JP5505137B2 - Adhesive wallpaper - Google Patents

Description

  The present invention relates to an adhesive wallpaper.

  Architectural interior materials such as wallpaper are required to have excellent design properties in order to enhance the comfort as an indoor living space. As a technique for imparting this excellent design property to wallpaper, the design is given a three-dimensional effect, and it is advantageous to use not only flexibility but also a material that can be highly foamed. In response to these demands, in recent years, foamed wallpaper that does not use vinyl chloride resin, which has been used preferably from the viewpoint of flexibility, workability, and cost, has been developed in consideration of the environment. A foamed wallpaper (non-vinyl chloride resin wallpaper) using a polyolefin resin made is proposed (Patent Documents 1 and 2).

  However, these wallpapers can be easily curled after application of glue at the time of construction, open after the construction, wrinkles are noticeable after the wallpaper is pasted, or wallpaper that has become old in wallpaper replacement However, there is a big problem in terms of workability such that it is difficult to construct a new wallpaper because the peeling interface varies even if it is peeled off.

  In addition, the backing paper that is usually used in conventional wallpaper, including these wallpapers, has a low peel strength, so that it is common to peel off the backing paper when the wallpaper is replaced. However, when it is necessary to reapply, especially when adjacent wallpaper overlaps at the time of construction, if you try to remove one wallpaper, the surface of the other wallpaper will be removed, so it is easy to reapply at the time of construction There was also a problem during construction, such as not.

JP 2007-70789 A JP 2007-55229 A

  Under such circumstances, the present invention can be easily constructed without opening the base when constructing the wallpaper, does not open the joints of the base, is difficult to cause hair cracks, and can be easily reattached during construction. The purpose is to provide adhesive wallpaper.

  As a result of intensive studies to achieve the above object, the present inventors have obtained a pressure-sensitive adhesive wallpaper having a foamed resin layer and a base material, the foamed resin layer being crosslinked, and the base material has a predetermined strength. It has been found that the above problems can be solved. The present invention has been completed based on such findings.

That is, the gist of the present invention is as follows.
1. An adhesive wallpaper having a foamed resin layer on one side of the substrate and an adhesive layer on the other side,
(1) The foamed resin layer contains polyethylene and an ethylene-α-olefin copolymer,
(2) The foamed resin layer is cross-linked,
(3) JAPAN TAPPI paper pulp test method no. 1: 2000 Adhesive wallpaper whose value measured by A method is 20 or more.
2. Item 2. The pressure-sensitive adhesive wallpaper according to Item 1, wherein an adhesive resin layer is provided between the substrate and the foamed resin layer, and the non-foamed resin layer is provided on the opposite side of the foamed resin layer from the substrate.
3. Item 3. The pressure-sensitive adhesive wallpaper according to Item 1 or 2, wherein the expansion ratio of the foamed resin layer is 2 to 15 times.
4). The adhesive wallpaper according to any one of Items 1 to 3, wherein the adhesive layer has an initial adhesive strength to steel of 7 N / 25 mm or less.
5. Item 5. The adhesive wallpaper according to any one of Items 1 to 4, wherein the substrate is a nonwoven fabric.
6). The adhesive wallpaper according to any one of Items 1 to 5, wherein 50% or more of the organic matter contained in the substrate is pulp.

  According to the present invention, it is possible to provide an adhesive wallpaper that can be easily constructed without spreading the ground when constructing the wallpaper, does not spread the seam of the foundation, is difficult to enter hair cracks, and can be easily reattached during construction. Can do.

It is a schematic diagram which shows the cross section of the adhesive wallpaper of this invention. It is a schematic diagram which shows the cross section of the adhesive wallpaper of this invention. It is a schematic diagram which shows the cross section of the adhesive wallpaper of this invention.

1. 1. Adhesive wallpaper Base material 3. Resin layer 31. Adhesive resin layer 32. Foamed resin layer 33. Non-foamed resin layer 4. 4. Adhesive layer Pattern layer 6. 6. Adhesive layer Film layer 8. Surface protective layer

An example of the preferable aspect of the adhesion wallpaper of this invention is demonstrated using FIGS. 1-3 is a schematic diagram showing a cross section of an example of the adhesive wallpaper 1 having a preferred layer structure of the present invention. In the example shown in FIG.1 and FIG.2, the adhesive wallpaper 1 of this invention consists of the resin layer 3 (in the case of FIG. 1, the foamed resin layer 32 on the base material 2, and in the case of FIG. 31, a foamed resin layer 32, and a non-foamed resin layer 33) are sequentially laminated, and the adhesive layer 4 is laminated on the back surface of the substrate 2. In the case of FIG. 3, a resin layer 3 (consisting of an adhesive resin layer 31, a foamed resin layer 32, and a non-foamed resin layer 33), a picture layer 5, an adhesive layer 6, and a film layer 7 are formed on the substrate 2. And the surface protective layer 8 are sequentially laminated, and the adhesive layer 4 is laminated on the back surface of the substrate 2.
[Substrate 2]
Hereinafter, the present invention will be described in detail with reference to FIGS. 1 and 2 showing one preferred embodiment of the present invention.

  The base material 2 used in the present invention is a JAPAN TAPPI paper pulp test method No. The value measured by 1: 2000 A method (hereinafter referred to as wax picking method) is required to be 20 or more. Further, from the viewpoint of facilitating reattachment during wallpaper construction, the value measured by the wax picking method of the substrate 2 is preferably 23 or more, and more preferably 25 or more. The upper limit of the measured value by the wax picking method is 32.

  As such a substrate, for example, a paper-reinforced paper (resin-impregnated paper) such as a thin paper in which a synthetic resin such as an acrylamide resin is added and mixed to enhance the paper strength, a nonwoven fabric, etc. are preferably mentioned. Nonwoven fabric is more preferable.

  Examples of the nonwoven fabric include a wet nonwoven fabric and a dry nonwoven fabric. Examples of the wet nonwoven fabric include a papermaking type, and examples of the dry nonwoven fabric include an adhesive type, a mechanical bond type (needle punch, stitch bond), and a spun bond type. More specifically, rayon paper, a mixture of pulp, Japanese paper, glass nonwoven fabric, asbestos nonwoven fabric, polyester nonwoven fabric, or the like can be used as the nonwoven fabric. Among these, a wet nonwoven fabric is preferable, and a nonwoven fabric mixed with pulp is particularly preferable. By adopting these base materials, it becomes easy to reattach the wallpaper.

  Moreover, when the base material used for this invention is a nonwoven fabric, it is preferable that 50% or more of the organic content contained in this base material is a pulp, and it is more preferable that it is 60% or more. Moreover, as an upper limit, 90% or less is preferable and 85% or less is more preferable. It is preferable for the content of the pulp in the base material to be within the above-mentioned range since the foaming treatment of the foamed resin layer described later can be sufficiently performed, and the heat foaming process at 200 ° C. or higher can be stably performed.

  These materials may be used alone, but may be a laminate of any combination, such as a composite of papers, and if necessary, flame retardant, inorganic agent, dry paper strength enhancer, A wet paper strength enhancer, a colorant, a sizing agent, a fixing agent, and the like may be appropriately added.

The thickness of the substrate 2 is not particularly limited, basis weight 50 to 300 g / ^{m 2} approximately, and preferably from 55~160g / ^{m 2.} In particular, a range of 60 to 160 g / m ² is preferable in order to make the so-called unevenness inconspicuous, which picks up the unevenness of the base during wallpaper construction.

Such a base material is available as a commercial product, and examples thereof include commercial products such as “8241 (product number)” and “8242 (product number)” manufactured by Ahlstrom.
[Foamed resin layer 32]
The adhesive wallpaper of the present invention is required to have a foamed resin layer 32, and preferably (i) an adhesive resin layer 31 and a foamed resin layer 32, and (ii) a foamed resin layer 32 and a non-foamed resin on the substrate 2. The layer 33 or (iii) the adhesive resin layer 31, the foamed resin layer 32, and the non-foamed resin layer 33 are laminated in this order. The above aspects (i) to (iii) can be appropriately selected according to the application of the adhesive wallpaper. However, when the pattern layer 5 described later is provided in the adhesive wallpaper, the ink used for the pattern layer 5 The non-foamed resin layer 33 is preferably provided for the purpose of preventing the composition from penetrating into the base material 2 via the foamed resin layer 32, and the adhesive force between the base material 2 and the foamed resin layer 32 is improved. For this purpose, it is preferable to provide the adhesive resin layer 31. Further, from the viewpoint of production stability, the embodiment (iii) is preferable.

  The foamed resin layer 32 is a layer that can be easily applied without spreading the ground when constructing the wallpaper, and is provided to prevent hair cracks from occurring without spreading the joint of the foundation. It is a layer obtained by foaming a foamed resin composition, which is essential to be crosslinked by irradiation with active energy rays, and preferably made of a thermoplastic resin containing a foaming agent.

  In the present invention, the foamed resin layer 32 is crosslinked when the gel fraction of the foamed resin layer 32 is 0.5 to 60%, preferably 0.5 to 30%, more preferably 1 to 10%. It means that there is. Since the foamed resin layer 32 is cross-linked, a foamed layer with few continuous pores and many independent micropores can be formed during the foaming process described later. Here, the gel fraction is determined by placing a thermoplastic resin (described later) used for the foamed resin layer 32 under reflux of the solvent, measuring the weight of the undissolved portion, and the weight of the thermoplastic resin before placing under reflux. It is the value which calculated the ratio.

Adjustment of the gel fraction of the foamed resin layer 32 (adjustment of the crosslinked state) is performed by appropriately adjusting irradiation conditions such as the intensity and irradiation time of active energy rays such as electron beams and γ rays, and the type of thermoplastic resin used. This can be done. Among these, the desired gel fraction can be easily adjusted by irradiation conditions such as the intensity of active energy rays and irradiation time, particularly the intensity.
"Thermoplastic resin"
As the thermoplastic resin, polyethylene and an ethylene-α olefin copolymer are essential components. Although the mixing ratio of each component is not limited, for example, it is preferable to contain 1 to 150 parts by weight, more preferably 10 to 100 parts by weight of ethylene-α-olefin copolymer with respect to 100 parts by weight of polyethylene. preferable. The polyethylene and the ethylene-α-olefin copolymer preferably have an MFR measured at 190 ° C. under a load of 2.16 kg of 10 to 40 g / 10 min. When the MFR of the polyethylene and ethylene-α olefin copolymer is within the above range, the resin composition containing the foaming agent has little temperature rise during extrusion film formation and can be formed in a non-foamed state. In the printing process, it is possible to perform a printing process on a smooth surface, and to obtain a printed matter with less design loss and excellent design. If the MFR is too large, the resin may be too soft and the resulting foam may have insufficient scratch resistance.

The thermoplastic resin may contain other resins in addition to the polyethylene and the ethylene-α-olefin copolymer. For example, polyolefin resin such as polypropylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), ethylene- (meth) acrylic acid resin, acrylonitrile-butadiene-styrene copolymer (ABS resin), acrylonitrile-styrene system Thermoplastic resins such as copolymers, nylon, polyacetal resins, acrylic resins, polycarbonate resins, polyester resins, polyvinyl acetate resins, polyvinyl alcohol resins, polyurethane resins, polyvinyl chloride resins, etc. Examples thereof include polymers and mixed resins thereof. When these resins are added, the content of polyethylene and ethylene-α-olefin copolymer in the thermoplastic resin (total amount of two components) is 60% by weight or more, preferably 70% by weight or more. It is preferable to set.
《Foaming agent》
Examples of foaming agents include inorganic foaming agents such as sodium bicarbonate, sodium carbonate, ammonium bicarbonate, ammonium carbonate, and ammonium nitrite, N, N′-dimethyl-N, N′-dinitrosotephthalamide, N, N′-di Nitroso compounds such as nitrosopentamethylenetetramine, azodicarbonamide, azobisformamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, azo compounds such as barium azodicarboxylate, benzenesulfonyl hydrazide, toluenesulfonyl hydrazide , P, p′-oxybis (benzenesulfonylhydrazide), sulfonylhydrazide compounds such as diphenylsulfone-3,3′-disulfonylhydrazide, calcium azide, 4,4′-diphenyldisulfoni Azide, etc. azide compounds such as p- toluenesulfonyl azide and the like. Low cost, low heat of decomposition, excellent flame retardancy and self-extinguishing properties, stable in water, non-toxic, and capable of processing heat decomposition chemical foaming agent below decomposition temperature Therefore, a thermally decomposable foaming agent of an azo compound such as azodicarbonamide or azobisformamide is preferable.

The addition amount of the foaming agent may be appropriately determined depending on the required design properties, but is preferably 0.5 to 15 parts by mass with respect to 100 parts by mass of the thermoplastic resin constituting the foamed resin layer 32. If necessary, a foaming aid that accelerates the decomposition of the foaming agent can be used in combination in order to obtain a further foaming effect. For example, when azodicarbonamide is used as the foaming agent, zinc oxide, lead sulfate, urea, zinc stearate or the like is used as the foaming aid.
<Inorganic filler>
The foamed resin composition used for forming the foamed resin layer 32 can contain an inorganic filler for the purpose of imparting an effect of suppressing see-through, improving surface characteristics, or flame retardancy to the adhesive wallpaper. There is no restriction | limiting in particular as an inorganic filler used for the adhesive wallpaper of this invention, A various thing can be used.

  Examples of inorganic fillers include calcium carbonate, magnesium carbonate, fly ash, dehydrated sludge, natural silica, synthetic silica, kaolin, clay, calcium oxide, magnesium oxide, titanium oxide, zinc oxide, barium sulfate, calcium hydroxide, water Aluminum oxide, alumina, magnesium hydroxide, talc, mica, hydrotalcite, aluminum silicate, magnesium silicate, calcium silicate, calcined talc, wollastonite, potassium titanate, magnesium sulfate, calcium sulfate, magnesium phosphate, sepiolite, zonolite , Aluminum borate, silica balloon, glass flake, glass balloon, silica, iron slag, copper, iron, iron oxide, carbon black, sendust, alnico magnet, various ferrite and other magnetic powder, cement , Glass powder, diatomaceous earth, antimony trioxide, magnesium oxysulfate, hydrated aluminum, hydrated gypsum, such as alum and the like. Among these, aluminum hydroxide is preferable because it has a low decomposition temperature, a large endothermic amount, and low cost. These inorganic fillers can be used alone or in combination of two or more.

  Many of these inorganic fillers have an effect of imparting flame retardancy to the pressure-sensitive adhesive wallpaper of the present invention, and the effect is further increased when incorporated in a large amount. The amount of the inorganic additive used is preferably 1 to 100 parts by mass with respect to 100 parts by mass of the thermoplastic resin constituting the foamed resin layer 32 for the purpose of obtaining the effect of suppressing see-through and improving the surface characteristics. From 70 parts by mass, more preferably 100 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin constituting the foamed resin layer 32 in order to obtain sufficient flame retardancy of the adhesive wallpaper.

  5-25 micrometers is preferable and, as for the average particle diameter of the inorganic filler used in this invention, 5-15 micrometers is more preferable.

These inorganic fillers may be used as they are, but the inorganic fillers are previously silane-based, titanate-based, aluminate-based, zircoaluminum-based coupling agents, phosphate-based, fatty acid-based surfactants, You may process by fats and oils, wax, a stearic acid, a silane coupling agent, etc.
<Various additives>
The foamed resin composition constituting the foamed resin layer 32 can contain a cell adjusting agent and a pigment as necessary.

  As the cell conditioner, 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 mass, more preferably about 1 to 5 parts by mass with respect to 100 parts by mass of the thermoplastic resin constituting the foamed resin layer 32.

  Examples of the pigment include inorganic pigments such as titanium white, zinc white, dial, vermilion, ultramarine, cobalt blue, titanium yellow, yellow lead, and carbon black, isoindolinone, Hansa yellow A, quinacridone, permanent red 4R, and phthalocyanine. Organic pigments (including dyes) such as Blue, Induslenbury RS, and aniline black, metal pigments such as aluminum and brass, titanium dioxide-coated mica, and pearlescent pigments made of foil powder such as basic lead carbonate Can be mentioned. These can select either a transparent colored pigment or an opaque colored pigment depending on the application. These pigments may be added and dispersed as powder or scaly foil pieces.

The foamed resin composition constituting the foamed resin layer 32 can contain various additives depending on the required physical properties. Examples of various additives include lubricants, fungicides, insect repellents, antiseptics, antibacterial agents, diluents, deodorants, light stabilizers, plasticizers, and the like.
<Formation method>
The foamed resin layer 32 is formed directly on the backing paper by forming a foamed resin composition containing the above resin or the like by an extrusion film forming method using a T-die, a calendar film forming method, an inflation film forming method, or the like. It can be formed by a known method such as a method for forming a film by the above-mentioned method or a method for adhering a film formed by the above-mentioned method on a backing paper by dry lamination using an adhesive.

  In addition, when an extrusion film forming method using a T die is employed for forming the foamed resin layer 32, the inorganic filler preferably contained in the foamed resin composition is likely to remain in the extrusion port (so-called die) of the extruder, Inorganic filler residues (so-called eyes and eyes) tend to become foreign matters on the sheet surface. In such a case, as described above, the pressure-sensitive adhesive wallpaper of the present invention has a configuration of the aspect (iii) in which the adhesive resin layer 31, the foamed resin layer 32, and the non-foamed resin layer 33 are laminated in this order from the substrate side. It is preferable that With such a configuration, it is possible to suppress the occurrence of eye spots by simultaneously forming the resin layer by sandwiching the foamed resin layer between two non-foamed resin layers, and excellent manufacturing stability can be obtained. Because it is.

When an extrusion film forming method using a T-die is adopted in the formation of the adhesive resin layer 31, the foamed resin layer 32, and the non-foamed resin layer 33, these layers may be formed separately or simultaneously. However, it is preferable to carry out simultaneously as described above. In the case of simultaneous extrusion film formation, a multi-manifold type T die or the like that enables simultaneous formation of a plurality of layers by simultaneously forming a molten resin corresponding to each layer.
(Crosslinking treatment)
The foamed resin composition needs to be subjected to a crosslinking treatment by irradiation with active energy rays such as electron beams and γ rays, preferably electron beams, for the purpose of strengthening the foamed resin layer and facilitating reattachment during construction. . For example, a layer made of the above-mentioned foamed resin composition is formed on a substrate, and cross-linked by irradiation with an electron beam in order to widen the temperature range of foaming suitable viscosity. Thereby, productivity is stabilized and the foamed resin layer 32 becomes strong. When the foamed resin composition is subjected to a crosslinking treatment, the foamed resin composition can preferably contain a crosslinking agent.

  The crosslinking agent can be used without particular limitation as long as it can crosslink the resin constituting the foamed resin layer, such as polyfunctional monomers such as neopentyl glycol dimethacrylate and trimethylolpropane trimethacrylate, oligomers, etc. And those that promote crosslinking by electron beam irradiation. The crosslinking agent is preferably 1 to 10 parts by mass, more preferably 1 to 4 parts by mass with respect to 100 parts by mass of the thermoplastic resin constituting the foamed resin layer 32.

In electron beam irradiation, as an electron beam source, for example, various electron beam accelerators such as a cockroft Walton type, a pandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type may be used. Good. The irradiation dose is usually selected in the range of 2 to 200 kGy (0.2 to 20 Mrad), preferably 2.5 to 100 kGy (0.25 to 10 Mrad).
(Foaming treatment)
The foamed resin layer 32 can be foamed by a known foaming method. For example, the foamed resin layer 32 can be foamed at a temperature of about 180 to 240 ° C. using a foaming heating furnace. The foaming treatment can be performed without particular limitation as long as the foamed resin composition is formed into a film as the foamed resin layer 32, but is usually performed after the above-described crosslinking treatment.

  The foaming ratio in forming the foamed resin layer is not particularly limited, but is preferably in the range of 2 to 15 times, and more preferably 3 to 10 times. If the expansion ratio is within the above range, when constructing the wallpaper, it can be easily constructed without spreading the groundwork, and the seam of the groundwork is not spread, making it difficult for hair cracks to occur, and obtaining good strength and workability. be able to.

Further, the thickness of the foamed resin layer 32 is not particularly limited and can be appropriately set according to desired characteristics and the like, but is preferably 50 to 300 μm in the film forming state, and the thickness after foaming is preferably 350 to 1200 μm. .
[Adhesive resin layer 31]
The adhesive resin layer 31 is a layer provided as necessary for the purpose of improving the adhesive force between the foamed resin layer 32 and the substrate 2.

The resin constituting the adhesive resin layer 31 is preferably an ethylene-vinyl acetate copolymer (EVA). EVA is not particularly limited, and known or commercially available EVA can be used. In particular, the vinyl acetate component (VA component) is preferably 10 to 30% by mass, and more preferably 15 to 30% by mass.
[Non-foamed resin layer 33]
As described above, the non-foamed resin layer 33 has an effect of preventing eyes when it is formed simultaneously with the formation of the foamed layer by a T die or the like, and is provided for the purpose of improving productivity. When the pattern layer 5 described later is provided on the resin surface, it is a layer provided as necessary for the purpose of, for example, clarifying the printed pattern and improving the scratch resistance of the foamed layer. The non-foamed resin layer 33 is formed of a non-foamed resin composition containing a resin and various additives.
"resin"
The resin constituting the non-foamed resin layer 33 is not particularly limited, but a single thermoplastic resin such as a polyolefin resin, a methacrylic resin, a thermoplastic polyester resin, a polyvinyl alcohol resin, and a fluorine resin, and various kinds of co-polymers. A coalesced resin can be mentioned, and among these, polyolefin resins are preferred.

Examples of the polyolefin-based resin include, for example, polyolefins such as polyethylene, polypropylene, polybutene, polybutadiene, polyisoprene, and various copolymers, copolymers of α-olefins having 4 or more carbon atoms (linear low density polyethylene), ethylene- Acrylic acid copolymer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene- (meth) acrylic acid copolymer such as ethylene-methacrylic acid copolymer, ethylene-vinyl acetate copolymer Examples thereof include a polymer (EVA), a saponified ethylene-vinyl acetate copolymer or ionomer, or a mixed resin composed of one or more of these.
《Other resins》
In this invention, other resin other than said resin may be contained as a resin component. For example, polyethylene, ethylene-propylene copolymer, ethylene-butene-1 copolymer, polypropylene, propylene-butene-1 copolymer, polybutene-1, butene-1, propylene-ethylene-3 terpolymer, butene In addition to -1-hexene-1-octene-1-terpolymer and polymethylpentene, olefin elastomers described in JP-A-6-16832 and JP-B-6-23278 can be used. . These resins can be used alone or in combination of two or more.
《Various additives》
Moreover, the non-foamed resin layer 33 can contain various additives as required. For example, an inorganic filler can be added to give an increase effect, or a flame retardant can be added to give flame retardancy. Moreover, when bridge | crosslinking, the crosslinking agent used with a foamed resin layer can also be mix | blended.

  Examples of the inorganic filler include inorganic hollow bodies such as mica, silica, alumina, diatomaceous earth, silica sand, and shirasu balloon, in addition to powders (particles) such as calcium carbonate, barium sulfate, clay, and talc.

  Suitable flame retardants include, for example, nitrogen compounds such as urea, hydroxides such as magnesium hydroxide and aluminum hydroxide (particularly compounds having crystal water), flame retardants containing self-extinguishing phosphorus or halogen elements, and the like. Yes. In particular, by blending a compound such as a hydroxide, flame retardancy can be achieved by the heat of vaporization of crystal water during combustion decomposition. Moreover, it is preferable when the mixed flame retardant compound which consists of a nitrogen compound and a phosphorus compound is mix | blended 25-100 mass parts with respect to 100 mass parts of polyolefin resin. This is because the compatibility with polyolefin is good and the thermal stability is also good.

  Various rubbers may be added for the purpose of imparting flexibility, impact resistance, and easy adhesion to the polyolefin resin.

  Examples of rubbers include diene rubbers, hydrogenated diene rubbers, and olefin elastomers. Among these, hydrogenated diene rubber is preferable. The hydrogenated diene rubber is obtained by adding a hydrogen atom to at least a part of a double bond of a diene rubber molecule, and is used as a modifier for a polyolefin resin in the present invention. There is a role to suppress the crystallization of the polyolefin resin and increase the flexibility and transparency. In general, when a diene rubber is added to a polyolefin resin, the weather resistance and heat resistance are lower than those of a polyolefin resin without the addition of a diene rubber due to the double bond of the diene rubber. Since the double bond is saturated with hydrogen, the weather resistance and heat resistance of the polyolefin resin are not deteriorated, and the double bond is satisfactory.

  Examples of the diene rubber include isoprene rubber, butadiene rubber, butyl rubber, propylene / butadiene rubber, acrylonitrile / butadiene rubber, acrylonitrile / isoprene rubber, and styrene / butadiene rubber. For the purpose of the present invention, styrene-butadiene rubber and the like are particularly preferable.

  Although it does not specifically limit as addition amount of rubber | gum, Usually, what is necessary is just to be about 1-90 mass parts with respect to 100 mass parts of polyolefin resin.

Moreover, the method of adding a pigment and performing transparent coloring or opaque coloring is mentioned. As the pigment, known or commercially available pigments can be used without limitation, and pigments described as those that can be used for the foamed resin layer 33 are preferred.
<< Formation of Adhesive Resin Layer 31 and Non-Foamed Resin Layer 33 >>
The adhesive resin layer 31 and the non-foamed resin layer 33 are formed using an adhesive resin composition and a non-foamed resin composition (hereinafter, collectively referred to as “resin composition”) including the resin as described above. Can do. For example, the pelletized resin composition is formed into a film by a known film forming method such as an extrusion film forming method using a T-die, a calender film forming method, an inflation film forming method, and the like on the substrate 2 or the foamed resin layer 32. Can be formed directly. Moreover, it can form also by adhere | attaching the resin film obtained by these film forming methods on the base material 2 or the foamed resin layer 32 by well-known methods, such as dry lamination using an adhesive agent. Alternatively, the resin composition can be formed by emulsifying the resin composition onto the substrate 2 or the foamed resin layer 32 by a known coating method such as comma coating. Here, emulsification can be performed by a usual method. For example, after emulsifying the thermoplastic resin of each resin composition by an emulsion polymerization method, the emulsion composition is added by adding a predetermined amount of other components. can get. In particular, when formed by an extrusion method, as described above, it can also be formed by multilayer extrusion formed simultaneously with the formation of the foamed resin layer 32.

  The adhesive resin composition and the non-foamed resin composition may be subjected to a crosslinking treatment for the purpose of reinforcing the layer or improving the surface characteristics. The method of the crosslinking treatment is not limited, but crosslinking treatment (curing treatment) with ionizing radiation such as ultraviolet rays and electron beams, preferably electron beams is preferable. For example, a layer made of the non-foamed resin composition is formed on a substrate, and cross-linked by irradiation with ionizing radiation such as an electron beam in order to widen the temperature range of foamable viscosity. Thereby, productivity is stabilized and the surface of the non-foamed resin layer 31 is hardened to improve surface characteristics. When these compositions are subjected to a crosslinking treatment, the composition can preferably contain a crosslinking agent. As the crosslinking agent, any crosslinking agent can be used as long as it can crosslink the resin constituting the adhesive resin layer and the non-foamed resin layer. However, a crosslinking agent used for forming the foamed resin layer may be used. .

  As ionizing radiation, ultraviolet rays, electron beams and the like are usually used. As the ultraviolet light source, for example, a light source such as an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a black light lamp, or a metal halide lamp can be used. Further, as the electron beam source, for example, various electron beam accelerators such as a Cockloft Walton type, a pandegraph type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type may be used. The irradiation dose is usually selected in the range of 5 to 300 kGy (0.5 to 30 Mrad), preferably 10 to 50 kGy (1 to 5 Mrad).

  The thickness of the adhesive resin layer 31 is preferably 3 to 20 μm, more preferably 3 to 15 μm, from the viewpoint of obtaining a sufficient adhesive effect and heat resistance. The thickness of the non-foamed resin layer 33 is preferably 5 to 20 μm, more preferably 7 to 12 μm, for the purpose of obtaining excellent surface characteristics and ensuring the unevenness followability of wallpaper by embossing.

  As the non-foamed resin layer 33, a transparent or opaque commercially available film made of the above resin can also be used. Commercially available films include polyolefin resin films, polyolefin resins coated with urethane or acrylic coating agents, ethylene-vinyl alcohol copolymer resin films, polyvinyl fluoride, polyvinylidene fluoride, ethylene tetrafluoroethylene, etc. And a film such as a fluororesin film. Among them, polyolefin resin is preferable, and it has excellent performance such as stain resistance, scratch resistance, chemical resistance, etc., and has excellent uneven followability in embossing, that is, the tensile elongation in the longitudinal direction is sufficiently large, and ionizing radiation. The ethylene-vinyl alcohol copolymer resin film is particularly preferred because it does not disintegrate and is low in production cost and low in smoke concentration during combustion.

When using a commercially available film for the non-foamed resin layer 33, the thickness is preferably 5 to 25 μm, and more preferably 12 to 20 μm. If the thickness of the film is within the above range, it is possible to obtain excellent surface characteristics without being restricted in the production of the film, and to ensure unevenness of the wallpaper by embossing.
[Adhesive layer 4]
The adhesive layer 4 is a layer for imparting adhesiveness to the wallpaper of the present invention and facilitating the construction of the wallpaper. The initial adhesive strength to steel is preferably 7 N / 25 mm or less, preferably 5 N / 25 mm or less. Is more preferable, and 3 N / 25 mm or less is more preferable. The lower limit of the initial adhesive strength is preferably 1 N / 25 mm or more, and more preferably 1.5 N / 25 mm or more. Moreover, it is preferable that it is 5-12 N / 25mm, and, as for the adhesive force with respect to steel after 24 hours, it is more preferable that it is 5-10 N / 25mm. If the adhesive strength is within the above range, it is preferable because it is easy to reattach the wallpaper, and this effect can be obtained particularly in combination with the inter-paper strength of the base material (value measured by the wax picking method). it can.

  Here, the adhesive force was measured according to JIS Z 0237: 2000. The test plate was a SUS304 steel plate specified in JIS G 4305 with a mirror finish, and an adhesive wallpaper provided with an adhesive layer on the polished surface was pasted, and the adhesive strength measured with a Tensilon tensile tester (unit: N / 25 mm) ). Moreover, the initial adhesive force in this invention is the adhesive force measured by the said method 1 hour after sticking a normal adhesive wallpaper.

  Examples of the pressure-sensitive adhesive used for the pressure-sensitive adhesive layer 4 include acrylic pressure-sensitive adhesives, rubber-based pressure-sensitive adhesives, and silicone-based pressure-sensitive adhesives. Among them, acrylic pressure-sensitive adhesives are preferably used in terms of durability and pressure-sensitive adhesive performance. .

  As an acrylic adhesive base, C2-C14 (meth) alkyl acrylate is mentioned preferably. Examples of such (meth) alkyl acrylate having 2 to 14 carbon atoms include ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, sec-butyl acrylate, t-butyl acrylate, n-octyl acrylate, and isooctyl acrylate. , Monomers such as 2-ethylhexyl acrylate, isononyl acrylate, octyl acrylate, and lauryl acrylate. These monomers may be used alone or in combination of two or more.

  Among these, n-butyl acrylate, sec-butyl acrylate and t- are used as (meth) alkyl acrylates having 2 to 14 carbon atoms in consideration of the balance between the adhesive strength and cohesive strength of the resulting adhesive composition. Butyl acrylate or 2-ethylhexyl acrylate selected from butyl acrylate is preferable, the acrylic adhesive base containing 50% by mass or more is preferable, and 70% by mass or more is most preferable. As the butyl acrylate, n-butyl acrylate is particularly preferable.

The thickness of the adhesive layer 4 is preferably about 0.025 to 0.045 mm. If the thickness of the pressure-sensitive adhesive layer 4 is within the above range, sufficient adhesive strength can be obtained. Further, in forming the adhesive layer 4, the coating amount of the adhesive is in the range of 10 to 60 g / ^{m 2,} preferably 20 to 40 g / ^{m 2.}
[Picture layer 5]
The pattern layer 5 is a layer that is preferably provided in order to give the base material 2 decorativeness, and is formed by printing various patterns using an ink composition and a printing machine. In general, it can be formed with ink by a known printing method such as gravure printing, offset printing, silk screen printing, transfer printing from a transfer sheet, and the like. Patterns include stone patterns that simulate the surface of rocks such as wood grain patterns, marble patterns (for example, travertine marble patterns), fabric patterns that simulate cloth and cloth-like patterns, tiled patterns, brickwork patterns, There are also patterns such as marquetry and patchwork that combine these. These patterns are formed by multi-color printing with normal yellow, red, blue, and black process colors, and also by multi-color printing performed by preparing individual color plates constituting the pattern. .

  As the ink composition used for forming the picture layer 5, a binder and a colorant such as a pigment and a dye, an extender pigment, a solvent, a stabilizer, a plasticizer, a catalyst, and a curing agent are appropriately mixed. The binder is not particularly limited, and examples thereof include polyurethane resins, vinyl acetate resins, vinyl chloride / vinyl acetate copolymer resins, vinyl chloride / vinyl acetate / acrylic copolymer resins, chlorinated polyethylene resins, Any one of chlorinated polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc., alone or 2 A mixture of seeds or more is used. Among these, for the purpose of the present invention, one of polyurethane resin, vinyl acetate resin, acrylic resin, polyester resin, cellulose resin, polyamide resin and the like may be used alone or in admixture of two or more. preferable.

  Colorants include carbon black (black), iron black, titanium white, antimony white, yellow lead, titanium yellow, petal, cadmium red, ultramarine, cobalt blue and other inorganic pigments, quinacridone red, isoindolinone yellow, phthalocyanine Organic pigments or dyes such as blue, metal pigments made of scaly foil pieces such as aluminum and brass, pearlescent pigments made of scaly foil pieces such as titanium dioxide-coated mica and basic lead carbonate, and the like are used.

The pattern layer 5 preferably has a thickness of about 1 to 20 μm.
[Film layer 7]
The film layer 7 is a layer that is laminated on the upper surface of the picture layer 5 as necessary via an adhesive layer 6. The adhesive wallpaper of the present invention has a stain resistance, cellophane tape resistance, scratch resistance, It is provided for imparting surface properties such as chemical resistance.

  Examples of the thermoplastic resin used in the film layer 7 of the present invention include thermoplastic resins such as polyolefin resins such as polyethylene, polypropylene, and polybutene, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, and fluorine resins. In addition, from the viewpoint of production efficiency, a transparent or translucent commercially available film made of the above resin can be preferably used.

  Examples of the commercially available film include fluorine resin films such as polyvinyl fluoride, polyvinylidene fluoride and ethylene tetrafluoroethylene, olefin resin films coated with urethane or acrylic coating agents, and ethylene-vinyl alcohol copolymer. A coalesced resin film and the like are listed. Among them, it is excellent in performance such as stain resistance, scratch resistance, chemical resistance, etc., and exhibits excellent uneven followability in embossing, that is, the tensile elongation in the longitudinal direction is sufficiently large, without collapsing due to ionizing radiation, An ethylene-vinyl alcohol copolymer resin film having a low production cost and a low smoke concentration during combustion is preferred.

The thickness of the film used for the film layer 7 of the present invention is preferably 10 to 25 μm. If the thickness of the film is within the above range, it is possible to ensure the unevenness followability of the wallpaper by embossing without being restricted in the production of the film.
[Surface protective layer 8]
The surface protective layer 8 is laminated on the outermost surface of the pressure-sensitive adhesive wallpaper of the present invention to improve surface characteristics such as stain resistance, cellophane tape resistance, scratch resistance and chemical resistance of the pressure-sensitive adhesive wallpaper. The surface protective layer 8 is formed of a resin composition containing a thermoplastic resin, a thermosetting resin, an ionizing radiation curable resin, or the like.

  Examples of the thermoplastic resin used in the surface protective layer 8 include acrylic resins, polyester resins, thermoplastic urethane resins, vinyl acetate resins, and cellulose resins. Examples of the thermosetting resin include phenol resin, urea resin, diallyl phthalate resin, melanin resin, guanamine resin, unsaturated polyester resin, urethane resin, epoxy resin, aminoalkyd resin, melamine-urea cocondensation resin, silicon resin, Examples include polysiloxane resins and curable acrylic resins.

Examples of the ionizing radiation curable resin used for the surface protective layer 8 include those having (meth) acrylate functional groups that are cured by ionizing radiation such as ultraviolet rays and electron beams, such as relatively low molecular weight polyester resins and polyether resins. Preferred examples thereof include polymerizable oligomers or prepolymers such as (meth) allylates of polyfunctional compounds such as acrylic resins, epoxy resins, urethane resins, alkyd resins, spiroacetal resins, polybutadiene resins, polythiol polyene resins, and polyhydric alcohols. .
<< Silicone (meth) acrylate >>
When an ionizing radiation curable resin is used for the surface protective layer 8, it is preferable to contain silicone (meth) acrylate. Silicone (meth) acrylate is added mainly for the purpose of controlling the surface tension of the surface protective layer 8 at the same time as imparting surface physical properties such as stain resistance to wallpaper due to a synergistic effect with the ionizing radiation curable resin. It is. Conventionally known silicone (meth) acrylates can be used, and are not particularly limited as long as the organic group is a (meth) acrylic group, and a modified silicone oil having 1 to 6 organic groups can be preferably used. .

The content of the silicone (meth) acrylate may be adjusted as appropriate so that the surface tension of the surface protective layer 8 is in a desired range. However, from the viewpoint of sufficiently improving the stain resistance and obtaining the effect of use thereof, ionization is performed. 0.5-4 mass parts is preferable with respect to 100 mass parts of radiation-curable resin, more than 1.0-2.5 mass parts is more preferable, and 1.5-2.5 mass parts is further more preferable. Moreover, as a functional group equivalent (molecular weight / functional group number) of silicone (meth) acrylate, what has the conditions of 100-20000, for example, Preferably it is 100-10000 is mentioned.
《Other additives》
If necessary, the resin composition for forming the surface protective layer 8 can be used by further adding a curing agent such as a crosslinking agent and a polymerization initiator, a polymerization accelerator, a solvent, a viscosity modifier and the like.

The surface protective layer 8 is formed by forming a film by crosslinking and curing the resin composition as described above by a known method. The formed surface protective layer 8 has various functions by adding various additives, for example, a so-called hard coat function, anti-fogging coat function, anti-fouling coating function, anti-glare, having high hardness and scratch resistance. A coating function, an antireflection coating function, an ultraviolet shielding coating function, an infrared shielding coating function, and the like can also be imparted.
[Adhesive layer 6]
When the adhesiveness between the film layer 7 and the non-foamed resin layer 33 is low, for example, when an ethylene-vinyl alcohol copolymer resin film is used for the film layer 7, an adhesive layer 6 is provided between the two layers as necessary. It is preferable to provide it. Although there is no restriction | limiting in particular as an adhesive agent used for the adhesive bond layer 6, A heat sensitive adhesive is preferable from the manufacturing process of this invention. A heat-sensitive adhesive is generally an adhesive that is a solid at normal temperature, melts or softens when heated, expresses adhesiveness, and solidifies and solidifies when cooled, with a thermoplastic resin as the main component. Say. This is dissolved in an appropriate solvent or melted by heating, applied to one or both adhesive surfaces of the adherend, and the two are overlapped and heated and pressed to bond them. Specific examples of the thermoplastic resin include (meth) acrylic resin, polyurethane resin, polyester, polyamide resin, (meth) acrylic acid ester-olefin copolymer resin, vinyl acetate resin, ethylene-acetic acid. Thermoplastic which is the main component of easily adhesive resins such as vinyl copolymer resins, ionomer resins, olefin-α olefin copolymer resins and copolymers, or mixed resins thereof, and olefin resins and foamed resin compositions. A blended product of a resin and a thermoplastic resin which is the main component of the film layer 7 can be mentioned.

  In addition to providing an adhesive layer, a physical or chemical surface treatment such as an oxidation method or an unevenness method can be applied to one or both sides of the film layer 7 as desired in order to improve the interlayer adhesion. .

Examples of the oxidation method include corona discharge treatment, chromium oxidation treatment, flame treatment, hot air treatment, ozone / ultraviolet treatment method, and examples of the unevenness method include a sand blast method and a solvent treatment method. These surface treatments are appropriately selected depending on the type of substrate, but generally, a corona discharge treatment method is preferably used from the viewpoints of effects and operability.
[Primer layer 9]
The pressure-sensitive adhesive wallpaper of the present invention is provided with a primer layer 9 between these layers as necessary for the purpose of improving the adhesion between the ionizing radiation curable resin composition used for the surface protective layer 8 and the film layer 7. Can be provided. The resin preferably used in the primer layer 9 is, for example, excellent in adhesion between the resin used in the film layer 7 such as acrylic resin, polyurethane resin, and urethane-acrylic resin and the ionizing radiation curable resin composition. Can be used. Moreover, the primer layer 9 can also be provided between the foamed resin layer 32 and the non-foamed resin layer 33 and between the non-foamed resin layer 33 and the film layer 7 for the purpose of reinforcing the interlayer adhesion.
[Uneven pattern]
The pressure-sensitive adhesive wallpaper of the present invention is preferably provided with an uneven pattern by embossing in order to impart excellent design properties. The concavo-convex pattern can be formed by heating and pressing with an embossed plate from the upper surface of the surface protective layer 8, that is, the outermost layer side, when the wallpaper in the manufacturing process is at a temperature at which it can be embossed by some means. A well-known sheet or rotary embossing machine is used to form the concavo-convex pattern. The shape of the concavo-convex pattern includes: wood grain pipe groove, stone plate surface unevenness, cloth surface texture, satin texture, sand texture, hairline, There are striated grooves.
[Production method]
The adhesive wallpaper of the present invention is produced, for example, by the following production method, but is not limited thereto.

  A resin constituting the primer layer 9 and an ionizing radiation curable resin composition are sequentially applied to one surface of the film layer 7 made of a thermoplastic resin film, and an adhesive and a primer layer are applied to the other surface as necessary. A constituent resin is applied, and a predetermined ionizing radiation is further applied to crosslink and cure the ionizing radiation curable resin composition to obtain a surface protective sheet. On the other hand, a foamed resin composition comprising an adhesive resin composition containing a resin constituting the adhesive resin layer 31 on the substrate 2, and a thermoplastic resin containing a foaming agent, an inorganic filler, and other additives as necessary. 32 is laminated with an adhesive resin layer 31 and a foamed resin layer 32 obtained by simultaneous film formation by an extrusion film forming method using a T-die (adhesive resin layer 31, foamed resin layer 32, non-foamed resin as necessary) After the ink composition constituting the pattern layer 5 is applied by gravure printing, the adhesive resin layer 31, the foamed resin layer 32, and the non-foamed resin layer 33 are irradiated with an electron beam. Is then cured by crosslinking, and the foamed resin composition is foamed at about 250 ° C. using a heating foaming furnace to form a foamed resin layer 32 to obtain a base sheet. Next, after the substrate sheet is cooled, it is reheated to about 150 ° C. and then between the cooling roll (surface protective sheet side) and the pressure roll on which the embossed plate is formed from the outermost layer side of the surface protective layer sheet. The adhesive wallpaper of the present invention in which the concavo-convex pattern is formed from the outermost layer side of the surface protective layer 8 to the adhesive resin layer 31 is obtained by cooling both sheets by thermocompression bonding and forming the concavo-convex pattern by passing through be able to. In addition, as above-mentioned, a primer layer and an adhesive bond layer can further be provided between desired layers.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation method)
The decorative sheet obtained in each example was evaluated by the following methods.
(1) Evaluation of workability (evaluation of base concealment)
The state of the wallpaper surface when the adhesive wallpaper produced in each example and comparative example was attached to the base of a gypsum board (manufactured by Yoshino Gypsum Co., Ltd., trade name: non-combustible tiger board) was evaluated according to the following criteria. .

○: The ground state is completely unrecognizable, and the wall finish is excellent. △: The ground state is slightly recognizable, but the wall finish is sufficient. ×: The ground state is recognizable, and the wall finish is Insufficient (2) Evaluation of workability (Evaluation of occurrence of hair cracks)
The condition of the surface of the wallpaper when the wallpaper produced in each of the examples and comparative examples was pasted on the base of a gypsum board having a seam (manufactured by Yoshino Gypsum Co., Ltd., trade name: non-combustible tiger board) was as follows. evaluated.

○: The groundwork seam is completely unrecognizable, and the wall finish is excellent. △: The groundwork seam is slightly recognizable, but the wall finish is sufficient. X: The groundwork seam is recognizable. Insufficient (3) Evaluation of workability (evaluation of ease of reattachment)
The wallpaper produced in each example and comparative example is pasted on the base of a gypsum board (trade name: non-combustible tiger board manufactured by Yoshino Gypsum Co., Ltd.), and then another wall paper is pasted so as to overlap 5 cm. It was. Immediately after that, I gently peeled off one of the wallpapers. At this time, the state of the wallpaper that was not peeled off was evaluated according to the following criteria.

◯: The surface of the wallpaper was not damaged at all. Δ: Although the surface of the wallpaper was slightly peeled, there was no problem in practical use. ×: The surface of the wallpaper was markedly peeled.
(4) Measurement of initial adhesive strength Initial adhesive strength is a value measured in accordance with JIS Z 0237: 2000 using a Tensilon tensile tester after 1 hour after pasting the wallpaper produced in each Example and Comparative Example. (N / 25 mm).

Example 1
As a base material, a non-woven fabric having a weight of 75 g / m ² (“8241 (product number)” manufactured by Ahlstrom Co., Ltd., wax picking: 26, pulp content in all organic matter: 70%) is used. A foamed resin composition having the following composition was sheeted to a thickness of 100 μm using a calendar molding machine. Next, from the side where the foamed resin composition was seated, an electron beam having a pressurization voltage of 175 kV and an irradiation dose of 50 kGy (5 Mrad) was applied to perform a crosslinking treatment. Next, after corona discharge treatment is applied to the surface on which the foamed resin composition is seated, a pattern layer is formed, heat treatment is performed at 220 ° C. for 30 seconds, and the foaming agent is foamed so that the foaming ratio is 5 times. To form a foamed resin layer. Thereafter, the adhesive A having the following composition was applied at a coating amount of 20 g / m ² on the surface opposite to the surface on which the foamed resin layer of the base material was provided to form an adhesive layer, thereby obtaining an adhesive wallpaper. It was. The evaluation results are shown in Table 1.

Example 2
As a base material, a non-woven fabric having a weight of 75 g / m ² (“8241 (product number)” manufactured by Ahlstrom Co., Ltd., wax picking: 26, pulp content in all organic matter: 70%) is used. An adhesive resin composition and a foamed resin composition having the following composition are simultaneously formed using an extruder with a T-die, and an adhesive resin layer and a foamed resin layer are formed to have a thickness of 10 μm and 100 μm, respectively. A substrate was laminated on the surface of the layer. The extrusion conditions at this time were such that the adhesive resin layer had a cylinder temperature of 100 ° C., the foamed resin layer had a cylinder temperature of 120 ° C., and the die temperature was 120 ° C. for both. After the corona discharge treatment is performed on it, the pattern layer is formed by gravure printing with an application amount of 3 g / m ² using an ink having an acrylic resin as a binder and carbon black and a petrol as a colorant. Formed. Next, the foamed resin layer was irradiated with an electron beam having a pressurization voltage of 175 kV and an irradiation dose of 50 kGy (5 Mrad) to perform a crosslinking treatment.

Separately from the above, an ethylene-vinyl alcohol copolymer resin (manufactured by Kuraray Co., Ltd., Eval Film HF-ME (thickness: 12 μm), ethylene content 44 mol%) coated with an adhesive in advance is used as the film layer. The primer layer is formed by gravure printing the urethane-acrylic copolymer resin at a coating amount of 2.0 g / m ² on the upper surface (the side where the adhesive is not applied) of the film layer. The ionizing radiation curable resin having the composition was applied at a coating amount of 2.0 g / m ² by a gravure offset coater method. After coating, an electron beam with a pressurization voltage of 125 kV and an irradiation dose of 30 kGy (3 Mrad) was irradiated to cure the ionizing radiation curable resin to form a surface protective layer, thereby obtaining a surface protective sheet.

Applying the above pattern layer, the base material on which the adhesive fat composition and the foamed resin composition are laminated is foamed using a heating foaming furnace at 230 ° C. for 30 seconds so that the foaming resin composition has a foaming ratio of 5 times. After obtaining the base material on which the foamed resin layer is formed, it is passed through between the cooling roll and the pressure roll on which the embossing mold is formed simultaneously with the surface protection sheet obtained above, and thermocompression bonding while embossing is performed. As a result, a wallpaper having an uneven pattern on the surface was obtained. Thereafter, an adhesive having the following composition was applied at a coating amount of 20 g / m ² on the surface opposite to the surface on which the foamed resin layer of the base material was provided, thereby forming an adhesive layer to obtain an adhesive wallpaper. . The evaluation results are shown in Table 1.

Example 3
As a base material, a non-woven fabric having a weight of 75 g / m ² (“8241 (product number)” manufactured by Ahlstrom Co., Ltd., wax picking: 26, pulp content in all organic matter: 70%) is used. An adhesive resin composition, a foamed resin composition, and a non-foamed resin composition having the following composition were simultaneously formed using an extruder with a T-die, and an adhesive resin layer having a thickness of 10 μm, 100 μm, and 15 μm, respectively. A foamed resin layer and a non-foamed resin layer were formed, and a substrate was laminated on the surface of the adhesive resin layer. The extrusion conditions at this time were such that the adhesive resin layer had a cylinder temperature of 100 ° C., the foamed resin layer had a cylinder temperature of 120 ° C., the non-foamed resin layer had a cylinder temperature of 160 ° C., and the die temperature was 120 ° C. After the corona discharge treatment is performed on it, the pattern layer is formed by gravure printing with an application amount of 3 g / m ² using an ink having an acrylic resin as a binder and carbon black and a petrol as a colorant. Formed. Next, the foamed resin layer was irradiated with an electron beam having a pressurization voltage of 175 kV and an irradiation dose of 50 kGy (5 Mrad) to perform a crosslinking treatment.

Applying the above pattern layer and laminating the adhesive resin composition, the foamed resin composition and the non-adhesive resin layer to the foamed resin composition at a foaming ratio of 5 times at 230 ° C. for 30 seconds using a heating foaming furnace. After foaming to form a foamed resin layer, it was passed between a cooling roll and a pressure roll on which an embossing mold was formed, and embossed to obtain a wallpaper having an uneven pattern on the surface. Thereafter, the adhesive A having the following composition was applied at a coating amount of 20 g / m ² on the surface opposite to the surface on which the foamed resin layer of the base material was provided to form an adhesive layer, thereby obtaining an adhesive wallpaper. It was. The evaluation results are shown in Table 1.

Example 4
In Example 1, a pressure-sensitive adhesive wallpaper was obtained in the same manner as in Example 1 except that the foaming treatment was performed at 230 ° C. for 10 seconds and the foamed resin composition was foamed to a foaming ratio of 2.5 times. . The evaluation results are shown in Table 1.

Example 5
In Example 1, a pressure-sensitive adhesive wallpaper was obtained in the same manner as in Example 1 except that the pressure-sensitive adhesive was the following pressure-sensitive adhesive B and the initial adhesive strength of the adhesive layer to the steel was 8 N / 25 mm. The evaluation results are shown in Table 1.
[Adhesive resin composition]
Ethylene-vinyl acetate copolymer (trade name: Ultrasen 750, manufactured by Tosoh Corporation): 100 parts by mass [non-foamed resin composition composition]
Polyethylene (manufactured by Tosoh Corporation, trade name: Petrocene 202): 100 parts by weight [foamed resin composition composition]
Polyethylene (manufactured by Tosoh Corporation, trade name: Petrocene 208): 50 parts by weight Ethylene-α-olefin copolymer (manufactured by Tosoh Corporation, trade name: LUMITAC 54-1): 50 parts by weight
Foaming agent (manufactured by Eiwa Chemical Industry Co., Ltd., trade name: VINYHALL AC # 3): 4 parts by mass Calcium carbonate (Shiraishi Kogyo Co., Ltd., trade name: Whiten H): 30 parts by mass Titanium dioxide (pigment) ( DuPont Co., Ltd., trade name: Taipure R-108): 20 parts by mass Foaming aid (manufactured by ADEKA, trade name: ADK STAB OF-101): 5 parts by mass Crosslinking agent (manufactured by JSR Co., Ltd., product) Name: Opster JUA702): 1 part by mass [adhesive A composition]
Acrylic adhesive (manufactured by Soken Chemical Co., Ltd., trade name: SK Dyne 1309): 100 parts by mass Curing agent (manufactured by Soken Chemical Co., Ltd., trade name: E-AX): 0.2 parts by mass [adhesive B composition]
Acrylic adhesive (manufactured by Soken Chemical Co., Ltd., trade name: SK Dyne 1306): 100 parts by weight Curing agent (manufactured by Soken Chemical Co., Ltd., trade name: E-AX): 0.2 parts by weight [ionizing radiation curing Resin composition]
Hexafunctional urethane acrylate: 60 parts by mass Trifunctional urethane acrylate: 40 parts by mass Silica (particle size: about 3 μm): 20 parts by mass Hexafunctional silicone methacrylate: 2 parts by mass
Comparative Example 1
In Example 1, the nonwoven fabric of the base material was lined with backing paper (backing paper for wallpaper having a weight of rice of 50 g / m ² (“WK-FKKD (product number)” manufactured by Kojin Co., Ltd.), a value measured by the wax picking method. : 16, Pulp content in total organic matter: 95%), an adhesive wallpaper was prepared in the same manner as in Example 1. The evaluation results are shown in Table 1.

Comparative Example 2
In Example 1, an adhesive wallpaper was produced in the same manner as in Example 1 except that the foamed resin layer was not subjected to crosslinking treatment with an electron beam. The evaluation results are shown in Table 1.

Comparative Example 3
In Example 1, an adhesive wallpaper was prepared in the same manner as in Example 1 except that the foamed resin layer was not provided. The evaluation results are shown in Table 1.

* 1, Substrate A: manufactured by Ahlstrom, “8241 (product number)”, wax picking: 26, pulp content in all organic matter: 70%
* 2, Substrate B: Backing paper for wallpaper (“WK-FKKD (product number)”: manufactured by Kojin Co., Ltd., rice weighing 65 g / m ² , wax picking: 16, pulp content in total organic matter: 95 %
* 3. Wax picking is based on JAPAN TAPPI paper pulp test method no. 1: 2000 Value measured by A method.

  According to the present invention, when constructing a wallpaper, it is possible to obtain an adhesive wallpaper that can be easily constructed without spreading the foundation, does not spread the joints of the foundation, is difficult to enter hair cracks, and can be easily reattached during construction. it can.

Claims (6)

An adhesive wallpaper having a foamed resin layer on one side of the substrate and an adhesive layer on the other side,
(1) The foamed resin layer contains polyethylene and an ethylene-α-olefin copolymer,
(2) The foamed resin layer is cross-linked,
(3) JAPAN TAPPI paper pulp test method no. 1: 2000 Adhesive wallpaper whose value measured by A method is 20 or more.   The pressure-sensitive adhesive wallpaper according to claim 1, further comprising an adhesive resin layer between the base material and the foamed resin layer, and a non-foamed resin layer on a side opposite to the base material side of the foamed resin layer.   The pressure-sensitive adhesive wallpaper according to claim 1 or 2, wherein the expansion ratio of the foamed resin layer is 2 to 15 times.   The adhesive wallpaper according to any one of claims 1 to 3, wherein an initial adhesive strength of the adhesive layer to steel is 7 N / 25 mm or less.   The adhesive wallpaper according to any one of claims 1 to 4, wherein the substrate is a nonwoven fabric.   Adhesive wallpaper according to any one of claims 1 to 5, wherein 50% or more of the organic matter contained in the substrate is pulp.

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