EP0546231A1 - Process for softening and providing hydrophilic textile material using a composition containing polyorganisiloxane - Google Patents

Abstract

Process for conditioning textile materials, in particular to give them a pleasant feel and good hydrophilicity, characterized in that the textile materials are brought into contact with a composition comprising a polydiorganosiloxane having per mole at least two units of general formula: <IMAGE> in which: X is chosen from the radicals: <IMAGE> R 'representing a C2 to C8 alkylene group, linear or branched, R' 'representing a hydrogen atom or a C1 to C6 alkyl group, the radicals R, 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, a is chosen from 1 and 2, n is between 1 and 10, limits included , - t = 0 or 1.

Description

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

An advantage of the process according to the present invention is that it makes it possible to obtain textile materials having the two properties announced 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 comes from the fact that it can be implemented with a polydiorganosiloxane of easy industrial preparation and stable in storage.

dans laquelle :

• - X est choisi parmi les radicaux :
  
  • . R' représentant un groupement alkylène en C₂ à Ca, linéaire ou ramifié,
  • . R" représentant un atome d'hydrogène ou un groupement alkyle en Ci à Cs,
• - 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,
• - a est choisi parmi 1 et 2,
• - n est compris entre 1 et 10, bornes comprises,
• - t = 0 ou 1.

It has therefore now been found, and this is what is the subject of the present invention, a process for conditioning textile materials, in particular to give them a pleasant feel and good hydrophilicity, characterized in that the textile materials are placed contact with a composition comprising a polydiorganosiloxane having per mole at least two units of general formula:

in which :

• - X is chosen from the radicals:
  
  • . R ′ representing a C ₂ to Ca alkylene group, linear or branched,
  • . R "representing a hydrogen atom or a C1 to Cs alkyl group,
• the radicals R, which are identical or different, are chosen from the phenyl, trifluoro-3,3,3 propyl radical and an alkyl radical having from 1 to 4 carbon atoms,
• - a is chosen from 1 and 2,
• - n is between 1 and 10, limits included,
• - t = 0 or 1.

• - dans laquelle les significations de X et R ont été spécifiées dans la revendication 1,
• - Y peut représenter un radical X ou un radical R,
• - p et q sont des nombres entiers positifs.

The polysiloxane used has, for example, the general formula:

• - in which the meanings of X and R have been specified in claim 1,
• - Y can represent an X radical or an R radical,
• - p and q are positive integers.

• - p est généralement compris entre 5 et 1 000 et
• - q est généralement compris entre 1 et 100, avec si q = 1 au moins un Y = X.

In this polysiloxane:

• - p is generally between 5 and 1000 and
• - q is generally between 1 and 100, with if q = 1 at least one Y = X.

The polydiorganosiloxane used can optionally comprise monoorganosiloxy units RSi ₁ , ₅ and / or Si0 _{2 units} , but if they exist, these units are in the proportion of at most 2% relative to the number of diorganosiloxy units R ₂ SiO, the meaning of R having been clarified 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.

• - de 50 à 150 atomes de silicium,
• - de 2 à 10 groupements X, précédemment définis.

Advantageously, in the process according to the present invention, the composition used comprises a polydiorganosiloxane having on average per mole:

• - from 50 to 150 silicon atoms,
• - from 2 to 10 groups X, previously defined.

Generally, in the process according to the present invention, 100 g of polydiorganosiloxane previously defined comprise 25 to 250 milliequivalents (meq) of amino nitrogen.

• n = 1 et
• R" = un atome d'hydrogène,
• t = 1.

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

• n = 1 and
• R "= a hydrogen atom,
• t = 1.

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

The polysiloxanes previously defined can be prepared in a similar manner to those described in American patent USP 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. Of course, mixtures of fibers can be used.

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 to quickly 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 treated dry fabric.

• 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 yarn, this test being known by textile specialists.

For the implementation of this test, the polyester thread 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 the 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 resure 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 examples which follow illustrate the preparation of polysiloxanes containing groups X and their use in the process according to the present invention.

- EXAMPLE 1:

• - 504,30 g (4,42 moles) d'allylglycidyléther,
• - 289 microlitres d'une solution dans l'hexane, (à 9,05 % en poids de platine métal) d'un complexe du platine préparé à partir d'acide chloroplatinique et de divinyl-1,3 tétraméthyl-1,1-3,3 disiloxane selon le brevet US-A-3 814 730.

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.

titrant 200,17 leq/100 g en fonction SiH (meq = milliéquivalent).The reaction mass is brought to and maintained by heating to 100 _° C. and 1,700 g of a random SiH copolymer of average formula are added over 2 hours 30 minutes:

measuring 200.17 leq / 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. Then added in 2 hours 30 minutes, 1,800 g of the organosiloxane derivative with glycidyl function prepared in l.a.

After 6 hours 30 of reaction, 2 113.4 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.

avec Me = -CH₃ 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 = -CH ₃

- EXAMPLE 2:

• - 1 500 g d'un copolymère statistique à SiH de formule :
  
  
  titrant 365,5 meq/100 g en fonction SiH,
• - 806,15 g (7,07 modes) d'allylglycidyléther,
• - 331,5 µ.l (microlitres) de solution catalysante au platine définie en 1.a.

2.a. - The same operations are carried out as in Example 1.a., using

• - 1,500 g of a random SiH copolymer of formula:
  
  
  measuring 365.5 meq / 100 g based on SiH,
• - 806.15 g (7.07 modes) of allylglycidylether,
• - 331.5 µ.l (microliters) of platinum catalyst solution defined in 1.a.

• - 1 700 g du dérivé organosiloxane à fonction glycidyl préparé en 2.a.,
• - 482 g (4,23 modes) de diéthanolamine.

After 5 hours of reaction, the SiH transformation rate is quantitative. After removal of the excess allyl glycidyl ether, 2 112 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 lb using:

• - 1,700 g of the organosiloxane derivative with a glycidyl function prepared in 2.a.,
• - 482 g (4.23 modes) of diethanolamine.

After 6 hours 30 of reaction, 2 179.5 g of a viscous yellow oil are obtained, the viscosity of which at 25 ° C. is 23,000 mPa.s. The various analyzes carried out confirm the structure of the product sought, namely:

- EXAMPLE 3:

• - 121,35 g (1,06 mole) d'allylglycidyléther,
• - 1 340 g d'un copolymère statistique à SiH de formule :
  
  
  titrant 61,11 meq/100 g en fonction SiH,
• - 228 µl de solution catalysante au platine définie en l.a.

3.a. - The same operations are carried out as in Example 1.a., using:

• - 121.35 g (1.06 mole) of allylglycidylether,
• - 1,340 g of a random SiH copolymer of formula:
  
  
  measuring 61.11 meq / 100 g based on SiH,
• - 228 µl of platinum catalyst solution defined in

• - 150 g du dérivé organosiloxane à fonction glycidyl préparé en 3.a.,
• - 8,92 g (0,078 mole) de diéthanolamine.

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 removing the excess of allylglycidyl ether, 1,423 g of organosiloxane oil is obtained, titrating 54.7 meq / 100 g as a glycidyl function. 3.b. - The same operations are carried out as in example lb 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 are obtained, with a viscosity of 9,500 mPa.s.

The various analyzes 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 functions:

- EXAMPLE 4:

• - 350 g d'un copolymère statistique à SiH de formule :
  
  
  titrant 9,48 meq/100 g en fonction SiH,
• - 11,34 g (1,00 mole) d'allylglycidyléther,
• - 46,55 µl de solution catalysante au platine.

4.a. - The operation is carried out 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 (1.00 mole) of allylglycidylether,
• - 46.55 µl 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 is obtained, titrating 9.5 meq / 100 g as a glycidyl function.

• - 2,2 g (0,019 mole) de diéthanolamine,
• - 200 g du dérivé organosiloxane à fonction glycidyle préparé en 4.a.

4.b. - The same operations are carried out as in example lb 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 of average formula:

- EXAMPLE 5:

5.a. - According to the operating conditions identical to those of Example 4.a. an organosiloxane oil of medium structure is synthesized:

grading 3.7 meq / 100 9 in glycidyl function.

5.b. - Under conditions similar 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:

- 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:

Table 1 below summarizes the characteristics of the organosiloxane oils with diethanolamine functionality synthesized in Examples 1 to 6.

- APPLICATION TESTS WITH THE PRODUCTS AS EXAMPLES 1 TO 6:

• + a) - Avec les produits selon les 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 l'exemple 1 ou 2.
• + b) - Avec les produits selon les exemples 4 et 5 des émulsions ont été préparées en opérant ainsi :
  • . on mélange dans un mélangeur de laboratoire de marque SILVERSON :
    • 10 % du produit selon les exemples 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 l'exemple 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'exemple 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.
  • A la fin l'émulsion est amenée à pH 6 avec de l'acide acétique.

Emulsions were prepared from the products obtained in Examples 1 to 6.

• + a) - With the products according to Examples 1 and 2, emulsions were prepared, 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 example 1 or 2.
• + b) - With the products according to Examples 4 and 5, emulsions were prepared by operating as follows:
  • . mixed in a SILVERSON brand laboratory mixer:
    • 10% of the product according to examples 4 or 5,
    • 0.55% of TERGITOL TMN 6,
    • 0.55% of RENEX 30.
  • . is then added slowly and continuously, to this well stirred mass: 88.9% of water by implementing the "phase inversion technique".
• + c) - With the product obtained according to example 6, the operation is carried out in the same way as in b), but using 73.9% of water and, after having introduced the water, 15% of propane 2 ol-.
• + d) - With the product obtained according to Example 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, 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.

• - 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),

• - determination of the coefficient of static friction,
• - hydrophilicity, by soaking the fabric (terry cotton) in a beaker specified in the description were carried out with the emulsions prepared above.

The results obtained are reported in Table 2 below.

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 (10)

1. A method of conditioning textile materials, in particular to give them a pleasant feel and good hydrophilicity, characterized in that the textile materials are brought into contact with a composition comprising a polydiorganosiloxane having per mole at least two units of general formula:

in which : - X is chosen from the radicals:

. R ′ representing a linear or branched C ₂ -C ₈ alkylene group, . R "representing a hydrogen atom or an alkyl to C _6, the radicals R, which are identical or different, are chosen from the phenyl, trifluoro-3,3,3 propyl radical and an alkyl radical having from 1 to 4 carbon atoms, - a is chosen from 1 and 2, - n is between 1 and 10, limits included, - t is 0 or 1. 2. Method according to claim 1, characterized in that the polydiorganosiloxane used has the general formula:

- in which the meanings of X and R have been specified in claim 1, - Y can represent an X radical or an R radical, - p and q are positive integers. 3. Method according to claim 2, characterized in that: - p is between 5 and 1000, and - q is between 1 and 100,
with if q = 1, at least one Y = X. 4. Method according to any one of the preceding claims, in which: n = 1 R "= a hydrogen atom, and t 1. 5. Method according to any one of the preceding claims, in which the nitrogen of group X is salified. 6. Method according to any one of the preceding claims, in which the composition used is an aqueous composition. 7. Method according to any one of the preceding claims, in which the composition used is an emulsion. 8. Method according to any one of claims 2 to 7, characterized in that the composition used comprises a polydiorganosiloxane having on average per mole: - from 50 to 150 silicon atoms, - from 2 to 10 X groups. 9. Method according to any one of the preceding claims, characterized in that the composition used comprises per 100 g of polydiorganodisiloxane from 25 to 250 meq of amino nitrogen. 10. Method according to any one of the preceding claims, characterized in that it is implemented on a cotton fabric.