Radiation imagery chemistry: process – composition – or product th – Visible imaging including step of firing or sintering
Reexamination Certificate
2001-06-22
2004-09-14
McPherson, John A. (Department: 1756)
Radiation imagery chemistry: process, composition, or product th
Visible imaging including step of firing or sintering
C430S292000, C430S295000, C430S321000, C430S330000
Reexamination Certificate
active
06790583
ABSTRACT:
TECHNICAL FIELD
This invention concerns a method of producing film coated articles, in particular, light absorbing film coated articles that are suitable as the glass, etc. for window materials and mirrors for automobiles and other vehicles and buildings, optical glass products, ceramic products, optical parts, miscellaneous goods, etc.
BACKGROUND ART
A general method for obtaining microparticle dispersed glass using gold is the ion exchange method, with which an inorganic salt of gold is coated onto a glass surface and then baked to cause the gold in the inorganic salt to permeate into the glass substrate and cause colloidal coloration of the glass. There are also methods with which a gold salt is dissolved in a silicon alkoxide solution, this solution is coated onto a substrate, and heat treatment is performed to form a silicon oxide film that contains gold microparticles and is colored by the surface plasmons of the gold microparticles.
In particular, glass colored by the surface plasmons of gold microparticles is excellent in heat resistance and light resistance and has been used since priorly as colored glass or filter glass. It is generally known that the coloration due to absorption by the surface plasmons of gold microparticles is dependent on the refractive index of the medium that surrounds the gold microparticles, and for example among silicon oxide-titanium oxide films that contain gold microparticles, films, which are rich in titanium oxide and have a high refractive index, take on a blue color while films, which are rich in silicon oxide and have a low refractive index, take on a red color. It is also known that in this case, the coloration tone is changed and the principal wavelength of visible transmitted light is changed by the irradiating of ultraviolet rays after coating of a liquid that contains the silicon alkoxide, titanium oxide raw material, and gold salt but before the baking of the film (for example, Japanese Unexamined Patent Publication No. 6-191896).
Such glass, with which gold microparticles are dispersed in the glass or gold microparticles are dispersed in a film that is coated onto the glass, have been used since priorly as ornamental glass. However, the color of the glass that is obtained is normally a single color since the color is determined by the refractive index of the medium that surrounds the gold microparticles and the size and shape of the microparticles. Thus in the case where various color tones are to be provided within the same substrate, separate coating had to be performed for the respective color tones by means of flexo coating, screen printing, etc. This not only required highly precise patterning position control technology for prevention of the overlapping of films on top of each other but liquid compositions corresponding to the respective color tones had to be developed as well, making it disadvantageous in terms of cost to provide such color tones.
Furthermore, though the color tone obtained by gold microparticles varies with the refractive index of the medium and whether or not ultraviolet irradiation is carried out prior to the baking of the film, the reflectivity of the film also becomes higher as the refractive index of the medium becomes higher. However, for example, glass plates for automobiles and glass plates for construction, etc. are required in many cases to be low in visible light reflectivity for the purpose of appearance, and in the case where various transmission color tones are to be realized by changing the refractive index of the film, the highness of the visible light reflectivity of the film can become a disadvantage.
The present inventors have noted such problems and have come to complete this invention, the object of which is to provide light absorbing film coated articles, with which while keeping the visible light reflectivity low, various transmission color tones or various transmitted light spectrum distribution are realized in a single light absorbing film coated article or among individual or differing lots of light absorbing film coated articles.
DISCLOSURE OF THE INVENTION
This invention provides in a method of producing a light absorbing pattern film coated article having a transmitted light spectrum distribution corresponding to the pattern of a photomask, a method wherein a light absorbing film coating solution, which contains silicon oxide raw material, a titanium oxide raw material, containing titanium oxide microparticles, and gold microparticle raw material, is coated onto the surface of a substrate, positioning the abovementioned photomask on top of the abovementioned coated film, irradiating ultraviolet light onto the abovementioned coated film, and thereafter heating the abovementioned coated film.
The various components of the composition of the light absorbing film coating solution of this invention shall now be described.
Silicon oxide is necessary as the matrix material for fixing the gold microparticles in the film and also serves an important role as a low refractive index material that keeps down the visible light reflectivity of the film. A hydrolyzable, condensable silicon compound is used as the raw material of the silicon oxide. If the content of the silicon oxide raw material among the solids of the light absorbing film coating solution is too low, the visible light reflectance of the film will become too high. The content of silicon oxide as SiO
2
in the total amount of metal oxides and metal components in the light absorbing film coating solution is therefore preferably 45 to 93 weight % and more preferably 55 to 90 weight %.
As the raw material of the silicon oxide that forms the film in this invention, a silicon compound, etc., with which a strong, transparent film can be formed by the sol-gel method and is excellent in stability, that is, a silicon compound, etc., which can be subject to hydrolysis and condensation polymerization, can be used. Such a silicon compound shall be described more specifically below.
As an organosilicon compound, which is to be the raw material for silicon oxide, an alkoxide of silicon is favorable. Examples include tetralkoxysilanes, such as tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, and tetrabutoxysilane. A condensation product of such a compound (with n≧2, where n indicates the degree of condensation) or a mixture of such condensation products may also be used favorably. Examples of condensation products that can be used include hexaethoxydisiloxane (n=2), octaethoxytrisiloxane (n=3), decaethoxytetrasiloxane (n=4), and ethoxypolysiloxane (n≧5). Also, “Ethyl Silicate 40” (trade name; made by Colcoat Co., Ltd.), which is comprised of a mixture of a monomer (n=1) and condensation products (n≧2) [the composition in terms of weight ratios of this product is indicated in the reference, J. Cihlar, Colloids and Surfaces A: Physicochem. Eng. Aspects 70 (1993) pp. 253 to 268, as being 12.8 weight % monomer (n=1), 10.2 weight % dimer (n=2), 12.0 weight % trimer (n=3), 7.0 weight % tetramer (n=4), 56.2 weight % polymer (n≧5), and 1.8 weight % ethanol], etc. can be used favorably.
An alkyltrialkoxysilane, with which a part of the alkoxyl groups of an abovementioned compound has been substituted by an alkyl group or other hydrocarbon group, may also be used. Examples include compounds with which an alkoxyl group has been substituted by a straight chain or branched chain alkyl group, such as the methyl group, ethyl group, propyl group, butyl group, 2-ethylbutyl group, octyl group, etc., a cycloalkyl group, such as the cyclopentyl group, cyclohexyl group, etc., an alkenyl group, such as the vinyl group, aryl group, &ggr;-methacryloxypropyl group, &ggr;-acryloxypropyl group, etc., an aryl group, such as the phenyl group, toluyl group, xylyl group, etc., an aralkyl group, such as the benzyl group, phenetyl group, etc., or the &ggr;-mercaptopropyl group, &ggr;-chloropropyl group, &ggr;-aminopropyl group, etc. Besides silicon alkoxides, silicon oxide micropartic
Conlin David G.
Edwards & Angell LLP
Hazzard Lisa S.
McPherson John A.
Nippon Sheet Glass Co. Ltd.
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