JP5884271B2 - Wallpaper with visible light photocatalytic function - Google Patents

Description

  The present invention relates to a wallpaper having a visible light photocatalytic function, that is, a wallpaper having a function of decomposing an organic volatile substance such as aldehyde in the atmosphere in the visible light region.

In recent years, building interior materials having a photocatalytic function for decomposing volatile organic compounds (VOC) have been used as countermeasures for the problems of sick houses caused by organic gases such as formaldehyde generated from housing materials, pet odors, and daily odors. Needs are increasing. Although many photocatalysts have photocatalytic activity in the ultraviolet region, in view of use in interior materials for buildings, a visible light type photocatalyst having a photoactive function that also responds to visible light in the room, and the Catalyst thin films have attracted attention and are being developed (Patent Documents 1 to 3).
When considering the decomposition of volatile organic compounds in building interior materials, it can be applied to building materials such as wall materials, ceiling materials, flooring materials, and furniture. It is thought that it is effective to give a function to a wall surface having the largest area as a member, and various wallpaper having a photocatalytic function by providing a photocatalytic layer has been proposed (Patent Documents 4 to 6).

  By the way, it is known that the performance (initial performance) of decomposing organic matter in the atmosphere by the photocatalyst appears after decomposing organic pollutants in the vicinity of the photocatalyst. That is, if there are many organic contaminants close to the photocatalyst, sufficient initial photocatalytic activity may not be obtained. There are various factors that cause organic pollutants to come close, and one of them is embossing on wallpaper. The wallpaper is sometimes embossed in order to provide a concavo-convex pattern on the surface. However, when embossing is applied to the wallpaper provided with the photocatalyst layer, the photocatalyst particles are pushed deeply into the substrate side (buried), and the photocatalyst The function may be degraded.

JP 11-197512 A JP 2002-146200 A JP 2004-161573 A JP 2010-084448 A Japanese Patent Laid-Open No. 10-180943 JP 2009-279813 A

  The present invention has been made in view of the above-described problems of the prior art, and provides a wallpaper having a sufficient photocatalytic function even after embossing.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the problem can be solved by the following invention. That is, the present invention
A wallpaper having a wallpaper substrate including a foamed resin layer, an intermediate layer, and a visible light photocatalyst layer in this order,
The intermediate layer contains at least silica particles and a binder;
When the BET specific surface area of the silica particles is S, S is 140 m ² / g or more,
A wallpaper having a P / V of 1 or less when the mass of the silica particles is P and the mass of the binder is V is provided.

  The wallpaper having the visible light type photocatalytic function of the present invention can suppress the embedding of the photocatalyst particles by embossing by providing an intermediate layer containing silica particles under the visible light type photocatalytic layer, and is excellent even after embossing. Has a photocatalytic function. Moreover, although the intermediate | middle layer containing a silica particle has unevenness | corrugation in the coating-film surface, wallpaper can maintain stain resistance.

FIG. 1 is a schematic diagram showing the wallpaper produced in Example 1. FIG.

Hereinafter, the “wallpaper having a visible light photocatalytic function” of the present invention will be described.
The wallpaper having a visible light photocatalytic function of the present invention (hereinafter sometimes simply referred to as “wallpaper”) includes a wallpaper substrate including a foamed resin layer, an intermediate layer, and a visible light photocatalyst layer in this order. It has wallpaper. The intermediate layer contains silica particles and a binder. When the BET specific surface area of the silica particles is S, S is 140 m ² / g or more, the mass of the silica particles is P, and the mass of the binder is V P / V is 1 or less.

(1) Wallpaper base material The wallpaper of this invention has a wallpaper base material. The wallpaper base material includes at least a foamed resin layer, and may further include a non-foamed resin layer A, a backing sheet layer, and / or a non-foamed resin layer B as necessary.

(1-1) Foamed resin layer The wallpaper base material of this invention contains a foamed resin layer. The foamed resin layer is a layer formed by foaming a layer containing a foaming agent and a resin (hereinafter referred to as “unfoamed resin layer”).

The resin contained in the unfoamed resin layer is not particularly limited as long as it is foamed by the action of a foaming agent (for example, foamed when heated), but is preferably an olefin resin, An ethylene resin is more preferable.
Examples of ethylene resins include ethylene homopolymer resin (PE), ethylene-vinyl acetate copolymer resin (EVA), ethylene-methyl acrylate copolymer resin (EMA), and ethylene-ethyl acrylate copolymer resin (EEA). ), An ethylene-based copolymer resin such as an ethylene-alkyl acrylate copolymer resin having 3 to 5 carbon atoms, an ethylene-methyl methacrylate copolymer resin (EMMA), an ethylene-methacrylic acid copolymer resin (EMAA), Examples thereof include a mixture of these resins. These resins can be easily crosslinked by irradiation with ionizing radiation. Among these resins, EVA resin and EMAA resin are preferable. Incidentally, the ionizing radiation referred to here means an electromagnetic wave or a charged particle beam having an energy quantum capable of polymerizing or crosslinking molecules, and usually ultraviolet (UV) or electron beam (EB) is used. In addition, electromagnetic waves such as X-rays and γ rays, and charged particle beams such as α rays and ion rays are also included. Among these, it is preferable to use an electron beam. This is because when an electron beam is used, a photocuring initiator is not required and stable curing characteristics can be obtained.
Examples of olefin resins other than ethylene resins include propylene resins, butene resins, pentene resins, and the like.

When an EVA resin is used as the resin component, the vinyl acetate unit (copolymerization ratio) in the EVA resin is not particularly limited, but is preferably about 5 to 30% by mass, and about 10 to 20% by mass. More preferred. The melt flow rate value (MFR) of the resin component is not particularly limited, but is preferably about 5 to 75 g / 10 minutes, and more preferably about 40 to 70 g / 10 minutes. In the present specification, MFR is a value measured by a test method described in JIS K 7210 (Method for testing the flow of thermoplastics). As test conditions, “190 ° C., 21.18 N (2.16 kgf)” described in JIS K 6760 is adopted. The foamed state of the foamed resin layer (for example, the size of the foamed cell, the foamed cell density, etc.) is not particularly limited, and can be appropriately designed within a range that does not impair the scope of the present invention.
Moreover, when using EMAA resin as a resin component, it is preferable that the methacrylic acid unit (copolymerization ratio) in EMAA resin is about 4-20 mass%. The melt flow rate value (JIS K 7210, 190 ° C., 2.16 kg) of the resin component depends on the type of polymer to be used, but is usually preferably 60 to 200 g / 10 minutes. In particular, it is advantageous in that a good foamed state can be maintained even in a high range of 100 to 200 g / 10 minutes.

  The foaming agent used in the present invention may be a chemical foaming agent or a physical foaming agent, but a chemical foaming agent is preferred, and among the chemical foaming agents, a pyrolytic foaming agent is preferred. The pyrolytic foaming agent can be selected from known foaming agents. For example, azo compounds such as azodicarbonamide (ADCA) and azobisformamide; and bidazides such as oxybenzenesulfonyl hydrazide (OBSH) and paratoluenesulfonyl hydrazide. The blending amount of the pyrolytic foaming agent can be appropriately set according to the type of foaming agent, the expansion ratio, and the like. Since the expansion ratio is 1.5 times or more, preferably about 3 to 7 times, the blending amount of the pyrolytic foaming agent should be about 1 to 20 parts by mass with respect to 100 parts by mass of the resin component. Is preferred. Examples of the physical foaming agent include thermal expansion type microcapsules. For example, a volatile liquid expansion agent such as propane, butane, isobutane, pentane, hexane or the like is used as a vinylidene chloride-acrylonitrile-divinylbenzene copolymer, methacrylate-acrylonitrile- A microcapsule encapsulated in a thermoplastic polymer polymer shell such as divinylbenzene copolymer having an average diameter in the range of 1 to 100 μm can be used.

The unfoamed resin layer may contain additives such as a cell regulator, an inorganic filler, and a pigment in addition to the foaming agent and the resin.
As the cell adjusting agent, for example, a metal soap such as zinc stearate can be used. The blending amount of the cell regulator 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 resin component.
Examples of the inorganic filler include calcium carbonate, aluminum hydroxide, magnesium hydroxide, antimony trioxide, zinc borate, and a molybdenum compound. By including the inorganic filler, an effect of suppressing see-through, an effect of improving surface characteristics, and the like are obtained. About 0-100 mass parts is preferable with respect to 100 mass parts of resin components, and, as for the compounding quantity of this inorganic filler, about 20-70 mass parts is more preferable.
As for the pigment, for example, titanium oxide, zinc white, carbon black, black iron oxide, yellow iron oxide, yellow lead, molybdate orange, cadmium yellow, nickel titanium yellow, chrome titanium yellow, iron oxide (valve), cadmium red, Inorganic pigments such as ultramarine, bitumen, cobalt blue, chromium oxide, cobalt green, aluminum powder, bronze powder, titanium mica, zinc sulfide; for example, aniline black, perylene black, azo (azo lake, insoluble azo, condensed azo), many Cyclic (isoindolinone, isoindoline, quinophthalone, perinone, flavantron, anthrapyrimidine, anthraquinone, quinacridone, perylene, diketopyrrolopyrrole, dibromanthanthrone, dioxazine, thioindigo, phthalocyanine, indanthrone And organic pigments halogenated phthalocyanine), or the like. About 10-50 mass parts is preferable with respect to 100 mass parts of resin components, and, as for content of this pigment, about 15-30 mass parts is more preferable.
In addition, stabilizers, lubricants, and the like can be used as additives.

  Although the thickness of a foamed resin layer is not specifically limited, About 20-200 micrometers is preferable and about 50-120 micrometers is more preferable.

(1-2) Non-foamed resin layer A
The wallpaper base material of the present invention may include a non-foamed resin layer (hereinafter referred to as “non-foamed resin layer A” for distinction from the non-foamed resin layer B described later) on the surface of the foamed resin layer on the intermediate layer side. Good. The non-foamed resin layer A mainly protects the foamed resin layer and lowers the visible light photocatalytic function due to volatile components such as foamed gas in the foaming process when the foamed resin layer is formed (specifically, titanium oxide) And the like to prevent adverse effects on particles of visible light type photocatalyst compounds such as. As the resin for forming the non-foamed resin layer A, the same olefin resin as that used for the foamed resin layer can be used. The resin used for the non-foamed resin layer A may be the same as or different from the resin type used for the foamed resin layer, but in order to improve the adhesion between the non-foamed resin layer A and the foamed resin layer. It is preferable to use the same type of resin or resin composition.

  As the resin component, for example, a copolymer obtained by a combination of at least one monomer of acrylic acid and methacrylic acid and ethylene can be suitably used as the resin component. More specifically, it is desirable to use at least one of an ethylene-methacrylic acid copolymer, an ethylene-acrylic acid copolymer, and an ionomer resin. As the ionomer resin, a resin having a structure in which the molecules of ethylene-methacrylic acid copolymer and / or ethylene-acrylic acid copolymer are intermolecularly bonded with metal ions such as sodium and zinc can be used. When such a resin component is used, it is possible to form a strong layer particularly due to hydrogen bonds in the resin, so that excellent scratch resistance, abrasion resistance, and the like can be obtained. These may be known or commercially available.

The content of acrylic acid or methacrylic acid in the copolymer is preferably about 4 to 15% by mass. Such a resin can also use a commercial item. A known additive can also be blended in the resin composition. The thickness of the non-foamed resin layer A is not particularly limited, but is preferably about 10 to 50 μm, and more preferably about 10 to 20 μm. Moreover, although content of the said resin component in a resin composition is not limited, Usually, it is preferable to set suitably in the range of 70-100 mass%.
Although the melt flow rate value (MFR) of the resin component depends on the type of the resin component to be used, etc., it is generally set as appropriate within a range of 10 g / 10 minutes or more. Usually, it is preferably 10 to 100 g / 10 minutes, particularly preferably 10 to 95 g / 10 minutes, and more preferably 20 to 80 g / 10 minutes. By using a material having such a numerical range, more excellent scratch resistance, wear resistance and the like can be obtained. The measurement conditions for the melt flow rate value (MFR) are the same as those described in the section of the foamed resin layer.

  Preferred combinations as the foamed resin layer / non-foamed resin layer A include EVA resin / EVA resin, EMAA resin / EVA resin, EVA resin / EMAA resin, EMAA resin / EMAA resin, PE resin / PE resin, and particularly EVA. Resin / EMAA resin is preferred.

(1-3) Backing Sheet Layer The wallpaper base material of the present invention may include a backing sheet layer. The backing sheet layer is provided on the surface opposite to the intermediate layer of the foamed resin layer or on the surface opposite to the intermediate layer of the non-foamed resin layer B described later. The backing sheet layer is not particularly limited. For example, a resin sheet, a fiber sheet such as paper can be generally used, but a fiber sheet such as paper is preferable. Specifically, flame retardant paper (pulp-based sheet is used). Treated with a flame retardant such as guanidine sulfamate, guanidine phosphate, and the like); inorganic paper containing inorganic additives such as aluminum hydroxide and magnesium hydroxide; fine paper; thin paper.
The basis weight of the backing sheet layer is not particularly limited, preferably about 50 to 300 g / m ^2, about 50 to 80 g / m ² is more preferable.

(1-4) Non-foamed resin layer B
The wallpaper base material of the present invention has a non-foamed resin layer (hereinafter referred to as “non-foamed resin layer B” for distinction from the aforementioned non-foamed resin layer A) on the surface opposite to the intermediate layer of the foamed resin layer. May be included. When the wallpaper substrate includes a backing sheet layer, the non-foamed resin layer B may be included between the foamed resin layer and the backing sheet layer, and the non-foamed resin layer B functions as an adhesive layer. High adhesion can be obtained. As the non-foamed resin layer B, the same olefin resin as that used for the foamed resin layer can be used, but an ethylene-vinyl acetate copolymer can be suitably used from the viewpoint of improving adhesion. . The non-foamed resin layer B may contain known additives in addition to the resin component, but is preferably blended so that the content of the resin component is 70 to 100% by mass.
The thickness of the non-foamed resin layer B is not particularly limited, but is preferably about 10 to 50 μm, and more preferably about 10 to 20 μm.

[Method for forming wallpaper substrate]
The wallpaper base material of the present invention includes (a) a step of forming a pre-foaming wallpaper base material including an unfoamed resin layer, and (a) a step of foaming the unfoamed resin layer to form a foamed resin layer. It is formed.
Since the unfoamed resin layer is foamed in the step (a) to form the foamed resin layer, the pre-foaming wallpaper substrate including the unfoamed resin layer is changed to the wallpaper substrate including the foamed resin layer in the step (a). And change. That is, the “pre-foaming wallpaper base material” and the “wallpaper base material” are obtained by distinguishing the name before foaming and the name after foaming for convenience.

(A) The process of forming the wallpaper base material before foaming including an unfoamed resin layer Although the formation method of the wallpaper base material before foaming is not specifically limited, For example, it can form with a T-die extruder. When forming a pre-foaming wallpaper substrate that includes not only an unfoamed resin layer but also a non-foamed resin layer A, a multi-layer capable of simultaneously forming two layers by simultaneously extruding molten resin corresponding to the two layers. A manifold type T-die can be used. In this case, the resin composition for forming the unfoamed resin layer and the resin composition for forming the non-foamed resin layer A are placed in separate cylinders, and two types and two layers are simultaneously extruded to form and laminate. That's fine. Similarly, when forming a non-foamed resin layer, a non-foamed resin layer A and a non-foamed resin layer B, a resin composition for forming the non-foamed resin layer, a non-foamed resin layer The resin composition for forming A and the resin composition for forming the non-foamed resin layer B may be placed in separate cylinders, respectively, and three types and three layers may be simultaneously extruded to form and laminate.

  In order to form a pre-foaming wallpaper substrate including a backing sheet layer, the laminate coextruded by the above method may be simultaneously laminated (film formation) on the backing sheet layer. The resin layer laminated simultaneously with extrusion on the backing sheet layer is bonded to the backing sheet layer because it has adhesiveness by heat melting. Alternatively, a laminate in which films are simultaneously formed in advance may be prepared, placed on the backing sheet layer, and bonded by thermal lamination.

  When the resin composition forming the unfoamed resin layer contains an inorganic filler, when the unfoamed resin layer is formed by extrusion molding, the residue of the inorganic filler at the extrusion port (so-called die) of the extrusion molding machine (So-called eyes) are likely to occur, and this tends to be a foreign matter on the sheet surface. Therefore, when an inorganic filler is contained in the non-foamed resin layer, the resin composition for forming the non-foamed resin layer A and the non-foamed resin layer B is simultaneously used together with the resin composition for forming the non-foamed resin layer. Extrusion molding is preferred. The coextrusion molding can be performed, for example, by using a multi-manifold type T die. Thus, by simultaneously extruding the unfoamed resin layer in such a manner that the non-foamed resin layer is sandwiched between the two non-foamed resin layers (the non-foamed resin layer A and the non-foamed resin layer B), it is possible to suppress the occurrence of the eyes.

  The pre-foaming wallpaper substrate may be irradiated with ionizing radiation, and particularly preferably irradiated with an electron beam. Thereby, since a resin component can be bridge | crosslinked, the surface strength of a wallpaper base material, a foaming degree, etc. can be controlled. The energy of the electron beam is preferably about 150 to 250 kV. The irradiation amount is preferably about 1 to 7 Mrad. A known electron beam irradiation apparatus can be used as the electron beam source. The crosslinking can also be performed using a chemical crosslinking agent (also referred to as a crosslinking agent or a crosslinking aid).

  When performing electron beam irradiation, you may contain a crosslinking agent in a resin composition. Any crosslinking agent that promotes crosslinking by electron beam irradiation may be used. Examples thereof include polyfunctional monomers such as neopentyl glycol dimethacrylate and trimethylolpropane trimethacrylate, oligomers, and the like. The cross-linking agent is preferably about 0 to 10 parts by mass, more preferably 1 to 4 parts by mass with respect to 100 parts by mass of the resin component.

(A) Step of foaming the unfoamed resin layer to form a foamed resin layer The method of foaming the unfoamed resin layer is appropriately selected from known methods according to the type of foaming agent, and is particularly limited. Not. When a pyrolytic foaming agent is used as the foaming agent, the heating conditions are not limited as long as the foamed resin layer is formed by the decomposition of the pyrolytic foaming agent, but the heating temperature is preferably about 210 to 240 ° C. The time is preferably about 20 to 80 seconds.

  In addition, it is preferable to perform process (I) after apply | coating the dispersion liquid for visible light type photocatalyst layer formation. By simultaneously drying the dispersion liquid to form the visible light type photocatalyst layer and foaming the unfoamed resin layer, the number of manufacturing steps can be reduced, and the cost can be reduced. In addition, when a pattern layer, an intermediate layer, and a visible light type photocatalyst layer are formed after foaming, it is difficult to apply the layer neatly due to the unevenness of the foamed resin layer. By forming it, it becomes possible to apply beautifully.

(2) Intermediate layer The wallpaper of the present invention has an intermediate layer. The intermediate layer contains at least silica particles and a binder.
The intermediate layer of the present invention has a function of suppressing a decrease in photocatalytic function due to embossing. When an intermediate layer is not provided, photocatalyst particles such as titanium oxide that exhibit the visible light photocatalytic function are embedded in the pattern layer or wallpaper substrate located under the visible light photocatalyst layer by embossing, and these layers The photocatalytic function of the photocatalyst particles may be consumed in the decomposition of the organic substances present in the photocatalyst. However, in the present invention, since an intermediate layer containing silica particles is provided, the photocatalyst particles on the silica surface protruding from the binder are suppressed from being buried by embossing due to the presence of the silica particles, thereby reducing the photocatalytic function. Can be suppressed. In the present invention, although the intermediate layer contains silica protruding from the binder, and the surface is uneven, the wallpaper has sufficient stain resistance (wiping of contaminants) compared to the case where silica is not included. Easy).

When the BET specific surface area of the silica particles of the present invention is S, S is 140 m ² / g or more. A larger S is preferable because the amount of photocatalytic particles present on the silica surface increases, and if S is 140 m ² / g or more, a decrease in the photocatalytic function due to embossing is sufficiently suppressed and a high photocatalytic function is exhibited. The upper limit of S is not particularly limited, but it is easy to obtain if S is 500 m ² / g or less. Further, if S is 500 m ² / g or less, the influence of thickening and thixotropic increase due to the increase of S is small, so P / V (where P: mass of silica particles, V: mass of binder) Can be added at an arbitrary ratio of 1 or less. In addition, said BET specific surface area is the value analyzed from the adsorption branch side nitrogen adsorption isotherm whose specific pressure is 0.05-0.35 or less according to the constant volume method of the BET multipoint method described in JISR1626. It is.
The particle size of the silica particles of the present invention is not particularly limited as long as S satisfies 140 m ² / g or more, but the average particle size is preferably 1 μm to 7 μm, more preferably 2.5 μm to 5 μm. In addition, the average particle diameter said here is measured by the laser method. When the average particle diameter is 1 μm or more, silica is not buried in the intermediate layer, and the surface area effect of silica can be utilized. If the average particle diameter is 7 μm or less, the silica can exhibit its function without falling off from the intermediate layer.

  In the present invention, when the mass of the silica particles is P and the mass of the binder is V, P / V is 1 or less. If P / V is 1 or less, the amount of silica particles added is not excessive with respect to the binder, and the intermediate layer is excellent in coating film formation (printability).

In the present invention, the intermediate layer preferably satisfies the following formula (1), and more preferably satisfies the formula (2).
S / (1 + V / P) ≧ 30 m ² / g Formula (1)
S / (1 + V / P) ≧ 45 m ² / g (2)
Here, the left side of the formulas (1) and (2) means the total surface area of the silica particles contained in the unit mass intermediate layer. When satisfying the formula (1), the silica particles can sufficiently suppress a decrease in the photocatalytic function due to the embossing, and exhibit a high photocatalytic function. When satisfying the formula (2), exhibit a higher photocatalytic function. Can do.
When Expressions (1) and (2) are transformed, P / V ≧ (30 m ² / g) / (S−30 m ² / g) (Equation (3))
P / V ≧ (45 m ² / g) / (S-45 m ² / g) (4)
Therefore, P / V is preferably equal to or greater than the right side of Formula (3), and more preferably equal to or greater than the right side of Formula (4).

  The binder included in the present invention is not particularly limited as long as it has heat resistance to a high temperature of 200 ° C. or higher in wallpaper film formation, and adhesion to the wallpaper substrate and the photocatalyst layer can be obtained. Organic binders and inorganic binders can be used. From the viewpoint of adhesion, an organic binder is preferable. Specific examples include carboxyl group-containing resins and oxazoline group-containing resins described in JP-A-2009-84446. Moreover, the highly elastic polyester resin and unsaturated polyester resin mixture, highly elastic acrylic resin, highly elastic urethane resin, etc. which are described in Unexamined-Japanese-Patent No. 2002-248715 [0028] are mentioned.

The coating amount of the intermediate layer is not particularly limited as long as it covers the wallpaper base material and the silica fine particles are held while protruding on the coating film surface of the intermediate layer, but preferably 0.2 to 5 g / m ^2. , more preferably from 0.5 to 2 g / m ^2. In this specification, “application amount” refers to the mass after drying unless otherwise specified.

[Method for forming intermediate layer]
The intermediate layer of the present invention can be formed by applying an intermediate layer coating solution on a pre-foaming wallpaper substrate and then drying it. An intermediate layer coating solution may be applied on the wallpaper substrate (that is, an intermediate layer coating solution is applied after foaming), but it becomes difficult to apply the intermediate layer cleanly due to the unevenness of the foamed resin layer. It is preferable to apply the intermediate layer coating liquid on the pre-foaming wallpaper substrate (that is, apply the intermediate layer coating liquid before foaming).
The intermediate layer coating liquid contains a solvent in addition to the silica particles and the binder described above. The solvent is not particularly limited, and examples thereof include water; an aqueous medium such as a mixed solvent of alcohols such as ethanol, methanol, 2-propanol, and butanol and water; Among these, water is particularly preferable.
In forming the intermediate layer using the intermediate layer coating liquid of the present invention, for example, the intermediate layer coating liquid is applied by a conventionally known method such as spin coating, dip coating, doctor blade, spraying or brushing, and then the intermediate layer coating liquid is applied. What is necessary is just to heat at the temperature which can remove the solvent in a layer coating liquid.

(3) Visible light type photocatalyst layer The wallpaper of this invention has a visible light type photocatalyst layer. The visible light type photocatalyst layer contains at least a visible light type photocatalytic compound and a binder.
The coating amount of the visible light type photocatalyst layer is not particularly limited, but can be arbitrarily selected and used within a range of about 0.2 to 5 g / m ² depending on the purpose and application.

(3-1) Visible Light Type Photocatalytic Compound The visible light type photocatalytic layer of the present invention contains a visible light type photocatalytic compound (hereinafter sometimes simply referred to as “photocatalytic compound”). The photocatalytic compound is not particularly limited as long as it is a compound that exhibits a photocatalytic action with visible light, but is preferably a compound that exhibits photocatalytic activity against light irradiation by a fluorescent lamp. Specifically, a compound exhibiting photocatalytic activity for light irradiation with a wavelength of about 430 nm to about 830 nm is preferable.
Specific examples of the photocatalytic compound include Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, as disclosed in JP-A-2007-268523. , Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, Ce Alternatively, two or more kinds of oxides, nitrides, sulfides, oxynitrides, oxysulfides, nitrofluorides, oxyfluorides, oxynitrofluorides, and the like can be given. Among these, anatase-type or rutile-type titanium oxide is preferable, and anatase-type titanium oxide is preferable as a catalyst that shows catalytic activity when irradiated with visible light or fluorescent light.
As a method for producing titanium oxide particles having visible light responsiveness, the production methods disclosed in JP-A Nos. 2001-278625, 2001-302241, 2003-275600 and the like are used. Can do.
The content of the photocatalytic compound in the visible light type photocatalyst layer of the present invention is preferably 5 to 95% by mass, and more preferably 10 to 60% by mass.

(3-2) Binder The visible light type photocatalyst layer of the present invention contains a binder. When a resin composition (organic binder) is used as a binder for the visible light photocatalyst layer, the visible light photocatalyst compound is dispersed in the resin composition or exists in a state coated with a resin. Is not sufficiently exposed, and the visible light photocatalytic function may not be sufficiently developed. Therefore, in the present invention, an organic binder is used rather than an organic binder as a binder for the visible light photocatalyst layer, and the photocatalyst compound is exposed on the surface of the visible light photocatalyst layer as a porous layer. desirable.
Specific examples of inorganic binders include condensates of alkoxysilanes, organopolysiloxanes, polycondensates of organic polysiloxane compounds, hydrolysates, silica compounds such as silicon varnish; zinc phosphate, polyphosphate, phosphoric acid Examples thereof include phosphates such as aluminum; inorganic binders such as silica, colloidal silica, water glass, cement, lime, gypsum, frit for enamel, glaze for glass lining, and plaster.
1-70 mass% is preferable and, as for content of the binder in the visible light type photocatalyst layer of this invention, 5-50 mass% is more preferable.

(3-3) Additives The visible light photocatalyst layer may contain various additives as a dispersion, if necessary.
Examples of such additives include amorphous silica, silicon oxide such as silica sol, amorphous alumina, aluminum oxide and hydroxide such as alumina sol, aluminosilicate such as zeolite and kaolinite. Oxides and hydroxides of alkaline earth metals such as salts, magnesium oxide, calcium oxide, strontium oxide, barium oxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, calcium phosphate, molecular sieve, activated carbon , And Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt, Cu, Ag, Au, Metal element hydroxides such as Zn, Cd, Ga, In, Tl, Ge, Sn, Pb, Bi, La, Ce Beauty and amorphous oxides of these metal elements and the like.
These additives may be only one type or two or more types.

[Method for forming visible light photocatalyst layer]
The visible light photocatalyst layer of the present invention comprises, for example, a dispersion in which a visible light photocatalyst compound and a binder are dispersed in a solvent (hereinafter also referred to as “visible light photocatalyst dispersion”), gravure coating, spray coating, dip coating. Examples of the method include coating on the intermediate layer by a method such as coating or brushing, and then heating at a temperature at which the solvent in the dispersion can be removed. However, the present invention is not limited to this method.
The visible light type photocatalyst dispersion may be applied directly on the intermediate layer, but it is also possible to prepare a photocatalyst layer transfer film and transfer it by a transfer method. As a means for applying, for example, various application methods such as gravure coating, spray coating, and dip coating as described above can be selected. The coating liquid may be applied not only once but a plurality of times.
Thereafter, the solvent is removed by heating at a temperature at which the solvent can be removed. After drying is completed, aging can be performed for a required time at a temperature of about 30 to 60 ° C. Thereby, the peeling strength of the coated visible light type photocatalyst layer can be improved.

The photocatalyst compound present in the visible light type photocatalyst dispersion of the present invention may be in the form of particles or fibers. The average primary particle diameter in the form of particles is preferably 500 nm or less, more preferably 200 nm or less, and even more preferably 180 nm or less, and the average secondary particle diameter is preferably 15 μm or less.
The content of the photocatalyst compound in the visible light type photocatalyst dispersion liquid of the present invention is not particularly limited as long as it is appropriately set depending on the application, but the lower limit is usually 0.1% by mass or more, preferably 1% by mass or more. The upper limit is set to be 30% by mass or less. In addition, as the content of the photocatalytic compound (that is, the amount of powder in the dispersion) increases, the later-described mixing (particularly initial mixing) can be performed more efficiently. Taking this into consideration, the content of the photocatalyst compound is set to be higher than the predetermined amount at the time of preparation, and a desired content is obtained by adding a solvent and diluting in a later step. You can also.

  The aqueous solvent in the present invention contains water as a main component, and examples thereof include water; an aqueous medium such as a mixed solvent of alcohols such as ethanol, methanol, 2-propanol, and butanol and water; Among these, water is particularly preferable.

When obtaining the visible light type photocatalyst dispersion of the present invention, the mixture obtained by the above mixing is further subjected to operations such as removal of coarse particles, adjustment of photocatalyst compound content (dilution, etc.), pH adjustment and the like. Can be applied. There is no restriction | limiting in particular as a specific method of these operation, What is necessary is just to employ | adopt a conventionally well-known method.
When storing the visible light type photocatalyst dispersion liquid of the present invention, it is preferable to store it under conditions where it is not exposed to light. For example, the visible light type photocatalyst dispersion liquid is stored in a dark room or has an ultraviolet and visible light transmittance of 10 each. It is preferable to store it in a light-shielding container of no more than%.

(4) Pattern Pattern Layer The wallpaper of the present invention may further have a pattern pattern layer between the wallpaper base material and the intermediate layer. The design pattern layer can impart design properties to the wallpaper. Examples of the pattern pattern in the pattern layer include a wood grain pattern, a stone pattern, a grain pattern, a tiled pattern, a brickwork pattern, a cloth pattern, a leather pattern, a geometric figure, a character, a symbol, and an abstract pattern. . The pattern can be selected according to the type of wallpaper of the present invention. The pattern pattern layer can be formed, for example, by printing a pattern pattern on the surface of the wallpaper substrate. In addition, when forming a pattern layer, you may form a primer layer previously as needed. Examples of printing methods include gravure printing, flexographic printing, silk screen printing, and offset printing. As the printing ink, a printing ink containing a colorant, a binder resin, and a solvent (or a dispersion medium) can be used. These inks may be known or commercially available.

  As the colorant, for example, a pigment used in the unfoamed resin layer can be appropriately used. The binder resin is, for example, an acrylic resin, a styrene resin, a polyester resin, a urethane resin, a chlorinated polyolefin resin, a vinyl chloride-vinyl acetate copolymer resin, a polyvinyl butyral resin, an alkyd resin, a petroleum resin, Examples include ketone resins, epoxy resins, melamine resins, fluorine resins, silicone resins, fiber derivatives, rubber resins, and the like.

  Examples of the solvent (or dispersion medium) include petroleum organic solvents such as hexane, heptane, octane, toluene, xylene, ethylbenzene, cyclohexane, and methylcyclohexane; ethyl acetate, butyl acetate, 2-methoxyethyl acetate, acetic acid- Ester organic solvents such as 2-ethoxyethyl; alcohol organic solvents such as methyl alcohol, ethyl alcohol, normal propyl alcohol, isopropyl alcohol, isobutyl alcohol, ethylene glycol, propylene glycol; acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone-based organic solvents; ether-based organic solvents such as diethyl ether, dioxane, and tetrahydrofuran; dichloromethane, carbon tetrachloride, trichloroethylene, tetrachloroethylene Chlorinated organic solvents emissions and the like; and water. The thickness of the design pattern layer is different from the type of design pattern, but is generally preferably about 0.1 to 10 μm.

  Hereinafter, the present invention will be specifically described with reference to examples. The present invention is not limited to the method described below.

(1) Creation of wallpaper [Example 1]
A wallpaper having a visible light type photocatalytic function schematically shown in FIG. 1 was prepared by the method described below.
Using a known T-die extruder, the non-foamed resin layer A / the unfoamed resin layer / the non-foamed resin layer B are formed in this order so that each layer has a thickness of 15 μm / 100 μm / 10 μm and consists of three layers. A laminate A was obtained.
The resin used for the non-foamed resin layer A and the non-foamed resin layer B and the resin composition used for the non-foamed resin layer are as follows.
(A) Resin used for non-foamed resin layer A and non-foamed resin layer B:
-Ethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Evertate CV5053), 100 parts by mass (b) Resin composition used for unfoamed resin layer:
・ Ethylene-vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., trade name: Evaate CV5053), 100 parts by mass ・ Foaming agent (manufactured by Eiwa Kasei, trade name: ADCA # 3), 4 parts by mass ・ Calcium carbonate ( Shiroishi Kogyo Co., Ltd., trade name: Whiteon H), 30 parts by mass Titanium dioxide (pigment) (DuPont, trade name: Taipure R-108), 20 parts by mass Light stabilizer (made by ADEKA, trade name) : OF-101), 1 part by mass ・ Crosslinking agent (manufactured by JSR Corporation, trade name: Obstar JVA-702), 1 part by mass

Next, a backing sheet layer (rice weighed 60 g / m ² , WK-FKKD, manufactured by Kojin Co., Ltd.) is laminated on the non-foamed layer resin B of the laminate A to obtain a laminate B (wall paper substrate before foaming). Got. Thereafter, for the purpose of improving the surface strength of the laminate A, the laminate B was irradiated with an electron beam at 200 kV and 5 Mrad.

Next, by gravure printing, a texture pattern (pattern pattern layer) is printed on the non-foamed resin layer A surface of the laminate B using water-based ink (manufactured by Dainichi Seika Kogyo Co., Ltd., trade name: Hydrick), The intermediate layer coating solution was applied on top so that the mass after drying was 1 g / m ² . Further, a visible light type titanium oxide photocatalyst coating agent (manufactured by Sumitomo Chemical Co., Ltd., trade name: TC-S4115, NV 5 wt%, titanium oxide particle size 100 nm) has a mass after drying of 1 g / m ^2. It apply | coated so that it might become, and the laminated body C was obtained.
The composition of the intermediate layer coating solution is as follows.
Binder component Solid content 15 parts by mass-Carboxyl group-containing acrylic emulsion (oxidation 20 mg / g, solid content 44%) Solid content ratio in component 10
・ Epocross WS700, manufactured by Nippon Shokubai (Oxazoline group-containing acrylic resin, solid content 25%), solid content ratio 1
Silica 5 parts by mass-Silica 1: Mizukasil P-705, manufactured by Mizusawa Chemical Co., Ltd. (specific surface area 300 m ² / g, particle diameter 3.0 μm)
Solvent: IPA / water = 1/1 (mass ratio)
The specific surface area of silica is a value measured by a nitrogen adsorption method using TriStar 3000 manufactured by Micromeritics.

Thereafter, the laminate C is foamed with an unfoamed resin layer containing a foaming agent in a heating exothermic furnace at 230 ° C. to form a foamed resin layer, and then embossed to form a textured pattern. And got a wallpaper.
[Example 2]
A wallpaper was obtained in the same manner as in Example 1 except that the silica was Silica 2: Mizukasil P-707, manufactured by Mizusawa Chemical Co., Ltd. (specific surface area 300 m ² / g, particle diameter 4.0 μm).
[Example 3]
Wallpaper was obtained in the same manner as in Example 2 except that the binder component solid content was 12.5 parts by mass and silica was 7.5 parts by mass.
[Example 4]
A wallpaper was obtained in the same manner as in Example 3 except that the silica was Silica 3: Mizukasil P-803 and Mizusawa Chemical Co., Ltd. (specific surface area 180 m ² / g, particle size 5.0 μm).
[Example 5]
Wallpaper was obtained in the same manner as in Example 4 except that the binder component solid content was 10 parts by mass and silica was 10 parts by mass.
[Example 6]
A wallpaper was obtained in the same manner as in Example 3 except that the silica was Silica 4: Mizukasil P-526N, manufactured by Mizusawa Chemical Co., Ltd. (specific surface area 140 m ² / g, particle size 3.3 μm).
[ Reference Example 1 ]
A wallpaper was obtained in the same manner as in Example 6 except that the binder component solid content was 15 parts by mass and the silica was 5 parts by mass.

[Comparative Example 1] (specific surface area <140 m ² / g)
A wallpaper was obtained in the same manner as in Example 3 except that the silica was Silica 5: Mizukasil P-603, manufactured by Mizusawa Chemical Co., Ltd. (specific surface area 40 m ² / g, particle size 3.0 μm).
[Comparative Example 2] (PV ratio> 1)
Wallpaper was obtained in the same manner as in Example 4 except that the binder component solid content was 9 parts by mass and the silica was 11 parts by mass.
[Comparative Example 3] (without silica)
Wallpaper was obtained in the same manner as in Example 1 except that no silica was added to the intermediate layer coating solution.
Wallpaper was obtained in the same manner as in Example 1.
[Comparative Example 4] (no intermediate layer)
Wallpaper was obtained in the same manner as in Example 1 except that no intermediate layer was provided.

(2) Evaluation of wallpaper (i) Initial photocatalytic activity The initial photocatalytic activity of each wallpaper was measured as follows.
The wallpaper test piece (10 cm × 10 cm) was subjected to an initialization treatment with black light of 1.5 mW / cm ² for 8 hours, and then inserted into a 5 liter (L) Tedlar bag. Using a 99.5% acetaldehyde solution and synthetic air ((nitrogen: oxygen) volume ratio: 4/1, RH 50%), a gas having an acetaldehyde concentration of 20 ppm was prepared, and 1 liter (L) was fed into the Tedlar bag.
Then, the fluorescent lamp 6000lx was irradiated and the decomposition test of acetaldehyde was implemented. The time-dependent change of the acetaldehyde concentration in the Tedlar bag was measured by gas chromatography. The evaluation was “4” at a concentration of 5 ppm or less at 6 hr, “3” if it was 10 ppm or less, “2” if it was 15 ppm or less, “1” if it exceeded 15 ppm, and 2 or more as having photocatalytic activity.
(Ii) Contamination resistance Contaminants (neutral detergent, soy sauce, coffee, crayon, aqueous pen) are each dropped on gauze placed on a sample, or a straight line is drawn, and water and neutral detergent are used after 24 hours. Wiped off. As a result of visual evaluation, “X” was indicated when there was a product that could not be wiped off, and “◯” was indicated when wiping was possible.

The evaluation results of Examples 1 to 6, Reference Example 1 and Comparative Examples 1 to 4 are shown in Table 1 below.

1 Wallpaper 2 Backing sheet layer 3 Non-foamed resin layer B
4 Foamed resin layer 5 Non-foamed resin layer A
6 wallpaper substrate 7 pattern layer 8 intermediate layer 9 visible light photocatalyst layer

Claims (5)

A wallpaper having a wallpaper substrate including a foamed resin layer, an intermediate layer, and a visible light photocatalyst layer in this order,
The intermediate layer contains at least silica particles and a binder;
When the BET specific surface area of the silica particles is S, S is 140 m ² / g or more,
When the mass of the silica particles is P and the mass of the binder is V, P / V is 1 or less,
Furthermore, the wallpaper which satisfy | fills following formula (2).
S / (1 + V / P) ≧ 45 m ² / g (2)   The wallpaper according to claim 1, wherein the wallpaper base material further includes a non-foamed resin layer A on a surface of the foamed resin layer on the intermediate layer side.   The wallpaper according to claim 1 or 2, wherein the wallpaper base material further includes a non-foamed resin layer B on a surface opposite to the intermediate layer of the foamed resin layer.   The wallpaper in any one of Claims 1-3 whose resin contained in the said foamed resin layer is an olefin resin. It is a laminate before foaming of a wallpaper having a pre-foaming wallpaper substrate including an unfoamed resin layer, an intermediate layer, and a visible light photocatalyst layer in this order,
The intermediate layer contains at least silica particles and a binder;
When the BET specific surface area of the silica particles is S, S is 140 m ² / g or more,
When the mass of the silica particles is P and the mass of the binder is V, P / V is 1 or less,
Furthermore, the laminated body before foaming of the wallpaper which satisfy | fills following formula (2).
S / (1 + V / P) ≧ 45 m ² / g (2)

Images