WO2022223934A1

WO2022223934A1 - Method for coating textile materials

Info

Publication number: WO2022223934A1
Application number: PCT/FR2022/050764
Authority: WO
Inventors: Wanxian Wang; Thu-Hoa Tran-Thi; Guillaume LE CHEVALLIER; Justine AGAUD
Original assignee: Commissariat A L'energie Atomique Et Aux Energies Alternatives; Centre National De La Recherche Scientifique - Cnrs -; Europrotect France Sa
Priority date: 2021-04-22
Filing date: 2022-04-21
Publication date: 2022-10-27
Also published as: FR3122190A1; EP4326938A1

Abstract

The invention relates to a method for coating a textile material, said method comprising the following steps: a) at least one cycle of impregnating the textile material with a sol-gel adhesion formulation, said sol-gel adhesion formulation being free of polycarboxylic acid; b) at least one cycle of drying the impregnated textile material obtained in step a); c) at least one cycle of impregnating the dried textile material obtained in step b) with an omniphobic or hydrophobic sol-gel formulation comprising sulphamic acid, said omniphobic or hydrophobic sol-gel formulation being different from the sol-gel adhesion formulation; d) at least one cycle of drying the impregnated textile material obtained in step c).

Description

Title: Process for coating textile materials Technical field

The present invention relates to a new process for coating textile materials for the preparation of textiles having high level omniphobic properties and resistance to at least 30 washes without loss of these properties.

Prior technique

[0002] Protective clothing against splashes of liquids containing corrosive and/or toxic chemicals (acidic or basic aqueous solutions, oils, hydrophilic or hydrophobic organic solvents) must have, depending on the applications, oleophobic properties and/or or hydrophobicity, the combination of its two properties on a material leads to a material that can be described as omniphobic.

[0003] To make clothing coatings omniphobic, that is to say both hydrophobic and oleophobic, the textile industry currently uses a formulation of fluorinated resins containing perfluorooctanoic acid and/or its salts. However, these compounds, which are released into the biosphere during washing of clothes, are carcinogenic and toxic to the biosphere. The REACH regulations (in English: "Registration, Evaluation, Authorization and restriction of Chemicals") will restrict, from July 4, 2023, for the PPE sector (personal protective equipment), the presence of perfluorooctanoic acid (PFOA). ) and its salts. Since April 8, 2020, European regulations have extended the ban to compounds related to PFOA such as perfluorooctane sulfonic acid and its derivatives (PFOS), C8F17S0 ₂ X (X= OH, metal salt, halide, amide and other derivatives y including polymers) which will make the use of fluorinated resins with long chains (at least 8 carbons) impossible. [0004] For the past ten years, in anticipation of the entry into force of this regulation, manufacturers and the scientific community have focused their attention on alternative solutions. However, it is very difficult to obtain both the water-repellent and oil-repellent properties, these being antagonistic. Indeed, if the presence of long hydrocarbon chains can be enough to make a fabric hydrophobic, these attract low polar compounds such as oils. On the other hand, if the coating is very polar, the fabric is oleophobic but is hydrophilic and attracts polar compounds such as water. Thus, the results of the literature show that it is known with hydrophobic coatings to obtain water repellency while allowing oils and aliphatic hydrocarbons to pass. Similarly, it is known to obtain water repellency with oils with a hydrophilic coating that lets water through. These coatings can then be used for the separation of water and oils.

[0005] The research field of hydrophobic and/or oleophobic coatings has been expanding rapidly since the 2000s. However, analysis of data from the literature shows that advances in the field of oleophobic and/or hydrophobic clothing do not meet still meet the very strict specifications required by the textile industry, particularly for protective clothing (firefighters, infantrymen, law enforcement, industrial workers). The level of oil repellency of the new textile must reach index 4, preferably index 5, even more preferably index 6 and be maintained at a minimum after 10 washes, preferably after 20 washes, even more preferably after 30 washes . According to the IS014419 standard, the indices from 1 to 8 correspond to an oil repellency reached with white mineral oil (1), the mixture white mineral oil: n-hexadecane at 65:35% by volume (2), n- hexadecane (3), n-tetradecane (4), n-dodecane (5), n-decane (6), n-octane (7) and n-heptane (8), respectively. Index 6 therefore corresponds to oleophobia with n-decane.

For oil repellency indices between 4 and 6, omniphobic and water-repellent coatings find an interest in consumer products, such as rainwear, non-soiling clothing for workers, or children's clothing. Omniphobic coatings with the highest oil repellency indices, in particular equal to or greater than 6, are particularly suitable for personal protective equipment for armies, police, firefighters and industry.

[0006] A large number of works on superhydrophobicity and superoleophobicity bring into play the surface nanometric texturing effect to reduce the points of contact between the water drops and the surface (LOTUS effect). But applying the LOTUS effect to textile coatings has proven to be complex because it is unsuitable for the textile industry. Indeed, not only the surface of the textiles is not flat but moreover these last are differentiated either by the composition of the materials (aramid, viscose, polyamide, glass, cotton, carbon, polyester), the composition of the thread in fibers or filaments, the size of the fibers and their title, or even by the weave and the texture of the fabric. Therefore, processes using the LOTUS effect are essentially multi-step processes (Leng et al. Langmuir, (2009) 25, 2456-2460. DOI: 10.1021/Ia8031144; Xue et al., Thin Solid Films, 517 (2009) 4593-4598; Luo et al. Journal of Sol-Gel Science and Technology (2019) 89:820-829, DOI: 10.1007/s10971 -019-04927-2) difficult to transpose to the textile industry where kilometers of "raw" material must be processed in one day in an open environment. Furthermore, the unwinding speeds of the fabric vary between 5 to 50 m/min only allow rapid soaking in baths, thus excluding any process requiring long-term impregnations of reagents. In addition, the methods proposed in the prior art involve large quantities of toxic and volatile solvents.

[0007] Other processes described in the literature involve a much smaller number of steps and/or essentially aqueous processes. Pan et al. (AlChE Letters, 60(8) (2014), 27522756. DOI: 10.1002/aic.14517) use the vacuum silanization method in a desiccator 30 cm in diameter by exposing a previously cleaned cotton square to various alkylsilanes: n-octyltrichlorosilane (C18H37CL3Si, CAS No. 5283-66-9), tridecafluoro-1,1,2,2-tetrahydrooctyl-trichlorosilane (C8H4F13Cl3Si, CAS No. 78560-45-9) or tridecaflf luoro- 1 ,1,2,2-tetrahydrooctyl-triethoxysilane (C14H19F1303Si,

CAS No. 51851-37-7). They obtain the omniphobic properties for fabrics treated only with C8H4F13CI3Si. The level of oil repellency reached is 8 with hexane with a contact angle of 151°. However, these authors did not carry out machine wash tests to demonstrate the washing resistance of the coating. More specifically, the vacuum silanization process involves a thorough preliminary cleaning of the fabric to obtain an extremely clean fabric free of any impurities, i.e. a large number of washes in various solvents. However, these necessary steps were not described by the authors, who probably used the vacuum pumping method adapted to small surface test samples. The 24 hour vacuum silanization time is also difficult to apply in the textile industry.

[0008] Patent application FR 2984343-A1 from the French Institute for Textiles and Clothing (IFTH) describes a sol-gel process in an aqueous medium which makes it possible to obtain a hydrophobic and water-repellent coating for a cotton cloth in 5 steps with a) the preparation of an aqueous "one pot" sol by mixing various reagents (sol-gel precursors =TEOS and hexadecyltrimethoxysilane (C19H4203Si, CAS No. 16415-12-6), an acid carboxylic acid and a catalyst, sodium hypophosphite) and water, b) impregnation under ultrasound for 5 min of a piece of cotton (11 x 15) cm2, followed by c) padding to remove the excess of solvent, then d) a 1st drying at 80° C. for 1 hour, followed by e) a 2nd drying at 170° C. for 2.5 min. The authors announce a durability of the water repellency after 20 household washes with detergent, but did not obtain any oleophobic property.

[0009] Patent application FR 3057581 -A1 describes a sol-gel process in an essentially aqueous medium which may contain a silylated precursor or a mixture of silylated precursors for obtaining a barrier property with respect to toxic gaseous compounds, at namely toluene gas and methyl salicylate gas. The textile used is a 50% blend of viscose and aramid fibers. With a formulation (H') of Sol comprising 9.92% by volume of TMOS (tetramethoxysilane), 2.1% of 1H,1H,2H,2H-perfluorodecyltriethoxysilane (C16H19F1703SÎ, CAS No. 101947-16-4), 76.5% of water and 11.48% acetonitrile, the authors obtained a hydrophobic coating resistant to 5 washes. By pre-coating the fabric with an ethanolic solution of Zr propoxide (C12H2804Zr, CAS No. 23519-77-9) before coating the formulation H', the authors manage to increase the resistance to washing to obtain a hydrophobic and water-repellent fabric for up to 20 washes. The protocol involves soaking the fabric in each of the solutions, followed by padding to remove excess solvent and drying at 120°C for 2-5 min. However, the authors have not described oil-repellent properties for these coatings.

[0010] Patent application WO2016/077532 A1 from the University of Houston proposes a dirt and stain resistant coating based on a double coating layer. By using for the ^1st layer a mixture containing at least 3 types of alkoxysilane, tetraethoxysilane, trimethoxypropylsilane, 3-glycidoxypropyltrimethoxysilane serving respectively as structuring agent, plasticizing agent and bridging agent, water, HCl MeOH, all diluted with MeOH and for the 2nd layer an acid solution (pH<1) of trichloro (1H,1H,2H,2H,-perfluorooctylsilane) in MeOH previously treated by heating between 50 and 100 °C, then neutralized with a KOH solution and filtered to remove solid particles, the authors obtained an oil repellency of level 6 to 9, but did not carry out a wash resistance test. By using a methanolic solution of trimethoxy(1H,1H,2H,2H-perfluorooctyl)silane for the ^2nd layer, the authors also obtained level 6 to 9 oil repellency, but did not carry out a resistance test to washes.

[0011] Wang et al. (Angew. Chem. Int. Ed., 2011, 50, 11433-11436. DOI 10.1002/anie.201105069) use a solution based on polyhedral silsesquioxane oligomers (O12Si8(C10H4F17)8) with long fluorinated chains (nanoparticles of ~30 nm in diameter) dissolved in tridecafluorooctyl triethoxysilane (FAS, Dynasylan F 8261 from Evonik) then diluted in ethanol. The mixture (100 mL) must be sonicated for 30 min to obtain a homogeneous and transparent solution, stable at room temperature for 10 h. To coat a polyester fabric, the protocol involves a) immersing the fabric for 10 min in this mixture, followed by b) pressing the fabric to remove the excess solvent and c) a first drying at room temperature and d) drying at 135° C. for 30 min. These authors obtain a fabric that is both hydrophobic and oleophobic with contact angles of 171°, 155°, 151° and 120° respectively for droplets of 13 pL of water, hexadecane, tetradecane and octane. According to the authors, this coating would be very little damaged even after 40 machine washes. according to the Australian standard AS2001 .1.4 equivalent to the European standard ISO 6330. Although this process is simple to implement and allows obtaining an oil repellency level of 7, the use of silsesquioxane oligomers of nanometric size (30 nm in diameter) could prove problematic for the environment in the event of loss of material during washing. Furthermore, the long impregnation and drying times are not compatible with an industrial process.

[0012] Zorko et al. (Cellulose (2015) 22, 3597-3607. DOI: 10.1007/s10570-015-0762-4) use mercerized cotton and the “in-situ” Lotus effect by growing nanoparticles at 25°C or 50°C of silica on the fabric during its soaking in a solution containing a silylated precursor (TEOS), alcohol (EtOH or i-PrOH) and an aqueous ammoniacal solution. The fabric is then thoroughly rinsed then pressed and heated in hot air at 150°C for 1 min. To make the fabric oleophobic, it undergoes a 2nd treatment by soaking/pressing in a solution of Dynasylan 8815 and Krytox 106 followed by a heat treatment. The authors obtained an oil repellency index of 3 with hexadecane and did not study the resistance of the coating to washing. This method has the same major drawback of risk of environmental pollution due to the presence of nanoparticles.

[0013] In summary, on the basis of the work presented in the literature, omniphobia (hydrophobia and oleophobia) can only be achieved in three cases: (1) by vacuum silanization of a fabric previously ultra-cleaned with a long chain trichlorinated silane fluorinated for 24 H, or (2) with the use of the Lotus effect (nanoparticles of functionalized silica or silsesquioxane) coupled with a fluorinated coating or (3) with the use of 2 layers of coating , including a first containing a structuring agent, a plasticizer and a bridging agent and a ^2nd layer of a fluorinated compound obtained from trichloro(1H,1H,2H,2H,-perfluorooctylsilane) or from trimethoxy(1H,1H,2H,2H-perfluorooctyl)silane.

[0014] However, as indicated above, vacuum silanization is a process that is difficult to industrialize in the textile industry, in particular when the fabric must be cleaned beforehand of all the impurities which are trapped in the network of fibers during its production. In the second case, the risk of losing material (fluorinated or functionalized nanometric particles) during successive washings exists with the fear of environmental pollution. In the third case, a large number of constituents with structuring, plasticizing and bridging properties must be used in methanol for the first coating and MeOH is preferentially used as solvent for the ^2nd coating, which in some cases requires a long treatment at high temperature. The wet loads mentioned for the coatings are in this important cases, between 115 and 160%. Moreover, most of the works do not report the permeability of the treated fabric, a strong reduction of this with a multi-layer coating would result in low breathability and consequently discomfort for the user. [0015] In the textile industry, the liquid coating of fabrics is carried out continuously over kilometers of fabric moving at a speed of 5 to 50 m/min. It is therefore necessary to reduce the number of steps and the duration of each step to a minimum, in particular that corresponding to the drying sequences.

[0016] There is therefore a need for a simple, industrializable process for coating textiles that makes it possible to make them omniphobic or hydrophobic while preserving sufficient breathability and not using nanoparticles that potentially pollute the environment, nor large quantities of toxic and volatile solvents.

Summary

[0017] It is to the credit of the inventors to have solved this problem by developing a process compatible with the liquid-based industrial processes commonly used in the textile industry and not requiring the fabric to be pre-washed. This process comprises a reduced number of steps including the deposition (by padding or by spraying) of two sol-gel formulations with an optional step of washing-neutralizing the fabric according to the formulations used, each of the steps being followed by a short-term drying (less than 10 min). [0018] The method involves non-toxic formulations that meet the expectations and requirements of the textile industry, namely preparations of the formulations at room temperature, very high stability of the formulations over time for flexibility of use, reduced number of steps and short-term heat treatments of the textile running at high speed and no worker exposure to a toxic environment.

This process results in obtaining a hydrophobic or omniphobic textile (both oleophobic and hydrophobic) with a high level of oleophobicity, breathable, resistant to acids and strong bases and washable without loss of properties.

A sol-gel material is a material obtained by a sol-gel process consisting in using as precursors metal alkoxides of formula M(OR) _x R' _nx where M is a metal or metalloid, in particular silicon, R a alkyl group and R' a group carrying one or more functions with n=4 and x which can vary between 2 and 4. In the presence of water, the alkoxy groups (OR) are hydrolyzed into silanol groups (Si-OH) with formation of ROH alcohol. The latter condense by forming siloxane bonds (Si-O-Si-) with release of water molecules. Small particles form generally less than 1 pm in size, which aggregate and form clusters which remain in suspension without precipitating, forming a sol. The increase in the clusters and their condensation increases the viscosity of the medium which gels. A porous solid material is obtained by drying the gel, with the expulsion of the solvent or solvents outside the polymeric network formed (syneresis). In industry, for the deposition of a sol-gel formulation on a textile, it is important that the formulation can be prepared quickly and/or that it can be stored for a long time in the event of technical hazards. The Liquid Sol must remain stable throughout the process, which can last more than 10 hours. To quickly prepare a Sol comprising a silicon alkoxide, the commonly used method consists in accelerating the hydrolysis step with an acid catalyst. In most patents and articles of the literature, a very wide range of acid is always proposed including nitric, nitrous, hydrochloric, sulfuric, phosphoric acid.

An object of the invention therefore relates to a process for coating a textile material, said process comprising the following steps: a) at least one cycle of impregnation of the textile material with a sol-gel formulation of grip, said sol-gel grip formulation being free of polycarboxylic acid; b) at least one drying cycle of the impregnated textile material obtained in step a); c) at least one impregnation cycle of the dried textile material obtained in step b) with an omniphobic or hydrophobic sol-gel formulation, said omniphobic or hydrophobic sol-gel formulation being different from the sol-gel tie formulation; d) at least one drying cycle of the impregnated textile material obtained in step c); optionally followed by a step of) maturing the material obtained in step d) by storage at room temperature in a humid atmosphere with a relative humidity of 50% for at least 16 to 18 hours. Unlike the processes of the prior art, the process according to the invention is adapted to be implemented industrially because it comprises a reduced number of steps, all easily achievable on an industrial scale, unlike vacuum silanization for example. Another advantage over the prior art is that it does not require the use of nanoparticles which can lead to pollution. This process makes it possible to prepare a textile material that is both omniphobic or hydrophobic, these properties being resistant to washing, and retaining its permeability, which makes it possible to have good breathability and comfort for the user.

The textile material used can be of any type. It may for example be a fabric, a nonwoven or a knit, preferably a fabric. The term “textile material” is understood to mean a material whose individual constituent elements are fibers. Advantageously, the textile material comprises fibers comprising reactive functions such as hydroxyl functions. An example of such a fiber is cellulose present in natural fibers like cotton or man-made fibers like viscose. Preferably, they are viscose fibers. The fibers comprising hydrolyzable functions can be used alone, mixed together and/or mixed with other synthetic fibers such as polyamide, polyamide/imide, polymeta-phenylene terephthalamide, polypara-phenylene terephthalamide, d acrylic, modacrylic, polyester, oxidized polyacrylonitrile, poly(p-phenylene-2,6-benzobisoxazole) and polybenzimidazole or natural like wool. In a preferred embodiment, the textile material is a material based on an intimate mixture of viscose and synthetic fibers, preferably polyamide fibers, in particular aromatic polyamide. An example of such a fabric is Kermel®/Lenzing FR® 50:50.

[0024] According to one embodiment, said at least one impregnation cycle a) of the textile material with a sol-gel gripping formulation comprises a step of pressing the impregnated textile material under pressure. Preferably, when the method comprises at least two impregnation cycles a), a step of pressing the impregnated textile material under pressure is carried out after each impregnation cycle.

According to one embodiment, said at least one impregnation cycle c) of the dried textile material obtained in step b) by an omniphobic or hydrophobic sol-gel formulation comprises a step of pressing the textile material under pressure imbued. Preferably, when the method comprises at least two impregnation cycles c), a step of pressing the impregnated textile material under pressure is carried out after each impregnation cycle.

[0026] Thus, when the impregnation is followed by a step of pressing under pressure, this makes it possible to evacuate the excess soil. After this step of pressing under pressure, it is possible to measure a wet carrying rate, which represents the quantity of soil carried away by the fabric before drying. The carryover rate is determined using the method described below.

[0027] Thus, the take-up rate is between 40 and 46%, preferably it is around 43%. This is a wet carry rate, before drying. According to one embodiment, the pressing under pressure is implemented under the following conditions. The impregnated fabric passes between two steam rollers maintained under a pressure which can be varied between 2 and 7 bars and a running speed varying from 1 to 9 m/min. The squeezing is preferably carried out at 5 bars and at a running speed of 2 m/min. According to one embodiment, said method comprises the following steps: a) at least one cycle of impregnation of the textile material with a sol-gel adhesion formulation, said sol-gel adhesion formulation being free of polycarboxylic acid; b) at least one drying cycle of the impregnated textile material obtained in step a); c) at least one impregnation cycle of the dried textile material obtained in step b) with an omniphobic or hydrophobic sol-gel formulation comprising sulfamic acid, said omniphobic or hydrophobic sol-gel formulation being different from the sol formulation - gripping gel; d) at least one drying cycle of the impregnated textile material obtained in step c); optionally followed by a step d') of maturing the material obtained in step d) by storage at room temperature in a humid atmosphere with a relative humidity of 50% for at least 16 to 18 hours.

Another important point for worker exposure is the choice of alkoxy groups. To avoid the formation of volatile and toxic methanol during the hydrolysis of the alkoxides (OR) of Si, it is preferable to choose R = CnH2n+1 with n= at least equal to 2.

The coating process may comprise the following additional steps: e) washing with a neutralizing aqueous solution of the impregnated textile material obtained in step d). f) drying the material obtained in step e).

According to a particular embodiment, the drying step f) is followed by a step) of maturing the material obtained in step f) by storage at room temperature in a humid atmosphere with a relative humidity of 50 % for at least 4 p.m. to 6 p.m. These additional steps for neutralizing the textile material are optional in the method according to the invention and are carried out only when neutralization is necessary.

The term “neutralizing aqueous solution” means an aqueous solution which makes it possible to neutralize acid residues present in the impregnated textile material obtained at the end of step d) of the method according to the invention. Suitable aqueous neutralizing solutions are well known to those skilled in the art. It is generally a basic aqueous solution, such as a solution of soda or potash, preferably a solution of soda.

[0034] Each of the impregnation steps of the process can be carried out independently by padding (Figure 1) or by spraying. [0035]. Compared to other coating techniques, padding achieves an even distribution of the soil as well as a better impregnation of the soil into the fabric. The scanning electron microscopy images show that the application of the coating composition according to the invention by padding results in sheathing of the textile fibers.

The padding step of the process according to the invention is carried out at a speed of 1 to 50 meters/minute, preferably approximately 2 meters/minute.

[0037] Spraying (Figure 2) consists of the vaporization of a liquid into fine droplets (also called aerosol) which can be achieved by means of a mechanical device of the spray type. Unlike padding, this deposition method allows the coating of only one side of the fabric and it is not necessary to remove a surplus of formulation. Thus, for certain applications, it is possible to have each side of the fabric covered with a different formulation. However, it is advantageous to carry out a pressing step after spraying. The spraying step according to the method is preferably carried out at a pressure of 3 to 5 bars, even more preferably 4 bars, on a textile material preferably placed at a distance of 5 to 15 cm from the spray system. , the textile material preferably being moved at a speed of 5 to 15 meters/minute, even more preferably of 6 to 12 meters/minute. The method may comprise at least 2 successive cycles a) and b), of impregnation of the textile material with a sol-gel adhesion formulation, said sol-gel adhesion formulation being free of polycarboxylic acid, and drying the impregnated textile material.

According to one embodiment, the method may comprise at least 2 successive cycles a) and b), of impregnation of the textile material with a sol-gel adhesion formulation, said sol-gel adhesion formulation prepared at ambient temperature between 18 and 28°C being free of polycarboxylic acid, and drying of the impregnated textile material.

[0041] According to one embodiment, the method may comprise at least 2 successive cycles a) and b), of impregnation of the textile material with a sol-gel grip formulation, said sol-gel grip formulation contains sulfamic acid and is free of polycarboxylic acid, and drying of the impregnated textile material.

According to one embodiment, the method may comprise at least 2 successive cycles a) and b), of impregnation of the textile material with a sol-gel grip formulation, said sol-gel grip formulation prepared at ambient temperature between 18 and 28°C being free of polycarboxylic acid, and containing sulfamic acid and drying of the impregnated textile material.

[0043] Advantageously, said sol-gel adhesion formulation is additionally free of plasticizer and/or chelating agent and/or viscosity agent. The sol-gel adhesion formulation used in the method according to the invention may be free of plasticizer.

The sol-gel adhesion formulation used in the method according to the invention may be free of chelating agent.

The sol-gel adhesion formulation used in the method according to the invention may be free of viscosity modifying agent.

The process can advantageously comprise only one or two successive cycles a) and b), of impregnation of the textile material by a sol-gel adhesion formulation, said sol-gel adhesion formulation being free of polycarboxylic acid, and b) drying the impregnated textile material. [0048] When the process comprises only one cycle, this then makes it possible to have a faster and simpler process to implement.

According to one embodiment, the method may comprise only one or two successive cycles a) and b), of impregnation of the textile material with a sol-gel tie formulation, said sol-gel formulation of hook prepared at room temperature between 18 and 28° C., said sol-gel hook formulation being free of polycarboxylic acid, and b) drying the impregnated textile material.

[0050]According to one embodiment, the process may comprise only one or two successive cycles a) and b), of impregnation of the textile material with a sol-gel tie formulation, said sol-gel formulation of grip contains sulfamic acid and is being free of polycarboxylic acid, and b) drying the impregnated textile material.

The process can advantageously comprise only one or two successive cycles a) and b), of impregnation of the textile material by a sol-gel adhesion formulation, said sol-gel adhesion formulation being free of polycarboxylic acid, and b) drying the impregnated textile material after each cycle. The process can advantageously comprise only one or two successive cycles a) and b), of impregnation of the textile material by a sol-gel adhesion formulation, said sol-gel adhesion formulation prepared at room temperature between 18 and 28°C being free of polycarboxylic acid, and containing sulfamic acid and b) drying of the impregnated material. Preferably, the drying step is carried out after each cycle. [0053] Advantageously, said sol-gel adhesion formulation is also free of plasticizer and/or chelating agent and/or viscosity agent.

[0054] When the process comprises only one cycle, this then makes it possible to have a faster and simpler process to implement. The method may also comprise at least 2 successive cycles c) and d), of impregnation of the dried textile material obtained in step b) with an omniphobic or hydrophobic sol-gel formulation, said omniphobic sol-gel formulation or hydrophobic being different from the sol-gel formulation for adhesion, and drying of the impregnated textile material. Nevertheless, it should be noted that the omniphobicity and/or hydrophobicity performances sought in the context of the present invention are achieved when there is only one cycle c) of impregnation of the dried textile material obtained in step b) with an omniphobic or hydrophobic sol-gel formulation, said omniphobic or hydrophobic sol-gel formulation being different from the sol-gel tie formulation, and d) drying the impregnated textile material. For example, the method can also comprise 3 successive cycles c) and d), of impregnation of the dried textile material obtained in step b) with an omniphobic or hydrophobic sol-gel formulation, said omniphobic sol-gel formulation or hydrophobic being different from the sol-gel adhesion formulation, and d) drying of the impregnated textile material. The method can therefore advantageously comprise only one cycle of impregnation of the dried textile material obtained in step b) with an omniphobic or hydrophobic sol-gel formulation, said omniphobic or hydrophobic sol-gel formulation being different from the sol-gel formulation for gripping and drying the impregnated textile material. This also makes it possible to have a faster and easier process to implement. The drying steps b) and d) are generally carried out at a temperature of 120 to 180° C., for a period ranging from 2 to 10 minutes, preferably at 180° C. for 2 minutes.

The sol-gel tie formulation used in the method according to the invention may comprise at least two silylated precursors, preferably chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), (3-glycidyloxypropyl )trimethoxysilane (GPTMOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and aminopropyltriethoxysilane. Preferably, the at least two silylated precursors are a combination of a silylated precursor chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) or their mixture and a silylated precursor chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS ), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and aminopropyltriethoxysilane and mixtures thereof. More preferably, the at least two silylated precursors are a combination of a silylated precursor chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and their mixture and of a silylated precursor chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS ), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and mixtures thereof. The sol-gel tie formulation according to the invention may in particular comprise a mixture of the silylated precursors TMOS and GPTEOS, or TMOS and aminopropyltriethoxysilane, or TEOS and GPTMOS, or TEOS and GPTEOS, or TEOS and aminopropyltriethoxysilane. The sol-gel tie formulation according to the invention may in particular comprise a mixture of the silylated precursors TMOS and GPTEOS, or TEOS and GPTMOS, or TEOS and GPTEOS. More preferably still, it is a mixture of tetraethoxysilane (TEOS) and (3-glycidyloxypropyl)triethoxysilane (GPTEOS). The sol-gel attachment formulation used in the method according to the invention may comprise an acid preferably chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid, paratoluenesulfonic acid , preferably sulfamic acid. Sulfamic acid has proven to be particularly interesting since it contributes to the remarkable stability duration of the sol-gel adhesion formulations.

According to one embodiment, the sol-gel tie formulation according to the invention may in particular comprise a mixture of the silylated precursors TMOS and GPTEOS, or TEOS and GPTMOS, or TEOS and GPTEOS, or TMOS and GPTMOS and sulfamic acid.

According to one embodiment, the sol-gel tie formulation according to the invention may in particular comprise a mixture of the silylated precursors TMOS and GPTEOS, or TEOS and GPTMOS, or TEOS and GPTEOS and sulfamic acid.

The sol-gel tie formulation used in the method according to the invention is preferably free of zirconium alkoxide and/or sodium hypophosphite.

The omniphobic sol-gel formulation used in the method according to the invention may comprise at least one silylated precursor, preferably chosen from 1H,1H,2H,2H-perfluorodecyltriethoxysilane (17FTEOS), 1H ,1H,2H,2H-perfluorooctyltriethoxysilane (13FTEOS), 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (13FTMOS), 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (17FTMOS), or a mixture of one or more of these precursors with tetraethoxysilane (TEOS).

The omniphobic sol-gel formulation used in the method according to the invention may comprise an acid preferably chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid, paratoluenesulfonic, preferably sulfamic acid or hydrochloric acid, even more preferably sulfamic acid.

According to one embodiment, the omniphobic sol-gel formulation used in the method according to the invention may comprise at least one silylated precursor, preferably chosen from 1H,1H,2H,2H-perfluorodecyltriethoxysilane ( 17FTEOS), 1H,1H,2H,2H-perfluorooctyltriethoxysilane (13FTEOS), 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (13FTMOS), 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (17FTMOS) , or a mixture of one or more of these precursors with tetraethoxysilane (TEOS) and sulfamic acid. The hydrophobic sol-gel formulation used in the method according to the invention may comprise at least one silylated precursor, preferably chosen from hexadecyltriethoxysilane (HDTEOS), n-octadecyltriethoxysilane (ODTEOS), n-decyltriethoxysilane (DTEOS), dodecyltriethoxysilane (DDTEOS), or a mixture of one or more of these precursors with tetraethoxysilane (TEOS). The hydrophobic sol-gel formulation implemented in the method according to the invention may comprise an acid preferably chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid, paratoluenesulfonic acid, preferably sulfamic acid or hydrochloric acid, even more preferably sulfamic acid. According to one embodiment, the hydrophobic sol-gel formulation used in the method according to the invention may comprise at least one silylated precursor, preferably chosen from hexadecyltriethoxysilane (HDTEOS), n-octadecyltriethoxysilane (ODTEOS ), n-decyltriethoxysilane (DTEOS), dodecyltriethoxysilane (DDTEOS), or a mixture of one or more of these precursors with tetraethoxysilane (TEOS) and sulfamic acid.

The omniphobic and/or hydrophobic sol-gel formulations used in the method according to the invention advantageously comprise sulfamic acid. The inventors have observed that sulfamic acid has advantages in terms of stability of the soils obtained. Sulfamic acid, NH ₂ S0 ₃ H, is a moderately strong acid (pKa=0.99) which allows rapid hydrolysis of silylated precursors while ensuring the stability of Sols. Indeed, sulfamic acid has the particularity of being able to be found in a zwitterionic form ⁺ H ₃ NS0 ₃ in aqueous solution. Thus, sulfamic acid in its zwitterionic form stabilizes the silanol groups and prevents them from rapidly condensing according to the following scheme: The sol-gel cling, omniphobic and/or hydrophobic formulations used in the process according to the invention are aqueous formulations and optionally comprise one or more C1 to C4 aliphatic alcohols, chosen in particular from methanol, ethanol, propan-1-ol, isopropanol and butan-1-ol, preferably from methanol, ethanol, propan-1-ol and isopropanol, more preferably from ethanol and isopropanol. Advantageously, in the case of omniphobic sol-gel formulations, the C1 to C4 aliphatic alcohol is ethanol and/or isopropanol and in the case of hydrophobic sol-gel formulations the C1 to C4 aliphatic alcohol is ethanol. The binding sol-gel formulation preferably does not comprise any C1 to C4 aliphatic alcohol.

Within the meaning of the present invention, the term “aqueous formulation” means a formulation whose solvent comprises water. The binding, omniphobic and/or hydrophobic sol-gel formulations used in the process according to the invention can also optionally comprise one or more C1 to C4 aliphatic alcohols which are miscible with water. The solvent of the sol-gel adhesion, omniphobic and/or hydrophobic formulations used in the process according to the invention can thus be water, or a mixture of water with one or more aliphatic alcohols in C1 to C4 , chosen in particular from methanol, ethanol, propan-1-ol, isopropanol and butan-1-ol, preferably from methanol, ethanol, propan-1-ol and isopropanol, more preferably from isopropanol and ethanol. Advantageously, in the case of omniphobic sol gel formulations, the solvent is water or a mixture of water and ethanol and/or isopropanol and in the case of hydrophobic sol gel formulations, the solvent is a mixture of water and ethanol. In the case of sol-gel tie formulations, the solvent is advantageously water or a mixture of water and ethanol. When one of the sol-gel formulations according to the invention is an aqueous formulation, the solvent advantageously contains from 1% to 100% by volume of water. In the sol-gel tie formulations, the solvent may in particular advantageously contain from 40% to 100%, preferably from 50% to 100%, more preferably from 60 to 100% by volume of water. Particularly preferably, the solvent is water. In omniphobic sol-gel formulations, the solvent may in particular advantageously contain from 10% to 100%, preferably from 14% to 100%, by volume of water. In the hydrophobic sol-gel formulations, the solvent may in particular advantageously contain from 1 to 10%, preferably from 2 to 5%, by volume of water. In sol-gel tie formulations, the C1-C4 aliphatic alcohol or the mixture of C1-C4 aliphatic alcohols can represent from 0 to 50% by volume, preferably from 0 to 40% by volume of the solvent. Preferably, the solvent of the sol-gel tie formulations does not contain any C1-C4 aliphatic alcohol. However, when the solvent of the sol-gel tie formulations contains an aliphatic C1-C4 alcohol or a mixture of aliphatic C1-C4 alcohols, this may for example represent from 5 to 50%, in particular from 10 to 40% by volume of the solvent.

In omniphobic sol-gel formulations, the C1-C4 aliphatic alcohol or the mixture of C1-C4 aliphatic alcohols can represent from 0 to 95% by volume, preferably from 0 to 90% by volume. solvent. Advantageously, the alcohol represents from 50 to 95%, preferably 60 to 90% by volume of the solvent. In one embodiment, the solvent of the omniphobic sol-gel formulations does not contain a C1-C4 aliphatic alcohol.

In hydrophobic sol-gel formulations, the C1-C4 aliphatic alcohol or the mixture of C1-C4 aliphatic alcohols can advantageously represent from 55 to 99% by volume, preferably from 70 to 98% by volume. volume of the solvent. Advantageously, the alcohol represents from 80 to 99%, preferably 85 to 98% by volume of the solvent.

The solvent advantageously represents 40 to 95% by volume, preferably 50 to 90% by volume, of the sol-gel adhesion, omniphobic and hydrophobic formulations. The solvent can in particular advantageously represent from 70 to 90% by volume, preferably from 80 to 90% by volume, even more preferably from 82 to 88% by volume of the sol-gel tie formulations.

The solvent can in particular advantageously represent from 40 to 95% by volume, preferably from 50 to 90% by volume of the omniphobic sol-gel formulations. The solvent can in particular advantageously represent from 60 to 90% by volume, preferably from 75 to 85% by volume of the hydrophobic sol-gel formulations.

In the sol-gel tie, omniphobic and hydrophobic formulations, the silylated precursor or the mixture of silylated precursors advantageously represents from 5 to 70% by volume, preferably from 10 to 55% by volume, even more preferably from 10 to 52% by volume of sol-gel gripping, omniphobic and hydrophobic formulations.

In the sol-gel tie formulations, the silylated precursors advantageously represent 5 to 30% by volume, preferably 10 to 20% by volume, of the sol-gel tie formulations. In omniphobic sol-gel formulations, the silylated precursor or the mixture of silylated precursors advantageously represent 5 to 70% by volume, preferably 10 to 55% by volume, of the omniphobic sol-gel formulations.

In the hydrophobic sol-gel formulations, the silylated precursor or the mixture of silylated precursors advantageously represent 10 to 40% by volume, preferably 15 to 25% by volume, of the hydrophobic sol-gel formulations.

A second object of the invention is a sol-gel tie formulation comprising at least two silylated precursors, a first precursor preferably being chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), a second precursor being preferably chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS), aminopropyltriethoxysilane, optionally, the combination of TMOS/GPTMOS precursors being excluded, and comprising an acid advantageously chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid, paratoluenesulfonic acid, preferably sulfamic acid, said sol-gel formulation being free of polycarboxylic acid.

According to one embodiment, the sol-gel tie formulation comprises sulfamic acid and at least two silylated precursors, a first precursor preferably being chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), a second precursor preferably being chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS), optionally, the combination of TMOS/GPTMOS precursors being excluded, said sol-gel formulation being free of polycarboxylic acid.

According to one embodiment, the sol-gel tie formulation comprises sulfamic acid and hydrochloric acid and at least two silylated precursors, a first precursor preferably being chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), a second precursor preferably being chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS), optionally, the combination of TMOS/GPTMOS precursors being excluded from said formulation sol-gel being free of polycarboxylic acid.

The sol-gel tie formulation may in particular comprise sulfamic acid, generally provided in the form of an aqueous solution. The presence of sulfamic acid makes it possible to contribute to the remarkable duration of stability of the sol-gel adhesion formulations, which can be greater than 1 month. Preferably, the at least two silylated precursors are a combination of a silylated precursor chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) or their mixture and of a silylated precursor chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS), (3-glycidyloxypropyl )triethoxysilane (GPTEOS) and aminopropyltriethoxysilane and mixtures thereof. Preferably, the at least two silylated precursors are a combination of a silylated precursor chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) or their mixture and a silylated precursor chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS ), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and mixtures thereof. More preferably, the at least two silylated precursors are a combination of a silylated precursor chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and their mixture and of a silylated precursor chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS ), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and mixtures thereof. The sol-gel tie formulation according to the invention may in particular comprise a mixture of the silylated precursors TMOS and GPTEOS, or TMOS and aminopropyltriethoxysilane, or TEOS and GPTMOS, or TEOS and GPTEOS, or TEOS and aminopropyltriethoxysilane. The sol-gel tie formulation according to the invention may in particular comprise a mixture of the silylated precursors TMOS and GPTEOS, or TEOS and GPTMOS, or TEOS and GPTEOS. More preferably still, it is a mixture of tetraethoxysilane (TEOS) and (3-glycidyloxypropyl)triethoxysilane (GPTEOS). The sol-gel tie formulation according to the invention is preferably free of zirconium alkoxide and/or sodium hypophosphite.

The sol-gel adhesion formulation according to the invention may be free of plasticizer.

The sol-gel tie formulation according to the invention may be free of chelating agent.

The sol-gel adhesion formulation according to the invention may be free of viscosity modifying agent.

The sol-gel tie formulation according to the invention is preferably an aqueous formulation, optionally comprising at least one C1 to C4 aliphatic alcohol, chosen in particular from methanol, ethanol, propan-1-ol , isopropanol and butan-1-ol, preferably from methanol, ethanol, propan-1-ol and isopropanol, more preferably the C1 to C4 aliphatic alcohol is ethanol.

[0094] The sol-gel tie formulation may thus in particular also comprise ethanol. Particularly advantageous performance in terms of stability has been obtained for the sol-gel tie formulation comprising a mixture of tetraethoxysilane (TEOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and sulfamic acid. This sol-gel adhesion formulation has a stability period greater than 1 month. This formulation can optionally comprise an alcohol, in particular ethanol.

The stability of the sol-gel formulations discussed here corresponds to their homogeneity. The homogeneity of a mixture corresponds to the fact that this mixture is composed of only a single homogeneous phase of refractive index n as opposed to a demixing of the mixture into 2 or more immiscible phases of refractive index n', n”, n'”, etc.... A homogeneous phase is therefore defined by a single refractive index, n, of light. Furthermore, a clear phase is a phase devoid of particles that can scatter light. Thus, a solution is considered stable as long as it is homogeneous and clear. The lifetime of the homogeneous and clear phase of the soil formulations is monitored using the light transmission analysis apparatus (Turbican Lab, Formulation). The measurement protocol applied is as follows: 10 mL of soil of refractive index n are introduced into the dedicated container, the transmission of incident light passing through the soil is measured and monitored over time. Homogeneous and clear soil expresses a constant transmission percentage over time (an example is shown in Figure 9 with a transmission percentage of 92±1%). If the soil demixes or becomes cloudy over time, the destabilization is characterized by a change in the percentage of transmission due either to a change in refractive index or to the scattering of light by the particles, causing the light transmission to drop. in this ^2nd case.

The increased stability of the sol-gel tie formulations according to the invention is of major interest for the industrialization of a process for coating textile material because such a coating process is then carried out continuously on rolls. fabrics that can measure several kilometers in length. Formulations having long stability times are then necessary to effectively implement this type of process on an industrial scale. When using a mixture of tetramethoxysilane or tetraethoxysilane with one or more other silylated precursors in the sol-gel tie formulation, the molar proportions of tetramethoxysilane or tetraethoxysilane (TMOS or TEOS) relative to the other (s) silylated precursor(s) can vary from 1 to 9, preferably from 1.5 to 5, even more preferably from 1.5 to 4. The hook formulation according to the invention can be used for applying a hook formulation to a textile by impregnation. The bonding layer thus formed on the textile can then be used to bond any type of sol-gel formulation. The presence of this tie layer according to the invention moreover quite advantageously makes it possible to provide increased washing stability of the coating deposited on the tie layer.

Another object of the invention is an omniphobic sol-gel formulation comprising at least one silylated precursor preferably chosen from 1H,1H,2H,2H-perfluorodecyltriethoxysilane (17FTEOS), 1H,H,H, H-perfluorooctyltriethoxysilane (13FTEOS), 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (13FTMOS) and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (17FTMOS), or a mixture of one or more of these precursors with tetraethoxysilane (TEOS), and comprising an acid, advantageously chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid, paratoluenesulfonic acid, preferably sulfamic acid or hydrochloric acid , even more preferably sulfamic acid.

[0101] According to one embodiment, the omniphobic sol-gel formulation comprises sulfamic acid and at least one silylated precursor preferably chosen from 1H,1H,2H,2H-perfluorodecyltriethoxysilane (17FTEOS), 1H, H,H,H-perfluorooctyltriethoxysilane

(13FTEOS), 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (13FTMOS) and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (17FTMOS), or a mixture of one or more of these precursors with tetraethoxysilane ( TEOS).

The omniphobic sol-gel formulation can advantageously comprise only one silylated precursor, thus making this formulation simpler and easier to implement.

The omniphobic sol-gel formulation comprises an acid, generally provided in the form of an aqueous solution. This acid is preferably chosen from sulfamic acid or hydrochloric acid, more preferably it is sulfamic acid.

The omniphobic sol-gel formulation according to the invention is preferably an aqueous formulation, as defined above. It may therefore in particular comprise a mixture of water and alcohol as solvent. The presence of sulfamic acid and alcohol makes it possible to contribute to a remarkable duration of stability of the omniphobic sol-gel formulations which can range from 22 to 48 hours.

[0106] Particularly advantageous performances in terms of stability were obtained for an omniphobic sol-gel formulation comprising 1H,1H,2H,2H-perfluorodecyltriethoxysilane (17FTEOS) and sulfamic acid. This sol-gel formulation omniphobe may comprise an alcohol, in particular ethanol or isopropanol, it then has a stability period ranging from 22 to 48 hours.

Another object of the invention is a hydrophobic sol-gel formulation comprising at least one silylated precursor preferably chosen from hexadecyltriethoxysilane (HDTEOS), n-octadecyltriethoxysilane (ODTEOS), n-decyltriethoxysilane (DTEOS) and dodecyltriethoxysilane (DDTEOS), or a mixture of one or more of these precursors with tetraethoxysilane (TEOS), and comprising an acid, advantageously chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid, paratoluenesulfonic acid, preferably sulfamic acid or hydrochloric acid, even more preferably sulfamic acid.

According to one embodiment, the hydrophobic sol-gel formulation comprises sulfamic acid and at least one silylated precursor preferably chosen from hexadecyltriethoxysilane (HDTEOS), n-octadecyltriethoxysilane (ODTEOS), n-decyltriethoxysilane (DTEOS) and dodecyltriethoxysilane (DDTEOS), or a mixture of one or more of these precursors with tetraethoxysilane (TEOS).

The presence of sulfamic acid and alcohol makes it possible to contribute to a remarkable duration of stability of the hydrophobic sol-gel formulations which can range from 1 day to 6 days at least.

Particularly interesting performances in terms of stability have been obtained for the hydrophobic sol-gel formulations comprising hexadecyltriethoxysilane (HDTEOS) and sulfamic acid or comprising hexadecyltriethoxysilane (HDTEOS), tetraethoxysilane (TEOS) and sulfamic acid. These formulations can comprise an alcohol, in particular ethanol.

The hydrophobic sol-gel formulation according to the invention is preferably an aqueous formulation as defined above. It may therefore in particular comprise a mixture of water and alcohol as solvent.

The amounts of solvent, water, alcohol and silylated precursors that can be used in the sol-gel formulations are those described above with respect to the process for coating a textile material according to invention. The invention also relates to an impregnated textile material comprising at least a first gripping layer obtained by applying a sol-gel gripping formulation according to the invention and at least a second omniphobic or hydrophobic layer on the above the adhesion layer. This omniphobic or hydrophobic layer can in particular be obtained by applying an omniphobic or hydrophobic sol-gel formulation as described above. This textile material according to the invention may in particular comprise at least a first tie layer obtained by applying a sol-gel tie formulation according to the invention and at least a second omniphobic layer above the tie layer obtained by applying an omniphobic sol-gel formulation according to the invention. This textile material according to the invention may also comprise at least a first tie layer obtained by applying a sol-gel tie formulation according to the invention and at least a second hydrophobic layer above the adhesion layer obtained by applying a hydrophobic sol-gel formulation according to the invention.

Another object of the invention is an impregnated textile material comprising at least a first grip layer and at least a second omniphobic layer above the grip layer obtained by application of a sol-gel formulation omniphobic according to the invention.

Another object of the invention is an impregnated textile material comprising at least a first adhesion layer and at least a second hydrophobic layer above the adhesion layer obtained by application of a sol-gel formulation hydrophobic according to the invention.

A textile material impregnated according to the invention can be obtained by the coating process according to the invention described above. It is therefore a textile material impregnated with at least one tie layer obtained by applying a sol-gel tie formulation according to the invention, and at least one omniphobic or hydrophobic layer obtained by application of an omniphobic or hydrophobic sol-gel formulation according to the invention. All the details and embodiments set out above for the nature of the textile material and the sol-gel formulations are also valid for the impregnated textile material according to the invention. The coating layers form a sheath around the fibers which constitute the impregnated textile material.

The impregnated textile material according to the invention is in particular characterized in that it has a hydrophobicity measured by contact angle greater than 120 degrees, preferably greater than 130 degrees, even more preferably greater than 140 degrees.

The contact angle is measured using an OCA 15EC (SCA 20) goniometer. 10 drops of 10 μL of water are deposited on the fabric using a needle (Hamilton 500 mL, HAMI91022) for each measurement. A coating is said to be hydrophobic when the contact angle of a drop of water with the surface of the support is greater than 90 degrees. [0122] The impregnated textile material according to the invention in which the second layer is an omniphobic layer, is in particular characterized in that it has an oil repellency measured by contact angle greater than 90 degrees, preferably greater than 100 degrees, even more preferably greater than 110 degrees or measured by an oil repellency index greater than 3, advantageously greater than 4, preferably greater than 5, even more preferably greater than 6.

The contact angle is measured using an OCA 15EC (SCA 20) goniometer. 4 to 8 drops of 10pL of an alkane are placed on the fabric using a needle (Hamilton 500mL, HAMI91022) for each measurement. A coating is said to be oleophobic when the contact angle of an alkane drop with the surface of the support is greater than 90 degrees.

For the tests for measuring the oil repellency index, drops of 50 μl of alkanes are deposited using a micropipette on at least 4 different locations distributed over the surface of the fabric. The drops are observed for 30 s and their shape is rated from A to D according to the references of the ISO 14419 standard (Figure 3). The oil repellency index of the coating is that of the alkane (n) whose shape of the drop was rated A. If the drop obtains the grade B, the alkane is changed by taking a lower index n-1 for which the drop obtains the grade A. Of the 4 drops deposited in a dispersed manner on a given fabric, it is enough for a single drop to have the index n-1 for the coating to be rated n/(n-1).

A major advantage of the present invention is that the coating layers applied to the textile material are very resistant to washing, the textile material can therefore be durable. Indeed, the impregnated textile materials according to the invention resist without loss of hydrophobicity and/or oil repellency to at least 30 washes, or even up to at least 70 washes.

Another major advantage of the present invention is that the coating layers applied to the textile material make it resistant to strong acids and bases.

A particular object of the invention is personal protective equipment comprising the impregnated textile material according to the invention. This personal protective equipment can for example be a full suit, trousers, a jacket, gloves, balaclavas, socks, masks. Thanks to the functional properties, in particular of hydrophobicity and/or oil repellency, of the textile material according to the invention, the personal protective equipment is particularly suitable for protection against splashes of liquids containing corrosive and/or toxic chemical products (solutions aqueous acids or bases, oils, hydrophilic or hydrophobic organic solvents). The textile materials having the highest oil repellency indices, in particular equal to or greater than 6, are particularly suitable for personal protective equipment for armies, police, firefighters, industry.

[0129] For oil repellency indices between 4 and 6, omniphobic and water-repellent textiles are of interest in consumer products, such as rainwear, non-soiling clothing for workers, or even clothing for children.

[0130] The omniphobic formulations can also be deposited by spraying on solid supports, glass, steel, brick, wall covering, as anti-graffiti coatings because the acrylic spray paints used for graffiti do not adhere to these coatings. omniphobic.

The combination of omniphobic and hydrophobic textile materials is of interest for use in the collection of polluting liquid, in particular oil, accidentally spilled in the open sea. It is thus possible for this application to assemble an omniphobic textile material, such as an omniphobic impregnated textile material according to the invention, with another hydrophobic textile material, such as a hydrophobic impregnated textile material according to the invention, to form a third textile material having the combined properties of the assembled textiles.

Brief description of the drawings

Fig. 1 [0132] [Fig. 1] shows a photo of a lab scarf.

Fig. 2

[0133] [Fig. 2] shows a photo of the laboratory spray system placed in a fume hood seen from the side.

Fig. 3 [0134] [Fig. 3] shows an example of classification for oil repellency tests according to the standard

IS014419. The grades given range from A to D for the shape of the drop, with A = pass, well rounded drop, B = partially pass with round drop with partial darkening, C = fail, visible wicking or complete wetting and D = fail , complete wetting. The oil repellency index n of the coating is that of the alkane (n) for which the shape of the drop is rated A.

Fig. 4 [0135] [Fig. 4] shows the shapes of drops of water and alkanes (50mI_) deposited on a new coated fabric according to the P(3) _F process. From left to right: water, hexadecane (index 3), dodecane (index 5), decane (index 6), octane (index 7).

Fig. 5

[0136] [Fig. 5] shows photos of the contact angles of drops of water and decane (10mI_) on a fabric coated according to the P(15)F process when new (Ow) and washed 30 times (30w).

Fig. 6

[0137] [Fig. 6] shows an SEM image of the blank K5204 (Kermel®/Lenzing FR® 50/50) fabric. 500 times magnification.

Fig. 7

[0138] [Fig. 7] shows an SEM image of the K5204 fabric (Kermel®/Lenzing FR® 50/50) of FIG. 6 coated according to the P(3) _F process with a magnification of 500 times.

Fig. 8

[0139] [Fig. 8] shows an SEM image of the K5204 fabric (Kermel®/Lenzing FR® 50/50) of FIG. 6 coated according to the P(3) _F process with a magnification of 1000 times.

Fig.9

[0140] [Fig. 9] shows an example of light transmission analysis of the ground(6) _0mnip with the Turbiscan lab device at different temperatures (30°C, 35°C, 40°C). When the soil is homogeneous and clear, the % transmission of the intensity of a light beam passing through the sample is here 92±1%. The drop in long-term transmission announces either the presence of scattering particles or the separation of the ground with a change in the refractive index of the liquid.

Fig.10

[0141] [Fig. 10] shows the results of resistance tests of the omniphobic coating to strong acids and bases. The contact angles of water and n-decane on the surface of the sample P(15) _F were measured before and after 24 hours of soaking the sample in acidic (pH=0) and basic solutions ( pH=12 and 14).

Examples

[0142] Chemical products used: Tetramethoxysilane (CAS No: 681-84-5) (TMOS, Acros Organics, 99%); Tetraethoxysilane (CAS No: 78-10-4) (TEOS, Acros Organics, 98%); (3-Glycidyloxypropyl)trimethoxysilane (CAS No: 2530-83-8) (GPTMOS, Sigma-Aldrich, >98%);

(3-Glycidyloxypropyl)triethoxysilane (CAS No. 2602-34-8) (GPTEOS, Gelest,);

1 H,H,H,H-Perfluorooctyltriethoxysilane (CAS No: 51851-37-7) (13FTEOS, Acros Organics, 98%);

1 H,H,H,H-Perfluorodecyltriethoxysilane (CAS No: 101947-16-4) (17FTEOS, Acros Organics, 97%);

Hexadecyltriethoxysilane (CAS No: 16415-13-7) (HDTEOS, Gelest, 95%

Hydrochloric acid (CAS No. 7647-01-0) (HCl, Merck 37%)

Sulfamic acid (CAS No. 5329-14-6) (AbSm, Sigma-Aldrich, >99%)

Sodium hydroxide (CAS No. 1310-73-2) (NaOH, Sigma-Aldrich, >99%)

Ethanol (CAS No: 64-17-5) (EtOH, Carlo Erba, HPLC-PLUS-Gradient);

Isopropanol (CAS No: 67-63-0) (iPrOH, Fisher, 99.9%);

H ₂ 0 demineralised

[0143] Textiles used:

[0144] Fabrics of a different nature were used to demonstrate the applicability of the omniphobic coating. It is :

- Kermel®/Lenzing FR® 50/50 (kermel-viscose fabric). The mixed fabric has a surface mass of 260 g/m ² and an air permeability of 57.5 L/m ² .s (average value measured according to the IS09237 standard under 100 Pa). Kermel® is a polyamide-imide that provides flame retardant and thermostable performance. Lenzing FR® is a flame retardant viscose (Modal manufacturing process) made of cellulose. Thus, the chemical nature of the two fibers of the fabric is very different.

- 100% cotton with a surface mass of 180g/m ² . Cotton is made of cellulose and contains hydroxyl functions.

The tests were carried out with fabric samples of A4 (21×30) cm ² format or with 100 m of fabric provided with a width of 30 cm. The coatings were carried out with various sol-gel formulations either by padding with a laboratory padding or by spraying with a motorized spraying system. The wet carryover, which represents the quantity of soil carried away by the fabric before drying, is of the order of 43±3%.

[0146] The carry-over rate is calculated by weighing the textile before and after treatment. The principle is to impregnate the fabric with a bath containing the desired product formulation, and squeeze it out, i.e. make the product penetrate and remove the excess bath from the fabric by exerting pressure between 2 rollers covered with elastomers. This makes it possible to control the quantity of bath deposited, one then speaks of the expressing rate or take-up rate. The material is treated in the heart and on both sides and retains its textile appearance. The textile is weighed again after the pressing step but before the drying step. The ratio [(Weight after deposition) - (Weight before deposition)]/(Weight before deposition) gives the take-up rate.

[0147] Example 1: preparation of the attachment formulations (SOIACC)

[0148] Sol(1) _A dc

In a hermetically sealed glass bottle, 9.1 mL of TMOS, 3.5 mL of GPTMOS and 87.5 mL of ultrapure water are successively added. The mixture is stirred at room temperature (20-24°C) at 500 rpm for 1 hour using an IKA WERKE RO10 power multiple stirring plate. SOI(1)ACC contains 12.5% v/v of silylated precursors with a molar ratio of TMOS/GPTMOS of 4. SOI(1)ACC has a stability of 6H.

SOI(2)ACC In a hermetically sealed glass bottle, 6.0 mL of TMOS, 6.0 mL of GPTMOS and 77.0 mL of ultrapure water are successively added. The mixture is stirred at ambient temperature (20-24° C.) at 500 rpm for 1 hour using an IKA WERKE RO10 power multiple stirring plate. Sol(2) _A cc contains 13.5% v/v of silylated precursors with a TMOS/GPTMOS molar ratio of 1.5. Sol(2) _A cc has a stability of 6H. [0150] SOI(3)ACC

In a hermetically sealed glass bottle, 6 mL of TMOS, 6 mL of GPTMOS and 77 mL of ultrapure water are successively added. The mixture is stirred at room temperature (20-24°C) at 500 rpm for 3 hours using an IKA WERKE RO10 power multiple stirring plate. The SOI(3)ACC contains 13.5% v/v of silylated precursors with a molar ratio of TMOS/GPTMOS of 1.5. SOI(3)ACC has a stability of 6H.

[0151] SOI(4)ACC

In a hermetically sealed glass bottle, 6. OmL of TMOS, 6. OmL of GPTMOS and 77. OmL of ultrapure water are successively added. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 4 hours using an IKA WERKE RO10 power multiple stirring plate. Sol(4) _A cc contains 13.5% v/v of silylated precursors with a TMOS/GPTMOS molar ratio of 1.5. Sol(4) _A cc has a stability of 6H.

[0152] SOI(5)ACC

In a hermetically sealed glass bottle, 9.5 mL of TEOS, 8.1 mL of GPTEOS, 82.4 mL of 3.2 mmol/L aqueous solution of sulfamic acid are successively added. The mixture is stirred at room temperature (20-24°C) at 500 rpm for 24 hours using of an IKA multi-shaker plate. The SOI(5)ACC contains 17.6% v/v of silylated precursors with a molar ratio of TEOS/GPTEOS of 1.5. The SOI(5)ACC has a stability of duration greater than 1 month.

[0153] SOI(6)ACC

In a hermetically sealed glass bottle, 9.5 mL of TEOS, 8.1 mL of GPTEOS, 10 mL of ethanol, 72.4 mL of 3.6 mmol/L aqueous sulfamic acid solution are successively added. The mixture is stirred at room temperature (20-24°C) at 500 rpm for 3 hours using an IKA multiple stirring plate. SOI(6)ACC contains 17.6% v/v of silylated precursors with a molar ratio of TEOS/GPTEOS of 1.5 and 10% v/v of ethanol. The SOI(6)ACC has a stability of duration greater than 2 months.

[0154] SOI(7)ACC

In a hermetically sealed glass bottle, 9.5 mL of TEOS, 8.1 mL of GPTEOS, 20 mL of ethanol, 62.4 mL of aqueous solution of sulfamic acid 4.2 mmol/L are successively added. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 hours using an IKA multiple stirring plate. Sol(7) _A cc contains 17.6% v/v of silylated precursors with a molar ratio of TEOS/GPTEOS of 1.5 and 20% v/v of ethanol. The Sol(7) _A cc has a stability of duration greater than 1 month.

[0155] SOI(8)ACC

In a hermetically sealed glass bottle, 9.5mL of TEOS, 8.1 mL of GPTEOS, 30mL of ethanol, 52.4mL of aqueous solution of sulfamic acid 5.0mmol/L are successively added. The mixture is stirred at room temperature (20-24°C) at 500 rpm for 3 hours using an IKA multiple stirring plate. SOI(8)ACC contains 17.6% v/v of silylated precursors with a molar ratio of TEOS/GPTEOS of 1.5 and 30% v/v of ethanol. The SOI(8)ACC has a stability of duration greater than 1 month.

Example 2: preparation of omniphobic formulations (Solomnip)

[0157] Sol(1)omniP

In a hermetically sealed glass bottle, 12.0 mL of ETOH, 2.0 mL of 17FTEOS and 3.7 mL of an aqueous solution of HCl 54.0 mmol/L are successively added. The mixture is stirred at ambient temperature (20-24° C.) at 500 rpm for 1 hour using an IKA WERKE RO10 power multiple stirring plate. Sol(1) _0mnip contains 11.3% v/v of silylated precursor and 67.7% v/v of EtOH. Sol(1) _0mnip has a stability of 3H.

[0158] Sol(2)omniP

34.0 mL of ETOH, 10.4 mL of 17FTEOS, 14.7 mL of an aqueous solution of HCl 70.0 mmol/L are successively added to a hermetically sealed glass bottle. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 1 hour using a multiple stirring plate IKA WERKE RO10 power. Sol(2) _0mnip contains 17.2% v/v silylated precursor and 59.1% v/v EtOH. Sol(2) _0mnip has a stability of 3H.

[0159] Sol(3)omniP

In a hermetically sealed glass bottle, 34.0 mL of ETOH, 10.4 mL of 17FTEOS, 5.6 mL of an aqueous solution of HCl 184.0 mmol/L are successively added. The mixture is stirred at ambient temperature (20-24° C.) at 500 rpm for 1 hour using an IKA WERKE RO10 power multiple stirring plate. Sol(3) _0mnip contains 20.7% v/v silylated precursor and 68.0% v/v EtOH. Sol(3) _0mnip has a stability of 5H.

[0160] Sol(4) _0mniP

In a hermetically sealed glass bottle, 24.9 mL of isopropanol, 10.4 mL of 17FTEOS, 14.7 mL of an aqueous solution of HCl 70.0 mmol/L are successively added. The mixture is stirred at ambient temperature (20-24° C.) at 500 rpm for 1 hour using an IKA WERKE RO10 power multiple stirring plate. Sol(4) _0mnip contains 20.7% v/v of silylated precursor and 49.8% v/v of isopropanol. Sol(4) _0mnip has a stability of 6H.

[0161] Sol(5)omniP

In a hermetically sealed glass bottle, 34.0 mL of ETOH, 10.4 mL of 17FTEOS, 5.6 mL of an aqueous solution of AcSm 184.0 mmol/L are successively added. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 1 hour 30 minutes (or 3 hours or 5 hours) using an IKA WERKE RO10 power multiple stirring plate. Sol(5) _0mnip contains 20.7% v/v silylated precursor and 68.0% v/v EtOH. Sol(5) _0mnip has a stability of 22H.

[0162] Sol(6)omniP

34.0 mL of ETOH, 10.4 mL of 17FTEOS, 5.6 mL of an aqueous solution of AcSm 93.0 mmol/L are successively added to a hermetically sealed glass bottle. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 hours using an IKA WERKE RO10 power multiple stirring plate. Sol(6) _0mnip contains 20.7% v/v silylated precursor and 68% v/v EtOH. Sol(6) _0mmp has a stability greater than 27H.

[0163] Sol(7)omniP

In a hermetically sealed glass bottle, 34.0 mL of ETOH, 10.4 mL of 17FTEOS, 5.6 mL of an aqueous solution of AcSm 46.0 mmol/L are successively added. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 hours using an IKA WERKE RO10 power multiple stirring plate. Sol(7) _0mnip contains 20.7% v/v silylated precursor and 68% v/v EtOH. Sol(7) _0mmp has a stability greater than 27H.

[0164] Sol(8)omniP

In a hermetically sealed glass bottle, are added successively 34.0 mL of ETOH, 10.4 mL of 17FTEOS, 5.6 mL of an aqueous solution of AcSm 23.0 mmol/L. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 hours using an IKA WERKE RO10 power multiple stirring plate. Sol(8) _0mnip contains 20.7% v/v silylated precursor and 68% v/v EtOH. The Sol(8) _0mnip has a stability of 48H. [0165] Sol(9)omniP

In a hermetically sealed glass bottle, 24.6 mL of ETOH, 30 mL of 17FTEOS, 4 mL of an aqueous solution of HCl 0.75 mol/L are successively added. The mixture is stirred at ambient temperature (20-24° C.) at 500 rpm for 1 hour using an IKA WERKE RO10 power multiple stirring plate. Sol(9) _0mnip contains 51.1% v/v silylated precursor and 42.0% v/v EtOH. Sol(9) _0mnip has a stability of 2H30.

[0166] Sol(10)omniP

15.0 mL of ETOH, 15.0 mL of 17FTEOS, 2.1 mL of a 1.0 mol/L aqueous HCl solution are successively added to a hermetically sealed glass bottle. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 30 min using an IKA WERKE R010 power multiple stirring plate (mixture 1). In a separate glass bottle, successively add 3.0 mL of ETOH, 4.0 mL of TEOS and 1.0 mL of water, and shake to homogenize (mixture 2). Introduce mixture 2 into mixture 1 and leave the mixture to stir for 30 min using an IKA WERKE R010 power multiple stirring plate. _Omnip Sol(10) contains 48% v/v of silylated precursors with a TEOS/17FTEOS molar ratio of 2.5 and 44.9% v/v of EtOH. The Sol(10) _om nip has a stability of 2H30.

[0167] Sol(11 )omniP

In a hermetically sealed glass bottle, 10.4 mL of 17FTEOS and 39.6 mL of an aqueous solution of AcSm 3.3 mmol/L are successively added. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 4 hours using an IKA WERKE R010 power multiple stirring plate. Sol(11) _0mmp contains 20.7% v/v of silylated precursor.

[0168] Sol(12)omnip

In a hermetically sealed glass bottle, 34.0 mL of ETOH, 10.4 mL of 13FTEOS, 5.6 mL of an aqueous solution of AcSm 23.0 mmol/L are successively added. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 hours using an IKA WERKE R010 power multiple stirring plate. Sol(14) _0mmp contains 20.7% v/v silylated precursor and 68% v/v EtOH. Sol(14) _0mmp has a stability of 89h.

[0169] Sol(13)omniP

In a hermetically sealed glass bottle, 29.8 mL of ETOH, 15.3 mL of 13FTEOS, 4.9 mL of an aqueous solution of AcSm 26.5 mmol/L are successively added. The mixture is stirred at room temperature (20-24°C) at 500 rpm for 3 hours using a multiple stirring plate IKA WERKE R010 power. Sol(15) _0mmp contains 30.7% v/v silylated precursor and 60% v/v EtOH. The Sol(15) _0mmp has a stability of 78h.

Example 3: preparation of hydrophobic formulations (SOIHYDRO)

SOI(1 )HYDRO

In a hermetically sealed glass bottle, 38.8 mL of ETOH, 9.7 mL of HDTEOS, 1.6 mL of an aqueous solution of AcSm 83.2 mmol/L are successively added. The mixture is stirred at room temperature (20-24°C) at 500 rpm for 3 hours using an IKA WERKE RO10 power multiple stirring plate. SOI(1)HYDRO contains 19.4% v/v silylated precursor and 77.4% v/v EtOH. SOI(1)HYDRO has a stability greater than 4H.

SOI(2)HYDRO

In a hermetically sealed glass bottle, 39.1 mL of ETOH, 8.4 mL of HDTEOS, 1.4 mL of TEOS, and 1.1 mL of an aqueous solution of HCl are successively added.

117.1 mmol/L. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 hours using an IKA WERKE RO10 power multiple stirring plate. Sol(2) HYDRO contains 19.6% v/v silylated precursor and 78.2% v/v EtOH. SOI(2) _H YDRO has a stability of 4H.

SOI(3)HYDRO

117.1 mmol/L. The mixture is stirred at room temperature (20-24°C) at 500 rpm for 5 hours using an IKA WERKE RO10 power multiple stirring plate. SOI(3)HYDRO contains 19.6% v/v silylated precursor and 78.2% v/v EtOH. SOI(3)HYDRO has a stability of 1J.

SOI(4)HYDRO

In a hermetically sealed glass bottle, 39.1 mL of ETOH, 6.6 mL of HDTEOS, 3.2 mL of TEOS, and 1.1 mL of an aqueous solution of HCl are successively added.

117.1 mmol/L. The mixture is stirred at ambient temperature (20-24° C.) at 500 rpm for 5 hours using an IKA WERKE RO10 power multiple stirring plate. SOI(4)HYDRO contains 19.6% v/v silylated precursor and 78.2% v/v EtOH. SOI(4) _H YDRO has a stability of 1J.

SOI(5)HYDRO

In a hermetically sealed glass bottle, 39.1 mL of ETOH, 6.6 mL of HDTEOS, 3.2 mL of TEOS, and 1.1 mL of an aqueous solution of AcSm are successively added. 117.1 mmol/L. The mixture is stirred at ambient temperature (20-24° C.) at 500 rpm for 5 hours using an IKA WERKE RO10 power multiple stirring plate. SOI(5)HYDRO contains 19.6% v/v silylated precursor and 78.2% v/v EtOH. SOI(5)HYDRO has a stability greater than 6J. SOI(6)HYDRO

In a hermetically sealed glass bottle, 39.1 mL of ETOH, 4.9 mL of HDTEOS, 4.9 mL of TEOS, and 1.1 mL of an aqueous solution of HCl 117.1 mmol are successively added. /L. The mixture is stirred at room temperature (20-24°C) at 500 rpm for 5 hours using an IKA WERKE RO10 power multiple stirring plate. SOI(6)HYDRO contains 19.6% v/v silylated precursor and 78.2% v/v EtOH. SOI(6)HYDRO has a stability greater than 6J.

SOI(7)HYDRO

In a hermetically sealed glass bottle, 39.1 mL of ETOH, 4.9 mL of HDTEOS, 4.9 mL of TEOS, and 1.1 mL of an aqueous solution of AcSm 117.1 mmol are successively added. /L. The mixture is stirred at ambient temperature (20-24° C.) at 500 rpm for 5 hours using an IKA WERKE RO10 power multiple stirring plate. SOI(7)HYDRO contains 19.6% v/v silylated precursor and 78.2% v/v EtOH. SOI(7) _H YDRO has a stability greater than 6J.

Example 4: preparation of fabrics coated by padding (Figure 1) according to the invention

[0172] P(1) _F

The Sol(1)ACC is deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven. Immediately afterwards, a 2 ^nd deposition of Sol(1) _A is carried out by padding at the same speed and the fabric is again dried for 2 min at 120° C. in an oven. The fabric is then stored for 18 hours in a desiccator with a relative humidity of 50%, at ambient temperature (20-24° C.) and atmospheric pressure. Sol(10) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests. [0173] P(2) _F

The Sol(1)ACC is deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven. Immediately afterwards, a 2 ^nd deposition of Sol(1)ACC is carried out by padding at the same speed and the fabric is again dried for 2 min at 120° C. in an oven. The fabric is then stored for 18 hours in a desiccator with a relative humidity of 50%, at ambient temperature (20-24° C.) and atmospheric pressure. Sol(10) _Omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 40 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0174] P(3) _F

The Sol(1)ACC is deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(9) _0mmp is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0175] P(4) _F The Sol(1)ACC is deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven. Immediately afterwards, a 2 ^nd deposition of Sol(1)ACC is carried out by padding at the same speed and the fabric is again dried for 2 min at 120° C. in an oven. The fabric is then stored for 18 hours in a desiccator with a relative humidity of 50%, at ambient temperature (20-24° C.) and atmospheric pressure. Sol(1) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in a oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/squeezing in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m /min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0176] P(5) _F

The Sol(1)ACC is deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven. Immediately afterwards, a 2 ^nd deposition of Sol(1) _A is carried out by padding at the same speed and the fabric is again dried for 2 min at 120° C. in an oven. The fabric is then stored for 18 hours in a desiccator with a relative humidity of 50%, at ambient temperature (20-24° C.) and atmospheric pressure. Sol(9) _0mnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0177] P(6)F

The SOI(2) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(9) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests. [0178] P(7) _F

The SOI(2) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. The Sol(3) _0mnip is then deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0179] P(8) _F The SOI(3) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(3) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0180] P(9) _F

The SOI(3) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(3) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120° C. in an oven, then left to cool in the open air at room temperature (20- 24°C) and atmospheric pressure before being stored for washing, water repellency and oil repellency tests.

[0181] P(10) _F

The SOI(4) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(3) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0182] P(11) _F

The SOI(2) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(2) ₀ mmp is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0183] P(12) _F The SOI(3) _ACC is deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(5) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0184] P(13) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(3) _0mmp is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0185] P(14) _F The SOI(6) _ACC is deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(5) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0186] P(15) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8) _omnip is then deposited by padding on the fabric at speed 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0187] P(16) _F The SOI(6) _ACC is deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure. before being stored for washing, water repellency and oil repellency tests.

[0188] P(17) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 5 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0189] P(18) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8) ₀ mmp is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 5 min at 120° C. in an oven, then is then kept for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before being stored for the washing, water repellency and oil repellency tests.

[0190] P(19) _F The SOI(6) _ACC is deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0191] P(20) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 150° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 150°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 minutes at 150°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests. [0192] P(21) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 150° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 minutes at 150°C in an oven and then stored for 16 to 18 hours in a desiccator with relative humidity. of 50%, at room temperature (20-24°C) and atmospheric pressure before being stored for washing, water repellency and oil repellency tests.

[0193] P(22) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 180° C. in an oven, then left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 min at 180°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 180°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0194] P(23) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 180° C. in an oven, then left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8) ₀ mmp is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 minutes at 180°C in an oven and then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before to be stored for washing, hydrophobicity and oleophobicity tests. [0195] P(24) _F

The SOI(5) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8) _omnip is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure for 10 to 30 min, before undergoing the final padding/ expression in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before being stored for washing, water repellency and oil repellency tests.

[0196] P(25) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 180° C. in an oven, then left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. The SOI(1) _HYDRO is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is dried for 2 minutes at 180°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure. before being stored for hydrophobicity testing.

[0197] P(26) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is dried for 2 min at 150° C. in an oven, then is left to cool and mature for 1 to 2 weeks in the open air, at room temperature (20-24° C.) and atmospheric pressure. The Sol(12) _0mnip is then deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is left to dry and mature in the air, at room temperature (20 - 24°C) and atmospheric pressure in the laboratory for 2 weeks, before being stored for washing, hydrophobicity and drying tests. oleophobia. [0198] P(27) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is left to dry and mature for 1 week to 3 months in the air, at ambient temperature (20-24° C.) and atmospheric pressure in the laboratory. The Sol(12) _0mnip is then deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is left to dry and mature in the air, at room temperature (20 - 24°C) and atmospheric pressure in the laboratory for 2 weeks, before being stored for washing, hydrophobicity and drying tests. oleophobia.

[0199] P(28) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is left to dry and mature for 1 week to 3 months in the air, at ambient temperature (20-24° C.) and atmospheric pressure in the laboratory. The Sol(13) _0mnip is then deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is left to dry and mature in the air, at room temperature (20 - 24°C) and atmospheric pressure in the laboratory for 2 weeks, before being stored for washing, hydrophobicity and drying tests. oleophobia. [0200] P(29) _F

The SOI(6) _ACC is deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is left to dry and mature for 1 week to 3 months in the air, at ambient temperature (20-24° C.) and atmospheric pressure in the laboratory. The Sol(13) _0mnip is then deposited by padding on the fabric at the speed of 2 m/min. After pressing, the fabric is left to dry and mature at 40°C in the oven for 4 days then mature for 3 days in the air, at room temperature (20 - 24°C) and atmospheric pressure in the laboratory, before being stored for washing, water repellency and oil repellency tests.

[0201] P(30) _F The SOI(6) _ACC is deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is left to dry for 1 day in the open air, at room temperature (20-24° C.) and atmospheric pressure in the laboratory. The fabric is then left to mature at 40° C. in the oven for 1 day then 5 days in the air, at room temperature (20-24° C.) and atmospheric pressure in the laboratory. Sol(13) _0mmp is then deposited by padding on the fabric at a speed of 2 m/min. After pressing, the fabric is left to dry and mature at 40°C in the oven for 4 days then 3 days in the air, at room temperature (20 - 24°C) and atmospheric pressure in the laboratory, before being stored. for washout, water repellency and oil repellency tests.

[0202] Example 5: preparation of spray-coated fabrics (Figure 2) according to the invention

[0203] P(1) _Sp

The SOI(3) _ACC is deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, the latter being moved at a speed of 6 m/min. The assembly is placed in an enclosure under pumping for the evacuation of the ethanol vapours. After deposition, the fabric is dried for 2 min at 120° C. in an oven, then is left to cool for 30 min to 1 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. The Sol(8) _0mnip is then deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, in a double pass, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3kg roller and dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure. for 10 to 30 min, before undergoing the last padding/squeezing in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before being stored for washing, water repellency and oil repellency tests.

[0204] P(2) _Sp

The SOI(3)ACC is deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, the latter being moved at a speed of 9 m/min. The assembly is placed in an enclosure under pumping for the evacuation of the ethanol vapours. After deposition, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 h in the open air, at ambient temperature (20-24° C.) and atmospheric pressure. The Sol(8) ₀ mnip is then deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, in a double pass, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3kg roller and dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure. for 10 to 30 min, before undergoing the last padding/squeezing in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0205] P(3) _Sp The SOI(3)ACC is deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, the latter being moved at a speed of 12 m/min. The assembly is placed in an enclosure under pumping for the evacuation of the ethanol vapours. After deposition, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 h in the open air, at ambient temperature (20-24° C.) and atmospheric pressure. The Sol(8) ₀ mnip is then deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, in a double pass, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3kg roller and dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure. for 10 to 30 min, before undergoing the last padding/squeezing in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before to be stored for washing, water repellency and oil repellency tests [0206] P(4) _Sp

The SOI(3)ACC is deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, the latter being moved at a speed of 12m/min. The assembly is placed in an enclosure under pumping for the evacuation of the ethanol vapours. After deposition, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 h in the open air, at ambient temperature (20-24° C.) and atmospheric pressure. The Sol(8) ₀ mnip is then deposited by spray (pressure 4 bars) at a distance of 20 cm from the fabric, in a double pass, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3kg roller and dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure. for 10 to 30 min, before undergoing the last padding/squeezing in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests. [0207] P(5) _Sp

The SOI(3)ACC is deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, the latter being moved at a speed of 12 m/min. The assembly is placed in an enclosure under pumping for the evacuation of the ethanol vapours. After deposition, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 h in the open air, at ambient temperature (20-24° C.) and atmospheric pressure. The Sol(8) ₀ mnip is then deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, in a double pass, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3kg roller and dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure. for 10 to 30 min, before undergoing the last padding/squeezing in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0208] P(6) _Sp

The SOI(6)ACC is deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, the latter being moved at a speed of 9 m/min. The assembly is placed in an enclosure under pumping for the evacuation of the ethanol vapours. After deposition, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 29 h in the open air, at room temperature (20-24° C.) and atmospheric pressure. The Sol(11 ) _om niP is then deposited by spray (pressure 4 bars) at a distance of 10 cm from the fabric, in double passage, the latter being moved at the speed of 9 m/min. After deposition, the fabric is compressed using a 3kg roller and dried for 10 min at 120°C in an oven, then left to cool to room temperature (20 - 24°C) and laboratory atmospheric pressure. for 10 to 30 min, before undergoing the last padding/squeezing in a 0.065 mol/L sodium hydroxide solution at a speed of 2 m/min. The fabric is dried for 2 min at 120°C in an oven, then stored for 16 to 18 hours in a desiccator with a relative humidity of 50%, at room temperature (20-24°C) and atmospheric pressure before be stored for washing, hydrophobicity and oleophobicity tests.

[0209] Example 6: Tests of the hydrophobic and oleophobic properties, permeability and resistance of the fabrics prepared according to the invention to washings and to strong acids and bases

[0210] The attachment of the sol-gel materials to the fibers is visualized thanks to the images obtained by Scanning Electron Microscopy (SEM, ZEISS Ultra-55, GEMINI column) and is checked after the washings with the hydrophobicity and dip tests. oleophobia.

[0211] The washing tests (1, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, and 80 washes) are carried out according to the ISO 6330 standard. The different fabrics undergo a washing cycle of 2h in a machine with horizontal axis and front loading. Washing is carried out at 60° C., in the presence of 77% ECE detergent (detergent A reference No. 3), 20% sodium perborate tetrahydrate, 3% tetra-acetyl-ethylene-diamine (TAED). Spinning is carried out at 1200 rpm. The fabrics are dried at 95°C using a tumble dryer for 45 min after each wash.

[0212] Resistance tests of the omniphobic coating to strong acids and bases are carried out by immersing the fabric in solutions of strong acid (HCl) or strong base (NaOH). The contact angles of water and n-decane on the surface of the P(15)F sample were measured before and after 24 hours of soaking the sample in acidic (pH=0) and basic solutions ( pH=12 and 14). The results obtained presented in Figure 10 show a very small variation in these contact angles and a hydrophobicity and oil repellency preserved even after contact of the textile with solutions of acids and strong bases, which demonstrates the great resistance of the textile thus coated to acids. and strong bases. Such a coating on protective gowns will protect the worker from strong acid or base splashes.

[0213] The hydrophobicity and oleophobicity tests were carried out on the coated fabrics (kermel-viscose fabric), when new, and after 1, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, and 80 washes.

For the visual hydrophobicity test, drops of 50 mI_ (approximately 5 mm in diameter) of water are deposited using a micropipette on at least 5 different locations distributed over the surface of the fabric. The drops are observed for 30±2 s (minimum) at an angle of 45°C. The fabric is shaken to remove the drops of water. The test is passed when the back of the fabric has remained dry. To have a more precise measurement of the hydrophobicity, the contact angle of the water on the coating is measured.

The contact angle is measured using an OCA 15EC (SCA 20) goniometer. 10 drops of 10pL of water are placed on the fabric using a needle (Hamilton 500mL, HAMI91022) for each measurement. A coating is said to be hydrophobic when the contact angle of a drop of water is greater than 90 degrees.

For the visual measurement tests of the oil repellency index, drops of 50 μL of alkanes are deposited using a micropipette on at least 4 different locations distributed over the surface of the fabric. The drops are observed for 30 s and their shape is graded according to the references of the ISO 14419 standard. The grades assigned range from A to D for the shape of the drop. A drop of an alkane of index n is placed on the surface of a coated fabric. If the drop is very round (grade A), the test is successful and the index n is assigned to the coating. If the drop obtains the note B, the alkane is changed by taking a lower index n-1 for which the drop obtains the note A. Of the 4 drops deposited in a dispersed manner on a given coating, only one drop is sufficient has the index n-1 so that the coating is rated n/(n-1). See examples in Table 1. To have a more precise measurement of oil repellency, the contact angle of alkanes on the coating is measured.

The contact angle is measured using an OCA 15EC (SCA 20) goniometer. 4 to 8 drops of 10pL of an alkane are placed on the fabric using a needle (Hamilton 500mL, HAMI91022) for each measurement. A coating is said to be oleophobic when the contact angle of an alkane drop is greater than 90 degrees

The results obtained are presented in Tables 1 and 2 below.

[0218] [Table 1]

Het = Heterogeneous [0219] [Table 2]

0ow = contact angle at nine in degrees; 0 ₃ ow = contact angle after 30 washes; P _v = permeability of the virgin fabric, P _e = permeability of the coated fabric.

[0220] An example of visual analysis of water and oil repellency with various alkanes is shown in Figure 4. Figure 5 gives an example of contact angle measurements with a new coated fabric that has been washed 30 times.

[0221] Examples of Scanning Electron Microscope (SEM) analysis of virgin fabrics and coated with sol-gel coating are shown in Figure 6, Figure 7 and Figure 8. These pictures allow to observe a homogeneous sheathing of the fibers by a coating according to the invention.

Claims

[Claim 1] Process for coating a textile material, said process comprising the following steps: a) at least one cycle of impregnation of the textile material with a sol-gel tie formulation, said sol-gel formulation of hook being free of polycarboxylic acid; b) at least one drying cycle of the impregnated textile material obtained in step a); c) at least one impregnation cycle of the dried textile material obtained in step b) with an omniphobic or hydrophobic sol-gel formulation comprising sulfamic acid, said omniphobic or hydrophobic sol-gel formulation being different from the sol formulation - gripping gel; d) at least one drying cycle of the impregnated textile material obtained in step c).

[Claim 2] Process according to claim 1, characterized in that at least one drying cycle is followed by a step d') of maturing the material obtained in step d) by storage at room temperature in a humid atmosphere with a relative humidity of 50% for at least 16 to 18 hours.

[Claim 3] Process for coating a textile material according to one of Claims 1 or 2, characterized in that it comprises the following additional steps: e) washing with a neutralizing aqueous solution of the impregnated textile material obtained by step d). f) drying the material obtained in step e).

[Claim 4] Process according to claim 3, characterized in that the step of drying the material obtained in step e) is followed by a step f) of maturing the material obtained in step f) by preservation at room temperature under a humid atmosphere with a relative humidity of 50% for at least 16H to 18H.

[Claim 5] Method according to one of the preceding claims, characterized in that each of the impregnation steps is carried out independently by padding or by spraying.

[Claim 6] Method according to one of the preceding claims, characterized in that it comprises at least 2 successive cycles a) and b) of impregnation of the textile material with a sol-gel tie formulation, said sol-gel formulation gripping gel being free of polycarboxylic acid, and drying of the impregnated textile material.

[Claim 7] Process according to one of the preceding claims, in which step a) comprises a step of pressing under pressure after the or each cycle impregnation and/or step c) comprises a pressurizing step after the or each impregnation cycle.

[Claim 8] Method according to one of the preceding claims, characterized in that the sol-gel tie formulation comprises at least two silylated precursors, preferably chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), ( 3-glycidyloxypropyl)trimethoxysilane (GPTMOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and aminopropyltriethoxysilane.

[Claim 9] Method according to one of the preceding claims, characterized in that the sol-gel tie formulation comprises an acid chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid, paratoluenesulfonic acid, preferably sulfamic acid.

[Claim 10] Process according to one of the preceding claims, characterized in that the sol-gel adhesion formulation is free of zirconium alkoxide and/or sodium hypophosphite.

[Claim 11] Method according to one of the preceding claims, characterized in that the omniphobic sol-gel formulation comprises at least one silylated precursor, preferably chosen from 1H,1H,2H,2H-perfluorodecyltriethoxysilane (17FTEOS), 1H,1H,2H,2H-perfluorooctyltriethoxysilane (13FTEOS), 1H,1H,2H,2H-perfluorooctyltrimethoxysilane (13FTMOS), 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (17FTMOS), or a mixture of one or more of these precursors with tetraethoxysilane (TEOS).

[Claim 12] Process according to one of the preceding claims, characterized in that the hydrophobic sol-gel formulation comprises at least one silylated precursor, preferably chosen from hexadecyltriethoxysilane (HDTEOS), n-octadecyltriethoxysilane (ODTEOS), n-decyltriethoxysilane (DTEOS), dodecyltriethoxysilane (DDTEOS), or a mixture of one or more of these precursors with tetraethoxysilane (TEOS).

[Claim 13] Process according to one of the preceding claims, characterized in that the omniphobic and/or hydrophobic sol-gel tie formulation is an aqueous formulation and optionally comprises one or more C1 to C4 aliphatic alcohols, chosen in particular from methanol, ethanol, propan-1-ol, isopropanol and butan-1-ol, preferably from isopropanol and ethanol.

[Claim 14] Sol-gel tie formulation comprising at least two silylated precursors, a first precursor preferably being chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), and a second precursor preferably being chosen from (3 -glycidyloxypropyl)trimethoxysilane (GPTMOS), the (3-glycidyloxypropyl)triethoxysilane (GPTEOS), aminopropyltriethoxysilane, optionally, the combination of TMOS/GPTMOS precursors being excluded, and comprising an acid chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid, paratoluenesulfonic acid, preferably sulfamic acid, said sol-gel formulation being free of polycarboxylic acid.

[Claim 15] Sol-gel tie formulation according to claim 14, said sol-gel formulation being free of zirconium alkoxide and/or sodium hypophosphite.

[Claim 16] Sol-gel tie formulation according to one of claims 14 to 15, said sol-gel formulation being an aqueous formulation, optionally comprising at least one aliphatic C1 to C4 alcohol, chosen in particular from methanol, ethanol, propan-1-ol, isopropanol and butan-1-ol, preferably the C1 to C4 aliphatic alcohol is ethanol.

[Claim 17] Sol-gel tie formulation according to one of claims 14 to 16 comprising tetraethoxysilane (TEOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and sulfamic acid.

[Claim 18] Omniphobic sol-gel formulation comprising at least one silylated precursor selected from 1H,1H,2H,2H-perfluorodecyltriethoxysilane (17FTEOS), 1H,H,H,H-perfluorooctyltriethoxysilane (13FTEOS), 1H ,1H,2H,2H-perfluorooctyltrimethoxysilane (13FTMOS) and 1H,1H,2H,2H-perfluorodecyltrimethoxysilane (17FTMOS), or a mixture of one or more of these precursors with tetraethoxysilane (TEOS), and comprising sulfamic acid.

[Claim 19] Omniphobic sol-gel formulation according to claim 18, said sol-gel formulation being an aqueous formulation optionally comprising at least one C1 to C4 aliphatic alcohol, chosen in particular from methanol, ethanol, propan-1 - ol, isopropanol and butan-1-ol, preferably chosen ethanol and isopropanol.

[Claim 20] Omniphobic sol-gel formulation according to one of claims 18 to 19 comprising 1H,1H,2H,2H-perfluorodecyltriethoxysilane (17FTEOS) and sulfamic acid.

[Claim 21] Hydrophobic sol-gel formulation comprising at least one silylated precursor selected from hexadecyltriethoxysilane (HDTEOS), n-octadecyltriethoxysilane (ODTEOS), n-decyltriethoxysilane (DTEOS) and dodecyltriethoxysilane (DDTEOS), or a mixture of one or more of these precursors with tetraethoxysilane (TEOS), and comprising sulfamic acid.

[Claim 22] Hydrophobic sol-gel formulation according to claim 20, said sol-gel formulation being an aqueous formulation optionally comprising at least one aliphatic C1 to C4 alcohol, selected from methanol, ethanol, propan-1-ol , isopropanol and butan-1-ol, preferably the C1 to C4 aliphatic alcohol is ethanol or isopropanol, more preferably the C1 to C4 aliphatic alcohol is ethanol.

[Claim 23] Hydrophobic sol-gel formulation according to one of claims 20 or 22 comprising hexadecyltriethoxysilane (HDTEOS) and sulfamic acid or comprising hexadecyltriethoxysilane (HDTEOS), tetraethoxysilane (TEOS) and sulfamic acid.

[Claim 24] Impregnated textile material comprising at least a first tie layer obtained by applying a sol-gel tie formulation according to one of claims 14 to 17 and at least a second omniphobic or hydrophobic layer above of the adhesion layer.

[Claim 25] Impregnated textile material according to claim 22 comprising at least one first tie layer obtained by applying a sol-gel tie formulation according to one of claims 14 to 17 and at least one second omniphobic layer on the above the tie layer obtained by applying an omniphobic sol-gel formulation according to one of claims 18 to 19.

[Claim 26] Impregnated textile material according to claim 22 comprising at least a first tie layer obtained by applying a sol-gel tie formulation according to one of claims 14 to 17 and at least a second hydrophobic layer on the above the tie layer obtained by applying a hydrophobic sol-gel formulation according to one of claims 21 to 23.

[Claim 27] Impregnated textile material comprising at least a first tie layer and at least a second omniphobic layer above the tie layer obtained by applying an omniphobic sol-gel formulation according to one of claims 18 to 20 or at least one second hydrophobic layer above the tie layer obtained by application of a hydrophobic sol-gel formulation according to one of Claims 21 to 23.

[Claim 28] Impregnated textile material obtained according to the coating process according to one of Claims 1 to 13.

[Claim 29] Personal protective equipment comprising the impregnated textile material according to any one of claims 24 to 28.