JP5152066B2 - Method for producing foam wallpaper - Google Patents

Description

  The present invention relates to a method for producing foamed wallpaper useful for decorating wall surfaces and the like.

  Conventionally, foamed wallpaper is known in which a foamed resin layer of vinyl chloride resin is formed on a base material (backing paper) such as paper. In recent years, in consideration of the environment, resins that do not contain halogen such as ethylene-vinyl acetate copolymer resin (EVA), acrylic resin, and olefin resin have been used for the foamed resin layer (Patent Document 1). ~ 3 etc.). More specifically, a foamed wallpaper is known in which a foamed resin layer and a non-foamed resin layer A (protective resin layer) are sequentially laminated on a substrate.

  The foamed resin layer and the non-foamed resin layer A of the foamed wallpaper are formed by, for example, extruding the foaming agent-containing resin layer and the non-foamed resin layer A simultaneously or sequentially to form the foaming agent-containing resin layer. Is formed. At this time, when the foaming agent contained in the foaming agent-containing resin layer is an azodicarbonamide (ADCA) thermal decomposition type foaming agent, the undecomposed thermal decomposition type foaming agent remains in the foamed resin layer. The problem of yellowing the layer has been pointed out.

  In order to improve the above problem, an attempt has been made to conceal the yellowing of the foamed resin layer by blending titanium oxide into the non-foamed resin layer A. For example, in Patent Document 4, “a base material layer, a foamed resin layer composed of a thermoplastic resin containing an additive mainly composed of a foaming agent, and a thermoplastic resin mainly composed of an additive mainly composed of titanium dioxide” The decorative resin sheet is provided with a colored resin layer that is sequentially provided.

  However, when a large amount of titanium oxide is blended in the non-foamed resin layer A, the dispersibility of titanium oxide deteriorates, and aggregates of titanium oxide (so-called eyes) are formed during extrusion film formation, resulting in poor film formation. There are harmful effects. In order to improve this, an attempt has been made to prepare a masterbatch by kneading titanium oxide with ethylene-methacrylic acid copolymer (EMAA) and the like, and blending it into the non-foamed resin layer A, but it is still sufficient. The effect is not acquired.

  Therefore, even when the non-foamed resin layer A containing titanium oxide is formed by extrusion film formation, the extrusion film forming property is good, and even if it contains a sufficient amount of titanium oxide necessary for concealing the base, Development of a method for producing foamed wallpaper having good dispersibility is desired.

Japanese Patent Laid-Open No. 6-47875 JP 2000-255011 A JP 2001-347611 A JP 2007-71365 A

  In the present invention, even when the non-foamed resin layer A containing titanium oxide is formed by extrusion film formation, the extrusion film formation property is good, and even if it contains a sufficient amount of titanium oxide necessary for concealing the base, it is oxidized. The main object is to provide a method for producing a foam wallpaper having good dispersibility of titanium.

  As a result of intensive studies, the inventor has found that the above object can be achieved when a specific master batch is used, and has completed the present invention.

That is, this invention relates to the manufacturing method of the following foam wallpaper.
1. A method for producing a foam wallpaper having at least a foam resin layer and a non-foam resin layer A in order on a substrate,
The non-foamed resin layer A is obtained by extruding a resin composition containing 1) a master batch containing low-density polyethylene and titanium oxide, and 2) a matrix resin of the non-foamed resin layer A. Forming ,
The matrix resin contains a polymer obtained using at least one of acrylic acid and methacrylic acid as a monomer,
A method for producing foamed wallpaper .
2. Item 2. The production method according to Item 1, wherein the polymer is an ethylene-methacrylic acid copolymer.
3 . The said master batch is a manufacturing method of the said claim | item 1 or 2 containing 5 to 240 weight part of the said titanium oxide with respect to 100 weight part of the said low density polyethylene.
4 . Item 4. The production method according to any one of Items 1 to 3, wherein a content of the titanium oxide is 5 to 60 parts by weight with respect to 100 parts by weight of the matrix resin in the resin composition.
5 . The said foaming resin layer is a manufacturing method in any one of said claim | item 1-4 formed by foaming the foaming agent containing resin layer containing an azodicarbonamide type | system | group foaming agent.
6 . The said foaming wallpaper is a manufacturing method in any one of said claim | item 1-5 with which the non-foaming resin layer B is further formed between the said base material and the said foaming resin layer.
7 . It said polymer is a methacrylic acid content less ethylene 15% by weight - methacrylic acid copolymer, production method according to any one of items 1-6.
Below is a detailed description of the method of manufacturing a sparkling wallpaper present invention.

  The method for producing foamed wallpaper according to the present invention is a method for producing foamed wallpaper having at least a foamed resin layer and a non-foamed resin layer A in this order on a substrate, the non-foamed resin layer A comprising: 1) low density polyethylene And a master batch containing titanium oxide, and 2) a resin composition containing the matrix resin of the non-foamed resin layer A is formed by extrusion film formation.

  The production method of the present invention having the above-described features is particularly obtained by extruding a resin composition containing 1) a masterbatch containing low-density polyethylene and titanium oxide, and 2) a matrix resin of the non-foamed resin layer A. Since the non-foamed resin layer A is formed by forming a film, good dispersibility of the titanium oxide can be obtained even when the non-foamed resin layer A is blended with a sufficient amount of titanium oxide necessary for concealing the base. Moreover, even when a sufficient amount of titanium oxide is blended, the generation of foreign matters such as eyes and the like can be suppressed, and good extrusion film forming properties can be obtained.

  Hereinafter, each requirement will be described separately.

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

  Of these, fiber sheets such as paper are preferable. Specifically, flame retardant paper (pulp-based sheets treated with flame retardants such as guanidine sulfamate and guanidine phosphate); aluminum hydroxide, magnesium hydroxide Inorganic paper containing inorganic additives such as: high-quality paper; thin paper.

Although the basis weight of the substrate is not critical, 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 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, ethylene-vinyl acetate copolymer (EVA) or the like can be suitably used.

  The non-foamed resin layer B 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.

  The thickness of the non-foamed resin layer B is not limited, but is preferably about 5 to 50 μm, more preferably about 8 to 20 μm.

Foamed resin layer The foamed resin layer is generally formed by foaming a 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, a thermally decomposable foaming agent, an inorganic filler, a pigment, a foaming aid (zinc compound), 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 10 to 30 g / 10 minutes.

  In addition, MFR of this specification is the value measured by the test method of JISK7210 (flow test method of thermoplastics). As test conditions, “190 ° C., 21.18 N (2.16 kgf)” described in JIS K 6760 is adopted.

  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. .

  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.

  As for the pigment, 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 And organic pigments halogenated phthalocyanine), or 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.

  Examples of the foaming aid (zinc compound) include zinc oxide, hydroxide, carbonate, basic carbonate, sulfate, nitrate, phosphite, carboxylate and the like. Such a zinc compound is preferably added from the viewpoint of improving the foaming speed. Examples of the carboxylate include acetic acid, propionic acid, 2-ethylhexanoic acid, nonanoic acid, isononanoic acid, isodecanoic acid, neodecanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, Examples include aliphatic acids such as 12-hydroxystearic acid, ricinoleic acid, and behenic acid, and aromatic acids such as benzoic acid, p-tert-butylbenzoic acid, toluic acid, salicylic acid, and naphthenic acid. The zinc carboxylate using these carboxylic acids may be in the form of a normal salt, an acid salt, or a basic salt. The above-mentioned carboxylic acids constituting the zinc carboxylate can be used, but from the viewpoint of reducing VOC, those which are powders at room temperature using fatty acids having 12 or more carbon atoms, such as zinc stearate And zinc laurate are preferred. When other carboxylic acid is used, it may be liquid or may need to be dissolved in an organic solvent in order to improve handling properties.

  The content of the zinc compound is preferably about 0.001 to 20 parts by weight, more preferably about 0.001 to 10 parts by weight with respect to 100 parts by weight of the resin composition. The thickness of the foam layer is not limited, but is preferably 70 to 150 μm in an unfoamed state (before foaming). 300-900 micrometers is preferable after foaming.

  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.

  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 A
A non-foamed resin layer A is formed on the front surface of the foamed resin layer. In the production method of the present invention, in particular, it is formed by extruding a resin composition containing 1) a master batch containing low-density polyethylene and titanium oxide, and 2) a matrix resin of the non-foamed resin layer A. To do. By extruding and forming such a resin composition, even when a sufficient amount of titanium oxide for concealing the coloration (color) of the foamed resin layer is blended in the non-foamed resin layer A, foreign matter such as eyes and the like are generated. A good film-forming property can be obtained while effectively suppressing. Further, even when a sufficient amount of titanium oxide is blended, the dispersibility of titanium oxide in the non-foamed resin layer A is improved.
(Master Badge)
In the production method of the present invention, a master batch (also referred to as MB) containing low density polyethylene (also referred to as LDPE) and titanium oxide is used. Density of the low density polyethylene is not critical, but preferably about 0.89~0.93g / cm ^3, about 0.90~0.92g / cm ³ is more preferable. Further, the MFR of the low density polyethylene is not limited, but is preferably about 5 to 100 g / 10 minutes, and more preferably about 20 to 80 g / 10 minutes. The average particle diameter of titanium oxide is not limited, but is preferably 2 μm or less, and more preferably 1 μm or less. The lower limit of the average particle diameter of titanium oxide is about 0.01 μm. These low density polyethylene and titanium oxide can also use a commercial item.

The master batch can be prepared, for example, by kneading low density polyethylene and titanium oxide. Specifically, it can be prepared by mixing low density polyethylene, titanium oxide, if necessary, metal soap and the like, and kneading with heating in a single screw extruder. At this time, the content of titanium oxide with respect to 100 parts by weight of the low density polyethylene is preferably about 5 to 240 parts by weight, and more preferably about 30 to 150 parts by weight. The average particle size of the master batch is not limited, but is preferably about 1 to 8 mm, and more preferably about 3 to 6 mm. This average particle size is a value obtained when an integrated distribution curve is prepared by the dry screening test method described in JISK0069 and the integrated percentage is 50%. This masterbatch can also use a commercial item.
(Resin composition)
The non-foamed resin layer A mainly protects the foamed resin layer. In the present invention, as the matrix resin of the non-foamed resin layer A, a polymer obtained using at least one of acrylic acid (CH ₂ = CHCOOH) and methacrylic acid (CH ₂ = C (CH ₃ ) COOH) as a monomer is used. It is preferable.

  As the matrix resin, for example, a copolymer obtained by a combination of at least one monomer of acrylic acid and methacrylic acid and ethylene can be used. More specifically, it is desirable to use at least one of ethylene-methacrylic acid copolymer (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 is used, a strong layer caused by hydrogen bonds in the resin can be formed, and thus excellent scratch resistance, wear resistance, and the like can be obtained. These may be known or commercially available.

  The content of acrylic acid or methacrylic acid in the copolymer is not limited, but is preferably 15% by weight or less, more preferably about 4 to 15% by weight. Such a resin can also use a commercial item.

  The melt flow rate value of the matrix resin depends on the type of resin used and the like, but generally may be set as appropriate within a range of 10 g / 10 minutes or more. Usually, it is preferably 10 to 100 g / 10 minutes, particularly preferably 10 to 95 g / 10 minutes, and more preferably 20 to 80 g / 10 minutes. By using a material having such a numerical range, more excellent scratch resistance, wear resistance and the like can be obtained.

  The resin composition used for extrusion film formation contains the master batch and the matrix resin. In addition, you may contain a well-known additive as needed. The content of titanium oxide with respect to 100 parts by weight of the matrix resin in the resin composition is not limited, but is preferably about 5 to 60 parts by weight, and more preferably about 10 to 50 parts by weight. What is necessary is just to set so that it may become the said titanium oxide content by adjusting the ratio of a masterbatch and matrix resin, when preparing a resin composition. By setting the content of titanium oxide with respect to the matrix resin within the above range, the non-foamed resin layer A having high whiteness can be obtained. Thereby, even if the foamed resin layer changes color, it can be concealed by the non-foamed resin layer A.

  In the production method of the present invention, by using the master batch, titanium oxide is highly dispersed even when containing 40 parts by weight or more (high content) of titanium oxide with respect to 100 parts by weight of the matrix resin of the non-foamed resin layer A Can be made. Moreover, the non-foamed resin layer A can be formed by extrusion while suppressing the generation of foreign matters such as eyes and the like. A known T-die extruder can be used for extrusion film formation.

  The thickness of the non-foamed resin layer A is not limited, but is preferably about 5 to 50 μm, more preferably about 8 to 20 μm.

Pattern Pattern Layer In the present invention, a pattern pattern layer may be provided 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 non-foamed resin layer A. 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 binder resin, and a solvent (or a dispersion medium) 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 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. Examples include resins, ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like.

  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, and acetic acid-2 -Ester-based organic solvents such as ethoxyethyl; alcohol-based organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone Organic solvents; ether organic solvents such as diethyl ether, dioxane, tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Chlorinated organic solvents; 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.

Surface protective layer (overcoat layer)
In the present invention, a surface protective layer may be provided on the surface of the design pattern layer for the purpose of adjusting the gloss and / or protecting the design pattern layer. The kind of surface protective layer is not limited. If it is a surface protective layer aiming at gloss adjustment, there exists a surface protective layer containing known fillers, such as a silica, for example. As a method for forming the surface protective layer, a known method such as gravure printing can be employed. In addition, when the adhesiveness of a pattern pattern layer and a surface protective layer is not fully acquired, a surface protective layer can also be provided after carrying out the adhesion process (primer process) of the surface of a pattern pattern layer.

  When forming a surface protective layer for the purpose of surface strength (such as scratch resistance) of foamed wallpaper, stain resistance, protection of the pattern layer, etc., those containing ionizing radiation curable resins as resin components are suitable. is there. The ionizing radiation curable resin is preferably one that undergoes radical polymerization (curing) by electron beam irradiation.

  The thickness of the surface protective layer is not limited, but is preferably about 0.1 to 15 μm.

Embossing In this invention, you may attach | subject an embossing pattern suitably. In this case, what is necessary is just to emboss from the outermost surface layer (an opposite side to a base material) of a foam wallpaper. Embossing can be performed by known means such as pressing an embossed plate. For example, when the outermost surface layer is a surface protective layer, 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 producing foam wallpaper>
As the method for producing the foamed wallpaper, a known production method can be used except that the method for forming the non-foamed resin layer A is defined as described above. For example, in order to produce a foamed wallpaper having a foamed resin layer and a non-foamed resin layer A on a substrate such as paper, coextrusion by 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 A are placed in separate cylinders, and two types and two layers are simultaneously extruded to form and laminate. do it. In this method, the coextruded laminate is simultaneously laminated (film formation) on the substrate. Since the resin layer laminated simultaneously with extrusion on the base material has adhesiveness by heat melting, it is bonded to the base material.

  In addition, a laminate in which two types and two layers are simultaneously formed in advance may be prepared, placed on the substrate, and bonded to the substrate by thermal lamination.

  In addition, when an inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer, an inorganic filler residue (so-called eyes) is easily generated at the extrusion port (so-called die) of the extrusion molding machine. It tends to be a foreign material on the sheet surface. Therefore, when an inorganic filler is contained in the resin composition forming the foaming agent-containing resin layer, the non-foaming resin layer A and the non-foaming resin layer B are coextruded with the foaming agent-containing resin layer (that is, 3 Layer coextrusion) is preferred. The coextrusion molding can be performed, for example, by using a multi-manifold type T die. Thus, by simultaneously extruding and molding the foaming agent-containing resin layer between the non-foamed resin layers A and B, it is possible to suppress the occurrence of the eyes. In the present invention, titanium oxide is contained in the non-foamed resin layer A, but since it is used in the form of the masterbatch, the dispersibility of titanium oxide in the non-foamed resin layer A is high and the non-foamed resin layer A is extruded. Occurrence of eyes and eyes during film formation is suppressed.

  After simultaneous lamination on the 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, 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 10 to 70 kGy. A known electron beam irradiation apparatus can be used as the electron beam source. The 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 0 to 4 parts by weight, based on 100 parts by weight of the resin component.

  When a surface protective layer containing an ionizing radiation curable resin is formed, the surface protective layer can be cured by electron beam irradiation. Such electron beam irradiation can be performed simultaneously (same processing) as electron beam irradiation performed to crosslink the resin contained in the foaming agent-containing resin layer. That is, after forming the foaming agent-containing resin layer, the non-foaming resin layer A, the pattern layer and the surface protective layer containing the ionizing radiation curable resin in order, the resin contained in the foaming agent-containing resin layer is irradiated with an electron beam. And the resin contained in the surface protective layer can be cured.

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

  The production method of the present invention is particularly by extruding and forming a resin composition containing 1) a master batch containing low-density polyethylene and titanium oxide, and 2) a matrix resin of the non-foamed resin layer A. Since the non-foamed resin layer A is formed, good dispersibility of the titanium oxide can be obtained even when the non-foamed resin layer A is blended with a sufficient amount of titanium oxide necessary for concealing the base. Moreover, even when a sufficient amount of titanium oxide is blended, the generation of foreign matters such as eyes and the like can be suppressed, and good extrusion film forming properties can be obtained.

It is a schematic diagram of the foaming decorative sheet produced by the Example and the comparative example.

  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, on the base material (backing paper) so that the thickness is 10 μm / 50 μm / 10 μm in the order of non-foamed resin layer A / foaming agent-containing resin layer / non-foamed resin layer B The film was formed by extrusion. Thereby, the laminated body which consists of non-foaming resin layer A / foaming agent containing resin layer / non-foaming resin layer B / base material was obtained.

  As a base material, backing paper “WK-665 (manufactured by Kojin)” was prepared, heated to 90 ° C., and then the above three layers were extruded to form a film.

  As for the extrusion conditions, the cylinder temperature containing the resin for forming the non-foamed resin layer A was 115 ° C., the cylinder temperature containing the resin composition for forming the foaming agent-containing resin layer was 110 ° C., and non-foamed The cylinder temperature in which the resin for forming the resin layer B was accommodated was 100 ° C. The die temperature was 110 ° C. for all.

  The laminate was irradiated with an electron beam (200 kV, 30 kGy) from the non-foamed resin layer A side to crosslink the foaming agent-containing resin layer and the non-foamed resin layer A. Further, a corona discharge treatment was performed on the non-foamed resin layer A.

Next, an EVA aqueous emulsion was applied to the non-foamed resin layer A (2 g / m ² ) to form a primer layer, and a fabric pattern was printed with an aqueous ink “Hydric” (manufactured by Dainichi Seika Kogyo). .

  Next, the laminate on which the fabric pattern was printed was heated in a gear oven (at 220 ° C. for 35 seconds) to foam the foaming agent-containing resin layer.

  Finally, the foam was embossed with a texture pattern to obtain a foam wallpaper.

  Each layer was formed using the following components.

  The non-foamed resin layer A was formed by 100 parts by weight of EMAA “Nucleel N1560 (MMA content: 15% by weight), made by Mitsui DuPont Polychemical” and 22 parts by weight of a titanium oxide master batch. Specifically, a mixed pellet was prepared by dry blending an EMAA resin pellet and a titanium oxide master batch, and the non-foamed resin layer A was formed by extruding the mixed pellet to form a film. Titanium oxide masterbatch is composed of 100 parts by weight of low density polyethylene (Petrocene 249, manufactured by Tosoh), 100 parts by weight of titanium oxide (CR-63, manufactured by Ishihara Sangyo) and 3 parts by weight of metal soap (zinc stearate). It was prepared by kneading with a screw extruder (kneading temperature: 110 ° C.).

  The foaming agent-containing resin layer is composed of 100 parts by weight of EVA “Evaflex V406 (VA content: 20% by weight, MFR = 20), manufactured by Mitsui DuPont Polychemical), 30 parts by weight of titanium oxide“ CR63, manufactured by Ishihara Sangyo ”, It was formed with 6 parts by weight of ADCA foaming agent “Uniform Ultra AZ3050I manufactured by Otsuka Chemical” and 4.2 parts by weight of kicker agent (zinc stearate).

  The non-foamed resin layer B was formed by EVA “Evaflex EV150 (VA content: 33 wt%, melting point: 61 ° C.), manufactured by Mitsui DuPont Polychemical”.

Example 2
For the non-foamed resin layer A, a foamed wallpaper was obtained in the same manner as in Example 1 except that the blending amount of the titanium oxide master batch with respect to 100 parts by weight of EMAA was 49 parts by weight.

Example 3
For the non-foamed resin layer A, a foamed wallpaper was obtained in the same manner as in Example 1 except that the compounding amount of the titanium oxide master batch with respect to 100 parts by weight of EMAA was 85 parts by weight.

Example 4
For the non-foamed resin layer A, a foamed wallpaper was obtained in the same manner as in Example 1 except that the blending amount of the titanium oxide master batch with respect to 100 parts by weight of EMAA was changed to 133 parts by weight.

Comparative Example 1
A foamed wallpaper was obtained in the same manner as in Example 1 except that the non-foamed resin layer A was formed by 100 parts by weight of EMAA and 10 parts by weight of titanium oxide “CR63, manufactured by Ishihara Sangyo”.

Comparative Example 2
For the non-foamed resin layer A, a foamed wallpaper was obtained in the same manner as in Comparative Example 1 except that the amount of titanium oxide was 20 parts by weight with respect to 100 parts by weight of EMAA.

Comparative Example 3
For the non-foamed resin layer A, a foamed wallpaper was obtained in the same manner as in Comparative Example 1 except that the blending amount of titanium oxide with respect to 100 parts by weight of EMAA was changed to 30 parts by weight.

Comparative Example 4
A foamed wallpaper was obtained in the same manner as in Comparative Example 1 except that the non-foamed resin layer A was formed with 100 parts by weight of EMAA.

Test example 1
(Whiteness)
With respect to the foamed wallpaper produced in the examples and comparative examples, the whiteness of the non-foamed resin layer A side was measured with a colorimetric device “color difference meter CR-300, manufactured by Konica Minolta”. As a result, a b value of 6 or less (that is, a whiteness is high) was evaluated as ◯, and a b value exceeding 6 (that is, a whiteness was low) was evaluated as ×.
(Weatherability)
An accelerated test (40 hours) was conducted with a fade meter (FOM) “Ultraviolet Fade Meter U48AU, manufactured by Suga Test Instruments” to examine the weather resistance of the foamed wallpaper.

  The case where ΔE after 40 hours of FOM is 1.5 or less (that is, weather resistance discoloration is not recognized) is ○, and the case where ΔE after 40 hours of FOM is more than 1.5 (that is, weather resistance discoloration is recognized) × It was evaluated.

The non-foamed resin layer A after 1000 hours of FOM was observed with the naked eye, ○ where no cracks were observed, ○ where some cracks were observed within the allowable range, Δ, cracks were recognized significantly and were outside the allowable range Was evaluated as x.
(Extrusion film forming)
When the non-foamed resin layer A is formed by extrusion, the case where no foreign matter such as eyes or the like is observed is ○, the case where foreign matter such as the eyes or the like is recognized but there is no problem in productivity, △, Foreign matter was recognized, and the problem of productivity was evaluated as x.

  The test results are shown in Table 1 below.

[The amount of titanium oxide ^* in Tables 1-1 and 1-2 indicates the content of titanium oxide with respect to 100 parts by weight of the matrix resin. Further, “non-film formation” means that productivity is extremely poor and the sheet cannot be formed. ]
As is apparent from the results of Tables 1-1 and 1-2, according to the production method of the present invention using the titanium oxide master batch (MB), 40 parts by weight of oxidation is performed with respect to 100 parts by weight of the matrix resin (EMAA). It can be seen that good film forming properties can be obtained even when titanium is blended. Such good film-forming properties are based on the highly dispersed titanium oxide. On the other hand, in the manufacturing method of the comparative example which does not use a titanium oxide masterbatch, even if it is less titanium oxide content, it turns out that extrusion film formation is difficult.

1. Backing paper2. Non-foamed resin layer B
3. 3. Foamed resin layer Non-foamed resin layer A

Claims (7)

A method for producing a foam wallpaper having at least a foam resin layer and a non-foam resin layer A in order on a substrate,
The non-foamed resin layer A is obtained by extruding a resin composition containing 1) a master batch containing low-density polyethylene and titanium oxide, and 2) a matrix resin of the non-foamed resin layer A. Forming ,
The matrix resin contains a polymer obtained using at least one of acrylic acid and methacrylic acid as a monomer,
A method for producing foamed wallpaper .   The production method according to claim 1, wherein the polymer is an ethylene-methacrylic acid copolymer. The said master batch is a manufacturing method of Claim 1 or 2 containing 5 to 240 weight part of the said titanium oxide with respect to 100 weight part of the said low density polyethylene. The manufacturing method according to any one of claims 1 to 3, wherein a content of the titanium oxide with respect to 100 parts by weight of the matrix resin in the resin composition is 5 to 60 parts by weight. The said foaming resin layer is a manufacturing method in any one of Claims 1-4 formed by foaming the foaming agent containing resin layer containing an azodicarbonamide type | system | group foaming agent. The said foaming wallpaper is a manufacturing method in any one of Claims 1-5 in which the non-foaming resin layer B is further formed between the said base material and the said foaming resin layer. It said polymer is a methacrylic acid content less ethylene 15% by weight - methacrylic acid copolymer, process according to any one of claims 1-6.

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