JP2000218751A - Decoration sheet and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To restrain an occurrence of a noxious incineration gas, improve various kinds of resistances such as adhesion, weatherability or the like, and a designing property, and reduce cost by providing a base material layer consisting of paper, a foam resin layer and pattern layer in this order, and giving uneven pattern from the pattern layer to the foam resin layer. SOLUTION: A decoration sheet 1 includes a foam resin layer 3 made up of a radical scavenger, a filling agent and an olefinic thermoplastic resin formed on a paper base material 2, and besides, a pattern layer 4 is formed on the foam resin layer 3, and further an uneven pattern 6 is formed from the pattern layer 4 to the foam resin layer 3. Herein, as olefinic thermoplastic resin, an ethylene-vinylacetate copolymer of an ethylene ratio of 10-40 wt.% and a glass transition temperature of -15% to +10 deg.C is suitable because of excellent processability and adherence with printing ink. In addition, a hindered amine radical trapping agent is preferable for a radical scavenger. Furthermore, a thermally expandible capsule is suitable for a foaming agent.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a decorative sheet to be attached to a wall or ceiling of a house or the like, and more particularly to a decorative sheet which is excellent in design and is environmentally friendly and a method for producing the same.

[0002]

2. Description of the Related Art Conventionally, a vinyl chloride resin layer has been formed on a paper base material, a picture layer has been provided on the vinyl chloride resin layer, and an irregular pattern has been formed by foaming the vinyl chloride resin layer. So-called PVC wallpaper (PVC decorative sheet) is widely used. However, when this PVC decorative sheet is incinerated, harmful gases such as hydrogen chloride gas are generated at the time of incineration. However, there is a problem of poisoning caused by inhaling harmful gas such as harmful gas, and a decorative sheet replacing this PVC decorative sheet has been desired.

Therefore, a non-PVC decorative sheet which does not include a vinyl chloride resin layer, that is, which is provided with a non-PVC resin layer made of an acrylic resin or an olefin resin in place of the vinyl chloride resin layer has been used. Have been. This non-PVC decorative sheet generally has a configuration in which a foamed resin layer made of non-PVC resin and a picture layer are sequentially provided on a paper base, and as a manufacturing method, for example, a paper base is used. ,
An aqueous emulsion composed of a non-PVC resin such as an acrylic resin or an olefin resin containing a foaming agent is applied and dried to form a non-PVC resin layer, and a picture layer is provided on the non-PVC resin layer. While foaming the non-PVC resin layer in a heating foaming furnace, a method of applying an embossing process from the picture layer to the foamed non-PVC resin layer to give an uneven pattern, or a paper base, a foaming agent. A non-PVC resin composed of an acrylic resin or an olefin resin contained is extruded by a well-known T-die extrusion method to provide a non-PVC resin layer, a picture layer is provided on the non-PVC resin layer, and then heated and foamed. There is a method in which the non-PVC resin layer is foamed in a furnace, and embossing is performed from the picture layer to the foamed non-PVC resin layer to form an uneven pattern.

However, regardless of the production method, acrylic resins have the problems of high cost and poor chemical resistance, and olefin resins have poor stain resistance but poor weather resistance. The problem, namely
When exposed to sunlight from the outdoors, the olefin-based resin is deteriorated, and there is a problem that the interlayer adhesion strength between the olefin-based resin and each of the adjacent layers decreases with time. It was inferior to conventional PVC decorative sheets using resin.

[0005]

SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above problems, and has as its object to generate harmful gases such as hydrogen chloride gas when incinerated. It can be suppressed as much as possible, and has excellent weather resistance despite the fact that the foamed resin layer is made of an olefin resin, has the same adhesive strength as a conventional PVC decorative sheet, and has abrasion resistance and chemical resistance An object of the present invention is to provide a relatively low-cost decorative sheet having a beautiful printed pattern and a concavo-convex pattern having excellent design properties, stain resistance, etc., and excellent in design properties, and a method for producing the same.

[0006]

The present inventor has conducted various studies to solve the above problems, and as a result, the decorative sheet of the present invention according to claim 1 has a base layer made of paper and a foamed sheet. A foamed resin layer mainly composed of an agent, a radical scavenger, an inorganic filler and an olefin-based thermoplastic resin, and a picture layer are sequentially provided, and an uneven pattern is formed from the picture layer side to the foamed resin layer. It is characterized by the following. With this configuration, generation of harmful gases such as hydrogen chloride gas during incineration and the like can be suppressed as much as possible, and the foamed resin layer made of an olefin-based thermoplastic resin deteriorates with time. As a result, it is possible to obtain a non-PVC decorative sheet in which the interlayer adhesive strength between the foamed resin layer and each layer adjacent to the foamed resin layer is not inferior to a conventional PVC decorative sheet.

[0007] The invention described in claim 2 is the first invention.
Wherein the adhesive layer is provided between the base material layer and the foamed resin layer and / or between the foamed resin layer and the picture layer. It is. With this configuration,
The interlayer adhesive strength between the foamed resin layer and each layer adjacent to the foamed resin layer can be further increased.

According to a third aspect of the present invention, in the decorative sheet according to any one of the first and second aspects, a protective layer comprising a resin having an isocyanate group is provided on the picture layer. It is a feature. With such a configuration, it is possible to provide a decorative sheet having more excellent abrasion resistance, chemical resistance, stain resistance, and the like.

The invention described in claim 4 is the first invention.
In the decorative sheet according to any one of Items 1 to 3, the olefin-based thermoplastic resin constituting the foamed resin layer comprises an ethylene-vinyl acetate copolymer resin, and the ethylene ratio of the ethylene-vinyl acetate copolymer resin is 10 to 40% by weight and a glass transition point (Tg) of -15 to +10
° C. With this configuration, the foamed resin has good adhesion to the printing ink, and does not block when the base material layer coated with the composition for forming the foamed resin layer is wound up. Layers can be obtained.

[0010] The invention described in claim 5 is the first invention.
In any of the decorative sheets described in any one of (1) to (3), among the layers constituting the decorative sheet, at least the base material layer, the foamed resin layer, and the protective layer do not contain a substance having chlorine. It is a feature. With this configuration, generation of harmful gas such as hydrogen chloride gas can be suppressed as much as possible.

[0011] The invention according to claim 6 is the first invention.
Wherein the foaming agent is a capsule foaming agent. With this configuration, a foamed resin layer composed of uniform foamed cells can be easily formed.

The invention according to claim 7 is the first invention.
Wherein the radical scavenger is a hindered amine-based radical scavenger. With this configuration, the weather resistance of the foamed resin layer is improved, and yellowing and deterioration can be prevented.

[0013] The method for producing a decorative sheet according to the invention of claim 8 mainly comprises a foaming agent, a radical scavenger, an inorganic filler and an olefin-based thermoplastic resin which are heated and melted on a base material layer made of paper. After extruding the composition to be extruded by an extruder and laminating, after printing a pattern layer on the laminated composition, while foaming the composition in a heating foaming furnace to form a foamed resin layer, the pattern layer side The uneven pattern is formed from the pattern layer to the foamed resin layer by applying irregularities to the embossing plate and then cooling after that. By producing in this manner, a drying step for drying the aqueous emulsion is not required as compared with a method of forming the foamed resin layer by applying the composition to the aqueous emulsion and coating the composition on the base layer. In addition, expansion and contraction of the base layer due to the influence of water during coating can be prevented.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described in more detail below with reference to the drawings and the like. First, FIG. 1 is a layer configuration diagram of a first embodiment of the decorative sheet of the present invention, and FIG. 2 is a layer configuration diagram of a second embodiment of the decorative sheet of the present invention. In the figures, reference numerals 1 and 11 denote decorative sheets, 2 a paper base, 3 a foamed resin layer, 4 a printed picture layer, 5 a protective layer, and 6 an uneven pattern.

FIG. 1 is a diagram showing the layer structure of a first embodiment of the decorative sheet according to the present invention. The decorative sheet 1 according to the present invention has a capsule foaming agent, a radical scavenger,
A foamed resin layer 3 mainly composed of a filler and an olefin-based thermoplastic resin is formed, a picture layer 4 is formed on the foamed resin layer 3, and an uneven pattern 6 is formed from the picture layer 4 to the foamed resin layer 3. It was done.

As the paper base material 2 used in the present invention, a pulp-based flame-retardant paper impregnated with a water-soluble flame retardant such as sulfanylguanazine or guanidine phosphate, or a paper such as aluminum hydroxide or magnesium hydroxide is used. It is possible to use what is usually called a backing paper for wallpaper, such as an inorganic paper mixed with an inorganic agent, and its basis weight is 50 to 300 g / m ^2.
Is appropriate.

Next, the foamed resin layer 3 of the present invention comprises an olefinic thermoplastic resin obtained by mixing at least a radical scavenger as a light stabilizer, a capsule foaming agent and an inorganic filler. Is extruded onto the paper substrate by a known T-die extrusion method and then foamed in a heating foaming furnace, or the olefin-based thermoplastic resin is applied as an emulsion type solution on the paper substrate and dried. After that, it can be provided by foaming in a heating foaming furnace.

The olefinic thermoplastic resin used in the foamed resin layer 3 of the present invention includes, for example, one of polyolefins such as polyethylene, polypropylene, polybutene, polybutadiene and polyisoprene and ethylene, propylene, butene, butadiene and isoprene. A copolymer of two or more olefins, or a copolymer of α-olefins having 4 or more carbon atoms (linear low-density polyethylene);
Alternatively, ethylene-vinyl acetate copolymer, ethylene-
Acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, saponified ethylene-vinyl acetate copolymer, or a resin mixture of these be able to. Here, the reason why the foamed resin layer 3 is limited to the olefin-based thermoplastic resin is that the foamed resin layer 3 has the same flexibility, workability at low temperature, and design as the conventional PVC decorative sheet, chemical resistance, solvent resistance, This is because the stainability is superior to that of a conventional PVC decorative sheet, and a relatively low-cost decorative sheet can be obtained. Among the olefin-based thermoplastic resins, an ethylene-vinyl acetate copolymer having an ethylene ratio of 10 to 40% by weight and a glass transition point of -15 to + 10 ° C is particularly suitable for processability and adhesiveness with printing ink. It is suitable because it is excellent in.

Further, a radical scavenger is added to the foamed resin layer 3 of the present invention as a light stabilizer for the purpose of preventing deterioration of the foamed resin layer 3 due to ultraviolet rays and improving weather resistance. Olefin-based thermoplastic resins have the property of deteriorating over time due to sunlight (ultraviolet rays), and are added to prevent this. As this radical scavenger, a hindered amine radical scavenger is preferable. The reason for this is that hindered amine radical scavengers have a tetraalkylpiperidine as a mother nucleus, have a radical scavenging action of scavenging radicals generated by ultraviolet rays, and have various actions such as an inactive action of hydroperoxide (ROOH). It is presumed that the mechanism exerts its effect, 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-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 JP-A-82625.
It is appropriate that the hindered amine radical scavenger is added in an amount of 0.01 to 3.0 parts by weight based on 100 parts by weight of the olefinic thermoplastic resin.

Further, if necessary, an ultraviolet absorber may be used in combination. In the present invention, an organic compound having an OH group in the molecule is used as the ultraviolet absorber. For example, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5-chlorobenzotriazole,
(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)
2′-hydroxyphenyl such as -5-chlorobenzotriazole, 2- (2′-hydroxy-3′-isobutyl-5′-propylphenyl) -5-chlorobenzotriazole
5-chlorobenzotriazole ultraviolet absorbers, 2-
(2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'
-Methylphenyl) benzotriazole and other 2′-hydroxyphenylbenzotriazole-based ultraviolet absorbers,
2,2′-dihydroxy-4-methoxybenzophenone,
2,2'-dihydroxybenzophenone 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- Cyanoacrylate-based ultraviolet absorbers such as cyano-3,3-diphenylacrylate, ethyl-2-cyano-3,3-diphenylacrylate, and octyl-2-cyano-3,3-diphenylacrylate can be used. The amount of these ultraviolet absorbers is usually about 0.1 to 10% by weight. When used in combination with a radical scavenger, particularly from the viewpoint of compatibility between weather resistance and hot water resistance, and for the purpose of the present invention, as a UV absorber non-chlorinated benzophenone-based, or cyanoacrylate Systems are preferred.

As the foaming agent used in the foamed resin layer 3 of the present invention, a heat-expandable capsule foaming agent containing a low-boiling hydrocarbon is preferable. The reason for this is that the thermal expansion type capsule foaming agent has a substantially constant expansion temperature and a substantially constant expansion rate, and can easily form a foamed resin layer composed of uniform foam cells. It is. Further, for the above reasons, it is suitable for forming a foamed resin layer with a T-die extruder. As the material of the shell of the thermal expansion type capsule foaming agent, vinylidene chloride-acrylonitrile copolymer, acrylonitrile-acrylic copolymer, nitrile-based copolymer, and the like can be used. Is pentane, isopentane,
Butane, isobutane, normal hexane, etc. can be used, but considering environmental friendliness and extruding with a T-die extruder, a non-chlorine-based nitrile-based copolymer is suitable as the shell material. Pentane is a suitable hydrocarbon. Further, as the foaming agent used for the foamed resin layer 3 of the present invention, a thermal decomposition type foaming agent of an azo compound such as azodicarbonamide can be used in addition to the above-mentioned thermal expansion type capsule foaming agent. The amount of the foaming agent to be mixed with the olefin-based thermoplastic resin may be appropriately determined according to the required design properties, but is generally from 0.5 to 15 parts by weight per 100 parts by weight of the olefin-based thermoplastic resin.

As the inorganic filler used in the foamed resin layer 3 of the present invention, one or more inorganic substances such as aluminum hydroxide, magnesium hydroxide, calcium carbonate, barium carbonate, antimony trioxide and titanium oxide are used. Can be used. The reason for using this inorganic filler is to make the flammable olefin-based thermoplastic resin flame-retardant, and the mixing amount of this inorganic filler with the olefin-based thermoplastic resin is It is necessary to mix at least 80 parts by weight with respect to 100 parts by weight of the plastic resin. By mixing the inorganic filler in this way, the foamed resin layer 3 can be provided with flame retardancy.

The foamed resin layer 3 of the present invention may be colored by adding a pigment or the like as needed. The coloring by adding the pigment may be transparent coloring or opaque (concealing) coloring.

Next, the picture layer 4 of the present invention generally comprises gravure printing, offset printing, silk screen printing,
It can be formed with ink by a known printing method such as 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 vehicle, chlorinated polyolefins such as chlorinated polyethylene and chlorinated polypropylene, polyester, polyurethane composed of isocyanate and polyol, acrylic, vinyl acetate, vinyl chloride-vinyl acetate copolymer, cellulose resin, polyamide resin These may be used as a mixture of one or more kinds, and pigments, solvents, various auxiliaries and the like may be added thereto to form inks (paints). For the purpose of the present invention, polyesters,
A non-chlorine-based resin obtained by mixing one or more of polyurethane, acrylic, vinyl acetate, cellulose-based resin, polyamide-based resin, and the like comprising an isocyanate and a polyol is preferable.

Next, the concavo-convex pattern 6 according to the present invention is
The sheet composed of the foamed resin layer 3 / the pattern layer 4 is heated and softened, pressed with an embossing plate, shaped, and solidified by cooling. The processing is performed by a well-known sheet-fed or rotary embossing. Machine is used. Examples of the shape of the concavo-convex pattern include a wood grain board conduit groove, a stone board surface irregularity, a cloth surface texture, a satin finish, a grain, a hairline, and a linear groove.

FIG. 2 shows a layer configuration diagram of a decorative sheet according to a second embodiment of the present invention.
Reference numeral 11 denotes a configuration in which a protective layer 5 is provided on the printed picture layer 4 of the first embodiment shown in FIG. The protective layer 5 is provided for protecting each layer such as the printed picture layer 4 and the foamed resin layer 3 covered with the protective layer.
It is provided for the purpose of imparting even better abrasion resistance, chemical resistance, stain resistance and the like to the decorative sheet 1 than the decorative sheet 1 of the first embodiment. The protective layer 5 can be expected to have a certain effect even with an epoxy resin, but it is more preferable to form the protective layer 5 using a resin having an isocyanate group. Examples of the resin include a two-component curable urethane resin and a one-component moisture-curable urethane resin.

The two-part curable urethane resin is a urethane resin containing polyol as a main component and isocyanate as a crosslinking agent (curing agent). As the polyol, one having two or more hydroxyl groups in the molecule, for example, polyethylene glycol, polypropylene glycol, acrylic polyol, polyester polyol, polyether polyol, polycarbonate polyol and the like are used. As the isocyanate, a polyvalent isocyanate having two or more isocyanate groups in a molecule is used. For example, aromatic isocyanate such as 2-4 tolylene diisocyanate, xylene diisocyanate, 4-4 diphenylmethane diisocyanate, or hexaisocyanate Aliphatic (or alicyclic) isocyanates such as methylene diisocyanate, isophorone diisocyanate, hydrogenated tolylene diisocyanate, and hydrogenated diphenylmethane diisocyanate are used. Alternatively, adducts or multimers of the above-mentioned various isocyanates can also be used. For example, there are an adduct of tolylene diisocyanate and a trimer of tolylene diisocyanate.

On the other hand, the one-component moisture-curable urethane resin is a composition containing a prepolymer having an isocyanate group at a molecular terminal as an essential component. The prepolymer is usually a polyisocyanate prepolymer having at least one isocyanate group at each terminal of the molecule, and is a solid thermoplastic resin at room temperature. Isocyanate groups react with each other due to moisture in the air to cause a chain extension reaction,
As a result, a reactant having a urea bond in the molecular chain is generated,
The urea bond further reacts with the isocyanate group at the molecular terminal, causing a biuret bond to branch and cause a crosslinking reaction.

The skeleton structure of the molecular chain of the prepolymer having an isocyanate group at the molecular terminal is arbitrary, and specific examples thereof include a polyurethane skeleton having a urethane bond, a polyester skeleton having an ester bond, and a polybutadiene skeleton. One or more skeleton structures are employed. When there is a urethane bond in the molecular chain, the terminal isocyanate group also reacts with the urethane bond,
An allophanate bond is formed, and the allophanate bond also causes a crosslinking reaction.

The protective layer 5 may be formed by applying a solution of a two-component curable urethane resin or a one-component moisture-curable urethane resin to a known coating method such as a gravure printing method or a roll coating method. In the case of a one-component moisture-curable urethane resin, the one-component moisture-curable urethane resin melted by heating is extruded by a known roll coating method and extrusion. It can be formed by coating on the print pattern layer 4 by a coating method such as a coating method. The thickness of the protective layer 5 is 0.5 to 100 μm when dry, usually about 1 to 10 μm.

The reason why the protective layer 5 is preferably formed of a resin having an isocyanate group rather than an epoxy resin is that the protective layer 5 is covered with the protective layer 5 and comes closer to the paper base 2 than the protective layer 5. By using an organic UV absorber having an OH group in the molecule in the layer, even if the UV absorber oozes out into the protective layer 5, the UV absorber can be used.
Since the OH group and the isocyanate group of the protective layer 5 form a urethane bond and are trapped in the protective layer 5, the ultraviolet absorber exudes onto the protective layer 5 with time and the surface of the protective layer 5 is removed. Contamination can be prevented. In particular, it is effective in the case of an olefin-based resin from which an organic ultraviolet absorber easily exudes.

Although not shown, an adhesive layer may be provided between the paper base 2 and the foaming agent layer 3 and / or between the foamed resin layer and the picture layer. As the resin used for the adhesive layer, the above-described two-component curable urethane resin or one-component moisture-curable urethane resin is suitable. As a method of forming this adhesive layer, a solution that has been made into a solution must be coated by a well-known gravure printing method, or a coating method such as a roll coating method, or in the case of a one-component moisture-curable urethane resin, 1
It can be formed by applying a liquid moisture-curable urethane resin by a known coating method such as a roll coating method or an extrusion coating method. An appropriate amount of the adhesive layer to be applied is 0.05 to 10 g / m ² when dry. In this manner, by providing an adhesive layer between the paper base 2 and the foaming agent layer 3 and / or between the foaming resin layer and the picture layer, the adhesive strength between the respective layers is further increased. Can be stronger. When this adhesive layer is also provided, it is natural that the ultraviolet absorbent is captured similarly to the protective layer 5.

In the decorative sheet of the present invention, the radical scavenger as a light stabilizer or the ultraviolet absorber is a layer other than the foamed resin layer, for example, a pattern layer, a protective layer,
It may be added to any layer such as an adhesive layer.

Further, the decorative sheet of the present invention comprises the protective layer 5
An antibacterial agent can be added to the composition to provide antibacterial properties. Examples of the antibacterial agent include activated carbon, activated alumina,
Inorganic adsorbents such as silica gel, zeolite, hydroxyapatite, zirconium phosphate, titanium phosphate, potassium titanate, bismuth hydroxide, zirconium hydroxide,
A silver-based antibacterial agent, or an antibacterial inorganic salt, which is carried on an inorganic ion exchanger such as hydrotalside in combination with silver ions or silver ions in addition to copper ions and zinc ions, is combined with zinc oxide particles. Well-known compounds such as zinc oxide compounds. Further, these antibacterial agents have an average particle diameter of 10 μm or less, preferably about 0.01 to 5 μm from the viewpoint of the effective area of the antibacterial agent. 1 to 10 parts by weight per part is suitable.

[0035]

Example 1 A flame-retardant backing paper having a basis weight of 140 g / m ² (E-140SRS manufactured by Kishu Paper) was used as a base layer made of paper, and a foamed resin layer having the composition shown in Table 1 was formed on this surface. composition by applying extruded from a T-die such that the 100 g / m ² in unfoamed state, 140 g / m ² flame retardant backing paper / laminate a consisting of foamed resin layer forming composition 100 g / m ² Was prepared.

[0036]

Next, a two-part curable urethane resin was applied to the entire surface of the foamed resin layer forming composition of the laminate A at a rate of 1 g / m 2 when dry.
While coating by a well-known gravure printing method to be ^2, acryl coating Kumen - using an acrylic polyol as the urethane resin (prepolymer means a two-liquid reaction type resin to form a urethane bond by reacting with the isocyanate ) To form a texture pattern layer by gravure printing with a printing ink consisting of), then foaming the foamed resin layer forming composition in a heating and foaming furnace (170 ° C. for 1 minute), and then from the texture pattern layer side At least 190 ° surface temperature with heater
C, and embossing was performed with a cloth-shaped embossing plate to obtain a decorative sheet according to one embodiment of the present invention.

Example 2 The entire surface of the foamed resin layer forming composition of the laminate A of Example 1 was
A liquid-curable urethane resin is applied by a well-known gravure printing method so as to be 1 g / m ² at the time of drying, and an acrylic-urethane resin (an acrylic polyol is used as a prepolymer, and is reacted with isocyanate to form a urethane resin on the coated surface. Gravure printing with a printing ink consisting of a two-component reactive resin that forms a bond) to form a cloth pattern layer,
A two-component curable urethane resin is applied to the entire surface of the cloth pattern layer by a well-known gravure printing method so as to become 1 g / m ² at the time of drying to form a protective layer, and then a heating foaming furnace (1 ° C. at 170 ° C.) ), The foamed resin layer forming composition is foamed, and then the fabric pattern layer side is heated with a heater so that the surface temperature becomes at least 190 ° C., and embossing is performed with a fabric-shaped embossing plate. Then, a decorative sheet of another example of the present invention was obtained.

The resulting decorative sheet of the present invention has excellent weather resistance and flexibility and design as compared with the conventional PVC decorative sheet even though the foamed resin layer is made of an olefin-based thermoplastic resin. There is no inferiority in sex,
Further, it is superior to the conventional PVC decorative sheet in chemical resistance, solvent resistance and stain resistance. In addition, by employing the method for manufacturing a decorative sheet of the present invention, the decorative sheet of the present invention can be manufactured at a relatively low cost.

[0040]

The decorative sheet of the present invention and the method for producing the same have been described in detail so far. However, by adding a radical scavenger as a light stabilizer to the foamed resin layer, a conventional PVC decorative sheet can be produced over time. And a decorative sheet having an interlayer adhesion strength equivalent to that of, a harmful gas such as hydrogen chloride gas can be suppressed as much as possible during incineration, and abrasion resistance and weather resistance , Stain resistance,
The effect is that it is possible to provide a non-PVC decorative sheet having excellent chemical resistance, a beautiful printed pattern and a concavo-convex pattern and an excellent design property at a relatively low cost.

[Brief description of the drawings]

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

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

[Explanation of symbols]

 1,11 decorative sheet 2 paper base material 3 foamed resin layer 4 printed picture layer 5 protective layer 6 uneven pattern

 ──────────────────────────────────────────────────の Continued on the front page F term (reference) 4F100 AA01B AA18 AA21 AH03 AH07 AK03B AK51D AK68B AR00C BA03 BA04 BA07 BA10A BA10D CA01B CA05B CA23B CB00 DE04B DG10A DJ01B EH232 EJ022 EJ392 EJ502 GB08 H08

Claims (8)

[Claims] 1. A base layer made of paper, a foamed resin layer mainly composed of a foaming agent, a radical scavenger, an inorganic filler and an olefin-based thermoplastic resin, and a picture layer are sequentially provided. A decorative sheet, wherein an uneven pattern is provided from the side to the foamed resin layer. 2. The decorative sheet according to claim 1, wherein an adhesive layer is provided between the base material layer and the foamed resin layer and / or between the foamed resin layer and the picture layer. The decorative sheet according to claim 1, wherein 3. The decorative sheet according to claim 1, wherein a protective layer made of a resin having an isocyanate group is provided on the pattern layer in the decorative sheet. 4. In the decorative sheet, the olefin-based thermoplastic resin forming the foamed resin layer comprises an ethylene-vinyl acetate copolymer resin, and the ethylene ratio of the ethylene-vinyl acetate copolymer resin is 10 to 10. The decorative sheet according to any one of claims 1 to 3, wherein the decorative sheet is 40% by weight and has a glass transition point of -15 to + 10 ° C. 5. The decorative sheet according to claim 1, wherein at least the base layer, the foamed resin layer, and the protective layer do not contain a chlorine-containing substance in each of the layers constituting the decorative sheet. The decorative sheet according to any one of claims 1 to 3, wherein 6. The decorative sheet according to claim 1, wherein in the decorative sheet, the foaming agent is a capsule foaming agent. 7. The decorative sheet according to claim 1, wherein in the decorative sheet, the radical scavenger is a hindered amine radical scavenger. 8. A composition mainly composed of a foaming agent, a radical scavenger, an inorganic filler and an olefin-based thermoplastic resin, which is heated and melted on a paper base layer, is extruded by an extruder, laminated, and laminated. After printing the pattern layer on the composition, while foaming the composition in a heating foaming furnace to form a foamed resin layer, by applying irregularities with an embossing plate from the pattern layer side, and then cooling, A method for manufacturing a decorative sheet, comprising forming an uneven pattern from a picture layer to the foamed resin layer.