Stock material or miscellaneous articles – Composite – Of quartz or glass
Reexamination Certificate
1998-10-14
2001-05-15
Lorin, Francis J. (Department: 1775)
Stock material or miscellaneous articles
Composite
Of quartz or glass
C106S031900, C252S301500, C428S546000
Reexamination Certificate
active
06231987
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to colorant compositions and, more particularly, to a colorant composition that is particularly suitable to being used on a glass surface.
BACKGROUND ART
It is known to color a surface of a glass substrate by coating a mixture of a glass powder and a colorant on the surface of the glass and then baking the mixture. This method has the advantage that the colorant can be readily coated upon the glass surface, facilitating design using the colorant. However, light may be scattered at a molten boundary of the glass powder so that parallel transmittance of light may be reduced to 80% or less.
To overcome the above problem, different methods have been devised. One of these methods is referred to as an ion exchange method. With this method, an inorganic salt containing Ag or Cu is coated upon the glass surface and then baked. Oxides deposited on the surface of the glass are removed. Generally, this method has the drawback that there may be poor selection capability since the ultrafine particles may not be easy to form for all elements.
It is also known to apply a dyed polymeric film on the glass surface. This method facilitates multiple tone selection and pattern formation. However, the resulting film may not have the desired durability.
It is also known to prepare a metal film paper that is deposited on a glass surface by a sputtering process. The desired film strength may not be realized using the sputtering process. Further, tone and pattern formation may be restricted. Additionally, the apparatus conventionally used to perform the sputtering process are often large. Still further, this type of apparatus may not be suitable for high volume mass production.
It is also known to form a metal oxide film on a glass substrate by baking an organic metal compound in atmospheric air. It may be difficult to form a pattern using this method.
It is also known to color a starting material for the glass. This method may also have the drawback that it is difficult to form a pattern.
In glass coloration, design properties are important. Facilitated tone and pattern formation is one important goal of those involved in the glass coloration field. Recent studies have reported glass colorants capable of producing various tones by fixing a gold colloid with a metal oxide. Pattern formation is carried out using screen printing. This overcomes a number of the problems in the prior art methods and is said to allow production of glass with excellent design characteristics.
However, since coloration is carried out by plasmon resonance absorption of gold colloids, yellow colors may not be developed effectively. Further, the desired variation in tone may not be possible. More particularly, when only gold is used for fine particles in the colorant, while transparent tones such as blue, purple, pink, grey, and green can be produced, the green may be heavily tinted with blue. Grey may also be tinted blue. It is possible that only a strongly reddish tone may be obtainable. A yellow color cannot be formed. Only the tone of a half mirror-like type metallic gloss can be provided for the reflection color, with the chemical resistance being potentially insufficient.
SUMMARY OF THE INVENTION
The invention is directed to a composition for transparent coloration of a glass surface. The composition has fine gold (Au) particles; fine silver (Ag) particles; a fixing agent including an organic Ti compound, an organic Fe compound, and an organic Si compound; a binder resin; and an organic solvent. The relationship between the amount of gold and silver particles to the titanium, iron, and silicon atoms of the fixing agent as a ratio of the number of metal atoms is as follows: (Au+Ag)/(Ti+Fe+Si)<½.
The relationship between the amount of gold and silver particles to the titanium, iron, and silicon atoms of the fixing agent as a ratio of the number of metal atoms may be as follows: (Au+Ag)/(Ti+Fe+Si)<¼.
One objective of the present invention is to provide a composition for transparent coloration of glass that lends itself to pattern formation, with clarity and extended, selectable variation of tones.
The inventive structure likewise lends itself to the formation of blue, purple, pink, yellow, green, grey, orange, and like transmission tones through the use of the fine gold and fine silver particles. The half mirror state in the reflection color can be avoided by controlling the density of the fine gold particles and fine silver particles so as to lower the reflecting qualities of the finished colored film, which may be baked on in its final form.
By using a fixing agent with the three organic compounds described, durability, such as resistance to alkali, water resistance, acid resistance, and abrasion resistance, may be improved. The reflection tone may also be varied for orange, yellow, green, blue, purple, white, and the like, depending on the amount of fixing agent that is blended into the composition.
The gold and silver particles may have a diameter of 1 to 100 nm, and more preferably, 1 to 50 nm.
The gold and silver particles may have a diameter of no more than 10 nm and may be dispersed in a first solvent before being combined with the organic solvent.
The first solvent may be at least one of &agr;-terepineol and toluene.
The first gold and silver particles may be dispersed in a polymer.
The polymer may be at least one of nylon 6, nylon 66, nylon 11, nylon 12, nylon 69, polyethylene terephthalate (PET), polyvinyl alcohol, polyphenylene sulfide (PPS), polystyrene (PS), polycarbonate and polymethyl methacrylate having a molecular coagulation energy of at least 2000 cal/mol.
The polymer may be at least one of a crystalline polymer and an amorphous polymer.
The fine gold particles may be dispersed in a polymer in a thermodynamically non-equilibrium state by at least one of a) vacuum vapor deposition by heating a polymer in vacuum, melting and evaporating the polymer, and solidifying the polymer on a substrate to define a polymer layer, and b) melting/quenching solidification by melting the polymer at a temperature higher than a melting temperature for the polymer, placing the melted polymer at the higher temperature into at least one of liquid nitrogen and another cooling medium to effect quenching, and depositing the polymer on a substrate to define a polymer layer.
In one form, the composition has a gold layer laminated to the polymer layer by one of a) vapor depositing the gold layer to the polymer layer and b) adhering the gold layer in the form of a gold foil to the polymer layer and thereafter heating the gold layer and polymer layer to a temperature higher than the glass transition point and lower than the melting point of the polymer to effect stabilization.
The organic solvent may be at least one of methacresol, dimethyl formamide, cyclohexane, and formic acid.
The organic Ti compound may be at least one of a) an alkoxide, b) an alkoxide comprising at least one of ethoxide and propoxide, c) acetyl acetonate, d) organic acid salt, e) a complex Ti salt, f) Ti-propoxide, g) Ti-acetyl acetonate, and h) Ti stearate.
The organic Fe compound may be at least one of a) an alkoxide, b) an alkoxide that comprises at least one of ethoxide and propoxide, c) acetyl acetonate, d) an organic acid salt, e) a complex Fe salt, f) Fe-propoxide, g) Fe-acetyl acetonate, h) Fe-ethoxide, i) Fe-acetate, j) Fe-propionate, k) Fe-naphthenate, and 1) Fe-citrate.
The organic Si compound may be at least one of a) an alkoxide, b) an alkoxide that comprises at least one of ethoxide and propoxide, c) acetyl acetonate of Si, d) organopolysiloxane, e) Si propoxide, f) Si acetyl acetonate, and g) polydimethyl siloxane.
The fixing agent may be present in relation to the number of metal atoms as follows: 10/90 to 95/5 for Ti/Fe and 1/99 to 95/5 for (Ti+Fe)/Si.
The binder resin may be at least one of a) cellulose and b) cellulose comprising at least one of i) nitrocellulose, ii) ethyl cellulose, iii) acetyl cellulose, and iv) butyl cellulose.
The organic s
Goto Kazuo
Maeda Yoshifumi
Lorin Francis J.
Mitsuboshi Belting Ltd.
Wood Phillips VanSanten Clark & Mortimer
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