HK1101819B - Silicone-coated architectural glass - Google Patents
Silicone-coated architectural glass Download PDFInfo
- Publication number
- HK1101819B HK1101819B HK07109799.7A HK07109799A HK1101819B HK 1101819 B HK1101819 B HK 1101819B HK 07109799 A HK07109799 A HK 07109799A HK 1101819 B HK1101819 B HK 1101819B
- Authority
- HK
- Hong Kong
- Prior art keywords
- terminated
- composite article
- component
- article according
- amount
- Prior art date
Links
Description
background
In recent years, coated glass has become increasingly used in the construction industry, particularly for berm and interior design applications, because coated glass is substantially less expensive than conventional exterior materials such as brick and granite, and coated glass is an aesthetically appealing choice for both the exterior and the interior. Metal films have been coated by low temperature vacuum deposition and high temperature pyrolysis to improve the aesthetic and reflective properties of such glass, which in turn saves energy in buildings using air conditioning. Ceramic glass coatings or so-called "ceramic enamels" have been used to color and shade pyrolytic metal coated glass. However, ceramic glass coatings cannot be used to coat metal-coated glass by vacuum deposition because the temperature of about 1400 ℃ required to apply the coating can cause distortion and melting of the vacuum-deposited metal coating. Another disadvantage of the high temperature heating required to apply the ceramic glass coating is that it severely limits the number of colours that can be selected.
To overcome this problem, attempts have been made to apply ceramic glass coatings to vacuum deposited metal coatings, and more recently a metal coated glass known as "post-temperable" has been developed. The glass is prepared by coating an intermediate silicon layer on a metal coating, curing the intermediate layer, then depositing the thus coated glass substrate in a tempering furnace, and then applying the ceramic glass coating at an elevated temperature. The main disadvantage of this process is the narrow temperature range that can be used for successful application of the ceramic glass coating.
It is known to coat substrates such as steel and glass with curable elastomeric polysiloxane compositions. See, e.g., U.S. patents US3,889,023, 4,115,356, 4,163,081, 4,495,340 and 5,364,921. Such compositions are also known for coating and reinforcing glass for architectural spandrel applications. See commonly-owned U.S. patent US4,814,230. Currently available elastomeric coatings for glass have a number of disadvantages: they are often applied together with a solvent, which leads to complicated application and prolonged curing times; many contain Volatile Organic Compounds (VOCs) and require protective measures for workers and the environment; many are chemically unstable at higher temperatures; they generally have a relatively short shelf life; and, perhaps most importantly, the adhesion of such coatings is inadequate and it is difficult to meet the four-sided structured glazing specification.
There is therefore a need in the industry for glass coatings that meet the following requirements: the glass can be made by increasing the tensile strength of various construction or architectural grade glasses, providing the same opacity and imparting a large color spectrum, very short curing times, being free of volatile organic compounds and having a solids content of 100%, being able to withstand the forces of nature, being chemically stable at higher temperatures, having a long shelf life, being sufficiently bonded to the glass substrate or to the metal coating side of the glass substrate to meet the specification for glazing a four-sided structure, and being able to be coated and cured at relatively low temperatures so as not to cause distortion or melting of the metal coating on the glass. The present invention fulfills these needs and is summarized and described in detail below.
Disclosure of Invention
There are several aspects of the present invention. In a first aspect, the present invention provides a flowable elastomeric composition containing 100% solids for coating glass, particularly for coating glass for architectural applications.
Secondly, the present invention provides novel composite articles comprising a glass substrate coated with the aforementioned elastomeric composition.
Third, the present invention provides novel composite articles comprising a coated metallic glass substrate wherein the metallic coating may be coated with the aforementioned elastomeric composition regardless of whether the metallic coating is applied using a high temperature pyrolysis process or a low temperature vacuum deposition process.
If the composition is stored as two separate components prior to use, its shelf life may be up to one year. Once the two components of the composition are mixed, the resulting coating is chemically stable at 260 ℃ and can readily pass all known tests for uv, humidity, adhesion, and bonds well to glass to allow the coated glass to meet the specifications for four-sided structural glazing. The composition is non-flammable, solvent-free, free of volatile organic compounds, and thus environmentally safe; can be roll-coated at relatively low temperature; can be put on coating equipment for a prolonged period of time without cleaning; and can be used with almost any pigment without changing the pigment because it is coated and cured at a relatively low temperature, which makes it possible to obtain coated glass of various colors.
Detailed Description
In the specification and claims, the word "about" refers to a range of values ± 10%, and the phrase "approximate weight percent" refers to ± 1 wt% of the wt% when integers and ± 0.1 wt% of the wt% when decimal. For example, a "weight percent approximation" of 75 wt% means 75 wt% + -1 wt%, or 74-76 wt%; and an "approximate weight percent" of 0.5 wt% means 0.5 wt% + -0.1 wt%, or 0.4-0.6 wt%.
Substrate
The coating composition of the present invention can be used on virtually any glass substrate, whether coated or uncoated. As noted above, in commercial architectural and architectural spandrel applications, vacuum deposited and pyrolytically produced metal film coated flat reflective glass is often used; both glasses are also suitable for use as substrates for the coating compositions of the present invention.
Coating composition
The coating composition of the present invention comprises a cross-linked polyvinyl siloxane/liquid polysiloxane rubber (PVS/LSR) component, which is modified by five other components.
The PVS/LSR component may be obtained from Dow CorningThe company is commercially available and is a two part product (part a and part B) that, when mixed and heated, forms a crosslinked PVS/LSR component. Dow CorningPart A of the company's PVS/LSR composition consists of the following three components: (1) dimethyl vinyl terminated dimethyl siloxane; (2) dimethylvinylated silica and/or trimethylated silica, and (3) dimethylvinyl-terminated dimethylsiloxane and/or dimethylvinyl-terminated methylvinylsiloxane. Component (4) of part a is a catalyst containing a platinum group metal complex. In the present invention, the term "platinum group metal" means a metal selected from platinum (Pt), palladium (Pd), ruthenium (Ru), rhodium (Rh), osmium (Os) and iridium (Ir), and preferred catalyst metals are platinum and rhodium, especially rhodium. The preferred form of the rhodium catalyst is a 20 wt% solution of trichlorotris (dibutylthio) rhodium complex in toluene containing from about 2.9 wt% to about 3.3 wt% rhodium. When used in this form in the preferred amounts of from about 0.003 wt% to about 0.012 wt% of the complex, the total rhodium metal content in the composition is from about 100 to about 400ppm, or from about 0.0001 to 0.0005 wt%.
Part B of the PVS/LSR complex is composed of the same components (1) - (3) as part A and dimethylsiloxane and/or methylhydrogensiloxane. Where, as is customary, weight percentages (wt%) are referred to throughout this specification and claims, based on the total weight of all components of the composition of the invention, part a and part B together preferably comprise from about 75 to about 90 wt% of the composition of the invention.
One of five possible components for modification of the PVS/LSR is an optional cocatalyst. A known hydrosilylation catalyst in the form of a platinum complex is initially contained in part A of the PVS/LSR composition to enhance and accelerate the crosslinking reaction. A particularly preferred platinum catalyst is a platinum-divinyltetramethyldisiloxane complex dissolved in a solution of a vinyl polysiloxane containing from 2 to 4% by weight of platinum metal. The catalyst-containing solution is preferably present in an amount of from about 0 to about 0.2 wt%.
Another PVS/LSR modifier contains two rheology or flow enhancing agents, which can be present in a total amount of about 20 wt%. Preferred such agents are vinyl terminated dimethyl siloxane and hydrogen terminated dimethyl siloxane. The hydrogen-terminated dimethyl siloxane having an SiH content, measured as H, of 0.01 to 2 weight percent is capable of crosslinking with a vinyl-terminated dimethyl siloxane containing 0.2 to 3 weight percent reactive vinyl groups, preferably the initial content of vinyl-terminated siloxane in part A of the PVS/LSR composition is from about 1 to about 10 weight percent, more preferably from about 5 to about 9 weight percent, and the initial content of hydrogen-terminated dimethyl siloxane in part B of the PVS/LSR composition is from about 0 to about 10 weight percent, more preferably from about 0 to about 5 weight percent.
The above-mentioned fluidity enhancer needs to be used in an amount such that the composition has sufficient viscosity to be applied to a glass substrate by roll coating and that the composition is easily bonded to the substrate at the time of application. The viscosity depends on the speed and thickness of the coating and can range widely from about 70,000 to about 120,000 centipoise.
Another PVS/LSR modifier is a coupling/adhesion promoter comprising a mixture of methylhydrogensiloxane and methylhydrogenocyclosiloxane having an SiH content, measured as H, of from 0.1 to 2% and which may be present in an amount of from about 1 to about 10% by weight, preferably in an amount of from about 5 to about 10% by weight. The coupling/adhesion promoter is preferably initially contained in part B of the PVS/LSR composition.
Finally, the PVS/LSR composition may contain pigments in an amount of from 0 to about 6 wt%, more preferably in an amount of about 1 wt%. The pigment can be of any type or state that is compatible with the composition and provides the same color or substantial opacity. Preferred examples are inorganic pigments such as iron oxides, titanium dioxide and processed mica; and organic pigments such as carbon black; and mixtures thereof, all in dry or powder form.
In general, the elastomeric compositions of the present invention, prior to application, contain the following components in approximate weight percent:
(a) a crosslinked polyvinylsiloxane/liquid silicone rubber component in an amount of from 75 to 90% by weight, which prior to crosslinking reaction contains the following components: dimethyl vinyl terminated dimethyl siloxane; dimethylvinylated silica and/or trimethylated silica; dimethyl-terminated dimethyl siloxane and/or dimethyl-terminated methyl vinyl siloxane; dimethyl siloxane and/or methyl hydrogen siloxane; and a platinum group metal complex used as a catalyst.
(b) A mixture of methylhydrogensiloxane and methylhydrogenocyclosiloxane in an amount of 1 to 10% by weight as coupling agent/tackifier;
(c) vinyl terminated dimethylsiloxane as a flowability enhancer in an amount of 1 to 10 weight percent;
(d) hydrogen terminated dimethyl siloxane as a flowability enhancer in an amount of 1 to 10 wt%;
(e) a pigment in an amount of 0 to 6% by weight.
Application of the coating
The composition is preferably coated onto the glass substrate by conventional roll coating. The coating is coated with a film having an average thickness of from about 4 to about 8 mils.
The composition may be cured by air drying, heating or infrared radiation, in which method infrared radiation curing at 145-175 ℃ and ambient relative humidity is preferred, and at a temperature more preferably about 145-155 ℃, is generally substantially complete within 2 minutes, depending on the thickness of the coating, the thickness of the glass, the pigment selected and the ambient temperature. The coated glass product typically cools sufficiently within a few minutes to be shipped and transported, depending on the glass thickness.
Example 1
A piece of architectural-grade spandrel-type glazing having a thickness of 6mm and having a vacuum-deposited titanium dioxide reflective coating applied to one side thereof was washed with hot water and a detergent and then dried. Dow Corning with platinum catalyst in part APart a and part B of the company PVS/LSR 3730 composition were poured in equal amounts of 43 wt% into two separate mixing vessels respectively and slowly stirred while adding thereto the following components expressed in wt% below:
to part a was added:
6% by weight of vinyl-terminated dimethylsiloxane
1 wt% low sulfur carbon black
To part B was added:
4.5 wt% of a hydrogen terminated dimethyl siloxane
2.5% by weight of methylhydrogensiloxane/methylhydrogenocyclosiloxane mixture
The thus modified parts a and B are then mixed until a homogeneous composition is formed. The resulting composition was coated as a substantially uniform coating layer average 5 mils thick on the metal-coated side of the glass substrate by a Model609RS roll coater system (available from Wallace corporation, montavia, california) and cured with an infrared lamp at 145 ℃ for 90 seconds at ambient relative humidity. The so coated substrates can be transported and shipped after 5 minutes of cooling by a fan. The coated glass has a light transmission of less than 5% in the visible spectrum, which renders it substantially opaque.
The adhesion properties of this coating were initially tested by a modified STM C794-80 peel test and the results demonstrate excellent adhesion properties. After 7000 hours of accelerated ageing in a QUV weatherometer, the silicone-coated glass samples were exposed alternately to an environment of 40 ℃ at 100% relative humidity and to an environment of strong UV irradiation at 60 ℃ in a cycle of 4 hours, and did not fade, became strong, did not crack, and did not suffer from a decrease in adhesion.
In a further test, another sample of the glass thus coated was irradiated with UV light for 6 months. The coating still keeps fadeless and crack-free, and the adhesion is excellent.
Other tests included exposure of a sample of the coated glass to boiling water for 250 hours, and exposure of the sample to an atmosphere of 100% relative humidity for 1000 hours, both of which did not adversely affect the adhesion of the coating.
Example 2
The procedure was essentially the same as in example 1, except that the following components were added to part A (40 wt%) and part B (40 wt%) of the PVS/LSR composition:
to part a was added:
9% by weight of vinyl-terminated dimethylsiloxane
1 wt% low sulfur carbon black
To part B was added:
3.2 wt% of a hydrogen terminated dimethyl siloxane
6.8% methylhydrogensiloxane/methylhydrogenocyclosiloxane mixture
Samples of the glass thus coated were also examined as in example 1, and the results were essentially the same.
Example 3
The procedure was essentially the same as in the examples except that the platinum catalyst in part A was replaced with 0.006 wt% rhodium complex [ trichlorotris (dibutylthio) rhodium ], parts A and B were each used in an amount of 43 wt%, and the following components were added to part B of the PVS/LSR composition:
to part B was added:
2.5 wt% of a hydrogen terminated dimethyl siloxane
4.5% by weight of methylhydrogensiloxane/methylhydrogenocyclosiloxane mixture
Samples of the glass thus coated were also examined as in example 1, and the results were essentially the same.
Example 4
The procedure was essentially the same as in example 3, except that the amounts of part A and part B were 40 wt%, respectively, and the following components were added to part A and part B:
to part a was added:
9% by weight of vinyl-terminated dimethylsiloxane
1 wt% low sulfur carbon black
To part B was added:
5 wt% of a hydrogen terminated dimethyl siloxane
5 wt.% methylhydrogensiloxane/methylhydrogenocyclosiloxane mixture
Samples of the glass thus coated were also examined as in example 1, and the results were essentially the same.
Example 5
The procedure was essentially the same as in example 3, except that the amounts of part A and part B were 40 wt%, respectively, and titanium dioxide (TiO)2) Instead of carbon black, the following components were added to part a and part B:
to part a was added:
6% by weight of vinyl-terminated dimethylsiloxane
4 wt% TiO2
Adding to part B:
10% by weight of methylhydrogensiloxane/methylhydrogenocyclosiloxane mixture
Samples of the glass thus coated were also examined as in example 1, and the results were essentially the same.
The words and phrases used in the foregoing specification are used in the specification as words of description rather than words of limitation, and the use of such words and phrases are not intended to exclude the same reference to features shown and described in the specification or other expressions which are part of the specification, it being recognized that the scope of the invention is defined and limited only by the claims which follow.
Claims (21)
1. A composite article comprising a glass substrate coated with an elastomeric coating, characterized in that the elastomeric coating comprises the following components in approximate weight percentages as follows:
(a) a crosslinked polyvinylsiloxane liquid silicone rubber component in an amount of from 75 to 90% by weight, which prior to crosslinking comprises the following components: dimethyl vinyl terminated dimethyl siloxane; dimethylvinylated silica and/or trimethylated silica; dimethylvinyl terminated dimethylsiloxane and/or dimethylvinyl terminated methylvinylsiloxane; dimethyl siloxane and/or methyl hydrogen siloxane; and a platinum group metal complex as a catalyst;
(b) a mixture of methylhydrogensiloxane and methylhydrogenocyclosiloxane as coupling agent and adhesion promoter in an amount of 1 to 10% by weight;
(c) vinyl terminated dimethylsiloxane as a flowability enhancer in an amount of 1 to 10 wt%;
(d) hydrogen-terminated dimethylsiloxane as a flowability enhancer in an amount of 1 to 10 wt%; and
(e)0-6 wt% of pigment.
2. The composite article according to claim 1, wherein the SiH content of component (b) is from about 0.1 wt% to about 2 wt%, measured as H; (c) the active vinyl content of the component is from about 0.2 wt% to about 3 wt%; and the SiH content of component (d) is from about 0.01 wt% to about 2 wt% measured as H.
3. A composite article according to claim 1 or 2, wherein the catalyst complex in component (a) comprises a platinum group metal selected from platinum, palladium, ruthenium, rhodium, osmium and iridium; and (e) component is selected from inorganic and organic pigments and mixtures thereof.
4. A composite article according to claim 3 wherein said catalyst comprises a rhodium complex and said (e) component is selected from the group consisting of carbon black, titanium dioxide, iron oxides, processed mica, and mixtures thereof.
5. A composite article according to claim 4 wherein the catalyst is the complex trichlorotris (dibutylthio) rhodium.
6. A composite article according to claim 1 or 2, wherein the concentration of the complex is from about 0.003 to about 0.012 wt%.
7. A composite article according to claim 1 or 2, wherein the glass substrate is float glass, sputter coated glass or pyrolytic glass.
8. A composite article according to claim 7, wherein said glass substrate has a metal coating thereon, said metal coating being coated with said elastomeric coating.
9. A composite article according to claim 8, wherein the metal coating has been applied by high temperature pyrolysis.
10. The composite article according to claim 9, wherein the metal coating has been applied by a low temperature vacuum deposition process.
11. A composite article according to claim 1 or 2, wherein the components are present in approximate weight percentages as follows:
(a)80-86wt％；
(b)2.5-7wt％；
(c)6-9wt％；
(d)3.2-4.5 wt%; and
(e)1wt％。
12. a composite article according to claim 1 or 2, wherein the components are present in approximate weight percentages as follows:
(a)86wt％；
(b)2.5wt％；
(c)6 wt%; and
(d)4.5wt％。
13. a composite article according to claim 1 or 2, wherein the components are present in approximate weight percentages as follows:
(a)80wt％；
(b)6.8wt％；
(c)9 wt%; and
(d)3.2wt％。
14. an elastomeric composition for coating a glass substrate or a metal-coated glass substrate, characterized in that said composition comprises the following components in the following approximate weight percentages:
(a) a crosslinked polyvinylsiloxane liquid silicone rubber component in an amount of from 75 to 90% by weight, which prior to crosslinking comprises the following components: dimethyl vinyl terminated dimethyl siloxane; dimethylvinylated silica and/or trimethylated silica; dimethyl-terminated dimethyl siloxane and/or dimethyl-terminated methyl vinyl siloxane; dimethyl siloxane and/or methyl hydrogen siloxane; and a platinum group metal complex as a catalyst;
(b) a mixture of methylhydrogensiloxane and methylhydrogenocyclosiloxane as coupling agent and adhesion promoter in an amount of 1 to 10% by weight;
(c) vinyl terminated dimethylsiloxane as a flowability enhancer in an amount of 1 to 10 wt%;
(d) hydrogen-terminated dimethylsiloxane as a flowability enhancer in an amount of 1 to 10 wt%;
(e)0-6 wt% of pigment.
15. The composition according to claim 14, wherein the SiH content of component (b) is from about 0.1 wt% to about 2 wt%, measured as H; (c) the active vinyl content of the component is from about 0.2 wt% to about 3 wt%; (d) the SiH content of the component is from about 0.01 wt% to about 2 wt%, measured as H.
16. A composition according to claim 14 or 15 wherein the catalyst complex in component (a) comprises a platinum group metal selected from platinum, palladium, ruthenium, rhodium, osmium and iridium; and (e) component is selected from the group consisting of carbon black, iron oxides, titanium dioxide, zinc oxide, processed mica, inorganic and organic pigments, and mixtures thereof.
17. The composition of claim 16 wherein the catalyst is a rhodium complex.
18. The composition according to claim 17, wherein the rhodium complex is tris (dibutylthio) rhodium trichloride.
19. A composition according to claim 1 or 2, which is packaged separately as part a and part B and has the following composition expressed in approximate weight ratios:
part A:
(1) a mixture in an amount of 37.5 to 45 wt%, comprising the following components: dimethyl vinyl terminated dimethyl siloxane; dimethylvinylated silica and/or trimethylated silica; dimethylvinyl terminated dimethylsiloxane and/or dimethylvinyl terminated methylvinylsiloxane; and a platinum group metal complex as a catalyst;
(2)1-10 wt% vinyl terminated dimethyl siloxane; and
(3)0-6 wt% of a pigment;
and part B:
(1) a mixture in an amount of 37.5 to 45 wt%, comprising the following components: dimethyl vinyl terminated dimethyl siloxane; dimethylvinylated silica and/or trimethylated silica; dimethylvinyl terminated dimethylsiloxane and/or dimethylvinyl terminated methylvinylsiloxane; and dimethylsiloxane and/or methylhydrogensiloxane;
(2)1-10 wt% of a hydrogen terminated dimethyl siloxane; and
(3)1-10 wt% of a mixture of methylhydrogensiloxane and methylhydrogenocyclosiloxane.
20. A composition according to claim 1 or 2, wherein the components are present in approximate weight percentages as follows:
part A:
(1)43wt％；
(2)6 wt%; and
(3)1wt％；
and part B:
(1)43wt％；
(2)4.5 wt%; and
(3)2.5wt％。
21. a composition according to claim 1 or 2, wherein the components are present in approximate weight percentages as follows:
part A:
(1)40wt％；
(2)9 wt%; and
(3)1wt％；
and part B:
(1)40wt％；
(2)3.2 wt%; and
(3)6.8wt％。
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/241,191 | 2005-09-30 | ||
| US11/241,191 US7309734B2 (en) | 2005-09-30 | 2005-09-30 | Silicone-coated architectural glass |
| US11/449,466 | 2006-06-08 | ||
| US11/449,466 US7531242B2 (en) | 2005-09-30 | 2006-06-08 | Silicone-coated architectural glass |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| HK1101819A1 HK1101819A1 (en) | 2007-10-26 |
| HK1101819B true HK1101819B (en) | 2012-09-14 |
Family
ID=
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP2617690B1 (en) | Method of decorating chemically strengthened glass | |
| US8877327B2 (en) | Silicone coating as a sealing layer for a decoration layer | |
| JP6231066B2 (en) | Preparation of glass or glass-ceramic articles with improved coating and the articles | |
| EP1835002B1 (en) | Non-stick ceramic coating composition and process | |
| US20070017402A1 (en) | Vitreous printing by means of a silkscreen process | |
| FR2993880B1 (en) | GLASS LACQUER | |
| US7531242B2 (en) | Silicone-coated architectural glass | |
| JP2007530405A (en) | Glass ceramic plate or glass plate reinforcement and reinforcement plate | |
| CN110385923B (en) | Printing equipment component | |
| US7309734B2 (en) | Silicone-coated architectural glass | |
| CN103596896A (en) | Low VOC media | |
| US7838116B2 (en) | Silicone-coated architectural and decorative glass | |
| HK1101819B (en) | Silicone-coated architectural glass | |
| DK3140261T3 (en) | HARDWARE PAINTED GLASS WITH IMPROVED MECHANICAL PROPERTIES | |
| US8916328B2 (en) | Coated glass substrate with ultraviolet blocking characteristics and including a rheological modifier | |
| CN115093131A (en) | Coated glass with heat insulation and preservation functions and preparation method thereof | |
| JP4177692B2 (en) | Manufacturing method of glass plate with low reflection film | |
| JPH09142887A (en) | Surface-protection film for noble metal | |
| WO2024033936A1 (en) | A glass substrate having a heat treatable enamel coating and a method of manufacturing the same | |
| JP2026022640A (en) | Glass substrate coating agent and coating formation method | |
| FR2868065A1 (en) | Reinforcing of glass-ceramic or glass plate useful as cooktop plate comprises fixing layer(s) comprising (co)polymer(s) which is resistant to high temperature onto part(s) of the surface of at least one of two main sides | |
| JP2020029525A (en) | Coating composition, coated article, and method for producing coated article | |
| JP2004043276A (en) | Window structure for vehicle | |
| JPH04164880A (en) | Ceramic-coated panel | |
| JP2006206411A (en) | Method for manufacturing substrate coated with silicon oxide membrane |