JP2000071370A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To express a pure-white design as pure whiteness as it is without receiving yellowish or reddish effect of a foamed layer by providing an intermediate layer consisting of at least a foamed resin layer and a colored resin layer on a base material layer so that the foamed resin layer is positioned on the side of the base material layer. SOLUTION: A decorative sheet 1 is constituted by successively forming a foamed resin layer 4 and a colored resin layer 5, both of which become an intermediate layer 3, on a paper base material 2 being a base material layer and applying an uneven pattern A from the side of the colored resin layer 5 to the foamed resin layer 4. By forming the foamed resin layer 4 and the colored resin layer 5 as separate layers, the colored resin layer 5 does not receive the effect of the yellowish or reddish foamed resin layer 4 generated by a foaming agent and shows the intrinsic color thereof to enhance design properties. For example, in the case of the colored resin layer 5 to which titanium dioxide being a high concealing pigment is added, the intrinsic whiteness of titanium dioxide can be obtained.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet used for interior decoration of buildings, surface decoration of fittings, interior decoration of vehicles, and the like.
More specifically, the present invention relates to a decorative sheet capable of preventing yellowing or redness of a foamed layer from affecting a design, and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, interior decoration of buildings, surface decoration of fittings,
As a decorative sheet used for a vehicle interior or the like, a decorative sheet having a design provided with a concavo-convex pattern by foaming or the like is generally used, and the concavo-convex pattern by foaming or the like is usually a foaming agent coated on a base material. Is formed by foaming a resin to be foamed such as a vinyl chloride resin or a polyolefin-based resin to which is added a heating foaming furnace.

[0003] However, the foamed layer formed by using this foaming agent usually shows a yellowish color or a reddish color under the influence of the foaming agent, and when a pure white design is required, the foamed layer is highly concealed. Titanium dioxide, a pigment, is added to enhance the whiteness. However, even if titanium dioxide is added to the foamed layer in this way, the original whiteness of titanium dioxide cannot be obtained due to the effect of the foaming agent, and the titanium dioxide has a yellowish or reddish whiteness. There is a problem that it is not preferable. Further, a decorative sheet configured so that a foamed layer is exposed has a problem that scratch resistance is poor.

[0004] Another problem is that when vinyl chloride resin is used as the foamed resin, harmful gases such as hydrogen chloride gas are generated during incineration. There is a problem such as the inability to dispose of waste materials and the problem that in the event of a fire, harmful gases such as hydrogen chloride gas are sucked and become poisoned.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention is directed to a method for producing a non-turbid color design without being affected by yellowing or redness of a foamed layer caused by a foaming agent, and in particular, a pure white design. Is to provide a decorative sheet which can be expressed as pure white as it is, is environmentally friendly, is excellent not only in scratch resistance but also in stain resistance and chemical resistance, and a method for producing the same.

[0006]

Means for Solving the Problems In order to solve the above-mentioned problems, the present inventors have proposed a decorative sheet of the present invention according to claim 1 which has at least a foamed resin layer on a base material layer. An intermediate layer comprising a colored resin layer is provided so that the foamed resin layer is located on the base layer side. By separately providing the foamed resin layer and the colored resin layer in this manner, for example, when a colored resin layer to which titanium dioxide is added is formed, even if the foamed resin layer becomes yellowish or reddish due to the foaming agent. Since the whiteness of titanium dioxide itself can be expressed without being affected by the colored resin layer, a decorative sheet having an extremely pure white design can be obtained. In addition, since the foamed resin layer is not exposed, the foamed resin layer is excellent in scratch resistance and the foaming efficiency of the foamed resin layer can be increased, and a decorative sheet having a foamed resin layer having a substantially uniform shape with less variation in foamed cells can be obtained. be able to.

[0007] The invention described in claim 2 is the first invention.
Wherein the intermediate layer has a first coating resin layer on the colored resin layer side. With this configuration, for example, when the first coating resin layer is used as the surface layer of the decorative sheet, the scratch resistance required for the surface layer of the decorative sheet,
The degree of freedom for imparting various physical properties such as stain resistance and chemical resistance is increased, and when a picture layer or the like is provided on the first coating resin layer, various properties such as adhesion to the picture layer or the like are reduced. The degree of freedom to give is increased.

According to a third aspect of the present invention, in the decorative sheet according to any one of the first and second aspects, the intermediate layer has a second covering resin layer on the foamed resin layer side. It is characterized by the following. With such a configuration, various physical properties such as adhesion between the foamed resin layer and the base material layer can be improved.

The invention described in claim 4 is the first invention.
3. The decorative sheet according to any one of items 1 to 3, wherein each layer forming the intermediate layer is made of an olefin-based thermoplastic resin. With such a configuration, an environmentally friendly decorative sheet can be obtained, and a decorative sheet excellent in scratch resistance, stain resistance, chemical resistance, and the like can be obtained.

[0010] The invention described in claim 5 is the first invention.
5. The decorative sheet according to any one of items 1 to 4, wherein a pattern layer is formed on the first coating resin layer, and a protective layer is formed on the pattern layer. With such a configuration, it is possible to provide a decorative sheet that is more excellent in design and has excellent scratch resistance, chemical resistance, and stain resistance.

[0011] The invention according to claim 6 is the first invention.
The decorative sheet according to any one of Items 1 to 5, wherein an uneven pattern is provided from the outermost layer on the base material layer to the foamed resin layer. With such a configuration, various patterns of concavo-convex patterns can be formed.

The invention according to claim 7 is the first invention.
5. The decorative sheet according to any one of items 1 to 4, wherein a radical scavenger and / or an ultraviolet absorber are added to at least one of the olefin-based thermoplastic resins forming the intermediate layer. Is what you do.
With such a configuration, a decorative sheet having excellent weather resistance can be obtained.

The invention described in claim 8 is the first invention.
7. In the decorative sheet according to any one of to 7, the base material layer is made of a paper base material, and the paper base material has a flame retardant, or
It is characterized in that an inorganic filler is added. With this configuration, flame retardancy can be imparted to the base material layer.

The invention according to claim 9 is the first invention.
The decorative sheet according to any one of Items 1 to 8, wherein the intermediate layer is formed by co-extrusion. By producing in this way, the intermediate layer formed on the base material layer can be formed on the base material layer in one step.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below with reference to the drawings. First, FIG. 1 is a layer configuration diagram of the first embodiment of the decorative sheet of the present invention, FIG. 2 is a layer configuration diagram of the second embodiment of the decorative sheet of the present invention, and FIG. FIG. 4 is a layer configuration diagram of an embodiment of FIG.
11, 21 are decorative sheets, 2 is a paper base, 3, 33 is an intermediate layer, 4
Is a foamed resin layer, 5 is a colored resin layer, 6 is a second coating resin layer,
Reference numeral 7 denotes a first coating resin layer, 8 denotes a picture layer, 9 denotes a protective layer, and A denotes an uneven pattern.

FIG. 1 is a diagram showing the layer structure of a first embodiment of a decorative sheet according to the present invention. The decorative sheet 1 according to the present invention comprises an intermediate layer 3 on a paper base 2 as a base layer. A foamed resin layer 4 and a colored resin layer 5 are sequentially formed, and a concavo-convex pattern A is applied from the colored resin layer 5 side to the foamed resin layer 4.

By forming the foamed resin layer 4 and the colored resin layer 5 as separate layers as described above, the colored resin layer 5 is formed of a yellowish or reddish foamed resin layer 4 generated by a foaming agent. Without being affected, the original color of the colored resin layer 5 is exhibited, and the design property can be improved.
For example, in the case of the colored resin layer 5 to which the titanium dioxide of the high hiding pigment is added, the original whiteness of the titanium dioxide can be obtained, and especially in a pure white design, the design property can be improved. it can. The foamed resin layer 4
And the colored resin layer 5, the foamed resin layer 4 is not exposed, so that the foamed resin layer 4 can be improved in foaming efficiency and the foaming efficiency of the foamed resin layer 4 can be improved. A foamed resin layer having a uniform shape can be formed.

FIG. 2 is a diagram showing the layer structure of a decorative sheet according to a second embodiment of the present invention. The decorative sheet 11 of the present invention forms an intermediate layer 33 on a paper substrate 2 as a substrate layer. (2) forming a coating resin layer 6, a foaming resin layer 4, a coloring resin layer 5, and a first coating resin layer 7 in this order, and forming an irregular pattern A from the first coating resin layer 7 side to the foaming resin layer 4; It was done.
By providing the second coating resin layer 6 in this manner, the adhesiveness between the foamed resin layer 4 and the base material layer 2 can be enhanced. Also, by providing the first coating resin layer 7, the makeup can be improved. Scratch resistance required for the surface layer of the sheet,
Various properties such as stain resistance and chemical resistance can be imparted, and when a pattern layer or the like is provided on the first coating resin layer described later, a layer considering the adhesiveness with the pattern layer or the like is used. can do.

FIG. 3 is a diagram showing the layer structure of a decorative sheet according to a third embodiment of the present invention. The decorative sheet 21 of the present invention forms an intermediate layer 33 on a paper substrate 2 as a substrate layer. (2) forming a coating resin layer 6, a foaming resin layer 4, a coloring resin layer 5, and a first coating resin layer 7 in this order, providing a pattern layer 8 on the first coating resin layer 7, 8, a protective layer 9 is provided on the entire surface,
Uneven pattern A from the protective layer 9 side to the foamed resin layer 4
It has been subjected to.

The decorative sheets according to the first to third embodiments of the present invention shown in FIGS. 1 to 3 show typical examples of the present invention. An intermediate layer (not shown) in which the second coating resin layer 6, the foamed resin layer 4, and the colored resin layer 5 are sequentially formed on the paper base material 2 as An intermediate layer (not shown) in which the foamed resin layer 4, the colored resin layer 5, and the first coating resin layer 7 are sequentially formed on the paper base 2 as the base layer. However, in the method for manufacturing a decorative sheet of the present invention described later, the intermediate layer 33 shown in the second and third embodiments is preferable.

Next, the decorative sheet of the present invention will be described in more detail. As the paper base material 2 used in the present invention,
Flame-retardant paper mainly composed of pulp impregnated with a water-soluble flame retardant such as sulfanylguanazine or guanidine phosphate, or inorganic paper mixed with an inorganic agent such as aluminum hydroxide or magnesium hydroxide can be used. An appropriate basis weight is 50 to 300 g / m ² .

Each of the intermediate layers 3 and 33 constituting the decorative sheet of the present invention is made of a thermoplastic resin. Suitable thermoplastic resins include, for example, vinyl chloride resin and vinyl chloride-vinyl acetate copolymer. Combined, vinyl chloride
Acrylic resin such as vinyl chloride resin such as acrylic copolymer, polyacrylonitrile, or copolymer of polyacrylonitrile, methyl acrylate and butadiene; and one kind of polyolefin such as polyethylene, polypropylene, polybutene, polybutadiene, polyisoprene Or a copolymer of two or more olefins such as ethylene, propylene, butene, butadiene, and isoprene, or a copolymer of α-olefins having 4 or more carbon atoms (linear low-density polyethylene);
Acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer, saponified ethylene-vinyl acetate copolymer, Alternatively, an olefin-based resin such as an ionomer, or a urethane resin, or a mixed resin thereof can be used. However, considering that it is environmentally friendly and is relatively inexpensive in terms of cost, the olefin-based resin is used. A mixed resin comprising one or more of the above is preferred.

As the foaming agent used for the foamed resin layer 4, a thermal expansion type capsule foaming agent containing a hydrocarbon having a low boiling point can be used, but it is low in cost, flame retardant and self-extinguishing. A thermal decomposition type foaming agent of an azo-based compound such as azodicarbonamide and azobisformamide is preferable from the viewpoints of excellent properties and the ability to impart flame retardancy to the foamed resin layer 3. The mixing amount of the pyrolytic foaming agent with respect to the olefin-based thermoplastic resin may be appropriately determined depending on the required design, but generally 2 to 10 parts by weight based on 100 parts by weight of the olefin-based thermoplastic resin. Appropriate.

The coloring agent used for the colored resin layer 5 may be any of an organic pigment and an inorganic pigment, and may be used arbitrarily according to the design. Yes, inorganic pigments such as titanium dioxide, zinc white, red iron oxide, vermilion, cobalt blue, titanium yellow, graphite, carbon black, or metal pigments such as aluminum and brass, titanium dioxide coated mica, basic lead carbonate, etc. A pearlescent (pearl) pigment or the like made of foil powder of the above is generally suitable. These are added and dispersed as a powdery or scaly foil piece to the thermoplastic resin used for the colored resin layer 5.

The embossed pattern A is formed by embossing from the colored resin layer 4 side when the decorative sheet 1 is in a heated state using a well-known sheet-fed or rotary embossing machine. By providing the plate with irregularities and then cooling the plate, an irregular pattern A can be formed from the colored resin layer 4 to the foamed resin layer 3. Examples of the shape of the uneven pattern A include a wood grain board conduit groove, a stone board surface unevenness, a cloth surface texture, a satin finish, a grain, a hairline, a linear groove, and the like.

In the case of the thermoplastic resin used for each of the intermediate layers 3 and 33, especially the olefin-based thermoplastic resin, it is necessary to prevent the deterioration of each layer due to ultraviolet rays and to improve the weather resistance. A radical scavenger and / or an ultraviolet absorber can be added as an agent.
As this radical scavenger, a hindered amine radical scavenger is preferable. The reason for this is that the hindered amine radical scavenger has a tetraalkylpiperidine in its mother nucleus and has a radical scavenging action of scavenging radicals generated by ultraviolet rays, and also has a hydroperoxide (RO)
It is presumed that the effect is exhibited by various action mechanisms such as the inactive action of OH), and excellent performance can be obtained as a multifunctional stabilizer. Specific examples of the hindered amine radical scavenger include bis- (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis- (N-methyl-2,2,6,6-tetramethyl-4). -Piperidyl) sebacate, bis- (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1,2,2
6,6-pentamethyl-4-piperidyl-tridecyl-
In addition to 1,2,3,4-butanetetracarboxylate, tetragis- (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate and the like, for example, Hindered amine radical scavengers such as the compounds disclosed in Japanese Patent Publication No. 4-82625 can be exemplified. It is appropriate to add 0.01 to 3.0 parts by weight of the hindered amine radical scavenger based on 100 parts by weight of the thermoplastic resin constituting the sheet.

As the ultraviolet absorber, for example,
2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole, 2- (2'
-Hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3'-tert-amyl-5'-isobutylphenyl) -5-chlorobenzotriazole , 2- (2'-hydroxy-3'-isobutyl-5'-methylphenyl) -5
-Chlorobenzotriazole, 2- (2'-hydroxy-
2'-hydroxyphenyl-5- such as 3'-isobutyl-5'-propylphenyl) -5-chlorobenzotriazole
Chlorobenzotriazole UV absorbers, 2- (2 ′
-Hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'-
2′-hydroxyphenylbenzotriazole ultraviolet absorbers such as methylphenyl) benzotriazole;
2'-dihydroxy-4-methoxybenzophenone, 2,
2,2′-dihydroxybenzophenone-based ultraviolet absorbers such as 2′-dihydroxy-4,4′-dimethoxybenzophenone, 2,2 ′, 4,4′-tetrahydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone,
2-hydroxybenzophenone UV absorbers such as 2,4-dihydroxybenzophenone; salicylate UV absorbers such as phenyl salicylate and 4-tert-butyl-phenyl-salicylate; 2-ethyl-
Use of cyanoacrylate ultraviolet absorbers such as hexyl-2-cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, octyl-2-cyano-3,3-diphenylacrylate and the like. be able to. The amount of these UV absorbers added is
It is usually about 0.1 to 10 parts by weight based on 100 parts by weight of the thermoplastic resin constituting the sheet. In addition, when used in combination with a radical scavenger, particularly from the viewpoint of compatibility between weather resistance and hot water resistance, and considering that it is environmentally friendly, non-chlorine-based benzophenone-based UV absorbers,
Alternatively, a cyanoacrylate type is preferable. The above-mentioned radical scavenger or ultraviolet absorber may be added to each of the intermediate layers 3 and 33 as necessary.

The thermoplastic resin used for each of the intermediate layers 3 and 33, especially the olefin-based thermoplastic resin, is flammable, and the intermediate layers 3 and 33 formed therefrom are also flammable. It becomes a flammable layer. However, the decorative sheet is generally required to have at least flame retardancy, and a flame retardant is added to each of the intermediate layers 3 and 33 made of the olefin-based thermoplastic resin, so that each of the intermediate layers 3 and 33 has flame retardancy. Is imparted. Examples of the flame retardant used here include those composed of a mixture of one or more inorganic substances such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, barium carbonate, and titanium oxide. The amount of the flame retardant added to the olefin-based thermoplastic resin may be any value as long as the flame retardancy required for a decorative sheet can be secured.
About 50 to 200 parts by weight, based on parts by weight, is suitable. Other examples include a flame retardant such as a phosphoric acid ester and silicone powder.

The pattern layer 8 can be generally formed by ink using a known printing method such as gravure printing, offset printing, silk screen printing, and transfer printing from a transfer sheet. Examples of the print pattern include a wood pattern, a stone pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and a print pattern such as a solid image. As the ink, as a vehicle, chlorinated polyethylene, chlorinated polyolefin such as chlorinated polypropylene, polyester, polyurethane composed of isocyanate and polyol, polyacryl, polyvinyl acetate, polyvinyl chloride,
Vinyl chloride-vinyl acetate copolymer, cellulosic resin,
One or more kinds of polyamide resins may be used as a mixture, and a pigment, a solvent, various auxiliaries and the like may be added thereto to form an ink. However, in consideration of an environmentally friendly decorative sheet, polyester may be used. Polyurethane, polyacrylic, polyvinyl acetate, cellulose resin, polyamide resin, etc.
A non-chlorine vehicle in which two or more kinds are mixed is preferable.

The protective layer 9 is provided for imparting scratch resistance, chemical resistance, stain resistance, and the like to the decorative sheet 21 of the present invention, and includes an epoxy resin, an acrylic resin, and a urethane resin. A resin such as a base resin, a polyamide resin, a polyester resin, or a resin such as the olefin resin described in the above-mentioned intermediate layers 3 and 33 is suitable, and is a layer directly in contact with the protective layer 9 such as the picture layer 8 or the like. A mixture of one or more of the above resins may be used as appropriate in consideration of the adhesiveness to the resin. As a method of forming the protective layer 9, for example, a solution of the resin or a solution obtained by heating and melting the resin is coated by a known coating method such as a gravure printing method, a roll coating method, or an extrusion coating method. Can be applied as appropriate, or can be formed by laminating the above resin into a film by a known dry lamination method or the like. The thickness of the protective layer 9 is 0.5 to 100 μm when dry.
m, usually about 1 to 15 μm.

Next, an example of the method for producing a decorative sheet according to the present invention will be described with reference to the decorative sheet 21 of the third embodiment described above as an example. First, a second coating resin layer 6 made of an olefin-based thermoplastic resin and a foamed resin layer 4 made of an olefin-based thermoplastic resin containing an additive mainly composed of a foaming agent are formed on a paper base material 2 serving as a base material layer. And an intermediate layer 33 composed of a colored resin layer 5 made of an olefin-based thermoplastic resin containing an additive mainly composed of titanium dioxide as a pigment, and a first coating resin layer 7 made of an olefin-based thermoplastic resin.
Are laminated in a four-layered manner so that the second coating resin layer 6 is in contact with the paper base material 2, and the foamed resin layer 4 is unfoamed to form a laminate. The first to issue
After performing a corona discharge treatment on the surface of the coating resin layer 7, a pattern layer 8 is formed by gravure printing on the surface subjected to the corona discharge treatment, and a protective layer 9 is formed on the entire surface of the pattern layer 8. The unfoamed foamed resin layer 4 is foamed in a heating foaming furnace to form the foamed resin layer 4, and the uneven pattern A is embossed on the foamed resin layer 4 from the protective layer 9 side.
After forming, the decorative sheet 21 can be obtained by cooling. By forming the intermediate layer 33 by co-extrusion in this way, the intermediate layer 33 composed of four layers can be formed at once, which is extremely efficient.

In the present manufacturing method, the second coating resin layer 6 and the first coating resin layer 7 are preferably made of an olefin-based thermoplastic resin containing no additives such as pigments, flame retardants and foaming agents. It is. The reason is that the foamed resin layer 4 and the colored resin layer 5 contain a large amount of an additive such as a pigment as a foaming agent or a coloring agent, or a flame retardant. In this case, since the foamed resin layer 4 and the colored resin layer 5 are co-extruded with the second covered resin layer 6 and the first covered resin layer 7 interposed therebetween, the foamed resin layer 4 And the additive added to the colored resin layer 5 does not adhere to the lip of the co-extruder, and the problem caused by this adhesion, that is, the lip is damaged, or the co-extruded The intermediate layer 33 including the second covering resin layer 6, the foamed resin layer 4, the colored resin layer 5, and the first covering resin layer 7.
A streak or the like can be completely prevented.

When the intermediate layer is formed by co-extrusion as described above, the second coating resin layer 6 or the olefin-based thermoplastic resin containing no additives such as a pigment, a flame retardant, and a foaming agent may be used. In a layer such as the first coating resin layer 7, a large amount of additives such as a pigment, a flame retardant, and a foaming agent are added. For example, the foamed resin layer 4 and the colored resin layer 5 are sandwiched. It is preferable to co-extrude the second coating resin layer 6 and the first coating resin layer 7 so as to be outside of the intermediate layer. However, due to cost and the like, the pigment, the flame retardant, and the foaming agent are thus used. In the case where it is not possible to form an olefin-based thermoplastic resin containing no additives such as the outermost layer, the second coating resin layer 6 or the first coating resin layer 7 is formed on at least one outermost side. It is better to configure it to be formed In addition, in the case where such a configuration cannot be made, a pigment, a flame retardant, and an additive amount such as a foaming agent to be added to the foamed resin layer 4 or the colored resin layer 5 are taken into consideration. An intermediate layer may be formed.

[0034]

The present invention will be described in more detail with reference to the following examples. Example 1 Using non-combustible paper having a basis weight of 97 g / m ² [WK-NRI manufactured by Kojin Co., Ltd.]
On this surface, an ethylene α-olefin copolymer (MI: 7) to be a second coating resin layer, a foamed resin layer-forming composition having a composition shown in Table 1, a colored resin layer-forming composition having a composition shown in Table 2, Ethylene α-olefin copolymer to be the coating resin layer (MI: 7)
And co-extruded from a T-die in four layers to obtain non-combustible paper 97g / m ² / second
A laminate comprising a coating resin layer of 20 μm / unfoamed foamed resin layer of 100 μm / colored resin layer of 40 μm / first coating resin layer of 20 μm was prepared, and the surface of the first coating resin layer of the laminate was subjected to corona discharge treatment. Thereafter, the corona discharge treated surface is gravure-printed with a printing ink made of an acrylic-urethane resin (which is an acrylic polyol as a prepolymer and which reacts with isocyanate to form a urethane bond) and is subjected to gravure printing. A pattern layer of a pattern was formed, and a two-component curable urethane resin was applied on the entire surface of the pattern layer by a well-known gravure printing method so as to be ² g / m ² when dry. This was foamed in an unfoamed foamed resin layer in a heating foaming furnace (200 ° C. for 1 minute), and embossed with a grain pattern embossing plate from the protective layer side. Was obtained.

[0035]

[Table 1]

[0036]

[Table 2]

Comparative Example 1 A non-combustible paper having a basis weight of 97 g / m ² [WK-NRI manufactured by Kojin Co., Ltd.] was used.
On this surface, a single layer of the foamed resin layer forming composition having the composition shown in Table 1 was extruded to obtain a non-combustible paper 97 g / m ² / unfoamed foamed resin layer 14.
After forming a laminate having a thickness of 0 μm and subjecting the unfoamed foamed resin layer surface of the laminate to a corona discharge treatment, an acryl-urethane resin (using an acrylic polyol as a prepolymer, an isocyanate Gravure printing with a printing ink consisting of a two-component reactive resin that forms a urethane bond by reacting with a resin to form a grain pattern pattern layer, and a two-component curable urethane resin is known on the entire surface of the pattern layer. Was applied so that the dry weight was 2 g / m ^{2 by} the gravure printing method. This is heated in a foaming furnace (200 ° C for 1
In step (i), the unfoamed foamed resin layer was foamed, and embossing was performed from the protective layer side with an embossed plate having a grain pattern, to obtain a decorative sheet as a comparative example.

The whiteness of the decorative sheets of Example 1 and Comparative Example 1 prepared above was compared, and the degree of influence on the pattern layer was visually checked. The results are shown in Table 3. Was.

[0039]

[Table 3] Note) Whiteness is a value when the standard (magnesium oxide) is 100%.

As is clear from the results shown in Table 3, Example 1 of the present invention has excellent whiteness as compared with Comparative Example 1, and the pattern layer of Comparative Example 1 was affected by the foamed resin layer. In contrast, the pattern layer of Example 1 of the present invention did not have yellowish color and was able to reproduce a design emphasizing whiteness as it was in a slightly yellowed state.

The decorative sheet of Example 1 of the present invention
A method of co-extruding the foamed resin layer forming composition and the colored resin layer forming composition in a four-layer configuration sandwiched between a first coating resin layer and a second coating resin layer made of an ethylene α-olefin copolymer is employed. Thus, in the decorative sheet of Comparative Example 1, the foamed resin layer-forming composition to which the additives such as the foaming agent, the pigment, and the flame retardant were added was extruded from the T-die in a single layer, thereby being added to the lip of the T-die. While the agent adheres and the surface of the extruded molten film (molten film) partially generates groove-shaped streaks, the above-described additive containing an additive such as a foaming agent, a pigment, or a flame retardant is added. In order to prevent the foamed resin layer forming composition or the colored resin layer forming composition from directly contacting the lip of the T-die, the extruded four-layered molten film (molten film) has a surface state. Is smooth and good molten film (melted Irumu) can be obtained, the yield is remarkably improved as compared with the decorative sheet of Comparative Example 1.

[0042]

As described above, the decorative sheet of the present invention has been described in detail. However, it is not affected by the yellowing or redness of the foamed layer caused by the foaming agent, and the design having a clear color is obtained without any turbidity. In particular, it is possible to express a pure white design as pure white as it is and it is environmentally friendly,
The decorative sheet is excellent not only in scratch resistance but also in stain resistance and chemical resistance. In addition, the decorative sheet of the present invention can produce a decorative sheet very efficiently by adopting a manufacturing method of forming at least an intermediate layer composed of a foamed resin layer and a colored resin layer by co-extrusion. By providing a layer sandwiching the resin layer and the colored resin layer from both sides, a foaming agent added to the foamed resin layer and the colored resin layer, a pigment as a colorant, additives such as a flame retardant are added to the co-extruder. This has the effect of improving productivity by preventing damage to the lip and preventing the additive from adhering to the lip and causing damage such as streaks in the intermediate layer.

[Brief description of the drawings]

FIG. 1 is a layer configuration diagram of a first embodiment of a decorative sheet according to the present invention.

FIG. 2 is a layer configuration diagram of a second embodiment of the decorative sheet according to the present invention.

FIG. 3 is a layer configuration diagram of a third embodiment of the decorative sheet according to the present invention.

[Explanation of symbols]

 1,11,21 Decorative sheet 2 Paper substrate 3,33 Intermediate layer 4 Foamed resin layer 5 Colored resin layer 6 Second coating resin layer 7 First coating resin layer 8 Picture layer 9 Protective layer A Concavo-convex pattern

 ────────────────────────────────────────────────── ─── Continued on the front page F-term (reference) 4F100 AA01A AK03B AK03C AK03D AK06 AK25 AK51 AK62 AT00A BA03 BA04 BA07 BA10A BA10B BA13 CA07C CA08A CA23A CA30C CB02 J10H DJBJJHJBJJHJBH

Claims (9)

[Claims] 1. A makeup, wherein an intermediate layer comprising at least a foamed resin layer and a colored resin layer is provided on a base material layer such that the foamed resin layer is located on the base material layer side. Sheet. 2. The decorative sheet according to claim 1, wherein the intermediate layer has a first coating resin layer on the colored resin layer side. 3. The decorative sheet according to claim 1, wherein the intermediate layer has a second covering resin layer on the foamed resin layer side. 4. The method according to claim 1, wherein each layer forming said intermediate layer is made of an olefin-based thermoplastic resin.
The decorative sheet according to any one of the above. 5. The decorative sheet according to claim 1, wherein a pattern layer is formed on the first coating resin layer, and a protective layer is formed on the pattern layer. . 6. The decorative sheet according to claim 1, wherein an uneven pattern is formed from an outermost layer on the base material layer to the foamed resin layer. 7. The method according to claim 1, wherein a radical scavenger and / or an ultraviolet absorber is added to at least one of the olefin-based thermoplastic resins forming the intermediate layer. The decorative sheet according to any one of the above. 8. The paper according to claim 1, wherein the base material layer is made of a paper base material, and a flame retardant or an inorganic filler is added to the paper base material. Makeup sheet. 9. The decorative sheet according to claim 1, wherein the intermediate layer is formed by co-extrusion.