JP2016199646A - Resin composition, laminated sheet, laminate, foamed wallpaper and method for producing foamed wallpaper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition allowing for production of wallpaper having a foamed resin layer having a sufficient expansion ratio and a good foamed state on a base material with less deterioration, a laminated sheet, a laminate, foamed wallpaper, and a method for producing foamed wallpaper.SOLUTION: There is provided the resin composition for forming a foamed resin layer of foamed wallpaper which has a base material and a foamed resin layer provided on the base material. The resin composition contains a filler, a foaming agent, a resin content containing an ethylene homopolymer or a copolymer of ethylene and other olefin and a silane crosslinkable resin, and a silane crosslinking aid, the silane crosslinking aid containing a sulfonic acid compound.SELECTED DRAWING: None

Description

  The present invention relates to a resin composition, a laminated sheet, a laminate, a foamed wallpaper, and a method for producing a foamed wallpaper. More specifically, the present invention relates to a resin composition that can be used for decorating wall surfaces of buildings such as detached houses, apartment houses, shops, and office buildings, laminated sheets, foamed wallpaper, and foamed wallpaper manufacturing methods.

  As wallpaper used for wall decoration of buildings, etc., vinyl chloride wallpaper in which a resin layer of vinyl chloride resin is provided on a paper base material is widely used. In recent years, foamed wallpaper having a foamed resin layer formed from a foamed polyolefin-based resin has been proposed in consideration of the environment.

  As such a foam wallpaper, for example, a foam resin composition in which a microcapsule type foaming agent is added to an emulsion containing an ethylene-vinyl acetate copolymer is applied to a paper substrate and dried, and then a pattern is formed on the surface. There is known a foamed wallpaper obtained by printing, then heating and foaming, and forming an uneven pattern with an embossed plate. In addition, a foamed resin composition obtained by adding a thermally decomposable foaming agent to an ethylene-vinyl acetate copolymer is extruded and laminated on a paper substrate using a T-die extruder, a pattern is printed on the surface, and then heated. Foamed wallpaper obtained by foaming and forming an uneven pattern with an embossed plate is known (Patent Documents 1 and 2).

  Patent Document 3 describes a production method in which a foaming agent-containing resin is directly heated and melt-extruded on a backing paper using a T-die extruder, the resin is crosslinked by electron beam irradiation, and then heated and foamed. There is.

Japanese Patent Laid-Open No. 6-47875 JP 2001-347611 A Japanese Patent No. 3923969

  By the way, when forming a foamed resin layer using an ethylene-vinyl acetate copolymer, there exists a problem resulting from vinyl acetate. Specifically, there is a concern about corrosion of the extruder, excessive thickening due to the combination of the polar compound and the inorganic filler, and deterioration over time due to hydrolysis.

  On the other hand, the resin composition for foamed wallpaper is required to have a satisfactory foaming state in which a sufficient foaming ratio is obtained when the formed resin sheet is foamed and the outgassing is not noticeable. . As in the method described in Patent Document 3, it is possible to adjust the viscosity to be suitable for foaming by performing a crosslinking treatment with an electron beam or the like after film formation. However, there is also a problem that problems such as deterioration of electron beam and mechanical strength decrease occur. This tendency is further increased by the heat history received in the subsequent heating and foaming process.

  Therefore, the present inventors examined water crosslinking using a silane crosslinkable resin as a resin crosslinking method instead of electron beam, and found that the crosslinking reaction takes longer time than electron beam crosslinking. As a means for improving the reaction rate of the silane coupling reaction, a method using a tin compound such as dibutyltin dilaurate as a catalyst is known. In the field of wallpaper, a tin catalyst is designated as a harmful substance.

  The present invention has been made in view of the circumstances as described above, and enables the production of a wallpaper including a foamed resin layer having a sufficient foaming ratio and a good foamed state on a substrate with little deterioration. It aims at providing the manufacturing method of a resin composition, a lamination sheet, a laminated body, a foaming wallpaper, and a foaming wallpaper.

  The present invention is a resin composition for forming the foamed resin layer of a foam wallpaper comprising a base material and a foamed resin layer provided on the base material, and a filler, a foaming agent, A resin composition comprising an ethylene homopolymer or a copolymer of ethylene and another olefin and a resin component containing a silane crosslinkable resin, and a silane crosslinking aid, wherein the silane crosslinking aid comprises a sulfonic acid compound. I will provide a.

  According to the resin composition of the present invention, the combination of the resin component and the sulfonic acid compound can sufficiently perform the crosslinking of the resin component. A wallpaper comprising a foamed resin layer having a good foamed state can be produced. Furthermore, according to the present invention, the resin content can be sufficiently cross-linked without using a tin catalyst, so that it is possible to realize a wallpaper with less environmental hormone action.

  Moreover, according to the resin composition of the present invention, a foamed resin layer having a sufficient foaming ratio and a good foamed state can be formed even when curing is performed for a long time. As a result, an original wallpaper having excellent temporal stability (for example, a laminated sheet and laminate of the present invention described later) can be obtained, and low-cost and efficient production of foamed wallpaper can be realized.

  Moreover, this invention provides a laminated sheet provided with a base material and the resin sheet obtained by bridge | crosslinking the said resin composition provided on this base material.

  Furthermore, the present invention is a foam wallpaper comprising a base material and a foamed resin layer provided on the base material, and obtained by foaming a foaming agent contained in the resin sheet in the laminated sheet. Provide wallpaper.

  The present invention also provides a method for producing a foam wallpaper comprising a base material and a foamed resin layer provided on the base material, wherein the resin sheet obtained by crosslinking the resin composition is used as a base material. There is provided a method for producing foamed wallpaper, comprising: a step of laminating a laminate sheet to obtain a laminate sheet; and a step of forming a foamed resin layer by foaming a foaming agent contained in the resin sheet in the laminate sheet.

  Moreover, this invention provides a laminated body provided with a base material and the resin composition layer formed on the base material from the said resin composition.

  Furthermore, the present invention is a method for producing a foam wallpaper comprising a base material and a foamed resin layer provided on the base material, wherein the resin composition layer in the laminate is cross-linked, A step of obtaining a laminated sheet in which a resin sheet comprising a crosslinked resin composition layer is formed, and a step of forming a foamed resin layer by foaming a foaming agent contained in the resin sheet in the laminated sheet. Provided is a method for producing foam wallpaper.

  Furthermore, the present invention is a method for producing a foamed wallpaper comprising a base material and a foamed resin layer provided on the base material, wherein the resin composition is laminated while laminating a sheet-like material of the resin composition. To form a foamed resin layer by foaming a foaming agent contained in the resin sheet in the laminated sheet, and a step of obtaining a laminated sheet in which a resin sheet made of a crosslinked sheet is formed on the substrate And a process for producing foamed wallpaper.

  According to the present invention, a resin composition, a laminated sheet, a laminate, and a foamed wallpaper that enable the production of a wallpaper comprising a foamed resin layer having a sufficient foaming ratio and a good foamed state on a substrate with little deterioration. And a method for producing foamed wallpaper.

  Furthermore, according to the present invention, the resin content can be sufficiently cross-linked without using a tin catalyst, so that it is possible to realize a wallpaper with less environmental hormone action.

  Furthermore, according to this invention, even if it is a case where curing is performed for a long time, the foamed resin layer which has sufficient foaming ratio and a favorable foaming state can be formed. As a result, an original wallpaper having excellent temporal stability (for example, a laminated sheet and laminate of the present invention described later) can be obtained, and low-cost and efficient production of foamed wallpaper can be realized.

It is sectional drawing of the foam wallpaper based on one Embodiment of this invention.

[Resin composition]
The resin composition according to the present embodiment is a resin composition for forming a foamed resin layer of a foamed wallpaper comprising a base material and a foamed resin layer provided on the base material, and a filler, A foaming agent, a resin component, and a silane crosslinking aid.

  Hereinafter, each component contained in the resin composition will be described in more detail.

[filler]
Examples of the filler include inorganic fillers and organic fillers. Examples of the inorganic filler include calcium carbonate and titanium dioxide. These can be used alone or in combination of two or more. Examples of the organic filler include melamine cyanurate, polytetrafluoroethylene (PTFE), wood flour, cellulose, and derivatives thereof. These may be used alone or in combination of two or more. it can.

  The content of the filler is not particularly limited, but the total amount is preferably 10 to 70% by mass based on the total amount of the resin composition. Reasons for adding the filler include securing the concealing property of the foam wallpaper, reducing the combustion calories per unit area, reducing the production cost by increasing the bulk, etc., but the filler content is the total amount of the resin composition. When it is 10 to 70% by mass as a reference, it is possible to produce a foam wallpaper having a low production calorie and a low calorie calorie while ensuring good concealment as a foam wallpaper.

  As the filler, for example, commercially available products such as Softon 1000 (Calcium Carbonate, manufactured by Bihoku Powder Co., Ltd.), and Taipei CR-60-2 (Titanium Dioxide, manufactured by Ishihara Sangyo Co., Ltd.) can be used.

[Foaming agent]
Examples of the foaming agent according to this embodiment include azo foaming agents such as azodicarbonamide, hydrazide foaming agents such as p-toluenesulfonyl hydrazide, and nitroso foaming agents such as N, N′-dinitrosopentamethylenetetramine. These can be used, and these can be used alone or in combination of two or more. The content of the foaming agent is not particularly limited, but the total amount is preferably 2 to 30% by mass based on the total amount of the resin composition. When the content of the foaming agent is within the above range, yellowing that occurs when the foaming agent remains in the foamed wallpaper after foaming can be suppressed, and a foamed wallpaper that is favorable in terms of compression recovery and feel can be produced. .

  As the foaming agent, for example, commercially available products such as VINYHALL AC # 3C-K2 (manufactured by Eiwa Kasei Co., Ltd., azodicarbonamide-based foaming agent) can be used.

[Resin content]
The resin component contains an ethylene homopolymer or a copolymer of ethylene and another olefin, and a silane crosslinkable resin.

  Ethylene homopolymers and copolymers of ethylene and other olefins are nonpolar, non-halogen thermoplastic resins. By using these, ethylene-methyl methacrylate copolymer resins, ethylene-methacrylic acid copolymers Higher quality because the increase in the viscosity when the filler is increased compared to the case of using polar resins such as resin, ethylene-acrylic acid copolymer resin, ethylene-vinyl acetate copolymer resin, and ionomer resin. The wallpaper can be produced stably.

  Examples of the ethylene homopolymer include low density polyethylene synthesized by a high pressure method, high density polyethylene not containing a comonomer synthesized by a medium pressure method, and the like. Among these, low density polyethylene is preferable.

Low density polyethylene, for example, those having a density in the range of 0.91 g / cm ³ or more 0.94 g / cm ³ or less. The density of low-density polyethylene is preferably not 0.91 g / cm ³ or more 0.93 g / cm ³ or less, more preferably 0.92 g / cm ³ or more 0.93 g / cm ³ or less. The molecular weight, melting point, melt flow rate (MFR) and the like of the low density polyethylene are not particularly limited, but the melting point is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 110 ° C. If the melting point is 140 ° C. or lower, it is not necessary to melt the resin and mold it at a higher temperature, and the foaming agent is less likely to decompose during molding. On the other hand, if the melting point is 50 ° C. or higher, sufficient heat durability in actual use can be obtained. The MFR is preferably from 3 to 150, more preferably from 4 to 100. If the MFR is 3 or more, shear heat generated during molding can be suppressed, the processing temperature can be easily controlled, and there is little possibility that the foaming agent will be decomposed during molding. On the other hand, if the MFR is 150 or less, the mechanical strength of the produced foamed wallpaper is maintained, and the workability and durability are excellent.

  As low-density polyethylene, for example, commercially available products such as Novatec LD LC802A, Novatec LD LC604 (manufactured by Nippon Polyethylene Co., Ltd.), Ube Polyethylene J2516 (produced by Ube Maruzen Polyethylene Co., Ltd.) can be used.

  Examples of the copolymer of ethylene and other olefins include linear low density polyethylene, ultra-low density polyethylene, high density polyethylene obtained by copolymerization with a comonomer, and the like. Alternatively, two or more kinds can be used in combination. Among these, ultra-low density polyethylene is preferable.

The ultra low density polyethylene, for example, those having a density in the range of less than 0.88 g / cm ³ or more 0.91 g / cm ^3. The density of the ultra-low density polyethylene is preferably 0.88 g / cm ³ or more and 0.90 g / cm ³ or less, more preferably 0.89 g / cm ³ or more and 0.90 g / cm ³ or less. The molecular weight, melting point, MFR, etc. of the ultra-low density polyethylene are not particularly limited, but the melting point is preferably 50 ° C to 140 ° C, more preferably 60 ° C to 110 ° C. If the melting point is 140 ° C. or lower, it is not necessary to melt the resin and mold it at a higher temperature, and the foaming agent is less likely to decompose during molding. On the other hand, if the melting point is 50 ° C. or higher, sufficient heat durability in actual use can be obtained. The MFR is preferably from 3 to 150, more preferably from 4 to 100. If the MFR is 3 or more, shear heat generated during molding can be suppressed, the processing temperature can be easily controlled, and there is little possibility that the foaming agent will be decomposed during molding. On the other hand, if the MFR is 150 or less, the mechanical strength of the produced foamed wallpaper is maintained, and the workability and durability are excellent.

  Examples of ultra-low density polyethylene include TAFMER DF140, DF940, DF7350 (all manufactured by Mitsui Chemicals), Kernel KJ640T (manufactured by Nippon Polyethylene Co., Ltd.), Excellen FX CX5508 (manufactured by Sumitomo Chemical Co., Ltd.), Engage 8400/8407. Commercial products such as Dow Chemical Co., Evolue P SP90100 (Prime Polymer Co., Ltd.) can be used.

  The total content of the ethylene homopolymer or the copolymer of ethylene and other olefins is preferably 20 to 80% by mass, and 40 to 75% by mass with respect to the total amount of the resin composition. More preferably, it is more preferably 50 to 70% by mass.

  As the silane crosslinkable resin, a conventionally known silane crosslinkable resin such as a silane crosslinkable polyolefin resin can be used. Examples of the silane crosslinkable polyolefin resin include a resin in which a hydrolyzable silyl group is mainly introduced into a side chain in a polyolefin polymer as a matrix. Examples of such a resin include a resin in which a hydrolyzable silyl group is mainly introduced into a side chain in a polymer such as a low density polyethylene type, a high density polyethylene type, an ethylene-vinyl acetate copolymer system, or a polypropylene type. . Crosslinking is carried out by hydrolysis of substituted silyl groups. In addition, the polyolefin resin which this silyl group is located in the terminal may be contained.

  Silane crosslinkable polyolefin resin is a method in which a monomer of polyolefin polymer and a silane compound having an ethylenically unsaturated group or epoxy group are randomly copolymerized in a container, or a peroxide in a polyolefin polymer melt. Can be obtained by a method such as graft copolymerization of the above silane compound. Here, the polyolefin polymer as a matrix can be used alone or in combination of two or more of the above resins. Further, the base polyolefin-based resin may be used in combination with the polyolefin-based resin and a resin different from the polyolefin-based resin as long as mixing or dispersion of the resins is allowed. The degree of mixing or dispersion varies greatly depending on the type of extruder used, and an appropriate compatibilizer can be used. Therefore, the combined resins cannot be generally classified, but are preferably the same type of resins.

  Examples of the silane compound having an ethylenically unsaturated group include a silane compound having a vinyl group, a silane compound having an acryloyl group, and a silane compound having a methacryloyl group. Examples of the silane compound having a vinyl group include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentyloxysilane, vinyltriphenoxysilane, vinyltribenzyloxy. Examples include silane, vinyltrimethylenedioxysilane, vinyltriethylenedioxysilane, vinylpropionyloxysilane, vinyltriacetoxysilane, and vinyltricarboxysilane. Examples of the silane compound having an acryloyl group include 3-acryloxypropyltrimethoxysilane. Examples of the silane compound having a methacryloyl group include 3-methacryloxypropylmethyldimethoxysilane.

  Examples of the silane compound having an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidoxypropylmethyldimethoxysilane.

  Commercially available products can be used as the silane crosslinkable resin, and for example, “Linkron XCF710” manufactured by Mitsubishi Chemical Corporation can be used.

  The content of the silane crosslinkable resin is not particularly limited, but from the viewpoint of molding stability such as generation of gel and surface roughness, 100 parts by mass of an ethylene homopolymer or a copolymer of ethylene and another olefin It is preferable that it is 2-20 mass parts with respect to.

[Silane crosslinking aid]
The silane crosslinking aid according to this embodiment includes a sulfonic acid compound. Examples of the sulfonic acid compound include inorganic sulfonic acids such as fluorosulfonic acid, sulfonic acids having an alkyl group such as methylsulfonic acid, and aromatic sulfonic acids such as benzenesulfonic acid, p-toluenesulfonic acid, and alkylbenzenesulfonic acid. Examples thereof include organic sulfonic acids and salts thereof. Among them, from the viewpoint of preventing bleed out, aromatic sulfonic acid or a salt thereof is preferable. In addition to preventing bleed out, alkylbenzene sulfonic acid is more preferable, and dodecylbenzene sulfonic acid is more preferable in terms of improving compatibility with the resin. preferable.

  Moreover, when the said sulfonic acid compound is a sulfonate, it is preferable to use together with an acid. Thereby, sulfonic acid can be produced in the resin composition. Examples of the sulfonate include sodium salts, potassium salts, calcium salts, and magnesium salts of the above sulfonic acid compounds. Examples of the acid include those that are stronger acids (having a smaller pKa value) than the sulfonic acid that is the base of the sulfonate used, and examples include hydrochloric acid, nitric acid, and sulfuric acid. Among these, from the viewpoint of suppressing flammability and corrosivity, the combination of the sulfonate and the acid is preferably a combination of the sodium salt of the sulfonic acid compound and hydrochloric acid.

  According to the sulfonic acid compound according to the present embodiment, it can sufficiently function as a silane crosslinking aid of a silane crosslinkable resin, has a sufficient foaming ratio and a good foamed state in a short period, and is an environmental hormone. A foamed resin layer with little action can be formed. Moreover, according to the sulfonic acid compound which concerns on this embodiment, even if it is a case where curing is performed for a long period of time, the foamed resin layer which has sufficient foaming ratio and a favorable foaming state can be formed. As a result, it is possible to obtain an original wallpaper having excellent temporal stability (for example, a laminated sheet and laminate according to this embodiment described later), and to realize low-cost and efficient production of foamed wallpaper. .

  Furthermore, the sulfonic acid compound according to the present embodiment is less likely to bleed out on the surface as compared with a fatty acid amide-based silane crosslinking aid, and can produce a foamed wallpaper having excellent printability.

  From the viewpoint of the progress rate of the crosslinking reaction and the film formation stability of the resin composition, the content of the sulfonic acid compound is preferably 0.01 to 5.0 parts by mass with respect to 100 parts by mass of the silane crosslinkable resin. It is more preferable that it is 0.05-1.0 mass part.

  Further, from the viewpoint of coloring of the resin composition and film formation stability, the content of the sulfonic acid compound is preferably 0.001 to 1.0% by mass based on the total amount of the resin composition, 0.005 More preferably, it is -0.2 mass%.

  Moreover, the resin composition according to the present embodiment may be colored by adding a pigment or the like as necessary. Coloring by adding a pigment may be transparent, translucent, or opaque. Examples of the pigment include inorganic pigments such as iron oxide and carbon black, and organic pigments such as aniline black and phthalocyanine blue.

  The addition amount of the pigment is preferably 5 to 50% by mass, more preferably 10 to 30% by mass based on the total amount of the resin composition.

  Moreover, well-known additives, such as a flame retardant, a cell regulator, a stabilizer, a lubricant, a foaming adjuvant, can be used for a resin composition as needed.

  Examples of the flame retardant include metal oxide flame retardants such as magnesium hydroxide and aluminum hydroxide, phosphorus flame retardants such as phosphate ester, and bromine flame retardants such as tetrabromobisphenol A.

  Examples of the cell modifier include acrylic ester resins and methacrylic ester resins.

  Examples of the stabilizer include amine-based antioxidants, radical scavengers such as hindered amine-based light stabilizers, peroxide-based and sulfur-based peroxide decomposers, and heat-based stabilizers such as phenol-based antioxidants. It is done.

  Examples of the lubricant include fatty acid series such as stearic acid and lauric acid, fatty acid amide series such as stearic acid amide and oleic acid amide, and metal soap type lubricants such as zinc stearate, calcium laurate, and zinc octylate. . As the lubricant, for example, commercially available products such as ADK STAB AP-546 (manufactured by ADEKA Corporation) can be used.

  Examples of the foaming aid include urea, zinc chloride, zinc oxide and the like in addition to the above metal soap lubricant.

[Laminated sheet]
The laminated sheet according to the present embodiment includes a substrate and a resin sheet provided on the substrate and obtained by crosslinking (for example, crosslinking by heating or water crosslinking). In the crosslinking of the resin composition, for example, the silane crosslinking resin contained in the resin composition can be crosslinked by heating the resin composition. The heating method is not particularly limited, and examples thereof include a method of treating superheated steam (also referred to as superheated steam) in an environment of 130 ° C. to 280 ° C. for 20 seconds to 15 minutes. The superheated steam treatment includes, for example, a method in which a sheet-like material is arranged in a superheated steam atmosphere and the superheated steam is brought into contact with the sheet-like material. Moreover, as a method of water-crosslinking, there is a method of water-crosslinking by curing for 1 day to 1 month in a temperature range of 40 ° C. to 70 ° C. in an environment with a humidity of 60% or more. There is a method of curing and hydrocrosslinking in an environment of a 90% constant temperature and humidity chamber.

  In the range which does not impair the effect of this invention, you may bridge | crosslink resin parts other than silane crosslinkable resin as needed.

  The laminated sheet can be obtained by laminating (transferring) the resin sheet onto a substrate.

  Moreover, the laminated sheet which concerns on other embodiment bridge | crosslinks the resin composition layer in a laminated body provided with a base material and the resin composition layer formed from the said resin composition provided on this base material. It can also be obtained by a method of forming a resin sheet comprising a crosslinked resin composition layer on a substrate.

  As a method of providing a resin composition layer formed from a resin composition on a base material, a resin composition layer is applied by a method such as applying a resin composition and drying it if desired, or applying a resin composition layer on a support in advance. A method of laminating (transferring) the resin composition layer (sheet-like product of the resin composition) onto a substrate, and a sheet-like product obtained by forming a film of the resin composition with an extruder or the like. The method of laminating on a base material etc. are mentioned.

  The laminating method is not particularly limited, but a method in which the resin sheet or the sheet-like material of the resin composition and the substrate are subjected to thermocompression bonding using a hot press machine, superheated steam is used. For example, a method of performing pressure bonding while using.

  From the viewpoint of improving the adhesiveness between the substrate and the resin composition layer formed from the resin sheet or the resin composition, on the surface on the side where the sheet-like material is provided on the surface of the substrate, for example, corona discharge treatment, An easy adhesion treatment such as plasma treatment or ozone treatment may be performed, or an easy adhesion treatment layer formed from an acrylic-butyl copolymer, polyurethane composed of isocyanate and polyol, or the like may be provided.

[Base material]
The base material is not particularly limited as long as it is usually used as a paper base material, such as a conventional backing paper for wallpaper. As such a substrate, for example, a pulp-based flame retardant paper impregnated with a water-soluble flame retardant such as guanidine sulfamate or guanidine phosphate, or an inorganic agent such as magnesium carbonate, aluminum hydroxide, magnesium hydroxide or the like. Examples include mixed paper. These weighings may be 50 to 300 g / m ² or 60 to 160 g / m ² .

[Foam wallpaper]
FIG. 1 is a cross-sectional view of a foam wallpaper according to an embodiment of the present invention. The foamed wallpaper 10 according to the present embodiment has a foamed resin layer 2 on a base material 1, and the surface of the foamed resin layer 2 opposite to the base material 1 has an uneven shape. In the foam wallpaper 10, the pattern layer 4 and the surface protective layer 5 are further provided on the foam resin layer 2, but these may be omitted.

  The surface of the foamed resin layer 2 opposite to the substrate 1 has an uneven shape. The method for providing the uneven shape in the present embodiment is not particularly limited. For example, using heat at the time of heating and foaming, the surface side is a cooling embossing roll, and the substrate 1 side is a rubber roll. In addition, a method of forming a concavo-convex shape on the surface by niping (embossing) with two torr and cooling. The uneven shape is not particularly limited, and examples thereof include a wood grain plate conduit groove, a stone plate surface unevenness, a cloth surface texture, a satin texture, a grained grain, a hairline, and a straight line groove. Can be selected as appropriate.

  The pattern layer 4 and the surface protective layer 5 can be appropriately provided using known materials. If the object of the present invention can be achieved, the pattern layer 4 and the surface protective layer 5 may not be provided. The pattern layer 4 and the surface protective layer 5 can be provided using a known printing technique such as gravure coating.

  Specifically, the foamed wallpaper forms a foamed resin layer by laminating the resin sheet on a base material to obtain a laminated sheet, and foaming a foaming agent contained in the resin sheet in the laminated sheet. It can obtain by the manufacturing method provided with the process to do.

  As yet another embodiment, the foamed wallpaper is formed by laminating the resin composition sheet-like material while cross-linking the resin composition to form a cross-linked sheet-like resin sheet on the substrate. It can obtain also by the manufacturing method provided with the process of obtaining the laminated sheet, and the process of foaming the foaming agent contained in the resin sheet in a laminated sheet, and forming a foamed resin layer.

  In this case, a superheated steam treatment is preferable as the laminating method and the crosslinking method. According to such a method, it becomes possible to laminate on the base material while maintaining the molten state of the surface of the sheet-like material by superheated steam, and the unevenness of the surface of the base material to be adhered is foamed resin due to its leveling effect. Transfer to the layer can be suppressed. In addition, the silane crosslinkable resin can be efficiently crosslinked by superheated steam.

  Foaming of the foaming agent can be performed by heating the resin sheet. The heating condition can be appropriately set depending on the components constituting the resin sheet, and is not particularly limited. However, heating is preferably performed at 160 ° C. to 280 ° C. for 10 seconds to 120 seconds, and 220 ° C. to 240 ° C. for 30 seconds. It is more preferable to heat for 2 seconds to 50 seconds, and further more preferable to heat at 220 ° C. for 40 seconds.

<Example 1>
[Production of sheet-like material]
Using a T-die having a coat hanger type manifold, using a barrier type screw with a screw diameter (D) of 65 mm and L / D (screw length divided by the screw diameter) = 32, using an extrusion lamination machine A sheet-like material having a thickness of 100 μm having the composition shown in Table 1 (in Table 1, the numerical values indicate parts by mass) was formed by extrusion. Extrusion conditions were set to 125 ° C. in all zones from the cylinder to the die.

[Production of resin sheet]
The film-formed sheet is cured under the environment shown in Table 2 (temperature: 40 ° C., relative humidity: 90%) for the period shown in Table 2 (1, 2, 3, 5 days) to perform water crosslinking. Four types of resin sheets were obtained.

[Production of laminated sheet]
Using a backing paper for wallpaper (manufactured by Kojin Co., Ltd .: WK-6651HT (trade name)) as a base material, and the resin sheet obtained above using a hot press machine, the temperature is 110 ° C., Thermocompression bonding was performed for 1 minute under the condition of a press pressure of 5 MPa to obtain a laminated sheet.

[Production of foam wallpaper]
After the corona discharge treatment was performed on the resin sheet side surface of the laminated sheet, a fabric pattern was printed as a pattern layer using a water-based ink by a gravure printer.

  Then, after heating at 220 ° C. for 40 seconds to foam the foaming agent, a metal roll (embossed plate) having a textured uneven pattern was pressed to form an uneven shape, thereby obtaining a foamed wallpaper. Moreover, the foamed wallpaper before shaping an uneven | corrugated shape was also prepared for performance evaluation.

<Example 2>
Except that the environment shown in Table 2 (temperature 40 ° C, relative humidity 10%) was cured for the period shown in Table 2 (5, 14 days) and subjected to water crosslinking to obtain two types of resin sheets. Sheets, laminated sheets and foamed wallpaper were prepared in the same manner as in Example 1.

<Example 3>
Except for having the composition shown in Table 1, a sheet-like material was prepared by the same method as in Example 1, and under the environment shown in Table 2 (temperature 40 ° C., relative humidity 90%), the period shown in Table 2 (3rd) A laminated sheet and foamed wallpaper were prepared in the same manner as in Example 1 except that the resin sheet was obtained by curing and water crosslinking.

<Example 4>
Except for having the composition shown in Table 1, a sheet-like material was prepared by the same method as in Example 1, and under the environment shown in Table 2 (temperature 40 ° C., relative humidity 90%), the period shown in Table 2 (3rd) A laminated sheet and foamed wallpaper were prepared in the same manner as in Example 1 except that the resin sheet was obtained by curing and water crosslinking.

<Example 5>
Except for having the composition shown in Table 1, a sheet-like material was prepared by the same method as in Example 1, and under the environment shown in Table 2 (temperature 40 ° C., relative humidity 90%), the period shown in Table 2 (3rd) A laminated sheet and foamed wallpaper were prepared in the same manner as in Example 1 except that the resin sheet was obtained by curing and water crosslinking.

<Comparative Example 1>
Except having the composition shown in Table 1, a sheet-like material, a resin sheet, a laminated sheet, and a foam wallpaper were prepared in the same manner as in Example 1.

<Comparative example 2>
A sheet-like material, a resin sheet, a laminated sheet, and a foamed wallpaper were prepared in the same manner as in Example 2 except that the composition shown in Table 1 was used.

<Comparative Example 3>
Except having the composition shown in Table 1, a sheet-like material, a resin sheet, a laminated sheet, and a foam wallpaper were prepared in the same manner as in Example 1.

<Comparative example 4>
A sheet-like material, a resin sheet, a laminated sheet, and a foamed wallpaper were prepared in the same manner as in Example 2 except that the composition shown in Table 1 was used.

  Table 1 shows the compositions and crosslinking conditions of the resin compositions according to the respective examples and comparative examples. In addition, the compounding quantity of each crosslinking adjuvant is the quantity adjusted to the ratio from which an active ingredient will be 0.1 mass% with respect to silane crosslinkable resin.

The following materials were used for each component shown in Table 1.
[Low density polyethylene]
Resin A: Novatec LD LC604 (manufactured by Nippon Polyethylene Co., Ltd., trade name, density = 0.918 g / cm ³ )
[Ultra low density polyethylene]
Resin B: Kernel KJ640T (manufactured by Nippon Polyethylene Corporation, trade name, density = 0.880 g / cm ³ )

[Silane crosslinkable resin]
Resin C: Linklon XCF710 (trade name, manufactured by Mitsubishi Chemical Corporation)

[Calcium carbonate]
Filler A: Softon 1000 (Bihoku Powder Chemical Co., Ltd., trade name)

[titanium dioxide]
Filler B: Taipei CR-60-2 (Ishihara Sangyo Co., Ltd., trade name)

Foaming agent: VINYHALL AC # 3C-K2 (manufactured by Eiwa Chemical Industry Co., Ltd., trade name, azodicarbonamide foaming agent)

Foaming aid: ADK STAB OF-101 (trade name, manufactured by ADEKA Corporation)

Crosslinking aid A: Dodecylbenzenesulfonic acid (Tokyo Kasei Kogyo Co., Ltd., soft mold, mixture)
Crosslinking aid B: Linkron LZ013 (Mitsubishi Chemical Corporation, trade name, tin-based silane crosslinking aid)
Crosslinking aid C: Diamond Y (Nippon Kasei Co., Ltd., trade name, fatty acid amide silane crosslinking aid)

Lubricant: ADK STAB AP-546 (trade name, manufactured by ADEKA Corporation)

[Performance evaluation]
The foamed wallpaper produced in the examples and comparative examples was evaluated for performance shown in the following items. The results for Examples 1-5 are shown in Table 2, the results for Comparative Examples 1-2 are shown in Table 3, and the results for Comparative Examples 3-4 are shown in Table 4.

<Foamed state>
The cross-section was taken out with a razor blade, and observed and measured with a microscope (manufactured by Keyence Corporation: VHX-600 (trade name)).

<Bubble state>
The cell state was cross-sectioned with a razor blade, observed and measured with a microscope, and visually checked for outgassing on the surface. It should be noted that “cell huge” is indicated when there is a difference in cell size and a large cell is seen, and “cell uniform” is indicated when the cell shape is uniform to some extent. If it is “cell uniform”, it can be said that the bubble state is good.

  By using a sulfonic acid compound as a silane crosslinking aid, a crosslinking reaction proceeds rapidly, and a foamed wallpaper having a good foaming ratio and a cell state can be produced. In addition, the resin sheets of Examples 1 and 2 have little influence on the expansion ratio and the bubble state even when the curing period is increased, and it is possible to produce a resin sheet and a laminated sheet having excellent temporal stability (storage stability). is there.

  On the other hand, when the tin-based silane crosslinking aid is used, if the curing period is increased, the influence on the expansion ratio is large and the temporal stability is poor. In addition, when a fatty acid amide-based silane crosslinking aid is used, the crosslinking reaction does not proceed quickly, and the cells become enormous and inferior in a bubble state.

  DESCRIPTION OF SYMBOLS 1 ... Base material, 2 ... Foamed resin layer, 4 ... Pattern layer, 5 ... Surface protective layer, 10 ... Foam wallpaper.

Claims (7)

A resin composition for forming the foamed resin layer of a foam wallpaper comprising a base material and a foamed resin layer provided on the base material,
A filler, a foaming agent, a resin component containing an ethylene homopolymer or a copolymer of ethylene and another olefin and a silane crosslinkable resin, and a silane crosslinking aid,
A resin composition in which the silane crosslinking aid contains a sulfonic acid compound.   A laminated sheet comprising: a base material; and a resin sheet obtained by crosslinking the resin composition according to claim 1 provided on the base material. A foam wallpaper comprising a base material and a foamed resin layer provided on the base material,
A foamed wallpaper obtained by foaming the foaming agent contained in the resin sheet in the laminated sheet according to claim 2. A foamed wallpaper manufacturing method comprising: a base material; and a foamed resin layer provided on the base material,
A step of laminating a resin sheet obtained by crosslinking the resin composition according to claim 1 on a substrate to obtain a laminated sheet;
Forming a foamed resin layer by foaming the foaming agent contained in the resin sheet in the laminated sheet;
A method for producing foam wallpaper.   A laminate comprising: a base material; and a resin composition layer formed on the base material and formed from the resin composition according to claim 1. A foamed wallpaper manufacturing method comprising: a base material; and a foamed resin layer provided on the base material,
A step of crosslinking the resin composition layer in the laminate according to claim 5 to obtain a laminated sheet in which a resin sheet composed of a crosslinked resin composition layer is formed on the substrate;
Forming a foamed resin layer by foaming the foaming agent contained in the resin sheet in the laminated sheet;
A method for producing foam wallpaper. A foamed wallpaper manufacturing method comprising: a base material; and a foamed resin layer provided on the base material,
A laminated sheet in which a resin sheet made of a crosslinked sheet is formed on the substrate by laminating the resin composition while laminating the sheet of the resin composition according to claim 1. Obtaining a step;
Forming a foamed resin layer by foaming the foaming agent contained in the resin sheet in the laminated sheet;
A method for producing foam wallpaper.

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