Method and apparatus for producing glass having photocatalyst formed thereon

0001Specification Light power' Russ's manufacture device and a manufacturing method Technical field

0002It is used for the present invention, the object for buildings, the windowpane for cars, or the antifog Myra first class. To, Anatase type TiO₂To a manufacture device and a manufacturing method of photocatalyst glass in which the film was formed It is related. Background art

0003Ti0 for photocatalysts₂When it irradiates with the glass in which the film was formed, and ultraviolet rays, it is Ti o by light excitation.₂the film surface is activated highly -- be alike so that hydrophilicity, fog resistance, self-consecration nature, etc. are shown To. And TiO activated once₂even if it is a weak light about a film and a fluorescent light -- Active it is maintenance about a sex -- or it is made to recover -- things can be carried out. Therefore, the building, the car, the train, the airplane and the windowpane for vessels in which the use of this photocatalyst is large, a car, a bathroom, and power 1 It can be used conveniently for the mirror for Bumirrors, an optical lens, etc.

0004On a glass board material, it is Ti0.₂It is related with the method of forming the photocatalyst film consisting of a film, and they are many. There is a proposal. For example, Provisional Publication No. 8 -- 3 0 9 2 0 Ti evening-get is used for No. 4 gazette. It is indicated.

0005Provisional Publication No. 8 -- 1 0 6 1 3 Sol which makes a titanium dioxide No. 2 gazette with the main ingredients Based on liquid, the method of forming a photocatalyst film by an application and Date Bing is indicated. ing.

0006Provisional Publication No. 8 - 5 2 8 2 9 No. 0 gazette -- the precursor of formless silica -- crystallinity the suspension which dispersed thia Tania particles is applied -- carrying out drying condensation -- light catalytic hydrophilicity The method of obtaining the surface is indicated.

0007Provisional-Publication-No. 91 -- 2 2 4 7 9 No. 6 gazette -- a substrate top -- one layer of alkali' barriers Light catalytic TiO after forming₂how to apply, dry and calcinate the film made into the main ingredients it is indicated -- Provisional Publication No. 9 -- 2 3 3 6 8 No. 9 gazette -- float glass manufacturing process the on-line C V D method which carries out gaseous phase composition all over an inner float bus -- light catalytic Ti 0₂The method of forming a tunic is indicated.

0008However, Provisional Publication No. 8 -- 3 0 9 2 0 The sputtering method of No. 4 gazette, and Offler Since the Spat evening device of an in method for exclusive use is required, device expenses are high and also it is TiO.₂It is thickness about a film. The effective means which carries out To is not found. the maximum size of the glass board material which can be processed in the size of a sputter device will be limited -- for example, long thing which exceeds 4 m It cannot manufacture.

0009on the other hand -- Provisional Publication No. 8 -- 1 0 6 1 3 No. 2 gazette and Provisional Publication No. 8 -- 5 2 8 2 9 No. 0 gazette Yes Provisional-Publication-No. 91 -- 2 2 4 7 9 The applying method indicated by No. 6 gazette, application and drying condensing method, and application - in dry and the calcinating method, automation is difficult -- size is restricted -- the quantity of production also has restrictions. About that a uniform application is difficult when it enlarges, and application and the dry' calcinating method In order to require heating, there is a difficulty that processing time starts.

0010Provisional Publication No. 9_2 3 3 6 8 With the on-line C VD method of No. 9 gazette, it is at the film formation time. Since temperature is too high, it is a low rutile type not an announcer evening 1 Ze type with high photocatalyst activity but active. That a crystal film is formed and TiO₂Cheap TiO for C VD suitable for formation₂acquisition of materials and the feeding method of these materials are difficult -- since it becomes large-scale [ equipment ] -- cost There is a problem of starting.

0011the above-mentioned various problems which the present invention and prior art have are solved -- it is low cost and is the efficiency from Takao continuously -- TiO excellent in photocatalyst activity₂Device which manufactures glass with a film It aims at providing a method. moreover -- for example, the long thing exceeding 4 m is included -- it is applicable to extensive glass size -- and optically uniform TiO₂a film is formed -- Rock Provide the manufacturing method which can obtain loose luster and a good film with little Hayes. It is considered as the object. The indication of an invention

0012In order to solve the above-mentioned subject, it is a manufacture device of the photocatalyst glass of the present invention, Fusion glass It is a ribbon about the fusion glass which flows through the float bus surface into the lower stream side of the float bus which it begins to pass. It is a sheet glass manufacture device which has arranged the forming station pulled out to A state, the above-mentioned fabrication the case which ribbon base glass passes is arranged at a station -- front surface temperature of glass a degree -- 3 5 0*2 5 or [ the middle of the above-mentioned case which becomes being at 0, or any of an exit ] -- glass table The spraying device which sprays titanic acid solution towards a field has been arranged.

0013ultrasonic nebulizer which makes titanic acid solution the above-mentioned spraying device at the shape of mist etc. -- it is preferred to attach a mist-ized device. Thus, it is Mi about titanic acid solution. Light touch formed in a Lepon-like glass surface by using the shape of a strike and supplying a spraying device Thickness of an intermediation film can be made uniform.

0014On the other hand, it is a manufacturing method of the photocatalyst glass of the present invention, Sheet glass is manufactured by the float bus method. The surface of the Lepon-like glass pulled out from the float bus exit the middle of the line to carry out Temperature is 3. 5 0*2 5 It is a position of the case interior used as 0, It is Chi to the surface of Lepon-like glass. It is the heat which sprays tongue acid water solution and glass holds, and is Anatase type TiO.₂It is To form about a film. To.

0015Thus, the heat which glass holds is used and it is TiO.₂By forming a film, it is cost. It is [-like ] advantageous and the skin temperature of ribbon base glass is 3. 50*2 5 Ke 1 used as 0 It is spraying titanic acid solution in the position inside A, Luchi inferior to photocatalyst activity Without it forms a Le type photocatalyst film (it is in abbreviation 8 0 0, and becomes a rutile type) photocatalyst activity the outstanding you 1Ze type tunic can be formed -- further -- the skin temperature of Lepon-like glass -- 3 5 if it is below 0^ -- titanic acid solution is contact to the surface of ribbon base glass the thermal shock at the time of carrying out also becomes small -- it becomes difficult to generate a crack.

0016As titanic acid solution, they are peroxy titanic acid and Z, or titanium Pelogy. It is preferred to use solution containing an acid Ammonium hydrate. Brief explanation of the drawings

0017It is Drawing 1 and the whole manufacture device figure of the photocatalyst glass concerning the present invention, and Drawing 2 is A of The 1 figure. -- It is the direction Arrow view figure of A. The best form for inventing

0018Below, the present invention is concretely explained with reference to drawings. here -- Drawing 1 -- the present invention the whole manufacture device figure of the photocatalyst glass to apply, and Drawing 2 -- a figure -- it is the direction Arrow view figure of A_A of 1. Manufacture of the sheet glass by a float process puts in fusion metal, such as like, tin, etc. which are shown in Drawing 1. All over a It was float bus, it is Flow continuously about the bottom of the mixed gas atmosphere of nitrogen and hydrogen, and fusion glass. It carries out. Then, glass is a spread and the shape of Lepon of fixed width uniformly on the surface of fusion metal liquid. It goes to a float bus exit, becoming glass and being cooled gradually. this float 6 which does not change even if it puts glass on a roll near a bus exit 0 O : a grade -- cold water -- Being done. And the glass which came out of the float bus goes via a lift out-roll. It is sent to the forming rolls stored in the case.

0019It is TiO if it sets to the present invention.₂Titanic acid solution which is the materials for forming a film is sprayed on a Lepon-like glass surface in somewhere in case interiors arranged to the forming station. It carries out. it sets to this forming step -- the skin temperature of glass -- about 6 0 0 -- 3 5 0 thru/or 2 5 since it is cooled 0 -- Anatase type TiO₂It is the best for forming a film and Ah. It is spray A jet just before immediately after Ri, for example, the entrance of a forming case interior, middle, or an exit. It is preferred to form a misty device. If it is in the illustrated example, it is immediately after the entrance within a case. The spray spraying device is arranged.

0020A pump is passed to the both ends of the pipe member in which the nozzle of the above-mentioned spraying device and a large number was formed. Titanic acid solution in a The tank is supplied, if it is especially in this example -- Chi It is arrangement about mist-ized devices, such as an ultrasonic nebulizer, in the middle of piping which supplies tongue acid water solution. it carries out -- the titanic acid solution made into the shape of mist is supplied to a nozzle -- titanic acid water Solution has composition uniformly sprayed on a ribbon base glass surface.

0021it is used that a spraying device can be gone up and down -- photocatalyst tunic made into the board thickness of glass, or the object It is supposed that responding to thickness freely is possible.

0022as the titanic acid solution sprayed on the other hand -- peroxy titanic acid and Z -- or -- What makes the main ingredients a titanium acid ammonium hydrate is preferred. This since the titanic acid of Re and others does not have crystallinity, and it is an infinite form, without it generates internal stress -- Gala it adheres to the A surface firmly -- as moisture of solution evaporates -- it is exertion about light catalytic Announcer evening-Ze type Ti0 to carry out₂It metamorphoses into a film gradually and goes.

0023Since titanic acid solution of these does not contain an organic matter, it has been used conventionally. TiO by sintering of organic titanium acid₂it differs from membranous formation -- charcoal resulting from combustion of an organic matter base -- there is no residual substance of a compound. therefore, the top where photocatalyst activity is high -- absorption of an organic matter there is no Coloring -- the photocatalyst film excellent in transparency is obtained. furthermore -- handling is easy This which does not have danger, such as ignition and explosion, even if it sprays to a certain thing and a hot ribbon base glass surface etc. -- there is the outstanding feature.

0024The concentration of titanic acid solution is 1*2. It is 2~1 still more preferably with 0 preferred % of the weight. It is 0 % of the weight. This concentration is TiO in less than 1 %.₂a membranous membrane formation speed becomes slow -- enough -- being Film thickness may be unable to be attained. 2 Viscosity is high if it exceeds 0 % of the weight. For a To reason, uniform thickness distribution cannot be acquired.

0025TiO formed in a ribbon base glass surface₂0 .1*1 .0 m of membranous thickness is 0 .2*0 .5 zm still more preferably [ it is desirable and ]. film thickness may be unable to demonstrate photocatalyst activity sufficient by less than 0 .l w m -- on the other hand -- 1 .0" -- m is exceeded It may not be suitable for the intermediary practical use with luster or high Hayes.

0026It is quite difficult to form the above-mentioned film thickness uniformly with the usual spray device. Uniformity It is effective to mist-ize titanic acid solution and to spray it, in order to obtain film thickness [ one ], and it is Ah. The above-mentioned ultrasonic nebulizer is preferred as Ri and a spraying device for that. vibrating an ultrasonic oscillation child according to the ultrasonic nebulizer -- titanic acid solution -- mist it turns -- it is easy to put it on the air which is a career and to spray to up to a glass ribbon it is . If an ultrasonic nebulizer is used, the path of the mist of titanic acid solution can supply this to a glass surface at 1 i m grade. Moisture is lost the supplied mist and near [ hot ] a glass surface, and it is Ti0.₂A film is formed.

0027It is To use at a temperature a little higher than the air used as a career, and glass ribbon temperature. To is preferred. the reason and mist are prevented from condensing in the gaseous phase -- Perexitan acid and a titanium acid ammonium hydrate -- a glass board material top -- For Way which forms many cores on a glass substrate and completes a thermolysis reaction after being supplied, Thermal decomposition of these materials is carried out, and it is uniform TiO.₂It is because it is effective for forming a film. Industrial applicability

0028Forming Stacy [ according to the present invention, it ends a forming step from a flow ♪ bus exit ] of a between It is a case interior arranged to To, Titanic acid solution is sprayed on a ribbon base glass surface. Since it was made like, ribbon base glass is abbreviation 3 in the forming step circumference. 5 0 to 2 5 It is the cold to 0. In the process in which To reject is carried out and it goes, thermal decomposition of the titanic acid is carried out using the heat concerned which carries out glass power possession. Announcer evening 1 Ze type TiO with high photocatalyst activity₂A film can be formed.

0029moreover -- as titanic acid solution -- peroxy titanic acid and Z, or Titanium bello in order to use solution containing a Xoquen acid ammonium hydrate -- a lot of organicity a thing is not included -- TiO by sintering of the organic titanium acid used conventionally₂membranous formation -- different -- There is no Leftovers of the carbon compounds resulting from combustion of an organic matter. therefore, organic matter there is no coloring by absorption -- the photocatalyst film excellent in transparency is obtained. It is dealt with. Even if it sprays to up to an easy thing and a hot glass ribbon, there is the feature which was excellent in that there is no danger, such as ignition and explosion, etc.

0030Solution is mist-ized for spraying of titanic acid solution with an ultrasonic nebulizer. Ti0 [ optically uniform at If you do it and uniform film thickness ]₂A film can be formed.