JP5065636B2 - Method for producing optical semiconductor fine particles - Google Patents

Description

The present invention relates to a method for producing photo-semiconductor fine particles having photocatalytic activity used for applications such as antifouling, anti-fogging, antibacterial, air purification, and water purification.

In recent years, optical semiconductors having photocatalytic activity, such as titanium oxide, have attracted attention in various applications such as antifouling, antifogging, antibacterial, air purification, and water purification, and active product development has been carried out. When light of a wavelength having energy greater than the band gap hits this optical semiconductor, holes and electrons are generated, and the electrons and oxygen in the air react to generate O ₂ ⁻ (superoxide ion). Holes and water react to generate hydroxy radicals. These active species have strong oxidizing power and oxidatively decompose organic substances.

  For example, a method is known in which semiconductor particles having photocatalytic activity (photocatalyst particles) are dispersed in an organic binder to prepare a composition, which is applied onto a substrate. The coating film containing the photocatalyst fine particles can be used indoors and outdoors, such as air purification by decomposition of bad odor and toxic VOC (Volatile Organic Compound) in the air, prevention of surface contamination by decomposition of the coating film, and antibacterial and antifungal properties. Very useful for environmental purification. However, in the long term, organic matter around the photocatalyst fine particles in the coating film is also decomposed, and there is a problem of coating film deterioration. Therefore, it is necessary to devise so that the organic binder does not directly contact the photocatalyst fine particles.

  Patent Document 1 describes that photocatalyst fine particles are coated with a porous calcium phosphate film. Patent Document 2 describes that photocatalyst fine particles are contained in silica particles. According to these methods, the organic binder deterioration suppressing effect can be obtained to some extent. However, the photocatalytic performance may be deteriorated by the coating, and a problem still remains in the weather resistance of the organic binder in long-term outdoor exposure.

Patent Document 3 describes that photocatalyst fine particles are coated with a porous coating portion made of an inorganic material such as silica or alumina, or an organic material such as a fluororesin. Specifically, when the photocatalyst fine particles are coated by a sol-gel method using a metal alkoxide, a hydrophilic polymer such as polyethylene glycol is added, and this porous coating is formed by baking after forming the coating film. ing. However, with this method, it is difficult to precisely control the pore diameter of the porous membrane, and the organic binder tends to enter into pores having a relatively large diameter, and as a result, the weather resistance of the organic binder may be reduced. .
Japanese Patent Laid-Open No. 10-244166 Japanese Patent Laid-Open No. 11-33100 JP-A-11-197515

The present invention has been made to solve the above-described problems. That is, the object of the present invention is to show sufficient photocatalytic performance, and when the photo semiconductor fine particles are dispersed in a medium such as an organic binder, the medium is not easily deteriorated. As a result, the weather resistance is far higher than that of the conventional one. It is to provide a method of manufacturing an optical semiconductor fine particles capable of forming an excellent coating film or the like.

  As a result of intensive studies, the present inventors have found that a coating film having excellent weather resistance can be obtained while maintaining sufficient photocatalytic activity by coating the photo semiconductor fine particles with a specific porous silica film, The present invention has been completed.

The present invention is a method for producing optical semiconductor fine particles coated with a porous silica film having a pore diameter of 0.5 nm to 10 nm,
Mixing at least a surfactant aqueous solution and a water-soluble organic solvent at 1 to 10 ° C. to prepare a mixed solution;
Adding a photo semiconductor fine particle and alkoxysilane to the mixed solution at 1 to 10 ° C. and stirring to form a film on the surface of the photo semiconductor fine particle; and
A step of forming a porous silica film by firing the photo-semiconductor fine particles coated with the film;
A method for producing optical semiconductor fine particles.

Furthermore, this invention is a manufacturing method of the composition for coating including the process of disperse | distributing the optical semiconductor fine particle manufactured by the method of the said invention in an organic binder.

Furthermore, this invention is a manufacturing method of the film including the process of apply | coating the coating composition manufactured by the method of the said invention on a base material, and drying and hardening | curing with a heat | fever or an active energy ray.

The optical semiconductor fine particles coated with the porous silica film produced by the method of the present invention are unlikely to deteriorate even when dispersed in a medium such as an organic binder. As a result, it is possible to form a coating film having much better weather resistance than conventional ones. In addition, the photo-semiconductor fine particles coated with the porous silica film produced by the method of the present invention exhibit sufficient photocatalytic performance. Therefore, applications using photocatalytic activity, for example, air purification by decomposition of bad odors and toxic VOCs in the air, water purification by BOD (Biochemical Oxygen Demand) decomposition treatment of household and industrial wastewater, surface by decomposition of coating film dirt It is very useful in applications for the purpose of preventing contamination, as well as antibacterial and antifungal.

  Furthermore, the manufacturing method of the optical semiconductor fine particles is a method capable of easily and satisfactorily manufacturing such excellent optical semiconductor fine particles.

<Optical semiconductor fine particles>
The photo-semiconductor fine particles in the present invention are not particularly limited as long as they exhibit photocatalytic activity by light such as UV lamp, black light, fluorescent lamp, and sunlight, for example. Examples of catalytically active _{components, TiO 2, ZnO, SrTiO 3} , CdS, GaP, InP, GaAs, BaTiO 3, KNbO 3, Fe 2 O 3, Ta 2 O 5, WO 3, SnO 2, Bi 2 O ₃ , NiO, Cu ₂ O, SiC, SiO ₂ , MoS ₂ , InPb, RuO ₂ , CeO ₂ , LaTaON ₂ , MTaO ₂ N (M: alkaline earth metal), Ta ₃ N ₅ , TaON, LaTiO ₂ N, _{TiN x O 2-X, TiN} x O y F z, and MNbO ₂ N: include compounds niobium-based, such as (M alkaline earth metal). In addition, a material that responds to visible light in which nanoscale metal ultrafine particles are supported on titanium oxide fine particles can also be used. Among these, from the viewpoint of durability, cost, and photocatalytic activity, photo semiconductor fine particles mainly composed of titanium oxide (TiO ₂ ) are preferable, and among the titanium oxide fine particles, anatase-type titanium oxide fine particles are particularly preferable.

  The particle diameter of the optical semiconductor is preferably 1 nm to 300 nm, and more preferably 10 nm to 100 nm. If the particle diameter is moderately large, it becomes easy to disperse into primary particles with a solvent when coating with a porous silica film. Moreover, if a particle diameter is moderately small, a surface area will become large and photocatalytic activity will improve.

<Porous silica membrane>
The optical semiconductor fine particles of the present invention are those coated with a specific porous silica film. These photo semiconductor fine particles are those in which individual fine particles are independently coated with the film. For example, silica fine particles containing photocatalyst fine particles, or a plurality of fine particle coated portions are integrated. It does not include those that are difficult to separate.

  The pore diameter of the porous silica membrane is 0.5 nm to 10 nm. If this is less than 0.5 nm, it becomes difficult for the organic matter to be decomposed to enter the pores and the decomposition performance becomes insufficient. On the other hand, if it exceeds 10 nm, the molecular segment of the organic binder easily penetrates, so that the organic binder is deteriorated and the weather resistance of the coating film becomes insufficient. The pore diameter is preferably 0.5 nm to 3 nm. Such a silica film having a uniform pore diameter can be easily and satisfactorily manufactured by a manufacturing method described in detail later.

  The pore diameter of the porous silica film is a value measured by a gas adsorption method using a constant volume method. When the pore diameter is 0.5 to 1 nm, the pore distribution curve is obtained by micropore analysis using a t-plot, and when the pore diameter is 1 to 10 nm, the BJH method is used to obtain the pore diameter distribution curve. It can be a diameter.

The thickness of the porous silica film is preferably 1 nm to 300 nm, more preferably 1 nm to 100 nm, and particularly preferably 2 nm to 100 nm.
If the porous silica film is made thick to some extent, the organic binder does not penetrate the film and reach the optical semiconductor fine particles, and deterioration of the organic binder can be avoided. Further, if the thickness is appropriately reduced, the organic matter to be decomposed can easily reach the optical semiconductor fine particles through the pores, so that sufficient decomposition performance can be obtained.

<Manufacturing method>
In the method for producing optical semiconductor fine particles coated with the porous silica film of the present invention, a film containing a specific component, a solution containing the optical semiconductor fine particles and the alkoxysilane is stirred on the surface of the optical semiconductor fine particles at a specific temperature. A porous silica film is formed by firing the photo-semiconductor fine particles coated with the film.

Specifically, a step of preparing a mixed solution by mixing at least a surfactant aqueous solution and a water-soluble organic solvent at 1 to 10 ° C. , and mixing the photo semiconductor fine particles and alkoxysilane at 1 to 10 ° C. or lower It was added to the solution by stirring, by a method comprising the steps of forming a film on the surface of the optical semiconductor fine particles, and forming a porous silica film by baking the optical semiconductor particles coated with the film There is . Hereinafter, this method will be described.

  First, at least a surfactant aqueous solution and a water-soluble organic solvent are mixed at a specific temperature below room temperature to prepare a mixed solution.

  In the surfactant aqueous solution, a cationic surfactant is usually used. As the cationic surfactant, a quaternary ammonium salt such as an alkyltrimethylammonium salt is particularly preferable. As the water-soluble organic solvent, alcohol solvents such as methanol and ethanol are usually used. In particular, methanol is preferable. Furthermore, it is preferable to adjust the pH of the mixed solution by mixing together a pH adjusting agent (for example, ammonia water, an amine solution, etc.).

  Next, a film is formed on the surface of the optical semiconductor fine particles by adding the optical semiconductor fine particles and the alkoxysilane to the mixed solution at a specific temperature below room temperature and stirring them. This film is a silica film mainly composed of a silica component derived from alkoxysilane.

  Specific examples of the optical semiconductor fine particles are as described above. Examples of the alkoxysilane include tetraalkoxysilane and phenyltrialkoxysilane. In particular, tetraalkoxysilane is preferable.

  This stirring can be performed, for example, by applying ultrasonic waves to the mixed solution and vibrating it. The stirring time is not particularly limited, and stirring may be performed for about 2 to 6 hours.

In each of the above steps, the solution temperature needs to be 1 to 10 ° C. If this temperature is too high, the coated fine particles are likely to aggregate and it becomes difficult to obtain optical semiconductor fine particles in which individual fine particles are independently coated with a film. This temperature is preferably 2 ° C. to 5 ° C., especially. The mixing time is not particularly limited as long as it is sufficient to uniformly mix the components. Usually, stirring is performed for several hours to 24 hours.

  Next, it is preferable to remove the optical semiconductor fine particles on which the film has been formed as described above from the mixed solution and wash it. Specifically, for example, the photo semiconductor fine particles may be collected by centrifugation, washed with a solvent such as methanol, and further centrifuged several times.

  Next, the recovered and washed photo-semiconductor fine particles are baked to form a porous silica film having a uniform pore diameter. The firing temperature is preferably about 300 ° C. to 600 ° C., and the firing time is preferably several hours to several tens of hours. By such firing, the surfactant in the film is removed, and the optical semiconductor fine particles coated with the so-called mesoporous silica film are obtained.

<Coating composition>
The photo semiconductor fine particles coated with the porous silica film of the present invention are very useful as a coating composition dispersed in various binders. The kind of the binder is not particularly limited, and various organic polymers, organic / inorganic composite organic polymers, and inorganic polymers that have been conventionally known in this application can be widely used. Specific examples of the organic binder include acrylic resin, fluororesin, polyester resin, alkyd resin, epoxy resin, phenol resin, polyurethane resin, amino resin, fiber resin, polyvinyl chloride resin, vinyl acetate resin, polyethylene resin, amino acid. Examples thereof include curable resins, isocyanate curable resins, acid epoxy curable resins, hydrolyzable silane curable resins, hydroxyl group epoxy group curable resins, and hydrazine curable resins.

  The coating composition of the present invention is used, for example, in applications where the composition is applied onto a substrate, dried and cured with heat or active energy rays to form a coating. Since this coating sufficiently exhibits the photocatalytic performance caused by the photo semiconductor fine particles, it is very useful for applications utilizing photocatalytic activity. In addition, since the organic binder is not easily deteriorated, the weather resistance of the film is also excellent.

<Example 1>
Cetyltrimethylammonium chloride (surfactant) 0.211 g, water 7.7 g, methanol 200 ml, and aqueous ammonia 7.2 g were mixed at a molar ratio of 1: 1935: 7505: 180 and treated at 3 ° C. for 1 day. Stir. Next, 200 mg of titanium oxide fine particles (Degussa, trade name P-25) was added, 0.368 ml of tetraethoxysilane (molar CTAC / Si ratio = 0.4) was added, and the mixture was further stirred at 3 ° C. for 3 hours. A film was formed on the surface of the titanium oxide fine particles.

  Next, the mixed solution was centrifuged (3500 rpm for 3 minutes) to recover the titanium oxide fine particles coated with the membrane. Further, the operation of adding an appropriate amount of methanol to the collected fine particles, stirring, and separating again by centrifugation was repeated three times to wash the fine particles.

  The washed fine particles were dried at 60 ° C. for 1 day. Furthermore, the titanium oxide fine particles covered with the porous silica film of the present invention were obtained by heating in an air atmosphere at a heating rate of 150 ° C. per hour and then performing firing at 350 ° C. for 10 hours.

The obtained fine particles were measured by constant volume gas adsorption and analyzed by the BJH method (pretreatment: dried at 120 ° C. in vacuum for 3 hours). As a result, a porous body having a peak pore diameter of about 2 nm was obtained. I found out. The fine particles had a specific surface area of 180 m ² / g. This value indicates that titanium oxide (P-25) has a specific surface area of 40 m ² / g, so that titanium oxide and porous silica are composited.

  FIG. 1 is a transmission electron micrograph of titanium oxide fine particles obtained by such a process. As shown here, each titanium oxide fine particle was covered with a porous silica film having a thickness of about 2.5 nm. From the above, it was confirmed that the optical semiconductor fine particles coated with the porous silica film of the present invention could be produced.

<Example 2>
Titanium oxide fine particles were coated with a porous silica film in the same manner as in Example 1 except that an equimolar amount of octadecyltrimethylammonium bromide was used instead of cetyltrimethylammonium chloride as a surfactant. As a result, optical semiconductor fine particles coated with the same porous silica film as in Example 1 were obtained.

<Example 3>
In Examples, except for changing the amount of each component to 0.422 g of cetyltrimethylammonium chloride, 15.4 g of water, and 0.736 ml of tetraethoxysilane (molar CTAC / Si ratio = 0.4). In the same manner as in Example 1, titanium oxide fine particles were coated with a porous silica film. As a result, optical semiconductor fine particles coated with the same porous silica film as in Example 1 (however, the film thickness was about 5 nm) were obtained.

<Example 4>
Titanium oxide fine particles were coated with a porous silica film in the same manner as in Example 1 except that an equimolar amount of dodecylmethylammonium chloride was used instead of cetyltrimethylammonium chloride as a surfactant. As a result, optical semiconductor fine particles coated with the same porous silica film as in Example 1 were obtained.

<Comparative example>
Except that the mixed solution was stirred at room temperature (28 ° C.), titanium oxide fine particles were coated with a porous silica film in the same manner as in Example 1. When the obtained powder was observed with a transmission electron microscope, the porous silica was not uniformly coated.

<Evaluation test 1>
In order to examine the photocatalytic activity of the porous silica-coated titanium oxide fine particles obtained in Example 1, the photocatalytic decomposability of formaldehyde was compared with that of titanium oxide fine particles (P-25) as follows.

First, 1.2 g of porous silica-coated titanium oxide fine particles (containing about 1.0 g of titanium oxide) were spread on a glass petri dish having a diameter of 8 cm and sealed in a 5 L capacity gas bag (Tedlar bag). 1 ppm formaldehyde gas was introduced into it, and it was irradiated with a black light at room temperature in the dark so that the exposure intensity at 365 nm was 1 mW / cm ^2, and the formaldehyde concentration after 1 hour was measured. Further, 1.0 g of uncoated titanium oxide fine particles (P-25) were similarly tested and compared.

  As a result, it was confirmed that the porous silica-coated titanium oxide fine particles obtained in Example 1 had a formaldehyde concentration of 0.17 ppm, and the uncoated titanium oxide fine particles were 0.13 ppm, indicating almost the same photocatalytic activity. .

<Evaluation Test 2>
In order to examine the weather resistance of the porous silica-coated titanium oxide fine particles obtained in Example 1, the weather resistance was compared with titanium oxide (P-25) as follows.

  First, 1.6 g of porous silica-coated titanium oxide fine particles were dispersed in 8.1 g of a 1% aqueous solution of a dispersant (trade name BYK-190), and 21.5 g of a 48% acrylic emulsion was added to form a coating composition. . This coating composition was applied to an aluminum substrate with a thickness of 150 μm by an applicator and dried to form a coating. In addition, a coating composition was prepared in the same manner for uncoated titanium oxide fine particles (P-25) to form a film.

  Next, these films were subjected to a 20-hour weather resistance test using a sunshine weather meter (water spray 12 minutes / UV irradiation 48 minutes). As a result, the gloss retention of the coating after the test was 92% in the case of the porous silica-coated titanium oxide fine particles obtained in Example 1, whereas it was 80% in the case of the uncoated titanium oxide fine particles. Met. From this result, it was confirmed that the weather resistance was significantly improved by the present invention.

2 is a transmission electron micrograph of porous silica-coated optical semiconductor fine particles of the present invention.

Claims (5)

A method for producing optical semiconductor fine particles coated with a porous silica film having a pore diameter of 0.5 nm to 10 nm,
Mixing at least a surfactant aqueous solution and a water-soluble organic solvent at 1 to 10 ° C. to prepare a mixed solution;
Adding a photo semiconductor fine particle and alkoxysilane to the mixed solution at 1 to 10 ° C. and stirring to form a film on the surface of the photo semiconductor fine particle; and
A step of forming a porous silica film by firing the photo-semiconductor fine particles coated with the film;
The manufacturing method of the optical semiconductor fine particle characterized by including these. 2. The method for producing optical semiconductor fine particles according to claim 1, wherein the porous silica film has a thickness of 1 nm to 300 nm. 3. The method for producing photo semiconductor fine particles according to claim 1, wherein the photo semiconductor fine particles are titanium oxide fine particles. The manufacturing method of the composition for coating including the process of disperse | distributing the optical semiconductor fine particle manufactured by the method as described in any one of Claims 1-3 in an organic binder. A method for producing a coating film comprising the steps of: coating a coating composition produced by the method according to claim 4 on a substrate; and drying and curing with heat or active energy rays.