Method and apparatus for carrying out prevention of pollution, purification of polluted fluid or production of radical by electroconductive polymer and electroconductive polymer and structure therefor

Description: TECHNICAL FIELD [Detailed description of the invention]

【0001】

[Technical field to which the invention belongs]

The present invention relates to a technique for producing an active radical species or peroxide for prevention of surface contamination, purification of a contaminated fluid, or purification by irradiating a conductive polymer with an electromagnetic wave having an absorption wavelength thereof. More specifically, the absorption wavelength of a conductive polymer or a conductive polymer such as a conductive polymer film formed on the surface of various structures manufactured of various materials such as glass, tile, metal or plastic has its absorption wavelength. The present invention relates to a technique for suppressing contamination of the surface of a conductive polymer by irradiating an electromagnetic wave, a technique for purifying a contaminated fluid such as a contaminated gas or a contaminated liquid, or a technique for generating an active radical species or peroxide for purification.

【0002】

[Conventional technology]

Regarding conductive polymers such as polyaniline or polypyrrole, various types such as electromagnetic wave shielding materials that shield electromagnetic waves generated from mobile phones, televisions, personal computers, home appliances, etc., battery electrodes, antistatic agents, capacitors, diodes, transitions, etc. Much research and development has been carried out with the expectation that it will be used in electronic devices, electrochromic elements, various sensors, etc., and some have reached the stage of practical use.

【0003】

Many substances have already been developed for this conductive polymer, and in addition to the above-mentioned polyaniline and polypyrrole, polythiophene, polythiophene sulfide, polyisothianaften, polyacetylene, polyalkylpyrrole, and polyalkylthiophene have been developed. , Poly-p-phenylene, polyphenylene vinylene, polymethoxyphenylene, polyphenylene sulfide, polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, polyazulene or polymers thereof. In addition, these conductive polymers are said to be used alone or as a mixture of two or more kinds in the above-mentioned use.

【0004】

These conductive polymers are preferably doped, and this doping improves the conductivity, and as a result, the electromagnetic wave shielding property. The dopant is an alkali metal such as Li, Na, K, a donor type dopant such as an alkaline earth metal such as Ca, or Cl.₂, Br₂, I₂Halogen, PF, etc.₃, AsF₅, BF₃Lewis acid, HF, HCl, HNO, etc.₃, H₂SO₄, HClO₄Etc. Protonic acid, FeCl₃, FeOCl₂, TiCl₄, WCl₃Transition metal compounds such as Cl^-, Br^-, I^-, ClO₄^-, PF₃^-, BF₃^-, AsF₃^-An acceptor-type dopant of an electrolyte anion such as is used.

【0005】

The above-mentioned use of these conductive polymers exclusively utilizes the property of high conductivity, and as described above, the property is particularly important when used as an electromagnetic wave shielding material. is there. It is also known that its properties change due to an oxidation or reduction reaction, particularly an electrical redox reaction, or a reaction with an acid or base. In particular, conductive polymers having the performance of electron donors and electron acceptors exhibit changes in electrical characteristics due to these reactions.

【0006】

For example, polyaniline is known to change according to the reaction formula (1) below due to an oxidation or reduction reaction or a reaction with an acid or base ("New Polymer Material One Point-5 Conductive Polymer", Yoshimura. Susumu, edited by the Society of Polymer Science, pp. 17-18).

【0007】

[Formula 1]

<img file="JP2002241522A_D0001.tif" />【0008】

As a result, when polyaniline is oxidized, the conductivity is metallic and the color is green, and when it is reduced, the conductivity is insulated from blue to colorless and transparent. Further, when it is acidified by reacting with an acid, the conductivity is improved and becomes green, and when it is reacted with a base and acidified, the conductivity is lowered and the color becomes blue.

【0009】

[Problems to be Solved by the Invention]

The present inventors have been involved in research and development of related technologies such as improvement of photocatalytic performance of photocatalysts, especially titanium oxides, especially titanium peroxide, and utilization means for many years, and have proposed many results. On the other hand, as described above, the conductive polymer has been mainly focused on the electrical conduction property, and only the utilization based on the property has been paid attention to. Under such circumstances, the present inventors focused on whether or not the conductive polymer also has photocatalytic performance as well as conductivity, and as a result of diligent research, it was found that this conductive polymer exhibits photocatalytic performance. It can be found and the present invention is completed.

【0010】

Therefore, the present invention has found that a conductive polymer exhibits photocatalytic performance by irradiating it with an electromagnetic wave to generate an active radical species or a peroxide, and utilizes the characteristics of the conductive polymer surface. It is an object to be solved by the invention to provide a technique for preventing pollution, purifying a polluted fluid, or producing an active radical species or peroxide for purification. That is, it is an object of the invention to provide those things.

【0011】

[Means for solving problems]

The present invention provides a method and apparatus for preventing contamination by a conductive polymer, purifying a contaminated fluid, or generating radicals, and a conductive polymer and a structure for that purpose, in order to solve the above problems. Among them, the method of preventing contamination, purifying the contaminated fluid, or generating the active radical species or peroxide for purification is performed by irradiating the conductive polymer with an electromagnetic wave having an absorption wavelength thereof.

【0012】

In that case, by irradiating the conductive polymer with electromagnetic waves under humidification, it is possible to improve the pollution prevention performance, the purification performance of the polluted gas, or the ability to generate active radical species for purification. Further, the contamination prevention performance and the contamination fluid purification performance can be improved by containing a photocatalytic semiconductor metal and irradiating an electromagnetic wave of 410 nm or less, and the conductivity can be improved by further containing a conductivity improving substance. it can.

【0013】

In addition, the conductive polymer is a conductive polymer for preventing surface contamination, purifying contaminated fluid, or generating active radical species or peroxides for purification by irradiating with electromagnetic waves of absorption wavelength. It is a conjugate polymer having a dopamine function and causing metal-insulator transfer, a conjugate polymer having irregular bond alternation in the polymer chain, or a conjugate polymer having a one-dimensional chain.

【0014】

Furthermore, by irradiating electromagnetic waves of absorption wavelength, a conductive polymer body or a conductive polymer film for preventing surface contamination, purifying contaminated fluid, or producing active radical species or peroxides for purification can be obtained. The formed structure is also one of the present inventions. Further, a structure in which a conductive polymer or a conductive polymer film for purifying a contaminated fluid or producing an active radical species or a peroxide for purification by irradiating an electromagnetic wave having an absorption wavelength is formed, and the above-mentioned structure. A device for purifying a contaminated fluid equipped with an electromagnetic wave irradiation device or for producing an active radical species or peroxide for purification is also one of the present inventions.

【0015】

Then, in the present invention, by irradiating the conductive polymer of the conductive polymer or the conductive polymer film formed on the surface of the structure with electromagnetic waves, for example, ultraviolet rays, contamination on the surface can be suppressed and the contaminated fluid can be prevented. We also found that it can be purified. In addition, by continuing the irradiation of electromagnetic waves, the anti-pollution effect or the purifying effect is maintained, but when the irradiation is stopped, those functions are exhibited even after the stop, but those functions are gradually reduced and eventually stopped. It is also known to do.

【0016】

Furthermore, when such antifouling action or purification action is sustained, the conductivity of the conductive polymer is in an insulating state, and when the conductivity is increased, these actions are reduced and the conductivity is metal. It has also been found that when it becomes a state, the anti-pollution effect, the purifying effect, and the effect of producing radical species and the like disappear.

【0017】

Contamination prevention (suppression) or purification in the present invention means prevention or post-adhesion of contaminated chemical substances, contaminated microorganisms, contaminated powder, etc. to the surface of a polymer or structure in which a conductive polymer is present. Decomposition of polluted chemicals, polluted microorganisms, etc. by photochemical catalysts, detoxification treatment by transfer to detoxified substances, or various causes of pollution such as polluted chemicals or polluted microorganisms existing in polluted fluids such as polluted gases or liquids Detoxification treatment by decomposition of components, transfer to detoxification substances, etc. is applicable. In that case, not only the contaminated fluid is introduced into the structure such as a purification device, but also the functional structure that generates active radical species and peroxides or the generated active radical species and peroxides are introduced into the contaminated fluid. You may put it in the water and purify it.

【0018】

In the present invention, the mechanism of action in which such antifouling performance or purification performance is exhibited has not been clearly confirmed, but the present inventors, etc., by irradiating the conductive polymer with electromagnetic waves. Oxygen radical ( O₂), Superoxide radical ( O₂^-) Or hydroxyl radical ( OH) is generated, and as a result, an oxidation / reduction reaction occurs, which prevents contamination of the surface of the structure or purifies the gas or liquid by the oxidation / reduction reaction around the surface. The inventor speculates.

【0019】

More specifically, when referring to these antifouling or purifying effects, in dissolved oxygen in the air or water, O₂ + e O₂^-The reduction reaction is mainly caused by. Also, in the air or underwater humidity, H₂O + e OH + H⁺Oxidation reaction mainly occurs. In total, 2O₂ + 2H H₂O₂ + O₂Peroxide is generated by this, and oxidative decomposition occurs.

【0020】

As a result, the present inventor speculates that these oxidation and reduction reactions prevent contamination of the surface of the structure itself or purify the contaminated gas or contaminated liquid. Furthermore, to mention, the electrons (e) required to generate these active radical species and peroxides have a dopamine function (electron donor / electron acceptor function) by irradiating the absorption wavelength of the conductive polymer. It is speculated that this works to generate radical species and peroxides that easily pop out from the surface of the conductive polymer. Especially it appears prominently in the insulated state.

【0021】

BEST MODE FOR CARRYING OUT THE INVENTION

As described above, the present invention provides a method for preventing contamination of the surface of a conductive polymer by irradiating a conductive polymer with an electromagnetic wave having an absorption wavelength thereof, purifying a contaminated fluid, or generating an active radical species or peroxide for purification. It is provided, and the antifouling performance or the purification performance can be improved by irradiating the irradiation under humidification. Further, by further containing a photocatalytic semiconductor metal containing a titanium peroxide in the conductive polymer, antifouling performance, purification performance or formation performance of radical species and the like can be improved. In particular, by sharing the excitation wavelengths of the conductive polymer and the photocatalytic semiconductor metal, their performance can be further improved.

【0022】

In addition to polyaniline and polypyrrole, conductive polymers include polythiophene, polythiophene vinylene, polyisothianaften, polyacetylene, polyalkylpyrrole, polyalkylthiophene, poly-p-phenylene, polyphenylene sulfide, and polymethoxy. There are many such as phenylene, polyphenylene sulfide, polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, polyazulene or polymers of these derivatives.

【0023】

In the present invention, the conductive polymer used for forming the conductive polymer film can be used in various ways and is not particularly limited, but is a conjugated polymer in which metal-insulator transfer occurs, or in a polymer chain. A conjugate polymer having an irregular bond alternation or a conjugate polymer having a one-dimensional chain and having a dopamine function, a so-called electron donor and electron acceptor function, can be preferably used. These include polyaniline, polyphenylene and the like, and polyaniline, which is an ionic polymer, is particularly preferable.

【0024】

The target structure for forming the conductive polymer film of the present invention is required to have various functions such as photocatalytic performance, antibacterial performance, antifouling performance, antifogging performance, antistatic ability, electromagnetic shielding property, and rust prevention property. This applies to structures made of various materials or structures having various shapes, and is not particularly limited. Examples of these materials include sheet glass, ceramics, metal plates such as stainless steel and aluminum, plastic plates such as acrylic, polycarbonate and PET, cotton cloth and fibers.

【0025】

The shape of the structure includes buildings, window glass for automobiles, vehicle exterior materials for automobiles, tanks, various water tanks for ornamental use, pipes for metal, plastic, etc., sanitary ware, eyeglasses, lenses, lens filters. , Water storage, bathtub equipment, wash basin, sink, door handle, water tap, road mirror, electromagnetic shield material, semiconductor material such as substrate, internal parts of copier, etc. can be exemplified.

【0026】

The purification performance and the ability to generate active radical species and peroxides are proportional to the total surface area of the conductive polymer and proportional to the total amount (watts) of the excited electromagnetic waves. For that purpose, unevenness is positively formed on the surface of the structure for forming the conductive polymer film by shot blasting or the like, or the surface is made uneven by laminating fine particles to make the surface uneven and excited. A metal such as stainless steel or aluminum having a function of reflecting wavelength is desirable.

【0027】

In particular, the case of purifying a contaminated gas or a contaminated liquid is specifically described by purifying an automobile exhaust gas purification device, a combustion exhaust gas purification device such as a factory or a waste incinerator, a wastewater purification device such as sewage or sewage. In order to form a conductive polymer film on these devices and purify contaminated gas or contaminated wastewater inside the device, a conductive polymer film is formed on the structure of the device itself, for example, on the wall of the vessel, or conductive. It is preferable to install a structure having a multi-surface surface and an active radical species generation function in which a conductive polymer film is formed.

【0028】

In order to purify a contaminated gas or a contaminated liquid using such a device, it is indispensable to irradiate the conductive polymer film formed therein with an absorbed electromagnetic wave peculiar to the polymer, particularly an absorbed electromagnetic wave in an insulated state. Therefore, it is desirable to continuously irradiate the device. Therefore, in principle, the electromagnetic wave is generated, and a light source for irradiating the electromagnetic wave is provided in the apparatus so that the generated light irradiates the conductive polymer film. It will be installed. At that time, when it contains titanium oxide that exhibits photocatalytic activity, it is preferable to install a light source that irradiates an electromagnetic wave of 410 nm or less.

【0029】

In the present invention, in order to form a conductive polymer film on the surface of a structure, it can be formed by applying a solution or dispersion of the conductive polymer to the surface of the structure. It is hard to say that the conductive polymer itself has a sufficient bonding force with the surface of the structure, and therefore, an auxiliary agent (referred to as a binding property improving component throughout the present specification) that improves the bonding force is used in combination. Is good.

【0030】

As the auxiliary agent, various kinds can be used without limitation, and they include silica sol, various peroxides of titanium, and inorganic polymer resins containing indium-tin oxide (ITO), so-called acrylic silicon. Examples include resins and fluororesins. In order to form a dispersion liquid containing such an auxiliary agent and a conductive polymer film, it is preferable to disperse the conductive polymer powder in the dispersion liquid of the binding property improving component. For example, it can be formed by dispersing a conductive polymer powder in a titanium peroxide dispersion liquid.

【0031】

In selecting the auxiliary agent, it is preferable to consider the affinity with the various structural materials described above. In general, for example, silica sol is preferable for glass, inorganic polymer resin is preferable for plastic, and titanium oxide is preferable for metal, glass, plastic, and other materials. Further, among titanium oxides, titanium peroxide is particularly preferable because it has a function as an auxiliary agent for improving the bonding force with the surface of the structure and also becomes titanium oxide after film formation and can also exhibit a photocatalytic function. ..

【0032】

There are two types of titanium peroxide, amorphous type and anatase type. Although anatase type titanium peroxide has catalytic ability, amorphous titanium peroxide does not have catalytic ability, so it is conductive without organic matter resolution. Suitable for forming a polymer film. On the other hand, the conductive polymer film formed of anatase-type titanium peroxide and the conductive polymer has both the excitation function and the photocatalytic ability of the conductive polymer, and thus has excellent pollution prevention function and purification function. It is particularly preferable. Further, since this anatase-type titanium peroxide has a particularly excellent affinity with a structure having a hydrophilic group, it is used when forming a conductive polymer film on the surface of a structure made of an inorganic material. Is particularly preferable.

【0033】

In the present invention, it is desirable to use a conductivity-improving substance in combination with the titanium peroxide. As such an improving substance, various substances such as a metal salt can be used as long as the conductivity can be improved as compared with the film formed by the film forming liquid containing titanium oxide alone. Metal salts include, for example, metal salts such as aluminum, tin, chromium, nickel, antimony, iron, silver, cesium, indium, cerium, selenium, copper, manganese, calcium, platinum, tungsten, zirconium, zinc, etc. In addition, hydroxides or oxides can also be used for some metals or non-metals.

【0034】

More specifically, they are represented by substance names: aluminum chloride, 1st and 2nd tin chloride, chromium chloride, nickel chloride, 1st and 2nd antimony chloride, 1st and 2nd iron chloride, silver nitrate, cesium chloride, Indium trichloride, cerium chloride, selenium tetrachloride, cupric chloride, manganese chloride, calcium chloride, platinum chloride, tungsten tetrachloride, tungsten oxydichloride, potassium tungstate, gold chloride, zirconium oxychloride , Zinc chloride and other various metal salts can be exemplified. Examples of the compound other than the metal salt include indium hydroxide, silicotungstic acid, silica sol, calcium hydroxide and the like.

【0035】

Then, in the present invention, as described above, in particular, the conductive polymer and the photocatalytic semiconductor metal can be contained together, and at that time, by sharing the excitation wavelength, the pollution prevention function, the pollution purification function and the radical species generation can be contained. The function can be further improved, and titanium oxide is an example of such a semiconductor metal or a compound thereof, and various semiconductor metals or compounds thereof can be used in addition to the above. For example, ZnO and SrTiOP can be used.₃, CdS, CdO, CaP, InP, In₂O₃, CaAs, BaTiO₃, K₂NbO₃, Fe₂O₃, Ta₂O₃, WO₃, NiO, Cu₂O, SiC, SiO₂, MoS₃, InSb, RuO₂, CeO₂And so on.

【0036】

In the present invention, as described above, in order to exhibit the antifouling or purifying function, it is indispensable to irradiate an electromagnetic wave having an absorption wavelength of the conductive polymer, and it is desirable to continuously irradiate the electromagnetic wave. In principle, a light source is installed in the vicinity of or near the conductive polymer, the structure on which the conductive polymer film is formed, so that the electromagnetic waves are generated and the generated light irradiates the conductive polymer. It is necessary to.

【0037】

The light source for generating such an electromagnetic wave is not particularly limited as long as it can generate an electromagnetic wave having an absorption wavelength of a conductive polymer, and various types can be used, which are metal halide lamps (HQI, HCI). ), Mercury lamp (low pressure, high pressure), halogen lamp, blue fluorescent lamp, black light, fluorescent sterilization, etc., but mercury lamp is preferable from the viewpoint of efficiency. As described above, the conductive polymer film of the present invention is originally intended to be used in a place where natural light or a lighting device does not exist, but of course, it is natural light such as sunlight or indoor lighting. However, it has the absorption wavelength of each conductive polymer (absorption wavelength in the conductive state and insulating state, especially the absorption wavelength in the insulating state), and in the case of a photocatalytic semiconductor metal-containing film containing titanium oxide, it is 410 nm or less. The component, that is, the one in which ultraviolet rays are present, is sufficient, and the presence of an artificial light source is not indispensable.

【0038】

In the present invention, as described above, a solution or dispersion of a conductive polymer is applied to the surface of the structure in order to form a conductive polymer film on the surface of the structure. Various types can be adopted without limitation, and examples thereof include a spray method, a roller method, and a dip method, but the spray method or the dip method is preferable from the viewpoint of economy. After forming the coating film, it is preferable to heat and dry it at room temperature to about 250 ° C.

【0039】

In the present invention, in order to prevent contamination of the structure surface or purify the contaminated gas by the conductive polymer film formed on the surface of the structure in a gas space such as in the air or a contaminated gas, the conductive polymer film is used. Is desirable to be humidified. By irradiating electromagnetic waves under humidification, it is possible to prevent stains on the surface of the structure or efficiently purify the polluted gas existing in the surroundings. At that time, it is desirable that the wet state of the film is such that the change of state of wet and dry is repeated in a short period of time.

【0040】

[Example]

An example of production of the conductive polymer film forming liquid of the present invention and a film forming example of preparing a conductive polymer film using the forming liquid are shown below. Further, an organic compound decomposition performance evaluation test is conducted according to an example in which an electromagnetic wave is applied to a conductive polymer film produced using the film forming example, and the decomposition performance of each conductive polymer film by electromagnetic waves is evaluated.

【0041】

[Production Example 1] A solution prepared by adding 10 g of a 50% titanium tetrachloride solution (manufactured by Sumitomo Citix Co., Ltd.) to 500 g of pure water and adding pure water to make 1000 g was prepared, and 25% ammonia water (Takasugi Pharmaceutical Co., Ltd.) was prepared. ) Was diluted 10-fold with aqueous ammonia to adjust the pH to 7.0 to precipitate titanium hydroxide. The precipitate is washed with pure water until the conductivity of the supernatant becomes 0.8 mS / m or less. When the washing was completed when the conductivity reached 0.783 mS / m, 403 g of a hydroxide-containing solution having a concentration of 0.78 wt% was prepared.

【0042】

Next, while cooling this content to 1 to 5 ° C, 25 g of 35% hydrogen peroxide (manufactured by Taiki Yakuhin Kogyo Co., Ltd.) was added, and when stirred for 16 hours, a light yellowish brown amorphous peroxidation with a concentration of 0.86 wt% was obtained. 425 g of titanium dispersion was obtained. This was diluted with pure water to prepare 430 g of an amorphous titanium peroxide dispersion of 0.85 wt%. In 30 g of this 0.85 wt% amorphous titanium peroxide dispersion liquid, 0.516 g of polyaniline fine powder was dispersed in a ratio of 1: 2 to the Ti content of amorphous titanium peroxide, and polyaniline fine powder (polyaniline fine powder) ( Approximately 30 g of 0.85 wt% amorphous titanium peroxide dispersion containing (average particle size 100 nm) was prepared.

【0043】

[Production Example 2] When 200 g of 0.85 wt% amorphous titanium peroxide dispersion prepared in the process of Production Example 1 is weighed and heated at 100 ° C. for 5 hours, a pale yellow anatase-type titanium peroxide dispersion is 1.82. 90 g was obtained at wt% concentration. This was diluted with pure water to prepare 96 g of a 1.70 wt% anatase-type titanium peroxide dispersion.

【0044】

In 30 g of this 1.70 wt% anatase-type titanium peroxide dispersion, 1.032 g of polyaniline fine powder was dispersed in a ratio of 1: 2 to the Ti content of anatase-type titanium peroxide, and polyaniline fine powder (average particle size) was dispersed. About 31 g of anatase-type titanium peroxide dispersion containing 1.70 wt% (100 nm) was prepared.

【0045】

[Production Example 3] 0.73 wt% polyaniline was mixed and dispersed in 25.5 g of 0.85 wt% amorphous titanium peroxide dispersion prepared in the step of Production Example 1 and 4.5 g of polyaniline dispersion containing 0.05 wt% polyaniline. Approximately 30 g of an amorphous titanium peroxide dispersion containing a dispersion (average particle size of 100 nm or less) was prepared.

【0046】

[Production Example 4] 4.5 g of polyaniline dispersion containing 0.05 wt% polyaniline was mixed and dispersed in 25.5 g of the 1.70 wt% anatase-type titanium peroxide dispersion prepared in the step of Production Example 2 to obtain 1.46 wt% polyaniline dispersion. About 30 g of anatase-type titanium peroxide dispersion containing (average particle size 100 nm or less) was prepared.

【0047】

[Manufacturing Example 5] 500 g of pure water with 97% purity CuCl₂ 2H₂Add 10 g of 50 wt% titanium tetrachloride solution (manufactured by Sumitomo Citix Co., Ltd.) to a solution in which 0.463 g of 0 (manufactured by Nihon Kagaku Sangyo Co., Ltd.) is completely dissolved, and add pure water to prepare a solution of 1000 g. .. Ammonia water diluted 10-fold with 25% ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) was added dropwise thereto to adjust the pH to 7.0, and a mixture of copper hydroxide and titanium hydroxide was precipitated.

【0048】

Washing of this precipitate with pure water until the conductivity in the supernatant becomes 0.8 mS / m or less is continued, and when the washing is completed when the conductivity reaches 0.755 mS / m, hydroxylation at a concentration of 0.82 wt% is completed. A liquid containing 345 g of the substance was prepared. Next, while cooling this content to 1 to 5 ° C, 25 g of 35% hydrogen peroxide (manufactured by Taiki Yakuhin Kogyo Co., Ltd.) was added, and when the mixture was stirred for 16 hours, 0.91 wt% blue-green transparent copper was doped. 370 g of a dispersion of amorphous titanium peroxide was obtained.

【0049】

The obtained amorphous titanium peroxide dispersion was diluted to prepare 395 g of an amorphous titanium peroxide dispersion doped with 0.85 wt% copper. Polyaniline fine powder (average particle size 100 nm) is contained in 30 g of this copper-doped amorphous titanium peroxide dispersion by dispersing polyaniline fine powder at a ratio of 1: 2 with respect to the Ti content in this dispersion. About 30 g of a 0.85 wt% amorphous titanium peroxide dispersion liquid doped with copper was prepared.

【0050】

[Production Example 6] 200 g of an amorphous titanium peroxide dispersion prepared in the process of Production Example 5 and doped with 0.85 wt% copper is weighed and heated at 100 ° C. for 5 hours to produce pale green-blue copper. 96 g of a doped amorphous titanium peroxide dispersion was obtained at a concentration of 1.74 wt%. This was diluted with pure water to prepare 98 g of anatase-type titanium peroxide dispersion liquid doped with 1.70 wt% copper.

【0051】

To 30 g of this 1.70 wt% copper-doped anatase-type titanium peroxide dispersion, 1.032 of polyaniline fine powder in a ratio of 1: 2 to the Ti content of copper-doped anatase-type titanium peroxide. Approximately 31 g of 1.70 wt% anatase-type titanium peroxide dispersion liquid doped with copper containing polyaniline fine powder (average particle size 100 nm) was prepared.

【0052】

[Production Example 7] 4.5 g of polyaniline dispersion containing 0.05 wt% polyaniline is mixed and dispersed in 25.5 g of the 0.85 wt% amorphous titanium peroxide dispersion prepared in the step of Production Example 5, and 0.73 wt% polyaniline dispersion. Approximately 30 g of an amorphous titanium peroxide dispersion liquid doped with copper containing John (average particle size of 100 nm or less) was prepared.

【0053】

[Production Example 8] 4.5 g of polyaniline dispersion containing 0.05 wt% polyaniline was mixed and dispersed in 25.5 g of anatase-type titanium peroxide dispersion prepared in the process of Production Example 6 and doped with 1.70 wt% copper, 1.46. Approximately 30 g of copper-doped anatase-type titanium peroxide dispersion containing wt% polyaniline dispersion (average particle size of 100 nm or less) was prepared.

【0054】

An example of film formation for preparing a conductive polymer film using the conductive polymer film forming liquid produced in the above production example is shown below.

[Film formation examples 1 and 2] SUS304 (2B finish, thickness 0.8 m / m, 10 x 10 mm) After removing organic components from the substrate surface in advance and treating it with hydrophilicity, the concentrations on the surface are 0.05 wt% and 4 wt%. Two types of commercially available polyaniline fine powder dispersion liquid (D1005w, D1002w: manufactured by Olmecon) 0.6g / 100cm²After coating with a spray coat, a conductive polymer film was formed by heating at 200 ° C. for 15 minutes. The SUS substrate on which the obtained conductive polymer film is formed on the surface is referred to as film formation examples 1 and 2.

【0055】

[Film formation examples 3 to 10] Using the same SUS304 substrate as in film formation examples 1 and 2, the surface of this substrate was previously irradiated with ultraviolet rays (UV) having a wavelength of 254 nm for 15 minutes to remove organic components. A coating film was formed on this substrate by spray coating using the dispersions of Production Examples 1 to 8, and after drying, the substrate was heated at 200 ° C. for 15 minutes to form a conductive polymer film.

【0056】

The SUS304 substrates on which the coatings thus obtained were formed were designated as coating formation examples 3 to 10, respectively. In forming the coating film at that time, the coating amount is 0.6 g / 100 cm when a 0.85 wt% dispersion is used in order to make the film thickness uniform.²Also, when using a 1.70 wt% dispersion, 0.3 g / 100 cm²And said.

【0057】

[Film formation example 11] 30 g of a 0.85 wt% amorphous titanium peroxide dispersion having no photocatalytic ability produced in Production Example 1 was collected on a substrate from which the same organic components as those in film formation examples 3 to 10 were removed. 0.6g / 100cm²After spray coating and drying at the coating amount of, the film formation example 11 as a comparative control example was prepared by heating at 200 ° C. for 15 minutes.

【0058】

[Film formation example 12] 30 g of a dispersion of 1.70 wt% anatase-type titanium peroxide having photocatalytic activity prepared in Production Example 2 was collected on a substrate from which the same organic components as those in film formation examples 3 to 10 were removed, and 0.3. g / 100cm²After spray coating and drying at the coating amount of, the film formation example 12 as a comparative control example was prepared by heating at 200 ° C. for 15 minutes.

【0059】

[Decomposition Performance Evaluation Test] An organic compound decomposition performance evaluation test was conducted by irradiating the conductive polymer film formed by the film formation example with an electromagnetic wave. When the film forming examples 1 to 10 are used, it is an example of the present invention, and when the film forming examples 11 and 12 are used, it is a comparative example. Therefore, when the film forming examples 1 to 10 are used, they are referred to as Examples 1 to 10, respectively, and when the film forming examples 11 and 12 are used, they are referred to as Comparative Examples 1 and 2.

【0060】

[Decomposition Performance Evaluation Test Method] As shown in FIG. 1, a part (60%) of the film-forming SUS substrate obtained in the film-forming example is covered with aluminum foil, and the surface of the rest (A) is exposed. The portion (B) covered with the aluminum foil was prevented from being irradiated with light. In such a state, an ultraviolet irradiation device (manufactured by SEN) equipped with a low-pressure mercury lamp (200 W) that generates an electromagnetic wave of 254 nm or less was used, and this was irradiated for 60 seconds at a distance of 3 cm from the substrate.

【0061】

After the irradiation, the substrate is taken out from an ultraviolet irradiation device (manufactured by SEN), and the aluminum foil is separated from the substrate. After that, about 60 g / 100 cm on the separated substrate so that the substrate is colored with red water prepared by diluting red ink (manufactured by Pilot) 20 times with pure water.²Was applied with. The coated substrate was irradiated with sunlight (direct sunlight) outdoors and the decolorization time was measured.

【0062】

[Disassembly Performance Evaluation Test Results] The results of this decomposition performance evaluation test are shown in Table 1. According to the results, polyaniline alone, which is a conductive polymer, both polyaniline and either amorphous or anatase-type titanium peroxide, or polyaniline, titanium peroxide, or a conductivity-improving substance. In the substrate on which the above is formed, in the substrate A portion, that is, the portion irradiated with ultraviolet rays, when red water prepared from the red ink is applied, the red color disappears immediately after the application and is not colored.

【0063】

[table 1]

<img file="JP2002241522A_D0002.tif" />【0064】

On the other hand, in the substrate B portion, that is, the portion not irradiated with ultraviolet rays, in the case of a coating film containing both polyaniline and anatase-type titanium peroxide, the coloring with red water is decolorized within a short time of 1 hour or less. However, it can be seen that in the case of polyaniline alone or a film containing polyaniline and amorphous titanium peroxide, the color is decolorized up to about 1/2, but the color is not completely decolorized after one month.

【0065】

Further, according to the result of this evaluation test, the decolorizing performance of the coating film not containing polyaniline, which is a conductive polymer, is lower than that of the film containing polyaniline. Furthermore, it can be seen that there is no difference in the decolorizing performance when red water is applied between the portion irradiated with ultraviolet rays and the portion not irradiated with ultraviolet rays. The anatase-type titanium peroxide coating is superior in decolorizing performance to the amorphous titanium peroxide coating because the former is superior in photocatalytic ability.

【0066】

[Effect of the invention]

The present invention has been completed by finding that a conductive polymer exhibits photocatalytic performance by irradiating it with an electromagnetic wave having an absorption wavelength thereof, and by utilizing this characteristic, a conductive polymer or a conductive polymer or It is possible to suppress surface contamination in a structure in which a conductive polymer film is formed on the surface of a structure formed of various materials such as glass, tile, metal or plastic.

【0067】

Specific structures include buildings, window glass for automobiles, vehicle exterior materials for automobiles, tanks, various water tanks for ornamental use, pipes such as metal and plastic, sanitary ware, eyeglasses, lenses, and lens filters. , Water storage, bathtub equipment, wash basin, sink, door handle, water tap, road mirror, electromagnetic shield material, semiconductor materials such as substrates, and various structures such as copying machine internal parts are prevented from being contaminated. ..

【0068】

Then, in the present invention, the contaminated fluid can be purified by forming the conductive polymer body or the conductive polymer film in the purifying device for the contaminated fluid such as the contaminated gas or the contaminated liquid. For example, these exhaust gases can be purified by forming a conductive polymer film on an automobile exhaust gas purification device or a combustion exhaust gas purification device and irradiating electromagnetic waves having an absorption wavelength of the conductive polymer.

【0069】

Further, the waste liquid can be purified by forming a conductive polymer film or the like in a contaminated waste liquid purification device such as a factory or a sewage treatment plant and irradiating it with electromagnetic waves. Not only when the contaminated fluid is introduced into the purification device as described above, but also a functional structure that generates active radical species and peroxides in the contaminated fluid, or the generated active radical species and peroxides. May be input.

[Simple explanation of drawings]

[Figure 1]

The figure which shows the state which covered with the aluminum foil of the SUS substrate used when irradiating the electromagnetic wave in this invention.