Classifications

• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06N—WALL, FLOOR, OR LIKE COVERING MATERIALS, e.g. LINOLEUM, OILCLOTH, ARTIFICIAL LEATHER, ROOFING FELT, CONSISTING OF A FIBROUS WEB COATED WITH A LAYER OF MACROMOLECULAR MATERIAL; FLEXIBLE SHEET MATERIAL NOT OTHERWISE PROVIDED FOR
  • D06N3/00—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof
  • D06N3/12—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins
  • D06N3/128—Artificial leather, oilcloth or other material obtained by covering fibrous webs with macromolecular material, e.g. resins, rubber or derivatives thereof with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. gelatine proteins with silicon polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/54—Silicon-containing compounds
  • C08K5/541—Silicon-containing compounds containing oxygen
  • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
  • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/56—Organo-metallic compounds, i.e. organic compounds containing a metal-to-carbon bond
  • C08K5/57—Organo-tin compounds
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
  • C09D183/04—Polysiloxanes
• • 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
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
  • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
  • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
  • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain

Definitions

• the field of the present invention is that of crosslinkable liquid silicone formulations which can be used to form a coating which makes it possible to provide long-lasting functionalities to a large number of sportswear.
• number of textile materials in particular those used in the field of sportswear (in English "sportwear”).
• Many treatments are applied to textile materials, they provide them with additional functionalities such as softness, hydrophilicity, hydrophobia, oleophobia.
• These treatments often consist of depositing on the textile surface polymers mainly of silicone type. For softness, these are long polydimethylsiloxane oils (or even polyorganosiloxane gums).
• hydrophilicity they are amino silicone oils or polyether groups.
• Organosilicon or purely organic fluorinated compounds are incorporated when seeking to provide oleophobia.
• one of the characteristics sought is the permanence of the treatment. It is observed in practice that the many current formulations do not allow satisfactory durability to be achieved.
• the main characteristics required are as follows: comfort, breathability, water repellency and a certain level of waterproofing: • • Comfort is provided mainly by the nature and type of textile used. In addition, these textiles may have elasticity properties. • Breathability is mainly ensured by the structure of the textile, in particular its open porosity.
• waterproof-breathable membrane significantly reduces the intrinsic breathability of the textile and no longer allows the evacuation of heat and water in the event of moderate activity, strong to very strong (this which is the case during a sporting practice).
• Water repellency is a feature of the textile surface. It corresponds to the fact that under moderate sprinkling (representative of a light rain) the water does not catch on the textile which thus emerges more or less dry.
• Impermeability to liquid water is a rather mass characteristic of textiles in the sense that water must invade and pass through the porosity of the textile surface. The number and the size of the pores are to be taken into consideration, but also the treatment of the surface of these pores (surface of the woven or knitted fibers).
• Impermeability is measured by the pressure that must be applied to force water to pass through the fabric. It is customary to speak of a raincoat as soon as the critical water pressure is equivalent to that of a meter of water. In practice, such protection is only useful in 10% of situations (very heavy rain, sustained contact with wet surfaces, etc.). It is instructive to keep in mind that a pressure of the order of 10 cm of water is equivalent to that exerted by a wind of 140 km / h. Bringing all of these functions to a textile material is already in itself a technical feat. In particular, combining water repellency and impermeability with breathability is notoriously difficult. Bringing durable functions to the textile material is an additional technical difficulty. It is known (cf.
• the present invention therefore aims to provide a treatment which allows to provide lasting functionality to textile materials and in particular functionality suitable for the field of sportswear. Its objective is in particular to provide a treatment which makes it possible to impart a very good breathability and / or a high water repellency and / or a high impermeability to the textile material in a lasting manner, preferably an impermeability corresponding to at least 10 cm of water, better still several tens of centimeters of water.
• a treatment which makes it possible to impart a durable water repellency and a high impermeability to the textile material (preferably a impermeability corresponding to at least 10 cm of water, better still several tens of centimeters of water), without substantially calling into question the intrinsic breathability properties of the textile material.
• Another objective of the invention is to provide a treatment which additionally gives the textile, in a sustainable manner, rapid drying capacities and / or reduced water uptake.
• Yet another object of the invention is to provide a treatment which gives the textile such properties which persist under conditions of wet abrasion and very particularly in the washing.
• An object of the invention is therefore to provide a method for producing textile materials and articles including them, eg clothing, having durable breathable properties and in particular having a certain resistance to washing and more generally to the constraints of use. .
• the present invention which relates to the use of at least one crosslinkable liquid silicone formulation as a base for coating a textile material intended preferably for the production of a sportswear : to allow, by crosslinking around the yarns, fibers and / or filaments constituting the textile material, to provide a broad protective cover for the textile material, protection little dependent on the nature of the said material because it requires little or no anchor points; to allow, by making a chemically crosslinking silicone sheath, to ensure lasting protection of the textile material by giving it excellent resistance to the aggressions encountered during use; by the term “durable protection” is meant to define protection on the one hand against the constraints imposed by textile processes such as in particular heat-setting treatments, dyeing treatments, and on the other hand -with respect to aggressions undergone during the life of the textile material (for example a garment) such as in particular abrasion when worn, washing in an aqueous detergent medium, dry cleaning in a solvent medium; to allow, by providing one or more hydrophobicity functionalities
• the present invention also relates to the use of a crosslinkable liquid silicone formulation comprising one or more hydrophobicity functionalities, for (i) coating a textile material capable of being used in the production of a sports garment and / or yarns, fibers and / or filaments constituting the textile material, the silicone formulation crosslinking around the yarns, fibers and / or filaments constituting the textile material and forming around them a crosslinked silicone sheath, and (ii) lastingly impart water repellency and impermeability to this textile material, preferably without substantially affecting the intrinsic breathability of the textile material.
• the durability of the above treatment and properties is paramount. Durability can be appreciated in a context including washing the textile material.
• Tests conducted by the applicant under drastic washing conditions have made it possible to show the remarkable resistance of the silicone treatment, correlated with a persistence of the properties.
• This durability can be measured by comparing the performance of the treated textile material, before and after having subjected this material to an intensive washing protocol, for example that described in Example 4 (continuous washing with water at 50 ° C., for 8 hours), the material being wrung and dried before undergoing the property testing protocol (s).
• the beading effect can be measured by the “Spray-Test” method AATC Test Method 22-1996; this method is described in the examples and can consist of a visual evaluation of the wet appearance of the sample: the test consists in spraying the sample of the textile article with a given volume of water; the appearance of the sample is then assessed visually and possibly compared to a standard; a score of 0 to 100% is assigned depending on the amount of water retained; for 0%, the sample is completely wet, for 100%, the sample is completely dry. The sample can also be weighed to measure the weight of water absorbed.
• the beading effect preferably corresponds to a score of at least 80%, more preferably of at least 90, better still of 100% (range 80-100%>).
• durability of the beading effect it is meant that, preferably, after the washing treatment, the note remains between 70 and 100%, preferably between 80 and 100%.
• Impermeability to liquid water can be measured by the Schmerber test (ISO Test Method 811-1981), which consists of applying water pressure to the textile through a water column and measuring the height limit that must be reached for water to pass through the fabric.
• the targeted waterproofing is preferably greater than or equal to 10 cm of water column according to this test, and so more preferred greater than or equal to 15 cm, better still 20 cm.
• this impermeability property is meant that, after the washing treatment described, the impermeability is not significantly affected and remains greater than or equal to 10, 15 or 20 cm of water column. Measuring the durability of the water repellency and impermeability properties makes it possible to assess the durability of the silicone treatment according to the invention. The other properties provided by the combination of the textile, these constituent yarns, fibers or filaments, and the silicone treatment also benefit from this durability.
• intrinsic breathability is meant the breathability of the textile material in the absence of treatment. The present invention makes it possible to produce a textile material having the above-mentioned water repellency and impermeability properties, without substantially calling into question the intrinsic breathability.
• the treatment makes it possible to limit the uptake of water (weight of water absorbed) of the treated textile and / or to provide it with a rapid drying capacity, and this in a sustainable way.
• the water uptake of a textile material and its drying speed can be measured by weighing a coupon of this textile material before and after dynamic humidification, and the values obtained expressed as a percentage by weight relative to the weight of the dry coupon. .
• the low level of water uptake observed makes it possible to limit the “freezing effect”, namely the feeling of cold resulting from heat exchanges in contact with wet clothing.
• tissue coupons to be tested are subjected to a dynamic humidification phase (placed in a bottle filled with water and subjected to strong stirring for a period of one hour; more precise conditions are indicated in Example 5), then the coupons are weighed (the comparison of the weights before and after humidification provides information on the water intake), put to dry on the scale , in a room conditioned at a temperature of 23 ° C and a relative humidity of 50%, and the change in their weight makes it possible to assess their drying capacity.
• the values observed will depend on the nature of the textile material.
• the treatment aims to limit the uptake of water so that the weight of the treated textile material coupon remains at least 50% o, preferably at least 60 or 70% less than the weight of the untreated control coupon.
• the uses according to the invention preferably aim to provide the textile material in a lasting manner with the three properties of breathability, water repellency and impermeability, preferably associated in addition with a low water recovery capacity. (thus conferring comfort to wear by limiting the heat losses due to the evaporation of water) and rapid drying lasting.
• the expression "textile material” means: on the one hand, yarns, fibers and / or filaments made of synthetic and / or natural materials which are used for the manufacture of textile articles; and on the other hand the textile articles made from said yarns, fibers and / or filaments, comprising at least one textile surface and consisting for example of woven, non-woven and / or knitted articles, said "made-up textile articles” also encompassing much fabric than clothing, such as jackets and pants.
• a functional siloxane network is permanently fixed on the textile surface and the treatment thus carried out makes it possible to successfully obtain the various advantageous properties mentioned above.
• the crosslinkable liquid silicone formulation used as a base for coating textile material comprises: A - a system for generating a film-forming silicone network comprising at least one polyorganosiloxane resin (POS) having, per molecule, on the one hand at least two different siloxyl units chosen from those of types M, D, T, Q, one of the units being a unit T or a unit Q and on the other hand at least three hydrolysable / condensable groups of types OH and / or OR 1 where R 1 is a linear or branched C- alkyl radical
• D optionally a non-reactive additive system consisting of: (i) at least one organic solvent / diluent and / or a non-reactive organosilicon compound; (2i) and / or in water in the case of the use of a liquid silicone formulation in emulsion or in aqueous dispersion; and E - optionally at least one auxiliary agent other than D known to those skilled in the art, which is chosen, when necessary, depending in particular on the applications in which the textile materials treated in accordance with the invention are used; with the condition according to which one commits (the parts are given by weight): - per 100 parts of component A, - from 0.5 to 200, preferably from 0.5 to 100 and more preferably from 1 to 70 parts of component B, - 1 to 1000, preferably from 1 to 300 parts of component C, - from 0 to 10,000, preferably from 0 to 5,000 parts of component D and - from 0 to 100 parts of component E.
• the components A which can be used, separately or as a mixture, are conventional film-forming resins among which may be mentioned: A-1: at least one organosilicon resin prepared by co-hydrolysis and co-condensation of chlorosilanes chosen from the group consisting of those of formulas (R 3 ) 3 SiCI, (R 3 ) 2 Si (CI) 2 , R 3 Si (CI) 3 , Si (CI) 4 . These resins are well known and commercially available branched organopolysiloxane oligomers or polymers.
• these resins are not completely condensed and they still have approximately from 0.001 to 1.5 OH group and / or alkoxyl OR 1 per silicon atom;
• the radicals R 3 are identical or different and are chosen from linear or branched alkyl radicals C-] - CQ, alkenyl radicals C2 - C4, phenyl, trifluoro-3,3,3 propyl.
• alkyl radicals R 3 examples include methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals; as examples of branched organopolysiloxane oligomers or polymers, mention may be made of MQ resins, MDQ resins, TD resins and MDT resins, OH and / or OR 1 groups which may be carried by the units M, D and / or T , the content by weight of OH and / or OR 1 groups being between 0.2 and 10% by weight;
• A-2 at least one mixed resin prepared by co-condensation of the organosilicon resins A-1 mentioned above with usual organic polymers such as: polyester and alkyd resins modified or not by fatty acids such as oleic acid, linoleic acid, ricinoleic or esters of fatty acids and aliphatic polyols such as castor oil, tallow; epoxy resins modified or not by fatty acids; phenol
• the mixtures A-3 may be cited: g - at least one resin of type A-1 (resin A-1/1) having, in its structure, at least two different siloxy units chosen from those of formula (R 3 ) 3 SiO Q 5 (unit M) , (R 3 ) 2 SiO (unit D) and R 3 SiO 1 5 (unit T), at least one of these units being a unit T, the groups OH and / or OR 1 being able to be carried by the units M , D and / or T and the content by weight of OH and / or OR 1 groups being between 0.2 and 10% by weight, and
• mixtures A-3 the respective proportions of the constituents are not critical and can vary within wide limits. These mixtures contain, for example, from 60 to 90% by weight of resin (s) A-1/1 and from 40 to 10%> by weight of resin (s) A-1/2.
• constituents B-1 there may be mentioned, as examples of symbols R 2 in the organic derivatives of metal M of formula (I), the radicals: methyl, ethyl, propyl, isopropyl, butyl, isobutyl , hexyl, 2-ethyl hexyl, octyl, decyl and dodecyl.
• alkyl titanates such as ethyl titanate, propyl titanate, isopropyl titanate, butyl titanate, ethyl titanate, 2 hexyl, octyl titanate, decyl titanate, dodecyl titanate, ⁇ -methoxyethyl titanate, ⁇ -ethoxyethyl titanate, ⁇ -propoxyethyl titanate, titanate of formula Ti [(OCH 2 CH 2 ) 2 OCH 3 ] 4 or mixture of at least two of them; alkyl zirconates such as propyl zirconate, butyl zirconate or a mixture of at least two of them; alkyl silicates such as methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate or a mixture of at least two of them; and mixtures of at least two of these products.
• alkyl titanates such as ethyl titanate, prop
• polyalkoxides B-2 which are preferred, originating from the partial hydrolysis of titanates, zirconates and silicate monomers, can be cited: polytitanates B-2 from the partial hydrolysis of isopropyl, butyl or 2-ethylhexyl titanates; polyzirconates B-2 originating from the partial hydrolysis of propyl and butyl zirconates; polysilicates B-2 from the partial hydrolysis of ethyl and isopropyl silicates; and mixtures of at least two of these products.
• constituents B-3/1 which are preferred, there may be mentioned the organosilanes optionally alkoxylated chosen from the products of the following general formula:
• R 4 , R 5 , R 6 are hydrogenated or hydrocarbon radicals identical or different from each other and preferably represent hydrogen, a linear or branched C-1-C4 alkyl or a phenyl optionally substituted by at least one CJ-C3 alkyl,
• - U is a linear or branched C-i-C alkylene or a divide grouping of formula -CO-O-alkylene- where the alkylene residue has the definition given above and the free valence on the right (in bold) is linked to Si via W,
• R 7 and R 8 are identical or different radicals and represent a linear or branched C 1 -C 4 alkyl
• vinyltrimethoxysilane or ⁇ - (meth) acryloxypropyltrimethoxysilane is a particularly suitable compound B-3/1 .
• constituents B-3/2 which are preferred, there may be mentioned the tris [(trialkoxysilyl) alkyl] isocyanurates where the alkyl groups contain from 1 to 4 carbon atoms and the organosilicon compounds are chosen:
• R 9 is a linear or branched C-1-C4 alkyl radical
• + R 10 is a linear or branched alkyl radical
• + y is equal to 0, 1, 2 or 3, preferably to 0 or 1 and, more preferably still to 0, + where X has the meaning:
• R 11 , R 12 , R 13 which are identical or different radicals representing hydrogen or a linear or branched C 1 -C 4 alkyl, hydrogen being more particularly preferred
• R 11 and R 12 or R 13 can alternately constitute together and with the two carbons carrying the epoxy, an alkyl ring having from 5 to 7 members,
• + X is the radical as defined above for the formula (B-3/2-a)
• the compounds B-3/2 are preferably tris [3- (trimethoxysilyl) propyl] isocyanurates and epoxyalkoxymonosilanes B
• GLYMO + 3-glycidoxypropyltrimethoxysilane
• the following titanates, zirconates and silicates B-1 are used more preferably, taken alone or as a mixture between them: ethyl titanate, propyl titanate, isopropyl titanate, butyl titanate (n-butyl), propyl zirconate, butyl zirconate, ethyl silicate, propyl silicate and isopropyl silicate.
• B-1 + B-3/1 or B-1 + B-3/2 the weight proportions of B-1 relative to the total B-1 + B3 / 1 or B-3/2 are notably from 5 to 100%, preferably from 8 to 80%.
• B-1 + B-3/1 + B-3/2 the weight proportions between B-1, B-3/1 and B-3/2, expressed in percentages by weight relative to the total of the three, are the following: B-1> 1, preferably between 5 and 25, B-3/1> 10, preferably between 15 and 70, B-3/2 ⁇ 90, preferably between 70 and 15, it being understood that the sum of these proportions in B-1, B-3/1, B-3/2 is equal to 100%.
• Component C has functions allowing it to cling to the silicone sheath and FH functions which confer hydrophobic properties on the textile material treated.
• the constituents C-1 which can be used, separately or as a mixture, are silanes,
• the FA functions are more precisely condensable / hydrolyzable functions corresponding to OH and / or OR 1 or functions capable of generating in situ functions
• the FH functions can comprise any known hydrophobic group or any combination of known hydrophobic groups.
• these groups are chosen from the following methods: alkyl groups, silicone groups, fluorinated groups and their various combinations. These groups can also develop softness properties.
• these groups are siloxane sequences comprising M, D and / or T units, preferably those defined above with regard to the constituents A-1.
• these groups are linear or branched C1 to C50 alkyl sequences, in particular from C1 to C30.
• these groups are fluorinated groups of general formula: -Z - (- R F ) k in which: + Z represents a divalent or trivalent ball joint of a hydrocarbon nature, which can be linear or branched, a cyclic residue or not, saturated or unsaturated aliphatic, aromatic, mixed aliphatic / aromatic, and which may contain one or more oxygenated heteroatoms containing from 1 to 30 carbon atoms, + k is 1 or 2, + R F represents the group -C 3 F 2s -CF 3 with s equal to or different from zero or the group C s F 2s H with s equal to or greater than 1.
• organosilicon compounds listed below can be cited: (i) the essentially linear diorganopolysiloxane comprising a hydroxyl group at each chain end, of formula:
• + the substituents R 18 identical or different, each represent a monovalent hydrocarbon radical saturated or not with C ⁇
• constituents C-1 which are very suitable, mention may be made of hydroxylated MDT resins having a content by weight of OH group of between 0.2 and 10%> by weight, taken alone or as a mixture with hydroxylated silicone oils of formula (III).
• proportions of use of the constituents C-1 they are, as explained above, in the range going from 1 to 1000 parts by weight of constituent C-1 according to the desired FH, per 100 parts in weight of component A. For example, in the case where FH provides hydrophobicity, then generally 2 to 30 parts by weight of component C-1 are used.
• the constituent A is a POS resin equipped with pattern (s) T and possibly M and / or possibly D
• this resin can then also play the role of water-repellent functional additive C-1, provided that it is used in sufficient proportions equal to the sum of the proportions corresponding to the set A + C-1.
• the constituents C-2 which can be used, separately or as a mixture, are hydrocarbon compounds carrying in their molecule, attached to carbon atoms, the two functionalities FA and FH.
• FA functions are more specifically functions condensable / hydrolyzable corresponding to OH and / or OR 1 or functions capable of generating in situ OH functions and / or OR 1.
• constituents C-2 which are preferred, mention may be made of fluorinated alcohols, preferably perfluorinated, of formula: R 19 - OH (IV) where R 19 represents an aliphatic radical, linear or branched, having from 2 to 20 atoms of carbon, said carbon atoms being substituted by at least one fluorine atom and optionally by at least one or hydrogen atom.
• R 19 represents an aliphatic radical, linear or branched, having from 2 to 20 atoms of carbon, said carbon atoms being substituted by at least one fluorine atom and optionally by at least one or hydrogen atom.
• R F perfluorinated alcohols of formula R F - (CH 2 ) m -OH where R F is as defined above and m is a number ranging from 0 to 10.
• constituents C-2 are, as explained above, in the range going from 1 to 1000 parts by weight of constituent C-2, per 100 parts by weight of constituent A.
• optional components D which are preferred, the following compounds can be cited, in addition to water:
• + the substituents R 21 identical or different, have the same meanings as those given above for the reactive diorganopolysiloxane of formula (III); + j 'has a sufficient value to give the polymers of formula (VI) a dynamic viscosity at 25 ° C ranging from 10 to 200,000 mPa.s;
• POS resins having the same meanings as those given above for component A, but which this time are free from any functional group of types OH and / or OR 1 .
• resins which can be used mention may be made of MQ, MDQ, TD and MDT resins.
• optional auxiliary components E which are preferred, the following compounds may be cited:
• polycondensation catalysts which are compounds of a metal generally chosen from tin, titanium and zirconium; it is thus possible to use monocarboxylates and tin dicarboxylates such as 2-ethylhexanoate of tin, dibutyltin dilaurate, dibutyltin diacetate, hexacoordinated valence IV tin chelates, etc., such as those described in EP-A-0 367 696;
• + metallic powders such as zinc, aluminum, magnesium powder
• + oxides such as silica, ground quartz, alumina, zirconium oxide, titanium, zinc, magnesium, iron, cerium, lanthanum, praseodymium, neodymium oxides
• + silicates such as mica, talc, vermiculite, kaolin, feldspar, zeolites
• + pigments such as phthalocyanines, chromium oxides, sulfide and cadmium sulfoselenides
• liquid silicone formulations used, in the context of the present invention, as textile coating bases are prepared by simple mixing at room temperature, and in any order of introduction, of the constituents A, B, C, D (optional ) and E (optional). The quantities committed are clearly defined as indicated above.
• the order of incorporation of the constituents can be arbitrary, but it is however preferable, to avoid any risk of precipitation of solid products or of gel formation, to add the constituent A in the form of a solution in the constituent D solvent / diluent or in the form of an aqueous emulsion / dispersion when component D comprises water.
• the introduction and intimate mixing of the optional fillers E, when used, with the constituents A, B, C and optionally D are carried out using the conventional methods used by the manufacturers of textile formulations. It is possible to use, for example, roller mills or turbine mills.
• the textile coating base formulations thus prepared have the advantage of hardening by simple air drying for a time interval which can range from a few tens of minutes to several hours or, if necessary, several tens of hours. This time can be shortened by heating to a temperature in the range of 50 ° C to 180 ° C.
• the textile coating bases thus prepared have excellent storage stability and can be used in all textile applications requiring the presence, after curing, of durable coatings with very high physical characteristics.
• the crosslinkable liquid silicone formulations used as a textile coating base can be prepared in concentrated form (for example, for 100 parts by weight of component A, from 0 to 100 parts of component D), then be then diluted at the time of their use with an organic diluent, an organic solvent or water in a proportion of 1 to 30 parts by weight of formulation per 100 parts by weight of solvent, diluent or water.
• the use in accordance with the present invention can be implemented directly on textile articles made from yarns, fibers and / or filaments, comprising at least one textile surface and consisting, for example, of woven, non-woven and / or knitted articles, by operating production processes at any time (for fabrics) and / or renovation and / or maintenance (for clothing) of the textile material.
• textile surface is meant a surface obtained by assembling yarns, fibers and / or filaments by any process such as, for example, gluing, felting, weaving, braiding, flocking, or knitting.
• the yarns, fibers and / or filaments used in the manufacture of these textile articles can be obtained from the transformation of a synthetic thermoplastic matrix consisting of at least one thermoplastic polymer chosen from the group consisting of: polyamides, polyolefins, polyvinylidene chlorides, polyesters, polyurethanes, acrylonitriles, (meth) acrylate-butadiene-styrene copolymers, their copolymers and mixtures.
• the thermoplastic matrix can include additives, such as pigments, delustrants, matifiers, catalysts, heat and / or light stabilizers, anti-bacterial, anti-fungal, and / or anti-mite agents.
• (I can for example be a mattifying agent, for example chosen from titanium dioxide and / or zinc sulfide particles.
• the threads, fibers and / or filaments can also be derived from natural materials such as in particular cotton, linen, wool, according to the transformation methods known to those skilled in the art. Of course, mixtures of synthetic and natural materials can be used.
• conventional techniques are used in the textile industry, in particular by using the so-called "padding" impregnation technique.
• the textile article is treated by a formulation comprising an organic diluent or solvent
• it is desirable then to remove the diluent or solvent for example to subject this article to a heat treatment to remove the diluent or the solvent in the form of vapor.
• the amount of base textile coating deposited on the textile article corresponds to an amount between 0.1 and 10% by weight based on the weight of dry treated textile article.
• the yarns, fibers and / or filaments can also be brought into contact with the textile coating base at any time during the textile material preparation processes.
• thread is meant, for example, a continuous multifilament object, a continuous thread obtained by assembling several threads or a continuous fiber yarn, obtained from a single type of fiber, or a mixture of fibers.
• fiber is meant, for example, a short or long fiber, a fiber intended to be worked in spinning or for the manufacture of nonwoven articles or a cable intended to be cut to form short fibers.
• the process for manufacturing yarns, fibers and / or filaments generally begins with the passing through the die of the thermoplastic matrix, and ends before the textile surface manufacturing step.
• the process for manufacturing threads, fibers and / or filaments notably comprises a spinning step.
• the term “spinning step” means a specific operation consisting in obtaining yarns, fibers and / or filaments.
• the spinning stage begins during the passage of the thermoplastic matrix through one or more dies and ends with the transfer of the threads, fibers and / or filaments obtained on a spool (for the threads or filaments) or in a pot (for the fibers), also called reclining.
• the spinning step can also include steps which are carried out between passing through the die and winding. These steps may for example be steps of sizing, reunification of the filaments (by one or more drive points or convergence guide), drawing, heating of the filaments, relaxation and thermofixation.
• the deposition on the yarns, fibers and / or filaments of the textile coating base according to the present invention can be carried out for example after the convergence of the yarns, fibers and / or filaments and / or during a stretching step. yarns, fibers and / or filaments. Said deposit can also be made between these two stages.
• the textile coating base according to the present invention is deposited on the yarns, fibers and / or filaments during the sizing step.
• a sizing composition comprising at least one textile coating base according to the present invention is deposited on the yarns, fibers and / or filaments.
• treatment step means treatment steps after recovery of the yarns, fibers and / or filaments, such as for example steps of texturing, stretching, stretching-texturing, sizing, relaxation, heat-fixing. , twisting, fixing, crimping, washing and / or dyeing.
• a textile coating base in accordance with the present invention it is possible in particular to deposit on the yarns, fibers and / or filaments, a textile coating base in accordance with the present invention during an operation chosen from the group consisting of: relaxation, twisting, fixing, crimping, stretching and / or the texturing of the yarns, fibers and / or filaments. It is also possible to deposit on the yarns, fibers and / or filaments a sizing composition comprising at least one textile coating base in accordance with present invention, in particular during a treatment step during the recovery of son, fibers and / or filaments. The yarns, fibers and / or filaments can also be placed in a washing and / or dyeing composition comprising at least one textile coating base in accordance with the present invention. According to a third general method of processing, the use in accordance with the present invention can be implemented in two stages:
• a second step by contacting the textile articles made from the treated yarns, fibers and / or filaments by operating at any time the preparation (for fabrics) and / or renovation processes and / or maintenance (for clothing) of the textile material.
• the treatment with the textile coating base can be applied either partially or completely on the one hand on the yarns, fibers and / or filaments and then on the other hand on the textile articles made from the yarns, fibers and / or treated filaments.
• partially is meant in particular an application which consists in treating the yarns, fibers and / or filaments with part of the constituent ingredients of the textile coating base and in providing the complement during the treatment of textile articles made from treated yarns, fibers and / or filaments.
• the attachment promoter system (component B) can be provided during the processing of the yarns, fibers and / or filaments, while the network generator system (component A) and the functional additive (component C) are brought in when articles are processed.
• “completely” is meant an application in which, on the one hand, the yarns, fibers and / or filaments and, on the other hand, the textile articles made from these yarns, fibers and / or filaments are treated , each time, with a textile coating base comprising all of its constituent ingredients, with the possibility that the latter are not necessarily present in the same proportions at the time of the treatment of the yarns, fibers and / or filaments then at the time of the treatment of the articles.
• composition C1 It has the following constitution (the parts are given by weight): A: mixture of: • hydroxylated MDT resin having 0.5% of OH by weight and constituted 62% by weight of CH3SÎO3 / 2 units, 24% by weight of units (CH3) 2 Si ⁇ 2 / 2 e 14% by weight of units (CH3) 3 SiO-j / 2: 47 parts; and of “hydroxylated MQ resin having 2% of OH by weight and consisting of 45% by weight of Si ⁇ 4 / 2 units and 55.% by weight of (CH3) 3 SiO- units
• composition C2 Comparison formulation (composition C2): The performance of composition C1 is compared to that of a conventional composition C2 ("Scotch Guard") which is a commercial product known for its excellent water-repellent properties. It is applied by spray according to the protocol recommended by the supplier.
• Scotch Guard a commercial product known for its excellent water-repellent properties. It is applied by spray according to the protocol recommended by the supplier.
• the treated textile article used is a Polyamide 6.6 knit of the interlock knitting type produced on a double needle circular knitting machine with PA6.6 yarns texture 78 dtex 68 strands and 78 dtex 23 strands.
• the textile article is treated by padding with 5% and 10% (by weight) solutions of composition C1 in heptane. It undergoes drying at room temperature (23 ° C) for 12 hours, then it is optionally heat treated for 3 minutes at
• the measurement of the beading effect is carried out by the standard water repellency test known as the “Spray-Test” (AATC Test Method 22-1996): -
• the test consists in spraying the sample of the textile article with a given volume of water. The appearance of the sample is then assessed visually and compared to the standards. A score of 0 to 100%> is assigned depending on the amount of water retained. For 0, the sample is completely wet, for 100%), the sample is completely dry.
• the samples are also weighed before and after spraying and the amount of water retained by the textile sample is determined by difference. This quantity is then related to the quantity of water initially retained by the unwashed textile sample.
• a GIROWASH testing machine (usually used for washing color stability studies - described in ISO 105 C06) was used.
• This system comprises a mechanical device allowing: the rotation at 40 rpm of a wheel mounted on a horizontal axis and at least half of which is immersed in a bath heated to the desired temperature (in this case 50 ° C); fixing on this wheel closed containers, made of stainless steel, having a capacity of 550 ml each, a diameter of 75 mm and a height of 125 mm, the bottom of the containers being 45 mm from the axis of the shaft.
• EXAMPLE 2 Dural hydrophobia with tincture. It is assumed 'the same composition C1 which is here diluted to 14% (by weight) in heptane.
• the textile used is a Polyamide 6.6 knitting of the pique knitting type produced on a single needle circular knitting machine with a PA6.6 yarn 140 dtex 102 strands vanized one fall out of two.
• a dye resistance test is carried out. The treatment protocol is as follows: impregnation, spinning, drying at room temperature (23 ° C), then heat treatment for 10 minutes at 150 ° C).
• Experimental results • A sample of the textile article treated with composition C1 was dyed in a Mathis Labomat laboratory dyeing machine.
• the bath ratio was 1/50 and the following auxiliary products were used: sodium acetate 0.5 g / l; Sandogene CN 1%; Sandogene NH 1%.
• the Nylosan N5GL Blue dye was used at a dose of 1.2%.
• the temperature rise in the bath was ensured at the speed of 1.5 ° C / min and the maximum temperature reached was 98 ° C.
• the total duration of the dye was 45 minutes. •
• the sample is then subjected to a series of machine wash cycles at 50 ° C for a total of 8 hours. At the end of these, it retains water repellency properties with an 80% rating in the Spray Test.
• EXAMPLE 3 Durable hydrophobia - Resistance to washing in an industrial machine.
• composition C3 It has the following constitution (the parts are given by weight): - A: mixture of: • hydroxylated MDT resin having 0.5%> of OH by weight and consisting of 62% by weight of CH3SÎO3 / 2 units, 24% by weight of units (CH 3 ) 2 Si ⁇ 2 / 2 and 14% by weight of units (CH3) 3 SiO-j / 2: 47 parts; and • hydroxylated MQ resin having 2% of OH by weight and consisting of 45% by weight of Si ⁇ 4 / 2 units and 55.%> by weight of (CH3) 3 SiO-d / 2 units: 7 parts; B: mixture of: • tris (3- (trimethoxysilyl) propyl) isocyanurate: 7 parts • n-propyl zirconate (Pr) of formula Zr (Opr) 4: 20 parts • n-butyl titanate (Bu) of formula Ti (OBu): 2 parts; and
• composition C4 It has the following constitution (the parts are given by weight): A: mixture of: • hydroxylated MDT resin having 0.5% of OH by weight and constituted 62% by weight of CH3SJO3 / 2 units, 24% by weight of units (CH 3 ) 2 Si ⁇ 2 / 2 and 14% by weight of units (CH3) 3 SiO-d / 2: 95 parts; and • hydroxylated MQ resin having 2%> OH by weight and consisting of 45% by weight of S1O4 / 2 units and 55% by weight of ( ⁇ 3) 3 SiO-1/2 units: 14 parts; B: mixture of: • tris (3- (trimethoxysilyl) propyl) isocyanurate: 1 1 parts • n-propyl zirconate (Pr) of formula Zr (Opr) 4 : 41 parts • n-butyl titanate (Bu) of formula Ti (OBu) 4 : 4 parts; and of • e
• composition C5 It has the following constitution (the parts are given by weight): A: mixture of: • hydroxylated MDT resin having 0.5% of OH by weight and constituted 62% by weight of CH3SÎO3 / 2 units, 24% by weight of units (CH3) 2 SÎO2 / 2 and 14% by weight of units (CH3) 3 SiO-
• Crosslinkable liquid silicone formulation according to the invention (composition C6): It has the following constitution (the parts are given by weight): A: hydroxylated MDT resin having 0.8% of OH by weight and consisting of 23% by weight of CH3Si ⁇ 3 / 2 units, 75% by weight of units (CH3) 2 SiO2 / 2 and 2% by weight of units (CH3 ) 3 SiO-
• composition C7 It has the following constitution (the parts are given by weight): A: hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% in weight of units CH3SÎO3 / 2, 24% by weight of units (CH3) 2 Si ⁇ 2 / 2 and 14% by weight of units (CH3) 3 SiO-d / 2: 100 parts B: mixture of: • sorting (3- ( trimethoxysilyl) propyl) isocyanurate: 13 parts; and • n-propyl zirconate (Pr) of formula Zr (Opr): 41 parts C-1: mixture of: • hydroxylated MDT resin having 0.5% OH by weight and consisting of 62%> by weight of CH3Si ⁇ 3 / 2 units, 24% by weight of units (CH3) 2 Si ⁇ 2 / 2 and 14% by weight of units ( ⁇ 3) 3 SiO-j / 2: 41 parts; and • linear hydroxylated silicone
• composition C8 Comparison formulation (composition C8): The performance of compositions C3 to C7 are compared with those of a conventional composition C8 (treatments known and marketed under the brands "Scotch Guard” or “Teflon”) known for its excellent water-repellent properties. It is applied by a solvent route according to the protocol recommended by the supplier.
• the treated textile article used is a bi-stretch fabric based on Polyamide 6.6 (80% by weight) and elastane (20%). This textile surface is woven in warp and weft from spun 44 dtex 1-strand elastane yarn and from polyamide 6.6 44 dtex 34 strands. The elasticity of the textile surface obtained is 100% in each direction and the surface weight is of the order of 130 g / m 2 .
• the textile article is treated by padding with compositions C3 to C8. It is subjected to a heat treatment at 150 ° C for 2 minutes, then it is stored at room temperature for 8 hours before testing.
• composition A It has the following constitution (the percentages are given by weight of the total composition): A: mixture of: • 1.63% of hydroxylated MDT resin having 0.8%) of OH by weight and consisting of 23% by weight of CH3Si ⁇ 3 / 2 units, 75% by weight of (CH3) SiO2 / 2 units and 2%> by weight of (CH3) 3 SiO ⁇ / 2 units “4.66% of hydroxylated MDT resin having 0.5%> of OH by weight and consisting of 62% by weight of CH3Si ⁇ 3 / 2 units, 24% by weight of (CH3) 2 Si ⁇ 2 / 2 units and 14% by weight of units ( ⁇ 3) 3 SiO-1/2 • 0.57% of hydroxylated MQ resin having 2% OH by weight and consisting of 45% by weight of Si ⁇ 4 / 2 units and 55% by weight of units ( ⁇ 3) 3 SiO-1/2 - B: mixture of: • 0.16%
• composition B Crosslinkable liquid silicone formulation according to the invention (composition B): It has the following constitution (the percentages are given by weight of the total composition): A: mixture of: • 4.56% of hydroxylated MDT resin having 0, 8% OH by weight and consisting of 23% by weight of CH3SÎO3 / 2 units, 75% by weight of units (CH3) 2 Si ⁇ 2 / 2 and 2% by weight of units ( ⁇ 3) 3 SiO-1/2 2.70% of hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH3SÎO3 / 2 units, 24% by weight of (CH3) 2 Si ⁇ 2 / 2 units and 14% by weight of patterns ( ⁇ 3) 3 SiO-
• composition C It has the following constitution (the percentages are given by weight of the total composition): A: mixture of: • 4.0% of hydroxylated MDT resin having 0, 8% of OH by weight and consisting of 23% by weight of CH3SÎO3 / 2 units, 75% by weight of units (CH3) 2 SiO2 / 2 and 2% by weight of units (CH3) 3 SiO ⁇ 2 "2.24 % of hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH3SÎO3 / 2 units, 24%> by weight of units (CH3) 2 Si ⁇ 2 / 2 and 14% by weight of units ( CH3) 3 SiO-
• composition D Comparative formulation (composition D): The performances of compositions A, B and C in accordance with the invention are compared with those of a conventional composition D ("Scotch Guard") which is a commercial product known for its excellent water-repellent properties. It is a fluorinated acrylate in butyl acetate.
• Comparative sample (sample E) The performances of compositions A, B and C in accordance with the invention are also compared with those of a commercial textile known for its excellent breathability and impermeability properties.
• This textile is sold under the name EPIC by the company NEXTEC, and consists of polyamide 6.6 and elastane, having an elasticity of the order of 50% in the weft direction. Its specific weight is around 160 g / m2.
• This elastic fabric has been treated with a silicone composition as described for example in US-A-5,876,792.
• the textile is a textile woven from Polyamide 6.6 and elastane (80/20). It is made of elastic warp and weft threads based on a 44 dTex elastane wrapped by a piece of PA 6.6 44 dTex / 34 strands. These textile surfaces have a significant bidirectional elasticity (100% elongation in both directions) and a specific weight of 130 g / m2.
• the textile is treated by padding with the compositions. It undergoes drying at room temperature for a few minutes and then is heated for 2 min at 180 ° C.
• Washing protocol To test the durability of the treatment, an industrial washing machine (Wascator - Electrolux) is used. The imposed cycle is as follows: washing in drinking water at 50 ° C continuously for 8 hours. Such treatment is assumed to be representative of the life of the textile in real situations (in a washing cycle in a domestic machine, the washing time is often only 15 min maximum and the level of friction induced is considerably lower than for industrial washing machine).
• EXAMPLE 5 Quick drying - Resistance to washing in a domestic machine 1 / Crosslinkable liquid silicone formulation according to the invention (composition F): It has the following constitution (the parts are given by weight): A: mixture of: • hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH3Si ⁇ 3 / 2 units , 24% by weight of units (CH3) Si ⁇ 2 / 2 and 14% by weight of units ( ⁇ 3) 3 SiO ⁇ / 2: 47 games; and • hydroxylated MQ resin having 2% of OH by weight and consisting of 45% by weight of Si ⁇ 4 / 2 units and 55.% by weight of units ( ⁇ 3) 3 SiO-d / 2: 7 parts; - B: mixture of: • tris (3- (trimethoxysilyl) propyl) isocyanurate: 7 parts • n-propyl zirconate (Pr) of formula Zr (Opr): 20 parts • n-butyl
• the treated textile articles used are: - a bi-stretch fabric based on Polyamide 6.6 (80% or by weight) and elastane (20%). This textile surface is woven in warp and weft from spun 44 dtex 1-strand elastane yarn and from polyamide 6.6 44 dtex 34 strands. The elasticity of the textile surface obtained is 100% in each direction and the surface weight 2 is of the order of 130 g / m. - a knit made from Polyamide 6.6 (100% by weight). It is obtained by interlock knitting made on a double needle circular knitting machine with PA6.6 yarns 78 dtex textures 68 strands.
• the coupons are placed in a 250 ml bottle containing 125 ml of distilled water, which is mounted on the beater. This is then programmed for a threshing time of 1 hour at a frequency of 5.5 / 10, thus making it possible to simulate dynamic conditions (pressure variations, etc.) for wetting a textile.
• the moisture uptake is measured by weighing the coupon before and after dynamic humidification, and the values obtained expressed as a percentage by weight relative to the weight of the dry coupon.
• the measurement and monitoring of drying are carried out on an instrumented Mettler balance (automatic weight acquisition every minute) on which the 8 cm circular coupon of fabric is placed (only one side of the sample being presented to the air ambient thus simulating wearing conditions).
• This balance is placed in a conditioned room where a temperature of 23 ° C and a relative humidity of 50% prevails.
• a low level of moisture uptake is essential for improved comfort because, in humidification conditions much milder than that practiced here obviously, the "freezing effect" well known to mountain sports practitioners will be all the more intense. that the amount of water absorbed by the fabric will be high.
• the 2 textile surfaces fabric and knitted fabric
• This drying rate remains higher in the case of samples which have been washed for 8 hours at 50 ° C.
• Dry cleaning tests The performances of Spray-Test (standard AATC 22-1996) were followed over the course of repeated cycles of dry cleaning. The same characteristics have been determined. The tests were carried out in an industrial pressing using a B ⁇ WE P 250 machine running on perchlorethylene. The textile surface subjected to this test is a bistretch fabric of 120 g / m2 having approximately 60%> elongation in warp and weft.

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