METHOD FOR COATING TEXTILE MATERIALS

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

TECHNICAL FIELD

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

BACKGROUND

Garments that protect against splashes of liquids containing corrosive and/or toxic chemicals (acidic or basic aqueous solutions, oils, hydrophilic or hydrophobic organic solvents) must, depending on the application, have oleophobic and/or hydrophobic properties. The combination of these two properties on a material leads to a material that can be termed omniphobic.

To make garment coatings omniphobic, i.e. both hydrophobic and oleophobic, the textile industry currently uses a formulation of fluorinated resins containing perfluorooctanoic acid and/or salts thereof. However, these compounds, which are released into the biosphere when the clothes are washed, are carcinogenic and toxic to the biosphere. The REACH regulation (“Registration, Evaluation, Authorization and restriction of Chemicals”) has restricted the presence of perfluorooctanoic acid (PFOA) and salts thereof in the PPE (personal protective equipment) sector since Jul. 4, 2023. Since Apr. 8, 2020, European regulations have extended the ban to PFOA-related compounds such as perfluorooctane sulfonic acid and its derivatives (PFOS), C₈F₁₇SO₂X (X=OH, metal salt, halide, amide and other derivatives including polymers), which will make the use of long-chain (at least 8 carbons) fluorinated resins impossible.

For the past ten years, in anticipation of the entry into force of these regulations, industry and the scientific community have been focusing their attention on alternative solutions. However, it is very difficult to achieve both hydrophobicity and oleophobicity, as these properties are antagonistic. Indeed, while the presence of long hydrocarbon-based chains may be sufficient to render a fabric hydrophobic, these attract low-polarity compounds such as oils. On the other hand, if the coating is highly polar, the fabric is oleophobic but hydrophilic, attracting polar compounds such as water. Thus, the literature results show that it is known with hydrophobic coatings to obtain water repellency while at the same time allowing oils and aliphatic hydrocarbons to pass through. Similarly, it is known to obtain oil repellency with a hydrophilic coating that lets water through. These coatings can then be used to separate water and oils.

The field of research into hydrophobic and/or oleophobic coatings has been in full expansion since the 2000s. However, analysis of the literature data shows that advances in the field of oleophobic and/or hydrophobic garments have yet to meet the very strict specifications demanded by the textile industry, notably for protective clothing (firefighters, infantrymen, law enforcement agents, industrial workers). The level of oleophobicity of the new textile must reach index 4, preferably index 5, even more preferentially index 6, and be maintained at least after 10 washes, preferably after 20 washes, even more preferentially after 30 washes. According to the standard ISO14419, indices from 1 to 8 correspond to an oleophobicity achieved 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 thus corresponds to oleophobicity with n-decane. For oleophobicity values between 4 and 6, omniphobic and water-repellent coatings are of interest in consumer products, such as rainwear, non-soiling workwear and children's clothing. Omniphobic coatings with the highest oleophobicity indexes, notably greater than or equal to 6, are particularly suitable for personal protective equipment for the armed forces, police, firefighters and industry.

A large number of studies on superhydrophobicity and superoleophobicity use nanometric surface texturing to reduce the contact points between water droplets and the surface (LOTUS effect). However, the application of the LOTUS effect to textile coatings has proven complex, as it is not adapted to the textile industry. Specifically, not only do textiles have uneven surfaces, they also differ in terms of material composition (aramid, viscose, polyamide, glass, cotton, carbon, polyester), yarn composition (fibers or filaments), fiber size and titre, weave and fabric context. As a result, processes using the LOTUS effect are essentially multi-step processes (Leng et al. Langmuir, (2009) 25, 2456-2460. DOI: 10.1021/1a8031144; 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) which are difficult to transpose to the textile industry, where kilometers of “raw” fabric have to be processed in a day in an open environment. Moreover, fabric unwinding speeds ranging from 5 to 50 m/min only allow rapid soaking in baths, thus ruling out any process requiring long-term reagent impregnations. Furthermore, the processes proposed in the prior art involve large amounts of toxic and volatile solvents.

Other processes described in the literature involve a much smaller number of steps and/or essentially aqueous processes. Pan et al. (AIChE Letters, 60(8) (2014), 27522756. DOI: 10.1002/aic.14517) use the vacuum silanization method in a 30 cm diameter desiccator by exposing for 24H a previously cleaned cotton square to various alkylsilanes: n-octyltrichlorosilane (C18H37CL3Si, CAS No. 5283-66-9), tridecafluoro-1,1,2,2-tetrahydrooctyltrichlorosilane (C8H4F13Cl3Si, CAS No. 78560-45-9) or tridecafluoro-1,1,2,2-tetrahydrooctyltriethoxysilane (C14H19F13O3Si, CAS No. 51851-37-7). They obtain omniphobic properties for fabrics treated only with C8H4F13C13Si. The oleophobicity level achieved is 8 with hexane at a contact angle of 151°. However, the authors did not conduct machine wash tests to demonstrate the wash resistance of the coating. More particularly, the vacuum silanization process involves prior in-depth 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 undoubtedly used the vacuum pumping method suitable for small-area test samples. The 24-hour vacuum silanization time is also difficult to apply in the textile industry.

Patent application FR 2984343-A1 from the Institut Français du Textile et de l'Habillement (IFTH) describes a sol-gel process in an aqueous medium which allows a hydrophobic, water-repellent coating to be obtained for a cotton fabric in five steps, with a) preparation of an aqueous “one-pot” sol by mixing various reagents (sol-gel precursors=TEOS and hexadecyltrimethoxysilane (C19H42O3Si, CAS No. 16415-12-6), a carboxylic acid and a catalyst, sodium hypophosphite) and water, b) ultrasonic impregnation for 5 min of a (11×15 cm²) piece of cotton, followed by c) padding to remove the excess solvent, then d) a first drying at 80° C. for 1 h, followed by e) a second drying at 170° C. for 2.5 min. The authors report water-repellency durability after 20 household washes with detergent, but no oleophobicity was obtained.

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 the production of barrier properties towards toxic gaseous compounds, namely gaseous toluene and gaseous methyl salicylate. The textile used is a 50% blend of viscose and aramid fibers. Using a Sol formulation (H′) comprising 9.92% by volume of TMOS (tetramethoxysilane), 2.1% of 1H, 1H,2H,2H-perfluorodecyltriethoxysilane (C16H19F17O3Si, CAS No. 101947-16-4), 76.5% water and 11.48% acetonitrile, the authors obtained a hydrophobic coating resistant to five washes. By precoating the fabric with an ethanolic solution of zirconium propoxide (C12H28O4Zr, CAS No. 23519-77-9) prior to coating with the H′ formulation, the authors were able to increase the wash resistance to obtain a fabric that was hydrophobic and water-repellent for up to 20 washes. The protocol involves soaking the fabric in each of the solutions, followed by padding to remove the excess solvent and drying at 120° C. for 2-5 min. However, the authors did not describe any oleophobicity properties for these coatings.

Patent application WO 2016/077532 A1 from the University of Houston proposes a soiling- and stain-resistant coating based on a double coating layer. By using for the first layer a mixture containing at least three types of alkoxysilane: tetraethoxysilane, trimethoxypropylsilane and 3-glycidoxypropyltrimethoxysilane, as structuring, plasticizing and bridging agents, respectively, water, HCl and MeOH, all diluted with MeOH, and for the second layer an acidic solution (pH<1) of trichloro(1H,1H,2H,2H-perfluorooctyl)silane in MeOH pretreated by heating to between 50 and 100° C., then neutralized with a KOH solution and filtered to remove solid particles, the authors achieved oleophobicity levels of 6 to 9, but did not perform a wash resistance test. Using a methanolic solution of trimethoxy(1H, 1H,2H,2H-perfluorooctyl)silane for the second layer, the authors also achieved oleophobicity levels from 6 to 9, but did not perform a wash resistance test.

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 ˜30 nm in diameter) dissolved in tridecafluorooctyltriethoxysilane (FAS, Dynasylan F 8261 from Evonik) and then diluted in ethanol. The mixture (100 mL) must be sonicated for 30 min to produce a homogeneous, transparent solution, which is stable at room temperature for 10H. 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) initial 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 13 μL droplets of water, hexadecane, tetradecane and octane. According to the authors, this coating shows very little damage 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 perform and allows the production of an oleophobicity level of 7, the use of nanosized silsesquioxane oligomers (30 nm in diameter) may prove problematic for the environment in the event of material loss during washing. Moreover, the long impregnation and drying times are not compatible with an industrial process.

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

In summary, on the basis of the work presented in the literature, omniphobicity (hydrophobicity and oleophobicity) may only be achieved in three cases: (1) by vacuum silanization of a fabric previously ultra-cleaned with a long-chain fluorinated trichlorosilane for 24 H, or (2) with the use of the Lotus effect (functionalized silica or silsesquioxane nanoparticles) coupled with a fluoro coating or (3) with the use of two coating layers, the first of which contains a structuring agent, a plasticizer and a bridging agent, and a second layer of a fluoro compound obtained from trichloro(1H, 1H,2H,2H,-perfluorooctyl)silane or from trimethoxy(1H, 1H,2H,2H-perfluorooctyl)silane.

However, as indicated previously, vacuum silanization is a process which is difficult to industrialize in the textile industry, notably when the fabric must first be cleaned of any impurities trapped in the fiber network during production. In the second case, there is a risk of losing material (fluorinated or functionalized nanometric particles) during successive washes, with the attendant risk 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 a solvent for the second coating, which in certain cases requires lengthy treatment at high temperature. In this case, the stated wet take-up values for the coatings are high, between 115% and 160%. Moreover, the majority of the studies do not report on the permeability of the treated fabric, and a sharp reduction thereof with a multilayer coating would result in poor breathability and consequently discomfort for the user.

In the textile industry, the liquid coating of fabrics is performed continuously on kilometers of fabric moving at a speed of 5 to 50 m/min. It is thus necessary to minimize the number of steps and the duration of each step, notably those corresponding to the drying sequences.

There is thus a need for a simple, industrializable process for coating textiles, allowing them to be made omniphobic or hydrophobic while at the same time preserving sufficient breathability, and not using potentially environmentally polluting nanoparticles or large amounts of toxic, volatile solvents.

SUMMARY

The inventors have, to their credit, solved this problem by developing a process which is compatible with the liquid-based industrial processes commonly used in the textile industry, and which does not require prewashing of the fabric. This process includes a reduced number of steps, including the deposition (by padding or spraying) of two sol-gel formulations, with an optional fabric wash-neutralization step depending on the formulations used, each of the steps being followed by a short drying time (less than 10 min).

The process uses nontoxic formulations that meet the expectations and requirements of the textile industry, i.e. formulation preparation at room temperature, very high formulation stability over time for flexibility of use, a reduced number of steps and short heat treatments of the textile running at high speed, and no exposure of workers to a toxic environment.

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

A sol-gel material is a material obtained via a sol-gel process consisting in using as precursors metal alkoxides of formula M(OR)_xR′_n-x where M is a metal or metalloid, notably silicon, R is an alkyl group and R′ is a group bearing one or more functions with n=4 and x may range between 2 and 4. In the presence of water, the alkoxy groups (OR) are hydrolyzed to silanol groups (Si—OH), with the formation of alcohols ROH. Said silanols condense to form siloxane bonds (Si—O—Si—), with the release of water molecules. Small particles, generally less than 1 μm in size, aggregate to form clusters that remain in suspension without precipitating, forming a sol. The increase of the clusters and their condensation increases the viscosity of the medium, which gels. A porous solid material is obtained by drying the gel, with expulsion of the solvent(s) out of the polymer network formed (syneresis). In industry, for the deposition of a sol-gel formulation on a textile, it is important for the formulation to be able to be prepared quickly and/or stored for a long time in case of technical contingencies. The liquid sol must remain stable throughout the process, which may last more than 10 hours. To rapidly prepare a sol including a silicon alkoxide, the method commonly used consists in accelerating the hydrolysis step with an acid catalyst. In most of the patents and literature articles, a very wide range of acids is always proposed, including nitric, nitrous, hydrochloric, sulfuric and phosphoric acids.

One subject of the invention thus relates to a process for coating a textile material, said process comprising the following steps:

• • a) at least one cycle of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding 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, said omniphobic or hydrophobic sol-gel formulation being different from the sol-gel bonding formulation;
  • d) at least one cycle of drying 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 under a humid atmosphere with a relative humidity of 50% for at least 16 to 18H. In contrast to prior art processes, the process according to the invention is suitable for industrial use, since it involves a reduced number of steps, all of which can be readily performed on an industrial scale, unlike vacuum silanization, for example. Another advantage relative to the prior art is that it does not require the use of nanoparticles, which may cause pollution.

Via this process, a textile material can be prepared that is both omniphobic or hydrophobic, these properties being resistant to washing, and retaining its permeability, thus providing good breathability and comfort for the user.

The textile material used may be of any type. For example, it may be a woven, nonwoven or knitted fabric, preferably a woven fabric. The term “textile material” refers to a material whose constituent unit elements are fibers. Advantageously, the textile material comprises fibers including reactive functions such as hydroxyl functions. An example of such a fiber is the cellulose present in natural fibers such as cotton or artificial fibers such as viscose. Preferably, they are viscose fibers. The fibers including hydrolyzable functions may be used alone, in blends with each other and/or in blends with other synthetic fibers such as polyamide, polyamide/imide, polymeta-phenylene terephthalamide, polypara-phenylene terephthalamide, acrylic, modacrylic, polyester, oxidized polyacrylonitrile, poly(p-phenylene-2,6-benzobisoxazole) and polybenzimidazole or natural fibers such as wool. In a preferred embodiment, the textile material is a material based on an intimate mixture of viscose and synthetic fibers, preferably polyamide fibers, notably aromatic polyamide. An example of such a fabric is Kermel®/Lenzing FR® 50:50.

According to one embodiment, said at least one cycle of impregnating a) the textile material with a sol-gel bonding formulation comprises a step of pressure squeezing the impregnated textile material. Preferably, when the process comprises at least two impregnation cycles a), a step of pressure squeezing the impregnated textile material is performed after each impregnation cycle.

According to one embodiment, said at least one cycle of impregnation c) of the dried textile material obtained in step b) with an omniphobic or hydrophobic sol-gel formulation comprises a step of pressure squeezing the impregnated textile material. Preferably, when the process comprises at least two impregnation cycles c), a step of pressure squeezing the impregnated textile material is performed after each impregnation cycle.

Thus, when the impregnation is followed by a pressure squeezing step, this allows the excess sol to be removed. After this pressure squeezing step, a wet take-up rate can be measured, representing the amount of sol taken up by the fabric before drying. This rate is determined via the method described hereinbelow.

Thus, the take-up rate is between 40% and 46%, preferably about 43%. This is the wet take-up rate, before drying.

According to one embodiment, pressure squeezing is performed under the following conditions. The impregnated fabric passes between two pressure rollers maintained at a pressure which may range between 2 and 7 bar, and at a throughput speed ranging from 1 to 9 m/min. Squeezing is preferably performed at 5 bar and a throughput speed of 2 m/min.

According to one embodiment, said process comprises the following steps:

• • a) at least one cycle of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding 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 sulfamic acid, said omniphobic or hydrophobic sol-gel formulation being different from the sol-gel bonding formulation;
  • d) at least one cycle of drying 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 under a humid atmosphere with a relative humidity of 50% for at least 16 to 18H.

Another important point for worker exposure is the choice of the alkoxy groups. To avoid the formation of volatile and toxic methanol during the hydrolysis of silicon alkoxides (OR), 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 the impregnated textile material obtained in step d) with a neutralizing aqueous solution.
  • 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 under a humid atmosphere with a relative humidity of 50% for at least 16H to 18H.

These additional steps for neutralizing the textile material are optional in the process according to the invention and are performed only when neutralization is required.

The term “neutralizing aqueous solution” means an aqueous solution which allows acid residues present in the impregnated textile material obtained via the process according to the invention to be neutralized on conclusion of step d). Suitable neutralizing aqueous solutions are well known to those skilled in the art. This is generally a basic aqueous solution, such as a sodium hydroxide or potassium hydroxide solution, preferably a sodium hydroxide solution.

Each of the impregnation steps of the process may be independently performed by padding (FIG. 1) or spraying.

Compared with other coating techniques, padding allows uniform distribution of the sol, and also better impregnation of the sol into the fabric. The scanning electron microscopy images show that 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 performed at a speed of 1 to 50 meters/minute, preferably about 2 meters/minute.

Spraying (FIG. 2) consists in vaporizing a liquid into fine droplets (also known as an aerosol), which may be performed using a mechanical spray device. Unlike padding, this deposition method allows only one side of the fabric to be coated, and there is no need to remove excess formulation. Thus, for certain applications, it is possible to have each side of the fabric coated with a different formulation. However, it is advantageous to perform a squeezing step after spraying.

The spraying step according to the process is preferably performed at a pressure of 3 to 5 bar, even more preferentially 4 bar, on a textile material preferably placed at a distance of 5 to 15 cm from the spraying system, the textile material preferably being moved at a speed of 5 to 15 meters/minute, even more preferentially 6 to 12 meters/minute.

The process may include at least two successive cycles, a) and b), of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding formulation being free of polycarboxylic acid, and of drying the impregnated textile material.

According to one embodiment, the process may include at least two successive cycles a) and b), of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding formulation prepared at room temperature between 18 and 28° C. being free of polycarboxylic acid, and of drying the impregnated textile material.

According to one embodiment, the process may include at least two successive cycles a) and b), of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding formulation containing sulfamic acid and being free from polycarboxylic acid, and of drying the impregnated textile material.

According to one embodiment, the process may include at least two successive cycles a) and b), of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding formulation prepared at room temperature between 18 and 28° C. being free from polycarboxylic acid and containing sulfamic acid, and of drying the impregnated textile material.

Advantageously, said sol-gel bonding formulation is additionally free of plasticizing agent and/or chelating agent and/or viscosity agent.

The sol-gel bonding formulation used in the process according to the invention may be free of plasticizing agent.

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

The sol-gel bonding formulation used in the process according to the invention may be free of viscosity modifiers.

The process may advantageously include only one or two successive cycles, a) and b), of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding formulation being free of polycarboxylic acid, and b) of drying the impregnated textile material.

When the process includes only one cycle, this allows a faster and simpler process to be performed.

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

According to one embodiment, the process may include only one or two successive cycles a) and b), of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding formulation containing sulfamic acid and being free of polycarboxylic acid, and b) of drying the impregnated textile material.

The process may advantageously include only one or two successive cycles, a) and b), of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding formulation being free of polycarboxylic acid, and b) of drying the impregnated textile material after each cycle.

The process may advantageously include only one or two successive cycles a) and b), of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding formulation prepared at room temperature between 18 and 28° C. being free of polycarboxylic acid, and containing sulfamic acid and b) of drying the impregnated material. Preferably, the drying step is performed after each cycle.

Advantageously, said sol-gel bonding formulation is additionally free of plasticizing agent and/or chelating agent and/or viscosity agent.

When the process includes only one cycle, this allows a faster and simpler process to be performed.

The process may also include at least two successive cycles c) and d), of impregnating 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 bonding formulation, and of drying the impregnated textile material. Nevertheless, it should be noted that the omniphobic and/or hydrophobic performance sought within the context of the present invention is achieved when there is only a single cycle c) of impregnating 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 bonding formulation, and d) of drying the impregnated textile material.

For example, the process may also include three successive cycles c) and d) of impregnating the dried textile material obtained in the step b) with an omniphobic or hydrophobic sol-gel formulation, said omniphobic or hydrophobic sol-gel formulation being different from the sol-gel bonding formulation, and d) of drying the impregnated textile material.

The process may thus advantageously include only one cycle of impregnating 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 bonding formulation, and of drying the impregnated textile material. This then also allows a faster and simpler process to be performed.

The drying steps b) and d) are generally performed at a temperature of 120 to 180° C., for a duration ranging from 2 to 10 minutes, preferably at 180° C. for 2 minutes.

The sol-gel bonding formulation used in the process 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 mixtures thereof and a silylated precursor chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and aminopropyltriethoxysilane and mixtures thereof. More preferentially, the at least two silylated precursors are a combination of a silylated precursor chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and mixtures thereof and a silylated precursor chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and mixtures thereof. The sol-gel bonding formulation according to the invention may notably 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 bonding formulation according to the invention may notably comprise a mixture of the silylated precursors TMOS and GPTEOS, or TEOS and GPTMOS, or TEOS and GPTEOS. Even more preferentially, it is s a mixture of tetraethoxysilane (TEOS) and (3-glycidyloxypropyl)triethoxysilane (GPTEOS). The sol-gel bonding formulation used in the process according to the invention may comprise an acid preferably chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid and para-toluenesulfonic acid, preferably sulfamic acid. Sulfamic acid proved to be particularly interesting since it can contribute to the noteworthy stability duration of the sol-gel bonding formulations.

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

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

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

According to one embodiment, the omniphobic sol-gel formulation used in the process 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 process 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 used in the process according to the invention may comprise an acid preferably chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid and para-toluenesulfonic acid, preferably sulfamic acid or hydrochloric acid, even more preferentially sulfamic acid.

According to one embodiment, the hydrophobic sol-gel formulation used in the process 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 process according to the invention advantageously comprise sulfamic acid. The inventors found that sulfamic acid offers advantages in terms of the stability of the sols obtained.

Sulfamic acid, NH₂SO₃H, is a moderately strong acid (pKa=0.99) which allows rapid hydrolysis of silylated precursors while at the same time ensuring sol stability. Specifically, sulfamic acid has the distinctive feature of being able to exist in the zwitterionic form ⁺H₃NSO₃⁻ in aqueous solution. Thus, sulfamic acid in its zwitterionic form stabilizes silanol groups and prevents them from condensing rapidly, as shown in the following diagram:

The sol-gel bonding, 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, notably chosen from methanol, ethanol, propan-1-ol, isopropanol and butan-1-ol, preferably from methanol, ethanol, propan-1-ol and isopropanol, even 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 sol-gel bonding formulation preferentially does not comprise any C1 to C4 aliphatic alcohol.

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

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

In the hydrophobic sol-gel formulations, the aliphatic C1-C4 alcohol or mixture of aliphatic C1-C4 alcohols may advantageously represent from 55% to 99% by volume, preferably from 70% to 98% by 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 omniphobic and hydrophobic sol-gel bonding formulations.

In particular, the solvent may represent advantageously from 70% to 90% by volume, preferably from 80% to 90% by volume, even more preferentially from 82% to 88% by volume of the sol-gel bonding formulations.

In particular, the solvent may advantageously represent from 40% to 95% by volume, preferably from 50% to 90% by volume, of the omniphobic sol-gel formulations.

In particular, the solvent may advantageously represent from 60% to 90% by volume, preferably from 75% to 85% by volume, of the hydrophobic sol-gel formulations.

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

In the sol-gel bonding formulations, the silylated precursors advantageously represent from 5% to 30% by volume, preferably from 10% to 20% by volume, of the sol-gel bonding formulations.

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

A second subject of the invention is a sol-gel bonding formulation comprising at least two silylated precursors, a first precursor preferably being chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), a second precursor preferably chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and 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 and para-toluenesulfonic acid, preferably sulfamic acid,
  • said sol-gel formulation being free of polycarboxylic acid.

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

The sol-gel bonding formulation may in particular comprise sulfamic acid, generally provided in the form of an aqueous solution. The presence of sulfamic acid can contribute to the noteworthy stability time of the sol-gel bonding formulations, which may 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 mixtures thereof and 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 mixtures thereof and a silylated precursor chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS) and (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and mixtures thereof. More preferentially, the at least two silylated precursors are a combination of a silylated precursor chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS) and mixtures thereof and a silylated precursor chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and mixtures thereof. The sol-gel bonding formulation according to the invention may notably 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 bonding formulation according to the invention may notably comprise a mixture of the silylated precursors TMOS and GPTEOS, or TEOS and GPTMOS, or TEOS and GPTEOS. Even more preferentially, it is a mixture of tetraethoxysilane (TEOS) and (3-glycidyloxypropyl)triethoxysilane (GPTEOS).

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

The sol-gel bonding formulation according to the invention may be free of plasticizing agent.

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

The sol-gel bonding formulation according to the invention may be free of viscosity modifiers.

The sol-gel bonding formulation according to the invention is preferably an aqueous formulation, optionally comprising at least one C1 to C4 aliphatic alcohol, notably chosen 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.

The sol-gel bonding formulation may thus in particular also comprise ethanol.

Particularly advantageous stability performance has been obtained for the sol-gel bonding formulation g a mixture of tetraethoxysilane (TEOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and sulfamic acid. This sol-gel bonding formulation has a stability time of more than 1 month. This formulation may optionally comprise an alcohol, in particular ethanol.

The stability of the sol-gel formulations discussed herein 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 the mixture being split into two or more immiscible phases of refractive indices n′, n″, n′″, etc. A homogeneous phase is thus defined by a single refractive index, n, for light. Moreover, a clear phase is a phase that is free 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, clear phase of the sol formulations is monitored using a light transmission analysis apparatus (Turbican Lab, Formulation). The measuring protocol applied is as follows: 10 mL of sol of refractive index n are introduced into the dedicated container, and the transmission of the incident light passing through the sol is measured and monitored over time. The homogeneous and clear sol exhibits a constant transmission percentage over time (an example is shown in FIG. 9, with a transmission percentage of 92±1%). If the sol demixes or becomes cloudy over time, destabilization is characterized by a change in the transmission percentage due either to a change in refractive index or to light scattering by the particles, causing the light transmission to fall in this second case.

The increased stability of the sol-gel bonding formulations according to the invention is of major interest for the industrialization of a textile material coating process, since such a coating process is then performed continuously on fabric rolls which may be several kilometers long. Formulations with a high stability time are thus required to efficiently perform 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 bonding formulation, the mole ratios of tetramethoxysilane or tetraethoxysilane (TMOS or TEOS) relative to the other silylated precursor(s) may range from 1 to 9, preferably from 1.5 to 5, even more preferentially from 1.5 to 4.

The bonding formulation according to the invention may be used for applying a bonding formulation to a textile by impregnation. The bonding layer thus formed on the textile may then be used for bonding any type of sol-gel formulation. Moreover, the presence of this bonding layer according to the invention very advantageously makes it possible to give the coating deposited on the bonding layer enhanced wash stability.

Another subject 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 and para-toluenesulfonic acid, preferably sulfamic acid or hydrochloric acid, even more preferentially sulfamic acid.

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 may advantageously comprise only one silylated precursor, thus making this formulation simpler and easier to use.

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

The omniphobic sol-gel formulation according to the invention is preferably an aqueous formulation, as defined above. It may thus notably comprise a mixture of water and alcohol as solvent.

The presence of sulfamic acid and alcohol can contribute toward a noteworthy stability time of the omniphobic sol-gel formulations, which may range from 22 to 48 hours.

Particularly advantageous stability performance has been obtained for an omniphobic sol-gel formulation comprising 1H,1H,2H,2H-perfluorodecyltriethoxysilane (17FTEOS) and sulfamic acid. This omniphobic sol-gel formulation may comprise an alcohol, in particular ethanol or isopropanol, then giving a stability time ranging from 22 to 48 hours.

Another subject 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 and para-toluenesulfonic acid, preferably sulfamic acid or hydrochloric acid, even more preferentially 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 can contribute toward a noteworthy stability time for the hydrophobic sol-gel formulations, which may range from 1 day to 6 days minimum.

Particularly advantageous stability performance has been obtained for hydrophobic sol-gel formulations comprising hexadecyltriethoxysilane (HDTEOS) and sulfamic acid or comprising hexadecyltriethoxysilane (HDTEOS), tetraethoxysilane (TEOS) and sulfamic acid. These formulations may 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 thus notably comprise a mixture of water and alcohol as solvent.

The amounts of solvent, water, alcohol and silyl precursors that may be used in the sol-gel formulations are those described above relative to the process for coating a textile material according to the invention.

A subject of the invention is also an impregnated textile material comprising at least a first bonding layer obtained by application of a sol-gel bonding formulation according to the invention and at least a second omniphobic or hydrophobic layer over the bonding layer. This omniphobic or hydrophobic layer may notably be obtained by application of 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 bonding layer obtained by application of a sol-gel bonding formulation according to the invention and at least a second omniphobic layer over the bonding layer obtained by application of an omniphobic sol-gel formulation according to the invention.

This textile material according to the invention may also comprise at least a first bonding layer obtained by application of a sol-gel bonding formulation according to the invention and at least a second hydrophobic layer over the bonding layer obtained by application of a hydrophobic sol-gel formulation according to the invention.

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

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

An impregnated textile material according to the invention may be obtained via the coating process according to the invention described above. This is thus a textile material impregnated with at least one bonding layer obtained by application of a sol-gel bonding 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 outlined above as regards the nature of the textile material and the sol-gel formulations also apply to the impregnated textile material according to the invention.

The coating layers form a sheath around the fibers constituting the impregnated textile material.

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

The contact angle is measured using an OCA 15EC goniometer (SCA 20). Ten 10 μL drops of water are applied to 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.

The impregnated textile material according to the present invention, in which the second layer is an omniphobic layer, is notably characterized in that it has an oleophobicity measured by contact angle greater than 90 degrees, preferably greater than 100 degrees, even more preferentially greater than 110 degrees, or measured by an oleophobicity index greater than 3, advantageously greater than 4, preferably greater than 5, even more preferentially greater than 6.

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

For the oleophobicity index measurement tests, 50 μL drops of alkanes are applied using a micropipette to at least four 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 standard ISO 14419 (FIG. 3). The oleophobicity index of the coating is that of the alkane (n) whose drop shape has been rated A. If the drop is rated B, the alkane is changed to a lower index n−1, for which the drop is rated A. Of the four drops dispersed on a given fabric, only one drop needs to have an index of 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 highly resistant to washing, the textile material may thus be durable. Specifically, textile materials impregnated according to the invention withstand at least 30 washes, and even up to at least 70 washes, without losing their hydrophobic and/or oleophobic properties.

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 subject of the invention is personal protective equipment comprising the impregnated textile material according to the invention. This personal protective equipment may, for example, be a full-body suit, pants, jacket, gloves, hoods, socks or masks. By virtue of the functional properties, notably the hydrophobicity and/or oleophobicity, 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 chemicals (acidic or basic aqueous solutions, oils, hydrophilic or hydrophobic organic solvents).

Textile materials with the highest oleophobicity ratings, notably greater than or equal to 6, are particularly suitable for personal protective equipment for the armed forces, police, firefighters and industry.

For oleophobicity indexes between 4 and 6, the omniphobic and water-repellent textiles are of interest in bulk consumer products, such as rainwear, non-soiling garments for workers, or children's clothing.

The omniphobic formulations can also be deposited by spraying onto solid supports, glass, steel, brick or wall cladding, as anti-graffiti coatings, since the acrylic spray paints used for graffiti do not adhere to these omniphobic coatings.

The combination of omniphobic and hydrophobic textile materials is of interest for use in collecting polluting liquids, in particular oil, accidentally spilled on 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 shows a photograph of a laboratory scarf.

FIG. 2 shows a photo of a laboratory spray system placed in an extractor hood, seen in profile.

FIG. 3 shows an example of grading for oleophobicity tests according to the standard ISO14419. The attributed grades range from A to D for drop shape, with A=pass, well rounded drop, B=partial pass with round drop with partial darkening, C=fail, visible wicking effect or complete wetting, and D=fail, complete wetting. The oleophobicity index n of the coating is that of the alkane (n) for which the drop shape is rated A.

FIG. 4 shows drop shapes of water and alkanes (50 μL) deposited on a freshly 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 shows photos of the contact angles of drops of water and decane (10 μL) on a fabric coated according to the P(15)_F process at new (0 w) and washed 30 times (30 w).

FIG. 6 shows an SEM image of untreated K5204 fabric (Kermel®/Lenzing FR® 50/50). At 500× magnification.

FIG. 7 shows an SEM image of the K5204 fabric (Kermel®/Lenzing FR® 50/50) shown in FIG. 6, coated according to the P(3)_F process, at 500× magnification.

FIG. 8 shows an SEM image of the K5204 fabric (Kermel®/Lenzing FR® 50/50) shown in FIG. 6, coated via the P(3)_F process, at 1000× magnification.

FIG. 9 shows an example of light transmission analysis of sol(6)_omniP with the Turbiscan lab apparatus at different temperatures (30° C., 35° C., 40° C.). When the sol is homogeneous and clear, the % transmission of the intensity of a light beam passing through the sample is 92±1% here. The loss in transmission over long time indicates either the presence of scattering particles or the demixing of the sol with a change in the refractive index of the liquid.

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

EXAMPLES

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);
  • 1H,H,H,H-Perfluorooctyltriethoxysilane (CAS No.: 51851-37-7) (13FTEOS, Acros Organics, 98%);
  • 1H,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) (AcSm, 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%);
  • demineralized H₂O

Textiles Used:

Different types of fabric were used to demonstrate the applicability of the omniphobic coating. These were

• • Kermel®/Lenzing FR® 50/50 (kermel-viscose fabric). The mixed fabric has a mass per unit area of 260 g/m² and an air permeability of 57.5 L/m²·s (average value measured in accordance with the standard ISO 9237 at 100 Pa). Kermel® is a polyamide-imide with flame-retardant and thermostable properties. Lenzing FR® is a flame-retardant viscose (Modal manufacturing process) constituted of cellulose. Thus, the chemical nature of the two fibers is very different.
  • 100% cotton with a mass per unit area of 180 g/m². Cotton is constituted of cellulose and contains hydroxyl functions.

Tests were performed with A4 (21×30 cm²) fabric samples or with 100 m of fabric with a 30 cm width. The coatings were performed with various sol-gel formulations, either by padding with a laboratory padding machine, or by spraying with a motorized spraying system. The wet take-up, which represents the amount of sol taken up by the fabric before drying, is of the order of 43±3%.

The take-up 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 to squeeze it out, i.e. to make the product penetrate and remove the excess bath from the fabric by exerting pressure between two elastomer-covered rollers. This allows the amount of bath deposited to be controlled, known as the “squeezing” or “take-up” rate. The material is treated throughout and on both sides, and maintains its textile appearance. The textile is weighed again after the squeezing step, but before the drying step. The ratio [(weight after deposition)−(weight before deposition)]/(weight before deposition) gives the take-up rate.

Example 1: Preparation of the Bonding Formulations (Sol_ACC)

Sol(1)_ACC

9.1 mL of TMOS, 3.5 mL of GPTMOS and 87.5 mL of ultrapure water are successively added to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 1H using an IKA Werke RO10 Power multiple stirrer plate. Sol(1)_ACC contains 12.5% v/v of silylated precursors with a TMOS/GPTMOS mole ratio of 4. Sol(1)_ACC has a stability of 6H.

Sol(2)_ACC

6.0 mL of TMOS, 6.0 mL of GPTMOS and 77.0 mL of ultrapure water are successively added to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 1H using an IKA Werke RO10 Power multiple stirrer plate. Sol(2)_ACC contains 13.5% v/v of silylated precursors with a TMOS/GPTMOS mole ratio of 1.5. Sol(2)_ACC has a stability of 6H.

Sol(3)_ACC

6 mL of TMOS, 6 mL of GPTMOS and 77 mL of ultrapure water are successively added to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 h using an IKA Werke RO10 Power multiple stirrer plate. Sol(3)_ACC contains 13.5% v/v of silylated precursors with a TMOS/GPTMOS mole ratio of 1.5. Sol(3)_ACC has a stability of 6H.

Sol(4)_ACC

6.0 mL of TMOS, 6.0 mL of GPTMOS and 77.0 mL of ultrapure water are successively added to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 4H using an IKA Werke RO10 Power multiple stirrer plate. Sol(4)_ACC contains 13.5% v/v of silylated precursors with a TMOS/GPTMOS mole ratio of 1.5. Sol(4)_ACC has a stability of 6H.

Sol(5)_ACC

9.5 mL of TEOS, 8.1 mL of GPTEOS and 82.4 mL of aqueous sulfamic acid solution at 3.2 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 24H using an IKA multiple stirrer plate. Sol(5)_ACC contains 17.6% v/v of silylated precursors with a TEOS/GPTEOS mole ratio of 1.5. Sol(5)_ACC has a stability time of more than 1 month.

Sol(6)_ACC

9.5 mL of TEOS, 8.1 mL of GPTEOS, 10 mL of ethanol and 72.4 mL of aqueous sulfamic acid solution at 3.6 mmol/L are successively added to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3H using an IKA multiple stirrer plate. Sol(6)_ACC contains 17.6% v/v of silylated precursors with a TEOS/GPTEOS mole ratio of 1.5 and 10% v/v of ethanol. Sol(6)_ACC has a stability time of more than 2 months.

Sol(7)_ACC

9.5 mL of TEOS, 8.1 of mL of GPTEOS, 20 mL of ethanol and 62.4 mL of aqueous sulfamic acid solution at 4.2 mmol/L are successively added to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3H using an IKA multiple stirrer plate. Sol(7)_ACC contains 17.6% v/v of silylated precursors with a TEOS/GPTEOS mole ratio of 1.5 and 20% v/v of ethanol. Sol(7)_ACC has a stability time of more than 1 month.

Sol(8)_ACC

9.5 mL of TEOS, 8.1 mL of GPTEOS, 30 mL of ethanol and 52.4 mL of aqueous sulfamic acid solution at 5.0 mmol/L are successively added to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3H using an IKA multiple stirrer plate. Sol(8)_ACC contains 17.6% v/v of silylated precursors with a TEOS/GPTEOS mole ratio of 1.5 and 30% v/v of ethanol. Sol(8)_ACC has a stability time of more than 1 month.

Example 2: Preparation of the Omniphobic Formulations (Sol_omniP)

Sol(1)_omniP

12.0 mL of EtOH, 2.0 mL of 17FTEOS and 3.7 mL of aqueous HCl solution at 54.0 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 1H using an IKA Werke RO10 Power multiple stirrer plate. Sol(1)_omniP contains 11.3% v/v of silylated precursor and 67.7% v/v of EtOH. Sol(1)_omniP has a stability of 3H.

Sol(2)_omniP

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

Sol(3)_omniP

34.0 mL of EtOH, 10.4 mL of 17FTEOS and 5.6 mL of aqueous HCl solution at 184.0 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 1H using an IKA Werke RO10 Power multiple stirrer plate. Sol(3)_omniP contains 20.7% v/v of silylated precursor and 68.0% v/v of EtOH. Sol(3)_omniP has a stability of 5H.

Sol(4)_omniP

24.9 mL of isopropanol, 10.4 mL of 17FTEOS and 14 mL of aqueous HCl solution at 70.0 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 1H using an IKA Werke RO10 Power multiple stirrer plate. Sol(4)_omniP contains 20.7% v/v of silylated precursor and 49.8% v/v of isopropanol. Sol(4)_omniP has a stability of 6H.

Sol(5)_omniP

34.0 mL of EtOH, 10.4 mL of 17FTEOS and 5.6 mL of aqueous AcSm solution at 184.0 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 1H30 (or 3H or 5H) using an IKA Werke RO10 Power multiple stirrer plate. Sol(5)_omniP contains 20.7% v/v of silylated precursor and 68.0% v/v of EtOH. Sol(5)_omniP has a stability of 22H.

Sol(6)_omniP

34.0 mL of EtOH, 10.4 mL of 17FTEOS and 5.6 mL of aqueous AcSm solution at 93.0 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 h using an IKA Werke RO10 Power multiple stirrer plate. Sol(6)_omniP contains 20.7% v/v of silylated precursor and 68% v/v of EtOH. Sol(6)_omniP has a stability of 27H.

Sol(7)_omniP

34.0 mL of EtOH, 10.4 mL of 17FTEOS and 5.6 mL of aqueous AcSm solution at 46.0 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 h using an IKA Werke RO10 Power multiple stirrer plate. Sol(7)_omniP contains 20.7% v/v of silylated precursor and 68% v/v of EtOH. Sol(7)_omniP has a stability of 27H.

Sol(8)_omniP

34.0 mL of EtOH, 10.4 mL of 17FTEOS and 5.6 mL of aqueous AcSm solution at 23.0 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 h using an IKA Werke RO10 Power multiple stirrer plate. Sol(8)_omniP contains 20.7% v/v of silylated precursor and 68% v/v of EtOH. Sol(8)_omniP has a stability of 48H.

Sol(9)_omniP

24.6 mL of EtOH, 30 mL of 17FTEOS and 4 mL of aqueous HCl solution at 0.75 mol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 1H using an IKA Werke RO10 Power multiple stirrer plate. Sol(9)_omniP contains 51.1% v/v of silylated precursor and 42.0% v/v of EtOH. Sol(9)_omniP has a stability of 2H30.

Sol(10)_omniP

15.0 mL of EtOH, 15.0 mL of 17FTEOS and 2.1 mL of aqueous HCl solution at 1.0 mol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 30 min using an IKA Werke RO10 Power multiple stirrer plate (mixture 1). Successively add 3.0 mL of EtOH, 4.0 mL of TEOS and 1.0 mL of water to a separate glass flask, and shake to homogenize (mixture 2). Add mixture 2 to mixture 1 and stir for 30 min using an IKA Werke RO10 Power multiple stirrer plate. Sol(10)_omniP contains 48% v/v of silylated precursors with a TEOS/17FTEOS mole ratio of 2.5 and 44.9% v/v of EtOH. Sol(10)_omniP has a stability of 2H30.

Sol(11)_omniP

10.4 mL of 17FTEOS and 39.6 mL of aqueous AcSm solution at 3.3 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 4H using an IKA Werke RO10 Power multiple stirrer plate. Sol(11)_omniP contains 20.7% v/v of silylated precursor.

Sol(12)_omniP

34.0 mL of EtOH, 10.4 mL of 13FTEOS and 5.6 mL of aqueous AcSm solution at 23.0 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 h using an IKA Werke RO10 Power multiple stirrer plate. Sol(14)_omniP contains 20.7% v/v of silylated precursor and 68% v/v of EtOH. Sol(14)_omniP has a stability of 89 h.

Sol(13)_omniP

29.8 mL of EtOH, 15.3 mL of 13FTEOS and 4.9 mL of aqueous AcSm solution at 26.5 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 h using an IKA Werke RO10 Power multiple stirrer plate. Sol(15)_omniP contains 30.7% v/v of silylated precursor and 60% v/v of EtOH. Sol(15)_omniP has a stability of 78 h.

Example 3: Preparation of Hydrophobic Formulations (Sol_HYDRO)

Sol(1)_HYDRO

38.8 mL of EtOH, 9.7 mL of HDTEOS and 1.6 mL of aqueous AcSm solution at 83.2 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 h using an IKA Werke RO10 Power multiple stirrer plate. Sol(1)_HYDRO contains 19.4% v/v of silylated precursor and 77.4% v/v of EtOH. Sol(1)_HYDRO has a stability of greater than 4H.

Sol(2)_HYDRO

39.1 mL of EtOH, 8.4 mL of HDTEOS, 1.4 mL of TEOS and 1.1 mL of aqueous HCl solution at 117.1 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 3 h using an IKA Werke RO10 Power multiple stirrer plate. Sol(2)_HYDRO contains 19.6% v/v of silylated precursor and 78.2% v/v of EtOH. Sol(2)_HYDRO has a stability of 4H.

Sol(3)_HYDRO

39.1 mL of EtOH, 8.4 mL of HDTEOS, 1.4 mL of TEOS and 1.1 mL of aqueous HCl solution at 117.1 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature)(20-24° C. at 500 rpm for 5H using an IKA Werke RO10 Power multiple stirrer plate. Sol(3)_HYDRO contains 19.6% v/v of silylated precursor and 78.2% v/v of EtOH. Sol(3)_HYDRO has a stability of 1 D.

Sol(4)_HYDRO

39.1 mL of EtOH, 6.6 mL of HDTEOS, 3.2 mL of TEOS and 1.1 mL of aqueous HCl solution at 117.1 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 5H using an IKA Werke RO10 Power multiple stirrer plate. Sol(4)_HYDRO contains 19.6% v/v of silylated precursor and 78.2% v/v of EtOH. Sol(4)_HYDRO has a stability of 1 D.

Sol(5)_HYDRO

39.1 mL of EtOH, 6.6 mL of HDTEOS, 3.2 mL of TEOS and 1.1 mL of aqueous AcSm solution at 117.1 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 5H using an IKA Werke RO10 Power multiple stirrer plate. Sol(5)_HYDRO contains 19.6% v/v of silylated precursor and 78.2% v/v of EtOH. Sol(5)_HYDRO has a stability of greater than 6 D.

Sol(6)_HYDRO

39.1 mL of EtOH, 4.9 mL of HDTEOS, 4.9 mL of TEOS and 1.1 mL of aqueous HCl solution at 117.1 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 5H using an IKA Werke RO10 Power multiple stirrer plate. Sol(6)_HYDRO contains 19.6% v/v of silylated precursor and 78.2% v/v of EtOH. Sol(6)_HYDRO has a stability of greater than 6 D.

Sol(7)_HYDRO

39.1 mL of EtOH, 4.9 mL of HDTEOS, 4.9 mL of TEOS and 1.1 mL of aqueous AcSm solution at 117.1 mmol/L are added successively to a hermetically sealed glass flask. The mixture is stirred at room temperature (20-24° C.) at 500 rpm for 5H using an IKA Werke RO10 Power multiple stirrer plate. Sol(7)_HYDRO contains 19.6% v/v of silylated precursor and 78.2% v/v of EtOH. Sol(7)_HYDRO has a stability of greater than 6 D.

Example 4: Preparation of Fabrics Coated by Padding (FIG. 1) According to the Invention

P(1)_F

Sol(1)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven. Immediately afterwards, a second deposit of Sol(1)_ACC is applied 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 kept for 18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure. Sol(10)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(2)_F

Sol(1)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven. Immediately afterwards, a second deposit of Sol(1)_ACC is applied 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 kept for 18 hours in a desiccator at 50% relative humidity, at room temperature)(20-24° C. and atmospheric pressure. Sol(10)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 40 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(3)_F

Sol(1)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(9)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(4)_F

Sol(1)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven. Immediately afterwards, a second deposit of Sol(1)_ACC is applied 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 kept for 18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure. Sol(1)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(5)_F

Sol(1)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven. Immediately afterwards, a second deposit of Sol(1)_ACC is applied 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 kept for 18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure. Sol(9)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(6)_F

Sol(2)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(9)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(7)_F

Sol(2)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(3)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(8)_F

Sol(3)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(3)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(9)_F

Sol(3)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(3)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 left to cool in the open air at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(10)_F

Sol(4)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(3)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(11)_F

Sol(2)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(2)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(12)_F

Sol(3)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(5)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(13)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(3)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(14)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(5)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(15)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(16)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(17)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature)(20-24° C. and atmospheric pressure. Sol(8)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 5 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(18)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 5 min at 120° C. in an oven, then kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(19)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(20)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 150° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 150° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 150° C. in an oven, then kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(21)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 150° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 150° C. in an oven, then kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(22)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 180° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 180° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 180° C. in an oven, then kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(23)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 180° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 180° C. in an oven, then kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(24)_F

Sol(5)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 120° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 10 min at 120° C. in an oven, then left to cool at room temperature (20-24° C.) and laboratory atmospheric pressure for 10-30 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(25)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 180° C. in an oven, then left to cool for 30 min to 1 hour in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(1)_HYDRO is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 180° C. in an oven, then kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the hydrophobicity tests.

P(26)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is dried for 2 min at 150° C. in an oven, then left to cool and to mature for 1 to 2 weeks in the open air, at room temperature (20-24° C.) and atmospheric pressure. Sol(12)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is left to dry and to mature in the open air, at room temperature (20-24° C.) and laboratory atmospheric pressure for two weeks, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(27)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is left to dry and to mature for 1 week to 3 months in the open air, at room temperature (20-24° C.) and laboratory atmospheric pressure. Sol(12)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is left to dry and to mature in the open air, at room temperature (20-24° C.) and laboratory atmospheric pressure for two weeks, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(28)

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is left to dry and to mature for 1 week to 3 months in the open air, at room temperature (20-24° C.) and laboratory atmospheric pressure. Sol(13)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is left to dry and to mature in the open air, at room temperature (20-24° C.) and laboratory atmospheric pressure for two weeks, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(29)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is left to dry and to mature for 1 week to 3 months in the open air, at room temperature (20-24° C.) and laboratory atmospheric pressure. Sol(13)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is left to dry and to mature at 40° C. in an oven for 4 days and then to mature for 3 days in the open air, at room temperature (20-24° C.) and laboratory atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(30)_F

Sol(6)_ACC is applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is left to dry for 1 day in the open air, at room temperature (20-24° C.) and laboratory atmospheric pressure. The fabric is then left to mature at 40° C. in an oven for 1 day and then for 5 days in the open air, at room temperature (20-24° C.) and laboratory atmospheric pressure. Sol(13)_omniP is then applied to the fabric by padding at a speed of 2 m/min. After squeezing, the fabric is left to dry and to mature at 40° C. in an oven for 4 days and then for 3 days in the open air, at room temperature (20-24° C.) and laboratory atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

Example 5: Preparation of Fabrics Coated by Spraying (FIG. 2) According to the Invention

P(1)_SP

Sol(3)_ACC is applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, said fabric being moved at a speed of 6 m/min. The assembly is placed in a chamber under pumping to evacuate the ethanol vapors. 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 room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, in two passes, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3 kg roller and dried for 10 min at 120° C. in an oven, then left to cool at 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(2)_SP

Sol(3)_ACC is applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, said fabric being moved at a speed of 9 m/min. The assembly is placed in a chamber under pumping to evacuate the ethanol vapors. 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 room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, in two passes, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3 kg roller and dried for 10 min at 120° C. in an oven, then left to cool at 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 kept for 16 to 18 h in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(3)_SP

Sol(3)_ACC is applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, said fabric being moved at a speed of 12 m/min. The assembly is placed in a chamber under pumping to evacuate the ethanol vapors. 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 room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, in two passes, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3 kg roller and dried for 10 min at 120° C. in an oven, then left to cool at 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(4)_SP

Sol(3)_ACC is applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, said fabric being moved at a speed of 12 m/min. The assembly is placed in a chamber under pumping to evacuate the ethanol vapors. 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 room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied by spraying (pressure 4 bar) at a distance of 20 cm from the fabric, in two passes, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3 kg roller and dried for 10 min at 120° C. in an oven, then left to cool at 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(5)_SP

Sol(3)_ACC is applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, said fabric being moved at a speed of 12 m/min. The assembly is placed in a chamber under pumping to evacuate the ethanol vapors. 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 room temperature (20-24° C.) and atmospheric pressure. Sol(8)_omniP is then applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, in two passes, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3 kg roller and dried for 10 min at 120° C. in an oven, then left to cool at 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

P(6)_SP

Sol(6)_ACC is applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, said fabric being moved at a speed of 9 m/min. The assembly is placed in a chamber under pumping to evacuate the ethanol vapors. 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. Sol(11)_omniP is then applied by spraying (pressure 4 bar) at a distance of 10 cm from the fabric, in two passes, the latter being moved at a speed of 9 m/min. After deposition, the fabric is compressed using a 3 kg roller and dried for 10 min at 120° C. in an oven, then left to cool at 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 kept for 16-18 hours in a desiccator at 50% relative humidity, at room temperature (20-24° C.) and atmospheric pressure, before being stored for the washing, hydrophobicity and oleophobicity tests.

Example 6: Tests of the Hydrophobic and Oleophobic Properties, Permeability and Resistance of Fabrics Prepared According to the Invention to Washing and to Strong Acids and Bases

The bonding of the sol-gel materials to the fibers is visualized by means of Scanning Electron Microscopy (SEM, ZEISS Ultra-55, GEMINI column) images, and is verified after the washes with hydrophobicity and oleophobicity tests.

The washing tests (1, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70, and 80 washes) are performed in accordance with the standard ISO 6330. The various fabrics undergo a 2-hour wash cycle in a horizontal-axis, front-loading machine. Washing is performed at 60° C., in the presence of 77% ECE detergent (reference detergent A No. 3), 20% sodium perborate tetrahydrate, 3% tetraacetylethylenediamine (TAED). Spin-drying is performed at 1200 rpm. The fabrics are tumble-dried at 95° C. for 45 min after each wash.

Tests of the resistance of the omniphobic coating to strong acids and bases are performed by immersing the fabric in solutions of strong acid (HCl) or of strong base (NaOH). The contact angles of water and n-decane on the surface of sample P(15)_F were measured before and after the sample had been soaked for 24 hours in acidic solutions (pH=0) and basic solutions (pH=12 and 14). The results obtained, presented in FIG. 10, show very little variation in these contact angles, and also show preserved hydrophobicity and oleophobicity even after placing the textile in contact with solutions of strong acids and bases, demonstrating the high resistance of the textile thus coated to strong acids and bases. Such a coating on protective gowns will allow workers to be protected from splashes of strong acids or bases.

Hydrophobicity and oleophobicity tests were performed on 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, 50 μL drops (about 5 mm in diameter) of water are deposited using a micropipette on at least five 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 water droplets. The test is successful when the reverse side of the fabric remains dry. For a more accurate measure of hydrophobicity, the contact angle of water on the coating is measured.

The contact angle is measured using an OCA 15EC goniometer (SCA 20). Ten 10 μL drops of water are applied to 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 is greater than 90 degrees.

For visual measurement of the oleophobicity index, 50 μL drops of alkanes are applied using a micropipette to at least four different locations distributed over the surface of the fabric. The drops are observed for 30 s and their shape is rated according to the references of the standard ISO 14419. The grades attributed range from A to D for drop shape. A drop of n-index alkane is placed on the surface of a coated fabric. If the drop is well rounded (grade A), the test is successful and the coating is attributed the n-index. If the drop is rated B, the alkane is changed to a lower index n−1 for which the drop is rated A. Of the four drops deposited dispersed on a given coating, only one drop needs to have an index of n−1 for the coating to be rated n/(n−1). See the examples in Table 1. For a more precise measure of the oleophobicity, the contact angle of alkanes on the coating is measured.

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

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

TABLE 1
Process	Oleophobic index according to the number of washes
Wash	0	1	5	10	15	20	25	30	40	50	60	70	80
	Fabric = Kermel ®/Lenzing FR ® 50/50 (kermel-viscose fabric)
P(1)F	6	6/5	6/5	6/5	6/5	6/5	5	3
P(2)F	6	6	6	6/5	6/5	5	5	5
P(3)F	6	6	6/5	6/5	6/5	6/5	6/5	5/4
P(4)F	6	5	5	5	5	5	5/4	5
P(5)F	6	5	5	5	5	5	5	Het
P(6)F	6	6/5	6/5	5	5	5	5	5
P(7)F	6/5	5	5	5	5	5	5	5/4
P(8)F	6/5	6/5	6/5	6/5	6/5	6/5	6/5	6/5
P(9)F	6	5	5	5	5	5	5/4	4/3
P(10)F	5	5	5	5	5	5	5	5
P(11)F	6/5	6/5	6/5	6/5	6/5	6/5	6/5	5
P(12)F	5	5	5	5	—	6/5	—	6/5
P(13)F	6	6	6	6	—	6	—	6
P(14)F	6	6	6	6	—	6	—	6
P(15)F	6	6	6	6	—	6	—	6
P(16)F	6	6	6	6	—	6	—	6
P(17)F	6	6	6	6	—	6	—	6
P(18)F	6	6	6	6	—	6/5	—	6/5
P(19)F	6	6	6	6	—	5	—	5
P(20)F	6	6	6	6	—	6	—	6
P(21)F	6	6	6	6	—	6	—	6
P(22)F	6	6	6	6	—	6	—	6
P(23)F	6	6	6	6	—	6	—	6	6	5	5	5/4
P(24)F	6	6	6	6	—	6	—	6	6	6/5	6/5	6/5	Het
P(1)SP	6	6	6	6	—	6	—	6/5
P(2)SP	6	6	6	6/5	—	6	—	6/5
P(3)SP	6	6	6	5		5		5
P(4)SP	6	6	6	6/5	—	6	—	6	6/5	6/5	6/5	4
P(5)SP	6	6	6	6	—	6	—	6	6	6/5	6/5	<3
P(6)SP	6	6	6/5	6/5	—	6/5	—	6/5
Cotton fabric
P(13)F	6	6	6	6		6		6
Het = Heterogeneous

TABLE 2
Process	Θ0 W water	Θ30 W water	Θ0 W decane	Θ30 W decane	Pv	Pe
Fabric = Kermel ®/Lenzing FR ® 50/50 (kermel-viscose fabric)
P(1)F	150.0	—	110	—	54.7	44.5
P(2)F	142.9	144.5	115.8	114.2		49.6
P(3)F	143.6	126.2	118.2	113.3		—
P(4)F	139.0	135.7	115.6	105.6		43.1
P(5)F	140.5	na	na	na		39.9
P(6)F	145.9	140.5	104.4	106.0		49.5
P(7)F	148.1	140.7	126.6	113.9		44.4
P(8)F	143.0	141.9	124.3	114.6		38.9
P(9)F	143.5	141.5	115.4	115.8		44.8
P(10)F	146.0	142.2	113.2	128.9		40.5
P(11)F	146.9	140.0	123.3	114.7		44.5
P(12)F	146.7	133.5	118.6	122.5		46.8
P(13)F	146.0	135.1	93.9	116.5		52.0
P(14)F	142.6	143.3	112.5	128.2		46.8
P(15)F	145.4	141.5	129.7	122.8		49.8
P(16)F	143.0	138.1	114.8	108.3		47.4
P(17)F	145.5	139.1	110.4	114.8		46.0
P(18)F	143.3	136.5	115.6	108.8		49.2
P(19)F	143.9	136.6	119.0	102.4		51.5
P(20)F	141.0	134.0	124.0	119.4		40.5
P(21)F	146.3	135.7	120.4	110.3		38.1
P(22)F	146.8	139.1	121.8	122.1		36.2
P(23)F	147.4	129.9	119.0	115.1		43.3
P(24)F	142.8	141.7	126.9	120.0		42.1
P(25)F	141.3	—	—	—
P(1)SP	147.7	133.8	116.7	105.2		51.0
P(2)SP	146.3	137.3	108.8	125.2		52.3
P(3)SP	145.6	137.9	114.8	123.7		53.0
P(4)SP	144.8	132.4	122.2	104.2		49.8
P(5)SP	—	135.0	—	109.9		51.2
P(6)SP	147.1	138.4	130.0	116.6		44.9
Fabric = cotton
P(13)F	144.29	125.09	119.50	117.89
Θ0 W = contact angle when the fabric is new, in degrees; Θ30 W = contact angle after 30 washes; Pv = permeability of untreated fabric, Pe = permeability of coated fabric.

An example of visual analysis of hydrophobicity and oleophobicity with various alkanes is shown in FIG. 4. FIG. 5 shows an example of contact angle measurements with a coated fabric when new, and after having been washed 30 times.

Examples of Scanning Electron Microscope (SEM) analysis of untreated fabrics and of fabrics coated with sol-gel coating are shown in FIG. 6, FIG. 7 and FIG. 8. These images make it possible to observe the homogeneous sheathing of fibers with a coating according to the invention.

Claims

1-29. (canceled)

30. A process for coating a textile material, said process comprising the following steps:

a) at least one cycle of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding 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 sulfamic acid, said omniphobic or hydrophobic sol-gel formulation being different from the sol-gel bonding formulation;

d) at least one cycle of drying the impregnated textile material obtained in step c).

31. The process as claimed in claim 30, wherein at least one drying cycle is followed by a step d′) of maturing the material obtained in step d) by storage at room temperature under a humid atmosphere with a relative humidity of 50% for at least 16H to 18H.

32. The process as claimed in claim 30, comprising the following additional steps:

e) washing the impregnated textile material obtained in step d) with a neutralizing aqueous solution.

f) drying the material obtained in step e).

33. The process as claimed in claim 32, wherein 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 storage at room temperature under a humid atmosphere with a relative humidity of 50% for at least 16H to 18H.

34. The process as claimed in claim 30, wherein each of the impregnation steps is independently performed by padding or spraying.

35. The process as claimed in claim 30, comprising at least two successive cycles, a) and b), of impregnating the textile material with a sol-gel bonding formulation, said sol-gel bonding formulation being free of polycarboxylic acid, and of drying the impregnated textile material.

36. The process as claimed in claim 30, wherein step a) comprises a squeezing step under pressure after the or each impregnation cycle and/or step c) comprises a squeezing step under pressure after the or each impregnation cycle.

37. The process as claimed in claim 30, wherein the sol-gel bonding formulation comprises at least two silylated precursors.

38. The process as claimed claim 30, wherein the sol-gel bonding formulation comprises an acid chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid and para-toluenesulfonic acid.

39. The process as claimed in claim 30, wherein the sol-gel bonding formulation is free of zirconium alkoxide and/or sodium hypophosphite.

40. The process as claimed in claim 30, wherein the omniphobic sol-gel formulation comprises at least one silylated precursor, 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).

41. The process as claimed in claim 30, wherein the hydrophobic sol-gel formulation comprises at least one silylated precursor 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).

42. The process as claimed in claim 30, wherein the sol-gel bonding, omniphobic and/or hydrophobic formulation is an aqueous formulation and optionally comprises one or more C1 to C4 aliphatic alcohols.

43. A sol-gel bonding formulation comprising at least two silylated precursors, a first precursor being chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), and a second precursor chosen from (3-glycidyloxypropyl)trimethoxysilane (GPTMOS), (3-glycidyloxypropyl)triethoxysilane (GPTEOS) and aminopropyltriethoxysilane,

optionally, the combination of TMOS/GPTMOS precursors being excluded,

and comprising an acid chosen from sulfamic acid, hydrochloric acid, sulfuric acid, nitric acid and para-toluenesulfonic acid, said sol-gel formulation being free of polycarboxylic acid.

44. An omniphobic sol-gel formulation comprising at least one silylated precursor 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 sulfamic acid.

45. \A hydrophobic sol-gel formulation comprising at least one silylated precursor 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 sulfamic acid.

46. An impregnated textile material comprising at least a first bonding layer obtained by application of a sol-gel bonding formulation as claimed in claim 43 and at least a second omniphobic or hydrophobic layer over the bonding layer.

47. An impregnated textile material obtained via the coating process as claimed in claim 30.

48. A personal protective equipment comprising the impregnated textile material as claimed in claim 46.