JP2007032142A - Decorative sheet for wall finish - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a decorative sheet for wall finish with excellent surface strength. <P>SOLUTION: In this decorative sheet for wall finish, at least foam resin layers and non-foam resin layers are formed in order on a paper base material. (1) The foam resin layer is formed by foaming a foaming agent-containing resin layer. (2) The non-foam resin layer is formed of a resin composition containing, as a resin component, an ethylene-vinyl alcohol polymer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a decorative sheet for wall covering.

  2. Description of the Related Art Conventionally, as a decorative sheet for wall covering (foaming decorative sheet) such as foamed wallpaper, a paper base material (backing paper) in which a foamed resin layer of vinyl chloride resin is formed is known. In recent years, in consideration of the environment, resins that do not contain halogen such as ethylene-vinyl acetate copolymer resin, acrylic resin, and olefin resin have been used for the foamed resin layer (Patent Documents 1 to 3). .

For example, paint containing a microcapsule type foaming agent added to an emulsion containing an acrylic resin and an ethylene-vinyl acetate copolymer resin, coated on a paper substrate, dried, printed with a pattern on the surface, and then heated. A foamed wallpaper is known which is foamed and has an uneven pattern formed by an embossed plate. Further, after forming an unfoamed resin layer made of a resin composition obtained by adding a pyrolytic foaming agent to an ethylene-vinyl acetate copolymer resin on a paper substrate using a T-die extruder, a pattern layer on the surface There is known a foamed wallpaper obtained by printing and then heating and foaming to form an uneven pattern with an embossed plate.
Japanese Patent Laid-Open No. 6-47875 JP 2000-255011 A JP 2001-347611 A

  However, in the conventional wallpaper, a protective layer may be formed to protect the foamed layer, but there is room for improvement in surface strength (scratch resistance, etc.).

  Therefore, the main object of the present invention is to provide a decorative sheet for wall covering excellent in surface strength.

  As a result of intensive studies, the inventor has found that the above object can be achieved by adopting a specific layer structure, and has completed the present invention.

That is, the present invention relates to the following wall covering decorative sheet.
1. A decorative sheet for wall covering in which at least a foamed resin layer and a non-foamed resin layer are sequentially formed on a paper substrate,
(1) The foamed resin layer is a layer formed by foaming the foaming agent-containing resin layer,
(2) The non-foamed resin layer is a layer formed of a resin composition containing an ethylene-vinyl alcohol polymer as a resin component.
This is a decorative sheet for wall covering.
2. Item 2. The decorative sheet for wall covering according to Item 1, wherein the polymer is contained in an amount of 70 to 100% by weight in the resin composition.
3. Item 3. The decorative sheet for wall covering according to Item 1 or 2, wherein the foaming agent-containing resin layer contains a resin obtained from a combination of monomers such that the resin layer does not contain hydrogen bonds.
4). Item 4. The decorative sheet for wall covering according to any one of Items 1 to 3, wherein the foaming agent-containing resin layer is formed of a resin composition containing an ethylene-vinyl acetate copolymer resin as a resin component.
5. Item 5. The decorative sheet for wall covering according to any one of Items 1 to 4, wherein the foaming agent is a pyrolytic foaming agent.
6). Any of the above items 1 to 5, wherein the foaming agent-containing resin layer is formed of a resin composition containing an ethylene-vinyl acetate copolymer resin, an inorganic filler, a pigment, a pyrolytic foaming agent, and a cell regulator. The decorative sheet for wall covering according to crab.
7). Item 7. The wall covering decorative sheet according to any one of Items 1 to 6, wherein at least the foaming agent-containing resin layer is crosslinked by electron beam irradiation.
8). Item 8. The decorative sheet for wall covering according to any one of Items 1 to 7, wherein a non-foamed resin layer is further formed between the paper substrate and the foamed resin layer.
9. Item 9. The decorative sheet for wall covering according to any one of Items 1 to 8, wherein the sheet is embossed from above the outermost surface layer.

  According to the decorative sheet for wall covering of the present invention, since the non-foamed resin layer comprising a specific component is formed on the foamed resin layer, it is excellent in scratch resistance, stain resistance and the like. In particular, since a polymer in which hydrogen bonds are generated in the non-foamed resin layer is used, excellent hardness and the like can be obtained.

<Wall decoration sheet>
The decorative sheet for wall covering of the present invention (present sheet) is a decorative sheet for wall covering in which at least a foamed resin layer and a non-foamed resin layer are sequentially formed on a paper base material,
(1) The foamed resin layer is a layer formed by foaming the foaming agent-containing resin layer,
(2) The non-foamed resin layer is a layer formed of a resin composition containing an ethylene-vinyl alcohol polymer as a resin component.
It is characterized by that.

The material of 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 fiber 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 including; fine paper; thin 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.

Non-foamed resin layer B
In the present invention, a non-foamed resin layer (non-foamed resin layer B) may be formed between the paper substrate and the foamed resin layer as necessary. In particular, when the non-foamed resin layer B is formed as an adhesive layer, excellent adhesion can be obtained. As the non-foamed resin layer B, the same configuration as the non-foamed resin layer A described later can be employed. For example, an ethylene-vinyl acetate copolymer can be suitably used.

Foamed resin layer The foamed resin layer is a layer formed by foaming the foaming agent-containing resin layer. The foaming agent-containing resin layer is not limited as long as it is foamed by the action of the foaming agent (for example, foamed when heated), but obtained from a combination of monomers such that the resin layer does not contain hydrogen bonds. It is preferable to use a resin that can be used. Therefore, for example, an ethylene copolymer resin obtained from a combination of ethylene and a monomer having no OH group or COOH group can be suitably used. From this viewpoint, examples of the ethylene copolymer resin include ethylene-vinyl acetate copolymer resin (hereinafter abbreviated as “EVA”), ethylene-methyl methacrylate (EMMA), ethylene-ethyl acrylate (EEA), ethylene-methyl. Acrylate (EMA) or the like can be used. In particular, it is desirable that the resin component is formed of a resin composition containing EVA resin. For example, a resin composition containing an EVA resin, an inorganic filler, a pigment, a thermal decomposable foaming agent, and a cell regulator can be suitably used. In addition, stabilizers, lubricants, and the like can be used as additives.

  When EVA resin is used as the resin component, the vinyl acetate content (copolymerization ratio) of the EVA resin is not limited, but is preferably about 5 to 30% by weight, more preferably about 10 to 20% by weight. .

  The melt flow rate value (MFR) of the resin component is not particularly limited, but is preferably about 5 to 75 g / 10 minutes, and more preferably about 40 to 70 g / 10 minutes.

  The foamed state of the foamed resin layer (for example, the size of foamed cells, the density of foamed cells, etc.) is not limited, and can be appropriately designed according to the type and use of the foamed wallpaper.

  The pyrolytic foaming agent can be selected from known foaming agents. For example, azo compounds such as azodicarbonamide (ADCA) and azobisformamide; and bidazides such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide. The content of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. From the viewpoint of the expansion ratio, it is 1.5 times or more, preferably about 3 to 7 times, and the pyrolytic foaming agent is preferably about 1 to 20 parts by weight with respect to 100 parts by weight of the resin component. .

  As the cell adjusting agent, for example, a metal soap such as zinc stearate can be used. The content of the cell modifier is preferably about 0.3 to 10 parts by weight and more preferably about 1 to 5 parts by weight with respect to 100 parts by weight of the resin component.

  Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including an inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained. About 0-100 weight part is preferable with respect to 100 weight part of resin components, and, as for content of an inorganic filler, about 20-70 weight part is more preferable.

  For pigments, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), cadmium red, Inorganic pigments such as ultramarine, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, zinc sulfide; for example, aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), many Cyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone, perylene, diketopyrrolopyrrole, dibromanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halo Organic pigments of emissions phthalocyanine), and the like. The content of the pigment is preferably about 10 to 50 parts by weight and more preferably about 15 to 30 parts by weight with respect to 100 parts by weight of the resin component.

  What is necessary is just to implement according to the method described in the manufacturing method of the postscript as a method of foaming a foaming agent containing resin layer.

Non-foamed resin layer The non-foamed resin layer (non-foamed resin layer A) mainly protects the foamed resin layer. In the present invention, a layer formed of a resin composition containing an ethylene-vinyl alcohol polymer as a resin component is defined as a non-foamed resin layer. A known or commercially available polymer can be used. Moreover, a well-known additive can also be mix | blended with the said resin composition.

  The thickness of the non-foamed resin layer is not limited, but is preferably about 10 to 50 μm, more preferably about 10 to 20 μm.

  Further, the content of the resin component in the resin composition is not limited, but it is preferably set appropriately within a range of usually 70 to 100% by weight.

Pattern Pattern Layer The foamed wallpaper of the present invention may have a pattern pattern layer on the front surface of the non-foamed resin layer as necessary.

  The pattern layer 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 pattern pattern layer can be formed, for example, by printing a pattern pattern on the front surface of the base sheet. In addition, when forming a picture pattern layer, you may form a primer layer previously as needed. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, and offset printing. As the printing ink, a printing ink containing a colorant, a vehicle, and a solvent can be used. These inks may be known or commercially available.

  As the colorant, for example, a pigment used in the above-described foaming agent-containing resin layer can be appropriately used.

  The vehicle can be set according to the type of the base sheet. For example, acrylic resin, styrene resin, polyester resin, urethane resin, chlorinated polyolefin resin, vinyl chloride-vinyl acetate copolymer resin, polyvinyl butyral resin, alkyd resin, petroleum resin, ketone resin, epoxy Resin, melamine resin, fluorine resin, silicone resin, fiber derivative, rubber resin and the like.

  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.

  The thickness of the design pattern layer is different from the type of design pattern, but is generally preferably about 0.1 to 10 μm.

The embossed invention sheet may be appropriately provided with an embossed pattern in addition to the foamed embossed pattern. In this case, embossing may be performed from the top surface layer of the sheet (on the side opposite to the paper-based substrate). Embossing can be performed by known means such as an embossed plate. For example, when the outermost surface layer is the non-foamed resin layer A, a desired embossed pattern can be formed by pressing the embossed plate after heat-softening the front surface. Examples of the embossed pattern include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grain texture, a hairline, and a multiline groove.

<Method for manufacturing wall covering sheet>
The manufacturing method of this invention sheet | seat is not specifically limited. For example, co-extrusion with a T-die extruder is suitable. A multi-manifold type T-die capable of simultaneously forming two layers by simultaneously extruding molten resin corresponding to two layers can be used. In this case, the resin composition for forming the foaming agent-containing resin layer and the resin composition for forming the non-foamed resin layer are placed in separate cylinders, and two types and two layers are simultaneously extruded to form and laminate. That's fine. In this method, the coextruded laminate is simultaneously laminated (film formation) on a paper-based substrate. The resin layer laminated simultaneously with extrusion on the paper base is bonded to the paper base because it has adhesiveness by heat melting.

  Alternatively, a laminate in which two types and two layers are simultaneously formed in advance may be prepared, placed on a paper base, and thermally laminated to adhere to the paper base. Moreover, after extruding and laminating one layer of the two types of two resin layers on the paper-based substrate, the second layer may be extruded on the first layer to form two resin layers.

  After simultaneous lamination on the paper substrate, the foamed resin layer is formed by heating the foaming agent-containing resin layer. The heating conditions are not limited as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent. The heating temperature is preferably about 210 to 240 ° C., and the heating time is preferably about 20 to 80 seconds.

  Electron beam irradiation may be performed before the heat treatment. Thereby, since the resin component can be crosslinked, the surface strength of the foamed wallpaper, the degree of foaming, etc. can be controlled. The energy of the electron beam is preferably about 150 to 250 kV. The irradiation amount is preferably about 1 to 7 Mrad. A known electron beam irradiation apparatus can be used as the electron beam source. Crosslinking can also be performed using a chemical crosslinking agent (also referred to as a crosslinking agent or a crosslinking aid).

  In the case of performing electron beam irradiation, the composition may contain a crosslinking agent. Any crosslinking agent that promotes crosslinking by electron beam irradiation may be used. Examples thereof include polyfunctional monomers such as neopentyl glycol dimethacrylate and trimethylolpropane trimethacrylate, oligomers, and the like. The crosslinking agent is preferably about 0 to 10 parts by weight, more preferably 1 to 4 parts by weight, based on 100 parts by weight of the resin component.

  When producing a foam wallpaper having a pattern layer, it is preferable to form the pattern layer on the surface of the non-foamed resin layer before the heat treatment. The pattern pattern layer may be formed as described above.

  Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the present invention is not limited to the examples.

Example 1
Using a three-type three-layer multi-manifold T-die extruder, a film was formed in the order of i) non-foamed resin layer / ii) foaming agent-containing resin layer / iii) non-foamed resin layer in the order of 15 μm / 100 μm / 10 μm, A backing paper was laminated on the surface of the iii) layer. The extrusion conditions at this time were as follows: i) the resin of the layer had a cylinder temperature of 190 ° C., the ii) the resin of the layer had a cylinder temperature of 120 ° C., and the iii) the resin of the layer had a cylinder temperature of 100 ° C. In both cases, the die temperature was 140 ° C. Next, after the electron beam (175 KV 3Mrad) was irradiated from above the i) layer to crosslink the ii) layer, the i) layer was subjected to a corona discharge treatment. Furthermore, 2 g / m ² of EVA water-based emulsion was applied as a primer treatment by a gravure printing machine, and a fabric pattern was printed thereon using a water-based ink “Hydric (manufactured by Dainichi Seika Kogyo)” as a pattern print. Next, the foaming agent contained in the foaming agent-containing resin layer was foamed by heating in a gear oven (220 ° C. × 30 seconds). Further, the foam was embossed with a textured pattern to obtain a desired wallpaper.

  Each layer was formed using the following components.

  The non-foamed resin layer i) was formed from an ethylene-vinyl alcohol copolymer “EVAL G156: manufactured by Kuraray”.

  The foamed resin layer ii) is composed of 100 parts by weight of EVA resin “Evaate CV5053 (MFR = 70, VA = 20%): manufactured by Sumitomo Chemical”, 30 parts by weight of calcium carbonate “Whiteon H: manufactured by Toyo Fine Chemical”, and titanium dioxide “R”. -108: DuPont "25 parts by weight, Foaming agent" Vinole AC # 3: Eiwa Kasei Kogyo "4 parts by weight, Stabilizer" ADK STAB OF-102: Asahi Denka Kogyo "5 parts by weight and cross-linking agent" OPSTAR JUA- " 702: JSR "was formed from a resin composition containing 1 part by weight.

  The non-foamed resin layer iii) was formed from EVA resin “Evaate CV5053 (MFR = 70, VA = 20%): manufactured by Sumitomo Chemical”.

Example 2
Ii) Wallpaper was prepared in the same manner as in Example 1 except that ethylene-methyl methacrylate resin “ACRIFTH WH401 (MFR = 20): manufactured by Sumitomo Chemical Co., Ltd.” was used to form the layer, and the cylinder temperature was 130 ° C. as the extrusion condition. did.

Comparative Example 1
Using a three-type three-layer multi-manifold T-die extruder, a film was formed in the order of i) non-foamed resin layer / ii) foaming agent-containing resin layer / iii) non-foamed resin layer in the order of 15 μm / 100 μm / 10 μm, A backing paper was laminated on the surface of the iii) layer. The extrusion conditions at this time were as follows: the i) layer resin had a cylinder temperature of 160 ° C., the ii) layer resin had a cylinder temperature of 120 ° C., and the iii) layer resin had a cylinder temperature of 100 ° C. In either case, the die temperature was 120 ° C. Subsequent steps were the same as in Example 1.

The non-foamed resin layer i) was formed of an ethylene-methyl methacrylate resin “ACRIFTH WH401 (MFR = 20): manufactured by Sumitomo Chemical”.
The foamed resin layer ii) and the non-foamed resin layer iii) were the same as in Example 1.

Test example 1
The sheets obtained in each Example and Comparative Example were examined for scratch resistance and the like. The results are shown in Table 1.

Each physical property in Table 1 was measured and evaluated by the following methods.
(1) Scratch resistance test The scratch resistance test was conducted in accordance with the “Surface Strengthening Wallpaper Performance Regulations” established by the Japan Vinyl Industry Association Vinyl Construction Committee. According to this method, it is described as follows. In other words, a test piece was attached to the Gakushin Abrasion Tester (JIS L0849 Abrasion Tester Type II), a metal nail specified by the same group was applied to the tester's friction element, and a 200 g load was applied to the tip of the metal nail. The specimen is reciprocated five times, the surface condition of the specimen after the test is observed, and judgment is made based on the degree of surface damage. As an evaluation, it is evaluated in 5 grades of 1st to 5th grades, 5th grade: no change, 4th grade: slight change on the surface, 3rd grade: surface appears torn, 2nd grade: backing material such as paper breaks the surface. Visible (less than 1 cm in length) Grade 1: The surface is torn and the backing material such as paper is visible (length is 1 cm or more). In this evaluation, it was set as ◎, ○, Δ, ×, and ◎: Grade 5 ○: Grade 4 Δ: Grade 3 ×: Grades 2 to 1 were evaluated.
(2) Contamination resistance It was performed in accordance with the “Smudge Prevention Wallpaper Performance Regulations” established by the Vinyl Research Foundation of the Japan Vinyl Industry Association. Using coffee, soy sauce, red crayon, and water-based sign pen as pollutants, adhere to the design surface of the test piece, and after 24 hours, wipe off with water or a cloth soaked in neutral detergent or tissue pepper, 1 hour later Judgment is based on the remaining amount of contaminants. As an evaluation, it is evaluated in five grades, grade 1 to grade 5. Grade 5: Contamination gray scale No. 5 (no dirt remains) Grade 4: Contamination gray scale No. 4 (no dirt remains) 3 Grade: Gray scale for pollution No. 3 (slightly dirty) Grade 2: Gray scale for pollution No. 2 (slightly dirty) Grade 1: Gray scale for pollution No. 1 or more (higher dirt) (Remaining gray scale for contamination: JIS L0805). In this evaluation, it was set as ◎, ○, Δ, ×, and ◎: Grade 5 ○: Grade 4 ×: Grades 3 to 1 were evaluated.

Claims (9)

A decorative sheet for wall covering in which at least a foamed resin layer and a non-foamed resin layer are sequentially formed on a paper substrate,
(1) The foamed resin layer is a layer formed by foaming the foaming agent-containing resin layer,
(2) The non-foamed resin layer is a layer formed of a resin composition containing an ethylene-vinyl alcohol polymer as a resin component.
This is a decorative sheet for wall covering. The decorative sheet for wall covering according to claim 1, wherein the polymer is contained in an amount of 70 to 100% by weight in the resin composition. The decorative sheet for wall covering according to claim 1 or 2, wherein the foaming agent-containing resin layer contains a resin obtained from a combination of monomers such that the resin layer does not contain hydrogen bonds. The decorative sheet for wall covering according to any one of claims 1 to 3, wherein the foaming agent-containing resin layer is formed of a resin composition containing an ethylene-vinyl acetate copolymer resin as a resin component. The decorative sheet for wall covering according to any one of claims 1 to 4, wherein the foaming agent is a pyrolytic foaming agent. The said foaming agent containing resin layer is formed of the resin composition containing ethylene-vinyl acetate copolymer resin, an inorganic filler, a pigment, a thermal decomposition-type foaming agent, and a cell regulator. The decorative sheet for wall covering according to crab. The decorative sheet for wall covering according to any one of claims 1 to 6, wherein at least the foaming agent-containing resin layer is crosslinked by electron beam irradiation. The decorative sheet for wall covering according to any one of claims 1 to 7, wherein a non-foamed resin layer is further formed between the paper substrate and the foamed resin layer. The decorative sheet for wall covering according to any one of claims 1 to 8, which is embossed from above the outermost surface layer of the sheet.