FR2851265A1 - Use of a silicon formulation as a textile coating base, which comprises a silicone resin, metallic alkoxide and functional additive capable of reacting with one of these constituents - Google Patents

Abstract

Use of a liquid cross-linkable silicone formulation as a coating agent for the surface treatment of a wide range of textile materials to impart properties such as softness, hydrophilicity, hydrophobicity and oleophobicity. Use of a liquid cross-linkable silicone formulation as a coating base for textile materials which enables (a) cross-linking around the fibers and/or filaments of the material, ensuring a protective covering regardless of the nature of the material and with little or no anchorage points; (b) ensuring, by forming a cross-linked silicon sheath, a lasting protection of the textile and conferring resistance to aggressive media; (c) by imparting supplementary functionalities, enabling fabrication of clothing with properties such as softness, hydrophobicity, oleophobicity and anti-static properties; and (d) allowing deposition of the formulation and cross-linking at any point in the preparation and/or renovation and/or maintenance of the natural or synthetic material.

Description

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USE OF A SILICONE FORMULATION AS A COATING BASE
TEXTILE COMPRISING A SILICONE RESIN, A METAL ALKOXIDE AND
A FUNCTIONAL ADDITIVE CAPABLE OF REACTING WITH AT LEAST ONE OF
PREVIOUS CONSTITUENTS
The field of the present invention is that of crosslinkable liquid silicone formulations that can be used to form a coating that can provide long-lasting functionalities to a large number of textile materials.

 Many treatments are applied to textile materials, they bring them additional functionalities such as in particular: softness, hydrophilicity, hydrophobicity, oleophobia. These treatments often consist in depositing on the textile surface polymers mainly of the silicone type. For softness, they are long polydimethylsiloxane oils (or even polyorganosiloxane gums). For hydrophilicity, these are silicone oils with amino groups or polyethers. Organosilicon or purely organic fluorinated compounds are incorporated when it is desired to provide oleophobia.

 For some applications, such as water repellency of clothing, one of the characteristics sought is the permanence of the treatment. It is observed in practice that the many current formulations do not achieve satisfactory durabilities.

 Bringing a sustainable function to a textile material is a technical difficulty. It is known (see DE-A-2,822,393) that, in order to improve the anchoring, it is desirable to carry out covalent chemical bonds between the support and the compound which is to be deposited on the textile surface. Nevertheless, given the nature and diversity of polymers used to make textile materials, this option is not always possible and, when it is, it remains specific to a certain type of textile support material.

 One of the essential objectives of the present invention is to provide a treatment that makes it possible to provide sustainable functionalities to a large number of textile materials.

 Another essential objective of the present invention is to provide a treatment for fixing a functional siloxane network on the surface of the textile material.

 These objectives, among others, are achieved by the present invention which relates to the use of at least one crosslinkable liquid silicone formulation as a base for coating textile material: to allow, by cross-linking around the yarns, fibers and / or constituent filaments of the textile material, to ensure a broad protective covering of the textile material,

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 protection little dependent on the nature of said material because it requires little or no anchor points; to allow, by making a chemically crosslinking silicone sheath, to ensure a durable protection of the textile material by conferring on it an excellent resistance against the aggressions encountered during use; by the term "durable protection", it is intended to define a protection on the one hand with respect to the constraints imposed by textile processes such as, in particular, thermal heat-setting treatments, dyeing treatments, and on the other hand, aggression during the lifetime of the textile material (for example a garment), such as in particular wear abrasion, washes in an aqueous detergent medium, dry cleaning in a solvent medium; to allow, by providing additional specific functional features, to form coatings with useful properties such as, in particular, softness, hydrophobicity, oleophobicity, hydrophilicity, an antistatic effect; and to allow, due to the special nature of the constituents of the formulation, to perform the operations of depositing the liquid formulation and its crosslinking at any point in the development and / or renovation processes and / or maintenance of the textile material.

 As used herein, textile material refers to: yarns, fibers and / or filaments of synthetic and / or natural materials which are used in the manufacture of textile articles; and on the other hand the textile articles themselves comprising at least one textile surface and consisting for example of woven, non-woven and / or knitted articles; by extension, the term "textile material" also refers to materials whose basic texture is in fibrillar form, such as in particular paper and leather.

 Thus, thanks to the use of this formulation, a functional siloxane network is permanently attached to the textile surface and the treatment thus obtained makes it possible to obtain successfully the various advantageous properties mentioned above. We have also observed that in some cases the treatment thus produced not only does not prevent the subsequent dyeing of the textile material, but may also create an effect of improving the color fastness to washes.

According to a preferred feature of the invention, the crosslinkable liquid silicone formulation used as a textile material coating base: # is that comprising:
A - a film-forming silicone network generating system comprising at least one polyorganosiloxane resin (POS) having, per molecule, on the one hand at least two

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different siloxyl units selected from those of types M, D, T, Q, one of the units being a T unit or a Q unit and on the other hand at least three hydrolyzable / condensable groups of OH and / or OR 'types, where R1 is a linear or branched C1-C6, preferably C1-C3, alkyl radical;
B - a promoter system for fastening said network on the surface of the textile material consisting of: # B-1 is at least one metal alkoxide of general formula:
M [(OCH 2 CH 2) a OR 2] (I) wherein: M is a metal selected from the group consisting of: Ti, Zr, Ge, Si, Mn and Al; n = valence of M; the substituents R2, which may be identical or different, each represent a linear or branched C1-C12 alkyl radical; - a represents zero, 1 or 2; with the conditions according to which, when the symbol a represents zero, the alkyl radical R 2 has from 2 to 12 carbon atoms, and when the symbol a represents 1 or 2, the alkyl radical R 2 has 1 to 4 carbon atoms; B-2 is at least one metal polyalkoxide resulting from the partial hydrolysis of the monomeric alkoxides of the above-mentioned formula (1) in which the symbol R2 has the abovementioned meaning with the symbol a representing zero; # be an association of B-1 and B-2; # is B-3 a combination of B-1 and / or B-2 with: - B-3/1 at least one optionally alkoxylated organosilane containing, per molecule, at least one C2-C6 alkenyl group, and / or B-3/2 at least one organosilicon compound comprising at least one epoxy, amino, ureido, isocyanato and / or isocyanurate radical;
C - a functional additive consisting in: # is C-1 at least one silane and / or at least one substantially linear POS and / or at least one POS resin, each of these organosilicon compounds being equipped, per molecule, on the one hand of function (s) (FA) capable of reacting with A and / or B or capable of generating functions in situ capable of reacting with A and / or B and secondly of function (s) (FU) which can be identical or different from FA;

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# is C-2 at least one hydrocarbon compound comprising at least one linear or branched hydrocarbon group, saturated or unsaturated, and optionally one or more heteroatom (s) other than Si (such as for example an oxygen, fluorine or nitrogen) and which is in the form of a monomeric, oligomeric (linear, cyclic or branched) or polymeric (linear, cyclic or branched) structure, said hydrocarbon compound being equipped, on a molecule basis, with a functional part ( s) (FA) capable of reacting with A and / or B or capable of generating in situ functions able to react with A and / or B and secondly function (s) (FU) which can be identical or different from FA; # be a mixture of C-1 and C-2;
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 implementation 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 it is needed, in particular according to the applications in which the textile materials treated according to the invention are used; # with the condition that one engages (parts are given by weight): - for 100 parts of component A, - from 0.5 to 200, preferably from 0.5 to 100 and more particularly from 1 to 70 parts of component B, 1 to 1,000, preferably 1 to 300 parts of component C according to the desired FU, 0 to 10,000, preferably 0 to 5,000 parts of component D and 0 to 100 parts of constituent E.

ceux de formule (R)gSiO (motif M), (R3),SiO (motif D), R3Si01.5 (motif T) et Si02 (motif Q), l'un au moins de ces motifs étant un motif T ou Q. Les radicaux R3sont répartis de telle sorte que les résines comportent environ 0,8 à 1,8 radicaux R3 par atome de The constituents 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 cohydrolysis and co-condensation of chlorosilanes selected from the group consisting of those of formulas (R3) 3SiCl, (R3) 2Si (Cl) 2, R3Si (Cl) 3, Si (Cl) 4 . These resins are branched organopolysiloxane oligomers or polymers well known and commercially available. They have, in their structure, at least two different siloxyl units chosen from

those of formula (R) gSiO (unit M), (R3), SiO (unit D), R3Si01.5 (unit T) and SiO2 (unit Q), at least one of these units being a T or Q unit The radicals R 3 are distributed such that the resins comprise approximately 0.8 to 1.8 R 3 radicals per atom of

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silicon. In addition these resins are not completely condensed and they still have about 0.001 to 1.5 OH and / or alkoxyl OR 'groups per silicon atom;
The radicals R3 are identical or different and are chosen from linear or branched C1-C6 alkyl radicals, C2-C4 alkenyl radicals, phenyl, 3,3,3-trifluoropropyl radicals. Mention may be made, for example, as R 3 alkyl radicals, the methyl, ethyl, isopropyl, tert-butyl and n-hexyl radicals;
Examples of oligomers or branched organopolysiloxane polymers include MQ resins, MDQ resins, TD resins and MDT resins, the OH and / or OR 'groups being able to be borne by the M, D and / or T units. the weight content of OH and / or OR 'groups being between 0.2 and 10% by weight;
A-2: at least one mixed resin prepared by cocondensation of organosilicon resins A-1 mentioned above with conventional organic polymers such as: polyester resins and alkyds modified or not modified with fatty acids such as oleic acid, linoleic acid, ricinoleic acid or esters of fatty acids and aliphatic polyols such as castor oil, tallow; epoxy resins modified or not with fatty acids; phenolic, acrylic, melamine-formaldehyde resins; polyamides; polyimides; polyamide imides; polyureas; polyurethanes; polyethers; polycarbonates; polyphenols.

(R3)2Si0 (motif D) et R3Si0,5 (motif T) et Si02 (motif Q), l'un au moins de ces motifs étant un motif Q, les groupes OH et/ou OR' pouvant être portées par les motifs M, D et/ou T et la teneur pondérale en groupes OH et/ou OR' étant comprise entre 0,2 et 10 % en poids. As concrete examples of components A which are preferred, mention may be made of mixtures A-3: of at least one resin of type A-1 (resin A-1/1) having, in its structure, at least two siloxyl units different from those of formula (R3) 3 SiO0.5 (unit M), (R3) 2SiO (unit D) and R3SiO1,5 (unit T), at least one of these units being a unit T, the OH groups and / or OR 'may be carried by the units M, D and / or T and the weight content of OH and / or OR' groups being between 0.2 and 10% by weight, and - at least one other type A-1 resin (resin A-1/2) having, in its structure, at least two different siloxyl units chosen from those of formula (R 3) 3 SiO 0.5 (M-unit),

(R3) 2SiO (unit D) and R3Si0.5 (unit T) and SiO2 (unit Q), at least one of these units being a unit Q, the groups OH and / or OR 'being able to be carried by the units M, D and / or T and the weight content of OH and / or OR 'groups being between 0.2 and 10% by weight.

 As concrete examples of constituents A which are suitable, mention may be made of mixtures A-3: of at least one hydroxylated MDT resin having a weight content of OH group of between 0.2 and 10% by weight, and at least a hydroxylated MQ resin having a weight content of OH group of between 0.2 and 10% by weight.

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 In mixtures A-3, the respective proportions of the constituents are not critical and may vary over wide areas. These mixtures contain, for example, 60 to 90% by weight of resin (s) A-1/1 and 40 to 10% by weight of resin (s) A-1/2.

 With regard to the constituents B-1, there may be mentioned, as examples of symbols R2 in the organic derivatives of the metal M of formula (1), the radicals: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, hexyl , 2-ethylhexyl, octyl, decyl and dodecyl.

titanate de décyle, le titanate de dodécyle, le titanate de (3-méthoxyéthyle, le titanate de [3 -éthoxyéthyle, le titanate de (3-propoxyéthyle, le titanate de formule Ti[(OCH2CH2)2 OCH3]4 ; les zirconates d'alkyles comme le zirconate de propyle, le zirconate de butyle ; les silicates d'alkyles comme le silicate de méthyle, le silicate d'éthyle, le silicate d'isopropyle, le silicate de n-propyle ; et des mélanges de ces produits. As concrete examples of preferred B-1 components, mention may be made of: alkyl titanates such as ethyl titanate, propyl titanate, isopropyl titanate, butyl titanate, ethyl titanate and the like. 2 hexyl, octyl titanate,

decyl titanate, dodecyl titanate, (3-methoxyethyl) titanate, [3-ethoxyethyl titanate, (3-propoxyethyl) titanate, titanate of formula Ti [(OCH 2 CH 2) 2 OCH 3] 4, zirconates of alkyls such as propyl zirconate, butyl zirconate, alkyl silicates such as methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate and mixtures of these products.

 As concrete examples of preferred polyalkoxides B-2 from the partial hydrolysis of titanates, zirconates and silicate monomers can be mentioned: polytitanates B-2 from the partial hydrolysis of isopropyl titanates, butyl or 2-ethylhexyl; polyzirconates B-2 from the partial hydrolysis of propyl and butyl zirconates; polysilicates B-2 resulting from the partial hydrolysis of ethyl and isopropyl silicates; and mixtures of these products.

dans laquelle : - R4, R5, R6 sont des radicaux hydrogénés ou hydrocarbonés identiques ou différents entre eux et représentent, de préférence, l'hydrogène, un alkyle linéaire ou ramifié en C1-C4 ou un phényle éventuellement substitué par au moins un alkyle en C1-C3, As concrete examples of constituents B-3/1 which are preferred, mention may be made of the optionally alkoxylated organosilanes chosen from the products of the following general formula:

in which: R4, R5, R6 are hydrogenated or hydrocarbon radicals that are identical to or different from each other and preferably represent hydrogen, a linear or branched C1-C4 alkyl or a phenyl optionally substituted by at least one alkyl group; C1-C3,

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- U is a linear or branched C1-C4 alkylene, or a divalent group of formula -CO-O-alkylene- where the alkylene residue has the definition given supra and the free valence of right (in bold) is connected to the Si via W, - W is a valence bond, - R7 and R8 are identical or different radicals and represent a C1-C6 alkyl;
C4 linear or branched, - x '= 0 or 1, - x = 0 to 2, preferably 0 or 1 and more preferably still 0.

 Without being limiting, it may be considered that vinyltrimethoxysilane or γ- (meth) acryloxypropyltrimethoxysilane is a particularly suitable compound B-3/1.

dans laquelle : + R9 est un radical alkyle linéaire ou ramifié en C1- C4, + R10 est un radical alkyle linéaire ou ramifié, + y est égal à 0, 1, 2 ou 3, de préférence à 0 ou 1 et, plus préférentiellement encore à 0, + où X a la signification :

avec : + E et D qui sont des radicaux identiques ou différents choisis parmi les alkyles en C1-C4 linéaires ou ramifiés, + z qui est égal à 0 ou 1, As concrete examples of preferred B-3/2 components, tris [(trialkoxysilyl) alkyl] isocyanurates where the alkyl groups have 1 to 4 carbon atoms and the selected organosilicon compounds: -3 / 2-a corresponding to the following general formula:

in which: + R9 is a linear or branched C1-C4 alkyl radical, + R10 is a linear or branched alkyl radical, + y is equal to 0, 1, 2 or 3, preferably 0 or 1 and, more preferably still at 0, + where X has the meaning:

with: + E and D which are identical or different radicals chosen from linear or branched C1-C4 alkyls, + z which is equal to 0 or 1,

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dans laquelle : + X est le radical tel que défini ci-dessus pour la formule (B-3/2-a), + G est un groupe hydrocarboné monovalent, exempt d'action défavorable sur l'activité du catalyseur et choisi, de préférence, parmi les groupes alkyles ayant de 1 à 8 atomes de carbone inclus, éventuellement substitués par au moins un atome d'halogène, avantageusement, parmi les groupes méthyle, éthyle, propyle et 3,3,3-trifluoropropyle et ainsi que parmi les groupes aryles et, avantageusement, parmi les radicaux xylyle et tolyle et phényle,

et (2i) éventuellement au moins un motif siloxyle de formule :

dans laquelle G a la même signification que ci-dessus et r a une valeur comprise entre 0 et 3, par exemple entre 1 et 3. + R11, R12, R'3 which are identical or different radicals representing hydrogen or a linear or branched C1-C4 alkyl, hydrogen being more particularly preferred, + R "and R12 or R13 may alternatively constitute together and with the two epoxy-bearing carbons, an alkyl ring having from 5 to 7 members, or from the B-3/2-b products consisting of epoxyfunctional polydiorganosiloxanes comprising: (i) at least one siloxyl unit of formula:

in which: + X is the radical as defined above for the formula (B-3/2-a), + G is a monovalent hydrocarbon group, which has no adverse effect on the activity of the catalyst and is chosen from preferably, from alkyl groups having from 1 to 8 carbon atoms inclusive, optionally substituted with at least one halogen atom, advantageously from methyl, ethyl, propyl and 3,3,3-trifluoropropyl groups, and also from aryl groups and, advantageously, among the radicals xylyl and tolyl and phenyl,

and (2i) optionally at least one siloxyl unit of formula:

in which G has the same meaning as above and r a value between 0 and 3, for example between 1 and 3.

 Compounds B-3/2 are preferably tris [3- (trimethoxysilyl) propyl] isocyanurates and epoxyalkoxymonosilanes B-3/2-a.

 By way of example of such compounds B-3/2-a, mention may be made of: + 3-glycidoxypropyltrimethoxysilane (GLYMO) + 3,4-epoxycyclohexylethyltrimethoxysilane.

 For the embodiment of the invention, the following titanates, zirconates and silicates B-1 are used more preferably, taken alone or as a mixture with one another: ethyl titanate, propyl titanate, isopropyl titanate, butyl titanate (n-butyl), propyl zirconate, butyl zirconate, ethyl silicate, propyl silicate and isopropyl silicate.

 When using 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%.

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B-1 1, de préférence compris entre 5 et 25, B-3/1 bzz 10, de préférence compris entre 15 et 70, B-3/2 < 90, de préférence compris entre 70 et 15 , étant entendu que la somme de ces proportions en B-1, B-3/1, B-3/2 est égale à 100 %. Quantitatively, when B-1 + B-3/1 + B-3/2 is used, it may be stated that 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 bzz 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%.

 As regards the constituents B-1, they may consist of a metal alkoxide where the metal M may be partially connected to one or more ligands such as for example those derived in particular from (3-diketones, (3-keto esters and malonic esters (such as acetylacetone) or triethanolamine.

 The constituents C-1 that can be used, separately or as a mixture, are silanes, essentially linear POSs and POS resins bearing in their molecules, attached to silicon atoms, the two functionalities FA and FU.

-R14~NR15R16 ou -R14~NH-R17~NR15R16 dans laquelle: + R14 et R17 = reste hydrocarboné divalent comme par exemple -(CH2)e- avec e = 1 à 10, + R15 = H ou -C@H2@+1 + R16 a la même définition que R15 et peut être identique ou différent de R15, le groupe amino pouvant ainsi être primaire, secondaire ou tertiaire ; selon des variantes, le groupe amino peut être inclus dans un cycle ou être inclus dans des groupements isocyanurates ou HALS (Hindered Amine Light Stabiliser, comme par exemple un groupement du type pipéridine ou autre) ; ' en pratique le groupe aminoalkyle peut consister dans les espèces suivantes : + aminopropyle(H2N)(CH2)3- + N-méthyl-3-aminopropyle (H3CNH)(CH2)3- + N-aminoéthyl-3-aminopropyle (H2N)(CH2)2NH(CH2)3- The FA functions are more precisely condensable / hydrolysable functions corresponding to OH and / or OR 'or functions capable of generating in situ OH and / or OR' functions. With regard to the FU functions, those which are more specifically referred to in the present invention, in the case of the constituents C-1, are the following: # to provide the properties of softness and / or hydrophobicity, mention may be made of: siloxane linkages comprising M, D and / or T units as defined above with respect to the constituents A-1, the aminoalkyl, non-salified group, for example of the general formula:

-R14 ~ NR15R16 or -R14 ~ NH-R17 ~ NR15R16 wherein: + R14 and R17 = divalent hydrocarbon residue such as - (CH2) e- with e = 1 to 10, + R15 = H or -C @ H2 @ +1 + R16 has the same definition as R15 and may be the same as or different from R15, the amino group may thus be primary, secondary or tertiary; according to variants, the amino group may be included in a ring or may be included in isocyanurate groups or HALS (Hindered Amine Light Stabilizer, such as, for example, a piperidine or other group); in practice, the aminoalkyl group may consist of the following species: + aminopropyl (H2N) (CH2) 3- + N-methyl-3-aminopropyl (H3CNH) (CH2) 3 + N-aminoethyl-3-aminopropyl (H2N) (CH2) 2NH (CH2) 3-

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dans laquelle : + Z représente une rotule divalente ou trivalente de nature hydrocarbonnée qui peut être un reste cyclique ou non, aliphatique saturé ou insaturé, aromatique, mixte aliphatique/aromatique, pouvant renfermer un ou plusieurs hétérotomes oxygénés contenant de 1 à 30 atomes de carbone, + k est 1 ou 2, + RFreprésente le groupe -CsF2s-CF3 avec s égal à ou différent de zéro ou le groupe CsF2sH avec s égal à ou supérieur à 1 ; # pour apporter les propriétés d'hydrophilie et/ou d'effet antistatique,on peut citer : ' les groupes polyéthers par exemple de formules générales :

+ avec v et w différents de 0 et notamment compris entre 5 et 30. + CgH5CH2NH (CH2) 2 (NH) (CH2) 3- + 3-ureidopropyl: (H2NCO NH) (CH2) 3- + 3,4,5-dihydroimidazol-1-yl-propyl; # to provide the properties of oleophobia, there may be mentioned: the fluorinated groups for example of general formula:

in which: + Z represents a divalent or trivalent hydrocarbon-type rocket, which may be a cyclic or non-cyclic aliphatic or saturated or unsaturated, aromatic, mixed aliphatic / aromatic radical, which may contain one or more oxygenated heterotomes containing from 1 to 30 carbon atoms; , + k is 1 or 2, + RFrepresents the group -CsF2s-CF3 with s equal to or different from zero or the group CsF2sH with s equal to or greater than 1; # to provide the hydrophilic and / or antistatic properties, mention may be made of: polyether groups, for example of general formulas:

+ with v and w different from 0 and in particular between 5 and 30.

dans laquelle : + les substituant R1 et R2 et le symbole a sont tels que définis supra à propos de la description des constituants A et B ; +best1,2ou3; # les diorganopolysiloxane essentiellement linéaire comprenant un groupement hydroxyle à chaque extrémité de chaîne, de formule :

As concrete examples of constituents C-1 which are preferred, mention may be made of the organosilicon compounds listed below: # polyalkoxysilanes of formula:

wherein: + the substituents R1 and R2 and the symbol a are as defined above with respect to the description of components A and B; + Best1,2ou3; the essentially linear diorganopolysiloxane comprising a hydroxyl group at each chain end, of formula:

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CH2=CH-CH2-[OCH2CH2Jv-[OCH2CH(CH3)Jw-OH sur une huile POS de formule :
Me3SiO(Me2SiO)x'(MeHSiO)y'SiMe3, + avec Me = méthyle ; + avec v et w différents de 0 et notamment compris entre 5 et 30 ; + avec x' allant de 20 à 150 ; avec y' allant de 2 à 10 ; + le copolymère pouvant être additionné d'un additif tel qu'un polyéther libre, par exemple en proportion allant de 40/60 à 60/40 ; les résines POS hydroxylées comprenant dans leur structure des motifs siloxyles T et éventuellement M et/ou éventuellement D tels que définis supra à propos des résines A-1 ; les résines POS hydroxylées obtenues notamment : # par hydrolyse d'un alkoxysilane S substitué par des FU ; il peut s'agir, par exemple, d'un trialkoxysilane FU-substitué permettant d'obtenir une résine hydroxylée à motifs T, dénommée également résine T (OH) ; # par homocondensation des silanes S hydrolysés ; # et par stripping entraînement à la vapeur des hydrolysats dérivant des FU ; # des mélanges des composés organosiliciques précités. in which: + substituents R 18, which may be identical or different, each represent a saturated or unsubstituted, aliphatic, cyclanic or aromatic monovalent hydrocarbon radical C1 to C13; + ja a value sufficient to give the diorganopolysiloxanes of formula (III) a dynamic viscosity at 25 C ranging from 1.000 to 10.000.000 mPa.s; it should be understood that, in the context of the present invention, it is possible to use as hydroxylated POS of formula (III) a mixture consisting of several hydroxylated polymers which differ from each other by the value of the viscosity and / or the nature of the substituents related to silicon atoms; it should be understood further that the POS of formula (III) may optionally comprise R units T of formula R18Si03 / 2 and / or SiO 2 units in the proportion of at most 1% (these% expressing the number of T units and / or or Q per 100 silicon atoms); POS-polyether copolymers resulting especially from the reaction of a polyether of formula:

CH2 = CH-CH2- [OCH2CH2] - [OCH2CH (CH3) Jw-OH on a POS oil of formula:
Me3SiO (Me2SiO) x '(MeHSiO) y'SiMe3 + with Me = methyl; + with v and w different from 0 and in particular between 5 and 30; + with x 'ranging from 20 to 150; with y 'ranging from 2 to 10; + the copolymer can be added an additive such as a free polyether, for example in a proportion ranging from 40/60 to 60/40; hydroxylated POS resins comprising in their structure siloxyl units T and optionally M and / or optionally D as defined above with regard to resins A-1; hydroxylated POS resins obtained in particular: # by hydrolysis of an alkoxysilane S substituted with FU; it may be, for example, a FU-substituted trialkoxysilane making it possible to obtain a hydroxylated resin with T units, also called T (OH) resin; by homocondensation of the hydrolysed silanes S; # and steam stripping stripping hydrolysates derived from FU; # mixtures of the aforementioned organosilicon compounds.

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The functions FU substituting S correspond to the same definitions as those given above. As an advantageous illustration of this embodiment of a component C-1 of POS resin type, there may be mentioned that obtained from yaminopropyltriethoxysilane hydrolysed and subjected to stripping of the ethanol formed by the hydrolysis. The polyhomocondensed resin obtained is a mixture of oligomers containing from 4 to 10 silicon and comprising units:
T (OH) = RSi (OH) 02/2
T = R Si03 / 2
T (OH) 2 = RSi (OH) 201/2
T (OH) 3 = RSi (OH) 3, these units being respectively present in decreasing quantity and R = NH 2 - (CH 2) 3This is then a resin T (OH) As concrete examples of constituents C-1 which Hydroxylated MDT resins having an OH group weight content of between 0.2 and 10% by weight, taken alone or as a mixture with hydroxylated silicone oils of formula (III), may be mentioned.

 With regard to the proportions of use of constituents C-1, they are, as explained above, in the range from 1 to 1000 parts by weight of component C-1 according to the desired FU, per 100 parts by weight. constituent weight A. For example, in the case where the FU brings the hydrophobicity, then generally from 2 to 30 parts by weight of component C-1 are used.

 As is apparent from the definitions given above, in the case where component A is a POS resin equipped with pattern (s) and optionally M and / or optionally D, it should be understood that this resin can then also play the role of functional additive C-1 water repellency, provided to be engaged in sufficient proportions equal to the sum of the proportions corresponding to the set A + C-1.

 The constituents C-2 that can be used, separately or as a mixture, are hydrocarbon compounds carrying in their molecule, attached to carbon atoms, the two functional groups FA and FU.

 The FA functions are more precisely condensable / hydrolysable functions corresponding to OH and / or OR 'or functions capable of generating in situ OH and / or OR' functions. As regards the FU functions, those more specifically referred to in the present invention, in the case of the constituents C-2, are those providing properties of oleophobicity, hydrophilicity and / or antistatic effect.

 As concrete examples of constituents C-2 which are preferred, mention may be made of the hydrocarbon compounds listed below:

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R20 -[OCH2CH2]v-[OCH2CH(CH3)]w-OH (V) où R20 représente un radical alkyle, linéaire ou ramifié, ayant de 1 à 4 atomes de carbone et les symboles v et w sont tels que définis supra. # (for the properties of oleophobia) fluorinated alcohols, preferably perfluorinated with formula:
R19-OH (IV) wherein R19 represents an aliphatic radical, linear or branched, having 2 to 20 carbon atoms, said carbon atoms being substituted by at least one fluorine atom and optionally by at least one or hydrogen atom ; # (for hydrophilic and / or antistatic properties) unblocked polyethers of formula:

Wherein R20 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms and the symbols v and w are as defined above.

 As concrete examples of constituents C-2 which are suitable, may be mentioned perfluorinated alcohols of formula RF- (CH2) m-OH where RFest as defined above and m is a number ranging from 0 to 10.

 With regard to the proportions of use of constituents C-2, they are, as explained above, in the range from 1 to 1000 parts by weight of component C-2 according to the desired FU, per 100 parts by weight. constituent weight A.

As concrete examples of optional D components which are preferred, mention may be made, in addition to water, of the compounds listed below: conventional organic solvents, which may play the role for some of the diluents chosen from the group consisting of: aliphatic solvents having 5 to 20 carbon atoms such as hexane, heptane, white spirit, octane, dodecane, and cycloaliphatic such as cyclohexane, methylcyclohexane, decalin; + chlorinated solvents such as trichlorethylene, trichloroethane, perchlorethylene, perchloroethane, dichloromethane; + aromatic solvents such as toluene, xylene; + alkanols such as ethanol, isopropanol, butanol, octanol; + aliphatic ketones such as acetone, methyl ethyl ketone, methyl butyl ketone and cycloaliphatics such as cyclopentanone, cyclohexanone; + esters of non-fatty carboxylic acids and alkanols such as ethyl acetate, butyl acetate, pentyl acetate; + esters derived from saturated C10 to C16, preferably C12 to
C14 and alkanols such as myristates (C14), laurates (C12) and mixtures;

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+ les éthers-oxydes tels que l'éther dibutylique, l'éther diisopropylique, le monoéther méthylique ou éthylique de l'éthylèneglycol, le monoéther éthylique ou butylique du diéthylèneglycol.

+ ether oxides such as dibutyl ether, diisopropyl ether, ethylene glycol methyl or ethyl monoether, diethylene glycol ethyl or butyl monoether.

dans laquelle : + les substituants R21,identiques ou différents, ont les mêmes significations que celles données ci-avant pour le diorganopolysiloxane réactif de formule (III) ; + j' a une valeur suffisante pour conférer aux polymères de formule (VI) une viscosité dynamique à 25 C allant de 10 à 200.000 mPa.s ; les résines POS ayant les mêmes significations que celles données ci-avant pour le constituant A, mais qui sont exemptes cette fois de tout groupement fonctionnel de types OH et/ou OR'. Comme exemples concrets de résines utilisables, on peut citer les résines MQ, MDQ, TD et MDT. # non-reactive linear diorganopolysiloxanes of formula:

in which: + the substituents R 21, which are identical or different, have the same meanings as those given above for the reactive diorganopolysiloxane of formula (III); + is of 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 are free this time of any functional group of OH and / or OR 'types. As concrete examples of resins that may be used, mention may be made of MQ, MDQ, TD and MDT resins.

 As concrete examples of optional auxiliary constituents E which are preferred, mention may be made of the compounds listed below: suitable fillers among which will be mentioned in particular: + metal powders such as zinc, aluminum, magnesium powder; + oxides such as silica, ground quartz, alumina, zirconium oxide, titanium oxide, zinc oxide, magnesium oxide, iron oxide, cerium oxide, lanthanum oxide, praseodymium oxide, neodymium oxide; + silicates such as mica, talc, vermiculite, kaolin, feldspar, zeolites; + calcium carbonate, barium metaborate, pyrophosphates of iron, zinc, calcium, zinc phosphate, carbon black; + pigments such as phthalocyanines, chromium oxides, sulfides and cadmium sulfoselenides.

 antifungals, bactericides known to those skilled in the art; thixotropic agents known to those skilled in the art;

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 # and, in the case of the implementation of a crosslinkable liquid silicone formulation in emulsion or aqueous dispersion, nonionic, ionic or amphoteric surfactants.

 The liquid silicone formulations used, as part of the present invention, as textile coating bases are prepared by simply mixing at room temperature, and in any order of introduction, constituents A, B, C, D (optional ) and E (optional). The quantities involved are clearly defined as indicated above.

 The order of incorporation of the constituents may be arbitrary, but it is however preferable, to avoid any risk of precipitation of solid products or gel formation, to add component A in the form of a solution in the solvent component D or diluent or in the form of an aqueous emulsion / dispersion when component D comprises water.

 The introduction and the intimate mixing of the optional fillers E, when used, with the constituents A, B, C and possibly D are carried out by means of the conventional processes used by manufacturers of textile formulations. For example, it is possible to use roller mills or turbine mills.

 The textile coating base formulations thus prepared have the advantage of hardening by simple drying in air for a time interval ranging from a few tens of minutes to several hours or if necessary several tens of hours. This period of time. can be accelerated by heating to a temperature in the range of 50 C to 180 C.

 The textile coating bases thus prepared have excellent storage stability, similar to those of conventional paints and can be used in all textile applications requiring the presence, after curing, of durable coatings with very high physical characteristics.

According to an advantageous characteristic, the crosslinkable liquid silicone formulations used as a textile coating base can be prepared in concentrated form (eg, for 100 parts by weight of component A, from 0 to
100 parts of component D), and then be diluted at the time of their use with an organic diluent, an organic solvent or water at a rate of 1 to 30 parts by weight of formulation per 100 parts by weight of solvent, diluent or water.

 The use according to the present invention can be carried out directly on textile articles comprising at least one textile surface and consisting for example of woven, non-woven and / or knitted articles.

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 By textile surface is meant a surface obtained by assembling yarns, fibers and / or filaments by any method such as, for example, gluing, felting, weaving, braiding, flocking, or knitting.

 The yarns, fibers and / or filaments used for the manufacture of these textile articles may be derived from the transformation of a synthetic thermoplastic matrix consisting of at least one thermoplastic polymer chosen from the group consisting of polyamides, polyolefins and chlorides. polyvinylidene, polyesters, polyurethanes, acrylonitriles, (meth) acrylate-butadiene-styrene copolymers, copolymers thereof and mixtures thereof. The thermoplastic matrix may comprise additives, such as pigments, delustrants, mattifying agents, catalysts, heat and / or light stabilizers, anti-bacterial, anti-fungal and / or anti-mite agents. It may for example be a matting agent, for example selected from titanium dioxide particles and / or zinc sulphide.

 The yarns, fibers and / or filaments may 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.

 In the use according to the present invention, in order to apply the textile coating base to the article to be treated, conventional techniques of the textile industry are used, in particular using the so-called "padding" impregnation technique. (padding in English).

 When the textile article is treated with a formulation comprising a diluent or organic solvent, it is desirable to subject the article thereafter to a heat treatment, in particular to drive off the diluent or the solvent in the form of steam.

 Generally, the amount of textile coating base deposited on the textile article corresponds to an amount of between 0.1 and 10% by weight relative to the weight of the treated textile dry article.

 According to the present invention, the yarns, fibers and / or filaments can also be brought into contact with the textile coating base at any time during the preparation and / or renovation and / or maintenance processes of the material. textile.

 One or more deposits can be made on the one hand textile articles and secondly on yarns, fibers and / or filaments.

 Wire means, for example, a continuous multifilament object, a continuous yarn obtained by assembling several yarns or a continuous yarn of fibers, obtained from a single type of fibers, or a mixture of fibers. By fiber is meant for example a short or long fiber, a fiber to be worked in spinning or for the manufacture of nonwoven articles or a cable to be cut to form short fibers.

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 The process for producing yarns, fibers and / or filaments generally starts with the die passing through the thermoplastic matrix, and ends before the step of manufacturing a textile surface.

 The process for manufacturing yarns, fibers and / or filaments comprises in particular a spinning step. By spinning step is meant a determined operation of obtaining yarns, fibers and / or filaments. The spinning step begins when the thermoplastic matrix passes through one or more dies and ends with the transfer of the yarns, fibers and / or filaments obtained on a spool (for the threads or filaments) or in a pot (for fibers), also referred to as winding. The spinning step may also include steps that are performed between the passage in the die and the winding. These steps can be, for example, steps of sizing, reunification of the filaments (with one or more points of training or convergence guide), drawing, warming of the filaments, relaxation and heat-setting.

 Thus, 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 performed between these two steps.

Preferably, the textile coating base according to the present invention is deposited on the yarns, fibers and / or filaments during the sizing step.

 According to another preferred object of the invention, is deposited on the son, fibers and / or filaments a sizing composition comprising at least one textile coating base according to the present invention.

 According to the present invention, it is also possible to deposit on the son, fibers and / or filaments, the textile coating base according to the present invention during a treatment step during the recovery of the son, fibers and / or filaments. Treatment step means processing steps after resumption of son, fibers and / or filaments, such as for example texturing steps, stretching, stretching-texturing, sizing, relaxation, thermofixation , twisting, fixing, crimping, washing and / or dyeing. In particular, it is possible to deposit, on the yarns, fibers and / or filaments, a textile coating base according to the present invention during an operation chosen from the group consisting of: relaxation, torsion, fixation, crimping, stretching and / or texturing of the yarns, fibers and / or filaments.

 It is also possible to deposit on the yarns, fibers and / or filaments of a sizing composition comprising at least one textile coating base according to the present invention, in particular during a treatment step during the recovery of the yarns, fibers and / or filaments.

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 The yarns, fibers and / or filaments can also be placed in a washing and / or dyeing composition comprising at least one textile coating base according to the present invention.

 As already mentioned above, the textile coating base can also be used in carrying out the renovation and / or maintenance operations of the textile material in the form of yarns, fibers and / or filaments or in the form of articles textiles themselves.

 The examples which follow illustrate the use, according to the present invention, of a crosslinkable liquid silicone formulation, as a textile coating base.

 EXAMPLE 1 Durable Hydrophobia

1) Crosslinkable liquid silicone formulation according to the invention (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 consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight of (CH3) 2 SiO2 / 2 and 14% by weight of (CH3) 3 SiO1 / 2 units: 47 parts; and hydroxylated MQ resin having 2% OH by weight and consisting of 45% by weight of SiO4 / 2 units and 55% by weight of (CH3) 3 SiO1 / 2 units: 7 parts; B: n-butyl titanate (Bu) of formula Ti (OBu) 4: 2 parts; and ethyl (Et) silicate of the formula Si (OEt) 4: 4 parts; C: hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight of (CH 3) 2 SiO 2/2 units and 14% by weight of units ( CH3) 3 SiO1 / 2: 10 parts; - D: White Spirit: 30 parts.

 The compound is re-diluted in solvent before application.

2) Comparison Formulation (Composition C2):
The performances of the composition C1 are compared with those 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.

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3) Permanent waterproofing tests:
The treated textile article used is a polyamide knit 6. 6 of the interlock knitting type made on a circular double needle knitting machine with PA6 threads. 6 textured 78 dtex 68 strands and 78 dtex 23 strands.

 The textile article is padded with 5% and 10% (by weight) solutions of composition C1 in heptane. It undergoes drying at ambient temperature (23 ° C.) for 12 hours, then it is optionally heat-treated for 3 minutes at 150 ° C.

 # The measurement of the beading effect is carried out by the standard water repellency test known as 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 evaluated 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 totally wet, for 100%, the sample is completely dry.

 In order to obtain a more quantitative measure of the durability performance of the water-repellent effect, the samples are weighed before and after spraying and the amount of water retained by the textile sample is determined by difference.

 This amount is then related to the amount of water initially retained by the unwashed textile sample.

 # To test the durability of the treatment, a GIROWASH test machine (usually used in the wash color stability study - 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, 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. These containers are fixed so as to be perpendicular to the axis of the rotor; the textile samples are placed in these small containers in the presence of water,

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 Calibrated steel balls 6 mm in diameter are added to increase turbulence and abrasion during washing. After a given stirring time, the samples are taken, dried (12 hours at room temperature 23 C) and the beading effect measured by the test described above. The same samples are then put back into the GIROWASH test machine to continue the experiment.

# Experimental results :
The results clearly show that the textile article treated with the composition C1 according to the invention retains its water repellency properties over time, whereas the conventional treatment with the composition C2 according to the prior art sees its performance significantly decrease at during the washings.

Ratio (Quantity retained on the textile sample after x hours of washing / Quantity retained before washing)

<Tb>
<tb> Compo <SEP> Rate <SEP> Treatment <SEP> Time <SEP> of <SEP> Wash <SEP>: <SEP>: <SEP> ~~~~~
<tb> -sition <SEP>: <SEP> in <SEP><SEP> Thermal <SEP> 0 <SEP> H <SEP> 4 <SEP> H <SEP> 8H <SEP> 11 <SEP> H <SEP> 15 <SEP> H <SEP> 38 <SEP> H
<tb> solution
<tb> C1 <SEP> 5 <SEP>% <SEP> - <SEP> 1 <SEP> 0.83 <SEP> 0.98 <SEP> 0.63 <SEP> 0.76 <SEP> 0.43
<tb> C1 <SEP> 5% <SEP> 3min-150c <SEP> 1 <SEP> 0.94 <SEP> 1.24 <SEP> 1.53 <SEP> 1.12 <SEP> 0.56
<tb> C1 <SEP> 10% <SEP> - <SEP> 1 <SEP> 1.90 <SEP> 1.28 <SEP> 1.21 <SEP> 1.34 <SEP> 1.14
<tb> C1 <SEP> 10% <SEP> 3min-150c <SEP> 1 <SEP> 1.3 <SEP> 1.6- <SEP> 1.35 <SEP> 0.40
<tb> C2 <SEP> Spray <SEP> - <SEP> 1 <SEP> 0.83 <SEP> 1.22 <SEP> 1.13 <SEP> 2.21 <SEP> 3.22
<tb> C2 <SEP> Spray <SEP> 3min-150 C <SEP> 1 <SEP> 3.53 <SEP> 4.47 <SEP> 2.84 <SEP> 5.16 <SEP> 3.84
<Tb>
Rating attributed to the Spray Test (%)

<Tb>
<tb> Compo- <SEP> Rate <SEP> Process <SEP> Time <SEP> of <SEP> Wash <SEP>: <SEP>
<tb><SEP>:<SEP> in <SEP><SEP> Thermal <SEP> 0 <SEP> H <SEP> 4 <SEP> H <SEP> 8H <SEP> 11 <SE> H <SE > 15 <SEP> H <SEP> 38 <SEP> H
<tb> solution
<tb> C1 <SEP> 5% <SEP> - <SEP> 80 <SEP> 80 <SEP> 80 <SEP> 80 <SEP> 80 <SEP> 88
<tb> C1 <SEP> 5% <SEP> 3min-150c <SEP> 90 <SEP> 80 <SEP> 85 <SEP> 80 <SEP> 80 <SEP> 85
<tb> C1 <SEP> 10% <SEP> - <SEP> 80 <SEP> 80 <SEP> 80 <SEP> 80 <SEP> 80 <SEP> 85
<tb> C1 <SEP> 10% <SEP> 3min-150c <SEP> 95 <SEP> 80 <SEP> 82 <SEP> 80 <SEP> 80 <SEP> 95
<tb> C2 <SEP> Spray <SEP> - <SEP> 98 <SEP> 90 <SEP> 85 <SEP> 88 <SEP> 80 <SEP> 72
<Tb>

C2 Spray 3min-150 C 92 85 82 80 75 70 EXEMPLE 2 Hydrophobie durale avec teinture.

C2 Spray 3min-150 C 92 85 82 80 75 70 EXAMPLE 2 Durical hydrophobia with dyeing.

 We start from the same composition C1 which is here diluted to 14% (by weight) in heptane.

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 The textile used is a knit made of Polyamide 6. 6 of the quilted knit type produced on a simple circular knitting machine with a PA6 thread. 6 140 dtex 102 strands vanized a fall on two.

 In this example, a dyeing resistance test is carried out. The treatment protocol is as follows: impregnation, spinning, drying at ambient temperature (23 ° C.) and then heat treatment for 10 minutes at 150 ° C.

Experimental Results: # A sample of the textile article treated with the composition C1 was dyed by 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%. Blue Nylosan N5GL stain was used at a dose of 1.2%. The temperature rise of 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 dyeing was 45 minutes.

# The sample comes out of the fully-dyed bath: most of it has retained its water repellency properties (since its Spray Test rating has increased from 90% to
80%).

 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 properties of water repellency with a rating of 80% Spray Test.

EXAMPLE 3
Durable Hydrophobia - Can be washed in an industrial machine.

1) Crosslinkable liquid silicone formulation according to the invention (composition C3):
It has the following constitution (the parts are by weight): A: # hydroxtated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight of (CH 3) 2 SiO 2/2 and 14 wt% units (CH 3) 3 SiO 2/2: 47 parts; and of

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hydroxylated MQ resin having 2% of OH by weight and consisting of 45% by weight of SiO4 / 2 units and 55% by weight of (CH3) 3 SiOi / 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) 4: 2 parts; and ethyl (Et) silicate of the formula Si (OEt) 4: 4 parts;
C-1: mixture of: # hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight of (CH 3) 2 SiO 2/2 and 14% units by weight of (CH 3) 3 SiO 1/2 units: 10 parts; and hydroxylated linear silicone oil having about 0.01% OH by weight and consisting of 100% by weight of (CH3) 2 SiO2 / 2 units, having a viscosity of 4,000,000 mPa.s: 20 parts;
D: White Spirit: 883 games.

2) Crosslinkable liquid silicone formulation according to the invention (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 consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight weight of units (CH3) 2 SiO2 / 2 and 14% by weight of (CH3) 3 SiO1 / 2 units: 95 parts; and hydroxylated MQ resin having 2% OH by weight and consisting of 45% by weight of SiO4 / 2 units and 55% by weight of (CH3) 3 SiO1 / 2 units: 14 parts; B: mixture of: # tris (3- (trimethoxysilyl) propyl) isocyanurate: 11 parts n-propyl zirconate (Pr) of formula Zr (Opr) 4: 41 parts # n-butyl titanate (Bu) of formula Ti (OBu) 4: 4 parts; and ethyl (Et) silicate of the formula Si (OEt) 4: 8parts; - C-1: mixture of: # hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight of (CH 3) 2 SiO 2/2 and 14 units % by weight of (CH 3) 3 SiO 1/2 units: 20 parts; and hydroxylated linear silicone oil having on the order of 0.01% of OH by weight and consisting of 100% by weight of (CH 3) 2 SiO 2/2 units, having a viscosity of

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4,000,000 mPa.s: 80 parts; # weight and constituted at 100% by weight of units (CH3) 2 SiO2 / 2: 80 parts.

 D: White Spirit: 727 games.

3) Crosslinkable liquid silicone formulation according to the invention (composition C5):
It presents the following constitution (the parts are given in weight):
A: mixture of: # hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight of (CH 3) 2 SiO 2/2 units and 14% by weight of (CH3) 3 SiO1 / 2 units: 40 parts; and hydroxylated MQ resin having 2% OH by weight and consisting of 45% by weight of SiO4 / 2 units and 55% by weight of (CH3) 3 SiO1 / 2 units: 6 parts;
B: mixture of: # 3-aminopropyl trimethoxy silane: 8 parts # n-propyl zirconate (Pr) of formula Zr (Opr) 4: 18 parts # n-butyl titanate (Bu) of formula Ti (OBu) 4: 2 parts ; and ethyl (Et) silicate of the formula Si (OEt) 4: 3 parts;
C-1: mixture of: # hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight of (CH 3) 2 SiO 2/2 and 14% units by weight of (CH 3) 3 SiO 1/2 units: 10 parts; and hydroxylated linear silicone oil having on the order of 0.01% of OH by weight and consisting of 100% by weight of (CH 3) 2 SiO 2/2 units, having a viscosity of
4,000,000 mPa.s: 18 parts;
D: White Spirit: 895 parts.

4) Crosslinkable liquid silicone formulation according to the invention (composition C6):
It has the following constitution (the parts are given by weight): A: hydroxylated MDT having 0.8% of OH by weight and consisting of 23% by weight of CH 3 SiO 3/2 units, 75% by weight of units (CH 3 SiO2 / 2 and 2% by weight of (CH3) 3 SiO1 / 2 units: 58 parts - B: mixture of: # 3-aminopropyl trimethoxy silane: 8 parts; of n-propyl zirconate (Pr) of formula Zr (Opr) 4: 18 parts

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C-1: mixture of: # hydroxylated MDT resin having 0.8% of OH by weight and consisting of 23% by weight of CH 3 SiO 3/2 units, 75% by weight of (CH 3) 2 SiO 2/2 and 2% units by weight of (CH 3) 3 SiO 1/2 units: 20 parts; and hydroxylated linear silicone oil having on the order of 0.01% of OH by weight and consisting of 100% by weight of (CH 3) 2 SiO 2/2 units, having a viscosity of
4,000,000 mPa.s: 25 parts;
D: White Spirit: 871 games.

5 / Crosslinkable liquid silicone formulation according to the invention (composition C7):
It has the following constitution (the parts are given by weight): A: hydroxylated resinMDT having 0.5% of OH by weight and consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight of units (CH 3 SiO2 / 2 and 14% by weight of (CH3) 3 SiO1 / 2 units: 100 parts - B: mixture of: # tris (3- (trimethoxysilyl) propyl) isocyanurate: 13 parts; of n-propyl zirconate (Pr) of formula Zr (Opr) 4: 41 parts - C-1: mixture of: # hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight of (CH 3) 2 SiO 2/2 units and 14% by weight of (CH 3) 3 SiO 1/2 units: 41 parts; and hydroxylated linear silicone oil having on the order of 0.01% of OH by weight and consisting of 100% by weight of (CH 3) 2 SiO 2/2 units, having a viscosity of
4,000,000 mPa.s: 62 parts; - D: White Spirit: 743 games.

6) Comparative Formulation (Composition C8):
The performances of compositions C3 to C7 are compared with those of a conventional C8 composition (treatments known and marketed under the trademarks 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.

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7) Permanent waterproofing tests:
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 elastane yarn 44 dtex 1 strand and 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 the compositions C3 to C8. It undergoes a heat treatment at 150 C for 2 minutes, then it is stored at room temperature for 8 hours before testing.

 # The measurement of the beading effect is performed by the standard water repellency test known as the Spray Test (AATC Test Method 22-1996).

# To test the durability of the treatment, a typical industrial washing machine
WASHCATOR (Electrolux) was used for continuous washing at 50 C for varying durations of 8, 16, and 24 hours.

# Experimental results :
The results clearly show that the textile article treated with compositions C3 to C7 according to the invention retains its water-repellency properties over time and during washing at 50 ° C. under severe wet abrasion conditions, while the conventional treatment with the composition C8 according to the prior art sees its performance collapse from the first hours of washing.

Rating attributed to the Spray Test after x hours of washing (%)

<Tb>
<tb> Composition <SEP> Treatment <SEP> Time <SEP> of <SEP> wash <SEP>: <SEP>: <SEP> ~~~~~~~~~~
<tb> Thermal <SEP> 0 <SEP> H <SEP> 8 <SEP> H <SEP> 16 <SEP> H <SEP> 24 <SEP> H
<tb> C3 <SEP> 2min <SEP> 50C <SEP> 100 <SEP> 90 <SEP> 80 <SEP> 70
<tb> C4 <SEP> 2min <SEP> 50C <SEP> 100 <SEP> 90 <SEP> 80 <SEP> 80
<tb> C5 <SEP> 2min <SEP> 50C <SEP> 100 <SEP> 80 <SEP> 70 <SEP> 70
<tb> C6 <SEP> 2min <SEP> 50C <SEP> 100 <SEP> 80 <SEP> 70 <SEP> 70
<tb> C7 <SEP> 2min <SEP> 50C <SEP> 100 <SEP> 80 <SEP> 70 <SEP> 70
<tb> C8 <SEP> 2min <SEP> 50C <SEP> 100 <SEP> 50 <SEP> 0 <SEP> 0
<Tb>

<Desc / Clms Page number 26>

Quantity of water retained on the textile sample after x hours of washing (in g)

<Tb>
<tb> Composition <SEP> Treatment <SEP> Time <SEP> of <SEP> wash <SEP>: <SEP>
<tb> thermal <SEP> 0 <SEP> H <SEP> 8 <SEP> H <SEP> 16 <SEP> H <SEP> 24 <SEP> H
<tb> C3 <SEP> 2min <SEP> 50C <SEP> 0.31 <SEP> 0.33 <SEP> 0.59 <SEP> 0.93
<tb> C4 <SEP> 2min <SEP> 50C <SEP> 0.46 <SEP> 0.48 <SEP> 0.58 <SEP> 0.81
<tb> C5 <SEP> 2min <SEP> 50C <SEP> 0.24 <SEP> 0.39 <SEP> 0.65 <SEP> 0.90
<tb> C6 <SEP> 2min <SEP> 50C <SEP> 0.42 <SEP> 0.45 <SEP> 0.68 <SEP> 0.81
<tb> C7 <SEP> 2min <SEP> 50C <SEP> 0.32 <SEP> 0.62 <SEP> 0.77 <SEP> 1.04
<tb> C8 <SEP> 2min <SEP> 50C <SEP> 0.30 <SEP> 1.18 <SEP> 1.33 <SEP> 1.62
<Tb>
EXAMPLE 4 Permanent oleophobia 1) Crosslinkable liquid silicone formulation according to the invention (C9):
It presents the following constitution (the parts are given in weight):
A: mixture of: hydroxylated MDT resin having 0.5% of OH by weight and consisting of 62% by weight of CH 3 SiO 3/2 units, 24% by weight of (CH 3) 2 SiO 2/2 units and 14% by weight of (CH3) 3 SiO1 / 2 units: 3.50 parts; and hydroxylated MQ resin having 2% OH by weight and consisting of 45% by weight of SiO4 / 2 units and 55% by weight of (CH3) 3 SiO1 / 2 units: 0.50 parts;
B: mixture of: # n-butyl titanate (Bu) of formula Ti (OBu) 4: 2.25 parts; and ethyl (Et) silicate of formula Si (OEt) 4: 0.25 parts;
C-2: perfluorinated alcohol of formula C8F17-C2H4-OH (product marketed under the reference FORALKYL EOH8 by the company ATOFINA): 2.0 parts;
D: White Spirit: 89.25 parts.

- alcool perfluoré de formule CeFi7-C2H4-OH : 10 parties ; - White Spirit : 90 parties. 2) Comparison Formulation (C10):

perfluorinated alcohol of formula CeF7-C2H4-OH: 10 parts; - White Spirit: 90 parts.

3) Oleophobia Test # The treated textile used is a woven fabric made of Polyamide 6. 6 and elastane (80/20). It consists of elastic warp and weft yarns based on an elastane 44 dTex

<Desc / Clms Page number 27>

 covered by a piece of PA 6. 6 44 dTex / 34 strands. These textile surfaces have a high bidirectional elasticity (100% elongation in both directions) and a specific weight of 130 g / m2.

 # The textile is treated by padding with the solution. It is dried at room temperature for a few minutes and is then heat-treated for 2 minutes at 150 C.

# The measurement of the oleophobic character is carried out by the standardized test (AATC
Test Method 118-1997) known as "Oil repellency: Hydrocarbon
Resistance Test ": The test consists of depositing drops of decreasing interfacial tension fluid on the textile and determining the liquid LH from which the spreading of the drops is observed.A score of 0 to 8 is attributed according to the LH obtained. When the Kaydol oil spreads (vaseline oil, low oleophobic character), 3 when the n-tetradecane spreads (labeled olephobia) and
8 when n-Heptane no longer spreads (very marked oleophobia).

# To test the durability of the treatment, the samples are washed 3 times at
50 C in a commercial washing machine (Miele brand, model
Novotronic 824) in the presence of a standardized detergent (ECE Non Phosphate -
Reference Detergent A - the wording of which is given in BS1006:
UK-TO). The amount of detergent used is 96 g (the volume of water used by the machine being 12 I, this amount corresponds to a conventional concentration of 8 g / l).

4) Experimental results:
The results show that the textile treated with the formulation (C9), functionalized oleophobic, shows well properties of non-existent oleophy for the untreated textile. The results also show that the textile treated with the formulation (C9) retains its oleophobic properties during the washings, whereas the textile treated solely with the fluorinated compound, sees its performance completely disappear.

<Desc / Clms Page number 28>

Oleophobia measurements (note obtained on the Oil Repellency test):

<Tb>
<tb> Composition <SEP> Treatment <SEP> Before <SEP> wash <SEP> After <SEP> 3 <SEP> cycles
<tb> of <SEP> washes <SEP>
<tb> No <SEP> Processed <SEP> 0 <SEP> 0 <SEP>
<Tb>

C9 2min à 150 C 3 3

C9 2min to 150c 3 3

<Tb>
<tb> C10 <SEP> 2min <SEP> to <SEP> 150 C <SEP> 1 <SEP> 0 <SEP>
<Tb>

Claims (11)

1) Use of at least one crosslinkable liquid silicone formulation as textile fabric coating base: to allow, by crosslinking around the constituent yarns, fibers and / or filaments of the textile material, to ensure a broad protective covering of the textile material; textile material, protection little dependent on the nature of said material because it requires little or no anchor points; to allow, by making a chemically crosslinking silicone sheath, to ensure a durable protection of the textile material by conferring on it an excellent resistance with respect to the aggressions encountered during use; to allow, by providing additional specific functional features, to form coatings having useful properties such as, in particular, softness, hydrophobicity, oleophobicity, hydrophilicity, an antistatic effect; and - to allow, due to the special nature of the constituents of the formulation, to carry out the operations of depositing the liquid formulation and its crosslinking at any point in the development and / or renovation processes and / or maintenance of the textile material made of natural and / or synthetic materials.  2) Use according to claim 1, characterized in that the crosslinkable liquid silicone formulation used as a textile material coating base: # is that comprising: A - a film-forming silicone network generating system comprising at least one polyorganosiloxane resin (POS) having, per molecule, on the one hand at least two different siloxyl units selected from those of types M, D, T, Q, one of the units being a T unit or a Q unit and, secondly, at least three hydrolysable / condensable groups of OH and / or OR 'groups in which R 1 is a linear or branched C1-C6 alkyl radical; B - a coupling promoter of said network system on the surface of the textile material consisting of: * B-1 at least one metal alkoxide of general formula: M [(OCH 2 CH 2) to OR 2] n (I) in which: <Desc / Clms Page number 30> 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 implementation of a liquid silicone formulation in emulsion or in aqueous dispersion; and C - a functional additive consisting in: # is C-1 at least one silane and / or at least one substantially linear POS and / or at least one POS resin, each of these organosilicon compounds being equipped, per molecule, on the one hand of function (s) (FA) capable of reacting with A and / or B or capable of generating functions in situ capable of reacting with A and / or B and secondly of function (s) (FU) which can be identical or different from FA; # is C-2 at least one hydrocarbon compound comprising at least one linear or branched, saturated or unsaturated hydrocarbon-based group, and optionally one or more heteroatom (s) other than Si and which is in the form of a monomeric, oligomeric or polymer, said hydrocarbon compound being equipped, by molecule, on the one hand function (s) (FA) capable of reacting with A and / or B or capable of generating in situ functions capable of reacting with A and / or B and on the other hand of function (s) of use (FU) which may be identical or different from the FA; # be a mixture of C-1 and C-2;  M is a metal selected from the group consisting of: Ti, Zr, Ge, Si, Mn and Al; n = valence of M; the substituents R 2, which are identical or different, each represent a linear or branched C 1 to C 12 alkyl radical; - a represents zero, 1 or 2; with the conditions according to which, when the symbol a represents zero, the alkyl radical R 2 has from 2 to 12 carbon atoms, and when the symbol a represents 1 or 2, the alkyl radical R 2 has 1 to 4 carbon atoms; or B-2 at least one metal polyalkoxide resulting from the partial hydrolysis of the monomeric alkoxides of the above-mentioned formula (I) in which the symbol R2 has the abovementioned meaning with the symbol a representing zero; # be an association of B-1 and B-2; # is B-3 a combination of B-1 and / or B-2 with: - B-3/1 at least one optionally alkoxylated organosilane containing, per molecule, at least one C2-C6 alkenyl group, and / or B-3/2 at least one organosilicon compound comprising at least one epoxy, amino, ureido, isocyanato and / or isocyanurate radical; <Desc / Clms Page number 31> E- optionally at least one auxiliary agent other than D known to those skilled in the art, which is chosen, when it is needed, in particular according to the applications in which the textile materials treated according to the invention are used; # with the condition according to which engagement (the parts are given by weight): - per 100 parts of constituent A, - from 0.5 to 200 parts of constituent B, - 1 to 1000 parts of constituent C according to the desired FU, from 0 to 10,000 parts of component D and from 0 to 100 parts of component E.  3) Use according to claim 2, characterized in that, in the definition of component A, the radical R1 is a linear or branched C1 to C3 alkyl radical 4) Use according to claims 2 or 3, characterized in that is committed as component A mixtures A-3: - at least one resin having, in its structure, at least two different siloxyl units selected from those of formula (R3) 3 SiO0.5 (unit M), (R3) 2SiO (unit D) and R3SiO1.5 (unit T), at least one of these units being a unit T, the groups OH and / or OR ' may be carried by the units M, D and / or T and the weight content of OH and / or OR 'groups being between 0.2 and 10% by weight, and - of at least one other resin having, in its structure, at least two different siloxyl units selected from those of formula (R3) 3SiO0.5 (M-unit), (R3) 2SiO (D-unit) and R3SiO1.5 (T-unit) and SiO2 (Q-unit), one at least of these units being a Q unit, the OH and / or OR 'groups being able to be borne by the M, D and / or T units and the weight content of OH and / or OR' groups being between 0.2 and 10% by weight, - radicals R 3 present ns these resins being identical or different and being chosen from linear or branched C1-C6 alkyl radicals, C2-alkenyl radicals; C4, phenyl, 3,3,3-trifluoropropyl.  5) Use according to any one of claims 2 to 4, characterized in that it engages: - as constituent B-1: alkyl titanates such as ethyl titanate, propyl titanate, titanate d isopropyl, butyl titanate, 2-ethylhexyl titanate, octyl titanate, decyl titanate, dodecyl titanate, sodium titanate and the like.

 methoxyethyl, (3-ethoxyethyl) titanate, (3-propoxyethyl) titanate, titanate of the formula [(OCH 2 CH 2) 2 OCH 3] 4, alkyl zirconates such as propyl zirconate, <Desc / Clms Page number 32>  butyl zirconate; alkyl silicates such as methyl silicate, ethyl silicate, isopropyl silicate, n-propyl silicate; and mixtures of these products; as constituent B-2: the B-2 polytitants resulting from the partial hydrolysis of isopropyl, butyl or 2-ethylhexyl titanates; polyzirconates B-2 from the partial hydrolysis of propyl and butyl zirconates; polysilicates B-2 resulting from the partial hydrolysis of ethyl and isopropyl silicates; and mixtures of these products.  6) Use according to any one of claims 2 to 5, characterized in that is engaged as component C-1: # polyalkoxysilanes of formula:

 wherein: + the substituents R1 and R2 and the symbol a are as defined above with respect to the description of components A and B; + Best1,2ou3; the essentially linear diorganopolysiloxane comprising a hydroxyl group at each chain end, of formula:

 in which: + substituents R 18, which may be identical or different, each represent a saturated or unsubstituted, aliphatic, cyclanic or aromatic monovalent hydrocarbon radical C1 to C13; + j has a value sufficient to give the diorganopolysiloxanes of formula (III) a dynamic viscosity at 25 C ranging from 1.000 to 10.000.000 mPa.s; POS-polyether copolymers resulting especially from the reaction of a polyether of formula:

 CH2 = CH-CH2-IOCH2CH2] v-IOCH2CH (CH3) 1w-OH on a POS oil of formula: Me3SiO (Me2SiO) x '(MeHSiO) y, SiMe3, <Desc / Clms Page number 33>  + with Me = methyl; + with v and w different from 0 and in particular between 5 and 30; + with x 'ranging from 20 to 150; with y 'ranging from 2 to 10; + the copolymer can be added with an additive such as a free polyether; hydroxylated POS resins comprising in their structure siloxyl units T and optionally M and / or optionally D as defined above with reference to resins A; # hydroxylated POS resins obtained in particular: # by hydrolysis of an alkoxysilane S substituted with FU; by homocondensation of the hydrolysed silanes S; # and steam stripping stripping hydrolysates derived from FU; # mixtures of the aforementioned organosilicon compounds.  7) Use according to any one of claims 2 to 6, characterized in that is engaged as component C-2: # fluorinated alcohols of formula: R19-OH (IV) wherein R19 represents an aliphatic radical, linear or branched, having 2 to 20 carbon atoms, said carbon atoms being substituted by at least one fluorine atom and optionally by at least one or hydrogen atom ; # the unblocked polyethers of formula:

 RZ - [OCH2CH2] [OCH2CH (CH3)] w -OH (V) wherein R20 represents a linear or branched alkyl radical having from 1 to 4 carbon atoms and the symbols v and w are as defined above in the claim 6.  8) Use according to any one of claims 2 to 7, characterized in that one engages: - per 100 parts of component A, - from 0.5 to 100 parts of constituent B, - 1 to 300 parts of constituent C according to the desired FU, - from 0 to 5000 parts of constituent D and - from 0 to 100 parts of component E.  9) Use according to any one of claims 2 to 8, characterized in that the crosslinkable liquid silicone formulations used as coating base <Desc / Clms Page number 34>  The textiles are prepared in concentrated form and then are diluted at the time of their use with an organic diluent, an organic solvent or water at a rate of 1 to 30 parts by weight of formulation per 100 parts by weight of solvent, diluent or water.  10) Use according to any one of claims 1 to 9, characterized in that it is carried out by directly contacting the textile articles comprising at least one textile surface and consisting for example in woven articles, nonwoven and / or knitted, with the base of coating of textile material.  11) Use according to any one of claims 1 to 9, characterized in that it is performed by contacting the son, fibers and / or filaments with the textile coating base at any time of the processes of development and / or renovation and / or maintenance of the material of textile material.