PATENT DOCUMENT

Publication Number: US-8974924-B2
Application Number: US-201314033890-A
Country: US
Kind Code: B2

Title: Oleophobic coating on sapphire

Abstract:
A component comprises a substrate having an alumina base layer, a transition layer, and a surface coating. The transition layer comprises alumina and silica, and the surface coating preferentially bonds to the silica as compared to the alumina.

Claims:
We claim: 
     
       1. A handheld, portable electronic device comprising:
 a window comprising:
 a substrate having an alumina base layer; 
 a transition layer on the substrate, the transition layer comprising alumina and silica; and 
 a surface coating on the substrate, wherein the surface coating bonds to the silica as compared to the alumina. 
 
 
     
     
       2. The electronic device of  claim 1 , wherein the alumina base layer comprises a substantially single-crystal sapphire. 
     
     
       3. The electronic device of  claim 1 , wherein the transition layer transitions substantially continuously from about 100% alumina at the base layer to include a substantial silica component at the surface coating. 
     
     
       4. The electronic device of  claim 1 , wherein the transition layer transitions substantially continuously from about 100% alumina at the substrate to about 100% silica or silica glass at the surface coating. 
     
     
       5. The electronic device of  claim 1 , further comprising a surface layer formed on the transition layer, wherein the surface layer comprises a substantially constant silica component and the surface coating bonds to the silica in the surface layer. 
     
     
       6. The electronic device of  claim 5 , wherein the surface layer comprises substantially 100% silica or silica glass. 
     
     
       7. The electronic device-of  claim 5 , wherein a thickness of the transition layer is within a range of approximately 10 nanometers (nm) and approximately 100 nm. 
     
     
       8. The electronic device of  claim 7 , wherein a thickness of the surface layer is less than the thickness of the transition layer. 
     
     
       9. The electronic device of  claim 7 , wherein the thickness of the surface layer is one of equal to, or less than, approximately 10 nm. 
     
     
       10. The electronic device of  claim 1 , wherein the surface coating comprises an oleophobic coating. 
     
     
       11. A handheld, portable electronic device comprising:
 a window comprising:
 a substrate having an alumina base layer; 
 a transition layer on the substrate, the transition layer comprising alumina and silica; and 
 an oleophobic coating on the substrate, wherein the oleophobic coating bonds to the silica as compared to the alumina. 
 
 
     
     
       12. The electronic device of  claim 11 , wherein the oleophobic coating is provided on an exterior surface of the window. 
     
     
       13. The electronic device of  claim 12 , further comprising a touch screen in the window. 
     
     
       14. A handheld, portable electronic device comprising:
 a window comprising:
 a substrate having a sapphire glass base layer; 
 a transition layer on the sapphire glass base layer, the transition layer comprising alumina and silica; and 
 an oleophobic surface coating on the substrate, wherein the oleophobic surface coating bonds to the silica as compared to the alumina. 
 
 
     
     
       15. The electronic device of  claim 14 , wherein the transition layer transitions from at least 90% alumina at the base layer to at least 50% silica or silica glass at the oleophobic coating. 
     
     
       16. The electronic device of  claim 15 , wherein the transition layer transitions to at least 90% silica or silica glass at the oleophobic coating. 
     
     
       17. The electronic device of  claim 14 , wherein the oleophobic coating comprises an alkylsilane and a perfluorinated end group. 
     
     
       18. The electronic device of  claim 14 , further comprising a touch screen provided in the window, wherein the oleophobic surface coating is provided on an exterior surface of the touch screen.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS 
     This application claims priority to and the benefit of U.S. Provisional Patent Application No. 61/704,275, filed Sep. 21, 2012 and titled “Oleophobic Coating on Sapphire,” the disclosure of which is hereby incorporated herein in its entirety. 
    
    
     TECHNICAL FIELD 
     The subject matter of this application relates generally to surface coatings on substrates. In particular, the application relates to oleophobic coatings and other surface coatings on substrates for uses as windows on electronic devices, including, but not limited to, mobile phones and portable computing devices. 
     BACKGROUND 
     Electronic devices may include a range of different touch-sensitive input surfaces, for example as incorporated into displays, track pads, keyboards, and combinations thereof. In use, however, oils and other deposits may affect appearance and performance, particularly where information is also displayed on the touch-sensitive surface (e.g., on a touch-sensitive display). 
     To address this problem, a number of different surface treatments are available, depending on substrate design and desired composition. Different surface treatments, however, may also exhibit different performance criteria, and not all surface treatments are compatible with all substrate materials. Thus, the issue of surface treatment raises a number of different design challenges, particularly for touch-sensitive surfaces subject to a range of different environmental conditions and operational demands. 
     SUMMARY 
     Various embodiments described herein encompass a component with a substrate having an alumina base layer, a transition layer comprising alumina and silica, and a surface coating that preferentially bonds to the silica. The base layer may comprise a single-crystal sapphire. The transition layer may transition substantially continuously from about 100% alumina at the base layer to include substantial silica content at the surface coating, or to about 100% silica or silica glass at the surface coating. 
     A surface layer may be formed on the transition layer, with a substantially silica content, for example substantially 100% silica or silica glass, and the surface coating may be oleophobic. A portable electronic device may comprise the coated component, the portable device may include a window, the oleophobic coating may be provided on an exterior surface of the window, and the window may also include a touch screen. 
     In additional embodiments, a window for a portable electronic device may include a substrate having a sapphire glass base layer, a transition layer of alumina and silica on the sapphire glass base layer, and an oleophobic coating. The oleophobic coating preferentially bonds to the silica as compared to the alumina. 
     The transition layer may transition from at least 90% alumina at the base layer to at least 50% silica or silica glass at the oleophobic coating, or to at least 90% silica or silica glass at the coating. The oleophobic coating may also comprise an alkylsilane and a perfluorinated end group, and a touch screen may be provided in the window, with the oleophobic coating on an exterior surface of the touch screen. 
     In method embodiments, a sapphire substrate for a touch screen window is provided with a substantially single-crystal base layer. A transition layer of alumina and silica and a surface coating are formed on the substrate, where the surface coating preferentially bonds to the silica as compared to the alumina. 
     The transition layer may be formed by vapor deposition of alumina and silica onto the sapphire substrate, and may transition from substantially 100% alumina at the sapphire substrate to more than 50% silica or silica glass at the surface coating, or to substantially 100% silica or silica glass at the surface coating. The surface coating may be formed as an oleophobic coating having an end group that preferentially bonds to the silica, as compared to the alumina. In addition, the sapphire substrate may be compressed by ion implantation. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
         FIG. 1  is a perspective view of an electronic device having a surface treatment. 
         FIG. 2A  is a cross-sectional schematic view of a substrate having a treated surface. 
         FIG. 2B  is a cross-sectional schematic view of the substrate, in a sapphire or sapphire glass embodiment with an alumina/silica transition layer and oleophobic coating. 
         FIG. 3  is a schematic view of a system for applying the surface treatment. 
         FIG. 4  is a block diagram of a method for coating a substrate. 
     
    
    
     DETAILED DESCRIPTION 
       FIG. 1  is a perspective view of electronic device  100 , for example a mobile phone, tablet computer or other portable device  100  having at least one surface on which an olephobic coating or other surface treatment is applied. For example, electronic device  100  may include window  102  with a bezel  104  about all or a part of its edge, where bezel  104  is couplable to housing  102  in a manner that secures window  106  to portable device  100 . 
     Depending on the application, bezel  104  and housing  106  may be formed of a variety of different materials including, but not limited to, plastics and other polymer materials, aluminum, steel and other metals, amorphous glass materials, composite materials, and combinations thereof. Window  102  is formed of a suitable transparent or translucent material, for example a transparent plastic or polymer material, a transparent, amorphous glass material, or a transparent crystalline material such as sapphire or sapphire glass. 
     A touch sensitive screen or other component with exterior surface  108  may be incorporated into device  100 , for example within or beneath window  102  as shown in  FIG. 1 . In this particular embodiment, device  100  bezel  104  incorporates a touch-sensitive layer beneath window  102  that is configured to recognize user input by manipulating virtual objects displayed on device  100 , sensing touches, and the like. 
     To reduce oils and other deposits on surface  108 , an oleophobic treatment or other coating  110  may be applied. Coating  110  may also include a range of different materials having suitable oleophobic or other properties, for example oleophobic polymer materials, optical coatings, scratch-resistant coatings, and combinations thereof. 
     In one embodiment, an oleophobic material or other coating is formed on surface  108  by liquid vapor deposition, for example as described in Weber and Matsuyuki, DIRECT LIQUID VAPORIZATION FOR OLEOPHOBIC COATINGS, U.S. patent application Ser. No. 13/024,964 filed Feb. 10, 2011, the entirety of which is incorporated by reference herein. Alternatively, oleophobic materials and other suitable coatings may be deposited by other processes, including, but not limited to, chemical vapor deposition, physical vapor deposition, electrochemical techniques, spraying, dipping, sputtering, optical coating processes, and combinations thereof. 
     In each of these applications, bonding of the coating material generally depends not only upon a coating process used to apply the oleophobic layer but also upon substrate composition, as expressed in the material of window  102  and bezel  104 . With respect to electronic devices, for example, the coating may bond differently to sapphire, sapphire glass, and other aluminum oxide based materials, as compared to silicate (silica or silicon-based) glass materials, including quartz glass and leaded glass, and as compared to other non-sapphire and non-aluminum oxide based substrate materials. To address this issue, the substrate forming window  102  or bezel  104  may be provided with a transitional layer, as described below. 
       FIG. 2A  is a cross-sectional schematic view of substrate  200  with an oleophobic coating or other surface treatment  110 . Substrate  200  is formed of base layer  202  with transitional layer  204  and surface layer  206 , to which surface treatment  110  is applied. 
     In one particular application, base layer  202  is formed of a sapphire or sapphire glass material, for example an aluminum oxide or alumina (Al 2 O 3  or α-Al 2 O 3 ) material. While suitable sapphire materials may be found naturally, base layer  202  may also be formed of a synthetic sapphire material, for example by sintering and fusing aluminum oxide, hot isostatic pressing, and processing the resulting polycrystalline product to form a substantially single-crystal sapphire base layer  202 . Suitable methods for forming such a base layer  202  also include, but are not limited to, Verneuil processes, Czochralski processes, flux methods, and variations and combinations thereof. 
     Alternatively, base layer  202  may be formed of an amorphous aluminum oxide, transparent alumina or other sapphire-like material, for example by thin film deposition, sintering, vapor deposition, or other process. In these examples, base layer  202  may also include a combination of amorphous and polycrystalline components, in order provide a selected combination of transparency and hardness. 
     Transitional layer  204  is formed of a combination of base layer materials and other components, for example a combination of alumina and silica or silica glass. Where base layer  202  is formed of sapphire, sapphire glass or another alumina-based material, for example, transition layer  204  may be formed of a combination of alumina and silica, in order to provide a smooth or continuous material composition transition from base layer  204  to surface layer (or surface interface)  206 . 
     Surface  206  of transition layer  204  may also have a substantially two-component composition, including both alumina and silica materials in any of these proportions. Alternatively, surface layer  206  may be formed of a substantially 100% silica-based material such as silica glass, with substantially no alumina content (e.g., less than 10%, less than 5%, less than 2%, or less than 1%). These options provide substrate  200  with a combination of different hardness and bonding properties across base layer  202 , transition layer  204  and surface layer  206 , which can be selected for different electronics devices and other applications. 
     In general, the relative alumina and silica or silica glass concentrations may be defined on a mass or volume basis. In addition, other materials may also be present, for example iron, titanium, chromium, copper, magnesium and other metals in the sapphire or alumina components, and soda, lime, or dolomite in the silica glass components, along with various fining agents and other processing components. 
     In general, the use of sapphire materials provides substrate  200  with substantially increased hardness, as compared to silica-based glass and other materials. For example, substantially single-crystal forms of sapphire glass may have a hardness of up to about 2000 points on the Vickers scale (about 19.6 GPa), or in a range of about 1800-2300 points on the Vickers scale (about 27.7-22.5 GPa). Alternatively, sintered polycrystalline forms of alumina or sapphire glass may have a Vickers hardness of about 1200-2000 points on the Vickers scale (about 11.8-19.6 GPa), depending on grain size, and fused amorphous forms may have a hardness of about 1000-1200 points on the Vickers scale (about 9.8-11.8 GPa). 
     This compares to a typical range of about 500-700 points on the Vickers scale (about 4.9-6.9 GPa) for silica-based glass materials, depending on composition. For example, high silica glass (e.g., &gt;70% silica) may range up to 640-700 points on the Vickers scale (about 6.3-6.9 GPa), and leaded glass may range from about 500-560 points on the Vickers scale (about 4.9-5.5 GPa), based on a lead oxide content of about 18-40%. 
     Thus, sapphire and alumina-based materials provide greater hardness and strength for increased scratch and impact resistance, as applicable to electronics display and touch-screen applications. At the same time, however, oleophobic coatings and other polymer-based surface treatments  110  are subject to different chemical bonding processes on alumina and silica-based substrates  200 , and these different bonding properties may affect performance. 
     In abrasion tests, for example, some coatings and surface treatments  110  exhibit wear at a lower number of abrasive cycles when applied to sapphire glass and other alumina-based base layers  202  (e.g., less than 300 cycles), as compared to silica glass, where the coatings may not exhibit wear until a higher number of abrasive cycles (e.g., 300 cycles or more). In addition, surface treatments  110  applied to silica surface layers  206  may also exhibit wear at a substantially lower number of cycles when no transition layer  204  is present (e.g., 150-170 cycles or less), for example due to separation along the abrupt sapphire/silicate or alumina/silica transition. 
     To address these concerns, transition layer  204  is provided to create a substantially continuous or less discrete transition between base layer  202  and surface layer  206 , and to provide a combination of improved bonding and hardness properties. For example, transition layer  204  may be provided by sputtering a mixture of alumina and silica (or silica glass) onto base layer  202  of substrate  200 , where the composition varies from substantially 100% alumina (or amorphous sapphire) at base layer  202  to substantially 100% silica (or silica glass) at surface layer  206 . 
     Alternatively, the composition of transition layer  204  may vary, as described above and below. Other deposition and surface treatment processes may also be used, including, but not limited to, electron beam and physical vapor deposition, electron beam evaporation, ion implantation, and particle vapor deposition. 
       FIG. 2B  is a cross-sectional schematic view of substrate  200 , in a sapphire or sapphire glass embodiment with an oleophobic coating  110 . In this particular configuration, base layer  202  is formed of a substantially single-crystal sapphire or sapphire glass material, and alumina/silica transition layer  204  includes surface layer  206  with oleophobic coating  110 . 
     The composition of transition layer  204  varies, depending on application. For example, transition layer  204  may transition from about 50% or more alumina content at base layer  202  to more than 50% silica or silica glass content at surface layer  206 , e.g., from about 80-90% or about 90-100% alumina content to about 80-90% or about 90-100% silica or silica glass content. Alternatively, the relative proportions of alumina and silica (or silica glass) may vary between these ranges, for example in a ratio of about 30%/70%, about 40%/60%, about 50%/50%, about 60%/40% or about 70%/30%, in either order (that is, alumina/silica or silica/alumina), depending on desired bonding and hardness properties at base layer  202  and surface layer  206 . 
     In some embodiments, surface layer  206  may have substantially uniform composition. For example, surface layer  206  may provide transition layer  204  with a thickness of substantially 100% silica or silica glass, or surface layer  206  may provide transition layer  204  with a thickness of a substantially uniform mixed silica or silica glass and alumina composition, at any of the composition ratios above, or at another value therebetween. Alternatively, surface layer  206  may be absent, or provided as a separate layer, distinct from transition layer  204 . 
     The total thicknesses of transition layer  204  (T 1 ), including any surface layer  206  (T 2 ) also varies, depending on application. In general, where transition layer  204  has a substantial silica content, for example greater than 10% or greater than 50%, thickness T 1  may be selected to have a relatively low value and thickness T 2  may be nominal, in order to increase hardness near the outer (top) surface of substrate  200 , or to keep any scratches from showing. 
     For example, thickness T 1  of transition layer  204  may be about 10-50 nm, about 10-70 nm, or about 10-100 nm, or less than about 100 nm, less than about 70 nm, or less than about 50 nm. In these designs, thickness T 2  of surface layer  206  may be less than 10 nm, or surface layer  206  may be substantially a monolayer, such that surface layer  206  is defined approximately at the outer (top) interface of transition layer  204 , where surface treatment  110  is applied. Alternatively, surface layer  206  may have substantially no thickness, or surface layer  204  may be absent. 
     In additional embodiments, surface treatment or coating layer  110  may be applied in combination with one or both of transition layer  204  and surface layer  206 , so that surface layer  206  provides a thin interface comprising both an oleophobic coating (or other surface treatment  110 ) and a silica or silicat/alumina layer, as described above. In these applications, components of surface treatment layer  110  may extend into the surface of substrate  200 , for example into voids, cracks or spaces in surface layer  206 , transition layer  204 , or both. 
     Ion implantation techniques may also be utilized to improve the performance of substrate  200 . In an ion implantation process, the surface of substrate  200  is bombarded with ions, for example N+ (nitrogen) ions, providing a compressive stress layer of up to about 600 nm or more in thickness, for improved resistance to defect propagation. Such a layer may be provided, for example, in base layer  202 , transition layer  204 , surface layer  206 , or a combination thereof. 
       FIG. 3  is a schematic view of surface processing apparatus  207  for example as applied to substrate  200  of electronic device  100 , as described above. In this particular example, deposition system  207  includes one or more reservoirs  210  with various coating materials  208  (e.g., silica, alumina, and an oleophobic material or other surface treatment). An inert gas  212  (e.g., argon or nitrogen) may be supplied by gas source  216  through purge or pressurization flow pipe  214 , in order to reduce oxidation, wetting and contamination within reservoirs  210 . 
     Depending on design, reservoirs  210  are coupled to vacuum chamber  218  by one or more delivery tubes  222 , as configured to deliver materials  208  from reservoirs  210  to supply systems  220 . Supply systems  220  utilize a suitable combination of tubes, pumps, valves and other components to direct materials  208  into vaporizing or deposition units  226  for deposition onto substrate  200 , for example on outer surface  108  of a window  102  or bezel  104  on electronic device  100 , as described above with respect to  FIG. 1 . 
     In the particular configuration of  FIG. 3 , deposition units  226  are provided in the form of physical or chemical vapor deposition (CVD or PVD) components. Alternatively, other processes and components may be utilized, for example to treat substrate  200  by sputtering, electron beam deposition or electron beam evaporation, or a combination of such processes. 
     In general, supply systems  220  and deposition units  226  are controlled to deposit selected amounts of material (e.g., silica, silica glass, alumina, oleophobic materials and other surface treatments) onto substrate  200  in particular orders and combinations, as described above with respect to  FIGS. 2A and 2B . 
     Some materials  208  such as oleophobic ingredients and other coating materials may be provided in concentration, for example 10% to 100% in combination with a dilutant or solvent, and such materials may also be applied by dip coating or other direct application process. Alternatively, solid materials  208  such as silica, silica glass, and alumina may also be provided within one or more supply systems  220  or deposition units  226 , without reservoir  210  and other external components. 
     In some embodiments, surface treatment system  207  also controls pressure, temperature and humidity to operate chamber  218  as a vacuum chamber or other cemical of physical vapor deposition environment. Surface treatment system  207  may also maintain a particular temperature for the surface coating process, for example between about 100 C and about 150 C, or between about 100 C and about 170 C. Air may also be provided within chamber  218 , either during or after the coating process, in order to expose substrate  200  to atmosphere in a controlled process, before removal from chamber  218 . 
       FIG. 4  is a block diagram of method  300  for coating a substrate, for example substrate  200  for use in electronic device  100  as described above with respect to  FIGS. 1 ,  2 A,  2 B and  3 . Method  300  includes one or more steps selected from preparing a substrate (step  302 ), forming a transition layer on the substrate (step  304 ), and forming a surface treatment or coating on the substrate (step  306 ). Depending on application, the surface coating may be provided directly onto the transition layer, or on a transition layer including a surface layer (step  308 ). 
     Preparing the substrate (step  302 ) may comprise cleaning and other surface preparation steps, for example using water or a chemical solvent, heat treatment, polishing, and other surface preparation processes performed on base layer  202  of substrate  200 , as shown in  FIGS. 2A and 2B . In one particular embodiment, the substrate is formed of a substantially single crystal (e.g., synthetic) sapphire, which may be cut to size for a particular application, for example a synthetic sapphire blank for a bezel  104 , window  102  or other component of a mobile phone or other portable electronic device  100 , as shown in  FIG. 1 . 
     Alternatively, a different sapphire, sapphire glass or alumina substrate may be utilized, for example including amorphous or polycrystalline alumina components. Preparing the substrate may also comprise ion implantation, as described above, for example after polishing the surface of the base layer, or after formation of the transition layer and any surface layer. 
     Forming a transition layer (step  304 ) may comprise sputtering, physical or chemical vapor deposition, or other material process to provide a transition from the base layer composition of the substrate to another material composition, as described above for transition layer  204  of  FIGS. 2A and 2B . The transition layer may have an amorphous or polycrystalline structure, so that there is a physical or structural transition at the interface to a substantially single-crystal base layer. 
     Depending on application, the material transition may nonetheless be continuous, for example from substantially 100% alumina at the base layer, transitioning substantially continuously to about 100% silica or silica glass at the surface layer, as described above. Alternatively, the transition layer may extend from a region of substantially 100% alumina to a region of less than 100% silica or silica glass at the surface layer, for example between about 10% and about 50% alumina and about 50% to about 90% silica or silica glass. 
     There may also be a discontinuous transition in the material composition of the transition layer, for example from substantially 100% alumina in the base layer to a relative concentration of about 90% to about 100% alumina at the base layer/transition layer interface. Alternatively, the transition layer may have a concentration of about 50% to about 90% alumina at the base layer, or between about 10% and about 90% alumina. 
     Forming a surface treatment (step  306 ) may be performed via physical vapor deposition or other processes, as described above, for example to provide surface treatment layer  110  on transition layer  204  or surface layer  206  of substrate  200 , as shown in  FIGS. 2A and 2B . In one particular embodiment, the surface treatment comprises an oleophobic coating material, for example perfluorinated hydrocarbon chain of a polymer with a perfluorinated hydrocarbon end group. Alternatively, a hydrophobic coating may be applied. 
     In these various embodiments, the coating material may also include an end group that bonds preferentially to silca, as compared to alumina. For example, an OH modified polymer or silane material may be used, or an alkyl end group or other suitable end group that preferentially bonds to the silica component of the transition layer (or surface layer), as compared to the alumina component. 
     The surface coating may thus be provided directly on the transition layer, or on a surface layer formed over or as part of the transition layer (step  308 ), for example surface layer  206  as shown in  FIGS. 2A and 2B . Depending on application, the surface layer may be provided as a substantially 100% silica or silica glass layer, in order to improve bonding to the surface coating. Alternatively, the surface layer may have mixed composition, for example between about 90% and about 100% silica, or between about 50% and about 90% silica, with a corresponding alumina content. 
     In addition, the surface layer may have a thickness of up to 10 nm or more, for example about 10-20 nm or about 10-50 nm. Alternatively, the surface layer may be relatively thin, for example 10 nm or less, or the surface layer may be absent. Depending on application, the surface layer may also be defined as a monolayer or other thin layer on the top surface of the transition layer. Thus, the surface coating may be applied directly to a transition layer, to a surface layer that is part of a transition layer, or to a separate surface layer. 
     While embodiments herein are described with reference to exemplary embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted in order to adapt these teachings to particular materials, structures, methods and applications, without departing from the essential scope and sprit of the invention as claimed. The invention is thus not limited to the particular examples that are disclosed herein, but encompasses all embodiments falling within the scope of the appended claims.

Metadata:
Filing Date: 20130923
Publication Date: 20150310
Grant Date: 20150310
Priority Date: 20120921
Inventors: WEBER DOUGLAS
MATSUYUKI NAOTO
Assignee: APPLE INC
CPC Classifications: [{"code": "G02B1/18", "inventive": true, "first": true, "tree": "[]"}, {"code": "G02B1/105", "inventive": true, "first": true, "tree": "[]"}, {"code": "H04M1/0202", "inventive": true, "first": false, "tree": "[]"}, {"code": "H04M1/0202", "inventive": true, "first": false, "tree": "[]"}, {"code": "G06F1/1637", "inventive": false, "first": false, "tree": "[]"}, {"code": "G06F1/1637", "inventive": false, "first": false, "tree": "[]"}, {"code": "G02B1/18", "inventive": true, "first": true, "tree": "[]"}, {"code": "Y10T428/31663", "inventive": false, "first": false, "tree": "[]"}, {"code": "Y10T428/31663", "inventive": false, "first": false, "tree": "[]"}]
Family ID: 49274895