ES2372024T3

Protective layers for sputter coated article

Abstract

A coated article comprising: (i) a substrate; (ii) a first dielectric layer deposited by sputtering on the substrate (i), the layer (ii) comprising: (iia) a first zinc stannate film deposited on the substrate (i) that has zinc in the range of percent by weight equal to and greater than 10 and equal to and less than 90, and tin in the range of percent in weight equal to and less than 90 and equal to and greater than 10, and (iib) an electrical enhancement film deposited on the zinc stannate film (iia), the electrical enhancement film being selected from the group of films consisting of a sputtering of zinc oxide, tin oxide deposited from an object having from 0.5 to 9.5 weight percent tin and from 99.5 to 90.5 weight percent zinc and a second zinc stannate film, wherein the composition of the first zinc stannate film (ia) is at least about 5 percent by weight different from the composition of the second zinc stannate film, and (iii) at least one infrared reflective layer on the first dielectric layer (ii); (iv) optionally, a first layer of metal primer on the first infrared reflective layer (iii); (v) optionally, a second dielectric layer on a first layer of metal primer (iv); and (vi) at least one protective layer consisting of two films, in which one film is selected from metals or silicon and the other film is selected from metal-oxy- or silica-oxy-materials, in which one of the films are first deposited with the other film deposited on the first deposited film, and in which the metal is the same or different and is selected from titanium, zirconium, niobium, tantalum, chromium, nickel and alloys thereof, and wherein the oxy-materials are selected from titanium oxides, titanium oxynitride, zirconium oxides, zirconium oxinitride, niobium oxides, niobium oxynitride, tantalum oxides, tantalum oxynitride, chromic oxides, chromic oxinitride nickel, nickel oxynitride, silicon oxide, silicon dioxide, aluminum nitride and silicon

Term

Term ended

Projected expiry passed 6 June 2020, 6.3 years ago.

28 claims: 8 independent, 20 dependent

1
ES 2 372 024 T3 REIVINDICACIONES 1. Un artículo recubierto que comprende:(i) un substrato;(ii) una primera capa dieléctrica depositada por pulverización catódica sobre el substrato (i), comprendiendo la capa (ii): (iia) una primera película de estannato de cinc depositada sobre el substrato (i) que tiene cinc en el intervalo de por ciento en peso de igual a y superior a 10 e igual a y menor de 90, y estaño en el intervalo de por ciento en peso de igual a y menor a 90 e igual a y superior a 10, y (iib) una película de potenciación eléctrica depositada sobre la película de estannato de cinc (iia), estando la película de potenciación eléctrica seleccionada entre el grupo de películas que consisten en una pulverización catódica de película de óxido de cinc, óxido de estaño depositada a partir de un objeto que tiene desde 0,5 hasta 9,5 por ciento en peso de estaño y desde 99,5 hasta 90,5 por ciento en peso de cinc y una segunda película de estannato de cinc, en la que la composición de la primera película de estannato de cinc (ia) es al menos aproximadamente 5 por ciento en peso diferente de la composición de la segunda película de estannato de cinc, y (iii) al menos una capa reflectante infrarroja sobre la primera capa dieléctrica (ii);(iv) opcionalmente, una primera capa de imprimador de metal sobre la primera capa reflectante infrarroja (iii);(v) opcionalmente, una segunda capa dieléctrica sobre una primera capa de imprimador de metal (iv);y (vi) al menos una capa protectora que consiste en dos películas, en la que una película está seleccionada entre metales o silicio y la otra película está seleccionada entre metal-oxi- o sílice-oxi-materiales, en la que una de las películas se deposita primeramente con la otra película depositada sobre la primera película depositada, y en la que el metal es el mismo o diferente y está seleccionado entre titanio, circonio, niobio, tántalo, cromo, níquel y aleaciones de los mismos, y en la que los oxi-materiales están seleccionados entre óxidos de titanio, oxinitruro de titanio, óxidos de circonio, oxinitruro de circonio, óxidos de niobio, oxinitruro de niobio, óxidos de tántalo, oxinitruro de tántalo, óxidos crómicos, oxinitruro crómico, óxido de níquel, oxinitruro de níquel, óxido de silicio, dióxido de silicio, nitruro de aluminio y silicio.
2
El artículo recubierto de la reivindicación 1, en el que la capa dieléctrica (ii) es una primera capa dieléctrica y la capa reflectante infrarroja (iii) es una primera capa reflectante infrarroja y el apilado incluye además:una segunda capa dieléctrica (v) sobre la capa de imprimador (iv) y (vii) una segunda capa reflectante infrarroja sobre la segunda capa dieléctrica (v);(viii) opcionalmente, una capa de imprimador sobre la segunda capa reflectante infrarroja (vii);y la capa protectora (vi) es una sobrecapa sobre la segunda capa dieléctrica (v).
3
El artículo recubierto de la reivindicación 2, en el que la capa protectora (vi) tiene al menos dos películas en cualquier orden de metal o silicio y metal-oxi o silicio-oxi-material localizadas entre la segunda capa dieléctrica (v) sobre la segunda capa dieléctrica (vii) y una tercera capa dieléctrica (ix).
4
El artículo recubierto de la reivindicación 1, en el que el apilado comprende:(i) un substrato;(ii) una primera capa dieléctrica pulverizada catódicamente depositada sobre el substrato (i), comprendiendo la capa (ii): (iia) una primera película de estannato de cinc depositada sobre el substrato (i) que tiene cinc en el intervalo de por ciento en peso de igual a y superior a 10 e igual a y menor de 90, y estaño en el intervalo de por ciento en peso de igual a y menor a 90 e igual a y superior a 10, y (iib) una película de potenciación eléctrica depositada sobre la película de estannato de cinc (iia), estando la película de potenciación eléctrica seleccionada entre el grupo de películas que consisten en una pulverización catódica de película de óxido de cinc, óxido de estaño depositada a partir de un objeto que tiene desde 0,5 hasta 9,5 por ciento en peso de estaño y desde 99,5 hasta 90,5 por ciento en peso de cinc y una segunda película de estannato de cinc, en la que la composición de la primera película de estannato de cinc (ia) es al menos aproximadamente 5 por ciento en peso diferente de la composición de la segunda película de estannato de cinc, y ES 2 372 024 T3 (iii) una capa reflectante infrarroja depositada sobre la capa dieléctrica (ii);(iv) una capa de imprimador de metal sobre la capa reflectante infrarroja (iii);(v) una segunda capa dieléctrica sobre la primera capa de imprimador (iv);y (vi) una capa protectora de al menos dos películas tal como se definen en la reivindicación 1, depositada sobre la segunda capa dieléctrica (v).
5
Un artículo recubierto de la reivindicación 1, en el que el apilado comprende:(i) un substrato;(ii) una primera capa dieléctrica pulverizada catódicamente depositada sobre el substrato (i);(iii) una primera capa reflectante infrarroja sobre la primera capa dieléctrica (ii);(iv) una primera capa de imprimador de metal sobre la primera capa reflectante infrarroja (iii);(v) una segunda capa dieléctrica sobre la primera capa de imprimador de metal (iv);conteniendo la segunda capa dieléctrica (v): (va) una primera película dieléctrica seleccionada entre el grupo que consiste en una película de óxido de cinc, óxido de estaño pulverizada catódicamente depositada a partir de un objeto que tiene desde 0,5 hasta 9,5 por ciento en peso de estaño y desde 99,5 hasta 90,5 por ciento en peso de cinc y una primera película de estannato de cinc, y (vb) una segunda película dieléctrica, teniendo la segunda película dieléctrica una composición diferente de la primera película dieléctrica de la segunda capa dieléctrica;(vii) una segunda capa reflectante infrarroja sobre la segunda capa dieléctrica (v);(viii) una segunda capa de imprimador de metal sobre la segunda capa reflectante infrarroja (vii);(ix) una tercera capa dieléctrica sobre la segunda capa de imprimador de metal (ix);y (vi) una capa protectora de al menos dos películas tal como se definen en la reivindicación 1, depositada sobre la tercera capa dieléctrica (ix).
6
Un artículo recubierto de la reivindicación 1, en el que el apilado comprende:(i) un substrato;(ii) una primera capa dieléctrica pulverizada catódicamente depositada sobre el substrato (i);(iii) una primera capa reflectante infrarroja sobre la primera capa dieléctrica (ii);(iv) una primera capa de imprimador de metal sobre la primera capa reflectante infrarroja (iii);(v) una segunda capa dieléctrica sobre la primera capa de imprimador de metal (iv);(vii) una segunda capa reflectante infrarroja sobre la segunda capa dieléctrica (v);(viii) una segunda capa de imprimador de metal sobre la segunda capa reflectante infrarroja;(ix) una tercera capa dieléctrica que tiene: (ixa) una primera película dieléctrica seleccionada entre el grupo que consiste en una película de óxido de cinc;película de óxido de cinc, óxido de estaño depositada a partir de un objeto que tiene desde 0,5 hasta 9,5 por ciento en peso de estaño y desde 99,5 hasta 90,5 por ciento en peso de cinc;una primera película de estannato de cinc, y (ixb) una segunda película dieléctrica depositada sobre la primera película dieléctrica (ixa), teniendo la segunda película dieléctrica una composición diferente de la primera película dieléctrica (ixa);y (vi) una capa protectora depositada sobre la tercera capa dieléctrica (ix), en la que la capa protectora es de al menos dos películas tal como se definen en la reivindicación 1.
7
Un artículo recubierto de la reivindicación 1, en el que el apilado comprende:ES 2 372 024 T3 (i) un substrato;(ii) una primera capa dieléctrica sobre el substrato (i);(iii) una primera capa reflectante infrarroja sobre la primera capa dieléctrica (ii);(iv) una primera capa de imprimador de metal sobre la primera capa reflectante infrarroja (iii);(v) una segunda capa dieléctrica que tiene: (va) una primera película dieléctrica seleccionada entre el grupo que consiste en una película de óxido de cinc, óxido de estaño depositada a partir de un objeto que tiene desde 0,5 hasta 9,5 por ciento en peso de estaño y desde 99,5 hasta 90,5 por ciento en peso de cinc y una primera película de estannato de cinc, y (vb) una segunda película dieléctrica depositada sobre la primera película dieléctrica (va) que tiene una composición diferente de la primera película dieléctrica (vb);(vii) una segunda capa reflectante infrarroja sobre la segunda capa dieléctrica (v);(viii) una segunda capa de imprimador de metal sobre la segunda capa reflectante infrarroja (vii);(ix) una tercera capa dieléctrica sobre la segunda capa de imprimador de metal (viii), teniendo la tercera capa dieléctrica: (ixa) una primera película dieléctrica seleccionada entre el grupo que consiste en una película de óxido de cinc, óxido de estaño depositada a partir de un objeto que tiene desde 0,5 hasta 9,5 por ciento en peso de estaño y desde 99,5 hasta 90,5 por ciento en peso de cinc;y una primera película de estannato de cinc, y (ixb) una segunda película dieléctrica, que tiene una composición diferente de la primera película dieléctrica (ixa);y (vi) una capa protectora depositada sobre la tercera capa dieléctrica (ix), en la que la capa protectora es de al menos dos películas tal como se definen en la reivindicación 1.
8
El artículo recubierto de la reivindicación 4, en el que el metal de la capa reflectante infrarroja (iii) es plata y la plata está depositada sobre la película de óxido de cinc, óxido de estaño o la segunda película de estannato de cinc (iib).
9
El artículo recubierto de la reivindicación 4, en el que la capa dieléctrica (ii) es una primera capa dieléctrica y la capa reflectante infrarroja (iii) es una primera capa reflectante infrarroja y la capa de imprimador de metal (iv) es una primera capa de imprimador de metal sobre la primera capa reflectante infrarroja (iii); y que incluye además:(vii) una segunda capa reflectante infrarroja sobre la segunda capa dieléctrica (v);(viii) una segunda capa de imprimador de metal sobre la segunda capa reflectante infrarroja (vii);(ix) una tercera capa dieléctrica sobre la segunda capa de imprimador de metal (ix), y la capa protectora (vi) está sobre la tercera capa dieléctrica (x).
10
El artículo recubierto de las reivindicaciones 4 y 6, en el que al menos una de la segunda y tercera capas dieléctricas (v,ix) incluyen una película de estannato de cinc que tiene 10-90 por ciento en peso de cinc y 90-10 por ciento en peso de estaño.
11
El artículo recubierto de la reivindicación 4, en el que la segunda capa dieléctrica (v) comprende:(va) una primera película dieléctrica, y (vb) una película de estannato de cinc que tiene cinc dentro del intervalo de por ciento en peso igual a y superior a 10 e igual a y menor de 90 y estaño dentro del intervalo de por ciento en peso de igual a y superior a 10 e igual a y menor de 90.
12
El artículo recubierto de la reivindicación 11, en el que la primera película dieléctrica (va) de la segunda capa dieléctrica (v) comprende una película de óxido de cinc;una película de óxido de cinc, óxido de estaño depositada a partir de un objeto que tiene desde 0,5 hasta 9,5 por ciento en peso de estaño y desde 99,5 hasta 90,5 por ciento en peso de cinc o una película de estannato de cinc que tiene una composición diferente de la composición de la película de estannato de cinc (vb) de la segunda capa dieléctrica (v). ES 2 372 024 T3
13
El artículo recubierto de la reivindicación 12, en el que la película de estannato de cinc (va) de la segunda capa dieléctrica (v) tiene cinc dentro del intervalo de por ciento en peso igual a y superior a 60 e igual a y menor de 90 y estaño dentro del intervalo de por ciento en peso de igual a y superior a 10 e igual a y menor de 40, y la tercera capa dieléctrica (ix) es una película de estannato de cinc.
14
El artículo recubierto de las reivindicaciones 5 a 9, en el que la tercera capa dieléctrica (ix) comprende:(ixa) una primera película dieléctrica, y (ixb) una película de estannato de cinc que tiene cinc dentro de un intervalo de por ciento en peso igual a y superior a 10 e igual a y menor de 90 y estaño dentro del intervalo de por ciento en peso de igual a y menor de 90 e igual a y superior a 10.
15
El artículo recubierto de la reivindicación 14, en el que la primera película dieléctrica (ixa) de la tercera capa dieléctrica (ix) está seleccionada entre el grupo que consiste en una película de óxido de cinc;unas películas de óxido de cinc, óxido de estaño depositadas a partir de un objeto que tiene desde 0,5 hasta 9,5 por ciento en peso de estaño y desde 99,5 hasta 90,5 por ciento en peso de cinc o una película de estannato de cinc que tiene una composición diferente de la composición de la primera película de estannato de cinc (ixb) de la tercera capa dieléctrica (ix).
16
El artículo recubierto de la reivindicación 15, en el que la película de estannato de cinc (ixa) de la tercera capa dieléctrica (ix) tiene cinc dentro del intervalo de por ciento en peso igual a y superior a 60 e igual a y menor de 90 y estaño dentro del intervalo de por ciento en peso de igual a y superior a 10 e igual a y menor de 40.
17
El artículo recubierto de las reivindicaciones 5 y 7, en el que la segunda capa dieléctrica (v) comprende:(va) una primera película dieléctrica, y (vb) una película de estannato de cinc que tiene cinc dentro de un intervalo de por ciento en peso igual a y superior a 10 e igual a y menor de 90 y estaño dentro del intervalo de por ciento en peso de igual a y superior a 10 e igual a y menor de 90, y la tercera capa dieléctrica (ix) comprende: (ixa) una primera película dieléctrica, y (ixb) una película de estannato de cinc que tiene cinc dentro de un intervalo de por ciento en peso igual a y superior a 10 e igual a y menor de 90 y estaño dentro del intervalo de por ciento en peso de igual a y menor de 90 e igual a y superior a 10.
18
El artículo recubierto de la reivindicación 17, en el que la primera película dieléctrica (va) de la segunda capa dieléctrica (v) y la primera película dieléctrica (ixa) de la tercera capa dieléctrica (ix) tienen una película cada una seleccionada entre el grupo que consiste en una película de óxido de cinc;película de óxido de cinc, óxido de estaño depositada a partir de un objeto que tiene desde 0,5 hasta 9,5 por ciento en peso de estaño y desde 99,5 hasta 90,5 por ciento en peso de cinc o una segunda película de estannato de cinc que tiene una composición diferente de la composición de la película de estannato de cinc (vb,ixb) en la respectiva segunda o tercera capa dieléctrica.
19
El artículo recubierto de la reivindicación 10, en el que la película de estannato de cinc (iia,va) de la primera y segunda capa dieléctrica (ii,v) incluye cada una cinc dentro del intervalo de por ciento en peso igual a y superior a 60 e igual a y menor de 90 y estaño dentro del intervalo de por ciento en peso de igual a y superior a 10 e igual a y menor de 40.
20
El artículo recubierto de las reivindicaciones 5, 7 ó 11, en el que la segunda capa dieléctrica (v) incluye además:(vc) una tercera capa dieléctrica sobre las películas de estannato de cinc (vb) de la segunda capa dieléctrica (v), en el que la tercera película dieléctrica (vc) es una película seleccionada entre el grupo que consiste en una película de óxido de cinc;una película de óxido de cinc, óxido de estaño depositada a partir de un objeto que tiene desde 0,5 hasta 9,5 por ciento en peso de estaño y desde 99,5 hasta 90,5 por ciento en peso de cinc que tiene una composición diferente de la composición de la película de estannato de cinc (vb) más próxima a la película de estannato de cinc (vc).
21
El artículo recubierto de la reivindicación 12, en el que la primera y tercera películas dieléctricas (va,vc) de la segunda capa dieléctrica (v) y la primera capa dieléctrica (ixa) de la tercera capa dieléctrica (ix) incluyen cada una cinc dentro del intervalo de por ciento en peso igual a y superior a 60 e igual a y menor de 90 y estaño dentro del intervalo de por ciento en peso de igual a y superior a 10 e igual a y menor de 40.
22
El artículo recubierto de cualquiera de las reivindicaciones 1 a 21, en el que la capa protectora (vi) tiene un espesor para las películas de 0,005 hasta 0,0060 pm (5 a 60 Á) para la película de metal o de silicio y de 0,0020 hasta 0,050 pm (20 a 50 Á), para las películas de oxi-material. ES 2 372 024 T3
23
El artículo recubierto de la reivindicación 22, en el que la capa protectora (vi) tiene un espesor para las películas de 0,0010 hasta 0,0030 pm (10 a 30 Á) para la película de metal o de silicio y de 0,0030 hasta 0,0040 pm (30 a 40 Á), para la película de oxi-material.
24
El artículo recubierto de la reivindicación 4, en el que o bien el silicio, o bien el metal o el metal oxi-material es la 5 primera película de la capa (vi).
25
El artículo recubierto de cualquiera de las reivindicaciones 1 a 24, en el que el substrato (i) es vidrio.
26
Uso del artículo recubierto de cualquiera de las reivindicaciones 1 a 25, como un producto transparente para automóvil.
27
Uso de la reivindicación 26, en el que el producto transparente para automóvil es un parabrisas que tiene un par 10 de láminas de vidrio laminadas conjuntamente y una de las láminas es el artículo recubierto de acuerdo con cualquiera de las reivindicaciones 1 a 25.
28
El uso de la reivindicación 27, en el que el artículo recubierto se calienta hasta su temperatura de plegado para proporcionar un objeto de parabrisas recubierto y, después del calentamiento, el recubrimiento tiene opalescencia reducida;y el objeto recubierto se lamina a otra pieza de vidrio para proporcionar el parabrisas para automóvil.

Independent claims28

133 paragraphs in 8 sections, as filed

ES 2 372 024 T3

DESCRIPTION

Protective coatings for sputter coated article

The present invention relates generally to protective layers for sputter coated articles such as coated or uncoated glasses or transparent products. Said articles with the protective layers are transportable, thermally treatable, they can have coating or coatings of low emission capacity. The invention also relates to coated articles and the use of coated articles.

US Patent No. 4610,771 ("PEUN'771") discloses an antireflective sputtered metal oxide film deposited using a zinc / tin alloy object. PEUN'771 at column 3, line 26, to column 4, line 12, discloses the use of the alloying object to deposit a zinc stannate film having, in general, zinc and tin oxides preferably in proportions of 10 to 90 percent zinc and 90 to 10 percent tin.

Although the zinc / tin alloy object in PEUN'771 for depositing the zinc stannate film is acceptable, it has limitations. More particularly, in a low-emission coating, such as the type described in PEUN'771, an infrared reflective metal layer or film, eg silver, is deposited on the zinc stannate film. A silver film deposited on a sputtered zinc stannate film has a higher electrical resistivity and emission capacity than a silver film deposited on a sputtered zinc oxide film or layer. More particularly, US Patent No. 5,821,001 (PEUN'001 ”) discloses a silver film deposited on a zinc oxide film; the atoms of the silver film are deposited in a form characterized by low electrical resistivity that gives the silver film a low emission capacity. During the deposition of the zinc oxide film, the process parameters are selected in order to deposit a zinc oxide layer with adequate crystallinity or preferential crystalline growth so as to favorably affect the deposition of the silver atoms of the silver film.

Spraying zinc in a reactive atmosphere, eg oxygen, in order to provide a zinc oxide film on which a silver film having low electrical resistivity is deposited has drawbacks. For example, it is difficult to reactively sputter a pure zinc object, that is, an object of about 100% zinc metal, in a reactive atmosphere such as oxygen, for reasons discussed in more detail below.

PEUN'001 also discloses a heat-treatable, low-emitting film. The thickness of the primer layers, eg titanium films, can be increased to provide increased mechanical durability, ie, better resistance to shear. The shear strength test consists of the application of 20 successive blows of a cloth moistened with deionized water against the glass-coated surface, followed by visual examination of the tested area. Depending on the appearance of the tested area, letter grades of D-, D, D + ... A, A + are assigned to the coating; then, for numerical analysis, assignments are made of 5 to D-, 10 to D, 55 to A, and 60 to A +. If a coating shows no signs of shear, or even barely visible scratches, then it receives a maximum score of 60. Coatings that show uniform shear and delamination on any multilayer coating interface within the test area receive a failed score. from zero. Other behavioral values receive intermediate scores. This coating life characterization procedure has been found to relate well to the performance environment of the coating. The drawback with using thick primer coats is that the coating stacks up after heating; for example, in glass tempering or glass bending operations, it is likely to appear opalescent when viewed using a focused bright light opalescence test in a dark chamber. In the oplescence test with focused bright light, in a dark chamber, the coated sample is observed by reflection in a dark chamber at various observation angles in relation to a point of light, in order to find the geometry that provides the maximum of light scattering, or, in other words, opalescence, possible from the coating.

If there is no geometry that can make opalescence observable, the sample is assigned a score of A +. Very few samples receive the D-. For numerical analysis purposes, letter grades are assigned values from 5 to 60, as described above for the shear test. Lower opalescence corresponds to higher numerical values.

EP-A-803 481 relates to high transmittance, low emission coated articles, in which a transparent substrate is coated with a stacked multi-layer coating including a protective hard overcoat of titanium oxide.

From GB-A-2 311 540 a coated sheet for use in a laminate assembly is known which has a high level of light transmission and a low energy transmission. The five-layer multi-coated substrate has layers from specific materials within specific thickness limits and specific ratios in the respective thickness of certain layers. It is disclosed that applying a protective layer that protects the stacked coating and provides improved chemical and / or mechanical durability with little or no consequential change.

ES 2 372 024 T3 of its optical properties. Silicon and SIO2 oxides, nitrides and oxynitrides are mentioned as protective materials. As sacrificial materials for the reflective metal layer, titanium and zinc are disclosed.

US-A-4,902,580 discloses multilayer coated articles which are coatings having high transmittance in the visible wavelength range, with low emissivity. A protective overcoat prepared from iron or nickel alloys, titanium, titanium oxide is disclosed.

US-A-5,059,295 relates to a procedure for obtaining low-emission windows. With regard to the protective overcoat, the use of iron or nickel and titanium / titanium oxide alloys is disclosed.

Document WO 99/58763, which is a document under Article 54 (3) EPC, refers to multilayer coated articles having high transmittance in the visible wavelength range and low emission capacity. To provide chemical and mechanical durability to the stacked coating, a protective overcoat is applied. As useful materials, titanium, titanium dioxide, silicon oxide, silicon dioxide, silicon nitride and aluminum are disclosed. If desired, more than one protective film can be used.

As may be appreciated by those skilled in the sputter coating art, it would be advantageous to provide a zinc object that can be sputtered in a reactive atmosphere without the drawbacks of currently available zinc objects and to provide articles coated with zinc. low emission capacity that have mechanical durability, so that the coated article can be transported and subsequently heated without the heated coating becoming opalescent.

The aforementioned objective is achieved by a coated article according to the present invention, the coated article comprising:

(i) a substrate;

(ii) a first dielectric layer deposited by sputtering on substrate (i), layer (ii) comprising:

(iia) a first zinc stannate film deposited on the substrate (i) having zinc in the weight percent range of equal to and greater than 10 and equal to and less than 90, and tin in the weight percent range of weight equal to and less than 90 and equal to and greater than 10, and (iib) an electrically enhancing film deposited on the zinc stannate film (iia), the electrically enhancing film being selected from the group of films consisting of a film of zinc oxide, sputtered tin oxide deposited from an object having from 0.5 to 9.5 weight percent tin, and from 99.5 to 90.5 percent by weight of zinc and a second film of zinc stannate, wherein the composition of the first zinc (ia) stannate film is at least about 5 percent by weight different from the composition of the second zinc stannate film, and (iii) at least one infrared reflective layer on the first dielectric layer (ii);

(iv) optionally, a first layer of metal primer over the first infrared reflective layer (iii);

(v) optionally, a second dielectric layer over a first metal primer layer (iv); and (vi) at least one protective layer consisting of two films, in which one film is selected from metals or silicon and the other film is selected from metal-oxy- or silica-oxy-materials, in which one of the films is deposited first with the other film deposited on the first deposited film, and in which the metal is the same or different and is selected from titanium, zirconium, niobium, tantalum, chromium, nickel and alloys thereof, and in which the oxy-materials are selected from titanium oxides, titanium oxynitride, zirconium oxides, zirconium oxynitride, niobium oxides, niobium oxynitride, tantalum oxides, tantalum oxynitrides, chromic oxides, chromic oxynitride, nickel, nickel oxynitride, silicon oxide, silicon dioxide, aluminum nitride and silicon.

A sputtering cathode object is disclosed having tin preferably in an amount greater than zero and less than 10 percent by weight of the total weight of the object material, and zinc in an amount preferably less than 100 percent by weight and greater than 90 percent by weight of the total weight of the subject material. Hereinafter, unless otherwise indicated, the term "weight percent" means the weight percent of the total weight of the object material.

As used herein, "a zinc stannate film," for example, of the type set forth in PEUN'771, is an oxide of a zinc-tin alloy. The cathode used is made of a zinc-tin alloy. A "film of zinc oxide, tin oxide", is a film that has oxides of tin and zinc. The

ES 2 372 024 T3 cathode used for sputtering the zinc oxide film, tin oxide is made of zinc containing tin additions as discussed in more detail below.

In one embodiment of the invention, a stacked coating has a zinc stannate film deposited on a glass substrate, a zinc oxide film, tin oxide deposited on the zinc stannate film; an infrared reflective film, for example silver, deposited on the zinc oxide film, tin oxide; a primer layer, for example a metal titanium film, deposited on the infrared reflective film; a zinc oxide film, tin oxide deposited on the primer film, a zinc stannate film deposited on the zinc oxide film, tin oxide; an infrared reflective film deposited on the zinc stannate film; a primer layer deposited on the infrared reflective layer; a zinc oxide film, tin oxide deposited on the primer layer, a zinc stannate film deposited on the zinc oxide film, tin oxide; and a protective layer. In another embodiment of the invention a zinc oxide film is used in place of the zinc oxide film, tin oxide. When a zinc stannate film is used in place of the zinc oxide film, tin oxide, the zinc stannate films differ in composition by at least 5 percent by weight. For example, when one of the zinc stannate films is about 50 weight percent zinc and 50 weight percent tin, the other zinc stannate film is about 10-45 or 55-90 percent. by weight of zinc and 55-90 or 45-10 percent by weight of tin. In yet another embodiment of the invention, a first zinc stannate film deposited is 50 ± 10 weight percent zinc and 50 ± 10 weight percent tin. The second zinc stannate film deposited or overcoated has tin equal to or greater than 10 percent by weight and less than 40 percent by weight, and preferably 20 percent by weight, and has zinc equal to or less than 90 percent by weight. weight and greater than 60 weight percent and preferably 80 weight percent. Overcoat zinc stannate films having 90 weight percent zinc and 10 weight percent tin have been used.

Another aspect of the present invention is the protective layer composition or films. Of course, the protective layer can be for any multi-layer stack with one or more anti-reflective layers on a substrate. This multi-layer stack has at least one layer of at least one infrared reflective film that can be preceded on the immediate face towards the substrate by one or more dielectric films and / or containing zinc and / or tin and can be followed on the facing away from the substrate by one or more layers of one or more dielectric films and / or containing zinc and / or tin and / or a primer layer. This is also the multi-layer stacking type for the protective layer. Any film containing zinc and / or tin can be of zinc oxides or tin oxides or zinc stannates of the type indicated in the '771 and' 001 patents. The protective layer is, in principle, either a metal film or a silicon film or an oxy-material metal film or an oxy-material silicon film, or both. The metal oxy-material or silicon oxy-material film is either either or both films of metal oxide or silicon oxides or films of metal oxynitride or silicon oxynitride. These metal, metal oxide and metal oxynitride films have one or more metals that are the same or different from the metal film or the metal oxide or oxynitride film, wherein the metals are the transition metals of the Groups 4, 5 and 10 of the Periodic Table of Elements according to the Revised Chemical Element Group Notation which has up to 18 groups and alloys thereof that are capable of being coated by sputtering. In detail, the protective layer is described below in connection with the coated article according to the present invention. For the protective layer, the order can be metal film and metal oxide or oxynitride film, or the other way around. The protective layer may be the outermost layer on the multi-layer stack, but it only needs to be in one position in the multi-layer stack in which it can perform the protective function to provide some chemical and / or mechanical durability to the stack. multi-layer. Thus, if desired, there may be an additional covering layer or films on the protective layer.

The coating stack described above has mechanical and chemical durability. The coatings of the present invention in addition to having mechanical and chemical durability that make them acceptable for shipping, can be heat treated with the heat treated coating having reduced haze. The reduction in haze after heating is achieved by selection of metal primer thicknesses, which is discussed below. The procedure for determining opalescence is discussed below. As used in the present invention, a reduction in haze is a numerical increase of about 10. An advantage of the coatings of the present invention is that a coating of the invention can be deposited onto a substrate, the coated substrate being transported to a manufacturing facility where the coated substrate is heat treated, for example heated to a temperature of up to about 732 ° C. The coating of the invention has particular application in obtaining solar control automotive windshields. Glass sheets having a low-emission coating of the invention are coated in one facility and then transported to another facility where the coated glass sheet is processed, for example, on an automobile windshield.

For a full appreciation of the various embodiments of the invention, the embodiments will be discussed separately and subsequently combined. The first embodiment of the invention to be discussed is the use of a zinc cathode having low amounts of tin in order to improve the deposition of zinc oxide films and the benefits of a zinc oxide film having low amounts of tin. tin.

ES 2 372 024 T3

Next, embodiments of the invention relating to the sputtering object of zinc having low amounts of tin and to a sputtering process reactively such as zinc objects to sputter deposit a zinc oxide film, oxide tin. As will be appreciated, the invention contemplates the use of the object of the present invention to deposit a film of zinc oxide, tin oxide on or below an infrared reflective film, for example, films of gold, silver, aluminum, other metals. , for example, primer films such as a titanium metal, or ceramic product films, or other dielectric films.

The subject cathode sputtering in one embodiment of the invention has more than zero weight percent and less than 10 weight percent tin, and less than 100 weight percent and more than 90 weight percent zinc. to improve the emissivity of an infrared reflective film, for example a silver film, deposited on the zinc oxide film, tin oxide and to improve sputtering of the zinc target cathode having low amounts of tin. The cathode object of the present invention can also be defined as having more than 0 and less than 10 percent by weight of tin, most of the rest being zinc, or having less than 100 percent by weight and more than 90 percent by weight. weight percent zinc, with most of the remainder being tin. Prior to the discussion of this embodiment of the invention, the drawbacks and / or limitations of reactive sputtering of a tin-free zinc target cathode and the limitations of zinc oxide films deposited using such cathodes are discussed, for a better appreciation of the invention.

Typically a target metal is reactively sputtered into a gas such as oxygen, or a mixture of oxygen with other gases such as nitrogen, argon, or helium. Sputtering into a gas mixture results in a higher sputtering rate for a stable process, but requires more control to maintain process stability, for example, it requires control of the flow rate of two gases. Due to the higher sputtering rate, it is preferred to sputter into a gas mixture rather than an oxygen mixture only. In both cases, the resulting coating is a metal oxide, for example zinc oxide when a zinc object is used.

Zinc oxide is a common dielectric material that is used as a high refractive index film in coatings stacks that have low emission capacity. In the flat glass industry, these coatings are usually applied by horizontal vacuum coaters using high amounts of energy supplied from a direct current source to power the cathodes that sputter layers onto the glass substrates. The higher passing speed of the coater requires higher energy densities to the target cathode. This, in turn, increases the tendency for objects to arc, particularly during reactive sputtering.

During reactive sputtering, the frequency of arcing of the zinc target cathode increases with time, and dust and flakes accumulate on the target surface and adjacent areas. Remnants in the form of powders, flakes and splashes eventually fall onto the substrate to be coated resulting in an unacceptable coated product. Additionally, arcing increases to a point such that the process becomes unstable. Furthermore, certain areas of the object surface have a tendency to blacken over time. These blackened areas are non-conductive, thus limiting the rate of sputtering and leading to non-uniformity in the coating.

Arc formation and debris build-up can be reduced to some extent by periodic cleaning of the sputter, as is known to those skilled in the art of sputter coating. One technique for sputtering cleaning is to periodically sputter the objects for a certain period of time in an inert gas, such as argon or helium, which sputters the object as a metal. Cleaning the sputter removes to some degree the oxide build-up on the target surface that causes arcing. Black areas on the object cannot be reduced by cleaning the sputter. However, debris and arcing continuously degrade the object, and after a period of time, the downtime of the coater is increased and consequently there is less production time for the coater. Zinc objects due to their tendency to arc frequently during sputtering are difficult to clean in the sputter and require a higher and more frequent cleaning frequency.

In the practice of the invention, tin is added to a zinc object to reduce, if not eliminated, the above drawbacks, for example, reduce the amount of flake debris, reduce dust build-up on the object, minimize arcing, and minimize, if not eliminated, blackening of the surface areas of the object. The amount of debris and degradation of the zinc object of the present invention is considerably less over time than for a pure zinc object. As a result, less periodic object cleaning is required with shorter cleaning duration in an inert gas.

As discussed above, PEUN'771 discloses a zinc-tin alloy object for depositing a film of zinc stannate, that is, an oxide of a zinc-tin alloy that is 10 to 90 percent by weight. zinc and 90-10 weight percent tin. PEUN'771's zinc-tin alloy target cathode provides a zinc stannate film that has better chemical durability than a zinc oxide film. Furthermore, the zinc-tin alloy target cathode has less arcing and minimal accumulation of

ES 2 372 024 T3 remains, for example there is no measurable accumulation of dust. As is well known in the sputter coating art, zinc oxide films dissolve readily in acidic and basic solutions; zinc stannate films have reduced solubility in acids or bases.

Although the properties of the zinc oxide, tin oxide film of the present invention have not been studied in great detail, it is estimated that the following will occur. As the tin approaches zero weight percent, the chemical durability of the deposited film decreases, and the problems associated with sputtering a zinc object in a reactive atmosphere increase. As the weight percent of tin approaches ten, the chemical durability of the zinc oxide film increases, and the problems associated with sputtering a zinc object in a reactive atmosphere decrease. The electrical resistivity of a silver film deposited on the zinc oxide film, tin oxide is expected to be similar to a silver film deposited on a zinc oxide film. In the practice of this embodiment of the invention, a zinc object having zinc greater than zero and less than ten percent by weight is a usable range; 0.5 to 9.5 weight percent tin is a practical range; 4 to 8.5 weight percent tin is a preferred range, and 5 to 9.5 weight percent tin is a more preferred range. The weight percent of tin and zinc in a zinc oxide film, tin oxide is expected to be similar to the weight percent of zinc and tin in the object.

As can now be appreciated, as the weight percent tin on the zinc cathode increases, the chemical durability of the deposited film is expected to increase. Furthermore, the crystalline structure of the zinc oxide film having tin in percent by weight greater than zero and less than ten is similar, if not identical, to the crystalline structure of the zinc oxide film which it has zero weight percent tin. In addition, a zinc stannate film having 60-90 weight percent zinc and 10-40 weight percent tin has crystal structures similar to zinc oxide. Consequently, it is expected that the emission capacity of the silver film deposited on a zinc oxide film will be similar to a silver film deposited on a zinc stannate film having 60-90 weight percent zinc. and 10-40 weight percent tin. At values less than 60 percent by weight of zinc, the crystal structure begins to change and the emission capacity and resistivity begin to increase. Transmission Electron Microscopy shows a weak zinc oxide electron diffraction pattern for a zinc stannate film that has 66 weight percent zinc and 34 weight percent tin, and an amorphous structure for a zinc stannate film. zinc stannate which is 47 weight percent zinc and 53 weight percent tin.

The coated articles disclosed in PEUN'001 and U.S. Patent Application Serial No. 09 / 023,746 filed February 13, 1998, in the names of Mehran Arbab, Russell C. Criss, Gary J. Marietti, and Paul A. Medwick for "Coated Articles" (hereinafter referred to as "SPEUNo. 09 / 023,746 ") can practice this embodiment of the present invention, including but not limited to sputtering an object cathode having 92 weight percent zinc and 8 weight percent tin, in an atmosphere that has more than 75% oxygen and the rest argon. Furthermore, it is hoped to minimize, if not eliminate, the problems discussed above associated with sputtering a zinc object.

Next, the discussion will be directed to the improvement of the chemical durability of the stacked coating, the reduction of opalescence of the stacked coating and the decrease of the emission capacity of the infrared reflective metal, for example, silver. By "chemical durability" is meant that the coating is not easily attacked by acidic or basic solutions. For a discussion of chemical durability, reference may be made to PEUN's '001 and' 771. The test for opalescence was set forth above.

From the above discussion, the emission capacity of the silver film can be reduced by depositing the silver layer on a zinc oxide film, a zinc oxide film, tin oxide or a zinc stannate film having zinc within the range of 60 to 90 percent by weight and tin within the range of 10 to 40 percent by weight. Furthermore, from the above discussion, the chemical durability of a layer having a zinc oxide film underneath a silver film and over a zinc stannate film can be enhanced by adding tin to a zinc object. to provide a film of zinc oxide, tin oxide, or a film of zinc stannate. As used in the present invention, "a chemical and electrical enhancement film" is a film of zinc oxide, tin oxide, and / or a film of zinc stannate having zinc within the range of 60 to 90 percent. by weight and tin within the range of 10 to 40 by weight. The chemical and electrical enhancement film of the invention can be used in place of zinc oxide films to enhance the chemical durability of the stacked coating, without obtaining a silver film having low emission capacity. By way of illustration, coated articles having a glass substrate / zinc stannate film / zinc oxide film / silver film / metal titanium primer film / zinc oxide film / zinc stannate film / zinc oxide film / zinc stannate film / protective overcoat of titanium metal and / or titanium oxide or oxynitride, they can be chemically enhanced using the chemical and electrical enhancement film of the invention for one or more or all of the zinc oxide film (s) from the above stacked coating.

Other coated article includes glass substrate / zinc stannate film / zinc oxide film / silver film / metal titanium primer film / zinc oxide film / zinc stannate film / pro overcoat

ES 2 372 024 T3 titanium metal and / or titanium oxide or oxynitride tensor. As can now be understood, the chemical and electrical enhancement film of the invention can be replaced by one or more or all of the zinc oxide film (s) from the previous coating.

In the practice of the present invention, a dielectric layer can include a zinc stannate film, and a chemical and electrical enhancement film. When the chemical and electrical enhancement film is zinc stannate, the difference between the composition of the zinc stannate film and the zinc stannate film of the chemical and electrical enhancement film is at least 5 percent by weight of zinc. For example, and without limiting the invention, a zinc stannate film having 58 weight percent zinc and 42 weight percent tin can be used with a zinc stannate film (chemical enhancement film and electrical) having 63 to 90 weight percent zinc and 10 to 37 weight percent tin.

The discussion will be directed hereafter to the embodiment of the invention in order to provide a stacked coating that is chemically and mechanically durable and to a stacked coating that has reduced opalescence after subjecting the stacked coating to elevated temperatures, for example, but not by this will limit the invention, above room temperature and below about 732 ° C. As will be understood by those skilled in the art, the coatings set forth below are presented for illustrative purposes only. Table 1 below provides a few embodiments of stacked coatings according to the invention and not according to the invention (*).

TABLE 1

<td>Coating samples</td><td>Substrate</td><td colspan="13">MOVIE</td>

<td>Layers</td><td></td><td colspan="2">TO</td><td>B</td><td>C</td><td colspan="3">D</td><td>AND</td><td>F</td><td colspan="2">G</td><td colspan="2">H</td>

<td colspan="15">* Not according to the invention</td>

The second column from the left is titled "Substrate." The substrate material is not limited to the invention and can be made of any material, for example, glass, fiberglass, plastic, metal, wood, or ceramic. The type of articles manufactured in the preferred embodiment of the invention are transparent materials for residential and commercial buildings, and ground, air, space, over and under water vehicles; therefore, the substrate is preferably transparent and made of glass, and flexible and rigid plastics. When glass is used, it can be transparent or tinted and manufactured by any process, including floating glass making process, and the type of glass is not limited to the invention. It is expected that the coated article will be subjected to elevated temperatures; therefore, the selected substrate should be able to withstand elevated temperatures. In our discussion, but not limited to the invention, the substrates are sheets or pieces of glass.

ES 2 372 024 T3

Columns numbered 1-13 are films, and columns marked AH are layers, of stacked coatings incorporating features of the invention. The layers (see bottom of Table 1) include at least one film and, as shown in Table 1, up to 3 films. Layers A, D and G are dielectric layers. The refractive index of the dielectric films of layers A, D and G is preferably higher than the refractive index of the transparent substrate in order to anti-reflect the infrared reflection layer. The invention is not limited to the type of dielectric films that can be used in combination with the chemical and electrical enhancement film of the invention. Dielectric films that can be used in the practice of the invention include, but are not limited to, zinc oxide, tin oxide, silicon oxide, silicon nitride, and silicon oxynitride. It is preferred that films 1, 6, and 11 of layers A, D, and G, respectively, are each a zinc stannate film having 52 weight percent zinc and 48 weight percent tin. Films 2, 5 and 7 and 10 of layers A, D and G, respectively, can be a zinc oxide film, or a chemical and electrical enhancement film of the invention. Coatings examples 12-13 in Table 1 are predictive examples, but these coatings examples show the presence of one or both films 12 and / or 13 as layer H. Coatings examples 12 and 13 are those with the fewest number of films that can have either or both of the protective films for the protective layer. Of course, any of the other coating examples 2-8 can equally have either or both for the protective layer H.

In the following discussion, the substrate is clear sodium-calcium silicate glass and has a refractive index of approximately 1.5. As is known in the art, varying the thickness of the film and the layers changes the color of the coated article, or can provide a coating with a neutral color. It is expected that, in the practice of the invention, the dielectric layers and / or films will have a thickness within the range of 600 ± 500 Angstroms. The thickness of the zinc oxide film or the chemical and electrical enhancement film should be sufficient to cause the crystalline structure of the silver film to be deposited thereon.

Films 3 and 8 of layers B and E, respectively, are infrared reflective films and can be of any material that reflects infrared energy, for example, but not limited to, gold, silver, and aluminum. In the practice of the invention silver is preferred. The thickness of the silver is not limited to the invention and is selected so as to provide a transparent coating having a low emission capacity. Silver films having a thickness of 200 ± 150 A and preferably 100 ± 25 A can be used in the practice of the invention.

Films 4 and 9 of layers C and F, respectively, are primer films that have the function of (1) protection of the infrared metal layer from oxidation during sputtering of dielectric films, (2) protection of the infrared reflection layer during high temperature treatment, (3) reduction of haze formation in the stacked coating during heating, and / or (4) provide the stacked coating with mechanical durability for transportation of the coated article. The primer films can be of any type known in the art, for example, metals such as titanium or ceramic materials, of the type disclosed in US Patent Application Serial No. 09 / 215,560, filed December 8. 1998, the disclosure of which is incorporated herein by reference. In the practice of the invention, the primer layer is preferably titanium.

Films 12 and 13 of the H layer are or are protective films to provide additional chemical and mechanical durability for the stacked coating during shipping and storage. Protective films are thin films of sputter coatings of metals or silicon and silicon metal oxy-materials, in which the metal and metal oxy-materials that can be used can be titanium, titanium dioxide, titanium oxynitride, zirconium, zirconium oxides, zirconium oxynitrides, niobium, niobium oxides, niobium oxynitrides, tantalum, tantalum oxide, tantalum oxynitride, chromium, chromic oxides, chromic oxynitrides, Nickel oxide and / or oxynitrides, and silicon oxide, silicon dioxide, aluminum and silicon nitride and alloys, combinations or mixtures of any two or more of these, including those of the chromium nickel, chromium silicon, chromium nickel silicon type , and nickel silicon. Likewise, the above-mentioned oxides can be oxynitrides. The aforementioned metals are useful as individual films for the protective layer in numerous places in a layer stack when the film stack is heat treated and the metals are heat converted to metal oxide films or metal oxynitride films. The heating temperatures are those usually found in the tempering and heating of a substrate for shape change. When both metal and metal oxy-material films are used, either film can be deposited first for the protective layer with the other film being deposited on the first film deposited for layer H. Generally, the thickness of the films are for the film. of metal from about 5 to about 60 Angstroms (A), preferably about 10 to about 30 A and most preferably 15 to 25 A. The metal oxy film may have a thickness within the range of from about 20 to about 50 A, preferably 30 to 40 A. Also, more than one protective film can be used. For example, but not limiting the invention, a zinc oxide film can be used on a titanium dioxide film. The thickness of the layer H is not limited to the invention; however, the thickness should be thick enough to provide protection. The metal oxymetal pellets can be deposited by any method known to those skilled in the art. Also, part of the metal film can be oxidized by heating instead of depositing a separate metal oxide film.

ES 2 372 024 T3

Before discussing the Samples in Table 1 in detail, the following basic information is provided for a better appreciation of the invention.

The use of zinc oxide film, as discussed above, provides a silver layer that has lower resistivity and emission capacity than a silver layer deposited on a zinc stannate layer that is less than about 60 percent. weight percent zinc and more than about 40 weight percent tin.

PEUN'001 discloses increasing the thickness of the primer layer to enhance the mechanical durability of the coated article in order to make the coated article transportable. More particularly, PEUN'001 states that it has been found that, when the coated article is to be exposed to heat treatment during its production, there is a point at which the primer layer may become too thin or too thick. Too thin a primer layer results in a lack of protection for the reflective metallic film against high temperature oxidation, thus rendering the coated article unacceptable for heat treatment and poor resistance to heat. shearing, which makes the item unsuitable for long-distance transportation for further heat treatment. Too thick a primer layer results in the formation of an undesirable haze on the coated article after heat treatment, also rendering it unacceptable for heat treatment. However, a limitation is that these films have opalescence after heating.

It has been determined that by selecting dielectric films and primer layers, a stacked coating can be obtained which has reduced haze after heating. For coated articles that are shipped but not heated, the primer layer should be thick enough to protect the silver during deposition of the superimposed dielectric film or layer on the silver layer. A primer coat thickness within the range of about 8 to 12 Angstroms is sufficient. The thickness of the primer layer is increased when the primer layer is to protect the silver during heating of the coated article. A thickness of approximately 20 ± 5 Á is acceptable.

For a coated article that is transportable and heatable with reduced haze, the thickness of the primer film is adjusted in order to fulfill the dielectric layer or film arrangement. In accordance with the precepts of the invention, the thickness of the primer layer within the range of 18-32 Angstroms (Á) and preferably 18-40 Á, is acceptable to provide a stacked coating with reduced opalescence after heating. The following Examples illustrate the invention.

In the discussion that follows, the thickness of the metal primer layer is as deposited. As can be appreciated, the thickness increases after heating, changing a portion of the primer film from titanium metal to titanium oxide. A procedure that will be referred to as the "XRF Procedure" is set forth in PEUN'001. In general, the XRF Procedure is used to measure the thickness of metallic layers. The XRF Procedure uses a calibrated X-ray fluorescence instrument to measure the weight of metal per unit area of the coating (primarily in pg / cm2). The XRF Procedure assumes that the metal film is dense in its bulk state. Based on this assumption, the measured weight per unit area of the metal films is then converted to an Angstrom thickness, using bulk density. For complete understanding, it should be noted that cationically pulverized metal films are often less dense than their corresponding bulk metals, such that the assumption described above is not exactly always correct, and the XRF Procedure may, in some cases, underestimate the thickness of the metal film due to this variation in density. Consequently, for thin metal films, the initial measurement of weight per unit area (pg / cm2) is more accurate than the corresponding bulk density conversion to thickness. Nevertheless, the XRF Procedure provides a useful approximation for comparing the relative thicknesses of the layers in the coating.

In the following discussion, the thickness of the dielectric layers and / or films is given in intervals. As can be appreciated by those skilled in the art, the ranges are not limiting of the invention and the thickness can be selected in order to provide a stacked coating of a desired color.

Example 1 (not according to the invention)

This Example 1 is Sample 1 of Table 1. Sample 1 is a coated article that is transportable and heatable. The coating is a high transmittance, low emitting coated article that has a single, infrared, reflective layer. The product having the stacked coating of Sample 1 has been manufactured, and the stacked coating includes:

a transparent glass substrate; an antireflective, dielectric layer deposited on the substrate, layer (1) including a zinc stannate film having 52 weight percent zinc and 48 weight percent tin (referred to herein as film of zinc stannate 52-48) and having a thickness of 260 ± 40 Á, and (2) a zinc stannate film having 90 weight percent zinc and 10 weight percent tin (referred to herein as 90-10 zinc stannate film) and having a thickness 80 ± 45 Á;

ES 2 372 024 T3 a silver film having a thickness of about 115 ± 15 A deposited on the 90-10 zinc stannate film;

a titanium primer film having a thickness of 24-28A deposited on the metallic reflective film;

a dielectric, antireflective top layer deposited on the titanium primer film, including the dielectric, antireflective top film, a 52-48 zinc stannate film having a thickness of about 230 ± 60 A deposited on the primer layer metal oxide; and a titanium oxide layer having a thickness of 36 ± 7 Á deposited on the 52-48 zinc stannate layer or film.

Example 2 (not according to the invention)

This Example 2 is Sample 2 of Table 1. The coated article has been manufactured and is transportable and heatable, with reduced haze. The coated article includes a glass substrate / a layer of a 52-48 zinc stannate film having a thickness of about 230 ± 40 A, and a zinc oxide film having a thickness of 80 ± 40 A; a silver film having a thickness of 110 ± 10 Á; a metal titanium primer film having a thickness of about 18-23A and preferably 19.5A; a 52-48 zinc stannate film having a thickness of about 820 ± 40A; a silver film having a thickness of 110 ± 10 Á; a metal primer having a thickness of about 18-31A and preferably 25A; a 52-48 zinc stannate film having a thickness of about 200 ± 20 A; and a titanium film having a thickness of about 29 ± 3 Á.

Example 3 (not according to the invention)

This Example 3 is Sample 3 of Table 1. The coated article was not manufactured; however, the subsequent coated article is expected to be transportable and heatable, with reduced haze. Example 3 includes a clear glass substrate; an antireflective, dielectric base layer deposited on the substrate includes a 52-48 zinc stannate film having a thickness of about 310 ± 20A deposited on the glass substrate; a first silver film having a thickness of about 110 ± 10 Á deposited on the 52-48 zinc stannate film; a first titanium primer film having a thickness of 18-29 A deposited on the first silver film; a dielectric, anti-reflective interlayer deposited on the first primer film, the interlayer including a zinc oxide film having a thickness of 80 ± 40A deposited on the first primer film, a 52-48 zinc stannate film having a thickness of 740 ± 40 Á deposited on the zinc oxide film; a second silver film having a thickness of about 110 ± 10 Á deposited on the 52-48 zinc stannate film of the intermediate layer; a second titanium primer film having a thickness of about 18-31A deposited on the second silver film; an antireflective, dielectric top layer deposited on the second primer film, the dielectric top layer being a 52-48 zinc stannate film having a thickness of about 200 ± 20A; and a protective titanium metal film having a thickness of about 29 ± 3 A, deposited on the 52-48 zinc stannate film of the dielectric top layer.

Example 4 (not according to the invention)

This Example 4 is Sample 4 of Table 1. The coated article of Example 4 was manufactured and is transportable and heatable, with the coated article having reduced haze. The coated article of this Example 4 includes a clear glass substrate; a 52-48 zinc stannate film having a thickness of 310 ± 20 A deposited on the glass substrate; a first silver film having a thickness of 110 ± 10 Á deposited on the zinc stannate film 52-48; a first titanium primer having a thickness of 18-29A and preferably 22.5A deposited on the first silver film; a 52-48 zinc stannate film having a thickness of 820 ± 40A deposited on the first titanium film; a second silver film having a thickness of about 110 ± 10 Á deposited on the 52-48 zinc stannate film; a second titanium film having a thickness of 18-32A and preferably 21.5A deposited on the second layer of silver; a zinc oxide film having a thickness of 80 ± 40A deposited on the second layer of titanium primer; a 52-48 zinc stannate film having a thickness of 120 ± 40A deposited on the zinc oxide film and a titanium metal overcoat film having a thickness of 29 ± 3A, on the stannate film zinc 52-48.

Example 5 (not according to the invention)

This Example 5 is Sample 5 of Table 1. The coated article was not manufactured; however, the coated article is expected to be suitable for transport and heat treatment, with the heated coated article having reduced haze. The coated article of this Example 5 includes films and layers similar to Example 3, except that Sample 5 has a 52-48 zinc stannate film having a thickness of about 230 ± 40A deposited on the substrate and zinc film. zinc oxide having a thickness of about 80 ± 40 A deposited on the 52-48 zinc stannate film. The first titanium primer film

ES 2 372 024 T3 on the first silver layer has a thickness of about 18-29 Á; the second titanium primer film on the second silver layer is about 18-31A thick. The remaining layers of Sample 5 are as shown in the Table and have the same composition and thickness for the same films described in Example 3.

Example 6 (not according to the invention)

This Example 6 is Sample 6 of Table 1 and was manufactured and is transportable and heatable, with the heated, coated article having reduced haze. The stacked coating is similar to the stacked coating of Example 2, except that a zinc oxide film having a thickness of about 80 ± 40 A was deposited on the second titanium primer and a 52-48 zinc stannate film having a thickness of 120 ± 40 Á was deposited on the zinc oxide film. The first layer of titanium primer had a thickness of 19-26 Á and preferably 19.5 Á and the second layer of primer had a thickness of 21.5-31 Á and preferably 25 Á. The composition and thickness of the remaining films / layers for Example 6 as shown for Sample 6 in the Table, are as described in Example 2.

Example 7 (not according to the invention)

This Example 7 is Sample 7 of Table 1 and was manufactured and is transportable and heatable, having the stacked, heated coating, reduced haze. The stacked coating of Sample 7 is similar to the stacked coating of Example 3, except that a zinc oxide film having a thickness of about 80 ± 40 Á was deposited on the second titanium film and a 52 zinc stannate film. -48 was deposited on the zinc oxide film. The first layer of titanium primer was 22-26 A and preferably 22.5 A thick and the second layer of titanium primer was 18-25 A and preferably 21.5 A thick. The composition and thickness of the remaining films / layers for Example 7 as shown for Sample 7 on the Table, are as described in Example 2.

Example 8 (not according to the invention)

This Example 8 is Sample 8 of Table 1. The coated article was manufactured and is a coated article suitable for transportation and heat treatment, the coated articles having reduced opalescence. The coated article of this Example 8 is a stacked coating deposited on a clear glass substrate. The thickness of the coating and the order of the films is as indicated with the film 1 deposited on the glass substrate.

TABLE 2

<td>Movie No. from Table</td><td>Film composition</td><td>Film thickness</td>

<td> 1</td><td>Zinc stannate 52-48</td><td>230 ± 40 Á</td>

<td> 2</td><td>Zinc oxide</td><td>80 ± 40 Á</td>

<td> 3</td><td> 1to silver</td><td>110 ± 30A</td>

<td> 4</td><td> 1er titanium primer</td><td>17-26 Á, preferably 19.5 Á</td>

<td> 5</td><td>Zinc oxide</td><td>80 ± 40 Á</td>

<td> 6</td><td>Zinc stannate 52-48</td><td>740 ± 40 Á</td>

<td> 8</td><td>2nd silver film</td><td>110 ± 30A</td>

<td> 9</td><td>Titanium primer</td><td>18-31 Á, preferably 28 Á</td>

<td> 10</td><td>2a zinc oxide</td><td>80 ± 40 Á</td>

<td> 11</td><td>Zinc stannate 52-48</td><td>120 ± 40A</td>

<td> 12</td><td>Titanium metal overlay</td><td>29 ± 3 Á</td>

The coated glass having the above coating was used in the manufacture of automotive windshields. The coated glass was cut to size, heated to form the coated glass, and then laminated to another shaped glass to provide an automotive windshield. The transmittance of the laminate was greater than 70%, and it reflects infrared energy. The windshield was manufactured as is known in the art. Likewise, coated glass was manufactured for use in automotive windshields by substituting the 90-10 zinc stannate for the film.

ES 2 372 024 T3 of zinc oxide. The coated article had film thicknesses within the ranges mentioned in Table

As can be appreciated, the thickness of the primer layers presented in Table 2 may vary, depending on the cathode and sputtering equipment. For example, a heatable, transportable stacked coating with reduced haze can be fabricated with a first titanium primer film having a thickness of 18 ± 0.5A and the second titanium primer film having a thickness of 22 ± 1A. .

Example 9 (not according to the invention)

This Example 9 is Sample 9 of the Table and is a coated article that was manufactured. The coated article was transportable and heatable, with the coated article having reduced haze. The coated article of this Example 9 is a stacked coating deposited on a clear glass substrate. The thickness of the coating and the order of the films is as indicated with the film 1 deposited on the glass substrate.

TABLE 3

<td>Movie No. from Table</td><td>Film composition</td><td>Film thickness</td>

<td> 1</td><td>Zinc stannate 52-48</td><td>230 ± 40 Á</td>

<td> 2</td><td>Zinc stanate 90-10</td><td>80 ± 40 Á</td>

<td> 3</td><td>1st silver</td><td>107 ± 30A</td>

<td> 4</td><td> 1er titanium primer</td><td>17-24 Á, preferably 21.5 Á</td>

<td> 5</td><td>Zinc stanate 90-10</td><td>80 ± 40 Á</td>

<td> 6</td><td>Zinc stannate 52-48</td><td>600 ± 100A</td>

<td> 7</td><td>Zinc stanate 90-10</td><td>80 ± 30 Á</td>

<td> 8</td><td>2nd silver film</td><td>127 ± 30A</td>

<td> 9</td><td>Titanium metal primer</td><td>20-26 Á, preferably 22.5 Á</td>

<td> 10</td><td>Zinc stanate 90-10</td><td>80 ± 40 Á</td>

<td> 11</td><td>Zinc stannate 52-48</td><td>160 ± 60A</td>

<td> 12</td><td>Titanium oxide overcoat</td><td>45 ± 15A</td>

As can be seen, a 90-10 zinc stannate film, a zinc oxide film and a zinc oxide film, tin oxide, can be interchanged and substituted for one another to obtain coated articles that are transportable and heatable. , with reduced opalescence. However, 9-10 zinc stannate film is preferred.

Example 10 (not according to the invention), Example 11 (according to the invention)

Examples 10 and 11 are Samples 10 and 11 of the Table. These examples were similar to Example 9 with the following exceptions. For Example 10, titanium metal was the overlay and for Example 11, according to the invention, titanium metal and titanium oxide were the overlay. Example 11 was carried out in an alternative manner, where the protective layer was first the titanium oxide film with the titanium film on top of it.

As can be appreciated, the thickness of the films is not limiting of the invention and can be selected to provide a coated article of a desired color, as is known in the art. Furthermore, the films of all the examples of the invention can be interchanged to achieve the characteristics of the invention.

A complete discussion of the heating of coated glass sheets for automotive windshields, residential and commercial windows and other transparent products has not been presented, since such technology is known in the art and, as can now be appreciated, used in practice. of the invention.

The invention is not limited to the examples presented above, various changes and alterations may be made without departing from the broader aspects of the invention, as defined by the claims set forth below and by the margin of equivalence permitted by law.

Contents8

41 members in 13 offices

This recordMember, by publication datePriority claim3 more offices are in the list below

Priority claims5

Priority claims
Document	Office	Kind	Date
334193	United States of America	–	1999-06-16
33419399	United States of America	A	1999-06-16
33419399	United States of America	A	1999-06-16
334193	–	–	–
US19990334193	–	–	–

Members41

Family members, oldest first
Document	Office	Kind
CA2328910A1	Canada	A1	1999-11-18
WO9958736A2	World Intellectual Property Organization (WIPO)	A2	1999-11-18
AU3972699A	Australia	A	1999-11-29
WO9958736A3	World Intellectual Property Organization (WIPO)	A3	2000-03-23
CA2374768A1	Canada	A1	2000-12-21
WO0076930A1	World Intellectual Property Organization (WIPO)	A1	2000-12-21
AU5467300A	Australia	A	2001-01-02
EP1080245A2	European Patent Office (EPO)	A2	2001-03-07
AR015088A1	Argentina	A1	2001-04-11
KR20010043456A	Republic of Korea	A	2001-05-25
CN1300327A	China	A	2001-06-20
KR20020012610A	Republic of Korea	A	2002-02-16
EP1194385A1	European Patent Office (EPO)	A1	2002-04-10
AU749510B2	Australia	B2	2002-06-27
MXPA01012881A	Mexico	A	2002-07-30
AR025532A1	Argentina	A1	2002-12-04
JP2003502259A	Japan	A	2003-01-21
AU764332B2	Australia	B2	2003-08-14
JP2003526732A	Japan	A	2003-09-09
US6833194B1	United States of America	B1	2004-12-21
US6899953B1	United States of America	B1	2005-05-31
US2005129863A1	United States of America	A1	2005-06-16
CN1209489C	China	C	2005-07-06
US2005155695A1	United States of America	A1	2005-07-21
KR100654483B1	Republic of Korea	B1	2006-12-05
CA2328910C	Canada	C	2007-08-21
CA2374768C	Canada	C	2007-08-21
US7329433B2	United States of America	B2	2008-02-12
KR100822516B1	Republic of Korea	B1	2008-04-16
US7413768B2	United States of America	B2	2008-08-19
JP2011184296A	Japan	A	2011-09-22
EP1194385B1	European Patent Office (EPO)	B1	2011-10-05
AT527219T	Austria	T	2011-10-15
ATE527219T1	Austria	T1	2011-10-15
JP4836376B2	Japan	B2	2011-12-14
ES2372024T3This record	Spain	T3	2012-01-13
EP1194385B9	European Patent Office (EPO)	B9	2012-02-29
JP5101763B2	Japan	B2	2012-12-19
EP1080245B1	European Patent Office (EPO)	B1	2014-04-02
PT1080245E	Portugal	E	2014-05-26
EP1080245B2	European Patent Office (EPO)	B2	2017-08-16

Protective layers for sputter coated article

Abstract

Term

ES 2 372 024 T3

DESCRIPTION

ES 2 372 024 T3

TABLE 1

ES 2 372 024 T3

ES 2 372 024 T3

TABLE 2

TABLE 3

Priority claims5

Members41

Numbers

Titles2

Classification