WO2006123426A1 - Procede pour preparer un film d'oxyde de titane et solution pour former le film d'oxyde de titane - Google Patents

Procede pour preparer un film d'oxyde de titane et solution pour former le film d'oxyde de titane Download PDF

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Publication number
WO2006123426A1
WO2006123426A1 PCT/JP2005/009277 JP2005009277W WO2006123426A1 WO 2006123426 A1 WO2006123426 A1 WO 2006123426A1 JP 2005009277 W JP2005009277 W JP 2005009277W WO 2006123426 A1 WO2006123426 A1 WO 2006123426A1
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WO
WIPO (PCT)
Prior art keywords
titanium oxide
oxide film
aqueous solution
layer
peroxotitanic acid
Prior art date
Application number
PCT/JP2005/009277
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English (en)
Japanese (ja)
Inventor
Mihoko Okada
Original Assignee
Axtis Company
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Axtis Company filed Critical Axtis Company
Priority to PCT/JP2005/009277 priority Critical patent/WO2006123426A1/fr
Publication of WO2006123426A1 publication Critical patent/WO2006123426A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0217—Pretreatment of the substrate before coating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0215—Coating
    • B01J37/0228—Coating in several steps

Definitions

  • the present invention relates to a method for producing a titanium oxide film and a solution for forming a titanium oxide film using an aqueous solution for forming an oxide titanic film containing peroxotitanic acid modified with a peroxo group.
  • Patent Document 1 Japanese Patent No. 2938376
  • Patent Document 2 Japanese Patent Laid-Open No. 9-262481
  • the titanium oxide film having photocatalytic activity as described above can cut ultraviolet rays on the surface of the film, but heat is conducted and reaches the substrate. Then, there was a problem that this heat caused the rubber to deteriorate.
  • the above-mentioned titanium oxide film is placed indoors, it does not matter so much, but when placed outdoors, the above problems are likely to occur.
  • the present invention has been made in view of such problems, and an object of the present invention is to form a titanium oxide film on a base material containing rubber, and to which a large amount of ultraviolet rays are irradiated.
  • an object of the present invention is to form a titanium oxide film on a base material containing rubber, and to which a large amount of ultraviolet rays are irradiated.
  • a new and improved method of manufacturing a titanium oxide film and a solution for forming a titanium oxide film capable of maintaining the flexibility of the rubber and preventing the deterioration of the rubber can be provided. is there.
  • a step of applying a peroxotitanic acid aqueous solution containing a predetermined binder to a base material having a material strength containing rubber A step of forming a first layer by drying a peroxotitanic acid aqueous solution followed by baking; a step of applying a peroxo-modified anatase sol on the first layer; and drying the coated peroxo-modified anatase sol Forming a second layer by providing a method for producing a titanium oxide film.
  • the predetermined noinda is at least one polymer containing a bond selected from the group consisting of Si-H, Si-C, Si-N, and Si-O forces. It is preferable that In particular, it is more preferable that the predetermined noinda includes polysiloxane or a carbonized polymer.
  • the method for producing the titanium oxide film includes applying a mixed solution of a peroxotitanic acid aqueous solution and a peroxo-modified anatase sol on the second layer; and applying the applied mixed solution.
  • a step of forming a third layer by baking after drying, and the titanium oxide film may have a three-layer structure.
  • a peroxotitanic acid aqueous solution used for manufacturing a titanium oxide film formed on a base material having a material strength including rubber.
  • a peroxotitanic acid aqueous solution containing 0.1 to 1% by mass of titanium oxide, a predetermined binder, and a solvent (mainly water) is provided.
  • the present invention even when a titanium oxide film is formed on a base material containing rubber by containing a predetermined substance in the binder layer, and a large amount of ultraviolet rays are irradiated to the titanium oxide film, It is possible to provide a method for producing a titanium oxide film and a solution for forming a titanium oxide film that can maintain rubber flexibility and prevent deterioration of rubber.
  • titanium oxide film according to the present embodiment includes a predetermined Noinda, the content of titanium oxide using Peruokisochitan acid aqueous solution is 0.1 to 1 mass 0/0, a material containing a rubber A first layer formed on the substrate; and a second layer formed on the first layer using a peroxo-modified anatase sol.
  • the peroxotitanic acid aqueous solution for forming the first layer is a yellow transparent viscous liquid, and can be prepared as follows. That is, first, a water-soluble titanium compound such as tetrasalt titanium dioxide, titanium sulfate, titanium nitrate, and alkoxy titanium is dissolved in water to form an aqueous solution.
  • titanium hydroxide gel is separated by washing with decantation using water.
  • peroxotitanic acid aqueous solution can be obtained by adding hydrogen peroxide water to decompose and remove excess hydrogen peroxide.
  • This aqueous solution is considered to contain peroxytitanium hydroxide titanium, or peroxotitanium, and is essentially different from the commercially available diacid titanium sol.
  • the titanium source of the aqueous solution chloride, sulfate, oxalate, etc., which are inexpensive and easy to handle, are preferable, and a basic solution for generating a precipitate of hydroxide.
  • Ammonia water, sodium hydroxide aqueous solution and the like are preferable.
  • a combination in which the salt by-produced by the reaction becomes a stable and harmless salt sodium salt, sodium sulfate, salt salt ammonium or the like is preferable.
  • the concentration of the raw material solution is not particularly limited. It is preferable that the pH of the precipitation is about 2 so that impurities such as Fe do not coprecipitate.
  • Precipitated titanium hydroxide (ortho titanic acid) is in the form of a gel that has been polymerized by polymerization of hydroxyl groups or hydrogen bonds, and as such, it can be used as a solution for forming an acid-titanium film. Can not. When peracid-hydrogen water is added to this gel, a part of the hydroxyl group is in a peroxidized state and dissolved as peroxotitanate ion, or it is in a kind of sol state in which the polymer chain is divided into low molecules, and excess excess hydrogen is formed. Hydrogen oxide is broken down into water and oxygen. This makes it possible to use it as a solution for forming a titanium oxide film.
  • this sol contains only oxygen and hydrogen in addition to titanium, only water and oxygen are generated when it is changed to titanium oxide by drying or firing, and the sol-gel method is not suitable for thermal decomposition methods such as sulfate. Since it is no longer necessary to remove the necessary carbon and halogen components, it is possible to produce a crystalline titanium oxide film having a relatively high density even at a lower temperature than in the past. In addition, since the pH is neutral, there is no need to consider the danger to the human body or corrosion of the substrate during use. Furthermore, hydrogen peroxide not only acts as a solubilizer but also as a stabilizer, so the sol is extremely stable at room temperature and can withstand long-term storage.
  • peroxotitanic acid aqueous solution is mainly used as a primer (binder) at 200 ° C or lower, a film with photocatalytic functions such as antibacterial and antifouling properties at 250 ° C or higher, or a mixed film with other particles. Used to form.
  • the content of titanium oxide is 0.1 to 1% by mass in the peroxotitanic acid aqueous solution that is directly applied to the substrate and used as a protective coating. It is also a powerful force that the effect of suppressing chiking is obtained by suppressing the content of titanium oxide to 0.1 to 1% by mass.
  • the content of titanium oxide in the peroxotitanic acid aqueous solution is the same as that described above in the washing step after precipitation of the titanium hydroxide gel in the aqueous solution production step. ! Adjust it! /
  • the peroxo-modified anatase sol for forming the second layer is a pale yellow transparent liquid, and is prepared by heat-treating the peroxotitanate aqueous solution at 80 ° C or higher. be able to.
  • the peroxotitanic acid aqueous solution is heated to 80 ° C or higher, it can be modified into a liquid in which fine particles of titanium oxide are produced.
  • the reason why the temperature is set to 80 ° C or higher is that the crystallization of titanium oxide does not proceed sufficiently at 80 ° C or lower.
  • a crystalline titanium oxide film can be formed at a temperature as low as 80 ° C or higher by drying the coating or heating. However, heat treatment at 200 ° C or higher is preferred for good adhesion.
  • the peroxo-modified anatase sol prepared in this way is a liquid containing fine particles of titanium oxide acid crystallized in anatase form (particle size is, for example, about lOnm).
  • titanium oxide contains anatase-type crystals that have photocatalytic activity! Therefore, the photocatalytic effect can be obtained simply by drying at room temperature. Therefore, peroxo-modified anatase sol is mainly used to form films having photocatalytic functions such as air purification, deodorization, water purification, and antibacterial functions.
  • the zeolite containing fine titanium oxide particles is in the neutral or weakly acidic range and does not contain substances other than titanium, oxygen and hydrogen, so it is essentially different from the commercially available titanium dioxide sol. .
  • a fine particle having a particle size of 0: m or less colloidal titanium oxide particles are used as a raw material. Yield force Such particles with a small particle size tend to aggregate and are difficult to disperse uniformly. Therefore, the particles are dispersed by applying electric charges to the particles and repelling them.
  • the particles usually have a charge in the strongly acidic or strongly alkaline region, and in the neutral region the charge is zero (the isoelectric point exists in the neutral region).
  • the titanium particles are difficult to disperse. Therefore, most ordinary acid titanium sols are charged by adsorbing H + on the acid titanium particles in the strongly acidic region.
  • the surface potential of the anatase type particles in the peroxo-modified anatase sol of this embodiment is measured, it is about ⁇ 50 mV at about pH 7. This value is higher than the surface potential of general titanium dioxide particles and has an absolute value several times higher. For this reason, the present inventor has modified the peroxo group (—O—O—) on the surface of the anatase-type particle present in the solution, and the repulsive force (repulsive force) between the peroxo groups, This is because anatase-type titanium oxide fine particles can be stably dispersed even in the neutral range.
  • a method for producing a titanium oxide film according to the present embodiment includes a step of applying a peroxotitanic acid aqueous solution containing a predetermined binder to a base material such as a rubber-containing material; Forming a first layer by baking after drying; applying a peroxo-modified anatase sol on the first layer; and drying the applied peroxo-modified anatase sol to form a first layer. Forming two layers; and It is characterized by that.
  • the titanium oxide film according to the present embodiment can be manufactured as follows.
  • the solutions for forming a titanium oxide film according to the present embodiment are all aqueous solutions that do not contain an organic solvent, the base material is subjected to a water repellent treatment, and an oil film adheres to it. In such a case, it is preferable to pre-treat these substrates because the above solution cannot be suitably applied to the substrates.
  • Such pretreatment is not particularly limited as long as it can remove the water repellent treatment or the oil film, and includes, for example, washing and washing (for example, washing using high-pressure water), interface There are cleaning using an activator, alcohol cleaning, surface wiping with an organic solvent, surface wiping with a polishing agent (fine polishing), ultrasonic cleaning, and chemical conversion treatment.
  • washing and washing for example, washing using high-pressure water
  • interface There are cleaning using an activator, alcohol cleaning, surface wiping with an organic solvent, surface wiping with a polishing agent (fine polishing), ultrasonic cleaning, and chemical conversion treatment.
  • the base material used in the production of the titanium oxide film according to the present embodiment is required to contain rubber, but other than that, there is no particular limitation.
  • the peroxotitanic acid aqueous solution according to this embodiment such as ceramic, ceramic, metal, plastic, fiber, building material, etc., can be applied to any substrate as long as it can withstand heat treatment according to the application. , It is also possible to perform the surface treatment of the inside of the porous body and the powder. In particular, since peroxotitanic acid aqueous solution is neutral, it is possible to effectively perform metal oxide-titanium coating.
  • the coating method is not particularly limited, and various known methods can be selected depending on the properties and shape of the substrate.
  • Examples of the application method include a spray method, a dip method, a brush 'roll coating method, and a bar coating method.
  • the spray method is a method of spraying using a spray gun or the like, and manages the state of the mist sprayed by the nozzle diameter and air pressure.
  • application is performed by a spray method using a spray gun.
  • spray gun application has the advantage of reducing the thickness of the formed titanium oxide film. For example, when the film thickness is normally 0.8 ⁇ : m, the film can be applied with a film thickness of 0.3 ⁇ 0.8 m by using a rotary spray gun so that it does not scatter within a certain range. can do.
  • the dip method is a method in which a substrate to be coated is immersed in a container containing a solution for forming a titanium oxide film, and the solution is adhered to the substrate.
  • the amount of coating is controlled by the concentration of the solution and the dipping time.
  • the brush 'roll coating method is a method of applying directly to the substrate using a brush or sponge roll. With this method, there is little loss of the solution for forming the titanium oxide film and it is easy and simple to apply, but irises due to uneven coating tend to occur.
  • the bar coating method is a method of forming a uniform coated surface on a flat surface by drawing a solution placed on the target surface with a special stainless steel mesh bar.
  • the amount of coating for example, applying about 200 ⁇ 240g per lm 2.
  • the thickness of the formed titanium oxide film is about 0.5 ⁇ m.
  • the drying method can be either natural air drying or hot air drying using a dryer! /, But in the case of natural drying, it takes about 3 to 12 hours to fix the film, so the time is shortened. For this purpose, hot air drying is preferred.
  • the rate of cure of the titanium oxide film formed after drying the applied peroxotitanic acid aqueous solution is proportional to the temperature and the amount of ultraviolet light. Sex can be improved early. [0042] When the titanium oxide film formed of the peroxotitanic acid aqueous solution is irradiated with ultraviolet rays, the peroxo group in the titanium oxide film is decomposed and changed to amorphous titanium dioxide.
  • the film becomes dense and the hardness increases.
  • the titanium oxide film becomes a solid film insoluble in water.
  • the titanium oxide film continues to harden and stabilizes at a hardness of about 2H after about 2 months in the natural state.
  • the rate of increase in the drying film is proportional to temperature and the amount of ultraviolet light.
  • the first layer is formed by firing the titanium oxide film.
  • the above peroxotitanic acid aqueous solution forms an amorphous (amorphous state) titanium oxide film slightly containing hydroxyl groups at a firing temperature of less than 200 ° C, and is crystalline (anatase type) high-density acid solution at 200 ° C or higher.
  • a titanium film can be formed. These films have excellent acid resistance and can be used for various anticorrosion coatings.
  • the hardness of the formed titanium oxide film can be increased and the adhesion to the substrate can be improved.
  • a peroxo-modified anatase sol is further applied on the first layer to the base material on which the first layer is formed. Since the coating method and the coating amount are the same as those for forming the first layer, a detailed description is omitted. In addition, when applying peroxo-modified anatase sol on the first layer, it is basically not necessary to add a surfactant, unlike direct application to the substrate.
  • a second layer is formed by drying the applied peroxo-modified anatase sol.
  • the drying method may be either hot air drying or natural drying, but the hot air drying is preferred for the purpose of shortening the time as described above.
  • the peroxo-modified anatase sol can be produced by simply drying after coating, without producing a crystalline (anatase-type) acid-titanium film. Therefore, it is particularly useful as a coating agent for substrates that cannot be heat-treated. In such a method, it can be used for various applications such as protective coatings and photocatalysts, and it is possible to obtain a comparatively high density and good adhesion at a relatively low temperature.
  • the step of forming the second layer may include a step of baking the applied peroxo-modified anatase sol after drying. By including the firing step in this way, the hardness of the formed titanium oxide film can be increased and the adhesion to the substrate can be further improved.
  • the case where the titanium oxide film has a two-layer force has been described.
  • a mixed solution of a peroxotitanic acid aqueous solution and a peroxo-modified anatase sol is formed on the second layer.
  • the predetermined binder is Si.
  • the predetermined noinda may include polysiloxane or a carbonized polymer.
  • this carbonized polymer for example, a molybdenum carbide-based silicon in which molybdenum is bonded to the carbonized silicon. System polymers can be used.
  • the titanium oxide film is formed on the base material containing rubber. Even if it is formed and irradiated with a large amount of ultraviolet rays, it can maintain the flexibility of the rubber and prevent the rubber from deteriorating. As a result, even if the titanium oxide film formed on the substrate is irradiated with ultraviolet rays so that the photocatalytic activity can be maintained, the flexibility of the rubber is maintained and the deterioration of the rubber is suppressed. Can do.
  • the present invention can be applied to a method for producing a titanium oxide film using an aqueous solution for forming an oxide titanic film containing peroxotitanic acid modified with a peroxo group and a solution for forming a titanium oxide film.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

Le problème à résoudre dans le cadre de la présente invention est de fournir un procédé pour préparer un film d'oxyde de titane qui, même lorsque le film d'oxyde de titane est formé sur un substrat contenant un caoutchouc et qu’il est irradié par une grande quantité de lumière UV, peut conserver la flexibilité du caoutchouc et peut empêcher la détérioration du caoutchouc, et une solution pour former le film d'oxyde de titane. La solution proposée consiste en un procédé pour préparer un film d'oxyde de titane, qui comprend une étape consistant à appliquer une solution aqueuse d'acide peroxotitanique contenant un liant prédéterminé sur un substrat, une étape consistant à sécher la solution aqueuse d'acide peroxotitanique appliquée, suivie d’une cuisson, de façon à former ainsi une première couche, une étape consistant à appliquer un sol d'anatase modifié avec un groupe peroxo sur la première couche ci-dessus et une étape consistant à sécher le sol d'anatase modifié avec un groupe peroxo appliqué, de façon à former ainsi une seconde couche.
PCT/JP2005/009277 2005-05-20 2005-05-20 Procede pour preparer un film d'oxyde de titane et solution pour former le film d'oxyde de titane WO2006123426A1 (fr)

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PCT/JP2005/009277 WO2006123426A1 (fr) 2005-05-20 2005-05-20 Procede pour preparer un film d'oxyde de titane et solution pour former le film d'oxyde de titane

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PCT/JP2005/009277 WO2006123426A1 (fr) 2005-05-20 2005-05-20 Procede pour preparer un film d'oxyde de titane et solution pour former le film d'oxyde de titane

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004155608A (ja) * 2002-11-05 2004-06-03 Hitachi Chem Co Ltd 酸化チタン膜形成用液体、酸化チタン膜の形成法、酸化チタン膜及び光触媒性部材
JP2004203692A (ja) * 2002-12-26 2004-07-22 Keiryu:Kk 酸化チタン膜形成方法

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004155608A (ja) * 2002-11-05 2004-06-03 Hitachi Chem Co Ltd 酸化チタン膜形成用液体、酸化チタン膜の形成法、酸化チタン膜及び光触媒性部材
JP2004203692A (ja) * 2002-12-26 2004-07-22 Keiryu:Kk 酸化チタン膜形成方法

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