JP2011218818A - Decorative sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a decorative sheet which is excellent in wear resistance and scratch resistance, and, which is easy in construction.SOLUTION: In the decorative sheet which includes a foaming resin layer made by resin crosslinking and foaming a composition for manufacturing the foaming resin layer including an ethylene copolymer and a foaming agent, (1) the ethylene copolymer is at least one kind selected from the group consisting of an ethylene-(meth)acrylate copolymer and an ethylene-(meth)acrylate-(meth)acrylate ester copolymer, and (2) the ethylene copolymer contains 4 to 20 mass% of (meth)acrylate unit content, and, 0 to 25 mass% of (meth)acrylate ester unit content, and the melt flow rate (190°C) is 10 to 100 g/10 min.

Description

  The present invention relates to a decorative sheet including a foamed resin layer obtained by resin crosslinking and foaming a composition for producing a foamed resin layer. In the present specification, the ethylene copolymer means a copolymer containing ethylene as a monomer component.

  Conventionally, a decorative sheet in which a vinyl chloride resin layer is formed on a paper base (backing paper) is known. In recent years, in consideration of the environment, ethylene-vinyl acetate copolymer resin (EVA) containing no halogen is used for the foamed resin layer (Patent Document 1). EVA is preferable as a resin component of the foamed resin layer because it is flexible without using a plasticizer, is excellent in low-temperature characteristics and light resistance, and has good processing stability. It is also preferable in that it is harmless to the human body. Furthermore, since EVA has high adhesiveness with other resins, it is easy to produce a decorative sheet including two or more resin layers.

  However, although a decorative sheet provided with a foamed resin layer containing EVA as a resin component has some degree of wear resistance and scratch resistance, its performance is still insufficient. Further, the decorative sheet has insufficient flexibility (strong stiffness). Therefore, it is difficult to follow construction sites such as corners and curved portions, and construction is not easy.

JP 20063074741

  Therefore, the main object of the present invention is to provide a decorative sheet that is excellent in wear resistance and scratch resistance and is easy to construct.

  As a result of intensive studies, the present inventor has found that the object can be achieved when a foamed resin layer obtained by resin-crosslinking a specific ethylene copolymer is included, and the present invention has been completed.

That is, the present invention relates to the following decorative sheet.
1. A decorative sheet comprising a foamed resin layer obtained by resin crosslinking and foaming a composition for producing a foamed resin layer containing an ethylene copolymer and a foaming agent,
(1) The ethylene copolymer is at least one selected from an ethylene- (meth) acrylic acid copolymer and an ethylene- (meth) acrylic acid- (meth) acrylic acid ester copolymer,
(2) The ethylene copolymer has a (meth) acrylic acid unit content of 4 to 20% by mass, a (meth) acrylic acid ester unit content of 0 to 25% by mass, and a melt flow rate (190 ° C.). Is 10 to 100 g / 10 min.
A decorative sheet characterized by that.
2. Item 2. The decorative sheet according to Item 1, wherein the composition further comprises a crosslinking agent.
3. Item 3. The decorative sheet according to Item 2, wherein the crosslinking agent is contained in an amount of 0.1 to 2 parts by mass with respect to 100 parts by mass of the ethylene copolymer.
4). Item 4. The decorative sheet according to any one of Items 1 to 3, comprising 0.5 to 10 parts by mass of the foaming agent with respect to 100 parts by mass of the ethylene copolymer.
5. The said item 1-4 the composition for foamed resin layer manufacture further contains 0.1-5 mass parts with respect to 100 mass parts of said ethylene copolymers at least 1 sort (s) chosen from the polyhydric alcohol and its multimer. A decorative sheet according to any one of the above.
6). The decorative sheet according to any one of Items 1 to 5, wherein the composition for producing a foamed resin layer further comprises 5 to 200 parts by mass of an inorganic compound with respect to 100 parts by mass of the ethylene copolymer.
7). Item 7. The decorative sheet according to Item 6, wherein the inorganic compound is at least one of calcium carbonate and titanium oxide.
8). The said resin crosslinking is electron beam crosslinking and / or bridge | crosslinking by the said crosslinking agent, The gel fraction of the crosslinked material obtained by this bridge | crosslinking is 20 to 90%, The said claim | item 1-7. Makeup sheet.
9. A decorative sheet comprising a layer of a crosslinked product obtained by resin crosslinking of a composition containing an ethylene copolymer as a surface protective layer,
(1) The ethylene copolymer is at least one selected from an ethylene- (meth) acrylic acid copolymer and an ethylene- (meth) acrylic acid- (meth) acrylic acid ester copolymer,
(2) The ethylene copolymer has a (meth) acrylic acid unit content of 4 to 20% by mass, a (meth) acrylic acid ester unit content of 0 to 25% by mass, and a melt flow rate (190 ° C.). Is 10 to 100 g / 10 min.
Item 10. The decorative sheet according to any one of Items 1 to 8, wherein
10. Item 10. The decorative sheet according to Item 9, wherein the composition further comprises a crosslinking agent.
11. Item 11. The decorative sheet according to Item 10, comprising 0.1 to 2 parts by mass of the crosslinking agent with respect to 100 parts by mass of the ethylene copolymer.
12 Item 12. The decorative sheet according to any one of Items 9 to 11, wherein the resin crosslinking is electron beam crosslinking and / or crosslinking with the crosslinking agent, and the gel fraction of the crosslinked product is 20 to 90%.

  The decorative sheet of the present invention is less scratched on the surface and excellent in wear resistance and scratch resistance as compared with a decorative sheet including a foamed resin layer containing EVA as a resin component. Moreover, the decorative sheet of the present invention easily follows the shape of the surface to be attached. For example, construction can be easily performed on construction parts such as corners and curved parts. Furthermore, it has a number of advantages such as being easily manufactured by extrusion or the like.

  The decorative sheet of the present invention can be suitably used particularly as a foam wallpaper.

The decorative sheet of the present invention is a decorative sheet comprising a foamed resin layer obtained by resin crosslinking and foaming a composition for producing a foamed resin layer containing an ethylene copolymer and a foaming agent,
(1) The ethylene copolymer is at least one selected from an ethylene- (meth) acrylic acid copolymer and an ethylene- (meth) acrylic acid- (meth) acrylic acid ester copolymer,
(2) The ethylene copolymer has a (meth) acrylic acid unit content of 4 to 20% by mass, a (meth) acrylic acid ester unit content of 0 to 25% by mass, and a melt flow rate (190 ° C.). Is 10 to 100 g / 10 min.
It is characterized by that.

  The decorative sheet of the present invention is superior in wear resistance and scratch resistance as compared with a conventional decorative sheet provided with a foamed resin layer containing EVA as a resin component. Moreover, the decorative sheet of the present invention has excellent followability and can be easily applied to construction sites such as corners and curved parts.

The composition for producing a foamed resin layer is a composition containing an ethylene copolymer and a foaming agent as a composition for producing a foamed resin layer,
(1) The ethylene copolymer includes an ethylene- (meth) acrylic acid copolymer and an ethylene-
It is at least one selected from (meth) acrylic acid- (meth) acrylic acid ester copolymers,
(2) The ethylene copolymer has a (meth) acrylic acid unit content of 4 to 20% by mass, a (meth) acrylic acid ester unit content of 0 to 25% by mass, and a melt flow rate (190 ° C.). Is 10 to 100 g / 10 min.

(Ethylene copolymer)
The ethylene copolymer is at least one copolymer selected from the group consisting of ethylene- (meth) acrylic acid copolymers and ethylene- (meth) acrylic acid- (meth) acrylic acid ester copolymers. Is used.

  The (meth) acrylic acid means acrylic acid or methacrylic acid. That is, the ethylene- (meth) acrylic acid copolymer includes any of ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, and ethylene-acrylic acid-methacrylic acid copolymer.

  Moreover, the said (meth) acrylic acid ester means acrylic acid ester or methacrylic acid ester. That is, when (meth) acrylic acid ester is used as a monomer component, one or both of acrylic acid ester and methacrylic acid ester are included as a monomer component.

  As said (meth) acrylic acid ester, ester of acrylic acid or methacrylic acid and a C1-C8 aliphatic alcohol is mentioned. Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, (meth) acrylic S-butyl acid, i-butyl (meth) acrylate, n-hexyl (meth) acrylate, i-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, etc. It is done.

  In the present invention, the ethylene copolymer includes an ethylene- (meth) acrylic acid copolymer (referred to as a binary copolymer) and an ethylene- (meth) acrylic acid- (meth) acrylic acid ester copolymer (ternary). At least one kind of copolymer). In the present invention, two or more kinds of ethylene- (meth) acrylic acid copolymers (binary copolymers) or ethylene- (meth) acrylic acid- (meth) acrylic acid ester copolymers (ternary copolymer) The above-mentioned ethylene copolymer may be obtained by mixing one or more binary copolymers and one or more terpolymers. Among these, it is preferable to use a ternary copolymer as an essential component, and it is particularly preferable to contain both a binary copolymer and a ternary copolymer. A decorative sheet including a foamed resin layer containing a ternary copolymer as an essential component can easily follow the shape of the surface to be attached. Moreover, when using a binary copolymer and a ternary copolymer together, there exists an advantage that it becomes easy to finely adjust the viscoelasticity etc. of a decorative sheet according to a use.

  The ethylene copolymer has a (meth) acrylic acid unit content of 4 to 20% by mass (preferably 9 to 18% by mass) and a (meth) acrylic acid ester unit content of 0 to 25% by mass (preferably 4 to 20%). And a melt flow rate (MFR) (190 ° C.) of 10 to 100 g / 10 minutes (preferably 20 to 80 g / 10 minutes) is used.

  In addition, MFR in this specification is the value measured based on "JISK7210-1999 190 degreeC 2160g load".

The ethylene- (meth) acrylic acid copolymer has a (meth) acrylic acid unit content of 4 to 4
What uses 20 mass%, Preferably it is 9-18 mass%, and MFR (190 degreeC) is 10-100 g / 10min, Preferably it is 20-80 g / 10min.

  The ethylene- (meth) acrylic acid- (meth) acrylic acid ester has a (meth) acrylic acid unit content of 4 to 20% by mass, preferably 9 to 18% by mass, and a (meth) acrylic acid ester unit content of 25% by mass. % Or less, preferably 4 to 20% by mass, and MFR (190 ° C.) of 10 to 100 g / 10 min, preferably 20 to 80 g / 10 min.

In the present invention, when the binary copolymers, or the ternary copolymers, or one or more of the terpolymers and one or more of the binary copolymers are used in combination, the above (meta) As long as acrylic acid unit content, (meth) acrylic acid ester unit content and MFR are obtained, the (meth) acrylic acid unit content, (meth) acrylic acid ester unit content and MFR of each copolymer before blending are not limited. The MFR of the ethylene copolymer after blending is 10 to 10 as described above.
It is 100 g / 10 minutes, and the MFR of each component before blending is preferably 1 to 600 g / 10 minutes. When the terpolymer and the binary copolymer are used in combination, the blending ratio of the ternary copolymer and the binary copolymer is, as an ethylene copolymer, ternary copolymer: binary copolymer (mass ratio) = 3: 7-10: 0. Is preferable, 5: 5 to 10: 0 is more preferable, and 7: 3 to 9: 1 is particularly preferable.

(Crosslinking agent and crosslinking aid)
The composition for producing the foamed resin layer may be a composition containing a crosslinking agent. Further, a crosslinking aid may be contained. For example, when crosslinking is performed by heat treatment, it is preferable to mix a crosslinking agent and a crosslinking aid. In the case of cross-linking by electron beam irradiation, a cross-linking agent is not necessary, but can be used in combination.

  As the crosslinking agent, a known radical generator that is decomposed by heating and generates free radicals to form a crosslinking bond between molecules or within a molecule can be used. For example, dicumyl peroxide, 1,1-ditertiarybutylperoxy-3,3,5-trimethylcyclohexane, 2,5-dimethyl-2,5-ditertiarybutylperoxyhexane, 2,5-dimethyl-2 Organic peroxides such as 1,5-ditertiarybutylperoxyhexyne, 1,3-bis (tertiarybutylperoxyisopropyl) benzene, tertiarybutylperoxyketone, and tertiarybutylperoxybenzoate. . These crosslinking agents can be used alone or in admixture of two or more.

  Although content of a crosslinking agent is not limited, 0.1-2 mass parts is preferable with respect to 100 mass parts of ethylene copolymers, and 0.1-1.5 mass parts is more preferable.

  Examples of the crosslinking aid include polyunsaturated compounds such as polyallyl compounds and poly (meth) acryloxy compounds. For example, polyallyl compounds such as triallyl isocyanurate, triallyl cyanurate, diallyl phthalate, diallyl fumarate, diallyl maleate, poly (meth) such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate Examples include acryloxy compounds and divinylbenzene. These crosslinking aids can be used alone or in admixture of two or more.

  Although content of a crosslinking adjuvant is not limited, 10 mass parts or less are preferable with respect to 100 mass parts of ethylene copolymers, and 0.1-3 mass parts is more preferable.

(Foaming agent and foaming aid)
The composition for producing a foamed resin layer contains a foaming agent.

As the foaming agent, for example, an inorganic foaming agent or an organic foaming agent is used. From among the known
A material that thermally decomposes above the softening temperature of the ethylene copolymer is selected and used.

  Examples of the inorganic foaming agent include ammonium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, azides and the like.

  Examples of the organic foaming agent include azo compounds such as azodicarbonamide, barium azodicarboxylate, azobisisobutyronitrile, azodicarboxylic acid amide, such as N, N′-dinitrosopentamethylenetetramine, N , N′-dimethyl-N, N′-dinitrosotephthalamide, nitroso compounds such as trinitrotrimethyltriamine, such as 4,4′-oxybis (benzenesulfonylhydrazide), paratoluenesulfonylhydrazide, diphenylsulfone-3, Hydrazide compounds such as 3′-disulfonylhydrazide and allylbis (sulfonylhydrazide), for example, semicarbazide compounds such as p-toluylenesulfonyl semicarbazide and 4,4′-oxybis (benzenesulfonyl semicarbazide), examples If, trichloromonofluoromethane, fluoride alkanes such dichloro monofluoromethane, for example, triazole compounds such as 5-morpholyl-1,2,3,4-thiatriazole and the like.

  These foaming agents can be used alone or in admixture of two or more.

  The content of the foaming agent is not limited, but is preferably set so that the expansion ratio is 2 to 20 times (preferably about 3 to 10 times) and substantially closed cells are obtained. For example, it selects from 0.5-10 mass parts (especially 1-5 mass parts) with respect to 100 mass parts of ethylene copolymers.

  The composition for producing a foamed resin layer may further contain a foaming aid.

  Examples of the foaming aid include urea compounds containing urea as a main component, metal oxides such as zinc oxide and lead oxide, higher fatty acids such as salicylic acid and stearic acid, and metal salts thereof. Among the above, higher fatty acid metal salts are particularly preferable. These foaming aids can be used alone or in admixture of two or more.

  The blending ratio of the foaming aid is not particularly limited, but is preferably 0.1 to 10 parts by mass and more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of the ethylene copolymer.

(Inorganic compounds)
The composition for producing a foamed resin layer may further contain an inorganic compound.

Examples of inorganic compounds include fillers such as calcium carbonate, barium sulfate, and silica, and pigments such as titanium oxide (TiO ₂ ). However, calcium carbonate and silica are inexpensive and versatile, and titanium oxide is white. From the viewpoint of property and hiding properties, calcium carbonate and / or titanium oxide are particularly preferable.

  Although content of an inorganic compound is not limited, 5-200 mass parts is preferable with respect to 100 mass parts of ethylene copolymers, and 10-100 mass parts is more preferable.

(Polyhydric alcohol and / or its multimer)
The composition for producing a foamed resin layer may further contain a polyhydric alcohol and / or a multimer thereof. By containing these, foaming can be promoted. Moreover, discoloration (yellowing) at the time of foaming can be suppressed.

Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol and the like. Examples of the multimer include diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, polypropylene glycol, diglycerin, and ditrimethylolpropane. These polyhydric alcohols can be used alone or in admixture of two or more. Among these, a trihydric or higher polyhydric alcohol such as glycerin or a multimer thereof is preferable.

  Although content of a polyhydric alcohol and / or its multimer is not limited, 0.1-5 mass parts is preferable with respect to 100 mass parts of ethylene copolymers, and 0.5-3 mass parts is more preferable.

(Other)
The said composition for foamed resin layer manufacture may also contain components other than the above in the range which does not affect the effect of this invention. Examples include resin components (such as hydrogenated petroleum resins), colorants, antioxidants, stabilizers, UV absorbers, flame retardants, processing aids, and the like.

Foamed resin layer The decorative sheet of the present invention includes a foamed resin layer obtained by resin crosslinking and foaming the composition for producing a foamed resin layer.

  Prior to resin crosslinking and foaming, the foamed resin layer-producing composition is preferably formed into a sheet or film. Although it does not specifically limit as a shaping | molding means, The extrusion molding mentioned later is preferable.

  Hereinafter, the case where the composition for producing a foamed resin layer is formed into a sheet shape or a film shape will be described as an example. In addition, in this specification, the said composition for foamed resin layer manufacturing is shape | molded in the sheet form or the film form, Comprising: The thing before resin bridge | crosslinking and foaming is called a "foaming agent containing resin layer." The foamed resin layer-producing composition is formed into a sheet or film and is further resin-crosslinked, and before foaming is referred to as a “crosslinked product”.

  As means for cross-linking the foaming agent-containing resin layer, for example, there is cross-linking by electron beam irradiation. In this case, the ethylene copolymer is crosslinked by irradiating the foaming agent-containing resin layer with an electron beam from an electric wire irradiation device.

  Electron beam irradiation conditions adjust an acceleration voltage and an irradiation amount according to the thickness of a foaming agent containing resin layer.

  The acceleration voltage is generally about 100 to 1000 kV, and is preferably about 100 to 600 kV in consideration of the flexibility, strength, and workability of the crosslinked product.

  The irradiation amount is generally about 10 to 500 kilogray (KGy), and is preferably about 10 to 100 kilogray when comprehensively considering the flexibility, strength and processability of the foamed resin layer. If it is this irradiation amount, an ethylene copolymer can fully be bridge | crosslinked, without impairing the softness | flexibility of a foamed resin layer, and abrasion resistance and scratch resistance will be exhibited. Moreover, if there exists this irradiation amount, even when a foamed resin layer is immersed in boiling water, it will be a grade which does not shrink substantially.

  Other means for crosslinking the foaming agent-containing resin layer include thermal crosslinking by heat treatment. In that case, the foaming agent-containing resin layer containing a crosslinking agent can be crosslinked by heat treatment. The heat treatment conditions are not limited, but usually about 120 to 200 ° C is preferable, and about 140 to 180 ° C is more preferable.

The degree of crosslinking is represented by, for example, a gel fraction. In the present invention, the gel fraction of the crosslinked product obtained by the crosslinking is preferably about 20 to 90%, more preferably about 50 to 90%. If the gel fraction is less than 20%, the degree of crosslinking tends to be insufficient. On the other hand, if it exceeds 90%, the flexibility as a film or sheet is lost, and the film becomes brittle and easily lacks in workability. In addition, the gel fraction in the present specification is obtained by immersing 1 g of the crosslinked product (sample) in 80 ml of xylene at 110 ° C. for 24 hours, taking out an undissolved sample and measuring the mass after drying at 120 ° C. for 24 hours, It is a value calculated from the following formula.

Gel fraction (%) = undissolved sample mass (g) / sample mass (1 g) × 100
When foaming the crosslinked product, the crosslinked product is heat-treated. The heat treatment conditions are not limited and can be set as appropriate according to the type of foaming agent, but are usually preferably about 200 to 240 ° C, more preferably about 210 to 230 ° C. The heat treatment time is not limited and can be appropriately set according to the heat treatment temperature, but is usually preferably about 20 to 60 seconds, and more preferably about 25 to 40 seconds. For the heat treatment, for example, a known foaming furnace can be used.

In addition to the above, there is a method in which crosslinking and foaming are simultaneously performed by heat treatment. In this case, the heat treatment condition is usually preferably about 200 to 240 ° C, more preferably about 220 to 240 ° C. The heat treatment time is not limited and can be appropriately set according to the heat treatment temperature. Usually, about 30 to 120 seconds is preferable, and about 40 to 100 seconds is more preferable.
The thickness of the foamed resin layer is not limited, but is preferably about 400 to 1000 μm, and more preferably about 500 to 800 μm.

Decorative sheet The decorative sheet of the present invention only needs to include the foamed resin layer. The decorative sheet of the present invention can be used as, for example, foam wallpaper, cushion floor material, foam leather, and the like. In particular, it is preferably used as a foam wallpaper or a cushion floor material, and more preferably used as a foam wallpaper.
Hereinafter, the decorative sheet of the present invention will be specifically described with foamed wallpaper and cushion flooring as representative examples.

As the foaming wallpaper foaming wallpaper, for example, on paper quality substrate, the adhesive layer, the foamed resin layer, foam wallpaper and the like having a decorative layer and a surface protective layer in this order.

(Paper base material)
The paper base is not particularly limited as long as it has mechanical strength, heat resistance and the like suitable as a wallpaper base, and a fibrous sheet can be generally used.

  Specifically, among fiber sheets, flame retardant paper (pulp-based sheets treated with flame retardants such as guanidine sulfamate and guanidine phosphate); inorganic additives such as aluminum hydroxide and magnesium hydroxide Inorganic paper to be included; fine paper; thin paper; backing paper and the like.

The basis weight of the paper quality substrate is not limited, but preferably about 50 to 300 g / ^{m 2,} about 50 to 80 g / ^{m 2} is more preferable.

(Adhesive layer)
When an adhesive layer is further formed between the paper-based substrate and the foamed resin layer, the foamed resin layer and the paper-based substrate can be more firmly adhered to each other.

Examples of the resin component constituting the adhesive layer include at least one of EVA, ethylene-methyl methacrylate copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methyl acrylate copolymer resin, and the like. Among these, EVA is particularly preferable.

  From the viewpoint of ease of pasting with a paper-based substrate, the MFR of the adhesive layer is preferably larger than the MFR of the ethylene copolymer.

  The thickness of the adhesive layer is not limited, but is preferably about 5 to 20 μm, more preferably about 10 to 15 μm.

(Decoration layer)
The decorative layer has a pattern and imparts design properties to the foamed wallpaper. Examples of the design pattern include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern. The pattern can be selected according to the type of foam wallpaper.

  The decorative layer is formed, for example, by printing a pattern on the front surface of the foaming agent-containing resin layer. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, and offset printing. As the printing ink, a known printing ink containing a colorant, a binder resin, and a solvent can be used.

  The pigment can be used as the colorant.

  Examples of the binder resin include acrylic resins, styrene resins, polyester resins, urethane resins, chlorinated polyolefin resins, vinyl chloride-vinyl acetate copolymer resins, polyvinyl butyral resins, alkyd resins, petroleum Resin, ketone resin, epoxy resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like. These can be used alone or in combination of two or more.

  Examples of the solvent (or dispersion medium) contained in the printing ink include petroleum-based organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, and 2-methoxyacetate. Ester-based organic solvents such as ethyl and 2-ethoxyethyl acetate; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl ketone Ketone organic solvents such as cyclohexanone; ether organic solvents such as diethyl ether, dioxane and tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, Chlorinated organic solvents such as tiger chloroethylene; and water. These can be used alone or in combination of two or more.

  The thickness of the decoration layer is different from the kind of pattern, but is preferably about 0.1 to 10 μm.

(Surface protective layer)
The surface protective layer is preferably a layer of a cross-linked product obtained by resin cross-linking the ethylene copolymer or a composition containing a cross-linking agent. In particular, the surface protective layer preferably contains the binary copolymer as an essential component, and more preferably contains only the binary copolymer without containing the ternary copolymer. When the blending amount of the terpolymer is too large, the scratch resistance and abrasion resistance of the foamed wallpaper are likely to be reduced. When the binary copolymer and the ternary copolymer are used in combination, the blending ratio is preferably about 5: 5 to 9.5: 0.5, and more preferably about 7: 3 to 9: 1.

  The surface protective layer may contain a resin such as hydrogenated petroleum resin and EVA in addition to the ethylene copolymer as long as the effect of the present invention is not hindered. The surface protective layer may further contain additives such as acrylate monomers and oligomers.

  Although the thickness of a surface protective layer is not limited, about 5-30 micrometers is preferable and about 10-20 micrometers is more preferable.

(Emboss)
The front surface of the foam wallpaper may be provided with an uneven pattern by embossing.

  The embossed pattern can be given by, for example, a known embossed plate. For example, a desired embossed pattern can be formed by pressing the embossed plate after heating and softening the front surface of the foamed resin layer. Embossed patterns include wood grain plate conduit grooves, stone plate surface irregularities, cloth surface textures, satin texture, sand texture, hair lines, and multi-line grooves.

(Method for producing foam wallpaper)
The method for producing the foam wallpaper is not particularly limited. For example, the composition for forming the foamed resin layer and the composition for forming the adhesive layer are placed in separate cylinders, and extruded and laminated simultaneously on a paper substrate, and then formed by the composition for manufacturing the foamed resin layer. A decorative layer is formed on the resin layer (foaming agent-containing resin layer), the foaming agent-containing resin layer is cross-linked by resin, and the resulting cross-linked product is foamed, and then the surface protective layer is extruded onto the decorative layer. It can be manufactured by molding.

  Moreover, after laminating | stacking a surface protective layer, you may shape an embossing pattern as needed.

As a cushion floor material , for example, a floor material having a fibrous base material, a non-foamed resin layer, the foamed resin layer, a decorative layer, and a surface protective layer in this order can be given.

(Fiber base material)
As a fibrous base material, the thing similar to the said fibrous sheet can be used.

Although the basis weight of the fibrous base material is not critical, preferably about 10 to 200 g / ^{m 2,} about 20 to 100 g / ^{m 2} is more preferable.

(Non-foamed resin layer)
A non-foamed resin layer is provided to support the foamed resin layer.

  The resin constituting the non-foamed resin layer is not limited, and examples thereof include polyolefin resins and polyvinyl chloride.

  Examples of polyolefin resins include polyethylene, polypropylene, polybutene, polymethylpentene, ethylene-propylene copolymer, EVA, ethylene-acrylic acid copolymer, ethylene-methyl methacrylate copolymer, and ethylene-propylene-butene copolymer. Examples thereof include at least one of a coalescence and a polyolefin-based thermoplastic elastomer.

The non-foamed resin layer may further contain a known additive. Examples of known additives include inorganic compounds. As the inorganic compound, the same inorganic compounds as those exemplified above can be used. Although content of the inorganic compound in a non-foaming resin layer is not specifically limited, It is 20-150 mass parts normally with respect to 100 mass parts of resin components, Preferably it is 50-100 mass parts.

  The thickness of the non-foamed resin layer is preferably about 50 to 2000 μm.

(Decoration layer)
The decorative layer has a pattern and imparts design properties to the cushion floor material. The pattern is the same as described above.

  The decorative layer can be formed by the same method as described above. It can also be formed by transferring a pattern provided on transfer paper or the like to a resin layer.

  The thickness of the decoration layer is different from the pattern type, but is preferably about 1 to 10 μm.

(Surface protective layer)
The surface protective layer is preferably a layer of a cross-linked product obtained by resin cross-linking the ethylene copolymer or a composition containing a cross-linking agent. In particular, the surface protective layer preferably contains the binary copolymer as an essential component, and more preferably contains only the binary copolymer without containing the ternary copolymer. When there is too much compounding quantity of the said ternary copolymer, it is easy to become a cause which the scratch resistance and abrasion resistance of a cushion flooring material fall. When the binary copolymer and the ternary copolymer are used in combination, the blending ratio is preferably about 5: 5 to 9.5: 0.5, and more preferably about 7: 3 to 9: 1.

  The surface protective layer may contain a resin such as hydrogenated petroleum resin and EVA in addition to the ethylene copolymer as long as the effect of the present invention is not hindered. The surface protective layer may further contain additives such as acrylate monomers and oligomers.

  Although the thickness of a surface protective layer is not limited, about 10-500 micrometers is preferable and about 50-200 micrometers is more preferable.

(Emboss)
The front surface of the cushion flooring may be provided with an uneven pattern by embossing.

  The type of embossed pattern and the application method are the same as described above.

(Method of manufacturing cushion flooring)
The method for producing the cushion floor material is not particularly limited. For example, the composition for producing the foamed resin layer and the composition for producing the non-foamed resin layer are respectively placed in a cylinder of an extrusion molding machine so that the non-foamed resin layer and the fibrous base material are in contact with each other. After extrusion lamination on the material, a decorative layer is formed on the resin layer (foaming agent-containing resin layer) formed by the foamed resin layer manufacturing composition, and the foaming agent-containing resin layer is resin-crosslinked. After the crosslinked product is foamed, it can be produced by extruding the surface protective layer on the decorative layer.

  Moreover, after laminating | stacking a surface protective layer, you may shape an embossing pattern as needed.

The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.
In addition, the measuring method of the tensile strength of a sheet | seat, elongation, and gel fraction was as follows.

  1) Tensile strength elongation test: compliant with JIS No. 3 (K6301). However, the tensile test speed was 200 mm / min.

  2) Gel fraction measurement: 1 g of a sample was immersed in 80 ml of xylene at 110 ° C. for 24 hours, an undissolved sample was taken out, the mass after drying at 120 ° C. for 24 hours was measured, and the gel fraction was calculated from the following formula. .

Gel fraction = undissolved sample mass (g) / sample mass (1 g) × 100
Example 1 (binary copolymer)
80 parts by mass of ethylene-methacrylic acid copolymer (methacrylic acid content: 10% by mass, MFR: 100 g / 10 min, density: 940 g / m ³ ) and hydrogenated petroleum resin (“Alcon P100”, manufactured by Arakawa Chemical Industries) 20 In a mixture with parts by mass, 35 parts by mass of calcium carbonate powder (“Whiteon H”, manufactured by Shiraishi Calcium Co., Ltd.), 25 parts by mass of titanium oxide powder (“Tai Pure R108”, manufactured by DuPont) with respect to 100 parts by mass of the mixture A foaming agent-containing resin layer was formed on a backing paper (65 g / m ² ) by extruding a resin composition containing 4 parts by weight of azodicarbonamide (foaming agent). Next, the foaming agent-containing resin layer was crosslinked by irradiating 175 kv electron beam with 3 Mrad, and then heat-treated at 220 ° C. to form a foamed resin layer (100 μm).

Example 2 (Ternary copolymer)
Calcium carbonate powder (“Whiteon” with respect to 100 parts by mass of ethylene-methacrylic acid- (meth) acrylic acid ester copolymer (methacrylic acid content: 10% by mass, MFR: 35 g / 10 min, density: 940 kg / m ³ ) H ”, 35 parts by mass of Shiraishi Calcium Co., Ltd.), 25 parts by mass of titanium oxide powder (“ Tai Pure R108 ”, manufactured by DuPont) and 4 parts by mass of azodicarbonamide (foaming agent) are extruded. Thus, a foaming agent-containing resin layer was formed on the backing paper (65 g / m ² ). Next, the foaming agent-containing resin layer was crosslinked by irradiating 175 kv electron beam with 3 Mrad, and then heat-treated at 220 ° C. to form a foamed resin layer (500 μm).

Example 3 (ternary: binary = 8: 2)
80 parts by mass of an ethylene-methacrylic acid- (meth) acrylic acid ester copolymer (methacrylic acid content: 10% by mass, MFR: 35 g / 10 min, density: 940 kg / m ³ ) and an ethylene-methacrylic acid copolymer (methacrylic acid) Acid content: 10% by mass, MFR: 500 g / 10 min, density: 930 kg / m ³ ) In a mixture with 20 parts by mass, calcium carbonate powder (“Whiteon H”, Shiraishi calcium ( Co., Ltd.) 35 parts by mass, titanium oxide powder (“Tai Pure R108”, manufactured by DuPont) 25 parts by mass, and azodicarbonamide (foaming agent) 4 parts by mass were extruded to form a backing paper ( A foaming agent-containing resin layer was formed on 65 g / m ² ). Next, the foaming agent-containing resin layer was crosslinked by irradiating 175 kv electron beam with 3 Mrad, and then heat-treated at 220 ° C. to form a foamed resin layer (500 μm).

Example 4 (ternary: binary = 7: 3)
70 parts by mass of an ethylene-methacrylic acid- (meth) acrylic acid ester copolymer (methacrylic acid content: 10% by mass, MFR: 35 g / 10 min, density: 940 kg / m ³ ) and an ethylene-methacrylic acid copolymer (methacrylic acid) Acid content: 10% by mass, MFR: 500 g / 10 min, density: 930 kg / m ³ ) In a mixture with 30 parts by mass, calcium carbonate powder (“Whiteon H”, Shiroishi calcium ( Co., Ltd.) 35 parts by mass, titanium oxide powder (“Tai Pure R108”, manufactured by DuPont) 25 parts by mass, and azodicarbonamide (foaming agent) 4 parts by mass were extruded to form a backing paper ( A foaming agent-containing resin layer was formed on 65 g / m ² ). Next, the foaming agent-containing resin layer was crosslinked by irradiating 175 kv electron beam with 3 Mrad, and then heat-treated at 220 ° C. to form a foamed resin layer (500 μm).

(Evaluation of workability)
After applying the starch-based adhesive ("Loua Mild" manufactured by Yayoi Chemical Industry Co., Ltd.) to the back of the foamed wallpaper produced in Examples 1 to 4 so as to have a solid content of 60 g / m ² , in an environment of 5 ° C A) Gypsum board surface, ii) 90 ° angled corners made of gypsum board, iii) 90 ° angle corners made of gypsum board, and observed after standing for 24 hours did. In i), two foamed wallpapers (same foamed wallpaper) were stuck on the surface of the gypsum board.

  The observation results are shown in Table 1 below.

○: No floating is observed at the corner and the abutting portion. Δ: Floating is observed at the corner and the abutting portion. As is apparent from Table 1, the terpolymer is used in comparison with the case where only the binary copolymer is used. It can be seen that the use of a single or a mixture of a binary copolymer and a ternary copolymer has higher flexibility of the sheet (foamed wallpaper) and better conformity to the shape of the construction surface.

(Surface enhancement performance)
The surface strengthening performance (abrasion resistance and scratch resistance) of the foamed wallpaper prepared in Examples 1 to 4 is applied to the surface strength evaluation method described in the Surface Strengthening Wallpaper Performance Regulation established by the Wallpaper Product Standards Council (SV Council). Based on the evaluation. The results are shown in Table 2 below.

  The evaluation method is as follows.

5th grade: No change on the surface, 4th grade: Some change on the surface, 3rd grade ... The surface appears torn, 2nd grade ... The surface is broken and the backing material such as paper is visible (less than 1cm in length), 1st grade ... The surface is torn and the backing material such as paper is visible (length 1cm or more)
As is apparent from Table 2, the produced wallpaper has excellent surface strength.

Reference example 1 (binary copolymer)
An ethylene-methacrylic acid copolymer (methacrylic acid content: 15% by mass, MFR: 25 g / 10 min, density: 940 kg / m ³ ) was processed into a 0.5 mm × 150 mm × 150 mm press sheet.

Next, resin crosslinking was performed by irradiating the press sheet with an electron beam using an electron beam irradiation apparatus “EPS-800, manufactured by NHV Corporation”. The electron beam irradiation conditions were as follows: acceleration voltage: 600 kV, electron current: 4.2 mA, speed: 2 m / min, irradiation width: 540 mm, irradiation atmosphere: in air, irradiation dose: 10 Mrad (50 KGy × 2 passes).

  The gel fraction, tensile breaking strength, and elongation of the obtained crosslinked product sheet were measured.

  The measurement results are shown in Table 3 below.

Comparative Reference Example 1 (EVA)
An ethylene-vinyl acetate copolymer (vinyl acetate content: 10% by mass, MFR: 9 g / 10 min, density: 930 kg / m ³ ) was processed into a 0.5 mm × 150 mm × 150 mm press sheet.

  Next, resin crosslinking was performed by irradiating the press sheet with an electron beam using an electron beam irradiation apparatus. The electron beam irradiation conditions were the same as in Example 1.

  The gel fraction, tensile breaking strength, and elongation of the obtained crosslinked product sheet were measured.

  The measurement results are shown in Table 3 below.

Comparative Reference Example 2 (EVA)
An ethylene-vinyl acetate copolymer (vinyl acetate content: 19% by mass, MFR: 2.5 g / 10 min, density: 930 kg / m ³ ) was processed into a 0.5 mm × 150 mm × 150 mm press sheet.

  Next, resin crosslinking was performed by irradiating the press sheet with an electron beam using an electron beam irradiation apparatus. The electron beam irradiation conditions were the same as in Example 1.

  The gel fraction, tensile breaking strength, and elongation of the obtained crosslinked product sheet were measured.

  The measurement results are shown in Table 3 below.

  As is clear from Table 3, it can be seen that the cross-linked product sheet of Reference Example 1 is superior in strength characteristics to the sheets of Comparative Reference Examples 1 and 2.

Reference example 2 (binary copolymer)
80 parts by mass of ethylene-methacrylic acid copolymer (methacrylic acid content: 10% by mass, MFR: 100 g / 10 min, density: 940 kg / m ³ ), hydrogenated petroleum resin (“Alcon P100”, manufactured by Arakawa Chemical Industries) 20 Parts by weight, 0.5 parts by weight of a crosslinking agent (“Park Mill D”, manufactured by NOF Corporation, Dicumyl Peroxide), 30 parts by weight of calcium carbonate powder (“Whiteon H”, manufactured by Shiraishi Calcium Co., Ltd.), 25 parts by mass of titanium oxide powder (“Tai Pure R108”, manufactured by DuPont) and 5 parts by mass of a foaming agent (“AC # 3K-2”, manufactured by Eiwa Chemical Industries, Ltd., azodicarbonamide) were blended.

  The above blend was mixed for 4 minutes with a lab plast mill. The set temperature at the time of mixing was 110 ° C., and the rotation speed was 100 rotations / minute.

  The mixed resin composition was press-molded at 150 ° C. for 6 minutes to prepare a sheet having a thickness of 200 μm.

  The sheet was then heated at 240 ° C. for 2 minutes to crosslink and foam.

  The obtained crosslinked foamed sheet was measured for scratch resistance and YI (yellowness index).

  The measurement results are shown in Table 4 below.

Reference Example 3 (binary copolymer)
Further, a crosslinked foamed sheet was produced in the same manner as in Reference Example 2 except that 1 part by mass of diethylene glycol was added.

  The obtained crosslinked foamed sheet was measured for scratch resistance and YI (yellowness index).

  The measurement results are shown in Table 4 below.

Reference Example 4 (binary copolymer)
A crosslinked foamed sheet was produced in the same manner as in Reference Example 3 except that diethylene glycol was changed to 1 part by mass of glycerin.

  The obtained crosslinked foamed sheet was measured for scratch resistance and YI (yellowness index).

  The measurement results are shown in Table 4 below.

Comparative Reference Example 3 (EVA)
Ethylene-vinyl acetate copolymer (vinyl acetate content: 20% by mass, MFR: 20 g / 10 min, density: 930 kg / m ³ ) 90 parts by mass, hydrogenated petroleum resin (“Alcon P100”, manufactured by Arakawa Chemical Industries) 10 Parts by weight, 0.5 parts by weight of a crosslinking agent (“Park Mill D”, manufactured by NOF Corporation, Dicumyl Peroxide), 30 parts by weight of calcium carbonate powder (“Whiteon H”, manufactured by Shiraishi Calcium Co., Ltd.), 25 parts by mass of titanium oxide powder (“Tai Pure R108”, manufactured by DuPont), 4 parts by mass of foaming agent (“AC # 3K-2”, manufactured by Eiwa Chemical Industries, Ltd., azodicarbonamide) and 4 parts by mass of zinc stearate (foaming aid) Parts were blended.

  The above blend was mixed for 4 minutes with a lab plast mill. The set temperature at the time of mixing was 110 ° C., and the rotation speed was 100 rotations / minute.

  The mixed resin composition was press-molded at 150 ° C. for 6 minutes to prepare a sheet having a thickness of 200 μm.

  The sheet was then heated at 240 ° C. for 2 minutes to crosslink and foam.

  YI (yellowness index) of the obtained crosslinked foamed sheet was measured according to JIS K 7105.

  Further, the scratch resistance of the obtained crosslinked foamed sheet was measured by the Gakushin type abrasion test method of JIS A6921 6.3.2 (reciprocating the friction element 400 times on the surface layer), and the surface state was observed. The surface condition is best (grade 5) ◎, good (grade 4 or more and less than grade 5) ○, slightly bad (grade 3 or more and less than grade 4) △, bad (less than grade 3) × It was evaluated.

  The measurement results are shown in Table 4 below.

  As is clear from Table 4, it can be seen that the crosslinked foamed sheets of Reference Examples 2 to 4 are superior to the foamed sheet of Comparative Reference Example 3 in terms of surface wear resistance and scratch resistance. Moreover, when a polyhydric alcohol is mix | blended, a hue is improved (yellowness falls), and when a glycerin which is trihydric alcohol is mix | blended especially, it turns out that an effect is high.

Reference Example 5 (binary copolymer on the surface)
An inner layer (100 μm) and a surface layer (10 μm) were laminated on a backing paper (110 μm).

The surface layer was formed of an ethylene-methacrylic acid copolymer (methacrylic acid content: 15% by mass, MFR: 25 g / 10 min, density: 940 kg / m ³ ).

The inner layer was composed of 90 parts by mass of an ethylene-vinyl acetate copolymer (vinyl acetate content: 20% by mass, MFR: 20 g / 10 min, density: 930 g / m ³ ) and hydrogenated petroleum resin (“Alcon P100”, Arakawa Chemical Industries). Made in 10 parts by weight of a mixture, 35 parts by weight of calcium carbonate powder (“Whiteon H”, manufactured by Shiraishi Calcium Co., Ltd.), titanium oxide powder (“Tai Pure R108”, DuPont) with respect to 100 parts by weight of the mixture ) 25 parts by mass and a resin composition containing 4 parts by mass of azodicarbonamide (foaming agent). Both the surface layer and the inner layer were formed by coextrusion molding.

  Next, the laminate was irradiated with 3 Mrad of 175 kv electron beam for 3 Mrad to crosslink the surface layer, and then heat treated at 220 ° C. for 35 seconds to foam the inner layer.

  The scratch resistance of the obtained cross-linked foamed laminate was measured by the Gakushin type abrasion test method of JIS A6921 6.3.2 (reciprocating the friction element 400 times on the surface layer), and the surface state was observed.

  The measurement results are shown in Table 5 below.

Reference Example 6 (binary copolymer on the surface and inner layers)
An inner layer (100 μm) and a surface layer (10 μm) were laminated on a backing paper (110 μm).

The surface layer was formed of an ethylene-methacrylic acid copolymer (methacrylic acid content: 15% by mass, MFR: 25 g / 10 min, density: 940 kg / m ³ ).

The inner layer was composed of 80 parts by mass of an ethylene-methacrylic acid copolymer (methacrylic acid content: 10% by mass, MFR: 100 g / 10 min, density: 940 g / m ³ ) and hydrogenated petroleum resin (“Alcon P1
00 ", manufactured by Arakawa Chemical Industry Co., Ltd.) and 20 parts by mass of calcium carbonate powder (" Whiteon H ", manufactured by Shiraishi Calcium Co., Ltd.) 35 parts by mass, titanium oxide powder (" It was formed from a resin composition containing 25 parts by mass of Taipure R108 "(manufactured by DuPont) and 4 parts by mass of azodicarbonamide (foaming agent). Both the surface layer and the inner layer were formed by coextrusion molding.

  Next, the laminate was irradiated with 3 Mrad of 175 kv electron beam for 3 Mrad to crosslink the surface layer, and then heat treated at 220 ° C. for 35 seconds to foam the inner layer.

  The scratch resistance of the obtained cross-linked foamed laminate was measured by the Gakushin type abrasion test method of JIS A6921 6.3.2 (reciprocating the friction element 400 times on the surface layer), and the surface state was observed.

  The measurement results are shown in Table 5 below.

Reference Example 7 (binary on the surface layer and ternary copolymer on the inner layer)
An inner layer (100 μm) and a surface layer (10 μm) were laminated on a backing paper (110 μm).

The surface layer was formed of an ethylene-methacrylic acid copolymer (methacrylic acid content: 15% by mass, MFR: 60 g / 10 min, density: 940 kg / m ³ ).

The inner layer consists of 70 parts by mass of ethylene-methacrylic acid- (meth) acrylic acid ester copolymer (methacrylic acid content: 10% by mass, MFR: 35 g / 10 min, density: 940 kg / m ³ ) and ethylene-methacrylic acid copolymer. In a mixture with 30 parts by mass (methacrylic acid content: 10% by mass, MFR: 500 g / 10 min, density: 930 kg / m ³ ), calcium carbonate powder (“Whiteon H”) with respect to 100 parts by mass of the mixture, It was formed from a resin composition in which 35 parts by mass of Shiraishi Calcium Co., Ltd.), 25 parts by mass of titanium oxide powder (“Taypure R108”, manufactured by DuPont) and 4 parts by mass of azodicarbonamide (foaming agent) were blended. Both the surface layer and the inner layer were formed by coextrusion molding.

  Next, the laminate was irradiated with 3 Mrad of 175 kv electron beam for 3 Mrad to crosslink the surface layer, and then heat treated at 220 ° C. for 35 seconds to foam the inner layer.

  The scratch resistance of the obtained cross-linked foamed laminate was measured by the Gakushin type abrasion test method of JIS A6921 6.3.2 (reciprocating the friction element 400 times on the surface layer), and the surface state was observed.

  The measurement results are shown in Table 5 below.

Comparative Reference Example 4 (EVA)
An inner layer (100 μm) and a surface layer (10 μm) were laminated on a backing paper (110 μm).

The surface layer was formed of an ethylene-vinyl acetate copolymer (vinyl acetate content: 20% by mass, MFR: 70 g / 10 min, density: 0.94 kg / m ³ ).

  The inner layer is composed of 35 parts by mass of calcium carbonate powder (“Whiteon H”, manufactured by Shiroishi Calcium Co., Ltd.), titanium oxide powder (“Tai Pure R108”, DuPont) with respect to 100 parts by mass of the same ethylene-vinyl acetate copolymer as described above. (Made) 25 mass parts and the resin composition which mix | blended 4 mass parts of azodicarbonamide (foaming agent) were formed. Both the surface layer and the inner layer were formed by coextrusion molding.

  Next, the laminate was irradiated with 3 Mrad of 175 kv electron beam for 3 Mrad to crosslink the surface layer, and then heat treated at 220 ° C. for 35 seconds to foam the inner layer.

  The scratch resistance of the obtained cross-linked foamed laminate was measured by the Gakushin type abrasion test method of JIS A6921 6.3.2 (reciprocating the friction element 400 times on the surface layer), and the surface state was observed. The surface condition is best (grade 5) ◎, good (grade 4 or more and less than grade 5) ○, slightly bad (grade 3 or more and less than grade 4) △, bad (less than grade 3) × It was evaluated.

  The measurement results are shown in Table 5 below.

  As is apparent from Table 5, the crosslinked foamed sheets of Reference Examples 5 to 7 are superior to the foamed sheet of Comparative Reference Example 4 in terms of surface wear resistance and scratch resistance.

Claims (13)

A decorative sheet comprising a foamed resin layer obtained by resin crosslinking and foaming a composition for producing a foamed resin layer containing an ethylene copolymer and a foaming agent,
(1) The ethylene copolymer includes an ethylene- (meth) acrylic acid- (meth) acrylic ester copolymer,
(2) The ethylene copolymer has a (meth) acrylic acid unit content of 4 to 20% by mass, a (meth) acrylic acid ester unit content of 4 to 25% by mass, and a melt flow rate (190 ° C.). Is 10 to 100 g / 10 min.
A decorative sheet characterized by that.   The decorative sheet according to claim 1, wherein the ethylene copolymer further comprises an ethylene- (meth) acrylic acid copolymer. The decorative sheet according to claim 1 or 2, wherein the composition further comprises a crosslinking agent. The decorative sheet according to claim 3, comprising 0.1 to 2 parts by mass of the crosslinking agent with respect to 100 parts by mass of the ethylene copolymer. The decorative sheet according to any one of claims 1 to 4, comprising 0.5 to 10 parts by mass of the foaming agent with respect to 100 parts by mass of the ethylene copolymer. The composition for producing a foamed resin layer further contains at least one selected from polyhydric alcohols and multimers thereof in an amount of 0.1 to 5 parts by mass with respect to 100 parts by mass of the ethylene copolymer. A decorative sheet according to any one of the above. The decorative sheet according to any one of claims 1 to 6, wherein the composition for producing a foamed resin layer further comprises 5 to 200 parts by mass of an inorganic compound with respect to 100 parts by mass of the ethylene copolymer. The decorative sheet according to claim 7, wherein the inorganic compound is at least one of calcium carbonate and titanium oxide. The resin cross-linking is electron beam cross-linking and / or cross-linking with the cross-linking agent, and the gel fraction of the cross-linked product obtained by the cross-linking is 20 to 90%. Makeup sheet. A decorative sheet comprising a layer of a crosslinked product obtained by resin crosslinking of a composition containing an ethylene copolymer as a surface protective layer,
(1) The ethylene copolymer is at least one selected from an ethylene- (meth) acrylic acid copolymer and an ethylene- (meth) acrylic acid- (meth) acrylic acid ester copolymer,
(2) The ethylene copolymer has a (meth) acrylic acid unit content of 4 to 20% by mass, a (meth) acrylic acid ester unit content of 0 to 25% by mass, and a melt flow rate (190 ° C.). Is 10 to 100 g / 10 min.
A decorative sheet according to any one of claims 1 to 9. The decorative sheet according to claim 10, wherein the composition further comprises a crosslinking agent. The decorative sheet according to claim 11, comprising 0.1 to 2 parts by mass of the crosslinking agent with respect to 100 parts by mass of the ethylene copolymer. The decorative sheet according to any one of claims 10 to 12, wherein the resin crosslinking is electron beam crosslinking and / or crosslinking with the crosslinking agent, and the gel fraction of the crosslinked product is 20 to 90%.