JP2012211401A - Anti-allergic wallpaper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an anti-allergic wallpaper that has an excellent anti-allergic property and persistence thereof.SOLUTION: The anti-allergic wallpaper has a substrate sheet, a resin layer, a film layer, and an anti-allergic function layer in this order, the film layer is made of a thermoplastic resin, the resin layer has at least a foamed resin layer, the anti-allergic function layer is formed with a composition for an anti-allergic function layer that includes an anti-allergen agent having a phenolic hydroxyl group.

Description

  The present invention relates to an antiallergenic wallpaper.

  With the recent improvement in energy conservation, there is a demand for highly airtight houses with improved energy efficiency in the residential environment. For example, when an outer heat insulating method or the like is used, the airtightness is improved and the efficiency of air conditioning in summer and winter is improved. However, on the other hand, because the air permeability in the room decreases, the so-called odor and house dust tend to stay in the room, and various fungi, molds, mites (parasites, carcasses, shells, feces) tend to accumulate. Become. These are allergens that cause allergies, and are said to cause many symptoms of allergic diseases such as atopic dermatitis, bronchial asthma, and allergic rhinitis. Therefore, it is considered effective to provide anti-allergen performance that removes or inactivates allergens such as mites and pollen that cause allergic diseases on the wall surface or floor surface having the largest area as an interior member. .

As a building material to which such antiallergen performance is imparted, there is known a building material in which an antiallergen agent composed of a zirconium salt is coated on the surface of a wood material such as a wood material or plywood (for example, a patent) Reference 1). In such a building material, since the anti-allergen agent was simply applied, it was easy to peel off and poor in durability.
In view of this, there has been proposed a method (for example, Patent Document 2) in which an allergen-reducing substance is applied to the upper surface of the carpet to reduce various allergens accumulated on the carpet. In addition, by making ceramic soluble organic materials from soluble organic materials such as catechins having deodorant and antibacterial effects, and using them mixed with the top coat agent of wallpaper made of Japanese paper, vinyl chloride, non-woven fabric, etc., it is firmly fixed A technique (for example, Patent Document 3) that can exhibit antibacterial and deodorizing effects over a long period of time has been proposed. Furthermore, an anti-allergen wallpaper (for example, Patent Document 4) is proposed in which a surface layer made of natural fibers is arranged on a base material made of cellulosic fibers, and astringent astringent is applied to the surface layer. Most of the anti-allergen agents (allergen-reducing substances) used in the methods as described in Patent Documents 1 to 3 are polyphenol compounds, and it is recognized that they exhibit high anti-allergen performance. However, when these anti-allergen agents are used for wallpaper, the hydroxyl groups present on the surface of the anti-allergen agent disappear due to exposure to high temperatures in the production process or reaction with the foaming gas of the wallpaper, and the like. There is a problem that the performance decreases.

  Further, a wallpaper (for example, Patent Document 5) in which an allergen adsorbent made of clay mineral is fixed on a vinyl chloride resin with a binder resin has been proposed. However, when an allergen adsorbent made of clay mineral is arranged directly on the wallpaper, the stain resistance is lowered. Furthermore, since clay minerals exhibit anti-allergen performance by adsorbing allergens in the pores, the anti-allergen performance cannot be exhibited at the time of adsorption saturation.

JP 2001-212806 A JP 2008-5489 A JP 2003-13372 A JP 2010-65344 A JP 2010-144295 A

  An object of the present invention is to provide an antiallergenic wallpaper having excellent antiallergenicity and durability.

  As a result of intensive research to achieve the above object, the inventors of the present invention are excellent in wallpaper having a foamed resin layer, a film layer, and an antiallergenic functional layer containing an antiallergenic agent having a phenolic hydroxyl group. It has been found that it has antiallergenicity and its persistence. That is, the present invention provides the following antiallergenic wallpaper.

1. A base sheet, a resin layer, a film layer, and an anti-allergen functional layer are sequentially provided, the film layer is composed of a thermoplastic resin, the resin layer has at least a foamed resin layer, and the anti-allergen functional layer is a phenol. An anti-allergenic wallpaper which is formed by a composition for an anti-allergen functional layer containing an anti-allergen agent having a functional hydroxyl group.
2. 2. The anti-allergen wallpaper as described in 1 above, wherein the anti-allergen functional layer composition is an ink composition containing an anti-allergen agent and a binder resin.
3. 2. The anti-allergen wallpaper as described in 1 above, wherein the anti-allergen functional layer composition comprises a curable resin and an anti-allergen agent having a phenolic hydroxyl group.
4). 4. The antiallergenic wallpaper according to 3 above, wherein the curable resin is an ionizing radiation curable resin.
5. 5. The antiallergenic wallpaper according to 4 above, wherein the ionizing radiation curable resin is a urethane (meth) acrylate oligomer having 2 to 10 functional groups.
6). The anti-allergenic wallpaper according to any one of 1 to 5 above, wherein the anti-allergen agent having a phenolic hydroxyl group is composed of a polyphenol compound.
7). 7. The antiallergenic wallpaper as described in 6 above, wherein the polyphenol compound is at least one selected from catechin and tannic acid and is supported on an inorganic solid acid.
8). The anti-allergenic wallpaper according to any one of 3 to 7 above, wherein the content of the anti-allergen agent in the composition for anti-allergen functional layer is 1 to 30 parts by mass with respect to 100 parts by mass of the curable resin.
9. The anti-allergenic wallpaper according to any one of 1 to 8 above, wherein the resin layer has a foamed resin layer and a non-foamed resin layer.
10. The anti-allergenic wallpaper according to any one of 1 to 9, wherein the resin layer has a non-foamed resin layer, a foamed resin layer, and a non-foamed resin layer in this order.
11. 11. The anti-allergenic wallpaper according to any one of 1 to 10 above, wherein the thermoplastic resin is a polyolefin resin.
12 12. The antiallergenic wallpaper as described in 11 above, wherein the polyolefin resin is an ethylene-vinyl alcohol copolymer resin.
13. The anti-allergenic wallpaper according to any one of 1 to 12 above, wherein the resin for foamed resin constituting the foamed resin layer is a polyolefin resin or a polyvinyl chloride resin.

  ADVANTAGE OF THE INVENTION According to this invention, the anti-allergenic wallpaper which has the outstanding anti-allergenic property and its persistence can be provided.

It is a schematic diagram which shows the cross section of the anti-allergenic wallpaper of this invention. It is a schematic diagram which shows the cross section of the anti-allergenic wallpaper of this invention. It is a schematic diagram which shows the cross section of the anti-allergenic wallpaper of this invention. It is a schematic diagram which shows the cross section of the anti-allergenic wallpaper of this invention. It is a schematic diagram which shows the cross section of the anti-allergenic wallpaper of this invention.

[Anti-allergenic wallpaper]
The anti-allergenic wallpaper of the present invention has a base sheet, a resin layer, a film layer, and an anti-allergen functional layer in this order, the film layer is composed of a thermoplastic resin, and the resin layer has at least a foamed resin layer. The anti-allergen functional layer is formed of a composition for an anti-allergen functional layer containing an anti-allergen agent having a phenolic hydroxyl group. Hereinafter, the anti-allergenic wallpaper of the present invention will be described in more detail with reference to FIGS. As shown in FIG. 1, the anti-allergenic wallpaper of the present invention has a base sheet 2, a resin layer 3, a foamed resin layer 32, a film layer 6, and an anti-allergen functional layer 8 in this order. Moreover, as an example of a preferable embodiment, a wallpaper having a foamed resin layer 32, a picture layer 4, a film layer 6, and an anti-allergen functional layer 8 in this order on the base sheet 2 shown in FIG. 2, and a base shown in FIG. A wallpaper having a laminate A1 (resin layer 3) composed of a non-foamed resin layer 31 and a foamed resin layer 32, a picture layer 4, a film layer 6, and an anti-allergen functional layer 8 in this order on the material sheet 2, FIG. On the substrate sheet 2 shown, a laminate A2 (resin layer 3) comprising a non-foamed resin layer 31A, a foamed resin layer 32 and a non-foamed resin layer 31B, a pattern layer 4, a film layer 6, and an anti-allergen functional layer 8 or a laminate A2 (resin layer 3) composed of a non-foamed resin layer 31A, a foamed resin layer 32, and a non-foamed resin layer 31B on the base sheet 2 shown in FIG. , Adhesive layer 5, film layer 6, primer Wallpaper, etc. with a layer 7 and an anti-allergen functional layer 8 in this order and the like. In addition, as shown in FIG. 4, the anti-allergenic wallpaper can preferably have an uneven pattern 9.

≪Base sheet 2≫
The base sheet is not particularly limited as long as it is usually used as wallpaper. For example, a paper base such as backing paper or flame retardant paper; a cloth base such as woven fabric, non-woven fabric, or knitted fabric; synthetic resin A sheet etc. can be suitably selected according to a use. Each of these materials may be used alone, but may be a laminate of any combination such as a composite of paper.

  Among these, pulp-based flame retardant paper impregnated with water-soluble flame retardants such as guanazine sulfanilate and guanazine phosphate, and inorganic paper mixed with inorganic agents such as calcium carbonate, aluminum hydroxide, and magnesium hydroxide These are usually referred to as backing paper for wallpaper, and from the viewpoint of curling prevention, the elongation in water is preferably 2% or less, more preferably 1.8% or less. Here, the elongation in water is measured by the JAPAN TAPPI paper pulp test method No. It is a value measured according to 27: 2000.

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, but the weight is about 50 to 300 g / m ² , preferably 55 to 160 g / m ² . In particular, a range of 60 to 160 g / m ² is preferable in order to pick up the unevenness of the groundwork during the construction of the wallpaper and make the so-called unevenness inconspicuous.

≪Resin layer 3≫
The resin layer 3 is a layer provided on the base sheet 2 in order to impart good workability and designability to the anti-allergen wallpaper, and is a layer having at least the foamed resin layer 32 as an essential layer. Although there will be no restriction | limiting in particular if the resin layer 3 has the foamed resin layer 32, The ink composition used for a flame retardance, a pattern layer, etc. in a wallpaper osmose | permeates the base material sheet 2 via the foamed resin layer 32. From the viewpoint of suppressing this, it is preferable to have the non-foamed resin layer 31. For example, from the base sheet 2 side as shown in FIG. 2, from the base sheet 2 side, as shown in FIGS. Preferred is an embodiment in which three or more layers having the non-foamed resin layer 31A, the foamed resin layer 32, and the non-foamed resin layer 31B are stacked in this order. Moreover, although not shown in figure, the aspect which has the foamed resin layer 32 and the non-foamed resin layer 31A in order from the base material sheet 2 side is also mentioned preferably.

≪Foamed resin layer 32≫
The foamed resin layer is a layer formed by foaming a foamed resin composition, and the foamed resin composition used in the present invention is not particularly limited as long as it is a material that normally forms a foam layer for wallpaper. Although it is possible, it is preferable that it contains the resin for foam layer resin layers, a foaming agent, a plasticizer, and an inorganic filler.
The thickness of the foamed resin layer 32 is preferably 30 to 300 μm in the film-formed state where the foamed resin composition is applied, and the thickness after foaming is preferably 350 to 1200 μm.

<Resin for foamed resin layer>
The resin for the foamed resin layer is preferably a thermoplastic resin. Thermoplastic resins include polyethylene, propylene, polystyrene, ethylene-vinyl acetate copolymer resin (EVA), polyolefin resins such as ethylene- (meth) acrylic acid resins, and polyvinyl chloride resins, as well as acrylonitrile-butadiene. -Styrene copolymer (ABS resin), acrylonitrile-styrene copolymer, nylon, polyacetal resin, acrylic resin, polycarbonate resin, polyester resin, polyvinyl acetate resin, polyvinyl alcohol resin, polyurethane resin Preferred examples include thermoplastic resins alone and copolymers, and mixed resins thereof. The wallpaper of the present invention can be provided with film formability, flexibility, processability at low temperature, and can be relatively low cost. From the viewpoint of versatility, polyolefin resins and polyvinyl chloride resins are preferred. From the viewpoint of environmental protection, a polyolefin resin is more preferable.

  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. Among these, at least one of ethylene-vinyl acetate copolymer (EVA) and ethylene-methyl methacrylate copolymer (EMMA) is particularly preferable. EVA and EMMA are not particularly limited, and known or commercially available products can be used. In particular, EVA preferably has a vinyl acetate component (VA component) of 15 to 30% by mass. Moreover, as for EMMA, what a methyl methacrylate component (EMA component) is 15-30 mass% is preferable.

<Foaming agent>
Examples of the foaming agent preferably contained in the foamed resin composition include inorganic foaming agents such as sodium hydrogen carbonate, sodium carbonate, ammonium hydrogen carbonate, ammonium carbonate, and ammonium nitrite; N, N′-dimethyl-N, N′-dinitrosotephthale Nitroso compounds such as amide, N, N′-dinitrosopentamethylenetetramine; azo compounds such as azodicarbonamide, azobisformamide, azobisisobutyronitrile, azocyclohexylnitrile, azodiaminobenzene, barium azodicarboxylate Sulfonyl hydrazide compounds such as benzenesulfonyl hydrazide, toluenesulfonyl hydrazide, p, p′-oxybis (benzenesulfonyl hydrazide), diphenylsulfone-3,3′-disulfonyl hydrazide; , 4,4'-diphenyl disulfonyl azide and azide compounds such as p- toluenesulfonyl azide are preferably exemplified.
Of these, low cost, low heat of decomposition, excellent flame retardancy and self-extinguishing properties, stable to water, non-toxic, and thermal decomposition chemical foaming agent can be processed at decomposition temperature or lower. Since it is possible, a thermally decomposable foaming agent of an azo compound such as azodicarbonamide or azobisformamide is preferably used.

  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 weight with respect to 100 parts by weight of the thermoplastic resin of the foamed resin layer 32, and 1 to 10 parts by weight. Is more preferable. If necessary, a foaming aid that promotes the decomposition of the foaming agent can be used in combination in order to improve the 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.

<Plasticizer>
Examples of the plasticizer preferably contained in the foamed resin composition include fatty acid ester compounds such as propylene glycol fatty acid ester, glycerin fatty acid ester, sorbitan fatty acid ester, and sucrose fatty acid ester; dibutyl phthalate (DBP), dioctyl phthalate (DOP), diisononyl phthalate Preferred examples include phthalic acid ester compounds such as (DINP). Among these, phthalic acid ester compounds such as dibutyl phthalate (DBP), dioctyl phthalate (DOP), and diisononyl phthalate (DINP) are preferable because they are low in cost and high in versatility.

  The amount of the plasticizer added is preferably 10 to 100 parts by mass, more preferably 10 to 80 parts by mass, and still more preferably 30 to 70 parts by mass with respect to 100 parts by mass of the thermoplastic resin. When the addition amount of the plasticizer is within the above range, excellent flexibility and weather resistance can be obtained.

<Inorganic filler>
The inorganic filler preferably contained in the foamed resin composition is not particularly limited, and various types can be used. For example, silica, alumina, kaolin, calcium carbonate, calcium oxide, calcium hydroxide, magnesium carbonate, Preferred examples include magnesium oxide, aluminum hydroxide, magnesium hydroxide, talc and mica, and these can be used alone or in combination. Of these, calcium carbonate and aluminum hydroxide are preferred because of their low decomposition temperature, large endotherm, and low cost.

These inorganic fillers have an effect of imparting flame retardancy to the anti-allergenic wallpaper of the present invention, and the effect is further increased by blending in a large amount. In order to sufficiently obtain the flame retardancy of the wallpaper, the amount of the inorganic filler added is preferably 70 parts by mass or more, more preferably 90 parts by mass or more with respect to 100 parts by mass of the thermoplastic resin.
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 blended as they are, but the inorganic fillers are previously combined with coupling agents such as silane, titanate, aluminate and zircoaluminum, and surfactants such as phosphate and fatty acid. , Oil and fat, wax, stearic acid, silane coupling agent, etc.

<Various additives>
The foamed resin composition can be blended with various additives according to the required physical properties. Examples of the additive include a cell conditioner, a light stabilizer, a fungicide, an insect repellent, an antiseptic, an antibacterial agent, a diluent, and a deodorant.
Moreover, when making it bridge | crosslink, it is preferable to mix | blend a crosslinking adjuvant. Preferred examples of the crosslinking aid include trifunctional crosslinking aids such as triallyl isocyanurate and triallyl isocyanate, and monofunctional crosslinking aids such as NK ester. As for the compounding quantity of a crosslinking adjuvant, about 0.1-10 mass parts is preferable with respect to 100 mass parts of resin for foamed resin layers.

≪Non-foamed resin layer 31≫
The non-foamed resin layer 31 improves the adhesive force between the foamed resin layer 32 and the base sheet 2, or the ink composition used for the pattern layer 4 described later passes through the foamed resin layer 32 in the base sheet 2. It is a layer preferably provided as a resin layer for the purpose of suppressing penetration into the resin layer. The non-foamed resin layer 31 is provided between the base sheet 2 and the foamed resin layer 32, that is, the resin layer 3 is preferably laminated in the order of the non-foamed resin layer 31 and the foamed resin layer 32 from the base sheet 2 side. . Also, a plurality of non-foamed resin layers 31 are provided. For example, as shown in FIGS. 3 and 4, the resin layer 3 includes a non-foamed resin layer 31 </ b> A, a foamed resin layer 32, and a non-foamed resin layer 31 </ b> B from the base sheet 2 side. It can be laminated in order. In this case, the plurality of non-foamed resin layers 31 may be the same or different. The same applies when a plurality of foamed resin layers 32 are present.

<Resin for non-foamed resin layer>
In the present invention, the non-foamed resin layer 31 is formed of a non-foamed resin composition containing a non-foamed resin layer resin and various additives as required.
The resin for the non-foamed resin layer is not particularly limited, but includes thermoplastic resins such as polyolefin resins, methacrylic resins, thermoplastic polyester resins, polyvinyl alcohol resins, fluorine resins, and various copolymer resins. Of these, polyolefin resins are preferred. Preferred examples of the polyolefin resin used as the resin for the non-foamed resin layer include polyolefin resins described as the resin for the foamed resin layer. The polyolefin resin for the foamed resin layer and the polyolefin resin for the non-foamed resin layer may be the same or different.

<Various additives>
The non-foamed resin composition 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, what was illustrated as a crosslinking adjuvant used with a foamed resin layer can also be preferably mix | blended. As the inorganic filler, those exemplified as the inorganic filler used in the foamed resin layer are preferable.

  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, the compounding quantity of a flame retardant 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 resin for non-foaming resin layers. This is because the compatibility with the resin for the non-foamed resin layer is improved and the thermal stability is also improved.

In the present invention, various rubbers can be added for the purpose of imparting flexibility, impact resistance, and easy adhesion to the resin for the non-foamed resin layer.
Examples of rubbers include diene rubbers, hydrogenated diene rubbers, and olefin elastomers, and hydrogenated diene rubbers are preferred. The hydrogenated diene rubber is formed by adding a hydrogen atom to at least a part of a double bond of a diene rubber molecule, and functions as a modifier for a resin for a non-foamed resin layer in the present invention. . That is, it exhibits a function of suppressing crystallization of a resin for a non-foamed resin layer, especially a polyolefin resin that is preferably used, and improving 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, styrene / butadiene rubber, and styrene / butadiene rubber is particularly preferable.
Although it does not specifically limit as addition amount of rubber | gum, Usually, it is preferable to set it as about 1-90 mass parts with respect to 100 mass parts of resin for non-foaming resin layers.

  Moreover, a pigment can be added and transparent coloring or opaque coloring can also be given to a non-foamed resin layer. As the pigment, known or commercially available pigments can be used without limitation. For example, titanium white, zinc white, petal, vermilion, ultramarine blue, cobalt blue, titanium yellow, yellow lead, carbon black and other inorganic pigments, isoindolinone, Hansa Yellow A, quinacridone, permanent red 4R, phthalocyanine blue, indanthrene Examples thereof include organic pigments (including dyes) such as Brie RS and aniline black, metal pigments such as aluminum and brass, pearlescent pigments made of foil powder such as titanium dioxide-coated mica and basic lead carbonate, and the like. 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.

<Film>
The non-foamed resin layer 31 can also be formed using a transparent or opaque film made of the above resin. Films include polyolefin resin films, polyolefin resins coated with urethane or acrylic coating agents, ethylene-vinyl alcohol copolymer resin films, polyvinyl fluoride, polyvinylidene fluoride, and fluorine-based polymers such as ethylene tetrafluoroethylene. Examples thereof include a resin 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.

  The thickness of the non-foamed resin layer 31 is preferably 3 to 50 μm, and more preferably 10 to 20 μm. If the thickness of the non-foamed resin layer 31 is within the above range, even when the non-foamed resin layer 31 is formed of a film, excellent surface characteristics can be obtained without being restricted in the production of the film. It is possible to ensure unevenness of the wallpaper by embossing.

  As described above, the non-foamed resin layer 31 may be a single layer or a plurality of layers. For example, as shown in FIGS. 3 and 4, the non-foamed resin layer 31 includes a non-foamed resin layer 31A and a non-foamed resin layer 31B. When two or more layers are provided, the plurality of non-foamed resin layers may be formed of the same material or different materials, and the thicknesses thereof may be the same or different.

≪Picture layer 4≫
The pattern layer 4 is a layer that is preferably provided to give decorativeness to the antiallergenic wallpaper, 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 4, 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. For example, polyurethane resin, vinyl acetate resin, vinyl chloride / vinyl acetate copolymer resin, vinyl chloride / vinyl acetate / acrylic copolymer resin, chlorinated polyethylene resin, chlorine Arbitrary polypropylene resin, acrylic resin, polyester resin, polyamide resin, butyral resin, polystyrene resin, nitrocellulose resin, cellulose acetate resin, etc. A mixture of the above is used. Among these, it is preferable to use one kind of polyurethane resin, vinyl acetate resin, acrylic resin, polyester resin, cellulose resin, polyamide resin or the like alone or in combination.
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 4 preferably has a thickness of about 1 to 20 μm.

≪Film layer 6≫
The film layer 6 is an essential layer provided mainly for imparting surface characteristics such as contamination resistance, cellophane tape resistance, scratch resistance, and chemical resistance. The film layer 6 prevents the composition for anti-allergen functional layer from penetrating into the foamed resin layer (or foamed resin composition), and further, the foam gas generated during foaming treatment with the composition for anti-allergen functional layer. Therefore, it is possible to suppress a decrease in the antiallergenicity of the antiallergenic wallpaper of the present invention. 1-5, the film layer 6 should just be provided in the opposite side to the base material sheet 2 of the resin layer 3 (foaming resin layer 32), Preferably as FIG. 5 shows. The upper surface of the pattern layer 4 is provided via the adhesive layer 5.

  The resin constituting the film layer 6 is not particularly limited, but is a polyolefin resin such as polyethylene, polypropylene, polybutene, ethylene-vinyl alcohol copolymer resin, methacrylic resin, thermoplastic polyester resin, Preferred examples include polyvinyl alcohol resins, fluororesins, and other thermoplastic resins and various copolymer resins. From the viewpoint of production efficiency, transparent or translucent commercially available films are preferably used. can do. The anti-allergenic wallpaper of the present invention is imparted with surface performance such as stain resistance, cellophane tape resistance, scratch resistance, chemical resistance, etc. From the viewpoint of low smoke concentration and low manufacturing costs, polyolefin resins and ethylene-vinyl alcohol copolymer resins are preferred.

  It is preferable that the thickness of the film used for the film layer 6 of this invention is 5-25 micrometers, More preferably, it is 10-25 micrometers. 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.

≪Adhesive layer 5≫
When the adhesiveness between the film layer 6 and the resin layer 3, particularly the non-foamed resin layer 31 is low, for example, when an ethylene-vinyl alcohol copolymer resin film is used for the film layer 6, FIG. 5 shows. Thus, it is preferable to provide the adhesive layer 5 between the two layers as necessary.
Although there is no restriction | limiting in particular as an adhesive agent used for the adhesive bond layer 5, 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 used as the main component of the adhesive include (meth) acrylic resin, polyurethane resin, polyester, polyamide resin, (meth) acrylate-olefin copolymer resin, Compositions of easy-adhesive resins and copolymers such as vinyl chloroacetate resin, ethylene-vinyl acetate copolymer resin, ionomer resin, olefin-α-olefin copolymer resin, or mixed resins thereof, and olefin resin and foamed resin composition The thermoplastic resin used as the main component of a thing and the blended product with the thermoplastic resin used as the main component of a film layer are mentioned.

The adhesive layer 5 is provided between the non-foamed resin layer 31B and the film layer 6 as shown in FIG. 5 for the purpose of improving the interlayer adhesion, and foaming with the base sheet 2 as necessary. It can also be provided between the resin layer 32 and the layer. In addition to providing the adhesive layer 5, the film layer 6 is formed with physical or chemical surface treatment such as an oxidation method or a concavo-convex method on one side or both sides as desired in order to improve the interlayer adhesion. It can be applied to a resin film.
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 sand blast method and 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 7≫
The anti-allergenic wallpaper of the present invention is necessary between these layers for the purpose of improving the adhesion between the anti-allergen functional layer composition used for forming the anti-allergen functional layer 8 described later and the film layer 6. Depending on the case, the primer layer 7 can be provided.
Examples of the resin used in the primer layer 7 include a resin having good adhesion between the resin used in the film layer 6 and the composition for an antiallergen functional layer, such as an acrylic resin, a polyurethane resin, and a urethane-acrylic resin. Are preferred. Moreover, a primer layer can also be provided between the foamed resin layer 32 and the non-foamed resin layer 31 and between the non-foamed resin layer 31 and the film layer 6 for the purpose of reinforcing the interlayer adhesion.

≪Anti-allergen functional layer 8≫
The anti-allergen functional layer 8 containing an anti-allergen agent not only imparts excellent anti-allergenicity and durability to the anti-allergenic wallpaper of the present invention, but also stain resistance, cellophane tape resistance, scratch resistance, It is a layer that can impart surface properties such as chemical resistance.

<Composition for anti-allergen functional layer (i)>
In the present invention, the anti-allergen functional layer 8 is formed of a composition for an anti-allergen functional layer containing an anti-allergen agent having a phenolic hydroxyl group, and preferably an antiallergen agent having a curable resin and a phenolic hydroxyl group. The anti-allergen functional layer composition (i) containing can be formed by curing.
<Curable resin>
The curable resin used in the present invention is not particularly limited as long as it is a resin that is cured by irradiation with heat or ionizing radiation. In the present invention, a resin that is cured by irradiation with ionizing radiation, that is, an ionizing radiation curable resin is preferable. Here, ionizing radiation means an electromagnetic wave or charged particle beam having an energy quantum capable of polymerizing or cross-linking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. It also includes electromagnetic waves such as rays and γ rays, and charged particle rays such as α rays and ion rays.

(Thermosetting resin)
Preferable examples of the thermosetting resin include phenol resin, phenol / formalin resin, urea resin, urea / formalin resin, melamine resin, melamine / formalin resin, alkyd resin, epoxy resin, and unsaturated polyester resin.

(Ionizing radiation curable resin)
The ionizing radiation curable resin can be appropriately selected from conventionally used polymerizable monomers and polymerizable oligomers or prepolymers.
As the polymerizable monomer, a (meth) acrylate monomer having a radical polymerizable unsaturated group in the molecule is preferable, and among them, a polyfunctional (meth) acrylate monomer is preferable. The polyfunctional (meth) acrylate monomer is not particularly limited as long as it is a (meth) acrylate monomer having two or more ethylenically unsaturated bonds in the molecule. These polyfunctional (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

Next, as the polymerizable oligomer, an oligomer having a radical polymerizable unsaturated group in the molecule, for example, urethane (meth) acrylate, epoxy (meth) acrylate, polyester (meth) acrylate, polyether (meth) acrylate And oligomers of the system.
Furthermore, other polymerizable oligomers include polybutadiene (meth) acrylate oligomers with high hydrophobicity that have (meth) acrylate groups in the side chain of polybutadiene oligomers, and silicone (meth) acrylate oligomers that have polysiloxane bonds in the main chain. In a molecule such as an aminoplast resin (meth) acrylate oligomer modified with an aminoplast resin having many reactive groups in a small molecule, or a novolak type epoxy resin, bisphenol type epoxy resin, aliphatic vinyl ether, aromatic vinyl ether, etc. There are oligomers having a cationic polymerizable functional group.

  Among the above-described polymerizable oligomers, urethane (meth) acrylate oligomers are preferable. The urethane (meth) acrylate oligomer can be obtained, for example, by esterifying a polyurethane oligomer obtained by reaction of polyether polyol or polyester polyol and polyisocyanate with (meth) acrylic acid, and is a radically polymerizable unsaturated group. It is what has. The urethane (meth) acrylate oligomer used in the present invention preferably has 2 to 10 and more preferably 2 to 8, more preferably 2 to 8, more preferably 2 to 8 and more preferably 2 to 8 radical polymerizable unsaturated groups. It is a sensual thing. When the number of functional groups is within the above range, excellent weather resistance and stain resistance can be obtained, and at the same time, excellent workability corresponding to various processes including V-cut can be obtained, and excellent antiallergenicity can be obtained. can get.

  The urethane (meth) acrylate oligomer has a weight average molecular weight (polystyrene equivalent weight average molecular weight measured by GPC method) of preferably about 600 to 5,000, more preferably 600 to 3,000, and still more preferably 600 to 2,200. It is. By using such a urethane (meth) acrylate oligomer together with an anti-allergen agent described later, a product excellent in weather resistance and stain resistance as well as anti-allergenic properties can be obtained. Moreover, since the composition for anti-allergen functional layers has an appropriate thixotropy, formation of an anti-allergen functional layer becomes easy.

  In the present invention, in addition to the above-described polyfunctional urethane (meth) acrylate oligomer and the like, the monofunctional or polyfunctional urethane (meth) acrylate monomer is impaired for the purpose of lowering the viscosity, etc. It can be used in combination as long as it is not present. These (meth) acrylate monomers may be used individually by 1 type, and may be used in combination of 2 or more type.

<Anti-allergen>
The anti-allergen agent used in the present invention has a phenolic hydroxyl group, that is, a water-insoluble polymer having a phenolic hydroxyl group, and the phenolic hydroxyl group adsorbs an allergenic substance and inactivates it. There is no particular limitation as long as it functions. Such anti-allergen agents include those composed of polyphenol compounds, which are organic compounds having a plurality of phenolic hydroxyl groups in the molecule, that is, hydroxyl groups bonded to aromatic rings such as benzene rings and naphthalene rings, for example, poly ( Preferred examples include polyphenol-based polymers such as 4-vinylphenol) and poly (vinyl 3,4,5-hydroxybenzoate). As a commercially available anti-allergen, “Marcalinker S-2P (trade name)” (Maruzen Petrochemical Co., Ltd.) can be used. This anti-allergen is used for various allergens such as mites and pollen. It works effectively.

  Also preferred are those in which a polyphenol compound is supported on an inorganic solid acid. Examples of the polyphenol compound used in such an embodiment include low molecular weight polyphenols called catechins such as epicatechin, gallotannin, epigallocatechin, epicatechin gallate, epigallocatechin gallate, and high molecular weight tannic acid. It is preferably mentioned from the viewpoint of having excellent antiallergenicity and being easily and inexpensively available industrially. As the polyphenol compound, those described above can be used alone or in combination. Among these, tannic acid is preferable from the viewpoint of antiallergenicity.

  The inorganic solid acid is an inorganic substance, and has an acid site or an active site that releases hydrogen ions on its surface and develops acidity. For example, zeolites such as H-substituted Y-type zeolite and H-substituted ZSM-5 type zeolite, phosphate compounds such as zirconium phosphate, aluminum phosphate, tin phosphate, cerium phosphate, titanium phosphate, antimonic acid, etc. Preferred examples include composite oxides such as silica alumina, silica titania, silica zirconia, titania alumina, and titania zirconia. Among these, from the viewpoint of excellent heat resistance and high solid acidity, zeolites and composite oxides are preferable, zirconium phosphate having particularly strong acid strength is preferable, and layered zirconium phosphate having a crystal system having a layered structure is preferable. preferable.

  Examples of the shape of the inorganic solid acid include powder, lump, plate, and fiber, but it is preferably powder from the viewpoint of handling. In the case of powder, the average particle size is preferably 0.01 to 50 μm, and more preferably 0.02 to 20 μm. When the average particle size is within the above range, handling is easy and it is preferable from the viewpoint of obtaining excellent antiallergenicity.

  In the present invention, when a polyphenol compound supported on an inorganic solid acid is used as an anti-allergen agent, the weight ratio of the polyphenol compound to the inorganic solid acid is preferably 10:90 to 95: 5, more preferably 20: It is 80-80: 20, More preferably, it is 20: 80-40: 60. When the weight ratio is within the above range, particularly excellent antiallergenicity can be obtained due to the synergistic effect of the polyphenol compound and the inorganic solid acid. Such an anti-allergen agent can also be obtained as a commercial product, for example, “Allelimbu (trade name)” (manufactured by Toagosei Co., Ltd.), which is a combination of a polyphenol compound and a zirconium compound, can be mentioned as a commercial product.

  The compounding quantity of an anti-allergen agent is 1-30 mass parts with respect to 100 mass parts of curable resin, Preferably it is 3-25 mass parts, More preferably, it is 8-15 mass parts. In the present invention, even in such a small blending amount, by combining with the above 2-10 functional urethane (meth) acrylate oligomer preferably used as a curable resin, excellent antiallergenicity is obtained, Excellent weather resistance and stain resistance are also obtained.

<Various additives>
Additives such as UV absorbers, light stabilizers, antibacterial agents, antiwear agents, matting agents, or anti-settling agents for the anti-allergen functional layer composition to meet various requirements depending on the application Can be contained.
The anti-allergen functional layer composition used in the present invention may contain various additives as long as the performance is not impaired. Examples of various additives include polymerization inhibitors, crosslinking agents, antistatic agents, adhesion improvers, antioxidants, leveling agents, thixotropic agents, coupling agents, plasticizers, antifoaming agents, fillers, and solvents. Etc.
When an ultraviolet curable resin is used as the curable resin, it is desirable to add about 0.1 to 5 parts by mass of a photopolymerization initiator with respect to 100 parts by mass of the curable resin. The agent can be appropriately selected from those conventionally used.

<Composition for anti-allergen functional layer (ii)>
In the present invention, the anti-allergen functional layer 8 is preferably formed by using an ink composition containing an anti-allergen agent and a binder resin as the anti-allergen functional layer composition (ii) and drying the ink composition. can do.

(Binder resin)
Binder resins include water-soluble resins such as water-soluble acrylic resins, water-soluble styrene-acrylic acid resins, water-soluble styrene-maleic acid resins, and water-dispersed resins such as acrylic emulsions, vinyl acetate emulsions, and urethane emulsions. Are preferred. In addition, a two-component curable resin such as a two-component curable urethane resin may be used. The amount used is preferably 3 to 15% by weight based on the total amount of the ink composition.

(solvent)
The ink composition can contain water, alcohol and the like as a solvent. Any alcohol can be used without particular limitation as long as it is usually used in ink compositions. For example, alicyclic alcohols such as cyclopentanol and cyclohexanol are preferred in addition to chain alcohols such as methanol, ethanol and isopropanol. Can be mentioned.

(Anti-allergen)
The anti-allergen agent contained in the ink composition is the same as described above. 5-25 mass% is preferable and, as for content of the anti-allergen agent in an ink composition, 5-20 mass% is more preferable. When the content of the anti-allergen agent is within the above range, a good anti-allergen functional layer is obtained and it is easy to apply.

(Other additives)
In the ink composition, additives that can be used in the anti-allergen functional layer composition (i) can be appropriately selected and used as long as the performance of the anti-allergen functional layer is not impaired.

«Uneven pattern 9»
The anti-allergenic wallpaper of the present invention preferably has a concavo-convex pattern 9 as shown in FIG. 5 in order to be excellent in design. The concavo-convex pattern is preferably formed by heating and pressing with an embossing plate from the upper surface of the anti-allergen functional layer 8, that is, the outermost layer side, when the wallpaper in the manufacturing process is at a temperature that can be embossed by any means. can do. The deepest portion of the unevenness formed by heating and pressing with the embossed plate reaches the upper surface of the foamed resin layer 32. For the formation of the concavo-convex pattern 9, a well-known sheet or rotary embossing machine is preferably used. As the shape of the concavo-convex pattern 9, a wood grain pipe groove, a stone surface unevenness, a cloth surface texture, a satin texture, a grain texture, Examples include hairlines and striated grooves.

[Production method]
The anti-allergenic wallpaper of the present invention includes, for example, step (1): a step of laminating a foamed resin composition on a substrate sheet, and foaming the foamed resin composition to form a foamed resin layer; and step (2) It can manufacture with the manufacturing method which has a process of laminating | stacking an anti-allergen functional layer in order on this foamed resin layer using the composition for anti-allergen functional layers containing the anti-allergen agent which has a phenolic hydroxyl group.

≪Process (1) ≫
Step (1) is a step of forming the foamed resin layer 32 by laminating the foamed resin composition on the base sheet 2 and foaming the foamed resin composition.

<Formation of foamed resin layer>
The foamed resin layer 32 is, for example, an unfoamed resin layer obtained by coating a foamed resin composition, for example, by emulsifying it into an emulsion composition or by pelletizing a foamed resin composition on a base sheet by a coating method such as a comma coater method. Then, the foamed resin composition is foamed at about 220 to 250 ° C. using a heating foaming furnace, and the unfoamed resin film can be made into the foamed resin layer 32. Further, an adhesive composition is used after forming an unfoamed resin layer by using an emulsion composition or pelletized or by a film forming method such as an extrusion film forming method using a T-die or a calender film forming method. After laminating the unfoamed resin layer on the base sheet by a known method such as a dry lamination method, the foamed resin composition is foamed at about 220 to 250 ° C. using a heating foaming furnace, The foamed resin layer can be the foamed resin layer 32.
Here, emulsification can be performed by a usual method. For example, the emulsion composition is obtained by emulsifying the thermoplastic resin in the foamed resin composition by an emulsion polymerization method or the like, and then adding a predetermined amount of other components. Obtainable.

The unfoamed resin layer can be foamed by a known foaming method to form a foamed resin layer 32. For example, the foamed resin layer can be foamed at a temperature of about 180 to 240 ° C. using a foaming heating furnace. . The foaming treatment is performed without particular limitation as long as it is after the foamed resin composition is formed to form an unfoamed resin layer and before the anti-allergen functional layer 8 is formed with the anti-allergen functional layer composition. be able to. In the production method of the present invention, the anti-allergen functional layer composition may be exposed to the high temperature of the foaming treatment by performing the foaming treatment before forming the anti-allergen functional layer 8 with the anti-allergen functional layer composition. In addition, it can suppress color change and deterioration of antiallergen performance due to reaction with foaming gas caused by the foamed resin composition, and as a result, it can exhibit excellent antiallergenicity and durability It is said.
In addition, the foaming ratio in forming the foamed resin layer 32 is not particularly limited, but is usually about 3 to 7 times. When the expansion ratio is within the above range, good surface strength, workability, and the like can be obtained.

The foamed resin composition may be subjected to a crosslinking treatment for the purpose of improving the surface characteristics. The method for the crosslinking treatment is not limited, but crosslinking treatment (curing treatment) with ionizing radiation is preferable. For example, a layer made of the above foamed resin composition is formed on a base sheet, and in order to widen the temperature range of foamable viscosity, it is crosslinked by irradiation with ionizing radiation. Thereby, productivity can be stabilized. When the foamed resin composition is subjected to a crosslinking treatment, the foamed resin composition can preferably contain a crosslinking agent. Any crosslinking agent can be used without particular limitation as long as it can crosslink the resin constituting the foamed resin layer 32.
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).

<Formation of non-foamed resin layer 31>
The non-foamed resin layer 31 can be formed using the non-foamed resin composition in the same manner as the above-described foamed resin layer 32 except for foaming treatment. Moreover, it is the same as that of the foamed resin layer 32 which can perform a crosslinking process. The non-foamed resin layer 31 can also be formed using a transparent or opaque film made of the resin for the non-foamed resin layer as described above.

<Formation of laminates A1 and A2>
When the resin layer 3 is a laminate A composed of a plurality of resin layers, for example, a laminate A1 composed of a non-foamed resin layer 31 and a foamed resin layer 32 as shown in FIG. 3, or shown in FIGS. In the case of the laminate A2 having the non-foamed resin layer 31A, the foamed resin layer 32, and the non-foamed resin layer 31B in order, these laminates can be formed as follows.
In forming the layered product A, the foamed resin layer 32 and the non-foamed resin layer 31 forming the layered product are respectively formed by applying a foamed resin composition and a non-foamed resin composition to the coating method such as the comma coater method as described above. The non-foamed resin layer and the non-foamed resin layer are formed by coating by T, extrusion film forming by T-die, and calendar film forming method, and the foamed resin layer 32 is obtained by foaming the unfoamed resin layer. When forming the laminate A such as the laminate A1 or A2, it is preferable to employ an extrusion film forming method using a T-die from the viewpoint of production efficiency. At this time, the foamed resin layer 32 and the non-foamed resin layer 31 may be formed separately or simultaneously, but are preferably performed simultaneously from the viewpoint of work efficiency. 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.

  When an extrusion film forming method using a T-die is adopted for forming the foamed resin layer 32, the inorganic filler that is preferably contained in the foamed resin composition tends to remain in the extrusion port (so-called die) of the extruder, and the inorganic filling is performed. The residue of the agent (so-called eyes and eyes) tends to become foreign matter on the sheet surface. In such a case, the resin layer is preferably a laminate A2 in which the non-foamed resin layer 31A, the foamed resin layer 32, and the non-foamed resin layer 31B are laminated in this order. That is, when the resin layer 3 is configured like the laminate A2, the non-foamed resin layer 31 has an ink composition used for the pattern layer that penetrates into the base sheet via the foamed resin layer 32. In addition to the function of suppressing, it is possible to suppress the occurrence of eye spots by simultaneously forming the foamed resin layer 32 with the two non-foamed resin layers 31A and 31B, thereby obtaining excellent manufacturing stability. There is an advantage.

  In the case of forming the laminate A such as the laminates A1 and A2, the laminate A and the base sheet may be attached via lamination or an adhesive. As an adhesive used here, what is used for the above-mentioned adhesive bond layer 5 is illustrated preferably. In addition, a foamed resin composition and a non-foamed resin layer composition are sequentially coated on a base sheet by a coating method to form a non-foamed resin layer and a non-foamed resin layer 31, and the unfoamed resin layer In the case where the foamed resin layer 32 is obtained by further foaming treatment, and the laminate A is obtained as a result, no adhesive is required when the laminate A is provided on the base sheet 2.

≪Process (2) ≫
The step (2) includes an anti-allergen agent having a phenolic hydroxyl group on the foamed resin layer 32 or, if the non-foamed resin layer 31 is provided on the foamed resin layer 32, the step (2). In this process, the anti-allergen functional layer 8 is laminated using the anti-allergen functional layer composition, and an anti-allergenic wallpaper is obtained.

<Formation of anti-allergen functional layer>
The formation of the anti-allergen functional layer 8 preferably comprises (i) the anti-allergen functional layer composition (i) containing the curable resin, the anti-allergen agent having a phenolic hydroxyl group, and various additives as necessary. An uncured layer is formed and cured by irradiating with ionizing radiation or the like, or (ii) by applying and drying an ink composition containing the above-described anti-allergen agent and binder resin. Specifically, the anti-allergen functional layer 8 is formed as follows.

  Application of the composition for anti-allergen functional layer is a gravure coat, bar coat, roll coat, reverse roll coat, so that the thickness of the anti-allergen functional layer 8 formed by curing is usually about 0.5 to 30 μm. Known methods such as comma coat, flow coater, spraying method, airless spraying method, air spraying method, brush coating, trowel coating, dipping method, lifting method, nozzle method, winding method, sink method, piling method, patching method, etc. Preferably, it is performed by gravure coating. Moreover, it is preferably 3 to 10 μm from the viewpoint of stain resistance and scratch resistance.

When using the anti-allergen functional layer composition (i), the uncured layer formed by applying the anti-allergen functional layer composition is cured by heat treatment when the curable resin is a thermosetting resin, When the curable resin is an ionizing radiation curable resin, the anti-allergen functional layer 8 is formed by curing by irradiating ionizing radiation or the like. In addition, when the composition for antiallergen functional layers contains a solvent, it is preferable to irradiate ionizing radiation after application | coating after heat-drying an application layer with a hot air dryer etc. after application | coating.
Here, when an electron beam is used for curing, the accelerating voltage can be appropriately selected according to the resin to be used and the thickness of the layer, but it is preferable to cure the uncured layer usually at an accelerating voltage of about 70 to 300 kV. The irradiation dose is preferably such that the crosslinking density of the ionizing radiation curable resin is saturated, and 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 electron beam source is not particularly limited, and for example, various electron beam accelerators such as a Cockloft Walton type, a bandegraft type, a resonant transformer type, an insulated core transformer type, a linear type, a dynamitron type, and a high frequency type are used. be able to.
When ultraviolet rays are used as ionizing radiation, those containing ultraviolet rays having a wavelength of 190 to 380 nm are emitted. There is no restriction | limiting in particular as an ultraviolet-ray source, For example, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a carbon arc lamp etc. are used.

  When using the anti-allergen functional layer composition (ii), the coating layer formed by coating the anti-allergen functional layer composition is evaporated by evaporating water and alcohol with a hot air dryer, etc. A layer can be formed. The temperature condition of the heat drying may be appropriately selected depending on the material of each layer used for the wallpaper, but is usually about 120 to 160 ° C., preferably 130 to 150 ° C.

<Formation of film layer>
In the present invention, when the anti-allergenic wallpaper has the film layer 6, the laminate B obtained by applying the anti-allergen functional layer composition on the film layer 6 and curing to form the anti-allergen functional layer 8 From the viewpoint of production efficiency, it is preferable to laminate the laminate B on the foamed resin layer 32 so that the film layer is on the foamed resin layer 32 side. Here, the method of applying the composition for anti-allergen functional layer, curing, and heat drying is as described above.
In this case, preferably, the adhesive layer 5 is provided on one surface of the film forming the film layer 6, the primer layer-forming resin composition is applied to the other surface, and the anti-allergen functional layer composition (i) Is used, the composition (i) is applied to form an uncured layer, and the uncured layer is cured by heat treatment or irradiation with ionizing radiation, or an anti-allergen functional layer composition ( When ii) is used, the composition (ii) is applied and dried by heating to form the anti-allergen functional layer 8 to obtain the laminate B. The obtained laminate B is such that the adhesive layer 5 is on the base sheet 2 side, that is, the anti-allergen functional layer 8 is the outermost surface, and the base sheet 2 is the anti-allergen functional layer 8 A laminate A having a foamed resin layer on the base sheet 2 so as to be the outermost surface on the opposite side, and preferably including a foamed resin layer and a non-foamed resin layer on the base sheet 2, and a pattern layer The laminate C is laminated with the laminate C by thermocompression bonding to obtain an antiallergenic wallpaper. Here, the thermocompression bonding may be performed according to a conventional method.

Further, in the present invention, when laminating and laminating by thermocompression bonding or the like, it is preferable from the viewpoint of production efficiency that mechanical embossing is simultaneously performed from the anti-allergen functional layer 8 side. The embossing may be performed by heating and pressing with an embossing plate as described above. Thus, when embossing is performed at the same time when stacking, it is efficient because it is not necessary to perform heat treatment only for embossing.
The thermocompression bonding and embossing are preferably performed under a temperature condition of about 90 to 150 ° C., and the cooling roll on which the embossing plate is formed is on the anti-allergen functional layer side, so that the cooling roll and the pressure roll are between The laminates B and C are embossed simultaneously with thermocompression bonding by passing through to form the concavo-convex pattern 9, and then cooled, so that the concavo-convex pattern 9 is formed from the anti-allergen functional layer 8 to the foamed resin layer 32 by cooling. Allergenic wallpaper can be obtained. As described above, the pattern layer 4, the adhesive layer 5, the primer layer 7, and the like can be provided between desired layers as necessary.

<When using a transfer film>
In the present invention, a transfer film can be used for forming the anti-allergen functional layer 8. That is, after forming a layer other than the anti-allergen functional layer 8 in the anti-allergen wallpaper, the anti-allergen wallpaper can be produced by transferring the anti-allergen function layer using a transfer film.
The transfer film used in the present invention has the anti-allergen functional layer 8 on the release film, and preferably has a release layer from the viewpoint of reliably transferring the anti-allergen functional layer 8.

(Peeling film)
The release film is not particularly limited as long as it is a resin film that is usually used for a transfer film, and is composed of a polyolefin resin, a vinyl resin, a polyester resin, an acrylic resin, a styrene resin, an elastomer resin, or the like. Polyester resins, particularly polyethylene terephthalate (PET) is preferable from the viewpoint of good releasability. The thickness of the release film is preferably in the range of 25 to 150 μm and more preferably in the range of 25 to 75 μm from the viewpoint of easy handling.

(Release layer)
For the release layer, melamine resin release agent, silicone resin release agent, fluororesin release agent, cellulose resin release agent, urea resin release agent, polyolefin resin release agent, paraffin type Release agents such as release agents, acrylic resin release agents, and composite release agents thereof are preferably used. Among these, from the viewpoint of reliably peeling the anti-allergen functional layer from the release film, a melamine resin release agent and an acrylic resin release agent, or a combination of these such as an acrylic-melamine type is preferable.

When using a melamine resin release agent, it is preferable to use a sulfonic acid catalyst such as para-toluenesulfonic acid in order to accelerate the curing of the release agent. The amount of the acid catalyst used is preferably about 0.05 to 3%, more preferably 0.05 to 1%, based on the solid content of the melamine resin contained in the melamine resin release agent. Moreover, in order to promote hardening of a mold release agent, it is preferable to perform 130-170 degreeC heat processing for about 30 second-2 minutes.
The release layer is formed by applying and drying ink prepared by dissolving or dispersing the above-mentioned additives added to a suitable solvent in a suitable solvent by a known means. The thickness is preferably about 0.1 to 5 μm.

(Anti-allergen functional layer)
The anti-allergen functional layer provided on the transfer film is the same as the anti-allergen functional layer 8 described above.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by this example.
(Evaluation method)
(Evaluation of antiallergenicity)
400 μl of an aqueous solution of mite allergen (“Derf2 (trade name)”, manufactured by Asahi Breweries Co., Ltd.) was dropped on the wallpaper produced in each Example and Comparative Example and allowed to stand for 24 hours, and then mite allergen on the wallpaper. The mite allergen was evaluated for antiallergenicity using the mite allergen simple measurement kit ("Daniscan (trade name)", manufactured by Asahi Breweries Co., Ltd.) according to the following criteria.
○: Anti-allergenicity is recognized ×: Anti-allergenicity is not recognized

Example 1
A non-foamed resin layer and an unfoamed resin layer having the following composition are simultaneously formed using an extruder with a T-die so as to have a thickness of 15 μm / 100 μm / 10 μm, respectively. / A laminate A1 composed of a non-foamed resin layer was formed. Extrusion conditions at this time were a cylinder temperature of 160 ° C. for the non-foamed resin layer, a cylinder temperature of 120 ° C. for the foamed resin layer, and a die temperature of 120 ° C. for both.
Non-foamed resin layer (thickness: 10 μm) of the obtained laminate A1 and backing paper (“WK-FKKD (trade name)”, manufactured by Kojin Co., Ltd., weighing: 60 g / m ² ) as a base sheet Were laminated by thermal lamination (about 100 ° C.) to obtain a laminate C1 having a laminate A. The substrate sheet is irradiated with an electron beam (conditions: 200 kV, 5 Mrad), and then textured by gravure printing using water-based ink (“Hydric (trade name)”, manufactured by Dainichi Seika Co., Ltd.). The pattern layer was provided.
Aside from this, a film (“EVAL FILM HF-ME (trade name)”, manufactured by Kuraray Co., Ltd., thickness: 12 μm, ethylene-vinyl alcohol copolymer resin, which is previously provided with an adhesive layer on one surface, (Ethylene content: 44 mol%) is used as a film layer, and an acrylic primer layer forming resin composition ("EBF primer (trade name)" is provided on the surface of the film layer opposite to the surface on which the adhesive layer is provided. ”, Manufactured by Showa Ink Industries Co., Ltd.) by gravure printing at a coating amount of 1.5 g / m ² to form the primer layer 7, on which a composition for anti-allergen functional layer having the following composition was applied at a coating amount of 3.0 g / It was applied by gravure offset coater method at m ² . After coating, electron beam irradiation (conditions: pressurization voltage 165 kV, irradiation dose 30 kGy (3 Mrad)) is performed, the anti-allergen functional layer composition is cured to form an anti-allergen functional layer, and laminate B1 is obtained. It was.
After the unfoamed resin layer of the laminate C1 is foamed at 230 ° C. using a heating foaming furnace to form a foamed resin layer, the laminate C1 and the laminate B1 are combined with the pattern layer of the laminate C1. The laminates B1 and C1 are placed on the cooling roll so that the adhesive layer of the laminate B1 faces the anti-allergen functional layer of the laminate B1 and the cooling roll on which the embossed plate is formed. The anti-allergenic wallpaper of the present invention having an uneven pattern from the anti-allergen functional layer side was obtained by passing between the pressure rolls at about 100 ° C., heat-pressing and embossing.

(Non-foamed resin composition)
Ethylene-vinyl acetate copolymer ("Evertate CV5053 (trade name)", manufactured by Sumitomo Chemical Co., Ltd.): 100 parts by mass (foamed resin composition composition)
Ethylene-vinyl acetate copolymer (“Evertate CV5053 (trade name)”, manufactured by Sumitomo Chemical Co., Ltd.): 100 parts by mass foaming agent (“ADCA # 3 (trade name)”, manufactured by Eiwa Kasei Kogyo Co., Ltd.): 4 Mass parts calcium carbonate (“Whiteon H (trade name)”, manufactured by Shiraishi Kogyo Co., Ltd.): 30 parts by weight Titanium dioxide (pigment) (“Tai Pure R-108 (trade name)”, manufactured by DuPont): 20 parts by weight light Stabilizer (“OF-101 (trade name)”, manufactured by ADEKA Corporation): 1 part by mass cross-linking agent (“Obstar JVA-702 (trade name)”, manufactured by JSR Corporation): 1 part by mass (anti-allergen function) Layer composition)
Bifunctional urethane acrylate oligomer (weight average molecular weight: 720): 100 parts by mass anti-allergen agent (“Alleluve (trade name)”, manufactured by Toagosei Co., Ltd., anti-allergen agent in which a polyphenol compound is supported on a zirconium compound): 10 mass Part matting agent (amorphous silica, particle size: 5 μm): 16 parts by mass

Example 2
In the same manner as in Example 1, a laminate C1 having a pattern layer was obtained, and this was designated as a laminate C2. Separately from this, a film (“EVAL FILM HF-ME (trade name)”, manufactured by Kuraray Co., Ltd., thickness: 12 μm, ethylene previously provided with an adhesive layer on one surface used in Example 1 -Vinyl alcohol copolymer resin, ethylene content: 44 mol%) is used as a film layer, and the antiallergen used in Example 1 is applied to the surface of the film layer opposite to the surface on which the adhesive layer is provided. An ink composition containing 10% by weight (acrylic resin-based water-based ink) is applied by a spray method so that the thickness after drying is 3 μm, and water and organic solvent contained in the ink composition are evaporated at 140 ° C. Thus, an anti-allergen functional layer was formed to obtain a laminate B2.
After the unfoamed resin layer of the laminate C2 is foamed at 230 ° C. using a heating foaming furnace to form a foamed resin layer, the laminate C2 and the laminate B2 are combined with the pattern layer of the laminate C2. The laminates B2 and C2 are placed on the cooling roll so that the adhesive layer of the laminate B2 faces the anti-allergen functional layer of the laminate B2 and the cooling roll on which the embossed plate is formed. The anti-allergenic wallpaper of the present invention having an uneven pattern from the anti-allergen functional layer side was obtained by passing between the pressure rolls at about 100 ° C., heat-pressing and embossing.

Example 3
A non-foamed resin layer and an unfoamed resin layer having the following composition are simultaneously formed using an extruder with a T-die so as to have a thickness of 15 μm / 100 μm / 10 μm, respectively. / A laminate A3 composed of a non-foamed resin layer was formed. Extrusion conditions at this time were a cylinder temperature of 160 ° C. for the non-foamed resin layer, a cylinder temperature of 120 ° C. for the foamed resin layer, and a die temperature of 120 ° C. for both.
Non-foamed resin layer (thickness: 10 μm) of the obtained laminate A3 and backing paper (“WK-FKKD (trade name)”, manufactured by Kojin Co., Ltd., weighing: 60 g / m ² ) as a base sheet Were laminated by thermal lamination (about 100 ° C.) to obtain a laminate C3 having a laminate A3. The substrate sheet is irradiated with an electron beam (conditions: 200 kV, 5 Mrad), and then textured by gravure printing using water-based ink (“Hydric (trade name)”, manufactured by Dainichi Seika Co., Ltd.). The pattern layer was provided.
Aside from this, a film (“EVAL FILM HF-ME (trade name)”, manufactured by Kuraray Co., Ltd., thickness: 12 μm, ethylene-vinyl alcohol copolymer resin, which is previously provided with an adhesive layer on one surface, (Ethylene content: 44 mol%) is used as a film layer, and an acrylic primer layer forming resin composition ("EBF primer (trade name)" is provided on the surface of the film layer opposite to the surface on which the adhesive layer is provided. ", Showa Ink Industries Co., Ltd.) was gravure-printed at a coating amount of 1.5 g / m ² to form a primer layer 7 to obtain a laminate B3.
After the unfoamed resin layer of the laminate C3 is foamed at 230 ° C. using a heating foaming furnace to form a foamed resin layer, the laminate C3 and the laminate B3 are combined with the pattern layer of the laminate C3. The laminated body B3 was made to face the adhesive layer, and the laminated bodies B3 and C3 were passed at about 100 ° C. using a pressure roll to obtain a laminated body D3.
Moreover, the thickness after drying the ink composition (acrylic resin-based aqueous ink) containing 10% by mass of the anti-allergen used in Example 1 on a release film (polyethylene terephthalate film, thickness: 50 μm) is 3 μm. It was applied by gravure printing, and water and an organic solvent contained in the ink composition were evaporated at 140 ° C. to form an antiallergen functional layer to obtain a transfer film. Next, the laminate D3 and the transfer film were heat-pressed using a pressure roll so that the primer layer of the laminate D3 and the anti-allergen functional layer of the transfer film were in contact, and the release film was peeled off. . Then, the anti-allergen functional layer side is subjected to embossing by passing between the cooling roll and the pressure roll at about 100 ° C. so that the cooling roll on which the embossed plate is formed and the anti-allergen functional layer are in contact with each other. From this, an antiallergenic wallpaper having an uneven pattern was obtained.

Examples 4-6
In Examples 1 to 3, anti-allergenic wallpapers of Examples 4 to 6 were obtained in the same manner as in Examples 1 to 3 except that the foamed resin composition was changed to the following composition.
(Foamed resin composition composition)
Vinyl chloride resin (trade name: R-720, manufactured by Tosoh Corporation): 100 parts by mass foaming agent (“Uniform AZ Ultra (trade name)”, manufactured by Otsuka Chemical Co., Ltd.): 3 parts by mass calcium carbonate (“Whiteon H ( Product name) ”, manufactured by Shiroishi Kogyo Co., Ltd .: 100 parts by weight light stabilizer (“ O-1305 (trade name) ”, manufactured by ADEKA Corporation): 5 parts by weight diluent (“ Shellsol S (trade name) ” , Manufactured by Shell Sekiyu Co., Ltd.): 20 parts by mass plasticizer (diisononyl phthalate): 38 parts by mass

Comparative Examples 1 and 2
In the same manner as in Examples 1 and 4, a laminate C having a pattern layer was obtained. Next, on the pattern layer of the laminate C, an acrylic primer layer forming resin composition (“EBF primer (trade name)”, manufactured by Showa Ink Industries Co., Ltd.) is applied at a coating amount of 1.5 g / m ² . The primer layer 7 is formed by gravure printing, and the anti-allergen functional layer composition having the following composition is applied thereon by a gravure offset coater method at a coating amount of 3.0 g / m ² , and irradiated with an electron beam (conditions: additional A voltage of 165 kV and an irradiation dose of 30 kGy (3 Mrad) were performed to cure the anti-allergen functional layer composition to form an anti-allergen functional layer. Thereafter, the embossed plate is passed through the cooling roll and the pressure roll at about 100 ° C. so that the cooling roll on which the embossed plate is formed and the anti-allergen functional layer are in contact with each other to have a film layer. First, wallpaper of Comparative Examples 1 and 2 each having a concavo-convex pattern from the anti-allergen functional layer side was obtained.

  The evaluation of the antiallergenicity of the antiallergenic wallpaper obtained in the Examples was all “◯”, and it was confirmed that the antiallergenicity was very excellent. On the other hand, since the wallpaper obtained in Comparative Examples 1 and 2 does not have a film layer, the hydroxyl group on the surface of the anti-allergen agent disappears due to the reaction between the anti-allergen agent and the foaming gas during the foaming treatment of the unfoamed resin layer. In addition, the evaluation of antiallergenicity was all x.

  According to the present invention, an antiallergenic wallpaper having excellent antiallergenicity and its durability can be obtained. This antiallergenic wallpaper is suitably used as a building interior material such as wallpaper.

1. 1. Anti-allergenic wallpaper 2. Base sheet Resin layer 31. Non-foamed resin layer 31A. Non-foamed resin layer 31B. Non-foamed resin layer 32. Foamed resin layer 4. Pattern layer 5. Adhesive layer 6. 6. Film layer Primer layer 8. 8. Anti-allergen layer Uneven pattern

Claims (13)

  A base sheet, a resin layer, a film layer, and an anti-allergen functional layer are sequentially provided, the film layer is composed of a thermoplastic resin, the resin layer has at least a foamed resin layer, and the anti-allergen functional layer is a phenol. An anti-allergenic wallpaper which is formed by a composition for an anti-allergen functional layer containing an anti-allergen agent having a functional hydroxyl group.   The anti-allergenic wallpaper according to claim 1, wherein the anti-allergen functional layer composition is an ink composition containing an anti-allergen agent and a binder resin.   The anti-allergenic wallpaper according to claim 1, wherein the anti-allergen functional layer composition contains a curable resin and an anti-allergen agent having a phenolic hydroxyl group.   The antiallergenic wallpaper according to claim 3, wherein the curable resin is an ionizing radiation curable resin.   The antiallergenic wallpaper according to claim 4, wherein the ionizing radiation curable resin is a urethane (meth) acrylate oligomer having 2 to 10 functional groups.   The anti-allergenic wallpaper according to any one of claims 1 to 5, wherein the anti-allergen agent having a phenolic hydroxyl group is composed of a polyphenol compound.   The antiallergenic wallpaper according to claim 6, wherein the polyphenol compound is at least one selected from catechin and tannic acid and is supported on an inorganic solid acid.   The anti-allergenic wallpaper according to any one of claims 3 to 7, wherein the compounding amount of the anti-allergen agent in the anti-allergen functional layer composition is 1 to 30 parts by mass with respect to 100 parts by mass of the curable resin.   The anti-allergenic wallpaper according to any one of claims 1 to 8, wherein the resin layer has a foamed resin layer and a non-foamed resin layer.   The anti-allergenic wallpaper according to any one of claims 1 to 9, wherein the resin layer has a non-foamed resin layer, a foamed resin layer, and a non-foamed resin layer in this order.   The anti-allergenic wallpaper according to any one of claims 1 to 10, wherein the thermoplastic resin is a polyolefin resin.   The anti-allergenic wallpaper according to claim 11, wherein the polyolefin resin is an ethylene-vinyl alcohol copolymer resin.   The anti-allergenic wallpaper according to any one of claims 1 to 12, wherein the resin for the foamed resin constituting the foamed resin layer is a polyolefin resin or a polyvinyl chloride resin.

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