JP3156150B2 - Olefin-based decorative sheet with weather resistance - Google Patents

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 as an exterior and interior material of a house, or a decorative material for furniture, home electric appliances and the like. In particular, it relates to a decorative sheet that does not use a vinyl chloride resin sheet and has excellent weather resistance.

[0002]

2. Description of the Related Art A decorative sheet using a vinyl chloride resin sheet has been frequently used as a decorative material for exterior and interior of a house. The sheet made of vinyl chloride resin is excellent in processability such as V-cut and hot embossing, adhesion to printing and lamination, and weather resistance, and is inexpensive in terms of cost. This is because it has performance. However, in recent years, global environmental issues have become increasingly important, and there has been a demand for alternative materials to vinyl chloride resins as decorative sheet materials. This is because hydrochloric acid gas is generated when incinerating waste materials such as houses, furniture, and home electric appliances. Therefore, various kinds of decorative sheets using a polyolefin resin as an alternative material to the vinyl chloride resin have been tried. For example, JP-A-6-798
The technique proposed in Japanese Patent Publication No. 30 attempts to improve the reproducibility of emboss of a polyolefin resin.
Japanese Patent Application Laid-Open No. 79850/1999 proposes a decorative sheet in which wiping is further attempted on embossing.

[0003]

However, the problem of weather resistance is inferior to a polyolefin resin alone, and it cannot achieve the same performance as a conventional vinyl chloride resin decorative sheet. Therefore, it has been attempted to add a weather resistance improver such as various ultraviolet absorbers to improve the weather resistance to the polyolefin resin. Not yet obtained. In particular, when using an ink that has been frequently used for a decorative sheet made of a vinyl chloride resin, using a vinyl chloride-vinyl acetate copolymer, a chlorinated polypropylene, or the like as a resin component of the vehicle for the printed pattern layer or the colored concealing layer. However, even when a hindered amine light stabilizer was added as a weather resistance improver for a polyolefin resin, sufficient weather resistance was not obtained.

[0004]

Therefore, in order to solve the above-mentioned problems, the decorative sheet of the present invention comprises a transparent olefin resin layer, a printed pattern layer, and a colored concealment layer in order from the front side. A light stabilizer such as a hindered amine light stabilizer is contained in the resin layer, and a resin containing no chlorine is used for the printed picture layer and the colored concealing layer. Also, in order from the front side, a transparent olefin-based resin layer, a printed pattern layer, and a decorative sheet having a configuration including a colored olefin-based resin layer, the transparent olefin-based resin layer contains a light stabilizer such as a hindered amine-based light stabilizer, and The printed pattern layer is made of a resin containing no chlorine. As a result, the adverse effect on the light stabilizer due to the chlorine component of the chlorine-containing resin such as chlorinated polypropylene or vinyl chloride-vinyl acetate copolymer, which has been frequently used as a component resin of the print pattern layer or the color hiding layer, has been eliminated. .

[0005]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a transparent olefin decorative sheet of the present invention will be described. FIG. 1 is a cross-sectional view showing a case where the olefin-based resin layer is a single layer as one embodiment of the transparent olefin-based decorative sheet of the present invention. FIG. 2 is a cross-sectional view showing another embodiment of the transparent olefin-based decorative sheet of the present invention in which the number of olefin-based resin layers is two. In the figure, 1 is a transparent olefin resin layer, 2 is a printed picture layer,
3 is a colored concealing layer, and 4 is a colored olefin-based resin layer.
1 is obtained by using a resin sheet as the transparent olefin-based resin layer 1, printing the printed picture layer 2 on the back surface thereof, and further printing or coating the colored concealing layer 3. be able to. In addition, the decorative sheet 20 of the two-layer specification in FIG. 2 is, for example, after printing the printed picture layer 2 on the colored olefin-based resin layer 4, laminating the resin sheet from above by heat lamination or dry lamination, It can be obtained by laminating at the same time as melt extrusion with a T-die and laminating as a transparent olefin-based resin layer 1. Alternatively, conversely, after forming a printed pattern layer on the back surface of the transparent olefin-based resin layer, an olefin-based resin sheet colored by heat lamination or dry lamination may be laminated, or the colored olefin-based resin may be melt-extruded with a T-die and simultaneously. It can also be obtained by lamination.

[0006] As a transparent olefin resin layer transparent olefin resin layer 1, polyethylene, polypropylene, ethylene - propylene copolymer, ethylene - butene-1 copolymer, propylene - butene-1 copolymer, polybutene-1, Butene-1, propylene, ethylene terpolymer, butene-1, hexene-1, octene-1 terpolymer, polymethylpentene, ethylene
Resins such as an ethylene ionomer such as a vinyl acetate copolymer, an ethylene-vinyl alcohol copolymer, or a polyethylene-acrylic acid copolymer can be used. As the resin of the transparent olefin resin layer, an olefin resin containing no chlorine atom in the molecule, such as chlorinated polypropylene, is used. For the purpose of improving flexibility and processability, an elastomer component may be used in combination with the above resin. Examples of the elastomer component include thermoplastic elastomers such as polyolefin-based thermoplastic elastomer (TPO), styrene-based thermoplastic elastomer, and polyester-based thermoplastic elastomer. Of these, the polyolefin-based thermoplastic elastomer can be used alone as a transparent olefin-based resin layer.

In a single-layer decorative sheet, the transparent olefin-based resin layer can be obtained in the form of a resin sheet by forming a film by a T-die method, a calendar method or the like. In this case, either a stretched or unstretched resin sheet can be used, but an unstretched resin sheet is more preferable in terms of formability such as suitability for V-cut processing. In the case of a single-layer specification, a corona treatment or a primer treatment may be performed to improve the adhesion of a printed picture layer printed thereon.
Incidentally, the decorative sheet shown in FIG. 3 shows a configuration example in which the primer layer 5 is applied to a resin sheet to be a transparent olefin-based resin layer, and then the printed picture layer 2 and the colored concealing layer 3 are formed. The transparent olefin-based resin layer 1 has a two-layer structure shown in FIG.
As described above, it can also be formed by a method of laminating simultaneously with melt extrusion on a colored olefin-based resin sheet on which a printed picture layer has been formed.

The thickness of the transparent olefin-based resin layer 1 is 25 to 500 μm, preferably 5 to 500 μm in the case of a single-layer specification, because the thickness is handled as a resin sheet to be printed or coated.
Usually, it is set in the range of 0 to 150 μm. If it is too thin, the strength will decrease and it will be difficult to convey it in a printing machine or a coating machine. The thickness of the transparent olefin resin layer 1 in the case of the two-layer specification is within the above range if it is handled as a resin sheet in the production of a decorative sheet, but the colored olefin resin layer side is treated as a resin sheet and melt-extruded. If the transparent olefin-based resin layer is formed simultaneously with the lamination by a method or a calendar method, the thickness can be made smaller than the lower limit. However, the transparent olefin resin layer on the surface side has
Since the weather resistance improver is contained, if the thickness is too small, the weather resistance is reduced. Therefore, the thickness is at most 10 μm or more, preferably 20 μm or more.

It is necessary for the transparent olefin-based resin layer to contain a light stabilizer as a weather resistance improver in order to improve weather resistance. The light stabilizer is preferably a hindered amine light stabilizer. The hindered amine light stabilizer has a tetraalkylpiperidine in its mother nucleus, has a radical scavenging action to scavenge radicals generated by ultraviolet rays, and exerts its effect by various action mechanisms such as an inactive action of hydroperoxide (ROOH). Thus, excellent performance can be obtained as a multifunctional stabilizer. Specific examples of the hindered amine light stabilizer include, for example, bis- (2,2,
6,6-tetramethyl-4-piperidyl) sebacate,
Bis- (N-methyl-2,2,6,6-tetramethyl-
4-piperidyl) sebercate, bis- (1,2,2,2)
6,6-pentamethyl-4-piperidyl) sebacate,
1,2,2,6,6-pentamethyl-4-piperidyl-
Tridecyl-1,2,3,4-butanetetracarboxylate, tetragis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like. And hindered amine radical scavengers such as the compounds disclosed in Japanese Patent Publication No. 4-82625. The content of the hindered amine light stabilizer is preferably in the range of 0.1 to 3% by weight based on the total amount of the resin. If the amount is less than this, the effect of improving the weather resistance cannot be sufficiently obtained, and if it is more than this, coloring occurs, and even if it is contained in a large amount, there is no effective change, which is not preferable.

In addition to the above-mentioned light stabilizer for improving the weather resistance, a conventionally known ultraviolet absorber may be used as a weather resistance improver in the transparent olefin resin layer. The combined use improves the weather resistance. As the ultraviolet absorber, specifically, for example, as an organic compound, 2- (2'-hydroxy-3 ', 5'-di-ter
t-butylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 '-Tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-3'-isobutyl-
2'-hydroxyphenyl-5-chlorobenzotriazole-based ultraviolet absorbers such as 5'-propylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butyl) 2′-hydroxyphenylbenzotriazole-based ultraviolet absorbers such as phenyl) benzotriazole and 2- (2′-hydroxy-5′-methylphenyl) benzotriazole;
2'-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxybenzophenone-based ultraviolet absorbers such as 2,2'-dihydroxy-4,4'-dimethoxybenzophenone and 2,2 ', 4,4'-tetrahydroxybenzophenone; 2-hydroxy-4-methoxy 2-hydroxybenzophenone UV absorbers such as benzophenone and 2,4-dihydroxybenzophenone; salicylate UV absorbers such as phenyl salicylate and 4-tert-butyl-phenyl-salicylate; 2-ethyl-hexyl-2- Examples include cyanoacrylate-based ultraviolet absorbers such as cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, and octyl-2-cyano-3,3-diphenylacrylate. Further, as the inorganic compound, the particle diameter is preferably 1 μm or less, and more preferably 0.1 μm from the viewpoint of visible light transparency.
UV absorbers of inorganic oxides such as zinc oxide, iron oxide, titanium oxide, cerium oxide and the like having a size of 2 μm or less.

In addition to the above-mentioned components for improving the weather resistance, the transparent olefin-based resin layer further contains aluminum hydroxide,
A flame retardant such as magnesium hydroxide and antimony trioxide or an inorganic filler such as calcium carbonate may be contained.
The content of the flame retardant is appropriately adjusted depending on the intended flame retardant grade, but is about 10 to 100 parts by weight based on 100 parts by weight of the resin. The transparent olefin-based resin layer may be colored with a coloring material such as a pigment or a dye as long as it is transparent.

Printing Pattern Layer The printing pattern layer 2 is made of a chlorine-free compound so as to be in contact with the transparent olefin resin layer 1 containing a light stabilizer such as a hindered amine light stabilizer as an essential component. Therefore, a resin containing a chlorine atom in a molecule, such as a vinyl chloride-vinyl acetate copolymer and a chlorinated polypropylene, which has been conventionally used for a decorative sheet of a vinyl chloride resin sheet, is not used. In these compounds such as chlorine-containing resins, the hydrochloric acid generated by the dehydrochlorination reaction by ultraviolet rays reaches the transparent olefin-based resin layer, deactivates the hindered amine-based light stabilizer present therein, or inhibits its light-stabilizing action. Therefore, the desired satisfactory weather resistance cannot be obtained. For this reason, any resin component that can be made into an ink and does not contain chlorine may be used as the resin component constituting the print pattern layer, and may be a curable resin such as a thermoplastic resin, a thermosetting resin, or an ionizing radiation-curable resin. Conventionally known various resins such as resins can be used.

Examples of the thermoplastic resin include various chlorine-free thermoplastic resins such as acrylic resin, urethane resin, polyester resin, polyamide resin, vinyl acetate resin, cellulose resin, and butyral resin. Further, as the thermosetting resin, polyester polyol,
Polyurethane resin used as a two-component curable ink for reacting polyacryl polyol, polyether polyol, etc. with an isocyanate compound, epoxy resin cured with polyamide, polyamine, etc., unsaturated polyester resin cured with a polymerization catalyst, or cured with acid Melamine resin, urea resin, alkyd resin and the like.
Further, as the ionizing radiation-curable resin, a resin composition comprising a prepolymer or oligomer having an ethylenically unsaturated bond in a molecule, a diluting monomer, or the like can be used. Examples of the prepolymer or oligomer include unsaturated polyester, polyester acrylate, urethane acrylate, epoxy acrylate, and polyether acrylate. As the diluent monomer, a monofunctional or polyfunctional monomer having low viscosity, low volatility and low skin irritation is preferably used. As the chlorine-free resin constituting the printed picture layer, two or more of the above-mentioned thermoplastic resins, thermosetting resins and ionizing radiation-curable resins may be used in combination.

The printed picture layer can be formed by using a known ink such as gravure printing, offset printing, letterpress printing, flexographic printing, silk screen printing, etc., using the above-mentioned chlorine-free resin as a vehicle. . As the colorant in the ink, any of conventionally known coloring materials such as pigments and dyes can be used. In particular, in terms of weather resistance, for example, red iron oxide, titanium dioxide, vermilion, ultramarine, patina (basic copper carbonate) In addition, inorganic pigments such as carbon black, and organic pigments such as azo pigments, phthalocyanine pigments, and condensed polycyclic pigments such as quinacridone pigments and isoindolinone pigments exhibit excellent properties. As the pigment, a brilliant pigment may be used, and if necessary, extender pigments such as calcium carbonate, silica, alumina, barium sulfate and the like may be used. The ink for forming the print pattern layer may be any of a solvent-based ink and an aqueous-based ink, and in each system, may be any of a dissolved system and a dispersed system.

The colored concealing layer colored concealing layer 3 is intended to be formed on the entire surface in order to conceal the surface of the decorative sheet is applied, the printed pattern layer 2
The same resins as those mentioned in the above can be used. However, the colored concealing layer is a layer facing the adhesive on the adherend when the decorative sheet is used, and a resin is selected in consideration of the adhesiveness to the adhesive used in the application. The same applies to pigments such as coloring agents. However, as the concealing pigment, a pigment having excellent concealing properties, such as titanium oxide and zinc oxide, may be used as a resin 10.
In many cases, 50 to 300 parts by weight is added to 0 part by weight. The colored concealing layer is usually made opaque, but depending on the application, a coloring agent may be used to reduce the amount of the concealing pigment to reduce the concealing property, thereby providing a transparent coloring. The colored concealing layer may be formed by a printing method like the printed picture layer, but can also be formed by a coating method. As a coating method, various conventionally known coating means such as a gravure coat, a roll coat, a reverse coat, and a doctor coat can be used. The coating amount is desirably in the range of ² to 30 g / m ² when dried. If the amount is too small, the hiding power decreases. Also, if the amount is too large, the hiding power is saturated and is meaningless.

Colored olefin-based resin layer Examples of the resin that can be used in the colored olefin-based resin layer 4 include the resins for the transparent olefin-based resin layer described above. However, in the case of a colored off-line resin layer, since the underlying layer is required to be concealed as in the case of the colored concealed layer, a concealing pigment such as titanium oxide or zinc oxide is contained, and is appropriately used in combination with a coloring agent such as a colored pigment. . The colored olefin-based resin layer is usually opaque, but depending on the application, a coloring agent may be used to reduce the blending amount of the concealing pigment to achieve transparent coloring. Further, like the transparent olefin-based resin layer, a flame retardant or the like may be contained. The colored olefin-based resin layer 4 is generally formed by forming a film as a colored resin sheet. However, as described above, after forming a printed pattern layer on the transparent olefin-based resin layer, the film is formed by melt extrusion from above. At the same time, it can be formed by stacking.

Primer Layer FIGS. 3 and 4 show examples of a decorative sheet provided with a primer layer 5. The primer layer 5 is appropriately provided for improving interlayer adhesion. For example, in the case of a single-layer specification, it is applied to a transparent olefin-based resin sheet to which a printed picture layer and a colored concealing layer are applied. In the two-layer specification, a colored olefin-based resin sheet or a transparent olefin-based resin sheet on which a printed picture layer is to be provided, or one or both of these sheets is used for laminating these resin sheets. In the decorative sheet of the present invention, it is preferable to use a chlorine-free resin also as the resin of the primer layer. Even with a chlorine-containing resin, a certain effect of improving the weather resistance (by making the printed picture layer and the color hiding layer non-chlorine-containing) can be obtained, but no remarkable effect can be expected. Particularly, a chlorine-free resin should be used for the primer layer in contact with the transparent olefin-based resin layer serving as the top clear layer. As the chlorine-free resin used for the primer layer, curable resins such as thermoplastic resins, thermosetting resins, and ionizing radiation-curable resins listed in the above-described pattern printing layer can be used. The formation of the primer layer may be performed by a conventionally known coating method or printing method on the surface that has been appropriately subjected to corona treatment.However, if necessary, various fillers and additives may be added in consideration of coating suitability, printing suitability, and the like. Agent is appropriately contained.

In the decorative sheet of the present invention, an uneven pattern having an uneven shape may be formed on the surface of the transparent olefin-based resin layer by embossing, sandblasting, hairline processing, or the like. The embossing is performed by using a hot-press type sheet-fed or rotary embossing machine, for example, after forming a printed pattern layer or the like, a single-layer sheet or a sheet laminated in a two-layer specification, and an embossing plate on its surface. Is pressed to shape the uneven shape of the plate to form an uneven pattern.
The concavo-convex pattern formed by embossing may be a wood grain conduit pattern, a wood grain texture, a stone surface unevenness, a fabric surface texture, a satin finish, a grain, a hairline, or a combination thereof. Further, the concave portions of the concavo-convex pattern formed on the surface of the transparent olefin-based resin layer may be filled with a coloring ink by a known wiping process using a doctor blade method, a roll coating method, or the like, if necessary. As the coloring ink, a resin containing no chlorine, such as a urethane resin, an acrylic resin, or a polyester resin, is preferable as in the case of the printed picture layer. Among them, a two-component curable ink that is a urethane resin is preferable because of good adhesion, solvent resistance, and the like. Further, as a picture layer other than the printed picture layer, there may be a partial metal deposition layer of aluminum or the like. The partial metal deposition layer and the pattern printing layer may be formed by transfer printing.

As a use of the decorative sheet of the present invention, there is a use in which the decorative sheet is laminated on the surface of various members to make the surface decorative.
Examples of the parts to be bonded include iron, metal plates such as aluminum, wood veneer, wood plywood, wood plates such as wood fiber plates, glass, ceramics such as ceramics, and plate materials such as cement plates such as ALC,
Examples include plate materials of resin plates such as polypropylene and phenolic resin, and three-dimensional articles made of these various materials, such as resin molding. Examples of a method of laminating a decorative sheet on these various members include, for example, a method of laminating a plate-like member by pressing with a pressure roller via an adhesive layer,
As described in Japanese Patent Application Laid-Open No. 19132, etc., a so-called simultaneous injection molding lamination method in which resin is injection-molded by disposing the resin between the male and female molds so that the surface on the surface side of the decorative sheet faces the cavity side. As described in JP-B-56-45768 and JP-B-60-58014, a decorative sheet is opposed to or placed on the surface of a three-dimensional article such as a molded article with an adhesive layer interposed therebetween. A decorative sheet is laminated on the surface of a molded article by a pressure difference caused by vacuum suction from the three-dimensional article side, a so-called vacuum press laminating method, as described in JP-B-61-5895, columnar members such as cylinders and polygonal columns. In the long-axis direction, while supplying the decorative sheet through an adhesive layer therebetween, the decorative sheets are sequentially pressure-adhered and laminated on a plurality of side surfaces constituting the columnar member by a plurality of rollers having different directions. So-called wrapping , Jitsuoyakedai 15-3112
No. 2, JP-A-48-47972, etc., first, a decorative sheet is laminated on a plate-like member via an adhesive layer, and then the decorative sheet is placed on the surface of the plate-like member on the side opposite to the decorative sheet. , Cut a V-shaped or U-shaped groove reaching the interface between the decorative sheet and the plate-shaped member, and then apply an adhesive in the groove, and then bend the box to form a box or column. For example, there is a so-called V-cut or U-cut processing method. And
Cosmetic sheets laminated by these methods and decoratively decorated are surface decoration materials for building interiors such as walls, ceilings, window frames,
Surface decoration materials for doors, handrails and other fittings, furniture surface decoration materials,
It can be used as a cabinet for light electric / OA equipment or as a surface decoration material for vehicle interior materials such as automobiles.

[0020]

Next, the decorative sheet of the present invention will be described more specifically with reference to examples and comparative examples. In the following description, “parts” is based on weight unless otherwise specified.

Example 1 A polyolefin-based thermoplastic elastomer (TPO) was used as a transparent olefin-based resin layer.
As a light stabilizer, 0.5 part of a hindered amine-based light stabilizer (manufactured by Asahi Denka Kogyo KK, [model number] LA-63) was added to 100 parts of (E-2900, manufactured by Idemitsu Petrochemical Co., Ltd.). The product was melt-extruded from a T-die to produce a 0.1 mm thick transparent resin sheet, and the printed surface side was corona treated.
Next, a medium ink made of a two-component curable urethane resin (AFS manufactured by Showa Ink Industry Co., Ltd., AFS
Media) and a two-component curable urethane resin pattern ink (Showa Ink Industries Co., Ltd.)
AFS), a two-part curable urethane-based concealing ink (AFS White, manufactured by Showa Ink Industries, Ltd.)
A printed pattern layer and a colored concealing layer were sequentially formed by gravure printing to obtain a decorative sheet of the present invention.

Comparative Example 1 In Example 1, the ink for forming a primer layer was replaced with an ink made of a vinyl chloride-vinyl acetate copolymer (Dick Seal A-100Z, manufactured by Dainippon Ink and Chemicals, Inc.). In addition, the ink used for forming the print pattern layer and the colored concealing layer is also a pattern ink (manufactured by Showa Ink Industry Co., Ltd., Chemical X) and a concealment, both using a vinyl chloride-vinyl acetate copolymer and an acrylic resin. A decorative sheet was obtained in the same manner as in Example 1 except that the ink was replaced with an ink (manufactured by Showa Ink Industries, Ltd., Chemical X No. 7).

Comparative Example 2 A decorative sheet was obtained in the same manner as in Example 1, except that the ink for forming the primer layer was changed to that used in Example 1.

Performance Comparison in Single-Layer Specification Table 1 shows the measurement results of the weather resistance test of Examples 1, 2 and 3 of the single-layer specification. As shown in Table 1, in Example 1, the weather resistance did not have any problem even when the weatherometer was used for 1000 hours.
In Comparative Example 1 in which a chlorine-containing resin was used for the primer layer, the printed pattern layer, and the colored concealing layer, the adhesion of the printed pattern layer and the colored concealing layer was reduced even after 500 hours, and these layers dropped off. Further, in Comparative Example 2 in which only the primer layer contained no chlorine-containing resin, the weather resistance was improved as compared with Comparative Example 1, but 500%.
Cracks occur on the surface of the decorative sheet over time.

[0025]

[Table 1] △: Surface crack generation ×: Dropout of printed picture layer etc.

Example 2 As a colored concealed olefin-based resin layer, a 10 μm-thick polyethylene sheet (Toughper, manufactured by Tanoto Chemical Co., Ltd.) was used.
A primer layer and a printed picture layer were formed with the same ink as in Example 1 to obtain a base sheet. On the other hand, for the transparent olefin-based resin layer, the same polyolefin-based thermoplastic elastomer sheet as in Example 1 was used, which had been subjected to corona treatment, and the corona-treated surface was treated with a polyester two-component curable ink (Showa Ink Kogyo Co., Ltd.) A primer layer was formed by gravure printing using SPP primer (manufactured by Sapphire Co., Ltd.). Next, the base sheet and the top sheet were thermally laminated by a doubling embossing machine and simultaneously the surface of the top sheet was subjected to hot embossing, thereby obtaining a decorative sheet of the present invention having an embossed pattern surface.

Example 3 In Example 2, the resin of the primer layer applied to the base sheet used as the colored concealed olefin resin layer was an acrylic two-component curable resin (SPA primer, manufactured by Showa Ink Industries, Ltd.) The decorative sheet of the present invention was obtained in the same manner as in Example 2 except for changing the above.

Comparative Example 3 In Example 2, the primer layer forming ink applied to the base sheet used as the colored concealed olefin-based resin layer was a vinyl chloride-vinyl acetate copolymer ink (Dainippon Ink Chemical Industry Co., Ltd.) ),
Instead of Dick Seal A-100Z), on the other hand, the primer layer forming ink applied to the top sheet used as the transparent olefin-based resin layer is also replaced with the same one for the base sheet, and the printing pattern layer forming ink is also used. A decorative sheet was obtained in the same manner as in Example 2 except that a pattern ink (manufactured by Showa Ink Industry Co., Ltd., Chemical X ) using a vinyl chloride-vinyl acetate copolymer and an acrylic resin was used.

Comparative Example 4 The same procedure as in Example 2 was repeated except that the ink for forming a primer layer applied to the top sheet used as the transparent olefin resin layer was used in Comparative Example 3.
A decorative sheet was obtained in the same manner as in Example 2, except that the ink was changed to a vinyl acetate copolymer ink.

Comparative Example 5 Comparative Example 3 was the same as Comparative Example 3, except that the ink for forming a primer layer applied to the top sheet used as the transparent olefin-based resin layer was replaced by the polyester-based two-part curable ink used in Example 2. A decorative sheet was obtained in the same manner as in Example 3.

Performance Comparison in Two-Layer Specifications Table 2 shows the measurement results of the weather resistance tests of Examples 2, Example 3, and Comparative Examples 3 to 5 of the two-layer specifications. As shown in Table 2, in Examples 2 and 3, there is no problem in weather resistance even with a weatherometer of 1000 hours, but Comparative Example 3 in which a chlorine-containing resin is used for a primer layer and a printed picture layer has a top sheet and a base sheet that are 500 hours. , A phenomenon (delamination) occurs in which the adhesive strengths of the substrates are separated from each other. This phenomenon is the same as in Comparative Example 4 even if a chlorine-free resin is used for the printed pattern layer and the primer layer of the base sheet, but the chlorine-containing resin is used for the primer layer of the top sheet. Further, even if a chlorine-containing resin is used for the printed pattern layer and the primer layer of the base sheet, if a chlorine-free resin is used for the primer layer of the top sheet, the weather resistance up to the degree of crack generation on the decorative sheet surface as in Comparative Example 5 Is improved to some extent, but is inferior to Examples 2 and 3 in which a chlorine-free resin is used for the printed picture layer and the primer layer of the base sheet.

[0032]

[Table 2] Δ: Surface crack generation ×: Delamination

[0033]

According to the present invention, the performance of a decorative sheet made of an olefin-based resin as a substitute for a decorative sheet made of a vinyl chloride resin is as good as that of a conventional decorative sheet made of a vinyl chloride resin.

[Brief description of the drawings]

FIG. 1 is a cross-sectional view (single-layer specification) showing one embodiment of a decorative sheet of the present invention.

FIG. 2 is a cross-sectional view (two-layer specification) showing another embodiment of the decorative sheet of the present invention.

FIG. 3 is a sectional view showing another embodiment of the decorative sheet of the present invention.

FIG. 4 is a sectional view showing another embodiment of the decorative sheet of the present invention.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Transparent olefin resin layer 2 Print pattern layer 3 Color hiding layer 4 Color olefin resin layer 5 Primer layer 10 Decorative sheet (single-layer specification) 20 Decorative sheet (2-layer specification)

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 23/00 C08L 23/00 E04F 13/00 E04F 13/00 B 13/18 13/18 A (56) References 8-34058 (JP, A) JP-A-8-90740 (JP, A) JP-A-6-198831 (JP, A) JP-A-8-34105 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 33/00 B32B 27/32 B32B 31/00 E04F 13/00 E04F 13/18

Claims (2)

(57) [Claims] 1. A transparent olefin resin layer in order from the front side,
Printing pattern layer, Rutotomoni such a colored concealing layer, colored concealing layer
The in decorative sheet to an adherend application surface, a transparent olefin resin layer contains a hindered amine light stabilizer, and print pattern layer and the colored concealing layer does not contain chlorine heat
A weather-resistant olefin-based decorative sheet made of a curable resin. 2. A transparent olefin resin layer in order from the front side,
In a decorative sheet comprising a primer layer, a printed picture layer, a primer layer and a colored olefin resin layer, the transparent olefin resin layer contains a hindered amine light stabilizer,
Heat-hardened primer layer and printed picture layer do not contain chlorine
A weather-resistant olefin-based decorative sheet made of a curable resin.