JP2010047475A - Glass product having multifunctional film, and method for production thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a glass product having a multifunctional film which is excellent in durability (high hardness and resistance to abrasion, chemicals, heat or the like) as a surface layer, can express super-hydrophilicity and functions as a visible light-response type photocatalyst, and also to provide a method for production thereof. <P>SOLUTION: The glass product has the multifunctional film comprising a titanium oxide or titanium alloy oxide on at least a part of the surface of which carbon is doped in such a state as a Ti-C bond, or has the multifunctional film, on the surface of which bristles of fine poles comprising the titanium oxide or titanium alloy oxide are erected in which carbon is preferably doped in such a state as the Ti-C bond. The method for production of the glass product is also provided. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a glass product having a multifunctional film and a method for producing the same, and more specifically, functions as a visible light responsive photocatalyst, can exhibit super hydrophilicity, and has durability (high hardness, scratch resistance, The present invention relates to a glass product having a multifunctional film excellent in wear resistance, chemical resistance, and heat resistance, and a method for producing the same.

Conventionally, a substance exhibiting a photocatalytic function has been applied to the surface of a glass product for the purpose of imparting antifouling properties, hydrophilicity, antifogging properties, deodorizing properties, antibacterial properties, etc. (for example, patents) References 1-3). As a substance exhibiting a photocatalytic function, titanium dioxide TiO ₂ (simply referred to as titanium oxide in the present specification, claims, and abstract) is known.

  In the case of forming a photocatalytic film capable of deodorizing, antibacterial, anti-fogging and antifouling by such a photocatalytic function, in general, a titanium oxide sol is applied onto a substrate by spray coating, spin coating, dipping or the like. The film is formed by applying (see, for example, Patent Documents 4 to 6). However, since the film formed in this way is easily peeled off or worn, it has been difficult to use it for a long time. Moreover, the method of forming a photocatalyst membrane | film | coat by sputtering method is also known (for example, refer patent documents 7-8).

  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 the sol solution is applied to the crystal nuclei, solidified, and heat-treated. It has been reported that by growing a titanium oxide crystal from the crystal nucleus, the crystal shape of the titanium oxide crystal grown from the crystal nucleus forms a columnar crystal, thereby obtaining a highly active photocatalytic function (for example, (See Patent Documents 9 to 11). 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.

  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, there is a report that nitrogen-doped titanium oxide is superior as a visible light responsive photocatalyst as compared with titanium oxide doped with F, N, C, S, P, Ni or the like (see Non-Patent Document 1). .

  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 12 to 15). However, a film made of such a photocatalyst is not always satisfactory in terms of durability such as wear resistance.

JP 09-071437 A JP 2001-150586 A JP 2001-246265 A 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 2002-253975 A JP 2002-370027 A JP 2002-370034 A JP 2001-205103 A JP 2001-205094 A JP 2002-95976 A WO 01/10553 pamphlet

R. Asahi et al., SCIENCE Vol. 293, July 13, 2001, p. 269-271

  Conventional titanium oxide-based photocatalytic coatings have a problem in durability (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance) for both UV-responsive and visible-light-responsive types. It has not been satisfactory as a multifunctional film that has become a bottleneck in practical use or can exhibit super hydrophilicity and functions as a visible light responsive photocatalyst.

  The first object of the present invention is excellent in durability (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance) as a surface layer, can exhibit super hydrophilicity, and has a visible light response. It is providing the glass product which has a multifunctional membrane | film | coat which functions as a type | mold photocatalyst, and its manufacturing method.

  In addition, the second object of the present invention is that the surface area is large and carbon is doped in a Ti-C bond state, has high activity as a photocatalyst, functions as a visible light responsive photocatalyst, and easily absorbs VOC. Another object of the present invention is to provide a glass product having a multi-functional film that is high in hardness and excellent in peel resistance, abrasion resistance, chemical resistance, and heat resistance, and a method for producing the same.

  Another object of the present invention is a multi-functionality that has high activity as a photocatalyst and functions as a visible light responsive photocatalyst, and also has a relatively high hardness, exfoliation resistance, abrasion resistance, chemical resistance, and heat resistance. It is providing the glass product which has a conductive film, and its manufacturing method.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have determined the surface of a film made of titanium, titanium alloy, titanium alloy oxide, or titanium oxide provided on at least a part of the surface of the glass molded article. Carbon is doped with Ti-C bonds by heat treatment at a high temperature using a gas flame containing unsaturated hydrocarbons as the main component, and durability (high hardness, scratch resistance, abrasion resistance) The present invention was completed by finding that a multi-functional film excellent in wearability, chemical resistance, and heat resistance) and capable of functioning as a visible light responsive photocatalyst can be formed.

  That is, the glass product of the present invention has a multifunctional film made of titanium oxide or a titanium alloy oxide in which carbon is doped in a Ti-C bond state on at least a part of the surface ( Hereinafter, it is set as the first aspect).

  In the method for producing a glass product of the present invention, the surface of a film made of titanium, a titanium alloy, a titanium alloy oxide, or titanium oxide provided on at least a part of the surface of a glass molded product is mainly composed of hydrocarbon. Directly apply a gas combustion flame to heat the surface temperature of the coating to be 900-1500 ° C., or treat the surface of the coating with unsaturated hydrocarbons so that the surface temperature is 900-1500 ° C. Heat-treating in a combustion gas atmosphere of a gas as a main component to form a multifunctional film composed of titanium oxide or titanium alloy oxide in which carbon is doped in a Ti-C bond state (Hereinafter referred to as the first production mode).

  Further, as a result of separate investigations to achieve the above object, the present inventors have determined that the surface of the film made of titanium, titanium oxide, titanium alloy, or titanium alloy oxide provided on at least a part of the surface of the glass molded product. Or a hydrocarbon, preferably an unsaturated hydrocarbon, particularly an acetylene combustion flame, directly subjected to heat treatment under specific conditions, or the surface of the coating is hydrocarbon, preferably unsaturated hydrocarbon, under specific conditions In particular, by performing heat treatment in an acetylene combustion exhaust gas atmosphere, a layer in which fine columns made of titanium oxide or titanium alloy oxide are formed is formed inside the coating, and the fine columns are The layer is cut in a direction along the surface of the coating to expose the fine columns, so that the surface area is large and the carbon is doped, preferably the carbon is in a Ti-C bond state. It is doped, has high activity as a photocatalyst, functions as a visible light responsive photocatalyst, can easily adsorb VOC, has high hardness, and has excellent peeling resistance, abrasion resistance, chemical resistance, and heat resistance The present inventors have found that a multi-functional film can be formed and completed the present invention.

  That is, the glass product of the present invention has a multifunctional film made of titanium oxide or titanium alloy oxide in which carbon is doped in a Ti-C bond state on at least a part of the surface, and the multifunctional A fine column made of titanium oxide or titanium alloy oxide doped with carbon, preferably titanium oxide or titanium alloy oxide doped with carbon in a Ti-C bond state stands on the surface of the film. (Hereinafter, referred to as a second aspect).

  Further, the method for producing a glass product of the present invention comprises a hydrocarbon, preferably unsaturated, on the surface of a film made of titanium, titanium oxide, titanium alloy or titanium alloy oxide provided on at least a part of the surface of the glass molded product. A fine flame made of titanium oxide or titanium alloy oxide is formed inside the coating by directly applying a combustion flame of a gas containing hydrocarbon as a main component and heat-treating the coating so that the surface layer temperature becomes 600 ° C. or higher. A layer in which the pillars are erected is formed, and then the layer in which the fine pillars are erected is cut in a direction along the surface of the coating to expose the fine pillars, and is preferably doped with carbon. A multi-functional film made of titanium oxide or titanium alloy oxide in which carbon is doped in a Ti—C bond state is formed (hereinafter referred to as a second production mode).

  The multi-functional film of the glass product of the present invention has excellent durability (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance), can exhibit super hydrophilicity, and has a visible light response. It functions as a type photocatalyst, or has a large surface area and is doped with carbon, preferably doped with carbon in a Ti-C bond state, and has a high activity as a photocatalyst and functions as a visible light responsive photocatalyst VOC can also be easily adsorbed, has high hardness, and is excellent in peel resistance, wear resistance, chemical resistance and heat resistance.

FIG. 1 is a view showing the results of the film hardness test of Test Example 1. FIG. FIG. 2 is a diagram showing the results of XPS analysis in Test Example 5. FIG. 3 is a graph showing the wavelength response of the photocurrent density in Test Example 6. FIG. 4 is a diagram showing test results of light energy conversion efficiency in Test Example 7. FIG. 5 is a diagram showing the results of the deodorization test of Test Example 8. FIG. 6 is a photograph showing the results of the antifouling test of Test Example 9. FIG. 7 is a diagram showing the results of Test Example 11. FIG. 8 is a photograph showing the light transmission state of the carbon-doped titanium oxide layers obtained in Examples 11 and 12. FIG. 9 is a photograph showing the surface state of the carbon-doped titanium oxide layer obtained in Example 12. FIG. 10 is a photomicrograph showing the state of the multifunctional material obtained in Example 13. 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 on the thin film and fine columns standing on the protrusions are exposed. is there. FIG. 12 shows a number of continuous narrow-width protrusions made of white titanium oxide on a thin film and a number of continuous narrow-width protrusions of a small piece member 3 in which fine columns standing on the protrusions are exposed. It is a microscope picture which shows the state of the surface of the side where the fine pillar standing on the protrusion part is exposed. FIG. 13 is a photomicrograph showing the state of the layer 2 in which fine columns made of white titanium oxide stand. FIG. 14 is a graph showing the results of Test Example 15 (antifouling test). FIG. 15 is a graph showing the results of Test Example 16 (crystal structure and bonding state).

  The shape of the glass product having the multifunctional film of the present invention is not particularly limited, for example, plate glass such as window glass, glass cooking utensils such as heat-resistant glass pans, glass storage containers, glass tableware, It may be a glass seasoning container, a glass cup, a glass laboratory instrument such as a beaker, a flower bottle, a mirror or the like.

  The glass product having a multifunctional film of the present invention is formed by sputtering, vapor deposition, thermal spraying, or the like, on a surface of at least a part of a glass molded product, a film made of titanium, titanium alloy, titanium alloy oxide, or titanium oxide. Or by applying a commercially available titanium oxide sol by spray coating, spin coating or dipping to form a film, followed by heat treatment at a high temperature using a combustion flame of a gas mainly composed of unsaturated hydrocarbons. Can be manufactured.

  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 a glass product having a multifunctional film of the present invention, a combustion flame of a gas mainly containing an unsaturated hydrocarbon, particularly acetylene, can be used, and it is particularly desirable to use a reducing flame. In the production of a glass product having a multifunctional film of the present invention, the gas containing unsaturated hydrocarbon as a main component means a gas containing at least 50% by volume of unsaturated hydrocarbon, such as at least acetylene. It means a gas containing 50% by volume and appropriately mixed with air, hydrogen, oxygen and the like. In the production of a glass product having a multifunctional film of the present invention, the gas mainly containing an unsaturated hydrocarbon preferably contains 50% by volume or more of acetylene, and the unsaturated hydrocarbon is 100% acetylene. Is most preferred. When unsaturated hydrocarbons, especially acetylene having a triple bond, are used, in the process of combustion, especially in the reducing flame part, the unsaturated bond part decomposes to form an intermediate radical substance. It is considered that carbon doping is likely to occur because of its high activity.

  In the production of a glass product having a multifunctional film according to the present invention, when the film to be heat-treated is titanium or a titanium alloy, oxygen that oxidizes the titanium or titanium alloy is necessary, and air or oxygen corresponding to that amount is required. Need to contain.

  In the production of the glass product having the multifunctional film of the present invention, the surface of the film made of titanium, titanium alloy, titanium alloy oxide or titanium oxide is used with a gas combustion flame mainly composed of unsaturated hydrocarbons. In this case, even if heat treatment is performed at a high temperature by directly applying a flame of unsaturated hydrocarbon as a main component to the surface of the film, the surface of such a film is unsaturated. Heat treatment may be performed at a high temperature in a combustion gas atmosphere of a gas containing hydrocarbon as a main component, and the heat treatment can be performed in a furnace, for example. When heat treatment is performed at a high temperature by directly applying a combustion flame, the above-described fuel gas is burned and the combustion flame is applied to the surface of the coating. When heat treatment is performed in a combustion gas atmosphere at a high temperature, the above fuel gas is burned in a furnace and the high-temperature combustion gas atmosphere is used.

  Regarding the heat treatment in the first production mode, for example, the surface temperature of the film is 900 to 1500 ° C., preferably 1000 to 1200 ° C., and the heat treatment time is doped with carbon in a state of Ti—C bonds. The time is sufficient to obtain a multifunctional film. This heat treatment time is correlated with the heating temperature, but is preferably about 400 seconds or less.

  In the production of a glass product having a multifunctional film of the present invention, carbon containing 0.3 to 15 at%, preferably 1 to 10 at%, is contained in the Ti—C bond by adjusting the heating temperature and the heat treatment time. Thus, a multifunctional film doped in the above state can be obtained relatively easily. In the first embodiment, when the carbon doping amount is small, the multifunctional film is transparent, and as the carbon doping amount increases, the multifunctional film becomes translucent and opaque. Therefore, it is excellent in durability (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance) by forming a transparent multifunctional film on the surface of the glass molded article, and a visible light responsive photocatalyst. A transparent plate that functions as a glass can be obtained, and durability (high hardness, scratch resistance, abrasion resistance) can be obtained by forming a transparent multifunctional film on the surface of a glass molded product having a colored pattern on the surface. A decorative glass plate that is excellent in properties, chemical resistance, and heat resistance and functions as a visible light responsive photocatalyst. In addition, when the thickness of the film made of titanium, titanium alloy, titanium alloy oxide or titanium oxide is 500 nm or less, when heated to the vicinity of the melting point of the film, many small island-like undulations floating in the sea are formed on the surface. It is translucent.

  In the glass product having the multifunction film of the first aspect of the present invention, the thickness of the multifunction film made of titanium oxide or titanium alloy oxide in which carbon is doped in a Ti-C bond state is 10 nm. Preferably, the thickness is 50 nm or more in order to achieve high hardness, scratch resistance, and wear resistance. When the thickness of the multifunctional film is less than 10 nm, the durability 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.

  The glass product having the multifunctional film of the present invention contains a relatively large amount of carbon, and doped carbon is contained in a Ti-C bond state. 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 multifunctional film of the glass product of the first aspect of the present invention has a Vickers hardness of 300 or more, preferably 500 or more, more preferably 700 or more, and most preferably 1000 or more. A Vickers hardness of 1000 or more is harder than that of hard chrome plating.

  The multifunctional film of the glass product of the present invention responds not only to ultraviolet rays but also visible light having a wavelength of 400 nm or more, and acts effectively as a photocatalyst. Therefore, since the multifunctional film of the glass product of the present invention functions as a visible light responsive photocatalyst, it exhibits a photocatalytic function not only outdoors but also indoors. Moreover, the multifunctional film of the glass product of the present invention exhibits super hydrophilicity with a contact angle of 3 ° or less.

  Furthermore, the multifunctional film of the glass product of the present invention is excellent in chemical resistance, and after being immersed in an aqueous solution of 1M sulfuric acid and 1M sodium hydroxide for one week, the film hardness, abrasion resistance, and photocurrent density. Were measured, and compared with those measured before 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.

  In the second production mode of the present invention, hydrocarbon, preferably unsaturated carbonization, is formed on the surface of the film made of titanium, titanium oxide, titanium alloy or titanium alloy oxide provided on at least a part of the surface of the glass molded product. A fine column made of titanium oxide or a titanium alloy oxide is formed inside the coating by directly applying a combustion flame of a gas containing hydrogen as a main component and heat-treating the coating so that the surface layer temperature becomes 600 ° C. or higher. Forming a forested layer, and then applying, for example, thermal stress, shear stress, and tensile force to cut the layer in which the microcolumns stand in a direction along the surface of the coating; A multifunctional coating comprising titanium oxide or titanium alloy oxide doped with carbon, preferably titanium oxide or titanium alloy oxide doped with carbon in a Ti-C bond state. It is formed.

  In the second production mode of the present invention, the thickness (amount) of the film on the surface of the glass molded article is comparable to the amount of the layer in which fine columns made of titanium oxide or titanium alloy oxide are formed. (I.e., the entire film becomes a layer in which fine columns made of titanium oxide or titanium alloy oxide stand) or thicker (i.e., in the thickness direction of the film). A fine column partly made of titanium oxide or titanium alloy oxide becomes a forested layer, and the rest remains without becoming a fine column). The thickness of this film is preferably 0.5 μm or more, more preferably 4 μm or more.

  For the heat treatment in the second production mode, a layer in which fine columns made of titanium oxide or titanium alloy oxide are erected is formed inside the film made of titanium, titanium oxide, titanium alloy or titanium alloy oxide, Next, heat, shear stress, and tensile force are applied, for example, so that the layer in which the fine pillars are erected can be cut in a direction along the surface of the coating to expose the fine pillars. It is necessary to adjust temperature and heat treatment time. This heat treatment is preferably performed at a temperature of 600 ° C. or higher.

  By performing the heat treatment under such conditions, the height of the layer in which the fine pillars stand is about 1 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 to 3 μm are formed. Thereafter, for example, by applying a thermal stress, a shear stress, or a tensile force, the layer in which the fine pillars are erected is cut in a direction along the surface of the coating, whereby the fine pillars can be exposed.

  When cutting a layer in which fine columns are erected by applying thermal stress in a direction along the surface of the film, for example, by cooling or heating the glass side (back surface) or the film side (front surface) A temperature difference is provided between them. As this cooling method, for example, either the surface or the back surface of the hot intermediate is brought into contact with a cooling object, such as a stainless steel block, or cold air (room temperature air) is applied to either the surface or the back surface of the hot intermediate. Spray.

  When shearing stress is applied to cut a layer in which fine columns are erected in a direction along the surface of the film, for example, a relatively reverse force is applied to the front and back surfaces of the intermediate by frictional forces. . Further, in the case where a layer in which fine columns are erected by applying a tensile force is cut in a direction along the surface of the film, for example, the surface and the back surface of the intermediate body described above are removed by using a vacuum suction disk or the like. Pull in the opposite direction in the vertical direction. The fine pillars can be exposed also by polishing, sputtering, or the like.

  The height of the layer where the fine column stands is changed depending on the height position of the fine column which cuts the layer where the fine column stands along the surface of the film. The height is generally about 1 to 20 μm, and the average thickness of the fine columns is about 0.5 to 3 μm. This multifunctional film can easily adsorb VOCs, has a large surface area, has high activity as a photocatalyst, and also has high film hardness, excellent peeling resistance, abrasion resistance, chemical resistance, and heat resistance. It is a functional material.

  On the other hand, on the thin film obtained as described above, a large number of continuous narrow protrusions made of titanium oxide or titanium alloy oxide and members with exposed fine columns standing on the protrusions are small. The height of the protrusion on each small piece is about 2 to 12 μm, and the height of the fine column is a fine column obtained by cutting the layer in which the fine column stands in the direction along the surface of the film. Although it varies depending on the height position, the height of the layer in which the fine pillars stand is generally about 1 to 5 μm, and the average thickness of the fine pillars is about 0.2 to 0.5 μm. However, depending on the conditions for cutting the layer in which the fine pillars are erected in the direction along the surface of the film, there are cases where a large number of continuous narrow protrusions are exposed with almost no fine pillars. These members can also adsorb VOC and have a large surface area, so that they have high activity as a photocatalyst. The pulverized material of this member can easily adsorb VOC and has a large surface area, and therefore has high activity as a photocatalyst. Therefore, it can be used by fixing it to the surface of a glass molded product using an inorganic binder. Here, examples of the inorganic binder include alkoxy silanes such as ethyl silicate, partial condensates of alkoxy silanes, and silica sols.

  The shape of each fine column of the layer in which fine columns made of titanium oxide or titanium alloy oxide are erected, as judged from the micrographs of FIGS. 1, 4 and 6, are prismatic and cylindrical. , Pyramids, cones, inverted pyramids, inverted cones, etc., extending straight or perpendicular to the surface of the substrate, extending while curving or bending, branching into branches And those that are in the form of composites. 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.

  It is to be noted that a powder having at least a surface layer made of titanium, titanium alloy, titanium alloy oxide or titanium oxide is introduced into a flame and is kept in the flame for a predetermined time to be heat-treated, or such powder is in a fluid state. By maintaining in a fluidized bed state in a high-temperature combustion gas for a predetermined time, the entire particle is made into carbon-doped titanium oxide doped with carbon in a Ti-C bond state, or carbon is doped in a Ti-C bond state. In addition, since such a powder also has high activity as a photocatalyst, it can be used by fixing it to the surface of a glass molded article using an inorganic binder. 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. Here, examples of the inorganic binder include alkoxysilanes such as ethyl silicate, partial condensates of alkoxysilanes, and silica sols.

Below, this invention is demonstrated further in detail based on an Example, a test example, and a comparative example.
Examples 1-3 (reference examples)
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 a molecular structure of TiO _2-x C _x based on the carbon content, carbon content 8at% for Example 1, TiO _1.76 C _0.24, carbon content of about 3.3At% for Examples 2, TiO _1.90 C _0.10 and Example 3 had a carbon content of 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 film whose adhesion was improved by heating was formed.

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 film of Comparative Example 2.

Test Example 1 (Vickers hardness)
For the carbon-doped titanium oxide layer in which the carbon obtained in Example 1 was doped in a Ti—C bond state and the titanium oxide film of Comparative Example 1, an indenter was formed using a nanohard nesting device (NHT) (manufactured by CSM Instruments, Switzerland) : Belkovic type, test load: 2 mN, load unloading speed: 4 mN / min. When film hardness was measured, carbon-doped titanium oxide layer doped with carbon in Example 1 in a Ti-C bond state Had a high Vickers hardness 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 doped with the carbon of Example 1 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 titanium oxide layer doped with carbon in Ti-C bond state)
The titanium oxide layer doped with carbon in Example 1 in a Ti—C bond state was subjected to Ar ion sputtering for 2700 seconds using an X-ray photoelectron spectrometer (XPS) with an acceleration voltage of 10 kV and a target of Al. Analysis 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 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. Accordingly, 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 films 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 j _p 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 to 10 at%. On the other hand, in the titanium oxide films of Comparative Examples 1 and 2, it was confirmed that the photocurrent density was extremely small and the wavelength absorption edge was about 410 nm.

Test example 7 (light energy conversion efficiency)
For the carbon-doped titanium oxide layer in which the carbons of Examples 1 to 3 are doped in a Ti—C bond state and the titanium oxide films of Comparative Examples 1 and 2, the formula η = j _p (E _ws −E _app ) / I
The light energy conversion efficiency η defined by Here, E _ws is the theoretical decomposition voltage of water (= 1.23 V), E _app 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 to 380 nm) of the 1 and 2 titanium oxide films 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. The surface area of each 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, 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 carried out 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 was attached 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 to 7 (reference examples)
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
The Vickers hardness (HV) of the carbon-doped titanium oxide layers of Examples 4 to 7 and the film of Comparative Example 3 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 the combustion gas of natural gas so that the surface temperature became 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 films 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. Figure 7 shows the resulting photocurrent density j _p with respect to the potential ECP (Vvs. 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 becomes 1000 to 1200 ° C. have relatively high photocurrent density and are excellent. all right. 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 (reference example)
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 (reference example)
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 to 16 (reference examples)
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 plurality of continuous narrow protrusions made of white titanium oxide and small piece members 3 in which fine pillars standing on the protrusions are exposed remain in a part on the layer 2. ing. 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 pillars standing on the protrusion are exposed, and FIG. 13 shows the state of the layer 2 where the fine pillars made of white titanium oxide are 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.

Test Example 12 (Scratch hardness test: pencil method)
Examples 13-18 About the fine column side surface of the member from which the layer which the fine column stands on the obtained board | substrate surface is exposed, based on JISK5600-5-4 (1999), Mitsubishi Pencil Co., Ltd. make A pencil scratch hardness test was performed 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 when 9H pencils were used for all the test pieces, and it was confirmed that the specimens had high heat resistance.

Test Example 15 (Anti-fouling test)
As a sample, a titanium plate surface area 8 cm ² having a titanium oxide film obtained in the member and Comparative Example 1 the surface area 8 cm ² of the layer minute columns the resulting substrate surface in Example 16 is bristled is exposed A deodorization 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 aqueous methylene blue 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 1. 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 diffraction (XRD) on the sample obtained from the fine column of the member in which the layer in which the fine column is erected on the substrate surface obtained in Example 15 is exposed, it has a rutile-type 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.

  As described above, the glass product of the present invention is excellent in durability (high hardness, scratch resistance, abrasion resistance, chemical resistance, heat resistance), can exhibit super hydrophilicity, and is a visible light responsive photocatalyst. Because it has a multifunctional film that functions as, for example, it can achieve antifouling properties, deodorizing properties, antibacterial properties, antifogging properties, environmental purification properties, etc. by providing it on window glass, and heat resistance It can withstand the damage caused by scratches, which is a drawback of heat-resistant glass, by providing it in glass pots and glass seasoning containers, and it can be kept hygienic by disposing deposits on glass seasoning containers. Yes.

Claims (16)

  A glass product comprising a multifunctional film made of titanium oxide or titanium alloy oxide in which carbon is doped in a Ti-C bond state on at least a part of the surface.   The glass product according to claim 1, wherein the multifunctional film has a Vickers hardness of 300 or more.   The glass product according to claim 2, wherein the multifunctional film has a Vickers hardness of 1000 or more.   At least a part of the surface has a multifunctional film made of titanium oxide or titanium alloy oxide doped with carbon, and the surface of the multifunctional film is doped with carbon dioxide or titanium oxide The glass product according to claim, wherein fine pillars made of oxide stand.   The glass product according to claim 4, wherein carbon is doped in a Ti-C bond state.   The glass product according to any one of claims 1 to 5, wherein the multifunctional film contains 0.3 to 15 at% of carbon.   The glass product according to claim 1, wherein the multifunctional film functions as a visible light responsive photocatalyst.   The glass product according to any one of claims 1 to 7, wherein the multifunctional film can exhibit super hydrophilicity.   The glass product according to claim 1, wherein the multifunctional film is excellent in durability.   The glass product according to claim 1, wherein the multifunctional film is transparent or translucent.   Titanium alloys are 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 The glass product according to claim 1, wherein the glass product is Ti-13V-11Cr-3Al.   The glass product is a plate glass, a glass cooking utensil, a glass storage container, a glass tableware, a glass seasoning container, a glass cup, a glass laboratory utensil, a flower bottle, or a mirror. The glass product in any one of.   The coating is obtained by directly applying a flame of unsaturated hydrocarbon as a main component to the surface of a coating made of titanium, titanium alloy, titanium alloy oxide or titanium oxide provided on at least a part of the surface of the glass molded article. In a combustion gas atmosphere of a gas mainly composed of unsaturated hydrocarbons so that the surface temperature of the coating film becomes 900 to 1500 ° C. A multi-functional film made of titanium oxide or titanium alloy oxide in which carbon is doped in a Ti-C bond state is formed by heat treatment at 1 to 6. The manufacturing method of the glass product in any one.   The surface of the film is formed by directly applying a combustion flame of a gas mainly composed of hydrocarbon to the surface of the film made of titanium, titanium oxide, titanium alloy or titanium alloy oxide provided on at least a part of the surface of the glass molded article. By performing heat treatment so that the layer temperature is 600 ° C. or higher, a layer in which fine columns made of titanium oxide or titanium alloy oxide are erected is formed inside the film, and then the fine columns are erected. A multi-functional film made of titanium oxide or titanium alloy oxide doped with carbon is formed by cutting the layer in a direction along the surface of the film to expose the fine columns. Item 5. A method for producing a glass product according to Item 4.   The coating is formed by directly applying a combustion flame of a gas mainly composed of an unsaturated hydrocarbon to the surface of a coating made of titanium, titanium oxide, a titanium alloy or a titanium alloy oxide provided on at least a part of the surface of the glass molded product. Heat treatment is performed so that the surface layer temperature of the film becomes 600 ° C. or more, thereby forming a layer in which fine columns made of titanium oxide or titanium alloy oxide stand in the film, and then the fine columns are A multi-functional film made of titanium oxide or a titanium alloy oxide in which carbon is doped in a Ti-C bond state by cutting the layer in a direction along the surface of the film, exposing the fine columns The method for producing a glass product according to claim 5, wherein:   At least a part of the surface of the glass molded article is fixed with particles made of titanium oxide or titanium alloy oxide in which carbon is doped in a Ti-C bond state using an inorganic binder, and the carbon is Ti-C bonded. The method for producing a glass product according to any one of claims 1 to 3 and 5 to 12, wherein a multifunctional film made of titanium oxide or titanium alloy oxide doped in the state of is formed.