Substrate having removable protective coating and corresponding methods
Abstract
FIELD: chemistry. SUBSTANCE: invention relates to the technology of producing removable protective coatings from carbonaceous materials and can be used in substrates, for example glass-type substrates with defined light transmission characteristics in the visible region. The substrate is made from tempered or non-tempered or heat-strengthened glass, and the removable coating contains at least 75 wt % carbon and can be amorphous and have a graphite crystal structure. EFFECT: substrate can have an additional functional low-radiating coating on which a blocking layer can be applied. 23 cl, 1 ex
Term
Term ended
Expired 20 December 2025, 0.8 years ago.
- Priority
- Filed
- Granted
- Expired
- Today
23 claims: 4 independent, 19 dependent
- 1Подложка с защитным покрытием на ее поверхности, характеризующаяся тем, что подложка выполнена из закаленного, или незакаленного, или термоупрочненного стекла, а покрытие является удаляемым, состоит из углеродсодержащего материала и нанесено, по меньшей мере, на части подложки.
- 2Подложка п.1, у которой удаляемое защитное покрытие содержит, по меньшей мере, 75 вес.% углерода.
- 3Подложка по п.1 или 2, у которой углеродсодержащий материал является аморфным.
- 4Подложка по п.1 или 2, у которой углеродсодержащий материал содержит структуру кристаллов графита.
- 5Подложка п.1, у которой удаляемое защитное покрытие имеет толщину в пределах до 10 мкм.
- 6Подложка по п.5, у которой удаляемое защитное покрытие имеет толщину в пределах до 3000 Å.
- 7Подложка по п.1, дополнительно имеющая функциональное покрытие, нанесенное поверх подложки, где функциональное покрытие находится между подложкой и удаляемым защитным покрытием.
- 8Подложка по п.7, у которой функциональное покрытие включает слабоизлучающее покрытие.
- 9Подложка по п.1, дополнительно имеющая блокирующий слой поверх функционального покрытия, где блокирующий слой находится между функциональным покрытием и удаляемым защитным покрытием.
- 10Подложка по п.9, где блокирующий слой выбирают из группы, включающей оксиды, нитриды и оксинитриды кремния, титана, циркония, ниобия, алюминия, гафния, иттрия, лантана и их смесей.
- 11Подложка по п.9, где блокирующий слой имеет толщину в пределах до 50 мкм.
- 12Подложка по п.11, где блокирующий слой имеет толщину в пределах от 25 Å до 500 Å.
- 13Способ защиты подложки, включающий нанесение, по меньшей мере, поверх части подложки удаляемого защитного покрытия, состоящего в основном из углеродсодержащего материала.
- 14Способ по п.13, дополнительно включающий нанесение функционального покрытия поверх, по меньшей мере, части подложки, где удаляемое защитное покрытие находится над функциональным покрытием.
- 15Способ по п.14, в котором функциональное покрытие включает в себя слабоизлучающее покрытие.
- 16Способ по п.13, дополнительно включающий нагрев подложки с покрытием до температуры, достаточной для сгорания удаляемого защитного покрытия.
- 17Способ по п.13 или 14, в котором подложкой является стекло.
- 18Способ по п.13, в котором нанесенное удаляемое защитное покрытие имеет толщину в пределах до 50 мкм.
- 19Способ по п.18, в котором нанесенное удаляемое защитное покрытие имеет толщину в пределах до 3000 Å.
- 20Способ по п.14, дополнительно включающий нанесение блокирующего слоя поверх функционального покрытия между функциональным покрытием и удаляемым защитным покрытием.
- 21Способ по п.20, в котором блокирующий слой выбирают из группы, включающей кремний, титан, цирконий, ниобий, алюминий, а также их оксиды, нитриды и оксинитриды и их смеси.
- 22Способ по п.20, в котором нанесенный блокирующий слой имеет толщину в пределах до 50 мкм.
- 23Способ по п.13, в котором нанесение удаляемого защитного покрытия включает распыление углеродсодержащей мишени в, по существу, свободной от кислорода атмосфере.
Independent claims23
49 paragraphs in 5 sections, as filed
REFERENCE TO RELATED APPLICATION
This application is a continuation in part application SU №09 / 567934, filed 10 May 2000, which is hereby incorporated herein by reference.
FIELD OF THE INVENTION
The present invention relates generally to removable protective coatings for substrates with any functional coating (s) or without it, and more particularly to a removable protective coating comprised predominantly of any carbon-based material.
BACKGROUND
Substrates such as glass, plastic, etc. may have two primary coating ending peripheral edge of which at least one surface has a light transmission in the visible range of from 0 to less than 100%. Some substrates, such as a mirror, can have a surface that transmits visible light, and another surface which reflects visible light. Substrates can be fabricated in a variety of products or intermediates.
In the glass industry large glass sheets, such as size of 1.2 m × 1,8 m, glass manufacturers are made and sent to the factory, where the sheets are cut into smaller substrates for use in various industrial products such as architectural glass, automotive glass parts, insulating glass, mirrors, etc. The glass substrates may or may not have one or more well-known functional coating, such as solar control coatings, conductive coatings, antireflection coatings and / or low emissivity coating. With factories manufactured goods sent to consumers.
As a rule, manufacturers of window glass sheets sent to the factory in bulk without packaging. For example, glass sheets may be collected and sent to a stack of any specialized pallet or any type of-departure containers are well known in the art transportation glass. Sometimes it happens that during the manipulation, processing, transportation or storage of the substrate itself and / or the functional coating on a substrate obtained damage.
The present invention provides a novel removable protective coating for substrates, particularly to substrates such as glass with certain characteristics of light transmission in the visible region. The removable protective coating of the invention is made mainly of carbonaceous material.
Disclosure of invention
One non-limiting embodiment of the present invention is a coated substrate comprising: a substrate having a surface and a removable protective coating comprised predominantly of a carbon material applied over at least a portion of the substrate.
Another non-limiting embodiment of the present invention is a method for protecting the surface, comprising: applying a removable protective coating consisting essentially of a carbon material on at least a portion of the substrate.
DISCLOSURE OF THE INVENTION
All numerical expressions relating to the dimensions, physical characteristics, quantities of ingredients, etc., which are used in the specification and claims are to be understood as equipped in all cases the expression "about." Accordingly, unless otherwise indicated, the numerical values set forth in the following specification and claims may vary depending on the properties that are desirable in the present invention. In the worst case (and without attempting to limit the application of the doctrine of equivalents to the scope of the invention), each numerical parameter should be taken, at least in the light of reported significant digits applying ordinary rounding techniques. Moreover, all ranges disclosed herein are values to be understood as including all related subintervals. For example, the range of "1 to 10" should be considered to include any and all subranges between (and inclusive of) between a minimum value of 1 and a maximum value equal to 10, i.e. all subranges beginning with 1 or more and ending with a maximum value of 10 or less, for example from 1.0 to 7.8, 3.0 to 4.5, from 6.3 to 10.0.
As used herein, spatial terms and the terms direction, such as "left", "right", "outer", "above", "below", "upper", "lower", etc. are understood to encompass various alternative orientations and, accordingly, such terms are not to be construed as limiting.
As used herein, the phrase "on", "deposited on / over", "formed on / over", "upper layer" and "cooked-on / over" mean formed, deposited or created on the surface, but not necessarily in contact with her. For example, any coating layer, "formed over" a substrate does not involve the presence of one or more other coating layers of the same or different from the composition located between the formed coating layer and the substrate. The substrate may for example have a conventional coating such as those known in the art as coatings for substrates, particularly glass or ceramic.
As used herein the term "functional coating" refers to a coating that modifies one or more physical properties of the substrate, such as: optical, thermal, chemical or mechanical properties, and is not intended to be removed from the substrate during subsequent processing. Functional coating is usually permanent or "undelete" the coating, ie, functional coating is regarded as an essential or necessary for the end use of the substrate with a functional coating.
As used herein, the coating layer is "homogeneous" when the outer surface or portion (i.e., surface or portion farthest from the substrate), the inner surface or portion (i.e., surface or portion closest to the substrate) and portion between the outer and inner surfaces have substantially the same composition.
As used herein, the coating layer is "graded" when the coating layer is characterized by increased content of one or more components and decrease in the content of one or more other components in the direction from the inner surface to the outer surface and vice versa.
As used herein, the coating layer is "non-homogeneous" when the coating layer is not homogeneous.
As used herein the term "low emissivity coating" describes a functional coating, which allows the transmission of energy through the coating at a wavelength in the visible region, i.e. visible spectrum from 400 to 780 nm but reflects the energy at longer infrared wavelengths and typically intended to improve the thermal insulation properties of architectural glasses. Typically, "low emissivity" coating is characterized by the emission of up to 0.3, e.g., 0.2.
One non-limiting embodiment of the present invention is a coated substrate having a removable protective cover, i.e. coating is temporary and not on the substrate in its final form. The removable protective coating of the invention may be formed over at least a portion of the substrate, or over at least a portion of the functional coating formed on the substrate, as described below.
In a non-limiting embodiment, the removable protective coating consists predominantly of a carbonaceous material. As is well known in the art, the carbon may exist in amorphous form or in the form of a plurality of crystal structures such as diamond or graphite. As used herein, "predominantly" means at least 50 wt.% Carbon, such as at least 75 wt.% Carbon, or at least 90 wt.% Carbon, or at least 95 wt.% Carbon, where the weight content It refers to the total weight of the removable protective coating. In one non-limiting embodiment, the amount of carbon in the material that forms the removable protective coating is in the range up to 100 wt.%.
According to the present invention, the removable protective coating can be applied by any conventional method such as (but not limited to) vapor deposition by magnetron sputtering (MSVD), chemical vapor deposition (CVD), spray pyrolysis (i.e., pyrolytic deposition) , chemical vapor deposition at atmospheric pressure (APCVD), chemical vapor deposition at low pressure (LPCVD), intensified by a plasma chemical vapor deposition (PECVD), carried by a plasma chemical vapor deposition (PACVD), thermal evaporation or evaporation under a beam of electrons, cathodic arc deposition, plasma spray deposition, and wet chemical deposition (e.g., sol-gel, mirror silvering, etc.), coating with an electron beam, causing the coal-arched and m. d.
Examples of suitable devices for coating by CVD and methods are disclosed in U.S. Patent №№3652246, 4,351,861, 4,719,126, 4,853,257, 5,356,718 and 5,776,236, which are hereby incorporated herein by reference.
Examples of suitable MSDVD-coating methods disclosed in U.S. Patent №№5018759, 4,898,789, 4,948,677, 4,834,857, 4,898,790 and 4,806,220, which are hereby incorporated herein by reference.
In a non-limiting embodiment, the substrate is coated with the covering in a traditional-MSVD apparatus. The removable protective coating can be applied by spraying carbon-containing sputtering target, for example, a graphite target such as the one that comes on the market MSI, Co in Columbus, OH, in one of the compartments of the cathode coater. Carbon target may be sprayed in any conventional manner to the application over a substrate removable protective coating.
In one non-limiting embodiment, the method may be spray MSDVD carbon target in an atmosphere substantially free from oxygen in order to minimize combustion of the carbon material sprayed. "Substantially free of oxygen" means not more than 20 vol.% Oxygen, e.g., not more than 10 vol.% Of oxygen or not comprising oxygen. Suitable non-limiting oxygen-free atmosphere is argon gas.
The removable protective coating can be applied to any thickness. For example, the removable protective coating can be deposited to a thickness of 50 .mu.m, for example, up to 10 micrometers or 3 micrometers, or to 3000 Å, or 350 Å.
According to the present invention, suitable substrates may be made of any material such as glass, metal, plastic, the type of polyacrylate, polycarbonate and polyethylene terephthalate (PET), ceramic, or mixtures or combinations thereof.
In one non-limiting embodiment, the substrate is glass. The glass may be, for example, conventional sodium silicate glass, i.e. transparent glass, or it can be tinted glass or in any other way colored glass, borosilicate glass, leaded glass, tempered, untempered, annealed, or heat strengthened glass. The glass can be of any type, such as conventional float glass or flat glass, and can have any form with any optical properties, e.g., any light transmission in the visible, ultraviolet, infrared and / or total solar energy transmission. Examples of glass substrates suitable for the invention are disclosed in U.S. Patent №№4746347, 4,792,536, 5,240,886, 5,385,872 and 5,393,593, which are incorporated herein by reference.
The substrate is not limited to any size. It may, for example, have a size greater than 1.2 m × 1.5 m. The substrate can be any thickness. For example, the substrate may have a thickness ranging from 1 mm to 50 mm, for example from 2 mm to 13 mm or from 2 mm to 6 mm. The substrate may have any shape. It may for example be curved, rounded or flat,
One skilled in the art can easily guess that the substrate may be of any type, such as a rigid, flexible or even a stable film or cloth provided on the possibility of causing a substrate removable protective coating according to the invention. For example, the substrate may be a conventional type of glass spandrel which was used in the industrial field sales window.
In a non-limiting embodiment, wherein the substrate is glass and is intended for the manufacture of transparent parts of the vehicle such as the windshield, side lights, reversing lights, sun roofs, transparent hatch etc., the removable protective coating of the invention can be applied over at least a portion of the entire surface of the transparent substrate, for example, over at least 50% or transparent surface over at least 80% or transparent surface over substantially the entire surface of the transparent.
In another non-limiting embodiment, the removable protective coating can be deposited on a substrate, which is used for architectural and structural glazing. The removable protective coating can be applied over any portion of the substrate.
In one non-limiting embodiment of the present invention, the removable protective coating can be applied over at least a portion of one or more functional coatings which are deposited over at least a portion of the substrate. The functional coating can have the same composition or functionality. The functional coating can comprise one or more "films".
In one non-limiting embodiment, the functional coating may be an electrically conductive coating such as the one disclosed in U.S. Patent №№5653903 and 5,028,759, which are incorporated herein by reference.
In another non-limiting embodiment, the functional coating can be a solar control coating, such as coating, reflect or absorb energy in the visible, infrared or ultraviolet region. Non-limiting examples of suitable solar control coatings are disclosed in US Pat №№4898789, 5,821,001, 4,716,086, 4,610,771, 4,902,580, 4,716,086, 4,806,220, 4,898,790, 4,834,857, 4,948,677, 5,059,295 and 5,028,759 and US patent application №09 / 058,440, which thus , incorporated herein by reference.
In another non-limiting embodiment, the functional coating can be a low emissivity coating. Low emissivity coating may be a monolayer or multilayer coating. Low emissivity coating may comprise one or more metals, non-metals, semi-metals, semiconductors and / or their compounds, composites, combinations, or mixtures thereof. Nonlimiting examples of low emissivity coatings disclosed in U.S. Patent №№4952423 and 4,504,109 and in British Patent GB 2,302,102, which are hereby incorporated herein by reference.
Nonlimiting examples of suitable for use in the present invention, the functional coating can be purchased from PPG Industries, Inc. (Pittsburgh, PA) as a family of coatings and SUNGATE® SOLARBAN®.
Functional coatings may be applied by any conventional methods such as those described above in relation to the removable protective coating.
In another non-limiting embodiment, to prevent damage to the functional coating a removable protective coating over the functional layer is applied to the blocking layer. More specifically, if the blocking layer is not used, the carbon-removable protective coating would chemically reducing the upper portion of the functional coating, i.e. carbon in the removable protective coating can be output from the oxygen atoms of the functional coating to form carbon oxides. The blocking layer comprises a material that prevents chemical reduction of the functional coating removable protective coating, but without prejudice or transmittance characteristics of the coated article appear. In one non-limiting embodiment, the blocking layer is selected from oxides, nitrides and oxynitrides of silicon, titanium, zirconium, niobium, aluminum, hafnium, yttrium, lanthanum and mixtures thereof.
The blocking layer may be applied by any conventional methods such as those described above in relation to the removable protective coating. The blocking layer may be applied to a thickness of 50 .mu.m, for example, up to 25 .mu.m or 10 .mu.m to 3.0 .mu.m, or, or up to 1.7 micrometers or 0.5 micrometers.
In another non-limiting embodiment, the blocking layer comprises silicon oxide thickness of 25 Å to 500 Å, for example a thickness of 50 Å.
The coated substrate according to the present invention may be sent to the factory for further processing as described above. Generally, the removable protective coating is removed in the factory. The removable protective coating can be removed without damaging the underlying substrate, the functional layer (s), or blocking layer (if present).
In another non-limiting embodiment, the removable protective coating can be removed by combustion. For example, if the substrate is a glass sheet, the removable protective coating can be removed in the furnace for tempering glass, which typically operates at a temperature above 1000 ° F (538 ° C). The temperature of the combustion exhaust protective coating must not be higher than the softening temperature of the substrate. In the process of hardening the carbonaceous material which includes a removable protective coating is burnt and removed from the substrate.
In other non-limiting embodiments, the removable protective coating can be removed with a liquid solvent or by wiping, spraying or immersing the substrate in an aqueous or non-aqueous solvents, such as organic, acidic or alkaline solvents.
In addition to the above-described coated substrates, the present invention includes a method of making a coated substrate. In one non-limiting embodiment of the present invention is a method of protecting a substrate comprising applying a removable protective coating comprised predominantly of a carbon material, over at least a portion of the substrate, as described above.
The coated substrate according to the present invention having a removable protective coating, which is composed mainly of carbonaceous material, has several advantages over the coated substrate, not having the removable protective coating. Firstly, the carbonaceous material may very well to protect the functional layer, because carbon is chemically inert at room temperature. Due to this the coated product has extended shelf life. Secondly, carbon in the removable protective coating can enhance radiation heat transfer to the substrate due to the volume reduction of heat energy reflected from a functional coating, and serve as a heat absorbing layer. This allows the coated substrate having improved properties during heat treatment of tempering, heat strengthening and bending etc. For example, the time for hardening of the coated substrate according to the present invention may be less than the time of hardening, required for a coated article that has no removable protective coating according to the present invention. Thirdly, the removable protective coating of the invention may act as a barrier for some materials such oxygen.
EXAMPLES
The present invention is illustrated by the following non-limiting examples. The coated substrate according to the present invention was prepared as follows. On the transparent substrate of the float glass with the coated Sungate®, which can be obtained from PPG Industries, a thickness of 1.8 mm was coated using a coater Airco ILS-1600 with planar magnetron cathodes. The operation was conducted on the substrate at room temperature.
Atop substrate coated blocking layer by moving it under the Si-Al-target containing 15 wt.% Alumina and 85 wt.% Of silicon, in an atmosphere of 80% oxygen and 20% argon, at a line speed of 300 cm / min. Minimum reference pressure in the coating chamber was 10-5 Torr and the operating pressure of 4 microns. Si-Al-target operated at a power setting of 2.0 kW, voltage of 320 V and a current of 6.4 A. After two movements under the target light transmittance was 70.1% at a thickness of about 60 Å.
Thereafter, the removable protective coating according to the present invention is applied by sputtering a graphite target in an atmosphere of 100% argon. The graphite target was operated at the installed capacity of 4.0 kW, a voltage of 686 V and a current of 5.8 A. After 6 movements under the target light transmittance was 29.8% when measured thickness of 250 Å.
One skilled in the art can easily guess that does not go beyond the disclosure in the above description, the essence of the invention, it is possible to make changes. Appropriately described herein in detail embodiments of the invention are illustrative only and are not restrictive iso invention, which is defined by the full scope of the appended claims, and each and all equivalents thereof.
Contents5
Every citation, both ways
| Document | Relation | Office |
|---|---|---|
| US6770321A | Cites | United States of America |
| WO03065081C1 | Cites | World Intellectual Property Organization (WIPO) |
| US5028759A | Cites | United States of America |
| GB1276834A | Cites | United Kingdom |
| RU2033348C1 | Cites | Russian Federation |
| RU2093485C1 | Cites | Russian Federation |
| RU2120919C1 | Cites | Russian Federation |
| RU2004126086A | Cites | Russian Federation |
20 members in 10 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 11017155 | United States of America | – | |
| 1715504 | United States of America | A | |
| 11017155 | – | – | – |
| US20040017155 | – | – | – |
Members20
| Document | Office | Kind | |
|---|---|---|---|
| CA2377714A1 | Canada | A1 | |
| WO0102496A2 | World Intellectual Property Organization (WIPO) | A2 | |
| AU5761800A | Australia | A | |
| WO0102496A3 | World Intellectual Property Organization (WIPO) | A3 | |
| KR20020031153A | Republic of Korea | A | |
| EP1200528A2 | European Patent Office (EPO) | A2 | |
| AR024640A1 | Argentina | A1 | |
| US2002176988A1 | United States of America | A1 | |
| JP2003504227A | Japan | A | |
| US6682773B2 | United States of America | B2 | |
| US6849328B1 | United States of America | B1 | |
| US2005153126A1 | United States of America | A1 | |
| WO2006069068A2 | World Intellectual Property Organization (WIPO) | A2 | |
| WO2006069068A3 | World Intellectual Property Organization (WIPO) | A3 | |
| CN101084279A | China | A | |
| CA2377714C | Canada | C | |
| US7361404B2 | United States of America | B2 | |
| RU2007127690A | Russian Federation | A | |
| JP2011105003A | Japan | A | |
| RU2429262C2This record | Russian Federation | C2 |
1 legal event, as the office reported them to INPADOC
Events
| Event | Code | |
|---|---|---|
| The patent is invalid due to non-payment of feesMM4A | MM4A |
Numbers
- Publication
- 2429262
- Publication, DOCDB
- 2429262
- Publication, EPODOC
- RU2429262
- Application
- 200712769005
- Application, DOCDB
- 2007127690
- Application, EPODOC
- RU20070127690
Titles2
- English
- SUBSTRATE HAVING REMOVABLE PROTECTIVE COATING AND CORRESPONDING METHODS
- Russian
- ПОДЛОЖКА С УДАЛЯЕМЫМ ЗАЩИТНЫМ ПОКРЫТИЕМ И СООТВЕТСТВУЮЩИЕ СПОСОБЫ
Classification
- CPC, 14
- C03C17/3441
- B65G49/069
- C03C17/22
- C03C17/32
- C03C17/38
- C03C17/42
- C03C2217/282
- C03C2218/154
- C03C2218/328
- C03C2218/355
- C09D5/008
- C23C14/0605
- Y10T428/265
- Y10T428/30
- IPC, 14
- B05D1 00
- B05D1 36
- B05D3 02
- B05D5 06
- B65G49 06
- C03C17 00
- C03C17 32
- C03C17 34
- C03C17 36
- C03C17 38
- C03C17 42
- C09D1 00
- C09D5 00
- C09D5 20