Central Glass Company, Limited

Nissan Motor Company Limited

Kensuke Makita

Katsuto Tanaka

Atsushi Takamatsu

Yasuo Moriguchi

Yuji Yamamoto

Yasuaki Kai

Hiroshi Inaba

Takashi Seino

Toshinobu Yoko

Seiji Yamazaki

Masahide Takahashi

Satoko Sugawara

Naohiko Matsuda

Toshiaki Itoh

Minoru Kuniyoshi

Michiharu Mishima

Naoya Hayakawa

Seiji Yamasaki

Seizi Yamazaki

Junichi Okuda

Sumio Sakka

Kanichi Kamiya

Akimasa Hattori

Naohiko Matuda

In a production process of an organic-inorganic hybrid glassy material, the invention relates to a process for producing an organic-inorganic hybrid glassy material, characterized in that the process comprises at least the three steps of producing a gel body by a sol-gel method; melting by heating; and aging, and it relates to an organic-inorganic hybrid glassy material produced by this process.

Organic-inorganic hybrid glassy materials and their production processes

The invention relates to a hydrophilic film formed on a substrate. This film has a hydrophilic outermost layer having a matrix phase containing titania and a disperse phase constituted of at least one compound of silica and alumina. The matrix phase may further contain an amorphous metal oxide. With this, the outermost layer becomes superior in abrasion resistance. The at least one compound of the disperse phase may be a non-spherical colloidal silica. With this, the outermost layer becomes substantially improved in scratch resistance. The outermost layer is formed on the substrate by a method including sequential steps of (a) providing a sol mixture including a first sol containing a precursor of the titania and a second sol containing the at least one compound; (b) coating the substrate with the sol mixture, thereby to form thereon a precursory film; and (c) baking the precursory film into the outermost layer.

Hydrophilic film and method for forming same on substrate

The invention relates to a reflectance-reducing glass pane which may be a laminated glass pane such as an automobile front windshield. The invention provides a reflectance-reducing glass pane including: a transparent glass substrate having first and second major surfaces opposed to each other; a first reflectance-reducing coating formed on the first major surface of the glass substrate; and a second reflectance-reducing coating formed on the second major surface of the glass substrate. The first coating has at least two metal-oxide layers which are different in refractive index. The second coating has a refractive index of up to 1.50 and is made of one selected from the group consisting of SiO.sub.2 and a mixture of SiO.sub.2 and another metal oxide. The reflectance-reducing glass pane optionally further includes a third water-repellent coating which is formed on the second coating. The third coating comprises a silane compound containing a polyfluoroalkyl group. The reflectance of the glass pane is substantially low, with respect to a visible light incident on the glass pane from a side of the first coating at an incidence angle within a range from 40 to 80 degrees.

Glass pane with reflectance reducing coating

An ink composition for forming a thin metal oxide film contains a glass-forming component, a solvent and 10-25 wt % of a viscosity-increasing agent. The glass-forming component is one of a halogen-containing metal alkoxide, a mixture of the halogen-containing metal alkoxide and another metal alkoxide, and a mixture of the halogen-containing metal alkoxide and a metal oxide sol. The viscosity-increasing agent is at least one selected from the group consisting of nitrocellulose H7, nitrocellulose H20, nitrocellulose H60. nitrocellulose H80 and nitrocellulose H120, each of which is according to Japanese Industrial Standard K 6703. The solvent is at least one selected from the group consisting of ethylcarbitol and butylcarbitol. The ink composition has a viscosity within a range from 200 to 300 poises. The thus prepared ink composition is prolonged in pot life. The thin metal oxide film prepared from the ink composition has a refractive index substantially the same as the theoretical value and is colorless, uniform in thickness, and excellent in optical characteristics, abrasion resistance, scratch resistance and durability.

Ink composition for forming thin film

The invention relates to a method for applying a coating composition to a substrate with a reverse roller coater so as to form a thin film on the substrate and then for baking the thin film so as to transform the thin film into a metal oxide film. The coating composition comprises: 0.1-10 wt % of at least one organic metal compound on a metal oxide basis; and at least one organic solvent. The at least one organic metal compound is selected from the group consisting of metal alkoxides, metal acetyl-acetonates and metallic soaps. The coating composition is adjusted to have a viscosity within a range from 0.1 to 100 centipoises. In this method, a reverse roller of the coater is rotated at a rotation speed within a range from 2 to 55 m/min. and the substrate is moved at a moving speed within a range from 1 to 30 m/min. while the coating composition is applied to the substrate. Furthermore, the rotation speed of the reverse roller is adjusted to be higher than the moving speed of the substrate. According to the invention, it is possible to form an optical metal oxide film which has a uniform thickness of up to about 10 .mu.m (more particularly up to about 1 .mu.m).

Coating composition and method for forming thin film on substrate using

The invention relates to a transparent coating on a transparent glass pane which may be a laminated glass pane such as an automobile windshield. The present invention provides a two-layer coating including a first layer which is a transparent oxide film in direct contact with the major surface of the glass substrate and a second layer which is a transparent oxide film. The first layer has a thickness of 70-230 nm and a refractive index of 1.80-2.10 and includes a major portion and a minor portion which is exposed and adapted to be used as a combiner of a head-up display system. The second layer is formed on the major portion of the first layer so as to expose the minor portion of the first layer. The second layer has a thickness of 110-130 nm and a refractive index of 1.40-1.50. An additional film is optionally formed on the minor portion of the first layer so as to fully or partly cover the minor portion. The additional layer is adapted to be used as a wavelength-selective combiner of the head-up display system. The two-layer coating except the minor portion is adapted to be used as a reflectance reducing coating. To reduce the reflectance of perpendicularly incident light the two-layer coating can be modified into a three-layer coating by interposing another oxide film.

Glass pane with reflectance reducing coating and combiner of head-up

An ink composition for forming a thin metal oxide film contains a glass component, a viscosity-increasing agent and a solvent. The glass component is one of a halogen-containing metal alkoxide, a mixture of the halogen-containing metal alkoxide and another metal alkoxide, and a mixture of the halogen-containing metal alkoxide and a metal oxide sol. The viscosity-increasing agent is nitrocellulose H60 according to Japanese Industrial Standard K6703. The solvent is at least one of ethylcarbitol and butylcarbitol. The formed thin metal oxide film is superior in transparency, abrasion resistance and scratch resistance.

The invention relates to a transparent coating on a transparent glass pane which may be a laminated glass pane such as an automobile windshield. The invention provides a two-layer coating made up of a first oxide film, e.g. a TiO.sub.2 -SiO.sub.2 mixed oxide film, which is in contact with the glass pane and has a thickness of 70-100 nm and a refractive index of 1.80-1.90 and an outer second oxide film, e.g. a SiO.sub.2 film, which has a thickness of 110-130 nm and a refractive index of 1.40-1.50. With respect to visible light obliquely incident on the coating side of the glass pane at an angle of 50-70 degrees with the normal, the reflectance of the coated glass pane becomes lower than that of the glass pane without coating by 4.5-6.5%. To reduce the reflectance of perpendicularly incident light the two-layer coating can be modified into a three-layer coating by interposing another oxide film, e.g. a TiO.sub.2 film, having a thickness of 130-160 nm and a refractive index of 2.05-2.30 between the above described first and second oxide films. The three-layer coating is nearly equivalent to the two-layer coating in the ability to reduce the reflectance of obliquely incident light.

The present invention relates to a head-up display system which includes an element thereof. The element is attached to, for example, an automobile windshield so as to project light rays carrying images of display information onto the element from a luminous source in a car. The element includes first and second reflection layers. The first layer is directly attached to the windshield and has a relatively uniform reflectance throughout visible light spectrum. The second layer is directly formed on the first layer and has a selective reflection against incident visible light of wavelengths in the range from about 500 nm to about 600 nm. Thus, the light rays from the luminous source are displayed on the first and second layers in different colors.

Head-up display system including a uniformly reflecting layer and a

The disclosure relates to a metal oxide film formed on a glass substrate by the sol-gel process using an alcohol solution of at least one metal alkoxide or acetylacetonato. To afford water repellency to the oxide film, carbon fluoride is dispersed in the metal oxide matrix by thermal decomposition of a fluoroalkylsilane compound, e.g. CF.sub.3 (CF.sub.2).sub.3 CH.sub.2 CH.sub.2 Si(OCH.sub.3).sub.3. An organic polymer, e.g. polyethylene glycol, is dissolved in the metal alkoxide or acetylacetonato solution, and the solution is applied to the glass substrate to form a sol film. By heating at a temperature not higher than 200.degree. C. the sol film turns into a porous gel film. Next, the porous gel film is impregnated with an alcohol solution of the fluoroalkylsilane compound and then heated at a temperature not lower than 500.degree. C. The obtained oxide film is good in durability and abrasion resistance, and on this film the contact angle of water drop becomes greater than 90 degrees.

Water-repellent metal oxide film coated on glass substrate and method of

The invention relates to a sol-gel method for forming a metal oxide film, e.g. TiO.sub.2 film or TiO.sub.2 -SiO.sub.2 film, on a substrate by applying a solution of at least one metal alkoxide to the substrate to form a sol film on the substrate, drying the sol film to cause it to turn into a gel film by hydrolysis and baking the gel film. According to the invention the viscosity of the metal alkoxide solution is adequately increased, preferably to 3-30 cP at 20.degree. C., by the addition of a combination of a hydroxypropyl cellulose of which 2 wt % aqueous solution has a viscosity of 150-400 cP at 20.degree. C. and another hydroxypropyl cellulose of which 2 wt % aqueous solution has a viscosity of 6-10 cP at 20.degree. C. Metal oxide films formed by this method are free from minute cracks and excellent in optical characteristics and durability. By this method it is possible to form a metal oxide film as thick as about 300 nm without repeating the application of the alkoxide solution to the substrate.

Method of forming metal oxide film by using metal alkoxide solution

A method and apparatus for coating a plate with a thin liquid film. In the method, a thin liquid film is coated on a surface of a substrate such as a glass plate by using an incomplete liquid tank having an opening of a shape similar to the shape of the substrate surface on one side thereof. The tank communicates with a flow streamlining channel by an aperture in a lower section of the tank. First the substrate and the incomplete tank are brought into tight contact with each other such that the side opening of the tank is closed by the substrate, whereby the tank is completed. Next, a coating liquid such as a metal alkoxide solution is fed into the tank to thereby wet the substrate surface. Preferably the coating liquid is allowed to overflow the tank to remove a surface layer of the liquid. Then the liquid is extracted from the tank through the streamlining channel so as to lower the liquid level in the tank at a predetermined rate while keeping both the tank and the substrate stationary. By this method a submicron coating film of uniform thickness can easily be formed even on a large-sized substrate, and it is easy to form a coating film on only a selected area of the substrate surface without using any masking.

Method and apparatus for coating thin liquid film on plate surface

A thin liquid coating film is coated on a surface of a solid substrate, e.g. a glass plate, by using an incomplete liquid container having an opening of a shape similar to the shape of the surface of the substrate on one side thereof. First the substrate and the incomplete container are brought into tight contact with each other such that the side opening of the container is closed by the surface of the substrate, whereby the container is completed. Next, a coating liquid is fed into the container to thereby wet the substrate surface, and then liquid is extracted from the container so as to lower the liquid level in the container at a predetermined rate while keeping both the container and the substrate stationary. By this method a submicron coating film of uniform thickness can easily be formed even on large-sized substrate, and it is easy to form a coating film on only a limited area of the substrate surface without using any masking.

Apparatus for coating thin liquid film on solid surface

The invention relates to a sol-gel method for forming a patterned film of a metal compound, e.g. TiO.sub.2, SiO.sub.2, ZrO.sub.2, Al.sub.2 O.sub.3, TiN or Si.sub.3 N.sub.4, on a substrate by applying a metal alkoxide sol to the substrate, allowing the sol film on the substrate to turn into a gel film by hydrolysis, removing the gel film in the unnecessary area(s) by selective etching and baking the gel film in the remaining aarea(s). The selective etching of the gel film is easily accomplished by the steps of moistening the gel film in the unnecessary area(s) with a viscous liquid containing, e.g., an organic solvent or an organic acid, hardening the gel film in the remaining area(s) by mild heating, and then removing the gel film in the unnecessary area(s) by washing with a suitable liquid such as an alkali solution or, when said viscous solution contains an organic acid and water, water.

Method of forming patterned film on substrate surface by using metal

In producing silica glass, which may contain additional metal(s) such as Ti or Zr, from a solution of a silicon alkoxide, mixed with alkoxide(s) of the additional metal(s) where necessary, in water and a hydrophilic organic solvent by shaping the solution into a desired form such as a coating film on a substrate, self-supporting film, fiber or lump when the solution exhibits a suitably high viscosity and sufficiently heating the shaped solution, a water-soluble organic polymeric substance is added to the solution as a viscosity adjusting agent to soon increase the viscosity of the solution to the desirable level. Therefore, shaping of the solution can be performed without awaiting the progress of hydrolysis of the alkoxide in the solution, and the glass can be obtained with improved uniformity of its properties. A cellulose ether is preferred as the viscosity adjusting agent, and hydroxypropyl cellulose is particularly preferable.

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Matsusaka, Japan

Kensuke Makita