Title of Invention

A HYDROPHOBIC COATING FOR A GLASS, CERAMIC OR VITROCERAMIC SUBSTRATE

Abstract

The invention relates to a hydrophobic coating for a glass, ceramic or vitroceramic substrate, characterized in that it comprises two layers: a priming layer directly applied onto said substrate and comprising groups Si-R3-Si, R3 being chosen from the group constituted by linear, branched or aromatic, preferably linear, alkyl chains in which the number of carbons establishing the bond between the two silicon atoms is less than 6 and is preferably between 1 and 4, a coating layer in connection with said priming layer and comprising an alkylsilane with a hydrophobic/oleophobic perfluorinated end group. The invention also relates to a process for obtaining such a coating on a substrate as described previously, and also to the substrate itself, of the monolithic, laminated or multiple glazing type, equipped on at least part of at least one of its surfaces with said coating.

Full Text

HYDROPHOBIC COATING COMPRISING A PRIMING INCLUDING A BIS-SILANE AND A HYDROPHOBIC LAYER INCLUDING A FLUORINATED ALKYLSILANE The present invention relates to the hydrophobic/oleo- phobic treatment of a substrate, especially constituted by a glass, ceramic, vitroceramic, etc. material. The glazing according to the invention is, for example, glazing made of glass. It is used, in particular, in the aeronautics, railway or automotive fields. It may also be used in the construction field or in the interior furnishing field, for instance decorative panels, for furnishing, household electrical goods (refrigerator doors, oven doors, windowpanes), etc. This type of treatment is directed, in a known manner, toward giving the substrate the non-wettabi.l.i ty character also known as rain repellency. The term "wettability" denotes the property according to which polar or nonpolar liquids adhere to the substrate and form an impeding film, and aJ so the tendency of a substrate to retain dust or soiling of any nature, finger marks, insects, etc. The presence of water and/or soiling is a nuisance in particular for a transparent substrate of the glazing type, especially used in the transportation field. The non wettability property of a substrate, more commonly referred to as the hydrophobicity/oleo- phobicity, is proportionately greater the higher the contact angles between a hydrophilic or oleophilic liquid and this substrate, for example at least 90° for water. The liquid then has a tendency to flow easily, in the form of drops, on the substrate, by simple gravity if the substrate is inclined, or under the effect of aerodynamic forces in the case of a vehicle - 2 - in motion. Known agents for imparting this hydrophobicity/oleophobicity property are, for example, fluorinated alkylsilanes as described in patent applications EP 0 492 417, EP 0 492 545 and EP 0 672 779. According to these documents, this layer may bo obtained by applying to the surface of a substrate a solution containing fluorinated organosilanes in a nonaqueous organic solvent. As nonaqueous organic solvent, document EP 0 4 92 545 in particular mentions n hexadecane, toluene, xylene, etc. These solvents are particularly suitable for a fluorinated chlorosilane. It is also possible, according to said document, to use a methyl or ethyl alcohol as solvent when the fluorinated silane is a fluorinated alkoxysilane. Common hydrophobic/oleophobic agents are, in particular, alkylsilanes in which the alky] group comprises at least one perfluorinated end, i.e. consisting of a group F3C-(CF2)n-, in which n is a positive integer or zero. For these, patent application EP 0 719 743 indicates perfluorinated carbons and suitable solvents. One of the problems most acutely perceived in the field of the invention is firstly that of abrasion of the hydrophobic/oleophobic coating. This abrasion takes place to a greater or lesser extent in the course of cleaning of the substrate, which is periodically essential in particular for restoring satisfactory vision through a transparent substrate. It is therefore continually sought to slow down the gradual removal of the hydrophobic/oleophobic coatings of the abovementioned types, which takes place especially under the action of windshield wipers in the case of a motor vehicle windshield. Moreover, such a removal may also result from degradation by ultraviolet radiation. It is also known practice from the abovementioned patent application EP 0 492 545 A2 to increase the - 3 - adhesion of the hydrophobic/oleophobic coating by- subjecting the substrate to a priming treatment before applying the coating. This treatment consists in forming a thin intermediate layer using "priming agents" or "primers", which are silicon compounds containing at least two hydrolyzable functions. In a known manner, one of the two hydrolyzable functions enables chemical bonding to the substrate via an oxygen atom linked to the silicon atom; the second hydrolyzable function enabling the fixing of the hydrophobic/oleophobic agent. The compounds SiCl4, SiHCl3, SiH2Cl2 and CI- (SiCl20) nSiCl3, n being an integer between 1 and 4, are mentioned in patent application EP 0 492 545 A2 as priming agents. Patent EP 944 687 more particularly describes rain- ropellent coatings developed via a liquid route and comprising a priming layer or sublayer based on silica sol gel obtained from a precursor of the Si(OEt)4 or S.LC 1-4 type and a functional layer based on perfluoro- aIkylsilane. In order to further improve the mechanical strength properties of the hydrophobic coating, patent EP 1 102 825 describes a composition for a hydrophobic/ oleophobic coating incorporating in the same layer both a fluorinated alkylsilane and a bis-silane. However, although such sublayers make it possible to obtain performance qualities that are in accordance with the vast majority of the current UV and mechanical strength specifications, for instance those imposed by motor vehicle constructors, especially with respect to abrasion, they do not generally have sufficient chemical inertness typically allowing them to satisfy salt corrosion resistance criteria. in particular, the tests conducted by the Applicant have demonstrated that, in the majority of cases, such - 4 - coatings have difficulty in satisfying the technical specifications imposed in the field by motor vehicle constructors .and measured, for example, via the Neutral Saline Fog (NSF) resistance test according to standard NF ISO 9227. Thus, the coatings described in patent applications EP 944 687 and EP 1 102 825, the UV resistance and mechanical strength properties of which wore found to be satisfactory, show insufficient saline corrosion performance, as measured by the NSF test. This insufficiency may limit their development, in particular in the Asiatic market where the standards arc tighter in this field. The main subject of the present invention is coatings that are not only resistant to abrasion and to UV radiation, but also show substantial chemical inertness, i.e. typically allowing them to satisfy the technical specifications currently imposed by the automotive industry, both in terms of abrasion and UV resistance and saline corrosion resistance. The coatings according to the present invention also have performance qualities substantially equal to those of the coatings known at the present time as regards the other specifications necessary for their various uses, for instance mechanical strength, water resistance, etc. To this end, according to a first aspect, a subject of the invention is a process for obtaining a hydrophobic/ oleophobic coating on a substrate preferably constituted of a glass, ceramic or vitroceramic material, said process being characterized in that it comprises: a) a first step that consists in applying to said substrate a first priming layer obtained from a priming agent of formula: (X1)3-q(R1)qSi-R3-Si(X2)3_q, (R2)q- in which Si is silicon; - 5 - R3 represents a linear, branched or aromatic, preferably linear, carbon-based chain in which the number of carbons establishing the bond between the two silicon atoms is less than 6 and is preferably between 1 and 4; R1 and R2 each represent an alkyl group or a hydrogen atom; X1 and X2 are identical or different hydrolyzable groups; q and q' are equal to 0 or 1 and are preferably 0, and b) a second step of depositing onto said first layer a hydrophobic coating comprising at least one fluorinated alkylsilane. For the purposes of the present description, the expression "number of carbons establishing the bond between two silicon atoms" means the smallest number of carbon atoms allowing the linear junction between two silicon atoms, rather than the total number of carbon atoms placed between the two silicons. This definition is especially relevant when a branched or aromatic-ring group is present therebetween. By way of example, this number of carbons is equal to 8 in the case of the bis si lylethyIbenzene described in example 8. In general, X1 and X2 are alkoxy groups, preferably methoxy or ethoxy, or halide groups. The step of depositing the hydrophobic coating is performed, for example, using a solution obtained from a porfluoroalkylsilane of the type represented by the general formula: F3C- (CF2)m- (CH2)n-Si(X)3-p(R)P in which: m = 0 to 15, preferably 5 to 9; n - 1 to 5, preferably n = 2 ,- p = 0, 1 or 2, preferably 0 or 1 and most preferably 0; - 6 - R is an alkyl group or a hydrogen atom; and X is a hydrolyzable group such as a halide group or an alkoxy group. According to one alternative mode, the step of depositing the hydrophobic coating is performed using a solution obtained from a perfluoroalkylsilane of the perfluoropolyethersilane type, as described, for example, in patent EP 844 265 or in patent application US 2004/0 247 886 or patent US 6 649 272 B2. Preferably, said perfluoropolyethersilane is of the type represented by the general formula: or by the general formula in which: m = 2 to 30; n = 1 to 3, preferably n = 1; p = 0, 1 or 2, preferably 0 or 1 and most preferably 0; R is an alkyl group or a hydrogen atom; and X is a hydrolyzable group such as a halide group or an alkoxy group. According to a second aspect, the present invention relates to the hydrophobic coating that may be obtained by performing the process as described previously. The invention more particularly relates to a hydrophobic coating for a glass, ceramic or vitro- ceramic substrate, and comprising: a priming layer directly applied onto said - 7 - substrate and comprising groups Si-R3-Si, R! being chosen from the group constituted by linear, branched or aromatic, preferably linear, alkyl chains in which the number of carbon atoms establishing the bond between the two silicon atoms is less than 6 and is preferably between 1 and 4, a coating layer in connection with said priming layer and comprising an alkylsilane with a hydrophobic/oleophobic perfluorinated end. According to a first mode, said alkylsilane is of the type represented by the general formula: with : m = 0 to 15, preferably 5 to 9 ; n = 1 to 5, preferably n = 2. According to ' a second mode, said alkylsilane comprises a group of the perfluoropolyether type. Preferably, said alkylsilane is of the type represented by the general formula: or by the general formula: in which - m = 2 to 30, n. = 1 to 3; preferably n = 1. The hydrophobic layer may also comprise or may be constituted by a mixture of an alkylsilane with a perf luorinated end according to the first mode and of an alkylsilane comprising a perfluoropolyether group according to the second mode, as described, for example, in patent application EP 1 229 085. - 8 - For example, the thickness of the priming layer is between 1 and 2 0 nm and preferably between 2 and 5 nm. The thickness of the coating layer may be between 1 and 10 nm and preferably between 1 and 5 nm. Another subject of the invention consists of a product whose outer surface, usually constituted by a glass, ceramic or vitroceramic material or a natural mineral material, is at least partly equipped with a hydrophobic/oleophobic coating as described previously or obtained from a process as described previously. The product of the invention is, for example, monolithic, laminated or multiple glazing. It is pointed out that these terms are defined as fo1 Lows: "monolithic glazing": glazing constituted by a single pane of glass; "Laminated glazing": a stack of several panes solidly fastened together, for example of glass or plastic panes fixed together by means of polyvinyl butyral, polyurethane, etc. adhesive layers; and "multiple glazing": an assembly of disjointed panes, i.e. of panes especially separated from each other by layers of air. The advantage of the hydrophobic/oleophobic coating of the invention for products of this type is twofold. F.i rstly, it allows drops of water or of other liquid to flow on vertical or inclined surfaces, under the effect, as the case may be, of aerodynamic forces, for example in the case of a vehicle in motion. Furthermore, these drops that flow incorporate soiling and entrains it. The visibility through the glazing is. - 9 - improved to a degree such that, in certain cases, cleaning devices (windshield washers, windshield wipers) may be dispensed with. Finally, a 'subject of the invention is also the applications of the product described previously: as glazing for a transportation vehicle (motor vehicle side windows, aviation or motor vehicle windshield) or for buildings; as vitroceramic cooking hobs or oven doors,- as a component of urban furnishing, especially such as a bus shelter component; and as a furnishing component, especially such as a mirror, a storage tray, a tray for a household electrical appliance such as a refrigerator, a shower cabin component or a partition wall; as a screen, especially a television screen, a touch screen or a plasma screen. The examples that follow serve to illustrate the invention without, however, limiting its scope, in any of the described aspects. In these examples, all the percentages are given on a mass basis. EXAMPLE 1 According to this example, a first sample El in accordance with the invention is prepared. 0.3% of bis(triethoxysilyl)ethane (CH,0)3Si (CH2)2Si (OCH3)3 is added to a solution comprising 90% isopropanol and 10% 0. 3N hydrochloric a c i d . In parallel, a solution containing 3% of perfluoro- dccyltriethoxysilane CF3 (CF2) 7 (CH2) 2Si (OC2H5) 3 in an isopropanol (90%)/0.3N hydrochloric acid (10%) mixture is prepared. The two solutions are stirred for - 10 - 1b minutes. According to a first deposition step, the bis(tri cthoxysilyl)ethane-based solution is then deposited by wiping (4 crossed sweeps) over the air face of a glass substrate polished beforehand using a cerium oxide solution and then rinsed thoroughly with demineralized water. The thickness of the priming layer thus obtained is about 4 nm. Once the sublayer has been deposited, the perfluoro- dccyltriethoxysilane solution is in turn deposited via the same wiping technique. In this example and in the following examples, the deposition of the various layers is performed via the well-known technique of wiping, in which the material or its precursor is deposited by means of a soaked cloth. Needless to say, it, would not, however, constitute a departure from the scope of the invention if the deposition were to be performed by any other technique known for this purpose in the field, in particular by spraying, which moreover al lows better control of the thickness of the layers, by centrifugation, according to processes known in the art under the term "spin-coating", by dip-coating or by f: 1 ow-coating. After a leave-on time of 15 minutes at room temperature, the excess fluorosilane is removed by cleaning with isopropanol. The thickness of the layer obtained is about 4 nm. As a variant, another sample E2 was prepared using the same reagents and techniques, the difference being that the successive depositions were performed this time on the tin face of the glass substrate. EXAMPLE 2: The same steps as previously are repeated for the preparation of a second sample E3, but the glass - 11 - substrate is treated this time on its air face with a priming solution of Si(OCH3)4 at 0.4% by weight in a solution of 90% by weight of ethanol and 10% by weight of water, during the first deposition step. The substrate thus coated with the sublayer is then placed in contact at room temperature with a solution containing 3% of CF3 (CF2) 7 (CH2) 2Si (OC2H5) 3 in a mixture of 90% ethanol and 10% water, acidified with 0.3N HC1. EXAMPLE 3: A third sample E4 is prepared according to a method identical to the previous methods and in accordance with the teachings of patent EP 1 102 825. The glass substrate, identical to the one used in the preceding examples and having undergone the same preparation on its air face, is treated with a priming solution of Si(OCH3)4 at 0.4% by weight in a solution of 90% by weight of ethanol and 10% by weight of water. The substrate and its priming are then placed in contact at room temperature with a solution of CI.', (CF2)7(CH2)2Si(OC2H5)3 and (CH30) 3Si (CH2) 2Si (OCH3) 3 in respective proportions of 3% and 1% by weight in a mixture of 90% by weight of ethanol and 10% by weight of water, acidified with 0.3N HC1. EXAMPLE 4: The four samples El, E2, E3 and E4 prepared according to examples 1 to 3 are evaluated according to the following criteria: 1) measurement of the initial contact angle of water, which gives a reference indication of the hydrophobic nature of the grafted substrate; 2) the abrasion resistance, obtained by measuring the residual contact angle of water on the sample after the grafted hydrophobic/oleophobic coating has undergone - 12 - abrasion according to two different tests: a) the Opel® friction test, performed on the samples with a felt of hardness HI, a load of 0.4 kg/cm2 on a surface of 1.5 cm2, with a translation speed of b0 cycles/minute and a rotation speed of 6 rpm. A sample is judged to be satisfactory in the test if the contact angle remains greater than 80° after 5000 cycles; b) the Toyota® friction test, performed according to standard TSR7503G, with a load of 0.3 kg/cm2 on a surface of 4 cm2 with a translation speed of 4 0 cycles/minute and using a device manufactured by the company Daiei Kagaku Seiki. A sample is judged to be satisfactory if the contact angle remains greater than 80° after 1500 cycles; 3) the UV-A radiation resistance, measured via tests of continuous illumination of the samples with a xenon Lamp emitting UV radiation whose integrated lighting between 300 and 400 nm is 60 W/m2. A sample is judged to be satisfactory in the test if the contact angle remains greater than 80° after 2 000 hours of exposure; 4) the saline corrosion resistance, measured according to the Neutral Saline Fog (NSF) test as described according to standard NF ISO 9227. The test consists in spraying fine droplets of saline water (NaCl solution at 5 0 g/1, of pH = 7) at a temperature of 35°C. The samples are inclined at 20° relative to the vertical. The strictest standard currently in force for an application on motor vehicle side windows demands a contact angle of water of greater than 70° after 3 00 test hours. The results obtained for the samples prepared in accordance with examples 1 to 3 are collated in table 1: - 13 - Sample Initial contact angle Angle after Opel test (5000 cycles) Angle after Toyota test (1500 cycles) Angle after UV-A test (2000 hours) Angle after NSF test 300 h 600 h E1 105° >95° >90° >8 5° >85° >80° R2 105° >95° >90° >85° >95° >85° K3 105° >95° 85° K4 105° >95° 85° Table 1 Comparison of the data collated in table 1 shows that the presence of a priming sublayer in accordance with the invention leads to initial rain-repellency properties of the treated surface that are identical to those obtained with the priming of the prior art. Similarly, the abrasion- and UV-resistance properties arc substantially identical, as shown by the results obtained in the Opel® test, the Toyota® test and the UV test on the various samples. Samples El and E2 comprising the hydrophobic/oleophobic coating according to the invention show a saline corrosion resistance, measured via the NSF test, that is considerably better than that of the coatings known hi Lherto. EXAMPLES 5 TO 8: These examples show the influence of the nature of the alkyl chain R3 present between the two silicon atoms in the bis-silane used for the priming layer on the properties of the hydrophobic coating finally obtained. The experimental protocol is the same as that described in example 1, except that the precursor used to obtain the priming layer is replaced in the following manner. - 14 - Example b-. preparation of a sample E5 using bis (tri~ ct.hoxysilyl) methane (CH30) 3Si (CH2) Si (OCH3) 3 Example 6: preparation of a sample E6 using bis(tri cLhoxysiJy.1.) hexane (CH30) 3Si (CH2) 6Si (OCH3) 3 Example 7: preparation of a sample E7 using bis(tri- othoxysilyl)octane (CH30) 3Si (CH2) 8Si (OCH3) 3 Example 8: preparation of a sample E8 using bis(tri~ ethoxysilylethyl)benzene (CH2) 2Si (OCH3)3, in which is a benzene ring. The results obtained for the various tests are collated in table 2: Sample Initial contact angle Angle after Opel test (5000 cycles) Angle after Toyota test (1500 cycles) Angle after UV-A test (2000 hours) Angle after NSF test 300 h 600 h E5 105° >95° >90° >85° >90° >80° E6 105° 85° >95° >85° K7 105° 85° >95° >85° K8 105° 85° >85° >75° Table 2 It is noted that the increase in the length of the alkyl chain R3 does not influence the saline corrosion resistance qualities. On the other hand, the abrasion resistance tests are less favorable when the linear carbon-based chain comprises 6 or more carbon atoms. - 15 - CLAIMS 1 . A process for obtaining a hydrophobic/olcophobic coating on a substrate preferably constituted of a glass, ceramic or vitroceramic material, said process being characterized in that it comprises: a) a first step that consists in applying to said substrate a first priming layer obtained from a priming agent of formula: (X1)3.-q(R1)qSi-R3-Si(X2)3-q' (R2)cr in which Si is silicon; R3 represents a linear, branched or aromatic, preferably linear, carbon-based chain in which the number of carbons establishing the bond between the two silicon atoms is less than 6 and is preferably between 1 and 4; R1 and R2 each represent an alkyl group or a hydrogen atom; Xa and X2 are identical or different hydrolyzable groups; q and q' are equal to 0 or 1 and are preferably 0, and b) a second step of depositing onto said first layer a hydrophobic coating comprising at least one fluorinated alkylsilane. 2. The process as claimed in claim 1, in which X1 and X' are alkoxy groups, preferably methoxy or ethoxy, or ha .1 i.de groups . 3. The process as claimed in claim 1 or 2, characterized in that the step of depositing the hydrophobic coating is performed using a solution obl.ained from a perfluoroalkylsilane of formula: F3C- (CF2)m- (CH2)n-Si(X)3.p(R)p in which: m = 0 to 15, preferably 5 to 9; n = 1 to 5, preferably n = 2; - 16 - p = 0, 1 or 2, preferably 0 or 1 and most preferably 0; R is an alkyl group or a hydrogen atom; and X is a hydrolyzable group such as a halide group or an alkoxy group. 4. The process as claimed in claim 1 or 2, characterized in that the step of depositing the hydrophobic coating is performed using a solution obtained from a perfluoroalkylsilane of the porfluoropolyethersilane type. b. The process as claimed in claim 4, in which said porfluoropolyethersilane is of formula: or of formula in which: m = 2 to 30; n = 1 to 3, preferably n = 1; p = 0, 1 or 2, preferably 0 or 1 and most preferably 0; R is an alkyl group or a hydrogen atom; and X is a hydrolyzable group such as a halide group or an alkoxy group. 6. A hydrophobic coating that may be obtained by performing a process as claimed in one of claims 1 to b. 7. A hydrophobic coating for a glass, ceramic or v.i troceramic substrate, characterized in that it comprises: a priming layer directly applied onto said - 17 - substrate and comprising groups Si-R3-Si, R3 being chosen from the group constituted by linear, branched or aromatic, preferably linear, alkyl chains in which the number of carbons establishing the bond between the two silicon atoms is less than 6 and is preferably between 1 and 4, a coating layer in connection with said priming layer and comprising an alkylsilane with a hydrophobic/oleophobic perfluorinated end group. 8. The hydrophobic coating as claimed in claim 7, in which said alkylsilane with a perf luorinated end group is of the type represented by the general formula: F3C-(CF2)m-(CH2)n-Si with : m -= 0 to 15, preferably 5 to 9; n - 1 to 5, preferably n = 2. 9. The hydrophobic coating as claimed in claim 7, in which said alkylsilane containing a perfluorinated end group comprises a group of the perfluoropolyether type. 10. The hydrophobic coating as claimed in claim 9, in which said alkylsilane is of the type represented by the general formula: or by the general formula: in which: m = 2 to 30; n = 1 to 3, preferably n = 1. 11. The hydrophobic coating as claimed in claim 7, in which the hydrophobic coating layer comprises or is constituted by the mixture of an alkylsilane as claimed in claim 8 and of an alkylsilane as claimed in claim 9 - 18 - or 10. 12. The hydrophobic coating as claimed in one of claims 6 to 11, in which the thickness of the coating layer is between. 1 and 10 nm and preferably between 1 and 5 nm. 13. A product whose outer surface, for example constituted by a glass, ceramic or vitroceramic material, is at least partly equipped with a hydrophobic/oleophobic coating as claimed in one of claims 7 to 12 or obtained from a process as claimed in one of claims 1 to 5. 1/1. The product as claimed in claim 13, consisting of monolithic, laminated or multiple glazing. lb. The application of a product as claimed in either of claims 13 or 14 as glazing for a transportation vehicle or for buildings. 16. The application of a product as claimed in claim 13 or 14 as a vitroceramic cooking hob or an oven door. 17. The application of a product as claimed in either of claims 13 and 14 as a component of urban furnishing, especially such as a bus shelter component, as a furnishing component, especially such as a mirror, a storage tray, a tray for a household electrical appliance such as a refrigerator, a shower cabin component or a partition wall, or as a screen, especially a television screen, a touch screen or a plasma screen. Dated this 24th day of JANUARY 2008 The invention relates to a hydrophobic coating for a glass, ceramic or vitroceramic substrate, characterized in that it comprises two layers: a priming layer directly applied onto said substrate and comprising groups Si-R3-Si, R3 being chosen from the group constituted by linear, branched or aromatic, preferably linear, alkyl chains in which the number of carbons establishing the bond between the two silicon atoms is less than 6 and is preferably between 1 and 4, a coating layer in connection with said priming layer and comprising an alkylsilane with a hydrophobic/oleophobic perfluorinated end group. The invention also relates to a process for obtaining such a coating on a substrate as described previously, and also to the substrate itself, of the monolithic, laminated or multiple glazing type, equipped on at least part of at least one of its surfaces with said coating.

Documents:

00336-kolnp-2008-abstract.pdf

00336-kolnp-2008-claims.pdf

00336-kolnp-2008-correspondence others.pdf

00336-kolnp-2008-description complete.pdf

00336-kolnp-2008-form 1.pdf

00336-kolnp-2008-form 2.pdf

00336-kolnp-2008-form 3.pdf

00336-kolnp-2008-form 5.pdf

00336-kolnp-2008-gpa.pdf

00336-kolnp-2008-international publication.pdf

00336-kolnp-2008-international search report.pdf

00336-kolnp-2008-pct request form.pdf

336-KOLNP-2008-(07-08-2012)-ABSTRACT.pdf

336-KOLNP-2008-(07-08-2012)-ANNEXTURE TO FORM-3.pdf

336-KOLNP-2008-(07-08-2012)-CLAIMS.pdf

336-KOLNP-2008-(07-08-2012)-DESCRIPTION (COMPLETE).pdf

336-KOLNP-2008-(07-08-2012)-EXAMINATION REPORT REPLY RECIEVED.pdf

336-KOLNP-2008-(07-08-2012)-FORM 1.pdf

336-KOLNP-2008-(07-08-2012)-FORM 2.pdf

336-KOLNP-2008-(07-08-2012)-OTHERS.pdf

336-KOLNP-2008-(07-08-2012)-PETITION UNDER RULE 137.pdf

336-KOLNP-2008-(09-12-2014)-ABSTRACT.pdf

336-KOLNP-2008-(09-12-2014)-CLAIMS.pdf

336-KOLNP-2008-(09-12-2014)-CORRESPONDENCE.pdf

336-KOLNP-2008-(09-12-2014)-FORM-1.pdf

336-KOLNP-2008-(09-12-2014)-FORM-2.pdf

336-KOLNP-2008-(09-12-2014)-PETITION UNDER RULE-137.pdf

336-kolnp-2008-(16-10-2014)-CORRESPONDENCE.pdf

336-KOLNP-2008-CORRESPONDENCE OTHERS 1.1.pdf

336-KOLNP-2008-CORRESPONDENCE.pdf

336-kolnp-2008-form 18.pdf

336-KOLNP-2008-PRIORITY DOCUMENT.pdf