JP2000185379A - Decorative material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To eliminate deterioration due to ultraviolet rays, especially, interlaminar delamination to be generated when a decorative material constituted by using a polyvinyl chloride resin sheet is replaced with a chlorine-free polyolefinic resin sheet. SOLUTION: A decorative material consists of a base material sheet 8, a primer layer 4, a pattern layer 5, an adhesive layer 6, a transparent polyolefinic resin sheet 3 and a topcoat layer 2. In this case, a light stabilizer and/or an oxidation inhibitor and an ultraviolet absorber are compounded with the topcoat layer 2, the transparent polyolefinic resin sheet 3 or the adhesive layer 6, especially, the transparent polyolefinic resin sheet 3 to obtain the decorative material high in durability.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate mainly composed of a synthetic resin, which is applied to the surface of miscellaneous goods, the surface of furniture, the surface of building materials used indoors and outdoors, and the like. The present invention relates to a material used as an artificial cosmetic material used for the purpose of protection of an object. The decorative material of the present invention contains an additive comprising an ultraviolet absorber and a light stabilizer in some of the layers constituting the laminate.

[0002]

2. Description of the Related Art Various kinds of materials are used as decorative materials. Among them, there is a so-called "PVC decorative material" using a polyvinyl chloride resin sheet as a material. One of the typical types of PVC decorative material is printing on the back of a transparent polyvinyl chloride resin sheet, followed by providing a concealing layer, and embossing the front side with paint and irregularities as needed. To obtain a “back print sheet”.
Another typical type is obtained by printing on a colored polyvinyl chloride resin sheet, heat-sealing a transparent polyvinyl chloride resin sheet over the printed surface, and simultaneously performing embossing and the like. "Double embossing sheet"
Alternatively, it is simply called a “doubling sheet”.

[0003] A polyvinyl chloride resin sheet used for a PVC decorative material is usually a vinyl chloride / vinyl acetate copolymer, and has a portion of vinyl acetate which contributes to adhesiveness. There is almost no shortage of adhesive strength during printing or lamination. Since the polyvinyl chloride resin sheet is softened by heating, processing such as embossing is easy. Also, as long as there is no burning thing in the vicinity of the polyvinyl chloride resin sheet in the event of a fire,
There is also an advantage that it does not burn itself, that is, there is no self-combustion.
Furthermore, the polyvinyl chloride resin sheet has the advantage that the degree of hardness and softness can be freely adjusted by adding a plasticizer, and the 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.

[0004] However, while the polyvinyl chloride resin sheet has the above advantages, it also has disadvantages. Since polyvinyl chloride resin contains chlorine in its structure, it is inevitable that the polyvinyl chloride resin discolors with time. During combustion, toxic gases can be generated and, if burned, smoke is generated. There are also various problems caused by containing a plasticizer.

Therefore, recently, a polyolefin resin decorative material in which a polyvinyl chloride resin sheet is replaced with a polyolefin resin sheet containing no chlorine has been studied.
However, polyolefin resin sheets originally have poor adhesiveness, and have problems in printing and laminating.
Further, the durability and weather resistance to light such as sunlight were not sufficient.

For example, in the case of a back print sheet using a polyolefin resin sheet, if primer coating is performed before printing on the back surface, peeling occurs between the polyolefin resin sheet and the primer, When the protective layer is formed, there is a drawback that the protective layer is peeled off in a test in which a cellophane tape is stuck and suddenly peeled off.

In a doubling sheet using a polyolefin-based resin sheet, heat fusion is difficult,
Lamination is performed by dry lamination, but there is a drawback that the polyolefin resin sheet on the surface is peeled off by an ultraviolet weathering test equivalent to one year of outdoor exposure, and if an overcoat layer is provided on the surface of the polyolefin resin sheet, As in the case of the back print sheet, there is a disadvantage that the overcoat layer is peeled off.

As a result of various studies conducted by the inventor, the portions that are easily peeled off are: (1) between the polyolefin resin sheet and the printing primer in the back print sheet; and (2) in the doubling sheet, ) Between the base sheet and the printing primer (b) It was found to be between the top sheet and the adhesive.

[0009]

SUMMARY OF THE INVENTION Accordingly, the object of the present invention is to provide, as described above, a cosmetic material which is currently constructed using a polyvinyl chloride resin sheet, by using a chlorine-free polyolefin. An object of the present invention is to eliminate deterioration caused by ultraviolet rays, particularly peeling occurring between layers, which occurs when a resin sheet is substituted.

[0010]

Means for Solving the Problems The inventor of the present invention has made it possible to add an additive consisting of a light stabilizer and / or an antioxidant in addition to an ultraviolet absorber to an upper layer of a portion where peeling is likely to occur. The present inventors have found that the peeling, which has been a problem in the art, is improved, and arrived at the present invention.

According to a first aspect of the present invention, an overcoat layer, a transparent polyolefin-based resin sheet, and a pattern layer are sequentially laminated from the surface side, and at least one of the overcoat layer and the transparent polyolefin-based resin sheet is provided with an optical coating. The present invention relates to a cosmetic material containing an additive comprising a stabilizer and / or an antioxidant and an ultraviolet absorber. The second invention relates to the decorative material according to the first invention, wherein a primer layer is laminated between the transparent polyolefin-based resin sheet and the pattern layer. In a third aspect, an overcoat layer, a transparent polyolefin-based resin sheet, an intermediate layer composed of a pattern layer and an adhesive layer, and a base sheet are sequentially laminated from the front side, and the overcoat layer, the transparent polyolefin-based resin are provided. The present invention relates to a decorative material characterized in that a light stabilizer and / or an antioxidant and an additive comprising an ultraviolet absorber are contained in at least one of the sheet and the adhesive layer. The fourth invention relates to a decorative material according to the third invention, wherein a primer layer is laminated between the base sheet and the pattern layer. The fifth invention is
In any one of the first to fourth inventions, the ultraviolet absorber is
The present invention relates to a cosmetic material characterized by being an ultraviolet absorber comprising a benzotriazole compound. The sixth invention relates to a cosmetic material according to any one of the first to fourth inventions, wherein the light stabilizer is a hindered amine light stabilizer. The seventh invention relates to a cosmetic material according to any one of the first to fourth inventions, wherein the antioxidant is an antioxidant comprising a hindered phenol compound. In an eighth aspect based on any one of the first to fourth aspects, the antioxidant is an antioxidant consisting of a hindered phenol compound and an antioxidant consisting of a phosphite aromatic ester compound.
The present invention relates to a decorative material characterized by being composed of different types.

[0012] As shown in FIG.
From the upper side of the figure (corresponding to the front side of the product), there are an overcoat layer 2, a transparent polyolefin-based resin sheet 3, a primer layer 4, a pattern layer 5a, and a concealing layer 5b, and these layers are laminated in this order. is there. What is shown in FIG.
It is a back print sheet. Also, as shown in FIG.
Another type of decorative material 1 of the present invention comprises an overcoat layer 2, a transparent polyolefin-based resin sheet 3, an adhesive layer 6
And an intermediate layer 7 composed of a picture pattern layer 5, a primer layer 4,
It consists of a base sheet 8 and these layers are laminated in this order. The one shown in FIG. 2 is often called a doubling embossed sheet if embossed, or a doubling sheet if not embossed.

The upper surface of the transparent polyolefin resin sheet 3 shown in FIGS. 1 and 2 may be subjected to a corona discharge treatment for the purpose of improving the adhesion of the overcoat layer 2. In the case of a doubling embossed sheet, the corona discharge treatment is preferably performed after embossing. Although not shown, a concave portion such as a wood grain conduit groove may be formed by embossing, and the concave portion may be filled with a coloring material, that is, a so-called wiping coating may be applied.

The overcoat layer 2 is obtained by applying, drying or solidifying a coating composition containing an appropriate binder resin. As the binder resin, a thermoplastic resin may be used, but a thermosetting resin composition using a thermosetting resin, or an ionizing radiation-curable resin composition that is cured by irradiation with ultraviolet light or an electron beam, and is applied. The physical and chemical performances can be further improved by subsequently heating or irradiating with ionizing radiation for crosslinking and curing.
For example, a polyurethane-based coating composition such as an acrylic urethane based on an acrylic polyol and an isocyanate compound may be used. The overcoat layer 2 is preferably provided as much as possible, but can be omitted when the required degree of weather resistance is low.

There are various types of polyolefin resins constituting the polyolefin resin sheet 3. When roughly classified, polyolefin resins which are non-elastomers and
There is a polyolefin-based thermoplastic elastomer.

One type of polyolefin resin constituting the polyolefin resin sheet 3 is a non-elastomer, and specifically, polyethylene (low density or high density), polypropylene (isotactic type, syndiotactic type, or These are high-crystalline ones such as mixed type, polymethylpentene, polybutene, ethylene / propylene copolymer, and propylene / butene copolymer. Another type of the polyolefin-based resin constituting the polyolefin-based resin sheet is a polyolefin-based thermoplastic elastomer, as described in the following (1) to (8).

(1) The main raw material is made of high-density polyethylene or isotactic polypropylene as 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 / 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 obtained by adding at least one polyene copolymerizable with two or three or more olefins. As the olefin, ethylene, propylene, α-olefin, or the like is used. , 1,4-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 and isobutylene as butene. The following (3a) to (3c) are typical. (3a) A tertiary random copolymer of ethylene / propylene / butene in which propylene in the monomer is preferably 90% by weight (described in JP-A-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 shear stress while being partially crosslinked (particularly). Kosho 53-34
No. 210).

(6) A peroxide-decomposable olefin polymer, such as isotactic polypropylene, propyne / ethylene copolymer, or propylene / butene-, which has a reduced molecular weight and increased fluidity when mixed and heated with peroxide. (1) A peroxide-crosslinked monoolefin polymer in which fluidity is reduced by a similar operation using a copolymer as a hard segment, for example, ethylene / propylene copolymer rubber, ethylene / propylene / non-conjugated diene terpolymer rubber Is a soft segment, and is obtained by mixing and heating a peroxide non-crosslinked hydrocarbon rubber which does not crosslink and does not change its fluidity by the same operation in the presence of a peroxide ( 56-1
No. 5741).

(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.

The polyolefin resin sheet 3 includes:
Either a stretched sheet or an unstretched sheet can be used.
Various additives such as a filler, a foaming agent, a flame retardant, a lubricant, an antioxidant, a processing stabilizer, an ultraviolet absorber, and a light stabilizer are added to the polyolefin resin sheet 3 as necessary. . The thickness of such a polyolefin-based resin sheet is about 20 to 300 μm. In the case of a doubling sheet or a doubling embossed sheet, the base sheet 8 may also be formed of a polyolefin-based resin sheet, in which case, a coloring agent of a dye or a pigment is added,
If necessary, the above additives are also added to obtain a colored sheet having an appropriate color. In addition, polyolefin resin sheet,
Since the adhesiveness is poor as it is, it is preferable to improve the adhesiveness by performing a corona discharge treatment on a surface involved in printing or adhesion.

When the transparent polyolefin-based resin sheet 3 or the base material 2 is a colored polyolefin-based resin sheet, the primer layer 4 is used to enhance the adhesion of the pattern layer 5 or 5a. Since the resin sheet has poor adhesiveness, it is preferable to interpose the primer layer 4 therebetween. Examples of the resin constituting the primer layer include a polyester resin, a polyurethane resin, an acrylic resin, a polycarbonate resin, a vinyl chloride / vinyl acetate copolymer, a polyvinyl butyral resin, and a nitrocellulose resin. These resins may be used alone or as a mixture to form a coating composition or an ink composition,
Alternatively, the primer layer 4 is formed using a printing means.

The picture pattern layer 5a is for giving the decorative material of the present invention an appearance design value, and is usually formed by a printing method. A gravure printing method in which the selection range of the binder in consideration of the adhesiveness is wide is suitable, but other methods may be used. The pattern of the pattern layer 5a may be arbitrary, and is selected according to the application. In the case of the back print sheet, since it is viewed from the side opposite to the side where the pattern pattern layer 5a is provided, in the case of a pattern with left and right,
Printing is performed using a so-called reverse version in which the left and right sides are created in reverse.
In the case of the doubling embossed sheet, if printing is performed on the base sheet 8 side, it is not necessary to consider the left and right directions of the pattern layer 5, but printing is performed on the back side of the upper transparent polyolefin resin sheet. In this case, printing is performed using a reverse printing.

In the case of the back print sheet, the lower layer can be seen through between the low-density portions of the pattern layer 5a and between the halftone dots of printing, so that the pattern layer 5a can be used as the pattern layer.
It is preferable to form not only a but also a concealing layer 5b that covers the lower side of the patterned one. The concealing layer 5b corresponds to the highlight portion of the picture pattern, and forms a part of the picture pattern layer.

Although the description of each layer in FIG. 2 is the same as the description of each layer of the decorative material shown in FIG. 1, the adhesive layer 6 and the base sheet 8, which do not appear in FIG. 1, will be described.

The adhesive layer 6 is a laminate of a pattern layer formed on the base sheet 8 with or without a primer layer and a transparent polyolefin resin sheet. In this bonding, since there is no permeability of the adhesive on any side to be bonded, the adhesive is applied to one or both of the surfaces to be adhered, then dried once, again laminated, pressurized, and pressed. Dry lamination is suitable. As the adhesive, it is preferable to use a polyurethane-based adhesive such as an acrylic urethane-based adhesive composed of an acrylic polyol and an isocyanate.

In FIG. 2, the adhesive layer 6 and the pattern layer 5 in the doubling sheet are composed of a base sheet (a primer layer may be laminated) and a transparent polyolefin resin sheet provided with the primer layer 4. It is located between the back side. As described above, the pattern layer 5 may be formed on the base sheet side 8 or may be provided on the back side of the transparent polyolefin-based resin sheet 3, so that the adhesive layer 6 and the pattern layer 5 may be upside down. It can be reversed. When the pattern layer 5 is formed on the side of the transparent polyolefin-based resin sheet, if a plurality of colored polyolefin-based resin sheets as base sheets having different hues are prepared, the pattern is common, and Cosmetic materials with different colors can be used.

The base sheet 8 gives the decorative material shown in FIG. 2 a thickness and rigidity, enhances the adhesiveness to an object to be affixed, gives a necessary degree of strength to the entire decorative material, or performs processing such as bending. It occupies the bottom layer for the purpose of giving ease, etc.
It also has a role as the above-mentioned concealing layer, and is usually used after being colored so as to have an appropriate color. As the base sheet 8, as the base 1, any material that is usually used for a decorative material can be used.
It can be roughly classified into various papers, plastic films or plastic sheets, metal foils, metal sheets and the like. 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 substrates may be colored or coated at the time of manufacture for the purpose of adjusting the color.

The following are typical examples of various papers that can be used as the material of the base sheet 8. That is, thin paper, kraft paper, titanium paper, and resin-impregnated paper that has been impregnated with a resin in advance 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 or nonwoven fabrics of the following various fibers having the same appearance and properties as paper can also be used as the base sheet 8. 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 sheet that can be used as a material of the base sheet 8 include polyethylene resin, polypropylene resin, polymethylene resin, polymethylpentene resin, polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, and 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, polymethacrylic acid Ethyl resin, polybutyl acrylate resin, nylon 6
Or a polyamide resin represented by nylon 66, a cellulose triacetate resin, a cellophane, a polystyrene resin, a polycarbonate resin, a polyarylate resin, a polyimide resin, or the like. The above-mentioned materials for the polyolefin resin sheet 3 can also be used. However, when the surface is composed of a polyolefin-based resin sheet, it is preferable that the substrate sheet is composed of a polyolefin-based resin containing no chlorine, since the significance of substituting the polyvinyl chloride resin sheet is not impaired.

The metal foil and the metal of the metal sheet that can be used as the base sheet 8 are aluminum, iron, stainless steel, copper, or the like. It is often used after plating.

In the present invention, an additive consisting of a light stabilizer or an antioxidant is contained in the upper layer of the layer where peeling is likely to occur, in addition to the ultraviolet absorber. In the case of a back print sheet, an additive is added to one or both of the overcoat layer 2 and the transparent polyolefin resin sheet 3.
In the case of a doubling sheet or a doubling embossed sheet, the above additives are added to one or more of the three layers of the overcoat layer 2, the transparent polyolefin-based resin sheet 3, and the adhesive layer 6. . Depending on which layer is added, when it is added to only one layer, it may be added to two layers, and in the case of a doubling sheet or a doubling embossed sheet, it may be added to three layers. It is more effective to add the additive to the two layers than to the additive in one layer, and it is more effective to add the additive to the doubling sheet.

To apply an additive comprising an ultraviolet absorber and a light stabilizer to the overcoat layer 2 and the adhesive layer 6, an appropriate amount is added to a coating composition or an ink composition for forming these layers. After kneading or dispersing, they are used for coating or printing. When the polyolefin-based resin sheet 3 or the base sheet is a colored polyolefin-based resin sheet, when manufacturing the sheet, the additives are mixed with the polyolefin-based resin pellets by heating and melting, or
Alternatively, a method in which an additive is previously melt-mixed in a small amount of resin pellets and melt-mixed with a required amount of resin pellets may be used.

As the ultraviolet absorber, the following (1)-
It can be used by selecting from those classified into groups as in (5). (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 (commercially available; Ciba Geigy, Tinuvin P), 2- (2′-hydroxy-3′-t-butyl-) 5'-methylphenyl)
-5-chlorobenzotriazole (commercially available; Ciba Geigy, Tinuvin 326), 2- (2'-hydroxy-
3 ′, 5′-di-t-butylphenyl) -5-chlorobenzotriazole (commercially available; Ciba Geigy, Tinuvin 327), 2- (2′-hydroxy-3 ′, 5′-dicumylphenyl) phenyl Benzotriazole, 2-
(2′-hydroxy-3′-dodecyl-5′-methylphenyl) benzotriazole, 2,2′-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6
(2H-benzotriazol-2-yl) phenol]
(Commercial product; Ciba Geigy, Tinuvin 360), 2-
[2′-hydroxy-3 ′, 5′-bis (α, α′-dimethylbenzyl) phenyl] -2H-benzotriazole (commercially available; Ciba Geigy, Tinuvin 234), 2
-(3 ', 5'-di-t-butyl-2-hydroxyphenyl) benzotriazole (commercially available; Ciba Geigy, Tinuvin 320), 2- (3', 5'-di-t-butyl-2-) (Hydroxyphenyl) -5-chlorobenzotriazole (commercial product; Ciba Geigy, Tinuvin 32)
7), 2- (3 ′, 5′-di-t-amyl-2-hydroxyphenyl) benzotriazole (commercial product; Ciba Geigy, Tinuvin 328), 2- (2′-hydroxy-5′-t-) Octylphenyl) benzotriazole (commercially available; Tinuvin 329, manufactured by Ciba-Geigy).

(3) Acrylates: ethyl-2-cyano-3,3'-diphenylacrylate, 2-ethylhexyl-2-cyano-3,3'-diphenylacrylate. (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.

When a benzotriazole-based UV absorber is used in the production of the polyolefin resin sheet when used in the production of the polyolefin resin sheet, the UV absorber is less likely to evaporate. Sometimes effective enough, there is no need to mix a large amount in anticipation of volatilization, and mist is not generated by volatilization and does not contaminate sheet manufacturing equipment and processing machines and their surroundings, During the embossing, there is an advantage that contamination of the embossing plate, the embossing roll and the like is small. This is because if the embossing plate or the embossing roll becomes contaminated, contaminants adhere to the surface of the decorative sheet and impair the appearance of the product. Among the benzotriazole-based ultraviolet absorbers, in particular, 2,2′-methylenebis [4-
(1,1,3,3-tetramethylbutyl) -6- (2H
-Benzotriazol-2-yl) phenol] (commercial product; Ciba Geigy, Tinuvin 360) has the above advantages. The reason is considered to be that this compound has a structure in a dimer, and thus has a molecular weight about twice that of other benzotriazole-based ultraviolet absorbers. The ratio of adding these ultraviolet absorbers is preferably 0.1 to 10% based on the resin content of the layer to be added.
It is 2% by weight, more preferably 1% by weight or less. 0.1
If it is less than 2% by weight, the effect of addition is poor, and if it exceeds 2% by weight, the effect is not improved.

As the light stabilizer, the following compounds which are hindered amines can be used. Bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate (commercial product; Ciba Geigy, Tinuvin 123), bis- (2,2,6,6-tetramethyl-
4-piperidinyl) sebacate, bis- (N-methyl,
2,2,6,6-tetramethyl-4-piperidinyl)
Sebacate, [dimethyl-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine] succinate condensate (commercially available; Ciba Geigy, Tinuvin 622), 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]｝ (commercial product; CibaGeigy, Timasolv 94)
4), N, N'-bis (3-aminopropyl) ethylenediamine-2,4-bis [N-butyl-N- (1,2,
2,6,6-pentamethyl-4piperidyl) amino]-
6-chloro-1,3,5-triazine condensate (commercial product;
Cimasorb 119, manufactured by Ciba-Geigy.

The ratio of adding these light stabilizers is preferably 0.1 to 2 with respect to the resin content of the layer to be added.
% By weight, more preferably 1% by weight or less. 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 effect is seen. In addition, although the ultraviolet absorber and the light stabilizer are effective even when each is used alone, it is preferable to use them together, although the reason is not clear, but the effect is synergistically improved. .

Another additive used with UV absorbers is an antioxidant. Some of the concepts of the antioxidant are called processing stabilizers, heat stabilizers and the like because of the meaning of use. Examples of the antioxidant include the following hindered phenol compounds or phosphorus compounds (phosphites).

(1) Hindered phenol type: 2,4-
Bis- (n-octylthio) -6- (4-hydroxy-
3,5-di-t-butylanilino) -1,3,5-triazine (commercially available; Ciba Geigy, Irganox 5)
65), pentaerythrityl-tetrakis [3- (3,
5-di-t-butyl-4-hydroxyphenyl) propionate] (commercially available; Ciba Geigy, Irganox 1010), 2,2-thio-diethylenebis [3-
(3,5-di-t-butyl-4-hydroxyphenyl)
Propionate] (commercially available; Ciba Geigy, Irganox 1035), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (commercially available; Ciba Geigy, Irganox 107)
6), 1,3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl)
Benzene (commercially available; Ciba Geigy, Irganox 1330). (2) Phosphorus (phosphorous aromatic ester); tris (2,4-di-t-butylphenyl) phosphite (commercially available; Ciba Geigy, Irgafos 168).

Although the above hindered phenol compound antioxidant is effective when used alone, there is an advantage that a great effect can be obtained when used in combination with a phosphorus compound (phosphite) antioxidant. . Further, an antioxidant of a phosphorus compound (phosphite) may be called a processing stabilizer. The ratio of adding the above antioxidant is
Preferably from 0.05 to the amount of the resin to be added.
0.2% by weight.

The above-mentioned decorative material of the present invention is applied to the surface of miscellaneous goods and furniture, the surface of building materials used indoors and outdoors, and the like, and is used for the purpose of decoration of the surface and protection of the lower layer. It is used as a decorative material, and is manually applied to an object, or mechanically applied to a plate-like object using a laminator, or applied using vacuum and / or compressed air molding, or conveyed. The sheet is affixed to a target having an irregular cross section, such as a sash, by a method of folding the sheet little by little and sticking it along the conveyance.

[0048]

EXAMPLES (Example 1) In order to describe a sample in which an additive was added to each layer of a back print sheet and a doubling sheet and to evaluate the evaluation results, first, a sample preparation and a test method were described in the following order. explain.

(Preparation of back print sheet sample) A transparent sheet (thickness: 80 μm) of a polypropylene-based thermoplastic elastomer comprising a polypropylene random copolymer as a hard segment and a hydrogenated styrene / butadiene rubber as a soft segment was prepared. Critical surface tension is 38 dyn / cm by corona discharge treatment on both sides
It was adjusted to become. A polyester urethane-based primer-forming composition containing polyester polyol and hexamethylene diisocyanate as resin components is used on one side of the transparent sheet, and the thickness is 2 μm by gravure coating.
m was formed as a primer layer.

Subsequently, on the primer layer, a gravure printing method using an ink composition containing acrylic polyol and hexamethylene diisocyanate as a binder was used.
A pattern layer and a hiding layer were formed. Thereafter, the pattern layer of the transparent sheet, and the surface opposite to the side on which the concealing layer was formed, by gravure coating using a composition for forming an overcoat layer containing acrylic polyol and hexamethylene diisocyanate as a resin component, to obtain a thickness, An overcoat layer of 3 μm was formed.

In the above, 2- (2'-hydroxy-3 ', 5'-dicumylphenyl) phenylbenzotriazole as an ultraviolet absorber and bis- (2,2,6,6-
An additive consisting of (tetramethyl-4-piperidinyl) sebacate was added to each layer. In order to see the effect of the additive, the total of the additive added only to the overcoat layer, the additive added only to the transparent sheet, the additive added to both the overcoat layer and the transparent sheet, and the additive not added to any of them for comparison Four adjustments were made. In addition, the addition amount is such that the ultraviolet absorber is 0.8% by weight based on the resin content of each layer,
The light stabilizer was adjusted to 0.4% by weight.

(Preparation of doubling sheet sample) The same transparent sheet as that of the back print sheet was prepared.
As the colored sheet, the same sheet as that of the transparent sheet was prepared by adding a pigment to the same resin as that of the transparent sheet and colored, and both sheets were subjected to corona discharge treatment on both surfaces in the same manner as in the case of the back print sheet. First, a primer layer and a pattern layer were sequentially formed on one side of a colored sheet using the same composition and means as in the case of the back print sheet.

Next, the painted layer side of the colored sheet and one surface of the transparent sheet were dried using an acrylic urethane-based adhesive having acrylic resin and hexamethylene diisocyanate as a resin, and the coating amount when dried was 15 g / m 2. ² was applied, and bonding was performed by dry lamination. After lamination, a thickness of 3 mm is applied to the surface of the transparent sheet using the same composition and means as in the case of the back print sheet.
An overcoat layer of μm was formed.

In the case of this doubling sheet, an additive consisting of an ultraviolet absorber and a light stabilizer was added to each layer of the overcoat layer, the transparent sheet, and the adhesive layer. All the added additives are the same as in the case of the back print sheet,
To see the effect of the addition, add the additive to the overcoat layer, transparent sheet,
Or those added to only one of the adhesive layers,
A total of eight samples were prepared, each of which was added to any two layers, added to three layers, and not added to any layer. The proportion of the additive was the same as that in the back print sheet.

The test and evaluation of the sample prepared as described above were performed by the following tests A, B and C. (Test A) Test A is for observing the weathering adhesion strength of the overcoat layer, and is performed commonly for the back print sheet and the doubling sheet. An ultraviolet weathering tester (Iwasaki Electric Co., Ltd., Super UV tester, SUV-W13)
The test was conducted using a black mold at a temperature of 63 ° C. and a humidity of 70% RH for 20 hours, and then left for 4 hours after dew condensation for a total of 2 hours.
The test is performed for 5 cycles, ie, 120 hours (corresponding to 2 years in outdoor exposure), with 4 hours as 1 cycle. After the test,
Using a cutter knife from the top coating layer side of the sample, cuts reaching the transparent sheet were formed in a grid pattern at 2 mm intervals, and a cellophane tape was stuck on the grid-shaped cuts and peeled off vigorously. Then, it is observed whether the overcoat layer peels off. The evaluation criteria are x when the topcoat layer is removed from the cellophane tape and peeled off, and o when the topcoat layer is not peeled off.

(Test B) Test B is for observing the weather resistance of the pattern layer of the back print sheet.
The cosmetic material of the sample was attached to the surface of MDF (= medium density fiberboard) using an adhesive obtained by adding an isocyanate to an emulsion of polyvinyl acetate resin to form a sample piece. The test is performed for 120 hours using a test machine. After that, peel the transparent sheet from the sample piece,
At that time, the state of peeling of the picture pattern layer is observed. The evaluation criteria are x when the pattern layer remains on the substrate side while adhering to it, o when the pattern layer adheres and adheres to the transparent sheet, and 、 in the middle.

(Test C) In test C, the weathering adhesion strength between two doubling sheets is observed. The sample cosmetic material is subjected to a test for 120 hours using an ultraviolet weathering tester in the same manner as in Tests A and B. After the test, the transparent sheet and the colored sheet are peeled, and the peel strength at that time is observed. As criteria for evaluation, a peel strength of less than 0.5 kg / 25 mm was evaluated as x, and 0.5 kg / 25 mm or more and 1.0 kg / 25 mm.
Less than Δ is 1.0 kg / 25 mm or more.

Table 1 shows the presence / absence of additives in each layer of the back print sheet and the test results. As shown in Table 1, when added to only one layer, the adhesion strength between that layer and the lower layer was improved, and when added to both, all resulted in satisfactory results. I have.

[0059]

[Table 1]

Table 2 shows the presence / absence of additives in each layer of the doubling sheet and the test results. As shown in "Table 2," those added to the overcoat layer improved the adhesion strength of the overcoat layer, and when added to either the transparent sheet or the adhesive layer, the adhesion strength of the pattern layer was improved. Is not sufficient, but is improved, and when added to both the transparent sheet and the adhesive layer, the adhesion strength of the pattern layer becomes satisfactory, and the overcoat layer, the transparent sheet, and the adhesive layer When it was added, both the adhesion strength of the overcoat layer and the adhesion strength of the picture pattern layer resulted in satisfactory results.

[0061]

[Table 2]

Example 2 Various doubling embossed sheets, which are susceptible to heat during production, obtained by adding an ultraviolet absorbent and other additives to an upper transparent polyolefin resin-based sheet, were evaluated. Was.

As a base sheet, a colored polyolefin resin sheet having a thickness of 0.06 mm (Mitsubishi Chemical MKV Co., Ltd.)
Using PB013), followed by primer coating,
After a pattern was formed by printing and a printing sheet was obtained, a two-component curable polyester resin adhesive was applied to the printing surface by gravure reverse coating to form an adhesive layer. Separately, polypropylene resin (Idemitsu Petrochemical Co., Ltd.)
And E2900), and additives such as an ultraviolet absorber are prepared, blended and melted to have a predetermined composition, form an adhesive layer of a previously prepared printing sheet, and extrude through a slit of a T-die. Immediately after coating, the sheet was cooled with a cooling roll, and only the end portion of the sheet was continuously cut and removed to obtain a composite sheet.

Thereafter, the composite sheet is preheated by a heating roll, and furthermore, the surface temperature of the polypropylene resin-coated surface of the composite sheet is rapidly heated to 160 ° C. by infrared heating, and the embossing roll is heated and heated. The multi-layer sheet was cooled at the same time as the pressing, and irregularities were formed on the surface.

After forming the irregularities on the surface, a corona discharge treatment is applied to the side having the irregularities, and an acrylic resin paint (OP-A4, manufactured by Showa Ink Co., Ltd.) is applied to the treated surface by a gravure method.
Coating was performed so that the coating amount at the time of drying was 2 g / m ² to obtain a decorative sheet product. Evaluation of the obtained decorative sheet,
(1) 2000 hours exposure test with sunshine weatherometer, (2) 240 with sunshine UV meter
The test was conducted by examining the time (the total UV exposure time was 200 hours), and (3) checking the contamination status of the embossing roll and the decorative sheet. Table 3 shows the blending of additives such as an ultraviolet absorber, and Table 4 shows the results of the above evaluation.

[0066]

[Table 3]

[0067]

[Table 4]

Example 3 The thickness of the base sheet was set at 0.
The same evaluation result as the decorative sheet obtained in Example 2 was obtained for the decorative sheet obtained in the same manner as in Example 2 above, except that the paper was changed to 1 mm polyolefin resin synthetic paper (Tatsuno Chemical Co., Ltd., Tufper). I got In the same manner as in Example 2, except that the concave and convex portions were formed on the surface, then the concave portions were subjected to wiping coating for filling with coloring ink, and then subjected to corona discharge treatment and surface coating. The same evaluation result as the decorative sheet was obtained. A two-component curing method in which a polypropylene resin film having a thickness of 80 μm (additives are added in the same ratio as in the case of melt coating) is applied to the printing surface of the base sheet instead of the melt coating of the polypropylene resin in Example 2. The same evaluation result as the decorative sheet obtained in Example 2 was obtained for the decorative sheet obtained in Example 2 except that the decorative sheet obtained in the same manner as in Example 2 was laminated by using the layer of the polyester resin adhesive of the mold type and then laminated in the same manner as in Example 2. Obtained.

[0069]

According to the first aspect of the present invention, in the back print sheet constituted by using the transparent polyolefin resin sheet, at least one of the overcoat layer and the transparent polyolefin resin sheet contains a light stabilizer and / or a light stabilizer. Or, since it contains an antioxidant and an additive consisting of an ultraviolet absorber, when added to the overcoat layer, the weather resistance of the overcoat layer is improved, and when added to the transparent polyolefin-based resin sheet, the pattern The weather resistance of the layer is improved. According to the invention of claim 2, in the back print sheet constituted by using the polyolefin resin sheet, in addition to the effect of the invention of claim 1, a primer layer is provided between the transparent polyolefin resin sheet and the pattern layer. Since they are laminated, the adhesion strength of the picture pattern layer is further improved.
According to the third aspect of the present invention, in the doubling sheet formed using the polyolefin resin sheet, at least one of the overcoat layer, the transparent polyolefin resin sheet, and the adhesive layer has a light stabilizer and / or an antioxidant. ,
In addition, since it contains an additive consisting of an ultraviolet absorber, when added to the overcoat layer, the weather resistance of the overcoat layer is improved, and the transparent polyolefin-based resin sheet, or the adhesive layer contains the additive. In this case, the adhesion strength between the transparent polyolefin resin sheet and the base sheet is improved. According to the invention of claim 4, in the doubling sheet constituted by using the polyolefin resin sheet, in addition to the effect of the invention of claim 3, a primer layer is laminated between the base sheet and the pattern layer. As a result, the adhesion strength of the pattern layer is further improved. According to the invention of claim 5, in addition to the effects of any one of claims 1 to 4, in addition to containing an ultraviolet absorber comprising a benzotriazole-based compound,
Since there is little volatilization of the ultraviolet absorber, it has a sufficient effect when it is made into a sheet, there is no need to mix a large amount in anticipation of volatilization, and mist is generated by volatilization, and sheet manufacturing equipment and processing machines, especially heat During such embossing, there is an advantage that contamination of the embossing plate or the embossing roll or the like is small, and contamination of the surface of the decorative material is extremely small. According to the invention of claim 6, since the hindered amine-based light stabilizer is used, in addition to increasing the resistance to deterioration due to light, the effect of the ultraviolet absorber is promoted. There are lasting benefits.
According to the invention of claim 7, in addition to the effects of any one of claims 1 to 4, in addition to containing an antioxidant composed of a hindered phenol compound, a cosmetic material which is frequently processed at a high temperature is used. Deterioration during processing is prevented, and resistance to aging degradation is increased. According to the invention of claim 8,
In addition to the effects of any one of claims 1 to 4, the antioxidant composed of a hindered phenol compound and the antioxidant composed of a phosphite are used in combination. In this case, the ability to prevent deterioration of the decorative material, which is frequently processed in the above, during processing, and the resistance to aging deterioration are further increased.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view of a decorative material of a back print sheet specification.

FIG. 2 is a cross-sectional view of a doubling sheet specification decorative material.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Cosmetic material 2 Top coat layer 3 Transparent polyolefin resin sheet 4 Primer layer 5 Pattern layer 6 Adhesive layer 7 Intermediate layer 8 Base sheet

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B32B 33/00 B32B 33/00 C09K 3/00 104 C09K 3/00 104C

Claims (8)

[Claims] An overcoat layer, a transparent polyolefin-based resin sheet, and a pattern layer are sequentially laminated from the front side, and at least one of the overcoat layer or the transparent polyolefin-based resin sheet includes a light stabilizer and / or a light stabilizer. A cosmetic material comprising an antioxidant and an additive comprising an ultraviolet absorber. 2. The decorative material according to claim 1, wherein a primer layer is laminated between the transparent polyolefin resin sheet and the pattern layer. 3. An overcoat layer, a transparent polyolefin resin sheet, an intermediate layer composed of a pattern layer and an adhesive layer, and a base sheet are sequentially laminated from the front side, and the overcoat layer and the transparent polyolefin resin sheet are laminated. Or a cosmetic material characterized in that at least one of the adhesive layers contains an additive comprising a light stabilizer and / or an antioxidant and an ultraviolet absorber. 4. The decorative material according to claim 3, wherein a primer layer is laminated between the base sheet and the pattern layer. 5. The cosmetic material according to claim 1, wherein the ultraviolet absorbent is an ultraviolet absorbent composed of a benzotriazole compound. 6. The cosmetic material according to claim 1, wherein the light stabilizer is a hindered amine light stabilizer. 7. The cosmetic material according to claim 1, wherein the antioxidant is an antioxidant comprising a hindered phenol compound. 8. An antioxidant comprising two kinds of an antioxidant consisting of a hindered phenol compound and an antioxidant consisting of a phosphite aromatic ester compound. Or the cosmetic material described.