JPH11216819A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet excellent in weatheraility and friendly to environment by making a surface protecting sheet a laminate which comprises a polyolefin resin layer with a polar functional group, an adhesive layer and a polyolefin resin layer having no polar functional group, and is produced by laminating them from the base material sheet side. SOLUTION: In order to impart concealing properties, pigment 2 is contained in a base material sheet 1 comprising an olefin thermoplastic elastomer or a non-elastomer olefin resin or the like. A decoratively treated layer 3 with a printed pattern is formed on the base material sheet 1. Further, a surface protecting sheet 8 comprising three laminated layers, a polyolefin resin layer 5 with a polar functional group, an adhesive layer 6 and a polyolefin resin layer 7 having no polar functional group, arranged from the base material sheet 1 side, through an anchoring agent layer 4, is formed on the decoratively treated layer 3. Since the polyolefin resin having a polar functional group is used for the surface protecting sheet, the adhesiveness with the anchoring agent layer 4 is improved.

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 which is a non-vinyl chloride-based ecology sheet useful as a surface decoration material for home electric appliances.

[0002]

2. Description of the Related Art Conventionally, as disclosed in JP-A-54-62255, JP-A-6-79830 and the like,
A base sheet made of a colored polyolefin resin is subjected to decoration processing such as pattern printing, and this printed sheet and a transparent sheet (surface protection sheet) made of a polyolefin resin are
2. Description of the Related Art A decorative sheet bonded with a general-purpose dry laminating adhesive such as polyester urethane or acrylic urethane is known. Such a decorative sheet is environmentally excellent as a non-vinyl chloride-based ecological sheet, and has a wall, a ceiling, a floor,
It is widely used as a surface decoration material for handrails and home appliances.

[0003]

However, in the conventional decorative sheet as described above, since the adhesiveness between the transparent sheet and the adhesive layer is poor, the transparent sheet made of polyethylene and the adhesive layer are easily peeled off. When exposed to ultraviolet rays such as sunlight, the adhesive layer portion tends to peel off, and there is a problem that the adhesive strength (the adhesive layer itself or the interlayer between the adhesive layer and the sheet) lacks the weather resistance. Therefore, there is a demand for a decorative sheet that is a non-vinyl chloride-based ecological sheet that is excellent in weather resistance and is environmentally friendly. An object of the present invention is to provide a decorative sheet that is a non-vinyl chloride 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, in a decorative sheet having a transparent surface protective sheet on a substrate sheet, the surface protective sheet is a polyolefin resin layer having a polar functional group, an adhesive layer, and a polar layer. It is a laminate comprising a polyolefin resin layer having no functional group.

[0005] The decorative sheet of the present invention preferably has a decorative layer between the base sheet and the surface protective sheet.

[0006] Preferably, the polyolefin resin layer having a polar functional group comprises at least one selected from unsaturated carboxylic acids, acid anhydrides and esters as olefins, and 10 ^-4 to 10 ^-10 It is composed of one or more modified polyolefins obtained by graft copolymerization in the range of weight%.

The decorative sheet of the present invention preferably comprises
An anchor agent layer made of a urethane resin is provided on the surface protection sheet side of the base sheet, and the adhesive layer is made of a urethane resin.

Further, in the decorative sheet of the present invention, an organic ultraviolet absorber having a hydroxyl group in a molecule is preferably added to at least a polyolefin resin layer having no polar functional group in the surface protective sheet. And an overcoat protective layer made of a resin containing a compound having an isocyanate group on the surface protective sheet. Hereinafter, the present invention will be described in detail.

The base sheet used in the decorative sheet of the present invention is not particularly limited as long as it is a non-vinyl chloride resin from an environmental point of view, but a polyolefin-based resin is particularly preferable from the viewpoint of versatility and the like.

[0010] Examples of such polyolefin resins include olefin thermoplastic elastomers and non-elastomeric olefin resins. Specifically, polyethylene, polypropylene, polymethylpentene, ethylene-propylene copolymer, ethylene-propylene-
A crystalline non-elastomeric polyolefin-based resin such as a butene-1 copolymer or an ionomer, or an olefin-based thermoplastic elastomer is used. From the viewpoint of suitability for forming a decorative sheet, an olefin-based thermoplastic elastomer is preferred.

The olefin-based thermoplastic elastomer resin is a thermoplastic elastomer of a composite material composed of an elastomer serving as a soft segment and a non-elastomeric polyolefin-based resin serving as a hard segment, and examples thereof include the following. . (1) A simple blend of an amorphous olefin-based elastomer as a soft segment and a crystalline non-elastomeric olefin resin as a hard segment (2) An elastomer to be a soft segment and a non-elastomeric olefin to be a hard segment A crosslinked type in which a resin is partially crosslinked to form a complex (3) A type in which an elastomer to be a soft segment is dispersed in a non-elastomeric olefin resin to be a hard segment, with or without crosslinking.

The elastomer includes an ethylene rubber represented by EPDM, and the non-elastomeric olefin resin includes a crystalline polymer such as polyethylene and polypropylene. If necessary, additives such as inorganic fillers, flame retardants, antioxidants and the like used in ordinary polyolefin resins can be added to the composition.

Among these, for example, the above-mentioned type (2) includes those described in A) JP-B-53-21021 and JP-B-53-34210.
B) Those described in JP-B-56-15741 are exemplified.

More specifically, for example, as (a), 60 to 80 parts by weight of a monopolyolefin copolymerized elastomer (A), 40 to 20 parts by weight of a non-elastomeric olefin resin (B), and And hardening them partially at the curing temperature to the extent that they do not become insoluble in the usual solvents of the uncured blend during mastication. The olefin-based copolymer elastomer is an elastic copolymer obtained by adding at least one polyene copolymerizable with two or three or more olefins.

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

The non-elastomeric olefin resin (B) includes ethylene, propylene, butene-1,
A crystalline thermoplastic resin obtained by polymerizing a polyolefin such as pentene-1,4-methylpentene by a conventional method,
For example, there are polyethylene such as high-density polyethylene, polypropylene such as isotactic polypropylene, polybutene-1, and the like, and also includes polyethylene and polypropylene modified with higher α-polyolefin.

Examples of the curing agent or crosslinking agent include peroxides such as aliphatic organic peroxides and aromatic organic peroxides, azide types, aldehyde-amine reaction products, substituted ureas, xanthates, dithiocarbamates, and the like. Examples thereof include imidazoles, sulfonamides, thiuram disulfites, paraquinone dioxime, dibenzoparaquinone dioxime, and sulfur.

Examples of the above (ii) include 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 for the base sheet of the present invention may be used alone or may be a laminate. Further, in the above-mentioned type (3), in order to impart flexibility, impact resistance, so-called necking in which stress is locally concentrated and unevenly stretched when stretched, and easy adhesion, to the polyolefin resin. , Isoprene rubber,
Various rubbers such as diene rubber such as styrene-butadiene rubber, hydrogenated diene rubber, and olefin elastomer can also be used. The rubber is added in an amount of preferably 10 to 60 parts by weight, more preferably about 10 to 30 parts by weight, based on 100 parts by weight of the non-elastomeric olefin resin.

In order to impart creep deformation resistance (mainly in the case of an olefinic thermoplastic elastomer), flame retardancy, and easy adhesion to each of the above-mentioned types of polyolefin-based resins, calcium carbonate may be used. , Alumina, barium sulfate, clay, talc and other inorganic fillers are added. Preferably, 1 to 60 parts by weight, more preferably 5 to 30 parts by weight is added.

The surface of the base sheet may be subjected to corona discharge treatment, plasma treatment, primer (also referred to as anchor) coating treatment, ozone treatment, acid treatment, degreasing treatment, if necessary.
A well-known adhesion treatment such as a surface roughening treatment or an activation treatment with a chemical such as cupric chloride can be performed. The primer layer (anchor agent layer) is usually subjected to a corona discharge treatment on the base sheet, and by reacting with a functional group present on the back surface, the adhesion between the base sheet and the decoration treatment layer is improved. It is provided in order to make it.

As the anchor agent layer (primer layer),
It is preferable to use a chlorinated polyolefin resin, a thermoplastic urethane resin formed from a polyol and an isocyanate, or a two-component curable urethane resin. In the case of a urethane resin, when hexamethylene diisocyanate (HMDI) is used as the isocyanate and a polyester polyol or an acrylic polyol is used as the polyol,
It can be used particularly preferably because of its good light resistance, but of course, other various materials similar to those exemplified for the adhesive layer described later may also be used. Note that the thickness of the anchor agent layer is about 1 to 50 μm.

Further, a coloring agent such as a pigment or a dye 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.

As the paint, chlorinated polyethylene resin,
Chlorinated polyolefin resin such as chlorinated polypropylene resin, polyester resin, urethane resin, acrylic resin,
One or a mixture of two or more of vinyl acetate resin, vinyl chloride-vinyl acetate copolymer, and cellulose resin can be used. In addition, those obtained by adding known pigments such as those listed above can also be used.

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 providing a pattern on the base sheet colored by adding a pigment by printing or the like, a method of providing a metal thin film layer (all or a part) on the base sheet, and the like Alternatively, a combination of two or more of these 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.

As the pattern, there are a wood grain pattern, a stone grain pattern, a cloth grain pattern, a leather pattern, a geometric pattern, a character symbol, a solid pattern, or the like.

As the ink or paint, a mixture of a vehicle and a coloring agent such as a pigment or a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, a curing agent, and the like may be used as needed. . The vehicle can be appropriately selected from a thermoplastic resin, a thermosetting resin, an ionizing radiation-curable resin, and the like according to necessary physical properties, printability, and the like. For example, chlorinated polyolefin resins such as chlorinated polyethylene resins and chlorinated polypropylene resins, polyester resins, urethane resins, acrylic resins, vinyl chloride-vinyl acetate copolymers, cellulosic resins, and the like can be used. Alternatively, a mixture of two or more kinds, or a mixture of the above and the pigments listed above is used.

In the case of printing directly on a polyolefin resin, a chlorinated polyolefin resin or a urethane resin is preferred as a binder from the viewpoint of adhesiveness. If a layer is formed by appropriately selecting an easily-adhesive anchor agent, sufficient adhesiveness can be imparted even if another binder is used.

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 may be omitted.

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

In order to bond the base sheet and the surface protection sheet, (1) a polyolefin having a polar functional group of the surface protection sheet formed in advance by forming the anchor agent layer on the bonding surface and then forming a film. A so-called dry lamination method in which the surface protection sheets are laminated and bonded together, and (2) a surface protection sheet obtained by co-extruding three layers of the surface protection sheet from a T-die by a melt extrusion (extrusion) method or the like. (3) a method of laminating the polyolefin-based resin side facing the other side of the base sheet side and pressing and cooling, more preferably a method of interposing an anchor agent layer between the base sheet and the surface protection sheet; Alternatively, the anchoring agent layer made of a thermoplastic resin is selected and provided on a base sheet, and the surface protective layer formed in advance on the anchoring agent layer is a polyolefin having the polar functional group. System resin layer side is stacked in the facing anchoring agent layer side, heating and pressing, bonding, by way of a so-called thermal lamination method.

In the decorative sheet according to the present invention, the surface protective sheet is a three-layer structure comprising a polyolefin resin layer having a polar functional group, an adhesive layer, and a polyolefin resin layer having no polar functional group, from the base sheet side. It is a laminate. By adopting such a structure of the surface protective sheet, the interlayer adhesion between the polyolefin resin layer having a polar functional group and the polyolefin resin having no polar functional group due to an adhesive layer interposed therebetween, and the base sheet and the surface The interlayer adhesion with the protective sheet is significantly increased, and the weather resistance of the decorative sheet can be improved.

On the base sheet side of the surface protection sheet,
A layer made of the polyolefin resin having the polar functional group is provided. The layer made of the polyolefin-based resin having the polar functional group plays a role of improving the adhesiveness to the base material sheet thereunder or the anchor agent layer thereover.

Examples of the polyolefin resin having a polar functional group include olefins such as ethylene, propylene, butene-1, butene-2, isobutylene and pentene-1 and unsaturated carboxylic acids such as maleic acid, fumaric acid and itaconic acid. Acid, at least one selected from acid anhydrides such as maleic anhydride, and unsaturated carboxylic acid esters such as acrylic acid and methacrylic acid, with respect to the olefin,
One or more modified polyolefins obtained by graft copolymerization in the range of ^-4 to 10% by weight are preferred.

The thickness of the layer comprising the polyolefin resin having a polar functional group is usually 1 to 30 μm,
In particular, 5 to 10 μm is preferable. When the thickness is less than 1 μm, sufficient adhesive strength between the base material sheet, the anchor agent layer or the decoration treatment layer and the adhesive layer is insufficient.
If it exceeds 30 μm, the effect of improving the adhesive strength is saturated, and
It is not preferred because the increase in the thickness of all the surface protective layers leads to a decrease in the suitability of the decorative sheet for forming (such as V-cutting).

The polyolefin-based resin layer having the polar functional group and the polyolefin-based resin layer are laminated via an adhesive layer.

Examples of resins that can be used as an adhesive for the adhesive layer of the surface protective sheet include urethane resins, polyester resins, polyamide resins, vinyl acetate-acrylate resins, carboxyl group-containing acrylic resins, and vinyl acetate resin. Each resin such as an ethylene resin, a polyvinyl ether resin, and a cyanoacrylic resin can be used. In the case where the bonding direction (1) or (3), which is to be bonded to the surface protective sheet formed as a three-layer laminate in advance, is used, either a thermoplastic resin or a thermosetting resin may be used. However, in the case of the melt extrusion method of the above (2),
It is preferred to choose a thermoplastic resin. Among these, it is particularly preferable to use a urethane resin adhesive which is particularly excellent in adhesion (including weather resistance) to the substrate sheet.

As the urethane resin adhesive, it is preferable to use a thermoplastic urethane resin, a one-component moisture-curable urethane resin or a two-component curable urethane resin. For example, a thermoplastic urethane resin or a two-component curable urethane resin is a urethane resin of a type in which a polyol and an isocyanate are urethane-bonded. In addition, the one-component moisture-curable urethane resin is a urethane resin of a system in which only isocyanate and moisture (moisture) are used to bond urethane. Hereinafter, these will be described in detail.

The polyol constituting the urethane resin has two or more hydroxyl groups in the molecule, and includes, 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 fats such as hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate Group (or alicyclic) isocyanates are used. Alternatively, adducts or multimers of the above various isocyanates can also be used. For example, an adduct of tolylene diisocyanate, a trimer of tolylene diisocyanate (trime)
r) or an isocyanate prepolymer having a skeleton of a urethane bond, polycarbonate, aliphatic polyester or the like in the molecular chain.

In a preferred embodiment of the two-component curable urethane resin, the number (mol number) of isocyanate groups (—NCO groups) in the isocyanate is changed to the number of hydroxyl groups (—OH groups) of the polyol to be reacted therewith. (Equivalent reaction equivalent) to ensure that unreacted isocyanate groups remain in large numbers even after the polyol and isocyanate have reacted. In this case, the ratio of -NCO group / -OH group is up to about 1.4 at the maximum.

The thickness of the adhesive layer is usually 1 to 30 μm.
m, particularly preferably about 5 to 15 μm. The reason for selecting the film thickness is the same as in the case of the polyolefin-based resin layer having a polar functional group.

It is to be noted that at least one of these polyols and isocyanates is trifunctional or more, and the polyol and the isocyanate are mixed at the time of adhesion to form urethane bonds, whereby the polyol and the isocyanate are crosslinked to form a three-dimensional network polymer. It is the two-component curable urethane resin adhesive that exhibits the adhesive strength. Both of these polyols and isocyanates are selected from bifunctional ones, and both are polymerized in advance by urethane bonds, polymerized, and then cooled and solidified again to develop an adhesive force. It is a plastic urethane resin adhesive. One-component curable urethane resin that uses only the isocyanate prepolymer having an isocyanate group and deactivates the three-dimensional network structure of the urethane polymer by reacting with the moisture (steam) in the air to exhibit adhesive strength. Adhesive.

Examples of the polyolefin resin which can be used in the polyolefin resin layer of the surface protective sheet include 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,
Non-elastomeric olefin resin composed of a crystalline polymer such as polymethylpentene, or Japanese Patent Publication No. 6-2327
No. 8, the isotactic polypropylene is defined as a hard segment, and the atactic polypropylene is defined as a soft segment.
A polypropylene-based olefin-based thermoplastic elastomer mixed at a ratio of 10/90 to 90/10 (weight ratio), ethylene-propylene-butene-based elastomer described in JP-A-5-77371, JP-A-9-111055, etc. It is possible to use an olefin-based thermoplastic elastomer such as an olefin-based thermoplastic elastomer made of a ternary copolymer-based random copolymer, preferably a random copolymer having a propylene weight ratio of 50% by weight or more. it can. These resins may be used alone or in combination of two or more.

The surface protective sheet is not limited to the three layers of the polyolefin-based resin layer having a polar functional group, the adhesive layer and the polyolefin-based resin layer, but may be a multilayer laminate with another resin. Is also good. Usually, the thickness of the polyolefin-based resin layer is preferably about 30 to 100 μm. When the thickness is less than 30 μm, the surface protection functions such as abrasion resistance, chemical resistance, water resistance, and weather resistance of the surface are insufficient.
If it exceeds 100 μm, the surface protection function is saturated,
An increase in thickness is not preferred because processability such as V-cut processability, particularly processability at room temperature becomes insufficient.

The decorative sheet of the present invention has an overcoat protective layer (OP coat layer) on the surface protective sheet. The overcoating protective layer further improves the scratch resistance of the decorative sheet surface, improves the scratch resistance, adjusts the surface gloss, or bleeds out the ultraviolet absorbent in the surface protective sheet to the surface. (Exudation) is provided.
Examples of the resin used for the OP coating process include a fluorine resin such as polyvinylidene fluoride, a silicon resin,
A liquid-curable urethane resin and a one-liquid moisture-curable urethane resin can be given. The two-component curable urethane resin is a urethane resin having a polyol as a main component and an isocyanate as a cross-linking agent (curing agent). The one-component moisture-curable urethane resin is composed of only an isocyanate prepolymer and has a moisture in the air. Curing (crosslinking) with
The same adhesives as those exemplified for the adhesive layer can be used.

In order to further improve the adhesive strength between the overcoat protective layer and the surface protective sheet, it is preferable to perform an easy adhesion treatment as listed for the surface protective sheet. Usually, corona discharge treatment or ozone treatment is used.

As a preferred mode for improving the weather resistance of the decorative sheet of the present invention and preventing bleed-out of the ultraviolet absorbent at the time of heat processing such as embossing, at least the outermost surface of the surface protective sheet is preferred. An organic UV absorber having a hydroxyl group in a molecule is added to a resin layer having no polar functional group, and a one-component moisture-curable urethane resin or a two-component curable urethane resin is used as an overcoat protective layer. There is an embodiment in which a resin having an isocyanate group in the molecule is selected and combined.

In the present invention, an organic compound having an OH group in the molecule is used as the ultraviolet absorber. 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'-isobutylphenyl) -5'-chlorobenzotriazole, 2-
2 ′ such as (2′-hydroxy-3′-isobutyl-5′-propylphenyl) -5-chlorobenzotriazole
-Hydroxyphenyl-5-chlorobenzotriazole ultraviolet absorbers, 2- (2′-hydroxy-3 ′,
Benzotriazole ultraviolet absorption such as 2'-hydroxyphenylbenzotriazole ultraviolet absorbers such as 5'-di-tert-butylphenyl) benzotriazole and 2- (2'-hydroxy-5'-methylphenyl) benzotriazole Agent, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-
Methoxybenzophenone, 2,2'-dihydroxy-
4,4′-dimethoxybenzophenone, 2,2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,
2,2′-dihydroxybenzophenone-based ultraviolet absorbers such as 2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
Benzophenone UV absorbers such as 2-hydroxybenzophenone UV absorbers such as 2,4-dihydroxybenzophenone, phenyl salicylate, 4-tert-
A salicylate-based ultraviolet absorber such as butylphenyl salicylate is used. In addition, a reactive ultraviolet absorber having an acryloyl group or a methacryloyl group introduced into a benzotriazole skeleton is also used. The amount of these ultraviolet absorbers is usually about 0.1 to 10% by weight.

It is preferable to use an organic system having an OH group in the molecule as an ultraviolet absorber and to form the surface layer using a resin having an isocyanate group. With such a combination, when the ultraviolet absorber bleeds out and enters the surface layer, the OH of the ultraviolet absorber becomes
The group reacts with the isocyanate group in the surface layer to form a urethane bond and is trapped in the surface layer, thereby preventing the ultraviolet absorber from bleeding out.

Under the base sheet of the decorative sheet of the present invention constructed as described above, a pressure-sensitive adhesive layer and a release sheet thereon can be provided as desired. When the decorative sheet is used by peeling the release sheet from the decorative sheet, an adhesive is applied to the base sheet before use, and the release sheet can be peeled and used at the time of use. It can be easily attached to an adherend.

As the resin constituting the pressure-sensitive adhesive layer,
For example, polyisoprene rubber, polyisobutylene rubber,
Rubber resins such as styrene-butadiene rubber, butadiene-acrylonitrile rubber, (meth) acrylate resin, polyvinyl ether resin, polyvinyl acetate resin, ethylene-vinyl acetate copolymer, vinyl chloride-vinyl acetate copolymer , A polystyrene resin, a polyester resin, a polyamide resin, a polychlorinated olefin resin, a polyvinyl butyral resin, and the like.

As tackifiers, 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 any of various materials, such as flat and curved plates, three-dimensional articles, and sheets (or films). Wood material such as density fiberboard (MDF), metals such as iron and aluminum, acrylic resin, polycarbonate, ethylene / vinyl acetate copolymer, ethylene vinyl acetate copolymer, polyester resin, polystyrene resin, olefin resin, ABS resin , Phenolic resin, polyvinyl chloride resin, cellulosic resin,
Resins such as rubber, materials exclusively used as plate materials or three-dimensional articles include ceramics such as glass and ceramics, cement such as ALC (foamed lightweight concrete), ceramic ceramic materials such as calcium silicate and gypsum, and sheets exclusively ( Examples of the material used as the film include paper such as high-quality paper and Japanese paper, and 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 processing method in which a groove having a V-shaped or U-shaped cross section is cut, and then an adhesive is applied to the groove, and then the groove is bent to form a box or column. Etc.

As described above, the decorative sheet of the present invention is characterized in that a polyolefin-based resin layer having a polar functional group is provided on the lowermost layer of the surface protective sheet, and the adhesive under the layer is provided. It has excellent adhesion to the layer. Therefore, the decorative sheet of the present invention is excellent in weather resistance, particularly in weather resistance of interlayer adhesion. 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 includes a wall,
It can be suitably used as a surface decoration material for buildings and furniture such as doors, ceilings and handrails, vehicle interiors, ship interiors, and aircraft interiors.

[0063]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in more detail with reference to various embodiments of the decorative sheet of the present invention. First Embodiment FIG. 1A shows a first embodiment of a decorative sheet according to the present invention. In this decorative sheet, a pigment sheet 2 is added to a base sheet 1 made of a polyolefin-based resin such as an olefin-based thermoplastic elastomer or a non-elastomer olefin-based resin in order to impart hiding power. A decoration processing layer 3 on which a pattern is printed is provided, and a polyolefin-based resin layer 5 having a polar functional group and an adhesive layer 6 are further provided on the decoration processing layer 3 via an anchor agent layer 4 from the substrate sheet side.
And a surface protection sheet 8 in which three layers of a polyolefin resin layer 7 having no polar functional group are laminated. Therefore, in the decorative sheet of the present embodiment, the adhesiveness to the lower anchor agent layer is remarkably increased by using a polyolefin resin having a polar functional group on the base sheet side of the surface protective sheet.

Second Embodiment FIG. 1B shows a second embodiment of the decorative sheet according to the present invention. This decorative sheet is the same as the decorative sheet of Embodiment 1, except that an ultraviolet absorber having a hydroxyl group in a molecule is added to the outermost surface of the topsheet, and a two-part curable urethane resin is further added to the outermost surface of the topsheet. Overcoat layer (O
(P coat layer) 9. The decorative sheet of the present embodiment has a polyolefin resin having a polar functional group on the base sheet side of the surface protective sheet, so that the adhesiveness with the lower adhesive layer is significantly enhanced. Further, since a top coat protective layer is provided on the surface, the decorative sheet is excellent in durability, surface polishing effect and weather resistance.

Third Embodiment FIG. 1C shows a third embodiment of the decorative sheet according to the present invention. In this decorative sheet, a pigment sheet 2 is added to a base sheet 1 made of a polyolefin-based resin such as an olefin-based thermoplastic elastomer or a non-elastomer olefin-based resin in order to impart hiding power. A decoration processing layer 3 on which a pattern is printed is provided, and a polyolefin-based resin layer 5 having a polar functional group and an adhesive layer 6 are further provided on the decoration processing layer 3 via an anchor agent layer 4 from the substrate sheet side.
And a surface protection sheet 8 in which three layers of a polyolefin resin layer 7 having no polar functional group are laminated. Further, the uppermost layer of the polyolefin resin of the surface protective sheet is subjected to a wiping process 10 to cover the surface with an overcoat protective layer 9. In the decorative sheet of the present embodiment, a polyolefin resin having a polar functional group is provided on the base sheet side, so that the adhesion to the lower anchor agent layer is remarkably enhanced. Further, since a top coat protective layer is provided on the surface, the decorative sheet is excellent in durability, surface polishing effect and weather resistance. Also, since the surface is subjected to wiping, the design effect is also high.

Fourth Embodiment FIG. 2D shows a fourth embodiment of the decorative sheet according to the present invention. In this decorative sheet, a decoration processing layer 3 in which a pattern is pattern-printed is provided on a base sheet 1 made of a polyolefin resin such as an olefin thermoplastic elastomer or a non-elastomeric olefin resin. Further, in the present embodiment, in order to enhance the adhesion to the adhesive layer 6 thereon, the primer layer 1 made of a two-component curable urethane resin is used.
1 is provided. Then, on the primer layer 11,
A surface protection sheet 8 in which three layers of a polyolefin resin layer 5 having a polar functional group, an adhesive layer 6 and a polyolefin layer 7 having no polar functional group are laminated from the base sheet side via the anchor agent layer 4 Have. Then, the uppermost layer of the polyolefin resin having a polar functional group of the surface protective sheet 8 is subjected to embossing 12 and the surface is covered with an overcoat protective layer 9. The decorative sheet of the present embodiment is made of a polyolefin-based resin having a polar functional group on the base sheet side of the surface protective sheet, so that the adhesion to the lower anchor agent layer is significantly improved. Also,
Since the top coat protective layer is provided on the surface, the decorative sheet is excellent in durability, shine effect on the surface, and weather resistance.

Fifth Embodiment FIG . 2E shows a fifth embodiment of the decorative sheet according to the present invention. In this decorative sheet, a pigment sheet 2 is added to a base sheet 1 made of a polyolefin-based resin such as an olefin-based thermoplastic elastomer or a non-elastomer olefin-based resin in order to impart hiding power. The decoration processing layer 3 on which a pattern is printed is provided. Furthermore, a polyolefin-based resin layer 5 having a polar functional group, an adhesive layer 6, and a polyolefin having no polar functional group are provided on the decorative treatment layer 3 from the substrate sheet side via a primer layer 11 and an anchor agent layer 4. It has a surface protection sheet 8 in which three layers of layers 7 are laminated. Then, the surface protection sheet 8
Is coated with an overcoating protective layer 9. In the decorative sheet of the present embodiment, a polyolefin resin having a polar functional group is provided on the base sheet side, so that the adhesion to the lower anchor agent layer is remarkably enhanced. Also,
Since a top coat protective layer is provided on the surface, the decorative sheet is excellent in durability, surface polishing effect, and weather resistance.

Sixth Embodiment FIG . 2F shows a sixth embodiment of the decorative sheet according to the present invention. In this decorative sheet, a pigment sheet 2 is added to a base sheet 1 made of a polyolefin-based resin such as an olefin-based thermoplastic elastomer or a non-elastomer olefin-based resin in order to impart hiding power. A metal thin film layer 13 of aluminum or the like is provided by vacuum evaporation, and further on the metal thin film layer 13 with an anchor agent layer 4 interposed therebetween.
There is provided a surface protection sheet 8 in which three layers of a polyolefin resin layer 5 having a polar functional group, an adhesive layer 6 and a polyolefin layer 7 having no polar functional group are laminated from the base sheet side. Then, the surface of the surface protection sheet is covered with an overcoat protection layer 9. In addition, an adhesive layer 14 made of an acrylate resin, a polyvinyl ether resin, a polyvinyl acetate resin, a vinyl chloride-vinyl acetate copolymer resin or the like is provided in a lower layer portion of the base sheet 1. The decorative sheet of this embodiment has a polyolefin resin layer having a polar functional group provided on the base sheet side of the surface protection sheet, so that the adhesion to the lower anchor agent layer is significantly enhanced. In addition, since a top coat protective layer is provided on the surface, the decorative sheet is excellent in durability, gloss effect on the surface, and weather resistance. 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.

[0069]

Next, the present invention will be described in more detail by way of examples. Example 1 As shown in FIG. 3A, a clear sheet including three layers forming a surface protection sheet of a decorative sheet was prepared. That is, a polyolefin of a thermoplastic thermoplastic elastomer obtained by mixing a hard segment of isotactic polypropylene and a soft segment of atactic polypropylene in a weight ratio of 50:50 by graft copolymerizing a carboxyl group having a thickness of about 10 μm. A two-part curable acrylic urethane resin adhesive composed of hexamethylene diisocyanate and acrylic polyol is applied on the base resin layer 15 to form an adhesive layer 16 having a thickness of about 10 μm. Polypropylene: atactic polypropylene = 50:50
By forming a polypropylene resin 17 obtained by adding 0.2% by weight of a benzotriazole-based ultraviolet absorber to a resin composed of a mixture in a weight ratio with a thickness of about 60 μm,
A clear sheet 18 was produced.

Next, 100 parts by weight of high-density polyethylene, 60 parts by weight of styrene-butadiene rubber, 25 parts by weight of an inorganic filler composed of fine particles of calcium carbonate, titanium white, red iron oxide, and a coloring pigment 20 composed of 5 parts by weight of graphite in total. A colored polyolefin-based resin sheet 19 having a thickness of 80 μm is prepared, corona discharge treatment is performed on both surfaces thereof, and a binder is formed on one surface thereof with a binder of vinyl chloride-vinyl acetate copolymer:
The pattern printing 21 was performed by using an acrylic resin = 1: 1 weight ratio and an ink in which the pigment was a red stencil. The printed sheet obtained and the clear sheet 18 obtained above were combined with a polyester polyol and hexamethylene diisocyanate.
Liquid curing type urethane resin anchor agent layer (coating amount = 16
g / m ² ) 22 by a dry lamination method. Then, after applying a corona discharge treatment to the surface of the clear sheet, a two-part curable acrylic urethane resin (composed of acrylic polyl and hexamethylene diisocyanate) is applied by a gravure printing method to a thickness of 2 μm. An overcoat protective layer 23 was provided to obtain a decorative sheet 24 of the present invention as shown in FIG.

Comparative Example 1 As a comparative example, a decorative sheet of a type conventionally used as shown in FIG. 4 was prepared. That is, picture printing 26 is performed on a base sheet 25 having a thickness of 80 μm obtained by adding a coloring pigment composed of 100 parts by weight of biaxially stretched polypropylene resin to graphite and a total of 5 parts by weight of a petal pattern. A single-layer biaxially stretched polypropylene transparent sheet 28 containing 0.2% by weight of a triazole-based ultraviolet absorber and having a corona discharge treatment on the surface to be adhered is used as a two-part curable urethane resin composed of acrylic polyl and hexamethylene diisocyanate. Anchor agent layer 27 (resin coating amount = 16 g /
The decorative sheet 29 of the comparative example was produced by laminating through m ² ) by a dry lamination method.

UV weather resistance test Iwasaki Electric Co., Ltd., super UV weather resistance tester, SUV
Using a -W13 type ultraviolet irradiation apparatus, the surfaces of the decorative sheet 24 of the present invention obtained above and the conventional decorative sheet 29 of Comparative Example 1 shown in FIG. 4 were irradiated with ultraviolet light for 100 hours under the following conditions. Experimental conditions: UV intensity 60 mW / cm ² Test temperature 63 ° C Test humidity 70% Test cycle Repeated UV irradiation for 20 hours and dew condensation for 4 hours After the test was completed, the surface layer of this decorative sheet and the conventional decorative sheet of Comparative Example 1 was applied. On the other hand, a visual comparison of the appearance and a cellophane tape peeling test were performed. As a result, in the conventional product, whitening was observed on the entire surface and peeling was observed between the transparent sheet (clear sheet) 28 and the anchor agent layer 27 together with the cellophane tape. However, in the decorative sheet of the present invention, both whitening and peeling of the transparent sheet were observed. I couldn't see it.

[0073]

As described above, in the decorative sheet of the present invention, the substrate sheet side of the surface protective sheet is made of a polyolefin resin having a polar functional group, so that the adhesiveness with the lower anchor agent layer is improved. This is a decorative sheet excellent in weather resistance, which has a significantly increased in. Further, an organic UV absorber having a hydroxyl group in a molecule is added to at least the outermost surface layer of the surface protection sheet, and an overcoating protection layer made of a resin having an isocyanate group is provided on the surface protection sheet, whereby the surface is protected. It is possible to prevent a decrease in weather resistance due to bleed-out of the ultraviolet absorbent from the protective sheet. Further, it is a decorative sheet provided with an arbitrary pattern having a high design effect by providing a decorative layer such as a pattern print or a metal thin film. 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 it is an environmentally friendly decorative sheet.

[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, 19, 25: base sheet, 2, 20: pigment, 3, 2
1, 26: decoration processing layer, 4, 6, 22, 27: anchor agent layer, 5, 15: polyolefin resin layer having polar functional group, 6, 16: adhesive layer, 7: no polar functional group Polyolefin-based resin layer, 8: surface protection sheet, 9,
23, 28: overcoat protective layer (OP coat layer), 10: wiping (wiping ink), 11: primer layer, 12: embossing, 13: metal thin film layer, 14: adhesive layer, 15: polyolefin resin layer , 17: polypropylene resin layer, 18: clear sheet (surface protection sheet), 19: base sheet made of colored polyolefin resin, 24: decorative sheet of the present invention obtained in Example 1,
28: transparent sheet made of polypropylene, 29: decorative sheet obtained in Comparative Example

Continuation of the front page (72) Inventor Kazuho Kono 1-1-1 Ichigaya Kagacho, Shinjuku-ku, Tokyo Dai Nippon Printing Co., Ltd.

Claims (4)

[Claims] 1. A decorative sheet having a transparent surface protective sheet on a substrate sheet, wherein the surface protective sheet is a polyolefin resin layer having a polar functional group, an adhesive layer, and a polar functional group. A decorative sheet, which is a laminate composed of a polyolefin resin layer having no resin. 2. The decorative sheet according to claim 1, further comprising a decorative layer between said base sheet and said surface protection sheet. 3. The polyolefin-based resin layer having a polar functional group, the olefin comprises at least one selected from unsaturated carboxylic acids, acid anhydrides and esters in an amount of 10 ^-4 to 10% by weight based on the olefin. One or more modified polyolefins obtained by graft copolymerization in the range described above, and an anchor agent layer made of a urethane resin is provided on the surface protective sheet side of the base sheet; The decorative sheet according to claim 1, wherein the layer is made of a urethane resin. 4. An organic ultraviolet absorber having a hydroxyl group in a molecule is added to at least a polyolefin-based resin layer having no polar functional group in the surface protection sheet. The decorative sheet according to claim 1, further comprising an overcoat protective layer made of a resin containing a compound having an isocyanate group.