is desired to utilize the texture of the surface of the adhered substrate as a transparent decorative sheet. There are advantages that can be.

The kind of the amorphous polyester resin used for the base sheet 1 of the decorative sheet of the present invention is not particularly limited as long as it is a thermoplastic polyester resin obtained by a condensation polymerization reaction of dicarboxylic acid and diol. Although not limited, generally, a polyethylene terephthalate-based resin having an ethylene terephthalate skeleton by a condensation polymerization reaction of terephthalic acid and ethylene glycol is mainly used.

The above-mentioned so-called A-PET sheet is made of pure or almost pure polyethylene terephthalate resin, and specifically, for example, “Teijin Tetron Sheet (A-PET)” manufactured by Teijin Limited, Toyobo Co., Ltd. Company-made "Toyobo PETMAX sheet A series",
Kanebo A-PET sheet manufactured by Kanebo Co., Ltd. and the like are commercially available.

On the other hand, the so-called copolymerized polyester resin sheet has a dicarboxylic acid component in the ethylene terephthalate skeleton such as sebacic acid or eicoic acid.
A long-chain aliphatic dicarboxylic acid and / or an alicyclic dicarboxylic acid such as dodecanedioic acid, dimer acid and cyclohexanedicarboxylic acid are introduced, and / or as a diol component, for example, polyethylene glycol, polytetramethylene glycol, cyclohexanedimethanol And the like, into which a polyether diol and / or an alicyclic diol are introduced.

Among them, the most typical one is a so-called PET-
G is a commercially available cyclohexane dimethanol copolymerized polyethylene terephthalate resin, which is formed into a sheet. Specifically, for example, "NAGASEA-PET" manufactured by Nagase & Co., Ltd .; And the like are commercially available.

The thickness of the base sheet 1 is not particularly limited.
A sheet having a thickness similar to that of a conventional decorative sheet of the same type can be used. However, if it is too thin, it tends to break during printing or lamination to a substrate to be adhered, etc. On the other hand, if it is too thick, bending workability and vacuum formability are impaired, and it is uneconomical, so 20 to 2
It is good to be within the range of about 00 μm, and especially 50 to 1
Most preferably, it is within the range of about 50 μm.

In order to adapt the decorative sheet of the present invention to the molding conditions of a conventionally used vacuum forming machine for a general decorative material, an amorphous polyester-based material constituting the base sheet 1 must be used. The resin has a glass transition temperature (Tg) of not less than 60 ° C. and not more than 85 ° C. and a cold crystallization temperature (Tg).
It is desirable to employ a resin whose c) is 120 ° C. or higher.

When the glass transition temperature exceeds 85 ° C., it is necessary to set the heating temperature during vacuum forming higher than usual.
It is disadvantageous in terms of thermal energy efficiency and molding cycle time, and disadvantageous in terms of moldability because the resin becomes hard. On the other hand, if 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.

If the cold crystallization temperature is lower than 120 ° C., the crystallization of the resin proceeds rapidly during molding due to heating during vacuum molding, and the resin loses flexibility and moldability decreases. A sea-island structure between the crystalline layer and the non-crystalline layer appears, and molding defects such as necking due to the difference in the deformation characteristics of the two and pattern distortion due to locally non-uniform elongation, and especially the surface of the adhered substrate This is because, in the case of a transparent decorative sheet for making use of the texture, problems such as a decrease in design due to whitening due to a difference in refractive index between the crystalline layer and the non-crystalline layer are likely to occur.

The glass transition temperature and the cold crystallization temperature depend not only on the composition and molecular weight of the resin, but also on the molding conditions at the time of molding the resin sheet. What is necessary is just to select suitably what is suitable for molding conditions, or to set suitably the molding conditions of a sheet | seat so that it may become a suitable range.

Other properties of the amorphous polyester resin constituting the base sheet 1 include a tensile elasticity of 100%.
It is desirable that the pressure be 0 MPa or more and 3000 MPa or less. If the tensile elasticity is less than 1000 MPa, the resin is too soft and easily damaged and the waist is weak, and wrinkles and scratches at the time of lamination, drawdown, and molding defects for picking up irregularities on the surface of the adhered substrate, etc. 3,000MPa
Is exceeded, the flexibility of the resin is insufficient, the processability is inferior, the molding cannot be completely followed in the three-dimensional three-dimensional shape of the base material, and molding failure or cracking, whitening, aging due to stress remaining after molding. This is because it is likely to cause peeling or the like.

If necessary, the amorphous polyester resin constituting the base sheet 1 may include, for example, a coloring agent, a filler, an antioxidant, an ultraviolet absorber, a light stabilizer, a heat stabilizer, a plasticizer, and a lubricant. One or more of various additives such as an antistatic agent and 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 substrate to be adhered, a coloring agent is added to the amorphous polyester resin constituting the base sheet 1 for coloring. It is desirable to improve the hiding power. Examples of the coloring agent include organic or inorganic dyes and pigments, and it is desirable to use at least an inorganic pigment from the viewpoint of hiding power.

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 silica, alumina, calcium carbonate, barium sulfate and the like can be used in combination.

Other additives include phenol-based, sulfur-based, phosphorus-based and the like as antioxidants, and benzophenone-based, benzotriazole-based, salicylate-based, cyanoacrylate-based, formamidine-, and oxanilide-based ultraviolet absorbers. 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,
Polyester-based lubricants such as fatty acid ester, fatty acid-based, metal soap-based, fatty acid amide-based, higher alcohol-based, paraffin-based, silicone-based, etc., and antistatic agents such as cationic, anionic, nonionic, etc.
Examples of flame retardants such as zwitterionics are bromine-based, phosphorus-based,
Chlorine-based, nitrogen-based, aluminum-based, antimony-based, magnesium-based, boron-based, zirconium-based, etc. fillers include, for example, one or more selected from calcium carbonate, barium sulfate, talc, clay, kaolin, mica, etc. Used in mixed systems.

The adhesive layer 2 is provided for the purpose of bonding the base sheet 1 made of an amorphous polyester resin to the picture layer 3 and the transparent thermoplastic olefin resin layer 4 thereon. As described above, by adopting a configuration in which the picture layer 3 is bonded to the base sheet 1 made of an amorphous polyester resin via the adhesive layer 2, the decorative sheet of the present invention has The erosion of the base sheet 1 by the solvent contained in the printing ink for the print formation of the picture layer 3, which is a problem when the print is formed directly on the surface of the base sheet 1 made of the crystalline polyester resin, The type of printing ink can be freely selected without causing problems such as blocking at the time of winding up after printing by the residual solvent in the sheet 1 and generation of bubbles at the time of lamination with the transparent thermoplastic olefin resin layer 4 or after lamination. Choice It is possible thick coating of printing ink,
By increasing the width of the design pattern that can be expressed by the pattern layer 3 or by providing a sufficient concealing property by thick coating of the concealed solid ink layer in the pattern layer 3, it becomes possible to manufacture a decorative material with higher design. is there.

The kind of the adhesive used for the adhesive layer 2 is not particularly limited, and the base sheet 1 made of an amorphous polyester resin and the picture layer 3 made of the printing ink composition can be firmly bonded. The material may be appropriately selected according to the bonding method. Specifically, for example, in the case of a dry laminating method, a polyester polyurethane-based or polyether polyurethane-based dry laminating adhesive, and in the case of a heat laminating method, for example, an ethylene-vinyl acetate copolymer system, a vinyl chloride-vinyl acetate copolymer system. , Chlorinated polyolefin-based, acrylic, urethane-based, polyamide-based, polyester-based, polyvinyl butyral-based heat-sensitive adhesives, if the hot melt method ethylene-vinyl acetate copolymer system, ethylene-ethyl acrylate copolymer system, Hot melt adhesives such as olefins, polyamides, polyesters, and polyurethanes, and thermoplastic resin adhesives such as olefins, carboxylic acid-modified olefins, ethylene-vinyl acetate copolymers, and ionomers for extrusion lamination From such, it It is can be appropriately selected and used one or two or more mixed system.

There is no particular limitation on the type of pattern of the pattern layer 3 provided on the adhesive layer 2, and examples thereof include a woodgrain pattern widely used in the field of conventional decorative sheets.
Stone pattern, cloth pattern, abstract pattern, geometric pattern, letters or symbols,
Alternatively, a combination of two or more of them or a solid color may be used. In short, any desired pattern can be adopted depending on the intended use of the decorative sheet.

There is no particular limitation on the constituent material and the forming method of the picture layer 3, and any image forming material or image forming method conventionally used for the picture layer of the decorative sheet according to the related art can be appropriately applied. Specifically, for example, a printing ink or paint obtained by dissolving or dispersing a colorant such as a dye or a pigment in a suitable solvent together with a suitable binder resin can be used. However, when the decorative sheet of the present invention is used for bending or three-dimensional forming such as V-cutting, lapping, or vacuum forming, the pattern layer 3 also follows the deformation during bending or three-dimensional forming as a constituent material. It is necessary to select a material having the possible flexibility.

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 powder and bronze powder, pearlescent pigments such as titanium oxide-coated mica, bismuth oxychloride and the like, other fluorescent pigments, luminous pigments and the like, or a mixture of two or more kinds 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, Various synthetic resins such as cellulose derivatives and rubber resins, or a mixture of two or more thereof can be used.

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.
Ester 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 Various organic solvents such as ketone organic solvents such as isobutyl ketone and cyclohexanone, ether organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; chlorine organic solvents such as dichloromethane, carbon tetrachloride, trichloroethylene, and tetrachloroethylene; and inorganics 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, drying agents, stabilizers, curing agents, curing accelerators or curing retarders, if necessary. Can be appropriately added.

The method of forming the picture layer 3 is not particularly limited.
For example, gravure printing, offset printing, gravure offset printing, dry offset printing, screen printing, flexo printing, letterpress printing, electrostatic printing, inkjet printing, etc. In the case of solid, in addition to the various printing methods described above, for example, roll coating, knife coating, air knife coating, die coating, lip coating, comma coating,
Various coating methods such as a kiss coating method, a flow coating method, and a dip coating method can be applied.

Prior to the formation of the picture layer 3, if necessary, a corona discharge treatment, a plasma treatment,
By applying a surface treatment such as an ozone treatment, a flame treatment, an ionizing radiation treatment, an acid treatment, an alkali treatment, an anchor or a primer treatment, the adhesion of the pattern layer 3 to the printing surface can be improved.

When the intended decorative sheet needs concealing properties against the color, defects and the like of the surface of the adhered substrate, when the substrate sheet 1 is transparent or deficient in concealing properties, the pattern A concealing layer may be provided on the back side as a part of the layer 3. The material and method for forming the concealing layer are the same as those for the above-described pattern layer 3, but in order to obtain good concealing properties, at least a concealing inorganic pigment such as a titanium oxide pigment or an iron oxide pigment is used. It is desirable to do. The concealing layer is colored in an appropriate color so that the pattern layer 3
Can also function as a background color.

In the decorative sheet of the present invention, the picture layer 3
In order to prevent the solvent contained in the printing ink or the like for forming the picture layer 3 from adversely affecting the base sheet 1 in the formation of the print, the picture layer 3 is directly formed on the surface of the base sheet 1 by printing. And laminating on the surface of the substrate sheet 1 via the adhesive layer 2 in a state where the picture layer 3 is sufficiently dried. As a specific method therefor, a transfer sheet in which a pattern layer 3 is formed in a releasable manner on the surface of a release sheet is prepared in advance, and the pattern layer 3 of the transfer sheet is replaced with the pattern layer 3 of the transfer sheet. And / or a method of transferring and forming the pattern layer 3 on the surface of the base material sheet 1 through the adhesive layer 2 formed on the surface of the base material sheet 1,
A method of forming and adhering on the adhesive layer 2 on the base sheet 1 by a spraying method, an electrostatic printing method, an electrophotographic method, or the like is also conceivable. However, productivity, printability, sharpness of a pattern, material loss, and the like are considered. From various viewpoints such as smallness, it is most desirable that the pattern layer 3 is formed by printing on the back surface of the transparent thermoplastic olefin resin layer 4.

The transparent thermoplastic olefin resin layer 4 having the pattern layer 3 printed and formed on its back surface is then coated with the adhesive layer 2 via the adhesive layer 2 to the surface of the substrate sheet 1 made of amorphous polyester resin. The basic structure of the decorative sheet of the present invention is completed. At the time of the lamination, the adhesive layer 2 may be formed on the pattern layer 3 of the transparent thermoplastic olefin resin layer 4 having the pattern layer 3 printed on the back surface in advance, or may be formed of an amorphous polyester-based resin. It may be formed on the surface of the base sheet 1 made of resin. In addition, it is of course possible to use both of them, and it can be said that this is the most desirable form from the viewpoint of the interlayer adhesion between the base sheet 1 and the transparent thermoplastic olefin-based resin layer 4.

However, when the adhesive layer 2 is thickly formed on the surface of the base sheet 1 made of an amorphous polyester resin, the solvent contained in the adhesive for forming the adhesive layer 2 causes the base sheet 1 to be removed. When the adhesive layer 2 needs to be provided thickly, there is a case where the adhesive layer 2 is eroded or a solvent component remains in the base sheet 1 to cause blocking or generation of air bubbles after lamination. The adhesive layer 2 may be provided only on the surface of the transparent thermoplastic olefin resin layer 4 on the side of the pattern layer 3 or may be provided on the pattern layer 3 of the transparent thermoplastic olefin resin layer 4.
Surface (the adhesive layer 2 provided in advance on the surface of the base sheet 1 is sufficiently thin). It is desirable to take such a form.

The kind of the olefin resin constituting the transparent thermoplastic olefin resin layer 4 is not particularly limited. For example, any thermoplastic olefin resin conventionally used as a constituent material of the same decorative sheet may be used. can do. Specifically, for example, various homopolymers such as polyethylene resin, polypropylene resin, polybutene-1 resin, poly-4-methylpentene-1 resin, etc., ethylene-α-olefin copolymer resin, ethylene- Olefinic copolymer resins such as vinyl acetate copolymer resins, ethylene- (meth) acrylic acid (ester) copolymer resins, and ethylene-vinyl alcohol copolymer resins can be exemplified.

Among them, the most suitable for the purpose of the present invention is a polypropylene resin, that is, a homopolymer or a copolymer containing polypropylene as a main component.
A block polypropylene resin or the like may be used alone or appropriately compounded, or a resin or the like further mixed with an atactic polypropylene may be used. Further, it may be a copolymer containing an olefin-based monomer other than propylene, for example, an α-olefin having 2 to 20 carbon atoms other than propylene, having a polypropylene crystal part, preferably ethylene, butene- 1,4-methylpentene-1,
Propylene-α- containing at least 15 mol% of one or more comonomers of hexene-1 or octene-1
Olefin copolymers and the like can be exemplified. In addition, a modifier such as an ethylene-α-olefin copolymer, an ethylene-propylene copolymer rubber, or an ethylene-propylene-nonconjugated diene copolymer rubber, which is usually used for softening a polypropylene resin, is appropriately added. Can also.

The above transparent thermoplastic olefin resin layer 4
Need not necessarily be completely colorless and transparent, and may be translucent or colored and transparent as long as at least the lower picture layer 3 has transparency enough to be seen through. For example, it may be colored by adding a dye or a pigment. If necessary, depending on the intended use of the decorative sheet, for example, antioxidants, light stabilizers, heat stabilizers, plasticizers, lubricants, antistatic agents, flame retardants, extenders, fillers, antibacterial agents, antifungal agents One or more conventionally known additives such as an agent, a gloss control agent, a lubricant and the like may be added.

The thickness of the transparent thermoplastic olefin-based resin layer 4 is not particularly limited, and can be, for example, equal to the thickness of the transparent resin layer in a conventional general multi-layer decorative sheet. In general, the thicker the transparent thermoplastic olefin-based resin layer 4 is, the more advantageous in terms of surface properties such as abrasion resistance and solvent resistance, weather resistance, design feeling such as painting feeling and depth feeling, emboss depth and the like. However, on the other hand, it is disadvantageous in terms of flexibility and flexibility as a decorative sheet, conformability to a three-dimensional three-dimensional shape on the surface of the adhered substrate during lapping or vacuum forming, and so on. A balanced thickness range is selected. Specifically, the intended use of the decorative sheet and the required quality according to it,
Although it depends on the type of the thermoplastic olefin-based resin to be used, it is generally selected from a range of about 20 to 200 μm, and a particularly preferred range is about 50 to 150 μm.

On the surface of the transparent thermoplastic olefin-based resin layer 4, as in the case of the conventional decorative sheet, a concavo-convex pattern 5 by embossing a desired appropriate pattern can be provided as necessary. There is no particular limitation on the type of the uneven pattern 5,
For example, woodgrain (especially conduit groove pattern), stonegrain, cloth gauze,
Various patterns such as Japanese paper, geometric patterns, etc. may be used, or matte patterns such as grain, satin, etc., hairline, suede, leather, etc. may be used. In addition, by adjusting these concavo-convex patterns 5 with the pattern of the pattern layer 3, it is possible to further improve the designability, but if it is not necessary, the pattern may be out of synchronization.
An uneven pattern 5 including both a pattern synchronized with the pattern of the pattern layer 3 and a pattern not synchronized with the pattern may be provided.

The method of forming the concavo-convex pattern 5 is not particularly limited, but a mechanical embossing method using a metal embossing plate is most common. There is no particular limitation on the timing of forming the concavo-convex pattern 5, for example, at the same time as the sheet formation of the transparent thermoplastic olefin-based resin layer 4 and the sheet formation of the transparent thermoplastic olefin-based resin layer 4 with the base sheet 1. Any time can be selected before, simultaneously with or after lamination. In addition, the same or different concavo-convex pattern 5 can be applied a plurality of times at a plurality of times selected from these. The concave portion of the concave-convex pattern 5 may be filled with the coloring agent 6 by a technique such as a wiping method as necessary, and thereby, the color pattern synchronized with the concave-convex pattern 5 on the surface is excellent in design. A decorative sheet can be obtained.

For the purpose of imparting more excellent surface properties to the surface of the decorative sheet, a top coat layer 7 can be provided on the surface of the transparent thermoplastic olefin resin layer 4.
As the constituent material of the top coat layer 7, any material selected from known top coat agents conventionally used as constituent materials of the top coat layer of the decorative sheet according to the related art can be used. In general, it is necessary to have at least transparency so that the underlayer can be seen through, and to provide surface properties such as abrasion resistance, abrasion resistance, solvent resistance, and stain resistance required by the use of the decorative sheet. For this reason, it is preferable to use a material containing a curable resin as a main component.

Specific examples of the constituent material of the top coat layer 7 include a melamine resin, a phenol resin,
Urea resin, epoxy resin, aminoalkyd resin,
Thermosetting resins such as urethane resins, polyester resins, silicone resins, and unsaturated polyester resins,
An ionizing radiation-curable resin that is cured by irradiation with ultraviolet light or an electron beam, such as a (meth) acrylate resin, can be suitably used. If necessary, various additives such as a gloss control agent, a lubricant, a lubricant, an antistatic agent, an anti-condensation agent, an antibacterial agent, and a fungicide can be appropriately added.

The method for forming the top coat layer 7 is not particularly limited. For example, a gravure coating method, a roll coating method, a dip coating method, a knife coating method, an air knife coating method, a comma coating method, a die coating method, a lip coating method,
Any conventionally known coating method such as a kiss coat method, a rod coat method, a spray coat method, a flow coat method, or the like can be appropriately employed.

The transparent thermoplastic olefin resin layer 4
If the adhesiveness between the resin and the top coat layer 7 is insufficient, the surface of the transparent thermoplastic olefin-based resin layer 4 is subjected to, for example, corona discharge treatment, ozone treatment, or plasma treatment before the top coat layer 7 is formed. By applying an appropriate surface treatment such as flame treatment, ionizing radiation treatment, acid treatment, alkali treatment, anchor or primer treatment, the adhesion between the two can also be improved.

The decorative sheet of the present invention is generally the same as a conventional decorative sheet, for example, wood-based materials such as veneer, plywood, laminated wood, medium density fiberboard, particle board, gypsum board, slate board, calcium silicate, and the like. Board, wood wool cement board,
Inorganic base materials such as glass fiber reinforced concrete and lightweight cellular concrete, metal base materials such as steel, brass, stainless steel, and aluminum, olefin resin, acrylic resin,
Styrene resin, polyester resin, ABS resin, polycarbonate resin, fiber reinforced plastic (FRP)
It is used by being attached (laminated) to the surface of various substrates to be adhered such as a synthetic resin-based substrate.

Then, at the time of the attachment (lamination),
For example, an appropriate adhesive such as urethane or vinyl acetate is generally used, but depending on the type of the adhesive, the amorphous polyester constituting the base sheet 1 of the decorative sheet of the present invention may be used. In some cases, the adhesiveness with the system resin is not always sufficient. In preparation for such a case, a primer layer made of a resin composition having excellent adhesion to a general-purpose laminating adhesive may be provided on the back surface of the base sheet 1.

The primer layer may be, for example, a urethane type, an acrylic type, an ethylene-vinyl acetate copolymer type,
Various types of primers such as vinyl chloride-vinyl acetate copolymers are known, and those selected according to the base sheet 1 are used. In addition, if a powder such as silica, alumina, calcium carbonate, barium sulfate, etc. is added to the primer layer, the surface of the primer layer is roughened, which prevents blocking during winding and preservation of the decorative sheet. It is also effective for improving the adhesive with the laminating adhesive by the anchor effect.

[0060]

Example 1 A pattern layer consisting of a woodgrain pattern layer and a concealed solid ink layer was formed on the back surface of a 70 μm-thick random copolymer polypropylene resin transparent film by gravure printing using a solvent-type urethane resin-based printing ink. Was formed by printing to produce a backside-printed transparent film, which was once wound up. Next, a two-component curable urethane resin-based dry laminating adhesive was applied onto the printing surface of the back-side printing transparent film after drying, at an application amount of 10 g / m
² and dried, and then, on the surface of the adhesive layer, a thickness of 100 μm
Is dry-laminated, and finally, a two-component curable urethane-based resin is applied to the surface of the transparent film by a gravure coating method to a coating amount of 6 g / m ² after drying. To form a topcoat layer, thereby producing a decorative sheet of the present invention. During this time, no blocking due to winding up or generation of bubbles between layers during dry lamination was observed.

The obtained decorative sheet was previously coated with an aqueous 2
10 g of liquid curable urethane resin adhesive after drying
/ M ² , dried and three-dimensionally molded and laminated on a surface of a wooden substrate having a three-dimensional three-dimensional shape with a radius of curvature of 5R at a sheet temperature of 70 ° C using a vacuum molding machine. No molding defects such as whitening and pattern elongation occur, and surface properties such as surface hardness, scratch resistance, and solvent resistance have no practical problems at all, and the color and defects of the surface of the wood substrate are sufficiently hidden. As a result, it was possible to obtain a good laminate product in which the color tone and the design of the hail surface were stable.

Comparative Example 1 A pattern layer composed of a concealed solid ink layer and a wood pattern layer was formed on a surface of a 100 μm-thick amorphous polyester resin colored film by gravure printing using a solvent type urethane resin printing ink. Was printed to form a surface-printed colored film, which was once wound up. Next, a two-component curable urethane resin-based dry laminating adhesive is applied to the printing surface of the surface printing colored film at a coating amount of 10 g / m ² after drying, and after drying, a thickness of A 70 μm transparent film made of a random copolymerized polypropylene resin is dry-laminated, and finally, a two-component curable urethane resin is coated on the surface of the transparent film by a gravure coating method to a coating amount of 6 g / m ² after drying. To form a decorative sheet. This decorative sheet was not practically usable, because a part of the pattern layer was damaged by blocking when the surface-printed colored film was wound, and bubbles were generated between layers during dry lamination.

Comparative Example 2 On the surface of a 100 μm-thick amorphous polyester resin colored film, a pattern layer consisting only of a wood pattern layer was formed by printing using a solvent type urethane resin printing ink by gravure printing. To produce a surface printing colored film,
Once wound up. Next, a two-component curable urethane resin-based dry laminating adhesive is applied on the back surface of the transparent film made of a random copolymerized polypropylene resin having a thickness of 70 μm to a coating amount of 10 g / m ² after drying. On the agent layer surface,
The printed surface of the surface-printed colored film is dry-laminated, and finally, a two-component curable urethane-based resin is coated on the surface of the transparent film by a gravure coating method after coating with a coating amount of 6 g / m 2.
² was applied to form a top coat layer to produce a decorative sheet.

The obtained decorative sheet was previously coated on the surface with an aqueous 2
10 g of liquid curable urethane resin adhesive after drying
/ M ² , dried and three-dimensionally laminated on a surface of a wooden substrate having a three-dimensional three-dimensional shape with a curvature radius of 5R at a sheet temperature of 70 ° C. using a vacuum forming machine. Due to insufficient hiding power, the color tone is not stable reflecting the color tone variation of the surface of the wooden base material,
Further, the defects existing on the surface of the woody base material were seen through, and were not sufficiently satisfactory in design.

[0065]

As described in detail above, the decorative sheet of the present invention is provided with a base sheet made of an amorphous polyester resin, so that not only bending processing such as V-cut processing and lapping processing, but also Even when used for vacuum molding, it can be molded uniformly without causing molding defects such as necking, whitening, and pattern elongation at the time of molding, and by providing a transparent thermoplastic olefin-based resin layer on its surface. It has excellent surface properties such as surface hardness, scratch resistance, abrasion resistance, and solvent resistance, and has an adhesive layer on the surface of a substrate sheet made of an amorphous polyester resin. The base sheet made of the amorphous polyester resin is damaged by the solvent contained in the printing ink or the like for forming the picture layer, Contains a solvent that permeates the amorphous polyester resin because there is no danger that the solvent that has permeated therein will evaporate during or after lamination with the transparent thermoplastic olefin-based resin layer or between layers. It is possible to easily select a wide range of printing inks, including printing inks, and to apply thick coatings of printing inks, etc. By providing concealing properties sufficient for concealing the color tone, defects, etc. of the surface of the material, an excellent effect of easily obtaining various cosmetic products having high design can be obtained.

[Brief description of the drawings]

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

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 ... Base sheet made of amorphous polyester resin 2 ... Adhesive layer 3 ... Picture layer 4 ... Transparent thermoplastic olefin resin layer 5 ... Concavo-convex pattern 6 ... Colorant 7 ... Top coat layer

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Yumiko Tsuruta 1-5-1, Taito, Taito-ku, Tokyo Toppan Printing Co., Ltd. F-term (reference) 4F100 AK03C AK07A AK07J AK41A AK51B AK51G AL03A BA03 BA07 BA10A BA10C BA13 GB07 GB08 GB48 GB81 HB00B HB31B JA12A JB16C JN01C

Claims (2)

[Claims] 1. A cosmetic comprising a pattern sheet and a transparent thermoplastic olefin resin layer sequentially laminated on a base sheet made of an amorphous polyester resin via an adhesive layer. Sheet. 2. The decorative sheet according to claim 1, wherein the picture layer is formed by printing on the back surface of a transparent thermoplastic olefin resin layer.