JP2007015876A - Bent glass article and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bent glass article in which transparency of the deep-bent region is improved while clouding or lowering of transparency due to dew formation is suppressed. <P>SOLUTION: This bent glass article of the invention is provided with a glass member including a deep-bent region, and a group of metal oxide particles having an average height of 10-150 nm formed on the surface of the glass member at least including the deep-bent region. The group of metal oxide particles is at least one kind selected from titanium oxide, zirconium oxide, indium oxide, zinc oxide and tin oxide formed by e. g. a chemical vapor phase growth method. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a bent glass article subjected to deep bending and a method for producing the same. More specifically, the present invention relates to a bent glass article having improved transparency in a deep-bent region while suppressing cloudiness due to condensation or a decrease in transparency, and a method for manufacturing the same.

  Deeply bent glass has been used in food cases represented by lids such as pans and hot plates, Chinese buns warmers or Chinese buns steamers. The deeply bent glass is suitable for the above-mentioned applications in terms of its function of being rich in design and being able to visually recognize articles such as food in a container from multiple directions.

  However, for example, when the inside of the case is kept warm and humidified, such as a Chinese manju warmer, the temperature difference between the inside of the case and the outside air is large, and there is a large amount of steam inside the case, so it was deeply bent. Condensation is likely to occur on the glass. When dew condensation occurs on the deeply bent glass, the inside of the case becomes difficult to see from the outside, and the function of the glass to make the product inside the case visible from the outside is impaired.

  As a technique for preventing the glass from fogging due to condensation, it is known to make the inside of the deeply bent glass hydrophilic. As an example of the technique related to the hydrophilic treatment of glass, for example, Patent Document 1 can be cited.

JP-A-8-119673

  As described above, as a means for suppressing the fogging of the glass, it is effective to impart hydrophilicity to the glass surface by forming a concavo-convex film made of a group of metal oxide particles on the glass surface. However, in the conventional bent glass article, when the glass is deep-bent, stress is applied to the concavo-convex film composed of the metal oxide particle group, and the metal oxide particle group peels off from the glass surface. Separation of the metal oxide particle group impairs the hydrophilicity of the glass surface. Moreover, the cloudiness generate | occur | produces on the glass surface by the density of peeling, and the problem of losing transparency also generate | occur | produces.

  The present invention has been made in view of these problems, and an object of the present invention is to provide a bent glass article having improved transparency in a deep bending region and a method for producing the same while suppressing fogging due to condensation or a decrease in transparency. .

  One aspect of the present invention is a bent glass article. The bent glass article includes a glass member including a deep bending region and a metal oxide particle group having an average height of 10 nm to 150 nm formed on the surface of the glass member including at least the deep bending region. To do.

  Here, the “deep bending region” refers to a region bent to a radius of curvature of 200 mm or less. According to this aspect, the metal oxide particle group is suppressed from peeling from the glass surface in the deep bending region. Moreover, hydrophilicity is imparted to the glass surface by the metal oxide particle group, and even in the presence of water vapor, clouding due to water droplets hardly occurs, and the haze ratio is kept at 5% or less. As a result, a bent glass article having improved transparency over the entire surface including the deep bending region is provided. In addition, although the area | region where the metal oxide particle group which falls in the range of the above-mentioned average height is formed may be the whole surface of any surface of the bent glass article, at least the above-mentioned glass surface in the deep bent area. The metal oxide particle group which falls in the range of average height should just be formed.

  In the above aspect, it is preferable that the metal oxide particle group covers at least 50% to 90% of the surface of the glass member including the deep bending region.

  In the above aspect, the metal oxide particle group is preferably a tin oxide particle group or a titanium oxide particle group.

  In the said aspect, it is preferable that the metal oxide particle group was formed in the surface of the glass member by the chemical vapor deposition method.

  The said aspect WHEREIN: It is preferable to further provide the at least 1 sort (s) of functional film chosen from the hydrophilic film | membrane and antifouling film | membrane which coat | covers a metal oxide particle group.

  In the above aspect, the glass member contains an alkali component, and the alkali barrier film formed on at least one selected between the glass member and the metal oxide particle group, and between the metal oxide particle group and the functional film. It is preferable to further provide.

  In the above aspect, the alkali barrier film preferably contains as a main component at least one selected from silicon oxide, aluminum oxide, silicon oxycarbide, and silicon oxynitride.

  Another aspect of the present invention is a method for producing a bent glass article. The bent glass article is produced by forming a group of metal oxide particles having an average height of 10 nm or more and 150 nm or less on a flat glass member by chemical vapor deposition using a raw material gas containing a metal compound and an oxidizing agent. And a bending step of forming a deep bending region having a radius of curvature of 200 mm or less by heating the glass member to a softening temperature and bending the softened glass article according to the mold. It is characterized by.

  According to this aspect, since the glass surface does not peel off due to stress due to deep bending of the metal oxide particle group, film peeling does not occur in the deep bending region, and a transparent hydrophilic bent glass as a whole is obtained.

  In the above aspect, in the metal oxide particle group forming step, the metal oxide particle group is preferably formed so as to cover at least 50% to 90% of the surface of the glass member including the deep bending region.

  In the above aspect, it is preferable that a tin oxide particle group or a titanium oxide particle group is formed as the metal oxide particle group in the metal oxide particle group forming step.

  In the above aspect, it is preferable that the glass member further includes a step of forming an alkali barrier film between the glass member and the metal oxide particle group by a chemical vapor deposition method.

  The said aspect WHEREIN: It is preferable to further provide the process of coat | covering a metal oxide particle group with the at least 1 sort (s) of functional film chosen from a hydrophilic film | membrane and an antifouling film | membrane.

  In the above aspect, the glass member contains an alkali component, and an alkali barrier film is formed in the chemical vapor phase at least one selected from the glass member and the metal oxide particle group and between the metal oxide particle group and the functional film. It is preferable to further include a step of forming by a growth method.

  A combination of the above-described elements as appropriate can also be included in the scope of the invention for which patent protection is sought by this patent application.

  According to the present invention, a bent glass article is provided in which fogging of the glass surface is suppressed and the transparency of the deeply bent region is improved.

  The bent glass article according to the embodiment of the present invention includes a deep bending region having a curvature radius of 200 mm or less. The deep bending region is formed by bending a flat glass member. In the bent glass article according to the embodiment, metal oxide particle groups are formed at least on the glass surface in the deep bending region. By this metal oxide particle group, an uneven structure is formed on the glass surface, and hydrophilicity is imparted to the glass surface. The bending direction of the glass member is not particularly limited, and the glass surface on which the metal oxide particle group is formed may be the inner side or the outer side, but from the viewpoint of suppressing peeling of the metal oxide particle group, the metal oxide particle The glass surface on which the group is formed is preferably inside.

  The average height of the metal oxide particle group is preferably from 10 nm to 150 nm, more preferably from 50 nm to 100 nm.

  When the average height of the metal oxide particle group is larger than 150 nm, white turbidity occurs on the glass surface, or the metal oxide particle group peels from the glass surface. When the metal oxide particle group is peeled off from the glass surface, the hydrophilicity of the glass surface is lowered and water droplets are easily generated. Due to the distribution of a large number of water droplets, fogging occurs on the glass surface. The peeling of the metal oxide particle group becomes remarkable in the deeply bent region, and the function and aesthetic appearance as a bent glass article are impaired.

  Further, as the average height of the metal oxide particle group increases, the interference color tends to stand out on the glass surface. If the average height of the metal oxide particle group is larger than 150 nm, the interference color on the glass surface becomes too conspicuous, and it is not suitable for the use of a bent glass article as described later.

  When the average height of the metal oxide particle group is smaller than 10 nm, a concavo-convex structure sufficient to obtain hydrophilicity is not formed.

  The area occupation ratio of the metal oxide particle group on the surface of the bent glass article is preferably 50% or more and 90% or less. In order to improve the hydrophilicity, it is preferable that a large number of convex portions due to the metal oxide particles exist, but if the metal oxide particles exist in the form of a continuous film in contact with each other, the unevenness due to the metal oxide particle group Becomes smaller. In consideration of this, it is desirable that the metal oxide particle group covers at least half of the bent glass article, if not completely. On the surface of the bent glass article, a flat part may be left in 10% or more, and at least a part of the flat part may be covered with a functional film.

  The metal oxide particles may be present such that a part thereof is stacked. The number of metal oxide particles is counted according to the number of particles until they are joined as long as it is recognized that they have grown separately as particles even if they are joined together and partially integrated.

  The average height of the metal oxide particle group can be determined based on a scanning microscope (SEM) photograph taken at a magnification of × 100,000 and an inclination angle of 5 °. The area occupancy and density (number density) of the metal oxide particle group can be determined based on SEM photographs taken at a magnification of 45,000 and an inclination of 30 °. A specific method for calculating the average height, area occupancy, and density (number density) of the metal oxide particle group will be described later.

  The metal oxide particles are preferably crystalline. The outer shape of the metal oxide particles is not limited, and is affected by the crystal growth process and the like, but may be dome-shaped, for example, substantially hemispherical, or polygonal, for example, quadrangular. The dome shape means that an acute angle portion does not exist in the outer shape of an SEM photograph taken at a magnification of 100000 and an dip of 5 °.

  Although there is no restriction | limiting in the material which comprises a metal oxide particle, It is preferable that a metal oxide particle contains at least 1 sort (s) chosen from a titanium oxide, a zirconium oxide, an indium oxide, a zinc oxide, and a tin oxide, for example. Metal oxide particles mainly composed of tin oxide or titanium oxide are excellent in chemical resistance and can be formed using inexpensive raw materials. From this viewpoint, metal oxide particles mainly composed of tin oxide or titanium oxide are particularly preferable.

  In the present specification, the “main component” means that the proportion of the component is 50% by mass or more according to common usage. The ratio containing the component is preferably 70% by mass or more, and more preferably 90% by mass or more.

  The frequency distribution with respect to the height of the metal oxide particle group may be one peak (one mountain), but if it is two or three peaks, excellent hydrophilicity is exhibited. That is, a form in which convex portions having a relatively high height are mixed in a group of metal oxide particles (convex portions) having a relatively low height is preferable. When the frequency distribution of the height of the metal oxide particle group is 2 peaks or 3 peaks, the average height of the metal oxide particle group (convex portion) group belonging to the highest peak is relatively It is preferable that the average height of the convex group belonging to the lowest peak is 2 times or more, particularly 3 times or more.

  The bent glass article in which the metal oxide particle group having the average height and the area occupancy as described above is formed provides a shape that can exhibit excellent hydrophilicity. By appropriately selecting the metal oxide, high hydrophilicity is imparted to the surface of the bent glass article. As the metal oxide particle group, a tin oxide particle group or a titanium oxide particle group is preferable. The degree of hydrophilicity is preferably such that the contact angle of water measured by dropping a 2 mg water droplet on the surface is 20 ° or less, and further 15 ° or less. Such a hydrophilic surface is excellent in affinity with a material for forming an alkali barrier film and a functional film, which will be described later, and is also suitable for manufacturing bent glass articles. In the region where the metal oxide particle group is not formed, the surface of the bent glass article may be exposed.

  The haze ratio of the bent glass article is preferably 5% or less. The typical haze ratio of the bent glass article is 0.2% when the average height of the metal oxide particle group is 10 nm or more and 50 nm or less, and 0.8% when the average height of the metal oxide particle group is 80 nm. When the average height of the particle group is 120 nm or more and 150 nm or less, it is 2.5%.

  When the moisture condenses in the presence of water vapor, the bent glass article of the present invention has high hydrophilicity, so that a large number of water droplets are not distributed and attached to the glass surface, and adhere to the glass surface as a relatively homogeneous film. For this reason, fogging of the glass due to condensation is suppressed, the haze ratio is suppressed to 5% or less even under water vapor, and the transparency of the glass is maintained.

Note that the haze ratio depends on the average height of the metal oxide particle group and the density of the metal oxide particles. For this reason, even if the average height of the metal oxide particle group is 150 nm, if the density of the metal oxide particles exceeds 150 particles / μm ² , the haze ratio can be greater than 5%. It is important from the viewpoint of fogging prevention to appropriately set the average height and density of the group.

  When the glass member contains an alkali component, it is preferable to form an alkali barrier film in order to suppress the diffusion of the alkali component into the functional film. That is, the bent glass article may further include an alkali barrier film formed on at least one selected from a glass member and metal oxide particles, and between a metal oxide particle group and a functional film. When an alkali barrier film is formed on the surface of the glass member, the functional film covers the metal oxide particle group and contacts the surface of the alkali barrier film instead of the glass member. When the alkali barrier film is formed so as to cover the metal oxide particle group, the functional film covers the metal oxide particle group via the alkali barrier film and is formed on the surface of the glass member via the alkali barrier film. . The alkali barrier film covering the metal oxide particle group can play a role of enhancing the durability of the uneven structure by the metal oxide particle group.

  The alkali barrier film is preferably a film containing at least one selected from, for example, silicon oxide, aluminum oxide, silicon oxycarbide and silicon oxynitride, and more preferably a film containing silicon oxide as a main component.

  The thickness of the alkali barrier film is preferably 5 nm or more and 100 nm or less, more preferably 10 nm or more and 50 nm or less, in order not to excessively relax the unevenness caused by the metal oxide particle group while suppressing the diffusion of the alkali component. An alkali barrier film made of the materials exemplified above and having a film thickness in the above range follows the metal oxide particle group well and reflects its shape, number, etc. well. In this case, the shape, number, and the like of the metal oxide particle group can be grasped from the surface shape of the alkali barrier film.

  The functional film is at least one selected from a hydrophilic film and an antifouling film. The functional film may have other functions such as anti-fogging properties, such as hydrophilicity and antifouling properties, hydrophilicity and antifogging properties, antifouling properties and antifogging properties. You may have a function simultaneously.

  The hydrophilic film may be a film containing a surfactant, for example.

  The antifouling film is preferably a film containing a polyalkyleneoxy group. This film can be formed using a silane compound containing a polyalkyleneoxy group. Examples of such silane compounds include [alkoxy (polyalkyleneoxy) alkyl] trialkoxysilane, N- (triethoxysilylpropyl) -O-polyethylene oxide urethane, [alkoxy (polyalkyleneoxy) alkyl] trichlorosilane, N- (trichlorosilylpropyl) -O-polyethylene oxide urethane and the like can be mentioned, and [methoxy (polyethyleneoxy) propyl] trimethoxysilane is preferable. These may be used alone or in combination.

(Use of bent glass products)
Applications of bent glass articles described above include, for example, lids for commercial oden containers used in pots, hot plates, convenience stores, etc., Chinese bun warmers or Chinese bun steamers, and frozen shows that contain ice cream Examples include food cases typified by refrigerated showcases that store cases, cakes, etc., washstands, water tanks, curved mirrors or corner mirrors, shaped glass, underwater glasses, and the like.

  In such an application, the fogging of the glass due to dew condensation becomes an obstacle to seeing a product or an article, or a factor that impairs the functionality and aesthetics of the bent glass article itself. When the bent glass article of the present invention is used for the above-described applications, fogging due to condensation is suppressed and transparency is maintained. Further, in the bent glass article of the present invention, the peeling of the metal oxide particles in the deep bending region is suppressed, so that the bent glass article becomes transparent as a whole, and the functionality and aesthetics as a bent glass article are improved. ing.

  In addition, when moisture adheres to the glass surface as water droplets, dirt such as water stains is noticeably generated in the process of evaporation of the water droplets. In the bent glass article of the present invention, since the surface is hydrophilized, moisture does not adhere as water droplets, and moisture becomes a uniform film and adheres to the glass surface. For this reason, dirt such as water stains is not noticeable, and transparency can be provided for a long period of time. Since the bent glass of the present invention is not easily soiled, it is suitable for lids such as pans and hot plates, food cases, washstands, etc. that require cleanliness.

  In addition, even when dirt adheres to the glass surface and the hydrophilicity is lowered, the hydrophilicity of the glass surface can be easily recovered by washing away with sponge cleaning using a detergent such as household detergent. . The hydrophilicity of the bent glass article of the present invention is not impaired by washing.

(Method for producing bent glass article)
In the method for producing a bent glass article according to the present embodiment, a metal oxide particle group having an average height of 10 nm or more and 150 nm or less is formed on a flat glass member by a CVD method using a raw material gas containing a metal compound and an oxidizing agent. A metal oxide particle group forming step to be formed, and a bending step of heating the glass member to a softening temperature and bending the softened glass article according to the mold to form a deep bending region having a curvature radius of 200 mm or less. Prepare.

  The metal oxide particle group is more preferably formed by a thermal CVD method. By forming the metal oxide particle group on the surface of the glass member using the CVD method, the metal oxide particle group is fixed to the surface of the glass member.

  The alkali barrier film can be formed by, for example, a CVD method. That is, the glass member constituting the bent glass article contains an alkali component, and the bent glass article is at least selected between the glass member and the metal oxide particle group, and between the metal oxide particle group and the functional film. In the case of further including an alkali barrier film formed on one side, the manufacturing method of the present invention may further include a step of forming the alkali barrier film by a CVD method. The alkali barrier film can be formed by a thermal CVD method using a source gas containing a metal compound and an oxidizing agent.

  When the glass member is a glass plate, a metal oxide particle group may be formed by a CVD method on a glass ribbon that becomes the glass plate in a process of manufacturing the glass plate by a float method. The metal oxide particle group is preferably formed on the surface of a glass member having a temperature of 600 ° C. or higher and 750 ° C. or lower. In this case, the alkali barrier film may also be formed on the glass ribbon by the CVD method. The CVD method (online CVD method) on the glass ribbon may be performed in a float bath or may be performed downstream of the float bath. In the online CVD method, since the heat of the glass ribbon can be used for the thermal oxidation reaction, the source gas can be thermally oxidized at the above-described high temperature without heating the substrate.

  When the bent glass article includes an alkali barrier film at least between the metal oxide particle group and the functional film, and the alkali barrier film is mainly composed of silicon oxide, a silane compound as exemplified above is used as a raw material. When a functional film is formed, the affinity between the alkali barrier film and the functional film is improved.

  As the metal compound used for the raw material gas for forming the metal oxide particles, a metal compound containing a halogen element, particularly chlorine, such as stannous chloride, stannic chloride, titanium chloride, zinc chloride, Indium chloride, aluminum chloride, zirconium chloride, monobutyltin trichloride, dimethyltin dichloride, dibutyltin dichloride, and dioctyltin dichloride are preferred. As the metal compound used for the raw material gas for forming the alkali barrier film, metal hydrides, chlorides, alkyl-modified products thereof and the like can be used, and examples thereof include hydrogen compounds such as monosilane. . Examples of the oxidizing agent include oxygen, water, water vapor, ozone, and dry air.

  FIG. 1 shows an example of an apparatus configuration for carrying out the online CVD method.

  The molten glass raw material flows out from the melting furnace 11 into the float bath 12, becomes a glass ribbon 10, moves on the molten tin bath 15, becomes semi-solid, and then is pulled up by the roller 17 and sent into the slow cooling furnace 13. It is. The glass ribbon solidified in the slow cooling furnace 13 is cut into a glass plate of a predetermined size by a cutting device (not shown).

  In the float bath 12, a predetermined number of coaters 16 (three coaters 16a, 16b, and 16c in the illustrated embodiment) are arranged at a predetermined distance from the surface of the glass ribbon 10. From these coaters 16, the source gas is continuously supplied onto the glass ribbon 10, and a metal oxide particle group and an alkali barrier film are formed on the surface of the glass ribbon 10.

  The source gas may be supplied after sufficiently mixing a metal compound, an oxidizing agent, a diluent, and the like. If the mixing is not sufficient, for example, variations in the composition and size of the metal oxide particles increase, or unevenness in the thickness of the alkali barrier film tends to occur.

  A reaction inhibitor may be further added to the raw material gas. An example of a reaction inhibitor for producing tin oxide from tin chloride is hydrogen chloride. When the mixing ratio of hydrogen chloride becomes too high, tin oxide is not generated, and therefore the molar ratio of hydrogen chloride to tin chloride is preferably less than 1. It is possible to form two or more metal oxide particle groups having different average heights by CVD using two or more source gases having different hydrogen chloride concentrations. For example, a small number of tin oxide particles having a low average height may be formed using a raw material gas having a high hydrogen chloride concentration, and then a raw material gas having a low hydrogen chloride concentration may be supplied. By supplying raw material gas with low hydrogen chloride concentration, a group of tin oxide particles with a high average height using the previously formed tin oxide particles as the nucleus for crystal growth, and an oxidation with a low average height formed directly on the glass surface Tin particles are formed. Thereby, the tin oxide particle group in which the frequency distribution has two peaks is obtained. Monosilane is also a highly reactive raw material. Examples of the reaction inhibitor for monosilane include unsaturated hydrocarbon gases such as ethylene, acetylene, and toluene.

  The functional film may be formed by applying a solution containing the silane compound exemplified above. The solvent in this case is not particularly limited, and examples thereof include hydrophilic solvents typified by alcohols, paraffinic hydrocarbons, chlorofluorocarbons, and silicone oil-based nonaqueous solvents. Although there is no restriction | limiting also about the method of apply | coating a solution, The flow coating method, the dip coating method, the curtain coating method, the spin coating method, the spray coating method, the bar coating method, the immersion adsorption method etc. are illustrated. Preferable application methods are a flow coating method and a spray coating method.

  The functional glass article of the present invention may include a member such as a film other than those exemplified above. For example, in order to firmly attach the functional film, a film may be formed by applying a primer before forming the functional film.

  Next, the bending process of the glass member will be described using a pan lid as an example. After cutting the glass plate to which the metal oxide particle group has been fixed to a predetermined size through the above-mentioned process, chamfering or processing to open a hole for installing a pan handle etc. is performed as necessary. A member is produced. Next, the glass member is bent.

  FIG. 2 shows an example of a device configuration for bending a glass member. The glass member 100 is installed on a lower mold 110 having a predetermined outer peripheral shape corresponding to the bent glass article. The mold 110 of this embodiment has a shape with a curvature radius of 200 mm or less. The mold 110 on which the glass member 100 is placed is introduced into the heating furnace 130 by the roller 120. The heating furnace 130 includes a heater 132, and the temperature in the heating furnace 130 is maintained at 600 to 750 ° C. The glass member 100 is heated so as to reach the softening point in the vicinity of the outlet of the heating furnace 130. The glass member 100 that has reached the softening point is taken out into the atmosphere and then bent by the upper mold 140. In this embodiment, the bending process is performed outside the heating furnace 130, but the bending process may be performed in the heating furnace 130.

  The bent glass member is gradually cooled by a cooling facility such as a cooling blower. For example, cooling is performed so that the water temperature of the cooling blower and the temperature of the glass member are about 200 ° C. by performing air cooling from the vertical direction of the glass member with the cooling blower. In this state, by removing the glass member and immersing the glass member in water, scratches, cracks, defective strength products and the like are damaged. Thereby, the thermal shock inspection of the glass member becomes possible. The glass member that has undergone the cooling step is used as a bent glass article after washing and visual inspection.

  A frame material such as a stainless steel ring may be fitted to the peripheral edge of the bent glass article. The stainless steel ring can be prepared as a semi-finished product that is pressed to the shape of the periphery of the bent glass article. The stainless steel ring is fitted to the peripheral portion of the bent glass article by attaching the stainless steel ring to the peripheral edge of the bent glass article and caulking.

  EXAMPLES Hereinafter, although an Example demonstrates this invention more concretely, this invention is not restrict | limited by the following Examples.

  First, the measurement method used for evaluation of a bent glass article will be described.

(Height measurement of metal oxide particles)
The bent glass article was cut to produce a glass cross section. The obtained glass cross section was photographed using an SEM (magnification × 100,000, dip angle 5 °). Image processing was performed on the cross-sectional image of the glass by the SEM photograph, and the binarization was performed by extracting the contour portion of the metal oxide particle group on the glass surface and the glass surface. The average height of the metal oxide particle group was determined by calculating the average distance between the extracted glass surface and the contour portion of the metal oxide particle group.

(Area occupancy and density of metal oxide particles)
The surface of the bent glass article was photographed using SEM (magnification x 45000, dip angle 30 °). From the obtained SEM photograph, the ratio of the area occupied by the metal oxide particle group in a predetermined region, for example, 1 μm × 1 μm, and the density (number density) of the particles were determined. More specifically, the obtained SEM photograph is subjected to image processing, the contour portion of the metal oxide particle group on the glass surface is extracted and binarized, and then the occupation area calculation program and the number counting program are used. Then, the occupation area and density of the metal oxide particle group in the region of 1 μm × 1 μm were analyzed. Instead of the occupied area calculation program and the number counting program, the SEM photograph subjected to image processing is traced on paper such as graph paper, and the occupied area and number of the metal oxide particles are obtained from the obtained trace image. May be.

(Haze ratio of glass)
The haze ratio of the glass was measured using a turbidimeter (Nippon Denshoku Co., Ltd., NDH2000).

(Contact angle of glass surface)
Using a contact angle meter (CA-DT, manufactured by Kyowa Interface Science Co., Ltd.), 2 mg of distilled water was dropped on the surface of the bent glass article maintained horizontally, and the static contact angle was measured.

Example 1
First, using a device having the configuration shown in FIG. 1, a glass member having metal oxide particle groups formed on the surface was manufactured with the following settings. Specifically, 98% by volume of nitrogen and 2% by volume of hydrogen are supplied into the float bath space, the inside of the bath is maintained in a non-oxidizing atmosphere, and dimethyltin dichloride is supplied from the coater 16a located on the most upstream side. (Vapor) Supplying a gas mixture diluted with helium, containing 0.2 mol%, water vapor 17.4 mol%, oxygen 7.2 mol%, and oxidized on a glass ribbon formed to a temperature of 720 ° C and a thickness of 4 mm Metal oxide particle groups mainly composed of tin were formed. It was later confirmed by SEM observation that the average height of the formed metal oxide particle group was 80 nm.

  After cooling the glass ribbon, the glass ribbon was cut into a size of 282 × 373 mm, the periphery was polished, and then deep bending with a curvature radius of 120 mm was performed with the uneven surface of the metal oxide particle group inside, and the metal oxide particle group No film peeling occurred and a transparent bent glass article was obtained. The haze ratio and contact angle of the bent glass article of Example 1 were 0.8% and 14 °, respectively. When water vapor was applied to the inner surface of the bent glass article of Example 1, it did not form water droplets but spread as a water film. Moreover, when this glass was drilled with a core drill, no cracks were observed.

FIG. 3 is an SEM photograph (magnification × 100,000, dip angle 5 °) of a deep bending region of the bent glass article of Example 1. The metal oxide particle group is distributed almost uniformly over the entire surface of the glass without covering the entire surface of the glass. As a result of the analysis, the area occupancy and density of the metal oxide particle group were 59% and 75 particles / μm ² , respectively.

  FIG. 4 shows the shape of the bent glass article of Example 1. FIG. 4A is a plan view of the bent glass article of Example 1. FIG. FIG.4 (b) is sectional drawing of the bending glass article of Example 1 along the AA line of Fig.4 (a). FIG.4 (c) is sectional drawing of the bent glass article of Example 1 along the BB line of Fig.4 (a). The bent glass article 200 of Example 1 includes a stainless steel ring 220 attached to the peripheral edge of the glass member 210 in addition to the glass member 210 on which the metal oxide particle group is formed. The glass member 210 is provided with two holes 212 having a diameter of 8 mm on the line AA. As shown in FIG. 4B and FIG. 4C, the peripheral region of the glass member 210 is deep-bent with a curvature radius of 120 mm.

  FIG. 5 is a photograph showing the appearance of the bent glass article of Example 1. The photograph of FIG. 5 was obtained by imaging the bent glass article of Example 1 placed on a white and black stripe pattern having a line width of 15 mm. As is clear from FIG. 5, the bent glass article of Example 1 is transparent as a whole including the deep bend region, and no cracks or the like are observed in the film of the metal oxide particle group around the hole.

(Comparative Example 1)
A mixed gas obtained by diluting monosilane, ethylene, and oxygen with nitrogen was supplied from the coater 16a, and an alkali barrier film containing silicon oxide as a main component was formed to a thickness of 30 nm. Subsequently, a mixed gas diluted with nitrogen containing 3.3 mol% of dimethyltin dichloride (steam), 36.3 mol% of water vapor, and 31.9 mol% of oxygen is supplied from the coater 16b, and a glass ribbon having a temperature of 680 ° C. A metal oxide fine particle group mainly composed of tin oxide was formed thereon. The formed metal oxide particle group was a continuous film of crystalline tin oxide, and it was confirmed later by SEM observation that the average height was 300 nm. When this glass member was bent deeply in the same manner as in Example 1, film peeling occurred and it became cloudy. In addition, cracks occurred from the periphery of the hole due to the drilling. The shape of the bent glass article of Comparative Example 1 is the same as that of the bent glass article of Example 1 shown in FIG.

  FIG. 6 is a photograph showing the appearance of the bent glass article of Comparative Example 1. The photograph of FIG. 6 was obtained by imaging the bent glass article of Comparative Example 1 placed on a white and black stripe pattern having a line width of 15 mm, as in FIG. As is clear from FIG. 6, in the bent glass article of Comparative Example 1, it was confirmed that film peeling occurred in the deep bending region and clouding occurred. As a result of the measurement, the haze ratio in the deep bending region was 50%.

  FIG. 7 is a photograph taken side by side to compare the bent glass article of Example 1 and the bent glass article of Comparative Example 1 side by side.

  As is clear from FIG. 7, in the bent glass article of Comparative Example 1 (see the right side of FIG. 7), the deep bending region is cloudy, and the stripe pattern placed under the bent glass article of Comparative Example 1 appears blurred. In contrast, in the bent glass article of Example 1 (see FIG. 7 left), the stripe pattern can be clearly seen in the entire area including the deep bent area, and the difference in transparency from the bent glass article of Comparative Example 1 It can be seen that is remarkable.

(Example 2)
Example 2 is the same as Example 1 except that the mixed gas supplied from the coater 16a is a mixed gas diluted with helium containing tin chloride (steam) at a concentration of 0.14 mol% and water vapor of 18.6 mol%. It was produced by the same manufacturing method. FIG. 8A is an SEM photograph (magnification × 100,000, dip angle 5 °) obtained by photographing the deep bending region of the bent glass article of Example 2. FIG. FIG. 8B is an SEM photograph (magnification × 45000, depression angle 30 °) obtained by photographing the deep bending region of the bent glass article of Example 2. As a result of the analysis, it was confirmed that the average height of the metal oxide particle group was 25 nm and the haze ratio was 0.2%. Moreover, the area occupation rate and density of the metal oxide particle group were 73% and 166 particles / μm ² , respectively.

(Example 3)
Example 3 was produced by the same manufacturing method as Example 1 except that the mixed gas supplied from the coaters 16a and 16b was changed as follows. In Example 3, a mixed gas obtained by diluting monosilane, ethylene, and oxygen with nitrogen was supplied from the coater 16a, and an alkali barrier film mainly composed of silicon oxide was formed to a thickness of 30 nm. Subsequently, a mixed gas diluted with nitrogen containing dimethyltin chloride (vapor) at a concentration of 0.33 mol% and water vapor of 67.3 mol% was supplied from the coater 16b. FIG. 9A is an SEM photograph (magnification × 100,000, dip angle 5 °) in which the deep bending region of the bent glass article of Example 3 was photographed. FIG.9 (b) is the SEM photograph (magnification x45000, depression angle 30 degrees) which image | photographed the deep bending area | region of the bending glass article of Example 2. FIG. As a result of analysis, it was confirmed that the average height of the metal oxide particle group was 50 nm and the haze ratio was 0.2%. The area occupancy and density of the metal oxide particle group were 83% and 170 particles / μm ² , respectively.

Example 4
Example 4 was produced in the same manner as Example 3 except that a gas mixture diluted with nitrogen containing 0.7 mol% of stannic chloride (steam) and 57.1 mol% of water vapor was supplied from the coater 16b. Produced by the method. FIG. 10A is an SEM photograph (magnification × 100,000, dip angle 5 °) in which the deep bending region of the bent glass article of Example 4 was photographed. FIG.10 (b) is the SEM photograph (magnification x45000, depression angle 30 degrees) which image | photographed the deep bending area | region of the bending glass article of Example 3. FIG. As a result of analysis, it was confirmed that the average height of the metal oxide particle group was 120 nm and the haze ratio was 2.5%. The area occupancy and density of the metal oxide particle group were 88% and 66 particles / μm ² , respectively.

  The present invention is not limited to the above-described embodiments, and various modifications such as design changes can be added based on the knowledge of those skilled in the art. The form can also be included in the scope of the present invention.

  For example, in the above embodiment, the metal oxide particle group is formed on the surface of the glass member using the chemical vapor deposition method, but the sol in which the metal hydroxide fine particles are dissolved using the sol-gel method. It is also possible to form a metal oxide particle group by firing the glass member after coating the surface of the glass member.

It is a figure which shows an example of the structure of the apparatus for forming a film | membrane on the surface of a glass ribbon by CVD method in the manufacturing process of the glass plate in a float glass process. It is a figure which shows an example of the apparatus structure for giving a bending process to a glass member. It is the SEM photograph (magnification x100,000, dip angle 5 degrees) which imaged the deep bending field of the bent glass article of Example 1. It is a figure which shows the shape of the bending glass article of Example 1. FIG. 2 is a photograph showing the appearance of a bent glass article of Example 1. 4 is a photograph showing the appearance of a bent glass article of Comparative Example 1. In order to contrast the bent glass article of Example 1 and the bent glass article of Comparative Example 1, it is a photograph taken side by side. It is the SEM photograph which image | photographed the deep bending area | region of the bending glass article of Example 2. FIG. It is a SEM photograph which image | photographed the deep bending area | region of the bending glass article of Example 3. FIG. It is the SEM photograph which image | photographed the deep bending area | region of the bending glass article of Example 4. FIG.

Explanation of symbols

10 glass ribbon, 11 melting furnace, 12 float bath, 15 molten tin bath, 16 coater, 17 roller, 100 glass member, 110 mold, 120 roller, 130 heating furnace, 140 mold.

Claims (13)

A glass member including a deep bending region;
A metal oxide particle group having an average height of 10 nm or more and 150 nm or less formed on the surface of the glass member including at least the deep bending region;
A bent glass article comprising:   The bent glass article according to claim 1, wherein the metal oxide particle group covers at least 50% to 90% of the surface of the glass member including the deep bent region.   The bent glass article according to claim 1 or 2, wherein the metal oxide particle group is a tin oxide particle group or a titanium oxide particle group.   The bent glass article according to any one of claims 1 to 3, wherein the metal oxide particle group is formed on a surface of the glass member by a chemical vapor deposition method.   The bent glass according to any one of claims 1 to 4, further comprising at least one functional film selected from a hydrophilic film and an antifouling film covering the metal oxide particle group. Goods. The glass member contains an alkali component;
An alkali barrier film formed on at least one of the glass member and the metal oxide particle group and at least one selected from the metal oxide particle group and the functional film is further provided. Item 6. The bent glass article according to any one of items 1 to 5.   The bent glass article according to claim 6, wherein the alkali barrier film contains, as a main component, at least one selected from silicon oxide, aluminum oxide, silicon oxycarbide, and silicon oxynitride. A metal oxide particle group forming step of forming a metal oxide particle group having an average height of 10 nm or more and 150 nm or less on a flat glass member by chemical vapor deposition using a raw material gas containing a metal compound and an oxidizing agent; ,
A bending step of forming a deep bending region by heating the glass member to a softening temperature and bending the softened glass article according to a mold;
A method for producing a bent glass article.   In the metal oxide particle group forming step, the metal oxide particle group is formed so as to cover at least 50% to 90% of the surface of the glass member including the deep bending region. The manufacturing method of the bending glass article of Claim 8.   The method for producing a bent glass article according to claim 8 or 9, wherein in the metal oxide particle group forming step, a tin oxide particle group or a titanium oxide particle group is formed as the metal oxide particle group. The glass member contains an alkali component;
The bent glass according to any one of claims 8 to 10, further comprising a step of forming an alkali barrier film between the glass member and the metal oxide particle group by a chemical vapor deposition method. Article manufacturing method.   12. The method according to claim 8, further comprising a step of coating the metal oxide particle group with at least one functional film selected from a hydrophilic film and an antifouling film. A method of manufacturing a bent glass article. The glass member contains an alkali component;
A step of forming an alkali barrier film by chemical vapor deposition on at least one selected between the glass member and the metal oxide particle group and between the metal oxide particle group and the functional film; The method for producing a bent glass article according to any one of claims 8 to 12, further comprising: