JP2006089858A - Photocatalytic wallpaper and porous photocatalytic wallpaper derived from the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a porous photocatalytic wallpaper that has excellent decomposition and removal effect on environmental pollution substances, stain resistant effect and their durability and a photocatalytic wallpaper being its precursor. <P>SOLUTION: The photocatalytic wallpaper carries a photocatalyst (a) and a complex compound BC obtained by combining with an organic component B of photocatalyst affinity photocatalyst, which has strong affinity for the photocatalyst and is decomposed by photocatalytic action with a slightly decomposable component C that is not readily decomposed by photocatalytic action. The porous photocatalytic wallpaper is derived from the photocatalytic wallpaper. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

The present invention relates to a photocatalyst wallpaper and a porous photocatalyst wallpaper that exhibits excellent photocatalytic activity over a long period of time derived therefrom.
Specifically, the present invention is useful for the decomposition, removal and sterilization of various malodorous gases, harmful gases, harmful compounds, etc. generated in daily life over a long period of time, fungicides, etc. The present invention relates to a porous photocatalyst wallpaper that can be decomposed and maintain its aesthetic appearance.

  Along with the remarkable improvement of the housing environment, and the enforcement of the Housing Quality Assurance Promotion Act, there is a strong demand for a longer life for buildings and therefore a longer life for interior components. In particular, in recent housing models, it is not easy to maintain and maintain the atrium space from the entrance part and the wall surface of the large space part of the living room and dining room that follows the original quality. In addition, in a room such as a general house, mold may occur on the wall surface due to moisture or the like. Conventionally, in such a case, the humidity itself causing the generation of mold is removed by the air conditioning equipment, or a wallpaper made of a synthetic resin film kneaded with a mold preventive agent is attached to the wall surface to prevent the generation of mold. However, there is a limit to dehumidification using air-conditioning equipment, which is not very effective for preventing the generation of mold, and the use of wallpaper made of a synthetic resin film kneaded with an antifungal agent can prevent the generation of mold. However, the fungicides are problematic because they cause adverse effects on the human body, such as causing allergic symptoms and poor physical condition. In a room such as a general house, there are many things causing generation of bad odor such as cigarette smoke, pet animals, and garbage.

Conventionally, as a method of deodorizing such malodors, a method of chemically reacting malodorous substances and chemicals, a method of masking malodorous substances with a fragrance, a method of adsorbing malodorous substances with an adsorbent such as activated carbon or zeolite, or There has been a method of combining these methods. Various such deodorization methods are used, but both chemicals and fragrances are almost impossible to regenerate after reacting with malodorous substances. Also, in the case of the adsorbent, the deodorization performance is significantly reduced when the adsorption capacity is saturated. Therefore, in any method, there is a problem that it must be periodically replaced with a new one.
In recent years, many wallpaper having a coating layer made of a paint containing a photocatalyst such as titanium dioxide has been proposed for these problems. Such wallpaper not only protects interior members and contributes to a longer life, but the photocatalyst also exhibits antibacterial performance, deodorization, and antifouling performance that is effective even with indoor fluorescent lamps and incandescent bulbs, etc. It is also effective for environmental purification of living spaces.

  Conventionally, as a photocatalyst-containing wallpaper coating, a paint containing a photocatalyst, an inorganic binder, an inorganic filler, an organic binder such as a synthetic resin, and the like has been proposed. For example, JP-A-10-183023 discloses emulsion polymerization of a carbonyl group-containing α, β-ethylenically unsaturated monomer such as diacetone (meth) acrylamide and other ethylenically unsaturated monomers as necessary. Copolymer emulsion comprising, hydrazine derivatives such as adipic acid dihydrazide, succinic acid dihydrazide, citric acid trihydrazide, naphthoic acid tetrahydrazide, pigment components such as activated alumina, activated clay, zeolite and photocatalyst such as titanium dioxide The paint is described. Further, for example, JP-A-10-251565 discloses a photocatalyst such as titanium dioxide, a carboxy group-containing polymerizable unsaturated monomer such as (meth) acrylic acid, maleic acid, and maleic anhydride, and methyl (meth) acrylate, Photocatalyst-containing paints containing copolymers with other polymerizable unsaturated monomers such as ethyl (meth) acrylate and styrene are described. However, these methods have a problem in terms of durability because the organic binder used for imparting adhesion between the photocatalyst and the wallpaper base material is decomposed by the photocatalytic action. In addition, when a large amount of organic binder is used to increase adhesion, the contact between the photocatalyst and the odor-causing substance or contamination-causing substance is hindered, and there is a problem that the deodorization and antifouling performance required for the photocatalyst is lowered. It was.

  As means for solving these problems, for example, in JP-A-2001-341217, photocatalyst fine particles are adhered to the surface of a synthetic resin sheet so that the photocatalyst fine particles are exposed on the surface of the synthetic resin. After the photocatalyst particles are pushed into the synthetic resin sheet or the thermoplastic resin film kneaded with the photocatalyst fine particles is laminated to the wallpaper substrate, the back surface of the thermoplastic film is heated and melted to expose a part of the photocatalyst fine particles on the film surface. A suggested wallpaper is proposed. As a result, the opportunity for the photocatalyst particles to come into direct contact with odors or contamination-causing substances is increased, and the deodorization and antifouling effects are increased, but the problem of degradation and degradation of the synthetic resin by the photocatalyst particles remains unsolved. Further, for example, JP-A-10-180943 includes a photocatalyst such as titanium dioxide and a photocatalyst containing an inorganic binder such as water glass, aluminosilicate, alkali metal silicate, phosphate, colloidal silica, and colloidal alumina. The paint is described. However, in this method, since the inorganic binder covers the surface of titanium dioxide, there is an effect of suppressing the decomposition of the organic wallpaper base material, but the anti-odor and antifouling functions originally expected for titanium dioxide are lowered. However, it is not an essential problem solution. Further, for example, in JP-A-10-264283, photocatalyst such as titanium dioxide, thermoplastic resin (acrylic resin, styrene-acrylic copolymer, styrene-butadiene copolymer, ethylene-vinyl acetate copolymer, etc.) Photocatalyst-containing paints including water-based emulsions, film-forming inorganic substances (colloidal silica, colloidal alumina, saponite, hectorite, kaolinite, sepiolite, etc.), vaniders such as colloidal silica composite thermoplastic polymer emulsions, etc. JP-A-11-279446 contains an inorganic binder such as colloidal silica, alumina sol, saponite, hectorite and sepiolite, a photocatalyst such as titanium dioxide, polyvinyl alcohol, and an organic binder such as aqueous latex and aqueous emulsion. You Photocatalyst-containing paints are described. However, in any of these methods, problems such as decomposition of the organic resin used as a binder component by titanium dioxide or decomposition of the base material itself when an organic substance is used as the base material of the wallpaper are solved. Not.

In order to prevent these problems, for example, Japanese Patent Application Laid-Open No. 2001-159090 discloses a method in which a protective layer is interposed between the photocatalyst-containing layer and the wallpaper substrate in order to prevent the above-described degradation of the wallpaper substrate due to the photocatalyst. Although this method has been proposed, the problem that the coating process is complicated and the workability is poor and the deterioration of the coating film when an organic resin is used as a binder is unsolved.
For the reasons described above, there has long been a desire for a wallpaper provided with a photocatalyst-containing coating film that does not require a protective layer, has self-cleaning properties, is superior in deodorization and antifouling performance, and has long-term durability.
JP-A-10-183023 Japanese Patent Laid-Open No. 10-251565 JP 2001-341217 A Japanese Patent Laid-Open No. 10-180943 JP-A-10-264283 JP-A-11-279446 Japanese Patent Laid-Open No. 2001-159099

An object of this invention is to provide the functional wallpaper to which the outstanding deodorizing and antifouling effect by a photocatalyst was provided, without requiring a complicated process.
Specifically, it is to provide a functional wallpaper having excellent durability without requiring a base material protective layer.

As a result of intensive studies, the present inventors have made the present invention.
That is, the present invention is as follows.
1. A composite compound (BC) in which a photocatalyst (a) has a strong affinity for the photocatalyst, and a photocatalytic affinity organic component (B) that is decomposed by photocatalysis and a hardly decomposable component (C) that is not easily decomposed by photocatalysis A photocatalyst wallpaper characterized by being supported.
2. A photocatalytic wallpaper comprising a modified photocatalyst (A) obtained by modifying a photocatalyst (a) with the composite compound (BC) of Invention 1.
3. The photocatalytic wallpaper according to any one of Inventions 1 and 2, wherein the photocatalytic affinity organic component (B) has a polyoxyalkylene group.
4). The photocatalyst wallpaper according to any one of Inventions 1 to 3, wherein the photocatalyst (a) is a visible light responsive photocatalyst.
5. The photocatalytic wallpaper according to any one of Inventions 1 to 4, wherein a sensitizing dye is supported.
6). A porous structure in which the BET surface area per gram of the photocatalyst (a) is increased by 10 m ² or more by irradiating the photocatalyst wallpaper of any one of the inventions 1 to 4 with light having energy higher than the band gap energy of the supported photocatalyst (a). Sex photocatalytic wallpaper.
7). A porous photocatalyst wallpaper in which the BET surface area per gram of photocatalyst (a) is increased by 10 m ² or more by irradiating the photocatalyst wallpaper of the invention 5 with the absorbed light of the supported sensitizing dye.
8). The porous photocatalytic wallpaper according to any one of Inventions 6 and 7, which has an organic substance decomposing activity.
9. The porous photocatalytic wallpaper according to any one of Inventions 6 and 7, which has antibacterial performance.
10. The porous photocatalyst wallpaper according to any one of Inventions 6 and 7, which has an antifungal property.

  From the photocatalyst wallpaper of the present invention, it is excellent as an environmental purification material (degradation of harmful substances such as sick house causative substances and tobacco dust), antifouling materials (antibacterial, antifungal, etc.) and easy-to-clean materials by simple operation of light irradiation. It is possible to obtain a porous photocatalyst wallpaper with good durability and good durability.

Hereinafter, the present invention will be described in detail.
The photocatalyst wallpaper of the present invention comprises a photocatalyst (a), a photocatalytic affinity organic component (B) that has a strong affinity for the photocatalyst and is decomposed by photocatalysis, and a hardly decomposable component (C) that is not easily decomposed by photocatalysis. The bonded composite compound (BC) is supported. In such a photocatalyst wallpaper, the photocatalytic affinity organic component (B) adjacent to the photocatalyst (a) is efficiently and selectively decomposed by light irradiation, and the photocatalyst (a) is present due to the presence of the hardly decomposable component (C). In order to prevent the decomposition of the wallpaper, the porous photocatalyst wallpaper is excellent in environmental purification effect and antifouling effect with little change in the structure of the appearance and increased BET surface area.

In addition, in the photocatalyst wallpaper of the present invention, the composite compound (BC) carrying the modified photocatalyst (A) obtained by modifying the photocatalyst (a) has a very large increase in BET surface area due to the light irradiation, It is most preferable because it is excellent in the uniformity of generated pores.
Here, the modification treatment means immobilizing the composite compound (BC) on the surface of the photocatalyst (a). Immobilization of the composite compound (BC) on the surface of the photocatalyst particles is due to van der Waals force (physical adsorption), Coulomb force or chemical bonding. In particular, modification using a chemical bond is preferable because the interaction between the composite compound (BC) and the photocatalyst is strong and the composite compound (BC) is firmly immobilized on the surface of the photocatalyst particles.

  In the present invention, the photocatalyst (a) refers to a substance that causes an oxidation or reduction reaction by light irradiation. That is, when light (excitation light) with an energy larger than the energy gap between the conduction band and the valence band (ie, a short wavelength) is irradiated, excitation (photoexcitation) of electrons in the valence band occurs, resulting in conduction. It is a substance that can generate electrons and holes. At this time, various chemical reactions are performed using the reducing power of electrons generated in the conduction band and / or the oxidizing power of holes generated in the valence band. Can do. For example, oxidative decomposition reaction of various organic substances can be mentioned. Therefore, if this photocatalyst is supported on the surface of the wallpaper, harmful substances existing indoors and various organic substances (pollutants) attached to the wallpaper can be oxidatively decomposed using light energy, and the air It becomes possible to purify and maintain the aesthetics of the surface of the wallpaper.

  In the present invention, the photocatalyst (a) useful for making the wallpaper surface photocatalytically active preferably has a band gap energy of 1.2 to 5.0 eV, more preferably 1.5 to 4.1 eV. The semiconductor compound can be mentioned. If the band gap energy is less than 1.2 eV, the ability to cause oxidation and reduction reaction by light irradiation is very weak, which is not preferable. If the band gap energy is larger than 5.0 eV, the energy of light necessary for generating holes and electrons becomes very large, which is not preferable.

Examples of the photocatalyst (a) include TiO ₂ , ZnO, SrTiO ₃ , CdS, GaP, InP, GaAs, BaTiO ₃ , BaTiO ₄ , BaTi ₄ O ₉ , K ₂ NbO ₃ , Nb ₂ O ₅ , Fe ₂ O ₃ , Ta ₂ O ₅ , K ₃ Ta ₃ Si ₂ O ₃ , WO ₃ , SnO ₂ , Bi ₂ O ₃ , BiVO ₄ , NiO, Cu ₂ O, SiC, MoS ₂ , InPb, RuO ₂ , CeO ₂ , Ta ₃ N _{5 and the} like, and further a layered oxide having at least one element selected from Ti, Nb, Ta, and V (for example, JP 62-74452 A, JP 2-172535 A, JP-A-7-24329, JP-A-8-89799, JP-A-8-89800, JP-A-8-89804, JP-A-8-198061 JP-9-248465, JP-A No. 10-99694 and JP-reference Publication No. Hei 10-244165) can be mentioned.
Of these photocatalysts (a), TiO ₂ (titanium oxide) is preferable because it is harmless and has excellent chemical stability. Any of anatase, rutile, and brookite can be used as titanium oxide.

  When a visible light responsive photocatalyst capable of expressing photocatalytic activity and / or hydrophilicity by irradiation with visible light (for example, a wavelength of about 400 to 800 nm) is selected as the photocatalyst (a) used in the present invention, The derivatization of the inventive photocatalytic wallpaper into a porous photocatalytic wallpaper also occurs with visible light. The generated porous photocatalyst wallpaper is preferable because it can sufficiently exhibit an environmental purification effect and an antifouling effect even in a place where ultraviolet rays such as indoors are not sufficiently irradiated. The bandgap energy of these visible light responsive photocatalysts is preferably 1.2 to 3.1 eV, more preferably 1.5 to 2.9 eV, and still more preferably 1.5 to 2.8 eV.

Any visible light responsive photocatalyst can be used as long as it exhibits photocatalytic activity and / or hydrophilicity with visible light. For example, TaON, LaTiO ₂ N, CaNbO ₂ N, LaTaON ₂ , and CaTaO ₂ N can be used. Oxynitride compounds such as JP-A-2002-66333, oxysulfide compounds such as Sm ₂ Ti ₂ S ₂ O ₇ (see JP-A-2002-233770, for example), and nitriding such as Ta ₃ N ₅ Compounds, oxides containing metal ions in the d10 electronic state such as CaIn ₂ O ₄ , SrIn ₂ O ₄ , ZnGa ₂ O ₄ , and Na ₂ Sb ₂ O ₆ (see, for example, JP 2002-59008 A), ammonia and urea In the presence of nitrogen-containing compounds such as titanium oxide precursors (titanium oxysulfate, titanium chloride, alkoxytita Etc.) or nitrogen-doped titanium oxide obtained by firing high surface titanium oxide (for example, JP 2002-29750 A, JP 2002-87818 A, JP 2002-154823 A, JP 2001-207082 A). See), sulfur-doped titanium oxide obtained by firing titanium oxide precursors (titanium oxysulfate, titanium chloride, alkoxytitanium, etc.) in the presence of sulfur compounds such as thiourea, hydrogen plasma treatment or under vacuum Or oxygen-deficient titanium oxide obtained by heat treatment (for example, see JP-A-2001-98219), and further, photocatalyst particles are treated with a halogenated platinum compound (for example, JP-A-2002-239353). And treatment with tungsten alkoxide (see JP 2001-286755 A). The surface-treated photocatalyst obtained by this can be mentioned suitably.

Among the visible light responsive photocatalysts, oxynitride compounds and oxysulfide compounds have a large photocatalytic activity by visible light and can be used particularly preferably.
The oxynitride compound that can be particularly preferably used in the present invention is an oxynitride containing a transition metal, and preferably has a high photocatalytic activity, and the transition metal is preferably selected from the group consisting of Ta, Nb, Ti, Zr, and W. The oxynitride is characterized in that it further comprises at least one element selected from the group consisting of alkali, alkaline earth and group IIIB metals. The oxynitride further includes at least one metal element selected from the group consisting of Ca, Sr, Ba, Rb, La, and Nd.

Examples of oxynitride containing the transition _{metal, LaTiO 2 N, La v Ca} w TiO 2 N (v + w = 3), La v Ca w TaO 2 N (v + w = 3), LaTaON 2, CaTaO 2 N, General formula AMO _x N _y such as SrTaO ₂ N, BaTaO ₂ N, CaNbO ₂ N, CaWO ₂ N, SrWO ₂ N (A = alkali metal, alkaline earth metal, group IIIB metal; M = Ta, Nb, Ti, Zr, W; x + y = 3), TaON, NbON, WON, Li ₂ LaTa ₂ O ₆ N, and the like. Among these, LaTiO ₂ N, La _v Ca _w TiO ₂ N (v + w = 3), La _v Ca _w TaO ₂ N (v + w = 3), and TaON are preferable because the photocatalytic activity in visible light is very large.

The oxysulfide compound that can be used particularly preferably in the present invention is an oxysulfide containing a transition metal, and has a high photocatalytic activity, and the transition metal is preferably selected from the group consisting of Ta, Nb, Ti, Zr, and W. Oxysulfide, characterized in that it is at least one, more preferably at least one element selected from the group consisting of alkali, alkaline earth and group IIIB metals More preferably, the oxysulfide is characterized by further containing a rare earth element.
Examples of the oxysulfide containing the transition metal include Sm ₂ Ti ₂ S ₂ O ₅ , Nd ₂ Ti ₂ S ₂ O ₅ , La ₆ Ti ₂ S ₈ O ₅ , Pr ₂ Ti ₂ S ₂ O ₅ , and Sm _3. NbS ₃ O _{4 and the} like can be mentioned. Among these, Sm ₂ Ti ₂ S ₂ O ₅ and Nd ₂ Ti ₂ S ₂ O ₅ are very preferable because of their very high photocatalytic activity under visible light.

Further, as a photocatalyst (a) in the present invention, a metal-modified apatite obtained by ion-exchange of a part of metal ions in an apatite crystal with a metal ion of a metal oxide having a photocatalytic action (for example, titanium ion) 2000-327315 public information) can also be suitably used because of its excellent adsorption characteristics against bacteria, viruses, dirt and the like.
Furthermore, the above-mentioned photocatalyst (a) is preferably added or fixed with a metal such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe and / or an oxide thereof, or coated with porous calcium phosphate or the like. It can also be used as a photocatalyst (see, for example, JP-A-10-244166).
The crystal particle size (primary particle size) of the photocatalyst (a) is preferably 1 to 400 nm, and more preferably a photocatalyst of 1 to 50 nm is suitably selected.

In the present invention, the composite compound (BC) is, for example, a hardly decomposable component (C) having a photocatalytic affinity organic component (B) as a functional group, or a graft of a photocatalytic affinity organic component (B) and a hardly decomposable component (C). A polymer, a block polymer, a random polymer, etc. can be illustrated.
Examples of the photocatalytic affinity organic component (B) in the present invention include, for example, a hydroxyl group present on the surface of the photocatalyst particles and a polyoxyalkylene group having affinity with physically adsorbed water, polyvinyl alcohol, modified polyvinyl alcohol, partially saponified polyvinyl acetate, and acrylic. Acid polymer (including copolymer), methacrylic acid polymer (including copolymer), acrylamide polymer (including copolymer), styrene sulfonic acid polymer (including copolymer), vinylpyrrolidone heavy Examples thereof include a combination (including a copolymer), polyallylamine, carboxymethylated cellulose, and carboxymethylated nitrocellulose.

Of these, polyoxyalkylene groups are preferred because they are generally excellent in affinity for photocatalysts and can be easily decomposed by photocatalytic action.
In the present invention, the hardly decomposable component (C) preferably has a mass loss of 5% or less when irradiated with black light for 5 hours so that the ultraviolet intensity of the photocatalyst wallpaper surface is 7 mW / cm ^2. Etc.
Specific examples of the hardly decomposable component (C) include inorganic compounds such as water glass, silicone resins, and fluorine resins.

  In the present invention, examples of the silicone resin include dimethylpolysiloxane, methylphenylpolysiloxane, methylhydrogenpolysiloxane, alkoxy group-containing silicone oil, silanol group-containing silicone oil, vinyl group-containing silicone oil, octamethylcyclotetra Silicone oils such as siloxane and decamethylcyclopentasiloxane, alcohol-modified silicone, alkyl-modified silicone, modified silicones such as fluoroalkyl-modified silicone, (alkyl) alkoxy such as tetraethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane Silane monomers, oligomers and polymers, vinyltrichlorosilane, vinyltrimethoxysilane, γ-aminopropyltrimethoxysilane, etc. Silane coupling agents and reaction products thereof, silicone surfactants or the like. These silicones can be used alone or in combination of two or more.

  In the present invention, examples of the fluororesin include 2-perfluorooctylethyltrimethoxysilane, 2-perfluorooctylethyltriethoxysilane, 2-perfluorooctylethylmethyldimethoxysilane, trifluoromethylethyltrimethoxysilane, Fluoroalkylsilanes such as trifluoromethylethyltriethoxysilane and their polycondensates, PTFE and polyvinylidene fluoride, and also fluoroolefins and monomers such as Nafion resin, chlorotrifluoroethylene and tetrafluoroethylene (vinyl ether, vinyl) And copolymers with esters and allyl compounds). These fluororesins can be used alone or in combination of two or more.

In the present invention, preferred examples of the composite compound (BC) include a Si compound represented by the following formula (1) and a fluorine-based resin having a polyoxyalkylene group.
_{R x X y Q z SiO (} 4-x-y-z) / 2 (1)
(In the formula, each R is independently a linear or branched alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched carbon number having 1 to 30 carbon atoms. It represents a group consisting of one or more selected from a fluoroalkyl group, a linear or branched alkenyl group having 2 to 30 carbon atoms, and a phenyl group.

Q represents a group containing a polyoxyalkylene group represented by the following formula (2).
— (O) _a R ¹ O (R ² O) _b R ³ (2)
(Wherein R ¹ and R ² each independently represents a linear or branched alkylene group having 1 to 10 carbon atoms. R ³ represents a hydrogen atom, a linear or branched carbon group having 1 to 30 carbon atoms. An alkyl group, a cycloalkyl group having 5 to 20 carbon atoms, or a linear or branched alkenyl group having 2 to 30 carbon atoms and a phenyl group, a is 0 or 1, and b is an integer of 1 to 100 Represents.)

X represents each independently a hydrogen atom, a hydroxyl group, an alkoxy group having 1 to 20 carbon atoms, an acyloxy group having 1 to 20 carbon atoms, an aminoxy group, an oxime group having 1 to 20 carbon atoms, or a halogen atom. Further, 0 ≦ x <4, 0 ≦ y <4, 0 <z <4, and 0 <(x + y + z) <4. )
In the photocatalyst wallpaper of the present invention, a system in which the photocatalyst (a) and the composite compound (BC) are supported at a mass ratio (A) / (BC) = 0.001 to 1000 is preferable.

In the present invention, the composite compound (BC) useful for modifying the photocatalyst (a) includes, for example, a Si—H group, a hydrolyzable silyl group (alkoxysilyl group, hydroxysilyl group, halogenated silyl group, acetoxy group). Suitable examples include those having reactivity with the photocatalyst particles (a) such as silyl group, aminoxysilyl group, etc.), epoxy group, acetoacetyl group, thiol group, acid anhydride group and the like.
In the present invention, the modification treatment of the photocatalyst (a) with the composite compound (BC) is preferably performed by mass ratio of the photocatalyst (a) and the composite compound (BC) in the presence or absence of water and / or an organic solvent. (A) / (BC) = 1/99 to 99.9 / 0.1, more preferably (a) / (BC) = 10/90 to 99/1, preferably at 0 to 200 ° C. Can be implemented.
In the present invention, when a compound containing a Si—H group is used as the composite compound (BC) used for modification of the photocatalyst (a), the particle surface of the photocatalyst (a) can be modified very efficiently. preferable.

As a preferable example of the composite compound (BC) having the Si—H group, for example, a Si—H group-containing compound (b1) represented by the formula (3) and / or the formula (4) can be exemplified.
_{H- (R 2 SiO) m -SiR} 2 -Q (3)
(In the formula, R and Q are as defined in formula (1). M is an integer, and 0 ≦ m ≦ 1000.)
(RHSiO) _p (R ₂ SiO) _q (RQSiO) _r (R ₃ SiO _1/2 ) _s (4)
(Wherein R and Q are as defined in formula (1)).
p is an integer of 1 or more, q and r are 0 or an integer of 1 or more, (p + q + r) ≦ 10000, and s is 0 or 2. However, when (p + q + r) is an integer of 2 or more and s = 0, the H silicone compound is a cyclic silicone compound, and when s = 2, the H silicone compound is a chain silicone compound. )

  In the present invention, the modification treatment of the photocatalyst (a) with the Si—H group-containing compound (b1) represented by the formula (3) and / or the formula (4) is performed in the presence or absence of water and / or an organic solvent. Below, the photocatalyst (a) and the Si—H group-containing compound (b1) are preferably mass ratio (a) / (b1) = 1/99 to 99.9 / 0.1, more preferably (a) / (B1) = A ratio of 10/90 to 99/1, preferably by mixing at 0 to 200 ° C.

By this modification operation, hydrogen gas is generated from the mixed solution, and when the photocatalyst sol is used as the photocatalyst (a), an increase in the average particle diameter is observed.
When titanium oxide is used as the photocatalyst (a), a decrease in Ti—OH group is observed as a decrease in absorption or disappearance of 3630 to 3640 cm ^{−1 in} the IR spectrum by the above modification operation.
Accordingly, the modified photocatalyst (A) modified with the Si—H group-containing compound (b1) represented by the formula (3) and / or the formula (4) is the Si—H group-containing compound (b1). It can be predicted that some kind of interaction is caused between the two and the photocatalyst (a) due to a chemical reaction.
In fact, the modified photocatalyst (A) thus obtained is very excellent in dispersion stability, transparency, chemical stability, durability and the like with respect to the solvent.

  In the photocatalyst wallpaper of the present invention, the sensitizing dye-supported one increases the BET surface area by light irradiation of the photocatalyst wallpaper described later, even if the photocatalyst (a) responds only to ultraviolet rays such as titanium oxide. (Generation of porous photocatalyst wallpaper) is caused by light in the visible light region, and the generated porous photocatalyst wallpaper can exhibit an environmental purification effect and an antifouling effect even in a place where ultraviolet rays such as indoors are not sufficiently irradiated. It is preferable because it is possible.

  The sensitizing dye that can be used in the present invention refers to various metal complexes and organic dyes having absorption in the visible light region. Examples of such sensitizing dyes include xanthene dyes, oxonol dyes, cyanine dyes, merocyanine dyes, rhodocyanine dyes, styryl dyes, hemicyanine dyes, merocyanine dyes, phthalocyanine dyes (metal complexes). ), Porphyrin dyes (including metal complexes), triphenylmethane dyes, perylene dyes, coronene dyes, azo dyes, nitrophenol dyes, and JP-A 1-220380 and patent application publications Examples thereof include a complex of ruthenium, osmium, iron, and zinc described in JP-A-5-504023 and a metal complex such as ruthenium red.

Among these sensitizing dyes, those having absorption in a wavelength region of 400 nm or more and having the lowest empty orbital energy level (excited state redox potential) higher than the energy level of the photocatalytic conduction band are preferably selected. Is done. Such sensitizing dyes can be selected by measuring light absorption spectra in the infrared, visible and ultraviolet regions, measuring redox potentials by electrochemical methods, calculating energy levels using molecular orbital methods, and It can be carried out depending on the presence / absence of electromotive force or the efficiency of the light irradiation of a Gratzel-type wet solar cell prepared with a photocatalyst and a spectral sensitizing dye.
Examples of preferred sensitizing dyes from such a viewpoint include compounds having a 9-phenylxanthene skeleton (such as fluorescein, eosin Y, eosin B, rose bengal, rhodamine B, phloxine, pyrogallol, uranin, acid red, etc.) Examples thereof include a ruthenium complex containing a 2,2-bipyridine derivative as a ligand, ruthenium red, a compound having a perylene skeleton, a phthalocyanine metal complex, and a porphyrin metal complex.

In the photocatalyst wallpaper of the present invention, when an adsorbent deodorant supported is selected, the deodorizing effect of the porous photocatalyst wallpaper obtained by light irradiation is imparted with a rapid effect, and the deodorizing function can be expressed more efficiently. Therefore, it is preferable.
The adsorptive deodorant used in the present invention refers to, for example, a physical adsorbent, a chemical adsorbent, a physicochemical adsorbent, etc., which adsorbs malodorous substances and exerts a deodorizing effect, and is colorless or white. Non-toxic materials are preferred. Examples of such adsorptive deodorants include zeolite (hydrophilic and hydrophobic), activated clay, acidic clay, hydrotalcite, sepiolite, silica-alumina, silica-magnesia, composition of silica and zinc oxide, activated carbon, and the like. Examples of physical adsorbents include Absenz (trade name, manufactured by Union Showa Co., Ltd.), and examples of chemical adsorbents include Schueklens (trade name, manufactured by Rasa Industrial Co., Ltd.) and Kyoward (manufactured by Kyowa Chemical Industry Co., Ltd.). Etc.) are commercially available. These can be used alone or in combination of two or more.

Further, in the photocatalyst wallpaper of the present invention, an adsorption-type deodorant-photocatalyst-modified modified photocatalyst (A) modified with the above-mentioned composite compound (BC) in the presence of the photocatalyst (a) and the adsorption-type deodorant (A) It is very preferable to use ') because the above-described synergistic effect of the adsorption deodorant and the photocatalyst can be efficiently expressed.
In the photocatalyst wallpaper of the present invention, when an antibacterial metal immobilized is selected, the antibacterial and antifungal effect of the porous photocatalyst wallpaper obtained by light irradiation is given to the antibacterial and antifungal functions, and the antibacterial and antifungal functions are provided. It is preferable because it can be expressed more efficiently. In other words, antibacterial metals are known to have antibacterial and strong antibacterial and antifungal effects due to photocatalysis when exposed to light. Can be combined with antibacterial and antifungal effects of antibacterial metals in the dark.

Examples of the antibacterial metal that can be used in the present invention include metals such as silver, copper, platinum, gold, palladium, nickel, cobalt, rhodium, niobium, tin, and / or oxides thereof and mixtures thereof. Can do. Among these, it is preferable to use silver or copper.
The antibacterial metal can be used by simply adding to or immobilizing the photocatalyst (a) (preferably the modified photocatalyst (A)). Examples of the method for immobilizing the antibacterial metal on the photocatalyst (a) (preferably the modified photocatalyst (A)) include a method of physically adsorbing the antibacterial metal, a method of immobilization by a photoreduction method or heat treatment. Alternatively, the antibacterial metal can be immobilized on the photocatalyst (a) by physical adsorption, photoreduction, heat treatment or the like, and then modified by the above-described method using the composite compound (BC).

The photocatalyst wallpaper of the present invention contains a resin (F) for the photocatalyst (a) of the present invention for the purpose of assisting the adhesion of the photocatalyst (a) (preferably the modified photocatalyst (A)) to the wallpaper. Further, it is possible to carry a material having a mass ratio (a) / (F) = 1/99 to 99/1, preferably (a) / (F) = 10/90 to 90/10.
As the resin (F) that can be supported on the photocatalyst wallpaper of the present invention, all synthetic resins and natural resins can be used.
As the synthetic resin, thermoplastic resin and curable resin (thermosetting resin, photocurable resin, moisture curable resin, etc.) can be used. For example, acrylic resin, methacrylic resin, fluororesin, alkyd resin, Amino alkyd resin, vinyl resin, polyester resin, styrene-butadiene resin, polyolefin resin, polystyrene resin, polyketone resin, polyamide resin, polycarbonate resin, polyacetal resin, polyether ether ketone resin, polyphenylene oxide resin, polysulfone resin, polyphenylene sulfone resin Polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, phenol resin, melamine resin, epoxy resin, urethane resin, silicone-acrylic resin, silicone resin, water glass and zirconi Beam compounds include inorganic compounds such as titanium peroxide.

Examples of the natural polymer include cellulose resins such as nitrocellulose, isoprene resins such as natural rubber, protein resins such as casein, and starch.
In addition, the photocatalyst wallpaper of the present invention carries a pigment, a cross-linking agent, a filler, a dispersant, a light stabilizer, a wetting agent, a plasticizer, a dye, an antiseptic, and the like according to each purpose, if necessary. be able to.
The photocatalyst wallpaper of the present invention is, for example, the above-described components that can be supported on a photocatalyst wallpaper such as a photocatalyst (a) and a composite compound (BC) (preferably a modified photocatalyst (A)) or, if necessary, a sensitizing dye, And by treating the wallpaper with a photocatalyst composition (D) containing a solvent and the like. Moreover, it can also obtain by creating a wallpaper from the wallpaper base material processed with this photocatalyst composition (D).

  Examples of the solvent that can be suitably used for the photocatalyst composition (D) include water, alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol, and methanol, and aromatics such as toluene and xylene. Aliphatic hydrocarbons such as hexane, cyclohexane and heptane, esters such as ethyl acetate and n-butyl acetate, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, Examples include amides such as dimethylacetamide and dimethylformamide, halogen compounds such as chloroform, methylene chloride, and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more of these.

  In the present invention, the wallpaper or wallpaper base material is treated with the photocatalyst composition (D), for example, after the photocatalyst composition (D) is applied or impregnated on the wallpaper or wallpaper material, dried and then preferably 20 ° C. if desired. It can be carried out by performing heat treatment, ultraviolet irradiation, etc. at ˜500 ° C., more preferably at 40 ° C. to 250 ° C. Examples of the coating method include spraying, flow coating, roll coating, brush coating, dip coating, padding, casting, sponge coating, knife coating, gravure coating, screen coating, Examples of the method include engraving roll coating and flexo coating.

At this time, the supported amount of the photocatalyst (a) in the photocatalyst wallpaper of the present invention is preferably 0.001 to 50% by mass, more preferably 0.1 to 30% by mass with respect to the mass of the wallpaper. When the content of the photocatalyst (a) is less than 0.001% by mass, the photocatalytic activity of the photocatalyst wallpaper is lowered, which is not preferable. Moreover, the film thickness of the formed film is preferably 0.1 to 200 μm, more preferably 0.2 to 20 μm, and still more preferably 0.5 to 10 μm.
In addition, the functional wallpaper of the present invention can be obtained by sticking a film coated with the photocatalyst composition (D) by the above-described method to the surface of the wallpaper base material with an adhesive, a hot-melt adhesion method, a heat seal method, a laminate adhesion. It can be obtained by immobilization by a method or the like. Here, a plastic film such as polyethylene terephthalate, polyester, polyethylene, polypropylene, acrylic resin, and polycarbonate can be suitably used for the film base.

  Typical examples of the wallpaper base material that can be used to obtain the functional wallpaper of the present invention include paper and plastic films. Examples of paper include thin paper, inter-paper reinforced paper, impregnated paper, and synthetic paper. Examples of plastic films include polyethylene terephthalate (PET), polybutylene terephthalate (PBT), and polyethylene-2,6-naphthalate (PEN). Polyesters such as nylon 6, nylon 6,6; polyolefins such as polyethylene (PE) and polypropylene (PP); polyacrylics such as polycarbonate (PC) and polymethyl methacrylate (PMMA). Other examples include fluorine films such as polytetrafluoroethylene (PTFE) and ethylenetetrafluoroethylene (ETFE), and vinyl chloride resins. Moreover, thin plates, such as a metal, a wooden base material, and an inorganic board, can also be used as a base material. Moreover, the pattern may be provided on these wallpaper base materials. Either an organic pigment or an inorganic pigment can be used for the ink forming the pattern, and as the vehicle, an organic resin such as a thermoplastic resin or a thermosetting resin, or a siloxane resin can be used. Furthermore, gravure printing, offset printing, silk printing, flexographic printing, etc. can be used as a painting method.

  Moreover, the said photocatalyst composition (D) of this invention is useful also for the repainting of the degraded wallpaper. These base materials can be subjected to surface treatment in advance for the purpose of adjusting the foundation, improving adhesion, sealing the porous base material, smoothing, patterning, and the like. Examples of the surface treatment for the paper-based substrate include sealing and insect-proofing treatments, and examples of the surface treatment for the plastic-based substrate include blast treatment, chemical treatment, degreasing, flame treatment, oxidation treatment, steam, and the like. Treatment, corona discharge treatment, ultraviolet irradiation treatment, plasma treatment, ion treatment and the like. Examples of the surface treatment for the metal base material include polishing, degreasing, plating treatment, chromate treatment, flame treatment, and coupling treatment. Examples of the surface treatment for the wood base material include polishing, Examples of the surface treatment for the inorganic ceramic base material include polishing, sealing, and patterning, and examples of the surface treatment for the deteriorated coating include: , Kelen and the like.

Application | coating operation by the photocatalyst composition (D) of this invention changes with kinds and states of a base material, and the application | coating method. For example, a primer may or may not be used depending on the application. The type of primer is not particularly limited, and may be any primer as long as it has an effect of improving the adhesion between the substrate and the composition, and is selected according to the type of substrate and the purpose of use. The primer may be used alone or in admixture of two or more, and may be an enamel containing a coloring component such as a pigment or a clear containing no such coloring component. Examples of primer types include alkyd resins, amino alkyd resins, epoxy resins, polyesters, acrylic resins, urethane resins, fluororesins, acrylic silicone resins, acrylic resin emulsions, epoxy resin emulsions, polyurethane emulsions, and polyester emulsions. Can do. These primers can also be provided with various functional groups when adhesion between the substrate and the coating film under severe conditions is required. Examples of such a functional group include a hydroxyl group, a carboxyl group, a carbonyl group, an amide group, an amine group, a glycidyl group, an alkoxysilyl group, an ether bond, and an ester bond. Further, the primer may contain an ultraviolet absorber, an ultraviolet stabilizer and the like.

The photocatalyst wallpaper of the present invention is irradiated with light having an energy higher than the band gap energy of the supported photocatalyst (a) (in the case of containing a sensitizing dye, light including light absorbed by the sensitizing dye). The BET surface area per gram of the photocatalyst (a) is preferably increased by 10 m ² or more. The porous photocatalyst wallpaper thus obtained is very excellent in environmental purification functions (toxic organic matter decomposition, antibacterial performance, antifungal performance, etc.) and antifouling functions (contaminated organic matter decomposition, etc.). These functions become significant when the BET surface area per gram of the photocatalyst (a) is 50 m ² or more, and become remarkable when the increase is 100 m ² or more.

In the present invention, as a light source of light containing energy higher than the band gap energy of the photocatalyst (a) or light absorbed by the sensitizing dye, for example, light sources in the environment such as sunlight, street lamps, nightlights, and more Lighting is available. As general illumination, fluorescent lamps, incandescent lamps, metal halide lamps, black light lamps, xenon lamps, mercury lamps, LEDs, and the like can be suitably used. Illuminance of the light is preferably in 0.001 mW / cm ² or more, more preferably when it 0.01 mW / cm ² or more, further preferably it 0.1 mW / cm ² or more.
The photocatalyst wallpaper of the present invention can be suitably used not only for interior decorations in general homes but also for interior decorations in offices, factories, sports, medical facilities, etc., and has excellent environmental purification functions (toxic organic matter decomposition, antibacterial performance, antifungal performance) Etc.) and antifouling function (decomposition of contaminated organic matter, etc.).

The following examples, reference examples and comparative examples will specifically explain the present invention, but these do not limit the scope of the present invention. In Examples, Reference Examples and Comparative Examples, various physical properties were measured by the following methods.
1. Particle size distribution and number average particle size The sample was diluted with an appropriate solvent so that the photocatalyst content in the sample was 1 to 20% by mass, and measured using a wet particle size analyzer (Nikkiso Microtrac UPA-9230).

2. Weight average molecular weight It calculated | required by the gel permeation chromatography (GPC) using the analytical curve created using the polystyrene sample.
The conditions for GPC are as follows.
Apparatus: Tosoh HLC-8020 LC-3A type chromatograph column: TSKgel G1000H _XL , TSKgel G2000H _XL, and TSKgel G4000H _XL (all manufactured by Tosoh) were used in series.
-Data processing device: CR-4A type data processing device manufactured by Shimadzu Corporation-Mobile phase:
Tetrahydrofuran, flow rate: 1.0 ml / min.
-Sample preparation method It diluted with the solvent used for a mobile phase (concentration was adjusted suitably in the range of 0.5-2 weight%), and used for the analysis.

3. Infrared absorption spectrum The infrared absorption spectrum was measured using an FT / IR-5300 type infrared spectrometer manufactured by JASCO Corporation.
4). BET surface area It measured using the nitrogen adsorption apparatus (autosorb-1-MP) made from Yuasa Ionics.

5. Deodorizing property A sample of 10 cm × 10 cm was put in a 5 l Tedlar bag, and after introducing 3 l of air containing 100 ppm acetaldehyde, the Tedlar bag was sealed. Next, the sample in the Tedlar bag was irradiated with light of a FL20SBLB type black light manufactured by Toshiba Lighting & Technology for 2 hours, and then the amount of acetaldehyde in the Tedlar bag was measured with a gas-tech detector tube.
At this time, the UV intensity measured using a Topcon UVR-2 type UV intensity meter {using a TOPCON UD-36 type light receiving part (corresponding to light with a wavelength of 310 to 400 nm) as the light receiving part} is 1 mW / cm ^2. It adjusted so that it might become.

6). Antifungal test A potato dextrose agar medium previously sterilized was placed in a petri dish and solidified. A test piece (5 cm × 1 cm) was placed on the agar medium. Subsequently, 5 platinum Aspergillus niger (IFO 4414) separately cultured in 10 ml of a 0.005% by mass dioctyl sodium sulfosuccinate aqueous solution was collected, and spores were separated by centrifugation. The fungus with 10 ml of GPLP medium is sprayed onto a petri dish test piece, irradiated with a fluorescent lamp (100 W) at room temperature for 14 days, and then antifungal based on the appearance (visual evaluation) of the sample. Evaluation was made in the following three stages.
○: No growth of mycelia △: Some growth of mycelia is observed ×: Mycelium covers 50-100% of the surface

7). Antibacterial test Put a 5 cm x 1 cm sample in a sterilized plastic petri dish, and add 0.5 ml of the bacterial solution adjusted so that the number of Escherichia coli to about 10 ⁵ cells / ml to each sample in the petri dish. The petri dish was covered with a polyethylene film and shielded from the outside air to prevent the bacterial solution on the specimen sample from drying and the entry of bacteria from the outside. Subsequently, after irradiating the light of FL20SBLB type black light manufactured by Toshiba Lighting & Technology from outside the petri dish for 4 hours, the bacterial solution was washed out from the petri dish, transferred to the medium, and the number of viable bacteria was measured. Based on the death rate, antibacterial properties were evaluated in the following three stages.
Death rate = {(initial viable cell count−viable cell count after test) / initial viable cell count} × 100
○: Death rate 80% or more △: Death rate 20% or more and less than 80% ×: Death rate 20% or less UV intensity is a UVR-2 type UV intensity meter made by Topcon {as a light receiving part, a UD-36 type light receiving part made by Topcon (Corresponding to light having a wavelength of 310 to 400 nm) was used to adjust the ultraviolet intensity measured to 1 mW / cm ² .

8). Light resistance After irradiating the sample with light of FL20S BLB type black light manufactured by Toshiba Lighting & Technology for 30 days, light resistance was evaluated in the following three stages based on the appearance (visual evaluation) of the sample.
At this time, the UV intensity measured using a Topcon UVR-2 type UV intensity meter {using a TOPCON UD-36 type light receiving part (corresponding to light with a wavelength of 310 to 400 nm) as the light receiving part} is 3 mW / cm ^2. It adjusted so that it might become.
○: No change in appearance △: Photocatalyst layer peeling ×: Partial decomposition of members

[Reference Example 1]
Synthesis of modified photocatalytic hydrosol (A-1).
LS-8600 [trade name of 1,3,5,7-tetramethylcyclotetrasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)] 474 g, LS-8620 [Octamethyl] Trade name of cyclotetrasiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.)] 76.4 g, product name of LS-8490 [1,3,5-trimethyl-1,3,5-triphenylcyclotrisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.) 408 g LS-7130 [trade name of hexamethyldisiloxane (manufactured by Shin-Etsu Chemical Co., Ltd.), 40.5 g, and sulfated zirconia 20 g were charged, stirred at 50 ° C. for 3 hours, and further stirred at 80 ° C. for 5 hours. . After filtering the sulfated zirconia, the low-boiling components were removed under vacuum at 130 ° C., and a methylhydrogensiloxane-methylphenylsiloxane-dimethylsiloxane copolymer (weight average molecular weight 6600, Si—H group content 7.93 mmol / g) ( 780 g of a synthetic silicone compound) was obtained.

Into a reactor equipped with a reflux condenser, a thermometer and a stirrer, 40 g of the synthetic silicone compound was put, and the temperature was raised to 80 ° C. with stirring. To this, UNIOX PKA-5118 [trade name of polyoxyethylene allyl methyl ether (manufactured by NOF Corporation), weight average molecular weight 800] 200 g, dehydrated methyl ethyl ketone 200 g, and chloroplatinic acid hexahydrate 5 mass% isopropanol solution 1 0.0 g of the mixed solution was added over about 1 hour with stirring, and the mixture was further stirred at 80 ° C. for 5 hours and then cooled to room temperature to obtain a Si—H group-containing compound solution (1). It was.
When 100 g of water was added to 4 g of the obtained Si—H group-containing compound solution (1), a transparent aqueous solution was obtained.

  Further, 8 g of butyl cellosolve was added to and mixed with 3.97 g of the obtained Si—H group-containing compound solution (1), and then 8 ml of 1N sodium hydroxide aqueous solution was added to generate hydrogen gas. 21.0 ml. The Si—H group content per 1 g of the Si—H group-containing compound solution (1) determined from this hydrogen gas production amount was 0.22 mmol / g (the Si—H group content calculated per 1 g of the synthetic silicone compound was about 2 .37 mmol / g).

To a reactor equipped with a reflux condenser, a thermometer and a stirrer, TKS-203 [trade name of titanium oxide hydrosol (manufactured by Teika), neutral, TiO2 concentration 19.2 mass%, average crystallite diameter 6 nm (catalog Value)] After adding 78.1 g and 221.9 g of water, 41.3 g of the synthesized Si—H group-containing compound solution (1) was added thereto at 40 ° C. with stirring over about 30 minutes, After further stirring for 12 hours at 40 ° C., methyl ethyl ketone was removed by distillation under reduced pressure, and water was added to obtain 5% by mass of a highly-dispersible modified photocatalyst hydrosol (A-1). At this time, the amount of hydrogen gas produced by the reaction of the Si—H group-containing compound solution (1) was 210 ml at 20 ° C. Further, when the obtained modified titanium oxide hydrosol (A-1) was coated on a KBr plate and the IR spectrum was measured, the disappearance of absorption of Ti—OH groups (3630 to 3640 cm ⁻¹ ) was observed.

Moreover, the particle size distribution of the obtained modified photocatalyst hydrosol (A-1) is a single dispersion (number average particle diameter is 55 nm), and further, the single dispersion of TKS203 before the modification treatment (number average particle diameter is 12 nm). It was confirmed that the particle size distribution of was shifted to the larger particle size side.
The BET surface area of the dried modified photocatalyst hydrosol (A-1) obtained was less than 0.1 m ² / g. In contrast, after applying the modified photocatalyst hydrosol (A-1) to a glass plate with a thickness of about 3 μm and drying at room temperature, the light of FL20S BLB type black light manufactured by Toshiba Lighting & Technology [UVR-2 type UV intensity manufactured by Topcon] Irradiate the meter {adjusted so that the UV intensity measured using Topcon UD-36 type light receiving part (corresponding to light of wavelength 310 to 400 nm) as the light receiving part is ² mW / cm ² ] for 5 days, The BET surface area of what was peeled off from the glass plate was 210 m < ² > / g.

[Reference Example 2]
Synthesis of modified photocatalytic hydrosol (A-2).

A reactor equipped with a reflux condenser, a thermometer, and a stirrer was charged with 15 g of TSS4110 [trade name of visible light responsive titanium oxide sol (manufactured by Sumitomo Chemical Co., Ltd., photocatalyst concentration 10 mass%)] and 15 g of water. 4.1 g of the Si—H group-containing compound solution (1) synthesized in Reference Example 1 was added at 40 ° C. over about 30 minutes with stirring, and stirring was continued at 40 ° C. for 12 hours, followed by vacuum distillation. Then, methyl ethyl ketone was removed and water was added to obtain a modified photocatalyst hydrosol (A-2) having a very good dispersibility of 5% by mass. At this time, the amount of hydrogen gas produced by the reaction of the Si—H group-containing compound solution (1) was 25 ml at 20 ° C.
Moreover, the particle size distribution of the obtained modified photocatalyst hydrosol (A-2) is monodisperse (number average particle size is 29 nm), and further monodispersion of TSS4110 before modification (number average particle size is 13 nm). It was confirmed that the particle size distribution of was shifted to the larger particle size side.

[Example 1]
The modified photocatalyst hydrosol (A-1) obtained in Reference Example 1 was applied to a commercially available wallpaper of 10 cm × 10 cm at a thickness of about 5 μm, and then dried at room temperature for 12 hours to obtain a photocatalyst loading of about 0.022 g. A photocatalyst wallpaper sample 1 was prepared. The BET surface area of the obtained photocatalyst wallpaper sample 1 was 0.1 m ² / g.
The photocatalyst wallpaper sample 1 was subjected to a light of a FL20SBLB type black light manufactured by Toshiba Lighting & Technology [UVR-2 type UV intensity meter manufactured by Topcon (light receiving unit: UD-36 type light receiving unit manufactured by Topcon), and the UV intensity measured was 2 mW / to obtain a porous photocatalyst wallpaper sample 1 BET surface area of 4.5 m ² / g by irradiating cm ² become as Reconciliation 24 hours. At this time, the increase in the BET surface area per 1 g of the photocatalyst supported on the photocatalyst wallpaper sample 1 can be calculated as about 200 m ² .

When the deodorizing property of this porous photocatalyst wallpaper sample 1 was evaluated, 100 ppm of acetaldehyde became 0 ppm (below the detection limit) after irradiation with black light. Moreover, the anti-fungal property of this porous photocatalyst wallpaper sample 1 was good (◯), and the antibacterial property was also good (◯). Moreover, the light resistance of the porous photocatalyst wallpaper sample 1 was good (◯).
Furthermore, when the deodorizing property was evaluated again using the porous photocatalyst wallpaper sample 1 after the light resistance test, 100 ppm of acetaldehyde became 0 ppm (below the detection limit) after the black light irradiation, and the deodorizing performance was maintained.

[Example 2]
Instead of the modified photocatalyst hydrosol (A-1) obtained in Reference Example 1, the same procedure as in Example 1 was carried out except that the modified photocatalyst hydrosol (A-2) obtained in Reference Example 2 was used. Produced about 0.020 g of photocatalyst wallpaper sample 2. The photocatalyst wallpaper sample 2 obtained had a BET surface area of 0.1 m ² / g.
The obtained photocatalyst wallpaper sample 2 was subjected to light from a fluorescent lamp (Mellow 5N) manufactured by Toshiba Lighting & Technology [Topcon UVR-2 type UV intensity meter {as the light receiving part, UD-40 type light receiving part made by Topcon (wavelength of 370 to 490 nm). Use) to adjust the visible light intensity to 0.5 mW / cm ² . At this time, the UV intensity measured with a Topcon UD-36 type light receiving unit (corresponding to light having a wavelength of 310 to 400 nm is 15 μW / cm ² ) is irradiated for 5 days, so that a BET surface area of 3.9 m ² / g is obtained. Photocatalytic Japanese paper 2 was obtained. At this time, the increase in the BET surface area per 1 g of the photocatalyst contained in the photocatalyst wallpaper sample 2 can be calculated as about 190 m ² .

When the deodorizing property of this porous photocatalyst wallpaper sample 2 was evaluated, 100 ppm of acetaldehyde became 5 ppm after irradiation with black light. Moreover, the anti-fungal property of this porous photocatalyst wallpaper sample 2 was good (◯), and the antibacterial property was also good (◯). Moreover, the light resistance of the porous photocatalyst wallpaper sample 2 was good (◯).
Furthermore, when the deodorizing property was evaluated again using the porous photocatalyst wallpaper sample 2 after the light resistance test, 100 ppm of acetaldehyde became 0 ppm (below the detection limit) after the black light irradiation, and the deodorizing performance was maintained.

[Example 3]
Photocatalyst wallpaper having a photocatalyst loading of about 0.025 g by adding 0.01 g of eosin Y as a sensitizing dye to 100 g of the modified photocatalyst hydrosol (A-1) obtained in Reference Example 1 and performing the same operation as in Example 1. Sample 3 was created. The obtained photocatalyst wallpaper sample 3 had a BET surface area of 0.1 m ² / g.
The resulting photocatalyst wallpaper sample 3 was irradiated with light from a fluorescent lamp made by Toshiba Lighting & Technology (Mellow 5N) having the same light intensity as in Example 2 for 5 days, whereby a porous photocatalyst wallpaper sample having a BET surface area of 4.3 m ² / g. 3 was obtained. At this time, the increase in the BET surface area per 1 g of the photocatalyst contained in the photocatalyst wallpaper sample 3 can be calculated to be about 170 m ² .
When the deodorizing property of this porous photocatalyst wallpaper sample 3 was evaluated, 100 ppm of acetaldehyde became 0 ppm (below the detection limit) after irradiation with black light. Moreover, the mold prevention property of this porous photocatalyst wallpaper sample 3 was good (◯), and the antibacterial property was also good (◯). Moreover, the light resistance of the porous photocatalyst wallpaper sample 3 was good (◯).
Furthermore, when the deodorizing property was evaluated again using the porous photocatalyst wallpaper sample 3 after the light resistance test, 100 ppm of acetaldehyde became 0 ppm (below the detection limit) after irradiation with black light, and the deodorizing performance was maintained.

[Reference Example 3]
When the photocatalyst wallpaper sample 1 obtained in Example 1 was irradiated with light from a fluorescent lamp manufactured by Toshiba Lighting & Technology (Mellow 5N) having the same light intensity as in Example 2, the BET surface area was slightly 0.4 m ² / g. Although increased, the increase in BET surface area was very small compared to the photocatalyst wallpaper sample 3 obtained in Example 3.
[Comparative Example 1]
The same operation as in Example 1 was performed using an aqueous dispersion obtained by diluting TKS203 (same as in Reference Example 1) with water to 5% by mass to prepare a photocatalyst wallpaper sample 4 having a photocatalyst loading of about 0.020 g. The photocatalyst wallpaper sample 4 obtained had a BET surface area of 4.0 m ² / g.
The obtained photocatalyst wallpaper sample 4 was irradiated with light of FL20SBLB type black light manufactured by Toshiba Lighting & Technology Co., Ltd. having the same intensity as in Example 1, but the BET surface area did not change to 4.0 m ² / g.
Moreover, the light resistance of the obtained photocatalyst wallpaper sample 4 was very bad (×).

  The porous photocatalyst wallpaper of the present invention is useful for the decomposition, removal and sterilization of various malodorous gases, harmful gases, harmful compounds, etc. generated in daily life over a long period of time, antifungal, etc. Since it can be disassembled and maintain its aesthetic appearance, it can be used as wallpaper having environmental purification performance and antifouling performance.

Claims (10)

A composite compound (BC) in which a photocatalyst (a) has a strong affinity for the photocatalyst, and a photocatalytic affinity organic component (B) that is decomposed by photocatalysis and a hardly decomposable component (C) that is not easily decomposed by photocatalysis A photocatalyst wallpaper characterized by being supported. A photocatalyst wallpaper comprising a modified photocatalyst (A) obtained by modifying the photocatalyst (a) with the composite compound (BC) according to claim 1. The photocatalytic wallpaper according to any one of claims 1 and 2, wherein the photocatalytic affinity organic component (B) has a polyoxyalkylene group. The photocatalyst wallpaper according to any one of claims 1 to 3, wherein the photocatalyst (a) is a visible light responsive photocatalyst. The photocatalyst wallpaper according to any one of claims 1 to 4, wherein a sensitizing dye is supported. The BET surface area per 1 g of the photocatalyst (a) is 10 m ² or more by irradiating the photocatalyst wallpaper according to any one of claims 1 to 4 with light having an energy higher than the band gap energy of the supported photocatalyst (a). Increased porous photocatalytic wallpaper. A porous photocatalyst wallpaper in which the BET surface area per gram of the photocatalyst (a) is increased by 10 m ² or more by irradiating the photocatalyst wallpaper according to claim 5 with absorption light of a supported sensitizing dye. The porous photocatalytic wallpaper according to any one of claims 6 and 7, which has an organic matter decomposing activity. The porous photocatalytic wallpaper according to claim 6, which has antibacterial performance. The porous photocatalytic wallpaper according to any one of claims 6 and 7, which has an antifungal property.