JP2018030297A - Raw fabric for wall paper, foamed wall paper and method for producing foamed wall paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a raw fabric for wall paper that resists the discoloration caused by starch.SOLUTION: A raw fabric for wall paper 1 has a structure in which: on a base material 2, a foaming agent-containing resin layer 4 that contains a foaming agent, and a discoloration prevention functional layer 7 are stacked in the stated order, where the discoloration prevention functional layer is disposed at the outermost surface layer and contains an additive containing at least one selected from the group consisting of zinc ions, pyrithione ions and salts thereof.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a raw material for wallpaper, a foam wallpaper, and a method for producing a foam wallpaper.

Conventionally, for example, starch-based aqueous adhesives are widely used as wallpaper adhesives used for wall decorations of buildings. However, the starch-based aqueous adhesive has a problem that it adheres to the surface of the wallpaper, and when the starch is discolored over time, the wallpaper looks discolored.
On the other hand, for example, in the techniques described in Patent Documents 1 and 2, an aqueous adhesive to which a compound composite is added is used. Further, for example, in the technique described in Example 3, a cutting underlay tape for preventing adhesion of starch-based aqueous adhesive to wallpaper is used.

Japanese Patent Laid-Open No. 6-47875 JP 2000-255011 A JP 2001-347611 A

However, the techniques described in Patent Documents 1 to 3 are not widely adopted by wallpaper contractors because they are expensive and complicated. Therefore, the above problem, that is, the problem that the wallpaper looks discolored due to starch-based discoloration has not been solved.
This invention pays attention to the above points, and it aims at providing the raw material for wallpaper which can suppress discoloration resulting from starch, a foam wallpaper, and the manufacturing method of a foam wallpaper.

  In order to solve the above-described problems, an aspect of the present invention includes a foaming agent-containing resin layer containing a foaming agent on a base material, and a group consisting of zinc ions, pyrithione ions, and salts thereof arranged on the outermost layer. A discoloration prevention functional layer containing an additive containing at least one selected is laminated in this order.

  According to one aspect of the present invention, since the zinc ions and pyrithione ions contained in the additive are dissociated, the pH of the aqueous adhesive attached to the surface side of the foam wallpaper is biased toward the acidic side. The starch contained in the agent can be decomposed, and discoloration caused by the starch can be suppressed.

It is an end view showing the composition of the original fabric for wallpaper according to the embodiment. It is an end elevation showing the composition of the original material for wallpaper concerning a modification. It is an end view showing the composition of the foam wallpaper according to the embodiment.

Next, embodiments of the present invention will be described with reference to the drawings.
Here, the drawings are schematic, and the relationship between the thickness and the planar dimensions, the ratio of the thickness of each layer, and the like are different from the actual ones. Further, the embodiment described below exemplifies a configuration for embodying the technical idea of the present invention, and the technical idea of the present invention is that the material, shape, structure, etc. of the component parts are as follows. It is not something specific. The technical idea of the present invention can be variously modified within the technical scope defined by the claims described in the claims.

(Original fabric for wallpaper 1)
As shown in FIG. 1, the raw paper 1 for wallpaper according to this embodiment includes a first non-foamed layer 3 (non-foaming agent-containing resin layer), a foaming agent-containing resin layer 4, and a second non-foaming material on a substrate 2. A foam layer 5 (non-foaming agent-containing resin layer), a pattern layer 6 and a discoloration prevention functional layer 7 are formed in this order. In addition, you may form another layer between the pattern pattern layer 6 and the discoloration prevention functional layer 7, between the base material 2 and the 1st non-foaming layer 3, etc. as needed. For example, as shown in FIG. 2, an intermediate layer 8 may be formed between the pattern / pattern layer 6 and the discoloration prevention functional layer 7 to increase the adhesion between the pattern / pattern layer 6 and the discoloration prevention functional layer 7. Good. Further, either the first non-foamed layer 3 or the second non-foamed layer 5 may be omitted.

(Substrate 2)
It does not specifically limit as the base material 2, A well-known fiber sheet can be used. Examples of the fibrous sheet include a general paper for wallpaper obtained by sizing a pulp-based sheet with a known sizing agent, a flame-retardant paper obtained by treating a pulp-based sheet with a flame retardant such as guanidine sulfamate and guanidine phosphate, and water. Inorganic paper, high-quality paper, and thin paper containing inorganic additives such as aluminum oxide and magnesium hydroxide can be used. In addition, what corresponds to a nonwoven fabric is also contained. The basis weight of the substrate 2, for example, preferably about 50 to 300 g / m ^2, 50 to 120 / m ² is more preferable.

(First non-foamed layer 3)
The first non-foamed layer 3 is a layer for improving the adhesion between the base material 2 and the foaming agent-containing resin layer 4. As the resin component of the first non-foamed layer 3, for example, an ethylene-vinyl acetate copolymer can be used. The first non-foamed layer 3 may contain known additives in addition to the resin component, but is preferably blended so that the content of the resin component is 70 to 100% by weight. Moreover, 10-50 micrometers is preferable and, as for the thickness of the 1st non-foaming layer 3, 10-20 micrometers is more preferable.

(Foaming agent-containing resin layer 4)
The foaming agent-containing resin layer 4 is a resin layer containing a foaming agent and foamed by heating. The foaming agent-containing resin layer 4 is obtained by melt-extruding a resin composition containing a foaming agent. As the resin component, for example, vinyl chloride resin and olefin resin can be used. In particular, in view of improvement in durability, embossing, and the like, an olefin resin is preferable, and an ethylene resin is more preferable.

  As an ethylene-type resin, it is preferable to contain at least 1 sort (s) of the ethylene copolymer which uses polyethylene and components other than ethylene and ethylene as a monomer, for example. As the polyethylene, for example, low density polyethylene, medium density polyethylene, high density polyethylene, and linear low density polyethylene can be used. In particular, low density polyethylene is preferred.

  Examples of the ethylene copolymer include an ethylene-vinyl acetate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene-ethyl acrylate copolymer, an ethylene-methyl acrylate copolymer, an ethylene-methacrylic acid copolymer, and ethylene. -Alpha olefin copolymer can be used individually or in mixture of 2 or more types. In particular, at least one of an ethylene-vinyl acetate copolymer, an ethylene-methyl methacrylate copolymer, and an ethylene-methacrylic acid copolymer is preferable. When these are used in combination with another resin, an ethylene-vinyl acetate copolymer is used. 70 mass% or more is preferable and at least 1 sort (s) of a polymer, an ethylene-methylmethacrylate copolymer, and an ethylene-methacrylic acid copolymer is more preferable.

  Moreover, as a foaming agent, an azo compound, ammonium carbonate, ammonium bicarbonate, and ammonium nitrite can be used, for example. As the azo compound, for example, azodicarbonamide (ADCA), azobisformamide and the like are preferable. In consideration of the expansion ratio, the content of the foaming agent is preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component. The foaming agent-containing resin layer 4 is resin-crosslinked by a chemical crosslinking method or radiation irradiation. Moreover, 10-50 micrometers is preferable and, as for the thickness of the foaming agent containing resin layer 4, 10-20 micrometers is more preferable.

(Second non-foamed layer 5)
The second non-foamed layer 5 is a layer for protecting the foaming agent-containing resin layer 4. As the resin component of the second non-foamed layer 5, for example, a polymer obtained by using as a monomer at least one of acrylic acid (CH2 = CHCOOH) and methacrylic acid (CH2 = C (CH3) COOH) is included as a resin component. A resin composition can be used. In particular, a copolymer obtained by a combination of at least one monomer of acrylic acid and methacrylic acid and ethylene is preferable.

  More specifically, it is desirable to use at least one of EMAA, ethylene-acrylic acid copolymer, and ionomer resin. As the ionomer resin, a resin having a structure in which EMAA and / or ethylene-acrylic acid copolymer molecules are intermolecularly bonded with metal ions such as sodium and zinc can be used. When such a resin component is used, it is possible to form a strong layer particularly due to hydrogen bonds in the resin, so that excellent scratch resistance, abrasion resistance, and the like can be obtained. These may be known or commercially available. The second non-foamed layer 5 may contain a known additive in addition to the resin component, but is preferably blended so that the content of the resin component is 70 to 100% by weight. Moreover, 10-50 micrometers is preferable and, as for the thickness of the 2nd non-foaming layer 5, 10-20 micrometers is more preferable.

(Pattern pattern layer 6)
The pattern pattern layer 6 is a layer for adding a pattern pattern to the wallpaper material 1. 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, and a geometric figure. The pattern can be selected as appropriate according to the type of the wallpaper material 1.
As a method for forming the picture pattern layer 6, for example, it can be formed by printing a picture pattern. In addition, when forming the pattern layer 6, you may form a primer layer beforehand as needed. Examples of the printing method include gravure printing, flexographic printing, silk screen printing, and offset printing. As the printing ink, for example, a printing ink containing a colorant, a binder resin, and a solvent can be used. These inks may be known ones.

  The binder resin is, for example, an acrylic resin, a styrene resin, a polyester resin, a urethane resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer resin, a polyvinyl butyral resin, an alkyd resin, or a petroleum resin. Resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like can be used. Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, acetic acid -2-Ethoxyethyl and other ester organic solvents; methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol and other alcohol organic solvents; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloro Chlorinated organic solvents, such as styrene; water, etc. can be used.

(Discoloration prevention functional layer 7)
The discoloration prevention functional layer 7 is disposed on the outermost layer and is a layer for protecting the pattern layer 6. As a resin component (hereinafter also referred to as “matrix resin”) of the discoloration prevention functional layer 7, for example, a vinyl chloride resin or an olefin resin can be used. Moreover, the discoloration prevention functional layer 7 contains an additive in addition to the matrix resin. As an additive, the additive (discoloration prevention agent) containing at least 1 sort (s) selected from the group which consists of zinc ion, pyrithione ion, and these salts is contained. The additive (anti-discoloration agent) is preferably 0.05 parts by mass or more and 20 parts by mass or less with respect to 100 parts by mass of the matrix resin. Further, the thickness of the discoloration prevention functional layer 7 is preferably 0.3 μm or more and 20 μm or less, and more preferably 0.3 μm or more and 10 μm or less.

(Method for producing foam wallpaper 9)
Next, the manufacturing method of the foam wallpaper 9 is demonstrated.
The manufacturing method of the foam wallpaper 9 of this embodiment manufactures the foam wallpaper 9 by foaming the foaming agent containing resin layer 4 by heating said raw material 1 for wallpaper. The heating temperature is preferably 180 to 240 ° C, and more preferably 210 to 230 ° C. The heating time is preferably 20 to 60 seconds, and more preferably 25 to 40 seconds. The expansion ratio is 3 times or more, preferably 4 to 5 times. If the expansion ratio is too low, it is difficult to impart an excellent appearance design, and if the expansion ratio is too high, the foaming agent-containing resin layer 4 becomes mechanically weak and the scratch resistance is likely to decrease.

Before the formation of the second non-foamed layer 5, the foamed agent-containing resin layer 4 after foaming may be resin-crosslinked by a chemical crosslinking method or radiation irradiation. Thereby, the scratch resistance of the foam wallpaper 9 can be improved.
Further, at least the discoloration prevention functional layer 7 (outermost layer) may be embossed. Thereby, for example, as shown in FIG. 3, the emboss 10 can be provided on the surface of the foam wallpaper 9, and the design by the emboss 10 can be felt in addition to the design by the pattern layer 6.

(Effect of this embodiment)
(1) As described above, in the raw paper 1 for wallpaper of the present embodiment, the foaming agent-containing resin layer 4 containing the foaming agent on the base material 2, zinc ions, pyrithione ions, and these disposed in the outermost layer. The discoloration prevention functional layer 7 containing an additive containing at least one selected from the group consisting of salts is laminated in this order. Thereby, the pH of the water-based adhesive adhering to the surface side of the foam wallpaper can be biased toward the acidic side by the separation of zinc ions and the like contained in the additive. As a mechanism for biasing the pH of the aqueous adhesive to the acidic side, for example, zinc ions contained in the additive bind to the hydroxyl group of the aqueous adhesive attached to the surface side of the foam wallpaper, and the proton in the aqueous adhesive increases. It is possible. Therefore, the starch contained in the aqueous adhesive can be decomposed, and discoloration caused by the starch contained in the aqueous adhesive can be suppressed.

Moreover, since zinc ion is a divalent ion, it binds to two hydroxyl groups. Therefore, for example, the pH of the aqueous adhesive can be sufficiently biased toward the acidic side as compared with monovalent sodium ions and the like. Thereby, the discoloration resulting from starch can be suppressed appropriately.
Incidentally, for example, monovalent ions such as sodium ions cannot sufficiently bias the pH of the aqueous adhesive toward the acidic side, unlike divalent ions such as zinc ions. Therefore, it becomes difficult to appropriately suppress discoloration caused by the starch contained in the aqueous adhesive.

(2) The discoloration prevention functional layer 7 has a thickness of 0.3 μm or more and 20 μm or less. Therefore, the effect of preventing discoloration can be obtained without affecting the pattern.
(3) Further, the discoloration prevention functional layer 7 is configured to contain 0.05 parts by mass or more and 20 parts by mass or less of additives with respect to 100 parts by mass of the matrix resin. Therefore, it is easy to apply and the effect can be more manifested.
(4) Moreover, it was set as the structure by which the foaming agent containing resin layer 4 was resin-crosslinked by the chemical crosslinking method or radiation irradiation. Therefore, the scratch resistance of the foamed wallpaper 9 can be improved.

(5) Further, the foaming agent-containing resin layer 4 has a non-foaming agent-containing resin layer on one or both sides. Therefore, the surface can be smoothed and the printability can be improved.
(6) The matrix resin of the discoloration prevention functional layer 7 is configured to be a vinyl chloride resin and / or an olefin resin. Therefore, sheet molding suitable for the foam wallpaper 9 can be performed.

(7) Further, the foaming agent is at least one selected from the group consisting of an azo compound, ammonium carbonate, ammonium bicarbonate, and ammonium nitrite. Therefore, safety and foamability controllability can be improved.
(8) Moreover, the base material 2 was made into the fibrous sheet. Therefore, it can be handled as a general-purpose wallpaper material 1.

(9) Further, the foamed wallpaper 9 of the present embodiment is formed by foaming the foaming agent-containing resin layer 4 of the raw wallpaper 1. Therefore, since the proton contained in the additive is separated, the pH of the aqueous adhesive attached to the surface side of the wallpaper can be biased to the acidic side, so that the starch contained in the aqueous adhesive can be decomposed, Discoloration due to starch contained in the aqueous adhesive can be suppressed.
(10) Further, the emboss 10 is formed on at least the discoloration prevention functional layer 7 (outermost layer). Therefore, it is possible to form the foamed wallpaper 9 having high design by the emboss 10.

(11) Furthermore, in the manufacturing method of the foam wallpaper 9 of the present embodiment, the base material 2, the foaming agent-containing resin layer 4 containing the foaming agent, and zinc ions, pyrithione ions and salts thereof arranged in the outermost layer. The foam-preventing resin-containing resin layer 1 is formed by forming a wallpaper original fabric 1 laminated with an anti-discoloration functional layer 7 containing an additive containing at least one selected from the group consisting of 4 was allowed to foam. Thereby, the discoloration prevention functional layer 7 containing the additive which has a proton as a counter cation can be formed in the outermost layer of the foam wallpaper 9. As shown in FIG.

Embodiments according to the present invention will be described.
Example 1
In Example 1, using a known T-die extruder, the first non-foamed layer 3, the foaming agent-containing resin layer 4, and the second non-foamed layer 5 were in this order, and the thickness of each layer was 10 μm, 70 μm, A film having a thickness of 10 μm was formed to obtain a laminate composed of three layers. Here, as resin of the 1st non-foamed layer 3 and the 2nd non-foamed layer 5, what used 100 mass parts of low density polyethylene (Nippon Polyethylene Co., Ltd., brand name: LJ802A) was used. Further, as the foaming agent-containing resin layer 4, the foaming agent (manufactured by Eiwa Kasei Kogyo Co., Ltd., trade name ADCA # 3) with respect to 100 parts by mass of low density polyethylene (Nippon Polyethylene Corporation, trade name: LJ802A). 8 parts by mass, calcium carbonate (manufactured by Bihoku Powder Co., Ltd., trade name: Softon 1000), 30 parts by mass, titanium dioxide (pigment) (Ishihara Sangyo Co., Ltd., trade name: TIPAQUE CR-60-2) 20 parts by mass Parts, foaming aid (manufactured by ADEKA, trade name: ADK STAB OF-101) 8 parts by mass were used.

Then, a laminated sheet is formed by laminating the first non-foamed layer 3 of the three-layered laminate described above on a backing paper (rice weighed 65 g / m ² , manufactured by Kojin Co., Ltd., WK-655T). did. Further, the second non-foamed layer 5 of the laminated sheet was irradiated with an electron beam having an acceleration voltage of 200 kV and an irradiation dose of 55 KGy to perform resin crosslinking on the foaming agent-containing resin layer 4. Next, the pattern pattern layer is printed by printing a texture pattern on the second non-foamed layer 5 of the laminated sheet using gravure printing using a water-based ink (trade name: Hydrick, manufactured by Dainichi Seika Kogyo Co., Ltd.). 6 was formed. Subsequently, an ink containing 10 parts by mass of an additive containing a salt of pyrithione ion (trade name: Suraoff 95, manufactured by Osaka Gas Chemical Co., Ltd.) on the pattern layer 6 with respect to 100 parts by mass of the matrix resin. (Acrylic resin-based water-based ink) was applied by a gravure direct coater method. The amount of ink applied was adjusted so that the film thickness after drying was about 1 [μm]. Subsequently, the applied ink was dried and cured in a drying furnace at 140 [° C.], whereby the discoloration prevention functional layer 7 was formed. Subsequently, the foaming agent-containing resin layer 4 was foamed by a 230 [° C.] heating exothermic furnace to form the foaming agent-containing resin layer, and then passed between a cooling roll and a pressure roll to perform embossing. The foamed wallpaper 9 having the emboss 10 (uneven pattern) on the surface was formed by thermocompression.

(Example 2)
In Example 2, the additive amount of the discoloration prevention functional layer 7 was 0.5 parts by mass with respect to 100 parts by mass of the matrix resin. Otherwise, the configuration was the same as in Example 1.
(Example 3)
In Example 3, the additive amount of the discoloration prevention functional layer 7 was 20 parts by mass with respect to 100 parts by mass of the matrix resin. Otherwise, the configuration was the same as in Example 1.

Example 4
In Example 4, the thickness of the discoloration prevention functional layer 7 was 0.3 μm. Otherwise, the configuration was the same as in Example 1.
(Comparative Example 1)
In Comparative Example 1, an additive having sodium ions (manufactured by Wako Pure Chemical Industries, Ltd., trade name: sodium stearate) was used as an additive for the discoloration prevention functional layer 7, and the additive amount of the additive was The amount was 1 part by mass with respect to 100 parts by mass of the matrix resin. Otherwise, the configuration was the same as in Example 1.

(Comparative Example 2)
In Comparative Example 2, an additive having a sulfonate ion (anion ion) (manufactured by Wako Pure Chemical Industries, Ltd., trade name: linear alkylbenzene sulfonate sodium salt) is used as an additive for the discoloration prevention functional layer 7, The additive amount was 1 part by mass with respect to 100 parts by mass of the matrix resin. Otherwise, the configuration was the same as in Example 2.

(Evaluation)
About Examples 1-4 and Comparative Examples 1-2, evaluation of the discoloration state of the foam wallpaper 9 was implemented.
Specifically, after a starch-based adhesive is thinly applied on the discoloration prevention functional layer 7 of the foamed wallpaper 9, ultraviolet rays are irradiated for a predetermined time to visually check the discolored state of the applied starch-based aqueous adhesive. It was evaluated with. And the case where there was no discoloration was determined to be a pass “◯”, and the case where there was a discoloration was determined to be a reject “x”.
The evaluation results are shown in Table 1.

  From Table 1, in Examples 1 to 4, there was no discoloration in the starch-based aqueous adhesive applied on the discoloration prevention functional layer 7. On the other hand, in Comparative Examples 1 and 2, there was discoloration. Thereby, it was confirmed that the discoloration of the starch-based aqueous adhesive could be suppressed by adding an additive containing a salt of pyrithione ion to the discoloration prevention functional layer 7 (outermost layer).

DESCRIPTION OF SYMBOLS 1 ... Wallpaper raw material, 2 ... Base material, 3 ... 1st non-foaming layer, 4 ... Foaming agent containing resin layer, 5 ... 2nd non-foaming layer, 6 ... Picture pattern layer, 7 ... Discoloration prevention functional layer , 8 ... Intermediate layer, 9 ... Foam wallpaper, 10 ... Emboss

Claims (11)

  The base material contains an additive containing a foaming agent-containing resin layer containing a foaming agent and at least one selected from the group consisting of zinc ions, pyrithione ions, and salts thereof arranged on the outermost layer. An original material for wallpaper, wherein the anti-discoloration functional layer is laminated in this order.   The raw material for wallpaper according to claim 1, wherein a thickness of the discoloration preventing functional layer is 0.3 µm or more and 20 µm or less.   3. The wallpaper raw material according to claim 1, wherein the anti-discoloration functional layer contains 0.05 to 20 parts by mass of the additive with respect to 100 parts by mass of the matrix resin. Anti.   The raw material for wallpaper according to any one of claims 1 to 3, wherein the foaming agent-containing resin layer is resin-crosslinked by a chemical crosslinking method or radiation irradiation.   The said foaming agent containing resin layer has the non-foaming agent containing resin layer in the single side | surface or both surfaces, The raw material for wallpaper of any one of Claim 1 to 4 characterized by the above-mentioned.   The raw material for wallpaper according to any one of claims 1 to 5, wherein the matrix resin of the discoloration prevention functional layer is a vinyl chloride resin and / or an olefin resin.   The wallpaper according to any one of claims 1 to 6, wherein the foaming agent is at least one selected from the group consisting of an azo compound, ammonium carbonate, ammonium bicarbonate, and ammonium nitrite. Original fabric.   The base material for wallpaper according to any one of claims 1 to 7, wherein the base material is a fibrous sheet.   The foamed wallpaper in which the foaming agent containing resin layer of the raw material for wallpaper of any one of Claim 1 to 8 is formed by foaming.   The foamed wallpaper according to claim 9, wherein an emboss is formed at least on the discoloration prevention functional layer.   A raw material for wallpaper in which a base material, a foaming agent-containing resin layer containing a foaming agent, and a discoloration preventing functional layer containing zinc ions, pyrithione ions, and salts thereof arranged on the outermost layer are laminated And foaming the formed foam-containing resin layer of the raw material for wallpaper.

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