EP0546231B1 - Process for softening and providing hydrophilic textile material using a composition containing polyorganisiloxane - Google Patents

Abstract

Textiles substrates, e.g., cotton fabrics, are conditioned to impart good feel and hydrophilicity thereto, by impregnating same with an effective conditioning amount of a polydiorganosiloxane containing, per mole, at least two structural units of the formula: XRaSiO(3-a)/2 in which X is a radical: (* CHEMICAL STRUCTURE *) R' is a linear or branched C2-C8 alkylene radical; R" is a hydrogen atom or a C1-C6 alkyl radical; the radicals R, which may be identical or different, are each a phenyl radical, a 3,3,3-trifluoropropyl radical or an alkyl radical having from 1 to 4 carbon atoms; a is either 1 or 2; n is a number ranging from 1 to 10; and t is 0 or 1.

Description

The present invention relates to a process for packaging textile materials to give them a pleasant touch by hand, that is to say softness, at the same time as good hydrophilicity.

The literature describes such processes for conditioning textile materials. US-A-4 409 267 describes the use of a mixed polyorganosiloxane carrying a part of primary amine function (s) or of secondary or tertiary amine function (s) (s) substituted (s) for example by residues containing an OH or O-alkyl group, and on the other hand of alkylene polyoxide function (s) as additive of a composition for the treatment of textile materials. GB-A-2 201 696 relates to a method for treating textile materials using a polyorganosiloxane carrying quaternary ammonium function (s) which does not have a substitution containing an OH or O-alkyl group.

EP-A-0 459 822 describes homogeneous and transparent detergent compositions comprising a polyorganosiloxane with secondary or tertiary amine function (s) substituted for example by residues containing an OH group, said group silicone being used in mixture with a softening agent based on a quaternary ammonium salt.

An advantage of the process according to the present invention is that it makes it possible to obtain textile materials having the two properties (softness and hydrophilicity) mentioned above.

Another advantage of the process according to the present invention is that it makes it possible to obtain textile materials exhibiting slight yellowing.

Another advantage of the process according to the present invention stems from the fact that it can be implemented with a polydiorganosiloxane of easy industrial preparation and stable in storage.

• · le polydiorganosiloxane utilisé a pour formule générale:
  
  dans laquelle :
  • X est choisi parmi les radicaux :
    
    • · R' représentant un groupement alkylène en C₂ à C₈, linéaire ou ramifié,
    • · R" représentant un atome d'hydrogène ou un groupement alkyle en C₁ à C₆,
    • · avec n étant compris entre 1 et 10, bornes comprises et t étant 0 ou 1,
  • les radicaux R, identiques ou différents, sont choisis parmi le radical phényle, trifluoro-3,3,3 propyle et un radical alkyle ayant de 1 à 4 atomes de carbone,
  • Y peut représenter un radical X ou un radical R,
  • p et q sont des nombres entiers positifs tels que le polyorganosiloxane utilisé comprenne en moyenne par molécule de 50 à 150 atomes de silicium et 2 à 10 groupements X;
• · 100 g du polyorganosiloxane défini ci-avant comprennent de 25 à 250 meq d'azote aminé.

It has therefore now been found, and this is what is the subject of the present invention, a process for conditioning textile materials to give them a pleasant feel and good hydrophilicity, in which the textile materials are brought into contact with a composition. comprising a polydiorganosiloxane carrying substituted amine function (s), characterized by the following points:

• · The polydiorganosiloxane used has the general formula:
  
  in which :
  • X is chosen from the radicals:
    
    • · R 'representing a C alkyl to C₈ alkylene group, linear or branched,
    • · R "representing a hydrogen atom or a C₁ to C₆ alkyl group,
    • · With n being between 1 and 10, limits included and t being 0 or 1,
  • the radicals R, which are identical or different, are chosen from the phenyl radical, trifluoro-3,3,3 propyl and an alkyl radical having from 1 to 4 carbon atoms,
  • Y can represent an X radical or an R radical,
  • p and q are positive integers such that the polyorganosiloxane used comprises on average per molecule from 50 to 150 silicon atoms and 2 to 10 X groups;
• · 100 g of the polyorganosiloxane defined above comprise from 25 to 250 meq of amino nitrogen.

The polydiorganosiloxane used can optionally comprise monoorganosiloxy units RSi _1.5 and / or SiO₂ units, but if they exist, these units are in the proportion of at most 2% relative to the number of diorganosiloxy units R₂SiO, the meaning of R having been specified above.

Generally, the composition containing the polydiorganosiloxane defined above is an aqueous composition, in the form of an emulsion.

The nitrogen of the group X defined above can be salified, for example with an organic acid such as acetic acid.

n

= 1 et

R"

= un atome d'hydrogène,

t

= 1.

Advantageously, the polydiorganosiloxane used, in its group X previously defined, has the following values:

not

= 1 and

R "

= a hydrogen atom,

t

= 1.

On the other hand if n is greater than 1, R "advantageously represents a C₁ to C₆ alkyl group.

The polysiloxanes previously defined can be prepared in a similar manner to those described in American patent US Pat. No. 3,389,160, but using diethanolamine in place of dimethylamine.

To prepare the emulsions containing the polysiloxane defined above, the procedure is carried out according to conventional methods using water and known surfactants, with stirring.

The method according to the present invention can be implemented on any woven or knitted fabric and even on those made of nonwoven.

The fibers used for the production of these fabrics can be in particular cotton, polyester, polyamide, viscose, polyacrylate, wool, linen, cellulose acetate, as well as elastomeric fibers. It is of course possible to use mixtures of fibers.

In the process according to the present invention, to apply the composition comprising the polysiloxane to the fabric to be treated, conventional techniques from the textile industry are used, in particular by using the so-called "padding" impregnation technique. ).

When the fabric is treated with an aqueous composition (for example an emulsion), this fabric is then subjected to a heat treatment in order to rapidly expel the water in the form of vapor.

Generally the amount of polysiloxane deposited on the treated fabric corresponds to an amount of between 0.1 and 1% by weight relative to the weight of the dry fabric treated.

• 1.- un test organoleptique, c'est-à-dire de toucher de l'étoffe à la main par 6 personnes et classement,
• 2.- un test mécanique, dit de détermination de coefficient de friction statique, effectué sur un fil polyester, ce test étant connu par les spécialistes du textile.

The tests used to assess the softness of the fabrics treated are for example:

• 1.- an organoleptic test, that is to say to touch the fabric by hand by 6 people and classification,
• 2.- a mechanical test, known as a static friction coefficient determination, carried out on a polyester thread, this test being known by textile specialists.

For the implementation of this test, the polyester yarn is coated (by a known technique) with a solution at 3% by weight of the polysiloxane with groups X previously defined in trichloroethane. The coated wire is then dried continuously at 180 ° C. in a hot air oven at a speed of 200 m per minute (200 m / min). A wire is thus obtained on which the deposit of polydiorganosiloxane product corresponds to 0.5% by weight relative to the weight of the dry wire. The wire is then stored for 48 hours at 22 ° C, at 65% relative humidity. The friction coefficient of the wire obtained is then determined on the ROTHSCHILD F device. Meter at the speed of 1 cm / min (centimeter per minute).

The test used to evaluate the hydrophilicity of the fabrics treated according to the method of the present invention is a test consisting in depositing a piece of treated fabric (25.4 x 25.4 mm) parallel to the surface of the distilled water located in a beaker and to measure the time between the deposition of this fabric on the water and the beginning of its descent into the water. This test is called "sinking test" in English.

The counterexamples and the examples which follow illustrate the preparation of polysiloxanes containing groups X and their use in a process for conditioning textile materials. The use of the product obtained according to Example 3 illustrates the process according to the present invention.

AGAINST EXAMPLE 1 :

• 1.a.- In a reactor equipped (with stirring, thermometer, dropping funnel, coolant, dry nitrogen introduction system) are introduced:
  • 504.30 g (4.42 moles) of allylglycidylether,
  • 289 microliters of a solution in hexane ((9.05% by weight of platinum metal) of a complex of platinum prepared from chloroplatinic acid and 1,3-divinyl-1,1-tetramethyl- 3.3 disiloxane according to US-A-3,814,730.
  
  The reaction mass is brought and maintained by heating to 100 ° C. and 1700 g of a random SiH copolymer of average formula are added over 2 hours 30 minutes.
  
  measuring 200.17 meq / 100 g as a SiH function (meq = milliequivalent).
  After 5 hours 30 of reaction, it can be seen, by assaying the residual SiH using butanolic potassium hydroxide, that the rate of transformation of the SiH functions is quantitative, that is to say that the SiH of the starting polymer have been transformed into:
  
  After elimination by distillation at 120 ° C. (under absolute pressure of 3.3 KPa) of the excess reagent (allylglycidylether), 2070 g of organosiloxane oil are obtained, titrating 156.25 meq / 100 g in glycidyl function.
• 1.b.- In another reactor are introduced 317 g (3.01 moles) of diethanolamine and the reaction medium is brought to 120 ° C. 30.1800 g of the organosiloxane derivative with glycidyl function prepared in 1.a. are then added over 2 hours.
  After 6 hours 30 of reaction, 2113.4 g of a pale yellow viscous oil are obtained, with a viscosity of 3300 mPa.s at 23 ° C. By titration of the diethanolamine in the final reaction medium (by polarography), a quantitative transformation rate of the diethanolamine is determined.
  A nuclear magnetic resonance (NMR) analysis of the proton and silicon is performed. The interpretation of the spectra confirms the structure of the expected product, that is to say a product of average formula:
  
  with Me = -CH₃

AGAINST EXAMPLE 2 :

• 2.a.- The same operations are carried out as in example 1.a. using:
  • 1500g of a random SiH copolymer of formula:
    
    measuring 365.5 meq / 100 g based on SiH,
  • 806.15 g (7.07 moles) of allylglycidylether,
  • 331.5 »l (microliters) of platinum catalyst solution defined in 1.a.
  
  After 5 hours of reaction, the SiH transformation rate is quantitative. After removal of the excess allyl glycidyl ether, 2112 g of oil titrating 251.44 meq / 100 g in glycidyl function are obtained.
• 2.b.- The same operations are carried out as in example 1.b., using:
  • 1700 g of the organosiloxane derivative with glycidyl function prepared in 2.a.,
  • 482 g (4.23 moles) of diethanolamine.
  
  After 6 hours 30 of reaction, 2179.5 g of a viscous yellow oil are obtained, the viscosity of which at 25 ° C. is 23000 mPa.s. The various analyzes carried out confirm the structure of the product sought, namely:
  

EXAMPLE 3 (according to the invention):

• 3.a.- The same operations are carried out as in Example 1.a. using:
  • 121.35 g (1.06 mole) of allylglycidylether,
  • 1340 g of a random SiH copolymer of formula:
    
    measuring 61.11 meq / 100 g based on SiH,
  • 228 »l of platinum catalyzing solution defined in 1.a.
  
  The reaction medium is brought to and maintained at 100 ° C. After 2 hours of heating, the transformation rate of the SiH functions is quantitative. After elimination of the excess of allylglycidylether, 1423 g of organosiloxane oil is obtained, titrating 54.7 meq / 100 g in glycidyl function.
• 3.b.- The same operations are carried out as in example 1.b., using:
  • 150 g of the organosiloxane derivative with glycidyl function prepared in 3.a.,
  • 8.92 g (0.078 mole) of diethanolamine.
  
  After 8 hours of reaction, 158.16 g of an ocher viscous oil with a viscosity of 9500 mPa.s are obtained.
  The various analyzes carried out confirm the structure of the product obtained, namely a product in which the SiH functions (of the product used in 3.a.) have been replaced by - Si - C₂H₄ - CH₂ - O - CH₂ - CH (OH ) - CH₂- N (C₂H₄OH) ₂.

COUNTER EXAMPLE 4 :

• 4.a.- We operate under the same conditions as in Example 1.a., using:
  • 350 g of a random SiH copolymer of formula:
    
    measuring 9.48 meq / 100 g based on SiH,
  • 11.34 g (1 mole) of allylglycidylether,
  • 46.55 ”l of platinum catalyst solution.
  
  After 2 hours of reaction at 100 ° C., the degree of transformation of the SiH functions is quantitative. After elimination of the excess reagent, 350.2 g of organosiloxane oil titrating 9.5 meq / 100 g are obtained as glycidyl function.
• 4.b.- The same operations are carried out as in Example 1.b., using:
  • 2.2 g (0.019 mole) of diethanolamine.
  • 200 g of the organosiloxane derivative with glycidyl function prepared in 4.a.,
  After 5 hours of heating at 125 ° C, an ocher oil with a viscosity of 16,400 mPa.s at 25 ° C is obtained. average :
  

AGAINST EXAMPLE 5 :

• 5.a.- According to the operating conditions identical to those of Example 4.a., an organosiloxane oil of medium structure is synthesized:
  
  measuring 3.7 meq / 100 g in glycidyl function.
• 5.b.- Under the conditions analogous to those of Example 4.b., the diethanolamine is condensed on the oil with a glycidyl function obtained in 5.a. The product corresponding to that according to 5.a. is thus obtained, but in which Z has been replaced by: -C₂H₄-CH₂-O-CH₂-CH (OH) -CH₂-N (C₂H₄OH) ₂.

AGAINST EXAMPLE 6 :

titrant 36,6 meq/100 g en fonction glycidyle.According to operating conditions similar to those of Example 4.b., the diethanolamine is condensed on an organosiloxane oil of average formula:

measuring 36.6 meq / 100 g in glycidyl function.

A product is thus obtained whose average formula corresponds to the above product, but in which Z has been replaced by :-( CH₂) ₃-O-CH₂-CH (OH) -CH₂-N (C₂H₄OH) ₂.

Table 1 below summarizes the characteristics of the organosiloxane oils with diethanolamine functionality synthesized in the counterexamples and examples 1 to 6. TABLE 1 Organosiloxane derivatives according to Average number of Si / mole of polymer Average number of X / mole of polymer Amine quantity in meq / 100 g of polymer counterexample 1 17 2.4 142 counterexample 2 17 4.5 210 3 114 5 46 counterexample 4 388 2.7 9.4 counterexample 5 588 1.6 3.7 counterexample 6 304 8.9 40 X = - (CH₂) ₃-O-CH₂CH (OH) -CH₂-N (C₂H₄OH) ₂.

- APPLICATION TESTS WITH THE PRODUCTS ACCORDING TO COUNTER-EXAMPLES AND EXAMPLES 1 TO 6 :

• + a) - avec les produits selon les contre-exemples 1 et 2, des émulsions ont été préparées en opérant ainsi :
  • . on mélange (en poids) 20% de TERGITOL TMN 10,
    5 % d'acide acétique glacial
    55 % d'eau.
    dans un ballon équipé d'un agitateur "tripales", de 5 cm d'écartement entre les extrémités de deux pales, et tournant à 550 tours à la minute.
  • . A cette solution agitée on ajoute alors lentement 20 % (en poids) du produit selon le contre-exemple 1 ou 2.
• + b) - Avec les produits selon les contre-exemples 4 et 5, des émulsions ont été préparées en opérant ainsi :
  • . on mélange dans un mélangeur de laboratoire de marque SILVERSON :
    100 % du produit selon les contre-exempls 4 ou 5,
    0,55% de TERGITOL TMN 6,
    0,55% de RENEX 30.
  • . on ajoute alors lentement et en continu, à cette masse bien agitée :
    88,9%d'eau.
  en mettant en oeuvre la "technique d'inversion de phase".
• + c) - Avec le produit obtenu selon le contre-exemples 6, on opère de la même façon qu'en b), mais en utilisant 73,9 % d'eau et on ajoute, après avoir introduit l'eau, 15 % de propane-2 ol-.
• + d) - Avec le produit obtenu selon l'exemples 3 on prépare deux types d'émulsions :
  • d.1. - une première émulsion en opérant selon a) mais avec :
    10% de TERGITOL TMN 6 et
    70% d'eau,
  • d.2. - une deuxième émulsion en opérant selon b) mais sans RENEX 30 et avec :
    0,8% de TERGITOL TMN 6 et
    89,2 % d'eau.

Emulsions were prepared from the products obtained in the counterexamples and examples 1 to 6.

• + a) - with the products according to counterexamples 1 and 2, emulsions were prepared by operating as follows:
  • . 20% of TERGITOL TMN 10 is mixed (by weight),
    5% glacial acetic acid
    55% water.
    in a flask fitted with a "three-bladed" agitator, 5 cm apart between the ends of two blades, and rotating at 550 revolutions per minute.
  • . To this stirred solution is then slowly added 20% (by weight) of the product according to counterexample 1 or 2.
• + b) - With the products according to counterexamples 4 and 5, emulsions were prepared by operating as follows:
  • . mixed in a SILVERSON brand laboratory mixer:
    100% of the product according to counterexamples 4 or 5,
    0.55% of TERGITOL TMN 6,
    0.55% of RENEX 30.
  • . then slowly and continuously added to this well-stirred mass:
    88.9% water.
  by implementing the "phase inversion technique".
• + c) - With the product obtained according to counterexamples 6, the procedure is the same as in b), but using 73.9% of water and, after having introduced the water, 15% propan-2 ol-.
• + d) - With the product obtained according to examples 3, two types of emulsions are prepared:
  • d.1. - a first emulsion by operating according to a) but with:
    10% of TERGITOL TMN 6 and
    70% water,
  • d.2. - a second emulsion by operating according to b) but without RENEX 30 and with:
    0.8% of TERGITOL TMN 6 and
    89.2% water.

At the end, the emulsion is brought to pH 6 with acetic acid.

The products, having the trade names TERGITOL TMN 10, TERGITOL TMN 6 and RENEX 30 are widely marketed surfactants known to those preparing emulsions.

TERGITOL TMN 6 comprises as active product a trimethylnonanol comprising 6 oxyethylene units.

TERGITOL TMN 10 comprises as active product a trimethylnonanol comprising 10 oxyethylene units.

These two products are marketed by UNION CARBIDE.

RENEX 30, manufactured by ICI, comprises as active product a tridecylol comprising 10 oxyethylene units.

• organoleptique (sur coton éponge),
• de détermination du coefficient de friction statique,
• d'hydrophilie, par trempage de l'étoffe (coton éponge) dans un bécher précisés dans la description ont été effectués avec les émulsions préparées ci-avant.

The tests :

• organoleptic (on cotton terry),
• determining the coefficient of static friction,
• hydrophilicity, by soaking the fabric (cotton terry) in a beaker specified in the description were made with the emulsions prepared above.

The results obtained are reported in Table 2 below. TABLE 2 Organosiloxane derivatives according to Counterexample 1 Counterexample 2 Example 3 Counterexample 4 Counter Example 5 Counterexample 6 organoleptic touch NOT NOT AT AT AT AT friction coefficient 0.70 0.21 0.17 0.10 0.45 0.14 hydrophilic time in seconds Sinking test 4 4 20 > 300 > 300 > 300 A = pleasant, soft touch,
N = not pleasant to touch, without softness.

It appears that the product prepared according to Example 3 is the one that best responds to the desired application, that is to say a soft feel and good hydrophilicity, when the fabric is cotton.

With regard to this product according to Example 3, it appeared that the emulsion prepared according to d.1. gave a white cotton fabric better resistance to yellowing than the emulsion prepared according to d.2.

Claims (6)

1. Method for conditioning textiles to give them a pleasant feel and good hydrophilicity, in which the textiles are placed in contact with a composition comprising a polydiorganosiloxane bearing substituted amine function(s), characterized by the following points:

   · the polydiorganosiloxane used has the general formula:

   

   in which:

   - X is chosen from the radicals:

   

   · R' representing a linear or branched C₂ to C₈ alkylene group,

   · R'' representing a hydrogen atom or a C₁ to C₆ alkyl group,

   · with n being between 1 and 10, limits inclusive, and t being 0 or 1,

   - the radicals R, which may be identical or different, are chosen from the phenyl radical, the 3,3,3-trifluoro-propyl radical and an alkyl radical having from 1 to 4 carbon atoms,

   - Y may represent a radical X or a radical R,

   - p and q are positive integers, such that the polyorganosiloxane used comprises on average per molecule from 50 to 150 silicon atoms and 2 to 10 groups X;

   · 100 g of the polyorganosiloxane defined above comprise from 25 to 250 meq of amino nitrogen.
2. Method according to Claim 1, in which:
      n = 1
      R'' = a hydrogen atom,
   and t = 1
3. Method according to either of the preceding claims, in which the nitrogen of the group X is salified.
4. Method according to any one of the preceding claims, in which the composition used is an aqueous composition.
5. Method according to any one of the preceding claims, in which the composition used is an emulsion.
6. Method according to any one of the preceding claims, characterized in that it is carried out on a cotton fabric.