Photocatalyst composite and process for producing the same

BACKGROUND OF THE INVENTION

FIELD OF THE INVENTION

0001The present invention relates to a photocatalyst composite, of adhering a substrate having thereon comprises photocatalyst particles, and a process for preparing thereof.

DESCRIPTION OF THE RELATED OF THE TECHNIQUE

0002The exposure of photocatalyst with radiation having a wavelength, not less than the band gap energy corresponds, causes the photoexcitation of electrons in a conduction band with a corresponding formation of holes in a valence band. The strong reducing power the electrons and the strong oxidation power of the optical through this Excitation holes generated were in the decomposition and purification of organic materials and used in the decomposition of water. The in such treatments to use photocatalyst particles are usually applied to a substrate, its dimensions greater than the photocatalyst particles are deposited, in order to prevent they are scattered in the air or discharged from the system, and then easy separation of the photocatalyst from the treatment system be able to achieve. The deposition of photocatalyst particles on a substrate is by a method comprising sintering the photocatalyst particles on the substrate at a temperature of 400 ° C or higher for securing the particles comprises on the substrate, or a method of spraying precursor, the converted by thermal decomposition in a photocatalyst can be on a heated to a temperature of about 400 ° C Substrate, thereby the particles are attached to the substrate, comprises achieved. Alternatively, a method of immobilization was photocatalyst particles using a certain type a fluorinated polymer proposed. For example, disclosed the (disclosed), Japanese Patent KOKAI Nos. Hei 4-284851 a Method comprising laminating a mixture of photocatalyst particles and a fluorinated polymer and compressing the laminate under includes pressure. The (Laid-open) Japanese Patent KOKAI Nos. Hei 4-334552 discloses a method of thermal fusion fluorinated polymer for adhering photocatalyst particles this includes.

0003Recently, an attempt has been made, Photocatalyst for decomposing harmful materials, malodorous Materials and oily Substances in the waste products, which generates daily in neighborhoods be, and for cleaning and sterilization of the waste products to use. Therefore photocatalyst find ever wider expectant applications. In this regard, there is a need to a method by which photocatalyst fixed on a Substrate can be attached, the liability an extended Period can be maintained without affecting their photocatalytic Effect is lost. unfortunateli sick those described in the preceding processes of the prior art to an insufficient adhesive strength, while for delamination under external pressure susceptible are, and they require heating at high temperatures, so that they for a non-heat-resistant substrate, such as plastics, interior materials such as office walls and the surfaces of various Products which are difficult to heat, and the like are not can be used. also there are problems that the thermal treatments at high temperatures cause the photocatalyst particles to reduce their specific surface area, leading to a reduction in their photocatalytic effect leads. Further, special agents, such devices for fastening under pressure or melting under heat, to be required.

SUMMARY OF THE INVENTION

0004An object of the present invention is to provide a photocatalyst composite, the a substrate having thereon via a little degradable adhesive attached photocatalyst includes.

0005Another object of the present Invention is to provide a method for producing the photocatalyst composite.

0006Another object of the present Invention is to provide a coating composition using the photocatalyst composite.

BRIEF DESCRIPTION OF THE DRAWING

0007<figref idrefs="S26">1</figref> shows the variations of weight loss per unit area of Adhesives in the Photokatalysatorverbundstoffen due to Exposure to non-visible light for Sample A of Example 1 and Sample C of Comparative Example 1st

DETAILED DESCRIPTION PREFERRED EMBODIMENTS

0008The inventors of the present invention led Researches to provide a method for achieving a firm adhesion of photocatalyst particles onto any substrate over a longer Period without damage of the photocatalytic effect of the particles to develop. Consequently The present invention was based on the following investigation achieved that <ul><li>(1) when photocatalyst particles be fixed with an adhesive to a substrate, the photocatalytic Effect of the photocatalyst degrade the adhesive and damage can what a release of the photocatalyst from the substrate causes, and however, the use of a less degradative adhesive a fixing of the photocatalyst particles at any A substrate without causing the release of the particles of this allows and in an unforeseeable manner enables the photocatalyst of the present invention, a satisfactory photocatalytic Effect shows </li><li>(2) the photocatalyst particles on a substrate without a Reducing the photocatalytic action of the photocatalyst composite formed can be fixed, when the amount of the photocatalyst particles in the range of 5-98%, based to the total volume of the photocatalyst particles and the less degradative adhesive is,</li><li>(3) the use of organic adhesives such as fluorinated polymers and silicone-based polymers, or inorganic adhesive as less degradative adhesive in a very much reduced decomposition and a greatly reduced degradation of Kl ebmittel due the photocatalytic action of the photocatalyst leads, so that the photocatalyst for a long time fixed adhere to and in particular fluorinated polymers, primarily a copolymer of vinylethers and / or olefins include vinyl esters and fluorine, are preferred,</li><li>(4) preferred photocatalyst particles are titanium oxide which has a high photocatalytic function, a high chemical stability and no toxicity which are, and that</li><li>(5) a process for adhering or fixing photocatalyst particles, which can be used to the surfaces of various products to make relatively easy photocatalytically, and the problem Use the photocatalytic action in domestic applications allows, the steps of applying the photocatalyst particles and a less degradative adhesive on a substrate and then fixing the adhesive as a preferably cheap and easy method includes, or in particular the step of applying the photocatalyst particles and a less degradative adhesive by coating or spray on a coating composition comprising the photocatalyst that, the adhesive and a solvent contains, to the surfaces a substrate such as various products and then fixing comprising the adhesive.</li></ul>

0009That is, object of the present Invention is to provide a photocatalyst composite, of any substrate having photocatalyst particles, without the a decrease in the photocatalytic effect of the partial surfaces laid over a longer Period attached thereto, comprising.

0010The present invention is a The photocatalyst composite comprising a substrate having a via little degradable adhesive attached thereto photocatalyst includes. The term used in the present invention "degradable little Adhesive designated " an adhesive having an extremely strong reduced rate of decomposition due to the photocatalytic action, which possess the photocatalyst particles in the range of 10% or less, usually 5% or less, expediently 3% or less, preferably 1% or less, which is expressed as weight loss of the adhesive in the photocatalyst composite, the determined according to the method described in the following example has been. A weight loss of greater than 10% are unfavorable strong Decomposition or unfavorable severe degradation of the adhesive, whereby a large amount of the photocatalyst particles is released on. To be used in the present invention less degradative adhesive include, for example, inorganic adhesive, such as silicon compounds, such as water glass, colloidal silica, Polyorganosiloxanes and the like, phosphates such as zinc phosphate, Aluminum phosphate and the like, biphosphates, cement, lime, gypsum, Glass frits, glass coating polishes, cleaning materials, organic Adhesive, such as fluorinated polymers, silicone-based polymers and the like, and these adhesives may be used in combination of two or more thereof may be used. In particular, inorganic Adhesives, fluorinated polymers and silicone based polymers in the With regard to the adhesive strength is preferred. The cement to be used includes, for example, Portland cements such as rapid-hardening Cement, general-purpose cement, moderate heat, sulfate resistant cement, white Cement, oil well cement and geothermishear-hole cement, Blended cement such as fly ash cement, sulfate slag, silica cement and blast furnace cement, alumina cement and the like. The to be used Putz includes, for example gypsum plaster, lime plaster, dolomite plaster and . like The fluorinated polymers to be used include, for example crystalline fluorinated resins such as polyvinyl fluorides, Polyinylidenfluoride, Polyethylentrifluorchloride, Polyethylene tetrafluoride, tetrafluoroethylene-hexafluoropropylene copolymers, Ethylene-polyethylene tetrafluoride copolymers, ethylene-Ethylentrifluorchlorid copolymers, Tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, amorphous fluorinated Resins such as Perfluorcyclopolymere, vinyl ether-fluoroolefin copolymers, Vinyl ester-fluoroolefin polymers, various fluorinated elastomers and the same. In particular fluorinated polymers, primarily vinylether-fluoroolefin copolymers and include vinyl ester-fluoroolefin copolymers are preferred because they for little decomposition and degradation susceptible and are easily zuhandhaben. The polymers to be used silicone-based include linear silicone resins, acryl-modified silicone resins, various Silicone elastomers and the like.

0011Of the present invention in the Term "photocatalyst" used denotes those a photocatalytic action when exposed to radiation having a wavelength, not less than the band gap energy equivalent, can show. The used photocatalyst include one or a combination of two or more of known metal compound semiconductors, such as titanium oxide, zinc oxide, tungsten oxide, iron oxide, strontium titanate and the same. In particular, titanium oxide having a high photocatalytic Effect, a high chemical stability and no toxicity comprising, prefers. It is also favorable, in the photocatalyst particles and / or on the surfaces thereof at least one metal and / or a compound thereof, which is selected from the group consisting of V, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Pt and Au existing Group, as a second component because of the higher photocatalytic function of the then incorporate formed photocatalyst. The in the previous said metal compounds include, for example, metal oxides, hydroxides, -oxyhydroxide, sulfates, halides, nitrates and Metal ions. The content of the second component may vary depending the type vary same. Preferred photocatalyst the compounds the above-mentioned metals and / or Metallverbin may include made of titanium oxide. The content of photocatalyst particles is preferably in the range of 5-98 Vol .-%, based on the total amount of the photocatalyst particles and the less degradative adhesive. If the content of the photocatalyst is less than the in the previous specified range inconveniently the tendency that this photocatalytic to a reduced Action of the photocatalyst formed leads, whereas at a higher content than the range specified in the previous also unfavorably there is a tendency that a reduction in the adhesive strength causes becomes. When cements or gypsum used as less degradative adhesive be, the content of the photocatalyst particles should expediently 5-40%, preferably 5-25% be. Alternatively, should, if different from cement and plaster organic or inorganic adhesives as less degradative adhesive be used, the content of the photocatalyst particles is usually 20-98%, expediently 50-98% and preferably 70-98% be.

0012The present invention in the can photocatalyst particles to be used according to any one known methods can be produced. For example, there are several Methods <ul><li>(1) a process comprising the thermal Hydrolyzing a titanium compound such as titanyl sulfate, titanium chloride, Titanium alkoxides, and the like, if necessary, in the presence of Vaccinees for nucleation comprises,</li><li>(2) a method, the neutralization of a titanium compound such as titanyl sulfate, titanium chloride, titanium alkoxides, and the like, by adding an alkali, if necessary, in the presence of vaccinees nucleation, comprises,</li><li>(3) a method which comprises the oxidation of titanium chloride, titanium alkoxide and the like, comprising in the vapor phase, and</li><li>(4) a method comprising firing or a hydrothermal treatment, the one of the methods (1) and (2) titanium oxides produced includes include. In particular, by the method (1) or the hydrothermal treatment at temperatures of 100 ° C or higher obtained Titanium oxides because of their higher photocatalytic action given to before. Of the present invention in the Term "titanium oxides" used to addition to titanium oxide so-called hydrated titanium oxide, hydrous titanium oxide, Metatitanate, Orthotitanates, titanium hydroxide, regardless of their crystal system, mean. In order to enable that at least one metal and / or a compound thereof, the from the group consisting of V, Fe, Co, Ni, Cu, Zn, Ru, Rh, Pd, Ag, Pt and Au existing selected group is, as a second component in the photocatalyst particles and / or on the surfaces the same is present, a method of adding Metal and / or the compound to be adsorbed while the Production of the photocatalyst comprises, or a method comprising adding the metal and / or the compound which adsorbs are to be after the production of the photocatalyst particles, if necessary, under heat, or if necessary, by reducing includes, be used.</li></ul>

0013The present invention in the substrates to be used include inorganic articles, as Ceramics and glass, organic items, such as plastics, elastomers, woods and paper sheets, and Metal objects, made of a metal such as aluminum, or an alloy such as steel, consist. The dimensions and shapes of substrates are not critical. Even coated articles can be used.

0014In the present invention, Preferably, both the photocatalyst particles and an adsorbent on the attached less degradative adhesive on a substrate as a Effect of adsorbing treatment materials coexists. The to be used adsorbents include general adsorbents such as activated carbon, zeolites, silica gels and the like.

0015In a further aspect of the present Invention, a first layer consisting of an adhesive and does not contain any photocatalyst particles is provided on a substrate, and then a second layer of a less degradable Adhesive and photocatalyst particles is, on the first layer provided. The provision of the first layer, which does not containing photocatalyst, allows a firm connection between the substrate and the second layer, containing the photocatalyst particles resulting in a firmer adhesion the photocatalyst particles on the substrate, over a longer period maintained, leads. Further, the first layer should preferably inorganic particles, having no photocatalytic function as filler contain. These include to use inorganic particles Particles of titanium oxides, silicon oxide, aluminum oxide, magnesium oxide and the like whose surfaces are coated with silica, alumina or zirconia.

0016The photocatalyst composite according to the present Invention, by applying the photocatalyst and a less degradative adhesive on at least a part of a Substrate and then Fixing of the adhesive, the photocatalyst particles via the Adhesive means are attached to the substrate can be manufactured. In the present invention, in particular the photocatalyst particles should and the less degradative adhesive in a solvent preferably are dispersed, wherein a coating composition prepared is, which is then coated on a substrate or sprayed, wherein the photocatalyst particles and the less degradative adhesive are distributed on at least part of the substrate. The to used solvent include water and organic solvents, such as toluene, alcohols and the like. The less degradative adhesive, which are contained in the coating composition comprise the in the foregoing mentioned, which is preferably used in the solvents soluble should be. In the present invention, is in the coating composition contained less degradative adhesive preferably one or more Polymers selected are from the on of a fluorinated polymer and a polymer Silicone-based existing group. The amount of the photocatalyst is in the range of 5-98 Vol .-%, usually 20-98 Vol .-%, expediently 50-98 Vol .-% and preferably 70-98 Vol .-%, based on the total amount of the photocatalyst particles and the less degradative adhesive. The coating compositions can netzungsmitteln with Ver, be formulated dispersants and fillers. The crosslinking agent to be used include conventional isocyanate family of include and melamine family and the dispersants to be used Coupling agent. In particular, when the content of the photocatalyst particles in the coating composition in the range of 40 -98 vol .-%, based on the total amount of the photocatalyst particles and the less degradative adhesive is located, the coating composition is preferably formulated with a coupling agent. The amount of be added coupling agent should expediently 5-50%, preferably 7-30% be.

0017The application of the coating composition can be prepared by coating or spraying according to any one of usual Coating method, the plunge, dip coating, Spin coating, blade coating, roll coating, coating bar coating, Include reverse roll coating, or an ordinary spraying method, such as spray coating, accomplished are, with the photocatalyst particles and the less degradative Adhesive are distributed on at least part of the substrate. If necessary, can take place before the application of the photocatalyst particles and the less degradative adhesive onto the substrate by coating or spraying a organic adhesive such as acrylic resins, epoxy resins, polyester resins, Melamine resins, urethane resins, alkyd resins and the like, or a little degradable adhesive, which has been mentioned in the preceding, applied to the substrate to form a first layer or sprayed and then on the first layer a second layer consisting of the Photocatalyst and the less degradative adhesive is, by coating or spraying the coating composition can be provided. The organic Adhesive may be of a type normally used.

0018After coating or spraying the composition is fixed, wherein the photocatalyst composite of the present invention is prepared. The fixation can by the method of drying, exposing to ultraviolet radiation, heating, cooling or the use of a crosslinking agent be carried out, and it is at a temperature which is lower than 400 ° C, preferably from Room temperature to 200 ° C reached. In this regard, a temperature higher than 400 ° C, unfavorably effect manner a thermal degradation of the adhesive, which the photocatalyst easily makes releasable. The present Invention preferably uses a method of fixation with Crosslinking agents of isocyanate family and melamine family.

0019The photocatalyst composite according to the present Invention, the cleaning and sterilization of products, which adverse Materials, malodorous Materials and oily contain materials as well as decomposition of the materials that near reach the photocatalyst particles, by exposure to radiation having a wavelength, not less than the band gap energy corresponding effect. To be used for the exposure radiation types include light radiation, ultraviolet radiation, for example, Sun rays and light a fluorescent lamp, black light, Halogen lamp, xenon flash lamp, mercury lamp and the like, includes. In particular light radiation, the radiation in the near Ultraviolet region of 300-400 comprises nm, are preferred. The intensity and duration of irradiation with the light radiation can routinely depending upon the amounts to Treated materials are determined.

0020The present invention is in the following explained on some examples with reference.

example 1

0021At a thermal hydrolysis of titanyl sulfate (CS-N, available obtained by Ishihara Sangyo Kaisha, Ltd.) acidic titanium oxide sol Sodium hydroxide was added to adjust the pH to 7, and then was filtered and washed. Thereafter, the wet cake was of Titanium oxide mixed with water to form a slurry of as TiO₂ expressed, 100 g / l to manufacture. Sodium hydroxide was added to this slurry to Adjusting the pH-value added to 10, followed by a hydrothermal treatment in a performed autoclave for 3 hours at a temperature of 150 ° C. Thereafter, the slurry was by the hydrothermal treatment by the addition of nitric acid to a pH of 7 is neutralized, filtered and washed with water and then 3 h dried at a temperature of 110 ° C, with titanium oxides were obtained.

0022Thereafter the mixtures below were specified compositions in a paint shaken to effect sufficient mixing for 3 hours and dispersed, wherein a coating composition prepared has been. The specified hereinafter LUMIFRON LF 200 ° C is a fluorinated polymer, which primarily comprises a copolymer of vinylether and fluoroolefin. <tables><table><tgroup cols="2"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colnum="1" colname="1" colwidth="3.346in" colsep="0" /><colspec colnum="2" colname="2" colwidth="3.346in" colsep="0" /><tbody><row><entry colname="1">titanium oxides</entry><entry colname="2">9.80 G</entry></row><row><entry colname="1">Fluorinated Polymer (LUMIFRON LF200C, available at Asahi Glass Co., Ltd.)</entry><entry colname="2">0.80 G</entry></row><row><entry colname="1">hardener isocyanate</entry><entry colname="2">0.16 G</entry></row><row><entry colname="1">Titanium coupling agent (PLANEACT 338X, available from Ajinomoto Co., Inc.)</entry><entry colname="2">1.00 G</entry></row><row><entry colname="1">toluene</entry><entry colname="2">23,60 ml</entry></row></tbody></tgroup></table></tables>

0023The coating composition the above formulation was applied to a glass plate of 20 cm² applied, followed by 20 minutes at a temperature of 120 ° C dried to give a photocatalyst composite of the present Invention (Sample A) was prepared. This Sample A had a Titanium oxide content of 90 vol .-%, based on the total amount of the titanium oxides and the less degradative adhesive.

example 2

0024Using the same as used in Example 1, the titanium oxides in the mixtures were following compositions indicated for 3 hours by a paint shaken to effect sufficient mixing and dispersed, A coating composition was prepared. <tables><table><tgroup cols="2"><colspec colname="1" colwidth="1.01*" /><colspec colname="2" colwidth="1.00*" /><colspec colnum="1" colname="1" colwidth="3.363in" colsep="0" /><colspec colnum="2" colname="2" colwidth="3.330in" colsep="0" /><tbody><row><entry colname="1">titanium oxides</entry><entry colname="2">7.64 G</entry></row><row><entry colname="1">Fluorinated Polymer (LUMIFRON LF200C, available at Asahi Glass Co., Ltd.)</entry><entry colname="2">2.36 G</entry></row><row><entry colname="1">hardener isocyanate</entry><entry colname="2">0.47 G</entry></row><row><entry colname="1">Titanium coupling agent (PLANEACT 338X available in Ajinomoto Co., Inc.)</entry><entry colname="2">0.76 G</entry></row><row><entry colname="1">toluene</entry><entry colname="2">22,50 ml</entry></row></tbody></tgroup></table></tables>

0025The coating composition the above formulation was applied to a glass plate of 20 cm² applied, followed by 20 minutes at a temperature of 120 ° C dried to give a photocatalyst composite of the present Invention (Sample B) was prepared. This Sample B had a Titanoxidgecontent of 70 vol .-%, based on the total amount of the titanium oxides and the less degradative adhesive.

Comparative Example 1

0026Using the same as used in Example 1, the titanium oxides in the mixtures were following specified compositions 1 hour by a paint shaken to effect sufficient mixing and dispersed, A coating composition was prepared. <tables><table><tgroup cols="2"><colspec colname="1" colwidth="1*" /><colspec colnum="1" colname="1" colwidth="3.346in" colsep="0" /><colspec colnum="2" colname="2" colwidth="3.346in" colsep="0" /><tbody><row><entry colname="1">titanium oxides </entry><entry colname="2">9.8 G</entry></row><row><entry colname="1">Vinyl acetate-acrylic copolymer (Boncoat 6290, available from Dainippon Ink &amp; Chemicals Inc.)</entry><entry colname="2">0.7 G</entry></row><row><entry colname="1">water </entry><entry colname="2">24.8 ml</entry></row></tbody></tgroup></table></tables>

0027The coating composition the above formulation was applied to a glass plate of 20 cm² applied, followed by 10 minutes at a temperature of 120 ° C dried to give a photocatalyst composite (Sample C) was prepared has been. This sample had a C Titanium oxide content of 90 vol .-%, based on the total amount of the titanium oxides and the adhesive.

0028In Examples and Comparative Examples obtained photocatalyst composite materials (samples A to C) were non-visible light with an ultraviolet intensity of 7 mW / cm² on the surface of each sample for 5 h exposed. The adhesive in the photocatalyst composite was measured before and after irradiation with the non-visible light weighed to determine the weight loss. As a result, for the Samples A and B according to the present Invention observed no weight loss, which no decomposition the adhesive displays. However, Sample C of the Comparative Example without the use of a less degradative adhesive, a weight loss of 85%, which indicates that most of the adhesive by The photocatalytic action of titanium oxides was decomposed. It was also observed that the Sample C was a yellow color and the titanium oxide partially released were. The variation of the weight loss of Adhesive in the photocatalyst composite owing to the irradiation with non-visible light for each sample A of Example 1 and Sample C of the Comparative Example is in <figref idrefs="S26">1</figref> shown. The Samples A and B from Examples 1 and 2 contained the coupling agent, on the surfaces the photocatalyst were adsorbed, being a bridge member between the less degradative adhesive and the photocatalyst were such that the photocatalyst with the adhesive not came in direct contact, which the latter made little decomposed.

0029Next, each of the samples A and B according to the present Invention in a 3-liter glass jar, and acetaldehyde as a malodorous given component at a concentration of 90 ppm to the vessel and then the vessel was sealed. Thereafter, the vessel having a mercury lamp was with an ultraviolet intensity of 14 mW / cm² on the surfaces of each Sample for 60 minutes irradiated. After irradiation, the concentration was the acetaldehyde detected in the glass vessel. The results are given in Table 1 below. Samples A and B achieved effective decomposition of acetaldehyde due to the photocatalytic Effect of titanium oxides.

TABLE 1 <img img-content="tb" img-format="tif" he="19" wi="135" file="00150001.tif" />

example 3

0030The total coating composition, by repeating a sign identical to that described in Example 1 procedure was obtained, was applied on a transparent acrylic plate with a surface 100 cm² applied and for 20 minutes at a temperature of 120 ° C dried to give a photocatalyst composite according to the present Invention (Sample D) was prepared. This sample had a D Titanium oxide content of 90 vol .-%, based on the total amount of the titanium oxides and the less degradative adhesive.

Comparative Example 2

0031A used in Example 3 Acrylic plate was used as a sample e.

0032Each of the samples D and E from the said preceding example 3 and Comparative Example 2 was on the inner walls a 50-liter water bath. 45 liters of water and 20 goldfish (Wakin) were placed in the bath and from outside irradiated with the light from two 20 W fluorescent lamps.

0033After the goldfish two weeks cultured were, it was observed that the on the surfaces Sample E had deposited from Comparative Example 2 algae, while on the surfaces the sample D was observed from Example 3 no algae deposits. The reason for that is that, even when the algae on the surfaces Sample D were deposited in Example 3, this immediately by the catalytic Effects were decomposed. Following the procedure described in the preceding The method was the weight loss of the fluorinated polymer in Sample D determined. It was not observed Ge weight decrease, which indicates that no decomposition of the fluorinated polymer was carried out.

example 4

0034The procedure of Example 3 was repeated except that a mixture of the composition shown in the following in a paint Shaken for 1 hour to effect sufficient mixing, and was dispersed, wherein a coating composition was prepared, the total transparent on an acrylic plate by means of a spin coater (1000 rpm^-1 × 10 s) was applied, and the formed transparent acrylic plate with a first layer without missing a less degradative adhesive any photocatalyst particles existed on the surface thereof was used as a substrate, a photocatalyst of the present Invention (Sample F) was prepared. The content of the titanium oxides, that is, the photocatalyst particles in the second layer of these Sample F was 90 Vol .-%, based on the total amount of the titanium oxides and the less degradative adhesive. <tables><table><tgroup cols="2"><colspec colname="1" colwidth="1*" /><colspec colname="2" colwidth="1*" /><colspec colnum="1" colname="1" colwidth="3.346in" colsep="0" /><colspec colnum="2" colname="2" colwidth="3.346in" colsep="0" /><tbody><row><entry colname="1">titanium oxides with no photocatalytic action (CR-90, available at Ishihara Sangyo Kaisha, Ltd.)</entry><entry colname="2">3.3 G</entry></row><row><entry colname="1">Fluorinated Polymer (LUMIFRON LF200C, available at Asahi Glass Co., Ltd.)</entry><entry colname="2">5.5 G</entry></row><row><entry colname="1">hardener isocyanate</entry><entry colname="2">1.1 G</entry></row><row><entry colname="1">toluene</entry><entry colname="2">20.7 ml</entry></row></tbody></tgroup></table></tables>

0035The investigations of weight loss the for Sample F used adhesive in the processes mentioned measures showed that no change in weight present in sample F according to the Invention exhibited and the adhesive was not degraded and the Titanoxidphotokatalysatorteilchen not released from the substrate were. The film strength of Sample F of Example 4 was 3H in terms of pencil hardness, which means that the photocatalyst particles firmly adhered. Further the sample was F in flowing ßendes of water and irradiated with non-visible light such that the surface ultraviolet intensity 2 mW / cm² while 3 weeks, respectively. However, it was no release of Titanoxidphotokatalysatorteilchen observed from the substrate.

example 5

0036The procedure of Example 1 was repeated, but coated with a zinc compound titanium oxide instead of the titanium oxides for producing a photocatalyst composite of the present invention (Sample G) were used. The content the photocatalyst titanium oxide particles, which were coated with the zinc compound in this Sample G was 90 Vol .-%, based on the total amount of the photocatalyst particles and the less degradative adhesive.

0037The surface coated with the zinc compound were titanium oxide particles prepared as follows: water and Sodium hydroxide were added to a slurry of titanium oxide, by thermal hydrolysis was obtained from titanyl, added, a slurry with a pH value of 10 and expressed as TiO₂. 100 g / l was formed. This slurry was 5 hours h at 150 ° C to a hydrothermal treatment subjected in an autoclave and then neutralized with nitric acid, filtered and washed with water. To the resulting wet Titanoxidkuchen was added water, whereby a slurry was prepared which contained, expressed as TiO₂, 100 g / l acid. To the resulting slurry hydrochloric acid to form a slurry optionally with a pH-value of the fourth To 1 liter of this slurry was dropwise 7.2 ml of an aqueous 1 mol / l of zinc chloride solution stirring given. Thereafter, the slurry was neutralized with a 2 N sodium hydroxide solution, filtered and washed with water. Thereafter, the formed product was 16 hours at 120 ° C dried and pulverized to obtain titanium oxide particles having thereon supported Zinc compound in a ZnO: TiO₂-Ratio of 1: 99 were formed.

example 6

0038The procedure of Example 1 was repeated, but coated with an iron compound titanium oxide instead of the titanium oxides for producing a photocatalyst composite of the present invention (sample H) were used. The content the photocatalyst particles coated with the iron compound were, in this sample H was 90 Vol .-%, based on the total amount degradable the photocatalyst titanium oxide particles and of little Adhesive.

0039The surface coated with the iron compound Titanium oxide particles were prepared as follows: 10 g of titanium oxide, obtained by hydrolysis of titanium sulfate under heating, were used to prepare a slurry of, expressed as TiO₂, 100 g / l. 2.9 ml of an aqueous solution of Iron (III) chloride (FeCl₃· 6H₂O) were incubated with a concentration of 5 g / l to the slurry and stirring was continued for 1 h. Thereafter, dilute aqueous ammonia to the slurry to Adjusting the pH value given on the seventh After stirring for 1 hour the slurry is the slurry filtered, washed with water and 3 hours at a temperature 110 ° C dried to obtain coated with the iron compound titanium oxide were obtained.

0040This titanium oxide exhibited iron compounds to the same in an Fe / TiO₂Ratio of 300 ppm.

example 7

0041The procedure of Example 6 was repeated, However, the concentration of the aqueous solution of iron (III) chloride 50 g / l, wherein a photocatalyst composite of the present Invention (Sample I) was prepared. The content of the photocatalyst titanium oxide particles, which were coated with the iron compound in this Sample I was 90 Vol .-%, based on the total amount of the photocatalyst particles and the less degradative adhesive.

0042This titanium oxide exhibited iron compounds to the same in an Fe / TiO₂Ratio of 3000 ppm.

example 8

0043The procedure of Example 1 was repeated, but 8.9 g of TiO₂ and 0.5 g of activated carbon were used, wherein a photocatalyst composite according to the present Invention (Sample J) was prepared. The total amount of the titanium oxide and the active carbon of Sample J was 90 Vol .-%, based on the degradable total amount of titanium oxide, activated carbon and the little Adhesive.

example 9

0044The procedure of Example 8 was repeated, but the activated carbon through a zeolite in an amount of 0.8 g was replaced with a photocatalyst composite according to the present Invention (Sample K) was prepared. The total amount of the titanium oxide and the zeolite was 90 Vol .-%, based on the total amount of Titanium oxide, zeolite and less degradative adhesive.

0045degradable Observing the little Adhesive resulted in each of the samples F to K that no weight loss occurred. In other words, the less degradative adhesive were the samples F to K not degraded, and the titanium oxide from the substrate not released.

0046Next, each of the samples A, H and I according to the present given invention in a 0.8-liter glass vessel and acetaldehyde as a malodorous given component to a concentration of 100 ppm to the vessel and thereafter the container sealed. Thereafter, the vessel was allowed to stand for 30 minutes and then with the non-visible light with an ultraviolet intensity of 1 mW / cm² long on the surfaces of each sample 60 min irradiated. After the irradiation, the concentration of acetaldehyde was determined in the glass vessel. The results are given in Table 2 below. Samples A, H and I decomposed the acetaldehyde due to the photocatalytic action of titanium oxides effectively.

TABLE 2 <img img-content="tb" img-format="tif" he="24" wi="135" file="00200001.tif" />

0047Thereafter, the samples G, J and were K added separately in respective 0.8-liter glass vessels. Evil-smelling was methyl mercaptan to the glass vessels in a concentration optionally from about 500 ppm. After the vials were sealed. After that these vessels were 2 hours without radiation left with ultraviolet radiation, and 60 min irradiated with the non-visible light such that the ultraviolet intensity on each of samples 1 mW / cm² amounted to. After irradiation the Methylmercaptankonzentration was determined in the vessels. The results are given in Table 3 below. From Table 3, it is clear that the methyl mercaptan due to the action of the photocatalyst particles of the sample G, J and K was effectively removed.

TABLE 3 <img img-content="tb" img-format="tif" he="25" wi="145" file="00200002.tif" />

0048In the above-mentioned exam was the Methylmercaptankonzentration in without irradiation with ultraviolet radiation for 2 hours left standing vessels 250 ppm for each of the samples. The Methylmercaptankonzentration in another left standing hour without irradiation with ultraviolet rays vessels was 240 ppm for Samples G and K and 220 ppm for the sample J.

0049The photocatalyst composite of the present invention comprises a substrate with a less photocatalyst abbauba res adhesive thereon, and it causes very little decomposition and very low Degradation of the adhesive owing to the photocatalytic action. The present invention allows a long lasting firm adhesion of photocatalyst on any substrate without damaging the photocatalytic Effect. The use of the photocatalyst composite of the present invention allows effective and prompt removal of deleterious materials, malodorous Materials, oily Components, bacteria, actinomycetes, fungi, algae and the like. Therefore, the photocatalyst composite is provided as deodorant and sterilizer both domestically and in industry very useful. In addition, the photocatalyst composite of the present invention can vary over a longer Period be used, it has a high degree of safety on, finds applicability to a wide variety of harmful Materials and can be distributed and disposed of without pollution. Therefore, it is very well used in the industry. In the method for producing the photocatalyst composite according to the present invention allows the use of fluorinated polymers as less degradative adhesive the preparation of preferred photocatalyst composites, whose surfaces a lower tendency to adsorb dust and contaminants Substances due to the weak adhesion of the fluorinated polymers exhibit.

0050The process for preparing the Photocatalyst composite of the present invention is a discount Method in which any materials such as plastics as substrate used and favorably and easily photocatalyst composites consistent quality produced can be.

0051The coating composition of the present invention to substrates of any shape or desired Filters are applied or sprayed the same, and it allows the ease of use, the photocatalytic action. Therefore, it is especially for Household applications.