JP2002036474A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet good in vacuum moldability, bending processability and adhesiveness without using a vinyl chloride resin sheet. SOLUTION: In the decorative sheet S wherein a pattern ink layer 2 and a surface layer 3 comprising a polyolefinic resin are laminated on a base material layer 1, the base material layer consists of a polyolefinic resin layer 4 formed on the side of the pattern ink layer and an amorphous polyester resin layer 5 provided on the undersurface side of the resin layer 4. A resin sheet formed, for example, by a coextrusion method is used as the base material layer. The polyolefinic resin layer and the amorphous polyester resin layer may be bonded and laminated through an adhesive layer 6. Since the layer on the side of the pattern ink layer of the base material layer is the polyolefinic resin layer even if a resin having lovo organic solvent resistance is used in the amorphous polyolefinic resin layer, a problem such as blocking or the like is not generated even if a printing sheet wherein the pattern ink layer is printed on the base material layer is taken up and preserved, and productivity is good.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet used for exterior decoration, interior decoration, fittings, furniture, vehicle interior decoration and the like of a building. In particular, it relates to a non-PVC-based decorative sheet that does not use a vinyl chloride resin sheet.

[0002]

2. Description of the Related Art Conventionally, a vinyl chloride resin sheet has been frequently used as a resin sheet used as a base layer or a surface layer of a decorative sheet, but recently, a non-vinyl chloride resin sheet such as a polyolefin resin sheet has been used instead. Resin sheets have come to be used. For example, (1) JP-A-6-16832, JP-A-2916130, and the like use a colored polyolefin-based resin sheet as a base layer, print a pattern layer on the base layer, and then form an olefin-based thermoplastic elastomer. A decorative sheet is disclosed in which a transparent surface layer (surface sheet) made of a polyolefin-based resin such as that described above is laminated, and both the base material layer and the surface layer are made of a polyolefin-based resin. (2) Although the surface layer is a polyolefin resin, decorative sheets using an acrylic resin for the base layer have been tried.

[0003]

SUMMARY OF THE INVENTION
A decorative sheet using a polyolefin resin for both the base layer and the surface layer as in (1), or a polyolefin resin for the surface layer using an acrylic resin for the base layer as in (2) above All of the decorative sheets have not always achieved satisfactory performance as compared with a decorative sheet using a conventional vinyl chloride resin sheet.

For example, there have been cases where vacuum formability is insufficient. For this reason, when a decorative sheet is laminated on an uneven surface of an adherend by a vacuum forming laminating method or the like, the followability of the decorative sheet to the unevenness becomes insufficient, or the range of appropriate conditions for thermoforming is narrow (particularly, high When a crystalline polyolefin is used),
Alternatively, necking may occur at a portion where the decorative sheet is extended, and uneven stretching may occur locally. In addition, bending workability such as V-cut processing was sometimes insufficient, and whitening, cracks, and cracks were easily generated. When the base material layer is made of a polyolefin resin, the polyolefin resin is generally difficult to adhere to. Therefore, when the decorative sheet is laminated on the adherend, an easy adhesion treatment such as a corona discharge treatment or an ozone treatment is performed. In addition, it is necessary to use a prescription with sufficient attention to adhesiveness, such as using a two-component curable urethane resin adhesive.

On the other hand, in the case of a decorative sheet using an acrylic resin for the base material layer and a polyolefin-based resin for the surface layer, the problem of adhesiveness to the adherend is solved, but the acrylic resin is resistant to organic solvents. When the pattern ink layer is printed and formed on the acrylic resin sheet used as the base material layer, or when the surface layer is formed by coating, the acrylic resin sheet swells and misregistration of the pattern ink layer occurs, The resin sheet sometimes wrapped around the plate or whitened. Also,
In some cases, vacuum formability or bending workability such as V-cut processing may not be sufficient.

In view of the above-mentioned problems with the prior art, the present inventors have studied a decorative sheet using an amorphous polyester resin for the base material layer. As a result, at the time of printing the pattern ink layer on the amorphous polyester resin sheet as the base material layer, in some cases, the solvent permeability of the resin sheet is so good that the solvent at the time of printing is difficult to dry, and blocking by the printing ink. It has been found that such a problem easily occurs. When the resin is used for a base material layer, it is desirable to solve this problem. That is, when a single-layer resin sheet composed of only the amorphous polyester resin is used for the base material layer, the amorphous polyester resin has a good affinity for the organic solvent, and therefore the content of the amorphous polyester resin is In this case, the base layer may absorb the organic solvent in the ink at the time of printing the pattern ink layer, swell, or cause stickiness on the surface. When a print sheet on which a pattern ink layer is printed by rotary printing is wound up in a roll, the front and back of the print sheet may adhere (so-called blocking) or a residual solvent may easily remain in the base material layer. In order to prevent this, it was necessary to lower the printing speed and lengthen the drying zone.

As described above, it is an object of the present invention to provide a decorative sheet that does not use a vinyl chloride resin sheet, but has a moldability such as vacuum moldability, a bending property such as V-cut processing, and an object to be adhered. It is an object of the present invention to improve the adhesion and to realize these without causing the problem of the organic solvent resistance of the resin sheet at the time of printing the picture ink layer.

[0008]

In order to solve the above-mentioned problems, the decorative sheet of the present invention is obtained by laminating a pattern ink layer and a surface layer made of a polyolefin resin on a base layer in this order. In the decorative sheet, the pattern ink layer side of the base layer was made of a polyolefin resin layer, and the other side was made of an amorphous polyester resin layer.

[0009] By adopting a structure in which an amorphous polyester resin is used for the base material layer, moldability such as vacuum moldability, bending workability such as V-cut processing, and adherend adherence can be achieved depending on its physical properties. Adhesiveness to the surface can be improved. Therefore, even when the decorative sheet is laminated on the uneven surface, the decorative sheet has good followability of the unevenness. In addition, the suitable range of the thermoforming process is wide, the forming process is easy, the necking does not occur due to the base material layer, and the whitening, cracking and cracking hardly occur during the bending process such as the V-cut process. When laminating on the adherend, the amorphous polyester resin layer having good adhesiveness is laminated on the adherend, so that it is not necessary to pay special attention to the easy-adhesion layer and the adhesive. Moreover, in the decorative sheet of the present invention, although the amorphous polyester resin is used for the base material layer, since the pattern ink layer side is a polyolefin resin layer, the amorphous polyester resin used for the base material layer is used. Even if a resin having poor organic solvent resistance is used for the layer, such as from the viewpoint of emphasizing moldability, bending workability, etc., the formation of the pattern ink layer on the base material is performed by the amorphous polyester resin layer. Since it is formed not on the polyolefin resin layer but on the polyolefin resin layer, the configuration is such that the picture ink layer can be formed on the base material layer without any problem at the time of printing. Accordingly, a decorative sheet having good productivity is obtained.

Further, the decorative sheet of the present invention has a configuration in which the polyolefin-based resin layer of the base layer and the amorphous polyester resin layer are further laminated via an adhesive layer.

[0011] With such a configuration, the interlayer adhesion between the polyolefin-based resin layer and the amorphous polyester resin layer can be further improved in the base material layer.

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the decorative sheet of the present invention will be described with reference to the drawings.

[Outline] FIG. 1 is a sectional view showing an embodiment of a decorative sheet according to the present invention. The decorative sheet S of FIG. 1A has a configuration in which a pattern ink layer 2 and a surface layer 3 made of a polyolefin-based resin are laminated on a base layer 1 in this order. The layer 2 comprises a polyolefin resin layer 4, the other side comprises an amorphous polyester resin layer 5, and the base material layer 1 comprises a polyolefin resin layer 4.
And an amorphous polyester resin layer 5.

Further, the decorative sheet S of FIG.
In contrast to the configuration of (A), a polyolefin-based resin layer 4 and an amorphous polyester resin layer 5 constituting the base material layer 1 are laminated with an adhesive layer 6 interposed therebetween, and the base material layer 1 is patterned. This is a three-layer configuration of a polyolefin resin layer 4, an adhesive layer 6, and an amorphous polyester resin layer 5 in this order from the ink layer 2 side. The adhesive layer 6 allows the polyolefin resin layer 4
And the amorphous polyester resin layer 5 can be easily improved in interlayer adhesion. 1A and 1B, the configuration in which the base material layer 1 is colored and opaque and the surface layer 3 is uncolored and transparent is also a typical configuration. Also,
In this case, in order to make the substrate 1 have a color concealing property, for example, the amorphous polyester resin layer 5 is made a color concealing property, and the polyolefin resin layer 4 is made non-colored and transparent. Alternatively, both layers may have colored hiding properties.

In the decorative sheet S of the present invention as described above, the pattern ink layer 2 is formed on the polyolefin resin layer 4 side of the base material layer 1 (resin sheet) using ink, and the pattern ink layer 2 is formed. It can be obtained by laminating the surface layer 3 on the formed base material layer 1 (printed sheet) by a dry lamination method of a polyolefin-based resin sheet or a melt extrusion coating method of the resin.

Hereinafter, each layer will be described in detail in order.

[Base Layer] The base layer 1 is composed of at least a polyolefin resin layer 4 and an amorphous polyester resin 5, and the polyolefin resin layer 4 side is the pattern ink layer 2 side. Further, the base layer 1 may have a configuration in which the polyolefin-based resin layer 4 and the amorphous polyester resin 5 are laminated with an adhesive layer 6 interposed therebetween. These multi-layered base material layers are co-extrusion method of two or three layers, hot press method,
Alternatively, it can be prepared as a resin sheet by a dry or wet lamination method using the adhesive layer 6 or the like.
In the case of the hot press method, a resin sheet as the amorphous polyester resin layer 5 and a resin sheet as the polyolefin-based resin layer 4 are laminated by heat fusion or bonding with the adhesive layer 6. Further, a polyolefin-based resin layer 4 can be formed on a resin sheet to be an amorphous polyester resin layer 5 by a melt coating method and can be prepared. At this time, when the adhesive layer 6 is provided, the adhesive layer 6 may be formed in advance on the sheet-like amorphous polyester resin layer 5 side, or may be laminated with the polyolefin resin layer 4 by a two-layer coextrusion method.

The (total) thickness of the base material layer 1 is usually 30 from the viewpoint of moldability such as vacuum moldability and bending workability.
About 350 μm. The thickness of the polyolefin-based resin layer 4 is not so necessary for its purpose (improving the organic solvent resistance of the base material layer by blocking the organic solvent with respect to the amorphous polyester layer). It is preferable to reduce the thickness as much as possible in consideration of the above factors. Therefore, the thickness of the polyolefin-based resin layer is usually about 5 to 20 μm. On the other hand, the thickness of the amorphous polyester resin layer 5 is set so as to occupy the main thickness of the base material layer from the viewpoint of moldability such as vacuum moldability and bending workability. The amorphous polyester resin layer 5 is co-extruded with the polyolefin resin layer 4,
Alternatively, it is formed from a resin sheet, and the thickness of such an amorphous polyester resin layer depends on the application and the like, but is usually 30 to 3
It is about 00 μm.

By forming the specific resin and the base layer having a specific multilayer structure as described above, the amorphous polyolefin-based resin layer can form, such as vacuum formability, bending workability, and formability. In addition to the improved adhesion to the adherend, the polyolefin-based resin layer, even when the amorphous polyester layer has poor organic solvent resistance, the polyolefin-based resin layer acts as an organic solvent barrier layer, It becomes the structure which can form a pattern ink layer without a problem at the time of printing. Accordingly, a decorative sheet having good productivity is obtained. For this reason, the problem of resistance to organic solvents during printing, which was likely to occur when a single acrylic resin sheet was used for the base material layer, hardly occurs. Moreover, since the base material layer in the present invention has a polyolefin-based resin layer on the side of the pattern ink layer in consideration of the resistance to organic solvents, the amorphous polyester resin layer used for the base material layer has good moldability and the like. Even if a resin having poor organic solvent resistance is used from the viewpoint, the formation of the pattern ink layer on the base layer is not on the amorphous polyester resin layer but on the polyolefin resin layer. Therefore, the pattern ink layer can be formed on the base material layer without causing a problem of organic solvent resistance during printing or coating.

[Base Material Layer: Amorphous Polyester Layer] As the amorphous polyester resin used for the amorphous polyester resin layer 5, commercially available products such as "Eastar PETG manufactured by Eastman Chemical Co., Ltd."
6763 ”(trade name) (extrusion grade) can be used, and“ Kanebo PET sheet ”(trade name) by Kanebo Co., Ltd. and“ Teijin Tetron sheet ”(Teijin Co., Ltd.) "Denka A-PET" by Denki Kagaku Kogyo Co., Ltd.
“Sheet” (trade name), “Toyobo PETMAX sheet” (trade name) by Toyobo Co., Ltd., “NAGASE A-PET sheet” (trade name) by Nagase & Co., Ltd.,
"Polytech A-PET Sheet" (trade name) by Polytech Co., Ltd., "SAEHAN" by SAEHAN
"APET SEET" (trade name), "Novaclear" (trade name) by Mitsubishi Chemical Corporation, "Sealer PT" (trade name) by DuPont Mitsui Polychemicals, and the like can be used. The resin or sheet referred to as A-PET in the field of packaging materials is an amorphous polyester resin.

The acid component and the diol component of the amorphous polyester resin are, for example, in the case of "Eastar PETG 6763" manufactured by Eastman Chemical Co., Ltd., terephthalic acid is used as the acid component, and other ethylene glycol is used as the diol component. Further, it is a copolymer resin using 1,4-cyclohexanedimethanol in combination. It is said that by adjusting the ratio between ethylene glycol and 1,4-cyclohexanedimethanol, the crystallization rate can be made substantially zero. Further, by adjusting this ratio, the physical properties can be adjusted.

Although the above is one example of the acid component and the diol component of the amorphous polyester resin, the amorphous polyester resin used in the present invention may be a resin composed of another acid component and a diol component. Any resin that exhibits non-crystallinity may be used. For example, as the acid component, in addition to terephthalic acid, isophthalic acid, aromatic dicarboxylic acid of 2,6-naphthalenedicarboxylic acid, or alicyclic dicarboxylic acid, or adipic acid, azelaic acid, sebacic acid, dimer acid, etc. And the like. Further, as the diol component, other alicyclic diols other than the above 1,4-cyclohexane dimethanol,
Alternatively, propylene glycol, butylene glycol,
Examples thereof include aliphatic diols such as polytetramethylene glycol and neopentyl glycol, and aromatic diols such as xylene glycol. Amorphous polyester resin is
Usually, one or more of these diol components and one or more diol components are added so that the total of the diol and acid components becomes three or more.
It is obtained as a copolymer with one or more kinds of acid components.
The term “amorphous” refers to a resin that does not cause crystallization at all, or a resin having a portion that exhibits crystallinity in addition to a portion that exhibits amorphousness. Further, the amorphous polyester resin may be mixed with a crystalline polyester resin.

When a polyester resin is conventionally used as a base layer of a decorative sheet, the polyester resin may be biaxially stretched polyethylene terephthalate (PE).
T) A sheet was generally used, and this polyethylene terephthalate was a crystalline polyester resin comprising an ethylene glycol component and a terephthalic acid component. Therefore, the formability such as vacuum formability and the bending property such as V-cut processing are poor, and it cannot be used for decorative sheets for such uses.

The substrate layer made of the amorphous polyester resin as described above may be non-colored and transparent, but may be non-colored and opaque, colored and transparent, colored and opaque (colored and opaque).
For coloring, a known colorant may be added to the resin as described later in the picture ink layer.

The amorphous polyester layer may have a multilayer structure such as two layers or three layers in addition to a single layer.

[Base Layer: Polyolefin Resin Layer] Polyolefin resins used for the polyolefin resin layer 4 on the picture layer side of the base layer 1 include polyethylene (low density, medium density or high density), polypropylene Highly crystalline non-elastomeric polyolefin resins such as polymethylpentene, polybutene, ethylene-propylene copolymer and propylene-butene copolymer, or various olefin thermoplastic elastomers are used. As the olefin-based thermoplastic elastomer, for example, the following can be used.

(1) The soft segment described in JP-B-6-23278 (A) has a number average molecular weight Mn of 25,000 or more, and a ratio Mw / Mn of the mass average molecular weight Mw to the number average molecular weight Mn. 10 to 90% by mass of atactic polypropylene soluble in boiling heptane of ≦ 7,
(B) A soft polypropylene comprising, as a hard segment, a mixture of 90 to 10% by mass of a heptane-insoluble isotactic polypropylene having a melt index of 0.1 to 4 g / 10 min.

Among olefin-based thermoplastic elastomers of this type, isotactic polypropylene which is less likely to cause so-called "necking" and has good suitability for forming into various shapes by heat and pressure or embossing is exemplified by isotactic polypropylene. The mixing ratio with the atactic polypropylene is 5% by mass or more and 50% by mass or less by mass ratio of the atactic polypropylene. The polypropylene-based olefin-based thermoplastic elastomer itself is already known, but when used in a conventionally known application such as a packaging container, the weight ratio of the atactic polypropylene as a soft segment is 5 to emphasize strength. Those having less than mass% were exclusively used. However, when this is applied to a novel use such as forming into a three-dimensional shape or a concavo-convex shape or embossing, necking occurs as described above, and good processing cannot be performed. Therefore, contrary to the conventional design of the composition, in the olefin-based thermoplastic elastomer of polypropylene, the mass ratio of the atactic polypropylene is set to 5% by mass or more, thereby embossing or three-dimensional shape or the like. It is possible to eliminate non-uniform sheet deformation due to necking in forming an uneven article surface shape, and resulting defects such as wrinkles and picture distortion. Particularly, the case where the mass ratio of the atactic polypropylene is 20% by mass or more is preferable. On the other hand, if the mass ratio of atactic polypropylene increases too much,
The sheet itself is easily deformed, and when the sheet is passed through a printing press, the sheet is deformed, a pattern is distorted, and defects such as misregistration in multicolor printing easily occur. Further, it is not preferable because it is easily broken during molding. As the upper limit of the mass ratio of the atactic polypropylene, the pattern layer is printed using a normal rotary printing machine such as rotary gravure printing, and embossing of the sheet, vacuum forming, V-cut processing, simultaneous lamination of injection molding, etc. 50 to hire
% By mass, more preferably 40% by mass or less.

(2) A thermoplastic elastomer comprising an ethylene-propylene-butene copolymer resin. Here, as the butene, any of the three structural isomers of 1-butene, 2-butene and isobutylene can be used. Preferred specific examples of the ethylene-propylene-butene copolymer, which is a random copolymer and partially includes an amorphous portion, include the following (i) to (iii). (i) Those described in JP-A-9-111055. It is a random copolymer of a terpolymer of ethylene, propylene and butene. The mass ratio of the monomer components is 90% by mass or more of propylene. The melt flow rate is preferably 1 to 50 g / 10 minutes at 230 ° C. and 2.16 kg. And, for 100 parts by mass of such a ternary random copolymer, 0.01 to 50 parts by mass of a transparent nucleating agent containing a phosphate aryl ester compound as a main component,
It is obtained by melting and kneading 0.003 to 0.3 parts by mass of a fatty acid amide having 12 to 22 carbon atoms. (ii) Those described in JP-A-5-77371. this is,
80 to 0% by mass of a crystalline polypropylene is added to 20 to 100% by mass of an amorphous polymer having a propylene content of 50% by mass or more, which is a terpolymer of ethylene, propylene and 1-butene. It is. (iii) Those described in JP-A-7-316358. This is a terpolymer of ethylene, propylene, and 1-butene, and the content of propylene and / or 1-butene is 50% by mass or more and 20 to 100% by mass of the low crystalline polymer. 0.5% by mass of an oil gelling agent such as N-acylamino acid amine salt or N-acylamino acid ester is added to a composition in which 80 to 0% by mass of a crystalline polyolefin such as isotactic polypropylene is mixed. It becomes.

The ethylene-propylene-butene copolymer resin may be used alone, or may be used in the above (i) to (iii).
If necessary, another polyolefin-based resin may be mixed and used.

(3) As described in JP-B-53-21021, (A) an olefin polymer (crystalline polymer) such as polyethylene, polypropylene or polymethylpentene is used as a hard segment, and (B) a partial cross-linking Monoolefin copolymer rubbers such as ethylene-propylene copolymer rubber and unsaturated ethylene-propylene-non-conjugated diene terpolymer rubber are used as soft segments, and these are uniformly blended and mixed. . In addition,
Monoolefin rubber / olefin polymer = 50 / 50-
Mix at a ratio of 90/10 (mass ratio).

(4) As described in JP-B-53-34210, (B) an uncrosslinked monoolefin copolymer rubber (soft segment) and (A) an olefin copolymer (crystalline, hard segment) ) And a cross-linking agent, and is heated to apply shear stress to dynamically partially cross-link an olefin-based elastomer. (B) monoolefin rubber / (A) olefin copolymer = 60/40 to 80/20
(Mass ratio).

(5) As described in JP-B-56-15741, (A) isotactic polypropylene, propylene-ethylene copolymer, propylene-butene-1
A peroxide-decomposable olefin polymer (hard segment), which decreases its molecular weight when mixed and heated with a peroxide such as a copolymer to increase fluidity, and (B) ethylene-propylene copolymer rubber, ethylene-propylene-nonconjugated diene Peroxide-crosslinked monoolefin copolymer rubber (soft segment), which crosslinks and reduces fluidity by mixing and heating with a peroxide such as an original copolymer rubber, (C)
Peroxide non-crosslinked hydrocarbon rubber (soft segment / fluidity-modifying component) that does not crosslink even when mixed and heated with peroxides such as polyisobutylene and butyl rubber and has constant fluidity, and (D) paraffinic and naphthene An olefin-based elastomer obtained by mixing a mineral oil-based softener such as an oil-based or aromatic oil-based softener and dynamically heat-treating the mixture in the presence of an organic peroxide. (A) is 90 to 40 parts by mass, (B) is 10 to 60 parts by mass.
In parts by mass, (A) + (B) = 100 parts by mass.
(C) and / or (D) have a compounding ratio of 5 to 100 parts by mass.

(6) An olefin-based thermoplastic elastomer comprising an ethylene-styrene-butylene copolymer as described in JP-A-2-139232.

(7) The olefin-based thermoplastic elastomer according to the above (1) to (6), having a hydroxyl group and / or a carboxyl group as a polar functional group. For example,
Use is made of an olefin-based thermoplastic elastomer in which a hydroxyl group is introduced by graft polymerization of an ethylene-vinyl alcohol copolymer or the like, and a carboxyl group is introduced by a copolymer of maleic acid, fumaric acid, itaconic acid or the like. When the polar functional group is, for example, a hydroxyl group and a carboxyl group, either one or both may be used in combination. Also,
The polar functional group may be a carbonyl group or the like. These polar functional groups have an effect of improving the adhesion of the pattern ink layer to (the polyolefin-based resin layer thereof).

The above (7) is an example of a polyolefin resin to which a polar functional group is added in an olefin thermoplastic elastomer. However, the above polar functional group is added to a non-olefin thermoplastic elastomer other than the olefin thermoplastic elastomer. The resin imparted to the polyolefin resin can also be used for the polyolefin resin layer. For example, high-crystalline non-elastomeric polyolefin resins such as polyethylene (low density, medium density or high density), polypropylene, polymethylpentene, polybutene, ethylene-propylene copolymer, propylene-butene copolymer, etc. It is a resin having a polar functional group as described above. By applying a polar functional group-containing resin to a polyolefin resin containing an olefinic thermoplastic elastomer, that is, a polar functional group-containing polyolefin resin for the polyolefin resin layer, a pattern ink layer, an amorphous polyester resin Adhesion between the polyolefin resin layer and another layer in contact with the polyolefin resin such as a layer can be improved.

The polar functional group-containing polyolefin resin includes ethylene, carboxylic acid, carboxylate,
Ethylenes having carbonyl groups based on carboxylic anhydrides, carboxylic esters, carboxylic amides or carboxylic imides, aldehydes, ketones, etc. alone or in combination with cyano groups, hydroxyl groups, ether groups, oxirane rings, etc. Copolymers with one or two unsaturated monomers can also be used. The copolymerization ratio of such a polar functional group-containing monomer is usually 0.1 to 10% by mass.
The effect of improving the adhesion can be obtained by the degree.

The above ethylenically unsaturated monomers include, for example, the following (A) to (D). Incidentally, preferably, (A) ethylenically unsaturated carboxylic acid, or (B)
Ethylenically unsaturated carboxylic anhydride is used. Also,
Metal neutralized products (ionomers) of a copolymer of ethylene and an ethylenically unsaturated carboxylic acid can also be used.

(A) Ethylenic unsaturated carboxylic acid; acrylic acid, methacrylic acid, maleic acid, fumaric acid, crotonic acid, itaconic acid, citraconic acid, 5-norbornene
2,3-dicarboxylic acid and the like. (B) ethylenically unsaturated carboxylic anhydride; tetrahydrophthalic anhydride and the like. (C) ethylenically unsaturated ester; ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate, monoethyl maleate, diethyl maleate, vinyl acetate,
Vinyl propionate, propyl γ-hydroxymethacrylate, ethyl β-hydroxyacrylate, glycidyl acrylate, glycidyl methacrylate, β-N-ethylaminoethyl acrylate, and the like. (D) ethylenically unsaturated amide or imide; acrylamide, methacrylamide, maleimide, and the like.

The polyolefin-based resin layer made of the polyolefin-based resin as described above may be non-colored and transparent, but may be non-colored and opaque, colored and transparent, colored and opaque (colored and opaque), and the like. For coloring, a known colorant may be added to the resin as described later in the picture ink layer.

[Base Layer: Adhesive Layer] The adhesive layer 6 of the base layer 1 may be made of a urethane resin, an epoxy resin, a chlorinated polyolefin resin such as chlorinated polypropylene, or a polyolefin containing a polar functional group. Use resin or the like. However, since the chlorinated polyolefin resin becomes a resin containing chlorine like the vinyl chloride resin, it is preferably not used as the non-vinyl chloride decorative sheet of the present invention. The polar functional group-containing polyolefin-based resin may be the resin described above for the polyolefin-based resin layer 4 or the like. Further, as the urethane resin, a two-component curable urethane resin, a thermoplastic urethane resin, or the like can be used. The thickness of the adhesive layer is usually 5 to 20 μm.
m.

In the case of a chlorinated polyolefin resin or a polar functional group-containing polyolefin resin, the adhesive layer is formed on a resin sheet to be an amorphous polyester resin layer by a two-layer coextrusion method with the polyolefin resin layer. Can be formed. In the case of a urethane resin or an epoxy resin or the like, a coating or ink using these resins is formed on a resin sheet to be an amorphous polyester resin layer by a known coating or printing method such as roll coating or gravure printing. Can do things.
The adhesive layer is usually formed on the resin sheet of the amorphous polyester resin layer 5, but may be formed of the resin sheet of the polyolefin resin layer 4, or both.

The two-component curable urethane resin has a polyol as a main component and an isocyanate as a crosslinking agent (curing agent).
Urethane resin. The polyol is a compound having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol, polyurethane polyol and the like. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, 2,4-tolylene diisocyanate, xylene diisocyanate,
Aromatic isocyanates such as naphthalene diisocyanate and 4,4'-diphenylmethane diisocyanate, or aliphatic (or alicyclic) such as 1,6-hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated diphenylmethane diisocyanate Isocyanates are used.
Alternatively, adducts or multimers of the above-mentioned various isocyanates, for example, adducts of tolylene diisocyanate, trimers of tolylene diisocyanate, and the like are also used.

The thermoplastic urethane resin is a linear polymer obtained by urethane bonding a divalent polyol and a divalent isocyanate.

The substrate layer having the above-described configuration is suitable for forming a pattern ink layer on the surface of the substrate layer (resin sheet) on the side of the polyolefin resin layer by printing or the like. However, if it is necessary to improve the adhesion between the pattern ink layer and the base material layer, the base material layer (the polyolefin resin layer) may be formed by subjecting the surface of the base material layer to a known easy adhesion treatment. good. The easy adhesion treatment includes, for example, corona discharge treatment, plasma treatment, ozone treatment and the like, and formation of a primer layer. The primer layer may be formed, for example, by applying or printing a primer agent made of a resin as described above for the adhesive layer or the like. In the case of forming a primer layer, the pattern ink layer is in contact with the base layer (because the primer layer is a layer included in the base layer), but the layer with which the pattern ink layer is in contact is the polyolefin resin layer. No, it becomes this primer layer.

[Picture Ink Layer] The pattern ink layer 2 is a layer formed as an essential decoration treatment among the decoration treatments that can be employed in the decorative sheet of the present invention. In the present invention, the pattern ink layer is preferably formed so as to be in contact with the base material layer in view of utilizing the above-mentioned organic solvent resistance characteristics of the base material layer.

The pattern ink layer 2 is formed with ink by a known printing method. In this case, since the printing method takes into consideration the organic solvent resistance of the base layer in the present invention, a printing method using an organic solvent for the ink is preferable, for example, gravure printing, offset printing, silk printing. Screen printing,
Alternatively, a printing method such as ink jet printing is used. However, the picture ink layer of the present invention can be formed by a printing method (not using ink directly), for example, a printing method such as transfer printing from a transfer sheet and sublimation transfer printing.
In the case where the pattern of the pattern ink layer is a solid pattern on the entire surface, the pattern ink layer can be formed of a paint by a known coating method such as gravure coating or roll coating. In the present invention, the term "pattern ink layer" is used, including the case where it is formed by such a paint or coating. The pattern of the picture ink layer may be a wood grain pattern, a stone grain pattern, a cloth grain pattern, a squeezed pattern, a geometric figure, a character, a symbol, a solid pattern on the entire surface, or the like, depending on the application. The picture ink layer is also used in combination with a pattern pattern layer expressing a pattern such as a wood grain pattern and a solid layer on the entire surface. The entire solid layer is usually a hiding layer,
It is used as a coloring layer, a coloring hiding layer, and the like.

The pattern ink layer is formed at a position other than the position between the substrate layer and the surface layer which is in contact with the substrate layer. In addition, the back surface and the surface layer of the substrate layer are formed of a resin sheet. In this case, the front surface, the back surface, the front and back surfaces, and the like of the resin sheet are also possible.

The ink (or) paint used for forming the pattern ink layer may be a polyester resin, a urethane resin, an acrylic resin, a vinyl acetate resin, a vinyl chloride-vinyl acetate copolymer, a cellulose resin, or a binder. And chlorinated polyolefin resins such as chlorinated polyethylene and chlorinated polypropylene are used alone or in combination of two or more. The chlorinated polyolefin resin is preferably not used as a non-PVC-based decorative sheet, similarly to the adhesive layer described above. Examples of the colorant used in the ink (or) paint include inorganic pigments such as titanium white, zinc white, red iron oxide, vermilion, ultramarine, cobalt blue, titanium yellow, graphite, and carbon black; isoindolinone yellow; Yellow A, quinacridone red, permanent red 4R, phthalocyanine blue,
Organic pigments (or dyes) such as Indaslen Blue RS and aniline black; metal pigments composed of metal powders such as aluminum and brass; pearl luster (pearl) composed of foil powders such as titanium dioxide-coated mica and basic lead carbonate ) Pigments, fluorescent pigments and the like are used alone or in combination of two or more.

[Surface Layer] The surface layer 3 is a layer composed of a polyolefin resin. As the polyolefin-based resin, various polyolefin-based resins as described above as the polyolefin-based resin layer 4 in the base layer 1 can be used. Therefore, further description is omitted here. The surface layer is formed by printing a resin sheet that has been formed into a sheet (film) in advance by a known film forming method such as a melt extrusion method or a calendar method, after forming a pattern ink layer on the resin sheet serving as a base material layer. It can be formed by laminating the sheet by dry lamination or heat fusion. The thickness of the surface layer depends on the application and the like, but is usually 10 to 3 times.
It is about 00 μm. Further, the surface layer may have a multilayer structure such as two layers. In this case, the side in contact with another layer such as the base layer is formed of a layer of a polar functional group-containing polyolefin-based resin (usually from the viewpoint of film forming technology). (5 μm or more) is a preferable embodiment from the viewpoint of improving interlayer adhesion.

Various additives such as a coloring agent, a filler, a flame retardant, a lubricant, an antioxidant, an ultraviolet absorber, and a light stabilizer are added to the surface layer 3 as needed. Also, the surface layer so that the pattern ink layer provided below it can be seen through,
It is transparent (uncolored or colored).

The ultraviolet absorber may be an organic ultraviolet absorber such as benzotriazole, benzophenone, or salicylate, and may have a particle diameter of 0.2 μm.
Inorganic substances such as the following fine particles of zinc oxide, cerium oxide, and titanium oxide can be used. As a light stabilizer,
A radical scavenger such as a hindered amine radical scavenger such as bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate and a piperidine radical scavenger can be used.

[Decoration processing] By the way, the decorative sheet of the present invention has a pattern ink layer as one type of decoration processing.
Other decoration processing may be performed as needed. For example, as a decoration treatment, coloring (transparent or opaque coloring) by adding a coloring agent to the base material layer, coloring (transparent coloring) by adding a coloring agent to the surface layer, or embossing (heating press), hairline processing And the like to form a concavo-convex pattern on the surface layer surface or the like. For such a decoration process, various conventionally known decoration processes for a decorative sheet can be employed.
Various decoration processes may be used in combination as appropriate depending on the application.

The above-described pattern ink layer is one of the typical layers formed as a decorative layer, but a metal thin film layer or the like can be used as the decorative layer. The metal thin film layer is formed by using a metal such as aluminum, chromium, gold, silver, copper, etc., by vacuum evaporation,
The film is formed by a method such as sputtering. Alternatively, a combination of these may be used. Even if the metal thin film layer is provided on the entire surface,
Alternatively, they may be provided partially in a pattern.

In the embossing process as a decoration process, the embossing process is performed by hairline processing, sandblasting, embossing, or the like. For example, embossing is performed by pressing an embossing plate on the surface of a heat-softened resin sheet using a hot press type sheet-fed or rotary embossing machine. The resin sheet is a resin sheet serving as a surface layer or a resin sheet serving as a base layer. The shaping of the uneven pattern may be performed simultaneously with the formation of the resin sheet. For example, a T-die melt extrusion method may be used, in which an embossing / cooling roller having a concavo-convex pattern on a cooling surface is used as a cooling roller, and the film is formed simultaneously with film formation. The shaping of the concavo-convex pattern is performed by laminating a resin sheet as a base material layer (a pattern ink layer is already formed) and a resin sheet as a surface layer, and simultaneously applying heat and pressure to the surface of the resin sheet as the surface layer. There is also a method of shaping by a so-called doubling embossing method in which shaping is performed by embossing. In addition, as an uneven | corrugated pattern, a wood grain board | tube groove | channel, a stone board surface unevenness (granite cleavage surface etc.), a cloth surface texture, a satin finish, a grain, a hairline, a linear groove, etc. are mentioned. The uneven pattern is usually the front side of the surface layer, but may be the back side of the surface layer, the front side of the base layer, or the back side of the base layer.

As a decoration process, a colored portion can be formed by filling a colored ink into the concave portion of the concavo-convex pattern by a known wiping method (see Japanese Patent Publication No. 58-14312, etc.). The coloring ink can be the same as the picture ink layer. However, from the viewpoint of abrasion resistance, a material using a two-component curable urethane resin as a binder is preferable. Note that the wiping method may be any of conventionally used wiping methods such as a dodder blade method and a roll coating method. In other words, the colored ink is applied to the entire surface of the uneven pattern, and thereafter, the ink of the convex portion is scraped off with a dough blade, a sponge roll, a cloth, or the like, or the colored ink is left in the concave portion. I do.

In the decoration treatment, there is a treatment for further forming an overcoat layer on the surface layer for giving a design property such as gloss adjustment and painting feeling. However, since the overcoat layer is the outermost surface layer of the decorative sheet, it is usually provided for the purpose of improving the surface physical properties such as scratch resistance and stain resistance rather than decorative treatment. Of course, it may be provided for both the decoration and the improvement of the physical properties of the surface. For the overcoat layer, a resin such as a two-component curable urethane resin, an epoxy resin, or an ionizing radiation curable resin such as an acrylate resin is used. The overcoat layer is formed by a known coating method such as gravure coating or roll coating using a coating liquid composed of these resins. In addition, known additives such as a matting agent such as calcium carbonate and silica, a lubricating agent such as alumina and silica, an ultraviolet absorber, a light stabilizer, and a coloring agent are appropriately added to the overcoat layer as needed. I do. The thickness of the overcoat layer is usually about 1 to 10 μm.

[Applied Body of Decorative Sheet] The application of the decorative sheet of the present invention is not particularly limited, and the decorative sheet is laminated on the surface of various adherends and used for decorative application of the surface. The adherend is a plate material such as a flat plate or a curved plate of various materials, a three-dimensional article, a sheet (or film), or the like. For example, wood veneer, wood plywood, particle board, wood material such as wood fiber board such as MDF (medium density fiber board), wood board material used as three-dimensional article, plate material such as iron and aluminum, three-dimensional article or Ceramics used as metal materials used as sheets, ceramics such as glass and ceramics, non-cement ceramic materials such as gypsum, non-ceramic ceramic materials such as ALC (lightweight cellular concrete) plates, etc. Material, acrylic resin, polyester resin, polystyrene resin, polyolefin resin such as polypropylene,
ABS (acrylonitrile-butadiene-styrene copolymer) resin, phenolic resin, vinyl chloride resin, cellulosic resin, rubber or other plate material, resin material used as a three-dimensional article or sheet, or high quality paper used exclusively as a sheet , Paper such as Japanese paper, non-woven fabric or woven fabric made of fibers such as carbon, asbestos, glass and synthetic resin, or a composite material of these two or more materials, for example, wood used as a plate material or a three-dimensionally shaped article, etc. Composite (base) materials such as powdered plastics, paper powdered plastics, and FRP (fiber reinforced plastics) are exemplified.

[Method of Laminating Decorative Sheet on Adherend] The method of laminating the decorative sheet on the adherend includes, for example, (1) pressing a plate-shaped adherend with a pressure roller via an adhesive. (2) As described in JP-B-50-19132, JP-B-43-27488, etc., a decorative sheet is placed between male and female molds for injection molding and then melted. A so-called simultaneous injection molding laminating method in which a resin is injected into a mold and a decorative sheet is adhered and laminated on the surface of the adherend as a resin molded product at the same time as the molding, (3) Japanese Patent Publication No. 56-4576.
No. 8, Japanese Patent Publication No. 60-58014, etc., a decorative sheet is opposed to or placed on the surface of a three-dimensional adherend with an adhesive therebetween, and is placed from the adherend side. A so-called vacuum forming and laminating method of laminating a decorative sheet on the surface of an adherend by at least a pressure difference caused by the combined use of vacuum suction and pressurized air pressing from the decorative sheet side, (4) JP-B-61-5
No. 895, JP-B-3-2666, etc., while supplying a decorative sheet through an adhesive in the long axis direction of a columnar adherend such as a column or a polygonal column, By a plurality of rollers having different directions, decorative sheets are successively pressed and adhered to a plurality of side surfaces constituting an adherend and laminated.
There is a so-called lapping method.

As a further processing method for a decorative sheet obtained by laminating decorative sheets, Japanese Utility Model 15-31
No. 122, JP-A-48-47972, first, a decorative sheet is laminated on a plate-shaped adherend with an adhesive therebetween to form a decorative sheet, and the decorative sheet is on the side opposite to the decorative sheet. A groove having a V-shaped or U-shaped cross section which reaches the interface between the decorative sheet and the adherend, and then applying an adhesive in the groove, and bending the groove to form a box body Alternatively, there is a bending method such as a so-called V-cut or U-cut method for forming a columnar body.

In particular, in the decorative sheet of the present invention, since formability such as vacuum formability and bending workability are ensured, the above methods (2), (3), (4), etc. A method and a bending method such as a V-cut method are preferred.

[Uses of the decorative sheet and its laminate] The decorative sheet of the present invention is laminated on various adherends, subjected to predetermined molding processing as required, and used for various purposes. For example,
Interior decoration of buildings such as walls, ceilings and floors, surface makeup of window frames, doors, handrails and other fittings (for example, kitchen cabinets), furniture or surface decoration of cabinets for light electric / OA equipment, automobiles,
Vehicle interiors such as trains, aircraft interiors, ship interiors, window glass makeup, and the like.

[0063]

EXAMPLES The decorative sheet of the present invention will be further described below with reference to examples.

Example 1 A decorative sheet S having the structure shown in FIG. 1A was produced as follows. First, as the base material layer 1, an amorphous polyester resin [Eastar PETG 6763 (trade name) manufactured by Eastman Chemical Co., Ltd.] A colored resin colored by adding yellowish brown,
Transparent polypropylene resin and a two-layer co-extrusion method to form a film,
10 μm thick polyolefin resin 4 and 50 μm thickness
And an amorphous polyester resin layer 5 of the formula (1), and a continuous band-shaped opaque colored resin sheet (60 μm in thickness) was prepared.
The surface on the polyolefin resin layer 4 side was subjected to ozone treatment as an easy adhesion treatment immediately after the resin was extruded from the T-die.

Next, on the surface of the colored resin sheet on the side of the polyolefin-based resin layer 4, a gravure rotary printing is used to represent the entire solid layer and the pattern of the grain pattern as the grain pattern ink layer 2 as the grain pattern ink layer 2. The patterned pattern layer thus formed was formed in this order to obtain a printed sheet. As the binder resin of the ink used for the pattern ink layer, a two-component curable urethane resin having a 100: 8 mass ratio of acrylic polyol and 1,6-hexamethylene diisocyanate was used for both the solid layer and the pattern pattern layer. Was. As the colorant of the ink used for the picture ink layer, titanium white, red petal and graphite were used for all solid layers, and red petal and carbon black were used for the pattern pattern layer.

Then, on the printing surface of the pattern ink layer of the printing sheet, a melt extrusion coating method from a T-die is used.
Surface layer 3 made of polyolefin resin having a thickness of 60 μm
Was laminated at the same time as the film formation to obtain a decorative sheet S. In addition,
As the polyolefin resin used for the surface layer, a resin obtained by adding 0.5% by weight of a benzotriazole-based ultraviolet absorber and 0.3% by weight of a hindered amine-based light stabilizer to an ethylene-propylene random copolymer was used.

Example 2 A decorative sheet S having the structure shown in FIG. 1C was prepared as follows. In Example 1, a decorative sheet S was obtained in the same manner as in Example 1, except that a resin sheet having a three-layer structure having an adhesive layer described below was used as the base layer 1. In addition, the resin sheet used as the base material layer is the same as in Example 1, together with a colored resin made of an amorphous polyester resin for the amorphous polyester resin layer 5 and a polypropylene resin for the polyolefin resin layer 4,
As the resin for the adhesive layer 6, a polypropylene-based olefin-based thermoplastic elastomer obtained by graft polymerization of maleic acid (isotactic polypropylene / atactic polypropylene = 75/25 mass ratio mixture) is used as a polar functional group-containing polyolefin-based resin. And these three
The seed resins were prepared by a three-layer coextrusion method. This resin sheet is composed of a polyolefin resin 4 having a thickness of 10 μm, an adhesive layer 6 having a thickness of 10 μm, and an amorphous polyester resin layer 5 having a thickness of 50 μm. Thickness 70 μm). Further, the surface on the polyolefin resin layer 4 side is subjected to ozone treatment as in the first embodiment.

Comparative Example 1 A 60 μm thick resin sheet made of an ethylene-propylene random copolymer was used as a substrate layer, and a pattern ink layer similar to that of Example 1 was formed by printing on one surface of the resin sheet. After forming the print sheet, an ethylene-propylene random copolymer-based olefin-based thermoplastic elastomer was laminated as a surface layer on the printing surface of the pattern ink layer by a melt extrusion coating method at the same time as forming a film, thereby producing a decorative sheet.

[Evaluation of Performance] Vacuum formability, bending workability (V
The cut processing suitability) and the adhesion (to the adherend) were evaluated. The vacuum formability was evaluated as follows.

Vacuum formability: 100 mm each in vertical and horizontal directions, thickness 30
5mm deep at an angle of 9mm
The above-described decorative sheet having a back surface to which a urethane-based adhesive is applied is bonded to the adherend by forming a straight V-shaped groove having a V-shaped cross section of 0 degree as an adherend by a vacuum forming lamination method. Was. Then, the one in which the decorative sheet was neatly formed and entered into the V-groove was good, and the one that floated from the V-groove was bad.

As a result of the performance evaluation, Examples 1 and 2
The samples had good vacuum moldability, bending workability, and adhesiveness. In Examples 1 and 2, an amorphous polyester resin was used for the base material layer. However, the printed sheet after the pattern ink layer was printed on the continuous belt-shaped resin sheet serving as the base material layer was a roll. No blocking occurred even after winding and storage. On the other hand, in Comparative Example 1, the vacuum formability, bending workability, and adhesiveness were all insufficient and were poor.

[0072]

(1) According to the decorative sheet of the present invention, formability such as vacuum forming, bending workability, and adhesion to an adherend are improved. As a result, the moldability is good, so that the decorative sheet has good followability of the unevenness even when laminating on the uneven surface, and the suitable condition range of the thermoforming process is wide. Also does not happen. Also,
Because of good bending workability, necking, whitening, cracking, and cracking hardly occur during bending processing such as V-cut processing. When laminating on the adherend, the amorphous polyester resin layer having good adhesiveness is laminated on the adherend, so that it is not necessary to pay special attention to the easy-adhesion layer and the adhesive. By the way, when the base material layer has a single-layer structure composed of only the amorphous polyester resin, the amorphous polyester resin has a good affinity with the organic solvent. May absorb the organic solvent in the ink at the time of printing the pattern ink layer, swell, or cause stickiness on the surface. For this reason, the pattern is printed on the continuous belt-shaped resin sheet as the base layer by rotary printing. When the printing sheet on which the ink layer is printed is wound up in a roll, the front and back sides of the printing sheet may adhere (so-called blocking) or a residual solvent may easily remain in the base material layer. Lower speeds and longer drying zones were required. However, in the decorative sheet of the present invention, since the base material layer has the pattern ink layer side as a polyolefin resin layer, the amorphous polyester resin layer used for the base material layer has moldability, bendability, and the like. Even when a resin with poor organic solvent resistance is used from the viewpoint of emphasis, the formation of the pattern ink layer on the base material is not on the amorphous polyester resin layer but on the polyolefin resin layer. Therefore, the configuration is such that the picture ink layer can be formed on the base material layer without any problem at the time of printing. Accordingly, a decorative sheet having good productivity is obtained.

(2) Further, if an adhesive layer is provided between the polyolefin resin layer of the base layer and the amorphous polyester resin layer, the interlayer adhesion in the base layer can be further improved. it can.

[Brief description of the drawings]

FIG. 1 is a sectional view showing a typical embodiment of a decorative sheet according to the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Base material layer 2 Picture ink layer 3 Surface layer 4 Polyolefin resin layer 5 Amorphous polyester resin layer 6 Adhesive layer S Decorative sheet

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AK03A AK03C AK07 AK41D AK51G BA04 BA10A BA10D CA13 CB00 CC00B GB07 GB08 GB33 GB81 HB00B HB01 HB31 JA12D JK06 JL01

Claims (2)

[Claims] 1. A decorative sheet having a pattern ink layer and a surface layer made of a polyolefin resin laminated in this order on a substrate layer, wherein the pattern ink layer side of the base layer is made of a polyolefin resin layer and the other is The side is made of an amorphous polyester resin layer,
Makeup sheet. 2. The decorative sheet according to claim 1, wherein the polyolefin resin layer of the base material layer and the amorphous polyester resin layer are laminated via an adhesive layer.