JPH11179864A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet of a non-vinyl chloride ecological sheet having an excellent weather resistance and gentle properties to an environment. SOLUTION: In the decorative sheet comprising a surface protective layer 8 on a base material sheet 1, the layer 8 is a laminate of a polyolefin resin layer 5 and a polyolefin resin layer 7 having a polar functional group from the sheet 1 side. Preferably, the layer 7 having the group is one or more types of each of mixtures of modified polyolefins obtained by graft copolymerizing an olefin with at least one type selected from an unsaturated carboxylic acid, an acid anhydride and an ester in a range of 10<4> to 10 wt.% to the olefin.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a wall, a ceiling, a door,
The present invention relates to a decorative sheet using a non-vinyl chloride-based ecology sheet (a sheet in consideration of ecology) useful as a surface decoration material for home electric appliances.

[0002]

2. Description of the Related Art Heretofore, a base sheet made of a colored polyolefin resin has been subjected to decoration processing such as pattern printing, and the printed sheet and a transparent sheet made of polyolefin have been pasted together. Japanese Patent Application Laid-Open No. 2-128843 discloses a decorative sheet which has been subjected to an adhesive treatment and further provided with an overcoat protective layer (OP coating treatment layer). Such decorative sheet is environmentally superior as a non-vinyl chloride ecological sheet,
It is widely used as a surface decoration material for handrails and home appliances.

[0003]

However, even if the conventional decorative sheet as described above is subjected to an easy-adhesion treatment on the transparent sheet, it has poor adhesion to the OP coat treatment layer on the upper surface thereof, so that the OP coat cannot be used. Are easily peeled off. In particular, when exposed to sunlight, there was a problem that the adhesiveness was rapidly reduced, and the weather resistance of the adhesiveness to the OP coat was lacking.
Accordingly, there is a need for the development of a decorative sheet that is an environmentally friendly non-vinyl chloride-based ecological sheet that is excellent in adhesiveness and weather resistance of an OP coat and that is environmentally friendly. An object of the present invention is to provide a decorative sheet that is a non-vinyl chloride-based ecological sheet that is excellent in weather resistance and is environmentally friendly.

[0004]

Means for Solving the Problems The decorative sheet of the present invention comprises:
In order to solve the above problems, a decorative sheet having a surface protective layer on a substrate sheet, wherein the surface protective layer is a polyolefin resin layer and a polyolefin resin layer having a polar functional group, from the substrate sheet side Characterized in that it is a laminate comprising

Preferably, the decorative sheet of the present invention has a decorative layer between the base sheet and the surface protective layer, and further comprises an overcoat protective layer (OP coat layer) on the surface protective layer. Have.

More preferably, the polyolefin resin layer having a polar functional group comprises at least one selected from the group consisting of unsaturated carboxylic acids, acid anhydrides and esters, in an amount of 10 ^-4 to 10 wt. % Of the modified polyolefin obtained by graft copolymerization in the range of
It is a kind or a mixture of two or more kinds. Hereinafter, the present invention will be described in detail.

[0007] The substrate sheet used in the decorative sheet of the present invention is not particularly limited as long as it is a non-vinyl chloride resin in view of the environment, but a polyolefin resin is particularly preferable.
Examples of the polyolefin resin include an olefin thermoplastic elastomer and a non-elastomeric olefin resin. Specifically, crystalline non-elastomeric polyolefin-based resin such as polyethylene, polypropylene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-butene-1 copolymer, ionomer, or olefin-based thermoplastic elastomer Although a stromer is used, an olefin-based thermoplastic elastomer is preferred from the viewpoint of suitability for forming a decorative sheet.

The olefin-based thermoplastic elastomer resin is a thermoplastic elastomer of a composite material composed of an olefin-based elastomer and a non-elastomeric polyolefin-based resin. (1) A simple blend of an amorphous olefinic elastomer as a soft segment and a crystalline non-elastomeric olefinic resin as a hard segment (2) The olefinic elastomer and the non-elastomeric olefinic resin are partially (3) A type in which an olefin-based elastomer is crosslinked and dispersed in a non-elastomeric olefin resin.

The olefin-based elastomers include ethylene-based rubbers typified by EPDM, and the non-elastomeric olefin-based resins include crystalline polymers such as polyethylene and polypropylene. In addition, if necessary, the composition may be appropriately
Additives such as flame retardants, antioxidants and the like used in ordinary polyolefin resins can be added.

As the type of the above (2), for example,
B) JP-B-53-21021, JP-B-53-34
No. 210, etc., b) Japanese Patent Publication No. 56
And those described in US Pat.

More specifically, for example, the above (a) includes 60 to 80 parts by weight of a monopolyolefin copolymerized elastomer (A), 40 to 20 parts by weight of a non-elastomeric polyolefin-based plastic (B), And those curing agents which are mixed and partially cured at the curing temperature to such an extent that they do not become insoluble in the usual solvents of the uncured blend during mastication. The olefin copolymer elastomer is an elastic copolymer to which at least one polyene copolymerizable with two or three or more olefins is added.

As the olefin, ethylene, propylene, α-polyolefin and the like are used, and as the polyene, 1,4-hexadiene, cyclic diene, norbonene and the like are used.

The non-elastomeric polyolefin-based plastic (B) is a crystalline thermoplastic resin obtained by polymerizing a polyolefin such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene by a conventional method. Yes, including polyethylene and polypropylene modified with higher α-polyolefin.

As the curing agent, peroxide,
Azide type, aldehyde-amine reaction products, substituted ureas, xanthates, dithiocarbamates, imidazoles, sulfonamides, thiuram disulfites, paraquinone dioxime, dibenzoparaquinone dioxime, sulfur and the like. it can.

The above-mentioned b) includes polyolefin copolymer rubbers such as ethylene-propylene copolymer rubber, ethylene-propylene non-conjugated diene rubber, ethylene-butadiene copolymer rubber, and propylene-ethylene copolymer. , Propylene-1-copolymer, propylene-1-
A hexene copolymer, a propylene-4-methyl-1-pentene copolymer, or the like, together with a mineral oil-based softener such as a high-boiling oil fraction, a paraffin-based, a naphthenic-based, or an aromatic-based, together with an organic peroxide, An olefin-based thermoplastic elastomer which is melt-kneaded and partially crosslinked can be used.

The polyolefin resin used in the present invention may be used alone or may be a laminate.
In order to impart flexibility, impact resistance, and easy adhesion to the polyolefin resin, preferably, various rubbers such as a diene rubber, a hydrogenated diene rubber, and an olefin elastomer can be added. The amount of the rubber is preferably about 1 to 90 parts by weight based on 100 parts by weight of the polyolefin resin.

If necessary, the surface of the base sheet may be subjected to known easy treatments such as corona discharge treatment, plasma treatment, anchor coating treatment, degreasing treatment, surface roughening treatment, and activation treatment with a chemical such as cupric chloride. An adhesive treatment can be performed.

Further, pigments, extenders, dyes and the like can be appropriately added to the base sheet in order to impart hiding power.

Examples of pigments to be added to the polyolefin resin layer include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, carbon black, isoindolinone, and Hansa yellow. A, quinacridone, permanent red 4R, organic pigments (or dyes) such as phthalocyanine blue, indathrene blue RS, and aniline black; metal pigments composed of foil powders such as aluminum and brass; titanium dioxide-coated mica; basic lead carbonate And other pearlescent pigments made of foil powder.

The coloring by adding the pigment may be transparent coloring or opaque (concealing) coloring. These are added and dispersed as powder or flaky foil pieces.

In the present invention, a decorative layer is preferably provided on the base sheet. The decorative layer is provided to improve the decorativeness of the decorative sheet. As a method of forming the decorative layer, for example, a method of adding a pigment, a method of printing a pattern such as a pattern on the base sheet by ink, paint, etc., a metal thin film layer, a partial metal thin film layer, etc. on the base sheet One method such as a providing method or a combination of two or more of these methods can be used.

As the pattern printing, a pattern can be formed with ink (or paint) by using a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet.

The patterns include a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric pattern, a character symbol, and a solid image on the entire surface.

As the ink or paint, a binder obtained by appropriately mixing a coloring agent such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like as necessary can be used. . As the binder, a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, etc.,
It can be appropriately selected depending on the required physical properties, printability, and the like. For example, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester resins, urethane resins, acrylic resins, vinyl chloride-vinyl acetate copolymers, cellulose resins and the like can be used, and one or two of these can be used. A mixture obtained by mixing the above and further adding the above-listed pigments is used.

In the case of printing directly on a polyolefin resin, a chlorinated polyolefin urethane resin or the like is preferable as a binder in terms of adhesiveness. However, if an easy-adhesion primer is appropriately selected to form a layer, other binders can be used. Even if used, sufficient adhesiveness can be provided.

The metal thin film is made of aluminum, chromium, gold,
Using a metal such as silver, copper, nickel, cobalt, zinc, brass, and stainless steel, a film can be formed by a method such as vacuum evaporation or sputtering. Alternatively, a combination of these may be used. The metal thin film may be provided on the entire surface, or
It can also be provided partially in a pattern. In the present invention, the decoration processing layer can be omitted.

Further, in the present invention, a primer layer can be provided on the base sheet as required in order to improve the adhesion between the base sheet and the decoration treatment layer. The primer layer is usually provided to improve the adhesion between the base sheet and the decoration treatment layer by reacting with a functional group present on the surface because the base sheet is subjected to corona discharge treatment. .

As the primer layer, it is preferable to use a two-component curable urethane resin. When hexamethylene diisocyanate (HMDI) is used as the isocyanate and acrylic polyol is used as the polyol, it is particularly preferably used because of its good light adhesion.

The decorative sheet of the present invention has a surface protective layer on the base sheet or via a decorative layer. The surface protective layer is provided to protect the base sheet and / or the decorative layer.

In order to bond the base sheet and the surface protective layer, a coating method is applied to the bonding surface in the case of a liquid adhesive, but a hot-melt solidifying type such as a hot melt adhesive is used. In this case, a method is used in which the mating substrate is laminated and heated and pressurized after coating and drying once on the bonding surface by extrusion coating, etc. In the case of a film type, an adhesive film is laminated between the substrates to be bonded and added. Pressure or by heating and pressing.

[0031] The decorative sheet of the present invention is characterized in that the surface protective layer is a laminate comprising a polyolefin resin layer and a polyolefin resin layer having a polar functional group from the base sheet side. If necessary, an adhesive layer may be further provided between the two layers in order to further enhance the adhesive strength between the two layers.

The polyolefin resin which can be used for the polyolefin resin layer of the surface protective layer includes:
For example, polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, polypropylene,
Propylene / butene-1 copolymer, polybutene-2, butene-1 / propylene / ethylene / terpolymer, butene-1 / hexene / octene / terpolymer, polymethylpentene, Japanese Patent Publication No. Hei 6-23278 JP-A-5-77371, JP-A-9-111055 and the like, a polypropylene-based olefin-based thermoplastic elastomer having an isotactic polypropylene as a hard segment and an atactic polypropylene as a soft segment. An olefin thermoplastic elastomer such as a propylene / butene / terpolymer copolymer olefin thermoplastic elastomer can be used.

These resins may be used alone or in combination of two or more. The thickness of the olefin resin layer is usually 3
It is preferably about 0 to 100 μm.

Examples of the resin which can be used as the adhesive for the adhesive layer between the surface protective layers include urethane resins, polyester resins, polyamide resins, and the like.
Resins such as vinyl acetate-acrylate resins, carboxyl group-containing acrylic resins, vinyl acetate-ethylene resins, polyvinyl ethers, and cyanoacrylic resins can be used. Of these, urethane-based resin adhesives are particularly preferable in consideration of the adhesion (including weather resistance) to the base sheet.

As the urethane-based resin adhesive, it is preferable to use a two-component curable urethane resin. For example, it is a urethane resin having a polyol as a main component and an isocyanate as a cross-linking agent (curing agent).

Polyols having two or more hydroxyl groups in the molecule include, for example, polyethylene glycol, polypropylene glycol, acrylic polyol,
Polyester polyol, polyether polyol, polycarbonate polyol and the like are used.

As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used.

For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, and 4,4-diphenylmethane diisocyanate; or aliphatic isocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate. (Or alicyclic) isocyanates are used. Alternatively, adducts or multimers of the above various isocyanates can also be used. For example, adducts of tolylene diisocyanate,
And trimer of tolylene diisocyanate. Usually, the thickness of the adhesive layer is preferably about 5 to 15 μm.

On the outermost surface side of the surface protective layer, a layer made of a polyolefin resin having the polar functional group is provided. The layer made of the polyolefin-based resin having the polar functional group improves the adhesion with the overcoat protective layer provided on the upper surface thereof, and enhances the weather resistance of the decorative sheet (particularly, the weather resistance of the adhesive force with the overcoat protective layer). Play a role.

Examples of the polyolefin resin having a polar functional group include olefins such as ethylene, propylene, butene-1, butene-2 and pentene-1 and monomers having a polar functional group such as a hydroxyl group and a carboxyl group. For example,
Maleic acid, fumaric acid, unsaturated carboxylic acids such as itaconic acid, acid anhydrides such as maleic anhydride, and acrylic acid,
At least one selected from unsaturated carboxylic acid esters such as methacrylic acid is used in an amount of 10 ^-4 to
One or a mixture of two or more modified polyolefins obtained by graft copolymerization in the range of 10% by weight is preferred. The thickness of the layer made of the polyolefin resin having a polar functional group is usually preferably about 5 to 10 μm.

In order to prevent the weather resistance of the decorative sheet as a whole, especially the deterioration of the surface protective layer such as discoloration, cracks and embrittlement, the discoloration of the decorative layer and the decrease in the adhesive strength between the surface protective layer and the substrate sheet. It is desirable to add an ultraviolet absorber to one or both of the polyolefin resin layer having a surface protective layer and the polyolefin resin layer having a polar functional group.

As the ultraviolet absorber, various organic and inorganic substances can be used. From the viewpoint of transparency, an organic compound having a hydroxyl group in the molecule is preferably used. For example, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-
Butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert
-Amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy- 2'-hydroxyphenyl-5-chlorobenzotriazole-based ultraviolet absorbers such as 3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'- Di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-
2′- such as 5′-methylphenyl) benzotriazole
Benzotriazole-based UV absorbers such as hydroxyphenylbenzotriazole-based UV absorbers, 2,2′-
Dihydroxy-4-methoxybenzophenone, 2,2 ′
2,2′-dihydroxybenzophenone-based ultraviolet absorbers such as dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, Benzophenone UV absorbers such as 2-hydroxybenzophenone UV absorbers such as 4-dihydroxybenzophenone, phenyl salicylate, 4-ter
A salicylic acid ester type ultraviolet absorber such as t-butylphenyl-salicylate or the like is used. In addition, a reactive ultraviolet absorber in which an acrylol group or a methacryloyl group is introduced into a benzotriazole skeleton is also used. In addition, the addition amount of these ultraviolet absorbers is usually preferably 0.1 to 5% by weight.

The deterioration of each layer due to ultraviolet rays is further prevented,
In order to improve weather resistance, it is preferable to add a radical scavenger as another light stabilizer. Examples of the radical scavenger include bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and bis- (N
-Methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate and others, for example, Japanese Patent Publication No. 4-82
For example, hindered amine radical scavengers such as the compounds disclosed in JP-A No. 625 and piperidinyl radical scavengers are used.

When a light stabilizer comprising a hindered amine radical scavenger is added to the polyolefin, not only the polyolefin resin but also the ink layer, adhesive layer and the like adjacent to the polyolefin resin sheet are added to the polyolefin resin.
Use of a resin containing no chlorine atom in the molecule, such as a polyurethane resin, a polyolefin resin, or a polyamide resin, is favorable in terms of improving weather resistance. If vinyl chloride-vinyl acetate copolymers, chlorinated polyolefins, and other resins containing chlorine atoms in their molecules are used, hydrogen chloride is generated from these resins by the action of ultraviolet light or heat, resulting in the generation of hindered amines. Since it reacts with the system radical scavenger to deactivate or inhibit its action, the weather resistance is not sufficiently improved.

The decorative sheet of the present invention has an overcoat protective layer (OP coat layer) on the surface protective layer. The overcoating protective layer is provided to cover the susceptibility of the decorative sheet surface to scratches and to improve the scratch resistance. The thickness of the overcoat protective layer is usually about 1 to 10 μm. Examples of the resin used for the OP coating include urethane resin, fluororesin, silicon resin, and polyfunctional acrylate that can be cured by ultraviolet light or electron beam. Preferred are two-component curable urethane resins, A resin having an isocyanate group such as a liquid urethane tree can be given. The two-component curable urethane resin is a urethane resin containing polyol as a main component and isocyanate as a crosslinking agent (curing agent). In the case of a two-component curable urethane resin, more preferably, the number (mol number) of isocyanate groups of the isocyanate is set to be larger than the number (mol number) of hydroxyl groups of the polyol to be reacted therewith, and a urethane bond is formed. Even afterward, it is preferable to make sure that excess isocyanate groups remain in a larger amount. In that case, the number of isocyanate groups / the number of hydroxyl groups is at most 1.4.
It is about.

The polyol has two or more hydroxyl groups in the molecule, and examples thereof include polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, and polycarbonate polyol.

As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, aromatic isocyanates such as 2,4-tolylene diisocyanate, xylene diisocyanate, 4,4'-diphenylmethane diisocyanate, or aliphatic (such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate). Is an alicyclic) isocyanate or the like.
Alternatively, adducts or multimers of the above-mentioned various isocyanates can also be used. For example, there are an adduct of tolylene diisocyanate, a trimer of tolylene diisocyanate, and the like.

The one-component moisture-curable urethane resin is a composition containing a prepolymer having an isocyanate group at a molecular terminal as an essential component. The prepolymer is usually a polyisocyanate prepolymer having at least one isocyanate group at each terminal of the molecule, and is a solid thermoplastic resin at room temperature. Isocyanate groups react with each other due to moisture in the air to cause a chain extension reaction,
As a result, a reactant having a urea bond in the molecular chain is generated, and the isocyanate group at the molecular terminal further reacts with the urea bond to cause a biuret bond and branch to cause a crosslinking reaction.

The skeleton structure of the molecular chain of the prepolymer having an isocyanate group at the molecular terminal is arbitrary, and specific examples include a polyurethane skeleton having a urethane bond, a polyester skeleton having an ester bond, and a polybutadiene skeleton. As appropriate, one or more of these skeletal structures are employed. When a urethane bond is present in the molecular chain, the terminal isocyanate group also reacts with the urethane bond to generate an allophanate bond, which also causes a cross-linking function.

It is preferable that an organic compound having a hydroxyl group in the molecule is used as the ultraviolet absorber, and the surface layer is formed using a resin having an isocyanate group. With such a combination, when the ultraviolet absorber bleeds out (elutes) and enters the surface layer, a hydroxyl group of the ultraviolet absorber reacts with an isocyanate group in the surface layer to form a urethane bond, Trapped in the surface layer. Therefore, bleeding out of the ultraviolet absorbent over time is prevented. In particular, it is effective in the case of a polyolefin resin in which an organic ultraviolet absorber easily bleeds out.

The back side of the base sheet of the decorative sheet of the present invention produced as described above (the side opposite to the OP coat).
May be provided with a pressure-sensitive adhesive layer and a release sheet as required. The decorative sheet is used by peeling the release sheet from the decorative sheet and the pressure-sensitive adhesive layer at the time of sticking to a wall surface or the like.
Thereby, the decorative sheet can be easily attached to the adherend. As a resin constituting such an adhesive layer,
For example, polyisoprene rubber, polyisobutylene rubber,
Rubber resins such as styrene butadiene rubber and butadiene acrylonitrile rubber, (meth) acrylate resin, polyvinyl ether resin, polyvinyl acetate resin, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer, polystyrene Resin, polyester resin, polyamide resin, polychlorinated olefin resin, polyvinyl butyral resin, and the like.

As the tackifier, rosin, dammar, polymerized rosin, partially hydrogenated rosin, ester rosin, polyterpene resin, modified terpene, petroleum resin, cyclopentadiene resin, styrene resin, xylene resin, Phenolic resins, chroman-indene resins, and the like can also be added. In addition, if necessary, a softener,
Fillers, antioxidants and the like can also be added, and the viscosity is adjusted with an organic solvent.

The pressure-sensitive adhesive layer can be formed by roll coating, die coating, knife coating, gravure coating, or the like.

The decorative sheet of the present invention can be laminated on another adherend. In the case of lamination, the adhesive layer can be omitted when the decorative sheet itself can be bonded to the adherend (by heat fusion or the like). When the decorative sheet does not adhere to the adherend, the decorative sheet is laminated with an appropriate adhesive. The adherend is the final product, and in some cases a decorative sheet is laminated for surface cosmetics, and if necessary, to enhance the mechanical strength of the decorative sheet or to provide concealment, An adherend may be laminated.

The adherend may be a plate material such as a flat plate or a curved plate of various materials, a three-dimensional article, or a sheet (or film). Wood material such as medium density fiberboard (MDF), metals such as iron and aluminum, acrylic resin, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate copolymer, polyester, polystyrene, olefin resin, ABS resin, Phenolic resin, polyvinyl chloride, cellulosic resin, rubber and other resins, materials exclusively used as plate materials or three-dimensional articles include glass, ceramics such as ceramics, and ALC
Non-cement ceramics materials such as cement (foamed lightweight concrete), calcium silicate, gypsum, etc. Materials used exclusively as sheets (or films) include high quality paper,
Examples include paper such as Japanese paper, or nonwoven fabric or woven fabric made of fibers such as carbon, asbestos, potassium titanate, glass, and synthetic resin.

As a method of laminating these various adherends,
For example, as described in Japanese Patent Publication No. 50-19132, Japanese Patent Publication No. 43-27488, etc., a decorative sheet is a method of laminating a plate-like substrate by pressing with a pressure roller via an adhesive. Into the injection-molded male and female molds,
Close both molds, inject and inject molten resin from the male mold gate, cool, and simultaneously mold and mold a resin molded product. As described in JP-A-45768, JP-B-60-58014, etc., a decorative sheet is opposed to or placed on the surface of a molded product via an adhesive layer therebetween, and is subjected to vacuum suction from the molded product. A so-called vacuum press laminating method in which a decorative sheet is laminated on the surface of a molded product by a pressure difference, Japanese Patent Publication No. 61-5895, Japanese Patent Publication No. 3-2
As described in JP-A-666, etc., in the major axis direction of a columnar substrate such as a cylinder and a polygonal pillar, while supplying a decorative sheet via an adhesive layer therebetween, by a plurality of rollers having different directions,
A decorative sheet is sequentially pressure-adhered and laminated on a plurality of side faces constituting a columnar body, and is described in a so-called lapping method, Japanese Utility Model Publication No. 15-31122, JP-A-48-47972, and the like. As described above, the decorative sheet is first laminated on the plate-shaped substrate via the adhesive layer, and then reaches the interface between the decorative sheet and the plate-shaped substrate on the surface of the plate-shaped substrate opposite to the decorative sheet. A so-called V-cut or U-cut in which a groove having a V-shaped or U-shaped cross section is cut, and then an adhesive is applied in the groove, and then the groove is bent to form a box or a column. There are processing methods and the like.

As described above, the decorative sheet of the present invention is characterized in that a polyolefin resin layer having a polar functional group is provided on the uppermost layer of the surface protective layer. It has excellent adhesion to the overcoat protective layer. Therefore, the decorative sheet of the present invention is excellent in weather resistance. Further, since non-vinyl chloride resin is mainly used, harmful chlorinated gas is hardly generated at the time of disposal or incineration, so that it is an environmentally friendly decorative sheet. The decorative sheet of the present invention is suitably used as interior decoration of buildings such as walls, floors, ceilings, doors, window frames, fixtures such as handrails, furniture such as chests of drawers, vehicle interiors, and surface decoration materials such as ship interiors. be able to.

[0058]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to various embodiments. First Embodiment FIG. 1A shows a first embodiment of a decorative sheet according to the present invention. This decorative sheet comprises a base sheet 1 made of a polyolefin-based resin such as an olefin-based thermoplastic elastomer or a non-elastomer olefin-based resin, containing a coloring pigment 2 for imparting color and hiding power. Sheet 1
A decorative layer 3 on which a design is printed is provided thereon, and a polyolefin-based resin layer 5, a second adhesive layer 6, and an adhesive layer 4 are further provided on the decorative layer 3 via an adhesive layer 4. It has a surface protection layer 8 in which three layers of a polyolefin-based resin layer 7 having a polar functional group are laminated. In the decorative sheet of the present embodiment, a polyolefin-based resin having a polar functional group is provided on the side of the upper protective layer on the surface protective layer, so that the adhesiveness with the upper protective layer is significantly improved.

Second Embodiment FIG. 1B shows a second embodiment of the decorative sheet according to the present invention. In this decorative sheet, an overcoat protective layer (OP coat layer) 9 made of a two-component curable urethane resin is further provided on the surface of the decorative sheet of the first embodiment, and a polyolefin resin layer having a polar functional group is provided. The organic ultraviolet absorber having a hydroxyl group in the molecule is added to both layers of the polyolefin resin layer 7 and the polyolefin resin layer 5. The decorative sheet of the present embodiment has a polyolefin-based resin having a polar functional group on the side of the upper protective layer on the surface protective layer, whereby the adhesion to the upper protective layer on the upper layer is significantly improved, and the weather resistance is excellent. It is a decorative sheet.

Third Embodiment FIG. 1C shows a third embodiment of the decorative sheet according to the present invention. This decorative sheet comprises a base sheet 1 made of a polyolefin-based resin such as an olefin-based thermoplastic elastomer or a non-elastomer olefin-based resin, containing a coloring pigment 2 for imparting color and hiding power. Sheet 1
A decorative layer 3 on which a pattern is printed is provided thereon, and a polyolefin layer 5, a second adhesive layer 6, and a polar functional group are further provided on the decorative layer 3 via an adhesive layer 4 from the substrate sheet side. And a surface protective layer 8 in which three layers of a polyolefin resin layer 7 having Then, a wiping process 10 is performed on the polyolefin resin having a polar functional group on the uppermost layer of the surface protective layer, and the surface is covered with an overcoat protective layer 9. The decorative sheet of the present embodiment has a polyolefin-based resin having a polar functional group on the side of the upper protective layer on the surface protective layer, whereby the adhesion to the upper protective layer on the upper layer is significantly improved, and the weather resistance is excellent. It is a decorative sheet. In addition, a wiping process is applied to the surface, and the design effect is high.

Fourth Embodiment FIG. 2D shows a fourth embodiment of the decorative sheet according to the present invention. This decorative sheet is formed on a base sheet 1 made of a colorless and transparent polyolefin resin such as an olefin thermoplastic elastomer or a non-elastomer olefin resin.
A decorative layer 3 having a pattern printed thereon is provided. Further, in the present embodiment, the primer layer 11 made of a two-component curable urethane resin is provided in order to enhance the adhesion to the upper surface protective layer. Then, on the decorative layer 3, a polyolefin-based resin layer 5, a second adhesive layer 6, and a polyolefin-based resin layer 7 having a polar functional group are arranged from the base sheet side via an adhesive layer 4. It has a surface protection layer 8 in which layers are laminated. Then, the polyolefin resin having a polar functional group on the uppermost layer of the surface protective layer is subjected to embossing 12, and the surface is covered with an overcoat protective layer 9. The decorative sheet of the present embodiment has a polyolefin-based resin having a polar functional group on the side of the upper protective layer on the surface protective layer, whereby the adhesion to the upper protective layer on the upper layer is significantly improved, and the weather resistance is excellent. It is a decorative sheet. In addition, a wiping process is applied to the surface to enhance the design effect. Further, since the primer layer is provided, the decorative sheet is particularly excellent in the adhesion of each layer.

Fifth Embodiment FIG . 2E shows a fifth embodiment of the decorative sheet according to the present invention. This decorative sheet comprises a base sheet 1 made of a polyolefin-based resin such as an olefin-based thermoplastic elastomer or a non-elastomer olefin-based resin, containing a coloring pigment 2 for imparting color and hiding power. Sheet 1
A decorative layer 3 on which a pattern is printed is provided on the upper side.
Further, on the decorative layer 3, three layers of a polyolefin-based resin layer 5, a second adhesive layer 6, and a polyolefin-based resin layer 7 having a polar functional group are provided from the base sheet side via an adhesive layer 4. It has a laminated surface protection layer 8. And
The surface of the surface protective layer is covered with an overcoat protective layer 9. The decorative sheet of the present embodiment has a polyolefin-based resin having a polar functional group on the side of the upper protective layer on the surface protective layer, whereby the adhesion to the upper protective layer on the upper layer is significantly improved, and the weather resistance is excellent. It is a decorative sheet.

Sixth Embodiment FIG . 2F shows a sixth embodiment of the decorative sheet according to the present invention. This decorative sheet comprises a base sheet 1 made of a polyolefin-based resin such as an olefin-based thermoplastic elastomer or a non-elastomer olefin-based resin, containing a coloring pigment 2 for imparting color and hiding power. Sheet 1
A metal thin film layer 13 of aluminum or the like is provided on the entire surface by vacuum deposition, and a polyolefin layer 5 is further formed on the metal thin film layer 13 from the base material sheet side via an adhesive layer 4.
It has a surface protective layer 8 in which three layers of a second adhesive layer 6 and a polyolefin-based resin layer 7 having a polar functional group are laminated. Then, the surface of the surface protective layer is covered with an overcoat protective layer 9. In addition, the base sheet 1
Is provided with an adhesive layer 27 made of an acrylate resin, a polyvinyl ether resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate copolymer resin, or the like. The decorative sheet of the present embodiment has a polyolefin-based resin having a polar functional group on the side of the upper protective layer on the surface protective layer, whereby the adhesion to the upper protective layer on the upper layer is significantly improved, and the weather resistance is excellent. It is a decorative sheet.
Further, since the metal thin film is provided, a unique design effect due to the metallic luster can be obtained. Furthermore, since it has a pressure-sensitive adhesive layer, a decorative sheet can be easily adhered to an adherend.

[0064]

Next, the present invention will be described in more detail by way of examples. Example 1 As shown in FIG. 3A, a clear sheet composed of three layers forming a surface protective layer of a decorative sheet was prepared. That is, a crystalline hard segment made of isotactic polypropylene having a thickness of 20 μm and an amorphous soft segment made of atactic polypropylene are combined with 80:
A two-part curable acrylic urethane-based resin (composed of acrylic polyol and hexamethylene diisocyanate) is applied onto the polypropylene-based thermoplastic elastomer polyolefin-based resin layer 14 mixed at a weight ratio of 20%, After forming an adhesive layer 15 having a thickness of about 10 μm, a benzotriazole-based ultraviolet absorber having a hydroxyl group in a molecule in a resin obtained by graft-polymerizing maleic acid on the same resin as the layer 14 on the adhesive layer 15 Was formed with a thickness of about 60 μm to produce a clear sheet 17.

Next, one surface of a polyolefin resin sheet 18 made of a thermoplastic thermoplastic elastomer made of polyethylene and made opaque by a coloring pigment consisting of titanium white, carbon black and red iron oxide having a thickness of 80 μm is subjected to corona discharge treatment. A pattern printing 19 is performed using a red pigment as a pigment, and a two-part curable urethane resin is bound, and the printed sheet and the clear sheet 17 obtained above are dry-laminated using a two-part curable urethane resin adhesive. And bonded together.

Next, a two-component curable acrylic urethane resin (100 parts by weight of acrylic polyol and 10 parts by weight of hexamethylene diisocyanate mixed with 100 parts by weight of acrylic polyol) was dried on the surface of the clear sheet by gravure printing as an OP coating treatment. Coating was performed at a thickness of 3 μm to obtain a decorative sheet 21 of the present invention as shown in FIG.

Comparative Example 1 As a comparative example, a decorative sheet of the type conventionally used as shown in FIG. 4 was prepared. That is, a pattern print 23 is applied to a base sheet 22 made of the same polyethylene-based thermoplastic elastomer as in Example 1 in the same manner as in Example 1, and the print sheet is applied in the same manner as in Example 1 having no polar functional group. A transparent sheet 25 in which 0.5 parts by weight of a benzotriazole-based ultraviolet absorber having a hydroxyl group in a molecule is added to a polypropylene-based thermoplastic elastomer,
After bonding by dry lamination in the same manner as in Example 1 through the adhesive layer 24, the surface was subjected to corona discharge treatment.
Next, a decorative sheet 28 of a comparative example was manufactured by applying an OP coating treatment 26 thereon using the same two-component curable acrylic urethane resin as in Example 1.

Comparative Example 2 In Comparative Example 1, a 1: 1 weight ratio mixture of a vinyl chloride / vinyl acetate copolymer and an acrylic resin was used as the OP coating treatment instead of the two-component curable acrylic urethane resin. Otherwise, the same decorative sheet as in Comparative Example 1 was produced.

UV Weathering Test An example of the present invention obtained above under the following conditions using an SUV-W13 type accelerated weathering tester capable of performing an ultraviolet irradiation and condensation cycle manufactured by Iwasaki Electric Co., Ltd. Decorative sheet 2
1. The surface of each of the conventional decorative sheet 28 of Comparative Example 1 shown in FIG. 4 and the decorative sheet of Comparative Example 2 (not shown) was irradiated with ultraviolet rays for 100 hours.

Experimental conditions: UV intensity 60 mW / cm ² Test temperature 63 ° C. Test humidity 70% Test cycle UV irradiation for 20 hours, repeated condensation for 4 hours

After the test, the OP-treated surface of the decorative sheet was subjected to a cellophane tape peeling test [cellophane tape (trade name of cellophane tape, manufactured by Nichiban Co., Ltd., industrial 24 mm
Was applied to the surface of the OP coat, and immediately after that, the tape was peeled off, and the presence or absence of peeling of the OP coat layer was confirmed].

As a result, in the conventional products of Comparative Examples 1 and 2, peeling of the OP coat layer on the surface was observed together with the cellophane tape, but no peeling was observed in the decorative sheet of the example of the present invention. Further, when the discoloration and fading of the decorative sheet were visually observed, neither the discoloration nor the fading was recognized in the decorative sheets of Example and Comparative Example 1. On the other hand, in the decorative sheet of Comparative Example 2, cloudiness was observed on the entire surface.

[0073]

As described above, the decorative sheet of the present invention is provided with a polyolefin resin having a polar functional group on the side of the upper protective layer of the surface protective layer, whereby the decorative sheet is in close contact with the upper protective layer of the upper layer. The decorative sheet has remarkably improved weatherability, and is excellent in weather resistance, particularly, weather resistance of the adhesive strength of the overcoat protective layer.

When at least one of the polyolefin-based resin layer of the surface protective layer and the polyolefin-based resin layer having a polar functional group contains an organic ultraviolet absorber having a hydroxyl group in the molecule, it may be exposed to sunlight or the like. It is a decorative sheet excellent in light deterioration resistance in which deterioration is more effectively prevented. Further, since the overcoat protective layer (OP coat layer) on the surface also plays a role of preventing the ultraviolet absorber from bleeding out, the ultraviolet absorber bleeds out on the surface of the decorative sheet even if the ultraviolet absorbent is contained. Nothing.

Further, since the decorative sheet of the present invention is provided with a decorative layer such as a pattern print or a metal thin film, it has a high design effect. Furthermore, in the case of having a releasable sheet, the effect of protecting the base sheet of the decorative sheet can be obtained, and the decorative sheet can be simply and reliably adhered to the adherend.

Furthermore, since a non-vinyl chloride resin is mainly used, harmful chlorinated gas is hardly generated at the time of disposal or incineration, so that the decorative sheet is environmentally friendly.

[Brief description of the drawings]

FIG. 1 is a sectional view of a decorative sheet of the present invention.
(A) is a sectional view of the decorative sheet of the first embodiment,
(B) is a sectional view of the decorative sheet of the second embodiment,
(C) shows a sectional view of the decorative sheet of the third embodiment.

FIG. 2 is a cross-sectional view of the decorative sheet of the present invention.
(D) is a sectional view of the decorative sheet of the fourth embodiment,
(E) is a sectional view of a decorative sheet according to a fifth embodiment,
(F) shows a sectional view of the decorative sheet of the sixth embodiment.

FIG. 3 is a cross-sectional view of the decorative sheet of the present invention produced in Example 1.

FIG. 4 is a cross-sectional view of a conventional decorative sheet produced in a comparative example.

[Explanation of symbols]

1, 22: base sheet, 2: pigment, 3, 19, 23: decoration treatment layer, 4, 6, 15, 24: adhesive layer, 5: polyolefin resin layer, 7: polyolefin having a polar functional group Resin layer, 8: Surface protective layer, 9, 20, ... Overcoat protective layer (OP coating layer), 10: Wiping process (wiping ink), 11: Primer layer, 12: Embossing, 13: Metal thin film layer, 14 ... Polyolefin-based resin layer, 16: polyolefin-based resin layer having a carboxyl group, 17: clear sheet (surface protective layer), 18: base sheet made of colored polyolefin-based resin, 21: the present invention obtained in Example 1 Cosmetic sheet, 25: Transparent polypropylene sheet, 26: OP coating treatment, 27: Adhesive layer, 28: Cosmetic sheet obtained in Comparative Example

 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Kazuho Kono 1-1-1 Ichigaya Kagacho, Shinjuku-ku, Tokyo Inside Dai Nippon Printing Co., Ltd.

Claims (5)

[Claims] 1. A decorative sheet having a surface protective layer on a substrate sheet, wherein the surface protective layer is a laminate comprising a polyolefin resin layer and a polyolefin resin layer having a polar functional group from the substrate sheet side. There is a decorative sheet. 2. The decorative sheet according to claim 1, further comprising a decorative layer between said base sheet and said surface protective layer. 3. The decorative sheet according to claim 1, further comprising an overcoat protective layer on the surface protective layer. 4. An organic ultraviolet ray having a hydroxyl group in a molecule, wherein a resin having an isocyanate group is used as the overcoat protective layer, and at least one of the polyolefin resin layer and the polyolefin resin having a polar functional group has a hydroxyl group in a molecule. The decorative sheet according to claim 1, 2 or 3, further comprising an absorbent. 5. The polyolefin-based resin layer having a polar functional group, the olefin comprises at least one selected from the group consisting of unsaturated carboxylic acids, acid anhydrides and esters in an amount of 10 ^-4 to 10% by weight based on the olefin. The decorative sheet according to claim 1, 2, 3 or 4, wherein the decorative sheet is one or a mixture of two or more modified polyolefins obtained by graft copolymerization in the range.