FR3068032A1 - GLAZING WITH ANTISOLAR PROPERTIES COMPRISING A TITANIUM NITRIDE LAYER - Google Patents

Abstract

Glass article having an antisolar function comprising at least one glass substrate and a stack of layers deposited on at least one face of said substrate, said stack of layers comprising at least: a first layer of titanium nitride TiNx in which 1.00 <x < 1.20, or titanium oxynitride of the general formula TiNxOy, wherein 1.00 <x <1.20 and wherein 0.01 <y <0.10, the thickness of said first layer of titanium nitride or of titanium oxynitride being between 10 and 80 nanometers, - a second metal layer based on chromium, nickel, titanium, niobium or a mixture of at least two of these elements, said second layer being optionally nitrided, said second layer being disposed between the first layer of titanium nitride and said face of said substrate.

Description

GLAZING WITH ANTI-SOLAR PROPERTIES COMPRISING A LAYER OF

TITANIUM NITRIDE

The invention relates to the field of glass substrates or articles, of the glazing type of buildings or cars, comprising on their surface coatings of the thin film type giving them sunscreen properties. By glazing is meant in the sense of the present invention any glass product consisting of one or more glass substrates, in particular single glazing, double glazing, triple glazing, etc. The present invention relates in particular to laminated glazing comprising at least two glass substrates linked together by a layer of plastic material such as PVB (polyvinyl butyral) or PU (polyurethane). By sunscreen is understood in the sense of the present invention the ability of glazing to limit the energy flow, in particular infrared radiation (IR), passing through from the outside to the inside of the house or passenger compartment, while retaining a light transmission allowing vision at least from the inside to the outside of the building or the cabin it equips.

Such glazing provided with stacks of thin layers thus act on the incident solar radiation and allow solar protection and / or thermal insulation of the passenger compartment or the dwelling. In addition, these coatings must be aesthetically pleasing, that is to say that they must have a colorimetry, in transmission as in reflection, sufficiently neutral to not inconvenience the users or alternatively a slightly blue or green tint, in particular in the field of the building. These coatings are conventionally deposited by deposition techniques of the CVD type for the simplest or most often at present by deposition techniques by vacuum spraying, often called magnetron in the field, in particular when the coating is consisting of a more complex stack of successive thin layers.

Most often, the stacks in thin layers having solar control properties comprise one or even several active layers. By active or still functional layer is meant a layer which acts appreciably on the flow of solar or thermal radiation passing through said glazing. Such an active layer, in a known manner, can operate either mainly in the mode of reflection of the incident infrared radiation, or mainly in the mode of absorption of the incident infrared radiation.

By neutral color is meant within the meaning of the present invention, in the colorimetry system (L *, a *.

b ’values b * and values close to zero, in particular less than 10, even less than 5, absolute values.

By blue-green color is meant within the meaning of the present invention, in the colorimetry system (L *, a *, b *), negative values b * negative, in particular at

-10, or even less than -15 and a * values close to zero, in particular less than 10, or even less than 5, in absolute values.

In particular, the most efficient stacks marketed at present incorporate at least one metallic layer of the silver type operating essentially on the mode of reflection of a major part of the incident IR (infrared) radiation. These layers are however very sensitive to humidity and are therefore exclusively used in double glazing, opposite 2 or 3 thereof to be protected from humidity. The stacks according to the invention do not include such layers of the silver (or gold, platinum, copper, aluminum) type.

Other metallic layers with sunscreen function have also been described in the field, comprising functional layers of the Nb, Ta or W type or nitrides of these metals, such as for example in application W001 / 21540. However, within such layers, the solar radiation is this time absorbed and / or reflected but in a not very selective manner, that is to say that infrared radiation of the solar radiation (whose wavelength is between approximately 780 nm and

2500 nm) and the visible are also non-selective. Such

In known manner light transmission and / or

T _The radiation absorbed / reflected in a glazing manner therefore has little or no selectivity.

Classically in the field of insulating glazing, selectivity is most often expressed as the ratio between the Light Transmission factor (T _L ) and the solar factor g (or FS). These quantities are in particular defined in standard NF EN 410.

conventional, the light transmission factor corresponds to the percentage of the incident light flux, that is to say in the wavelength range 380 to 780 nm, passing through the glazing, according to the illuminant D ₆₅ .

In known manner the solar factor g is it equal to the ratio of the energy passing through the glazing (that is to say entering the room) and the incident solar energy. More particularly, it corresponds to the sum of the flux transmitted directly through the glazing and the flux absorbed by the glazing (including the stacks of layers possibly present at one of its surfaces) then possibly re-emitted inward (the local).

In general, all the light characteristics presented in this description are obtained according to the principles and methods described in European (and French) standard EN 410 relating to the determination of the light and solar characteristics of the glazing used in glass for construction.

In addition, glazing having a mirror effect, that is to say a strong external light reflection, in particular of the order of 15 to 40%, is particularly sought after at present, in particular in the building sector. 20 to 40%, so that the glazing appears as a mirror surface seen from the outside of the building but that vision remains possible and easy from the inside to the outside of the building.

Such an arrangement logically results in a large reduction in the light transmission through the glazing and consequently a significant reduction in the selectivity of the glazing, in the sense described above.

The first object of the present invention is thus to provide glazings having such a mirror effect, that is to say a strong external reflection, in particular between 15 and 40%, and comprising a stack of layers giving them sunscreen properties while having a relatively high selectivity, in the sense described above, that is to say an optimized T _L / g ratio, in particular of the order of 1 or slightly less than 1, and in any event significantly improved compared to glazing proposed in application W001 / 21540 previously cited.

A glazing unit according to the invention thus advantageously makes it possible to select the radiation passing through it, by promoting the transmission of light waves in the visible range, that is to say the wavelength of which is between approximately 380 and 780 nm , and by selectively absorbing and / or reflecting the majority of solar infrared radiation, that is to say the wavelength of which is greater than 780 nm, in particular the infrared A, that is to say whose wavelength is between about 780nm and about 1400nm.

According to another optional aspect of the present invention, it is sought to provide sunscreen glazing, said stacking of which confers on said glazing a color in transmission and in substantially neutral external reflection or even a light blue-green tint, as sought in particular in building sector.

By neutral color is meant within the meaning of the present invention, in the colorimetry system (L *, a *, b *), b * values and a * values close to zero, in particular less than 10, or even less to 5, in absolute values.

By blue-green color is meant within the meaning of the present invention, in the colorimetry system (L *, a *, b *), negative b * values, in particular less than -10, or even less than -15 and values a * close to zero, in particular less than 10, or even less than 5, in absolute values.

In the case where the sunscreen glazing according to the invention is a laminated glazing, it also becomes possible to obtain neutral colors, in particular whose values of the parameters a * and b * are less than 5, in absolute values or alternatively of the glazing having in external reflection a blue color which is particularly sought after in the building sector, due to a value of b * less than -10, or even less than -15, the value of a * being preferably less than 5, or even less to 2, in absolute value.

In particular, the applicant company discovered that such objectives could be achieved by the use on glass substrates of a stack of layers comprising at least two layers, of which:

a first layer of titanium nitride or of titanium oxynitride, a second layer disposed closer to the glass substrate in the stack, and preferably directly on the glass substrate, this second layer being based on chromium, nickel , titanium, niobium or a mixture of at least two of these elements, said second layer possibly being nitrided (except of course titanium). Said nitriding can be partial or total.

Thanks to the combined use of such layers, possibly in combination with other layers of the dielectric type, it was thus possible to obtain glazings as described above, that is to say glazings having a strong reflection. exterior light, while maintaining a selectivity close to 1 or slightly less than 1.

More specifically, the present invention relates to a glass article with an anti-sun function comprising at least one glass substrate and a stack of layers deposited on at least one face of said substrate, said stack of layers comprising at least:

a first layer of titanium nitride TiN _x in which 1.00 <x <1.20, or of titanium oxynitride of general formula TiN _x O _y , in which 1.00 <x <1.20

Ί and in which 0.01 <y <0.10, the thickness of said first layer of titanium nitride or titanium oxynitride being between 10 and 80 nanometers,

a second metallic layer based on chromium, nickel, titanium, niobium or a mixture of at least two of these elements :, said second layer being optionally nitrided, said second layer being deposited between the first layer of titanium nitride or titanium oxynitride and said face of said substrate,

- possibly one or more layers of dielectric materials,

By dielectric material is meant any material whose massive form devoid of impurities has a resistivity initially greater than 10 ^l ohm-meters (Ω.γπ). Such materials, once deposited in thin layers, may however include: additional elements substantially increasing their electrical conductivity, useful in particular for improving the sputtering efficiency of the precursor material constituting the magnetron target. For example, layers of silicon nitride used in the stack according to the invention can comprise a small amount of aluminum, the target of metallic silicon conventionally used during sputtering comprising for example in general from 6 to 10% by weight. aluminum, to increase the conductivity.

According to certain preferred embodiments of the present invention, which can be combined with one another if necessary:

- The stack consists of said at least first and second layers and layers of dielectric materials.

- The thickness of said first layer of titanium nitride or titanium oxynitride is between 10 and 30 nanometers, and very particularly between 10 and 25 nanometers.

- The thickness of said second metallic layer, possibly nitrided, is between 3 and 15 nm, in particular between 5 and 10 nanometers.

- The thickness of said first layer is greater than the thickness of said second layer by a factor at least equal to 1.3, preferably by a factor equal to at least 1.5.

- The second metal layer is deposited directly on said face of said substrate.

- Said first and said second layer are in contact with each other.

- Said first and said second layer are separated by at least one layer of dielectric material.

- Said first layer of titanium nitride TiN _x O _y is such that 1.05 <x <1.18.

- Said first layer of titanium nitride is such that 0.02 <y <0.08.

- The dielectric material (s) are chosen from silicon nitride optionally doped with Al, Zr, B, aluminum nitride, tin oxide, a mixed zinc or tin oxide Sn _y Zn _z O _x , silicon oxide, titanium oxide, silicon oxynitrides SiO _x N _y .

- The second layer is a layer of nickel and chromium, preferably nitrided.

- Said stack consisting of a succession of said first and second layers and possibly layers of dielectric materials separating said first and second layers.

- The stack comprises or consists of the succession of the following layers, starting from the surface of the glass substrate:

at least said second metallic layer based on chromium, nickel, titanium, niobium or a mixture of at least two of these elements, said layer being optionally nitrided, optionally one or more lower layers of dielectric materials of thickness, in total, between 10 and 120 nm, said first layer of titanium nitride TiN _x with 1.00 <x <1.20, or of titanium oxynitride of general formula TiN _x O _y , in which 0, 01 <y <

0.10 and in which 1.00 <x <1.20, of thickness between 10 and 80 nm, preferably between 10 and 30 nanometers, and more preferably between 10 and 25 nanometers, optionally at least one metallic layer based on chromium, nickel, titanium, niobium or a mixture of at least two of these elements, said layer being optionally nitrided, one or more upper layers of dielectric materials, of physical thickness, in total, between 10 and 100 nm, optionally an upper layer based on a titanium oxide, a zirconium oxide or a titanium and zirconium oxide.

- The stack comprises or consists of the succession of the following layers, starting from the surface of the glass substrate:

a metallic layer based on chromium, nickel, titanium, niobium or a mixture of at least two of these elements, said layer being optionally nitrided, said layer having a thickness of between 3 and 15 nanometers, preferably between 5 and 10 nanometers,

a layer of titanium nitride TiN _x with 1.00 <x <1.20, or of titanium oxynitride of general formula TiN _x O _y , in which 0.01 <y <0.10 and in which 1, 00 <x <1.20, including thickness

between 10 and 8 0 nm, from preference between 10 and 30 nanometers, and preferably between 10 and 25 nanometers, a diaper based nitride silicon, thick range between 20 and 80 nm, of

preferably between 25 and 70 nm,

- optionally an upper layer based on a titanium oxide, a zirconium oxide or a titanium and zirconium oxide, preferably of thickness between 3 and 50 nm.

- Said article is a glazing comprising only a single glass substrate, said stack being arranged on at least one face of said glazing.

said article at undergone treatment thermal Phone a quenching, a bending or annealing. said article East laminated glazing consisting through

a set of at least two glass substrates linked together by a thermoplastic sheet, in particular of polyvinyl butyral (PVB), said stack preferably being arranged on at least one face of one of the glass substrates turned towards the inside of said laminated glazing .

The examples which follow are given purely by way of illustration and do not limit the scope of the present invention in any of the aspects described. For comparison purposes, all the stacks of the examples which follow are synthesized on glass substrates mounted in single glazing or in laminated glazing (see below).

All the layers of the stacks were deposited according to conventional vacuum deposition techniques by magnetron sputtering.

Example 1:

In this example according to the invention, a stack consisting of the following sequence of layers was deposited, according to conventional magnetron techniques, on a glass substrate of the Planilux® type:

Glass / NiCrN / TiN _x / Si ₃ N ₄ (9nm) (14nm) (62nm)

The TiN _x layer is obtained by the magnetron sputtering technique from a metallic titanium target in an atmosphere of nitrogen and argon.

The silicon nitride layers are deposited according to conventional techniques in the field, from a silicon target comprising 8% by weight of aluminum in an atmosphere of nitrogen and argon.

The NiCrN layer is deposited from the spraying of a NiCr target in an argon and nitrogen atmosphere, the elements Ni and Cr being present in the target in the following proportions: 80% by weight of Ni and 20 % Cr weight.

In the following table, the main characteristics of the deposition process are reported:

Line speed (m / min) 2 NiCrN Power on cathode (kW) 19 Pressure (qbar) 3.5 Ar flow (sccm) 1150 Flux N ₂ (sccm) 600 TiN Power (kW) 92 Pressure (qbar) 6 Ar flow (sccm) 1600 Flux N ₂ (sccm) 500 S13N4 Power (kW) 150 Pressure (qbar) 4 Ar flow (sccm) 700 Flux N ₂ (sccm) 850

According to the invention, the glazing thus obtained can be used as simple glazing or as the first substrate for obtaining a laminated glazing by laminating with another glass substrate of the Planilux® type by means of a PVB sheet, l stack being disposed between the two glass substrates in the final glazing.

On the single glazing and the laminated glazing thus obtained, the factors T _L and g were measured in order to determine the selectivity and their colorimetric properties. The results are reported in the following tables.

Example 2:

In this example, according to the glass magnetron techniques of the Planilux® type, by the sequence of layers of the invention, it was deposited, according to classics, on a substrate in another stack consisting of the following:

Glass / NiCrN / Si ₃ N ₄ / TiN _x / Si ₃ N ₄ (7nm) (102nm) (19nm) (51nm)

The layers of TiN _x , NiCrN and S13N4 are obtained according to the same principles as previously exposed.

In the following table, the main characteristics of the deposition process are reported:

Line speed (m / min) 1.3 NiCrN Power on cathode (kW) 12.5 Pressure (gbar) 3.5 Ar flow (sccm) 1150 Flux N ₂ (sccm) 600 S13N4 Power on cathodes (kW) 150 Pressure (gbar) 4 Ar flow (sccm) 700 Flux N ₂ (sccm) 850 TiN Power on cathode (kW) 80 Pressure (gbar) 6 Ar flow (sccm) 1600 Flux N ₂ (sccm) 500 S13N4 Power on cathodes (kW) 90 Pressure (gbar) 4 Ar flow (sccm) 700 Flux N ₂ (sccm) 850

As in the previous example, the glazing thus obtained is used as single glazing or as the first substrate for obtaining laminated glazing by laminating with another glass substrate of the Planilux® type by means of a sheet. of PVB, the stack being placed between the two glass substrates in the final glazing.

On the single glazing and the laminated glazing thus obtained, the factors T _L and g were measured in order to determine the selectivity and their colorimetric properties. The results are reported in the following tables.

Example 3 (comparative):

In this example, a glazing from the applicant company sold under the reference Cool-Lite STB120 was used, the stack of which comprises a layer of niobium nitride as reflective / absorbent layer of solar radiation, surrounded by two layers of silicon nitride.

On the single glazing and the laminated glazing thus obtained, the factors T _L and g were measured in order to determine the selectivity and their colorimetric properties. The results are reported in the following tables.

The selectivity characteristics of the various glazings obtained, measured according to the standards specified, are given in Table 1 below:

Example 1 Example 2 Example 3 R-Lext Glazing simple 37 15 21 Glazing laminated 31 17 21 T _L (%) Glazing simple 34 27 22 Glazing laminated 31 26 22 g (%) Glazing simple 33 31 32 Glazing laminated 33 32 33 selectivity Glazing simple 1.02 0.88 0.66 (T _L / g) Glazing laminated 0.94 0.80 0.67

Table 1

The comparison of the data reported in Table 1 shows that greater selectivity is obtained for a stack comprising the two layers in accordance with the present invention, that is to say for the stack of Examples 1 and 2, and even very close to 1 for the stack according to Example 1, despite the presence of the highly reflective NiCrN layer.

The colorimetric characteristics of the glazing according to examples 1 to 3 were also measured in the international system (CIE L * b * a *) in transmission and in external reflection (external side).

All the optical data are shown in Table 2 below:

Example LIGHT TRANSMISSION EXTERNAL REFLECTION T _L a * _T b * _T R-Lext 3- * Rext Ή -L2 Rext Example 1 Glazing simple 34 -2.2 5.5 37 -5.1 0.3 Glazing laminated 31 -2.7 2.7 31 -2.5 -0.8 Example 2 Glazing simple 27 -2.9 -4.3 15 3.9 -31.6 Glazing laminated 26 -3.6 -2.5 17 -0.5 -20.8 Example 3 Glazing simple 22 -1.4 0.5 21 -2.9 -16 Glazing laminated 22 -1.4 2.7 21 -3, 6 -10.8

Table 2

The data reported in Table 2 show the ideal properties of colorimetry in transmission and in external reflection of glazing provided with stacks according to the invention:

- In transmission the parameters a * _T and b * _T are most often negative and remain relatively weak, ensuring a relatively neutral color in transmission.

- In reflection, the parameter a * _ext according to the glazings according to the invention is always relatively low and most often negative, while the parameter b * is either close to 0 for example 1, which ensures a neutral color in reflection, or strongly negative (example 2), which ensures a blue color as sought in reflection.

Such colorimetric properties therefore lead to a neutral color of the glazing in transmission and a neutral or blue-green color in external reflection, as is currently sought in the building sector.

According to another advantage, the sunscreen stacks according to the present are extremely simple to manufacture, in particular by the technique of vacuum deposition by cathode sputtering known as magnetron.

In addition, additional durability tests have shown that such layers could be easily deposited on face 2 of a single glazing, without risk of degradation thereof, by chemical action (humidity) or by mechanical action (abrasion of the stack).

Claims (18)

1. Glassware with sunscreen function including 5 at least one glass substrate and a stack of layers deposited on at least one face of said substrate, said stack of layers comprising at least: a first layer of titanium nitride TiN _x in which 1.00 <x <1.20, or of titanium oxynitride of 10 general formula TiN _x O _y , in which 1.00 <x <1.20 and in which 0.01 <y <0.10, the thickness of said first layer of titanium nitride or titanium oxynitride being between 10 and 80 nanometers, - a second metallic layer based on chromium, 15 nickel, titanium, niobium or a mixture of at least two of these elements, said second layer being optionally nitrided, said second layer being disposed between the first layer of titanium nitride or titanium oxynitride 20 and said face of said substrate. 2. Glass article according to the preceding claim, wherein the stack consists of said at least first and second layers and layers of materials. 25 dielectrics. 3. Glass article according to one of the preceding claims, in which the thickness of said first layer of titanium nitride or titanium oxynitride 30 is between 10 and 30 nanometers, and very particularly between 10 and 25 nanometers. 4. Glassware according to one of the preceding claims, wherein the thickness of said second 35 possibly nitrided metal layer is between 3 and 15 nm, in particular is between 5 and 10 nanometers. 5. Glassware according to one of the preceding claims, in which the thickness of said first layer is greater than the thickness of said second layer by a factor at least equal to 1.3, preferably by a factor equal at least 1.5. 6. Glassware according to one of the preceding claims, wherein the second metal layer is deposited directly on said face of said substrate. 7. Glassware according to one of the preceding claims, wherein said first and said second layer are in contact with each other. 8. Glassware according to one of claims 1 to 6, wherein said first and said second layer are separated by at least one layer of dielectric material. 9. Glass article according to one of the preceding claims, in which 1.05 <x <1.18. 10. Glassware according to one of the preceding claims, in which 0.02 <y <0.08. 11. Glass article according to the preceding claim, in which the dielectric material or materials are chosen from silicon nitride optionally doped with Al, Zr, B, aluminum nitride, tin oxide, a mixed zinc oxide. or tin Sn _y Zn ₂ O _x , silicon oxide, titanium oxide, silicon oxynitrides SiO _x N _y . 12. Glass article according to the preceding claim, wherein the second layer is a layer of nickel and chromium, preferably nitrided. 13. Glass article according to one of the preceding claims, wherein said stack consisting of a succession of said first and second layers and optionally layers of dielectric materials separating said first and second layers. 14. Glass article according to one of the preceding claims, in which the stack comprises or consists of the succession of the following layers, starting from the surface of the glass substrate: at least said second metallic layer based on chromium, nickel, titanium, niobium or a mixture of at least two of these elements, said layer being optionally nitrided, - optionally one or more lower layers of dielectric materials of thickness, in total, between 10 and 120 nm, - Said first layer of titanium nitride TiN _x with 1.00 <x <1.20, or of titanium oxynitride of general formula TiN _x O _y , in which 0.01 <y <0.10 and in which 1 .00 <x <1.20, of thickness between 10 and 80 nm, preferably between 10 and 30 nanometers, and more preferably between 10 and 25 nanometers, optionally at least one metallic layer based on chromium, nickel, titanium, niobium or a mixture of at least two of these elements, said layer being optionally nitrided, - one or more upper layers of dielectric materials, of physical thickness, in total, between 10 and 100 nm. - optionally an upper layer based on a titanium oxide, a zirconium oxide or a titanium and zirconium oxide. 15. Glass article according to one of the preceding claims, in which the stack comprises or consists of the succession of the following layers, starting from the surface of the glass substrate: a metallic layer based on chromium, nickel, titanium, niobium or a mixture of at least two of these elements, said layer being optionally nitrided, said layer having a thickness of between 3 and 15 nanometers, preferably between 5 and 10 nanometers, a layer of titanium nitride TiN _x with 1.00 <x <1.20, or of titanium oxynitride of general formula TiN _x O _y , in which 0.01 <y <0.10 and in which 1, 00 <x <1.20, of thickness between 10 and 80 nm, preferably between 10 and 30 nanometers, and more preferably between 10 and 25 nanometers, a layer based on silicon nitride, of thickness between 20 and 80 nm, preferably between 25 and 70 nm, - optionally an upper layer based on a titanium oxide, a zirconium oxide or a titanium and zirconium oxide. 16. Glass article according to one of the preceding claims, wherein said article is a glazing comprising only a single glass substrate, said stack being disposed on at least one face of said glazing. 17. 5 18. Glass article according to the preceding claim, wherein said article has undergone a heat treatment such as quenching, bending or even annealing. of the claims 1 to 15, East glazing laminated from to less two substrates them by a leaf thermoplastic, in particular of polyvinyl butyral (PVB), said stack being preferably arranged on at least one face of one of the glass substrates facing inwards of said laminated glazing. FRENCH REPUBLIC National registration number FA 842466 FR 1755810 irai - I NATIONAL INSTITUTE INDUSTRIAL PROPERTY PRELIMINARY SEARCH REPORT based on the latest claims filed before the start of the search DOCUMENTS CONSIDERED AS RELEVANT Relevant claim (s) Classification attributed to the invention by ΙΊΝΡΙ Category Citation of the document with indication, if necessary, of the relevant parts US 2012/275018 Al (LU SONGWEI [US] ET AL) November 1, 2012 (2012-11-01) * paragraph [0069] - paragraph [0071]; figure 4 * DE 10 2014 114330 Al (ARDENNE GMBH VON [DE]) April 7, 2016 (2016-04-07) * paragraph [0050] - paragraph [0054]; figures 3,4 * US 2017/088461 Al (TAVARES-CORTÉS JOSÉ LUIS [MX] ET AL) March 30, 2017 (2017-03-30) * tables 3-5,7-9 * US 5,091,244 A (BIORNARD ERIK J [US]) February 25, 1992 (1992-02-25) * the examples * 1-7 9-11, 13-18 1-5 8-13, 16-18 1-5 8 to 11.13, 16.18 1-18 C03C17 / 34 C03C17 / 38 G02B1 / 115 TECHNICAL AREAS SOUGHT (IPC) C03C EPO FORM 1503 12.99 (P04C14) Examiner Saldamli, Saltuk Research completion date November 21, 2017 T: theory or principle underlying the invention E: patent document with a date prior to the filing date and which was only published on that filing date or on a later date. D: cited in the request L: cited for other reasons CATEGORY OF DOCUMENTS CITED X: particularly relevant on its own Y: particularly relevant in combination with another document in the same category A: technological background O: unwritten disclosure P: interlayer document &: member of the same family, corresponding document ANNEX TO THE PRELIMINARY RESEARCH REPORT RELATING TO THE FRENCH PATENT APPLICATION NO. FR 1755810 FA 842466 This appendix indicates the members of the patent family relating to the patent documents cited in the preliminary search report referred to above. The said members are contained in the computer file of the European Patent Office on 21 ^- ll ^- 201 / The information provided is given for information only and does not engage the responsibility of the European Patent Office or the French Administration EPO FORM P0465 Patent document cited in the research report Publication date Patent family member (s) Publication date US 2012275018 Al 01-11-2012 US 2012275018 Al 01-11-2012 W0 2012148744 Al 01-11-2012 DE 102014114330 Al 07-04-2016 CN 105481266 A 13-04-2016 DE 102014114330 Al 07-04-2016 US 2017088461 Al 30-03-2017 US 2017088461 Al 30-03-2017 W0 2015 119 490 Al 13-08-2015 US 5091244 A 25-02-1992 AT 143927 T 15-10-1996 CA 2066043 Al 11-02-1992 DE 69122602 DI 14-11-1996 DE 69122602 T2 05-28-1997 DK 0495979 T3 17-03-1997 EP 0495979 Al 29-07-1992 JP 3446833 B2 16-09-2003 JP H05502311 A 22-04-1993 US 5091244 A 25-02-1992 W0 9202364 Al 20-02-1992 For further information on this annex: see Official Journal of the European Patent Office, No.12 / 82