Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
2000-01-13
2001-07-17
Dawson, Robert (Department: 1712)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C106S287160, C106S481000, C427S387000, C428S447000, C528S029000, C528S043000
Reexamination Certificate
active
06262187
ABSTRACT:
TECHNICAL FIELD
The present invention relates to colored coating compositions which can easily form a colored glass gel coating film which is practical and excellent in water resistance, boiling water resistance, alkali resistance, weather resistance, etc. and, at low temperatures on the outer surface of glass products such as glass bottles, ceramic products, metal products, etc. In particular, the present invention relates to colored coating compositions to color the outer surface of the glass bottles which can be recycled in the form of transparent cullet.
BACKGROUND ART
Glass products has hitherto been colored by incorporating metal ions such as iron ion, chromium ion and cobalt ion as a coloring agent in raw materials of glass. However, collected colored cullet does not become colorless by heating and fusing due to the above-mentioned metal ions. A demand for recycling glass bottles has been increasing in recent years. However, the other colored bottles than brown bottles are not suitable for recycling because their colors remain even after fusion. Such bottles are disposed mainly as waste products.
In order to make the heated and fused products colorless, Japanese Laid-open Patent Publication No. 320742/1989 proposed a method of forming a glass gel coating film at heating temperatures of 500° C. or lower by a sol-gel method through hydrolysis and polycondensation of metal alkoxides using coating compositions containing the metal alkoxides, water, acids, alcohols, and organic pigments and dyes as coloring agents. However, the glass gel coating film obtained at the heating temperatures of 500° C. or lower by the sol-gel method has a lot of pores and tends to become porous. As a result, no dense film is obtained, and the obtained film causes the problems that the film is not good in water resistance and the dyes are eluted owing to invasions of water, chemicals, etc. into the pores of the film surface.
In order to solve these problems, Japanese Laid-open Patent Publication No. 178623/1993 proposed a method of forming a glass gel coating film wherein heating is carried out at the temperature of 500° C. lower by the sol-gel method using coating compositions containing pigment particles having particle diameters being larger than those of pores of the glass gel coating film.
However, the method has the following defects. Adjustment of the particle diameters to obtain the pigment particles having the particle diameters being larger than that of the pores of the glass gel coating film is troublesome. Further, the compositions cannot provide the products having desired sufficient water resistance.
As mentioned above, the glass gel coating films having photo absorptivity have hitherto been formed by the sol-gel method. In this process, however, heating temperatures of the films were controlled at a low temperature in terms of heat resistance of coloring agents. Consequently, the obtained glass gel coating films were porous and caused the problems with water resistance, boiling water resistance, alkali resistance, weather resistance, etc. as mentioned above.
An object of the present invention is to provide colored coating compositions which can easily form a colored glass gel coating film which is excellent in water resistance, boiling water resistance, alkali resistance, weather resistance, etc. at low temperatures on the outer surface of glass products, metal products, etc. in view of the above-mentioned problems.
There also hitherto existed the problem that when coloring coating operation of bottles is carried out under high-humidity environment in rainy weather, obtained colored bottles have haze.
Another object of the present invention is to provide colored coating compositions with which colored bottles having no haze can be obtained even if coating is carried out under the high-humidity environment.
DISCLOSURE OF THE INVENTION
In order to solve the above-mentioned problems, a first colored coating composition according to the present invention comprises a sol-gel liquid obtained by polycondensation of phenyltrialkoxysitane or oligomer thereof, one polyol selected from the group consisting of acryl polyol, polyester polyol, polyether polyol and lower alkyl polyol or a combination thereof, and an organic coloring agent.
A second colored coating composition according to the present invention comprises a liquid obtained by polycondensation of phenyltrialkoxysilane or oligomer thereof, one polymer selected from the group consisting of acryl polyol, polyester polyol and polyether polyol or a combination thereof, a polyisocyanate resin and the organic coloring agent.
In the coating compositions of the present invention, polycondensates obtained by the polycondensation of the phenyltrialkoxysilane or the oligomer thereof act as base substances for forming sol-gel glass.
In the present specification, the polycondensation of the phenyltrialkoxysilane or the oligomer thereof includes not only single polycondensation of the phenyltrialkoxysilane or the oligomer thereof but also copolycondensation of the phenyltrialkoxysilane or the oligomer thereof with small amounts of other metal alkoxides such as tetraethoxysilane and tetraisopropoxytitanium.
The phenyltrialkoxysilane is represented by the general formula: Si(C
6
H
5
).(OR)
3
wherein R means a lower alkyl group, preferably an alkyl group having 1 to 5 carbon atoms.
Phenyltrimethoxysilane or phenyltriethoxysilane is particularly preferable as the phenyltrialkoxysilane.
Examples of the acryl polyol are a homopolymer of hydroxyalkyl (meth)acrylate, a copolym or of hydroxyalkyl (meth)acrylate with alkyl (meth)acrylate, etc., as the polymer selected from the group consisting of the acryl polyol, the polyester polyol, the polyether polyol and the lower alkyl polyol or a combination thereof (hereinafter referred to as “acryl polyol or the like”) to be used for the coating compositions of the present invention. More specifically, there can be used a homopolymer of hydroxyethyl (meth)acrylate, a copolymer of hydroxyethyl (meth)acrylate with isobutyl (meth)acrylate, etc. Weight-average molecular weight of the acryl polyol is, for example, 1000 to 100000, preferably 5000 to 50000, more preferably 10000 to 30000. Number-average molecular weight of the acryl polyol is, for example, 500 to 50000, preferably 2500 to 25000, more preferably 5000 to 15000. Typical examples of the acryl polyol are a base of a paint composition “Retan PG80” manufactured by Kansai Paint Co., Ltd. (The base contains the acryl polyol at the rate of 58.7% by weight.) and a resin composition “Acrydic A-801P”(hydroxyl value: 50)manufactured by Dai Nippon Ink & Chemicals Inc.
Examples of the polyester polyol are a resin composition “Baiknock D6-520”(hydroxyl value: 210) manufactured by Dai Nippon Ink & Chemicals Inc., etc. Weight-average molecular weight of the polyester polyol is, for example, 250 to 10000, preferably 300 to 5000, more preferably 500 to 1500.
Typical examples of the polyether polyol are an adduct of glycerin with propylene oxide such as “Sannix GP-600” manufactured by Sanyo Chemical Co., Ltd. (hydroxyl value: 280) and an adduct of sorbitol with propylene oxide (hydroxyl value: 490). Other examples of the polyether polyol are an adduct of glycerin with ethylene oxide, polyethylene glycol, polypropylene glycol, etc.
Examples of the lower alkylpolyol are dihydric alcohols such as 1,4-butanediol, ethylene glycol, diethylene glycol, tetraethylene glycol and 2-methyl-2,4-pentanediol and trihydric alcohols such as glycerin, trimethylolpropane and 1,2,6-hexanetriol.
An amount of ethylene glycol as lower alkylpolyol to be added is preferably 1 to 10% by weight, more preferably 3 to 5% by weight to the whole composition. A carbon number of the lower alkylpolyol is preferably 2 to 10.
1,3,5-tris(isocyanatehexamethylene)isocyanurate, which is a cyclic trimer of hexamethylenediisocyanate, is preferable as the polyisocyanate resin to be used for the second colored coating composition according to the present invention. A typical example of the polyisocyanate resin is a cu
Funato Masayuki
Ishii Kazuhisa
Kanazawa Hidefumi
Minami Tsutomu
Nakazumi Hiroyuki
Armstrong Westerman Hattori McLeland & Naughton LLP
Dawson Robert
Nagase Chemtex Corporation
Zimmer Marc S.
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