JP4752377B2 - Foam wallpaper - Google Patents

Description

    The present invention relates to foam wallpaper.

Foamed wallpaper is used for the wall interior of buildings.
Conventionally known foamed wallpaper includes a foamed resin layer provided with a non-foamed resin layer for the purpose of protecting the foamed resin layer. In particular, it is known that when an olefin resin is used as the resin constituting the non-foamed resin layer, the scratch resistance of the foamed wallpaper surface is improved.

  For example, Patent Document 1 discloses a foamed wallpaper in which a foamed layer made of an ethylene-based resin, a protective layer made of an ethylene-based resin, and a surface layer are sequentially provided on a paper base material, and the protective layer contains a polyether polyol. A foam wallpaper characterized by being a layer to be disclosed is disclosed.

  However, although the foamed wallpaper of Patent Document 1 has good scratch resistance, there is still room for improvement with respect to curl resistance. In general, since olefin-based resins have high crystallinity, foamed wallpaper obtained by using them is easily curled. Curled foam wallpaper is disadvantageous in various respects, such as being difficult to handle.

Accordingly, development of a foam wallpaper having both scratch resistance and curl resistance is eagerly desired.
JP 2004-308039 A

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

  As a result of intensive research, the inventor has found that the above object can be achieved by including a specific resin in the foamed wallpaper having at least a foamed resin layer and a non-foamed resin layer in order. The invention has been completed.

That is, the present invention relates to the following foamed wallpaper.
1. A foam wallpaper having at least a foamed resin layer and a non-foamed resin layer in order on a paper-based substrate,
(1) The non-foamed resin layer contains an ethylene-methacrylic acid copolymer resin,
(2) The content of methacrylic acid in the ethylene-methacrylic acid copolymer resin is 10 to 20 % by weight.
Foam wallpaper characterized by that.
2. The foamed resin layer is a layer formed by foaming a foaming agent-containing resin layer,
Item 2. The foamed wallpaper according to Item 1, wherein the foaming agent-containing resin layer and / or the non-foamed resin layer is crosslinked by electron beam irradiation.
3. Item 3. The foamed wallpaper according to Item 1 or 2, wherein the content of the ethylene-methacrylic acid copolymer resin in the non-foamed resin layer is 70 to 100% by weight.
4). Item 4. The foamed wallpaper according to any one of Items 1 to 3, wherein the foamed resin layer contains a resin obtained from a combination of monomers such that the resin layer does not contain hydrogen bonds.
5. Item 4. The foamed wallpaper according to any one of Items 1 to 3, wherein the foamed 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 4. The foamed wallpaper according to any one of Items 1 to 3, wherein the foamed resin layer comprises an ethylene-vinyl acetate copolymer.
7). Item 7. The foamed wallpaper according to any one of Items 1 to 6, further comprising a non-foamed resin layer between the paper substrate and the foamed resin layer.

  The foamed wallpaper of the present invention has a non-foamed resin layer containing an ethylene-methacrylic acid copolymer resin (hereinafter abbreviated as “EMAA”) having a methacrylic acid content of 10% by weight or more on the foamed resin layer. Exhibits excellent scratch resistance and curl resistance.

  The foamed wallpaper of the present invention is a foamed wallpaper having at least a foamed resin layer and a non-foamed resin layer in order on a paper-based substrate, and (1) the non-foamed resin layer contains an ethylene-methacrylic acid copolymer resin. (2) The content of methacrylic acid in the ethylene-methacrylic acid copolymer resin is 10% by weight or more.

The paper-based substrate is not particularly limited as long as it has mechanical strength, heat resistance and the like suitable as a wallpaper substrate, 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 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.

Foamed resin layer The foamed resin layer is formed in contact with the paper-based substrate.

  The resin component which comprises a foaming agent containing resin layer is not specifically limited, What is necessary is just to set suitably according to the foaming agent to be used, the kind of paper-type base material, etc. In particular, the foaming agent-containing resin layer is preferably a resin obtained from a combination of monomers that does not contain hydrogen bonds in the resin layer. 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, as the ethylene copolymer resin, for example, ethylene-vinyl acetate copolymer resin (hereinafter abbreviated as “EVA”), ethylene-methyl methacrylate copolymer resin (hereinafter abbreviated as “EMMA”), An ethylene-ethyl acrylate copolymer resin (EEA), an ethylene methyl acrylate copolymer resin (EMA), or the like can be used. Among these, EVA is particularly preferable.

  The foamed resin layer may further contain known additives such as inorganic fillers, pigments, flame retardants, and heat stabilizers.

  Among these, examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By using an inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained. The content of the inorganic filler is preferably about 0 to 100 parts by weight and more preferably about 20 to 70 parts by weight with respect to 100 parts by weight of the resin constituting the foamed resin layer.

  Examples of the pigment include the following. Examples of inorganic pigments include 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), and cadmium. Examples thereof include red, ultramarine blue, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, and zinc sulfide. Examples of organic pigments include aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), polycyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone, Perylene, diketopyrrolopyrrole, dibromoanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone, halogenated phthalocyanine) and the like.

  Additives are not limited to those described above, and other known additives can also be used. The amount of addition can be selected from a wide range depending on the type of foam wallpaper.

  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 set as appropriate according to the type of foamed wallpaper.

  The thickness of the foamed resin layer is not limited, but is preferably about 400 to 800 μm, and more preferably about 500 to 700 μm.

Non-foamed resin layer (hereinafter abbreviated as “resin layer A”)
The resin layer A is formed in contact with the foamed resin layer.

  The resin layer A includes EMAA having a methacrylic acid content of 10% by weight or more. In particular, the methacrylic acid content is preferably about 10 to 20% by weight. When the methacrylic acid content is less than 10% by weight, the resulting foamed wallpaper tends to curl. This is because if the methacrylic acid content is less than 10% by weight, the ratio of the ethylene component becomes large, so that the crystallinity of the resin layer A becomes too high. As a result, after the resin layer A is melt extruded, This is thought to be due to contraction.

  The content of EMAA in the resin layer A is not particularly limited, but is preferably 70 to 100% by weight.

  The resin layer A may contain a resin such as hydrogenated petroleum resin or EVA in addition to the EMAA as long as the effect of the present invention is not hindered.

  The resin layer A may further contain additives such as acrylate monomers and oligomers.

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

A non-foamed resin layer (hereinafter abbreviated as “resin layer B”) may be further formed between the paper-based substrate and the foamed resin layer.
When the resin layer B is formed, the adhesiveness between the foamed resin layer and the paper-based substrate can be improved.

  Although the kind of resin contained in the resin layer B is not limited, EVA is preferable from a viewpoint of adhesiveness with a foamed resin layer. The vinyl acetate content of EVA is not limited, but is preferably about 10 to 40% by weight, more preferably about 20 to 40% by weight.

  Although the thickness of the resin layer B is not limited, about 5-20 micrometers is preferable and about 10-15 micrometers is more preferable.

A picture pattern layer may be formed on the front surface of the foam pattern 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. 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 vehicle, and a solvent can be used.

  The pigment can be used as the colorant.

  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 Examples include butyral resins, alkyd resins, petroleum resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, and rubber resins.

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

An embossed pattern may be attached to the front surface of the embossed wallpaper decorative sheet as necessary.

  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 of the present invention is not particularly limited as long as the above foam wallpaper is obtained.

  For example, the foaming agent-containing resin layer and the resin layer A are sequentially laminated on a paper base material, and the present invention is performed by heating the foaming agent after simultaneous lamination so that the foaming agent-containing resin layer is in contact with the paper base material. Can be suitably produced.

  For the simultaneous lamination, for example, multi-layer coextrusion using a T-die extruder can be suitably used.

  Specifically, the composition for forming the foaming agent-containing resin layer and the composition for forming the resin layer A are placed in separate cylinders, and two types and two layers are simultaneously extruded to form and laminate. do it.

  Further, when the resin layer B is further formed between the foaming agent-containing resin layer and the paper substrate, a composition for forming the resin layer A, a composition for forming the foaming agent-containing resin layer, and The composition for forming the resin layer B may be put in a separate cylinder, and three types and three layers may be extruded simultaneously to form a film and laminate it.

  The composition for forming the foaming agent-containing resin layer is not limited. For example, a resin composition containing a resin, an additive, and a foaming agent can be used.

  Although it does not specifically limit as said resin, The ethylene copolymer resin shown above can be used suitably.

  As the additive, the inorganic filler described above may be used as appropriate. What is necessary is just to adjust the usage-amount of an additive suitably according to the objective.

  The said foaming agent is not limited, For example, well-known foaming agents, such as an inorganic type foaming agent and an organic type foaming agent, can be used.

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

Examples of the organic foaming agent include nitroso compounds, azo compounds, sulfonyl hydrazide compounds, azide compounds and the like. Examples of the nitroso compound include N, N′-dimethyl-N, N′-dinitrosoterephthalamide, N, N′-dinitrosopentamethylenetetramine and the like. Examples of the azo compound include azodicarbonamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiamminobenzene, barium azodicarboxylate, and the like. Examples of the sulfonyl hydrazide compound include benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p′-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3′-disulfonyl hydrazide and the like. Examples of the azide compound include calcium azide, 4,4′-diphenyldisulfonyl azide, p-toluenesulfonyl azide and the like.
These foaming agents can be used alone or in combination of two or more.

  The addition amount of the foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like.

  As a composition for forming the foaming agent-containing resin layer, a foaming aid may be further added. Examples of the foaming aid include zinc oxide, zinc stearate, salicylic acid, phthalic acid, and oxalic acid. The addition amount of the foaming aid is not limited, and may be appropriately adjusted according to the foaming agent and the like.

  The composition for forming the resin layer A is not particularly limited as long as it contains EMAA having a methacrylic acid content of 10% by weight or more.

  As the composition for forming the resin layer B, the above-described composition containing EVA can be suitably used.

  The molten resin temperature at the time of co-extrusion is not particularly limited, and may be appropriately set according to the resin used, the foaming agent, and the like.

  In the above production method, the coextruded laminate can be simultaneously laminated (film formation) on the 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.

  It is also possible to prepare a laminated body that has been simultaneously formed in advance, place it on a paper-based substrate, and bond it to the paper-based substrate by thermal lamination.

  After simultaneously laminating on a paper-based substrate, the foaming agent-containing resin layer is made into a foamed resin layer by heating the foaming agent. 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. The heating time is preferably about 20 to 90 seconds.

  Before the heat treatment, the resin layer A and / or the foaming agent-containing resin layer may be irradiated with an electron beam. Thereby, since the resin contained in each layer can be crosslinked, the surface strength of the foamed wallpaper, the degree of foaming, and the like 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).

When performing electron beam irradiation, the composition may contain a crosslinking aid.
Any crosslinking assistant may be used as long as it promotes crosslinking by electron beam irradiation. Examples thereof include polyfunctional monomers such as neopentyl glycol dimethacrylate and trimethylolpropane trimethacrylate, oligomers, and the like. The crosslinking aid is preferably about 0 to 10 parts by weight and more preferably 1 to 4 parts by weight with respect to 100 parts by weight of EVA.

  Further, the surface of the non-foamed resin layer A may be subjected to corona discharge treatment. The corona discharge treatment can be performed according to a known method.

  When producing a foam wallpaper having a pattern layer, it is preferable to form the pattern layer on the surface of the resin layer A before the heat treatment. The method for forming the pattern layer is 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
In order to form the non-foamed resin layer A, 100 parts by weight of EMAA (product name “Nucleel N1525”, MFR: 25 g / 10 min, methacrylic acid content: 15 wt%, manufactured by Mitsui DuPont Polychemical) was prepared.

  In order to form the non-foamed resin layer B, 100 parts by weight of EVA (product name “Evaate CV5053”, MFR: 70 g / 10 min, vinyl acetate content: 20% by weight, manufactured by Sumitomo Chemical Co., Ltd.) was prepared.

  In order to form a foaming agent containing resin layer, the composition containing the component of following Table 1 was prepared.

  The resin and the resin-containing composition were melted, and three layers were coextruded and laminated on a paper substrate (basis weight 70 g) having a thickness of 110 μm using a three-kind three-layer multi-manifold T-die extruder, and a non-foamed resin layer B The layers were laminated in the following order: / foaming agent-containing resin layer / non-foamed resin layer A. The thickness of each layer was 10 μm / 100 μm / 15 μm in the above order. In the T-die extruder in the three-layer coextrusion lamination, a cylinder containing EVA for forming the resin layer B, a cylinder containing each component of Table 1 for forming the foaming agent-containing resin layer, And the temperature of the cylinder containing EMAA for forming the resin layer A was 100 ° C., 120 ° C., and 160 ° C., respectively. The die temperatures were all 120 ° C.

  Thereafter, an electron beam (175 kV, 5 Mrad) was irradiated from above the resin layer A to crosslink the EVA resin. And the corona discharge process was performed on the surface of the non-foamed resin layer A.

Subsequently, the primer treatment was performed by applying 2 g / m ² of the EVA aqueous emulsion to the surface of the non-foamed resin layer A by gravure printing. Furthermore, a texture pattern (pattern printing layer) was printed thereon using a water-based ink (product name “Hydric” manufactured by Dainichi Seika Kogyo Co., Ltd.).

  Then, the laminate was heated in a gear oven at 220 ° C. for 30 seconds. Thereby, the foaming agent was decomposed, and the foaming agent-containing resin layer was used as the foamed resin layer. The expansion ratio was 5 times, and the thickness of the foamed resin layer was 500 μm.

Furthermore, the embossing was given to the front side of the foam, and the texture pattern was shaped.
Through the above process, a foam wallpaper was produced.

Example 2
The resin constituting the non-foamed resin layer A is EMAA (product name “Nucleel N1035”, MFR: 35 g / 10 min, methacrylic acid content: 10% by weight, manufactured by Mitsui DuPont Polychemical), and the foamed resin layer is constructed. The resin is EMMA (product name “ACRIFTH WH401” MFR: 20 g / 10 min, methyl methacrylate content: 20% by weight, manufactured by Sumitomo Chemical Co., Ltd.), and the cylinder containing each component for forming the foaming agent-containing resin layer A foam wallpaper was prepared in the same manner as in Example 1 except that the temperature was 130 ° C.

Comparative Example 1
Example 1 except that the resin constituting the non-foamed resin layer A is EMAA (product name “Nuclerel AN4311”, MFR: 30 g / 10 min, methacrylic acid content: 8 wt%, manufactured by Mitsui DuPont Polychemical) A foamed wallpaper was prepared in the same manner.

Comparative Example 2
A foamed wallpaper was prepared in the same manner as in Example 1 except that the resin constituting the non-foamed resin layer A was EMMA (product name “Aclift WH401”, MFR: 20 g / 10 minutes, manufactured by Sumitomo Chemical).

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 (wallpaper decorative sheet) 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. Thereafter, the scratch resistance (good / bad) was evaluated by checking the surface condition (degree of damage) of the test piece with the naked eye.

Test Example 2 (Curl resistance)
Starch paste was applied to the entire paper-based substrate side of the foamed wallpaper produced in the examples and comparative examples, and left in a 5 ° C. atmosphere for 10 minutes. Then, the edge part of the wallpaper was lifted and the curl state of the wallpaper was confirmed.

  A starch paste that did not adhere to the surface was evaluated as good, and a starch paste that adhered to the surface was evaluated as poor.

Test example 3 (extrudability)
In Examples and Comparative Examples, the processing characteristics (good / bad) at the time of co-extrusion of three resin layers were evaluated.

  The results of the above test are shown in Table 2 below.

Claims (7)

A foam wallpaper having at least a foamed resin layer and a non-foamed resin layer in order on a paper-based substrate,
(1) The non-foamed resin layer contains an ethylene-methacrylic acid copolymer resin,
(2) The content of methacrylic acid in the ethylene-methacrylic acid copolymer resin is 10 to 20 % by weight.
Foam wallpaper characterized by that. The foamed resin layer is a layer formed by foaming a foaming agent-containing resin layer,
The foamed wallpaper of Claim 1 in which the said foaming agent containing resin layer and / or the said non-foaming resin layer are bridge | crosslinked by electron beam irradiation. The foamed wallpaper according to claim 1 or 2, wherein the content of the ethylene-methacrylic acid copolymer resin in the non-foamed resin layer is 70 to 100% by weight. The foamed wallpaper according to any one of claims 1 to 3, wherein the foamed resin layer contains a resin obtained from a combination of monomers such that hydrogen bonds are not contained in the resin layer. The foamed wallpaper according to any one of claims 1 to 3, wherein the foamed resin layer comprises an ethylene copolymer resin obtained from a combination of ethylene and a monomer having no OH group or COOH group. The foamed wallpaper according to any one of claims 1 to 3, wherein the foamed resin layer contains an ethylene-vinyl acetate copolymer. The foamed wallpaper according to any one of claims 1 to 6, further comprising a non-foamed resin layer between the paper-based substrate and the foamed resin layer.