JP2007031895A - Foamed wallpaper - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide foamed wallpaper excellent in scratch resistance and suppressed in curl development. <P>SOLUTION: The foamed wallpaper is such that a paper substrate is laminated with a foamed resin layer and a nonfoamed resin layer in this order, wherein (1) the foamed resin layer is a layer formed by foaming a foaming agent-containing resin layer and (2) the nonfoamed resin layer comprises an ethylene-methacrylic acid copolymer resin and a hydrogenated petroleum resin, wherein the content of the hydrogenated petroleum resin in the nonfoamed resin layer is 5-30 wt.%. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a foamed wallpaper having a non-foamed resin layer containing a hydrogenated petroleum resin.

  Conventionally, as foam wallpaper, a paper base (backing paper) in which a foam resin layer made of a 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). .

  Specifically, paint containing a microcapsule type foaming agent in an emulsion containing an acrylic resin and ethylene-vinyl acetate copolymer resin is applied to a paper substrate, dried, and then a pattern layer printed on the surface. Then, after foaming the resin layer, a foamed wallpaper is known in which a concavo-convex pattern is formed by an embossed plate. In addition, an unfoamed resin layer made of a composition containing an ethylene-vinyl acetate copolymer resin and a thermally decomposable foaming agent is extruded on a paper substrate by a T-die extruder, and then a pattern layer is formed on the surface. There is known a foamed wallpaper obtained by printing, then foaming an unfoamed resin layer, and then forming an uneven pattern with an embossed plate.

  Here, an ethylene copolymer resin is used as a non-foamed resin layer for protecting the foamed layer. Among these, ethylene-methacrylic acid copolymer resin is excellent in terms of scratch resistance.

  However, since ethylene-methacrylic acid copolymer resin has high crystallinity, a problem arises that wallpaper using the resin is easily curled. Therefore, when using an ethylene-methacrylic acid copolymer resin, it is necessary to suppress the occurrence of curling by increasing the methacrylic acid content in the resin. On the other hand, when the content of methacrylic acid is increased in order to suppress the occurrence of curling, there arises a problem that scratch resistance is deteriorated.

Therefore, when ethylene-methacrylic acid copolymer resin is used as a protective layer for the foamed resin layer, it is desired to develop a foam wallpaper that has excellent scratch resistance and further suppresses curling.
Japanese Patent Laid-Open No. 6-47875 JP 2000-255011 A JP 2000-347611 A

  The main object of the present invention is to provide a foam wallpaper having excellent scratch resistance and curling is suppressed.

  In light of the problems of the prior art, the present inventor has found that the above object can be achieved by using a laminate having a specific configuration as a decorative wallpaper, and has completed the present invention. .

That is, the present invention relates to the following foamed wallpaper.
1. A foam wallpaper in which at least a foamed resin layer and a non-foamed resin layer are laminated in order on a paper base material,
(1) The foamed resin layer is a layer formed by foaming the foaming agent-containing resin layer,
(2) The foamed wallpaper, wherein the non-foamed resin layer contains an ethylene-methacrylic acid copolymer resin and a hydrogenated petroleum resin.
2. Item 2. The foamed wallpaper according to Item 1, wherein the content of the hydrogenated petroleum resin is 5 to 30% by weight in the non-foamed resin layer.
3. Item 3. The foamed wallpaper according to Item 1 or 2, wherein the methacrylic acid content of the ethylene-methacrylic acid copolymer resin is 10% by weight or less.
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 contains a resin obtained from a combination of monomers such that the resin layer does not contain hydrogen bonds.
5. Item 5. The decorative sheet for wall covering according to any one of Items 1 to 4, wherein the foaming agent-containing resin layer comprises an ethylene copolymer resin obtained from a combination of ethylene and a monomer having no OH group or COOH group.
6). Item 6. The decorative sheet for wall covering according to any one of Items 1 to 5, wherein the foaming agent-containing resin layer is formed of a resin composition containing an ethylene-vinyl acetate copolymer resin as a resin component.
7). Item 7. The wall covering decorative sheet according to any one of Items 1 to 6, wherein the foaming agent is a pyrolytic foaming agent.
8). Item 8. The foamed wallpaper according to any one of Items 1 to 7, further comprising a non-foamed resin layer between the paper substrate and the foamed resin layer.
9. Item 9. The foamed wallpaper according to any one of Items 1 to 8, which has a pattern layer on the outermost surface of the non-foamed resin layer.
10. Item 10. The foamed wallpaper according to any one of Items 1 to 9, which is embossed from above the outermost surface layer of the foamed wallpaper.

  According to the present invention, since the non-foamed resin layer contains an ethylene-methacrylic acid copolymer resin and a hydrogenated petroleum resin, a foamed wallpaper having excellent scratch resistance and curling is suppressed at the same time. Can do.

The foam wallpaper of the present invention is a foam wallpaper in which at least a foam resin layer and a non-foam resin layer are sequentially laminated on a paper-based substrate,
(1) The foamed resin layer is a layer formed by foaming the foaming agent-containing resin layer,
(2) The non-foamed resin layer contains an ethylene-methacrylic acid copolymer resin and a hydrogenated petroleum resin.

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, for example, an ethylene-vinyl acetate copolymer or the like 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, the non-foamed resin layer contains an ethylene-methacrylic acid copolymer resin (hereinafter abbreviated as “EMAA”) and a hydrogenated petroleum resin. By the hydrogenated petroleum resin, the non-foamed resin layer can effectively suppress the occurrence of curling due to the crystallinity of EMAA.

  The hydrogenated petroleum resin is obtained by hydrogenating a petroleum resin, and a known or commercially available one can be used. Examples thereof include hydrogenated aliphatic petroleum resins, hydrogenated aromatic petroleum resins, hydrogenated copolymerized petroleum resins, hydrogenated alicyclic petroleum resins, and hydrogenated terpene resins.

  The hydrogenated petroleum resin content of the non-foamed resin layer can be appropriately set according to the resin component of the non-foamed resin layer, the type of the hydrogenated petroleum resin, etc., but in particular, about 5 to 30% by weight, and more preferably 10 to 20% by weight % Is desirable. The content of EMAA in the non-foamed resin layer is usually about 70 to 95% by weight.

  Further, although the methacrylic acid content of EMAA is not limited, particularly in the present invention, even if it is EMMA having a methacrylic acid content of 10% by weight or less, excellent scratch resistance is obtained while curling is suppressed. It is advantageous in that it can be performed. Of course, when the methacrylic acid content exceeds 10% by weight, more excellent effects can be obtained.

  Further, the non-foamed resin layer may contain additives such as other resins and pigments to the extent that the effects of the present invention are not impaired.

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

Patterned Pattern Layer The foamed wallpaper of the present invention may have a patterned pattern layer on the front surface of the non-foamed resin layer A 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 B, 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.

  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: 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. 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 composed of an ethylene-methacrylic acid copolymer “Nucleel N410 (MFR = 25, MA = 9%): Mitsui DuPont Polychemicals” 90 parts by weight and hydrogenated petroleum resin “Alcon P-115: "Arakawa Chemical Industries" was formed from a resin composition containing 10 parts by weight.

  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”.

Comparative Example 1
The wallpaper was obtained in the same manner as in Example 1 except that the i) layer was formed using an ethylene-methacrylic acid copolymer “Nucleel N410 (MFR = 25, MA = 9%): made by Mitsui DuPont Polychemical”. Produced.

Comparative Example 2
I) Formation of layer: ethylene-methacrylic acid copolymer “Nucleel N410 (MFR = 25, MA = 9%): made by Mitsui DuPont Polychemical” 60 parts by weight and hydrogenated petroleum resin “Alcon P-115: Arakawa A wallpaper was prepared in the same manner as in Example 1 except that a resin composition containing 40 parts by weight of “Chemical Industry” was used.

Test Example 1 (Scratch resistance)
A scratch resistance test was performed on the foamed wallpaper produced in the examples and comparative examples.

  The scratch resistance test was conducted in accordance with the “Surface Strengthening Product Performance Labeling Regulations” established by the Japan Vinyl Industry Association Building Subcommittee. That is, the test was performed according to the following procedure.

  First, a test piece (foamed wallpaper) was attached to a Gakushin abrasion tester (JIS L0849 abrasion tester type II). A metal claw designated by the same group was attached as a friction element of the testing machine, and a load of 200 g was applied to the tip of the metal claw and the test piece was reciprocated five times. Then, scratch resistance was evaluated by confirming the surface state (degree of damage) of the test piece with the naked eye. “Good” means “good” and bad means “good”. This is shown in Table 1 below.

Test Example 2 (Curl resistance)
Under an atmosphere of 5 ° C., starch paste was applied to the entire back surface (paper base material) of the wallpaper and allowed to stand for 10 minutes, and then the edge of the sheet was lifted to confirm the curl state.

  The case where the surface to which the paste was applied did not contact the pattern layer surface was evaluated as “◯”, and the case where it contacted was evaluated as “x”. This is shown in Table 1 below.

Claims (10)

A foam wallpaper in which at least a foamed resin layer and a non-foamed resin layer are laminated in order on a paper base material,
(1) The foamed resin layer is a layer formed by foaming the foaming agent-containing resin layer,
(2) The foamed wallpaper, wherein the non-foamed resin layer contains an ethylene-methacrylic acid copolymer resin and a hydrogenated petroleum resin. The foamed wallpaper of Claim 1 whose content of hydrogenated petroleum resin is 5 to 30 weight% in a non-foamed resin layer. The foamed wallpaper of Claim 1 or 2 whose methacrylic acid content of ethylene-methacrylic acid copolymer resin is 10 weight% or less. The decorative sheet for wall covering according to any one of claims 1 to 3, 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 4, wherein the foaming agent-containing resin layer comprises an ethylene copolymer resin obtained from a combination of ethylene and a monomer having no OH group or COOH group. The decorative sheet for wall covering according to any one of claims 1 to 5, 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 6, wherein the foaming agent is a pyrolytic foaming agent. The foamed wallpaper according to any one of claims 1 to 7, further comprising a non-foamed resin layer between the paper-based substrate and the foamed resin layer. The foamed wallpaper according to any one of claims 1 to 8, which has a pattern layer on the outermost surface of the non-foamed resin layer. The foamed wallpaper according to any one of claims 1 to 9, which is embossed from above the outermost surface layer of the foamed wallpaper.