JP4763316B2 - Equipment - Google Patents

Description

  The present invention relates to an application of a functional material containing titanium oxide or a titanium alloy oxide and functioning as a visible light responsive photocatalyst. In particular, the present invention relates to horticultural or agricultural equipment to which such functional materials are applied, equipment for fishing, equipment for dredging, equipment for paving, equipment for construction work, equipment for construction work, The present invention relates to equipment including painting equipment, facility equipment, and electrical equipment.

Conventionally, titanium dioxide TiO ₂ (simply referred to as titanium oxide in the present specification and claims) is known as a substance exhibiting a photocatalytic function. As a method of forming a titanium oxide film on titanium metal, since the 1970s, a method of forming a titanium oxide film on titanium metal by anodic oxidation, thermal titanium oxide on a titanium metal plate in an electric furnace supplied with oxygen A method of forming a film, a method of heating a titanium plate in a flame of city gas at 1100 ° C. to 1400 ° C. to form a titanium oxide film on titanium metal, and the like are known (see Non-Patent Document 1). In addition, many studies for practical application of photocatalysts have been carried out in many technical fields.

  When producing photocatalyst products that can provide deodorant, antibacterial, anti-fogging and antifouling effects by such photocatalytic function, titanium oxide sol is generally applied to the substrate by spray coating, spin coating, dipping, etc. (For example, refer to Patent Documents 1 to 3). However, since the film formed as such is easily peeled off or worn, it has been difficult to use for a long time. Moreover, the method of forming a photocatalyst film by sputtering method is also known (for example, refer patent documents 4-5).

  Further, in order to make titanium oxide function as a photocatalyst, ultraviolet rays having a wavelength of 400 nm or less are necessary. However, many studies of titanium oxide photocatalysts that function by visible light by doping various elements have been conducted. For example, comparing titanium oxides doped with F, N, C, S, P, Ni, etc., there is a report that nitrogen-doped titanium oxide is superior as a visible light responsive photocatalyst (see Non-Patent Document 2). .

In addition, titanium oxide photocatalysts doped with other elements in this way include titanium compounds in which the oxygen sites of titanium oxide are replaced with atoms such as nitrogen, and atoms such as nitrogen are doped between the lattices of titanium oxide crystals. There has been proposed a photocatalyst comprising a titanium compound or a titanium compound in which atoms such as nitrogen are arranged at grain boundaries of a polycrystalline aggregate of titanium oxide crystals (see, for example, Patent Documents 6 to 9). However, such a photocatalyst is not always satisfactory in terms of durability such as wear resistance. Further, for example, n-TiO ₂ -xCx, which is a chemically modified titanium oxide, is obtained by applying a natural gas combustion flame in which the temperature of the combustion flame is maintained at around 850 ° C. by adjusting the flow rates of natural gas and oxygen to titanium metal. There is a report that this absorbs light of 535 nm or less (see Non-Patent Document 3).

Furthermore, crystal nuclei prepared by various production methods such as CVD or PVD are put into a sol solution composed of an inorganic metal compound or an organometallic compound, or a sol solution is applied to the crystal nuclei, solidified, and heat-treated. A patent application has been filed that a highly active photocatalytic function can be obtained by growing a titanium oxide crystal from the crystal nucleus and forming a columnar crystal from the crystal shape of the titanium oxide crystal grown from the crystal nucleus (for example, And Patent Documents 10 to 12). However, in that case, since the columnar crystal is merely grown from the seed crystal placed on the substrate, the formed columnar crystal has insufficient adhesion strength to the substrate, and thus was produced as such. The photocatalyst is not always satisfactory in terms of durability such as wear resistance.
JP 09-2441038 A Japanese Patent Application Laid-Open No. 09-262481 Japanese Patent Laid-Open No. 10-053437 JP-A-11-012720 JP 2001-205105 A JP 2001-205103 A (Claims) JP 2001-205094 A (Claims) JP 2002-95976 A (Claims) WO 01/10553 pamphlet (claims) JP 2002-253975 A JP 2002-370027 A JP 2002-370034 A A. Fujishima, et al., Journal of The Electrochemical Society, November 1975, Vol. 122, No. 11, p. 1487-1489 R. Asahi, et al., "Visible-Light Photocatalysis in Nitrogen-Doped Titanium Oxides", Science, AAAS, July 13, 2001, No. 293, p. 269-271 Shahhead, Khan, et al., “Efficient Photochemical Water Splitting by Chemically Modified n-TiO2”, SCIENCE, September 27, 2002 Day, 297, p. 2243-2245

By the way, in fields such as horticulture or agriculture, fishing, dredging, pavement, construction, construction, painting, electrical construction, etc., because dirt easily adheres to machines, instruments, members, etc. used for work, There are problems that work efficiency is lowered and that the service life of machines and instruments is shortened. When dirt adheres to members installed outdoors, it looks not only that a poor function decreases. Furthermore, there is a problem that water around toilets and the like used in public facilities and nursing care facilities tends to be unsanitary.

  There is a possibility that the above problem can be improved by applying the titanium oxide photocatalyst to such a field. However, conventional titanium oxide-based photocatalysts have problems in durability (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance), both of which are UV responsive and visible light responsive. It became a bottleneck in terms of practical use.

  In view of the above points, the present invention is applied to a multifunctional material that is excellent in durability including high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance, etc., and functions as a visible light responsive photocatalyst. The purpose is to provide equipment.

To solve the above problems, materials and equipment according to one aspect of the present invention is a surface layer formed with the core material being formed by a titanium or titanium alloy, the surface of the core, the surface of the core Is heated for a heating time of 400 seconds or less under the condition that the surface temperature of the core material is 900 ° C. to 1500 ° C. using a gas combustion flame containing hydrocarbon as a main component, or a hydrocarbon as a main component In the combustion gas atmosphere of the gas, the carbon is doped in a Ti-C bond state by performing a heat treatment for 400 seconds or less under the condition that the surface temperature of the core material is 900 ° C. to 1500 ° C. comprising a surface layer which is a titanium oxide or titanium alloy oxide.

  In the present application, the equipment includes materials and equipment, and the equipment includes instruments and materials thereof. Specifically, the equipment in this application includes horticultural or agricultural equipment, fishing equipment, dredging equipment, paving equipment, construction equipment, construction equipment, painting equipment, Includes facility equipment or electrical equipment.

  According to one aspect of the present invention, a film containing titanium oxide or titanium alloy oxide doped with carbon by Ti—C bonds is formed on the surface of the equipment, so that the visible light response of such a film is provided. With the mold photocatalytic function, an antifouling effect, a deodorizing effect, etc. can be obtained in the equipment. In addition, the coating containing titanium oxide or titanium alloy oxide doped with carbon by Ti-C bond is excellent in durability including high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance, etc. Therefore, it is possible to obtain a material having high durability and having an antifouling effect and the like continuing for a long time.

Hereinafter, the best mode for carrying out the present invention will be described in detail with reference to the drawings. The same constituent elements are denoted by the same reference numerals, and the description thereof is omitted.
First, two types of multifunctional materials applied to the equipment according to the first to fifth embodiments of the present invention will be described.

  The first multifunctional material is a material in which at least a surface layer is formed of a carbon-doped titanium oxide layer, and the carbon is doped in a Ti—C bond state. Such a multifunctional material is excellent in durability and functions as a visible light responsive photocatalyst. Hereinafter, a carbon-doped titanium oxide layer doped with carbon in a Ti—C bond state is also referred to as “a carbon-doped titanium oxide layer having a Ti—C bond”.

  The first multifunctional material heats at least the surface of a substrate whose surface layer is made of titanium, a titanium alloy, a titanium alloy oxide, or titanium oxide at a high temperature using, for example, a gas combustion flame mainly composed of hydrocarbons. Manufactured by processing. The substrate whose at least surface layer is made of titanium, titanium alloy, titanium alloy oxide or titanium oxide may be composed of titanium, titanium alloy, titanium alloy oxide or titanium oxide as a whole. The core material and a surface portion forming layer formed of a material different from the core material may be used. In addition, regarding the shape of the substrate, the final product shape (flat or three-dimensional) where durability such as high hardness, scratch resistance, abrasion resistance, chemical resistance, and heat resistance is desired, or visible light on the surface It may be a final product shape that is desired to have a responsive photocatalytic function, or may be a powder.

  The thickness of the surface portion forming layer when at least the substrate made of titanium, titanium alloy, titanium alloy oxide or titanium oxide is constituted by the core material and the surface portion forming layer of a material different from the core material. The thickness may be the same as the thickness of the carbon-doped titanium oxide layer to be formed (that is, the entire surface portion forming layer becomes a carbon-doped titanium oxide layer) or may be thicker than the carbon-doped titanium oxide layer ( That is, a part of the surface portion forming layer in the thickness direction becomes a carbon-doped titanium oxide layer, and a part remains as it is). The material of the core material is not particularly limited as long as it does not burn, melt, or deform during the heat treatment in the production process of the multifunctional material. In addition, if the heat treatment is performed while cooling the region other than the surface portion formation layer in the core material, or if the heat treatment is performed only on the surface portion formation layer for a short time, the melting point is higher than the heat treatment temperature described later. Alternatively, a material having a low glass transition point can be used as the core material. For example, iron, iron alloy, non-ferrous alloy, ceramics, other ceramics, high temperature heat resistant glass, etc. can be used as the core material. For example, a film made of titanium, titanium alloy, titanium alloy oxide, or titanium oxide is formed on the surface of such a core material using a method such as sputtering, vapor deposition, or thermal spraying, or a commercially available titanium oxide sol is spray-coated, spin A substrate can be produced by coating or dipping to form a film.

  The first multifunctional material is composed of a layer made of carbon-doped titanium oxide or titanium alloy oxide, an intermediate layer, and a core material, and the intermediate layer is made of titanium, titanium alloy, titanium alloy oxide or It is titanium oxide, and the core material may be made of a material other than titanium, a titanium alloy, and titanium oxide.

  If the substrate is at least a surface layer made of titanium, a titanium alloy, a titanium alloy oxide or titanium oxide, and the particle size of the powder is small, the entire particle is carbonized by the heat treatment described above. It can be doped titanium oxide. In the first multifunctional material, it is sufficient that at least the surface layer is made of carbon-doped titanium oxide, so the particle size of the powder is not limited at all. However, considering the ease of heat treatment and the ease of production, it is preferably 15 nm or more.

  Various known titanium alloys can be used as the titanium alloy, and are not particularly limited. For example, Ti-6Al-4V, Ti-6Al-6V-2Sn, Ti-6Al-2Sn-4Zr-6Mo, Ti-10V-2Fe-3Al, Ti-7Al-4Mo, Ti-5Al-2.5Sn, Ti- 6Al-5Zr-0.5Mo-0.2Si, Ti-5.5Al-3.5Sn-3Zr-0.3Mo-1Nb-0.3Si, Ti-8Al-1Mo-1V, Ti-6Al-2Sn-4Zr- 2Mo, Ti-5Al-2Sn-2Zr-4Mo-4Cr, Ti-11.5Mo-6Zr-4.5Sn, Ti-15V-3Cr-3Al-3Sn, Ti-15Mo-5Zr-3Al, Ti-15Mo-5Zr, Ti-13V-11Cr-3Al or the like can be used.

  In the production of the first multifunctional material, a gas combustion flame mainly composed of hydrocarbons, particularly acetylene can be used, and it is particularly desirable to use a reducing flame. In the case of using a fuel with a low hydrocarbon content, the carbon doping amount is insufficient or not at all, and as a result, the hardness becomes insufficient and the photocatalytic activity under visible light also occurs. This is because it becomes insufficient. In the production of the first multifunctional material, the gas containing hydrocarbon as a main component means a gas containing at least 50% by volume of hydrocarbon. For example, a gas containing at least 50% by volume of acetylene and appropriately mixed with air, hydrogen, oxygen, or the like is applicable. In the production of the first multifunctional material, the gas containing hydrocarbon as a main component preferably contains 50% by volume or more of acetylene, and the hydrocarbon is most preferably 100% acetylene. When an unsaturated hydrocarbon, particularly acetylene having a triple bond, is used, an unsaturated radical portion is decomposed during the combustion process, particularly in the reducing flame portion, and an intermediate radical substance is formed. Since this radical substance is highly active, it is considered that carbon doping is likely to occur.

  In the production of the first multifunctional material, when the surface layer of the substrate to be heat-treated is titanium or a titanium alloy, oxygen that oxidizes the titanium or titanium alloy is necessary. The gas to be produced needs to contain air or oxygen accordingly.

  The first multifunctional material is obtained by heat-treating a surface of a substrate whose surface layer is made of titanium, a titanium alloy, a titanium alloy oxide, or titanium oxide at a high temperature using a combustion flame of a gas containing hydrocarbon as a main component. Manufactured by. In that case, a combustion flame of a gas containing hydrocarbon as a main component may be directly applied to the surface of the substrate and heat-treated at a high temperature, or the substrate may be heated in a combustion gas atmosphere of a gas containing hydrocarbon as a main component. The surface may be heat-treated at a high temperature. Such heat treatment can be performed, for example, in a furnace. When the combustion flame is directly applied to the substrate and heat treatment is performed at a high temperature, the fuel gas is burned in the furnace, and the combustion flame is applied to the surface of the substrate. When the substrate is heated at a high temperature in the combustion gas atmosphere, the fuel gas is burned in the furnace and the high-temperature combustion gas atmosphere is used. In addition, in the case where the substrate made of at least a surface layer of titanium, titanium alloy, titanium alloy oxide or titanium oxide is in powder form, such a powdery substrate is introduced into the flame and stays in the flame for a predetermined time. The powder is made into carbon-doped titanium oxide having Ti—C bonds as a whole by maintaining the powdered substrate in a fluidized high-temperature combustion gas in a fluidized bed state for a predetermined time. And a powdery multifunctional material in which a carbon-doped titanium oxide layer having a Ti—C bond is formed can be produced.

  Regarding the heat treatment, the surface temperature of the substrate is 900 ° C. to 1500 ° C., preferably 1000 ° C. to 1200 ° C., and a carbon-doped titanium oxide layer doped with carbon in a Ti—C bond state is formed as the surface layer of the substrate. It is necessary to do so. When the surface temperature of the substrate remains below 900 ° C. in the heat treatment, the durability of the substrate having the carbon-doped titanium oxide layer obtained is insufficient, and the photocatalytic activity under visible light is also insufficient. On the other hand, when the surface temperature of the substrate exceeds 1500 ° C. in the heat treatment, the ultrathin film is peeled off from the surface of the substrate during cooling after the heat treatment, so that the first multifunctional material to be manufactured is durable. Effects (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance) cannot be obtained. Even if the surface temperature of the substrate in the heat treatment is in the range of 900 ° C. to 1500 ° C., if the heat treatment time becomes long, the ultrathin film peels off from the surface of the substrate during cooling after the heat treatment. Therefore, the durability (high hardness, scratch resistance, wear resistance, chemical resistance, heat resistance) cannot be obtained in the first multifunctional material to be manufactured. Therefore, it is necessary to set the heat treatment time to a time that does not cause peeling on the surface of the substrate during subsequent cooling. That is, the heat treatment time is sufficient to make the surface layer a carbon-doped titanium oxide layer in which carbon is doped in a Ti-C bond state, but from the surface portion of the substrate during cooling after heating. It is necessary that the time does not cause the peeling of the ultrathin film. Although this heat treatment time depends on the relationship with the heating temperature, it is preferably about 400 seconds or less.

  In the production of the first multifunctional material, a carbon dope having a Ti—C bond containing 0.3 at% to 15 at%, preferably 1 at% to 10 at% of carbon by adjusting the heating temperature and the heat treatment time. A titanium oxide layer can be obtained relatively easily. When the carbon doping amount is small, the carbon-doped titanium oxide layer is transparent, and as the carbon doping amount increases, the carbon-doped titanium oxide layer becomes translucent or opaque. Therefore, by forming a transparent carbon-doped titanium oxide layer on a transparent plate-shaped core material, it has excellent durability (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance) and visible light A transparent plate that functions as a responsive photocatalyst can be obtained. In addition, by forming a transparent carbon-doped titanium oxide layer on a plate with a colored pattern on its surface, it has excellent durability (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance) and is visible A decorative board that functions as a photoresponsive photocatalyst can be obtained. In the case where the substrate having at least the surface layer made of titanium, titanium alloy, titanium alloy oxide or titanium oxide is composed of the surface portion forming layer and the core material, and the thickness of the surface portion forming layer is 500 nm or less. When heated to the vicinity of the melting point of the surface portion forming layer, many small island-like undulations floating in the sea are generated on the surface and become translucent.

  In the first multifunctional material, that is, the multifunctional material having a carbon-doped titanium oxide layer doped with carbon in a Ti—C bond state, the thickness of the carbon-doped titanium oxide layer is preferably 10 nm or more. In order to achieve high hardness, scratch resistance, and wear resistance, the thickness is more preferably 50 nm or more. When the thickness of the carbon-doped titanium oxide layer is less than 10 nm, the durability of the multifunctional material having the carbon-doped titanium oxide layer tends to be insufficient. The upper limit of the thickness of the carbon-doped titanium oxide layer is not particularly limited, although it is necessary to consider the cost and the effect achieved.

  As described in Non-Patent Document 3, the carbon-doped titanium oxide layer of the first multifunctional material is formed by chemically modifying titanium oxide or titanium doped with various conventionally proposed atoms or anions X. Unlike titanium oxide containing the compound Ti—O—X, it contains a relatively large amount of carbon and contains doped carbon in the form of Ti—C bonds. As a result, it is considered that mechanical strength such as scratch resistance and abrasion resistance is improved, and the Vickers hardness is remarkably increased. Moreover, heat resistance is also improved.

  The carbon-doped titanium oxide layer of the first multifunctional material has a Vickers hardness of 300 Hv or higher, preferably 500 Hv or higher, more preferably 700 Hv or higher, and most preferably 1000 Hv or higher. The Vickers hardness of 1000 Hv or higher is harder than that of hard chrome plating. Therefore, the first multifunctional material can be significantly used in various technical fields in which hard chrome plating has been conventionally used.

  The carbon-doped titanium oxide layer contained in the first multifunctional material effectively responds to visible light having a wavelength of 400 nm or more as well as ultraviolet rays, and functions effectively as a photocatalyst. Therefore, such a first multifunctional material can be used as a visible light responsive photocatalyst and exhibits a photocatalytic function not only outdoors but also indoors. The carbon-doped titanium oxide layer of the first multifunctional material exhibits super hydrophilicity with a contact angle of 3 ° or less.

  In addition, the carbon-doped titanium oxide layer contained in the first multifunctional material is also excellent in chemical resistance, and after being immersed in an aqueous solution of 1M sulfuric acid and 1M sodium hydroxide for one week, the coating hardness and abrasion resistance When the photocurrent density was measured and compared with the measured value before the treatment, no significant change was observed. Incidentally, with respect to commercially available titanium oxide films, generally, the binder dissolves in acid or alkali depending on the kind thereof, so that the film peels off, and there is almost no acid resistance and alkali resistance.

  Furthermore, the carbon-doped titanium oxide layer contained in the first multifunctional material can be used as a catalyst that also responds to radiation such as gamma rays. That is, the present inventors have invented that a sprayed film such as titanium oxide suppresses stress corrosion cracking and scale adhesion of a nuclear reactor structural member in response to radiation. When the carbon-doped titanium oxide layer contained in the first multifunctional material is used as the mold catalyst, the potential of the substrate can be lowered to suppress pitting corrosion, overall corrosion, and stress corrosion cracking, and scale can be scaled by oxidizing power. There is an effect that it is possible to decompose dirt and dirt. It is simpler than other radiocatalyst film-forming methods, and is excellent from the viewpoint of durability such as chemical resistance and wear resistance.

Next, the 2nd multifunctional material applied to the equipment which concerns on the 1st-5th embodiment of this invention is demonstrated.
The second multifunctional material has a large number of protrusions made of titanium oxide or a titanium alloy oxide and doped with carbon on at least a part of the surface. The protrusions may be, for example, a layer in which fine columns (fine columnar structures) stand, or a large number of continuous narrow-width protrusions exposed on the thin film and on the protrusions. It may be a forested fine pillar.

  The second multifunctional material is manufactured as follows. First, the surface of the substrate having at least a surface layer made of titanium, titanium oxide, a titanium alloy, or a titanium alloy oxide is heat-treated by, for example, a combustion flame of an unsaturated hydrocarbon, particularly acetylene. Thereby, a layer in which fine columns made of titanium oxide or a titanium alloy oxide stand is formed inside the surface layer. Next, by applying, for example, thermal stress, shear stress, and tensile force to the substrate, the layer in which the fine columns are erected is cut in a direction along the surface layer. Accordingly, a member in which a layer in which fine columns made of titanium oxide or titanium alloy oxide are forested is exposed on at least a part (generally, most of the substrate) on the substrate, and on the thin film A member in which a large number of continuous narrow protrusions made of titanium oxide or titanium alloy oxide and fine columns standing on the protrusions are exposed is obtained. Both the substrate side member and the thin film side member have a large number of protrusions made of titanium oxide or titanium alloy oxide on at least a part of the surface, and both are used as the second multifunctional material. It is done.

  The substrate whose at least surface layer is made of titanium, titanium oxide, titanium alloy or titanium alloy oxide, the entire substrate may be composed of titanium, titanium oxide, titanium alloy or titanium alloy oxide, Or you may be comprised by the surface part formation layer which consists of titanium, titanium oxide, a titanium alloy, or a titanium alloy oxide, and the core material which consists of a material different from a surface part formation layer. Further, the shape of the substrate may be any final product shape (flat plate shape or three-dimensional shape) where photocatalytic activity and / or super hydrophilicity is desired.

At least the surface layer is made of titanium, titanium oxide, titanium alloy or titanium alloy oxide, and the substrate is composed of a surface portion forming layer made of titanium, titanium oxide, titanium alloy or titanium alloy oxide and a core material made of other materials. In this case, the thickness (amount) of the surface portion forming layer may be a thickness corresponding to a layer in which fine columns made of titanium oxide or titanium alloy oxide are formed. (That is, the entire surface portion forming layer is a layer in which fine columns made of titanium oxide or titanium alloy oxide stand), and may be thicker (that is, one in the thickness direction of the surface portion forming layer). The part is a layer in which fine columns made of titanium oxide or titanium alloy oxide are erected, and the rest remains unchanged). The material of the core material is not particularly limited as long as it does not burn, melt, or deform during the heat treatment in the manufacturing process of the second multifunctional material. In addition, if the heat treatment is performed while cooling the region other than the surface portion formation layer in the core material, or if the heat treatment is performed only on the surface portion formation layer for a short time, the melting point is higher than the heat treatment temperature described later. Alternatively, a material having a low glass transition point can be used as the core material. For example, iron, iron alloy, non-ferrous alloy, glass, ceramics, and other ceramics can be used as the core material. Such a substrate composed of a thin film-like surface layer and a core material can be produced in the same manner as in the first multifunctional material. The thickness of this surface layer is preferably 0.5 μm or more, more preferably 4 μm or more.
Moreover, as a titanium alloy, well-known various titanium alloys can be used, it does not restrict | limit in particular, The thing similar to the 1st multifunctional material is used.

  In the production of the second multifunctional material, for example, it is desirable to use a combustion flame of a gas mainly composed of unsaturated hydrocarbons, particularly acetylene, and particularly to use a reducing flame. When producing the second multifunctional material, a gas containing at least 50% by volume of unsaturated hydrocarbon, for example, a gas containing at least 50% by volume of acetylene and appropriately mixed with air, hydrogen, oxygen, etc. It is preferable to use it. In the production of the second multifunctional material, the fuel component is most preferably 100% acetylene. When an unsaturated hydrocarbon, particularly acetylene having a triple bond, is used, an unsaturated radical portion is decomposed during the combustion process, particularly in the reducing flame portion, and an intermediate radical substance is formed. Since this radical substance has strong activity, carbon doping is likely to occur, and doped carbon is contained in a Ti-C bond state. Thus, when carbon dope arises in a micro pillar, the hardness of a micro pillar will become high, As a result, mechanical strength, such as hardness of a multifunctional material and abrasion resistance, will improve, and heat resistance will also improve.

  In the production process of the second multifunctional material, the surface layer is subjected to heat treatment by directly applying a combustion flame to the surface of the substrate made of titanium, titanium oxide, titanium alloy or titanium alloy oxide, or the surface of the substrate Is heated in a combustion exhaust gas atmosphere. This heat treatment can be performed using, for example, a gas burner or in a furnace. When the combustion flame is directly applied and heat treatment is performed at a high temperature, the combustion flame may be applied to the surface of the substrate by a gas burner. When heat treatment is performed at a high temperature in a combustion exhaust gas atmosphere, the above-described fuel gas may be burned in a furnace and an atmosphere containing the high temperature combustion exhaust gas may be used.

  For the heat treatment, at least the surface layer is made of titanium, titanium oxide, a titanium alloy or a titanium alloy oxide, and a layer in which fine columns made of titanium oxide or a titanium alloy oxide stand is formed inside the surface layer. For example, by applying a thermal stress, a shear stress, a tensile force, and cutting the layer in which the fine columns are erected in a direction along the surface layer, the titanium oxide or the titanium alloy is formed on at least a part of the substrate. A member in which a layer in which fine columns made of oxide are forested is exposed, a number of continuous narrow projections made of titanium oxide or titanium alloy oxide on a thin film, and a forest on the projections It is necessary to adjust the heating temperature and the heat treatment time so that a member with exposed fine columns can be obtained. This heat treatment is preferably performed at a temperature of 600 ° C. or higher.

  By performing heat treatment under such conditions, the height of the layer in which the fine pillars are erected is about 1 μm to 20 μm, and the thickness of the thin film thereon is about 0.1 to 10 μm. Intermediates having an average thickness of about 0.2 μm to 3 μm are formed. Then, for example, by applying thermal stress, shear stress, tensile force, and cutting the layer in which the fine columns are erected in a direction along the surface layer, at least part of the titanium oxide or titanium alloy oxide The member on the substrate side where the layer in which the fine pillars are made of is exposed (that is, all or most of the thin film existing on the layer in which the fine pillars on the substrate are raised is peeled off) A part of the thin film existing on the layer where the fine pillars are erected may remain without being peeled), and a number of continuous narrow protrusions made of titanium oxide or titanium alloy oxide, and It is possible to obtain a member on the thin film side in which fine pillars standing on the protrusions are exposed.

  When applying a thermal stress to the hot intermediate to cut the layer in which the fine columns are erected in a direction along the surface layer, for example, either the front or back surface of the hot intermediate is cooled or heated. By doing so, a temperature difference is provided between the front surface and the back surface of the intermediate body. As a cooling method, for example, a cooling object such as a stainless steel block is brought into contact with either the front surface or the back surface of the hot intermediate, or cold air (normal temperature air) is blown onto either the front surface or the back surface of the hot intermediate. . It should be noted that thermal stress is generated even when the hot intermediate is allowed to cool, but the degree is low.

  When the layer in which the fine pillars are erected is cut in a direction along the surface layer by applying shear stress to the intermediate body, for example, the surface and the back surface of the intermediate body are relatively opposite to each other by friction force. Give power. In addition, when the layer in which the fine columns are erected is cut in a direction along the surface layer by applying a tensile force to the intermediate, for example, the front and back surfaces of the intermediate are removed using a vacuum suction disk or the like. Pull in the opposite direction, perpendicular to their plane. When using only a member in which a layer in which fine columns made of titanium oxide or titanium alloy oxide are forested is exposed on at least a part of the substrate, oxidation is performed on the intermediate thin film. A portion corresponding to a member in which a large number of continuous narrow protrusions made of titanium or titanium alloy oxide and fine columns standing on the protrusions are exposed may be removed by polishing, sputtering, or the like.

  In the member on the substrate side where the layer in which fine columns made of titanium oxide or titanium alloy oxide are forested is exposed at least in part obtained as described above, the layer in which the micro columns are forested is The height of the layer in which the fine column stands is changed depending on the height position of the fine column cut in the direction along the surface layer, but the height of the layer in which the fine column stands is generally 1 μm to The average thickness of the fine pillars is about 0.5 μm to 3 μm. This substrate-side member can easily adsorb VOC (volatile organic compounds) and has a large surface area, so it has high activity as a photocatalyst, and also has high film hardness, peel resistance, abrasion resistance, chemical resistance, and heat resistance. It is a multifunctional material with excellent properties.

  On the other hand, a member on the thin film side where a large number of continuous narrow protrusions made of titanium oxide or titanium alloy oxide obtained as described above and fine columns standing on the protrusions are exposed, It is a small piece. The height of the protrusion on each small piece is about 2 μm to 12 μm, and the height of the fine column varies depending on the height position of the fine column obtained by cutting the layer in which the fine column stands in the direction along the surface layer. However, the height of the layer in which the fine columns stand is generally about 1 μm to 5 μm, and the average thickness of the fine columns is about 0.2 μm to 0.5 μm. However, depending on the conditions for cutting the layer in which the fine columns are erected in the direction along the surface layer, there are cases where a large number of continuous narrow protrusions are exposed without the presence of the fine columns. This member on the thin film side can adsorb VOC and has a large surface area, so that it has high activity as a photocatalyst. Further, the thin film side member may be used as it is, or may be used after being pulverized. The pulverized product of the thin film side member can easily adsorb VOC and has a large surface area, and therefore has high activity as a photocatalyst.

  In the second multifunctional material, fine columns made of titanium oxide or titanium alloy oxide, or many continuous narrow-width projections and fine columns standing on the projections are carbon-doped. It responds to visible light having a wavelength of 400 nm or more as well as ultraviolet rays. Therefore, it acts particularly effectively as a photocatalyst and can be used as a visible light responsive photocatalyst, and exhibits a photocatalytic function not only outdoors but also indoors.

  The shape of each fine column of the layer in which the fine column made of titanium oxide or titanium alloy oxide constituting the second multifunctional material stands is determined from the micrographs of FIGS. 10 and 13. , Prismatic, cylindrical, pyramidal, conical, inverted pyramid or inverted conical, etc., extending straight or perpendicular to the surface of the substrate, extending while curving or bending , Branched and extended, and composites thereof. Moreover, as the whole shape, it can show by various expressions, such as a frost column shape, a raising carpet shape, a basket shape, a row column shape, and the column shape assembled with blocks. In addition, the thickness and height of the fine columns, the size of the base (bottom surface), and the like vary depending on heating conditions and the like.

  In the second multifunctional material, in the member on the thin film side where a large number of continuous narrow protrusions made of titanium oxide or titanium alloy oxide and fine columns standing on the protrusions are exposed. As can be seen from the photomicrograph of FIG. 12, the multiple consecutive narrow protrusions can be seen as the outer appearance of the walnut shell, the appearance of pumice, and each successive It can be seen that the narrow-width protrusions are bent in a hot water and stagnation pattern. Further, the shape of the fine pillars standing on the protrusions is the same as the shape of each of the fine pillars in the layer where the fine pillars on the base stand, but the junction between the fine pillars and the thin film. Therefore, the density of the fine columns standing on the protrusion is generally smaller than the density of the fine columns in the layer where the fine columns on the base are standing.

Hereinafter, the present invention will be described in more detail based on examples and comparative examples.
Examples 1-3
Carbon dope in which carbon is doped in a Ti—C bond state as a surface layer by heat-treating a titanium plate having a thickness of 0.3 mm using an acetylene combustion flame so that its surface temperature is about 1100 ° C. A titanium plate having a titanium oxide layer was formed. By adjusting the heat treatment time at 1100 ° C. to 5 seconds (Example 1), 3 seconds (Example 2), and 1 second (Example 3), respectively, the amount of carbon doping and the thickness of the carbon-doped titanium oxide layer were reduced. Titanium plates with different carbon doped titanium oxide layers were formed.

The carbon content was calculated | required with the fluorescent-X-ray-analysis apparatus about the carbon dope titanium oxide layer with which the carbon formed in this Example 1-3 was doped in the state of Ti-C bond. Assuming the molecular structure of TiO ₂ -xCx based on the carbon content, the carbon content of Example 1 is 8 at%, TiO _1.76 C _0.24 , the carbon content of Example 2 is about 3.3 at%, and TiO _1.90. Regarding C _0.10 and Example 3, the carbon content was 1.7 at% and TiO _1.95 C _0.05 . In addition, the carbon-doped titanium oxide layer in which the carbon formed in Examples 1 to 3 was doped in a Ti—C bond state was superhydrophilic with a contact angle of about 2 ° with water droplets.

Comparative Example 1
A commercially available titanium oxide sol (STS-01 manufactured by Ishihara Sangyo Co., Ltd.) was spin-coated on a titanium plate having a thickness of 0.3 mm, and then a titanium plate having a titanium oxide coating with improved adhesion was formed by heating.
Comparative Example 2
A commercially available product in which titanium oxide was spray-coated on a SUS plate was used as the substrate having the titanium oxide coating of Comparative Example 2.

Test Example 1 (Vickers hardness)
The carbon-doped titanium oxide layer doped with the carbon of Example 1 in a Ti—C bond state and the titanium oxide film of Comparative Example 1 were subjected to indenter: Belkovic using a nanohard nester (NHT) (manufactured by CSM Instruments, Switzerland). When the coating hardness was measured under the conditions of type, test load: 2 mN, load unloading rate: 4 mN / min, the carbon-doped titanium oxide layer doped with carbon in the state of Ti—C bond in Example 1 had a Vickers hardness. Was a high value of 1340. On the other hand, the Vickers hardness of the titanium oxide film of Comparative Example 1 was 160.

  These results are shown in FIG. For reference, the literature values of Vickers hardness of hard chrome plating layer and nickel plating layer (Tomono, “Practical Plating Manual”, Chapter 6, Ohmsha (1971)) are also shown. It is obvious that the carbon-doped titanium oxide layer in which the carbon of Example 1 is doped in a Ti—C bond state has higher hardness than the nickel plating layer and the hard chromium plating layer.

Test Example 2 (Scratch resistance)
For the carbon-doped titanium oxide layer doped with the carbon of Example 1 in a Ti—C bond state and the titanium oxide film of Comparative Example 1, a microscratch tester (MST) (manufactured by CSM Instruments, Switzerland) was used as an indenter: Rockwell. The scratch resistance test was performed under the conditions of (diamond), tip radius 200 μm, initial load: 0 N, final load: 30 N, load speed: 50 N / min, scratch length: 6 mm, stage speed: 10.5 mm / min. A “peeling start” load at which a small film peels off within the scratch mark and an “overall peel” load at which the film peels across the scratch mark were determined. The results were as shown in Table 1.

Test Example 3 (Abrasion resistance)
The carbon-doped titanium oxide layer in which the carbon of Example 1 was doped in a Ti—C bond state and the titanium oxide film of Comparative Example 1 were tested at a test temperature using a high-temperature tribometer (HT-TRM) (manufactured by CSM Instruments, Switzerland). A wear test was performed under the conditions of: room temperature and 470 ° C., ball: SiC sphere having a diameter of 12.4 mm, load: 1 N, sliding speed: 20 mm / sec, rotation radius: 1 mm, test rotation speed: 1000 rotations.

  As a result, for the titanium oxide film of Comparative Example 1, peeling occurred at both room temperature and 470 ° C., but for the carbon-doped titanium oxide layer in which the carbon of Example 1 was doped in a Ti—C bond state, No significant trace wear was detected under both room temperature and 470 ° C conditions.

Test Example 4 (Chemical resistance)
After immersing the titanium plate having the carbon-doped titanium oxide layer doped with the carbon of Example 1 in a Ti—C bond state in a 1M sulfuric acid aqueous solution and a 1M sodium hydroxide aqueous solution for 1 week at room temperature, When the wear resistance and the photocurrent density described below were measured, no significant difference was observed in the results before and after immersion. That is, it was confirmed that the carbon-doped titanium oxide layer in which the carbon of Example 1 was doped in a Ti—C bond state had high chemical resistance.

Test Example 5 (Structure of carbon-doped titanium oxide layer doped with carbon in a Ti-C bond state)
For the carbon-doped titanium oxide layer in which the carbon of Example 1 was doped in a Ti—C bond state, the acceleration voltage was 10 kV, the target was Al, and Ar ion sputtering was performed for 2700 seconds using an X-ray photoelectron spectrometer (XPS). Done and started the analysis. If this sputtering rate is 0.64 Å / s, which is equivalent to a SiO ² film, the depth is about 173 nm. The result of the XPS analysis is shown in FIG. The highest peak appears when the binding energy is 284.6 eV. This is judged to be a C—H (C) bond commonly found in Cls analysis. The next highest peak is seen when the binding energy is 281.7 eV. Since the bond energy of the Ti—C bond is 281.6 eV, it is determined that C is doped as a Ti—C bond in the carbon-doped titanium oxide layer of Example 1. As a result of XPS analysis at 11 points at different positions in the depth direction of the carbon-doped titanium oxide layer, similar peaks appeared in the vicinity of 281.6 eV at all points.

  Ti-C bonds were also confirmed at the boundary between the carbon-doped titanium oxide layer and the substrate. Therefore, the hardness is increased due to the Ti—C bond in the carbon-doped titanium oxide layer, and the film peeling strength is significantly increased due to the Ti—C bond at the boundary between the carbon-doped titanium oxide layer and the substrate. Is expected.

Test Example 6 (wavelength response)
The wavelength responsiveness of the carbon-doped titanium oxide layer in which the carbons of Examples 1 to 3 were doped in a Ti—C bond state and the titanium oxide coatings of Comparative Examples 1 and 2 were measured using an Oriel monochromator. Specifically, a voltage of 0.3 V was applied to each layer and film between the counter electrode in a 0.05 M aqueous sodium sulfate solution, and the photocurrent density was measured.

  The result is shown in FIG. FIG. 3 shows the obtained photocurrent density jp with respect to the irradiation wavelength. The wavelength absorption edge of the carbon-doped titanium oxide layer in which the carbons of Examples 1 to 3 are doped in a Ti—C bond state extends to 490 nm, and the photocurrent density increases as the carbon doping amount increases. Was recognized. Although not shown here, it has been found that when the carbon doping amount exceeds 10 at%, the current density tends to decrease, and when the carbon doping amount exceeds 15 at%, the tendency becomes remarkable. Therefore, it was recognized that the carbon doping amount has an optimum value of about 1 at% to 10 at%. On the other hand, in the titanium oxide films of Comparative Examples 1 and 2, it was recognized that the photocurrent density was extremely small and the wavelength absorption edge was about 410 nm.

Test example 7 (light energy conversion efficiency)
The light energy conversion efficiency η defined by the following formula was determined for the carbon-doped titanium oxide layers in which the carbons of Examples 1 to 3 were doped in a Ti—C bond state and the titanium oxide films of Comparative Examples 1 and 2.
η = jp (Ews−Eapp) / I
Here, Ews is the theoretical decomposition voltage of water (= 1.23 V), Eapp is the applied voltage (= 0.3 V), and I is the irradiation light intensity. The result is shown in FIG. FIG. 4 shows the light energy conversion efficiency η with respect to the irradiation light wavelength.

  As is clear from FIG. 4, the carbon-doped titanium oxide layer in which the carbons of Examples 1 to 3 are doped in a Ti—C bond state has extremely high light energy conversion efficiency, and the conversion efficiency in the vicinity of a wavelength of 450 nm is a comparative example. It was recognized that the conversion efficiency in the ultraviolet region (200 nm to 380 nm) of the titanium oxide films 1 and 2 was superior. Further, the water decomposition efficiency of the carbon-doped titanium oxide layer in which the carbon of Example 1 is doped in a Ti—C bond state is about 8% at a wavelength of 370 nm, and an efficiency exceeding 10% can be obtained at 350 nm or less. I understood.

Test Example 8 (Deodorization test)
A deodorizing test was performed on the carbon-doped titanium oxide layer in which the carbons of Examples 1 and 2 were doped in a Ti-C bond state and the titanium oxide film of Comparative Example 1. Specifically, after acetaldehyde generally used in deodorization tests is enclosed in a 1000 ml glass container together with a substrate having a carbon-doped titanium oxide layer, the influence of concentration reduction due to initial adsorption can be ignored. Visible light was irradiated with a fluorescent lamp with a UV cut filter, and the acetaldehyde concentration was measured by gas chromatography at every predetermined irradiation time. In addition, the surface area of each coating film was 8.0 cm ² .

  The result is shown in FIG. FIG. 5 shows the acetaldehyde concentration with respect to the elapsed time after irradiation with visible light. The acetaldehyde decomposition rate of the carbon-doped titanium oxide layers of Examples 1 and 2 is higher than the acetaldehyde decomposition rate of the titanium oxide film of Comparative Example 1 by a high value, and the carbon doping amount is large. It was found that the carbon-doped titanium oxide layer of Example 1 having a higher energy conversion efficiency has a higher decomposition rate than the carbon-doped titanium oxide layer of Example 2.

Test example 9 (antifouling test)
An antifouling test was conducted on the carbon-doped titanium oxide layer of Example 1 and the titanium oxide film of Comparative Example 1. Each coating was placed in a smoking room in the Central Research Institute of Electric Power Co., Ltd., and surface contamination after 145 days was observed. There is no direct incidence of sunlight in the smoking room.
A photograph showing the results is shown in FIG. Fat adhered to the surface of the titanium oxide film of Comparative Example 1 and had a pale yellow color, but the surface of the carbon-doped titanium oxide layer of Example 1 was not particularly changed and was kept clean, It was confirmed that the antifouling effect was sufficiently exhibited.

Examples 4-7
By using an acetylene combustion flame in the same manner as in Examples 1 to 3, a titanium plate having a thickness of 0.3 mm was heated at the surface temperature shown in Table 2 for the time shown in Table 2, thereby forming a surface layer. A titanium plate having a carbon-doped titanium oxide layer was formed.

Comparative Example 3
Using a natural gas combustion flame, a 0.3 mm thick titanium plate was heat-treated at the surface temperature shown in Table 2 for the time shown in Table 2.
Test Example 10
With respect to the carbon-doped titanium oxide layers of Examples 4 to 7 and the coating film of Comparative Example 3, Vickers hardness (HV) was measured in the same manner as in Test Example 1 above. The results are shown in Table 2. Moreover, the carbon dope titanium oxide layer formed in Examples 4-7 was super hydrophilicity whose contact angle with a water droplet was about 2 degrees.

  As is apparent from the data shown in Table 2, when the heat treatment was performed with natural gas combustion gas so that the surface temperature was 850 ° C., only a film having a Vickers hardness of 160 was obtained, but the surface temperature was 1000 ° C. In Examples 4 to 7 where heat treatment was performed using acetylene combustion gas as described above, a carbon-doped titanium oxide layer having a Vickers hardness of 1200 was obtained.

Test Example 11
For the carbon-doped titanium oxide layers of Examples 4 to 7 and the titanium oxide coatings of Comparative Examples 1 and 3, as in Test Example 6, a voltage of 0.3 V was applied between the counter electrode in a 0.05 M sodium sulfate aqueous solution. The photocurrent density was measured by irradiating with light of 300 nm to 520 nm. The result is shown in FIG. FIG. 7 shows the obtained photocurrent density jp with respect to the potential ECP (V vs. SSE).

  The carbon-doped titanium oxide layers of Examples 4 to 6 obtained by heat treatment using an acetylene combustion gas so that the surface temperature is 1000 ° C. to 1200 ° C. are relatively excellent in photocurrent density. I understood. On the other hand, the titanium oxide of Comparative Example 3 obtained by heat treatment so that the surface temperature becomes 850 ° C. and the carbon-doped titanium oxide layer of Example 7 obtained by heat treatment so that the surface temperature becomes 1500 ° C. It was found that the current density was relatively small.

Example 8
A titanium alloy whose surface layer contains carbon-doped titanium oxide by heat treatment of a Ti-6Al-4V alloy plate having a thickness of 0.3 mm using an acetylene combustion flame so that its surface temperature is about 1100 ° C. An alloy plate made of The heat treatment time at 1100 ° C. was 60 seconds. The layer containing carbon-doped titanium oxide thus formed is superhydrophilic with a contact angle with water droplets of about 2 °, and has the same photocatalytic activity as that of the carbon-doped titanium oxide layer obtained in Example 4. showed that.

Example 9
A titanium thin film having a thickness of about 500 nm was formed on the surface of a stainless steel plate (SUS316) having a thickness of 0.3 mm by sputtering. A stainless steel sheet having a carbon-doped titanium oxide layer as a surface layer was formed by heat treatment using an acetylene combustion flame so that the surface temperature was about 900 ° C. The heat treatment time at 900 ° C. was 15 seconds. The carbon-doped titanium oxide layer thus formed is superhydrophilic with a contact angle with water droplets of about 2 °, and exhibits the same photocatalytic activity as the carbon-doped titanium oxide layer obtained in Example 4. It was.

Example 10
A titanium oxide powder having a particle size of 20 μm is supplied into an acetylene combustion flame, and is retained in the combustion flame for a predetermined time, and heat-treated so that the surface temperature is about 1000 ° C. A titanium powder having a layer was formed. The heat treatment time at 1000 ° C. was 4 seconds. The titanium powder having the carbon-doped titanium oxide layer formed as described above showed the same photocatalytic activity as that of the carbon-doped titanium oxide layer obtained in Example 4.

Examples 11-12
A titanium thin film having a thickness of about 100 nm was formed by sputtering on the surface of a 1 mm thick glass plate (Pyrex (registered trademark)). A glass plate having a carbon-doped titanium oxide layer as a surface layer is obtained by heat treatment using an acetylene combustion flame so that the surface temperature is 1100 ° C. (Example 11) or 1500 ° C. (Example 12). Formed. The heat treatment time at 1100 ° C. or 1500 ° C. was 10 seconds. The carbon-doped titanium oxide layer thus formed was transparent as shown in the photograph in FIG. 8A when the surface temperature was 1100 ° C., but when the surface temperature was 1500 ° C., FIG. As shown in FIG. 8, many small island-like undulations floating in the sea are generated on the surface, and it became translucent as shown in FIG.

Examples 13-16
The surface of the titanium plate having a thickness of 0.3 mm was subjected to heat treatment with an acetylene combustion flame at the surface layer temperature shown in Table 3 for the time shown in Table 3. After that, when the surface to which the flame is applied is brought into contact with a flat surface of a stainless steel block having a thickness of 30 mm and cooled, a layer in which fine columns made of white titanium oxide stand on the most part of the titanium plate surface is exposed. And a small piece member in which a large number of continuous narrow protrusions made of white titanium oxide on the thin film and fine columns standing on the protrusions are exposed. That is, the layer in which the fine columns made of titanium oxide formed in the surface layer by heat treatment are erected is cut in the direction along the surface layer by the subsequent cooling. Thus, the multifunctional material of Examples 13-16 was obtained.

  FIG. 10 is a photomicrograph of the multifunctional material obtained in Example 13, in which a layer 2 in which fine columns made of white titanium oxide stand on the titanium plate surface 1 is exposed, and on the thin film. A state in which a small piece member 3 in which a large number of continuous narrow protrusions made of white titanium oxide and fine columns standing on the protrusions are exposed remains in a part on the layer 2 is shown. Yes. In addition, in the manufacturing method of Examples 13-16, although the titanium plate surface 1 is not exposed, the micrograph of FIG. 10 has shown the state which removed a part of layer 2 in which the fine pillar stands. FIG. 11 is a photomicrograph showing the state of the surface on the thin film side of the small piece member 3 in which a large number of continuous narrow protrusions made of white titanium oxide and thin columns standing on the protrusions are exposed on the thin film. FIG. 12 shows a number of continuous narrow widths of small piece members 3 in which a large number of continuous narrow-width projections made of white titanium oxide are exposed on a thin film and fine columns standing on the projections are exposed. FIG. 13 is a photomicrograph showing the state of the protrusion and the surface on the side where the fine pillar standing on the protrusion is exposed, and FIG. 13 is the state of the layer 2 where the fine pillar made of white titanium oxide is standing FIG.

Example 17
The surface of a Ti-6Al-4V alloy plate having a thickness of 0.3 mm was heat-treated with an acetylene combustion flame at the surface layer temperature shown in Table 3 for the time shown in Table 3. After that, when the surface to which the flame is applied is brought into contact with a flat surface of a stainless steel block having a thickness of 30 mm and cooled, a layer in which fine columns made of titanium alloy oxide stand on most of the surface of the titanium alloy plate is exposed. And a small piece member in which a number of continuous narrow protrusions made of titanium alloy oxide on the thin film and fine columns standing on the protrusions are exposed.

Example 18
A titanium thin film having a thickness of about 3 μm was formed on the surface of a stainless steel plate (SUS316) having a thickness of 0.3 mm by electron beam evaporation. The surface of the thin film was heat-treated with an acetylene combustion flame at the surface layer temperature shown in Table 3 for the time shown in Table 3. After that, when the surface to which the combustion flame is applied is brought into contact with a flat surface of a 30 mm thick stainless steel block and cooled, a layer in which fine columns made of white titanium oxide are forested is exposed on the majority of the surface of the stainless steel plate. And a small piece member in which a large number of continuous narrow protrusions made of white titanium oxide on the thin film and fine columns standing on the protrusions are exposed.

Comparative Example 4
A commercially available titanium oxide sol (STS-01 manufactured by Ishihara Sangyo Co., Ltd.) was spin-coated on a titanium plate having a thickness of 0.3 mm, and then a titanium plate having a titanium oxide coating with improved adhesion was formed by heating.

Test Example 12 (Scratch hardness test: pencil method)
Mitsubishi Pencil Co., Ltd., based on JIS K 5600-5-4 (1999), on the surface of the fine column side of the member in which the layer in which the fine column is grown is exposed on the substrate surface obtained in Examples 13 to 18 A pencil scratch hardness test was carried out using Uni 1H-9H pencils. The results were as shown in Table 3. That is, no damage was observed when a 9H pencil was used for all the test pieces.

Test Example 13 (Chemical resistance test)
The members having exposed layers with fine pillars exposed on the substrate surfaces obtained in Examples 13 to 18 were immersed in 1M sulfuric acid aqueous solution and 1M sodium hydroxide aqueous solution for 1 week at room temperature, washed with water and dried. Then, the above scratch hardness test: the pencil method was carried out. The results were as shown in Table 3. That is, even when a 9H pencil was used for all the test pieces, no damage was observed, and it was confirmed that the test pieces had high chemical resistance.

Test example 14 (heat resistance test)
A member in which a layer in which fine columns are erected is exposed on the surface of the substrate obtained in Examples 13 to 18 is placed in a tubular furnace, and the temperature is raised from room temperature to 500 ° C. in an air atmosphere over 1 hour. After holding at a constant temperature of 500 ° C. for 2 hours and further allowing to cool to room temperature over 1 hour, the above-described scratch hardness test: pencil method was performed. The results were as shown in Table 3. That is, no damage was observed even when a 9H pencil was used for all the test pieces, and it was confirmed that the specimen had high heat resistance.

Test Example 15 (Anti-fouling test)
As a sample, an 8 cm ² surface area member having a surface area of 8 cm ² exposed from the surface of the substrate obtained in Example 16 and a layer having fine pillars and a titanium oxide film having a surface area of 8 cm ² obtained in Comparative Example 4. An antifouling test was conducted using Specifically, each of these samples was immersed in 80 mL of an aqueous methylene blue solution adjusted to a concentration of about 10 μmol / L, and the influence of the decrease in concentration due to initial adsorption became negligible. Matsushita Electric Industrial Co., Ltd. Visible light was irradiated with a fluorescent lamp with a UV cut filter manufactured, and the absorbance of the methylene blue aqueous solution at a wavelength of 660 nm was measured with a water quality inspection apparatus DR / 2400 manufactured by HACH at every predetermined irradiation time. The result was as shown in FIG.

  From FIG. 14, the member in which the layer with the fine pillars exposed on the surface of the substrate obtained in Example 16 is exposed to methylene blue as compared with the titanium plate having the titanium oxide film obtained in Comparative Example 4. It can be seen that the decomposition speed of is high and the antifouling effect is high.

Test Example 16 (Crystal structure and bonding state)
As a result of performing X-ray analysis (XRD) on the sample obtained from the fine column of the member in which the layer with the fine column grown on the substrate surface obtained in Example 15 is exposed, it has a rutile crystal structure. It has been found.

Further, with respect to the fine column portion of the member in which the layer with the fine columns grown on the surface of the substrate obtained in Example 15 is exposed, an X-ray photoelectron spectrometer (XPS) is used to accelerate voltage: 10 kV, target: Al was used for Ar sputtering for 2700 seconds, and analysis was started. If this sputtering rate is 0.64 Å / s corresponding to the SiO ₂ film, the depth is about 173 nm. The result of the XPS analysis was as shown in FIG. The highest peak appears when the binding energy is 284.6 eV. This is judged to be a C—H (C) bond commonly found in Cls analysis. The next highest peak is seen when the binding energy is 281.6 eV. Since the bond energy of the Ti—C bond is 281.6 eV, it is determined that C is doped as a Ti—C bond in the fine column of Example 15. As a result of XPS analysis at 14 points at different heights of the fine columns, similar peaks appeared in the vicinity of 281.6 eV at all points.

Example 19
A disc having a diameter of 32 mm and a thickness of 0.3 mm was used as a test piece, and the surface thereof was heated by an acetylene combustion flame so that the surface temperature was maintained at about 1150 ° C. About the 1st test piece, the heating was stopped at the time of the heating time of 120 seconds, and it stood to cool. About the 2nd test piece, the heating was stopped at the time of 180 second and it stood to cool. The third test piece was heated for 480 seconds, and immediately the surface to which the flame was applied was brought into contact with the flat surface of a 30 mm thick stainless steel block and cooled. By this cooling, a thin film was peeled off from the surface of the titanium plate, and a member in which a layer in which fine columns made of white titanium oxide were erected was exposed. With respect to these three test pieces, a hole of 3 μm × 12 μm and a depth of 10 μm was dug on the surface of the test piece using a FIB-SEM apparatus SMI8400SE manufactured by Seiko Instruments Inc., and the side and bottom surfaces thereof were observed with a SEM apparatus VE7800 manufactured by Keyence Corporation. Went. The SEM photograph of the test piece after 120 seconds is FIG. 16, the SEM photograph of the test piece after 180 seconds is FIG. 17, and the SEM photograph of the test piece after 480 seconds is FIG. In FIG. 17 after 180 seconds, signs of a fine column structure begin to appear in the lower part of the film, and it is considered that by continuing the flame treatment, the fine column is elongated and a fine column structure as intended in the present invention is formed. .

  Next, the equipment according to the first to fifth embodiments of the present invention will be described. In these embodiments, the layer or coating containing carbon-doped titanium oxide or titanium alloy oxide refers to the carbon-doped titanium oxide or titanium alloy oxide (desirably, the first or second multifunctional material described above) And a layer or film having a Ti-C bond).

First, the equipment according to the first embodiment of the present invention will be described with reference to FIG. The equipment according to the present embodiment is a fishing net.
FIG. 19 is a partial cross-sectional perspective view showing a part of a fishing net as an equipment material according to the present embodiment. This fishing net includes a core material layer 101 formed of titanium, a titanium alloy, titanium oxide, or a titanium alloy oxide, and a surface layer 102 covering the surface of the core material layer 101. The surface layer 102 is formed of a layer containing carbon-doped titanium oxide or titanium alloy oxide in the first or second multifunctional material described above.

  Such a fishing net is manufactured as follows. First, a fishing net compact is made of titanium, a titanium alloy, titanium oxide, or a titanium alloy oxide. The fishing net compact is heat-treated under predetermined conditions in the same manner as described in the first or second multifunctional material production method. Thereby, a layer containing carbon-doped titanium oxide or titanium alloy oxide (that is, the surface layer 102) is formed on the surface of the molded body. Furthermore, the fishing net shown in FIG. 19 is completed by subjecting the heat-treated molded body to post-treatment as necessary and naturally cooling. Note that this post-treatment includes peeling of a member on the thin film side that is simultaneously formed by heat treatment for forming the second multifunctional material.

  Or the wire rope in which the film containing carbon dope titanium oxide or a titanium alloy oxide was formed by said method may be produced, and a fishing net may be formed using the wire rope.

  In this way, by forming a layer containing carbon-doped titanium oxide or titanium alloy oxide on the surface of a molded body such as titanium, it is lightweight and highly rigid, and dirt is difficult to adhere due to the photocatalytic function of the coating. You can get a fishing net. In particular, in the present embodiment, a part of a molded body (substrate) such as titanium is changed to carbon-doped titanium oxide or titanium alloy oxide, so that it is clear that the flow of photocurrent is prevented between the substrate and the surface layer. There is no interface and the electrical conductance is high. Therefore, the effect of reducing the potential of the base material to suppress pitting corrosion and corrosion, or to decompose dirt by oxidizing power is exhibited very efficiently.

  Here, since fishery equipment is exposed to seawater or the like during normal use, it tends to cause microbial corrosion due to the contamination of fish and shellfish, or the growth of aquatic organisms and bacteria. Such stains are difficult to remove, but if left unattended, not only the appearance will be impaired, but also hygiene problems will occur, the work will be hindered by dirt contamination, chloric corrosion and microbial corrosion As a result of damage, the service life is shortened. Corrosion due to salt damage is also a major problem. Titanium has durability against chlorine, so in the past, it was tried to produce anti-fouling performance by making fishing nets with titanium or coating the fishing nets with a substance having a photocatalytic function. It was. However, in the normal use state of fishing nets, fretting wear occurs at the contact points between members, so that the coating peels off or the fishing net itself is shaved, and any high effect may not be obtained. all right. Here, fretting wear is damage caused by a minute relative reciprocating sliding motion (fretting motion).

  However, the carbon-doped titanium oxide or titanium alloy oxide contained in the surface layer of the equipment according to this embodiment has not only a high photocatalytic function but also high mechanical strength including wear resistance. is doing. In particular, the first multifunctional material described above has very high rigidity, abrasion resistance, and scratch resistance of the coating surface. Therefore, since the surface layer due to fretting wear can be prevented from being scraped or peeled off, the antifouling effect produced by the photocatalytic function can be obtained over a long period in the fishing net. As a result, it is difficult for fish and shellfish to be attached to the equipment, so that the equipment is not lost, workers can be engaged in work hygienically, and work safety is improved. In addition, since the surface of the first multifunctional material is extremely smooth, there is an advantage that marine organisms and the like are difficult to adhere physically.

  In addition, the high mechanical strength of the surface layer increases the service life of the fishing net, leading to cost reduction in the long run. Further, as in the present embodiment, since the equipment made of titanium up to the inside is relatively lightweight, there is also an advantage that a burden such as fishing net lifting work is reduced.

  The same structure as the equipment according to the present embodiment, that is, a layer containing carbon-doped titanium oxide or titanium alloy oxide as a film was formed on the surface of titanium, titanium alloy, titanium oxide, or titanium alloy oxide. The structure can be applied to various other equipment. For example, in the fishery field, pipes for fishing rods and fishing hooks can be mentioned. In this case, a tube material or the like formed of titanium is prepared, and a layer containing carbon-doped titanium oxide or a titanium alloy oxide is formed as a coating on the surface of the tube material by heat treatment under predetermined conditions. . A fishing rod using such a pipe material has high rigidity and antifouling performance and is lightweight, so it is considered that the usability is improved for a wide range of users.

  Or you may apply the structure similar to the equipment which concerns on this embodiment to equipment, such as a shovel, a scoop, a rake, a sickle, and a gardening basket used in the field of gardening or agriculture. 21 is a cross-sectional view of the shovel shown in FIG. This shovel includes a core material layer 111 formed of titanium, titanium alloy, titanium oxide, or titanium alloy oxide, and a surface layer 112 covering the surface of the core material layer 111. The surface layer 112 is formed of a layer containing carbon-doped titanium oxide or titanium alloy oxide in the first or second multifunctional material described above. In the same manner as the equipment according to the present embodiment, such an equipment may be formed by using titanium or the like and heat-treating the formed body under predetermined conditions.

  Here, soil and dirt are likely to remain in the horticulture or agricultural equipment, but if left untreated, the equipment will be corroded by the influence of microorganisms, agricultural chemicals, etc. in the soil. Therefore, by forming a layer containing carbon-doped titanium oxide or titanium alloy oxide as a coating on the surface of the core material made of titanium or the like, an equipment material that is easy to maintain and has a long service life can be obtained. In particular, the layer containing carbon-doped titanium oxide or titanium alloy oxide in the first multifunctional material has a very smooth surface, and exhibits a high self-cleaning effect due to superhydrophilicity and high oxidative decomposition power due to the photocatalytic function. . Therefore, the equipment provided with such a film has the advantage that it is difficult for dirt to adhere and it can be cleaned only by washing with water.

  Or you may apply the structure similar to the equipment which concerns on this embodiment to the electrical equipment used in electrical construction. Specifically, parts for electric piping such as a heat insulating box, an L-shaped bracket, a cable bracket, a device mounting angle, a stand pipe, and the like can be given. Here, dirt is likely to adhere to electrical piping parts placed outdoors and electrical construction equipment used outdoors, but if the dirt is left untreated, the durability of those parts and equipment will be increased due to corrosion. It will decline. In general, hard chrome plating is applied to such electrical equipment materials, but by using the multifunctional material in this embodiment instead, durability superior to hard chrome plating (high hardness, scratch resistance, abrasion resistance) Wear resistance, chemical resistance, heat resistance) and antifouling performance can be obtained.

  In addition, when applying the same structure as the equipment according to the present embodiment to a field where high mechanical strength is required, such as electrical equipment materials, the carbon-doped oxidation in the first multifunctional material is performed as a coating. It is more preferable to form a layer containing titanium or a titanium alloy oxide. This is because in this carbon-doped titanium oxide or titanium alloy oxide, the surface Vickers hardness can be 1000 Hv or higher, which is harder than hard chromium.

  Furthermore, you may apply the structure similar to the equipment which concerns on this embodiment to the member for construction. Specifically, panels for exterior walls, interior panels, roof tiles, furniture components (for example, door fences, sliding door panels, shutters, window frames), assembly rooms, assembly garages, verandas, balconies, window panels It can be applied to fixing brackets, suspensions, joints, curtain rails, and their accessories (for example, connecting brackets).

  Since the layer containing carbon-doped titanium oxide or titanium alloy oxide has high rigidity and scratch resistance, the use of equipment with such a layer as a coating makes it possible to improve the exterior and interior of a building. It is possible to keep the aesthetic for a long time. In addition, this carbon-doped titanium oxide or titanium alloy oxide layer can decompose acetaldehyde, which causes sick house syndrome, at a higher speed than conventional photocatalytic products, and is sufficient for visible light having a wavelength of 400 nm or more. Respond to. Therefore, when the equipment is installed outdoors, the photocatalytic function can be efficiently expressed indoors, so that it is also suitable as an interior member. Furthermore, as described above, the equipment according to the present embodiment can change the texture and color of the surface by controlling the processing temperature and processing time during the heat treatment, so that the design surface Therefore, it is suitable for interior parts.

  In addition, when the same structure as the equipment according to the present embodiment is applied to an interior member that is not required to have high mechanical strength, carbon-doped titanium oxide or titanium alloy oxidation in the second multifunctional material It is more preferable to form a layer containing an object. Micro is because the surface area of the entire equipment is increased by the fine columnar structure formed on the surface of such a layer, so that the photocatalytic function is more efficiently expressed.

  Furthermore, in recent years, the number of women and elderly people working on construction sites is increasing. Therefore, as in the present embodiment, by reducing the weight while maintaining the strength of the equipment, it is possible to improve the efficiency and quality of the work while reducing the burden on the worker.

  Or you may apply the structure similar to the equipment which concerns on this embodiment to the frame, support | pillar, and connection tool of the assembly greenhouse used in the horticulture or the agricultural field, a greenhouse. In this case, due to the antifouling effect and corrosion resistance caused by the photocatalytic function of the equipment according to this embodiment, in addition to being able to use these equipment for a long period of time, it is lightweight, so it is easy to assemble and carry There are advantages such as being easy.

Next, equipment according to a second embodiment of the present invention will be described with reference to FIG. The equipment according to the present embodiment is equipment used in the fishing industry, specifically, aquaculture props.
FIG. 22 is a cross-sectional view showing an aquaculture prop as an equipment according to the present embodiment. This culture support post includes a core material 201 and a surface layer 202 disposed outside the core material 201. The core material 201 is made of, for example, iron, an iron alloy, a non-ferrous alloy, or the like. The surface layer 202 includes titanium, a titanium alloy, titanium oxide, or a titanium alloy oxide, and at least the outermost surface thereof is carbon-doped oxidized in the first or second multifunctional material described above. A layer containing titanium or a titanium alloy oxide is formed. In FIG. 22, the entire surface layer 202 is a layer containing carbon-doped titanium oxide or titanium alloy oxide.

  Such a fishing support is manufactured as follows. First, as a core material 201, a support pillar molded body is made of iron, an iron alloy, a non-ferrous alloy, or the like. A film containing titanium, a titanium alloy, titanium oxide, or a titanium alloy oxide is formed on the surface of the core material 201. This coating can be formed using a known method such as sputtering, vapor deposition, or thermal spraying. Further, a commercially available titanium oxide sol may be spray-coated, spin-coated, or dipped. Alternatively, a thin film such as titanium or a thin plate may be joined by pressure welding or the like. Next, the molded body of the column on which the film is formed is heat-treated under a predetermined condition in the same manner as described in the first or second multifunctional material manufacturing method. This heat treatment is performed until a layer containing carbon-doped titanium oxide or titanium alloy oxide is formed on at least the surface of the coating. In other words, in the deep layer of the surface layer 202 (portion on the core material 201 side), titanium or a titanium alloy, or a titanium oxide or titanium alloy oxide layer (intermediate layer) that is not carbon-doped may remain. Absent. Thereby, the surface layer 202 is formed. Furthermore, the post for a culture | cultivation shown in FIG. 22 is completed by performing a post-process as needed with respect to the heat-processed film, and making it cool naturally.

In this way, by forming a layer containing carbon-doped titanium oxide or titanium alloy oxide as a coating on the surface of the core material, the antifouling effect produced by the photocatalytic function of the coating can be obtained in the equipment.
Here, fishery equipment such as fishing net sinks, fishing net floats, aquaculture rafts, aquaculture props, aquaculture feeders, fish tanks, ginger, fishing scaffolding boards, wire ropes, etc. In addition, the service life is short due to microbial corrosion and chlorine corrosion due to the contamination of fish and shellfish, aquatic organisms and bacteria and the propagation of bacteria. In addition, if such dirt is left unattended, not only the appearance is impaired, but also hygiene problems occur, and the work is hindered by dirt smearing.

  However, in fishery equipment having a coating film containing carbon-doped titanium oxide or titanium alloy oxide on the surface, dirt from fish and shellfish is less likely to adhere to the equipment due to the antifouling effect produced by the photocatalytic function of the coating film. Become. Thereby, since there is no waste of equipment, the worker can be engaged in the work in a sanitary manner, and the safety of the work is also improved. Moreover, in such fishery equipment, the deodorizing effect due to the photocatalytic function can be expected, so that the comfort in work is improved. In addition, when a comparatively high mechanical strength is requested | required in an equipment, it is more preferable to form the layer containing the carbon dope titanium oxide or titanium alloy oxide in a 1st multifunctional material as a film. This is because such a coating has a very high mechanical durability including scratch resistance and abrasion resistance, so that the coating does not scrape or peel off during use of fishery equipment. . As a result, the core material made of metal or alloy is not damaged by salt damage, and the useful life of the equipment is prolonged. Therefore, cost reduction can be achieved in the long term. Further, since the surface of the membrane is extremely smooth, there is an advantage that marine organisms are hardly attached physically.

  The structure similar to the equipment according to the present embodiment, that is, the structure having a core material such as a metal or an alloy and a film containing carbon-doped titanium oxide or titanium alloy oxide is applied to various other fields. be able to. For example, the same structure as that in the equipment according to this embodiment may be applied to the ship bottom. Here, if aquatic organisms and bacteria adhere to the bottom of the ship and propagate, the surface of the bottom of the ship becomes rough, leading to a reduction in ship speed and a deterioration in fuel consumption. Further, if the adhered dirt is left unattended, the surface paint on the bottom of the ship will be corroded, and the function of the entire ship will deteriorate. However, the work of removing dirt from the ship bottom is a great effort. By applying a multifunctional material having antifouling performance as a constituent member of such a ship bottom, it is possible to prevent dirt from adhering to the ship bottom, thereby greatly reducing the maintenance burden. In particular, the layer containing carbon-doped titanium oxide or titanium alloy oxide in the first multifunctional material described above has a very smooth surface and exhibits a high self-cleaning effect. There is an advantage that it is difficult to adhere and can be easily removed only by washing with water. In order to form a film containing carbon-doped titanium oxide or titanium alloy oxide on the bottom of the ship, for example, a titanium oxide film is formed on the bottom of the ship by spray-coating a titanium oxide sol, and predetermined components are used using a gas burner or the like. What is necessary is just to heat-process by applying the combustion flame containing this to this film.

  Furthermore, you may apply the structure similar to the equipment which concerns on this embodiment, for example to the equipment for painting construction. Specifically, a jig or tool for holding the paint can and a chiseling tool can be used. Here, in the field of painting work, there is a problem that dirt is likely to adhere to the jigs and tools to be used, but it is difficult to remove, and the organic solvent is often directly touched, so that it is easily corroded. Therefore, a film containing carbon-doped titanium oxide or titanium alloy oxide is formed on the surface of the jig or tool. Thereby, the antifouling effect produced by the photocatalytic function of the coating can be obtained. Further, the high chemical resistance of such a coating makes it possible to extend the service life of jigs and tools for painting work.

  Alternatively, the same structure as the equipment according to the present embodiment may be applied to bolts and bearings including bolts, nuts, screws, and the like. Here, galling is a problem in bolts and bearings. The galling refers to surface damage caused by the assembly of minute seizures generated on a sliding surface or the like. For example, if the thread of the bolt is galling, the tightened bolt will not move. Or in a bearing, precise operation will be prevented. Therefore, a film containing carbon-doped titanium oxide or titanium alloy oxide is formed on the surfaces of these members. In particular, the layer containing carbon-doped titanium oxide or titanium alloy oxide in the first multifunctional material is extremely smooth in surface, and thus is suitable as a surface forming layer for components of precision equipment and has scratch resistance. Since the mechanical strength is extremely high, there is an advantage that the occurrence of galling can be suppressed.

  In addition, the same structure as the equipment according to the present embodiment may be applied to water-related equipment in public facilities and care facilities as described above. Specifically, equipment that generally uses metal or an alloy, such as a cooking table, a washstand, and a water-fitting bracket, which are easily contaminated, is produced by the same manufacturing method as the equipment according to the present embodiment. . Thereby, a hygienic environment can be easily maintained by the antifouling effect produced by the photocatalytic function of the layer containing carbon-doped titanium oxide or titanium alloy oxide. Moreover, the deodorizing effect and air cleaning effect which arise by a photocatalyst function can also be anticipated. Furthermore, as described above, in the layer containing carbon-doped titanium oxide or titanium alloy oxide, the texture and color of the surface can be changed by controlling the treatment temperature and treatment time during the heat treatment. Therefore, from such a design aspect, it is suitable as a structural material for equipment in public facilities and nursing care facilities.

  Or you may apply the structure similar to the equipment which concerns on this embodiment to the instrument (for example, shovel, a pickaxe, etc.) used in the equipment used in dredging construction, pavement construction, etc. Here, dirt such as sludge and residue adheres to the equipment used in the dredging construction of the channel and dam. Similarly, in pavement construction, dirt that is difficult to remove adheres to the appliance. If such dirt is left unattended, there is a risk that pitting corrosion or general corrosion will occur in the instrument, causing damage. Therefore, in order to prevent the shortening of the service life of dredging equipment, maintenance such as removal of dirt is important, but removing sludge stuck to the equipment is a lot of work and is difficult to remove. The problem is not being able to complete.

  Therefore, by forming a layer containing carbon-doped titanium oxide or titanium alloy oxide as a coating on the surface of such devices, a high antifouling effect can be obtained in those devices. Therefore, it is possible to prolong the service life of the appliance by reducing corrosion and the like while reducing maintenance work. In particular, the layer containing carbon-doped titanium oxide or titanium alloy oxide in the first multifunctional material described above has a very smooth surface and exhibits a high self-cleaning effect. It has the advantage that it is difficult to adhere and dirt can be easily removed only by washing with water. Therefore, it is more suitable for applications in the fields such as the dredging industry and the paving industry. In addition, the layer containing carbon-doped titanium oxide or titanium alloy oxide has high rigidity and scratch resistance, so that the surface layer of the device can be peeled off or scraped under normal use in dredging and paving work. There is no.

Next, about the equipment which concerns on the 3rd Embodiment of this invention, FIG. 23 is sectional drawing which shows the equipment which concerns on the 1st Embodiment of this invention. The equipment according to the present embodiment is a cultivation container used in horticulture or agriculture.
The cultivation container shown in FIG. 23 includes a core material 301 and a surface layer 302 disposed outside the core material 301. The core material 301 is made of ceramics, for example. The surface layer 302 is made of titanium, titanium alloy, titanium oxide, or titanium alloy oxide, and at least the outermost surface thereof is doped with carbon in the first or second multifunctional material described above. A layer containing titanium oxide or a titanium alloy oxide is formed. In FIG. 23, the entire surface layer 302 is a carbon-doped titanium oxide or titanium alloy oxide layer.

Such a cultivation container is manufactured as follows. First, as a core material 301, a molded body of a ceramic cultivation container is produced. A film containing titanium, a titanium alloy, titanium oxide, or a titanium alloy oxide is formed on the surface of the core material 301. The method for forming the coating is the same as in the second embodiment. Next, the ceramic cultivation container on which the coating film of titanium or the like is formed is heat-treated under predetermined conditions in the same manner as described in the first or second multifunctional material production method. Thereby, the surface layer 302 is formed. This heat treatment is performed until a layer containing carbon-doped titanium oxide or titanium alloy oxide is formed on at least the surface of the coating.
Furthermore, the cultivation container shown in FIG. 23 is completed by performing a post-process as needed with respect to the cultivation container after heat processing, and making it cool naturally.

  In this way, by forming a layer containing carbon-doped titanium oxide or titanium alloy oxide as a coating on the surface of the core material, the antifouling effect produced by the photocatalytic function of the coating can be obtained in the equipment. Therefore, it is possible to keep the cultivation containers such as flower pots, planters, seedling boxes, bean sprouts, etc. clean, and prevent the cultivation containers from deteriorating due to the adhesion of dirt, and use them for a long time without impairing the beauty. Is possible. In addition, such a high self-cleaning effect of the coating makes it possible to easily remove deposits by simply washing the used cultivation container with water and storing it hygienically until the next use. Become. Furthermore, as described above, in the layer containing carbon-doped titanium oxide or titanium alloy oxide, the texture and color of the surface can be changed by controlling the treatment temperature and treatment time during the heat treatment. Therefore, the equipment which concerns on this embodiment is suitable also for the use to the indoor cultivation container from a design surface.

  In addition to this, the structure having the same structure as the equipment according to the present embodiment, that is, the structure having a non-metallic core material including ceramics, high-temperature heat-resistant glass, and the like, and a film including carbon-doped titanium oxide or titanium alloy oxide, Can also be applied to various fields. For example, paving blocks that are one of road paving materials, paving stones arranged in station premises, and bricks for outer walls that are building materials. The paving block shown in FIG. 24 has a core material 311 formed of ceramics or the like, and a surface layer 312 containing carbon-doped titanium oxide or titanium alloy oxide. The surface layer 312 does not necessarily have to be formed on the entire surface of the core material 311, and may be formed on at least a surface exposed to the road when installed. If a paved road is formed using such a paving block, road cleaning is facilitated by the antifouling effect and self-cleaning effect produced by the photocatalytic function of the surface layer 312, so that the cost required for maintenance can be reduced. Become. Moreover, improvement of the urban environment can be expected by the deodorizing effect and the air cleaning effect produced by the photocatalytic function.

  Or you may apply the structure similar to the equipment which concerns on this embodiment to the equipment around the water in a public facility, a nursing care facility, etc. in which a sanitary environment is always calculated | required. Specifically, in the same manner as the equipment according to the present embodiment, fixtures that generally use ceramic materials, such as toilet bowls, toilet tanks, bathtubs, wall surfaces or floor tiles that are particularly susceptible to contamination, are used. Make it. Thereby, the hygienic environment of the facility can be easily maintained by the antifouling effect and the self-cleaning effect generated by the photocatalytic function of the surface layer. Moreover, the deodorizing effect and air cleaning effect which arise by a photocatalyst function can also be acquired. In the case of equipment that is not required to have high mechanical strength, such as the equipment exemplified above, a layer containing carbon-doped titanium oxide or titanium alloy oxide in the second multifunctional material is formed as a coating. More preferably. Micro is because the surface area of the entire equipment is increased by the fine columnar structure formed on the surface of the second multifunctional material, so that the photocatalytic function is more efficiently expressed.

  In the manufacturing method of equipment according to the first to third embodiments described above, the core material is also heat-treated in order to form a layer containing carbon-doped titanium oxide or titanium alloy oxide. Therefore, the relationship between the melting point or glass transition point of the substance constituting the core material and the heat treatment temperature may be a problem. However, even when a substance having a melting point or glass transition point lower than the heat treatment temperature is used, the heat treatment is performed only in a limited area or the core material is cooled from the side opposite to the heat treatment surface. However, the above problem can be avoided by performing the heat treatment.

Next, the equipment which concerns on the 4th Embodiment of this invention is demonstrated, referring FIG. The equipment according to the present embodiment is an interior tile.
FIG. 25 is a view for explaining the method for manufacturing the equipment according to the present embodiment. The equipment according to the present embodiment is manufactured as follows.

  First, as shown in FIG. 25A, a thin plate 401 containing titanium, a titanium alloy, titanium oxide, or a titanium alloy oxide is prepared. Alternatively, a thin film such as titanium may be prepared instead of a thin plate such as titanium. The thin plate 401 such as titanium is oxidized with carbon-doped titanium oxide or titanium alloy by performing heat treatment under predetermined conditions in the same manner as described in the first or second method for producing a multifunctional material. A layer containing an object is formed. Further, the multi-functional material 402 shown in FIG. 25B is manufactured by subjecting the heat-treated thin plate to post-processing as necessary. Note that the layer containing carbon-doped titanium oxide or titanium alloy oxide may be formed on at least a part of the multifunctional material 402 (for example, the upper surface in FIG. 25B).

  Next, as shown in FIG. 25C, the multifunctional material 402 is joined to the core material 403. As a joining method, a known method such as pressure welding or pasting using an adhesive can be used. Thereby, the equipment shown in (d) of FIG. 25 is completed. The thin plate 401 may be formed in advance according to the shape of the core material, or the multifunctional material 402 may be formed according to the shape of the core material after the heat treatment of the thin plate.

Thus, in this embodiment, since the multifunctional material prepared in advance is joined to the surface of the core material, not only the ceramics constituting the tile but also the core material that cannot withstand heat treatment such as a relatively low melting point. However, a very high photocatalytic function can be imparted. Moreover, in this embodiment, the area | region where a multifunctional material is arrange | positioned can be laid out freely on the surface of a core material. For this reason, it is possible to design the surface of the equipment by partially arranging the multifunctional material or using a plurality of types of multifunctional materials having different colors and textures. In order to change the color and texture of the multifunctional material, the processing conditions such as the heat treatment temperature and time may be changed in the step of heat treating the thin plate 401.
Alternatively, as a modification of the method for manufacturing an equipment material according to the present embodiment, the second multifunctional material described above may be produced, and the thin-film side member peeled off from the substrate may be joined to the core material.

Next, the equipment which concerns on the 5th Embodiment of this invention is demonstrated. The equipment according to the present embodiment is an interior tile.
FIG. 26 is a diagram for explaining the method for manufacturing the equipment according to the present embodiment. The equipment according to the present embodiment is manufactured as follows.

  First, a powdery multifunctional material is produced. For example, the powdery first multifunctional material can be obtained by subjecting a powdery substrate containing titanium to a heat treatment under predetermined conditions. The powdery second multifunctional material can be obtained by producing a second multifunctional material using a substrate such as a thin plate and pulverizing the member on the thin film side separated from the substrate.

  Next, as shown in FIG. 26, the multi-functional material powder 501 is arranged and fixed on the surface of the core material 502 formed in a tile shape. As this fixing method, a known method can be used. For example, a method in which an adhesive is applied to the surface of the core material 502 and the powder 501 of the multi-functional material is dispersed thereon can be considered.

  As described above, in this embodiment, since the powder of the multifunctional material prepared in advance is arranged on the surface of the core material, not only the ceramic forming the tile but also the core material made of a material that cannot withstand heat treatment. In contrast, a very high photocatalytic function can be imparted. In addition, since the area where the powder is arranged can be freely laid out on the surface of the core material 502, it is possible to partially arrange the multifunctional material or use a plurality of types of multifunctional materials having different colors and textures. It is also possible to design the surface of equipment.

  Alternatively, as a method of fixing the multifunctional material powder to the core material, the surface of the core material may be heated and softened, and the multifunctional material powder may be sprayed and pressed from the surface. This method can be used when the core material is formed of resin, glass or the like.

  The present invention relates to horticultural or agricultural equipment, fishing equipment, dredging equipment, paving equipment, building construction equipment, construction equipment, painting equipment, facility equipment, and electrical equipment. It can be used in materials.

It is a figure which shows the result of the film hardness test of Test Example 1. 10 is a diagram showing the results of XPS analysis in Test Example 5. FIG. It is a figure which shows the wavelength response of the photocurrent density of Test Example 6. It is a figure which shows the test result of the light energy conversion efficiency of Test Example 7. It is a figure which shows the result of the deodorizing test of Test Example 8. 10 is a photograph showing the results of an antifouling test in Test Example 9. It is a figure which shows the result of Test Example 11. It is a photograph which shows the light transmission state of the carbon dope titanium oxide layer obtained in Example 11 and 12. 6 is a photograph showing the surface state of the carbon-doped titanium oxide layer obtained in Example 11. FIG. 14 is a photomicrograph showing the state of the multifunctional material obtained in Example 13. It is a microscope picture which shows the state of the thin film side surface of the small piece member 3 which has exposed many fine narrow protrusions which consist of white titanium oxide on a thin film, and the fine pillar standing on a protrusion part. On a large number of continuous narrow-width projections and projections of the small piece member 3 in which a large number of continuous narrow-width projections made of white titanium oxide on the thin film and fine columns standing on the projections are exposed It is a microscope picture which shows the state of the surface of the side where the fine pillar which stands is exposed. It is a microscope picture which shows the state of the layer 2 in which the micro pillar which consists of white titanium oxide stands. It is a graph which shows the result of Test Example 15 (antifouling test). It is a graph which shows the result of Test Example 16 (crystal structure and bonding state). It is a SEM photograph after a heating time of 120 seconds in Example 19. It is a SEM photograph after a heating time of 180 seconds in Example 19. It is a SEM photograph after the heating time of 480 seconds in Example 19. It is a partial cross section perspective view which shows the fishing net which is an equipment material which concerns on the 1st Embodiment of this invention. It is a schematic diagram which shows the shovel to which the structure similar to the equipment which concerns on the 1st Embodiment of this invention is applied. It is sectional drawing in the dashed-dotted line XXI-XXI of FIG. It is sectional drawing which shows the culture | cultivation support | pillar which is an equipment material concerning the 2nd Embodiment of this invention. It is sectional drawing which shows the cultivation container which is an equipment material which concerns on the 3rd Embodiment of this invention. It is sectional drawing which shows the block for paving to which the structure similar to the equipment which concerns on the 3rd Embodiment of this invention was applied. It is a figure for demonstrating the manufacturing method of the equipment which concerns on the 4th Embodiment of this invention. It is a figure for demonstrating the manufacturing method of the equipment which concerns on the 5th Embodiment of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Titanium plate surface 2 Layer in which fine pillars are erected 3 Small piece member 201, 301, 311, 403, 502 in which narrow projection is exposed Core material 102, 112, 202, 302, 312 Surface layer 101, 111 Core material Layer 401 Titanium, titanium alloy, titanium oxide, or thin plate 402 containing titanium alloy oxide Multifunctional material 501 Multifunctional material powder

Claims (11)

A core formed of titanium or a titanium alloy;
A surface layer formed on the surface of the core material, wherein the surface temperature of the core material is 900 ° C. to 1500 ° C. using a combustion flame of a gas containing hydrocarbon as a main component. Heat treatment is performed for a heating time of 400 seconds or less , or only for a heating time of 400 seconds or less under the condition that the surface temperature of the core material is 900 ° C. to 1500 ° C. in a combustion gas atmosphere of a gas containing hydrocarbon as a main component. By the heat treatment, the surface layer made of titanium oxide or titanium alloy oxide doped with carbon in a Ti-C bond state;
Equipment equipped with. With heartwood,
A surface layer formed on the outside of the core material, wherein the surface temperature of the titanium or titanium alloy is 900 ° C. to 1500 ° C. using a gas combustion flame mainly composed of hydrocarbon. A condition in which the surface temperature of the titanium or titanium alloy is 900 ° C. to 1500 ° C. in a combustion gas atmosphere of a gas containing hydrocarbon as a main component, or heat treatment for 400 seconds or less under the condition of The surface layer is made of titanium oxide or titanium alloy oxide in which at least the outermost surface is doped with carbon in a Ti-C bond state by heat treatment for 400 seconds or less at
Equipment equipped with.   The equipment according to claim 1 or 2, wherein the surface layer has a Vickers hardness of 300 or more.   The equipment according to claim 3, wherein the surface layer has a Vickers hardness of 1000 or more. It said core is formed of a metal or alloy, according to claim 2 Symbol mounting materials and equipment of. The core is formed by non-metal, according to claim 2 Symbol mounting materials and equipment of. The equipment according to claim 6 , wherein the core material is made of ceramics. The equipment according to any one of claims 1 to 7 , wherein the core material is previously formed into a finished product shape. The equipment according to any one of claims 1 to 8 , wherein the surface layer contains carbon at 0.3 to 15 at%. The titanium alloy is Ti-6Al-4V, Ti-6Al-6V-2Sn, Ti-6Al-2Sn-4Zr-6Mo, Ti-10V-2Fe-3Al, Ti-7Al-4Mo, Ti-5Al-2.5Sn. Ti-6Al-5Zr-0.5Mo-0.2Si, Ti-5.5Al-3.5Sn-3Zr-0.3Mo-1Nb-0.3Si, Ti-8Al-1Mo-1V, Ti-6Al-2Sn -4Zr-2Mo, Ti-5Al-2Sn-2Zr-4Mo-4Cr, Ti-11.5Mo-6Zr-4.5Sn, Ti-15V-3Cr-3Al-3Sn, Ti-15Mo-5Zr-3Al, Ti-15Mo The equipment according to any one of claims 1 to 9 , comprising -5Zr or Ti-13V-11Cr-3Al. The equipment is horticultural or agricultural equipment, fishery equipment, dredging equipment, paving equipment, building construction equipment, construction equipment, painting equipment, facility equipment, or The equipment according to any one of claims 1 to 10 , comprising an electrical equipment material.