JP2000202964A - Cosmetic material - Google Patents

Abstract

(57) [Summary] [Object] To provide a decorative material in which insufficient adhesive strength is generated when the decorative material is composed of a polyolefin resin. A pattern layer (2) formed on a colored layer (4) by laminating a polyolefin resin layer (1b) having an adhesive maleic acid component or the like below a polyolefin resin layer (1a) as an outermost layer. Adhesive layer 3 between layer 1b
Was able to improve the adhesive force.

Description

DETAILED DESCRIPTION OF THE INVENTION TECHNICAL FIELD OF THE INVENTION

The present invention relates to a decorative material having a surface on which a polyolefin resin layer is laminated.

[0002]

2. Description of the Related Art Various cosmetic materials are used for interior and exterior of buildings such as interior and exterior walls, ceilings, floors, etc., for surface decoration of furniture and household appliances, and for surface decoration of personal miscellaneous goods and accessories.
The decorative material is a relatively thin sheet, which is suitable for sticking to various articles with an adhesive or the like, plywood,
There is a decorative board in which makeup is applied to a substrate such as an MDF, or as a decorative board, a decorative sheet is applied to these substrates by applying a decorative sheet. In this specification, any decorative material is used. Shall be included.

By the way, there are various types of conventional decorative materials depending on the material and the method of manufacturing. However, the one which is closely related to the present invention and which can be compared is a polyvinyl chloride resin sheet. This is a so-called “PVC decorative sheet” that uses as a base material.

[0004] The material constituting the polyvinyl chloride resin sheet, which is the base material of the decorative PVC sheet, is usually a vinyl chloride / vinyl acetate copolymer. Since the vinyl chloride / vinyl acetate copolymer has a vinyl acetate component that contributes to adhesiveness, the polyvinyl chloride resin sheet has adhesiveness, and there is almost no shortage of adhesive strength during printing or lamination. Moreover, since the polyvinyl chloride resin sheet is softened by heating, processing such as embossing is easy. Further, the polyvinyl chloride resin sheet has an advantage that it does not burn itself out, that is, has no self-combustibility, unless there is a burning thing nearby. Furthermore, the polyvinyl chloride resin sheet has an advantage that the degree of hardness and softness can be freely adjusted by adding a plasticizer,
Hardness can be selected according to the application. The polyvinyl chloride resin sheet has an economical advantage that it is widely used and stable in price.

[0005] Although the polyvinyl chloride resin sheet has the above advantages, it also has disadvantages. Since polyvinyl chloride resin contains chlorine in its structure, it is unavoidable that the polyvinyl chloride resin will be discolored over time, toxic gas may be generated at the time of combustion, and smoke is generated. There are also various problems caused by containing a plasticizer.

Therefore, recently, there has been a movement to replace a polyvinyl chloride resin sheet, which is a base material of a PVC decorative sheet, with a polyolefin resin sheet. However, even considering typical polyolefin resins such as polyethylene resin and polypropylene resin, sheets made of these resins have heat-sealing properties, but the adhesion of ink and adhesive during printing and laminating is poor. It is poor and has drawbacks such as insufficient strength during various processing in the application of cosmetic materials.

[0007] The conventional laminated structure of a decorative material is roughly divided into a structure in which a pattern is formed between two base material sheets,
In addition, there are two types of base material sheets, one with a single layer and a pattern on the back surface. When a decorative material is composed of a polyolefin-based resin, the conventional structure is often followed in principle. However, when the base sheet is replaced with a polyolefin-based resin, the adhesiveness is poor. Therefore, when the base sheet is composed of two layers, the upper layer is laminated between the two layers, particularly after the pattern is provided on the lower layer. Adhesive strength is insufficient, it is necessary to use an adhesive, and it is necessary to use a large amount of adhesive. In the case of a single layer, the adhesive strength between the base sheet and the pattern provided on the back surface However, in practice, it is necessary to form a pattern via a primer layer.

[Problems to be solved by the invention]

It is an object of the present invention to improve insufficient bonding strength which occurs when the above-described base sheet is replaced with a polyolefin resin from a polyvinyl chloride resin sheet. .

[0009]

In the present invention, among the polyolefin resins, the adhesive strength of the surface involved in the adhesion can be improved by using a polyolefin resin layer having a maleic acid component.

[0010] According to the first aspect of the present invention, a polyolefin-based resin layer composed of a plurality of two or more layers is laminated on a base material, and at least the polyolefin-based resin layer has an adhesive property at a side facing the base material. The present invention relates to a decorative material characterized by being a polyolefin resin layer.

[0011] According to a second aspect of the present invention, in the first aspect, the two layers each comprising a polypropylene resin layer having a maleic acid component on the side facing the substrate and a layer of a polypropylene homopolymer resin on the side opposite to the substrate. The present invention relates to a decorative material on which a polyolefin-based resin layer is laminated.

According to a third aspect of the present invention, in the first aspect, the side facing the substrate is formed of a polypropylene resin layer having a maleic acid component, and the side opposite to the substrate is formed of an ethylene-propylene-butene copolymer resin. The present invention relates to a decorative material comprising two laminated polyolefin-based resin layers.

According to a fourth aspect of the present invention, in the first aspect of the present invention, the polyolefin resin layer laminated on the substrate is formed of a polypropylene homopolymer resin containing an amorphous polypropylene on the side opposite to the substrate. The present invention relates to a decorative material comprising two polyolefin resin layers.

According to a fifth aspect of the present invention, there is provided a decorative material according to the first aspect, wherein the polyolefin-based resin layer comprises three layers, and the front and back two layers comprise a polyolefin resin layer having a maleic acid component. Things.

[0015]

1 to 4 are views showing a sectional structure of a decorative material according to an embodiment of the present invention. The present invention, for example,
As shown in FIG. 1, two layers of transparent sheets 1a and 1b are laminated on each other, and a pattern layer 2 is laminated on the lower surface. it can. Two-layer transparent sheet 1a, 1b
Among them, 1b which requires an adhesive force with the pattern layer 2 is made of an adhesive material. The cosmetic material of the present invention is shown in FIG.
As shown in the figure, two transparent sheets 1a and 1b are laminated on the colored layer 4 of the colored layer 4 on which the pattern layer 2 is laminated, and the colored layer 4 and the transparent sheet 1b are 1
b and the pattern layer 2 are laminated via an adhesive layer 3. This is a so-called doubling sheet having two top layers. In the case of the doubling sheet as shown in FIG. 2, the pattern layer 2 and the adhesive layer 3 can be replaced with each other. In any case, 1b, which requires an adhesive force with the lower layer, is made of an adhesive material. In any of the decorative materials of the above two embodiments, the surface protective layer 5 may be laminated on the uppermost layer for the purpose of protecting the surface.
3 and 4 show the decorative material 1 of FIGS. 1 and 2, respectively.
Reference numerals 0 and 20 show the state where the surface protective layer 5 is laminated.
FIGS. 3 and 4 show a state in which the lower surface of the lowermost layer is laminated on the substrate 7 via the adhesive layer 6, and the structure shown in FIGS. It is also a structure when decorating makeup by pasting it on an article, but also shows a form when applied to other articles as a thick decorative material reinforced with a relatively thin decorative sheet with a thick backing material. .

Hereinafter, the transparent sheets 1a and 1b, the colored sheet 4, the pattern layer 2, the adhesive layers 3 and 6, the substrate 7, and the like will be described.

In the decorative material of the present invention, at least the upper transparent sheets 1a and 1b of the pattern are made of a polyolefin resin layer. Adhesive polyolefin resin layer,
Although included in this category, the details will be described later. Polyolefin resins suitable for use in cosmetics are roughly classified into two types: non-elastomer polyolefin resins and polyolefin thermoplastic elastomers.

One type of polyolefin-based resin constituting the polyolefin-based resin layer is a non-elastomer, specifically, polyethylene (low density or high density),
Highly crystalline ones such as polypropylene (isotactic type, syndiotactic type, or a mixture thereof), polymethylpentene, polybutene, ethylene / propylene copolymer, and propylene / butene copolymer.

Another type of the polyolefin-based resin constituting the polyolefin-based resin layer is a polyolefin-based thermoplastic elastomer, which is described in the following (1) to (8).
It is something like

(1) The main raw material is made of high-density polyethylene or isotactic polypropylene, which is a hard segment, and further contains an elastomer as a soft segment and, if necessary, an inorganic filler.
Here, as the elastomer, a diene rubber, a hydrogenated diene rubber, an olefin elastomer or the like is used. Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile /
Examples include isoprene rubber and styrene / butadiene rubber.
The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of the double bond of the diene rubber molecule, and suppresses crystallization of the polyolefin resin (high-density polyethylene or polypropylene in the present invention).
It has improved flexibility. The olefin elastomer is an elastic copolymer to which at least one polyene copolymerizable with two or three or more olefins is added, and the olefin is ethylene, propylene, α
An olefin or the like is used;
Hexadiene, cyclic dienes, norbornene and the like are used. Preferred olefin copolymer rubbers include, for example, elastic copolymers containing an olefin as a main component, such as ethylene / propylene copolymer rubber. In addition, these elastomers may be appropriately cross-linked by using a cross-linking agent such as an organic peroxide or sulfur, if necessary.

(2) The hard segment is made of isotactic polypropylene and the soft segment is made of atactic polypropylene, and preferably the latter is less than 5% by weight (described in Japanese Patent Publication No. Hei 6-23278).

(3) A copolymer of ethylene / propylene / butene containing one of three structural isomers of 1-butene, 2-butene or isobutylene as butene. The following (3a) to (3c) are typical. (3a) A ternary random copolymer of ethylene / propylene / butene, in which propylene in the monomer is preferably 90% by weight (described in JP-A No. 9-111055). (3b) An amorphous material comprising a terpolymer of ethylene / propylene / butene and a crystalline polypropylene having a propylene component content of 50% by weight or more (described in JP-A-5-77371). . (3c) The content of propylene and / or 1-butene is 5
0% by weight or more of low-crystalline and crystalline polyolefin such as isotactic polypropylene,
One containing 0.5% by weight of an oil gelling agent (Japanese Patent Laid-Open No. 7-3)
No. 16358).

(4) The hard segment is polyethylene,
A crystalline rubber such as polypropylene or polymethylpentene, and a monoolefin copolymer rubber such as an ethylene / propylene non-conjugated diene terpolymer rubber having a soft segment partially cross-linked (described in JP-B-53-21021) ).

(5) An olefin copolymer (crystalline) as a hard segment and an uncrosslinked monoolefin copolymer rubber as a soft segment are heated and subjected to a shear stress while being partially crosslinked (particularly). Kosho 53-34
No. 210).

(6) A peroxide-decomposable olefin polymer such as an isotactic polypropylene, a propylene / ethylene copolymer, or a propylene / butene copolymer, which has a reduced molecular weight and increased fluidity when mixed and heated with a peroxide. 1
A copolymer as a hard segment, a peroxide-crosslinked monoolefin polymer whose fluidity is reduced by the same operation, for example,
Ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene terpolymer rubber, etc. are used as soft segments. Hydrogen rubber, etc., obtained by mixing and heating in the presence of a peroxide (JP-B-56
No. 15741).

(7) Ethylene / styrene / butadiene copolymer (described in JP-A-2-139232).

(8) The olefin elastomer of the above (1) to (7) having a hydroxyl group or a carboxyl group.

In the present invention, the above-mentioned general polyolefin resin layer for a decorative material is used as a layer of the transparent sheet which is the top layer of the decorative material, which does not participate in the adhesion to the lower layer. Further, in a so-called doubling sheet, the coloring sheet 4 can be constituted without necessarily being a polyolefin resin layer. However, originally, the coloring sheet 4 was replaced with a polyolefin in order to compensate for the drawbacks of the PVC decorative material. Since the mechanical behavior such as expansion and contraction at the time of heating differs between the front and back, it is easy to cause curl of the cosmetic material or peeling when pasted on other articles. It is preferable to select and configure in the range of the resin.

In the present invention, the transparent sheets 1a, 1b
Of these, the lower transparent sheet 1b, which is a surface requiring adhesive strength, is formed of an adhesive polyolefin resin layer. Here, the adhesive polyolefin resin layer is polyethylene,
Maleic acid, acrylic acid, or fumaric acid is ^added to polyolefins, which are polypropylene or ethylene / propylene copolymers, or copolymers thereof with other α-olefins or vinyl acetate, in a broad sense, from 10 ^-4 to 10
It is a layer of an adhesive polyolefin resin obtained by graft copolymerization in a range of 10% by weight, preferably ^{10-3 to} 5% by weight. Of the substances to be graft-copolymerized, maleic acid is preferred. In addition, as long as the effect of improving the adhesiveness is observed, an ordinary polyolefin resin may be melt-mixed in addition to the adhesive polyolefin resin to form the adhesive polyolefin resin layer.

Even if the transparent sheets 1a and 1b are separately formed into a film and laminated with an adhesive, they can be used for the purpose of constituting the decorative material of the present invention. However, a separate lamination process is required, and an adhesive is also required. In order to efficiently form a laminate of the transparent sheets 1a and 1b, a polyolefin resin layer constituting the transparent sheet 1a and an adhesive polyolefin resin layer constituting the transparent sheet 1b are separately heated and melted, and finally, 1
It is good to extrude from two T dies, to use a melt extrusion method, or to form one of the resin layers and then laminate the other resin layer by extrusion coating.

The transparent sheet 1a used in the present invention,
As 1 and 1b, both stretched sheets and unstretched sheets can be used. Various additives such as fillers, matting agents, foaming agents, flame retardants, lubricants, antioxidants, ultraviolet absorbers, or light stabilizers are added to the transparent sheets 1a and 1b as necessary. . The total thickness of the transparent sheets 1a and 1b is 20 to 100 μm, and the ratio of the thickness of the transparent sheets 1a and 1b is 1a / 1b = 2/1 to 10
/ 1. A preferred example is that the transparent sheet 1a has a thickness of 50 μm.
m, the transparent sheet 1b is 10 μm.

In the case of a doubling sheet (an embossed sheet is also referred to as a doubling embossed sheet), the coloring sheet 4 may also be constituted by a polyolefin resin layer. Is adjusted so as to obtain an appropriate hue.
The coloring sheet 4 may have a thickness of about 20 μm to 100 μm. The coloring sheet 4 is not limited to the polyolefin resin layer, and may be another resin-based one. However, if the coloring sheet 4 is formed of the polyolefin resin layer, it is most convenient to avoid the weak points of the conventional PVC decorative sheet. . In addition,
Instead of the colored sheet, a general base material of a decorative material can be used.

The transparent sheets 1a and 1b and the colored sheet 4 may be subjected to a corona discharge treatment on a surface involved in printing or adhesion to improve adhesion. Since the upper surface of the transparent sheet 1a is often laminated with the surface protective layer 5, it is better to perform a corona discharge treatment. The inner surfaces of the transparent sheets 1a and 1b are subjected to a corona discharge treatment as needed, depending on the manufacturing method. The upper surface of the colored sheet 4 is preferably adhered to the pattern layer 2 or the adhesive layer 3, and the lower surface is preferably subjected to a corona discharge treatment in order to secure an adhesive force when applied to an object to be decorated.

For the same purpose, preferably, a primer layer may be formed on the surface after the corona discharge treatment. As the resin constituting the primer layer, polyester resin, polyurethane resin, acrylic resin, polycarbonate resin, vinyl chloride / vinyl acetate copolymer, polyvinyl butyral resin, nitrocellulose resin, etc. can be used, as well as alkyl titanate and ethylene imine resins. Can also be used. These resins and compounds are used alone or as a mixture to form a coating composition or an ink composition, which is then formed into a primer layer using an appropriate coating means or printing means.

The pattern layer 2 is for giving the decorative material of the present invention an appearance design value, and is usually formed by a printing method using ink. At present, there is not much use, but electrophotography, ink jet and the like can be used in principle as a means for forming the pattern layer 2. As a printing method,
A wide selection range of binders in consideration of adhesiveness,
The gravure printing method is suitable, but other methods may be used. The pattern of the pattern layer 2 may be arbitrary, and is selected according to the application. For back print sheets,
Since the pattern layer 2 is viewed from the side of the transparent sheet 1a, in the case of a picture pattern having left and right sides, it is preferable to print using a so-called reverse plate in which the left and right sides are created upside down. In the case of a doubling sheet, when printing on the colored sheet 4 side, the pattern layer 2
It is not necessary to consider the left and right directions of the pattern, but when printing on the back surface of the upper transparent polyolefin resin sheet, it is preferable to use the reverse printing as described above.

In the case of a back print sheet, when the pattern layer 2 is formed of a low density portion or a printed halftone dot, the lower layer can be seen through. Instead, a concealing layer that covers the lower side of the patterned one may be formed together. The concealing layer corresponds to the highlight part of the picture pattern and forms a part of the pattern layer. In the case of a doubling sheet, since the hue of the colored sheet plays the role of the above-mentioned concealing layer, it is usually unnecessary to form a special concealing layer.

When the pattern layer 2 is formed by a printing method, there is a problem of the adhesiveness of the ink to the polyolefin resin layer. Examples of the binder for the ink include those having good adhesion to the polyolefin resin layer, such as a vinyl chloride / vinyl acetate copolymer, an acrylic resin, a polyurethane resin, and a polyamide resin, which are used alone or in combination. In the case where the pattern layer 2 is formed of ink, a coloring agent such as a pigment or a dye contained in the ink tends to have a negative effect on the adhesiveness.
A colorless reducer (also referred to as an extender, a medium, or the like) containing the same binder as the ink used to form the pattern layer 4 of the pattern layer 2 and containing no coloring agent is applied to form a transparent resin layer. If you form it,
The adhesion on the pattern layer 2 is improved, which is preferable.

In the case of a doubling sheet, if it is a PVC decorative sheet, it is usually applied by heat sealing.
When the front side is a polyolefin resin layer, lamination using an adhesive provides more secure adhesion. A colored sheet (or a primer layer on it)
The pattern layer 2 on the lower surface of the transparent sheet 1b (or the pattern layer 2
Between the transparent resin layer formed on the colored sheet, or the pattern layer 2 (or the transparent resin layer formed on the patterned layer 2) formed on the colored sheet and the transparent sheet 1b (or the primer layer thereunder). Is laminated using an adhesive. As the adhesive, a polyurethane resin-based adhesive composed of a polyester polyol and an isocyanate compound is suitable. The adhesive is applied to one or both of the two surfaces to be bonded, and is usually once dried, then, the two are overlaid, heated and Press and adhere.

If the outermost layer of the decorative material of the present invention is left as it is, the physical and chemical properties of the surface may be insufficient. For this reason, the surface protection layer 5 is preferably formed on the upper surface of the transparent sheet 1a. Surface protective layer 5
Is formed using an acrylic urethane resin-based resin or an ionizing radiation-curable resin composition that is cured by irradiation with ultraviolet rays or electron beams, and curing is performed in accordance with each of them. The surface protective layer may contain an anti-wear agent for improving the abrasion resistance of the surface, a matting agent for adjusting the gloss of the surface, and the like. Examples of the former include alumina, silica, or calcium carbonate, and examples of the latter include silica,
Alternatively, there are calcium carbonate, shirasu balloon, resin beads and the like.

In the decorative material of the present invention, when the outermost layer is a polyolefin resin layer, and the lower layer is accompanied by a synthetic resin layer, the lower layer is also made of a polyolefin resin in order to avoid the drawbacks of the conventional PVC decorative sheet. Therefore, when the decorative material is actually used, there is an adverse effect of ultraviolet rays such as sunlight from the transparent sheet side. Since this adverse effect is accompanied by a decrease in the adhesiveness between the laminated layers and, in severe cases, peeling, it is preferable to take measures for this. For this reason, in the decorative material of the present invention, among the layers of the decorative material,
Preferably, an additive consisting of an ultraviolet absorber and a light stabilizer is contained in the upper layer of the portion where peeling easily occurs.

In the case of a back print sheet, an additive is added to at least one of the surface protective layer 5, the transparent sheet 1a and the transparent sheet 1b, and in the case of a doubling sheet,
The above additives are added to at least one of the surface protective layer 5, the transparent sheet 1a or 1b, or the pattern layer 2 or the adhesive layer 3. The part to which the additive is added is preferably the upper layer where the peeling easily occurs, and
Adding the additive to the two layers is more effective in adding the additive to the two layers than adding the additive to one layer.
The layer to which the additive is added may be increased.

To apply an additive comprising an ultraviolet absorber and a light stabilizer, an appropriate amount is kneaded or dispersed in a resin composition, a coating composition or an ink composition for forming a target layer. Thereafter, film formation, application or printing is performed using them. When adding an additive to a transparent sheet or a colored sheet, the additive is heated and melted and mixed together with the resin pellets, or a small amount of resin pellets are added in advance.
A method in which the additives are melt-mixed and melt-mixed with a required amount of resin pellets may be used.

As the ultraviolet absorber, the following (1)-
Something like (5) can be used. (1) Benzophenones; 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxy-benzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2-hydroxy-4-methoxy-benzophenone-5-sulfonic acid. (2) benzotriazole type; 2- (2′-hydroxy-5′-methylphenyl) benzotriazole,
(2′-hydroxy-3′-t-butyl-5′-methylphenyl) -5-chlorobenzotriazole, 2-
(2′-hydroxy-3 ′, 5′-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2′-
Hydroxy-3 ', 5'-dicumylphenyl) phenylbenzotriazole, 2- (2'-hydroxy-3'-
Dodecyl-5'-methylphenyl) benzotriazole, 2,2'-methylenebis [4- (1,1,3,3-
Tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol]. (3) Acrylate; ethyl-2-cyano-3,3 ′
-Diphenyl acrylate, 2-ethylhexyl-2-
Cyano-3,3'-diphenyl acrylate. (4) salicylate; phenyl salicylate, 4-t
-Butylphenyl salicylate. (5) oxanilide; 2-ethoxy-2′-ethyloxalic acid bisanilide, 2-ethoxyxin-5
t-Butyl-2'-ethyloxalic acid bisanilide. The ratio of adding these ultraviolet absorbers is preferably in the range of 0.1 to 2% by weight based on the resin content of the layer to be added. If less than 0.1% by weight, the effect of addition is poor,
Even if it exceeds 2% by weight, no improvement in the effect is observed.

As the light stabilizer, a hindered amine light stabilizer (Hindered Amine Light) is used.
Take the initials of the English name of Stabilizer, H
The following compounds, commonly referred to as ALS, can be used.
Bis- (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis- (N-methyl, 2,2,6,
6, -tetramethyl-4-piperidinyl) sebacate,
[Dimethyl succinate-1- (2-hydroxyethyl)-
4-hydroxy-2,2,6,6, -tetramethylpiperidine] condensate, poly {[6- (1,1,3,3-tetramethylbutyl) imino] -1,3,5-triazine-
2,4-diyl [(2,2,6,6-tetramethyl-4
-Piperidyl) imino] hexamethylene [(2,2,
6,6-tetramethyl-4-piperidyl) iminol]}. The ratio of adding these light stabilizers is preferably in the range of 0.1 to 2% by weight based on the resin content of the layer to be added. If it is less than 0.1% by weight, the effect of addition is poor, and if it exceeds 2% by weight, no improvement in the effect is observed.

Although the ultraviolet absorber and the light stabilizer are effective even when used alone, it is not clear why they are used together, but the effects are synergistically improved. Things are desirable. In addition, the ultraviolet absorber and the light stabilizer are inevitable for bleeding during use, and various measures have been taken. However, for the above-mentioned HALS, for example, 4-acryloyloxy is used for the resin constituting the layer. −
2,2,6,6-tetramethylpiperidine, or 4
-Practical use of technology to prevent bleeding by graft copolymerizing a cyclic amine compound having a (meth) acryloyloxy group such as methacryloyloxy-2,2,6,6-tetramethylpiperidine has been started. Good to use.

As described above, the decorative material of the present invention can be used by being laminated on the substrate 7 via the adhesive layer 6. As described above, when the decorative material of the present invention is a back print sheet, a base material of a general decorative material can be used instead of the colored sheet. The substrate 7 is assumed to be relatively thick, and the base material used in place of the colored sheet is assumed to be relatively thin. However, the present invention is not limited to these, and both are basically Those which are the same and which will be hereinafter described as the substrate 7 can be used in place of the coloring sheet.

As the substrate 7, any material which is generally used as a target to which a decorative material is to be pasted can be used, and if roughly classified, various papers, plastic films or plastic sheets, metal foils , A metal sheet, a metal plate, a wood-based plate such as wood, and various ceramic materials. The materials contained in each of these groups may be used alone, but a laminate of any combination of these materials, such as a composite of paper and a composite of paper and a plastic film, can also be used. These bases may be painted for the purpose of adjusting colors, or may be formed with a normal pattern in advance from the viewpoint of design. Prior to painting or normal pattern formation, the surface may be smoothed or a base treatment may be applied to increase the degree of adhesion of the pattern. After painting or forming a normal pattern, an adhesion improving treatment for facilitating subsequent processing may be performed.

The following are typical examples of various papers. That is, tissue paper, kraft paper,
Titanium paper and resin-impregnated paper which has been impregnated with a resin for the purpose of reinforcing between papers can also be used. In addition to these, a group of raw materials often used in the field of building materials, such as linter paper, paperboard, gypsum board raw paper, or vinyl wallpaper raw material provided with a vinyl chloride resin layer on the surface of paper, may be mentioned. Further, the following papers used in the office field, ordinary printing, packaging, and the like can also be used. That is, it is coated paper, art paper, sulfuric acid paper, glassine paper, parchment paper, paraffin paper, Japanese paper, or the like. Although different from these papers, woven and non-woven fabrics of the following various fibers having the same appearance and properties as paper can also be used as the substrate 1.
Available as The various fibers are inorganic fibers such as glass fibers, asbestos fibers, potassium titanate fibers, alumina fibers, silica fibers, or carbon fibers, or synthetic fibers such as polyester fibers or vinylon fibers.

Examples of the plastic film or plastic sheet include those made of various synthetic resins as exemplified below. Various synthetic resins include polyethylene resin, polypropylene resin, polymethylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, vinyl chloride-vinyl acetate copolymer resin, ethylene-vinyl acetate copolymer Resin, ethylene-vinyl alcohol copolymer resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyethylene naphthalate-isophthalate copolymer resin, polymethyl methacrylate resin, polyethyl methacrylate resin, polybutyl acrylate resin, nylon 6 or Polyamide resin represented by nylon 66, etc.,
Examples include cellulose triacetate resin, cellophane, polystyrene resin, polycarbonate resin, polyarylate resin, and polyimide resin.

The metal foil, metal sheet or metal plate is made of a metal as exemplified below. That is, aluminum, iron, stainless steel, copper, or the like. It is often used after plating. Various wood-based boards include wood boards, plywood, particle boards,
Alternatively, a medium-density fiberboard called MDF may be used. Examples of the ceramic material include ceramic building materials such as gypsum board, calcium silicate plate, and wood chip cement plate, ceramics, glass, enamel, and fired tile. In addition to these, composites of various materials such as a fiber reinforced plastic plate, a paper honeycomb having iron plates stuck on both sides, and a two aluminum plate sandwiched by a polyethylene resin can also be used as the base 1.

The adhesive layer 6 for bonding the decorative material of the present invention to the substrate 7 is formed using an adhesive selected in consideration of the adhesiveness between the decorative material and the substrate 7. The adhesive includes a thermoplastic resin adhesive and a thermosetting resin adhesive.

Examples of the thermoplastic resin adhesive include polyvinyl acetate resin, polyvinyl alcohol, polyvinyl acetal (polyvinyl formal, polyvinyl butyral, etc.), cyanoacrylate, polyvinyl alkyl ether, polyvinyl chloride, polyamide, polymethyl methacrylate, nitromethyl Examples include cellulose, cellulose acetate, thermoplastic epoxy, polystyrene, ethylene-vinyl acetate copolymer, or ethylene-ethyl acrylate copolymer.

Examples of the thermosetting resin adhesive include urea resin, melamine resin, phenol resin, resorcinol resin, furan resin, epoxy resin, unsaturated polyester resin, polyurethane resin, polyimide, polyamideimide, polybenzimidazole, and polybenzo. Thiazole and the like. As a rubber (elastomer) adhesive,
Natural rubber, recycled rubber, sutylene-butadiene rubber, acrylonitrile-butadiene rubber, chloroprene rubber,
Butyl rubber, polysulfide rubber, silicone rubber, polyurethane rubber, stereo rubber (synthetic natural rubber), ethylene propylene rubber, block copolymer rubber (SB
S, SIS, SEBS, etc.).

Examples of natural adhesives include low molecular adhesives (pine, polyterpene, wax), polysaccharides (starch,
Denatured starch, gum arabic) and proteins (casein, gelatin, glue) and the like.

[0055]

(Example 1) A colored polypropylene resin sheet having a thickness of 60 μm was prepared by subjecting both sides of the sheet to corona discharge treatment, and a two-component curable acrylic urethane resin ink was used for the colored polypropylene resin sheet. Then, a pattern layer was formed by printing to obtain a printed sheet. The colored polypropylene resin sheet used here was prepared by adding a polypropylene resin, hydrogenated butadiene / styrene rubber, calcium carbonate as a filler, and titanium dioxide and ferric oxide as a coloring material, melting, kneading and slitting. It is extruded from and made into a sheet.

The printing surface of the obtained printing sheet was coated with a two-component curable acrylic urethane resin adhesive at a rate of 6 g / m ² (at the time of drying), dried with a drying hood provided in the coating machine, and then dried. At the outlet side of the hood, two layers, a maleic acid-containing polypropylene resin layer and an ethylene-propylene-butene terpolymer resin layer, are co-extruded so that the former has a thickness of 10 μm and the latter has a thickness of 50 μm. Then, the polypropylene resin layer containing the maleic acid component was overlapped so as to be in contact with the surface to which the adhesive was applied, and pressure was applied between nip rollers to perform lamination.

The laminated body was heated by a preheater installed on the exit side of the nip roller, and immediately embossed using an embossing roll. After embossing, use a gravure roll coater on the entire surface on the front side, and use an acrylic urethane-based resin. Further, on top of the ethylene-propylene-butene terpolymer resin layer, which is the uppermost layer, a top coat layer Was formed. The peel strength of the laminate part of the obtained decorative material is 2.7 kg / cm.
Met.

(Comparative Example 1) As in Example 1, except that
Instead of forming two layers, a polypropylene resin layer containing a maleic acid component and an ethylene-propylene-butene terpolymer resin layer, only the ethylene-propylene-butene terpolymer resin layer has a thickness of 60 μm. And laminated, and ethylene-propylene-butene 3
In order to compensate for the low adhesiveness of the base copolymer resin layer, the applied amount of the adhesive was set to 12 g / m ² (at the time of drying), which was twice that of Example 1. The decorative material obtained in Comparative Example 1 had a peel strength of 2.2 kg / cm and low adhesiveness.

[0059]

According to the first aspect of the present invention, since the lower layer of the polyolefin layer formed on the base material of the decorative material is formed of the adhesive polyolefin resin layer, the peel strength between the base material and the polyolefin layer is improved. We can provide cosmetic materials.

According to the invention of claim 2, in addition to the effect of the invention of claim 1, it is possible to provide a decorative material having improved adhesion when polypropylene is laminated on a substrate.

According to the third aspect of the invention, in addition to the effects of the first aspect, the adhesive resin comprises a polypropylene resin layer having an acid component, and the side opposite to the substrate is ethylene-propylene-butene. The decorative material according to claim 1, wherein two polyolefin-based resin layers each comprising a layer of the copolymer resin are laminated.

According to the fourth aspect of the present invention, in addition to the effects of the first aspect of the present invention, since the polypropylene homopolymer resin containing the non-crystalline polypropylene is used, the adhesiveness with the base material is excellent. I have.

According to the fifth aspect of the invention, in addition to the effects of the first aspect, the polyolefin resin layer formed on the substrate has a three-layer structure, so that the properties required for a transparent sheet close to the surface can be obtained. The middle layer can be contracted to provide a transparent sheet with high adhesion between the top and bottom surfaces.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of an example of the decorative material of the present invention.

FIG. 2 is a sectional view of another example of a decorative material according to the present invention.

FIG. 3 is a cross-sectional view when a surface protective layer and a substrate are laminated on the decorative material of FIG. 1;

FIG. 4 is a cross-sectional view when a surface protective layer and a substrate are laminated on the decorative material of FIG. 2;

[Explanation of symbols]

 1a Transparent sheet 1b Adhesive transparent sheet 2 Pattern layer 3 Adhesive layer 4 Colored sheet 5 Surface protective layer 6 Adhesive layer 7 Substrate

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4F100 AA08H AA21H AA23H AK03B AK03C AK04C AK04J AK07C AK07J AK09C AK09J AK51 AK51G AK70B AK70D AK73 AK80C AL01C AL06 AT00ABA BABA BA03 BA03 BA03 BA03 BA03 HB00 HB31 JA12C JK06 JL12B JL12D JN01

Claims (5)

[Claims] 1. A polyolefin-based resin layer composed of a plurality of two or more layers is laminated on a base material, and at least the polyolefin-based resin layer facing the base material is an adhesive polyolefin resin layer. A cosmetic material characterized by that. 2. A two-layer polyolefin resin layer comprising a layer of a polypropylene resin having a maleic acid component on the side facing the substrate and a layer of a polypropylene homopolymer resin on the side opposite to the substrate. Item 4. The cosmetic material according to Item 1. 3. A two-layer polyolefin resin layer comprising a polypropylene resin layer having a maleic acid component on the side facing the substrate and a layer of an ethylene-propylene-butene copolymer resin on the side opposite to the substrate. The decorative material according to claim 1, wherein is laminated. 4. The polyolefin-based resin layer laminated on the base material is composed of two polyolefin-based resin layers on the side opposite to the base material, the layer being composed of a polypropylene homopolymer resin containing amorphous polypropylene. The decorative material according to claim 1, wherein: 5. The decorative material according to claim 1, wherein the polyolefin resin layer is composed of three layers, and the front and back two layers are composed of a polyolefin resin layer having a maleic acid component.