JP2007264360A - Stainproof display body - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stainproof display body having superior weatherability without requiring a complicated process. <P>SOLUTION: The stainproof display body has a light-diffusive material, a lighting body having a plurality of LEDs arranged right below the light-diffusive material, and a photocatalyst layer laminated on the light-diffusive material, and has an LED light source comprising at least an LED emitting light with a peak wavelength of 350 to 390 nm, and an LED emitting visible light and/or an LED emitting white light as the plurality of LEDs. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antifouling display body using a light diffusive material having a photocatalytic surface layer portion that is photocatalytically active and / or highly hydrophilic over a long period of time and having a photocatalytic layer that is photoexcited by light from an LED light source. It is. Specifically, the present invention relates to an antifouling display body having a photocatalyst layer capable of exhibiting actions such as antibacterial, antifungal, antifouling, deodorizing, and air purification over a long period of time.

   The following are known as photocatalysts.

  For certain substances, light having an energy larger than the energy gap (band gap) between the conduction band and valence band of the substance, that is, light having a shorter wavelength than the light corresponding to the band gap of the substance ( When excitation light is irradiated, excitation of electrons in the valence band (photoexcitation) occurs due to light energy, and electrons are generated in the conduction band and holes are generated in the valence band. At this time, various chemical reactions can be performed using the reducing power of electrons generated in the conduction band and / or the oxidizing power of holes generated in the valence band.

   That is, the above substances can be used like a catalyst under excitation light irradiation. Therefore, the above substances are called photocatalysts, and titanium oxide is known as the most typical example.

  Examples of chemical reactions promoted by this photocatalyst include oxidative decomposition reactions of various organic substances. Therefore, if this photocatalyst is immobilized on the surface of various base materials, various organic substances adhering to the surface of the base material can be oxidatively decomposed using light energy.

  Many photocatalysts, such as titanium oxide, are known in which the hydrophilicity of the surface of the photocatalyst is greatly increased by light irradiation.

  Therefore, if these photocatalysts are immobilized on the surface of various base materials, the hydrophilicity of the surface of the base material can be enhanced by the organic substance decomposing action and / or the hydrophilizing action by light irradiation.

  In recent years, research for applying the above-mentioned characteristics of photocatalysts to various fields such as environmental purification, prevention of dirt adhesion to the surface of various base materials and prevention of fogging has become active. Yes.

  At this time, there is no problem when the photocatalyst is used by supporting the photocatalyst film or the photocatalyst particles on the inorganic base material. When used, the organic substrate surface is decomposed by the photocatalytic action, and various problems occur. Specifically, when the surface portion of the organic base material is decomposed, the photocatalyst layer present on the organic base material loses a scaffold and falls off. In addition, not only the intended function (antifouling property, antibacterial property, deodorizing property, etc.) using photocatalysis is lost, but also the original appearance characteristics such as surface gloss is lowered and powder is blown. And design will be lost.

  With respect to these problems, Patent Documents 1 and 2 propose a method in which a hardly decomposable intermediate layer that is difficult to be decomposed by a photocatalytic action is interposed between an organic base material and a photocatalyst layer. In order to photoexcite a photocatalyst, Patent Document 3 introduces fluorescent lamps, incandescent bulbs, metal halide lamps, mercury lamps, and ultraviolet rays in sunlight.

JP-A-11-188271 JP 2000-6303 A Japanese Patent No. 2756474

  However, in the method of Patent Document 1 or 2, long-term adhesion at the interface between the intermediate layer and the photocatalyst layer is insufficient, and the coating process is complicated and workability is poor, resulting in an increase in production loss and cost. In addition, it is very difficult to obtain a uniform film, and it is difficult to completely prevent the deterioration of the organic base material. Further, in this method, since a clear film interface exists between the photocatalyst layer and the layer made of the hardly decomposed substance, the photocatalyst layer may be peeled off.

  Patent Document 3 introduces fluorescent lamps, incandescent lamps, metal halide lamps, mercury lamps, and ultraviolet rays in sunlight. However, these are all light from an external light source and are naturally limited.

  The object of the present invention is that a complicated process is not required, interface deterioration between the light diffusing material and the surface layer portion containing the photocatalyst and deterioration due to the photocatalyst of the surface layer portion itself do not occur, and light irradiation for a long period of time. In addition to providing a light diffusive material having a photocatalyst surface layer with excellent weather resistance, the surface of which exhibits photocatalytic activity and / or hydrophilicity, and excellent in photoexcitation of the photocatalyst by the light source of the display itself, for indoor use It is another object of the present invention to provide an antifouling display body using a light emitting system having a suitable energy saving and space saving LED light source.

That is, the present invention
[1] It has a light diffusing material, an illuminating body in which a plurality of LEDs are disposed immediately below the light diffusing material, and a photocatalyst layer laminated on the light diffusing material, An antifouling display body comprising: an LED that emits at least a peak wavelength of 350 to 390 nm; and an LED light source that includes an LED that emits visible light and / or an LED that emits white light.

[2] The light emitting time of the LED emitting the peak wavelength of 350 to 390 nm is 1/100 to 99/100 per unit light emitting time of the LED emitting visible light and / or the LED emitting white light. The antifouling display body according to [1], which is controlled to emit light as described above.

[3] The antifouling display body as described in [1] or [2] above, wherein the photocatalyst layer comprises a photocatalyst composition containing a photocatalyst and a binder component.

[4] The antifouling display body according to any one of [1] to [3], wherein the light diffusing material is formed of a thermoplastic resin and a light diffusing agent.

  In the present invention, by using a special LED light source, strong photocatalytic activity and / or hydrophilicity (water contact angle is 20 ° or less, preferably 10 ° or less) without degrading the light diffusing material itself. A light-transmitting material having a surface layer portion that develops, and having a photocatalyst surface layer portion that can maintain the aesthetics of the light-transmitting material for a long period of time by rainfall or simple water washing, and can purify the environment by decomposing harmful substances A display body using a light-transmitting material can be provided. In particular, since the photocatalyst is activated by the light source inside the display body, it is effective for indoor use.

  As an application example of the present invention, it can be widely applied to display devices such as signs, indicator lights such as emergency exits and toilets, lighting fixtures with design properties, panels with design properties, building materials such as partitions and walls, signboards, etc. is there.

  Hereinafter, the present invention will be described in detail.

  The light diffusive material having a photocatalyst surface layer part of the present invention is a light diffusible material having a surface layer part containing a photocatalyst (A) and a binder component (B), and the concentration of the photocatalyst (A) in the surface layer part Is higher from the inner side of the light diffusing material toward the other exposed surface.

  At this time, the relative concentration in the vicinity of the surface side in contact with the exposed surface is preferably 120 or more with respect to the photocatalyst content (concentration) of 100 in the entire surface layer portion. If comprised in this way, the improvement effect of a photocatalytic capability and a hydrophilization capability will be expressed, and an antifouling effect will become large. The relative concentration in the vicinity of the surface side is more preferably 150 or more, and further preferably 200 or more.

  Moreover, it is preferable from the point of the interface deterioration prevention effect that the relative density | concentration of the surface vicinity which contacts a light diffusable material is 50 or less. The relative concentration in the vicinity of the surface in contact with the light diffusing material is more preferably 10 or less, and even more preferably 0.

  Further, the concentration of the photocatalyst (A) in the surface layer portion in the present invention may gradually increase from the surface in contact with the light diffusing material toward the other exposed surface. Alternatively, the photocatalyst concentration on the surface in contact with the light diffusing material may be low, the photocatalyst concentration on the other exposed surface may be high, and the change therebetween may be discontinuous.

  Furthermore, in the surface layer portion of the present invention, it is preferable that there is no clear film interface that occurs when a photocatalyst layer is applied on the protective layer. That is, when there is no clear film interface that occurs when a photocatalyst layer is applied on the protective layer, the photocatalyst is firmly fixed in the surface layer portion, and problems such as separation of the photocatalyst do not occur.

  In the present invention, the photocatalytic activity means that an oxidation or reduction reaction is caused by light irradiation. It is possible to determine whether or not the surface is photocatalytically active by measuring the decomposability of the organic material such as a dye during light irradiation on the surface of the material. A surface having photocatalytic activity exhibits excellent decomposition activity and contamination resistance of contaminating organic substances.

  In the present invention, the term “hydrophilic” means that the contact angle of water at 20 ° C. is preferably 60 ° or less. Here, a hydrophilic surface with a water contact angle of 20 ° or less is particularly preferable since it exhibits contamination resistance due to water self-purification (rain cleaning) such as rainfall. Further, from the standpoint of developing excellent stain resistance, the contact angle of water on the surface is preferably 10 ° or less, more preferably 5 ° or less.

  As the light diffusing material of the present invention, inorganic materials such as ground glass and organic materials such as materials obtained by blending various thermoplastic resins with a light diffusing agent are applicable. The thermoplastic resin is preferably a light-transmitting resin used for optical applications, for example, optical materials such as methacrylic resin, polycarbonate resin, styrene resin, cyclic olefin resin, amorphous polyester resin, and more preferably Methacrylic resin.

  Further, a light transmissive material and a light diffusing material may be used in combination.

  Hereinafter, resins applicable as the light transmissive resin of the present invention will be described in more detail.

  The methacrylic resin can be obtained by copolymerizing 70% by weight or more of methyl methacrylate or ethyl methacrylate and a monomer having copolymerizability with these. Monomers that are copolymerizable with these include butyl methacrylate, ethyl methacrylate, and methyl methacrylate. Methacrylic acid esters such as propyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, 2-ethylhexyl methacrylate, methyl acrylate, ethyl acrylate, butyl acrylate, cyclohexyl acrylate, phenyl acrylate, 2-ethylhexyl acrylate, etc. Acrylic acid esters, unsaturated acids such as methacrylic acid and acrylic acid are applicable.

  Further, heat-resistant methacrylic resin, low-hygroscopic methacrylic resin, impact-resistant methacrylic resin, and the like are also applicable. The impact resistant methacrylic resin is, for example, a blend of a rubber elastic body and a methacrylic resin. An example of the rubber elastic body is a multistage polymer produced by a multistage sequential polymerization method in which an elastic layer and an inelastic layer are alternately generated around an acrylic polymer core material. By blending this rubber elastic body with a methacrylic resin, the above impact-resistant methacrylic resin can be obtained.

  When a polycarbonate resin is used, a polymer derived from a dihydric phenol compound represented by bisphenol A is used as the polycarbonate resin. The production method of the polycarbonate resin is not particularly limited, and those produced by a well-known conventional method such as a phosgene method, a transesterification method or a solid phase polymerization method can be applied.

  The cyclic olefin-based resin is a polymer containing a cyclic olefin skeleton in a polymer chain such as norbornene or cyclohexadiene or a copolymer containing these, and belongs to an amorphous thermoplastic resin. The manufacturing method is not particularly limited. For example, as an example of a cyclic olefin resin mainly composed of norbornene, “Topas” (trade name) manufactured by Ticona Co., Ltd., which is an ethylene-norbornene copolymer, can be applied. As an example of a cyclopentadiene ring-opening polymer For example, “Zeonex” (trade name) manufactured by Nippon Zeon Co., Ltd. is applicable.

  The styrenic resin is a homopolymer, a copolymer or a polymer blend obtained from such a polymer and another resin containing styrene as an essential component. In particular, it is preferable to use an AS resin which is a copolymer resin of polystyrene, acrylonitrile and styrene, or an MS resin which is a copolymer resin of methacrylic acid ester and styrene.

  Further, transparent reinforced polystyrene in which rubber is distributed in the styrene resin phase can be preferably used. The manufacturing method of a styrene resin is not specifically limited, The thing manufactured by the well-known and usual method can be used.

  Amorphous polyesters include aliphatic glycols such as ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, hexaethylene glycol, alicyclic glycols such as cyclohexanedimethanol, bisphenol, 1,3-bis. Aromatic dihydroxy compounds such as (2-hydroxyethoxy) benzene and 1,4-bis (hydroxyethoxy) benzene, or dihydroxy compound units selected from two or more of these, terephthalic acid, isophthalic acid, 2,6 -An aromatic dicarboxylic acid such as naphthalene dicarboxylic acid, an aliphatic dicarboxylic acid such as oxalic acid, adipic acid, sebacic acid, succinic acid and undecadicarboxylic acid, an aliphatic dicarboxylic acid such as hexahydroterephthalic acid, or 2 of these Zikaru selected from more than one kind Amorphous resin in the polyester formed from the phosphate unit is applicable.

  The production method of the amorphous polyester is not particularly limited, and can be produced by a well-known and commonly used method. As a commercially available brand that can be easily obtained as an amorphous polyester, a product of Eastman Kodak Company is available. Some KODAR PETG or PCTA is applicable.

  Moreover, you may add a soft polymer to the light transmissive resin of the said invention as needed. For example, an olefin-based soft polymer composed of α-olefin, an isobutylene-based soft polymer composed of isobutylene, a diene-based soft polymer composed of conjugated dienes such as butadiene and isoprene, and a cyclic olefin-based soft composed of a cyclic olefin such as norbornene and cyclopentene. Polymer, organopolysiloxane-based soft polymer, soft polymer composed of α, β-unsaturated acid and its derivative, soft polymer composed of unsaturated alcohol and amine or acyl derivative or acetal thereof, polymer of epoxy compound, Fluorine rubber or the like can be applied.

  Materials that can be used as light scattering agents include inorganic fine particles such as calcium carbonate, barium sulfate, alumina, titanium dioxide, silicon dioxide, and glass beads, organic fine particles such as styrene crosslinked beads, MS crosslinked beads, and siloxane crosslinked beads. Can be mentioned. Further, hollow crosslinked fine particles made of a highly transparent resin material such as methacrylic resin, polycarbonate resin, MS resin, and cyclic olefin resin, hollow fine particles made of glass, and the like are also applicable as the light scattering agent.

  In addition, the shape of the light scattering agent is not particularly limited, and for example, a light scattering agent such as a spherical shape, a spherical shape, a flat fan shape, a cubic shape, a flat rhombus shape, a hexagonal crystal shape, and an indefinite shape can be applied. .

  The particle size of the light diffusing agent is not limited, but the average particle size is preferably in the range of 1 μm to 50 μm. This is because when the average particle diameter of the light diffusing agent is in the range of 1 μm or more and 50 μm or less, the effect as the light diffusing agent is efficiently expressed, and fine adjustment of the total light transmittance is easy. .

  The light diffusivity of the light diffusing material of the present invention needs to be 60% or more, preferably 70% or more. When the light diffusivity is 60% or more, the image of the light source does not appear on the surface of the display body, and the display visibility is excellent.

  The manufacturing method of the molded object which consists of a diffusible material of this invention is not restrict | limited in particular, It can shape | mold by a well-known shaping | molding method. For example, a sheet or film extrusion method using an extruder having a polishing roll, an injection molding method using an injection molding machine having a shaping mold, a press molding method using a press molding machine having a shaping mold, and a sheet molding using a cast polymerization method Any method can be used, but a sheet extrusion method using an extruder having a polishing roll is preferable because it can be produced in large quantities at low cost. Also, a coextrusion method using a feed block type extrusion die or a multi-manifold type extrusion die can be used to obtain a laminated sheet. The co-extrusion method is a method in which a resin composition to be a base resin layer and a resin composition to be a film resin layer are heated and melt-extruded in separate extruders, merged and laminated in a mold widened into a sheet shape, and polished. -It is a method of forming a sheet through a roll or the like.

  The thickness of the coating resin layer is not limited, but is preferably 300 μm or less. When the thickness of the coating resin layer is 300 μm or less, lamination itself becomes easy, and a laminated sheet having a good appearance can be obtained.

  It is preferable for obtaining a sheet having a good appearance that the resin temperature when the sheet is formed by an extrusion molding method is in the range of 180 to 280 ° C.

In the present invention, examples of the photocatalyst (A) useful for making the surface of the light transmissive material photocatalytically active and / or hydrophilic include, for example, 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 layer having at least one element selected from Ti, Nb, Ta, and V Oxides (Japanese Patent Laid-Open Nos. 62-74452, 2-172535, 7-24329, 8-89799, 8-89) 800, JP-A-8-89804, JP-A-8-198061, JP-A-9-248465, JP-A-10-99694, JP-A-10-244165, etc.), nitrogen doping Titanium oxide (see JP-A-13-278625, JP-A-13-278627, JP-A-13-335321, JP-A-14-029750, JP-A-13-207082, etc.), oxygen defect type A visible light responsive titanium oxide photocatalyst such as titanium oxide (see JP-A No. 13-212457) can also be suitably used. Also, oxynitride compounds such as TaON, LaTiO ₂ N, CaNbO ₂ N, LaTaON ₂ and CaTaO ₂ N, and oxysulfide compounds such as Sm ₂ Ti ₂ S ₂ O ₇ have large photocatalytic activity by visible light, and are preferably used. can do.

  Further, a photocatalyst coated with a metal such as Pt, Rh, Ru, Nb, Cu, Sn, Ni, Fe and / or an oxide thereof, or a porous calcium phosphate coated with these photocatalysts. (Refer to Unexamined-Japanese-Patent No. 10-244166) etc. can also be used.

  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.

  Of these photocatalysts, titanium oxide is preferred because it is non-toxic and excellent in chemical stability, and the hydrophilicity of titanium oxide itself is greatly enhanced by light irradiation.

  As the titanium oxide, any crystal form of anatase type, rutile type and brookite type may be used. Further, the above nitrogen-doped titanium oxide and oxygen-deficient titanium oxide that are responsive to visible light can be suitably used as the titanium oxide.

  As the photocatalyst (A) of the present invention, a modified photocatalyst (A1) obtained by modifying the photocatalyst (A) with at least one modifier compound (b) described later is preferably used.

  In the present invention, the modification of the photocatalyst (A) means that at least one modifier compound (b) described later is immobilized on the surface of the photocatalyst (A) particles. The immobilization of the above modifier compound on the surface of the photocatalyst particles is considered to be 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 modifier compound and the photocatalyst is strong, and the modifier compound is firmly immobilized on the surface of the photocatalyst particles.

  By using the photocatalyst (A) of the present invention as the modified photocatalyst (A1), when the surface layer portion containing the photocatalyst (A) is formed on the surface light emitter of the present invention, the photocatalyst (A ) In the surface layer portion from the inner side of the surface light emitter to the other exposed surface, the formation of the structure is particularly easy when combined with the binder component (B) described later, preferable.

  In the present invention, the properties of the photocatalyst (A) used for modification are important factors for the dispersion stability of the modified photocatalyst (A1), film-forming properties, and expression of various functions. That is, as the photocatalyst (A) used in the modification of the present invention, the photocatalyst having a number average dispersed particle size of a mixture of primary particles and secondary particles of 400 nm or less effectively utilizes the surface characteristics of the modified photocatalyst. It is preferable because it is possible. In particular, when a photocatalyst having a number average dispersed particle size of 100 nm or less is used, in the surface layer portion of the present invention formed from a photocatalyst composition (C) containing a modified photocatalyst (A1) to be produced and a binder component (B) described later, The modified photocatalyst (A1) can be efficiently present on the surface (exposed surface) of the surface layer portion, which is very preferable. More preferably, the photocatalyst (A) of 80 nm or less and 3 nm or more, and more preferably 50 nm or less and 3 nm or more is selected.

  As these photocatalysts (A), it is preferable to use a photocatalyst sol instead of a photocatalyst powder for the following reasons. In general, powders composed of fine particles form secondary particles in which single crystal particles (primary particles) are strongly agglomerated, so there are many surface properties that are wasted, but it is very difficult to disperse to primary particles. It is. On the other hand, in the case of a photocatalyst sol, the photocatalyst particles do not dissolve but exist in a form close to primary particles, so that the surface characteristics can be used effectively. It can be preferably used because it effectively exhibits various functions. Here, the photocatalyst sol used in the present invention means that the photocatalyst particles are 0.01 to 70% by mass in water and / or an organic solvent, preferably 0.1 to 50% by mass as primary particles and / or secondary particles. It is distributed.

  Here, examples of the organic solvent used in the photocatalyst sol include alcohols such as ethylene glycol, butyl cellosolve, n-propanol, isopropanol, n-butanol, ethanol and methanol, and aromatic hydrocarbons 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, dimethylacetamide, dimethyl Examples include amides such as formamide, halogen compounds such as chloroform, methylene chloride, and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more of these.

  Taking a titanium oxide sol as an example of the photocatalyst sol, for example, a titanium oxide hydrosol in which water is substantially used as a dispersion medium and titanium oxide particles are peptized therein can be exemplified. (Here, substantially using water as a dispersion medium means that water is contained in the dispersion medium in an amount of about 80% by mass or more.) Adjustment of such a sol is known and can be easily produced ( (See JP-A-63-17221, JP-A-7-819, JP-A-9-165218, JP-A-11-43327, etc.). For example, metatitanic acid produced by heating and hydrolyzing an aqueous solution of titanium sulfate or titanium tetrachloride is neutralized with aqueous ammonia, and the precipitated hydrous titanium oxide is filtered, washed, and dehydrated to obtain aggregates of titanium oxide particles. It is done. Titanium oxide hydrosol can be obtained by peptizing the agglomerates under the action of nitric acid, hydrochloric acid, ammonia or the like and performing hydrothermal treatment. In addition, as titanium oxide hydrosol, titanium oxide particles are peptized under the action of acid or alkali, or dispersion stabilizer such as sodium polyacrylate is used as required without using acid or alkali. Sols that are used and dispersed in water under strong shear forces can also be used. Further, an anatase-type titanium oxide sol having excellent dispersion stability even in an aqueous solution having a pH near neutral and having a particle surface modified with a peroxo group can be easily obtained by the method proposed in JP-A-10-67516. it can.

  The titanium oxide hydrosol described above is commercially available as a titania sol (for example, “STS-02” manufactured by Ishihara Sangyo Co., Ltd., “TO-240” manufactured by Tanaka Transcription Co., Ltd., etc.).

  The titanium oxide in the titanium oxide hydrosol is preferably 50% by mass or less, and preferably 30% by mass or less. More preferably, it is 30 mass% or less and 0.1 mass% or more.

  Such hydrosols have a relatively low viscosity (20 ° C.). In the present invention, the viscosity of the hydrosol is preferably in the range of about 0.5 mPa · s to 2000 mPa · s. More preferably, it is 1 mPa * s-1000 mPa * s, More preferably, it is 1 mPa * s-500 mPa * s.

  Further, for example, a cerium oxide sol (see JP-A-8-59235) or a layered oxide sol having at least one element selected from the group consisting of Ti, Nb, Ta, and V (JP-A-9-25123). The manufacturing method of various photocatalytic sols such as JP-A-9-67124, JP-A-9-227122, JP-A-9-227123, JP-A-10-259023, etc.) is the same as that of titanium oxide sol. Known to.

  In addition, a photocatalyst organosol in which an organic solvent is substantially used as a dispersion medium and in which photocatalyst particles are dispersed is a compound having a phase transfer activity such as polyethylene glycol (for example, different first phase and second phase). A third phase is formed at the interface with the phase, the first phase, the second phase, the third phase are mutually dissolved and / or solubilized compounds) and diluted with an organic solvent (special (Kaihei 10-167727), a method of preparing a sol by dispersing and transferring it in an organic solvent insoluble in water using an anionic surfactant such as sodium dodecylbenzenesulfonate (Japanese Patent Laid-Open No. 58-29863) or butyl cellosolve After adding alcohols having a boiling point higher than water, such as water, to the photocatalyst hydrosol, the water can be obtained by a method of removing the water by (vacuum) distillation or the like. In addition, a titanium oxide organosol in which an organic solvent is substantially used as a dispersion medium and titanium oxide particles are dispersed therein is commercially available (for example, “TKS-251” manufactured by Teika Co., Ltd.). Here, substantially using an organic solvent as a dispersion medium means that the dispersion medium contains about 80% by mass or more of the organic solvent.

In the present invention, at least one modifier compound (b) used to obtain the modified photocatalyst (A1) is a triorganosilane unit represented by the formula (1), a monooxy represented by the formula (2). From the group consisting of compounds having at least one structural unit selected from the group consisting of diorganosilane units, dioxyorganosilane units represented by formula (3), and methylene fluoride (—CF ₂ —) units. To be elected.

  In the modified photocatalyst (A1) in which the surface of the photocatalyst particle is modified with the modifier compound (b) having the structural unit described above, the surface energy of the particle surface becomes very small.

  In the present invention, the modification treatment of the photocatalyst (A) with the modifier compound (b) is carried out in the presence or absence of water and / or an organic solvent in the same manner as the above-described photocatalyst (A) and the modifier compound ( b) is preferably mixed at a mass ratio (A) / (b) = 1/99 to 99.9 / 0.1, more preferably (A) / (b) = 10/90 to 99/1. It can be obtained by heating at 0 to 200 ° C., more preferably at 10 to 80 ° C., or by changing the solvent composition of the mixture by (reduced pressure) distillation or the like.

  Here, when performing the above modification treatment, examples of organic solvents that can be used include aromatic hydrocarbons such as toluene and xylene, aliphatic hydrocarbons such as hexane, cyclohexane, and heptane, ethyl acetate, and n-butyl acetate. Esters, alcohols such as ethylene glycol, butyl cellosolve, isopropanol, n-butanol, ethanol and methanol, ketones such as acetone, methyl ethyl ketone and methyl isobutyl ketone, ethers such as tetrahydrofuran and dioxane, amides such as dimethylacetamide and dimethylformamide , Halogen compounds such as chloroform, methylene chloride, carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and a mixture of two or more thereof.

  Examples of the modifier compound (b) used for obtaining the modified photocatalyst (A1) of the present invention include a Si—H group, a hydrolyzable silyl group (alkoxysilyl group, hydroxysilyl group, halogenated silyl group, Acetoxysilyl group, aminoxysilyl group, etc.), epoxy compounds, acetoacetyl groups, thiol groups, acid anhydride groups and other photocatalyst particles (a) reactive with silicon compounds, fluoroalkyl compounds, fluoroolefin polymers, etc. Can be mentioned.

  Other examples of the modifier compound (b) include a silicon compound having a structure that interacts with photocatalyst particles (a) such as a polyoxyalkylene group by van der Waals force, Coulomb force, etc. Examples thereof include a fluoroalkyl compound and a fluoroolefin polymer.

  In the present invention, when the Si-H group-containing silicon compound (b1) represented by the composition formula (4) is used as the modifier compound (b), the surface of the photocatalyst particles can be modified very efficiently. preferable.

In the present invention, the modification of the photocatalyst (A) with the Si—H group-containing silicon compound (b1) represented by the above composition formula (4) is carried out in the presence or absence of water and / or an organic solvent. The mass ratio (A) / (b1) = 1/99 to 99.9 / 0.1, more preferably (A) / (b1), between (a) and the Si—H group-containing silicon compound (b1). = It can be carried out by mixing at a ratio of 10/90 to 99/1, preferably 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 dispersed particle size is observed. For example, when titanium oxide is used as the photocatalyst (A), a decrease in Ti—OH groups is observed as a decrease in absorption at 3630 to 3640 cm ^{−1 in} the IR spectrum by the above modification operation.

  From these, when the Si-H group-containing silicon compound (b1) represented by the above formula (4) is selected as the modifier compound (b), the modified photocatalyst (A1) of the present invention is Si-H. This is very preferable because it is not a mere mixture of the group-containing silicon compound (b1) and the photocatalyst (A), but it can be predicted that some kind of interaction accompanying a chemical reaction occurs between the two. In fact, the modified photocatalyst (A1) obtained in this way is very excellent in dispersion stability, chemical stability, durability and the like in an organic solvent.

  In the present invention, the modification of the photocatalyst (A) with the Si—H group-containing silicon compound (b1) represented by the above formula (4) is preferably performed using a dehydrogenative condensation catalyst for Si—H groups. It can also be carried out at 150 ° C.

  In this case, the dehydrogenative condensation catalyst may be fixed to the photocatalyst (A) in advance by a method such as a photoreduction method and may be modified with the Si-H group-containing silicon compound (b1), or the presence of the dehydrogenative condensation catalyst. The photocatalyst (A) may be modified with the Si—H group-containing compound silicon (b1) below.

  Here, the dehydrogenative condensation catalyst for the Si-H group is an active hydrogen group such as a Si-H group and a hydroxyl group (Ti-OH group in the case of titanium oxide) existing on the photocatalyst surface, a thiol group, an amino group, or a carboxyl group. Furthermore, it means a substance that accelerates the dehydrogenation condensation reaction with water or the like, and the use of the dehydrogenation condensation catalyst makes it possible to modify the surface of the photocatalyst under mild conditions.

  Examples of the dehydrogenative condensation catalyst include platinum group catalysts, that is, ruthenium, rhodium, palladium, osmium, iridium, platinum simple substance and compounds thereof, and simple substances such as silver, iron, copper, cobalt, nickel, tin and compounds thereof. Can be mentioned. Of these, platinum group catalysts are preferred, and platinum alone and its compounds are particularly preferred.

  Here, examples of the platinum compound include platinum chloride (II), tetrachloroplatinic acid (II), platinum chloride (IV), hexachloroplatinic acid (IV), hexachloroplatinum (IV) ammonium, hexachloroplatinum (IV). Potassium, platinum hydroxide (II), platinum dioxide (IV), dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex, etc. can be used. .

  In the Si—H group-containing silicon compound represented by the above formula (4) of the present invention, the Si—H group is a preferable functional group for modifying the photocatalyst with good selectivity under mild conditions. On the other hand, the hydrolyzable group can also be used for the modification of the photocatalyst, but in order to suppress side reactions and improve the stability of the resulting modified photocatalyst, the content thereof should be smaller. preferable.

  Examples of the Si—H group-containing silicon compound (b1) represented by the above formula (4) that can be suitably used in the present invention include a mono-Si—H group-containing compound represented by the formula (5) and the formula (6). An at least one S—H group-containing compound having no hydrolyzable silyl group selected from the group consisting of Si-H group-containing compounds represented by formula (7) and H silicone represented by formula (7): Can be mentioned.

  In the present invention, specific examples of the mono-Si—H group-containing compound represented by the above formula (5) include, for example, bis (trimethylsiloxy) methylsilane, bis (trimethylsiloxy) ethylsilane, bis (trimethylsiloxy) n-propylsilane. Bis (trimethylsiloxy) i-propylsilane, bis (trimethylsiloxy) n-butylsilane, bis (trimethylsiloxy) n-hexylsilane, bis (trimethylsiloxy) cyclohexylsilane, bis (trimethylsiloxy) phenylsilane, bis (triethylsiloxy) ) Methylsilane, bis (triethylsiloxy) ethylsilane, tris (trimethylsiloxy) silane, tris (triethylsiloxy) silane, pentamethyldisiloxane, 1,1,1,3,3,5,5-heptamethyltrisiloxy 1,1,1,3,3,5,5,6,6-nonamethyltetrasiloxane, trimethylsilane, ethyldimethylsilane, methyldiethylsilane, triethylsilane, phenyldimethylsilane, diphenylmethylsilane, cyclohexyldimethylsilane , T-butyldimethylsilane, di-t-butylmethylsilane, n-octadecyldimethylsilane, tri-n-propylsilane, tri-i-propylsilane, tri-i-butylsilane, tri-n-hexylsilane, triphenyl Examples thereof include silane, allyldimethylsilane, 1-allyl-1,1,3,3-tetramethyldisiloxane, chloromethyldimethylsilane, and 7-octenyldimethylsilane.

  Among these mono-Si-H group-containing compounds, bis (trimethylsiloxy) methylsilane and tris are preferred because of the good reactivity (dehydrogenation condensation reaction) and low surface energy of Si-H groups during photocatalytic modification treatment. Those represented by the formula (9) having a siloxy group in the molecule such as (trimethylsiloxy) silane and pentamethyldisiloxane and having no phenyl group are preferable.

  In the present invention, specific examples of the both-terminal Si—H group-containing compound represented by the formula (6) include 1,1,3,3-tetramethyldisiloxane, 1,1,3,3,5, H-terminal polydimethylsiloxanes having a number average molecular weight of 50000 or less, such as 5-hexamethyltrisiloxane, 1,1,3,3,5,5,7,7-octamethyltetrasiloxane, and 1,1,3,3 -Number average molecular weight of 50,000 or less such as tetraethyldisiloxane, 1,1,3,3,5,5-hexaethyltrisiloxane, 1,1,3,3,5,5,7,7-octaethyltetrasiloxane H-terminated polydiethylsiloxanes, 1,1,3,3-tetraphenyldisiloxane, 1,1,3,3,5,5-hexaphenyltrisiloxane, 1,1,3,3,5,5,5 7,7-octapheny H-terminal polydiphenylsiloxanes having a number average molecular weight of 50000 or less, such as tetrasiloxane, 1,3-diphenyl-1,3-dimethyl-disiloxane, 1,3,5-trimethyl-1,3,5-triphenyl- H-terminal polyphenylmethylsiloxanes having a number average molecular weight of 50000 or less, such as trisiloxane, 1,3,5,7-tetramethyl-1,3,5,7-tetraphenyl-tetrasiloxane, dimethylsilane, ethylmethylsilane , Diethylsilane, phenylmethylsilane, diphenylsilane, cyclohexylmethylsilane, t-butylmethylsilane, di-t-butylsilane, n-octadecylmethylsilane, allylmethylsilane, and the like.

  Among these, the number average molecular weight is preferably 10000 or less, more preferably 2000 or less, more preferably due to the good reactivity of the Si—H group (dehydrogenation condensation reaction) and low surface energy during the modification treatment of the photocatalyst. Preferably, 1000 or less H-terminal polydialkylsiloxane (formula (10)) can be suitably used as the Si-H group-containing compound at both ends.

  The H silicone represented by the formula (7) used in the present invention has a number average molecular weight of preferably 5000 or less, more preferably from the viewpoint of dispersion stability (prevention of aggregation of photocatalyst particles) during photocatalytic modification treatment. 2000 or less, more preferably 1000 or less H silicone can be used suitably.

  Further, in a preferred form of the modified photocatalyst (A1) of the present invention, the number average dispersed particle size of the mixture of primary particles and secondary particles of the modified photocatalyst is 400 nm or less, more preferably 1 nm or more and 100 nm or less, particularly preferably 5 nm or more. 80 nm or less. A sol state is preferable.

  In particular, when a modified photocatalyst sol having a number average dispersed particle size of 100 nm or less is used in the photocatalyst composition (C) of the present invention, the concentration of the modified photocatalyst particles is small in the vicinity of the interface contacting the surface light emitter, and in the vicinity of the surface of the surface layer portion. Then, it is advantageous to form a surface layer portion anisotropically distributed in the surface direction, which is largely distributed, and is very preferable because a surface layer portion having a large photocatalytic activity is formed without interfacial deterioration with a surface light emitter due to photocatalytic action. Such a modified photocatalyst sol can be obtained by using the above-mentioned photocatalyst sol as a photocatalyst to be modified with the above modifier compound (b).

  Conventionally, a numerical value simply displayed as a particle size in titanium dioxide or the like is a primary particle diameter (crystallite diameter) in many cases, and is not a numerical value considering a secondary particle diameter due to aggregation.

  The photocatalyst composition (C) forming the surface layer part of the present invention comprises a photocatalyst (A) (preferably a modified photocatalyst (A1)) and a binder component (B), and its mass ratio (A1) / ( B) is preferably 0.1 / 99.9 to 90/10, more preferably (A1) / (B) is included at 1/99 to 50/50.

  Since the modified photocatalyst (A1) of the present invention is modified with the modifier compound (b) having a structure (formulas (1) to (3)) having a very small surface energy, when forming the surface layer portion, It has the property of easily moving to the surface layer surface on the side in contact with air.

  Here, as the binder component (B) of the present invention, by using the photocatalyst (A), particularly the binder resin (B ′) having a surface energy higher than that of the modified photocatalyst (A1), the above properties of the modified photocatalyst (A1) can be obtained. In order to promote, the photocatalyst composition (C) of the present invention can have a large self-gradient with respect to the distribution of the photocatalyst (A), particularly the modified photocatalyst (A1). Here, the self-gradient property means that when the surface layer portion is formed from the photocatalyst composition (C), the photocatalyst (A), particularly the modified photocatalyst (A1) in the formation process, is the property of the interface (particularly hydrophilic / Corresponding to (hydrophobic), it means that a structure having a concentration gradient of the photocatalyst (A), particularly the modified photocatalyst (A1) is autonomously formed.

  As the binder component (B) of the present invention, when a resin having a surface energy of 2 mN / m or more, preferably 5 mN / m or more larger than the photocatalyst (A) (preferably the modified photocatalyst (A1)) is selected, the self-gradient Is very preferable.

  Here, the surface energy and the relative difference between the surface energies can be determined by referring to, for example, Polymer Handbook (published by A Wiley-interscience publication in the United States) or by the following method.

  That is, the base material which has each surface layer part from the photocatalyst (A) which comprises the said photocatalyst composition (C), especially modified photocatalyst (A1), and a binder component (B) is adjusted, and deionized water is dripped. The contact angle (θ) at 20 ° C. is measured, and the surface energy of each can be determined by the following empirical formulas for Sell and Neumann.

  In the photocatalyst composition (C) of the present invention, the compound that can be used for the binder component (B) is not particularly limited as long as it has a surface energy that satisfies the above conditions. Various monomers, synthetic resins, natural resins, and the like In addition, it is also possible to include those that are cured by drying, heating, moisture absorption, light irradiation, or the like after the formation of the film. Further, the form thereof may be in a solvent-free state (pellet, powder, liquid, etc.) or may be dissolved or dispersed in a solvent, and is not particularly limited.

  As the synthetic resin, a thermoplastic resin and a curable resin (thermosetting resin, photocurable resin, moisture curable resin, etc.) can be used. For example, silicone resin, 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, Examples thereof include polyphenylene sulfone resin, polyether resin, polyvinyl chloride resin, polyvinylidene chloride resin, urea resin, phenol resin, melamine resin, epoxy resin, urethane resin, and silicone-acrylic resin.

  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 the present invention, as the binder component (B) used in the photocatalyst composition (C), the phenyl group-containing silicone (BP) represented by the formula (11) has a surface energy higher than that of the modified photocatalyst (A1) of the present invention. The siloxane bond (—O—Si—) constituting the skeleton is high and can be most preferably used because it does not undergo oxidative decomposition due to photocatalytic action.

  Examples of the phenyl group-containing silicone (BP) represented by the above formula (11) include at least one structure of a siloxane bond represented by the general formulas (12), (13), (14), and (15). Mention may be made of silicone.

The silicone containing the above-described structure is, for example, a general formula R ⁷ SiX ₃ (wherein R ⁷ is a phenyl group, a linear or branched alkyl group having 1 to 30 carbon atoms, or a cycloalkyl group having 5 to 20 carbon atoms). Each X independently represents 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. Represents a reactive group selected from the group. The same shall apply hereinafter.) A bifunctional silane derivative represented by the general formula R ⁷ ₂ SiX ₂ and / or a general formula SiX ₄ tetrafunctional silane derivative represented partially by hydrolysis and polycondensation, prepared by end-stopped by monofunctional silane derivative and / or alcohols of the general formula R ^{7 3} _SiX necessary Kill. The polystyrene-converted weight average molecular weight of the partial condensate of the silane derivative monomer thus obtained is preferably 100 to 100,000, more preferably 400 to 50,000.

Among these, when the phenyl group-containing silicone represented by the above formula (11) is selected to contain a ladder structure represented by the above formula (12) of 10 mol% or more, preferably 40 mol% or more, the present invention The photocatalyst-containing surface layer portion formed from the photocatalyst composition (C) is preferable because it is extremely excellent in terms of hardness, heat resistance, weather resistance, stain resistance, chemical resistance, and the like. In particular, the ladder structure having a phenyl ladder structure (all R ⁷ in Formula (12) is a phenyl group) is preferable because the physical properties of the above-described photocatalyst-containing surface layer portion are greatly improved. Such ladder structure, for example can be identified by the presence of absorption derived from two siloxane bonds near 1040 cm ^-1 and 1160 cm ^-1 in the infrared absorption spectrum.

(See JFBrown.Jr., Etal .: J. Am. Chem. Soc., 82, 6194 (1960).)
The phenyl group-containing silicone (BP) represented by the above formula (11) used in the present invention preferably has a Ph—Si bond (Ph: phenyl group).

  That is, in the photocatalyst composition (C) of the present invention, the modified photocatalyst (A1) modified with the modifier compound (b) having a structure (formulas (1) to (3)) having a very small surface energy. By using a binder component (B) containing a phenyl group-containing silicone (BP) having a surface energy higher than that of the modified photocatalyst (A1) as a binder, the photocatalyst composition (C) of the present invention is a modified photocatalyst (A1). It becomes possible to have a high self-tilting property for the distribution.

Such a self-gradient effect by the phenyl group-containing silicone (BP) having a high surface energy is obtained by converting the phenyl group (R ¹ ) into the phenyl group (R ¹ ) and R ² (R ² is linear or branched). Represents an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 5 to 20 carbon atoms, and an alkenyl group having 2 to 20 carbon atoms) (hereinafter referred to as (R ¹ + R ² )). }, A phenyl group-containing silicone (BP) represented by the above formula (11) having 5 mol% or more of Is preferred.

In addition, the self-tilting effect described above increases as the ratio of the phenyl group (R ¹ ) to (R ¹ + R ² ) increases. Therefore, the more preferable one as the phenyl group-containing silicone of the binder component (B) used in the photocatalyst composition of the present invention is such that the ratio of the phenyl group (R ¹ ) to (R ¹ + R ² ) is 10 mol% or more, more preferably Is 20 mol% or more, more preferably 50 mol% or more.

  In addition, the phenyl group-containing silicone (BP) has good adhesion to an organic substrate such as an organic resin, and the siloxane bond (—O—Si—) constituting the skeleton does not undergo oxidative decomposition due to photocatalysis, The photocatalyst-containing surface layer portion obtained by coating the surface light emitter with the photocatalyst composition (C) of the present invention has extremely excellent weather resistance.

  In the photocatalyst composition (C) of the present invention, the phenyl group-containing silicone (BP) used for the binder component (B) is more preferably an alkyl group represented by the following formula (16), which exhibits the above-described effects. It is a phenyl group-containing silicone (BP1) that does not contain.

  In addition, when the binder component (B) further contains an alkyl group-containing silicone (BA) represented by the following formula (17), the surface layer portion formed from the photocatalyst composition of the present invention has a film formability, hardness, This is preferable because of excellent heat resistance, contamination resistance, chemical resistance, and the like.

  Furthermore, as the alkyl group-containing silicone (BA) to be mixed with the phenyl group-containing silicone (BP1), the monooxydiorganosilane unit (D) represented by the formula (18) and the diester represented by the formula (19) are used. When the oxyorganosilane unit (T) has a structure having a molar ratio of preferably (D) / (T) = 100/0 to 5/95, more preferably 90/10 to 10/90. As a result, the stress relaxation action of the alkyl group-containing silicone (BA) is increased, and the crack resistance of the photocatalyst-containing surface layer portion produced from the photocatalyst composition (C) of the present invention is improved. As a result, the weather resistance is extremely excellent. Become.

  In the present invention, in order to improve long-term weather resistance, the binder component (B) preferably forms a phase separation structure, and particularly preferably forms a microphase separation structure.

  For example, as the binder component (B), the above-mentioned photocatalyst (A), particularly the binder resin (B ′) having a higher surface energy than the modified photocatalyst (A1) and the alkyl group-containing silicone (BA) represented by the above formula (6) ), Preferably in a mass ratio (B ′) / (BA) = 5/95 to 95/5, more preferably (B ′) / (BA) = 30/70 to 90/10 And the photocatalyst-containing surface layer portion formed from the photocatalyst composition (C) of the present invention has a photocatalyst (A) in a binder in which the binder resin (B ′) having a high surface energy and the alkyl group-containing silicone (BA) are phase-separated. Is preferable because it has a dispersed structure and excellent long-term weather resistance.

Here, the phase separation between the binder component (B ′) having a high surface energy and the alkyl group-containing silicone (BA) is preferably a phase that is not a continuous layer, preferably 1 nm ³ to 1 μm ³ , more preferably 10 nm ^{3 to} 0.1 μm ³ , More preferably, a more effective effect can be obtained when a domain having a size of 10 nm ^{3 to} 0.001 μm ³ is formed and microphase separation is performed.

  In addition, the state in which the photocatalyst (A) is present in the alkyl group-containing silicone (BA) phase that is in a phase-separated state with the binder resin (B ′) having a high surface energy is more on the surface of the surface layer part. Preferred because it can be present.

  As the binder resin (B ′) having a high surface energy that is phase-separated from the alkyl group-containing silicone (BA) in the present invention, the above-described phenyl group-containing silicone (BP) is a siloxane bond (—O—Si—) constituting the skeleton. ) Is preferable because it does not undergo oxidative degradation due to photocatalysis, and phenyl group-containing silicone (BP1) not containing an alkyl group is particularly preferable.

  At this time, the polystyrene-converted weight average molecular weight of each of the phenyl group-containing silicone (BP1) and the alkyl group-containing silicone (BA) measured by GPC is preferably 100 to 10,000, more preferably 500 to 6, 000, more preferably 700 to 4,000 is preferable because the above-described binder component (B) easily forms a microphase separation structure.

  The binder component (B) used in the photocatalyst composition (C) of the present invention is any of a type dissolved in a solvent, a type dispersed in a solvent, and a type not mixed with a solvent (liquid or solid). Also good.

  In the photocatalyst composition (C) of the present invention, the phenyl group-containing silicone (BP) represented by the above formula (11) does not have a reactive group (X in the formula (11)). The photocatalyst-containing surface layer obtained from the photocatalyst composition (C) of the present invention may have a reactive group (X in the formula (11) (that is, 0 <r in the formula (4)). The part is preferable because it has excellent hardness, heat resistance, chemical resistance, durability, and the like. Further, for the same reason, 0 <t in the formula (16) and 0 <v in the formula (17) are preferable.

  In the photocatalyst composition (C) of the present invention, the phenyl group-containing silicone (BP) represented by the above formula (11) is reactive (X in the formula (11)) as a hydroxyl group and / or a hydrolyzable group. In the case where it has, a conventionally known hydrolysis catalyst or curing catalyst is preferably added in an amount of 0.01 to 20% by mass, more preferably 0.1 to 5% by mass with respect to the phenyl group-containing silicone (BP). be able to.

  The hydrolysis catalyst is preferably an acidic hydrogen halide, a carboxylic acid, a sulfonic acid, an acidic or weakly acidic inorganic salt, or a solid acid such as an ion exchange resin. The amount of the hydrolysis catalyst is preferably in the range of 0.001 to 5 mol with respect to 1 mol of the hydrolyzable group on the silicon atom.

  Examples of the curing catalyst include basic compounds such as sodium hydroxide, potassium hydroxide, sodium methylate, sodium acetate, tetramethylammonium chloride, tetramethylammonium hydroxide; tributylamine, diazabicycloundecene, ethylenediamine. Amine compounds such as diethylenetriamine, ethanolamines, γ-aminopropyltrimethoxysilane, γ- (2-aminoethyl) -aminopropyltrimethoxysilane; titanium compounds such as tetraisopropyl titanate, tetrabutyl titanate; Aluminum compounds such as propoxide, aluminum acetylacetonate, aluminum perchlorate, aluminum chloride; tin acetylacetonate, dibutyltin octoate Tin compounds such as tyrates and dibutyltin dilaurate; metal-containing compounds such as cobalt octylate, cobalt acetylacetonate and iron acetylacetonate; acidic such as phosphoric acid, nitric acid, phthalic acid, p-toluenesulfonic acid and trichloroacetic acid Examples thereof include compounds.

  In the photocatalyst composition (C) of the present invention, when the phenyl group-containing silicone (BP) represented by the above formula (11) has a Si—H group, a crosslinking agent such as a polyfunctional alkenyl compound is used for the Si—H group. The alkenyl group is preferably added so that the amount is preferably 0.01 to 2 equivalents, more preferably 0.1 to 1 equivalents. The polyfunctional alkenyl compound may be anything as long as it has an alkenyl group and reacts with the Si—H group to accelerate curing, but has 2 to 30 carbon atoms such as a vinyl group, an allyl group, or a hexenyl group. Alkenyl group-containing silicones having monounsaturated hydrocarbon groups are generally used.

  Further, for the purpose of promoting the reaction between the Si—H group and the polyfunctional alkenyl compound, the catalyst is preferably from 1 to 10,000 ppm, more preferably from 1 to 10,000 ppm, based on the total amount of the phenyl group-containing silicone (BP) and the polyfunctional alkenyl compound. You may add in the ratio of 1000 ppm. As the catalyst, a platinum group catalyst, that is, a ruthenium, rhodium, palladium, osmium, iridium, or platinum compound is suitable, and a platinum compound and a palladium compound are particularly suitable. Examples of platinum compounds include platinum chloride (II), tetrachloroplatinic acid (II), platinum chloride (IV), hexachloroplatinic acid (IV), hexachloroplatinum (IV) ammonium, hexachloroplatinum (IV) potassium, hydroxide Platinum (II), platinum dioxide (IV), dichloro-dicyclopentadienyl-platinum (II), platinum-vinylsiloxane complex, platinum-phosphine complex, platinum-olefin complex, platinum simple substance, alumina, silica and activated carbon The thing which carry | supported solid platinum is mentioned. Examples of the palladium compound include palladium (II) chloride, ammonium tetraamminepalladium (II) chloride, palladium (II) oxide and the like. The platinum group catalyst is preferably used in an amount of 5 to 1000 ppm in terms of platinum group metal based on the total amount of Si-H group-containing silicone and polyfunctional alkenyl compound. It can be increased / decreased according to the curing rate and the like. Moreover, you may add activity inhibitors, such as various organic nitrogen compounds, an organic phosphorus compound, and an acetylene type compound, for the purpose of suppressing the activity of a platinum group catalyst and extending pot life if desired.

  Further, the photocatalyst composition (C) of the present invention includes silica, alumina, zirconium oxide, antimony oxide, rare earth oxide, etc. for the purpose of improving the hardness, scratch resistance and hydrophilicity of the photocatalyst-containing surface layer portion formed therefrom. The metal oxide fine particles may be added in the form of powder or sol. However, these metal oxide fine particles do not have the ability as a binder like the binder component (B) in the present invention, and reduce the flexibility (flexibility, impact resistance) of the surface layer portion in the same manner as the photocatalyst. Therefore, the addition amount of the metal oxide is preferably such that the total weight of the photocatalyst (A) and the metal oxide is 50% by mass or less in the photocatalyst-containing surface layer formed from the photocatalyst composition (C).

  The photocatalyst composition (C) of the present invention may be in a solvent-free state (liquid, solid) or dissolved or dispersed in a solvent, and is not particularly limited, but when used as a coating agent, A dissolved or dispersed state in a solvent is preferred. At this time, the total amount of the photocatalyst (A) and the binder component (B) in the photocatalyst composition (C) is preferably 0.01 to 95% by mass, more preferably 0.1 to 70% by mass.

  Examples of the solvent used in the photocatalyst composition (C) of the present invention include water, alcohols such as ethylene glycol, butyl cellosolve, isopropanol, n-butanol, ethanol and methanol, aromatic hydrocarbons such as toluene and xylene, hexane, Aliphatic hydrocarbons such as 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, dimethylacetamide, dimethylformamide and the like Examples include amides, halogen compounds such as chloroform, methylene chloride, and carbon tetrachloride, dimethyl sulfoxide, nitrobenzene, and the like. These solvents are used alone or in combination.

  In addition, the photocatalyst composition (C) of the present invention usually contains components that are usually added and blended with a paint, for example, pigments, fillers, dispersants, light stabilizers, wetting agents, thickeners, rheology control agents, An antifoaming agent, a plasticizer, a film forming aid, a rust preventive agent, a dye, a preservative, and the like can be selected, combined and blended depending on the purpose.

  In the photocatalyst composition (C) of the present invention, when the self-gradient property is very high (that is, with respect to the photocatalyst (A) content (concentration) 100 in the surface layer portion, the exposed surface, which is the side that is not a surface light emitter, When the relative concentration in the vicinity of the contacting surface is preferably 150 or more, more preferably 200 or more), the mass ratio of the photocatalyst (A) to the binder component (B) in the photocatalyst composition (C) is preferably (A) / (B) = 0.1 / 99.9 to 40/60, more preferably (A) / (B) = 0.1 / 99.9 to 30/70 The content of the photocatalyst (A) is very small. Even in the range, the formed surface layer portion has a sufficient hydrophilization ability (superhydrophilicity ability: water contact angle at 20 ° C. of 10 ° or less) by light irradiation and excellent photocatalytic activity. Further, the surface layer portion having a small photocatalyst content as described above exhibits the original physical properties of the binder component (B), and thus has excellent strength and flexibility (flexibility, impact resistance) and the like.

  The light transmissive material having a photocatalyst surface layer portion in the present invention includes a surface layer portion containing a photocatalyst (A) and a binder component (B), and the concentration of the photocatalyst (A) in the surface layer portion is from the light transmissive material side. It is characterized by becoming higher toward the surface. However, the light transmissive material having the photocatalyst surface layer part in the present invention can contain the photocatalyst (A) and / or the binder component (B) in a part other than the surface layer part as long as the effects of the present invention are not hindered.

  The light transmissive material having a photocatalyst surface layer part in the present invention is a form in which the surface layer part is formed into a film shape and the film containing the photocatalyst (A) and the binder component (B) is provided on the light transmissive material as a base material. It can be. By adopting such a form, a structure in which the functions are shared between the base material and the surface layer portion becomes possible, which is preferable.

  In addition, a part other than the surface layer part, for example, the one containing the photocatalyst (A) and / or the binder component (B) in the base part can be molded at once and can compensate for a defective part of the surface layer part. This is preferable. Such a form is preferable when, for example, a thin film member is used.

  The manufacturing method of the light transmissive material which has a photocatalyst surface layer part in this invention is not limited to when forming a membrane | film | coat from the photocatalyst composition of this invention on a base material. You may shape | mold simultaneously the base material used as a light transmissive material, and the photocatalyst composition of this invention, for example, integral molding and lamination molding. Moreover, it is good also as a light transmissive material which has a photocatalyst surface layer part by adhesion | attachment, melt | fusion, etc., after shape | molding the photocatalyst composition of this invention and the light transmissive material as a base material separately.

  The light-transmitting material having a photocatalyst surface layer portion in the present invention is preferably, if desired, after applying the photocatalyst composition (C) to the light-transmitting material and drying, for example, when the surface layer portion is formed into a film. It can be obtained by forming a film by performing heat treatment at 20 ° C. to 500 ° C., more preferably 40 ° C. to 250 ° C. or ultraviolet irradiation. Examples of the coating method include spray spraying, flow coating, roll coating, brush coating, dip coating, spin coating, casting, and sponge coating.

  Under the present circumstances, the film thickness of the film | membrane formed from the photocatalyst composition (C) of this invention becomes like this. Preferably it is 0.1-200 micrometers, More preferably, it is 0.5-20 micrometers, More preferably, it is 1.5-10 micrometers.

  In the present specification, the expression “film” is used. However, the film is not necessarily a continuous film, and may be a discontinuous film, an island-shaped dispersion film, or the like.

  Moreover, metals such as Ag, Cu, and Zn can be added to the surface of the light transmissive material having the photocatalyst surface layer portion of the present invention. The surface layer portion to which the metal is added can kill bacteria and sputum attached to the surface even in the dark.

  The light-transmitting material having the photocatalyst surface layer part of the present invention exhibits photocatalytic activity and / or hydrophilicity by irradiating light (excitation light) with energy higher than the band gap energy of the photocatalyst (A) contained in the surface layer part. Shows excellent antifouling performance.

  At this time, the photocatalyst (A) is a triorganosilane unit represented by the above formula (1), a monooxydiorganosilane unit represented by the formula (2), or a dioxyorgano represented by the formula (3). In the case of the modified photocatalyst (A1) modified with at least one modifier compound (b) selected from the group consisting of compounds having at least one structural unit selected from the group consisting of silane units, excitation light At least a part of the organic group (R) bonded to the silicon atom of the modifier compound (b) present in the vicinity of the photocatalyst (A) particles by irradiation is substituted with a hydroxyl group by the decomposition action of the photocatalyst. As a result, the hydrophilicity of the surface of the surface layer portion of the present invention is increased, and when the generated hydroxyl groups are subjected to a dehydration condensation reaction to form a siloxane bond, the hardness of the surface layer portion becomes very high. Such a state is preferable in the aspect of the present invention.

  Similarly, when the above-described silicone is used as the binder component (B), at least a part of the organic group bonded to the silicon atom of the silicone present in the vicinity of the photocatalyst (A) particles by excitation light irradiation is the photocatalyst. When the hydroxyl group is substituted by the decomposition action, the hydrophilicity of the surface of the surface layer portion of the present invention is increased, and the dehydration condensation reaction between the generated hydroxyl groups proceeds to form a siloxane bond, the hardness of the surface layer portion is very high. Become. Such a state is preferable in the aspect of the present invention.

  It describes about the LED light source which is a structural component of this invention.

  In order to excite the photocatalyst in the present invention, light (excitation light) having an energy higher than the band gap energy of the photocatalyst (A) is required, and the wavelength of the light needs to be 390 nm or less. An LED (1) emitting a wavelength of a peak wavelength of 350 to 390 nm is used as a light source used in the present invention from a wavelength region that is put into practical use as a light source emitting a wavelength of 390 nm or less. Examples of the LED (1) used in the present invention include NSHU550A, NSHU590A, NSHU550B, NSHU590B, NCCU001, NCCU033 and the like manufactured by Nichia Corporation, but are not limited thereto.

  The LED (2) that emits visible light can obtain a desired color tone by monochromatic or mixing three primary color LEDs. Further, the LED (3) that emits white light can be mixed with three primary color LEDs, or white light composed of a blue LED and a phosphor can be used. Examples of these include surface mounted light emitting diodes “PowerLED Series”, “Top View Series”, “Side View Series”, “Full Color Series”, “C Series”, and shell-type light emitting diode “Warm” manufactured by Nichia Corporation. “White Series”, “F3 Series”, “F5 Series”, “F7.5 Series”, “Ovel Series / Super Over Series”, “Flat Series”, “Full Color, Series”, and the like. It is not something.

  The LED (1) emitting a wavelength of a peak wavelength of 350 to 390 nm excites the photocatalyst and degrades the light transmissive organic material when irradiated for a long time. Therefore, in the LED (1) and the LED (2) that emits visible light and / or the LED (3) that emits white light, the light emission time of the LED (1) is a unit of the LED (2) and / or LED (3). It must be controlled to emit between 1/100 and 99/100, preferably between 10/100 and 90/100, more preferably between 20/100 and 80/100 per emission time. If it is in the said range, LED (1) can excite a photocatalyst and can prevent deterioration of a light-transmissive organic material by intermittent light emission.

  The distance between the LED light source and the light transmissive material having the photocatalyst surface layer is not particularly specified, but photoexcitation of the photocatalyst by the LED (1) emitting a wavelength of 350 to 390 nm at a wavelength of 500 mm or less is effectively expressed. This is preferable.

  When using the lighting body of the present invention with designability, the designability imparting method is not particularly limited, and photographs, illustrations, characters, etc. are transferred to or pasted on the surface of the light-transmitting material. Design is given by printing. Also, illustrations, characters, etc. may be displayed by engraving. Further, the light transmissive material itself may be colored and used.

[Examples, reference examples, comparative examples]
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.

Ｌ（５）は光源から直角に入光させた光が光拡散材料を通し５°の角度で出光した透過光輝度（ｃｄ／ｍ２）である。同様にＬ（２０）は２０°、Ｌ（７０）は７０°の角度で出光した透過光輝度である。
（４）視認性
光拡散材料の片面に１ｃｍ角の黒色格子模様（線幅１ｍｍ）を印刷し、その上に光触媒層を設け、光源を点灯し、格子の見え具合を４段階評価した。
◎…極めてきれいに格子模様が視認される。
○…きれいに格子模様が視認される。
△…格子模様がはっきり視認出来ない。
×…格子模様が視認出来ない。
（５）光源イメージ
表示装置直上から目視で観察し、得られた光源イメージの度合いを４段階で評価した。
◎ 光源が見えない。
○ 光源が殆ど見えない。
△ 光源が確認できる。
× 光源がはっきり見える。 1. Light diffusing material (1) Total light transmittance: measured in accordance with JIS K-7105.
(2) Average particle diameter of light scattering agent: Fine particles of the scattering agent are dispersed in an organic solution by ultrasonic waves, and the obtained dispersion is measured using a microtrack method. Adopted as.
(3) Light diffusivity: Calculated by the following formula defined in DIN 5035.

L (5) is the transmitted light luminance (cd / m 2) where light incident at a right angle from the light source is emitted at an angle of 5 ° through the light diffusion material. Similarly, L (20) is the transmitted light luminance emitted at an angle of 20 ° and L (70) is 70 °.
(4) Visibility A 1 cm square black lattice pattern (line width: 1 mm) was printed on one side of the light diffusing material, a photocatalyst layer was provided thereon, a light source was turned on, and the appearance of the lattice was evaluated in four stages.
◎… The lattice pattern is very clearly visible.
○: The lattice pattern is clearly visible.
Δ: The lattice pattern is not clearly visible.
×: The lattice pattern is not visible.
(5) Light source image The light source image was visually observed from directly above, and the degree of the obtained light source image was evaluated in four stages.
◎ I can't see the light source.
○ The light source is almost invisible.
△ The light source can be confirmed.
× The light source is clearly visible.

2. Photocatalyst (1) Particle size distribution and number average particle size Diluted by adding a suitable solvent so that the photocatalyst content in the sample is 1-20% by mass, and using a wet particle size analyzer (Nikkiso Microtrac UPA-9230) Measured.
(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-8020LC-3A type chromatography _column: TSKgelG1000H XL, (both manufactured by Tosoh Corporation) TSKgel G2000H _XL and TSKgel G4000H _XL was used connected in series.
-Data processor: CR-4A type data processor manufactured by Shimadzu Corporation-Mobile phase:
Tetrahydrofuran (used for analysis of phenyl group-containing silicone)
Chloroform (used for analysis of silicones that do not contain phenyl groups)
-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.
(4) Measurement of ²⁹ Si nuclear magnetic resonance It measured using JEOL JNM-LA400.
(5) Contact angle of water with respect to film surface A drop of deionized water was placed on the surface of the film and allowed to stand at 20 ° C for 1 minute, and then measured using a CA-X150 contact angle meter manufactured by Kyowa Interface Science.
The smaller the contact angle of water with the film, the higher the hydrophilicity of the film surface.
(6) Photocatalytic activity of the film After applying a 5% by weight ethanol solution of methylene blue to the film surface, the LED light source was turned on for 30 days, and then the degree of decomposition of methylene blue by the action of the photocatalyst (based on the degree of fading of the film surface) ), The activity of the photocatalyst was evaluated in the following four stages.
A: Methylene blue is completely decomposed.
○: A little blue of methylene blue remains.
Δ: Blue of methylene blue remains.
X: Methylene blue was hardly decomposed and blue color remained.

[Reference Example 1]
Manufacture of single layer sheet-1 Delpet LP-1 (methacrylic resin: manufactured by Asahi Kasei Chemicals Corporation) 100 parts by weight, techpolymer SBX-4 (polystyrene crosslinked beads, average particle size 4.5 μm: manufactured by Sekisui Plastics Co., Ltd.) 0.8 parts by weight, 1.5 parts by weight of Tospearl 2000B (siloxane crosslinked beads, average particle size 6 μm: manufactured by Toshiba Silicon Co., Ltd.), calcium carbonate (average particle size 0.7 μm) as an inorganic light scattering agent 5 parts by weight were mixed with a drive renderer and kneaded and granulated at a resin temperature of 250 ° C. using a twin screw extruder to obtain a resin composition. The composition is fed to an extruder having a screw diameter of 120 mmφ and L / D (extruded length / extruded diameter) = 32, and a single layer sheet having a thickness of 2 mm and a width of 1000 mm is extruded to obtain a single layer sheet-1. It was.
A test piece was cut out from the obtained sheet, and the total light transmittance and light diffusivity were measured. As a result, the total light transmittance was 52% and the light diffusivity was 82%.

[Reference Example 2]
Manufacture of single layer sheet-2 Delpet LP-1 (methacrylic resin: manufactured by Asahi Kasei Chemicals Corporation) 100 parts by weight, techpolymer SBX-4 (polystyrene crosslinked beads, average particle size 4.5 μm: manufactured by Sekisui Plastics Co., Ltd.) ) 3.8 parts by weight were mixed with a drive renderer and kneaded and granulated at a resin temperature of 250 ° C. using a twin screw extruder to obtain a resin composition. The composition was fed to an extruder having a screw diameter of 120 mmφ and L / D (extruded length / extruded diameter) = 32, and a single layer sheet having a thickness of 2 mm and a width of 1000 mm was extruded to obtain a single layer sheet-2. It was.
A test piece was cut out from the obtained sheet and the total light transmittance and light diffusivity were measured. As a result, the total light transmittance was 53% and the light diffusivity was 85%.

[Reference Example 3]
Production of single-layer sheet-3 Delpet LP-1 (methacrylic resin: manufactured by Asahi Kasei Chemicals Corporation) 100 parts by weight, Tospearl 2000B (siloxane crosslinked beads, average particle size 6 μm: manufactured by Toshiba Silicon Co., Ltd.) 3.8 parts by weight The mixture was mixed with a drive renderer and kneaded and granulated at a resin temperature of 250 ° C. using a twin screw extruder to obtain a resin composition. The composition was fed to an extruder having a screw diameter of 120 mmφ and L / D (extruded length / extruded diameter) = 32, and a single layer sheet having a thickness of 2 mm and a width of 1000 mm was extruded to obtain a single layer sheet-3. It was.
A test piece was cut out from the obtained sheet and measured for total light transmittance and light diffusivity. As a result, the total light transmittance was 52% and the light diffusivity was 83%.

[Reference Example 4]
Manufacture of single layer sheet-4 Delpet LP-1 (methacrylic resin: manufactured by Asahi Kasei Chemicals Corporation) 100 parts by weight and calcium carbonate (average particle size 0.7 μm) 3.8 parts by weight were mixed with a drive renderer, biaxial A resin composition was obtained by kneading and granulating at a resin temperature of 250 ° C. using an extruder. The composition is fed to an extruder having a screw diameter of 120 mmφ and L / D (extruded length / extruded diameter) = 32, and a single layer sheet having a thickness of 2 mm and a width of 1000 mm is extruded to obtain a single layer sheet-4. It was.
A test piece was cut out from the obtained sheet and measured for total light transmittance and light diffusivity. As a result, the total light transmittance was 46% and the light diffusivity was 74%.

[Reference Example 5]
Manufacture of laminated sheet-1 The resin composition used in Reference Example 1 was used as a base layer, and Delpet LP-1 (methacrylic resin: manufactured by Asahi Kasei Chemicals Corporation) 100 parts by weight and talc (average particle size 0. 7 μm) 10 parts by weight and Tospearl 120 (siloxane cross-linked beads, average particle size 2 μm: manufactured by Toshiba Silicon Co., Ltd.) 10 parts by weight were laminated to produce a laminated sheet-1 having a layer of a resin composition. The thickness of the laminated resin layer was 30 μm on both sides. A test piece was cut out from the obtained sheet and the total light transmittance and light diffusivity were measured. As a result, the total light transmittance was 51% and the light diffusivity was 82%.

[Reference Example 6]
Production of monolayer sheet-5 Except that the blending amount of Tospearl 2000B in Reference Example 3 was 0.5 parts by weight, the monolayer sheet was extruded and formed in the same manner as in Reference Example 3 to obtain a monolayer sheet-5. . A test piece was cut out from the obtained sheet, and the total light transmittance and light diffusivity were measured. As a result, the total light transmittance was 80% and the light diffusivity was 40%.

[Reference Example 7]
Production of Laminated Sheet-2 The resin composition used in Reference Example 6 was used as a base material layer, and Delpet LP-1 (methacrylic resin: manufactured by Asahi Kasei Chemicals Co., Ltd.) 100 parts by weight and talc (average particle size 0. 0) on both surfaces. 7 μm) A laminated sheet-2 in which layers of a resin composition consisting of 15 parts by weight were laminated was produced. The thickness of the laminated resin layer was 30 μm on both sides. A test piece was cut out from the obtained sheet and measured for total light transmittance and light diffusivity. As a result, the total light transmittance was 80% and the light diffusivity was 36%.

[Reference Example 8]
Synthesis of phenyl group-containing silicone (BP1-1).
After adding 26.0 g of phenyltrichlorosilane to 78 g of dioxane in a reactor having a reflux condenser, a thermometer and a stirrer, the mixture was stirred at room temperature for about 10 minutes. A mixture of 3.2 g of water and 12.9 g of dioxane was added dropwise thereto over about 30 minutes while maintaining the reaction solution at 10 to 15 ° C., followed by further stirring at 10 to 15 ° C. for about 30 minutes, The reaction solution was heated to 60 ° C. and stirred for 3 hours. The resulting reaction solution was cooled to 25-30 ° C., 392 g of toluene was added dropwise over about 30 minutes, and then the reaction solution was again heated to 60 ° C. and stirred for 2 hours.
The resulting reaction solution was cooled to 10 to 15 ° C., and 19.2 g of methanol was added over about 30 minutes. Thereafter, stirring was further continued at 25-30 ° C. for about 2 hours, and then the reaction solution was heated to 60 ° C. and stirred for 2 hours. The solvent was distilled off from the resulting reaction solution at 60 ° C. under reduced pressure to obtain a phenyl group-containing silicone (BP1-1) having a ladder skeleton having a weight average molecular weight of 3600 (the obtained phenyl group-containing silicone ( In BP1-1), absorptions (1130 cm ⁻¹ and 1037 cm ⁻¹ ) derived from the stretching vibration of the ladder skeleton in the IR spectrum were observed.
The formula of the phenyl group-containing silicone (BP1-1) obtained from the measurement result of ²⁹ Si nuclear magnetic resonance was (Ph) ₁ (OCH ₃ ) _0.58 SiO _1.21 (where Ph is Represents a phenyl group).

[Reference Example 9]
Synthesis of alkyl group-containing silicone (BA-1).
After adding 136 g (1 mol) of methyltrimethoxysilane and 120 g (1 mol) of dimethyldimethoxysilane to 300 g of methanol in a reactor equipped with a reflux condenser, a thermometer and a stirrer, the mixture was stirred at room temperature for about 10 minutes. did. A mixture of 12.6 g (0.7 mol) of 0.05N aqueous hydrochloric acid and 63 g of methanol was added dropwise thereto over about 40 minutes under ice-cooling to carry out hydrolysis. After completion of the dropwise addition, the mixture was further stirred at 10 ° C. or lower for about 20 minutes and at room temperature for 6 hours.
Then, the alkyl group containing silicone (BA-1) of the weight average molecular weight 3600 was obtained by distilling a solvent off under reduced pressure at 60 degreeC from the obtained reaction liquid. When the structure of the obtained alkyl group-containing silicone (BA-1) was measured by ²⁹ Si nuclear magnetic resonance, signals indicating T structure and D structure were confirmed, and the ratio was T structure: D structure = 1: 1. there were.
^The average composition formula of the above alkyl group-containing silicone obtained from the measurement results of 29 Si nuclear magnetic resonance (BA-1) _{was (CH 3) 1.5 (OCH 3} ) 0.27 SiO 1.12 .

[Reference Example 10]
Adjustment of silicone composition (B-1).
A mixture of 6 g of the phenyl group-containing silicone (BP1-1) synthesized in Reference Example 8 and 3 g of the alkyl group-containing silicone (BA-1) synthesized in Reference Example 9 was mixed with 14.7 g of toluene, 29.8 g of isopropanol, and butyl cellosolve. 15.1g was added and the solution of the binder component (B-1) was obtained by stirring at room temperature.
From the average composition formula of each composition, the average composition formula of the binder component (B-1) is (Ph) _0.67 (CH ₃ ) _0.5 (OCH ₃ ) _0.47 SiO _1.18. (Where Ph represents a phenyl group).

[Reference Example 11]
TKS-251 {trade name of titanium oxide organosol (manufactured by Teica), dispersion medium: mixed solvent of toluene and isopropanol, TiO2 concentration 20% by weight, average crystal in a reactor having a reflux condenser, a thermometer and a stirrer By adding 40 g of a 20% by weight toluene solution of bis (trimethylsiloxy) methylsilane to 40 g of a child diameter of 6 nm (catalog value) at 50 ° C. over about 5 minutes, and further stirring at 50 ° C. for 12 hours, A modified photocatalyst organosol (A-1) having good dispersibility was obtained. At this time, the amount of hydrogen gas generated by the reaction of bis (trimethylsiloxy) methylsilane was 718 ml at 23 ° C. Moreover, when the obtained modified titanium oxide organosol was coated on a KBr plate and IR spectrum was measured, the disappearance of absorption of Ti—OH group (3630 to 3640 cm ⁻¹ ) was observed.
The resulting modified photocatalyst organosol (A-1) has a single particle size distribution (number average particle size is 25 nm), and further a single dispersion of TKS-251 before the modification treatment (number average particle size is 12 nm). The particle size distribution completely disappeared.
Subsequently, 20 g of the modified photocatalyst organosol (A-1) was added to 68 g of the solution of the silicone component (B-1) prepared in Reference Example 10 at room temperature with stirring, and a curing catalyst (dibutyltin dilaurate) 0 was added. .5 g was added with stirring to obtain a photocatalyst composition (C-1).

[Examples 1-5, Comparative Examples 1-2]
After printing a 1 cm square black lattice pattern (line width: 1 mm) on the light diffusive material sheet formed in Reference Examples 1 to 7, the photocatalyst composition (C-1) prepared in Reference Example 11 is formed on the surface. Is spray-coated to be about 3 μm, dried at room temperature for 2 days, and then heated at 50 ° C. for 3 days to give a light-diffusing material sheet having a smooth photocatalyst-containing film (D-1 to 7) Got.
1 and 2 are schematic views of the illuminating bodies of Examples 1 to 6 and Comparative Examples 1 to 4. FIG. D1-7 were incorporated in the display device (the gap between the light source and the light diffusing material sheet was 10 cm) shown in FIGS. NSHA590B (peak wavelength 365 nm) manufactured by Nichia Corporation was used as the LED (1) of the LED light source of the lighting device, and NSPW500BS (white) manufactured by Nichia Corporation was used alternately as the LED (3). .
The light emission time of LED (1) is controlled to be 50/100 per unit light emission time of LED (3) (LED (3) always emits light per hour, LED (1) emits light for 30 minutes The remaining 30 minutes were not allowed to emit light), and after lighting for 30 days, photocatalytic activity, water contact angle, visibility, and light source image were evaluated. The results are shown in Table 1.

[Comparative Example 3]
Using D-1 of Example 1, the LED (1) is not emitted, and only the LED (3) is emitted, except that the LED (3) is lit for 30 days, and the same evaluation as in Example 1 is performed. It was. The photocatalytic activity was x, the contact angle of water was 105 °, the antifouling property was poor, and it was not practically usable.

[Comparative Example 4]
Using D-1 of Example 1, the LED (1) and LED (3) were lit for 30 days in the same manner as in Example 1 except that the LED (1) and LED (3) were always lit, and the same evaluation as in Example 1 was performed. The photocatalytic activity was excellent, and the contact angle of water was 0 °, and the antifouling property was excellent. However, the surface light emitter itself deteriorated and the appearance was poor due to turbidity, which was not practical.

[Example 6]
It is lit for 30 days in the same manner as in Example 1 except that NSPR510AS (red) manufactured by Nichia Corporation is used as the LED (2) instead of the LED (3) in Example 1, and the same evaluation as in Example 1 Went. The photocatalytic activity was ◎, water contact angle 0 °, visibility ◎, and light source image ◎, which could be put to practical use.

[Examples 7 to 8]
FIG. 3 is a schematic view from above of the illuminating bodies of Examples 7-8. Using the same type of LED (1) and LED (3) as the LED light source of the illuminating device used in Example 1, the number of LEDs (1) and LED (3) is set to one LED (1) (3 ) Except for the ratio of 3 pieces, D-1 of Example 1 was used, and it was lit for 30 days in the same manner as in Example 1, and the same evaluation as in Example 1 was performed. The photocatalytic activity was ◎, water contact angle 0 °, visibility ◎, and light source image ◎, which could be put to practical use. Moreover, as a result of performing the same evaluation using D-4 of Example 4, the photocatalytic activity was ○, the contact angle of water was 5 °, the visibility ◎, and the light source image ◎, which could be put to practical use. .

  The present invention is applicable to an antifouling display body having a photocatalyst layer.

The schematic diagram from the upper side of the illumination body of Examples 1-6 and Comparative Examples 1-4. The schematic diagram from the side of the illuminating body of Examples 1-6 and Comparative Examples 1-4. Schematic view from above of illuminating bodies of Examples 7-8

Explanation of symbols

1 ... LED light source: LED (1),
2 ... LED light source: LED (2) or LED (3),
3 ... display body housing,
4 ... Light diffusing material sheet,
5 ... Photocatalyst layer,
6 ... Print grid

Claims (4)

A light diffusing material and an illuminating body in which a plurality of LEDs are disposed directly under the light diffusing material;
A photocatalytic layer laminated on the light diffusing material,
The plurality of LEDs are at least:
An LED emitting a wavelength of a peak wavelength of 350 to 390 nm;
An LED light source comprising an LED emitting visible light and / or an LED emitting white light;
An antifouling display body characterized by comprising: The emission time of the LED emitting the wavelength of the peak wavelength of 350 to 390 nm,
The LED that emits visible light and / or the LED that emits white light is controlled to emit light at a unit emission time of 1/100 to 99/100. Antifouling display body.   The antifouling display body according to claim 1 or 2, wherein the photocatalyst layer comprises a photocatalyst composition containing a photocatalyst and a binder component. The antifouling display body according to any one of claims 1 to 3, wherein the light diffusing material is formed of a thermoplastic resin and a light diffusing agent.

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