JP2003113262A - Method for preventing or cleaning contamination by electrically conductive polymer film and structure having contamination preventing or cleaning function - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for preventing or cleaning the surface contamination of a cover of a lighting fixture, a panel for tunnel wall and a case and inner parts of various precision instruments such as a copying machine by forming a film of an electrically conductive polymer such as polyaniline on the surface of the protecting object, especially a technique useful for the prevention or cleaning of the contamination of the cover and panel light of a lighting fixture installed in a tunnel. SOLUTION: The surface contamination of a structure of various materials, especially a panel light installed in a tunnel or a cover of the light is prevented or cleaned by forming a film of an electrically conductive polymer such as polyaniline on the protecting object and applying a DC or AC voltage to the polymer film preferably under the radiation of electromagnetic wave having a wavelength of 300-900 nm such as visible light.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention uses a conductive polymer such as polyaniline to provide a highly conductive material for cases such as lighting equipment covers, tunnel wall panels, and cases of various precision instruments such as copying machines, and interior and exterior members. The present invention relates to a technique for preventing or purifying contamination on the surface by forming a molecular film. More specifically, the cover of the lighting equipment installed in the tunnel,
Prevents pollution that can be particularly preferably adopted for members that are constantly exposed to visible light emitted from an illumination lamp, such as glass bulbs of light bulbs or fluorescent tubes of fluorescent lamps, and are also constantly exposed to pollution by automobile exhaust gas. Or, it relates to purification technology.

[0002]

2. Description of the Related Art Regarding conductive polymers such as polyaniline and polypyrrole, electromagnetic wave shielding materials for shielding electromagnetic waves generated from mobile phones, televisions, personal computers, home appliances, battery electrodes, antistatic agents, capacitors, diodes. , Various electronic devices such as transistors,
Many researches and developments have been conducted with the expectation that they will be used in electrochromic devices and various sensors, and some have reached the stage of practical application.

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

Doping these conductive polymers
Preferably, this doping improves conductivity
As a result, the electromagnetic wave shielding property is improved. That dopa
As the components, alkali metals such as Li, Na and K, Ca
Donor type dopant such as alkaline earth metal such as
Is Cl₂, Br₂, I₂Such as halogen, PF₃, AsF_Five，
BF₃Lewis acid such as HF, HCl, HNO₃, H₂S
O_Four, HClO_FourProtic acid such as FeCl₃, FeOC
l₂, TiCl_Four, WCl₃Transition metal compounds such as Cl ^-，
Br^-, I^-, ClO_Four ^-, PF₃ ^-, BF₃ ^-, AsF₃ ^-Etc.
Electrolyte anion acceptor type dopants are used
It

The above-mentioned use of these electroconductive polymers is to make full use of its characteristic of high electroconductivity, and particularly when it is used as an electromagnetic wave shielding material,
As described above, the characteristics are important. It is also known that its properties are changed by an oxidation or reduction reaction, especially an electrical redox reaction, or a reaction with an acid or a base. In particular, a conductive polymer having the functions of an electron donor and an electron acceptor exhibits changes in electrical characteristics due to these reactions.

For example, polyaniline can be produced by the following (1) by an oxidation or reduction reaction or a reaction with an acid or a base.
It is known that it changes depending on the reaction formula (“New Polymer High Material One Point-5 Conductive Polymer”, Susumu Yoshimura, Polymer Society of Japan, pp. 17-18). As a result, when polyaniline is oxidized, the electrical conductivity is metallic and the color is green, and when it is reduced, the electrical conductivity is electrically insulating and changes from blue to colorless and transparent. When it is acidified by reacting with an acid, the conductivity is improved and becomes green, and when it is made basic by reacting with a base, the conductivity is decreased and the color is blue.

[0007]

[Formula 1]

The present inventor has long been involved in the research and development of photocatalysts, in particular, the oxides of titanium, in particular, the photocatalytic performance of titanium peroxide, the research and development of related techniques such as utilization means, and proposed many results. On the other hand, as described above, the conductive polymer has been paid attention mainly to the electric conduction property, and the use based on the property has been paid attention. Under such circumstances, the present inventor paid attention to whether or not the electroconductive polymer also has the photocatalytic performance together with the electroconductivity, and as a result of diligent research, found that the electroconductive polymer exhibits the photocatalytic performance. The invention related to this has already been applied for a patent (Japanese Patent Application No. 2001-44586).

According to the invention of the application, the conductive polymer is irradiated with an electromagnetic wave having its absorption wavelength to prevent the surface from being contaminated, purify the contaminated fluid, or generate an active radical species or peroxide for purification. Regarding technology. More specifically, the conductive polymer, or glass, tile, the absorption wavelength to the conductive polymer such as a conductive polymer film formed on the surface of various structures manufactured by various materials such as metal or plastic, A technique for suppressing the contamination of the surface of the conductive polymer, a technique for purifying a contaminated fluid such as a contaminated gas or a contaminated liquid, or a purifying active radical species or peroxidation, preferably by irradiating an electromagnetic wave having an absorption wavelength in an insulating state. The present invention relates to a technology for producing an object.

[0010]

DISCLOSURE OF THE INVENTION The invention proposed by the patent application is that a conductive polymer is irradiated with an electromagnetic wave having an absorption wavelength, particularly an absorption wavelength in an insulating state, as described above. The present invention relates to a technique for preventing contamination on the surface of a conductive polymer film formed on the surface of a body or a structure, cleaning pollution, or generating an active radical species or peroxide for cleaning.

Therefore, the present inventor further diligently studied to develop a technique for preventing or purifying pollution on the surface of the conductive polymer film, regardless of whether or not the electromagnetic wave having the absorption wavelength in the insulating state is irradiated. Then, it was found that by applying a direct current or an alternating voltage to the conductive polymer film, it is possible to prevent the contamination on the surface of the film or to purify the contamination, and as a result, the invention of the present invention succeeded in the development. is there.

Therefore, according to the present invention, a DC or AC voltage is applied to the conductive polymer film regardless of whether or not the conductive polymer film is irradiated with an electromagnetic wave having an absorption wavelength in its insulating state. We have found that pollution on the surface can be prevented or pollution can be purified, and by utilizing its characteristics, a technology for forming a conductive polymer film on the structure surface to prevent pollution on the structure surface or to purify pollution It is an object of the invention to provide the object. That is, it is an object of the invention to provide a technique for preventing the pollution or purifying the pollution.

[0013]

In order to solve the above problems, the present invention provides a method for preventing or purifying contamination by a conductive polymer film, and a performance for preventing or purifying contamination having a conductive polymer film. And particularly preferably a tunnel illuminating lamp including a fluorescent tube or a glass bulb on which a conductive polymer film having the performance is formed, and a conductive polymer film having the performance. Provided is a tunnel lighting device including a formed transparent or translucent cover.

The former method of preventing or purifying contamination is to prevent or purify contamination on the surface of the conductive polymer film by applying a voltage. In the latter structure, the conductive polymer film is provided on the conductive polymer film or the conductive film so that a DC or AC voltage can be applied to the conductive polymer film in the structure body. By providing the above, the performance of preventing or purifying pollution is exhibited, and in both cases, the performance of preventing or purifying pollution is improved by irradiating an electromagnetic wave having a wavelength of visible light or shorter.

Further, the luminaire having an anti-contamination performance or a purification performance for a tunnel, which is a particularly preferable aspect of the structure, has a conductive polymer film on the cover surface, and the polymer film has a DC or AC voltage. An illuminating lamp having a similar performance has a fluorescent tube or a glass bulb having a conductive polymer film on the surface thereof and an electrode for applying a DC or AC voltage to the polymer film. It is a thing.

Further, in the present invention, conductive polymers such as polyaniline and polypyrrole are used to form conductive polymers in cases such as lighting fixture covers, panels for tunnel walls, and cases and interior members of various precision equipment such as copying machines. By forming a film and applying a DC or AC voltage to the polymer film, it is possible to prevent contamination on the surfaces of the various precision equipment cases and interior members, etc., and to be contained in various exhaust gas such as automobile exhaust gas. The unburned or incompletely burned hydrocarbon, carbon monoxide, or SO _X or NO _X , which is a harmful component produced by combustion, can be decomposed or oxidized to be purified.

Simultaneously with the application of DC or AC voltage, electromagnetic waves of visible light or shorter wavelength, preferably 300
By irradiating the electromagnetic wave in the range of up to 900 nm, the pollution prevention performance and the pollution purification performance are remarkably improved. further,
The conductive polymer in the conductive polymer film is preferably in a semiconductive state or an insulating state. Therefore, the conductive polymer film should be subjected to electromagnetic wave irradiation treatment at an absorption wavelength or acid or alkali treatment in the conductive state. This further improves the pollution purification performance.

In particular, when the conductive polymer film and the conductive film to which an AC or DC voltage is applied are used for a cover of a lighting fixture installed in a tunnel, a fluorescent tube of a fluorescent lamp, a glass bulb of a light bulb, etc., The conductive polymer film is inevitably always irradiated with electromagnetic waves of visible light or shorter wavelength by the illumination lamp such as the fluorescent lamp installed in the tunnel, and the pollution of those surfaces, particularly automobile exhaust gas. Contamination due to the contamination is prevented, and as a result, reduction of illumination light due to the contamination can be effectively prevented.

At the same time, it is also possible to decompose or oxidize unburned harmful components or harmful combustion components such as NO _x in the exhaust gas of the vehicle discharged into the tunnel and convert them into detoxified substances. Furthermore, when this conductive polymer film is installed on the entire surface of the tunnel wall and the amount of illumination is increased, the inside of the tunnel becomes brighter, which is not only useful for safe driving, but also the air inside the tunnel. It is also very effective for purification.

[0020]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the present invention provides a method for preventing or purifying contamination by a conductive polymer film to which direct current or alternating current is applied, and a conductive polymer film to which direct current or alternating current is applied. The present invention provides a structure having anti-pollution or purification performance, and in both cases, irradiation with an electromagnetic wave having a wavelength of visible light or shorter can improve both anti-pollution and anti-pollution performance. Incidentally, the prevention or purification of pollution in the present invention, various harmful pollutant components such as exhaust gas adhere to the surface of the conductive polymer film, the pollutant components are purified by decomposition or oxidation by the conductive polymer film, as a result Contamination of the surface is prevented. At that time, OH ⁻ and · O ₂ radicals are formed from H ₂ O and O ₂ in the atmosphere to exert a purification function.

Further, particularly preferably, a conductive polymer film having the above performance is used for an illuminating lamp or a luminaire, which is a member used in a tunnel under a severely polluted environment and constantly irradiated with visible light. When formed, it provides a lighting fixture and the like with excellent pollution purification performance. Specifically, a tunnel lighting including a fluorescent tube or a glass bulb on the surface of which a conductive polymer film having the performance is formed, and a transparent or transparent conductive polymer film having the performance formed on the surface. The present invention provides a lighting device for a tunnel having a translucent cover.

In addition to the above-mentioned polyaniline and polypyrrole, the conductive polymer includes polythiophene, polythiophene vinylene, polyisothianaphthene, polyacetylene, polyalkylpyrrole, polyalkylthiophene,
There are many polymers such as poly-p-phenylene, polyphenylene vinylene, polymethoxyphenylene, polyphenylene sulfide, polyphenylene oxide, polyanthracene, polynaphthalene, polypyrene, polyazulene and their derivatives.

In the present invention, as the conductive polymer used for forming the conductive polymer film, the above-mentioned various compounds can be used and are not particularly limited, but metal-insulator transfer occurs. A conjugated polymer, a conjugated polymer having a bond alternating disorder in the polymer chain, or a conjugated polymer having a one-dimensional chain and having a dopamine function, so-called electron donor and electron acceptor function can be preferably used. Examples thereof include polyaniline and polyphenylene, and particularly ionic polymer polyaniline is preferable.

The target structure for forming the conductive polymer film of the present invention includes structures made of various materials or structures having various shapes, which are required to have pollution prevention performance and pollution purification performance, and tunnel wall panels. , Ceiling plate, interior plate, airway material, air conditioning equipment and case, surveillance camera lens cover, toilet equipment, refrigerator case and interior material, lighting equipment storage case, air purification filter, semiconductor manufacturing line Examples include covers for precision equipment manufacturing lines, members for gas decomposition devices, and cases and interior members for copiers, printers and other various precision equipment.

In addition to these, window glass for buildings, automobiles, vehicle exterior materials for automobiles, tanks, various aquariums for ornamental use, pipes of metals, plastics, sanitary ware, glasses, lenses, lenses Various materials such as filters, hot water storage, bathtub equipment, washbasin equipment, sinks, door handles, water stopcocks, road mirrors, electromagnetic shielding materials, semiconductor materials such as substrates, internal parts of copying machines, etc. can be exemplified, but are not particularly limited. It will not be done. Further, particularly, an image display surface glass of a television, an image display surface glass of a liquid crystal display device, an image reading surface glass of a copying machine and the like can be exemplified.

As a particularly preferable object for forming a conductive polymer film, as described above, a luminaire which is installed in a tunnel under an environment where pollution by automobile exhaust gas is significant and which is constantly irradiated with visible light and its related members. Specifically, there are transparent or translucent covers for lighting equipment, fluorescent tubes for fluorescent lamps, and glass bulbs for various electric bulbs such as incandescent lamps.
Materials used for the above-mentioned various members include plate glass, ceramics, metal plates such as stainless steel and aluminum, plastic plates such as acrylic, polycarbonate and PET,
Examples include cotton cloth and fibers.

The present inventor has long been involved in the research and development of related technologies such as improvement of the fixing performance and photocatalytic performance of titanium peroxide, that is, titanium oxide having a peroxo group, utilization means, and proposed many achievements. ing. Therefore, also in the present invention, a combined use of a conductive polymer and titanium peroxide, or in addition to it was also tried in combination with a conductivity improving substance, other than in the case of using the conductive polymer alone ,
It has been found that it exhibits more excellent pollution prevention performance and pollution purification performance.

In the present invention, the conductive polymer film can be formed on the structure by applying a dispersion containing the conductive polymer onto the surface of the structure. However, in this case, it is difficult to say that the binding strength of the conductive polymer with the surface of the structure is sufficient, and therefore, it is preferable to use an auxiliary agent for improving the binding strength in combination. In addition, the above-mentioned titanium peroxide also has excellent performance as an auxiliary agent for improving the binding strength and can be preferably used.

As the auxiliary agent, various kinds other than titanium peroxide can be used without limitation, and include silica sol, indium-tin oxide (ITO) and an inorganic polymer containing the same. Examples of the resin include so-called acrylic silicone resin and fluororesin. In order to form a dispersion liquid containing the auxiliary agent and the conductive polymer film, it is preferable to disperse the conductive polymer powder in the auxiliary agent dispersion liquid. For example, it can be formed by dispersing a conductive polymer powder in a titanium peroxide dispersion.

In selecting the auxiliary component, it is preferable to determine it in consideration of the affinity with the above-mentioned various structural materials. Generally, for example, silica sol or titanium oxide 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 the titanium oxides, titanium peroxide is preferable since it can improve the prevention of pollution and the purification performance together with the function as an auxiliary agent for improving the bonding force with the surface of the structure, and particularly, it is used in combination with the conductivity improving substance. In that case, the conductivity can be further improved, which is preferable.

There are two types of titanium peroxide, an amorphous type and anatase type. The former amorphous type titanium peroxide has no photocatalytic ability and even if a film is formed on a polymer material plate It is suitable for forming a conductive polymer film that does not deteriorate or decompose. On the other hand, anatase-type titanium peroxide has a photocatalytic ability, and although it may cause deterioration etc. when a film is formed on a polymer material, it has an excellent affinity with a structure having a hydrophilic group. Therefore, it is preferable to use it when forming a conductive polymer film on the surface of a structure made of an inorganic material.

When this titanium peroxide is used in combination with a conductive polymer to form a conductive polymer film, it can improve the conductivity of the conductive polymer film, particularly the conductivity in the insulating state. . Furthermore, by adding a conductivity improving substance in addition to titanium peroxide to the conductive polymer film, the conductivity in the insulating state can be further improved. Further, the coating film containing titanium peroxide and the conductivity improving substance has conductivity, and by interposing this film as a conductive film between the conductive polymer and the structure body,
It is effective as a conductive film when a voltage is applied to a conductive polymer film, particularly a conductive polymer film containing only a conductive polymer.

As the conductivity improving substance, the conductivity can be improved as compared with a film formed by a dispersion liquid containing a conductive polymer and titanium peroxide or a film containing titanium peroxide alone. Any substance can be used without particular limitation, and various substances such as metal salts can be used. Examples of the metal salt include aluminum,
There are metal salts such as tin, chromium, nickel, antimony, iron, silver, cesium, indium, cerium, selenium, copper, manganese, calcium, platinum, tungsten, zirconium, and zinc. For metals and the like, hydroxides or oxides can be used.

The various substances such as the metal salts are shown by the concrete substance names: aluminum chloride, first and second chlorides.
Tin, chromium chloride, nickel chloride, first and second antimony chloride, ferrous and ferric chloride, silver nitrate, cesium chloride,
Indium trichloride, cerium chloride, selenium tetrachloride,
Cupric chloride, manganese chloride, calcium chloride, second chloride
Examples include various metal salts such as platinum, tungsten tetrachloride, tungsten oxydichloride, potassium tungstate, gold (II) chloride, zirconium oxychloride and zinc chloride. Examples of compounds other than metal salts include indium hydroxide, silicotungstic acid, silica sol, calcium hydroxide and the like.

The electroconductive polymer-containing dispersion used for forming the electroconductive polymer film on the surface of the structure in the present invention can be prepared by dispersing electroconductive polymer powder such as polyaniline in water. In that case, it is preferable to use a dispersant such as a surfactant or a disperser having an ultrasonic wave generating function. To prepare a dispersion containing a conductive polymer used to form a particularly preferable conductive polymer film and titanium peroxide, etc., Japanese Patent Application No. 2001-4458.
6 or Japanese Patent Application No. 2001-159265, it is preferable to add polyaniline powder or a dispersion liquid to a dispersion liquid containing titanium peroxide and mix them.

Further, the production of a dispersion liquid containing titanium peroxide is also made in Japanese Patent Application No. 2001-44586 or No. 2001-2001.
It may be performed as described in 159265. Specifically, it can be manufactured by carrying out as described in FIG. For example, in the case of an amorphous titanium peroxide dispersion, a diluted titanium tetrachloride solution is first prepared, and a diluted alkaline solution such as diluted ammonia water is added to the solution for neutralization to precipitate titanium hydroxide. This precipitate is washed with pure water to prepare a hydroxide-containing liquid. Then, it can be produced by adding hydrogen peroxide while stirring the containing liquid and stirring. Furthermore, the anatase-type titanium peroxide dispersion is obtained by heating the amorphous titanium-peroxide dispersion prepared above for a predetermined period of time so that the amorphous titanium peroxide is transformed into anatase-type.

Then, in order to form the conductive polymer film,
As described above, a dispersion of a conductive polymer on the structure surface, preferably a dispersion containing a conductive polymer and titanium peroxide, more preferably a conductive polymer, titanium peroxide and a conductivity improving substance. The contained dispersion liquid is applied to the surface of the structure, and various application means can be adopted without limitation, and examples thereof include spray method, roller method, dip method and the like. However, the spray method or the dip method is preferable in terms of economy. After forming the coating film in this way,
It is preferable to heat dry at about 250 ° C. As a result,
A conductive polymer film having the structure shown in (a) is formed.

Separately from this, a dispersion liquid of titanium peroxide and a conductivity improving substance is first applied to the surface of the structure to form a conductive film, and then a dispersion liquid of a conductive polymer is applied to increase the conductivity. A molecular film may be formed to have a laminated structure shown in FIGS. 3B and 3C, which is a preferred embodiment of the present invention. Further, the conductive polymer film can be formed on the structure in which the entire structure or only the surface thereof is conductive. The laminated structure as described above is preferably adopted when the surface of the structure does not have conductivity or when the purification performance is further improved. As the coating means at that time, the above various types can be used.

In the present specification, regarding the structure of the present invention, the entire structure (for example, a glass plate provided with the film) in a state where the conductive polymer film is formed, and the portion excluding the film (for example, the glass plate). In order to distinguish it from a glass plate without a film before forming the film or a glass plate as a base material excluding the film after forming the film), the latter is referred to as a structure body as necessary. Sometimes.

In the present invention, the electrode for applying a voltage to the conductive polymer film has only to be attached so that the voltage can be applied to the polymer film, and it is not necessary to directly connect to the conductive polymer film. . For the connection of the electrodes, various electrical connections can be used without particular limitation as long as a voltage can be applied to the conductive polymer film. For example, as a preferable embodiment, there are three types shown in FIGS. 3 (a) (b) (c). That is, those in which both electrodes for applying DC or AC voltage are directly connected to the conductive polymer film, those in which one electrode is connected to the conductive polymer film and the other electrode is connected to the conductive film, both electrodes Are connected to the conductive film.

There is no particular limitation on the structure for attaching the electrode to the structure or the like, and an example is shown in FIG. That is, as shown in the left side of FIG. 2, the electrodes to be connected to the lead wires are first temporarily joined to the surface of the flat plate which is the structure, a conductive polymer film is coated on it, and then dried, and then flat plate is formed with bolts and nuts. Secure it firmly. Further, as shown on the right side, the conductive polymer film may be first coated and dried, and then the electrode connected to the lead wire may be firmly fixed to the flat plate with bolts and nuts as described above. The voltage applied is preferably 1 to 100 V, and more preferably 5 to 50 V in the case of a DC voltage.

According to the present invention, as described above, the pollution prevention performance and the pollution purification performance are remarkably improved by irradiating the electromagnetic wave having a wavelength of visible light or shorter at the same time as the application of the direct current or the alternating current voltage. 300-900 nm
Electromagnetic waves in the range of are preferred. In the preferred case described above, it is not necessary that all of the electromagnetic waves fall within the above range, but the greater the amount of electromagnetic waves falling within this range, the better the pollution prevention performance and the like. Light sources that emit electromagnetic waves falling within this range include incandescent lamps, halogen lamps, fluorescent lamps, HID lamps, sodium lamps, LEs.
Various types of lighting such as D lamps or mercury lamps are applicable,
A fluorescent lamp or a mercury lamp is preferable in terms of economy.

The conductive polymer in the conductive polymer film is preferably in a semiconductive state or an insulating state,
For that purpose, there is an electromagnetic wave irradiation treatment of the absorption wavelength in the conductive state of the conductive polymer or an acid or alkali treatment of the conductive polymer. The electromagnetic wave irradiation treatment may be performed on either the dispersion liquid before film formation or the conductive polymer film after film formation, but is preferably performed on the dispersion liquid before film formation. As a light source used for the irradiation treatment, a low-pressure or high-pressure mercury lamp that emits long, medium, and short ultraviolet rays from visible light,
Alternatively, a germicidal ozone generating lamp or the like is preferable.

The above-mentioned acid or alkali treatment may be carried out on either the conductive polymer before film formation or the conductive polymer film after film formation as in the case of the electromagnetic wave irradiation treatment, but the structure body or It is preferable to perform it on the conductive polymer before film formation because it may deteriorate the peripheral materials. The acid and alkali used for the treatment are not particularly limited, but the acid is preferably hydrochloric acid, sulfuric acid, nitric acid, citric acid or the like, and the alkali is preferably ammonia water, caustic soda solution or the like.

[0045]

EXAMPLES Examples of the present invention and experimental examples using the same are shown below, but the present invention is not limited to these examples and experimental examples, and is specified by the provisions of the claims. Of course, it is one. Further, the dispersion liquid used for producing the plate-like body coated with the conductive polymer film corresponding to the example of the present invention and the plate-like body of the comparative example is as follows.

[Preparation of Dispersion Liquid] A. [Conductivity Improving Substance-Containing Titanium Peroxide Dispersion] The titanium peroxide content of this dispersion is 0.85 wt%, and its preparation is performed as follows. To 500 g of pure water, 2.5 g of silica gel (concentration 30 wt%) and 10 g of titanium tetrachloride solution (concentration 50 wt%, Sumitomo Sitix Co., Ltd.) were added, and then pure water was added to make 1000 g. 25 to this
% Ammonia water (manufactured by Takasugi Pharmaceutical Co., Ltd.) was diluted 10 times and added dropwise to adjust the pH to 6.9 to precipitate a complex of silica and titanium hydroxide.

The precipitate is washed with pure water until the conductivity in the supernatant reaches 0.8 mS / m,
When it was stopped when it reached 0.688 mS / m, 350 g of a solution containing a composite hydroxide of titanium oxide and silica with a concentration of 0.96% was prepared. Then, 25 g of 35 wt% hydrogen peroxide (manufactured by Taiki Yakuhin Kogyo Co., Ltd.) was added while cooling the contained liquid to 1 to 5 ° C., and the mixture was stirred for 16 hours to obtain silica-doped amorphous 1.5 wt% amorphous. 350 g of type titanium peroxide dispersion was obtained. A part of this dispersion was diluted to prepare 60 g of an amorphous titanium peroxide having a concentration of 0.85 wt%, and a silver nitrate solution was further added to the concentration of 0.05 to adjust the concentration to 0.055 mol.
g was added to prepare a dispersion liquid having a concentration of 0.85 wt% of amorphous titanium peroxide doped with silica and silver.

B. [Conductive Polymer Dispersion (Polymeline Water Dispersion Made by Olmecon, Germany (Brand Name: D1005W)] The polyaniline concentration of this dispersion is 3.0 wt%.

C. [Conductive Polymer + Titanium Peroxide-Containing Dispersion Liquid] The conductive polymer dispersion liquid of B above was added to the dispersion liquid of silica and silver-doped titanium peroxide concentration of 0.85 wt% prepared in A above. , A dispersion containing polyaniline and titanium peroxide doped with silica and silver was prepared. At this time, the ratio of the polymer dispersion liquid of B to the titanium peroxide dispersion liquid of A was 1:10. The resulting dispersion has a polyaniline concentration of 0.278 wt% and a titanium peroxide concentration of 0.771 wt%.

[Experimental Example 1] Transparent float glass plate (4 × 2
The dispersion liquid of B and C was used to form a film as shown in FIG. 3 (a) in a size of 10 × 300 mm, and various kinds of glass plates were produced. The concrete manufacturing method of each example glass plate is as follows. In Comparative Test Example 1, electrodes were attached to a glass plate without film formation before film formation, and only a DC voltage was applied.

Example 1 The transparent float glass plate was sprayed with the dispersion liquid of B in an amount of 1.0 g / 100 cm ² (wet), and then dried by heating at 100 ° C. for 15 minutes to a thickness of 0. A glass plate coated with a 95 μm polyaniline-containing polymer film was prepared. Electrodes for voltage application were attached to both ends of this glass plate as shown in FIG.

Example 2 The transparent float glass plate was sprayed with the dispersion liquid of C in an amount of 0.6 g / 100 cm ² (wet), and then dried by heating at 100 ° C. for 15 minutes to give a thickness of 0. A glass plate coated with a polymer film containing 6 μm of polyaniline and titanium oxide was prepared. A voltage application electrode was attached in the same manner as in Example 1.

(Example 1 ') 0.5 g / 100 cm ² (w) of hydrochloric acid (concentration: 1.0 wt%) was added to the polymer film of the glass plate coated with the polyaniline-containing polymer film prepared in Example 1 above.
et) was sprayed and dried to prepare a glass plate coated with an acid-treated polymer film. Then, a voltage application electrode was attached in the same manner as in Example 1.

(Example 2 ') The polymer film of the glass plate coated with the polymer film prepared in Example 2 was sprayed with hydrochloric acid and dried in the same manner as in Example 1', and the polymer film was treated with acid. A glass plate coated with was prepared. Then, a voltage application electrode was attached in the same manner as in Example 1.

Experimental Example 2 Transparent float glass plate (4 × 2
10 × 300 mm), a film is formed by using the dispersion liquid of A first, and then a film is formed by using the dispersion liquid of B or C, and a laminated structure including an electrode illustrated in FIG. Various types of glass plates having various shapes were manufactured. The concrete manufacturing method of each example glass plate is as follows.

Example 3 The transparent float glass plate was sprayed with the dispersion A of 0.3 g / 100 cm ² (wet) and then dried by heating at 100 ° C. for 15 minutes to a thickness of 0. A 3 μm coating was formed. Next, the dispersion liquid of B was sprayed on the second layer in an amount of 0.72 g / 100 cm ² (wet) and then dried by heating at 100 ° C. for 15 minutes to obtain a polyaniline-containing polymer film having a thickness of 0.4 μm. A laminated coated glass plate having a total thickness of 0.7 μm was produced. 4 and 3 are provided on both ends of this glass plate.
Electrodes for voltage application were attached as shown in FIG.

(Example 4) The transparent float glass plate was sprayed with the dispersion liquid of A in an amount of 0.3 g / 100 cm ² (wet), and then dried by heating at 100 ° C for 15 minutes to a thickness of 0. A 3 μm coating was formed. Next, the dispersion liquid of C was sprayed on the second layer in an amount of 0.72 g / 100 cm ² (wet) and then dried by heating at 100 ° C. for 15 minutes to obtain polyaniline and titanium oxide having a thickness of 0.4 μm. A glass plate having a laminated coating structure with a total thickness of 0.7 μm coated with the contained polymer film was prepared. Electrodes for voltage application were attached to both ends of this glass plate as shown in FIGS. 4 and 3C.

(Example 3 ') 0.5 g of hydrochloric acid (concentration: 0.5 wt%) was added to a polymer film of a glass plate having a laminated coating structure coated with the polyaniline-containing polymer film prepared in Example 3 above.
An amount of 100 cm ² (wet) was sprayed and dried to prepare an acid-treated glass plate having a laminated coating structure. Then, a voltage application electrode was attached in the same manner as in Example 3.

(Example 4 ') The same procedure as in Example 3'was applied to the polymer film of the glass plate having a laminated coating structure coated with the polymer film containing polyaniline and titanium oxide prepared in the above Example 4. Was sprayed and dried to prepare a glass plate having an acid-treated laminated coating structure. Then, a voltage application electrode was attached in the same manner as in Example 3.

(Example 3 ") 0.5 g / sulfuric acid (concentration: 0.5 wt%) was added to a polymer film of a glass plate having a laminated coating structure coated with the polyaniline-containing polymer film prepared in Example 3 above.
An amount of 100 cm ² (wet) was sprayed and dried to prepare an acid-treated glass plate having a laminated coating structure. Then, a voltage application electrode was attached in the same manner as in Example 3.

Example 4 "The same procedure as in Example 3" was applied to the polymer film of the glass plate having a laminated coating structure coated with the polymer film containing polyaniline and titanium oxide prepared in Example 4 in the same manner as in Example 3 ". Was sprayed and dried to prepare a glass plate having an acid-treated laminated coating structure. Then, a voltage application electrode was attached in the same manner as in Example 3.

(Comparative Test Example 2.3) In Comparative Test Example 2, a glass plate having a voltage application electrode attached thereto was used. In the organic dye fading experiment, a diluted red ink described below was applied to the glass plate, DC 12V was applied, and at the same time, a fluorescent lamp was irradiated. In Comparative Example Test 3, the glass plate having the laminated coating structure produced in Examples 3 and 4 was used. In the organic dye fading experiment, DC12V was applied without applying the diluted red ink, and at the same time, the fluorescent lamp was irradiated.

[Organic Dye Discoloration Experiment] An organic dye discoloration test was conducted to evaluate the pollution purification performance. The outline of the test is as follows. That is, a mercury lamp (100W) or a fluorescent lamp (32W) is installed under the glass plate coated with the polymer film as shown in FIG. Applying a predetermined voltage of direct current or alternating current to the applying electrode, then applying the organic dye solution,
A colorimeter (Minolta CR-2
00).

[Applied Voltage and Current, and Illumination Lamp Used] In Experimental Example 1, a direct current of 10 V was applied, and in Experimental Example 2, a direct current of 12 V or an alternating current of 12 V was applied to the titanium oxide film to form a conductive polymer film. Voltage was applied. In addition, the illumination lamp that irradiates the glass plate is the mercury lamp (100 W) and the fluorescent lamp (32
W), in Experiment 2, a fluorescent lamp (32 W) was used. KENWOOD PA18-1.2A / LA is used to control the DC voltage, and "Slider (SD)" is used to control the AC voltage (YAMABISHI TYPE N-130
-10) was used. A digital multimeter (YOKOGAWA MODEL 7552) was used as the current measuring device.

[Color Measurement Procedure] As the organic dye solution used for measuring the color change, a solution prepared by diluting the red ink manufactured by Pilot Co. 20 times is used. The application of the diluted solution to the glass plate or the conductive polymer film is performed after the lighting lamp is turned on and the voltage application to the conductive polymer film is started, and after they are normally operated. The color change is measured with a colorimeter immediately after application,
The measurement is performed 1 hour and 48 hours later, and during the measurement, the operation of the illumination lamp and the voltage application are stopped, and then the measurement is performed.

Since the measurement of the color change is performed as described above, the measurement immediately after the application is actually about one minute after the application of the organic dye solution after the illumination lamp and the voltage application are normally operated. After. Further, by installing an illuminating lamp below the glass plate coated with the conductive polymer film, irradiating the conductive polymer film with light transmitted through the glass substrate, and measuring the fading performance of the organic dye, The same manner as when the film is formed on the cover of the lighting fixture, the result can evaluate the pollution purification performance of oil (organic matter) in the exhaust gas in the tunnel of the lighting fixture.

[Evaluation of Color Change] The measurement value of the colorimeter is
It is represented by L ^* , a ^* , b ^* and ΔE ^* , and represents the following, respectively. L ^* : Indicates lightness. A large number indicates a bright a ^* : a change in color between red and green. When the value is on the + side, it indicates red. When the value is large, the red color is deep. When the value is on the negative side, it is green, and when it is large, the green is dark.
A numerical value of 0 indicates that the color is achromatic. b ^* : represents the color change between yellow and blue. When the value is on the + side, it indicates yellow. When the value is large, it indicates that the yellow color is deep. A numerical value on the negative side indicates blue, and a large value indicates deep blue. ΔE ^* : represents a color difference (amount of change in color over time). This value is large when the amount of color change over time is large. Note that ΔE ^* is calculated by the following calculation formula. ΔE ^* ab = [(ΔL ^* ) ² + (Δa ^* ) ² + (Δb ^* ) ² ] ^1/2

[Measurement Result of Experimental Example 1] The measurement result of Experimental Example 1 is as shown in Table 1. According to Table 1, in the case where only the DC voltage is applied (“DC10V only”), L ^* and Δ are obtained when any of the glass plates of Examples 1, 2, 1 ′ and 2 ′ is used. The value of E ^* gradually increases,
You can see that it is getting brighter. Moreover, the value of a ^* is gradually decreased when any of the glass plates is used, and it can be seen from these that the red color is gradually faded. It should be noted that this becomes clearer in comparison with the case of Comparative Test Example 1 in which only a DC voltage was applied without forming a film on the glass plate.

[0069]

[Table 1]

Compared to the case where only the DC voltage is applied, when the application of the DC voltage and the irradiation of the mercury lamp or the fluorescent lamp are used in combination, the L ^* value of It can be seen that the increase and the decrease in the a ^* value are rapid, and the red color has rapidly faded. Further, comparing the case where the mercury lamp is used together with the case where the fluorescent lamp is used together, in the case where the mercury lamp is used together, the a ^* value immediately after the ink application is greatly reduced, and it may be extremely reduced depending on the glass plate used. There is a large ΔE ^* value after 1 hour and after 48 hours in most of the glass plates, indicating that the red fading effect is excellent.

Further, application of a DC voltage and irradiation with a mercury lamp were carried out.
In some cases, depending on whether or not the glass plate is treated with hydrochloric acid.
For the effects, use the glass plates of Examples 2 and 2 '.
1 when treated with hydrochloric acid except after 48 hours
△ E after 48 hours and after 48 hours ^*The value of
It can be seen that the red fading effect is great.

In addition, when using the glass plates of Examples 1 and 1'and applying 10 V DC and irradiating a mercury lamp at the same time, the value of a ^* after 48 hours becomes a relatively large negative value. However, this means that the original red color disappeared and polyaniline was present in the conductive polymer film, and therefore the color of the film itself became green. In contrast, when the glass plates of Examples 2 and 2 ′ were used and tested under the same conditions as above, the red color disappeared and the a ^* value was a small negative value, but it was It is considered that the color of the existing polyaniline and the color of titanium peroxide offset each other, and the color becomes almost colorless and transparent.

[Measurement Result of Experimental Example 2] The measurement result of Experimental Example 2 is as shown in Table 2. Each of the glass plates used for the measurement had a structure in which a conductive film containing titanium oxide and a conductivity improving substance and a polymer film containing polyaniline were laminated in this order on the glass plate. However, both direct current and alternating current were used as the voltage, but both were energized to the conductive film and the voltage was applied to the conductive polymer film. Fluorescent lamps were used for lighting in all cases.

[0074]

[Table 2]

From the experimental results, it can be seen that the organic dye has excellent fading performance regardless of whether a voltage of alternating voltage is applied. Further, it can be seen that the tendency is similar to that in the case of irradiation with the fluorescent lamp of Experimental Example 1. Example 4
When the glass plate of No. 3 was used, the value of a ^* was almost the same as that of Comparative Test Example 3 immediately after the diluted red ink was applied, and almost all the organic dye was decomposed immediately after the application. It indicates that Further, when the substrate of Example 3 is used, the organic dye decomposing performance is better when AC is applied than DC when the a ^* value is compared. The ΔE ^* value is smaller when AC is applied, as in the case described later.

Numerical value of a ^* was obtained when the glass plates of Examples 3 and 4 which were not acid-treated and when the glass plates of Examples 3 ', 3 ", 4'and 4" which were acid-treated were used. Looking at
It can be seen that the red ink is more excellent in the fading ability than the case where the acid treatment is not performed. On the other hand, looking at the value of ΔE ^*, the value of the glass plate not treated with acid increased with the passage of time, and the value was large compared with the case of the glass plate treated with acid. Seems to be questionable.

However, in the case of the acid-treated glass plate, there is almost no difference and the a ^* value sharply decreases. From these facts, the red organic dye is almost decomposed at the same time as the fluorescent lamp irradiation. It is thought to be because it ends up. From the above, it can be said that the glass plate of the example subjected to the acid treatment is more excellent in the fading ability of the red ink than the glass plate of the example not subjected to the acid treatment.

[0078]

INDUSTRIAL APPLICABILITY According to the present invention, conductive polymers such as polyaniline and polypyrrole are used to form conductive polymers for lighting equipment covers, tunnel wall panels, cases and interior members of various precision instruments such as copying machines. By a simple means of forming a film and applying a DC or AC voltage to the polymer film,
It is possible to prevent contamination on the surfaces of various precision equipment cases and interior members, etc., and generate hydrocarbons or carbon monoxide, which are unburned or incompletely burned components, contained in various exhaust gases such as automobile exhaust gases. It is possible to purify by decomposing or oxidizing SO _x or NO _x , which is a harmful component, or various harmful organic compounds or inorganic gases.

Simultaneously with the application of DC or AC voltage, visible light or an electromagnetic wave having a wavelength shorter than that, preferably 300
Irradiation with electromagnetic waves in the range of up to 900 nm improves the pollution prevention performance and pollution purification performance. Further, the conductive polymer in the conductive polymer film is preferably in a semi-conductive state or an insulating state, and therefore, the conductive polymer in the conductive polymer film or the conductive polymer dispersion is electrically conductive. The contamination purification performance and the like are further improved by the electromagnetic wave irradiation treatment of the absorption wavelength in the state or the acid or alkali treatment.

As described above, in particular, when the conductive polymer film to which an AC or DC voltage is applied is used for a cover of a lighting fixture installed in a tunnel, a fluorescent tube of a fluorescent lamp, a glass bulb of a light bulb, etc. In addition, the conductive polymer film is inevitably always irradiated with electromagnetic waves having a wavelength of visible light or shorter by the illumination lamp installed in the tunnel. Contamination is prevented, and as a result, reduction of illumination light due to the contamination can be prevented.

At the same time, it is also possible to decompose or oxidize the unburned harmful components in the automobile exhaust gas discharged into the tunnel or the harmful components generated by the combustion of NO _x, etc. to convert them into detoxified substances. Furthermore, when this conductive polymer film is installed on the entire surface of the tunnel wall and the amount of illumination is increased, the inside of the tunnel becomes brighter, which is not only useful for safe driving, but also the air inside the tunnel. It is also very effective for purification. As described above, the present invention has excellent operational effects.

[Brief description of drawings]

FIG. 1 illustrates an outline of a manufacturing process of a titanium peroxide dispersion liquid used in the present invention.

FIG. 2 illustrates an example of a mounting (fixing) structure of a voltage applying electrode to a structure.

FIG. 3 is a sectional view showing a state in which a conductive polymer film is formed on the surface of a plate-shaped structure. (a) shows the film and electrode arrangement structure when a conductive polymer film is directly formed on the surface of the structure.
(b) and (c) show a laminated structure and an electrode arrangement structure when a conductive polymer film is formed on the surface of the structure through a conductive film containing a titanium oxide and a conductivity improving substance.

FIG. 4 illustrates a voltage application electrode arrangement structure in a plate-like structure such as a glass plate having a conductive polymer film used in Examples.

FIG. 5 illustrates an arrangement structure of an illuminating lamp with respect to a glass plate having a conductive polymer film used in an experimental example.

Front page continuation (51) Int.Cl. ⁷ Identification code FI theme code (reference) C08K 3/22 C08K 3/22 C08L 101/00 ZAB C08L 101/00 ZAB C09K 3/00 112 C09K 3/00 112Z (72 ) Inventor Shiro Ogata 5-8-6 Yoyogi, Shibuya-ku, Tokyo Inside Olive Building 1st floor, Sustainable Technology Co., Ltd. Incorporated Saga Research Institute (72) Inventor Yoshifumi Kono 110 Ayuhara Nishi, Goshiki-cho, Tsuna-gun, Hyogo Prefecture Misaki Denki Co., Ltd. G-color factory F-term (reference) 4D019 AA01 BA13 BB08 BC07 4F073 AA23 BA20 BA32 BA34 BB11 CA41 CA45 CA53 4G069 AA03 AA08 BA04A BA04B BA22A BA22B BA48A CA01 CA02 CA03 CD10 DA06 EA08 FA03 FB24 4J002 AA001 CM051 DE136 FD207 GL00 GQ00

Claims (12)

[Claims] 1. A method for preventing or purifying contamination on the surface of a conductive polymer film by applying a voltage thereto. 2. The method for preventing or purifying pollution according to claim 1, wherein the electroconductive polymer film is irradiated with an electromagnetic wave having a wavelength of visible light or shorter. 3. The method for preventing or purifying pollution according to claim 1, wherein the conductive polymer film contains titanium oxide, or titanium oxide and a conductivity improving substance. 4. A structure having a conductive polymer film on a structure body and having an electrode for applying a voltage to the polymer film, which has a property of preventing or purifying contamination. 5. A conductive polymer film formed on the surface of a structure body having a conductive surface, or a conductive film containing titanium oxide and a conductivity improving substance on the surface of the structure body. The structure having the ability to prevent or purify pollution according to claim 4. 6. The structure having the ability to prevent or purify pollution according to claim 4 or 5, wherein the conductive polymer film contains titanium oxide, or titanium oxide and a conductivity improving substance. 7. The structure having the ability to prevent or purify pollution according to claim 4, 5 or 6, wherein the conductive polymer film is irradiated with an electromagnetic wave having a wavelength of visible light or shorter. 8. The structure having the ability to prevent or purify pollution according to claim 4, wherein the conductive polymer film is in a semi-conductive state or an insulating state. 9. The contamination prevention according to any one of claims 4 to 8, wherein the conductive polymer film is treated by irradiation with an absorption wavelength in a conductive state or treated with an acidic or alkaline solvent. A structure that has the ability to purify. 10. The conductive polymer in the polymer dispersion for forming a conductive polymer film, which has been treated by irradiation with an absorption wavelength or treated with an acidic or alkaline solvent. A structure having the ability to prevent or purify the pollution according to item 1. 11. A tunnel wall panel, a ceiling plate,
Ultra-precision equipment manufacturing line such as interior board, air duct material, air conditioning equipment and case, surveillance camera lens cover, toilet equipment, refrigerator case and interior material, lighting equipment storage case, air purification filter, semiconductor production line Cover for
A structure having the ability to prevent or purify pollution according to any one of claims 4 to 10, which is any one of a member for a gas decomposing device, a case and an interior member of a copying machine, a printer and other various precision equipment. body. 12. A transparent or semi-transparent cover for a tunnel lighting fixture, or a fluorescent tube or a glass bulb for a tunnel lighting lamp.
A structure having the ability to prevent or purify the pollution described in the item.