JPH11188703A - Porous article treated product and its manufacture - Google Patents

Abstract

PROBLEM TO BE SOLVED: To possess antibiotic physical properties, non-environmental pollution properties, etc., which are effective for a long period of time by improving photocatalyst activity of a semiconductor particulate and its dispersibility by a method wherein a treating agent containing the semiconductor particulate having photocatalyst action which is fluorinated is applied to a porous article and/or the article is impregnated therewith. SOLUTION: As a semiconductor particulate used for a fluorinated semiconductor particulate-containing treating agent wherein it is applied to a porous article and/or the article is impregnated therewith, titanium oxide is preferable. As a pretreatment, a coincidence treatment, or an after-treatment of a porous article treatment with a treating agent containing the fluorinated semiconductor particulate, the treatment with a treating agent containing a phenolic compound and/or a metallic compound can be executed. Thereby, the fluorinated semiconductor particulate is more firmly bonded to the porous article, a sticking tendency of the fluorinated semiconductor particulate can be raised, and antibiotic physical properties to be added to the porous article can be adjusted. Then, the antibiotic physical properties of the semiconductor particulate come to be enabled to be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a processed article of a porous article treated with semiconductor fine particles having a photocatalytic action, and a method for producing the same. More specifically, the surface of the porous article is treated and / or impregnated with a treatment agent containing semiconductor fine particles whose surface has been fluorinated and the photocatalytic activity of which has been adjusted, thereby obtaining antibacterial properties.
The present invention relates to a method for producing a processed article of a porous article having excellent antibiotic properties such as antiseptic properties, insect repellency, insecticidal properties, antiviral properties, and biological repellency, and a processed article of a porous article obtained by the method.

[0002]

2. Description of the Related Art Conventionally, porous articles have been provided with antibacterial, bactericidal,
In order to impart desirable antibiotic properties such as antiseptic properties, insect repellency, insecticidal properties, antiviral properties, and biological repellency, treatments for impregnating porous articles with various agents have been performed. Specific examples of the drug include copper compounds such as copper sulfate, chromium compounds such as potassium chromate, arsenic compounds such as arsenous acid, fluorine compounds such as sodium fluoride, and boron compounds such as boric acid. By injecting into porous articles such as wood, porous articles having antibiotic efficacy have been manufactured. Among the above-mentioned drugs, particularly, a combination of a copper compound, a chromium compound, and an arsenic compound is widely used as a CCA drug, and a combination of a copper compound, a chromium compound, and a boron compound is widely used as a CCB drug.

[0003] However, a drug containing a chromium compound or an arsenic compound has the characteristics of being relatively inexpensive and having excellent long-term antibiotic efficacy, but contains a highly toxic arsenic compound or a chromium compound. It is necessary to take various measures to prevent environmental pollution during the preparation of chemicals, the process of injecting wood, and the disposal of treated wood. Therefore, there is a need for the development of a drug that can be more safely prepared, used, and disposed of.

[0004] As a safer agent for treating porous articles, an agent using a relatively safe copper compound or zinc compound in combination with various organic compounds has hitherto been used. However, in a porous article treated with these agents, the organic compound used as a component of the agent is gradually decomposed, volatilized, or leached during a long period of use of the treated article. There is a drawback that the long-term stability is inferior to inorganic drugs such as CCA drugs or CCB drugs. Therefore, development of a new treatment agent that is safe and can maintain efficacy for a long period of time is desired.

On the other hand, it has been known that semiconductor particles having a photocatalytic action typified by titanium oxide have an antibiotic action, and development of a material having an antibiotic action has been developed in various fields by utilizing this. Is underway. For example, Japanese Patent Application Laid-Open No. 2-6333 discloses an antibacterial powder using titanium oxide, and teaches that an antibacterial composition can be obtained by blending this powder. Titanium oxide generates active oxygen when used as a photocatalyst, which provides antibacterial properties.However, compounds such as active oxygen have a short life and do not pose a problem of environmental safety, and semiconductors that have such a photocatalytic action The use of particles is very useful. However, when semiconductor particles having a photocatalytic action such as titanium oxide are impregnated and / or applied to a plant-derived porous article such as wood and used to exhibit a sufficient photocatalytic action in expectation of an antibiotic effect, Organic compounds around the semiconductor particles are decomposed, resulting in a decrease in strength and a change in appearance of the porous article, and furthermore, the semiconductor particles are leached out of the porous article together with the decomposed porous article components, and the porous article is treated. However, there was a problem that the antibiotic property given immediately after was reduced. Further, semiconductor fine particles having a photocatalytic action, such as titanium oxide, have a high surface energy, so that aggregation is likely to occur and dispersibility is poor. Therefore, when impregnating or applying to a porous article such as a plant, there has been a problem that the working liquid cannot be sufficiently impregnated or the stability of the working liquid is poor.

[0006]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to solve the above-mentioned problems in producing a processed porous article by utilizing the antibiotic properties of semiconductor fine particles having a photocatalytic action. It is an object of the present invention to provide a method for producing a processed porous article, which is excellent in safety during preparation of a varnish, injection processing into a porous article, and disposal of the treated porous article. Another object of the present invention is to adjust the photocatalytic activity of the semiconductor fine particles, maintain a long-term antibiotic effect, and suppress the degradability of the porous article constituents. An object of the present invention is to provide a production method, and a treated product obtained by the method, which is provided with antibiotic properties such as antibacterial property, bactericidal property, antiseptic property, insect repellent property, insecticidal property, antiviral property, and biological repellency.

[0007]

Means for Solving the Problems The present inventors prepared a treating agent containing semiconductor fine particles having a photocatalytic action, injected a porous article, and disposed of the treated porous article. For treating porous articles that are excellent in safety and can provide long-term antibiotic efficacy, and that have excellent permeability to the inside of the porous articles used for that purpose, and that have excellent stability of the processing working liquid Intensive research was conducted to develop the agent. As a result, by using the fluorinated semiconductor particles, the photocatalytic activity is appropriately adjusted, the antibiotic efficacy of the highly safe semiconductor particles having a photocatalytic effect such as titanium oxide is maintained, and the porous particles are porous. Decomposition of article components is suppressed, and it is possible to impart long-term antibiotic efficacy to the porous article, and the surface energy of the semiconductor fine particles is suppressed by fluorination,
It has been found that sufficient injectability and working fluid stability for a porous article can be obtained and the object of the present invention can be solved, and the present invention has been completed.

As a pre-treatment, a simultaneous treatment, or a post-treatment of a porous article using a fluorinated treatment agent containing photocatalytic semiconductor fine particles, a treatment containing a phenolic compound and / or a metal compound. By conducting the treatment with the agent, it has been found that the antibacterial property is increased and that the adverse effect of the photocatalysis on the antibiotic for porous articles can be more effectively suppressed, and the present invention has been completed. Although the principle of obtaining the effect of the present invention by using fluorinated semiconductor fine particles is not clear, it is generally recognized in fluorinated semiconductor fine particles, for example, even in fluorinated titanium oxide, in titanium oxide and the like. The photocatalytic reaction proceeds, holes and excited electrons are generated on the surface of the fine particles, and the action of the holes reduces oxygen in the air to generate oxygen radicals, which show excellent antibiotic properties It is considered something. On the other hand, the photocatalytic action is moderately suppressed by fluorinating the semiconductor fine particles, and the decomposition of the components of the porous article such as wood is suppressed, whereby the strength is reduced and the leaching of the semiconductor fine particles is suppressed. It is considered that a processed porous article having a long-term antibiotic effect can be obtained.

The present invention provides the following method for producing a processed porous article and a processed porous article. [1] A method for producing a treated porous article, which comprises applying and / or impregnating a porous article with a treatment agent containing fluorinated semiconductor fine particles having a photocatalytic action. [2] The semiconductor fine particles are TiO ₂ , MnO ₂ , ZnO,
The method for producing a treated porous article according to the above [1], which is selected from RuO ₂ , GeO ₂ , Cs ₃ Sb, InAs, InSb, and GaAs. [3] The method for producing a treated porous article according to [1] or [2], wherein the semiconductor fine particles are TiO ₂ . [4] The method for producing a treated porous article according to any one of [1] to [3], wherein the particle size of the semiconductor particles is 100 μm or less. [5] The method for producing a treated porous article according to the above [4], wherein the semiconductor particles have a particle size of 1 μm or less. [6] The method for producing a treated porous article according to the above [1], wherein semiconductor particles fluorinated with a fluorine gas are used.

[7] The method for producing a treated porous article according to the above [1], wherein the treating agent further contains a phenolic compound and / or a metal compound. [8] The porous article according to any one of [1] to [6], wherein a pretreatment, a simultaneous treatment, or a post-treatment with a treatment agent containing a phenolic compound and / or a metal compound is performed. Manufacturing method of processed material. [9] The above-mentioned [7] or [8], wherein the phenolic compound is at least one compound selected from pyrocatechol, hydroquinone, pyrogallol, gallic acid, tannic acid, ferulic acid, lignin, ligninsulfonic acid and derivatives thereof. 4. The method for producing a treated porous article according to item 1. [10] At least one metal compound selected from zirconium, titanium, vanadium, molybdenum, manganese, iron, cobalt, nickel, palladium, copper, silver, zinc, cadmium, aluminum, tin, lead, antimony, calcium, magnesium, and barium The method for producing a treated porous article according to the above [7] or [8], which is a compound containing a kind of metal element.

[11] The above-mentioned [1] to [1], wherein the impregnation of the porous article with the treating agent is carried out by applying pressure and / or pressure.
0]. The method for producing a treated porous article according to any one of the above items. [12] The above-mentioned [11], wherein the pressurization is performed at 1 to 20 atm.
4. The method for producing a treated porous article according to item 1. [13] The method for producing a treated porous article according to any one of [1] to [12], wherein the porous article is a plant-derived porous article. [14] Plant-derived porous articles are wood, wood chips, wood flour,
The method for producing a treated porous article according to the above [13], which is a processed wood product, a fir, a rush, a straw, a bamboo material, a plant fiber, or a processed plant fiber product. [15] A treated porous article obtained by the production method according to any one of [1] to [14].

[0012]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. [Processing Agent Containing Fluorinated Semiconductor Fine Particles] Semiconductor Fine Particles: In the present invention, the semiconductor fine particles used in the processing agent containing fluorinated semiconductor fine particles to be coated and / or impregnated on a porous article have a comparative electron-hole mobility ratio. Any semiconductor fine particles which are large and have a photocatalytic action can be used. For example, TiO ₂ , Mn
O ₂ , ZnO, RuO ₂ , GeO ₂ , Cs ₃ Sb, InA
s, InSb, and GaAs, among which titanium oxide is particularly desirable. Any of these can be used as long as they have a photocatalytic action. For example, in the case of titanium oxide, various semiconductor fine particles such as anatase type, rutile type and brookite type can be used. Further, any method of producing semiconductor fine particles such as a hydrochloric acid method, a sulfuric acid method, a gas phase method, and a liquid phase method can be used as a raw material of the fluorinated semiconductor fine particles of the present invention.

The semiconductor fine particles used have a particle size of 100 in order to increase the permeability into the interior of a porous article such as wood.
μm or less, more preferably 1 μm or less is desirable. However, it maintains a proper dispersibility in the state of the porous article treating agent solution, and furthermore has sufficient permeability to the inside of the porous article, or If permeability is not important,
Semiconductor fine particles having a larger particle size can also be used. As the lower limit of the particle diameter of the semiconductor fine particles used in the present invention, if the particle diameter is smaller than 1 nm, there occurs a problem that the photocatalytic performance can not be obtained unless under irradiation of light having a large energy such as ultraviolet rays, If the particle size is too small, dispersibility deteriorates and handling inconvenience occurs,
Desirably, the particle size is 1 nm or more.

Fluorination of semiconductor fine particles: As a means for fluorinating raw material semiconductor fine particles, a known method, for example,
A method in which sodium fluoride is added to a slurry in which titanium oxide is suspended, and the mixture is stirred (JP-A-59-184263). An organic fluorine compound is used as a hydrophobicity-imparting substance when producing hydrophobic spherical titanium oxide particles. Method (JP-A-61-21521)
Known methods such as a method of contacting ultrafine titanium oxide with Freon gas and fluorinating the surface at a high temperature of 200 to 400 ° C. (Japanese Patent Laid-Open No. 3-40919) can be used. This is a method of directly fluorinating the surface of semiconductor fine particles directly with fluorine gas developed by the present applicant (Japanese Patent Application No. 8-339806).

For example, a fluorination reaction of semiconductor fine particles with fluorine gas is performed as follows by a gas phase method. That is, the semiconductor fine particle raw material is directly charged into a reactor such as a normal-pressure gas-phase flow system, and the reactor is heated to a predetermined temperature (usually 0 ° C).
To 200 ° C., preferably 20 to 150 ° C.), and reacting for a predetermined time (instantaneously to 3 hours, preferably instantaneously to 1 hour) while flowing a fluorine gas or a fluorine gas diluted with nitrogen, argon or the like into this reactor. And a surface fluorination treatment. The surface fluorinated semiconductor fine particles obtained by this method maintain the particle shape and high specific surface area of the raw material, exhibit water and oil repellency effects, have excellent acid and alkali resistance, and have good dispersibility.

The fluorine content of the fluorinated semiconductor fine particles by the method of substantially directly fluorinating the surface of the raw material semiconductor fine particles with fluorine gas is a quantitative value by XPS (X-ray photoelectron spectrum), preferably 0.001 to 61%, Particularly preferably, it is 0.1 to 61%. Incidentally, the fluorination rate of the surface of the semiconductor fine particles is determined by XPS (X-ray photoelectron spec.).
The ratio is determined from the total amount of elements existing from the particle surface to a depth of about 100 angstroms determined by troscopy (X-ray photoelectron spectroscopy). For example, all of the Ti on the surface (ie, 100
%) Becomes TiF ₄ , the fluorine content on the particle surface becomes (4F / TiF ₄ ) × 100 = 61.3% by weight.

Fluorinated semiconductor fine particle treating agent: In the present invention, fluorinated semiconductor fine particles are usually applied or impregnated on a porous article as a slurry-like treating agent suspended in a solvent. Water, ethanol, or the like is used as the solvent. The concentration of the fluorinated semiconductor fine particles in the treating agent is 0.01
５０50% by weight, preferably 0.1-20% by weight. Further, a dispersant or a surfactant can be added in order to improve the stability of the treatment agent, the permeability to the object to be treated, and the spreadability. Further, if necessary, a pH adjuster such as an inorganic alkali, a natural or synthetic coloring matter, a pigment, a thickener, a high molecular weight compound, a solid, or the like can be added to the treating agent of the present invention for use.

[Phenolic Compound and Metal Compound] In the present invention, a phenolic compound and / or a metal compound is used as a pre-treatment, a simultaneous treatment, or a post-treatment of a porous article with a treatment agent containing fluorinated semiconductor fine particles. The treatment with the contained treating agent can be performed.
In the case of simultaneous treatment, a phenolic compound and / or a metal compound are usually contained in the treating agent containing the fluorinated semiconductor fine particles.

As the phenolic compound contained as a component of the treating agent, a compound which is oxidized by air (oxygen) can be used. In particular, pyrocatechol, hydroquinone, pyrogallol, gallic acid, tannic acid, ferulic acid, Lignin, ligninsulfonic acid, or derivatives thereof can be suitably used. By using these compounds, it is possible to more firmly bond the fluorinated semiconductor fine particles and the porous article, and to enhance the adhesion of the fluorinated semiconductor fine particles. At the same time, the photocatalytic action of the fluorinated semiconductor fine particles makes it possible to more effectively prevent the decomposition reaction of the components of the porous article. The concentration of the phenolic compound in the treating agent is 0.001 to 5% by weight, preferably 0.01 to 1% by weight.

Various metal compounds can be used as constituents of the treating agent. For example, zirconium, titanium, vanadium, molybdenum,
Manganese, iron, cobalt, nickel, palladium, copper,
A compound containing at least one metal element selected from silver, zinc, cadmium, aluminum, tin, lead, antimony, calcium, magnesium, and barium can be suitably used. By using these compounds, the antibiotic properties imparted to the porous article can be adjusted.

These metal compounds can be used with a variety of existing chelating agents, especially the above-mentioned pyrocatechol, hydroquinone, pyrogallol, gallic acid, tannic acid, ferulic acid, lignin, ligninsulfonic acid, or By simultaneously using a phenolic compound such as a derivative thereof and a metal compound, it is possible to simultaneously impart the effects of the phenolic compound and the metal compound to the porous article. When a phenolic compound and a metal compound are used simultaneously, these compounds can be used in various combinations.For example, by using pyrogallol and copper sulfate together, pyrogallol improves the fixation of fluorinated semiconductor fine particles. In addition, the decomposition reaction of the components of the porous article due to the photocatalysis of the fluorinated semiconductor fine particles can be suppressed by the action of copper sulfate and pyrogallol. Further, pyrogallol undergoes a decomposition reaction due to the photocatalytic action of the fluorinated semiconductor fine particles, and when the decomposition product leaches out of the porous article, the copper compound or copper ion is leached together. A porous article having a release property can be manufactured. As described above, by using the phenolic compound and the metal compound together, it is possible to adjust the strength of the antibiotic property imparted to the porous article and the degree of diffusion of the antibacterial metal ion (or complex) around the article. It is. The concentration of the metal compound in the treating agent is 0.01 to 90% by weight, preferably 1 to 50% by weight.

Porous articles: The treating agent containing the fluorinated semiconductor fine particles according to the present invention is a metal sintered body, a cast product, an alloy, a die-cast product, a ceramic, a brick, a concrete, a wood, a piece of wood, a wood powder, a wood-processed product. , Fir, rush, straw,
It can be used as a treatment agent for surface treatment and / or internal treatment of various porous articles such as bamboo, charcoal, fiber, processed textiles, and synthetic resin foams. For example, by using wood, wood chips, wood flour, wood products, fir, rush, straw, bamboo, plant fiber, plant fiber processed products, etc., organic compounds that are conventionally porous article components are decomposed. In addition, even when the strength of the porous article is reduced, and the semiconductor fine particles having a photocatalytic action cannot be used, the antibiotic properties of the semiconductor fine particles can be utilized.

In the treatment of the porous article of the present invention, the amount of the fluorinated semiconductor fine particles necessary for imparting the desired antibiotic property to the porous article is adjusted depending on the type of the porous article, the use of the treated porous article, and the like. However, for example, when processing wood for the purpose of producing preserved wood, 0.01-20
It is desirably in the range of 0% by weight. If the amount of the fine particles is less than 0.01% by weight, a sufficient antibiotic effect cannot be obtained, while if the amount of the fine particles exceeds 200% by weight, the properties as wood significantly change.

[Treatment Method] When performing article treatment using the treatment agent containing the fluorinated semiconductor fine particles of the present invention,
A coating operation using a brush or a roller, a spraying operation using a spray, an aerosol, or the like, or an impregnation operation is performed. In particular, the impregnation operation is extremely useful for fixing a sufficient amount of the treating agent to the article in the treatment of the porous article of the present invention. The impregnation operation can be simply performed by immersing the article in a treatment agent solution, but in order to inject a sufficient amount of the treatment liquid into various types of porous articles that are difficult to impregnate,
Pressurizing and / or depressurizing operations are very useful. The pressurizing operation is performed in a range from atmospheric pressure (1 atm) to 20 atm, more preferably 3 to 15 atm.

The depressurizing operation can be performed at any pressure up to a vacuum pressure, but for effective treatment of a porous article which is difficult to impregnate, it is desirable to reduce the pressure in the range of 100 to 760 mmHg. In addition, the pressure reducing operation is more preferably performed by a pre-venting method in which the pressure is reduced before the treatment liquid is added to the porous article. Further, in order to impregnate the treatment liquid in a larger amount in the porous article, it is also effective to combine these pressurizing operation and depressurizing operation. After impregnating the porous article with the treatment liquid, a reduced pressure treatment is performed, and a part of the treatment liquid is collected outside the porous article, so that the degree to which the porous property is maintained can be easily adjusted. It is possible.

[0026] The treated material whose porosity is maintained or adjusted has a humidity adjusting ability, a water holding ability, an adsorbing ability, and an ion exchange ability, and can be used for various applications utilizing such ability. It is possible. In addition, a porous article having various composite properties can be manufactured by further impregnating the treated substance having a porous property with a drug, a polymer, or a prepolymer.

When the porous article is wood, various commonly used pressurizing and / or depressurizing treatment methods can be used, and specifically, a packed cell method (Vesel method) and a semi-empty cell method (Lowry method) , Empty cell method (Leuping method), double vacuum method (double vacuum method), pressurization / decompression alternate method (Osci
llating Pressure Method, Pulsation P
ressure Method, Constant Pressure Me
thod, Slow Pressure Change Metho
d) and a method combining these operations are applicable. Also, the insizing method can be applied to increase the impregnation amount. It is also effective to perform a compression treatment using a roller or the like, a microwave heating, a freezing treatment, a steaming treatment, a steam treatment, or a heat treatment as a pretreatment of the porous article that is difficult to impregnate. The coating and / or impregnating treatment using the antibiotic of the present invention is carried out at 0 to
It is carried out at 150C, preferably 10-100C. Heating during curing is 20 to 300 ° C, more preferably 40 to 1 ° C.
It is carried out at a temperature of 50 ° C.

[0028]

EXAMPLES The present invention will be described more specifically with reference examples, examples and test examples. However, these are merely examples, and the present invention is not limited to only these. In the following examples, “%” means “% by weight” unless otherwise specified.

REFERENCE EXAMPLE 1 Production Method of Fluorinated Titanium Oxide 100 g of ultrafine titanium oxide (specific surface area: 80 m ² / g, primary particle diameter: 20 nm) was charged into a normal-pressure gas-phase flow type reactor at 200 ° C. under reduced pressure. 1 hour firing and pre-treatment,
After cooling to 150 ° C., a gas obtained by diluting a fluorine gas with a nitrogen gas was fed into the reactor for 15 minutes to perform a fluorination treatment. The specific surface area of the fluorinated surface-treated fine particle titanium oxide was 80 m ² / g, and the high specific surface area was maintained. In addition, the fluorine content of the ultrafine titanium oxide is X
As a result of quantification by PS, the fluorine content was 19%. Table 1 shows the results.

Reference Example 2 Production Method of Fluorinated Titanium Oxide An atmospheric pressure gas-phase flow reactor was charged with 100 g of ultrafine titanium oxide (specific surface area: 80 m ² / g, primary particle diameter: 20 nm), and reduced pressure at 200 ° C. 1 hour firing and pre-treatment,
After cooling to 70 ° C., a gas obtained by diluting fluorine gas with nitrogen gas was sent to this reactor for 1 minute to perform a fluorination treatment. The specific surface area of the fluorinated surface-treated fine particle titanium oxide was 80 m ² / g, and the high specific surface area was maintained. Also, the fluorine content of the ultrafine titanium oxide was determined by XPS
As a result, the fluorine content was 8%. Table 1 shows the results.

Reference Example 3 Production Method of Fluorinated Titanium Oxide An atmospheric pressure gas phase flow type reactor was charged with 100 g of ultrafine titanium oxide (specific surface area: 80 m ² / g, primary particle diameter: 20 nm), and the pressure was reduced to 200 ° C. at 200 ° C. 1 hour firing and pre-treatment,
After cooling to 20 ° C., a gas obtained by diluting fluorine gas with nitrogen gas was sent to this reactor for 1 minute to perform a fluorination treatment. The specific surface area of the fluorinated surface-treated fine particle titanium oxide was 80 m ² / g, and the high specific surface area was maintained. Also, the fluorine content of the ultrafine titanium oxide was determined by XPS
As a result, the fluorine content was 4%. Table 1 shows the results.

Reference Example 4 Method for Producing Fluorinated Zinc Oxide 100 g of ultrafine zinc oxide (specific surface area: 40 m ² / g, primary particle diameter: 40 nm) was charged into an atmospheric pressure gas-phase flow reactor, and the pressure was reduced to 200 ° C. at 200 ° C. 1 hour firing and pre-treatment
After cooling to 50 ° C., a gas obtained by diluting a fluorine gas with a nitrogen gas was fed into this reactor for 15 minutes to perform a fluorination treatment. The specific surface area of the fluorinated surface-treated fine particle zinc oxide was 40 m ² / g, and the high specific surface area was maintained. Further, as a result of quantifying the fluorine content of the ultrafine zinc oxide by XPS, the fluorine content was 20%. Table 1 shows the results.

[0033]

[Table 1]

Example 1 Preparation of Wood Treatment Agent and Wood Treatment
Fluorinated semiconductor fine particles A to D produced in Production Reference Examples 1 to 4
Was suspended in 100 ml of distilled water to obtain wood treating agent solutions (treating agent solutions A to D). Using this treating agent solution, cedar wood chips (2 cm x 2 cm x 1 cm,
cm × 2 cm, sapwood). The impregnation operation was performed after immersing the cedar wood pieces in the treatment liquid.
Decompression at 50 to 700 mmHg was performed for 30 minutes, and furthermore, it was performed by placing the device at normal pressure for 30 minutes while immersed. By this impregnation operation, a sufficient amount of processing solution (3.0 to 3.4 g)
Was confirmed by measuring the weight of the wood pieces before and after the impregnation operation. Further curing was performed at room temperature for one week. Next, 40 ml of water was added to the treated pieces of wood, and the rotor was rotated with a magnetic stirrer under the condition that the pieces of wood were submerged under water. Place in the container for 48 hours, then 30
It was dried sufficiently by placing it in a desiccator for minutes, and treated wood pieces (wood pieces A to D) were obtained. As a control, unfluorinated titanium oxide and zinc oxide were subjected to the same treatment to obtain treated wood pieces (wood pieces E and F). When the injection amount of the treatment liquid by this impregnation operation was calculated, both wood pieces were around 1 g, and poor injection properties of titanium oxide and zinc oxide were confirmed.

Example 2 Preparation of Wood Treatment Agent and Wood Treatment
Production Dissolve 0.63 g of pyrogallol in 100 ml of distilled water,
Reference Example 1 after adjusting the pH to 9.0 with sodium hydroxide
5 g of the fluorinated semiconductor fine particles A produced in the above was suspended to obtain a wood treatment agent solution (treatment agent solution G). Next, 10
After dissolving 0.63 g of pyrogallol and 1.25 g of copper sulfate pentahydrate in 0 ml of distilled water and adjusting the pH to 9.0 with sodium hydroxide, 5 g of the fluorinated semiconductor fine particles A produced in Reference Example 1 was suspended, A wood treating agent solution was obtained (treating agent solution H). As a control, a processing solution having the same composition but not containing only the fluorinated semiconductor fine particles A was prepared (processing solutions G ′ and H ′). Using this treating agent solution, the same impregnation operation and weathering operation as in Example 1 were performed to obtain treated wood chips (treated wood chips G, G ′, H, H ′).

Test Example: Antiseptic test of treated wood The antibacterial test of the wood pieces prepared in Examples 1 and 2 was carried out.
JIS A 9201 (Wood preservative performance standards and test methods 1991
), According to the Japanese quail (Tyromyces palustris)
The test was performed using FEPRI 0507 (obtained from Forest Research Institute, Ministry of Agriculture, Forestry and Fisheries). However, this test was performed under fluorescent lamp irradiation. After the antibacterial operation, remove the wood chips from the culture bottle, sufficiently remove the mycelium on the wood chip surface, and air-dry for about 24 hours.
In the same manner as described above, the weight was measured after sufficiently drying using a drier and a desiccator, and the reduction rate of the weight of the wood piece was calculated. As a result, it was shown that the wood treatment method of the present invention can effectively impart antibacterial properties. Table 2 shows these detailed results.

[0037]

[Table 2]

[0038]

According to the method for producing a treated article of porous article using the treating agent of the present invention containing a fluorinated semiconductor fine particle having a photocatalytic action, the photocatalytic activity and dispersibility of the semiconductor fine particle are improved, and the semiconductor fine particle is effective for a long time. It is possible to obtain a processed porous article having useful effects such as excellent antibiotic properties and non-environmental pollution.

Continued on the front page (51) Int.Cl. ⁶ Identification symbol FI B01J 35/02 B01J 35/02 J B27K 3/32 BBA B27K 3/32 BBA 3/52 BBA 3/52 BBAA C01G 9/04 C01G 9/04 17/04 17/04 23/02 23/02 A 45/00 45/00 55/00 55/00 (72) Inventor Ryuji Kadota 1-1-1 Ohnodai, Midori-ku, Chiba City, Chiba Prefecture Showa Denko KK In the laboratory

Claims (15)

[Claims] 1. A method for coating a porous article with a treating agent containing fluorinated semiconductor fine particles having photocatalytic activity and / or
Alternatively, a method for producing a treated porous article characterized by impregnation. 2. The method according to claim 1, wherein the semiconductor fine particles are TiO ₂ , MnO ₂ , Z
nO, RuO ₂ , GeO ₂ , Cs ₃ Sb, InAs, In
The method for producing a treated porous article according to claim 1, wherein the article is selected from Sb and GaAs. 3. The method according to claim 1, wherein the semiconductor fine particles are TiO _2.
Or the method for producing a treated porous article according to item 2. 4. The method for producing a treated porous article according to claim 1, wherein the particle size of the semiconductor particles is 100 μm or less. 5. The method according to claim 4, wherein the semiconductor particles have a particle size of 1 μm or less. 6. The method according to claim 1, wherein semiconductor particles fluorinated with fluorine gas are used. 7. The method according to claim 1, wherein the treating agent further contains a phenolic compound and / or a metal compound. 8. The porous article treatment according to claim 1, wherein a pretreatment, a simultaneous treatment, or a post-treatment with a treatment agent containing a phenolic compound and / or a metal compound is performed. Method of manufacturing a product. 9. The phenolic compound is pyrocatechol,
The method for producing a treated porous article according to claim 7 or 8, wherein the method is at least one compound selected from hydroquinone, pyrogallol, gallic acid, tannic acid, ferulic acid, lignin, ligninsulfonic acid, and derivatives thereof. 10. The method according to claim 1, wherein the metal compound is zirconium, titanium, vanadium, molybdenum, manganese, iron, cobalt, nickel, palladium, copper, silver, zinc, cadmium, aluminum, tin, lead, antimony, calcium,
The method for producing a treated porous article according to claim 7 or 8, wherein the compound is a compound containing at least one metal element selected from magnesium and barium. 11. The process for producing a treated porous article according to claim 1, wherein the impregnation of the treating agent into the porous article is performed by applying pressure and / or pressure. 12. The method for producing a treated porous article according to claim 11, wherein the pressurization is performed at 1 to 20 atm. 13. The method for producing a treated porous article according to claim 1, wherein the porous article is a plant-derived porous article. 14. The plant-derived porous article is made of wood, wood chips,
Wood flour, wood products, fir, rush, straw, bamboo, plant fiber,
Or a processed vegetable fiber product.
4. The method for producing a treated porous article according to 3. 15. A treated porous article obtained by the production method according to claim 1. Description: