EP1325187B1 - Treating textile materials with polyorganosiloxanes - Google Patents

Treating textile materials with polyorganosiloxanes Download PDF

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Publication number
EP1325187B1
EP1325187B1 EP01976352A EP01976352A EP1325187B1 EP 1325187 B1 EP1325187 B1 EP 1325187B1 EP 01976352 A EP01976352 A EP 01976352A EP 01976352 A EP01976352 A EP 01976352A EP 1325187 B1 EP1325187 B1 EP 1325187B1
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Prior art keywords
radical
radicals
textile material
formula
carbon atoms
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EP01976352A
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German (de)
French (fr)
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EP1325187A1 (en
Inventor
Josette Chardon
Philippe Olier
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Elkem Silicones France SAS
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Bluestar Silicones France SAS
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    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • 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
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/25—Resistance to light or sun, i.e. protection of the textile itself as well as UV shielding materials or treatment compositions therefor; Anti-yellowing treatments
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/50—Modified hand or grip properties; Softening compositions

Definitions

  • the present invention relates to the utitisation of a composition for providing the textile fiber with good hydrophilicity, an absence of yellowing and a soft hand feel, that is to say softness properties.
  • the document US 4,409,267 describes for example the use of a mixed polyorganosiloxane carrying on the one hand primary (or secondary) amine function (s) substituted for example by residues containing an OH or O-group; alkyl, and secondly function (s) polyoxide (s) alkylene (s) as additive of a composition for the treatment of textile materials.
  • the document EP 546 231 discloses another approach via the use of a polyorganosiloxane bearing a unit (s) of formula Si - (CH 2 ) y - (OCH 2 ) y ' - CH (OH) CH 2 --N (CH 2 CH 2 OH) 2 where y is between 2 and 8 and y 'is 0 or 1.
  • EP 659 930 discloses silicone-based fabric softeners comprising from 2 to 1600 silicon atoms, carrying one to one hundred sterically hindered amine units and optionally other units such as, for example, alkyl radicals of 5 to 20 carbon atoms or radicals ( CH2) p-COO-R.
  • FR 2,745,825 discloses silicone fabric softeners carrying at least one sterically hindered amine unit and at least one polyether group of the formula (CH 2 ) n - (OCH 2 CH 2 ) ⁇ (OCH 2 CHCH 3 ) ⁇ - OR.
  • Another advantage of the use according to the present invention stems from the fact that it can be implemented with an industrially easy and storage stable polyorganosiloxane.
  • Another advantage of the use according to the present invention comes from the easy treatment of the composition containing the polyorganosiloxane according to the invention for its application to the materials to be treated.
  • the silicone oil used in the context of the invention does not require in particular the presence of other functions to provide hydrophilic properties to the treated textile material. However, if it is desired to obtain a hydrophilicity greater than that intrinsic to the material before treatment, the silicone oil used may contain other functions promoting this property.
  • the polyorganosiloxane of formula (I) used is linear.
  • the functional group V of the polyorganosiloxane of formula (I) used is chosen from the functional groups of formula (II).
  • the treatment process may be carried out on woven, non-woven or knitted form materials.
  • the fibers of these materials are at least partially hydrophilic, and this hydrophilicity is preserved after treatment with silicone according to the invention, notwithstanding the hydrophobic nature of its skeleton.
  • the at least partially hydrophilic materials may consist in particular of or based on cotton, linen, wool, viscose, rayon, hemp, silk or a mixture of these materials. These materials may be optionally mixed with other low or non-hydrophilic materials such as polyester (eg cotton-polyester blend), keratin, polypropylene, polyethylene, polyurethane, polyamide, cellulose acetate.
  • composition containing the polyorganosiloxane can be prepared in many forms: liquid, gaseous or solid.
  • a liquid preparation of the composition it will advantageously be aqueous in the form of solution, dispersion or emulsion.
  • the composition is prepared in the form of an aqueous emulsion.
  • the composition according to the process of the invention may also be used in solution in an organic solvent.
  • aqueous emulsions are generally based on a mixture of oil and water, and are prepared according to standard methods well known to those skilled in the art using surfactants.
  • the emulsions can be done by the so-called direct methods or by inversion. Their production is easy and does not require the use of equipment with high stirring speed. Normal speed stirring apparatus may be used.
  • the aqueous emulsions prepared according to the invention preferably contain between 20 and 90% by weight of water relative to the total mass of the constituents of the emulsion.
  • the emulsions prepared according to the invention are preferably diluted to contain between 95 and 99.5% by weight of water, relative to the total weight of the emulsion.
  • the application of the polyorganosiloxane according to the invention to the materials to be treated can be carried out in very different forms. Applications can be made by immersion, coating, spraying, printing, padding, or any other existing means.
  • the fabric when the fabric is treated with an aqueous composition containing a polyorganosiloxane according to the invention, said fabric is subjected to a heat treatment to quickly expel water in the form of steam.
  • the amount of polyorganosiloxane deposited on the material to be treated varies according to the constitution and manufacture of said material.
  • the applications of the compositions and in particular aqueous emulsions on the treated materials are carried out so that the increase in weight of the treated material does not exceed 0.1 to 20% by weight relative to the weight of the material before treatment.
  • the best results have been observed with a quantity of polyorganosiloxane of between 0.1 and 2% by weight relative to the weight of the material to be treated.
  • the previously defined polyorganosiloxanes may be prepared by different methods; for example: distribution or hydrosilylation.
  • oils are tested in application in the form of an aqueous emulsion and the measurements of hydrophilicity, non-yellowing and evaluation of the feel are carried out according to the tests described below.
  • the evaluation of the yellowing is carried out by measuring the color of the fabric (white cotton terry cloth at the beginning) after impregnation with the silicone oil and heat treatment for 9 minutes at 150 ° C.
  • the color measurement is made on a Sprectrophotocolorimeter ACS Sensor It sold by the company Datacolor.
  • the measurement conditions are the use of illuminant D65, reproducing daylight. From the measurement of the color of the tissue sample, the instrument calculates the values of different indices of white and yellow, among which we use the CIE white index.
  • the cotton terry cloth After applying the oil, the cotton terry cloth is dried in ambient air for 24 hours. After 1 minute heat treatment at 150 ° C, the fabric is placed 24 hours in conditioning (23 ⁇ 2 ° C, 50 ⁇ 5% relative humidity).
  • the polyester-cotton fabric (50/50) undergoes a heat treatment of 5 minutes at 170 ° C. It is then conditioned for 24 hours (23 ⁇ 2 ° C, 60 ⁇ 5% relative humidity).
  • the hydrophilicity measurements are given by the TEGEWA test in which the absorption time of a drop of water deposited on the surface of the fabric is measured. The shorter the time, the more the tissue is hydrophilic.
  • the silicone oils of the emulsions tested E1 to E7 have the following structure:
  • the emulsions are prepared using an inversion emulsification method, and have the following composition: 20 g of silicone oil tested, 8 g of surfactant (C 13 E 6 fatty alcohol), an amount of glacial acetic acid stoichiometrically necessary for the neutralization of the amine and the complement at 100 g with water.
  • 20 g of silicone oil tested 8 g of surfactant (C 13 E 6 fatty alcohol), an amount of glacial acetic acid stoichiometrically necessary for the neutralization of the amine and the complement at 100 g with water.
  • surfactant C 13 E 6 fatty alcohol
  • an amount of glacial acetic acid stoichiometrically necessary for the neutralization of the amine and the complement at 100 g with water.
  • the evaluations were carried out on textiles treated with 0.6% by weight of silicone oil.
  • the emulsions are applied to the fabric by padding.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Silicon Polymers (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

The invention concerns a method for treating textile materials providing said textile materials with a soft feel, absence of yellowing and good hydrophily, which consists of contacting the textile materials with a composition comprising at least a linear, cyclic or three-dimensional polyorganosiloxane of formula (I), wherein: the symbols Z, identical or different, represent R1, and/or V; and the symbols V represent a group of sterically hindered piperidinyl function(s).

Description

La présente invention concerne l'utitisation d'une composition pour apporter à la fibre textile une bonne hydrophilie une absence de jaunissement et un toucher doux à la main, c'est-à-dire des propriétés de douceur.The present invention relates to the utitisation of a composition for providing the textile fiber with good hydrophilicity, an absence of yellowing and a soft hand feel, that is to say softness properties.

Différentes approches sont décrites dans l'art antérieur pour obtenir des traitements adoucissants textiles.Different approaches are described in the prior art to obtain textile softening treatments.

Le document US 4 409 267 décrit par exemple l'utilisation d'un polyorganosiloxane mixte porteur d'une part de fonction(s) amine(s) primaire(s) ou secondaire(s) substituée(s) par exemple par des restes renfermant un groupe OH ou O-alkyle, et d'autre part de fonction(s) polyoxyde(s) d'alkylène(s) comme additif d'une composition pour le traitement de matières textiles. Le document EP 546 231 décrit une autre approche via l'utilisation d'un polyorganosiloxane porteur de motif(s) de formule Si - (CH2)y - (OCH2)y' - CH (OH) CH2 - N (CH2CH2OH)2 où y est compris entre 2 et 8 et y' est égal à 0 ou 1.The document US 4,409,267 describes for example the use of a mixed polyorganosiloxane carrying on the one hand primary (or secondary) amine function (s) substituted for example by residues containing an OH or O-group; alkyl, and secondly function (s) polyoxide (s) alkylene (s) as additive of a composition for the treatment of textile materials. The document EP 546 231 discloses another approach via the use of a polyorganosiloxane bearing a unit (s) of formula Si - (CH 2 ) y - (OCH 2 ) y ' - CH (OH) CH 2 --N (CH 2 CH 2 OH) 2 where y is between 2 and 8 and y 'is 0 or 1.

La déposante a également proposé des solutions décrites notamment dans EP 659 930 et FR 2,745,825 .The applicant has also proposed solutions described in particular in EP 659 930 and FR 2,745,825 .

EP 659 930 décrit des adoucissants textiles à base de silicone comprenant de 2 à 1600 atomes de silicium, portant un à cent motifs aminés encombrés stériquement et éventuellement d'autres motifs tels que par exemple des radicaux alkyles de 5 à 20 atomes de carbone ou des radicaux -(CH2)p-COO-R. EP 659 930 discloses silicone-based fabric softeners comprising from 2 to 1600 silicon atoms, carrying one to one hundred sterically hindered amine units and optionally other units such as, for example, alkyl radicals of 5 to 20 carbon atoms or radicals ( CH2) p-COO-R.

FR 2,745,825 décrit des adoucissants textiles à base de silicone portant au moins un motif aminé encombré stériquement et au moins un radical de type polyether de formule (CH2)n - (OCH2CH2)α(OCH2CHCH3)β - OR. FR 2,745,825 discloses silicone fabric softeners carrying at least one sterically hindered amine unit and at least one polyether group of the formula (CH 2 ) n - (OCH 2 CH 2 ) α (OCH 2 CHCH 3 ) β - OR.

Ces approches ont conduit à la préparation de silicones dans lesquelles les propriétés adoucissantes sont apportées au textile notamment par la présence de fonctions aminées, et les propriétés hydrophiles sont apportées notamment par la présence de fonctions polaires telles que des fonctions de type polyether, ces dernières compensant au moins partiellement la perte d'hydrophilie du matériau traité avec de la silicone. Il est à noter en outre que la préparation de ces produits utilise des voies de synthèses relativement complexes et donc peu viables économiquement.These approaches have led to the preparation of silicones in which the softening properties are provided to the textile in particular by the presence of amine functions, and the hydrophilic properties are provided in particular by the presence of polar functions such as polyether type functions, the latter compensating for at least partially the loss of hydrophilicity of the material treated with silicone. It should also be noted that the preparation of these products uses relatively complex synthesis routes and therefore not economically viable.

A présent, la déposante a trouvé de manière inattendue que des composés silicones présentent des avantages remarquables par rapport aux autres composés connus de l'art antérieur.At present, the Applicant has unexpectedly found that silicone compounds have remarkable advantages over other known compounds of the prior art.

En effet, la déposante a mis au point une nouvelle utilisation des huiles silicones adoucissantes, hydrophiles et non jaunissantes portant des fonctions aminées encombrées stériquement. Cette approche innovante consiste à apporter la douceur et l'absence de jaunissement au matériau textile par un traitement avec une huile silicone portant une fonction aminée encombrée, sans masquer l'hydrophilie intrinsèque du matériau textile traité.Indeed, the applicant has developed a new use of softening, hydrophilic and non-yellowing silicone oils carrying amine functions hindered sterically. This innovative approach consists of bringing the softness and absence of yellowing to the textile material by treatment with a silicone oil carrying a hindered amine function, without masking the intrinsic hydrophilicity of the treated textile material.

Un autre avantage de l'utilisation selon la présente invention provient du fait que celle-ci peut être mise en oeuvre avec un polyorganosiloxane de préparation facile industriellement et stable au stockage.Another advantage of the use according to the present invention stems from the fact that it can be implemented with an industrially easy and storage stable polyorganosiloxane.

Un autre avantage de l'utilisation selon la présente invention provient du traitement aisé de la composition contenant le polyorganosiloxane selon l'invention pour son application sur les matières à traiter.Another advantage of the use according to the present invention comes from the easy treatment of the composition containing the polyorganosiloxane according to the invention for its application to the materials to be treated.

Il a donc maintenant été trouvé, et c'est ce qui fait l'objet de la présente invention, pour l'utilisation d'une composition pour apporter un toucher doux, une absence de jaunissement et une bonne hydrophilie aux matières textiles ladite composition comprenant au moins un polyorganosiloxane linéaire, cyclique ou tridimensionnel de formule (I):

Figure imgb0001
dans laquelle :

  1. (1) les symboles Z, identiques ou différents, représentent R1, et/ou V;
  2. (2) les symboles R1, R2 et R3, identiques et/ou différents, représentent un radical hydrocarboné monovalent choisi parmi les radicaux alkyles linéaires ou ramifiés ayant de 1 à 4 atomes de carbone, les radicaux alkoxy linéaires ou ramifiés ayant de 1 à 4 atomes de carbone, un radical phényle et, de préférence un radical hydroxy, un radical éthoxy, un radical méthoxy ou un radical méthyle;
  3. (3) les symboles V, groupements fonctionnels identiques et/ou différents, représentent un groupement à fonction(s) pipéridinyle(s) stériquement encombrée(s) choisi parmi :
    Figure imgb0002
     ou
    Figure imgb0003
    Pour les groupements de formule (II) :
    Figure imgb0004
    • * R4 est un radical hydrocarboné divalent choisi parmi :
      • ◆ les radicaux alkylènes linéaires ou ramifiés, ayant 2 à 18 atomes de carbone;
      • ◆ les radicaux alkylène-carbonyle dont la partie alkylène linéaire ou ramifiée, comporte 2 à 20 atomes de carbone;
      • ◆ les radicaux alkylène-cyclohexylène dont la partie alkylène linéaire ou ramifiée, comporte 2 à 12 atomes de carbone et la partie cyclohexylène comporte un groupement OH et éventuellement 1 ou 2 radicaux alkyles ayant 1 à 4 atomes de carbone;
      • ◆ les radicaux de formule -R7 - O - R7 dans laquelle les radicaux R7 identiques ou différents représentent des radicaux alkylènes ayant 1 à 12 atomes de carbone;
      • ◆ les radicaux de formule -R7 - O - R7 dans laquelle les radicaux R7 ont les significations indiquées précédemment et l'un d'entre eux ou les deux sont substitués par un ou deux groupement(s) -OH;
      • ◆ les radicaux de formule -R7 - COO - R7 dans laquelle les radicaux R7 ont les significations indiquées précédemment;
      • ◆ les radicaux de formule -R8 -O -R9 - O-CO-R8 dans laquelle les radicaux R8 et R9 identiques ou différents, représentent des radicaux alkylènes ayant 2 à 12 atomes de carbone et le radical R9 est éventuellement substitué par un radical hydroxyle;
      • ◆ U représente -O- ou -NR10-, R10 étant un radical choisi parmi un atome d'hydrogène, un radical alkyle linéaire ou ramifié comportant 1 à 6 atomes de carbone et un radical divalent de formule :
        Figure imgb0005
      dans laquelle R4 a la signification indiquée précédemment, R5 et R6 ont les significations indiquées ci-après et R11 représente un radical divalent alkylène, linéaire ou ramifié, ayant de 1 à 12 atomes de carbone, l'un des liens valentiels (celui de R11) étant relié à l'atome de -NR10-, l'autre (celui de R4) étant relié à un atome de silicium;
    • * les radicaux R5 sont identiques ou différents, choisis parmi les radicaux alkyles linéaires ou ramifiés ayant 1 à 3 atomes de carbone et le radical phényle;
    • * le radical R6 représente un radical hydrogène ou le radical R5 ou O•.

    Pour les groupements de formule (III) :
    Figure imgb0006
    • ◆ R'4 est choisi parmi un radical trivalent de formule :
      Figure imgb0007
       où m représente un nombre de 2 à 20, et un radical trivalent de formule :
      Figure imgb0008
       où p représente un nombre de 2 à 20;
      • ◆ U' représente -O- ou NR12-, R12 étant un radical choisi parmi un atome d'hydrogène, un radical alkyle linéaire ou ramifié comportant 1 à 6 atomes de carbone;
      • * R5 et R6 ont les mêmes significations que celles données à propos de la formule (II); et
  4. (4)
    • le nombre de motifs ηsi sans groupement V est compris entre 50 et 250
    • le nombre de motifs ηSi avec un groupement V est compris entre 1 et 3
    • 0 ≤ w ≤ 10 et 8 < y < 448
It has now been found, and this is the subject of the present invention, for the use of a composition to provide a soft feel, a lack of yellowing and good hydrophilicity to textile materials said composition comprising at least one linear, cyclic or three-dimensional polyorganosiloxane of formula (I):
Figure imgb0001
 in which :
  1. (1) the symbols Z, identical or different, represent R 1 , and / or V;
  2. (2) the symbols R 1 , R 2 and R 3 , which are identical and / or different, represent a monovalent hydrocarbon radical chosen from linear or branched alkyl radicals having from 1 to 4 carbon atoms, the linear or branched alkoxy radicals having from 1-4 carbon atoms, phenyl and preferably hydroxy, ethoxy, methoxy or methyl;
  3. (3) the symbols V, identical and / or different functional groups, represent a group with sterically hindered piperidinyl function (s) chosen from:
    Figure imgb0002
     or
    Figure imgb0003
    For groups of formula (II):
    Figure imgb0004
    • R 4 is a divalent hydrocarbon radical chosen from:
      • Linear or branched alkylene radicals having 2 to 18 carbon atoms;
      • Alkylene-carbonyl radicals, the linear or branched alkylene portion of which contains 2 to 20 carbon atoms;
      • Alkylene-cyclohexylene radicals in which the linear or branched alkylene part contains 2 to 12 carbon atoms and the cyclohexylene part comprises an OH group and optionally 1 or 2 alkyl radicals having 1 to 4 carbon atoms;
      • Radicals of formula -R 7 -O-R 7 in which the radicals R 7, which may be identical or different, represent alkylene radicals having 1 to 12 carbon atoms;
      • Radicals of formula -R 7 -O-R 7 in which the radicals R 7 have the meanings indicated above and one or both of them are substituted by one or two group (s) -OH;
      • The radicals of formula -R 7 -COO-R 7 in which the radicals R 7 have the meanings indicated above;
      • The radicals of formula -R 8 -O -R 9 -O-CO-R 8 in which the radicals R 8 and R 9, which are identical or different, represent alkylene radicals having 2 to 12 carbon atoms and the radical R 9 is optionally substituted with a hydroxyl radical;
      • U represents -O- or -NR 10 -, R 10 being a radical chosen from a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms and a divalent radical of formula:
        Figure imgb0005
      in which R 4 has the meaning indicated above, R 5 and R 6 have the meanings given below and R 11 represents a linear or branched divalent alkylene radical having from 1 to 12 carbon atoms, one of the valence bonds (that of R 11 ) being connected to the atom of -NR 10 -, the other (that of R 4 ) being connected to a silicon atom;
    • the radicals R 5 are identical or different, chosen from linear or branched alkyl radicals having 1 to 3 carbon atoms and the phenyl radical;
    • the radical R 6 represents a hydrogen radical or the radical R 5 or O •.

    For groups of formula (III):
    Figure imgb0006
    • R '4 is chosen from a trivalent radical of formula:
      Figure imgb0007
       where m represents a number from 2 to 20, and a trivalent radical of formula:
      Figure imgb0008
       where p represents a number from 2 to 20;
      • U 'represents -O- or NR 12 -, R 12 being a radical chosen from a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms;
      • R 5 and R 6 have the same meanings as those given in relation to formula (II); and
  4. (4)
    • the number of units ηsi without grouping V is between 50 and 250
    • the number of units ηSi with a group V is between 1 and 3
    • 0 ≤ w ≤ 10 and 8 <y <448

L'huile silicone utilisée dans le cadre de l'invention ne nécessite notamment pas la présence d'autres fonctions pour apporter des propriétés hydrophiles au matériau textile traité. Toutefois, si on souhaite obtenir une hydrophilie supérieure à celle intrinsèque au matériau avant traitement, l'huile silicone utilisée peut contenir d'autres fonctions favorisant cette propriété.The silicone oil used in the context of the invention does not require in particular the presence of other functions to provide hydrophilic properties to the treated textile material. However, if it is desired to obtain a hydrophilicity greater than that intrinsic to the material before treatment, the silicone oil used may contain other functions promoting this property.

Selon un mode préféré de l'utilisation de l'invention, le polyorganosiloxane de formule (I) mis en oeuvre est linéaire.According to a preferred embodiment of the use of the invention, the polyorganosiloxane of formula (I) used is linear.

Selon un autre mode préféré, le groupement fonctionnel V du polyorganosiloxane de formule (I) mis en oeuvre est choisi parmi les groupements fonctionnels de formule (II).According to another preferred embodiment, the functional group V of the polyorganosiloxane of formula (I) used is chosen from the functional groups of formula (II).

Quelle que soit la constitution choisie pour la composition contenant le polyorganosiloxane, le procédé de traitement peut être mis en oeuvre sur des matières de forme tissée, non tissée ou tricotée. Les fibres de ces matières sont au moins partiellement hydrophiles, et cette hydrophilie est conservée après traitement à la silicone selon l'invention nonobstant la nature hydrophobe de son squelette.Regardless of the constitution chosen for the composition containing the polyorganosiloxane, the treatment process may be carried out on woven, non-woven or knitted form materials. The fibers of these materials are at least partially hydrophilic, and this hydrophilicity is preserved after treatment with silicone according to the invention, notwithstanding the hydrophobic nature of its skeleton.

Les matières au moins partiellement hydrophiles peuvent être notamment constituées ou à base de coton, lin, laine, viscose, rayonne, chanvre, soie ou d'un mélange de ces matières. Ces matières peuvent être éventuellement mélangées avec d'autres matières peu ou non hydrophiles telles que le polyester (par exemple mélange coton-polyester), la kératine, polypropylène, polyéthylène, polyuréthanne, polyamide, acétate de cellulose.The at least partially hydrophilic materials may consist in particular of or based on cotton, linen, wool, viscose, rayon, hemp, silk or a mixture of these materials. These materials may be optionally mixed with other low or non-hydrophilic materials such as polyester (eg cotton-polyester blend), keratin, polypropylene, polyethylene, polyurethane, polyamide, cellulose acetate.

La composition contenant le polyorganosiloxane peut être préparée sous de nombreuses formes : liquide, gazeuse ou solide. Dans le cas d'une préparation liquide de la composition, celle-ci sera avantageusement aqueuse soit sous forme de solution, dispersion ou d'émulsion.The composition containing the polyorganosiloxane can be prepared in many forms: liquid, gaseous or solid. In the case of a liquid preparation of the composition, it will advantageously be aqueous in the form of solution, dispersion or emulsion.

De préférence, la composition est préparée sous forme d'émulsion aqueuse. Toutefois, la composition selon le procédé de l'invention peut être également utilisée en solution dans un solvant organique.Preferably, the composition is prepared in the form of an aqueous emulsion. However, the composition according to the process of the invention may also be used in solution in an organic solvent.

Les émulsions aqueuses sont généralement à base d'un mélange d'huile et d'eau, et sont préparées selon les méthodes classiques bien connues de l'homme du métier en utilisant des agents tensioactifs. Par exemple, les émulsions peuvent se faire par les méthodes dites directes ou par inversion. Leur réalisation est aisée et ne nécessite pas l'utilisation d'appareillage à haute vitesse d'agitation. Un appareillage à vitesse normale d'agitation peut-être utilisé.The aqueous emulsions are generally based on a mixture of oil and water, and are prepared according to standard methods well known to those skilled in the art using surfactants. For example, the emulsions can be done by the so-called direct methods or by inversion. Their production is easy and does not require the use of equipment with high stirring speed. Normal speed stirring apparatus may be used.

En général, les émulsions aqueuses préparées en accord avec l'invention contiennent de préférence entre 20 et 90% en poids d'eau par rapport à la masse totale des constituants de l'émulsion. Pour une meilleure application, les émulsions préparées en accord avec l'invention sont de préférence diluées pour contenir entre 95 et 99.5% en poids d'eau, par rapport au poids total de l'émulsion. Ces émulsions s'avèrent stables à température ambiante.In general, the aqueous emulsions prepared according to the invention preferably contain between 20 and 90% by weight of water relative to the total mass of the constituents of the emulsion. For a better application, the emulsions prepared according to the invention are preferably diluted to contain between 95 and 99.5% by weight of water, relative to the total weight of the emulsion. These emulsions are stable at room temperature.

L'application du polyorganosiloxane selon l'invention sur les matières à traiter peut être effectuée sous des formes très diverses. Les applications peuvent être réalisées par immersion, enduction, pulvérisation, impression, "foulardage" (padding en anglais), ou par tout autre moyen existant.The application of the polyorganosiloxane according to the invention to the materials to be treated can be carried out in very different forms. Applications can be made by immersion, coating, spraying, printing, padding, or any other existing means.

Par exemple, lorsque l'étoffe est traitée par une composition aqueuse contenant un polyorganosiloxane selon l'invention, on fait subir à ladite étoffe un traitement thermique pour chasser rapidement l'eau sous forme de vapeur.For example, when the fabric is treated with an aqueous composition containing a polyorganosiloxane according to the invention, said fabric is subjected to a heat treatment to quickly expel water in the form of steam.

La quantité de polyorganosiloxane déposée sur la matière à traiter varie selon la constitution et la fabrication de ladite matière. Les applications des compositions et notamment des émulsions aqueuses sur les matières traitées sont réalisées de telle sorte que l'augmentation de poids de la matière traitée n'excède pas 0.1 à 20% en poids par rapport au poids de la matière avant traitement. En général, les meilleurs résultats ont été observés avec une quantité de polyorganosiloxane comprise entre 0.1 et 2% en poids par rapport au poids de la matière à traiter.The amount of polyorganosiloxane deposited on the material to be treated varies according to the constitution and manufacture of said material. The applications of the compositions and in particular aqueous emulsions on the treated materials are carried out so that the increase in weight of the treated material does not exceed 0.1 to 20% by weight relative to the weight of the material before treatment. In general, the best results have been observed with a quantity of polyorganosiloxane of between 0.1 and 2% by weight relative to the weight of the material to be treated.

Les polyorganosiloxanes précédemment définis peuvent être préparés selon différents procédés; par exemple : distribution ou hydrosilylation.The previously defined polyorganosiloxanes may be prepared by different methods; for example: distribution or hydrosilylation.

Exemples.Examples.

Les exemples ci-dessous illustrent les propriétés des huiles silicones selon l'invention.The examples below illustrate the properties of the silicone oils according to the invention.

Les huiles sont testées en application sous forme d'émulsion aqueuse et les mesures d'hydrophilie, de non-jaunissement et d'évaluation du toucher sont effectuées selon les tests décrits ci-dessous.The oils are tested in application in the form of an aqueous emulsion and the measurements of hydrophilicity, non-yellowing and evaluation of the feel are carried out according to the tests described below.

□ Mesure de non-jaunissement (indice de blanc). □ Non-yellowness measurement (white index).

L'évaluation du jaunissement est réalisée par la mesure de la couleur du tissu (tissu éponge coton blanc au départ) après imprégnation avec l'huile silicone et traitement thermique 9 minutes à 150 °C.The evaluation of the yellowing is carried out by measuring the color of the fabric (white cotton terry cloth at the beginning) after impregnation with the silicone oil and heat treatment for 9 minutes at 150 ° C.

La mesure de couleur est faite sur un Sprectrophotocolorimètre ACS Sensor Il commercialisé par la société Datacolor. Les conditions de mesure sont l'emploi de l'illuminant D65, reproduisant la lumière du jour. A partir de la mesure de la couleur de l'échantillon de tissu, l'appareil calcule les valeurs de différents indices de blanc et de jaune, parmi lesquels nous utilisons l'indice de blanc CIE.The color measurement is made on a Sprectrophotocolorimeter ACS Sensor It sold by the company Datacolor. The measurement conditions are the use of illuminant D65, reproducing daylight. From the measurement of the color of the tissue sample, the instrument calculates the values of different indices of white and yellow, among which we use the CIE white index.

□ Test de toucher. □ Touch test.

Après application de l'huile, le tissu éponge coton est séché à l'air ambiant pendant 24 heures. Après un traitement thermique 1 minute 30 à 150 °C, le tissu est placé 24 heures en conditionnement ( 23 ± 2°C, 50 ± 5 % d'humidité relative).After applying the oil, the cotton terry cloth is dried in ambient air for 24 hours. After 1 minute heat treatment at 150 ° C, the fabric is placed 24 hours in conditioning (23 ± 2 ° C, 50 ± 5% relative humidity).

L'évaluation de la douceur se fait par un groupe de testeurs à qui on demande de classer les échantillons de tissu du plus rêche (note minimum = 1) au plus doux (note maximum = nombre total d'échantillons).The evaluation of the softness is done by a group of testers who are asked to classify the tissue samples from the rough (minimum score = 1) to the softest (maximum score = total number of samples).

□ Mesure d'hydrophilie. □ Hydrophilic measurement.

Après application de l'huile, le tissu polyester-coton (50/50) subit un traitement thermique de 5 minutes à 170°C. Il est ensuite conditionné 24 heures ( 23 ± 2 °C, 60 ± 5 % humidité relative).After application of the oil, the polyester-cotton fabric (50/50) undergoes a heat treatment of 5 minutes at 170 ° C. It is then conditioned for 24 hours (23 ± 2 ° C, 60 ± 5% relative humidity).

Les mesures d'hydrophilie sont données par le test TEGEWA dans lequel on mesure le temps d'absorption d'une goutte d'eau déposée à la surface du tissu. Plus le temps est court, plus le tissu est hydrophile.The hydrophilicity measurements are given by the TEGEWA test in which the absorption time of a drop of water deposited on the surface of the fabric is measured. The shorter the time, the more the tissue is hydrophilic.

□ Préparation des émulsions. □ Preparation of emulsions.

Les huiles silicones des émulsions testées E1 à E7 ont pour structure :

Figure imgb0009
The silicone oils of the emulsions tested E1 to E7 have the following structure:
Figure imgb0009

Le nombre de motifs D et de motifs aminés des huiles utilisées est précisé dans le tableau I.The number of D units and amino units of the oils used is specified in Table I.

Les émulsions sont préparées en mettant en oeuvre une méthode d'émulsification par inversion, et ont la composition suivante: 20 g d'huile silicone testée, 8 g de tensioactif (alcool gras en C13E6), une quantité d'acide acétique glacial stoechiométriquement nécessaire à la neutralisation de l'amine et le complément à 100g avec de l'eau. Tableau I. Emulsion b a Exemples E1 * 100 0,5 E2 100 1 E3 100 2 E4 * 100 4 E5 250 2,5 Contre - exemples E6 350 9 E7 450 16,5 * E1 et E4 ne font pas partie de l'invention. The emulsions are prepared using an inversion emulsification method, and have the following composition: 20 g of silicone oil tested, 8 g of surfactant (C 13 E 6 fatty alcohol), an amount of glacial acetic acid stoichiometrically necessary for the neutralization of the amine and the complement at 100 g with water. <u> Table I. </ u> Emulsion b at Examples E1 * 100 0.5 E2 100 1 E3 100 2 E4 * 100 4 E5 250 2.5 Counterexamples E6 350 9 E7 450 16.5 * E 1 and E 4 do not form part of the invention.

Les évaluations ont été réalisées sur des textiles traités à 0,6% en poids d'huile silicone. Les émulsions sont appliquées sur le tissu par foulardage.The evaluations were carried out on textiles treated with 0.6% by weight of silicone oil. The emulsions are applied to the fabric by padding.

Les propriétés des tissus traités avec les différentes émulsions E1 à E7 ont été évaluées et comparées entre elles par série. Les résultats obtenus pour chaque série ne sont pas des valeurs absolues mais des valeurs relatives comparables au sein d'une même série.The properties of the tissues treated with the various emulsions E1 to E7 were evaluated and compared with each other by series. The results obtained for each series are not absolute values but comparable relative values within the same series.

Première série.First series.

EmulsionEmulsion Non - jaunissementNo - yellowing E1E1 52,752.7 E2E2 53,253.2 E3E3 52,152.1 E4E4 53,953.9 TémoinWitness 54,254.2

Cette série met en évidence le non-jaunissement des tissus traités avec une émulsion à base d'huiles silicones selon l'invention; en effet, l'indice de blanc est voisin de celui d'un tissu non traité.This series demonstrates the non-yellowing of the treated fabrics with an emulsion based on silicone oils according to the invention; indeed, the white index is close to that of an untreated fabric.

Deuxième série.Second series.

EmulsionEmulsion ToucherTo touch Hydrophilie (s)Hydrophilic (s) E1E1 33 6,56.5 E2E2 66 77 E3E3 1010 8,58.5 E5E5 77 9,79.7 E6E6 1111 15,815.8 E7E7 1212 17,917.9

Cette série met en évidence les propriétés hydrophiles et adoucissantes des huiles selon l'invention.This series highlights the hydrophilic and softening properties of the oils according to the invention.

Troisième série.Third series.

EmulsionEmulsion ToucherTo touch Hydrophilie (s)Hydrophilic (s) E1E1 11 6,16.1 E3E3 66 7,47.4 E4E4 44 8,58.5 E7E7 88 18,518.5

Cette série, comme la précédente, met en évidence les propriétés hydrophiles et adoucissantes des huiles selon l'invention.This series, like the previous one, demonstrates the hydrophilic and softening properties of the oils according to the invention.

Claims (8)

  1. Use of a composition comprising at least one silicone oil carrying a hindered amino functional group for treating a textile material with the aim of providing a soft feel, absence of yellowing and good hydrophilicity to the said textile material, the said composition comprising at least one linear, cyclic or three-dimensional polyorganosiloxane of formula (I):
    Figure imgb0018
     in which:
    (1) the symbols Z, which are identical or different, represent R1, and/or V;
    (2) the symbols R1, R2 and R3, which are identical and/or different, represent a monovalent hydrocarbon radical chosen from linear or branched alkyl radicals having from 1 to 4 carbon atoms, linear or branched alkoxy radicals having from 1 to 4 carbon atoms, a phenyl radical and, preferably, a hydroxyl radical, an ethoxy radical, a methoxy radical or a methyl radical;
    (3) the symbols V, functional groups which are identical and/or different, represent a group containing a sterically hindered piperidinyl functional group or groups chosen from:
    Figure imgb0019
     or
    Figure imgb0020
     For the groups of formula (II):
    Figure imgb0021
    * R4 is a divalent hydrocarbon radical chosen from:
    ◆ linear or branched alkylene radicals having 2 to 18 carbon atoms;
    ◆ alkylene-carbonyl radicals in which the linear or branched alkylene portion contains 2 to 20 carbon atoms;
    ◆ alkylene-cyclohexylene radicals in which the linear or branched alkylene portion contains 2 to 12 carbon atoms and the cyclohexylene portion contains an OH group and optionally 1 or 2 alkyl radicals having 1 to 4 carbon atoms;
    ◆ radicals of formula -R7-O-R7 in which the radicals R7, which are identical or different, represent alkylene radicals having 1 to 12 carbon atoms;
    ◆ radicals of formula -R7-O-R7 in which the radicals R7 have the meanings indicated above and one of them or both of them are substituted by one or two -OH group or groups;
    ◆ radicals of formula -R7-COO-R7 in which the radicals R7 have the meanings indicated above;
    ◆ radicals of formula -R8-O-R9-O-CO-R8 in which the radicals R8 and R9, which are identical or different, represent alkylene radicals having 2 to 12 carbon atoms and the radical R9 is optionally substituted by a hydroxyl radical;
    ◆ U represents -O- or -NR10-, R10 being a radical chosen from a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms and a divalent radical of formula:
    Figure imgb0022
    in which R4 has the meaning indicated above, R5 and R6 have the meanings indicated below and R11 represents a linear or branched divalent alkylene radical having from 1 to 12 carbon atoms, one of the valency bonds (that of R11) being linked to the atom of -NR10-, the other (that of R4) being linked to a silicon atom;
    * the radicals R5, which are identical or different, are chosen from linear or branched alkyl radicals having 1 to 3 carbon atoms and the phenyl radical;
    * the radical R6 represents a hydrogen radical or the radical R5 or O•.
    For the groups of formula (III):
    Figure imgb0023
    ◆ R'4 is chosen from a trivalent radical of formula:
    Figure imgb0024
     where m represents a number from 2 to 20, and a trivalent radical of formula:
    Figure imgb0025
     where p represents a number from 2 to 20;
    ◆ U' represents -O- or NR12-, with R12 being a radical chosen from a hydrogen atom, a linear or branched alkyl radical containing 1 to 6 carbon atoms;
    * R5 and R6 have the same meanings as those given with respect to the formula (II); and
    (4)
    - the number of units ηSi with no group V is between 50 and 250, and the number of units ηSi with a group V is between 1 and 3,
    - 0 ≤ w ≤ 10 and 8 ≤ y ≤ 448.
  2. Use of a composition comprising at least one silicone oil carrying a hindered amino functional group for treating a textile material with the aim of providing a soft feel, absence of yellowing and good hydrophilicity to the said textile material according to Claim 1, characterized in that the polyorganosiloxane of formula (I) is linear.
  3. Use of a composition comprising at least one silicone oil carrying a hindered amino functional group for treating a textile material with the aim of providing a soft feel, absence of yellowing and good hydrophilicity to the said textile material according to either of the preceding claims, characterized in that V is chosen from the functional groups of formula (II).
  4. Use of a composition comprising at least one silicone oil carrying a hindered amino functional group for treating a textile material with the aim of providing a soft feel, absence of yellowing and good hydrophilicity to the said textile material according to any one of the preceding claims, characterized in that the composition containing the polyorganosiloxane is in liquid form.
  5. Use of a composition comprising at least one silicone oil carrying a hindered amino functional group for treating a textile material with the aim of providing a soft feel, absence of yellowing and good hydrophilicity to the said textile material according to Claim 1, characterized in that the composition containing the polyorganosiloxane in liquid form is an aqueous emulsion.
  6. Use of a composition comprising at least one silicone oil carrying a hindered amino functional group for treating a textile material with the aim of providing a soft feel, absence of yellowing and good hydrophilicity to the said textile material according to any one of the preceding claims, characterized in that the said textile material is a woven, knitted or nonwoven material, the said material being at least intrinsically hydrophilic.
  7. Use of a composition comprising at least one silicone oil carrying a hindered amino functional group for treating a textile material with the aim of providing a soft feel, absence of yellowing and good hydrophilicity to the said textile material according to any one of the preceding claims, characterized in that the said textile material is based on cotton, flax, wool, viscose, rayon, hemp, silk or a mixture of these materials.
  8. Use of a composition comprising at least one silicone oil carrying a hindered amino functional group for treating a textile material with the aim of providing a soft feel, absence of yellowing and good hydrophilicity to the said textile material according to any one of the preceding claims, characterized in that the quantity of polyorganosiloxane deposited on the said textile material corresponds to a quantity of between 0.1 and 2% by weight relative to the weight of the treated dry textile material.
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FR0012739A FR2815049B1 (en) 2000-10-05 2000-10-05 PROCESS FOR SOFTENING, MAKING HYDROPHILIC AND NON-YELLOWING A TEXTILE MATERIAL, IN WHICH A COMPOSITION COMPRISING A POLYORGANOSILOXANE IS USED
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