RU2642775C1 - Method of applying hydrophobic and oleophobic coating to textile material and textile material with hydrophobic and oleophobic coating - Google Patents

Abstract

FIELD: textile, paper.

SUBSTANCE: method for applying a hydrophobic and oleophobic coating to a textile material includes holding the textile material in a copolymer solution in supercritical carbon dioxide in a high pressure reactor, characterized in that said solution contains a copolymer containing fluorinated (meth)acrylic hydrophobic units affine to CO₂, and (meth)acrylic functional units containing a functional group, and a cross-linking agent containing at least two functional groups reactive with the functional groups of the copolymer, said cross-linking agent being not part of said copolymer. The invention also relates to a textile material with a hydrophobic and oleophobic coating, having a wetting angle with a drop of water ≥130°, the index in the water-repellent ability test ATCC 22 is above 90 points, the index in the oil resistance test AATSS 118 is 6 points or higher, the vapour permeability in the vapour permeability test according to the standard ATSM E 96 (Procedure B) after modification not less than 0.95 from the result of the unmodified material, retaining water-repellent and oil-repellent properties and vapour permeability after 10 or more washes in a washing machine, carried out according to the standard ISO 6330 procedure, procedure 6A, obtained by the method according to the invention.

EFFECT: method according to the invention makes it possible to obtain a textile material with a hydrophobic and oleophobic coating resistant to repeated washing cycles in a washing machine.

18 cl, 2 dwg

Description

FIELD OF THE INVENTION

The present invention relates to the field of finishing of textile materials. More specifically, the invention relates to the field of application to woven and non-woven textile materials of hydrophobic and oleophobic coatings, resistant to wear, multiple machine wash cycles that do not reduce the vapor permeability of the material. In particular, the invention relates to a method for applying a hydrophobic and oleophobic fluoropolymer coating using a solution of a fluorine-containing copolymer and a crosslinking agent in supercritical carbon dioxide. The method in accordance with the invention allows the formation of hydrophobic and oleophobic coatings on textile materials from synthetic and natural fabrics, non-woven materials, including non-woven filter materials, giving them water- and oil-repellent properties that persist after repeated machine wash cycles.

State of the art

The prior art method for creating an antisplash coating on textile materials - fabrics, in which a perfluorinated modifying agent of polymer nature and a crosslinking agent are applied to the textile material from their water-based solution or dispersion [US 2012/0094564 A1, 04/19/2012]. The disadvantage of this method is the use of a liquid aqueous solution or dispersion for applying a perfluorinated modifying agent. The use of a liquid aqueous solution or dispersion for impregnating a textile material with a perforated modifying agent does not allow uniformity of the coating of textile material with such a perforated agent due to the presence of capillary effects due to surface tension in the liquid solvent at the impregnation and drying stages. The surface tension of the liquid solvent does not allow to apply uniform coatings in the depth of small pores of the material, and also leads to the destruction of the already applied coating when leaving the liquid solvent during its drying. Thus, this method does not allow the processing of the entire surface of micro- and nanoporous materials, and also leads to the formation of defects and inhomogeneities in the coating. All this worsens the resistance of the coating to wear, to multiple machine wash cycles, and also reduces the vapor permeability of the material due to partial blocking of the pores due to the inhomogeneous distribution of the perforated modifying agent over the surface of the material.

Known methods for creating a water-repellent coating on rough materials, including textile materials, in which a fluorinated polymer is applied from solutions in supercritical carbon dioxide [RU 2331532, 08.20.2008 and US 6,030,663 A, 29.02.2000]. The use of supercritical carbon dioxide as a solvent allows you to create a uniform coating on the material, which leads to high water-repellent properties. The disadvantage of this method is the low durability of the created coatings. Due to the absence of a chemical bond between the polymer and the textile material, the coatings obtained in this way on textile materials are not resistant to wear and to multiple machine wash cycles.

Known method of modifying a porous membrane of expanded PTFE to make it oleophobic properties, wherein the fluorine-containing polymer is applied from solution in the supercritical carbon dioxide (SC CO ₂₎ [US 7,534,471 B2, 16.06.2005]. This method provides high resistance to wear of coatings due to the mechanism of swelling of the membrane from expanded polytetrafluoroethylene (ePTFE) in SC СО ₂ and subsequent collapse during decompression. As a result, the polymer chains of the modifying agent are mechanically bonded to the material being modified. The disadvantage of this method is that it is impossible to give resistance to wear of coatings on materials that poorly swell in SC CO ₂ . Obtained on materials that poorly swell in SC ₂ , such as synthetic textile materials, coatings have low resistance to wear and to multiple machine wash cycles.

Closest to the claimed is a method of coating a porous laminate, consisting of a membrane of expanded polytetrafluoroethylene and two layers of synthetic fabric, from a solution of a fluorinated copolymer containing functional isocyanate groups in supercritical carbon dioxide [US 8,735,306 B2]. The isocyanate groups in the copolymer are able to react with the hydroxyl, amide and amino groups of the fabric fibers that make up the laminated material and provide covalent bonding of the coating to the fabric fibers. The disadvantage of this coating is that the crosslinking agent is one of the blocks of the copolymer, and not a separate component of the coating. Such a crosslinking agent can only provide the sewing of the polymer molecule to the tissue fiber, but is not able to ensure the crosslinking of the polymer molecules between themselves. This leads to low durability of the coating on materials that do not contain the indicated functional groups, and on which the coating cannot be sewn to the processed material.

Disclosure of the invention

The objective of the invention is to develop a method of applying a hydrophobic and oleophobic coating to textile material, which allows you to get a durable water-repellent and oleophobic coating on textile materials, allows you to apply a uniform coating on porous materials, providing a uniform coating of the surface of micropores and nanopores of textile material, allows you to save vapor permeability of the textile material and allows to obtain textile material with a wetting angle with a drop of water ≥130 °, the indicator in the test for the AATC 22 self-repellent ability is higher than 90 points, with an AATCC 118 oil resistance test of 6 points or more, with a vapor permeability test according to ATCM E 96 (Procedure B) after modification not less than 0.95 from the result of unmodified material, with preservation of water-repellent and oil-repellent properties and vapor permeability after 10 or more washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A.

This problem is solved by a method of applying a hydrophobic and oleophobic coating to a textile material, including exposing the textile material in a copolymer solution in supercritical carbon dioxide in a high pressure reactor, said solution containing a copolymer containing fluorinated (meth) acrylic hydrophobic units affinity for CO ₂ , and (meth) acrylic functional units containing a functional group, and a crosslinking agent containing at least two functional groups, reactivity s with respect to the functional groups of the copolymer, wherein said crosslinking agent is not part of the copolymer.

Preferably, said fluorinated (meth) acrylic hydrophobic units affine with respect to CO _2, are acrylic or methacrylic units containing fluorinated alkyl chains with a terminal CF ₃ group.

According to one embodiment of the invention, said (meth) acrylic functional units preferably comprise a hydroxyl, amide or amino group.

In accordance with one embodiment of the invention, said crosslinking agent comprises at least two isocyanate groups.

Preferably, said textile material also contains functional groups reactive with the functional groups of the crosslinking agent, and most preferably functional groups similar to the functional groups of the copolymer.

According to another embodiment of the invention, the (meth) acrylic functional units of the copolymer contain isocyanate groups. In this case, compounds containing two or more functional groups selected from the series can be used as crosslinking agents: amino group, amide group, hydroxyl group.

In this case, it is preferable to choose crosslinking agents with functional groups that coincide with functional groups on the surface of the material to be processed, in order to ensure close reaction rates of the functional groups of the copolymer with functional groups on the surface of the material, on the one hand, and functional groups of a crosslinking agent, on the other, and, accordingly, the uniform distribution of crosslinkers of the type copolymer-textile material and copolymer-copolymer.

Typically, the coating is carried out at a temperature of 35-200 ° C and the density of supercritical carbon dioxide in the high pressure reactor is 0.5-1.5 g / ml.

Preferably the mass content of the copolymer in the solution of supercritical carbon dioxide is 0.1-10 wt. % by weight of textile material.

Preferably, the mass content of the crosslinking agent in the supercritical carbon dioxide solution is 0.01-1 wt. % by weight of textile material.

In one embodiment, the hydrophobic units of the copolymer contain perfluoroalkyl acrylate, the functional units of the copolymer contain hydroxyalkyl acrylate, and the proportion of perforated units to functional units is 10: 1

Preferably, diisocyanate is used as the crosslinking agent.

Preferably, a textile fabric of nylon 6.6 material, a fabric of polyester material, a non-woven filter material based on polyparaphenylene oxadiazole fibers, a non-woven filter material based on aromatic polyamides are used as textile material.

Preferably, after deposition of the coating, it is heat treated at a temperature of 80-200 ° C for 20-200 minutes.

Another objective of the invention is to obtain a textile material with a hydrophobic and oleophobic coating, having a wetting angle with a drop of water ≥130 °, the indicator in the test for water-repellent ability AATSS 22 above 90 points, the indicator in the test for oil resistance AATCC 118 from 6 points and above, the vapor permeability in the test on vapor permeability according to ATCM E 96 (Procedure B) after modification not less than 0.95 from the result of unmodified material, which retains water-repellent and oil-repellent properties and vapor permeability after 10 or more washes in the washing machine carried out according to the standard procedure of ISO 6330, procedure 6A. The specified textile material can be obtained by the method in accordance with the present invention.

In accordance with the invention, a method of applying a hydrophobic and oleophobic coating to a textile material is that the textile material is kept in a solution of a copolymer in supercritical carbon dioxide in a high pressure reactor. The method in accordance with the invention is characterized in that said copolymer comprises fluorinated (meth) acrylic hydrophobic units affinity for CO ₂ and (meth) acrylic functional units containing functional groups. In addition, the method in accordance with the invention is characterized in that, in addition to the copolymer, a crosslinking agent is dissolved in supercritical carbon dioxide containing at least two functional groups reactive with the functional groups of the copolymer, said crosslinking agent not being part of the copolymer macromolecules, but is a separate chemical compound placed in a reactor. The functional groups of the crosslinking agent react with the functional groups of the copolymer macromolecules, providing chemical crosslinking of the copolymer macromolecules with each other. Also, in a preferred embodiment of the invention, if there are functional groups on the surface of the modifiable textile material that are reactive with the functional groups of the crosslinking agent, chemical suturing of the coating to the textile material to be treated is also provided.

As a hydrophobic copolymer unit, fluorinated (meth) acrylic units affinity for CO ₂ (CO ₂ -philic) are used. In particular, it is preferable to use (meth) acrylic units containing fluorinated alkyl chains with a CF ₃ group at the end as hydrophobic units, since the tight packing of CF ₃ groups makes it possible to obtain coatings with the lowest surface energy, repellent with respect to liquids not only with high ( water), but also with low surface tension (oils). In addition, the presence of fluorinated fragments contributes to the affinity of the unit with respect to CO ₂ and, as a rule, positively affects the solubility of polymers containing such units in liquid and supercritical CO ₂ . In particular, it is preferable to use fluorinated acrylic or methacrylic units resulting from the polymerization of, for example, the following fluorinated acrylic or methacrylic monomers as hydrophobic units: 1,1-dihydroperfluorooctyl acrylate, 1,1-dihydroperfluorooctyl methacrylate, 1,1,2,2- tetrahydroperfluoroalkyl methacrylate, 1,1,2,2-tetrahydroperfluoroalkyl acrylate, 1,1,2,2,3,3-hexahydroperfluoroalkyl methacrylate, 1,1,2,2,3,3-hexahydroperfluoroalkyl acrylate, 2- (N-ethylperfluorooctanesulfonamido ) ethyl acrylate, 2- (N-ethylperfluorooctanesulfones d) ethyl methacrylate, 2- (N-methylperfluorooctanesulfonamido) ethyl acrylate, 2- (N-methylperfluorooctanesulfonamido) ethyl methacrylate, 2- (N-methylperfluorohexanesulfonamido) ethyl acrylate, 2- (N-ethylperfluorohexanesulfonamide-2) methylperfluorobutanesulfonamido) ethyl acrylate, 2- (N-methylperfluorobutanesulfonamido) ethyl methacrylate.

If necessary, in addition to the indicated fluorinated (meth) acrylic hydrophobic units and the indicated (meth) acrylic functional units, the copolymer may further comprise non-fluorinated hydrophobic units, which may be used acrylic and methacrylic units containing chains of different length polydimethylsiloxanes, such as monomethacryloxypropyl terminated polydimethylsiloxane, methacryloxypropyl T-structured polydimethylsiloxane, monomethacryloxypropyl polytrifluoropropylmethylsiloxane, p manufactured by Gelest. Also, (meth) acrylic units containing non-fluorinated alkyl moieties, for example, butyl acrylate, butyl methacrylate, octyl acrylate and the like, can be used as non-fluorinated hydrophobic units.

In particular, it is preferable to use acrylic or methacrylic units containing hydroxy, amino, amide or isocyanate groups as a functional unit of the copolymer: hydroxyalkyl acrylate (hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate), hydroxyalkyl methacrylate (hydroxyethyl methacrylate, hydroxypropyl acrylate) , acrylamide, aminoalkyl acrylate (aminoethyl acrylate, aminopropyl acrylate, aminobutyl acrylate), aminoalkyl methacrylate (aminoethyl methacrylate, aminopropyl methacryl atm aminobutyl methacrylate) izopropenildimetilbenzil isocyanate. It is preferable to choose functional units containing functional groups similar to functional groups on the surface of the processed material, if there are any. This will provide close rates of crosslinking macromolecule crosslinking reactions and the reaction of suturing the coating to the fiber, which will provide the most uniform crosslinking distribution between the coating macromolecules and the macromolecules of the processed fibers.

In particular, as a crosslinking agent, it is preferable to use compounds containing two or more functional groups reactive both with respect to the functional groups of the functional units of the applied copolymer and with respect to functional groups on the surface of the processed material, if any. It is preferable to use compounds containing isocyanate groups, since they are reactive with hydroxy, amino and amide groups, which are often found in both natural and synthetic fibers of textile materials. In particular, it is preferable to use compounds with two or more isocyanate groups. It is advisable to use, for example, the following diisocyanates from the series: toluene diisocyanate, phenylene diisocyanate, hexamethylene diisocyanate, methylene diphenyl diisocyanate, isophorondiisocyanate. It is also possible to use triisocyanates, for example: triphenylmethane triisocyanate, undecane triyl triisocyanate, toluene triyl triisocyanate. In order to protect against hydrolysis and increase the chemical stability of isocyanate groups, the blocked forms of the above diisocyanates and triisocyanates containing isocyanate groups blocked by oximes, pyrazoles, malonates can be used.

In the case where the functional units of the copolymer contain isocyanate groups, and compounds containing two or more functional groups selected from the series are used as crosslinking agents: amino group, amide group, hydroxyl group, it is possible to use, for example, the following compounds as crosslinking agents: diols (ethylene glycol, propylene glycol, hydroxyterminated polydimethylsiloxane), triols (glycerin, trimethylolpropane, trimethylolethane), diamines (hexamethylenediamine, paraphenylenediamine), dicarb diamides New acids, tri (melamine).

In particular, it is preferable to use fabrics of different weaving based on polyester or polyamide fibers, as well as fabrics of different weaving based on cotton, as textile materials. As textile materials based on polyamide fibers, for example, the following textile materials can be used: twisted nylon 6.6 straight weave (spun nylon 6.6 plane weave, material density 190 g / m ² ), nylon weave fabric bunting (nylon oxford bunting, material density 108 g / m ² ), stretch nylon 6.6 double weave (texturized nylon 6.6 stretch fabric, material density 260 g / m ² ), nylon knit material (filament nylon 6 tricot-bright, material density 73 g / m ² ) For example, Ivuniforma nylon fabrics can be used as polyamide fiber fabrics. As textile materials based on polyester fibers, for example, the following textile materials can be used: polyester artificial suede (poly suede, material density 240 g / m ² ), polyester georgette (poly georgette, material density 57 g / m ² ), polyester rayon (poly "silk", material density 73 g / m ² ), polyester pongee (poly pongee, material density 73 g / m ² ). As fabrics based on polyester fibers, for example, Itkani polyester fabrics can be used. Also, natural textile materials can be used, for example, the following textile materials: unbleached cotton flannel (unbleached cotton flannel, material density 125 g / m ² ), bleached cotton flannel (bleached cotton flannel, material density 152 g / m ² ), cotton canvas (greige cotton duck, material density 500 g / m ² ), cotton velveteen (Cotton Corduroy, material density 255 g / m ² ).

In particular, non-woven materials based on polyparaphenylene oxadiazole fibers or based on fibers of aromatic polyamides are also preferably used as textile materials. For example, as a nonwoven material, a material based on aromatic polyamides Nomex KD from DuPont can be used. Also, as a nonwoven material, material based on Arpelon polyparaphenylene oxadiazole fibers from Volbrock can be used.

The application of the copolymer and a crosslinking agent is preferably carried out in a high pressure reactor with operating pressures from 1 to 1000 atm, in particular from 1 to 300 atm.

The application of the copolymer and a crosslinking agent is preferably carried out from supercritical carbon dioxide with a density of 0.5-1.5 g / ml.

The application of the copolymer and a crosslinking agent is preferably carried out at a temperature of 35-200 ° C.

The application of the copolymer and a crosslinking agent is preferably carried out within 1-24 hours.

Preferably the mass content of the copolymer in the solution of supercritical carbon dioxide is 0.1-10 wt. % by weight of textile material.

Preferably, the mass content of the crosslinking agent in the supercritical carbon dioxide solution is 0.01-1 wt. % by weight of textile material.

Preferably, the proportion of fluorinated (meth) acrylic hydrophobic units to (meth) acrylic functional units is from 1: 1 to 20: 1, most preferably from 3: 1 to 10: 1. The choice of the range of relations between the links is due to the need to maintain a balance between water and oil repellent properties, on the one hand, and resistance to machine wash, on the other. At ratios lower than 1: 1 of the fluorinated (meth) acrylic hydrophobic units to the (meth) acrylic functional units, the required water and oil repellent properties are not achieved. With ratios higher than 20: 1 of fluorinated (meth) acrylic hydrophobic units to (meth) acrylic functional units, the coatings become machine washable.

Preferably, the molecular weight of the applied copolymer, as measured by gel permeation chromatography, is from 10,000 to 400,000 g / mol, most preferably from 100,000 to 300,000 g / mol.

Preferably, after deposition of the coating, it is heat treated at a temperature of 80-200 ° C for 20-200 minutes. Heat treatment allows the functional groups of the applied copolymer and fibers of the material to be processed to react with the functional groups of a crosslinking agent and is necessary to obtain a durable chemically crosslinked coating. In addition, heat treatment facilitates the orientation of the fluorinated side chains of the copolymer based on fluorinated acrylic monomers perpendicular to the surface of the material and the concentration of non-polar CF ₃ groups on the coating surface, which is necessary to provide the lowest surface energy and, accordingly, the highest oil-repellent properties of the coating.

The method in accordance with the invention allows to obtain a durable hydrophobic and oleophobic coating on a textile material that does not reduce the vapor permeability of the modified textile material. The advantages of the claimed invention when achieving a technical result are due to the fact that a copolymer containing fluorine-containing hydrophobic units is used to modify the surface of a textile material, which provides contact angles of the modified surface with a water drop of more than 130 ° and an oil resistance index of AATCC 118 of at least 6 points. In addition, the technical result is achieved by the fact that supercritical carbon dioxide is used as a solvent for the copolymer, which makes it possible to uniformly apply a thin film of the copolymer to each individual fiber of textile material, treating pores of any diameter, including micro-sized and nano-sized pores of textile material, which allows to achieve 22 100 points in the AATCC water resistance test, and also allows to achieve vapor permeability in the test according to the ATCM E 96 standard (Procedure B) after coating is not less than 0.95 of the result of unmodified material. In addition, the technical result is achieved by the fact that a crosslinking agent with two or more functional groups reactive with respect to the functional groups of the copolymer is added separately from the copolymer. This allows you to provide both the crosslinking of the functional groups of the copolymer with each other, and, preferably, the sewing of the copolymer along the functional groups to the surface of the fibers of textile materials. This creates a chain of chemical crosslinking of the copolymer around the fabric fiber and ensures that the water and oil repellent properties of the coating are maintained after 10 washes in the washing machine, carried out according to the standard procedure of ISO 6330, procedure 6A.

In particular, when using fabrics based on polyamide or polyester fibers as a modifiable textile material, a waterproof and oil-resistant fabric is obtained as a product that retains water and oil repellent properties after repeated washing in a washing machine. Such a fabric can be used as an outer layer of membrane fabrics, as a fabric for clothing for sports recreation, as a fabric for accessories for outdoor activities and tourism.

In particular, when using non-woven filter materials based on polyparaphenylene oxadiazole fibers or based on aromatic polyamide fibers as a modifiable textile material, an oil-resistant filter material is obtained as a product. Oil resistance of the filter material increases its service life. Thus, an additional technical result in this case is the creation of an oil-resistant filter material with an increased service life.

Brief Description of the Drawings

In FIG. 1 is a schematic diagram illustrating an example of an apparatus allowing the implementation of the method in accordance with the invention.

In FIG. 2 shows a schematic representation of the mechanism of crosslinking of the applied coating with a fiber of a hydrophobizable fabric, implemented in the claimed method.

The implementation of the invention

Next, the method in accordance with the invention will be described in more detail with reference to the accompanying drawings.

The claimed method is carried out using the installation, a diagram of which is presented in FIG. 1. In the thermostatically controlled high pressure reactor (number 8 in Fig. 1) is placed the textile material to be modified, as well as the copolymer. Using a high pressure generator (number 5 in FIG. 1) connected to a CO ₂ cylinder (number 3 in FIG. 1) through a bi-directional valve (number 4 in FIG. 1) in a thermostatic high pressure reactor (number 8 in FIG. 1), the required CO ₂ pressure is generated. The pressure is measured with a pressure gauge (number 6 in Fig. 1) connected to the system through a three-way valve (7 in Fig. 1). The temperature is measured with a thermocouple (9). After the required CO ₂ pressure in the reactor is reached, the reactor is cut off from the system by shutting off the bi-directional valve. After that, the contents of the reactor are mixed using the mixing system (10 in Fig. 1) the required amount of time. After that, the pressure is released using the exhaust system (number 11 in Fig. 1). When the pressure in the reactor becomes atmospheric, the reactor is opened and the modified tissue is removed.

As a result of the modification, a copolymer (number 14 in FIG. 2) is applied to the fabric fiber (number 13 in FIG. 2). The functional units of the copolymer (number 16 in Fig. 2) reacted and formed a chemical bond with one of the functional groups of the crosslinking agent (number 17 in Fig. 2), and the second functional group of the crosslinking agent (number 18 in Fig. 2) reacted with functional group of the fiber of the textile material, thereby chemically suturing the copolymer to the fiber of the textile material, or with another functional group of the copolymer, thereby crosslinking the macromolecules of the copolymer with each other.

Example 1

As the copolymer (14), polyperfluorodecyl acrylate-co-polyhydroxypropyl methacrylate is used. 1,4-toluene diisocyanate is used as a crosslinking agent (17, 18). As the material to be hydrophobized (13), Spun nylon fabric, which is a twisted nylon fiber. The density of the fabric is 200 g / m ² , the diameter of the fibers is 20 microns, the thickness of the fabric is 390 microns.

A tissue 20 × 20 cm in size tightly rolled up into a roll is placed in a high pressure reactor (8). The copolymer is placed in the reactor in a mass ratio to the weight of the fabric roll 1:50. A crosslinking agent is placed in the reactor in a mass ratio to the mass of the modifying agent 1:10. After that, using a high-pressure generator (5) connected to a cylinder with CO ₂ (3), the reactor is filled with CO ₂ . The pressure is controlled using a pressure gauge (6). After the required pressure of 200 bar has been reached, the reactor is closed and placed in a thermostat, at a temperature of 90 ° C. After being placed in a thermostat and equalizing the temperature, an exposure is carried out for 3 hours. Temperature control is carried out using a thermocouple (9). Then the cell is cooled to 50 ° C and slowly decompressed, thereby ensuring the transition of the solvent from the supercritical to the gaseous state, bypassing the liquid phase. The deposited coated fabric sample is annealed at 140 ° C. for 30 minutes.

After hydrophobization, the marginal angle of a drop of water on the surface of the tissue is about 150 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the fabric are not reduced.

Example 2

Under the conditions of example 1, polyester rayon is used as the substrate.

After modification, the contact angle of the water drop on the surface of the fabric is 150 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the fabric are not reduced.

Example 3

In the conditions of example 1 use a non-woven filter material Nomex KD (DuPont, USA).

After modification, the contact angle of the water drop on the surface of the fabric is 150 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, conducted according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the non-woven filter material are not reduced.

Example 4

In the conditions of example 1, a non-woven filter material based on Arselon fibers Arsefil (Volbrok, Russia) is used.

After modification, the contact angle of the water drop on the surface of the fabric is 150 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, conducted according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the non-woven filter material are not reduced.

Example 5

As the copolymer (14), 2- (N-ethylperfluorooctanesulfonamido) ethyl methacrylate-co-polyhydroxypropyl methacrylate is used. As a crosslinking agent (17, 18), 1,4-toluene diisocyanate is used. As the material to be hydrophobized (13), a natural fabric consisting of cotton canvas.

A tissue 20 × 20 cm in size tightly rolled up into a roll is placed in a high pressure reactor (8). The copolymer is placed in the reactor in a mass ratio to the weight of the fabric roll 1:30. A crosslinking agent is placed in the reactor in a mass ratio to the mass of the modifying agent 1: 5. After that, using a high-pressure generator (5) connected to a cylinder with CO ₂ (3), the reactor is filled with CO ₂ . The pressure is controlled using a pressure gauge (6). After the required pressure of 150 bar has been reached, the reactor is closed and placed in a thermostat at a temperature of 50 ° C. After being placed in a thermostat and equalizing the temperature, an exposure is carried out for 2 hours. Temperature control is carried out using a thermocouple (9). Then the cell is cooled to 40 ° C and slowly decompressed, thereby ensuring the transition of the solvent from supercritical to gaseous state, bypassing the liquid phase.

After hydrophobization, the marginal angle of a drop of water on the surface of the tissue is about 135 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the fabric are not reduced.

Example 6

Under the conditions of Example 1, polyperfluorodecyl acrylate-co-acrylamide is used as the copolymer. After hydrophobization, the marginal angle of a drop of water on the surface of the tissue is about 150 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the fabric are not reduced.

Example 7

Under the conditions of Example 1, polyperfluorodecyl acrylate-co-acrylamide is used as a copolymer, and toluene triyl triisocyanate is used as a crosslinker. After hydrophobization, the edge angle of a drop of water on the surface of the tissue is about 150 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the fabric are not reduced.

Example 8

Under the conditions of Example 1, the copolymer used is a copolymer of 1,1,2,2-tetrahydroperfluorodecyl acrylate (60 mol%) as a fluorinated hydrophobic unit, monomethacryloxypropyl terminated polydimethylsiloxane (20 mol%) as a non-fluorinated hydrophobic unit, hydroxypropyl methacrylate as a functional link. Toluene diisocyanate is used as a crosslinking agent. After hydrophobization, the marginal angle of a drop of water on the surface of the tissue is about 150 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the fabric are not reduced.

Example 9

In the conditions of example 1, a copolymer of 1,1,2,2-tetrahydroperfluorodecyl acrylate (60 mol%) is used as a fluorinated hydrophobic unit, butyl acrylate (20 mol%) as a non-fluorinated hydrophobic unit, hydroxypropyl methacrylate as a functional unit . Toluene diisocyanate is used as a crosslinking agent. After hydrophobization, the marginal angle of a drop of water on the surface of the tissue is about 150 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the fabric are not reduced.

Example 10

Under the conditions of example 1, the copolymer used is a copolymer of 1,1,2,2-tetrahydroperfluorooctyl acrylate, butyl acrylate and isopropenyl-dimethylbenzyl isocyanate (the molar fraction of tetrahydroperfluorooctyl acrylate is more than 50%), and a hydroxyterminated polydimethylsiloxane (Ge 14 ) After hydrophobization, the marginal angle of a drop of water on the surface of the tissue is about 150 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the fabric are not reduced.

Example 11

Under the conditions of Example 1, the copolymer used is a copolymer of 1,1,2,2-tetrahydroperfluorooctyl acrylate, butyl acrylate and isopropenyl-dimethylbenzyl isocyanate (the molar fraction of tetrahydroperfluorooctyl acrylate is more than 50%), and hexamethylenediamine is used as a crosslinking agent. After hydrophobization, the marginal angle of a drop of water on the surface of the tissue is about 150 °. The loss of vapor permeability does not exceed 5%, according to measurements according to the ATCM E 96 standard, Procedure B. Oil resistance of the tissue sample after coating is 6 according to the AATCC 118 standard. The level of water repellent ability is 100 points according to the AATCC 22 test. After 10 washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A, contact angle, oil resistance and the level of water-repellent ability of the fabric are not reduced.

Comparative example 1 in accordance with the patent RU 2331532. In the conditions of example 1, the ultrafine polytetrafluoroethylene (UPTFE) Forum is used as a copolymer, following the patent RU 2331532, and no cross-linking agent is used. After 10 washings of the material in the washing machine, carried out according to the standard procedure of ISO 6330, procedure 6A, the contact angle tends to zero (a drop is absorbed), oil resistance and water-repellent ability of the fabric material are not detected.

Comparative example 2 in accordance with the patent RU 2331532. In the conditions of example 1, as a copolymer, following the patent RU 2331532, a commercial Teflon AF2400 copolymer is used and no cross-linking agent is used. After 10 washings of the material in the washing machine, carried out according to the standard procedure of ISO 6330, procedure 6A, the contact angle tends to zero (a drop is absorbed), oil resistance and water-repellent ability of the fabric material are not detected.

Comparative example 3 in accordance with patent US 8,735,306. Under the conditions of Example 1, a copolymer of 1,1,2,2-tetrahydroperfluorooctyl acrylate, butyl acrylate and isopropenyl-dimethylbenzyl isocyanate is used as a copolymer, and does not use a crosslinking agent. After 10 washings of the material in the washing machine, carried out according to the standard method ISO 6330, procedure 6A, the level of water repellent ability - 80 points according to the test of AATCC 22 standard, oleophobicity - 5 points according to AATCC 118 standard.

Claims (20)

1. The method of applying a hydrophobic and oleophobic coating on a textile material, comprising exposing the textile material in a solution of a copolymer in supercritical carbon dioxide in a high pressure reactor, characterized in that said solution contains: a copolymer containing fluorinated (meth) acrylic hydrophobic units affinity for CO ₂ and (meth) acrylic functional units containing a functional group, and a crosslinking agent containing at least two functional groups reactive with respect to the functional groups of the copolymer, said crosslinking agent not being part of said copolymer. 2. The method according to p. 1, characterized in that said fluorinated (meth) acrylic hydrophobic units are fluorinated acrylic or methacrylic units containing fluorinated alkyl chains with a terminal CF ₃ group. 3. The method according to p. 1, characterized in that the copolymer further comprises non-fluorinated hydrophobic units, which are acrylic or methacrylic units containing chains of polydimethylsiloxanes or non-fluorinated alkyl chains. 4. The method according to p. 1, characterized in that these (meth) acrylic functional units contain a functional hydroxyl, amide or amino group. 5. The method according to p. 4, characterized in that the crosslinking agent contains at least two isocyanate functional groups. 6. The method according to claim 1, characterized in that said (meth) acrylic functional units contain an isocyanate functional group. 7. The method according to p. 6, characterized in that the crosslinking agent contains at least two functional hydroxyl, amide or amino groups. 8. The method according to any one of paragraphs. 1-7, characterized in that the said textile material also contains functional groups reactive with respect to the functional groups of the crosslinking agent. 9. The method according to p. 8, characterized in that said textile material contains functional groups similar to the functional groups of the copolymer. 10. The method according to p. 1, characterized in that the application is carried out at a temperature of 35-200 ° C. 11. The method according to p. 1, characterized in that the density of supercritical carbon dioxide in the high pressure reactor is 0.5-1.5 g / ml 12. The method according to p. 1, characterized in that the mass content of the copolymer in the solution of supercritical carbon dioxide is 0.1-10 wt.% By weight of the textile material. 13. The method according to p. 1, characterized in that the mass content of a crosslinking agent in a solution of supercritical carbon dioxide is 0.01-1 wt.% By weight of the textile material. 14. The method according to p. 1, characterized in that the quantitative ratio of fluorinated (meth) acrylic hydrophobic units to (meth) acrylic functional units is from 1: 1 to 20: 1. 15. The method according to p. 1, characterized in that the diisocyanate is used as the crosslinking agent. 16. The method according to p. 1, characterized in that the textile material is a fabric made of nylon 6.6 material, a fabric made of polyester material, a non-woven filter material based on polyparaphenylene oxadiazole fibers, a non-woven filter material based on aromatic polyamides. 17. The method according to p. 1, characterized in that after the deposition of the coating spend its heat treatment at a temperature of 80-200 ° C for 20-200 minutes 18. Textile material with a hydrophobic and oleophobic coating, obtained by the method according to any one of paragraphs. 1-17, having a wetting angle with a drop of water ≥130 °, the indicator in the AATCC 22 water-repellent test is above 90 points, the indicator in the AATCC 118 oil resistance test is from 6 points and above, the vapor permeability in the vapor permeability test according to ATCM E 96 (Procedure C) after modification, not less than 0.95 from the result of the unmodified material, which retains water-repellent and oil-repellent properties and vapor permeability after 10 or more washes in the washing machine, carried out according to the standard method ISO 6330, procedure 6A.

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