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EP3565925B1 - Procédé de revêtement de matériaux textiles - Google Patents

Procédé de revêtement de matériaux textiles Download PDF

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Publication number
EP3565925B1
EP3565925B1 EP18700795.0A EP18700795A EP3565925B1 EP 3565925 B1 EP3565925 B1 EP 3565925B1 EP 18700795 A EP18700795 A EP 18700795A EP 3565925 B1 EP3565925 B1 EP 3565925B1
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EP
European Patent Office
Prior art keywords
tmos
activated carbon
textile material
organosilicon precursor
sol
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EP18700795.0A
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German (de)
English (en)
French (fr)
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EP3565925A1 (fr
Inventor
Thu-Hoa Tran-Thi
Philippe Charton
Franck TIRARD
Eva GRINENVAL
Sébastien Chatard
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Centre National de la Recherche Scientifique CNRS
Safran Electronics and Defense SAS
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Europrotect France SA
Original Assignee
Centre National de la Recherche Scientifique CNRS
Commissariat a lEnergie Atomique CEA
Safran Electronics and Defense SAS
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Europrotect France SA
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Publication of EP3565925A1 publication Critical patent/EP3565925A1/fr
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D5/00—Composition of materials for coverings or clothing affording protection against harmful chemical agents
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/73—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof
    • D06M11/74—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with carbon or compounds thereof with carbon or graphite; with carbides; with graphitic acids or their salts
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/503—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms without bond between a carbon atom and a metal or a boron, silicon, selenium or tellurium atom
    • D06M13/507—Organic silicon compounds without carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/50—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with organometallic compounds; with organic compounds containing boron, silicon, selenium or tellurium atoms
    • D06M13/51—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond
    • D06M13/513—Compounds with at least one carbon-metal or carbon-boron, carbon-silicon, carbon-selenium, or carbon-tellurium bond with at least one carbon-silicon bond
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • D06M23/08—Processes in which the treating agent is applied in powder or granular form
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/16—Synthetic fibres, other than mineral fibres
    • D06M2101/30—Synthetic polymers consisting of macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M2101/34—Polyamides
    • D06M2101/36—Aromatic polyamides
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/12—Hydrophobic properties
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2400/00—Specific information on the treatment or the process itself not provided in D06M23/00-D06M23/18
    • D06M2400/02—Treating compositions in the form of solgel or aerogel

Definitions

  • the invention relates to a novel process for coating textile materials for the preparation of coated textiles having gas barrier properties.
  • activated carbon Today, the use of activated carbon in gas filtration is the appropriate solution. However, activated carbon poorly traps toxic molecules of small size and polar and it must be impregnated with various chemicals suitable to compensate for this inefficiency. Activated carbon is found in various forms of mixed media with textiles: textiles impregnated with activated carbon and pressed, or activated carbon stuck to the fabric. In these cases, it becomes difficult to wash the garment without losing the original properties of the garment. To obtain good protection against chemical risks, a large amount of activated carbon is necessary, which makes the garment heavier. Furthermore, for protection against the projection of corrosive or / and toxic liquids, it is necessary to have a water-repellent fabric, either hydrophobic or both hydro- and oleophobic depending on the field of activity. Another desirable property for protective clothing is its resistance to wear by abrasion or washing.
  • an NBC military protective suit (nuclear, bacteriological, chemical) consists of two layers with the following characteristics and functions. The outer layer, the main functions of which are to ensure the robustness of the outfit (resistance to abrasion and tearing) and to guarantee the non-penetration of war toxins in liquid form.
  • the non-penetration of war toxins in liquid form corresponds to the water repellency function (hydrophobicity / oleophobicity).
  • This function is obtained by surface treatment of the outer fabric with a fluorinated resin.
  • the inner layer performs the function of filtering toxic substances in gaseous form. This function is obtained from activated carbon in different forms.
  • the patent application EP 1468732 A2 describes a monolayer of activated carbon which is bonded to a textile material as an inner lining. These activated carbon beads preferentially have a specific surface area of 900 to 1200 m 2 / g.
  • activated carbon beads (0.1 to 0.4 mm) are integrated into a textile (woven or not) by mixing them with hot-melt fibers, non-hot-melt fibers, a dispersing agent and water. The whole is heated between 80 and 150 ° C and compressed.
  • the targeted applications concern filtration: gas masks, protective clothing, air filters.
  • the patent US6844122 describes a process making it possible to print particles, of activated carbon or of silica in particular, on a support which can be a textile (woven, non-woven, thread, etc.). Many applications are mentioned concerning filtration and protection (chemical, bacterial, against fire, etc.).
  • the patent application FR 2868956 A1 describes an activated carbon mesh whose adsorption properties are characterized by a preferred specific surface area of approximately 800 to 1200 m 2 / g and by a preferred microporosity percentage of 80% to 100%.
  • activated carbon is in the form of polyurethane foam impregnated with activated carbon.
  • the polyurethane foam layer is impregnated with activated carbon then compressed and contrc-glued on a fabric
  • the patent application TW200951269A describes the spraying of an activated carbon powder solution pretreated with a silane coupling agent onto a textile material, for filtration applications.
  • the patent application WO 2015163969 A2 describes an activated carbon fabric containing metal oxide nanoparticles for gas filters or liquid purification.
  • the specific surface area of the activated carbon fabric is given between 100 and 2000 m 2 / g.
  • the average diameter of the pores of the activated carbon is between 0.3 and 3 nm and represents 30 to 50% of the overall porosity.
  • An activated carbon fiber texture having bactericidal activity is described in the patent application FR 2819420 A1 . This activity is due to treatment with an adjuvant active against the effects of biological agents such as silver salts, quaternary ammonium salts, copper salts, organophosphorus compounds and mixtures thereof.
  • the BET specific surface area of the activated texture is generally of the order of approximately 1000 to 1200 m 2 / g.
  • the patent application relates more to the properties of the fabric (weight, composition, weave, mechanical properties) than to the sol-gel formulations themselves. It is only mentioned that a hydrophobic coating is obtained thanks to a mixture of organosilanes containing a biogen or nanoparticles based on silver ions, or a mixed hydrophobic / antibacterial coating.
  • the durability of the coating is also an important property of textiles used for protective clothing against civilian or military toxic chemicals. It also reflects the grip of the sol-gel on the textile. In the case of materials such as cotton or cellulose, the adhesion of the sol-gel is easily increased by the chemical condensation of silanol groups with the hydroxyl groups of the textile surface: the very nature of the sol-gel is sufficient to allow its grip on certain types of textile fibers ( J. Colloid Interf. Sci. 2005, 289, 249-261, Silane adsorption onto cellulose fibers: Hydrolysis and condensation reactions, M.-CB Salon, M. Abdelmouleh, S. Boufi, MN Belgacem, A. Gandini ).
  • FR2984343A1 reports that the attachment of the sol-gel formulation to the tissue can be achieved by incorporating polycarboxylic acid and a catalyst (sodium hypophosphite).
  • the role of the polycarboxylic acid is to promote the bridging between the material and the hydrolyzed siliceous precursors.
  • the role of the catalyst is to ensure the grafting of the polycarboxylic acid on the material by catalyzing the formation of an anhydrous acid intermediate from the polycarboxylic acid (formation of an ester function with the alcohol functions free to the surface of the support).
  • the objective of these two chemical compounds is therefore to improve the chemical adhesion of the polycondensed chains.
  • the durability of the coating is said to be improved, in particular with regard to abrasion and washing.
  • the tests relating to the durability to washing and to the abrasion resistance are reported for the only exemplary embodiment given using a sol-gel formulation from the hydrophobic silane hexadecyltrimethoxysilane.
  • the process involved, the Advantex process is complex and involves several steps: the first corresponds to the reaction between three siliceous precursors, a functionalized alkoxysilane, a cyclic siloxane and a methylated and hydrogenated siloxane in the presence of catalysts to obtain catalysts. a mixed methylated and methylated-hydrogenated polysiloxane (product A).
  • the 2nd step corresponds to the reaction of the latter with an allylic derivative (C3H5R) carrying a function in the presence of a catalyst (Pt) for the transformation of the SiH groups of compound A into Si-C2H4R carrying the function R.
  • the reactions take place in organic solvents, and in particular in alcohols, which must be partially removed under partial vacuum at 150 ° C. Variants of this protocol are proposed, depending on the siloxanes and siliceous precursors used.
  • Karran Woan et al. (Photocatalytic carbon-nanotube-TiO2 composites, Advanced materials 21 (2009) 2233-2239 ) describe the combination of TiO 2 obtained by the sol-gel method by grafting or coating with carbon nanotubes. The aim here is also to improve the photocatalysis yield of TiO 2 , with applications in the environmental sector.
  • sol-gel materials with activated carbon for applications in the field of filtration have been proposed.
  • the objective of this work is to combine the complementary properties of the two materials, namely the mechanical resistance, the adjustable porosity and the adjustable polarity of the porous sol-gel material and the very high adsorption capacity of the activated carbon.
  • activated carbon in the form of particles is modified by impregnation of a sol-gel solution containing amine functions in order to improve its adsorption capacities, in particular of the CO 2 contained in the air.
  • the patent application CN103334298 describes a textile composed of activated carbon fibers (0.1-1 mm) coated with silica (airgel - 5-30 wt%). The fibers are immersed in a sol-gel solution before being dried. Many properties are claimed: mechanical performance, adsorption, anti-fire, anti-virus properties, lightness.
  • the targeted applications relate to high protection clothing, in particular for the biochemistry sector, firefighter and military equipment.
  • activated carbon is a material very widely used in the field of filtration where it is often associated with textiles.
  • the processes for combining these two materials are quite varied.
  • activated carbon particles are fixed to a textile by means of glue, however this has the drawback of blocking part of the pores of the activated carbon and reducing its filtration performance.
  • the activated carbon is trapped in a nonwoven or foam.
  • solutions remaining in the state of the art consist in producing a fabric of activated carbon, either by weaving fibers of activated carbon, or by carrying out a heat treatment on a fabric of natural or synthetic fibers.
  • they have a significant drawback, since the textiles obtained have low mechanical strength and are therefore relatively fragile.
  • activated carbon has been combined with soil-gels for several years. It is used in the majority of cases in order to increase the photocatalysis yield of TiO 2 . Work associating activated carbon with a silicon-based sol-gel is rarer. The activated carbon can simply play the role of a support therein before being removed by carbonization, and is not present in the final product obtained.
  • two patent applications describe the coating of activated carbon (particles or fibers) with a silicon-based sol-gel material, with applications in the field of filtration or high protection clothing.
  • none of these solutions target the filtration of toxic compounds, the patent CN104801279 for CO 2 sequestration and the patent CN103334298 aimed at thermal insulation in the case of clothing for firefighters and military personnel.
  • An aim of the invention is therefore to provide a method for manufacturing a simple and effective coated textile making it possible to achieve these performances.
  • the alkoxy groups (OR) are hydrolyzed to silanol groups (Si — OH).
  • the latter condense to form siloxane bonds (Si-O-Si-).
  • Small particles are formed, generally less than 1 ⁇ m in size, which aggregate and form clumps which remain in suspension without precipitating, forming a soil.
  • the increase in clusters and their condensation increases the viscosity of the medium which gels.
  • a porous solid material is obtained by drying the gel, with the expulsion of the solvent outside the polymer network formed (syneresis).
  • the textiles obtained with the process according to the invention make it possible to filter polar and non-polar toxic gases.
  • the incorporation of a polycarboxylic acid modifies the sol-gel making it unsuitable for an application in gas filtration, in particular polar.
  • the textiles obtained with the process according to the invention make it possible to filter polar and non-polar toxic gases.
  • the incorporation of a polycarboxylic acid modifies the sol-gel making it unsuitable for an application in gas filtration, in particular polar.
  • the coating composition is additionally free of catalyst.
  • the coating composition according to the invention does not require the presence of a catalyst for the formation of an anhydrous acid intermediate from the acid either.
  • polycarboxylic such as phosphorus catalysts such as sodium hypophosphite.
  • the coating composition is in particular free of such a catalyst.
  • catalyst within the meaning of the invention also includes acids, in particular mineral acids, such as hydrochloric acid, and monocarboxylic acids.
  • the coating composition is further free of surfactant.
  • surfactant would modify the sol-gel by inducing the formation of a network of large pores, either mesopores (20-500 ⁇ ) or even macropores (> 500 ⁇ ), which would be detrimental to the property. filtration.
  • the impregnated textile material according to the invention is flexible, light, breathable, water-repellent, and has barrier properties against polar and non-polar toxic gases.
  • the textile material used can be of any type. It may for example be a fabric, a nonwoven, such as a felt, or a knitted fabric, preferably a fabric or a nonwoven such as a felt.
  • the textile material comprises fibers comprising hydrolyzable functions, such as hydroxyl functions.
  • An example of such a fiber is cellulose present in natural fibers such as cotton or artificial fibers such as viscose. Preferably, they are viscose fibers.
  • the fibers comprising hydrolyzable functions can be used alone, as a mixture with one another and / or as a mixture with other synthetic fibers such as polyamide, polyamide / imide, polymeta-phenylene terephthalamide, polyparphenylene terephthalamide, d acrylic, modacrylic, polyesterterephthalate, oxidized polyacrylonitrile.
  • the textile material is a material based on an intimate blend of viscose and synthetic fibers, preferably polyamide fibers, in particular aromatic polyamide. Examples of such a fabric are Kermel® / Lenzing FR® 50: 50 and Conex® / Lenzing FR® 50: 50.
  • the textile material is a nonwoven, in particular a felt. An example of such a felt is that of Duflot Industries in Nomex®.
  • the aqueous solvent used in the coating composition can be water or a mixture of water and an organic solvent, in particular polar, protic or aprotic.
  • This organic solvent may for example be chosen from linear C1 to C4 aliphatic alcohols, in particular methanol, ethanol and propan-1-ol.
  • the organic solvent is ethanol.
  • the aqueous solvent advantageously contains 50% to 100% by volume of water.
  • the aqueous solvent advantageously represents 50 to 92% by volume, preferably 55 to 80% by volume and more preferably still 60 to 70% by volume of the coating composition.
  • the organosilicon precursor used in the coating composition can consist of a single organosilicon precursor or a mixture of organosilicon precursors. It is advantageously chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), methyl trimethoxysilane (MTM), methyl triethoxysilane (MTE), phenyltrimethoxysilane (PhTMOS), phenyltriethoxysilane, a fluoxylane (Phoxysilane), a fluoxylane (Phoxysilane), a fluoxysilane (Phoxysilane), a fluoxysilane (PhoTEOS) and a fluoxysilane (TEOS) ETHoxysilane (ETH-O-TEOS-ETH-O-TEOS-OH-O-TEOS-OH-O-TEOS-OH-ET-OH-ET-OH-TEOS chloroalkylmethoxysilane, a
  • the organosilicon precursor is chosen from tetramethoxysilane (TMOS), tetraethoxysilane (TEOS), phenyltrimethoxysilane, methyl trimethoxysilane (MTM), methyl triethoxysilane (MTE), phenyltrimethoxysilane (TEOS), phenyltrimethoxysilane, methyl trimethoxysilane (MTM), methyl triethoxysilane (MTE), phenyltrimethylethoxysilane (Phenoxysilane) (Phoxysilane) a fluoroalkyltrimethoxysilane, a fluoroalkyltriethoxysilane, an aminopropyltriethoxysilane, (3-glycidyloxypropyl) trimethoxysilane (GPTMOS) and their mixtures, preferably from tetramethoxysilane (TMOS), methyl
  • the organosilicon precursor is tetramethoxysilane.
  • the organosilicon precursor is a mixture of tetramethoxysilane and a precursor chosen from methyl trimethoxysilane (MTM), methyl triethoxysilane (MTE), phenyltrimethoxysilane (PhTMOS), phenyltriethoxysilane (PhoxTEOS), a fluorohydrin (PhoxTEOS) a fluoroalkyltriéthoxysilane a chloroalkylméthoxysilane a chloroalkyléthoxysilane, an aminopropyltriethoxysilane, (3-glycidyloxypropyl) trimethoxysilane (GPTMOS) and mixtures thereof, preferably from methyl trimethoxysilane (MTM), phenyltrimethoxysilane (PhTMOS), a fluoroalkyl
  • the mixture contains neither chloroalkylmethoxysilane nor chloroalkylethoxysilane.
  • Preferred organosilicate precursor mixtures include mixtures of tetramethoxysilane (TMOS) with methyl trimethoxysilane (MTM), with aminopropyl triethoxysilane (APTES), with 1H, 1H, 2H, 2H-perfluoroheptadecyltrimethoxysilane), withTM deTM aminopropyl triethoxysilane (APTES) and 1H, 1H, 2H, 2H-perfluoroheptadecyltriethoxysilane (17FTOS). Particularly good bonding and filtration performances were obtained with mixtures of TMOS and PhTMOS respectively.
  • the molar proportions of tetramethoxysilane (TMOS) / other organosilicon precursor (s) can be varied between 100/0 and 50/50, preferably between 90/10 and 75/25.
  • the organosilicon precursor advantageously represents 5 to 50% by volume, relative to the aqueous solvent and organosilicon precursor combination. If the aqueous solvent is water, the organosilicon precursor preferably represents 8 to 35% by volume relative to the whole aqueous solvent and organosilicon precursor. By using a mixture of water and an organic solvent, in particular ethanol (eg 90/10 by volume), the precursor can represent up to 50% by volume relative to the aqueous solvent assembly. and organosilicon precursor.
  • the activated carbon used for the present invention can be of plant or animal origin. Those skilled in the art will choose it as a function of the properties, in particular of filtration, sought. Thus, it is possible to use different forms of activated carbon, such as, for example, beads, powder, granules or fibers.
  • the activated carbon can be mixed at different concentrations with the coating composition (sol-gel composition) to modulate the quantity of activated carbon deposited on the textiles after impregnation.
  • the incorporation of the activated carbon into the sol-gel solution can take place from the start of the reaction until the moment of impregnation of the textile material. It can for example be added at the same time as the sol-gel precursors.
  • the coating composition is applied directly to the textile material.
  • This strategy directly uses the functionality of the organosilicon precursors used for the barrier function for the attachment of the sol-gel to the textile, in particular via hydroxyl functions at the surface.
  • the method according to the invention comprises, before step b), a step of applying a pre-coating composition comprising an organic solvent and a zirconium alkoxide, said pre-coating composition.
  • a pre-coating composition comprising an organic solvent and a zirconium alkoxide, said pre-coating composition.
  • -coating being free of polycarboxylic acid. Due to the absence of polycarboxylic acid, the precoating composition according to the invention also does not require the presence of a catalyst for the formation of an anhydrous acid intermediate from the polycarboxylic acid. , such as phosphorus catalysts such as sodium hypophosphite. Thus, the precoating composition is advantageously free of such a catalyst.
  • Zr 4+ has a high coordination number (+7) which promotes adhesion to the textile material via the complexation with the functionalities coming from the textile.
  • the application of the coating composition in step b) covers this first tie layer to form the “barrier” coating.
  • the zirconium alkoxide can be chosen from tetra-n-propyl zirconate ( CAS 23519-77-9 ), tetra-n-butyl zirconate ( CAS 1071-76-7 ), tetra- iso -propyl zirconate ( CAS 14717-56-7 ), tetra-tert-butyl zirconate (2081-12-1), bis (diethyl citrato) -dipropyl zirconate ( CAS 308847-92-9 ), bis (2,2,6,6-tetramethyl-3,5-heptanedionate) -di- isopropyl zirconate ( CAS 204522-78-1 ), preferably t
  • the textile material is impregnated by padding with the coating composition containing activated carbon.
  • the padding comprises a step of impregnating the textile material in the soil followed by a step of pressing under pressure which allows the excess soil to be evacuated.
  • this technique makes it possible to obtain a uniform distribution of the soil as well as a better impregnation of the soil in the fabric.
  • the scanning electron microscopy images show that the application of the coating composition according to the invention by padding results in a sheathing of the textile fibers.
  • the dip coating on the other hand results in a non-homogeneous deposit and essentially on the surface because it consists of the soaking of the textile material in the coating solution followed by the exit of the textile material vertically.
  • Step b) of impregnation of the textile material by padding can be carried out once or repeated several times.
  • the process according to the invention can thus comprise several, in particular 1 to 3, successive cycles of impregnation of the textile material by padding.
  • the textile material used in step b) of the process according to the invention is dried prior to impregnation with the coating composition in order to remove water from the surface.
  • This drying is particularly advantageous in the case of textile materials incorporating cellulosic fibers such as cotton or viscose.
  • the textile material is dried at a temperature of 80 to 180 ° C, preferably 100 to 150 ° C, more preferably about 120 ° C.
  • the drying time is advantageously a few minutes, for example 2 to 10 minutes, in particular 2 to 5 minutes.
  • Another subject of the invention is a coating composition
  • a coating composition comprising an aqueous solvent, an organosilicon precursor and activated carbon in powder form as described above.
  • the subject of the invention is also an impregnated textile material obtained by the coating process according to the invention described above. It is therefore a textile material impregnated with a sol-gel material and activated carbon in powder form. All the details and embodiments set out above for the nature of the textile material, the sol-gel material and the activated carbon are also valid for the textile material impregnated according to the invention.
  • the impregnated textile material according to the invention is characterized in particular in that it has a specific surface area S BET (determined from the adsorption isotherms using the Brunauer, Emmet and Teller (BET) model) of between 600 ⁇ 50 and 950 ⁇ 80 m 2 .g -1 , in particular between 700 ⁇ 60 and 940 ⁇ 80 m 2 .g -1 .
  • S BET Brunauer, Emmet and Teller
  • the porosity of the impregnated textile material according to the invention was determined from the adsorption isotherms using the model based on the density functional theory (DFT, for English: Density Functional Theory).
  • DFT density functional theory
  • the proportion of micropores ( ⁇ 20 ⁇ ) is preferably greater than 40%, and more preferably still greater than 50%.
  • the proportion of mesopores (20 ⁇ - 500 ⁇ ) is preferably less than 60%, and more preferably still less than 50%.
  • the textile material is preferably free of macropores (> 500 ⁇ ).
  • the basis weight of the sol-gel material can vary from 10 to 435 g / m 2 , preferably from 20 to 400 g / m 2 , more preferably from 30 to 300 g / m 2 .
  • the impregnated textile material according to the invention finds a particular application for the filtration of gases, in particular for personal protective equipment such as for example clothing, in particular against toxic chemicals, but also for textiles intended to protect the respiratory tract (masks ), textiles that absorb unwanted odors such as frying or tobacco, such as for example consumable filters.
  • the invention therefore also relates to a filter, in particular a gas filter, comprising the textile material according to the invention.
  • a particular object of the invention is personal protective equipment comprising the textile material according to the invention.
  • This personal protective equipment may for example be a full suit, pants, jacket, gloves, balaclavas, socks, masks. Thanks to the functional properties, in particular of filtration of polar and non-polar toxic gases of the textile material according to the invention, the personal protective equipment is particularly suited to NBC risks (nuclear, bacteriological, chemical). Thus, in one embodiment, the personal protective equipment is NBC personal protective equipment.
  • 0.268 g of succinic acid and 0.284 g of sodium hypophosphite are mixed in 18.02 mL of ultra pure water and 18.02 mL of ethanol.
  • the mixture is stirred at mark 4 on the IKA WERKE RO10 power multiple stirrer plate (approximately 500 rpm) and at room temperature (20-22 ° C) until the polyacid and the catalyst have dissolved.
  • 4.107 g of activated carbon, 4.800 mL of TMOS and 0.226 mL of APTES are added to the initial mixture.
  • a hermetically sealed glass bottle 0.127 g of succinic acid and 0.135 g of sodium hypophosphite are mixed in 8.57 mL of ultra pure water. The mixture is stirred at mark 4 of the IKA WERKE RO10 power multiple stirrer plate (approximately 500 rpm) and at room temperature (20-22 ° C) until the polyacid and the catalyst have dissolved, before adding 0.773 g of activated carbon.
  • 8.57 mL of ethanol, 0.337 mL of 17FTMOS, 2.100 mL of TMOS and 0.108 mL of APTES are mixed. The contents of the second flask are then poured into the first, which is kept under stirring.
  • a hermetically sealed glass bottle 0.127 g of succinic acid and 0.135 g of sodium hypophosphite are mixed in 8.57 mL of ultra pure water. The mixture is stirred at mark 4 on the IKA WERKE RO10 power multiple stirrer plate (approximately 500 rpm) and at room temperature (20-22 ° C) until the polyacid and the catalyst have dissolved, before adding 1.937 g of activated carbon.
  • 8.57 mL of ethanol, 0.337 mL of 17FTMOS, 2.100 mL of TMOS and 0.108 mL of APTES are mixed. The contents of the second flask are then poured into the first, which is kept under stirring.
  • a hermetically sealed glass bottle 1.816 g of activated charcoal is mixed with a volume of 19.97 mL of ultra pure water.
  • a second hermetically sealed glass vial 19.97 mL of ethanol, 5,000 mL of TMOS and 0.502 mL of APTES are mixed.
  • the contents of the second vial are then poured into the first vial and the mixture is stirred at room temperature (20-22 ° C) at mark 4 of the IKA WERKE RO10 power multiple stirrer plate (approximately 500 rpm).
  • a hermetically sealed glass bottle 4.541 g of activated carbon are mixed with a volume of 19.97 mL of ultra pure water.
  • a second hermetically sealed glass vial 19.97 mL of ethanol, 5,000 mL of TMOS and 0.502 mL of APTES are mixed.
  • the contents of the second vial are then poured into the first vial and the mixture is stirred at room temperature (20-22 ° C) at mark 4 of the IKA WERKE RO10 power multiple stirrer plate (approximately 500 rpm).
  • a hermetically sealed glass bottle 1.129 g of activated charcoal is mixed with a volume of 12.24 mL of ultra pure water.
  • 12.24 mL of ethanol, 0.482 mL of 17FTMOS, 3.000 mL of TMOS and 0.154 mL of APTES are mixed.
  • the contents of the second vial are then poured into the first vial and the mixture is stirred at room temperature (20-22 ° C) at mark 4 of the IKA WERKE RO10 power multiple stirrer plate (approximately 500 rpm).
  • a hermetically sealed glass bottle 2.813 g of activated charcoal is mixed with a volume of 12.24 mL of ultra pure water.
  • 12.24 mL of ethanol 12.24 mL of ethanol, 0.482 mL of 17FTMOS, 3.000 mL of TMOS and 0.154 mL of APTES are mixed.
  • the contents of the second vial are then poured into the first vial and the mixture is stirred at room temperature (20-22 ° C) at mark 4 of the IKA WERKE RO10 power multiple stirrer plate (approximately 500 rpm).
  • a hermetically sealed glass bottle 0.397 g of activated carbon is mixed with a volume of 17.52 mL of ultra pure water. Then 2.100 mL of TMOS and 0.293 mL of PhTMOS are added and the mixture is stirred at room temperature (20-22 ° C) at mark 4 of the IKA WERKE RO10 power multiple shaker plate (approximately 500 rpm).
  • a hermetically sealed glass bottle 0.411 g of activated charcoal is mixed with a volume of 18.02 mL of ultra pure water. Then 1.800 mL of TMOS and 0.753 mL of PhTMOS are added and the mixture is stirred at room temperature (20-22 ° C) at mark 4 of the IKA WERKE RO10 power multiple stirrer plate (approximately 500 rpm).
  • the deposition of this formula on textiles indicates a basis weight of 20 g / m 2 .
  • Example 2 Properties of the impregnated fabrics of Example 1
  • the textiles were characterized by SEM before and after impregnation with the solutions.
  • Scanning Electron Microscopy is a powerful technique for observing surface topography. It is based mainly on the detection of secondary electrons emerging from the surface under the impact of a very fine primary electron brush which scans the observed surface and makes it possible to obtain images with a resolving power often less than 5 nm and great depth of field.
  • the instrument makes it possible to form an almost parallel, very thin (down to a few nanometers) brush of electrons strongly accelerated by adjustable voltages of 0.1 to 30 keV, to focus it on the area to be examined and to sweep it gradually.
  • Appropriate detectors collect significant signals while scanning the surface and form various ones meaningful images. Images of tissue samples were taken with Zeiss "Ultra 55" SEM. The samples are observed directly without any particular deposit (metal, carbon). A low acceleration voltage of 3 keV and the InLens detector (backscattered and secondary electron detector) allow the samples to be observed and avoid an excessive charge phenomenon due to the nature of the tissues.
  • the samples of fabrics A impregnated with formulations D 1 , D 2 , D 1 'and D 2 ' were also observed by SEM.
  • the SEM images show that the sol-gel coats the activated carbon particles and fixes them on the fibers, forming a continuous sheath ( Figures 4 and 5 ).
  • the SEM images of the tissues impregnated with formulations D1 'and D2' prepared according to strategy II show that the deposits are similar to those obtained with the solutions of strategy I.
  • the sol-gel which is thicker and fractured, coats the particles of activated carbon and fixes them on the fibers forming a sheath.
  • the air permeability is lowered after deposition but remains suitable.
  • the structure of the impregnated textile plays a predominant role in the permeability since, for the same formula deposited, the fabric C (felt) is eight times more permeable than the fabric A (Kermel® / Lenzing fabric). , yet with a deposit ten times larger.
  • the sol-gel deposit with activated carbon is uniform and changes the appearance of textiles, whatever their structure ( Figures 10, 11, 12 , 13 ).
  • the sol-gel formula has no impact on the visual appearance of textiles after deposition, unlike its activated carbon content: the higher the concentration, the more the color will tend towards black.
  • the flexibility of the textiles before / after deposition is evaluated by measuring the drop angle.
  • FIG. 14A The flexibility of the textiles before / after impregnation was evaluated with the flexibility measurement tool shown in Figure 14A .
  • This tool 1 consists of two parts, a lower part 2 serving as a support for the fabric T and an upper part 3 which fits on the lower part to block the fabric T.
  • the Figure 14B shows the block diagram for the measurement. To make a measurement 5 cm of fabric are positioned "in the void", that is to say outside the measuring tool, a photo is taken in profile, then, on the profile photo, the The angle ⁇ formed between the fabric and the vertical is measured using a protractor to assess the drop off of the fabric.
  • This tool allows a comparison of samples with a reference (tissue without sol-gel) as shown in the photos shown in figure 15 .
  • textiles are more rigid after deposition. These measurements also show that the flexibility of textiles can vary with the sol-gel formulas (precursors) and their activated carbon concentration.
  • textiles impregnated with formulations according to strategy II are generally more flexible than those impregnated with formulations according to strategy I.
  • the precursors used for the formation of the sol-gel can be chosen in order to provide water-repellency properties.
  • formulations containing fluorinated precursors such as formulas E 1 , F 1 , F 2 and E ' 1 make it possible to obtain hydrophobic fabrics.
  • the hydrophobic properties of fabrics impregnated with formulations E 1 , E 2 , F 1 , F 2 , E ' 1 and E' 2 were determined by contact angle measurements with the “OCA 15EC” goniometer from DataPhysics and the “SCA20” software in dynamic mode with the acquisition of 4 measurements per second for 1 min in order to to determine the stability of the water drop (10 ⁇ L) on the tissue
  • Table 7 summarizes the average contact angles over 2 or 3 measurements at t0.
  • Example 3 Gas phase filtration
  • a test bench was installed in the laboratory. For this, a “Porometer 3G, sample holder 37 mm” porometer from Quantachrome was used. This porometer makes it possible to test a tissue with a diameter of 37 mm (cutout carried out with a punch). Sealing is ensured by O-rings. Thus, the gas flow passes through all of the tissue being tested.
  • Methyl salicylate permeability tests consist of measuring the salicylate content (in ppm) as a function of time. This path is called a drilling curve whose shape in "S" is more or less marked.
  • the comparison of the standardized methyl salicylate piercing curves with a deposit of 20 g / m 2 for the initial tissue, formula D 2 (strategy I) and formula D ' 2 (strategy II) is presented in Figure 16 .
  • the drilling curves obtained were used by two methods: decomposition of the drilling curve and modeling of the drilling curve. Both methods are detailed below.
  • the first method to assess filtration is to break down the piercing curve and analyze the total trapping times.
  • the total trapping times are determined for a methyl salicylate content at 0 ppm (t @ 0 ppm), a methyl salicylate content of less than 1 ppm (t ⁇ 1 ppm), less than 5 ppm (t ⁇ 5 ppm) ) and less than 20 ppm (t ⁇ 20 ppm). These total trapping times constitute the characteristic times of the decomposition method.
  • the second method for evaluating the filtration consists in modeling the borehole curve by a sigmoid function according to the Hill model described below.
  • This model resulting from enzymatic catalysis, models strictly positive data following a sigmoid (“S” -shaped curve) which corresponds well to the piercing curves obtained by exposure of tissues impregnated with sol-gel to methyl salicylate.
  • the characteristic time of the drilling curve modeling method is therefore: t 1/2 .
  • the slope of the curve can be calculated. For this, two points are necessary: A (t A ; T A ) and B (t B ; T B ). The calculation of the coordinates and the slope are recalled in the table below.
  • the toluene permeability tests consist of measuring the toluene content (in ppm) as a function of time. This path is called a drilling curve whose shape in "S" is more or less marked.
  • the comparison of the normalized toluene piercing curves with a deposit of 20 g / m 2 for the initial tissue, formula D 2 (strategy I) and formula D ' 2 (strategy II) is presented in Figure 16 .
  • the porosity of sol-gel materials was determined from the establishment of nitrogen adsorption isotherms (specific surface area, pore volume, pore size distribution).
  • the intrapore polarity is revealed by the material's ability to more effectively trap methyl salicylate compared to toluene.
  • Nitrogen adsorption consists of the physisorption of nitrogen at the surface of a solid: this is a reversible phenomenon (adsorption / desorption).
  • Nitrogen adsorption a volumetric technique a volume of gas of known temperature and pressure is sent to the previously degassed sample and maintained at the temperature of liquid nitrogen. An adsorption isotherm corresponding to the volume of adsorbed gas as a function of the partial pressure of nitrogen is established.
  • adsorption isotherms The interpretation of adsorption isotherms is carried out based on various analytical models: Brunauer, Emmett and Teller (BET) model which is an adsorption model of a monomolecular layer of nitrogen molecules in the pores, and model based on the density functional theory (DFT) which reproduces with the help of Monte Carlo methods the adsorption isotherm for pores of given size.
  • BET Brunauer, Emmett and Teller
  • DFT density functional theory
  • sol-gel with activated carbon does indeed exhibit significant porosity, the presence of the sol-gel therefore not obstructing the pores of the activated carbon.
  • a higher concentration of activated carbon in the same sol-gel formulation results in a higher specific adsorption surface area and a higher pore volume.
  • the sol-gel formulations according to strategy II have a greater porosity (specific adsorption surface area and pore volume) than those according to strategy I. For filtration applications, strategy II again appears to be the most suitable.

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