Glass panel comprising a solar control layer

Abstract

The invention relates to a solar control glass panel comprising, on at least one of the surfaces of a glass substrate, a multilayer stack including at least one solar radiation absorption layer, and dielectric coatings surrounding said solar radiation absorption layer. According to the invention, the solar radiation absorption layer is a metal alloy layer made from zirconium and chromium. The multilayer stack includes, between the substrate and the solar radiation absorption layer, as well as on top of the solar radiation absorption layer, at least one coating made of a dielectric material made from a compound selected from among silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, mixed aluminum/silicon nitrides, silicon oxynitride, and aluminum oxynitride. The invention is particularly useful as a motor vehicle glass panel, particularly for the roof, as a building glass panel, or as a household stove door.

Claims

1. A solar-control glazing, comprising: a glass substrate; a multilayer stack comprising a first dielectric layer, a second dielectric layer, and a solar radiation-absorbing layer, wherein said multilayer stack is present on the glass substrate, said solar radiation-absorbing layer is present between said first dielectric layer and said second dielectric layer, the solar radiation-absorbing layer is a metal alloy layer that comprises zirconium and chromium, said zirconium and chromium together being present in an amount greater than 60 wt % of said solar radiation-absorbing layer, and each of the first dielectric layer and the second dielectric layer comprises a compound selected from the group consisting of silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, a mixed aluminum-silicon nitride, silicon oxynitride, and aluminum oxynitride.

2. The glazing of claim 1, wherein the solar radiation-absorbing layer comprises from 25% to 75% by weight of zirconium.

3. The glazing of claim 2, wherein the solar radiation-absorbing layer comprises from 45% to 65% by weight of zirconium.

4. The glazing of claim 3, wherein the solar radiation-absorbing layer has a geometrical thickness of between 10 nm and 25 nm.

5. The glazing of claim 1, wherein the solar radiation-absorbing layer has a geometrical thickness of between 0.5 nm and 30 nm.

6. The glazing of claim 4, wherein the solar radiation-absorbing layer has a geometrical thickness of between 0.5 nm and 10 nm.

7. The glazing of claim 1, wherein the first dielectric coating has an optical thickness of at least 10 nm and of not more than 200 nm.

8. The glazing of claim 1, wherein the second dielectric coating has an optical thickness of at least 15 nm and of not more than 200 nm.

9. The glazing of claim 1, wherein the multilayer stack comprises at least two solar radiation-absorbing layers.

10. The glazing of claim 1, wherein the multilayer stack further comprises at least one silver-based metallic layer such that the silver-based metallic layer is surrounded by dielectric coatings.

11. The glazing of claim 10, wherein at least one of the dielectric coatings surrounding the silver-based metallic layer comprises at least two dielectric lavers and the solar radiation-absorbing layer is inserted between said at least two dielectric layers of said dielectric coating.

12. The glazing of claim 11, wherein the at least two dielectric layers sandwiching the solar radiation-absorbing metallic layer are based on silicon nitride or aluminum nitride.

13. The glazing of claim 12, wherein the multilayer stack comprises the following succession: a layer of silicon nitride or of aluminum nitride/a solar radiation-absorbing layer/a layer of silicon nitride or of aluminum nitride/a layer of intercalating transparent oxide based on Zn, Sn, Ti or Zr oxide, or a mixture thereof, different from a wetting layer/a wetting layer based on zinc oxide/a silver metallic layer.

14. The glazing of claim 13, wherein the solar radiation-absorbing metallic layer has a geometrical thickness of between 0.5 and 8 nm.

15. The glazing of claim 13, wherein the intercalating transparent oxide is a mixed zinc-tin oxide or a mixed titanium-zirconium oxide.

16. The glazing of claim 10, wherein the at least one silver-based metallic layer is located in the stack directly over and/or under the solar radiation-absorbing metallic layer.

17. The glazing of claim 10, wherein the at least one silver-based metallic layer has a thickness of at least 9 nm.

18. The glazing of claim 10, wherein the solar radiation-absorbing metallic layer has a geometrical thickness of between 0.5 and 8 nm.

19. The glazing of claim 1, in which a colorimetric variation in transmission, E*.sub.TLr, is less than 8, when said glazing is subjected to a temperature of at least 630 C. and of not more than 670 C. for 7 minutes.

20. The glazing of claim 1, in which a colorimetric variation in glass-side reflection, E*.sub.Rg, is less than 8, when said glazing is subjected to a temperature of at least 630 C. and of not more than 670 C. for 7 minutes.

21. The glazing of claim 1, in which a thickness of the solar radiation-absorbing metallic layer is chosen so that light transmission for a substrate consisting of clear glass 4 mm thick is at least equal to 2% and not more than 75%.

22. The glazing of claim 1, in which an optical thickness of the dielectric coatings is chosen so that layer-side reflection is at least 1% and not more than 55%.

23. The glazing of claim 1, wherein substrate-side measured light reflection is at least 27%.

24. The glazing of claim 1, wherein light reflection measured on the substrate side is at least 2 times greater than light reflection measured on layer-system side.

25. A glazed element of a motor vehicle, a glazing element of buildings or a glazed element of a household electrical appliance, comprising the glazing of claim 1.

26. A solar-control glazing, comprising: a glass substrate; and a multilayer stack, said multilayer stack further comprising, a first dielectric layer, a second dielectric layer, a solar radiation-absorbing layer, and a metallic layer comprising silver surrounded by dielectric coatings, wherein at least one of the dielectric coatings surrounding the silver-based metallic layer comprises the first and second dielectric layers, and said solar radiation-absorbing layer is present between said first dielectric layer and said second dielectric layer, said multilayer stack is present on the glass substrate, the solar radiation-absorbing layer is a metal alloy layer that comprises zirconium and chromium, said zirconium being present in an amount of at least 20 wt % and said chromium being present in an amount of at least 25 wt %, and each of the first dielectric layer and the second dielectric layer comprises a compound selected from the group consisting of silicon oxide, aluminum oxide, silicon nitride, aluminum nitride, a mixed aluminum-silicon nitride, silicon oxynitride, and aluminum oxynitride.

Description

DESCRIPTION OF PREFERRED EMBODIMENTS OF THE INVENTION

(1) Examples of glazings according to the invention, but also comparative examples (R), are given in table I below. The optical properties are defined, as single glass, for glazings whose substrate is made of ordinary clear float glass 4 mm thick. The layers are in order, from left to right, starting from the glass. The approximate geometrical thicknesses are expressed in nm.

(2) Tables I and Ia: Examples of glazings according to the invention and comparative examples of the performance of glazings according to the invention with prior art glazings, the coatings being deposited on clear glass 4 mm thick. The light transmissions (TL) and the layer-side light reflections (Rl) and glass-side light reflections (Rg) are also indicated (in %) for certain examples. In the comparative examples below, NiCr is an alloy containing 80% of Ni and 20% by weight of Cr. in the examples according to the invention below, CiZr is an alloy containing 40% of Cr and 60% by weight of Zr.

(3) TABLE-US-00001 TABLE I Ex. Coating TL Rl Rg E*.sub.Tl E*.sub.Rg 1R SiN (20 nm)/NiCr (8.5 nm)/SiN 39 11 17 1.70 3.84 (35 nm) 2R SiN (20 nm)/NiCr (13.7 nm)/SiN 27 15 25 2.61 2.32 (35 nm) 3R SiN (20 nm)/NiCr (22 nm)/SiN 14 22 36 3.56 1.74 (35 nm) 4R SiN (87 nm)/NiCr (13.7 nm)/SiN 28 22 17 1.95 4.60 (30 nm) 1 SiN (20 nm)/CrZr (12.5 nm)/SiN 34 17 25 0.96 0.30 (35 nm) 2 SiN (20 nm)/CrZr (20.5 nm)/SiN 23 20 32 3.25 1.03 (35 nm) 3 SiN (20 nm)/CrZr (33 nm)/SiN 12 22 39 3.72 0.96 (35 nm) 4 SiN (87 nm)/CrZr (20.5 nm)/SiN 23 24 23 2.76 1.74 (30 nm)

(4) TABLE-US-00002 TABLE Ia Coating (thickness in nm) Ex. SiN CrZr SiN CrZr SiN TL Rl Rg E*.sub.Tl E*.sub.Rl E*.sub.Rg 18 28.5 7.8 27.4 0.0 0.0 33.3 24.1 17.4 0.8 1.1 1.2 19 22.9 7.9 23.9 0.0 0.0 31.1 25.4 17.6 0.7 0.9 1.1 20 10.0 4.3 34.0 2.0 26.5 38.4 9.0 25.0 0.7 1.7 1.3 21 26.0 11.0 46.0 0.0 0.0 32.6 7.4 31.0 0.5 7.3 0.6 22 54.1 4.4 64.5 7.0 44.8 22.5 5.2 6.6 1.1 2.5 2.6 23 22.9 7.9 23.9 0.0 0.0 31.1 25.4 17.6 0.7 0.9 1.1 24 72.1 4.0 50.9 6.5 20.0 20.9 16.2 8.3 1.1 0.6 0.6 25 54.5 2.9 89.4 9.6 34.2 21.2 19.8 12.0 1.2 2.0 2.3 26 95.0 5.7 70.7 4.5 19.0 20.9 21.9 13.5 0.7 2.3 2.2 27 100.0 1.8 28.7 5.1 51.0 38.6 3.4 26.5 0.7 0.9 3.9 28 100.0 1.8 28.7 5.1 47.0 38.5 3.6 25.5 0.7 1.0 3.7 29 129.1 5.2 52.0 0.0 0.0 45.8 4.9 30.0 0.9 1.2 3.8 30 140.0 6.8 39.0 0.0 0.0 37.4 10.3 26.3 1.0 2.6 3.6 31 138.0 6.8 39.0 0.0 0.0 37.4 10.1 26.0 1.0 2.2 3.6 32 39.0 1.0 79.3 6.0 118.7 29.0 28.0 13.9 1.4 2.6 1.8 33 17.7 4.4 60.0 4.9 25.0 24.6 14.1 9.8 0.6 0.1 0.6 34 78.3 3.0 69.4 5.8 62.6 30.9 4.7 10.8 1.8 7.8 4.6 35 15.0 6.1 55.0 5.5 33.7 19.2 8.8 13.2 0.6 0.4 0.3 36 15.0 6.1 57.5 5.5 33.7 19.0 9.0 12.6 0.7 0.5 0.3 37 14.6 4.7 62.1 3.1 95.0 27.6 16.7 12.1 0.4 1.2 2.5 38 14.6 4.7 62.1 3.1 92.5 28.2 15.9 11.8 0.4 1.3 2.4 39 9.5 5.7 61.3 3.3 100.0 23.9 15.4 15.7 0.4 2.2 2.3 40 90.0 12.0 12.0 0.0 0.0 19.0 42.3 17.4 1.3 0.8 3.8 41 24.2 19.9 25.0 0.0 0.0 47.0 39.8 37.3 3.6 4.2 3.4

(5) The solar radiation absorbing metallic layers and the dielectric layers are applied via a cathodic sputtering technique under usual conditions for this type of technique. As a variant, the dielectric layers are applied via the well-known technique known as PECVD (plasma-enhanced chemical vapor deposition).

(6) The silicon nitride dielectric layers are produced from metal targets in an atmosphere consisting of a mixture of argon (30-70%) and nitrogen (70-30%) at a total pressure of 4 mTorr (0.53 Pa). The chromium-zirconium (40% by weight of Cr and 60% of zirconium in the CrZr alloy) layers are deposited from metal cathodes in an atmosphere of argon alone. As a variant, the deposition atmosphere of this CrZr metal alloy comprises a small amount of nitrogen or oxygen originating from the neighboring deposition zones. As a result, the formed CrZr layer, while conserving its essentially metallic nature, contains a small amount of nitrogen or oxygen. The properties obtained are similar. The silicon oxide dielectric layers are produced starting with a silicon-based target in an atmosphere containing argon and oxygen.

(7) The substrate-side light transmission TL and light reflection are measured on the samples with the illuminant D65, 2. The CIE colorimetric coordinates L*, a* and b* are also measured before and after heat treatment with the illuminant D65, 10. The angle at which the measurements are taken is 8.

(8) The samples are subjected to a heat treatment comprising maintaining at 670 C. for 7 minutes 30 seconds. The transmission and reflection variations in E* are also given in the tables. In the examples, the notations SiN denote the silicon nitrides without representing a chemical formula, it being understood that the products obtained are not necessarily rigorously stoichiometric, but are those obtained under the indicated deposition conditions and which are in the region of the stoichiometric products. The SiN layers may contain up to a maximum of about 10% by weight of aluminum originating from the target. The dielectric layer according to the invention may furthermore consist of a plurality of individual layers comprising or essentially consisting of the above materials.

(9) The mechanical strengths and chemical resistances of the glazings according to the invention without a silver-based layer are characterized by successfully passing the tests defined in standard EN1096-2 for class B coatings. In addition, the glazings according to the invention also satisfy the requirements of the following tests: the salt spray test (NSS: Neutral Salt Spray) according to standard ISO 9227-2006, preferably for at least 10 days; the air-conditioned chamber test according to standard EN1036-2008, preferably for at least 10 days; and the Cleveland test according to standard ISO 6270-1:1998, preferably for at least 10 days; the acid resistance test (SO.sub.2) according to standard EN 1096-2; the AWRT test (Automatic wet rub test) described below: A piston covered with a cotton cloth is brought into contact with the layer to be evaluated and moved back and forth over its surface. The piston bears a weight so as to apply a force of 33 N to a finger having a diameter of 17 mm. The rubbing of the cotton over the coated surface damages (removes) the layer after a certain number of cycles. The test is used to define the limit at which the layer discolors (partial removal of the layer) and scratches appear therein. The test is carried out for 10, 50, 100, 250, 500 and 1000 cycles in various separate locations on the sample. The sample is observed under an artificial sky in order to determine whether discoloring or scratching is visible on the sample. The AWRT result indicates the number of cycles resulting in no or very little degradation (invisible to the naked eye under a uniform artificial sky at a distance of 80 cm from the sample); the dry brush test (DBT) according to standard ASTM D2486-00 (test method A), preferably for at least 1000 cycles,
this being measured before and after optional heat treatment.

(10) TABLE-US-00003 TABLE II The examples that follow were performed with other proportions of Cr and of Zr in the solar radiation absorbing metal alloy. As for the preceding examples, the example numbers bearing the letter (R) are comparative examples, and the numbers without this letter are examples according to the invention. The results (OK for good; KO for unacceptable; and S for satisfactory) for two chemical resistance tests are also indicated: air-conditioned chamber (CC) and Cleveland test (Clev). The same structure below was used: 30 nm SiN/15 nm functional layer/30 nm SiN (SiN means Si.sub.3N.sub.4, optionally doped with aluminum to make the starting silicon target conductive). The various layers are deposited in the same manner as in the preceding examples. The constitution of the functional layer is given in table II below. The Cr and Zr percentages relative to the total alloy are given on a weight basis. Functional Ex. layer E*.sub.Tl E*.sub.Rl E*.sub.Rg TL Rl Rg CC Clev 5 80% Cr/20% 1.44 1.44 1.55 21 30 28 OK OK Zr 6 60% Cr/40% 0.94 1.65 1.80 24 27 25 OK OK Zr 7 40% Cr/60% 0.63 1.43 1.46 26 25 22 OK OK Zr 8 25% Cr/75% 2.44 3.56 2.42 26 26 21 OK OK Zr

(11) TABLE-US-00004 TABLE III The comparative example and the example according to the invention of multilayer stacks, deposited on a glass substrate, reproduced in table III below present an additional silver-based metallic layer which is inserted between two solar radiation absorbing metallic layers. The notation conventions are the same as for the preceding tables. Ex. Coating TL Rl Rg E*.sub.Tl E*.sub.Rg CC Clev 5R SiN (40 nm)/NiCr 54 13 24 2.26 1.88 OK OK (1 nm)/Ag (18 nm)/ NiCr (1 nm)/SiN (56 nm) 9 SiN (40 nm)/CrZr 59 15 23 1.61 1.03 OK OK (1 nm)/Ag (18 nm)/ CrZr (1 nm)/SiN (56 nm)

(12) The variation in the thicknesses of the dielectric layers, within reasonable limits, does not significantly affect the modification of the tint during the heat treatment, or the durability, but, of course, it does modify the starting esthetic appearance (and in particular the tint).

(13) As for the preceding examples, the solar radiation absorbing metallic layers, the silver-based additional metallic layers and the dielectric layers are applied via a cathodic sputtering technique under usual conditions for this type of technique. As a variant, the dielectric layers are applied via the well-known technique known as PECVD (plasma-enhanced chemical vapor deposition).

(14) TABLE-US-00005 TABLE IV Examples 10-17 of the multilayer stack, deposited on a glass substrate, reproduced in table IV below relate more particularly to the embodiment of the invention in which the light reflection on the substrate side is high, and in particular higher than the light reflection on the multilayer-stack side. The solar radiation absorbing layer is an alloy comprising 40% chromium and 60% zirconium. The notation conventions are the same as for table I. The figures in parentheses are the physical thicknesses in nm for the various layers. The properties (in % for the light transmission and reflection) are given in monolithic glazing after heat treatment. The name TZO represents a mixed oxide comprising 50% TiO.sub.2 and 50% ZrO.sub.2. Ex. Coating TL Rl Rg 10 SiN (13)/CrZr (6.7)/SiN (50.6) 33.8 7.4 34.6 11 SiN (13)/CrZr (10.3)/SiN (46.7) 23.5 13.8 39.9 12 SiN (17)/CrZr (17)/SiN (40) 12.6 29.2 45.5 13 SiN (79.2)1 CrZr (14)/SiN (50.1) 22.2 15 30.9 14 SiN (16.4)/CrZr (7.6)/TZO (24.1)/SiN (25) 31.3 8.6 39 15 SiN (13)/CrZr (11.6)/TZO (21.4)/SiN (25) 21.6 12.7 44.7 16 SiN (13.4)/CrZr (21.3)/TZO (18.2)/SiN (31.3) 10.8 15.7 51.2 17 SiN (78)/CrZr (14.7)/TZO (22.5)/SiN (25.1) 22 13.4 33

(15) Table Va below gives examples with two additional silver-based metallic layers, the solar radiation absorbing layer being in the first dielectric coating arranged between the substrate and the first silver-based layer. The various layers are deposited under the same conditions as for the examples of table I. The properties are measured in the same manner and are given in table Vb. The examples of table Va also underwent a heat treatment identical to that described for the examples of table I and the variations in the properties are, in the same manner, given in E*, either in transmission E*.sub.Tl (or E*.sub.tr), or in layer-side reflection (E*.sub.Rl), or in glass substrate-side reflection (E*.sub.Rg). Furthermore, the coordinates L*, a*, b* and Y (which represents either the total light transmission or the total light reflection) are also indicated as transmission (TL), as glass substrate-side reflection (Rg) and as layer-system-side reflection (Rl), and also the variation in total light transmission (.sub.TL), and the variation in glass substrate-side (.sub.Rg) and layer-system-side (.sub.Rl) total reflection. The name ZSO5 represents a mixed zinc-tin oxide formed from a cathode of a zinc-tin alloy containing 52% by weight of zinc and 48% by weight of tin to form the spinel structure of zinc stannate Zn.sub.2SnO.sub.4. The term AZO refers to a zinc oxide doped with aluminum, obtained by cathode sputtering, from a ceramic cathode formed by the oxide to be deposited, under a neutral or slightly oxidizing atmosphere. As a variant, AZO may be replaced with other barriers that are well known in the field and suited to the desired properties for the formed layer system, for instance a Ti oxide, which is undoped or doped with niobium or zirconium, preferably obtained from a ceramic target formed from the oxide to be deposited, or pure ZnO. B represents a layer acting as a barrier to the oxidation of silver, which is well known in the field. D represents one or more dielectric layers, especially based on zinc stannate, doped or undoped ZnO, or another material known in the field, which is suited to this type of layer stacking, for example a nitride such as AlN. M represents the wetting layer based on ZnO, which is undoped or doped with aluminum. IR represents the functional layers that reflect infrared radiation. ABS represents the solar radiation absorbing layer.

(16) The examples given in table VIa are, in the same manner, examples with two additional silver-based metallic layers as for table Va, but this time the solar radiation absorbing layer is in the second dielectric coating arranged between the first silver-based layer and the second silver-based layer. The properties obtained are given in table VIb in the same manner as for table Vb. The name TZO.sub.65 means a mixed titanium-zirconium oxide with 35% zirconium and 65% titanium, different from TZO (50/50).

(17) Table VIIa below gives examples with three additional silver-based metallic layers, the solar radiation absorbing layer being in the first dielectric coating arranged between the substrate and the first silver-based layer. The corresponding properties are given in table VIIb, as single glass, for a clear glass substrate 6 mm thick, not heat-treated. The solar factor value (g) is also indicated.

(18) Table VIIIa below also gives examples with three additional silver-based metallic layers, but this time the solar radiation absorbing layer is in the second dielectric coating arranged between the first silver-based layer and the second silver-based layer. The corresponding properties are given in table VIIIb, as single glass, for a clear glass substrate 6 mm thick, not heat-treated. The solar factor value (g) is also indicated.

(19) Needless to say, the invention is not limited to the implementation examples mentioned.

(20) TABLE-US-00006 TABLE Va D1a ABS D1b M IR1 B D2 M IR2 B D3 Ex. SiN CrZr SiN ZSO5 ZnO Ag AZO ZSO5 SiN ZSO5 ZnO Ag AZO ZSO5 SiN TZO 42 10 0.9 10 8 5 10.5 5 15.35 35 15.35 5 14.7 5 11.7 20 3 43 10 1.2 10 10.4 5 11.4 5 14.2 35 14.2 5 14.9 5 11.6 20 3 44 10 1.7 10 12.8 5 12.6 5 14.05 35 14.05 5 14.8 5 11.9 20 3

(21) TABLE-US-00007 TABLE Vb TL Rg Rl Ex. .sub.TL .sub.Rl .sub.Rg E*.sub.TL E*.sub.Rl E*.sub.Rg Y L* a* b* Y L* a* b* Y L* a* b* 42 1.2 0.4 0.6 2.3 3.1 6.2 68.9 86.4 3.3 2.6 6.8 31.7 0.5 11.8 4.3 24.8 3.5 5.6 43 1.2 0.4 0.1 1.3 1.5 1.3 61.2 82.5 4.4 2.9 5.8 29.1 0 9.3 4.4 25 3 2.1 44 2.2 0.6 0.5 1.3 5.3 2.1 50.5 76.5 4.4 1.1 6.4 30.6 0.6 7.6 7.9 33.7 0.4 6.3

(22) TABLE-US-00008 TABLE VIa D1 M IR1 B D2a ABS D2b M IR2 B D3 P Ex. ZSO5 ZnO Ag AZO ZSO5 SiN CrZr SiN ZSO5 ZnO Ag AZO ZSO5 SiN TZO 45 34.0 4.0 14.7 5.5 22.5 20.0 0.6 25.0 10.5 4.0 15.5 5.5 10.5 21.0 3.0 46 39.0 4.0 14.1 5.5 23.8 20.0 0.9 25.0 11.5 4.0 15.5 5.5 10.2 21.0 3.0 47 39.0 4.0 16.6 5.5 22.7 20.0 1.3 25.0 10.7 4.0 16.5 5.5 10.3 21.0 3.0 ZSO5 ZnO Ag AZO ZSO5 SiN CrZr SiN TZO.sub.65 ZnO Ag AZO ZSO5 SiN TZO 48 38.0 4.0 14.1 5.5 24.1 20.0 0.9 25.0 10.0 4.0 15.5 5.5 9.9 21.0 3.0 ZSO5 ZnO Ag AZO ZSO5 SiN CrZr SiN ZSO5 TZO.sub.65 ZnO Ag AZO ZSO5 SiN TZO 49 42 4 14.1 5.5 24.8 20 09 25 9.2 3 4 15.5 5.5 8.4 21 3

(23) TABLE-US-00009 TABLE VIb TL Rg Rl Ex. .sub.TL .sub.Rl .sub.Rg E*.sub.TL E*.sub.Rl E*.sub.Rg Y L* a* b* Y L* a* b* Y L* a* b* 45 2.0 1.4 0.8 0.9 3.9 2.7 60.3 81.9 4.1 4.8 11.9 41.2 2.6 8.0 6.9 32.0 2.2 16.2 46 1.2 1.8 0.3 1.5 4.4 2.5 55.9 79.6 4.5 3.6 12.3 41.8 2.2 4.8 5.9 29.6 0.6 16.4 47 1.0 2.1 0.4 2.1 5.4 1.4 39.3 69.0 5.8 1.8 20.7 52.6 1.3 1.1 7.6 33.7 5.4 18.9 48 0.7 2.0 0.1 2.0 5.2 2.2 55.9 79.6 4.4 3.7 12.3 41.8 1.9 4.9 5.9 29.6 0.5 15.4 49 2.8 1.6 0.8 1.6 4.7 2.0 55.9 79.6 4.6 3.5 12.3 41.8 2.3 4.7 5.9 29.6 0.4 17.4

(24) TABLE-US-00010 TABLE VIIa D1a ABS D1b M IR1 B D2 M IR2 Ex. SiN CrZr SiN ZSO5 ZnO Ag AZO ZSO5 SiN ZSO5 ZnO Ag 50 16.2 1.8 13.4 1.1 5 11.5 4 20 20 21.1 5 15.2 51 16.2 1.8 13.4 1.1 5 11.5 4 61.1 0 0 5 15.2 B D3 M IR3 B D4 Ex. AZO ZSO5 SiN ZSO5 ZnO Ag AZO ZSO5 SiN 50 4 15 17 29.1 5 16.2 4 14 18 51 4 32 0 29.1 5 16.2 4 14 18

(25) TABLE-US-00011 TABLE VIIb TL Rg Rl Ex. g E*.sub.TL E*.sub.Rl E*.sub.Rg Y L* a* b* Y L* a* b* Y L* a* b* 50 37 3 4 8 36.5 80 6 0.8 6.7 31.1 3.9 0.9 2.9 19.6 12.8 9 51 37 3 4 8 36.5 80 6 0.8 6.7 31.1 3.9 0.9 2.9 19.6 12.8 9

(26) TABLE-US-00012 TABLE VIIIa D1 M IR1 B D2a ABS D2b M IR2 B D3 M IR3 B D4 Ex. ZSO5 ZnO Ag AZO ZSO5 SiN CrZr SiN ZSO5 ZnO Ag AZO ZSO5 SiN ZSO5 ZnO Ag AZO ZSO5 SiN 52 17.7 5 9.2 4 19 20 0.8 15 10 5 15.1 4 20 20 25.8 5 15.5 4 14 18.9

(27) TABLE-US-00013 TABLE VIIIb TL Rg Rl Ex. g E*.sub.TL E*.sub.Rl E*.sub.Rg Y L* a* b* Y L* a* b* Y L* a* b* 52 37.5 1.5 7.1 3.5 57 80.3 5.9 1.5 5.1 27.1 1.6 5.8 4.1 24.8 5.4 13.5