MXPA01013196A

Light-transmitting and/or coated article with removable protective coating and methods of making the same.

Abstract

A method and coating are provided for temporarily protecting a substrate or article during shipping, handling or storage by applying a removable protective coating over at least a portion of the substrate. The substrate may be flat or curved and may have zero, one or more functional coatings. A plurality of substrates with the protective coating of the invention may be arranged in a shipping container so that the protective coating reduces the possibility of damage to the substrate or optional functional coating. In one embodiment, the protective coating is the evaporation or reaction product of an aqueous coating composition containing a polyvinyl alcohol polymer which may be subsequently removed by aqueous washing, thermal decomposition or combustion. In another embodiment, the protective coating is formed by sputtering a substantially carbon coating onto the substrate. The carbon coating is subsequently removed by combustion. The protective coating may have identification materials, such as colorants or fragrance materials, such that different types of substrates and/or functional coatings can be distinguished from each other. Additionally, the temporary protective coating can improve the heating of a functionally coated glass substrate.

Term

Term ended

Expired 23 June 2020, 6.3 years ago.

68 claims: 14 independent, 54 dependent

1
REIVINDICACIONES 1. Un articulo recubierto que comprende:un substrato que tiene una primera superficie;un recubrimiento funcional depositado sobre al menos una porcion de la primera superficie;у un recubrimiento protector eliminable depositado sobre al menos una porcion del recubrimiento funcional;donde el recubrimiento funcional se selecciona del grupo que consiste en recubrimientos de una sola capa о de multiples capas, у donde el recubrimiento protector eliminable esta esencialmente libre de material espaciador cuando el recubrimiento funcional es un oxido metalico en una sola capa.
2
El articulo segun la reivindicacion 1, donde el recubrimiento funcional comprende uno о mas metales, nomet ales, semi-metales, semiconductores, о aleaciones, compuestos, materiales compuestos, combinaciones у mezclas de ellos
3
El articulo segun la reivindicacion 1, donde el recubrimiento protector comprende un polimero que forma pelicula.
4
El articulo segun la reivindicacion 1, donde el recubrimiento protector comprende el producto de evaporacion о el producto de reaccion de una composicion de recubrimiento liquida que comprende un polimero que forma pelicula.
5
El articulo segun la reivindicacidn 3, donde la composicion de recubrimiento incluye un vehiculo substancialmente acuoso.
6
El articulo segun la reivindicacion- - 1, donde el substrato tiene al menos una superficie que transmite la luz.
7
El articulo segun la reivindicacion 1, donde el substrato se selecciona del grupo que consiste en vidrio, polimeros, poliesteres, policarbonatos, poli tereftalato de etileno, plastico, ceramica, metal, celulosa, у mezclas о combinaciones de ellos.
8
El articulo segun la reivindicacion 1, donde el substrato se selecciona del grupo que consiste en vidrio piano, vidrio sin templar, vidrio templado, у vidrio mejorado en resistencia al calor.
9
El articulo segun la reivindicacion 3, donde el polimero se selecciona del grupo que consiste en poliesteres, policarbonatos, poliestirenos, poliacrilatos, materiales celulosicos у derivados, mezclas, copolimeros, materiales compuestos, combinaciones у mezclas de ellos.
10
El articulo segun la reivindicacion 1, donde el substrato es vidrio у tiene dimensiones mayores de aproximadamente 1,8 m por aproximadamente 2,1 m.
11
El articulo segun la reivindicacion 1, donde el substrato tiene dimensiones menores de aproximadamente 1,8 m por aproximadamente 2,1 m.
12
El articulo segun la reivindicacion 1, donde el recubrimiento funcional se selecciona del grupo que consiste en recubrimientos depositados piroliticamente, recubrimientos depositados por bombardeo ionico, recubrimientos depositados quimicamente en humedo, у recubrimientos depositados por deposito quimico con vapor.
13
El articulo segun la reivindicacion 1, donde el recubrimiento funcional se selecciona del grupo que consiste en recubrimientos de baja emisividad, recubrimientos que absorben о reflejan la energia solar, у recubrimientos que reflejan о absorben la energia termica infra-roja, у combinaciones de ellos.
14
El articulo segun la reivindicacion 4, donde el polimero se selecciona del grupo que consiste en materiales solubles en agua, emulsionables у dispersables en agua.
15
El articulo segun la reivindicacion 14, donde el polimero formador de pelicula se selecciona del grupo que consiste en polimeros acrilicos, latex sint£ticos, polimeros de poli oxido de alquileno, poli acetato de vinilo, poli alcohol vinilico, polivinilpirrolidina, copolimeros de estireno/acido acrilico, copolimeros de etileno/acido acrilico, polimeros celulosicos, almidones, caseins, gelatinas, у mezclas, derivados, combinaciones у copolimeros formados de cualquiera de sus monomeros.
16
El articulo segun la reivindicacidn 4, donde el polimero que forma pelicula comprende poli alcohol vinilico que tiene un grado de hidrolizacion superior a aproximadamente el 80 por ciento.
17
El articulo segun la reivindicacion 15, donde el polimero comprende hasta aproximadamente el 50 por ciento de la composicion de polimero
18
El articulo segun la reivindicacion 17, donde el polimero comprende aproximadamente 5 a aproximadamente 12 por ciento en peso de la composicion de polimero.
19
El articulo segun la reivindicacion 3, donde la composicidn de recubrimiento incluye ademas, al menos un aditivo seleccionado del grupo que consiste en cargas, biocidas, agentes tensioactivos, eliminadores de espuma, colorantes, agentes de flujo, agentes de nivelacion, agentes hidrofilos, agentes hidrofobos, materiales espaciadores у substancias aromatizantes.
20
El articulo segun la reivindicacion 1, donde el recubrimiento eliminable es un recubrimiento substancialmente continuo.
21
El articulo segun la reivindicacion 1, donde el recubrimiento eliminable es un recubrimiento que no es sustancialmente continuo.
22
El articulo segun la reivindicacion 16, donde el recubrimiento eliminable tiene una cobertura en peso superior a cero hasta aproximadamente 1 gramo por pie cuadrado (0,09 m 2 )
23
El articulo segun la reivindicacion 16, donde el recubrimeinto eliminable tiene una cobertura en peso de aproximadamente 0,1 a aproximadamente 0,2 gramos por pie cuadrado (0,09 m 2 ).
24
El articulo segun la reivindicacion 5 donde la composicion de recubrimiento comprende uno о mas vehiculos no-acuosos
25
El articulo segun la reivindicacion 24, donde el vehiculo no acuoso comprende al menos uno entre isopropanol, metanol о etanol.
26
Un articulo recubierto que comprende.un substrato de vidrio piano que tiene . una primera superficie;у un recubrimiento protector eliminable depositado sobre al menos una porcion de la primera superficie, donde el recubrimiento protector tiene un espesor de menos de aproximadamente 50 micras у se deposita desde una composicion de recubrimiento que esta esencialmente libre de material espaciador.
27
El articulo segun la reivindicacion 26, que incluye un recubrimiento funcional depositado sobre al menos una porcion de la primera superficie, con el recubrimiento protector eliminable depositado sobre al menos una porcion del recubrimiento funcional, donde el recubrimiento funcional se selecciona del grupo que consiste en recubrimientos de una sola capa у recubrimientos de multiples capas, donde el recubrimiento funcional comprende uno о mas metales, no-metales, semimetales, semiconductores, о aleaciones, compuestos organicos, materiales compuestos, combinaciones, у mezclas de los mismos, у donde el recubrimiento protector eliminable esta esencialmente libre de material espaciador cuando el recubrimiento funcional es un oxido metalico de una sola capa.
28
Una composicion de recubrimiento para formar un recubrimiento protector eliminable sobre un substrato que tiene un recubrimiento funcional que contiene plata, comprendiendo la composicion de recubrimiento:un material que forma pelicula;у un biocida substancialmente libre de haluro.
29
Un metodo de proteccion de un substrato frente a danos mecdnicos que comprende las etapas de:aportar un substrato que tiene aplicado a una primera superficie un recubrimiento funcional sobre al menos una porcion de esta primera superficie depositar una composicion de recubrimiento liquida sobre al menos una porcidn del recubrimiento funcional, comprendiendo la composicion de recubrimiento un material que forma pelicula, у formacion de un recubrimiento protector eliminable de la composicion de recubrimiento, donde el recubrimiento funcional se selecciona entre recubrimientos de una sola capa у recubrimientos de multiples capas, en las que el recubrimiento funcional comprende uno о mas metales, no-metales, semi-metales, semi-conductores, о aleaciones, compuestos, materiales compuestos, combinaciones у mezclas de ellos, у donde el recubrimiento de proteccion eliminable esta esencialmente libre de material espaciador cuando el recubrimiento funcional es un dxido metalico de una sola capa.
30
El metodo segun la reivindicacion 29, que comprende ademas el contacto del recubrimiento protector eliminable con un liquido para eliminar el recubrimiento protector.
31
El metodo segun la reivindicacion 30, donde el liquido comprende agua.
32
El metodo segun la reivindicacion 29 que comprende ademas calentamiento del substrato a una temperatura suficiente para quemar о descomponer termicamente el recubrimiento protector eliminable.
33
Un metodo de identificacion de substratos seleccionados, que comprende las etapas de:formacion de un recubrimiento protector renovable de un color о aspecto seleccionado diferente о de diferente aroma sobre substratos diferentes para distinguir los diferentes substratos.
34
Un metodo segun la reivindicacion 33, donde el recubrimiento protector eliminable esta formado por:aplicacion de una composicion de recubrimiento liquida sobre al menos una porcion del substrato, comprendiendo la composicion de recubrimiento un material formador de pelicula у al menos un material colorante о aromatizante seleccionado;у curado о secado de la composicion de recubrimiento para formar un recubrimiento protector eliminable sobre el substrato.
35
Un articulo recubierto, que comprende:un substrato que tiene una superficie;у un recubrimiento protector eliminable substancialmente de carbono sobre al menos una porcion del substrato.
36
El articulo segun la reivindicacion 35, que incluye ademas un recubrimiento funcional depositado sobre al menos una porcion del substrato, estando depositado el recubrimiento protector sobre al menos una porcion del recubrimiento funcional.
37
El articulo segun la reivindicacion 35, donde el substrato es vidrio.
38
El artlculo segun la reivindicacion -35, donde el recubrimiento protector tiene un espesor de superior a aproximadamente cero A a aproximadamente 1000 A.
39
El artlculo segun la reivindicacion 35, que incluye una capa de bloqueo situada entre el substrato у la capa protectora.
40
El artlculo segun la reivindicacion 36, que incluye ademas una capa bloqueante de oxidacion situada entre el recubrimiento funcional у el recubrimiento protector.
41
El artlculo segun la reivindicacion 38, donde la capa de bloqueo se selecciona del grupo que consiste en silicio, titanio, zirconio, niobio, aluminio, у combinaciones, oxidos, nitruros у oxinitruros de ellos.
42
El artlculo segun la reivindicacion 39, donde la capa bloqueante tiene un espesor desde superior a aproximadamente 0 A a aproximadamente 50 A.
43
Un metodo de proteccion de un substrato que comprende las etapas de:aportar un substrato;у aplicar un recubrimiento protector substancialmente de carbono sobre al menos una porcion del substrato.
44
El metodo segun la reivindicacion 43, donde la etapa de aplicacidn incluye el bombardeo ionico de una diana que contiene carbono en una atmosfera de bombardeo ionico substancialmente libre de oxigeno para formar el recubrimiento protector.
45
El metodo segun la reivindicacion 44, en el que la atmdsfera de bombardeo ionico es menos de un 20 por ciento en volumen de oxigeno.
46
El metodo segun la reivindicacion 43, que incluye el deposito de al menos un recubrimiento funcional sobre al menos una porcion del substrato у el deposito del recubrimiento protector sobre al menos una porcion del recubrimiento funcional.
47
El metodo segun la reivindicacion 46, que incluye aportacion de una capa de bloqueo de oxidacion entre el recubrimiento funcional у el recubrimiento protector.
48
El metodo segun la reivindicacion 47, donde la etapa de aportacion se practica por bombardeo ionico de una diana que contiene silicio en una atmosfera de bombardeo ionico que contiene oxigeno para formar una capa de bloqueo de silice.
49
El metodo segun la reivindicacion 48, donde la capa de bloqueo tiene un espesor de superior a aproximadamente 0 A a aproximadamente 50 micras.
50
El metodo segun la reivindicacion 43, que incluye la combustion del recubrimiento protector para eliminar el recubrimiento protector del substrato.
51
El metodo segun la reivindicacion 50, donde la etapa de combustion se practica por calentamiento del substrato a una temperatura suficiente para oxidar el recubrimiento protector.
52
Un metodo de preparacidn de un contenedor de transporte de substratos en forma de laminas planas о curvas, que comprende las etapas de:aportar una pluralidad de substratos en laminas, teniendo cada substrato una primera superficie sobre la que esta aplicado un recubrimiento protector eliminable sobre al menos una porcion de esa primera superficie de al menos una parte de los substratos;disposicion de los substratos en un contenedor de transporte de manera que al menos un recubrimiento protector queda situado entre al menos un par de substratos adyacentes.
53
El metodo segun la reivindicacion 32, donde la etapa de aplicacion comprende:aplicar una composicion de recubrimiento liquida sobre al menos una porcidn de la primera superficie, comprendiendo la composicion de recubrimiento un material formador de pelicula;у formacion del recubrimiento protector eliminable desde la composicidn de recubrimiento.
54
El metodo segun la reivindicacidn 52, donde el recubrimiento protector eliminable es un recubrimiento substancialmente de carbono.
55
Un metodo de fabricacion de un articulo, que comprende las etapas de:recepcion de un contenedor de envio que lleva una pluralidad de substratos, teniendo cada substrato una primera superficie con un recubrimiento protector eliminable situado sobre la primera superficie de al menos una parte de los substratos у estando los substratos colocados de manera que al menos un recubrimiento protector queda situado entre al menos un par de substratos adyacentes;у eliminacion del material de recubrimiento protector de al menos uno de los substratos.
56
El metodo segun la reivindicacion 55, donde la etapa de eliminacion incluye el contacto del recubrimiento protector con un liquidg.
57
El mdtodo segun la reivindicacion 55, donde la etapa de eliminacidn incluye el calentamiento del substrato a una temperatura suficiente para quemar о descomponer termicamente el recubrimiento protector.
58
El metodo segun la reivindicacion 55, que incluye la incorporacion de al menos un substrato en un articulo de produccion, у aplicacion de un recubrimiento protector eliminable sobre al menos una porcion del articulo de produccion.
59
El metodo segun la reivindicacion 55, que incluye ademas la recuperacion del material de recubrimiento protector eliminado у la re-utilizacion del material de recubrimiento protector eliminado para formar un recubrimiento protector eliminable sobre otro substrato.
60
En un contenedor de envio que tiene una pluralidad de substratos adyacentes teniendo cada substrato una primera superficie, la mejora que comprende:: aplicar un recubrimiento protector eliminable sobre al menos una porcidn de la primera superficie de al menos un substrato de manera que al menos un recubrimiento protector quede situado entre al menos un par de substratos adyacentes.
61
El metodo segun la reivindicacidn 59, donde el recubrimiento protector es substancialmente carbono.
62
Un metodo de proteccion de un substrato del dano mecdnico que comprende las etapas de:aportacion de un substrato de vidrio piano;у deposito de un recubrimiento protector eliminable sobre al menos una porcion del substrato, donde el recubrimiento protector tiene un espesor de al menos aproximadamente 50 micras у se deposita desde una composicion de recubrimiento que esta esencialmente libre de material espaciador.
63
El metodo segun la reivindicacion 62, donde la etapa de deposito incluye el secado con cuchillo de aire dirigido hacia el substrato con un angulo que varia entre mayor de 90° a menos de 180° con respecto a la superficie del substrato.
64
Un metodo de promover un calentamiento uniforme de un substrato que tiene un recubrimiento funcional, que comprende las etapas de:aplicacion de un recubrimiento de alta emisividad, eliminable, sobre al menos una porcion del substrato antes de calentarlo;у calentar el substrato de manera que el recubrimiento de alta emisividad sufra combustion о se descomponga termicamente durante el calentamiento.
65
El metodo segun la reivindicacion 64, donde el recubrimiento funcional se selecciona del grupo que consiste en:recubrimientos de baja emisividad, recubrimientos de control solar у combinacion de los mismos.
66
El metodo segun la reivindicacion 64, donde el recubrimiento de alta emisividad tiene una emisividad superior a aproximadamente 0,8.
67
El metodo segun la reivindicacion 64, donde el recubrimiento funcional tiene una emisividad menor de aproximadamente 0,3.
68
El metodo segun la reivindicacion 64, donde la etapa de calentamiento incluye al menos una etapa de templado, 5 conformado, impartir resistencia al calor, у curvado.

Independent claims68

224 paragraphs in 14 sections, as filed

(57) Summary

A method and liner is provided to temporarily protect a substrate or article during transportation, handling or storage, by applying a removable protective liner to the protective liner of the invention can be adapted in a shipping container, so that the liner protector reduces the chance of damaging the substrate or an optional functional coating. In one embodiment, at least a part of the substrate. The substrate can be piano or curved, and can have zero, one or more functional coatings. A plurality of substrates with the protective coating is the product of evaporation or reaction of an aqueous coating composition containing a polyvinyl alcohol polymer that can be subsequently removed by aqueous washing, combustion, or thermal decomposition. In another embodiment, the protective coating is formed by bombarding a substantially carbon coating on the substrate. The carbon coating is subsequently removed by combustion. The protective coating may have identification materials, such as colorants or fragrance materials, so that the different types of substrates and / or functional coatings can be distinguished from each other. Additionally, the temporary protective coating can improve the heating of a functionally coated glass substrate.

(57) Abstract

A method and coating are provided for temporarily protecting a substrate or article during shipping, handling or storage by applying a removable protective coating over at least a portion of the substrate. The substrate may be flat or curved and may have zero, one or more functional coatings. A plurality of substrates with the protective coating of the invention may be arranged in a shipping container so that the protective coating reduces the possibility of damage to the substrate or optional functional coating. In one embodiment, the protective coating is the evaporation or reaction product of an aqueous coating composition containing a polyvinyl alcohol polymer which may be subsequently removed by aqueous washing, thermal decomposition or combustion. In another embodiment, the protective coating is formed by sputtering a substantially carbon coating onto the substrate. The carbon coating is subsequently removed by combustion. The protective coating may have identification materials, such as colorants or fragrance materials, such that different types of substrates and / or functional coatings can be distinguished from each other. Additionally, the temporary protective coating can improve the heating of a functionally coated glass substrate.

jt '(12) INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (19) World Intellectual Property Organization International Bureau (43) International Publication Date 11 January 2001 (11.01.2001)

PCT (10) International Publication Number

WO 01/02496 A2 (51) International Patent Classification7: C09D 5/00 (21) International Application Number: PCT / USOQ / 17326 (22) International Filing Date: 23 June 2000 (23.06.2000) (25) Filing Language: English (26) Publication Language: English (30) Priority Data:

60 / 142,090 2 July 1999 (02.07.1999) US

09 / 567,934 10 May 2000 (10.05.2000) US (71) Applicant: PPG INDUSTRIES OHIO, INC. [US / US]; 3800 West 143rd Street, Cleveland, OH 44111 (US).

—J- (72) Inventors: MEDWICK, Paul, A .; 4117 Stonecliffe = Drive, Monroeville, PA 15146 (US). GOODREAU, Erin;

== 213 Amber Street ,, Pittsbutgh, PA 15206 (US). LAWsss TON, Ernest, L / 3432 Kilcash Drive, Clemmons, NC

SS 27012 (US). FINLEY, James, J .; Ill Cornwall Drive, »Pittsburgh, PA 15238 (US). MARTIN, George, M .; 839

SS Freeport Road, Freeport, PA 16229 (US). THIEL, James,

BBS P .; 296 Mt. Royal Boulevard, Pittsburgh, PA 15223 (US).

SsS MARIETTI, Gary, /!.; 56 Greene Drive, Cheswick, PA

15024 (US) SCRIVEN, Roger, L .; 3850 Grove Road, Gibsonia, PA 15044 (US).

(74) Agents: STACHEL, Kenneth, J .; PPG Industries, Inc., One PPG Place, Pittsburgh, PA 15272 et al. (US)

(81) Designated States (national): AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CR, CU, CZ, DE, DK, DM, EE , ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS, JP, KE, KG, KP, KR, KZ, LC, LK-LlU LS, LT, LU, LV, MA, MD, MG, MK, MN, MW, МХЦNO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, TZ, UA, UG, UZ, VN, YU, ZA, ZW.

(84) Designated States (regional): ARIPO patent (GH, GM, KE, LS, MW, MZ, SD, SL, SZ, TZ, UG, ZW). Eurasian patent (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), European patent (AT, BE, CH, CY, DE, DK, ES, H, FR, GB, GR, IE, IT , LU, MC, NL, PT, SE), OAPI patent (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG).

Published:

- Without international search report and to be republished upon receipt of that report.

For two-letter codes and other abbreviations, refer to the Guidance Notes on Codes and A bbreviations appearing at the beginning of each regular issue of the PCT Gazette.

= (54) Title: LIGHT-TRANSMITTING AND / OR COATED ARTICLE WITH REMOVABLE PROTECTIVE COATING AND = METHODS OF MAKING THE SAME

WO 01/02496 A2 (57) Abstract: A method and coating are provided for temporarily protecting a substrate or article during shipping, handling or storage by applying a removable protective coating over at least a portion of the substrate. The substrate may be flat or curved and may have zero, one or more functional coatings. A plurality of substrates with the protective coating of the invention may be arranged in a shipping container so that the protective coating reduces the possibility of damage to the substrate or optional functional coating. In one embodiment, the protective coating is the evaporation or reaction [noduct of an aqueous coating composition containing a polyvinyl alcohol polymer which may be subsequently removed by aqueous washing, thermal decomposition or combustion. In another embodiment, the protective coating is formed by sputtering a substantially carbon coating onto the substrate. The carbon coating is subsequently removed by combustion. The protective coating may have identification materials, such as colorants or fragrance materials, such that different types of substrates and / or functional coatings can be distinguished from each other. Additionally, the temporary protective coating can improve the heating of a functionally coated glass substrate.

ARTICLES THAT TRANSMIT LIGHT AND / OR ARE COVERED WITH A REMOVABLE PROTECTIVE COATING AND PRODUCTION METHODS THEREOF

This application claims the benefits of

US Provisional Application 60 / 142,090, filed July 2, 1999, entitled A substrate bearing a film with a protective coating and Methods, which is incorporated herein by reference.

one. Field of the invention

The present invention relates generally to temporary or removable protective coatings for substrates with and without functional coatings, and more particularly to removable protective coatings to reduce the vulnerability of substrates such as glass substrates having one or more functional coatings, versus to mechanical damage during working, handling, transport or storage.

2. Technical considerations

Some substrates in the form of sheet or panel, whether they are pianos or curved, can have two larger surfaces that end in a peripheral edge, for example, glass sheets or some plastics, where at least one surface has a visible light transmittance that It varies from more than 0% to less than 100%. These types of substrate can have a functional coating deposited on one or more surfaces. In some substrates, such as mirrors, one of the surfaces of the substrate can be light transmitting, for example by transmitting visible light, and the other surface can reflect visible light. With these types of substrates other articles or products can also be manufactured.

For example, in the glass industry, large pieces of glass larger than about 1.2mx 1.8m are prepared by glassmakers who ship them to industrialists to be cut into smaller pieces and incorporated into various articles. of production, such сото windows of buildings, transparencies for automobiles, insulated glass units (IG), mirrors and others, articles of production that are sent later by the industrialist to the clients. The term manufacturing substrates, so used here, refers to those large pieces of substrate that are then worked or cut to incorporate them into the production of smaller production items. Manufacturing substrates may or may not include one or more functional coatings, such as coatings for solar control, driving, anti-reflective and / or low-emission coatings. In addition, light transmitting glass and plastic substrates can have one or more functional coatings that modify various physical properties, for example, optical, thermal or mechanical properties of coated plastic or glass (s) surface (s). . In addition to large glass or plastic manufacturing substrates that do not have or have one or more functional coatings, functionally coated glass pieces of any size can be shipped by an industrial manufacturer.

These substrates are typically sold and shipped to the industrialist, in batches of several pieces together. The pieces of the substrate can be assembled and shipped on a wooden pallet in a conventional manner well known in the field of glass shipping. In addition to wooden pallets, shipping containers are known. For example, US patent numbers. 4,512,473 and 5,860,539 describe fiete containers for the transport of a plurality of sheets. These known transport methods are quite suitable for shipping substrates that do not have functional coatings or substrates of a substantially uniform size. However, when substrates with functional coatings or substrates of different sizes have to be transported, a prominent part or corner of the surface of a substrate may remain, for example functionally coated, in contact with the adjacent substrate during handling, working , shipping or storage, which can damage the functional coating or scratch the surface of the adjacent substrate.

Protective coatings have been used in some industries to reduce transportation damage. For example, the French patent of reference FR 2,295,100 describes a protective coating that can be peeled off, for metal, glass and plastic surfaces. This release liner is comprised of a liquid composition of 5 to 40 percent soluble copolyamide, 55 to 85 percent ethanol, and 0 to 20 percent water. However, the disadvantages of these removable coatings with a large amount of organic solvent are triple. A large amount of organic solvent may be required, recycled, or disposed of after disposal after use in the release liner reservoir. In addition, the detached solid film must be disposed of with such waste in an appropriate manner. Furthermore, considerable time is required to fully peel the coating from the surface of the substrate. If this peeling is performed hastily, small patches of the release liner may remain on the substrate and will be required. additional time and labor costs for inspection and removal of these small patches. In addition, some organic solvents can be flammable.

Other types of temporary protective coatings used in various industries are typically made up of applied polymers or waxes, which, after shipment, are removed with polar and / or non-polar solvents, for example organic and / or inorganic solvents, such as solvents. Acids or alkalines, hydrocarbons or lower monohydric alcohols. For example, see Japanese Patent JP 7567845 where inorganic alkaline cleaning solvents remove a polymeric transport coating. This method still has the disadvantage of the need to eliminate wastes from corrosive solvents or cystic solvents and / or inorganic salts, which require treatment or neutralization of the residual water that accumulates them. In addition, alkaline or acidic solvents may be incompatible with certain substrates or with any of the functional coatings present on the surface of these substrates. Additionally, in the case of plastic substrates, certain organic solvents can discolor, stain, oxidize or swell the substrate or make it more fragile.

US Patent No. 4,315,947 (equivalent to German Application No. 2926197) describes the removal of a protective wax-based coating, using a mixture of water and steam at a temperature of 90 ° C-95 ° C. The steam removal process requires a high energy expenditure and has the risk of causing burns from the hot water / steam mixture.

US Patent No. 5,026,597 describes a temporary protective coating consisting of a water-soluble film-forming polymer and insoluble spacer particles such as acrylic or polyethylene beads. The spacer particles become integrated into the structure of the dry coating. There are no thicknesses of the coating and no mention is made of the incorporation of identification materials such as dyes into the coating.

It would therefore be highly advantageous to provide a method of forming a removable protective coating on a substrate that does, or does not, have one or more functional coatings, in particular a substrate with characteristics of visible light transmission, such as glass, it reduces or eliminates at least part of the advantages discussed above.

Summary of the invention

An article of the invention includes a substrate, preferably a substrate having at least one light transmitting surface, with a removable protective coating deposited on at least a portion of the surface. The substrate may be coated with one or more functional coatings of various kinds. The removable protective coating is deposited on the surface of the substrate to be protected. This protection may be against mechanical, chemical or handling damage and / or due to misidentification. For large size substrates or light transmitting manufacturing substrates of the order of more than about 1.2m by about 1.8m, the protective coating is preferably deposited on most, preferably all, of the exposed substrate which may be left unprotected by some form of packaging, for example corner guards, frames or edges. Substrates with at least two larger surfaces can have one or more of the surfaces (for example, a first surface) coated with the protective coating. For substrates with one or more functional coatings, (eg, a functional coating on the first surface) the protective coating is preferably deposited on at least a portion of the functional coating (s) to protect the ) functional coating (s) against mechanical and / or chemical damage and / or misidentification, during shipping, storage, handling, and working. The functional coating may consist of a single layer or be a multi-layer coating, and may include one or more metals, non-metals, semi-metals, semiconductors or alloys, compounds, composite formations, combinations, or mixtures thereof.

In one aspect of the invention, the protective coating is the product resulting from the evaporation or reaction product of a polymeric coating composition, for example a solution, emulsion, suspension, thick suspension, or dispersion, liquids, deposited on the substrate. . For substrates without functional coatings or with a single layer metal oxide coating, the coating composition can be essentially free of spacer material. The protective coating can then be removed by washing with an appropriate solvent or by combustion or thermal decomposition.

In another aspect of the invention, the protective coating is a substantially carbon coating that has been applied to a substrate, for example, by conventional techniques or methods of chemical or steam deposition. This substantially carbon protective coating can subsequently be removed by combustion.

Another aspect of the invention includes a method of identifying selected substrates. The method comprises forming a removable protective coating of a different, selected color, texture, pattern, appearance, odor, or having an otherwise discernible identifying property, on different substrates to distinguish different substrates from each other. The removable protective coating may have been formed by application. of a coating composition, for example solution, emulsion, suspension, pasty suspension or dispersion, on at least a portion of the substrate. The coating composition can then be cured or dried to form a protective coating of the desired color, shade or desired color on the substrate. The protective coating can then be removed with an appropriate solvent о by combustion or thermal decomposition.

In another aspect of the invention, a coated article is provided that includes a piano glass substrate having a first surface and a removable protective coating on at least a portion of that first surface. The protective coating is less than about 50 microns thick and is deposited from a coating composition that is essentially free of spacer material.

A further aspect of the invention is a method of preparing a plywood or curved sheet transport container, each having a first surface. A removable protective coating is applied to at least a portion of the first surface of at least part of the substrates. The substrates are arranged in the shipping container so that there is at least one protective coating located between a pair of adjacent substrates.

Another aspect of the invention is a method of manufacturing an article that includes receiving a shipping container, this shipping container containing a plurality of substrates, and each of the substrates having a first surface with a removable protective coating placed on the first surface of at least part of the substrates such that there is at least one protective coating between at least one pair of adjacent substrates. The protective coating is then removed from at least one of the substrates, for example, by washing, combustion or thermal decomposition. The substrate can be worked, for example, by cutting, adjusting, flexing, shaping and / or can be incorporated into a production article, before or after removing the protective coating. Another removable protective coating that may be the same or different from that discussed above, can be applied to at least a portion of the production item prior to shipping or handling of the production item.

Still another aspect of the invention is a method of providing uniform heating, for example tempered, curved, shaped or imparting heat resistance, of a substrate having a functional coating as well as a coating for low emissivity or for solar control. . The method includes applying a removable high emissivity coating on at least a portion of the functionally coated substrate prior to heating. The high emissivity coating provides increased heat absorption compared to that of the functional coating and hence decreases the time required to heat the substrate to the desired treatment temperature. The high emissivity coating is configured to undergo combustion or thermal decomposition during the heating process.

Brief description of the drawings

Figure 1 is a cross-sectional view, not to scale, of a coated glass article incorporating a removable protective coating of the invention.

Figure 2 is a final view, not to scale, of a plurality of glass articles put together for shipment and incorporating removable protective coatings of the invention; and

• 9

Figure 3 is a graph of Taber score as a function of the number of Taber cycles for the selected coated glass substrates discussed in Example 11.

Description of the invention

Unless otherwise indicated, all numbers expressing amounts of ingredients, reaction conditions, etc. used in the specification and claims are to be considered as modified in all cases by the term approximately. In addition, as used here, the term polymer refers to oligomers, both homopolymers and copolymers. In addition, any numerical reference to quantities, unless otherwise specified, is by weight, for example, the term solids of 34% means solids of 34% by weight. The

<td colspan="3">following appointments indicated after s <</td><td>5 incorporate</td><td>here сото</td>

<td>references</td><td colspan="2">: US Patents</td><td>numbers:</td><td> 4.746.347;</td>

<td> 4.504.109;</td><td>application</td><td>patent</td><td colspan="2">American number</td>

<td> 09/058.440</td><td colspan="3">and the British GB patent reference</td><td> 2.302.102.</td>

<td>In the</td><td colspan="2">Figure 1 is designated by the</td><td>number10 in</td><td>general a</td>

<td colspan="2">coated article that</td><td colspan="2">has a coating</td><td>protective</td>

<td>temporary</td><td>the invention</td><td>Article</td><td>covered</td><td>10 includes</td>

a substrate 12 that can be of any material, tai сото metal, but in the preferred practice of the invention is a material that has a light-transmitting surface, tai сото, although not limited to only, plastics, polyacrylates, polycarbonates and ethylene polyterephthalate (PET), ceramic or, more preferably, glass or mixtures or combinations of them. The glass may be, for example, conventional unconventional sodium calcium silicate glass, i.e., clear glass, or it may be stained glass or otherwise colored, borosilicate glass, leaded glass, tempered glass, glass without tempered, annealed glass, or heat resistant glass. The glass can be of any type, such as floating glass (which has been passed as a bath of liquid metal at a lower temperature to solidify) or. Piano glass and can have any composition that leads to optical properties, for example, a visible transmission value, ultraviolet transmission, infra-red transmission and / or total solar energy transmission. Types of glass suitable for the practice of the invention, without being limited only to them, are those described, for example, in: US Patent Nos. 4,746,347, 4,792,536; 5,240,886; 5,385,872; and 5,393,593: The glass substrate can be of any dimension, but in present preferred practice for glass substrates without functional coatings, the uncoated glass substrate 12 is preferably a piano glass, and more preferably a piano glass. greater than about 1.2m by 1.5m. The glass substrate 12 can be of any thickness but preferably has a thickness of from about 1mm to about 50mm, more preferably from about 2mm to about 13mm, and even more preferably from about 2mm to about 6mm. The shape of the glass is preferably a panel having a first surface and opposite it a second surface terminating both surfaces at a peripheral edge. As will be appreciated by any person skilled in the art, the substrate could be of any type, for example, rigid, flexible, or even a film or self-supporting fabric, provided that the substrate can be covered with the removable protective coating of the present invention. described later. For example, the substrate 12 may be a conventional window sill glass - the conventional glass on the market. The substrate 12 can also have any shape, such a curved, round or flat shape.

One or more of the optional functional coatings 14 can be deposited on at least a portion of the surface of the substrate 12. For a panel, a functional coating 14 can be deposited on most of one or both surfaces of the substrate 12. As used herein, the term functional coating refers to a coating that modifies one or more physical properties of the substrate, for example, optical, thermal, chemical or mechanical properties, and is not intended to be removed from the substrate 12 during subsequent work. . Functional coating 14 is typically a more permanent or non-removable coating, this functional coating being considered to be intrinsic or required for end-use application of the functionally coated substrate. Functional coating 14 can have one or more functional coating films of the same or different composition or functionality. As used herein, the terms layer or film refer to a coating region of the desired or selected coating composition. The film can be homogeneous, non-homogeneous, or have a gradual change in composition. A film is homogeneous when the outer surface о portion (i.e. the farthest surface о portion of the substrate), the inner portion о surface (i.e. the closest substrate surface), and the portion between the outer and inner surfaces have substantially the same composition. A film is gradual when the film has a substantially increasing fraction of one or more components and a substantially decreasing fraction of one or more other components when passing from the inner surface to the outer surface or vice versa. A film is non-homogeneous when the film is neither homogeneous nor gradual. A coating is composed of one or more films. In addition, as used herein, the terms "deposited on" or "placed on" means "deposited" or "arranged on top," that is, it may be further away from the substrate 12 and not necessarily in contact with the surface. For example, a first coating film deposited on the substrate does not prevent the presence of one or more other coating films of the same or different composition located between the first coating film and the substrate.

Functional coating 14 may be an electrically conductive coating, such as, for example, an electrically conductive heated window covering described in US Patent Nos. 5,653,903 and 5,028,759, or a single-film coating о multi-film capable of -operating an antenna. Also, functional coating 14 may be a solar control coating, for example a coating that absorbs or reflects visible, infrared, or ultraviolet energy. Examples of suitable solar control coatings include, for example, those of US Patent Nos. 4,898,789; 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, as well as US patent application number 09 / 058,440. Analogously, functional coatings 14 may consist of a. low emissivity coating. Low emissivity coatings allow transmission of wave energy of approximately 4,000 nm through the coating, but visible, for example, approximately 780 nm, reflect the longest wavelength infrared energy and / or infrared energy thermal and are typically intended to improve the thermal insulating properties of architectural glazing. By low emissivity is meant an emissivity of less than about 0.3, preferably less than about 0.2. Examples of low-emissivity coatings include, for example, those in US Patent Numbers.

4,952,423 and 4,504,109 and British patent reference GB 2,302,102. Functional coating 14 can be a single-layer or multi-layer coating and can comprise one or more metals, non-metals, semi-metals, semiconductors, and / or alloys, compounds, composites, combinations, as well as mixtures of they. For example, functional coating 14 may be a layer of non-metal layers, single-layer multi-oxide metal oxide, metal oxide, or coating one-coat multi-layer coated coating.

Examples of functional coatings suitable for use in the invention are the commercial SUNGATE® and SOLARBAN® series of coatings from PPG Industries, Inc. of Pittsburgh, Pennsylvania., These functional coatings typically include one or more anti-reflective coating films comprising dielectric or anti-reflective materials, such as metal oxides or metal alloy oxides, which are preferably transparent or substantially transparent to the visible light. Functional coating 14 may also include infrared reflecting films comprising a reflective metal, for example, a noble metal such as gold, copper, or silver, or combinations or alloys thereof, and may further comprise a film. primer or barrier film, tai сото titanium, well known in the art, located on and / or under the reflective metal layer.

The functional coating 14 can be deposited on the substrate 12 in any conventional way, tai сото, without being limited only to them, deposit of metallized by ionic vapor bombardment with magnetron (MSVD) chemical deposit of vapor (CVD), pyrolysis with pulverization ( that is, pyrolytic deposit), chemical vapor deposit (CVD) at atmospheric pressure (APCVD), low pressure CVD (LPCVD), plasma powered CVD ((PEVCD), plasma assisted CVD (PACVD), thermal evaporation о by electron beam, cathode arc deposit, plasma spray deposit, and wet chemical deposit (for example, mirror plating, sol-gel, etc.). It should be noted the observation that coatings deposited by ion bombardment are sometimes less mechanically durable than coatings deposited by spray pyrolysis or chemical vapor deposit (CVD) coating methods. Examples of appropriate CVD coating apparatus and methods include, for example, without limitation of the invention, those of US Patent Nos. 3,652,246; 4,351,861; 4,719,126; 4,853,257; 5,356,718; and 5,776,236.

The present invention is particularly useful for protecting coatings deposited by MSVD (Magnetron Ion Spray Vapor Deposition), which are sometimes perceived to be more prone to cracking and damage than pyrolytically deposited coatings. MSVD coating techniques are well known to those skilled in the glass coating technique, so they will not be discussed in detail here. Examples of suitable MSVD coating are, for example, without being construed as limiting only to them, those of US Patent Nos. 5,028,759; 4,898,789; 4,948,677; 4,834,857; 4,898,790; and 4,806,220.

An inventive temporary film or removable protective coating 16 is applied to at least a portion of the substrate 12. Here, the term removable protective coating refers to a coating (ie, one or more films) that can be removed. be subsequently removed and non-abrasive or spider-free or easily spoil the substrate 12 or the optional functional coating 14, which is under it. If one or more functional coatings are present 14, the removable coating 16 is preferably applied to at least a portion of the optional functional coating 14, that is, it is applied to the same face of the substrate 12 to which the functional coating 14 has been applied, such that at least a portion of the functional coating 14 is located between the removable protective coating 16 and the substrate 12. Protective coating 16 may also be applied to at least a portion of the other side, ie, to the side of substrate 12 that is not functionally coated. Alternatively, functional coatings 14 can be applied to both sides of substrate 12 with a removable protective coating 16 of the invention applied on at least a portion of functional coating 14.

For substrates 12 to be incorporated into automobile transparencies such as windshields, side lights, rear lights, sunroofs, moonroofs, etc. Protective coating 16 is preferably applied over substantially the entire viewing area of the substrate 12, i.e. preferably over at least 50% of the viewing area, more preferably over at least about 80%, and more preferably over the area of entire vision.

Removable protective coating 16 can be removed without damaging underlying substrate 12 or optional functional coating (s) 14. In a preferred embodiment of the invention, protective coating 16 can be removed using a liquid solvent, more preferably it can be removed by washing with water. Although not the most preferred method, the protective coating 16 can also be removed by spraying or immersion with aqueous solvents, organic solvents, alkalis or acids. Furthermore, although not the preferred case, the protective coating 16 may be designed for removal by mechanical peeling of the protective coating 16 from the surface of the substrate and / or optional functional coatings.

In a present preferred first embodiment, the removable protective coating 16 comprises a film-forming, water-soluble or water-dispersible material, for example a polymeric material comprising one or more homopolymers or copolymers of starches, casein, and related polymers. protein derivatives, acrylic polymers, polyacrylamide, alkylene oxide polymers, such as ethylene oxide, polyvinyl acetate, polyvinyl alcohol, polyvinyl pyrrolidine, styrene / acrylic acid copolymers, ethylene / acrylic acid copolymers, cellulosic materials and cellulose derivatives such сото, but not limited to, methyl cellulose, hydroxypropyl methyl cellulose, carboxymethyl cellulose, ethyl cellulose, alkyl hydroxy derivatives, chemicals, combinations, mixtures, alloys and / or mixtures thereof, so that the coating (s) 16 formed using these coating compositions retain the ability to remove the previously described coating, the coating may have any weight percent of film-forming material that provides acceptable deposition parameters. For example, all of the film-forming material, or a portion of it by wiping, aqueous, or its ability to composition may be present in a precipitated solution.

In a first embodiment, the protective coating 16 is the reaction product or evaporation product of an aqueous coating composition of the invention comprising one or more of the above polymeric materials. The coating composition comprises a substantially aqueous solution of polyvinyl alcohol polymer having up to about 30 weight percent polyvinyl alcohol polymer based on the total weight of the coating composition, more preferably up to about 24 weight percent, and even more preferably up to about 12 weight percent, and most preferably from about 5 weight percent to about 12 weight percent of polyvinyl alcohol polymer. As used herein, the term "substantially aqueous" means that it has more than about 10 volume percent of water, preferably more than about 15 volume percent of water, and most preferably more than about 21 volume percent of Water,

The polyvinyl alcohol preferably has a degree of hydrolysis greater than 80%, preferably greater than about 85 percent. For example, vinyl alcohol may be partially hydrolyzed (eg, be 87 to 89 percent hydrolyzed), may have an intermediate degree of hydrolysis (eg, be 95.5 to 97.5 percent hydrolyzed), be fully hydrolyzed (for example being 98 to 98.8 percent hydrolyzed), or being super-hydrolyzed (for example being more than 99.3 percent hydrolyzed). Generally, as the percentage of hydrolysis increases, the resistance to water, resistance to traction, resistance to solvents and adherence to hydrophilic surfaces increase. The film-forming polymer generally has an average weight molecular weight, Mw, of from about 13,000 to about 23,000. As a general rule, as Mw increases, viscosity, tensile strength, water resistance, adhesion resistance and solvent resistance increase.

Polyvinyl alcohol polymers suitable for the practice of this invention are commercially available and are from Air products and Chemicals, Inc. of Allentown, PA, сото AIRVOL® 203, and 203S, polyvinyl alcohol powder or aqueous poly alcohol solution vinyl AIRVOL 24-203 (24% by weight) or dilutions thereof. The aqueous coating composition of the invention may further include a low molecular weight alcohol, such as methanol, ethanol, or isopropanol with co-solvents in the vehicle water. The amount of alcohol co-vehicle that can be added to the solution without precipitation of the polyvinyl alcohol resin occurs depends on the molecular weight and the percentage of hydrolysis of the resin as well as the identity of the specific alcohol added. For example, aqueous solutions of certain grades of polyvinyl alcohol are stable up to about 60 to 70 volume percent isopropanol. Preferably, the alcohol co-solvent is present in an amount of not more than 50 volume percent, more preferably less than about 10 volume percent, and most preferably about zero volume percent of the coating composition.

The coating composition may also optionally include a surfactant to enhance the wetting characteristics of the coating composition when applied to substrate 12. Surfactants are commercially available and are from BYKChemie of Wallingford, Conneticut сото Byk-306. , 307 or 333, polyether modified polydimethyl polysiloxane. If present, the surfactant may be present in amounts of up to about 5 weight percent, preferably in amounts of up to about 3 weight percent, and most preferably in amounts of up to about 1 weight percent of the composition. of coating based on the total weight of the coating composition.

The coating composition may also include other additives, such as conventional and / or commercially available ones, foam removers, leveling agents, surfactants, flow agents, rheology modifiers, waxes, paraffins, animal, vegetable or mineral oils , emulsifying agents, thickeners, stabilizers, anti-inflammation agents, antiblocking agents to avoid bonding, lubricants, hydrophobic agents, hydrophilic agents, biocides, fungicides, algicides, anti-mildew agents, organic and / or inorganic fillers or extenders, 'plasticizers, flavoring materials, or crosslinking agents. As will be described in more detail later, the coating composition may also include organic and / or inorganic dyes, dyes, fluorescent dyes, or pigments to obtain the resulting removable protective coating 16 with the selected color. For MSVD coatings, especially silver-containing coatings, biocides may consist of a substantially halide-free biocide to reduce the possibility of interaction of the halide, for example chloride, with silver. Substantially halide free means that the biocide contains less than 5 weight percent halide, more preferably less than 1 weight percent halide, and most preferably contains no halide.

In the present preferred practice, the coating composition of the invention is applied to one or more surfaces of the substrate 12, with о no functional coating 14, in any conventional manner, tai сото by pouring, spraying, dipping, flow coating, coating curtain, brush application, roller application, spray, mist, down drag, squeeze roller coating or rotational coating.

In a preferred present practice, if the functional coating is a single layer metal oxide coating, the coating composition is preferably essentially free of spacer material. Being essentially free of spacer material means that there is no solid spacer in particles or interspersed materials such as organic or insoluble polymeric particles (for example acrylic beads or polyethylene particles), inorganic particles, for example colloidal silica, or similar materials added to the composition. of coating before application to the substrate.

In a first preferred present practice, the coating composition of the invention is spray applied on one or more surfaces, eg, on the first and / or second largest surfaces, of substrate 12 having zero, one or more coatings functional4. As any person skilled in the art will appreciate, the spraying area should include a device to evacuate possible excess spray material. For example, conventional evacuation technology and conventional washing bottles can be used for exhaustion and / or capture of excess pulverized material. The coating composition can be applied as part of a process of the float glass passing operation (glass that is passed through a liquid metal bath at a lower temperature so that it solidifies), as part of a conventional tempering process, о сото part of a conventional glass coating process.

The substrate 12 bearing the coating composition applied is then cured, for example, by drying, to provide an evaporative film formation mechanism, or a reagent cure film formation mechanism. This can be done in any conventional way, tai сото with convection air flow (either hot air or room temperature air), radiant heat (eg quartz lamp, gas fired radiant heater, electric radiant heater ), heat by convection of (forced air), by conduction (for example, heating of a spray-coated substrate on a plate or heatable support), vacuum drying (for example, pumping solvent extraction from the applied coating composition) or radiation curing (eg, IR, UV, microwave or RF radiation curing). The speed with which the coating composition cures to form one or more protective coatings may be dictated by additional restrictions not related to the details of the coating chemistry and application technique. .

In a present preferred practice, the substrate 12 with the applied protective coating composition is dried by convection air drying using one or more air knives or slot-shaped air nozzle (s) connected to a fan to provide turbulent air flow at room temperature, at about 305 m / minute on the liquid coating composition applied to evaporate the aqueous solvent and the possible cosolvent and to leave a dry product by evaporation, evaporation product that forms the protective coating 16. Conventional fans can also be used to evaporate the solvent aqueous. In a preferred method of drying the liquid coating composition, such as that applied to a functional coating, the discharge of the air knife is directed towards the surface of the substrate carrying the coating composition. By directed toward is meant that the air from the air knife is directed from less than about 180 ° (i.e. parallel to the surface of the substrate) to greater than approximately 90 ° (i.e. normal to the surface of the substrate) with respect to the substrate surface.

Preferably, the dry evaporation product, tai сото polyvinyl alcohol, has a weight coverage on substrate 12 of up to about 1000 g / m2, preferably up to about 250 g / m2, more preferably up to about 25 g / m2 and even more preferably up to about 10 g / m2 and even more preferably up to about 2 g / m2 and most preferably between about 1 g / m2 and about 2 g / m2.

Assuming a uniformly dried protective coating that has an average density of approximately 1 gram per cubic centimeter (lg / cm3), the protective coating 16 may have an average physical protective coating thickness of up to about 1000 microns, preferably up to 250 microns, more preferably up to about 25 microns, and even more preferably up to about 10 microns, even more preferably up to about 2 microns, and most preferably between about 1 micron and 2 microns on the surface of the substrate. In particular for piano or curved panel substrates without functional coating 14, the protective coating 16 can be up to about 50 microns thick. The exact thickness of the protective coating selected for a particular application depends on several factors, such as the morphology of the coating, the degree of protection desired, the type of substrate, the presence or absence of functional coatings, the type of functional coating present, the Similarity of properties of the protective coating film 16. to those of polyvinyl alcohol, and the environment of handling and / or use of the substrate.

The degree of protection provided by the protective coating 16 is influenced by, among other things, the type of coating material used, the thickness of the applied protective coating 16, and the morphology of the coating. For example, using conventional surfactants with those described above, the resulting protective coating 16 can be of substantially uniform or continuous thickness on the substrate 12. Alternatively, some coating compositions can form non-continuous protective coatings or islands, which can also provide adequate protection against mechanical damage.

The removable and cured removable protective coating 16 can optionally be sprinkled in a conventional manner with spacer or interleaving material, such as polymethyl methacrylate spheres approximately 149 microns in diameter, organic or inorganic particles, acrylic beads, colloidal silica particles , polyethylene spheres, or sawdust to help further separate adjacent glass2 substrates during transport and / or storage. These spacer materials are preferably applied to the dry coating and therefore do not become integrated into the protective coating film. Suitable spacer material is described, for example, in US Patent No. 5,026,597, which is incorporated herein by reference.

Therefore, one or more substrates 12, such as a glass or plastic manufacturing substrate, having the removable protective coating 16 of the invention can be packed and shipped to an industrialist in the conventional manner. A plurality of substrates 12 of any shape or size can be packaged, for example flat sheets of glass, incorporating the removable protective coating 16 of the invention, and shipped together in a conventional manner. For example, Figure 2 illustrates a conventional packaging о goods pallet о a container 20 containing a plurality of substrates 12 of different dimensions, eg, in thickness and / or side dimensions. The transport container 20 can be a conventional wooden pallet for goods or any other type of packaging or transport device used in the shipment of glass articles. The substrates can be of uniform size and shape or can be of different sizes and shapes. Individual substrates can have zero, one or more functional coatings. Various combinations of substrates of different sizes with or without functional coating 14 are also possible, but should be separated by a removable protective coating 16 of the invention. The protective coating 16 of the invention may have a spacer material sprinkled on it, such сото polymer spheres сото has been noted above. The substrates 12 may have the protective coating 16 of the invention on one or on both sides so that at least one protective coating 16 of the invention is located between a pair of adjacent substrates 12. Protective coating 16 can prevent or prevent chemical and / or mechanical damage to the substrate surface 12 or functional coatings.

14.

By receiving the packaged substrates 12, the industrialist can cut and / or chip the substrates 12 into the desired smaller pieces of glass and then divide the pieces before further processing of the individual pieces.

In the case of glass substrates, having a thickness of approximately 6 millimeters or less, this burr is typically carried out with a tungsten carbide glass cutting / notching wheel with an angle of 135 ° to 140 °, which It is the one commonly used in the glass cutting / trimming technique. If the removable protective coating 16 is too thick, the conventional cutter wheel will not be able to make the sharp notches in large pieces of glass, which can be adversely affected by cutting into smaller pieces of glass. The preferred present weight cover is from about 1.1 to about 2.2 g / m2 for a 12 weight percent solution of AIRVOL® 203 polyvinyl alcohol in water, which has been found to provide adequate protection against mechanical damage during transportation without adversely affecting this conventional burr technique and cutting procedure performed by the industrial, so that there will be no adverse impact on conventional cutting practice. For other film-forming materials, the preferred weight coverage may vary depending on the molecular weight о percent hydrolysis of the material о the weight percent of the film-former in the solution.

After the grinding and cutting operation, the protective coating 16 can be removed by the industrialist, for example, by washing with water. Water at room temperature or at room temperature is adequate. that typically comes out of the tap. The removal of the protective layer 16 does not necessarily require the use of warm water or hot water, although these can also be used to remove the temporary protective coating 16. No special nonaqueous solvents, detergents, surfactants, or high-temperature removal procedures (eg steam) will be required although these additives or refined ones can be used to make the removal of the temporary coating optimal, you want ..

Wash-removed coating material can be collected and recycled for reuse. For example, if the protective coating is removed by washing, for example, aqueous washing, the washing liquid carrying the separated coating material can be collected, the liquid evaporated, and the dry coating material recovered and reused. Alternatively, the washed liquid carrying the removed coating material can be precipitated, gelled or coagulated, and then filtered off the coating material for reuse. Alternatively still, the washing liquid with the coating material removed can be gelled or coagulated for reuse in another protective coating operation

The washing liquid can also be evaporated and the coating material can be collected.

As previously discussed, the coating composition of the invention may include one or more colorants (eg pigments and / or dyes) so that the protective coating 16 can be selectively colored. Suitable dyes include, but are not limited to, inorganic dyes such as titanium dioxide, carbon black, lead chromates, zinc and barium, cadmium sulfide, iron oxides, Prussian blue, Ultramarine blue, Cobalt Blue, Chromium Oxide, Red Iron Oxides, Cadmium Selenide, Red Lead, Chromium Red, and various aluminosilicates and clays, and / or organic dyes such as azo dyes, fluorescent dyes, and phosphorescent dyes. You can also use the so-called special effect pigments, such сото, without being limited only to them, powders, flakes, or sheets of metal composition or appearance of metallic reflections, dyes that have variable colors depending on the angle of vision, о aesthetic, pearlescent or opalescent pigments.

This coloring of the removable protective coating 16 can be useful for the manufacturer as well as for the industrial as it is an aid in the identification of the particular type of substrate, for example, glass substrate 12 and / or functional coating 14 shipped, stored or received . The manufacturer may use different colored protective coatings 16 with different types of coated or uncoated substrates 12 to help the industrialist quickly and easily identify the type of glass and / or functional coating received. For example, the manufacturer may apply a removable protective coating 16 held in red only to substrates having a first functional coating layer 14 and a different color, for example, a removable protective green coating, only to substrates having a second functional coating different 14. Accordingly, the industrialist can receive, cut, and store the coated glass pieces, and then easily identify the type of glass and / or functional coating simply by the color of the removable protective coating 16 applied thereto. This can facilitate storage and eliminate identification problems for the industrialist since some functional coatings 14, which may have significantly different functional properties (for example, optical properties, solar control properties, thermal properties, etc.) are frequently difficult. visually distinguish. Alternatively, the coating composition can be free of these colorants, because it allows the visual distinction of different substrates. For example, the protective coating 16 may be applied in the form of a pattern, or the protective coating 16 may change the visual characteristics of the substrate 12 enough to visually distinguish one type of substrate from another. Alternatively, о in addition to the above, the protective coating composition may include a particular о selected flavoring material, to impart a selected scent to a selected type of substrate so that different substrates can be distinguished by their odor. In addition, printing ink can be deposited on the protective coating for writing words, markings or other identifying signs.

Although in the preferred practice discussed above, the removable protective coating 16 was removed by washing the substrate 12 with an aqueous wash at room temperature, the protective coating can also be removed by combustion or thermal decomposition. For example, after the notches and cuts made by the industrialist to obtain smaller pieces of glass of the desired size, depending on the type of glass, the smaller pieces of glass can be heated in a tempering furnace to temper the glass. Typical tempering furnaces operate at a range of approximately 648 ° C704 ° C. At these temperatures, the above discussed polymeric protective coating 16 will either thermally decompose or burn off from substrate 12. However, this combustion removal procedure is not preferred here for substrates functionally coated by MSVD with polymeric protective coating 16 of the invention discussed above.

The industrialist can then incorporate the cut piece (s) of substrate into a production article, such as an automotive transparency, architectural windows, IG glass units, mirror, liquid crystal display (LCD), etc. and then send the production item to the customer. For example, the cut piece (s) of substrate (s) can be incorporated into a conventional window unit that has a frame or is sliding. Before shipping the production item to the customer, the industrialist may apply a protective coating 16, which may be the same or different from that described above, on at least a portion of the item, for example, on the entire window unit including the frame. and the sliding frame, to protect the production item during shipment to the customer. The customer can then remove the protective coating 16 in a manner similar to that described above.

In the first embodiment of the removable protective coating 16 of the invention described above, the protective coating 16 is formed by a product of evaporation or reaction of an aqueous polymeric coating material. However, a removable protective coating alternative 16 of the invention is described below. A second embodiment of a removable protective coating 16 of the invention comprises a carbon-containing film or coating. The carbon-containing coating is preferably substantially carbon, that is, it consists of more than about 50 weight percent carbon, more preferably more than about 75 weight percent carbon, even more preferably more than about 90 percent by weight in carbon, and most preferably 100 percent by weight is carbon, over the total weight of the carbon-containing coating. This carbon-containing coating can be deposited on the substrate 12 and / or the optional functional coating 14 in a convenient way, without being limited only to them, by MSVD or carbon arc deposition. For example, the substrate 12 can be placed in a conventional ionic spatter coating apparatus as well as an MSVD apparatus and the desired functional coating 14 can optionally be applied in a conventional manner. To form a substantially carbon protective coating 16 of the invention, one of the cathode elements of the coater may have a graphite or carbon-containing ion bombardment target, which can be found commercially by MSI, Co. La Carbon target can be spray-coated in a conventional manner to apply a substantially carbon protective coating 16 on substrate 12 and optional functional coating 14. The protective carbon-containing coating preferably has a thickness from greater than 0 A to approximately 50 microns, more preferably less than 10 microns, even more preferably less than 3 microns, even more preferably less than 1000 A, and in a preferred embodiment present is approximately 300 A. For MSVD application, the carbon target is bombarded with ions preferably in an atmosphere that is essentially free of oxygen to minimize combustion of the carbon material bombarded using ions. Essentially oxygen free means it is less than about 20 volume percent oxygen, more preferably less than about 10 volume percent oxygen, and most preferably is oxygen free. An oxygen-free atmosphere suitable for the identical bombardment of a carbon-containing target is one comprising argon gas.

Before applying the removable protective carbon-containing protective coating 16 of the invention on a substrate 12 with or without functional coating 14, a blocking layer 18 (represented with dotted lines in Figure 1) can be applied on the substrate 12, for example on the functional covering 14. Applying the carbon-containing protective coating 16 directly onto a functional coating 14 can damage the functional coating 14, by chemical reduction of the upper portion of the functional coating 14, i.e., dragging oxygen atoms from the functional coating 14 to form carbon oxides . Therefore, if a functional coating 14 is present, a blocking layer 18- is preferably applied over the functional coating 14 prior to the application of the carbon-containing protective coating 16 to prevent the carbon protective coating 16 from capturing oxygen from the functional coating 14. The blocking layer 18 preferably comprises a material that avoids the chemical reduction of the functional coating 14 but does not adversely affect the transmission or vision characteristics of the coated article 10. For example, the blocking layer 18 may comprise silicon, titanium, zirconium, niobium, aluminum or combinations, oxides, nitrides or oxynitrides thereof. The blocking layer 18 can be applied in any convenient way, as described above for the application of the functional coating 14. The blocking layer 18 can have a thickness of from more than 0 A to approximately 50 microns, preferably less than 25 microns, more preferably less than 10 microns, even more preferably less than 1.7 microns, and most preferably less than 0.5 microns. In a preferred present practice, the blocking layer 18 comprises silicon having a thickness of 25 A to 100 A, preferably 50 A, The blocking layer of silicon 18 can be applied in any of the conventional ways, also by ion bombardment of a silicon target in an oxygen-containing atmosphere to form a silicon layer on the functional coating 14 prior to sputtering of the carbon target to form the carbon-containing protective coating 16. The use of blocking layer 18 is not limited to substrates having functional coatings but can also be applied to non-functionally coated substrates prior to application of the coating in place, the substantially carbon protector 16 is removed.

Once the carbon-containing protective coating 16 has been applied, the coated article 10 is removed. You can send to the industrialist and work as described above. However, unlike the previously discussed polymeric temporary protective coating of the invention, this carbon-containing protective coating probably cannot be removed by aqueous washing. In a carbon-containing coating preferably by combustion, for example, in a tempering oven сото has been discussed above. During tempering, the protective coating 16 containing carbon is oxidized and removed from article 10.

The carbon-containing protective coating 16 of the invention also provides improved tempering characteristics to certain functionally coated substrates. For example, typical 14 low-emissivity or solar control functional coatings act as a mirror for heat during the tempering process, increasing the time required to temper coated glass compared to that required to temper uncoated glass. The carbon-containing protective coating 16 of the invention absorbs heat during the tempering process, deflecting some of the heat reflective effects of the functional coating 14 and reducing the tempering time from that required for a coated article without this carbon-containing protective coating6 .

To generally improve the heating characteristics, for example tempering, of functionally coated substrates, such as low-emissivity or solar-controlled coated substrates, a high-emissivity temporary coating, tai сото, may be applied without being limited only to e, a Substantially carbon coating tai сото has been described above, on the functionally coated substrate before heating, to help absorb heat and counteract the heat reflective characteristics of the functional coating. By high emissivity is meant an emissivity greater than about 0.4, preferably greater than about 0.5, more preferably greater than about 0.6, and even more preferably greater than about 0.8. The high emissivity coating promotes even heating of the functionally coated substrate. In addition, used in tempering, this high-emissivity coating can be used for other operations, such as warping, shaping, or imparting heat resistance, just to name a few. Anyone skilled in the art will appreciate that the high-emissivity coating is not limited to just carbon but to any coating capable of undergoing combustion or thermal decomposition during the selected heating process without adversely affecting the substrate and / or functional coating, as well as polymer coating, for example.

The following examples are given below to illustrate the invention, which are not to be considered as limiting the invention in their details. In Examples 1-10, the glass samples used for testing the protective coating of the invention were each coated with the same silver-based, multi-layer, solar control MSVD applied coating Controls were functionally coated glass pieces without the protective coating of the invention.

EXAMPLE 1

285 ml of deionized water (DI) was heated to a temperature of about 80 ° C. Using a magnetic stir bar, the water was vigorously stirred while slowly adding 15,000 g of polyvinyl alcohol (PVOH) (Airvol® 103, thus all other Airvol® materials discussed in the examples are commercial products of Air Products and Chemicals, Inc.). The solution was continuously stirred and kept at a temperature of about 85 ° C for about 15 minutes. Heating was then stopped but stirring was continued while the solution was allowed to cool to room temperature (approximately 20 ° C). This procedure resulted in a 5 weight percent solution of PVOH in deionized water. Using a polyethylene pipette, an amount of PVOH solution, with a small stream, was applied to a 10 cm x 10 cm sample of 2 mm thick glass that had a multi-layer coating, applied by MSVD, of control. solar, silver-based. The jet was then distributed more evenly across the surface of the sample using a stainless steel downward drag rod to a wet film thickness of 0.013 cm. The sample was allowed to dry under a 250 watt heat lamp (commercially available from Sylvania) for approximately five minutes. After drying, the sample was weighed using a Sartorius balance with a sensitivity of 0.0001 gram; The weight of the uncoated sample was subtracted from the weight of the coated sample, whereby the weight of the polymer coating on the 10 cm x 10 cm sample was obtained, which was 0.0714 grams. From this result, it was calculated that the expected average weight for each square foot (0.09 m2) was approximately nine times that number, i.e. approximately 0.64g / square foot (7.1g / m2). The glass sample coated with polyvinyl alcohol (PVOH) was subjected to a modified 100 cycle Taber abrasion test with an applied load of 500 grams on each of the two abrasion wheels. The modified Taber Abrasion Test comprises the fixed placement of the sample to be tested on a flat, circular rotary table. Two rotating Calibrase® CS-10F abrasive circular wheels are lowered (commercially available from Taber Industries of N. Tonawanda, NY) on the surface above the sample to be tested; There is a 500 gram load applied to each abrasive wheel. Calibrase® CS-10F wheels are made of an elastomeric material that is impregnated with an abrasive. To perform the test, the rotary table switch is turned on and the wheels begin to rotate and cause abrasion on the surface of the sample when the sample and the rotary table rotate around the vertical axis until the desired number of rotations is completed о cycles. After testing, the sample is removed from the rotary table and examined for damage to the top surface. After the Taber test, the PVOH coating is removed by washing the sample with flowing deionized cold (room temperature) water. Once washed, the sample is blown dry with compressed air. When compared to the control samples subjected to the same Taber test, the abrasion was found to be significantly less visible on the PVOH protected sample. The degree of scratching was determined by measuring the diffuse or specular-excluded reflectance, Y, of locations according to the four cardinal points around a circle corresponding to the Taber abrasion section using a Spectrogard (commercial, BYKGardner) colorimeter; in the excluded-specular mode (Illuminant D65, excluded-specular large-aperture reference mode, 2-degree observer), using the chromaticity space Y, x, and ICE 1931. A reference measurement was also taken of the excluded-specular, background reflectance of the sample surface outside the annular section of the Taber abrasion; the reference reflectance of the undamaged surface was typically measured within the inside diameter of the abrasion section. Up to four baseline or baseline measurements were made and the mean was found. The average background specular-excluded reflectance of a sample was

Ti -ij typically very low, frequently approximately Y = 0.00, indicating that the diffuse reflectance of the undamaged area of the sample surface was essentially сего сото expected for a glass sample that was specular for visible light in reflectance outside the abrasion section. The mean of the four measurements at the four cardinal points of the diffuse reflectance of the Taber abrasion stretch, minus the mean background reflectance excluding specular reference, is quoted Taber excluded-specular score or Taber score. In this scheme, a higher Taber score indicates a more diffuse reflectance of the abrasion section, and therefore an indication of a greater degree of deterioration is interpreted. The mean Taber score of the sample protected by PVOH was 0.10; the mean Taber score of an unprotected control sample (ie, a functionally coated but unprotected glass sample of the invention) subjected to the same abrasion test was 2.85 (see Table 1 below);

here simply

EXAMPLE 2

An Airvol® 203 polyvinyl alcohol (PVOH) solution was prepared in Example 1. The solution was poured into a Sure Shot® Model A® pneumatic spray container, commercially available from

Manufacturing Company, Inc., and with approximately 7 kg / ст2. PVOH solution was sprayed

Milwaukee Sprayer a pressure of approximately 30.5 cm x 30.5 cm on a test sample and glass measuring 2 mm thick and having the same functional coating as that of Example 1; Two passes and a distance from the spray tip to substrate of approximately 15.2 cm were used. After spraying, the PVOH-coating was dried under a heat lamp for approximately 5 minutes. After the PVOH coating had dried, a tungsten carbide glass cutting hand tool was used to chip the test sample in order to divide it into nine 10 cm x 10 cm pieces. The cut piece from the center of the sample was weighed and then subjected to a modified Taber test for 100 cycles as described in Example 1. After the Taber test, the PVOH coating was removed from the sample by washing with flowing deionized water at room temperature and dried with compressed air. The sample was then weighed and the two measurements were subtracted, whereby it had a weight of the PVOH coating coverage of 0.1991 grams in the sample of 10 cm x 10 cm. The expected weight per square foot was estimated to be nine times that number or approximately 1.8 g / square foot (20 g / m2). Examination of the sample after peeling off the PVOH coating showed that compared to control samples subjected to the same Taber test, there was significantly less visible abrasion on the PVOH protected sample. The degree of scratching was determined by measuring the diffuse reflectance at the positions of the four cardinal points around the circle corresponding to the Taber abrasion section using a Spectrogard calorimeter in excluded-specular mode as described in Example 1 above. The mean Taber score of the sample protected by PVOH was 0.02; the mean Taber score of an unprotected control sample subjected to the same abrasion test was 3.01 (see Table 1 below

EXAMPLE 3

25 ml of aqueous Spraylat® A polymer dispersion (available from Spraylat Corporation) were mixed with an equal volume of deionized water at room temperature, this is quoted as 50% concentrated Spraylat dispersion). Using a polyethylene pipette, a 50% concentrated amount of Spraylat A dispersion was applied with a small stream to a 10 cm x 10 cm sample coated with the same functional coating as in Example 1. This jet was then more evenly distributed over the sample surface using a stainless steel level down drag bar up to 0.013 cm thick of the wet film. The sample was allowed to dry under a 250 watt heat lamp for approximately 5 minutes. After drying the sample, it was weighed; The weight of the uncoated sample is subtracted from the weight of the coated sample to determine the weight of the polymer coating on the sample that turned out to be 0.3061 grams, giving an expected average weight per square foot of 2.8 g / square foot (31 grams / m2). The glass sample coated with 50% concentrated Spraylat A was then subjected to the Taber Abrasion Test (described above) for 100 cycles. After the Taber test, the Spraylat A coating was removed by manual peeling. This was done easily and did not appear to cause any negative effect on the underlying MSVD coating. Examination of the sample after the Spraylat A coating had been removed showed that no Taber abrasion stretch was visible; the mean Taber score for this sample was 0.00. A control sample of functionally coated glass without protective coating of the invention showed extensive deterioration of the coating by MSVD; the corresponding mean Taber score for the control sample was 2.96. .

EXAMPLE 4

50 ml of ethylene / acrylic acid (EAA) copolymer Michem® Prime 4983R-HS (sold by Michelman,

Inc.) with an equal volume of deionized water; the resulting solution is quoted сото concentrated at 50% Approximately 0.5 ml of ammonium hydroxide (NH4OH) 1 N to stabilize dispersion after dilution. In addition, 1 ml of Dynol® 604 surfactant (marketed by Air Products and Chemicals, Inc.) was added to improve the wetting behavior of the dispersion. 50% concentrated dispersion (with NH additives4OH and Dynol® 604) a small jet was applied to a 10 cm x 10 cm sample of glass coated with the functional coating of Example 1. This jet was then more evenly distributed over the surface of the sample as described above. In Example 1, it was dried under the heat lamp and then weighed. The weight of the polymer coating on the 10 cm x 10 cm sample was determined at 0.1529 g giving the expected average weight of 15.6 g / m2. The EAA copolymer coated glass sample was then subjected to a Taber abrasion test (described above) for 100 cycles. After the Taber test, the polymer coating was removed by immersing the coated glass sample in a NH solution4OH (pH 11) for approximately three minutes and scrubbed with Kaydry® Cleaner (available from Kimberly-Clark Corporation) followed by flushing deionized cold water. After rinsing, the sample was dried by blowing with compressed air. Compared to control samples (i.e. functionally coated substrates without the protective coating) subjected to the same Taber test, the EAA polymer coated sample had significantly less visible abrasion. The degree of scratching was determined by measuring the diffuse reflectance of positions according to the four cardinal points around the circular section of Taber abrasion using a Spectrogard colorimeter in excluded-specular mode. The sample coated with copolymer

EAA had a Taber score of 0.02. An unprotected control sample subjected to the same 100-cycle Taber abrasion test had an average Taber score of 2.78.

EXAMPLE 5

A 10 cm x 10 cm glass sample having the same functional coating as that of Example 1 was coated with 6 weight percent aqueous solution of polyethylene oxide (PEO) and dried in an oven at a temperature at about 121 ° C for about 5 to 15 minutes. In a similarly prepared sample, the resulting dried polymer coating was estimated to be approximately 7 pm thick and corresponded to an estimated weight coverage (dry coating weight) of approximately 7.8 grams / ms assuming a uniform coating with an average density of approximately 1 g / m3. The PEO-coated glass sample was then subjected to the Taber Abrasion Test (described above) for 100 cycles. Although being. poly ethylene oxide a water soluble polymer, the polymer coating could have been removed from the substrate by exposing it to water (it has been done with the previous polyvinyl alcohol coated samples), the PEO coating had sufficient mechanical integrity to to be able to eliminate it also by mechanical peeling. The PEO coating peeled off the glass substrates and the substrate was washed in deionized water. After washing, the sample was blown dry with compressed air. When compared to a control sample subjected to the same Taber test, there is significantly less visible abrasion on the PEO coated sample. The degree of scratching was determined as described above. The PEO coated sample had a mean Taber score of 0.01: An unprotected control sample subjected to the same 100 cycle Abrasion Taber test had a mean Taber score of 2.98.

EXAMPLE 6

A glass sample (10 cm x 10 cm) having the same functional coating as that of Example 1 was coated with a 10 weight percent aqueous solution of poly ethylene oxide (PEO) with aluminum oxide nanoparticles (Al2OR3) dispersed and dried in a stove was described in Example 5. The weight ratio of PEO to aluminum oxide in solution was 46% / 54%. In a similarly prepared sample, the resulting dried polymer coating was estimated to be approximately 10 рта thick and corresponded to an estimated weight coverage (dry coating weight) of approximately 26.7 g / m2 assuming a uniform film with an estimated average density of approximately 2.6 g / cm3. This estimate. it was calculated assuming an average density of approximately 3.95 g / cm3 for aluminum oxide (alpha phase), an average density of about 1 g / cm3 for PEO, and weighting the densities assumed by their weight fractions in the dry coating. PEO / A1 coated glass sample2OR3 it was then subjected to a Taber abrasion test (сото described above) of 100 cycles. The PEO polymer matrix of the protective coating is a water-soluble material; This makes it possible to remove the protective coating by washing / rinsing with water. After removing the PEO / A1 coating2OR3 by rinsing with water, the sample is blown dry with compressed air. Compared to a control sample subjected to the same Taber test, there was significantly less visible abrasion on the PEO / A1 coated sample2OR3. The degree of scratching was determined as described above. The sample coated with PEO / A12OR3 had an average specular excluded Taber score of 0.00. An unprotected control sample subjected to the same 100 cycle Taber Abrasion Test had an average Taber score of 2.98.

EXAMPLE 7

Using a polyethylene pipette, an amount of Chempeel ™ 'WB polymer dispersion (marketed by PPG Industries, Inc.) was applied in the form of a small jet onto a 10 cm x 10 cm glass sample having the same functional coating as the Example 1. This small jet was then more evenly distributed over the sample surface using a stainless steel bar drag down to a wet film thickness of 0.013 cm. The sample was allowed to dry under a 250 watt heat lamp for approximately 5 minutes. After drying, the sample was weighed; The weight of the uncoated sample was subtracted from the weight of the coated sample and the weight of the polymer coating on the sample was determined to be approximately 0.5314 grams. From this result, the expected average weight was estimated to be approximately 53.3 g / m2. The glass sample coated with Chempeel WB was then subjected to a Taber Abrasion Test (described above) of 100 cycles. After the Taber test, the Chempeel WB coating was removed by manually peeling it off the sample. Compared to control samples subjected to the same Taber test, there was no visible Taber abrasion stretch on samples protected with Chempeel WB. The degree of scratching was determined by measuring the diffuse reflectance around a circle where it is expected to normally present the Taber abrasion section. The samples protected by Chempeel WB had a mean Taber score of 0.00, while an unprotected control sample had a mean score of 2.91.

EXAMPLE 8

50 ml of Rhoplex® WL96 polymer emulsion (available from Rohm and Haas Company) was mixed with an equal volume of deionized water, - the resulting emulsion is quoted as 50% concentrated. Approximately 1 ml of Dynol® 604 surfactant (marketed by Air Products and Chemicals, Inc.) was added to improve the emulsion performance on wetting. The 50% concentrated emulsion was applied with a small jet to a 10 cm x 10 cm glass sample that had the same functional coating as that of Example 1. This jet was then more evenly distributed over the surface of the sample using a stainless steel bar drag down to a wet film thickness of 0.013 cm. The sample was then dried under the 250 watt heat lamp for approximately 5 minutes. Once dry, the sample was weighed, the weight of the uncoated sample was subtracted from the weight of the coated sample, determining the weight of the polymeric coating which was 0.2137 grams. From this result the weight of the polymer coating was deduced which was approximately 21 g / m2. The polymer coated glass sample was then subjected to a 100 cycle Taber Abrasion Test (described above). After the Taber test, the polymer coating was removed by immersion of the coated glass sample in a NH solution40H (pH 11) for about five minutes and the dissolved polymer coating was flushed from the substrate by washing with cold flowing deionized water. After washing, the sample is blown with compressed air. Compared to control samples subjected to the same Taber test, there was no significant visible abrasion on the RhoplexWL-96 polymer coated sample. The degree of scratching was determined as described in Example 8. The Rhoplex WL-96 coated sample had a score

Taber average of 0.00. An unprotected control sample subjected to the same 100-cycle Taber abrasion test had a mean Taber score of 3.02.

EXAMPLE 9

An amount of Transeal ™ polymer dispersion (marketed by PPG Industries, Inc.) was applied in the form of a small jet on a 10 cm x 10 cm glass sample having the same functional coating as Example 1. This jet was then distributed more evenly on the sample surface using a stainless steel bar drag down to a thickness of 0.013 cm of the wet film. The sample is seed under the 250 watt heat lamp for approximately 5 minutes. Once dried, the sample was weighed; The weight of the uncoated sample was subtracted from the weight of the coated sample and the weight of the polymer coating was determined to be 0.4455 grams. From this result it was deduced that the weight per square meter was approximately 44.4 g / m2. . The polymer-coated glass sample was then subjected to a 100-cycle Taber abrasion test (as described above). After the Taber test, the polymer coating was manually removed by peeling the substrate. This peeling operation left some residues on the MSVD-coated surface, these residues being removed by sweeping the sample with a 50% by volume mixture of isopropanol and deionized water. Once cleaned, compressed air was blown over the sample to dry it. Comparing to control samples subjected to the same Taber test, there was no visible stretch of Taber abrasion on the Transeal polymer coated sample. The degree of scratching was determined as described above. The Transeal polymer coated sample had a mean Taber score of 0.13. An unprotected control sample subjected to the same 100-cycle Taber abrasion test had an average Taber score of 2.57.

EXAMPLE 10

2,885 ml of deionized water was heated to 90 ° C. 15.0634 grams of hydroxypropyl methylcellulose Methocel® K100LV (available from the Dow Chemical Company) were added; it was added to the hot water and stirred until the powder dissolved. Heating and stirring of the solution was maintained for approximately 30 minutes. The heat was then removed from the solution but stirring was continued to cool for approximately 60 to 120 minutes. This procedure resulted in a hydroxypropyl methyl cellulose in a 5% by weight solution in deionized water. Using a polyethylene pipette, an amount of solution was applied with a small stream on a 10 cm x 10 cm glass sample with the same functional coating as that of Example 1. This small stream was then more evenly distributed with a Downward drag stainless steel to a wet film thickness of 0.013 cm. The sample was dried under the 250 watt heat lamp for 5 minutes. After drying , the sample was weighed; The weight of the uncoated sample was subtracted from the weight of the coated sample to determine the weight of the polymer coating which turned out to be 0.2462 grams. From this result, it was deduced that the average weight per square meter was approximately 24.4 grams / m2. The polymer-coated glass sample was then subjected to a 100-cycle Taber abrasion test (described above). After the Taber test, the hydroxypropyl methylcellulose coating was removed by washing with cold flowing deionized water. Once washed, the sample was blown dry with compressed air. Compared to a control sample subjected to the same Taber test, there was significantly less visible abrasion on the polymer protected sample. The degree of scratching was determined as described above. The average Taber score of the sample protected with hydroxypropyl methyl cellulose was 0.02; the mean Taber score of an unprotected control sample subjected to the same abrasion test was 2.80 (see Table 1 below)

TABLE 1-EXAMPLES OF TEMPORARY PROTECTIVE POLYMERIC COATINGS (REMOVABLE) FOR GLASS SUBSTRATES COATED BY MSVD

<td>ID</td><td>Name of</td><td>Concentration</td><td>Weight</td><td>of the</td><td>Punctuation</td><td>Taber</td>

<td>Shows</td><td>material of</td><td>(wt% о</td><td colspan="2">coating of</td><td colspan="2">excluded mean</td>

<td></td><td>covering</td><td>factor of</td><td>polymer</td><td>dry in</td><td>speculate</td><td>after</td>

<td></td><td>protective</td><td>with-</td><td colspan="2">glass sample</td><td>separation</td><td>of the</td>

<td></td><td></td><td>centering)</td><td>10 x 10 cm</td><td>(g)</td><td>coated</td><td>I lie</td>

<td></td><td></td><td></td><td></td><td></td><td>polymer</td><td></td>

<td>Example</td><td>Poly alcohol</td><td>5% by weight</td><td> 0,0714</td><td></td><td> 0,10</td><td></td>

<td> 1</td><td>vinyl Airvol</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>None (control)</td><td>N / E</td><td colspan="2">N / E</td><td colspan="2"> 2,85</td>

<td>Example</td><td>Poly alcohol</td><td>5% by weight</td><td> 0,1991</td><td></td><td> 0,02</td><td></td>

<td> 2</td><td>vinyl Airvol</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>None (control)</td><td>N / E</td><td colspan="2">N / E</td><td colspan="2"> 3,01</td>

<td>Example</td><td>Spraylat A</td><td> 50%</td><td> 0,3061</td><td></td><td> 0,00</td><td></td>

<td> 3</td><td>(formulation</td><td>concentration</td><td></td><td></td><td></td><td></td>

<td></td><td>patented)</td><td> •</td><td></td><td></td><td></td><td></td>

<td></td><td></td><td>in volume</td><td></td><td></td><td></td><td></td>

<td></td><td>None (control)</td><td>N / E</td><td colspan="2">N / E</td><td colspan="2"> 2,96</td>

<td>Example</td><td>Michem Prime</td><td> 50%</td><td> 0,1529</td><td></td><td> 0,02</td><td></td>

<td> 4</td><td>4983R-HS</td><td>concentration</td><td></td><td></td><td></td><td></td>

<td></td><td>(formulation</td><td>. in volume</td><td></td><td></td><td></td><td></td>

<td></td><td>patented)</td><td></td><td></td><td></td><td></td><td></td>

<td></td><td>(control)</td><td></td><td></td><td></td><td></td><td></td>

<td>Example</td><td>Poly oxide</td><td>6% by weight</td><td>Thickness</td><td>approx = 7</td><td> 0,01</td><td></td>

<td> 5</td><td>ethylene (PEO)</td><td></td><td>pm 0.07</td><td>-0.08 g</td><td></td><td></td>

<td></td><td>None (control)</td><td>N / E</td><td colspan="2">N / E</td><td colspan="2"> 2,98</td>

<td>Example</td><td>PE0 / A20j</td><td>10 wt%</td><td>Thickness</td><td>approx = 10</td><td colspan="2"> 0,00</td>

<td> 6</td><td></td><td></td><td>Mm; Estimated 0.3g</td><td></td>

<td></td><td>None (control)</td><td>N / E</td><td>N / E</td><td> 2,98</td>

<td>Example 7</td><td>Chempeel WB (formulation patented)</td><td>100% concentration</td><td> 0,5314</td><td> 0,00</td>

<td></td><td>None (control)</td><td>N / E</td><td>N / E</td><td> 2,91</td>

<td>Example 8</td><td>Rhoplex WL-96 (formulation patented</td><td>fifty% concentration in volume</td><td> 0,2137</td><td> 0,00</td>

<td></td><td>None (control)</td><td>N / E</td><td>N / E</td><td> 3,02</td>

<td>Example 9</td><td>Transeal (formulation patented)</td><td>100% concentration</td><td> 0,4455</td><td> 0,13</td>

<td></td><td>None (control)</td><td>N / E</td><td>N / E</td><td> 2,57</td>

<td>Example 10</td><td>Hydroxy- propylmethyl cellulose Methocel slab K100LV</td><td>15 wt%</td><td> 0,2462</td><td> 0,02</td>

<td></td><td>None (control)</td><td>N / E</td><td>N / E</td><td> 2,80</td>

EXAMPLE 11

The test substrates used in Example 11 had a different functional coating than the substrates used in Examples 1-10. The functional coating used for Example 11 was a silver-based, multi-layer, solar control, MSVD deposited coating.

A 12 weight percent solution of Airvol® 203 polyvinyl alcohol in distilled water was prepared in substantially the manner described in Example 1. Also added to the above was polyether polydisthyl polysiloxane surfactant modified by BYK-306 (available from BYK-Chemie) at a level of. about 0.55 weight percent of coating solution. The composition or coating solution was applied using an air atomizing spray device on two glass substrates 61 cm x 91 cm and 3.2 mm thick that had a multi-layer, solar control coating based on silver deposited by MSVD, using the spray coating parameters given below.

The coating solution was applied by spraying at a flow rate of 37.0 ml / minute, a liquid pressure of lkg / cm2, an atomization pressure of 6 kg / cm2, and a fan pressure of 0.7 kg / cm2, with the spray nozzle approximately 2.5 cm from the substrate. Coated substrates were dried for approximately 30 seconds under turbulent air flow and the 1 square foot (0.09 m) sample was then cut2) of each of the dry substrates into nine 10 cm x 10 cm square sections. The coverage weight of each sample was determined by subtracting the weight of the uncoated sample from the weight of the coated sample. As seen in Table 2, given below, the mean weight of coverage was 0.1639 grams for the coated samples. Taber tests (as described above) of 10, 25, 50, 75 and 100 cycles were carried out for pairs of samples from each substrate. After the Taber tests, the PVOH coating was removed by washing with flowing cold deionized water and blown dry with compressed air. When compared to control samples (ie, functionally coated samples without the protective coating of the invention), there was significantly less abrasion visible on the PVOH coated samples. The degree of scratching was determined as described above. Medium weight coverage (g / m2) actual or estimated, and the Taber score for the samples and the control is shown in Table 2.

In the sample designations in Table 2, the prefix 1 means a sample of the 61 cm x 91 cm first substrate subjected to spraying. The prefix 2 means that the sample had been cut from the second 61 cm x 91 cm substrate to which a plate spray had been applied. The numbers 10, 25, 50, 75, 100 refer to the number of Taber cycles used for abrasion of a given sample and A and В designate 10 cm x 10 cm samples cut from two different locations on each 61 cm substrate x 91 cm.

TABLE 2

<td>Shows</td><td>g / foot2</td><td>(g / m2)</td><td>Cycles</td><td>Taber</td><td>Punctuation</td><td>Taber</td>

<td></td><td colspan="2">approximately</td><td colspan="2">(dimensionless)</td><td>half</td><td>excluded</td>

<td></td><td></td><td></td><td></td><td></td><td>speculate</td><td></td>

<td></td><td></td><td></td><td></td><td></td><td colspan="2">(adimens iona1)</td>

<td>Control-0</td><td colspan="2">N / E</td><td colspan="2"> 0</td><td colspan="2"> 0,00</td>

<td>Control-10</td><td colspan="2">N / E</td><td colspan="2"> 10</td><td colspan="2"> 0,72</td>

<td>Control-25</td><td colspan="2">N / E</td><td colspan="2"> 25</td><td colspan="2"> 1,29</td>

<td>Control-50</td><td colspan="2">N / E</td><td colspan="2"> 50</td><td colspan="2"> 1,84</td>

<td>Control-75</td><td colspan="2">N / E</td><td colspan="2"> 75</td><td colspan="2"> 2,21</td>

<td>Control-100</td><td colspan="2">N / E</td><td colspan="2"> 100</td><td colspan="2"> 2,32</td>

The control coating used in the previous tests was a coating applied by MSVD. In order to determine the effect of the type of coating on the resistance to abrasion, glass samples, which had, by pyrolytic application (APCVD), a low emissivity coating, were subjected to Taber tests of 10, 25, 50, 75 and 100 cycles tai сото has been described before. The degree of scratching was determined by measurement of the specular excluded diffuse reflectance сото described above. The results of the tests are shown in Table 3 below,

TABLE -3

<td>Shows Control -S5 S5-10 S5-25 S5-50 S5-75 S5-100</td><td>Taber Cycles (dimensionless) 0 10 25 fifty 75 100</td><td>Taber score excluded mean speculate (dimensionless) 0.01 0.09 2.35 0.35 0.45 0.61</td>

Figure 3 is a graph of Taber Score as a function of the number of Taber cycles for the substrates of the

<td>Table 2</td><td>than</td><td>have been applied by</td><td>MSVD</td><td>a</td><td>covering</td>

<td>functional</td><td>У</td><td>that have been tried</td><td>with</td><td>the</td><td>covering</td>

<td>20 protector</td><td>of</td><td>the invention (0) and</td><td>without</td><td>the</td><td>covering</td>

<td>protective</td><td> (□)</td><td colspan="2">, and for substrates</td><td>of</td><td>Table 3</td>

functionally coated by pyrolytic procedure without the protective coating of this invention (A) The AC curves shown in Figure 3 were calculated more closely adjusted to these data which were (A): у = -0,0003x2 + 0.0497x + 0.0162 for pyrolytically coated substrates without a protective coating;

(B): у = 0.0214x - 0.143 7 for MSVD-coated substrates with a protective coating; у (С): у =

0.0059x + 0.0162 for the tested pyrolytic coated substrates without protective coating.

As shown in Figure 3, MSVD-coated substrates with the protective coating of the invention are favored when compared to substrates that have the pyrolytically applied coating but do not have a protective coating, at the lowest Taber cycles of 10 and 25 , but they begin to deviate when the number of Taber cycles increases. Although increasing the thickness, for example, the weight coverage of the protective layer of the invention would undoubtedly improve abrasion resistance, the thickness of the protective coating should be balanced against process requirements for an article covered with the protective coating. . For example, thicker protective coatings can make conventional glass beading more troublesome or can make the task of quick and clean removal difficult.

Those skilled in this art will readily understand that modifications of the invention can be made without departing from the concepts described in the foregoing specification. Accordingly, the descriptive modes.

Particulars described herein in detail of embodiment are only illustrative and non-limiting of the scope of the invention, the full scope of which is given in the appended claims, as well as in all and each of the equivalents thereof.

21 members in 11 offices

This recordMember, by publication datePriority claim1 more office is in the list below

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Priority claims
Document	Office	Kind	Date
14209099	United States of America	P	1999-07-02
56793400	United States of America	A	2000-05-10
0017326	United States of America	W	2000-06-23

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Document	Office	Kind
CA2377714A1	Canada	A1	2001-01-11
WO0102496A2	World Intellectual Property Organization (WIPO)	A2	2001-01-11
AU5761800A	Australia	A	2001-01-22
WO0102496A3	World Intellectual Property Organization (WIPO)	A3	2001-07-12
KR20020031153A	Republic of Korea	A	2002-04-26
EP1200528A2	European Patent Office (EPO)	A2	2002-05-02
MXPA01013196AThis record	Mexico	A	2002-06-04
AR024640A1	Argentina	A1	2002-10-16
US2002176988A1	United States of America	A1	2002-11-28
JP2003504227A	Japan	A	2003-02-04
US6682773B2	United States of America	B2	2004-01-27
US6849328B1	United States of America	B1	2005-02-01
US2005153126A1	United States of America	A1	2005-07-14
WO2006069068A2	World Intellectual Property Organization (WIPO)	A2	2006-06-29
WO2006069068A3	World Intellectual Property Organization (WIPO)	A3	2006-08-31
CN101084279A	China	A	2007-12-05
CA2377714C	Canada	C	2008-02-12
US7361404B2	United States of America	B2	2008-04-22
RU2007127690A	Russian Federation	A	2009-01-27
JP2011105003A	Japan	A	2011-06-02
RU2429262C2	Russian Federation	C2	2011-09-20

Light-transmitting and/or coated article with removable protective coating and methods of making the same.

Abstract

Term

EXAMPLE 1

EXAMPLE 2

EXAMPLE 3

EXAMPLE 4

EXAMPLE 5

EXAMPLE 6

EXAMPLE 7

EXAMPLE 8

EXAMPLE 9

EXAMPLE 10

EXAMPLE 11

TABLE 2

TABLE -3

Priority claims3

Members21

Events

Numbers

Titles2

Classification

Abstract

Term

CROSS REFERENCE TO A RELATED REQUEST

EXAMPLE 1

EXAMPLE 2

EXAMPLE 3

EXAMPLE 4

EXAMPLE 5

EXAMPLE 6

EXAMPLE 7

EXAMPLE 8

EXAMPLE 9

EXAMPLE 10

EXAMPLE 11

TABLE 2

TABLE -3

Priority claims3

Members21

Events

Numbers

Titles2

Classification