(19)
(11)EP 2 948 804 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
13.05.2020 Bulletin 2020/20

(21)Application number: 14702417.8

(22)Date of filing:  21.01.2014
(51)Int. Cl.: 
G02B 5/08  (2006.01)
C03C 17/36  (2006.01)
(86)International application number:
PCT/US2014/012232
(87)International publication number:
WO 2014/116551 (31.07.2014 Gazette  2014/31)

(54)

MIRROR

SPIEGEL

MIROIR


(84)Designated Contracting States:
AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

(30)Priority: 25.01.2013 US 201313749760

(43)Date of publication of application:
02.12.2015 Bulletin 2015/49

(73)Proprietor: Guardian Glass, LLC
Auburn Hills MI 48326 (US)

(72)Inventors:
  • KRASNOV, Alexey
    Canton, MI 48187 (US)
  • DEN BOER, Willem
    Brighton, MI 48116 (US)

(74)Representative: Hoyng Rokh Monegier LLP 
Rembrandt Tower, 31st Floor Amstelplein 1
1096 HA Amsterdam
1096 HA Amsterdam (NL)


(56)References cited: : 
EP-A2- 0 301 755
US-A- 4 780 372
WO-A1-98/39262
US-A1- 2012 307 386
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    FIELD OF THE INVENTION



    [0001] This invention relates to mirrors. More particularly, certain example embodiments relate to mirrors having at least one of: (a) a reflective film including a first layer of or including aluminum and a second layer of or including silver or the like, and/or (b) a color tuning layer between first and second layers. The mirrors may be second surface mirrors in certain example embodiments. The mirrors may be flat or bent in different instances, and may or may not be heat treated (e.g., thermally tempered and/or thermally bent). In certain example instances, such mirrors may be used in interior residential, commercial, furniture, appliance, and/or other applications.

    BACKGROUND AND SUMMARY OF EXAMPLE EMBODIMENTS OF THE INVENTION



    [0002] Mirrors have been in existence for years and have been used in interior building applications such as, for example, in bathrooms, as decorations, for furniture, etc., and for exterior applications. Mirrors generally are either first surface mirrors where the mirror coating is provided between the viewer and the supporting glass substrate, or second surface mirrors, where the supporting glass substrate is interposed between the viewer and the mirror coating. See, for example, U.S. Patent Nos. 7,276,289 and 7,678,459; U.S. Publication Nos. 2006/0077580; 2007/0178316; 2008/0073203; 2008/0164173; 2010/0229853; 2011/0176212; and 2011/0176236. US 2012/0307386 A1 also describes a mirror from the prior art relevant for the understanding of the invention.

    [0003] Fig. 1 is a cross sectional view of a conventional second surface mirror. The mirror in Fig. 1 includes a mirror coating on glass substrate 100, the mirror coating being composed of silicon nitride layer 101, sputter-deposited aluminum reflective layer 102, silicon nitride layer 103, and optional PPF (permanent protective film) or paint layer 108. Despite the fact that aluminum is highly reactive, it possesses defense against corrosion and tarnishing, namely by way of forming a very thin stable aluminum oxide layer at a surface thereof which prevents/reduces the rest of the aluminum in the aluminum reflective layer from further oxidation. Aluminum is also cheaper than silver. However, the mirror of Fig. 1 suffers from the following problems. First, its visible reflectance is not as good as a high priced silver mirror. Aluminum mirrors are cheaper than silver mirrors, but provide for a lower amount of visible light reflectance. This problem affects the general quality of reflected images and often limits the use of such mirrors to clean-cut applications using thinner glass such as glass less than 4 mm thick. Thicker glass, used for example in beveled mirrors, absorbs a greater portion of light and often requires the use of reflective material which reflectance higher than that of aluminum. Second, its glass side reflective color tends to shift toward the blue color range (compared to a silver mirror), i.e., a blue color shift, which some consider to be aesthetically undesirable. In home/residential mirrors, especially under fluorescent light, the blue shift of the spectrum adds "cool cast" to the reflected image which some believe to be aesthetically undesirable. Given that fluorescent lights are becoming more popular in home/residential and certain commercial/office applications, there is a need in the art to add a "warm cast" to aluminum mirrors in order to make reflected images appear more natural.

    [0004] Thus, it will be appreciated that there is a need in the art for improved mirrors and/or methods of making the same, where one or both of the problems identified above are addressed. Thus, certain embodiments of this invention relate to mirrors that solve one or both of the problems discussed above. The scope of the invention is defined in the appended claims.

    [0005] Certain example embodiments of this invention relate to mirrors including at least one of: (a) a first reflective layer of or including aluminum and a second reflective layer of or including silver or the like, and/or (b) a color tuning layer between first and second reflective layers. The mirrors may be second surface mirrors in certain example embodiments of this invention.

    [0006] Certain example embodiments of this invention relate to providing a thin reflective layer of low refractive index material (silver) that is sputter deposited on the glass substrate (directly or indirectly) so as to be located between the glass substrate and an aluminum inclusive reflective layer. This provides adds a "warm cast" to reflected images. In other words, compared to reflected images from the conventional mirror discussed above, this shifts the reflection spectrum to longer wavelengths as well in order to increase the intensity of reflected visible light. This allows the images from the mirror to appear more pleasant, and permits better image quality compared to the use of only an aluminum reflective layer as in the conventional mirror discussed above.

    [0007] Certain example embodiments of this invention relate to mirrors including a color tuning layer, typically of a transparent dielectric material, provided between first and second reflective layers. The reflective layers may be of or include aluminum and/or silver. The color tuning layer embodiment may or may not be used in combination with the embodiment where both aluminum and silver reflective layers are provided.

    [0008] In certain example embodiments of this invention, there is provided a mirror, comprising: a glass substrate; a reflective film on the glass substrate, the reflective film comprising or consisting essentially of a first metallic or substantially metallic layer and a second metallic or substantially metallic layer; and wherein the first metallic or substantially metallic layer of the reflective film comprises silver, and the second metallic or substantially metallic layer of the reflective film comprises aluminum, and wherein the first metallic or substantially metallic layer comprising silver is located between at least the glass substrate and the second metallic or substantially metallic layer comprising aluminum.

    [0009] In certain example embodiments of this invention, there is provided a a dielectric film between and directly contacting the first and second layers of the reflective film.

    BRIEF DESCRIPTION OF THE DRAWINGS



    [0010] 

    FIGURE 1 is a cross sectional view of a conventional second surface mirror;

    FIGURE 2 is a cross sectional view of an example second surface mirror according to an example embodiment of this invention;

    FIGURE 3 is a cross sectional view of an example second surface mirror according to another example embodiment of this invention;

    FIGURE 4 is a visible reflectance (%) versus thickness graph, illustrating the visible reflectance of Al and Ag layers at various thicknesses; and

    FIGURE 5 is visible reflectance (%) versus x graph, where x is the thickness of the silver layer making up the combination of a 50 nm thick film of both the silver layer and the aluminum layer in the Fig. 2 embodiment.


    DETAILED DESCRIPTION OF EXAMPLE EMBODIMENTS OF THE INVENTION



    [0011] Referring now more particularly to the drawings in which reference numerals indicate like parts/materials throughout the several views. Mirrors according to example embodiments of this invention may be flat or bent in different instances, and may or may not be heat treated (e.g., thermally tempered and/or thermally bent).

    [0012] Referring to Figs. 2-3, example embodiments of this invention relate to mirrors 1, 2 including at least one of: (a) a reflective film including a layer of or including aluminum 102 and a layer of or including silver 110 (e.g., see Figs. 2-3), and/or (b) a color tuning layer 112 between layers 102, 110 of a reflective film wherein the layers 102, 110 may be of or include Ag, A1 or the like (e.g., see Fig. 3). The reflective film is made up of layers 102 and 110. The mirrors may be second surface mirrors in certain example embodiments. The mirrors may be flat or bent in different instances, and may or may not be heat treated (e.g., thermally tempered and/or thermally bent). In certain example instances, such mirrors may be used in interior residential, commercial, furniture, bathroom, door, appliance, and/or other applications.

    [0013] Certain example embodiments of this invention relate to providing a thin reflective layer 110 of low refractive index material (e.g., silver) that is sputter deposited on the glass substrate (directly or indirectly) 100 so as to be located between the glass substrate 100 and an aluminum inclusive reflective layer 102, as show in Figs. 2-3. This provides adds a "warm cast" to reflected images. In other words, compared to reflected images from the conventional mirror in Fig. 1, this shifts the reflection spectrum to longer wavelengths (e.g., toward yellow) as well in order to increase the intensity of reflected visible light. This allows the images from the mirror 1, 2 to appear more pleasant, and permits better image quality compared to the use of only an Al reflective layer as in the conventional mirror of Fig. 1. This effect is achieved due to at least the use of an optical interference effect and is similar to the "warm" and pleasant appearance of images reflected by silver mirrors, but at a lower cost than conventional silver mirrors. This also allows aluminum reflective layers 102 to be used in mirrors with thicker glass if desired.

    [0014] Certain example embodiments of this invention relate to mirrors including a color tuning layer 112, typically of a transparent dielectric material, provided between layers 102, 110 of the reflective film (e.g., see Fig. 3). Each layer 102 and 110 of the reflective film may be of or include aluminum and/or silver. The color tuning layer embodiment (e.g., see Fig. 3) may or may not be used in combination with the embodiment where both aluminum and silver reflective layers are provided. Thus, while reflective layer 102 is of or includes aluminum and the other layer 110 of the reflective film may be of or include silver as shown in Fig. 3, the color tuning layer 112 may also be used in embodiments where both reflective layers 102 and 110 are of or include aluminum as indicated in Fig. 3.

    [0015] Fig. 2 is a cross-sectional view of a second surface mirror 1 in accordance with certain example embodiments of this invention. As shown in Fig. 2, a glass substrate 100 supports a mirror coating including transparent seed layer 109 which may be a dielectric or semiconductor, metallic or substantially metallic conductive reflective layer 110 of or including silver, and metallic or substantially metallic conductive reflective layer 102 of or including aluminum. Transparent seed layer 109 may be of or include dielectric silicon nitride (e.g., Si3N4), which may optionally be doped with oxygen and/or from about 1-10% aluminum. Alternatively, transparent seed layer 109 may be of or include any of the following other dielectric materials: silicon oxynitride, silicon oxide (e.g., SiO2), silicon aluminum oxide, zinc oxide, tin oxide, zinc aluminum oxide, zinc gallium oxide, aluminum oxynitride, or zinc stannate. The mirror coating may also optionally include dielectric layer 103 (e.g., of or including one or more of silicon nitride which may be doped with 1-10% aluminum, silicon oxide which may be doped with 1-10% aluminum, silicon oxynitride which may be doped with 1-10% aluminum, aluminum oxynitride, or aluminum oxide) and/or PPF (e.g., tape) or paint layer 108, in order to protect the reflective layers and provide for a more durable mirror.

    [0016] Glass substrate 100 may be soda-lime-silica based glass, and may be from about 1-10 mm thick, more preferably from about 2-6 mm thick, in example embodiments of this invention.

    [0017] Thus, the transparent seed layer 109 is first sputter-deposited or otherwise provided on glass substrate 100, using ceramic or metal sputtering target(s). For example, in embodiments where the transparent dielectric seed layer 109 is of silicon nitride, the silicon nitride seed layer may be sputter deposited on the glass substrate using one or more silicon targets (which may be doped with Al). Then, the reflective silver layer 110 is then sputter deposited on the glass substrate 100 over the seed layer 109, e.g., via one or more silver sputtering targets, possibly in the same sputter coating apparatus without breaking vacuum. The provision of the thin silver based layer 110 does not significantly compromise the line speed of the sputtering process, and preferably adds only a small cost premium (compared to aluminum) due to higher silver material cost, because the silver based layer 110 is preferably thinner than the aluminum based layer 102.

    [0018] The role of the transparent dielectric seed layer 109 (e.g., of or including one or more of silicon nitride, silicon oxynitride, silicon oxide, silicon aluminum oxide, zinc oxide, tin oxide, zinc aluminum oxide, zinc gallium oxide, aluminum oxynitride, or zinc stannate) is twofold. First, the layer 109 acts as a "seed" layer to improve the adhesion of the reflective layer(s) to the glass substrate. Second, the layer 109 minimizes or reduces the potential for sodium migration from the glass substrate 100 into the reflective layer(s), such as during optional heat treatment such as thermal tempering or heat bending. It has also surprisingly been found that if the seed layer 109 (i) is not of material having a low refractive index (n) and/or (ii) does not have a low thickness, then the seed layer can undesirably reduce the reflectance of the mirror of Fig. 1. Thus, in certain example embodiments of this invention, the seed layer 109 has an index of refraction (n, measured at 550 nm) of from about 1.45 to 2.05, more preferably from about 1.45 to 2.0, even more preferably from about 1.5 to 1.85, and most preferably from about 1.5 to 1.75. For low refractive index values (e.g., around 1.45 to 1.65) of seed layer 109, thickness of the layer 109 is not overly important because even as the thickness of the seed layer 109 increases it does not significantly adversely affect the visible reflectance of the mirror when the layer 109 has a low refractive index value. However, at higher refractive index values (e.g., from about 1.9 to 2.05), it is desirable to minimize or reduce the thickness of the seed layer 109 so that the layer does not significantly adversely affect (i.e., so that it does not significantly reduce) the visible reflectance of the mirror. Thus, in certain example embodiments of this invention, especially when the layer 109 has higher refractive index value(s) such as silicon nitride which has a refractive index of about two, the transparent dielectric seed layer 109 is from about 2-50 nm thick, more preferably from about 2.5-30 nm thick, more preferably from about 2.5-10 nm thick, and most preferably from about 3-6 nm thick. Of course, the drop in reflectance caused by thick seed layers 109 of higher index materials such as silicon nitride can be made up for, in part or in full, by the provision of the higher reflectance silver material in layer 110. Thus, these thickness values for the seed layer 109 are optional, may be used in preferred embodiments, but are not necessary in all embodiments.

    [0019] Layers 102 and 110 together make up a reflective film for the mirror, and therefore both layers 102 and 110 are referred to as reflective layers even though a thin silver layer 110 alone may not be truly reflective if not combined with the aluminum layer in the same coating. In example embodiments, reflective layer 110 of or including silver is from about 4-50 nm thick, more preferably from about 4-25 nm thick, more preferably from about 7-25 nm thick, more preferably from about 8-24 nm thick, still more preferably from about 9-20 nm thick, and most preferably from about 10-14 nm thick, with an example thickness of a silver layer 110 being about 10 nm. In example embodiments, reflective layer 102 of or including aluminum is from about 15-200 nm thick, more preferably from about 18-100 nm thick, even more preferably from about 18 -70 nm thick, still more preferably from about 18-40 nm thick, more preferably from about 20-37.5 nm, and most preferably from about 25-37.5 nm thick, with an example thickness of an aluminum layer 102 being about 30 nm. For the reasons explained above, in certain preferred embodiments, the silver based layer 110 is thinner than the aluminum based layer 102. For example, in certain example embodiments, silver based layer 110 is at least about. 5 nm thinner (more preferably at least about 10 nm thinner) than aluminum based layer 102.

    [0020] Fig. 4 is a visible reflectance (%) versus thickness graph, illustrating the visible reflectance of Al and Ag layers at various thicknesses. Fig. 4 demonstrates the dependence of reflectance on layer thickness of sputter A1 (aluminum), and the reflectance of sputtered Ag (silver) is also shown for purposes of comparison. Al thickness of about 40-50 nm (400-500 Å), for example, allows for achieving approximately maximum intensity of reflected light using a minimum amount of material, and thus allows for a highest line speed of the sputtering process in making mirrors.

    [0021] Fig. 5 is visible reflectance (%) versus x graph, where x is the thickness of the silver layer making up the combination of a 50 nm thick film of both the silver layer and the aluminum layer in the Fig. 2 embodiment, where the graph illustrates the effect of thickness of the silver layer on total visible reflectance of the Ag/Al stack with total thickness of 40-50 nm. As shown in Fig. 5, substitution of the front 10 nm of Al with silver in a 50 nm thick Al/Ag film (film made up of layers 102 and 110 in Fig. 2), for a 40 nm thick A1 layer 102 and a 10 nm thick Ag layer 110, results in a 3% increase in visible reflectance compared to if the 50 nm film was made up of solely Al. Fig. 5 illustrates that if the 50 nm film was made up of solely A1 then the reflectance is about 84% (see the horizontal dotted line in Fig. 5). Thus, the advantage of using Ag for part of the film is appreciated, as it allows for improved reflectance. This increase caused by the 10 nm of Ag in Figs. 2 and 5 is enough, for example, to compensate for loss of reflectance intensity caused by increasing glass 100 thickness by about 3 mm. Fig. 5 also shows that substitution of 20 nm of Al with Ag (resulting in a 20 nm thick Ag layer 110 and a 30 nm thick Al layer 102 in Fig. 2) results in a maximum reflectance increase of 4.5% compared to if the 50 nm film was made up of solely Al. Further increase of the Ag layer, however, may result in decreased reflectance due to an optical interference effect. Thus, the advantage of providing Ag layer 110 in combination with Al layer 102 can be seen due to the increased reflectance that can be achieved. And when the overall film made up of layers 102 and 110 is about 50 nm thick it can be seen that the optimum Ag layer 110 thickness is from about 8-24 nm (80-240 Å). It will be appreciated that the reflective film (layer 102 + layer 110) may be from about 30-200 nm thick, more preferably from about 40-100 nm thick, and most preferably from about 40-60 nm thick in example embodiments of this invention, and that the Al layer 102 is generally thicker than the Ag (or Cu) layer 110.

    [0022] In addition to the increase in reflectance with the Ag based layer 110 is used in combination with the Al based layer 102, it has been found that this also provides for a long wavelength (yellow) shift of the reflectance spectrum which adds a warm and aesthetically pleasant cast to images reflected by the mirror, particularly under cool illumination such as fluorescent lighting. This represents yet another advantage associated with example embodiments of this invention.

    [0023] Fig. 2 illustrates that the additional layer 110 is of or includes Ag in certain preferred embodiments of this invention. However, it is also possible for layer 110 to be of a different low index material such as copper (Cu).

    [0024] Optionally, dielectric protective layer 103 (e.g., silicon nitride of Si3N4 or other suitable stoichiometry) may also be sputter-deposited on the substrate 100, over the reflective film 102, 110. Protective layer 103 may be of or include materials such as silicon nitride, silicon oxynitride, silicon oxide, aluminum oxynitride, and/or aluminum oxide in example embodiments. Sputter-deposited protective dielectric layer 103, if provided, may be from about 5-100 nm thick, more preferably from about 10-40 nm thick, in certain example embodiments.

    [0025] Instead of, or in addition to, layer 103, a protective film 108 of paint or PPF may be provided on the substrate 100 over the reflective film 102, 110. Permanent protective film (PPF) 108 may have high adhesion levels, good chemical resistance, and/or excellent environmental durability. The protective film 108 may be resistant to delamination from moisture penetration and/or the use of asphalitic based adhesives applied to the exterior surface of the protective film. In certain example embodiments, the PPF 108 may be thin, e.g., having a thickness of < 200 microns, and sometimes about 40-100 microns in thickness. Peel strength may be increased through the incorporation of additional cross-linking polymers in certain example embodiments. Example protective films 108 from Nitto-Denko include: SPV-9310, SPV-9320, SPV-30800, SPV 5057 A5, and SPV 5057 A7. Other manufacturers of similar preferred protective films include Permacel, Tessa Tapes, B&K Films, and Novacell. These plastic films come in a wide variety of opacities and colors.

    [0026] In Fig. 2, the seed layer 109 is in direct contact with the glass substrate 100. However, it is possible that other layer(s) may be provided therebetween in various embodiments.

    [0027] Fig. 3 is a cross sectional view of an example second surface mirror according to another example embodiment of this invention. It will be appreciated that the mirror coating in Fig. 3 may be the same as shown and described with respect to Fig. 2, except that: (a) color tuning layer 112 is present in the Fig. 3 embodiment between layers 102 and 110, and (b) the layer 110 may be of or include aluminum in the Fig. 3 embodiment (instead of Ag or Cu). Color tuning layer 112 may be from about 3-30 nm thick, more preferably from about 4-10 nm thick, in example embodiments of this invention. The color tuning layer 112 may be of or include a material such as silicon nitride and/or silicon oxynitride (possibly doped with 1-10% Al) in example embodiments of this invention, although other material(s) may instead be used. The reflective film (layer 102 + layer 110) in the Fig. 3 embodiments provides for two reflected waves, one reflected by layer 102 and the other reflected by layer 110. The mirror structure of Fig. 3 allows for increased visible reflectance compared to the conventional mirror of Fig. 1, and does not necessarily need Ag or Cu in layer 110. The mirror 2 in Fig. 3, like the mirror in Fig. 2, is a second surface mirror because the incident light first passes through glass substrate 100 before it is reflected by reflective film made up of layers 102 and 110.

    [0028] Mirrors shown in Figs. 2-3 may have a visible transmission of from about 1-15%, more preferably from about 1-12%, more preferably from about 1-8%. And the mirrors shown in Figs. 2-3 may have a visible glass side reflectance of from about 85-95%, more preferably from about 85-90%, even more preferably from about 85-89%, and most preferably from about 86-89%, in example embodiments of this invention (e.g., see Fig. 5).

    [0029] While a layer, layer system, coating, or the like, may be said to be "on" or "supported by" a substrate, layer, layer system, coating, or the like, other layer(s) may be provided therebetween. Thus, for example, the coatings or layers described above may be considered "on" and "supported by" the substrate and/or other coatings or layers even if other layer(s) are provided therebetween.

    [0030] According to the invention, there is provided a mirror according to claim 1.

    [0031] The mirror of the preceding paragraph may further comprise at least one seed layer located between the glass substrate and the first metallic or substantially metallic layer comprising silver and wherein the seed layer directly contacts the first metallic or substantially metallic layer. The seed layer may comprise one or more of silicon nitride, silicon oxynitride, silicon oxide, zinc oxide, tin oxide, aluminum oxynitride, and zinc stannate.

    [0032] In the mirror of any of the preceding paragraphs, the first metallic or substantially metallic layer comprising silver is from 8-24 nm thick, more preferably from 9-20 nm thick.

    [0033] In the mirror of any of the preceding paragraphs, the second metallic or substantially metallic layer comprising aluminum may be from 18-70 nm thick, more preferably from 18-40 nm thick.

    [0034] In the mirror of any of the preceding paragraphs, the reflective film may be from 40-100 nm thick.

    [0035] In the mirror of any of the preceding paragraphs, the mirror may have a glass side visible reflectance of from about 85-95%.

    [0036] In the mirror of any of the preceding paragraphs, the first and second layers of the reflective film may be sputter-deposited layers.

    [0037] The mirror of any of the preceding paragraphs may further comprise a layer comprising paint, with the reflective film being located between at least the glass substrate and the layer comprising paint.

    [0038] The mirror of any of the preceding paragraphs may further comprise a protective layer, the reflective film being located between at least the glass substrate and the protective layer. The protective layer may comprise silicon nitride for example.

    [0039] The mirror of any of the preceding paragraphs may be a second surface mirror.

    [0040] The mirror of any of the preceding paragraphs may further comprise a dielectric layer provided between the first metallic or substantially metallic layer comprising silver and the second metallic or substantially metallic layer comprising aluminum. Optionally, the dielectric layer may directly contact one or both of the first and second layers of the reflective film. The dielectric layer may comprise silicon nitride and/or silicon oxynitride for example. Alternatively, in the mirror of any of the preceding paragraphs, the first metallic or substantially metallic layer comprising silver may directly contact the second metallic or substantially metallic layer comprising aluminum.

    [0041] In the mirror of any of the preceding paragraphs, the first metallic or substantially metallic layer comprising silver may be at least 5 nm thinner than the second metallic or substantially metallic layer comprising aluminum.

    [0042] While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims.


    Claims

    1. A mirror (1), comprising:

    a glass substrate (100);

    a reflective film on the glass substrate, the reflective film comprising a first metallic or substantially metallic layer (110) and a second metallic or substantially metallic layer (102); and

    wherein the first metallic or substantially metallic layer (110) of the reflective film comprises silver and the second metallic or substantially metallic layer (102) of the reflective film comprises aluminum, and;

    wherein the first metallic or substantially metallic layer (110) comprising silver is located between at least the glass substrate (100) and the second metallic or substantially metallic layer (102) comprising aluminum; and characterised in that the first metallic or substantially metallic layer (110) comprising silver is from 8-24 nm thick.


     
    2. The mirror of claim 1, further comprising at least one seed layer (109) located between the glass substrate (100) and the first metallic or substantially metallic layer (110) comprising silver, and wherein the seed layer (109) directly contacts the first metallic or substantially metallic layer (110) comprising silver.
     
    3. The mirror of claim 2, wherein the seed layer (109) comprises one or more of silicon nitride, silicon oxynitride, silicon oxide, zinc oxide, tin oxide, aluminum oxynitride, and zinc stannate.
     
    4. The mirror of any preceding claim, where the first metallic or substantially metallic layer (110) comprising silver is from 9-20 nm thick.
     
    5. The mirror of any preceding claim, wherein the second metallic or substantially metallic layer (102) comprising aluminum is from 18-70 nm thick, and preferably from 18-40 nm thick.
     
    6. The mirror of any preceding claim, wherein the reflective film is from 40-100 nm thick.
     
    7. The mirror of any preceding claim, wherein the mirror (1) has a glass side visible reflectance of from about 85-95%.
     
    8. The mirror of any of claims 1-7, further comprising a protective layer (103), the reflective film being located between at least the glass substrate (100) and the protective layer (103), and wherein the protective layer (103) preferably comprises silicon nitride.
     
    9. The mirror of any preceding claim, further comprising a dielectric layer (112) provided between the first metallic or substantially metallic layer (110) comprising silver and the second metallic or substantially metallic layer (102) comprising aluminum.
     
    10. The mirror of claim 9, wherein the dielectric layer (112) comprises silicon nitride and/ or silicon oxynitride.
     
    11. The mirror of any preceding claim, wherein the first metallic or substantially metallic layer (110) comprising silver is at least 5 nm thinner than the second metallic or substantially metallic layer (102) comprising aluminum.
     
    12. The mirror of any of claims 1-8, wherein the first metallic or substantially metallic layer (110) comprising silver directly contacts the second metallic or substantially metallic layer (102) comprising aluminum.
     


    Ansprüche

    1. Spiegel (1), umfassend:

    ein Glassubstrat (100);

    einen reflektierenden Film auf dem Glassubstrat, wobei der reflektierende Film eine erste metallische oder im Wesentlichen metallische Schicht (110) und eine zweite metallische oder im Wesentlichen metallische Schicht (102) umfasst; und

    wobei die erste metallische oder im Wesentlichen metallische Schicht (110) des reflektierenden Films Silber umfasst und die zweite metallische oder im Wesentlichen metallische Schicht (102) des reflektierenden Films Aluminium umfasst, und

    wobei die erste metallische oder im Wesentlichen metallische Schicht (110), die Silber umfasst, zwischen mindestens dem Glassubstrat (100) und der zweiten metallischen oder im Wesentlichen metallischen Schicht (102), die Aluminium umfasst, angeordnet ist; dadurch gekennzeichnet, dass die erste metallische oder im Wesentlichen metallische Schicht (110), die Silber umfasst, 8 bis 24 nm dick ist.


     
    2. Spiegel nach Anspruch 1, ferner umfassend mindestens eine Keimschicht (109), die zwischen dem Glassubstrat (100) und der ersten metallischen oder im Wesentlichen metallischen Schicht (110), die Silber umfasst, angeordnet ist, und wobei die Keimschicht (109) die erste metallische oder im Wesentlichen metallische Schicht (110), die Silber umfasst, direkt berührt.
     
    3. Spiegel nach Anspruch 2, wobei die Keimschicht (109) eines oder mehrere von Siliziumnitrid, Siliziumoxynitrid, Siliziumoxid, Zinkoxid, Zinnoxid, Aluminiumoxynitrid und Zinkstannat umfasst.
     
    4. Spiegel nach einem der vorhergehenden Ansprüche, wobei die erste metallische oder im Wesentlichen metallische Schicht (110), die Silber umfasst, 9 bis 20 nm dick ist.
     
    5. Spiegel nach einem der vorhergehenden Ansprüche, wobei die zweite metallische oder im Wesentlichen metallische Schicht (102), die Aluminium umfasst, eine Dicke von 18 bis 70 nm und vorzugsweise eine Dicke von 18 bis 40 nm aufweist.
     
    6. Spiegel nach einem der vorhergehenden Ansprüche, wobei der reflektierende Film eine Dicke von 40 bis 100 nm aufweist.
     
    7. Spiegel nach einem der vorhergehenden Ansprüche, wobei der Spiegel (1) ein sichtbares Reflexionsvermögen auf der Glasseite von etwa 85 bis 95 % aufweist.
     
    8. Spiegel nach einem der Ansprüche 1 bis 7, ferner umfassend eine Schutzschicht (103), wobei der reflektierende Film zwischen mindestens dem Glassubstrat (100) und der Schutzschicht (103) angeordnet ist und wobei die Schutzschicht (103) vorzugsweise Siliziumnitrid umfasst.
     
    9. Spiegel nach einem der vorhergehenden Ansprüche, ferner umfassend eine dielektrische Schicht (112), die zwischen der ersten metallischen oder im Wesentlichen metallischen Schicht (110), die Silber umfasst, und der zweiten metallischen oder im Wesentlichen metallischen Schicht (102), die Aluminium umfasst, vorgesehen ist.
     
    10. Spiegel nach Anspruch 9, wobei die dielektrische Schicht (112) Siliziumnitrid und/oder Siliziumoxynitrid umfasst.
     
    11. Spiegel nach einem der vorhergehenden Ansprüche, wobei die erste metallische oder im Wesentlichen metallische Schicht (110), die Silber umfasst, mindestens 5 nm dünner ist als die zweite metallische oder im Wesentlichen metallische Schicht (102), die Aluminium umfasst.
     
    12. Spiegel nach einem der Ansprüche 1 bis 8, wobei die erste metallische oder im Wesentlichen metallische Schicht (110), die Silber umfasst, die zweite metallische oder im Wesentlichen metallische Schicht (102), die Aluminium umfasst, direkt berührt.
     


    Revendications

    1. Miroir (1) comprenant :

    un substrat en verre (100) ;

    un film réfléchissant sur le substrat en verre, le film réfléchissant comprenant une première couche métallique ou sensiblement métallique (110) et une seconde couche métallique ou sensiblement métallique (102) ; et

    la première couche métallique ou sensiblement métallique (110) du film réfléchissant comprenant de l'argent et la seconde couche métallique ou sensiblement métallique (102) du film réfléchissant comprenant de l'aluminium, et ;

    la première couche métallique ou sensiblement métallique (110) comprenant de l'argent étant située entre au moins le substrat en verre (100) et la seconde couche métallique ou sensiblement métallique (102) comprenant de l'aluminium ; et

    caractérisé en ce que la première couche métallique ou sensiblement métallique (110) comprenant de l'argent présente une épaisseur de 8 à 24 nm.


     
    2. Miroir selon la revendication 1, comprenant en outre au moins une couche germe (109) située entre le substrat en verre (100) et la première couche métallique ou sensiblement métallique (110) comprenant de l'argent, et la couche germe (109) étant en contact direct avec la première couche métallique ou sensiblement métallique (110) comprenant de l'argent.
     
    3. Miroir selon la revendication 2, la couche germe (109) comprenant du nitrure de silicium et/ou de l'oxynitrure de silicium et/ou de l'oxyde de silicium et/ou de l'oxyde de zinc et/ou de l'oxyde d'étain et/ou de l'oxynitrure d'aluminium et/ou du stannate de zinc.
     
    4. Miroir selon l'une quelconque des revendications précédentes, la première couche métallique ou sensiblement métallique
    (110) comprenant de l'argent présentant une épaisseur de 9 à 20 nm.
     
    5. Miroir selon l'une quelconque des revendications précédentes, la seconde couche métallique ou sensiblement métallique (102) comprenant de l'aluminium présentant une épaisseur de 18 à 70 nm, et de préférence une épaisseur de 18 à 40 nm.
     
    6. Miroir selon l'une quelconque des revendications précédentes, le film réfléchissant présentant une épaisseur de 40 à 100 nm.
     
    7. Miroir selon l'une quelconque des revendications précédentes, dans lequel le miroir (1) présente une réflectance visible côté verre d'environ 85 à 95 %.
     
    8. Miroir selon l'une quelconque des revendications 1 à 7, comprenant en outre une couche protectrice (103), le film réfléchissant étant situé entre au moins le substrat en verre (100) et la couche protectrice (103), et la couche protectrice (103) comprenant de préférence du nitrure de silicium.
     
    9. Miroir selon l'une quelconque des revendications précédentes, comprenant en outre une couche diélectrique (112) disposée entre la première couche métallique ou sensiblement métallique (110) comprenant de l'argent et la seconde couche métallique ou sensiblement métallique (102) comprenant de l'aluminium.
     
    10. Miroir selon la revendication 9, la couche diélectrique (112) comprenant du nitrure de silicium et/ou de l'oxynitrure de silicium.
     
    11. Miroir selon l'une quelconque des revendications précédentes, la première couche métallique ou sensiblement métallique (110) comprenant de l'argent étant au moins 5 nm plus mince que la seconde couche métallique ou sensiblement métallique (102) comprenant de l'aluminium.
     
    12. Miroir selon l'une quelconque des revendications 1 à 8, la première couche métallique ou sensiblement métallique (110) comprenant de l'argent en contact direct avec la seconde couche métallique ou sensiblement métallique (102) comprenant de l'aluminium.
     




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    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description