WO1997033034A1

WO1997033034A1 - Method for softening a fabric material, preventing yellowing thereof and conferring hydrophilic properties thereto by means of a polyorganosiloxane composition

Info

Publication number: WO1997033034A1
Application number: PCT/FR1997/000378
Authority: WO
Inventors: Paul Branlard; Nathalie Guennouni; Gérard Mignani
Original assignee: Rhodia Chimie
Priority date: 1996-03-06
Filing date: 1997-03-04
Publication date: 1997-09-12
Also published as: FR2745825A1; FR2745825B1; AU1931497A

Abstract

A method for conditioning fabric materials by conferring a pleasant feel and good hydrophilic properties thereto as well as preventing yellowing thereof, wherein the fabric materials are contacted with a composition including at least one linear, cyclic or three-dimensional polyorganosiloxane. The polyorganosiloxane includes identical or different units of general formula (I), wherein (1) a is 0, 1, 2 or 3, b is 0, 1, 2 or 3, c is 0, 1, 2 or 3, and a+b+c≤3, (2) the R symbols are monovalent hydrocarbon radicals, (3) the X symbols are identical and/or different functional residues and represent a polyether of formula (CH2)n-(OCH2CH2)α(OCH2CHCH3)β-OR2, and (4) the V symbols are identical and/or different functional residues and represent a residue with one or more sterically hindered piperidinyl groups.

Description

PROCESS FOR SOFTENING AND MAKING NON-YELLOWING AND HYDROPHILIC

A TEXTILE MATERIAL IN WHICH A COMPOSITION IS USED

COMPRISING A POLYORGANOSILOXANE

The present invention relates to a process for conditioning textile materials providing the textile fiber with good hydrophilicity, an absence of yellowing and a pleasant feel in the hand, that is to say properties of softness.

The literature describes processes for conditioning textile materials.

US-A-4409 267 describes the use of a mixed polyorganosiloxane carrying a share of primary amine function (s) or substituted secondary amine function (s) ) for example by residues containing an OH or Oa! kyte group. and on the other hand, alkylene oxide function (s) as additive to a composition for the treatment of textile materials.

EP-546231 describes the use of a polyorganosiloxane carrying motif (s) of formula:

If - (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 equal to 0 or 1. EP -A-0459822 describes homogeneous and transparent detergent compositions comprising a polyorganosiloxane with amine function (s) secondary (s) or tertiary (s) substituted (s) for example by residues containing an OH group, said silicone being used mixed 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 non-yellowing, softness and hydrophilic properties previously announced.

Another advantage of the process according to the present invention comes from the fact that it can be implemented with a polyorganosiloxane of easy industrial preparation and stable in storage. Another advantage of the process according to the present invention comes from the easy packaging of the composition containing the polyorganosiloxane according to the invention for its application to the materials to be treated.

It has therefore now been found, and this is what is the subject of the present invention, a process for conditioning textile materials to provide them with a pleasant feel, good hydrophilicity and an absence of yellowing, in which the textile materials are brought into contact with a composition comprising at least one linear, cyclic or three-dimensional polyorganosiloxane, carrying, among other things, substituted amine function (s) and, of molecular weight of the order of 5,000 to 500,000 grams, preferably of the order of 10,000 to 300,000 grams, characterized in that the polyorganosiloxane comprises identical or different units of general formula (I):

R _a Xb ^v c ^Si ° 4-frιfod ω

2 in which:

(1) a = 0, 1, 2 or 3 b = 0, 1, 2 or 3 c = 0, 1, 2 or 3 a + b + c ≤ 3

(2) the symbols R are identical and / or different and 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 hydroxy radical, an ethoxy radical, a methoxy radical or a methyl radical.

(3) the symbols X are identical and / or different functional residues and represent a polyether of formula:

(CH ₂ ) _n - (OCH ₂ CH ₂ ) _α (OCH ₂ CHCH3) _p - OR ² with 0 <π <10 α and β are completely independent decimal values such as: α> 0, β ≥ O and 100 x α / (α + β) ≥ 50,

R ² is a hydrogen atom, COR ³ or a linear alkyl radical, and R ³ is a hydrogen atom or a linear alkyl radical.

(4) the symbols V are identical and / or different functional residues and represent a residue containing sterically hindered piperidinyl group (s) chosen from:

(H) or

For the remains of formula (II):

* 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 part of which contains 2 to 20 carbon atoms;

• alkylene-cyclohexylene radicals, the linear or branched alkylene part of which comprises 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 identical or different radicals R ⁷ represent alkylene radicals having 1 to 12 carbon atoms;

• the radicals of formula -R ⁷ - O - R ⁷ in which the radicals R ⁷ have the meanings indicated above and one of them or both are substituted by one or two group (s) -OH;

• 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:

in which R ⁴ has the meaning indicated above, R ⁵ and R ⁶ have the meanings indicated below and R ¹¹ represents a divalent alkylene radical, linear or branched, having from 1 to 12 carbon atoms, one of the valential bonds (that of R ¹¹ ) being connected to the atom of -NR ¹⁰ -, the other (that of R ⁴ ) being connected to a atom of silicon;

* 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 the remains of formula (III):

* R ' ⁴ is chosen from a trivalent group of formula:

- (CH ₂ ) -CH m

\ co— where m represents a number from 2 to 20, and a trivalent group of formula:

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 and 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 connection with formula (II).

(5) the rate of O and T units being less than or equal to 10% by mole;

(6) the level of units of formula (I) in which the silicon atom carries a functional residue X is less than or equal to 20% by mole; and,

(7) the level of units of formula (I) in which the silicon atom carries a functional residue V is less than or equal to 20 mol%;

Advantageously, the values α and β of at least one functional residue X are such that α is between 0 and 80 (excluding 0), β is between 1 and 60 and

100 x α / (α + β) ≥ 80

More particularly, at least one of the functional residues X of the polyorganosiloxane is such that α is between 8 and 25 and β is between 1 and 7.

According to one of the preferred modes of the process of the invention, at least one of the functional residues X of the polyorganosiloxane used in said process is such that n is equal to 3. Advantageously, the same functional residue X is such that n is equal to 3, α is between 8 and 25 and β is between 1 and 7.

According to another preferred embodiment of the process of the invention, the polyorganosiloxane used in said process is a polyorganosiloxane of average formula:

in which :

0 ') the symbols R are identical or different and have the meanings given above;

(2 ') the symbols X are identical or different and have the meanings given above; (3 ') the symbols V are identical or different and have the meanings given above;

(4 ') the symbols Z are identical or different and represent R, X and / or V as defined above; and (5 ') x, y, z and w are totally independent decimal values chosen while respecting the unit rates of (5), (6) and (7) of claim 1 and such that:

10.4 <x + y + z + w <3000 10 <x <2500 0.2 <y <450

0.2 <z <450 0 <w <300

More particularly, the independent decimal values x, y, z, and w of the polyorganosiloxane are chosen such that:

100 <x <2000 2 <y <20 0.8 <z <20 0 <w <20

Whatever the constitution chosen for the composition containing the polyorganosiloxane, the conditioning process can be carried out on any natural or synthetic material in woven, nonwoven or knitted form.

The fibers of these materials can be, in particular, made up or based on keratin, cotton, linen, wool, viscose, rayon, hemp, silk, polypropylene, polyethylene, polyester, polyurethane, polyamide, cellulose acetate or a mixture of these. this.

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, either in the form of a solution, dispersion or emulsion.

Preferably, the composition is prepared in the form of an aqueous emulsion. However, the composition according to the process of the invention can also be used in solution in an inert organic solvent. This solvent can be for example toluene or xylene.

The aqueous emulsions are generally based on a mixture of oil and water, and are prepared according to conventional methods well known to those skilled in the art. using surfactants. For example, the emulsions can be made by the so-called direct methods or by inversion. They are easy to make and do not require the use of high-speed agitation equipment. Apparatus at normal stirring speed may be used. In general, the aqueous emulsions prepared in accordance with the invention preferably contain between 20 and 90% by weight of water relative to the total mass of the constituents of the emulsion. For better application, the emulsions prepared in accordance with 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 found to be stable at room temperature.

The application of the polyorganosiloxane according to the invention to the materials to be treated can be carried out in very diverse forms. The applications can be carried out by immersion, coating, spraying, printing, "padding" (padding in English), coating with a doctor blade or by any other existing means. 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 vapor.

The quantity of polyorganosiloxane deposited on the material to be treated varies according to the constitution and the 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 an amount of polyorganosiloxane of between 0.1 and 2% by weight relative to the weight of the material to be treated.

The polyorganosiloxanes previously defined can be prepared according to various methods.

In particular, the Applicant has developed an original synthesis process which makes it possible to prepare the compounds of formula (I) according to the invention. This process involves redistribution-condensation reactions or redistribution reactions.

The reactions are carried out from at least one polyorganosiloxane compound, functionalized or not, linear, branched and cyclic. Depending on the case, these reactions are carried out in the presence of at least one silane having at least one Si-C bond linked to a monovalent organic group with at least an Si-OC bond carrying a hydrocarbon group which can be replaced by an ether-oxygen bond.

Without silane, the reactions are carried out in the presence of at least two polyorganosiloxane compounds, functionalized or not, linear, branched and cyclic.

The compounds used in the reaction medium are selected such that at least a first compound is functionalized with a V motif and a second compound is functionalized with an X motif. This selection is moreover perfectly illustrated by Examples 1 to 15 below. The silanes used have the formula:

ZaSiRa-a M

• where the symbols Z are identical or different functional residues and have the meanings given above for the formula (IV);

• where the symbols R are identical or different and have the meanings given above for formula (I).

The polyorganosiloxanes used are:

° cyclic polydiorganosiloxanes having as general formula:

(RZSiO) _s (VI)

- where the symbols R are identical and / or different having the meanings given above for formula (I) and, preferably, the symbols R are alkyl radicals;

^• where the symbols Z are identical or different and have the meanings given above for formula (IV) and, preferably the groups Z are identical. ^• where s is an integer between 3 and 10.

Advantageously, in the case where Z is equal to R for (VI), the radicals R are alkyl radicals and preferably methyl radicals (for example: hexamethyltrisiloxane or octamethyltetrasiloxane). ° functionalized linear polyorganosiloxanes having as general formula:

R Z-rSi-CHSiZ, (VII)

2 " in which :

^• the symbols R are identical and / or different and have the meanings given above for formula (I) and, preferably, the symbols R are alkyl radicals;

- the symbols Z are identical or different and have the meanings given above for formula (IV);

^• u is an integer between 2 and 3000.

Advantageously, the radicals R of (VII) are alkyl, methoxy and / or hydroxy radicals, and more particularly methyl radicals.

The compounds defined by formula (VII) are preferably:

RR (R ₂ S "0) _u SiR ₃ (VIII), or Rf S ^ -CHSiR _j OX)

HO (Me ₂ SiO) _u H or Me (Me ₂ Si-0) _u SiMe ₃

or

Me i MeOtSi-CHMe or MeO (Me, SiO). _u ... ( _ι M _n .e ^ SiiOO)) „ _u ... Me

X ^u X

Me i or MeCHSi-CHMe or MeO (Me.SiO) _u> (Me ^ iO) _u "Me

^U

Me i or Mβ _j SKHSJ-CHsiMe, or Me (Me, SiO) ... (MeSiO) „..SiMe.

X ^U X

or O) _u „SiMe ₃

in which u 'and u "are whole numbers and are defined such that u' + u" = u. u being an integer between 2 and 3000. The compounds of the invention corresponding to formula (I) can be prepared according to an original synthesis process bringing together the raw materials defined above: a) in the case of redistribution-condensation reactions: - a silane or a mixture of silanes of formula (V),

^• a cyclic poiydiorganosiloxane or a mixture of cyclic polydiorganosiloxanes of formula (VI) wherein Z is R,

- a cyclic functionalized polyorganosiloxane or a mixture of cyclic functionalized polyorganosiloxanes of formula (VI), ^• and optionally a linear polyorganosiloxane of formula (VII). b) in the case of redistribution reactions:

a cyclic poiydiorganosiloxane or a mixture of cyclic polydiorganosiloxanes of formula (VI) where Z is equal to R,

a cyclic polyorganosiloxane or a mixture of cyclic polyorganosiloxanes of formula (VI), and

- a linear polyorganosiloxane of formula (VII).

The processes for preparing the products for their use according to the invention require the use of very specific conditions. In particular, the redistribution-condensation or redistribution reactions involved in the processes for preparing the compounds of the invention are carried out in the presence of a basic catalyst. The catalyst generally used is a base such as a hydroxide, a carbonate or a bicarbonate of alkali metal (for example sodium, potassium). The amount of pure base expressed as a percentage by weight relative to the weight of all of the silicone reactants present in the reaction medium is in the range from 0.005 to 5%.

In addition, the redistribution-condensation and redistribution reactions are carried out respectively at temperatures ranging from 70 ° C to 160 ° C and at temperatures ranging from 120 ° C to 160 ° C. The heating time of the reaction medium for these reactions depends on the temperature chosen above and can vary from 3 to 8 hours.

In addition, at the end of the reaction, the reaction medium is brought to a neutral pH by addition of an appropriate quantity of a neutralizing agent. The introduction of the reagents which constitute the mixtures, as defined above, must be carried out in such a way that the reactive medium is favorable for obtaining a redistribution equilibrium after 3 to 8 hours, from preferably 3 to 6 hours of heating time for the reaction medium. Furthermore, it has been observed that the experimental conditions used in the preparation processes are particularly favorable when the functionalized polyorganosiloxanes are poured. More specifically, the formation of the desired products according to the invention is favored by casting the compounds of formula (VI) when Z is equal to R or V, and / or the compounds of formula (VII) when Z is equal to V on the composed of formulas (VI) and / or (VII) when Z is equal to X.

It was also observed that the casting time was also a determining parameter for optimizing the experimental conditions for preparing the polyorganosiloxanes used in the process of the invention. In general, the casting time is at most equivalent to half the overall heating time of the reaction medium. In the examples described below, the casting time is of the order of 1 to 4 hours.

EXJEMELES

The examples below illustrate the preparation of polyorganosiloxanes with sterically hindered pyperidinyl function (s) and with polyether function (s) for their use in the process according to the invention.

Examples 1 to 8 relate to the synthesis of non-hydrolyzable oils di-substituted with polyether and tetramethylpiperidine functions of general formula: Me ₃ SiO (Me ₂ SiO) x

Examples 9 to 15 illustrate the synthesis of hydrolyzable oils substituted with polyether and tetramethylpiperidine functions. The synthesized oils have the general formula:

y '+ y "being equal to y.

The polydimethylsiloxanes substituted with polyether units A, B, C or D and, used in Examples 1 to 15 are of formula: Me, SiOMe ₂ SiO) x (MeSiO) y " ¹ SiMe ₃

(OCH- Cr ^) a (OCH- CHCH,) bOH

Examples 1 to 5 a) General procedure

The following reagents are introduced into a reactor equipped with mechanical stirring, a temperature probe, a dropping funnel, a vertical cooler, a sample-taking opening:

- polydimethylsiloxane with polyether A functions,

- octamethylcyclotetrasiloxane D4,

- 1, 3,5,7-tetramethyl 1,3,5,7-tetrakis (3 (2,2,6,6, -tetramethylpypéridinyl 4-oxy) propyDcyclotetrasiloxane D * 4,

- Tetradimethylsiloxane of average formula Me ₃ SiO (Me ₂ SiO) 4SiMe ₃ (for Example 1).

The agitation is started and the sky above the reactor is oxygenated by a circulation of nitrogen. The reaction medium is then heated to 150 ° C. At this temperature, the potassium dissolved in water is introduced. The stirring and heating conditions are maintained for 6 hours. The medium is then neutralized by adding phosphoric acid (10% by weight of pure acid) and the reaction medium is then heated for 1 hour at 150 ° C.

The oil thus obtained is devolatilized (150 ° C, 200 Pa, 2 h). b) The quantities of reagents (in grams) used are given in table I. c) The characteristics of the oils obtained are given in table III. The structures of the different oils were confirmed by nuclear magnetic resonance and steric exclusion chromatography analyzes.

Example 6 a) Experimental procedure:

Polydimethylsiloxane with polyether functions (B) is charged into a reactor fitted with a central mechanical agitation, a temperature probe, a vertical coolant of an isobaric pouring bulb and an opening for taking the sample. ). The agitation is started and the sky above the reactor is oxygenated by a circulation of nitrogen. The reaction medium is then heated to 150 ° C. At this temperature, a 27.55% by mass solution of potassium hydroxide in water is introduced via a syringe. Pouring the mixture of octamethylcyclotetrasiloxane (D4) and 1, 3,5,7-tetramethyl 1, 3,5,7-tetrakis (3 (2,2,6,6, -tetramethylpypéridinyl 4-oxy) propyl) cyclotetrasiloxane (D * 4) begins and lasts 2 hours. The stirring and heating conditions are then maintained for 4 hours. The medium is then neutralized by adding phosphoric acid (10% by weight of pure acid) and the reaction medium is then heated for 1 hour at 150 ° C.

The oil thus obtained is devolatilized (105 ° C, 13 Pa, 1 h). b) The quantities of reagents (in grams) used are given in table I. c) The characteristics of the oils obtained are given in table III. The structures of the different oils were confirmed by nuclear magnetic resonance and steric exclusion chromatography analyzes.

Examples 7 at fi a) General procedure:

Polydimethylsiloxane with polyether functions is charged in a reactor fitted with a central mechanical agitation, a temperature probe, a vertical coolant, an isobaric pouring bulb and an opening for taking the sample. VS). The agitation is started and the sky above the reactor is oxygenated by nitrogen circulation. The reaction medium is then heated to 150 ° C. At this temperature, potassium hydroxide is introduced (15% by weight of pure base). Pouring the mixture of octamethylcyclotetrasiloxane (D4) and 1, 3,5,7-tetramethyl 1,3,5,7- tetrakis (3 (2,2,6,6, -tetramethylpypéridinyl 4-oxy) propyl) cyclotόtrasiloxane (D * 4) begins and lasts 2 hours. The stirring and heating conditions are then maintained for 4 hours. The medium is then neutralized by adding phosphoric acid (10% by weight of pure acid) and the reaction medium is then heated for 1 hour at 150 ° C.

The oil thus obtained is devolatilized (120 ° C, 13 Pa, 1 h). b) The quantities of reagents (in grams) used are given in Table II. c) The characteristics of the oils obtained are given in table III. The structures of the different oils were confirmed by nuclear magnetic resonance and steric exclusion chromatography analyzes.

Example 9 a) In a reactor provided with a central mechanical agitation, a temperature probe, a vertical cooler and a distillation column provided with a receiving flask and an opening for taking the sample , 1, 3,5,7-tetramethyl 1, 3,5,7-tetrakis (3 (2,2,6,6, -tetramethylpypéridinyl 4-oxy) propyl) cyclo-tetrasiloxane (D * 4, 2.294) is charged g), octamethylcyclotetrasiloxane (D4, 64.99 g) and trimethoxysilane containing polyether functions, the formula of which is described below:

(MeO) ₃ Si (CH ₂ ) ₃ (OCH ₂ CH ₂ ) ιoOMe

The agitation is started and the sky above the reactor is oxygenated by a circulation of nitrogen. The receiving flask is cooled by an acetone-dry ice bath. The reaction medium is then heated to 90 ° C. and 0.05 g of a 14% potassium hydroxide solution in water is then injected at this temperature.

The stirring and heating conditions are maintained for 2 hours and during this time, the methanol is collected in the receiving flask.

Phosphoric acid (10% by weight of pure acid, 0.117 g) is then introduced into the reactor and the reaction medium is then heated for 2 hours at the same temperature.

The oil thus obtained is devolatilized (150 ° C, 400 Pa, 1 h 30 min). b) The characteristics of the oil obtained are given in Table IV. The structure of the oil was confirmed by nuclear magnetic resonance and steric exclusion chromatography analyzes. Example 1Q a) In a reactor equipped with a central mechanical agitation, a temperature probe, an isobaric pouring bulb and a distillation column provided with a receiving flask and an opening for taking sample, 1,3,5,7-tetramethyl 1,3,5,7-tetrakis (3 (2,2,6,6-tόtramethylpypéridinyl 4-oxy) - propyOcyclotetrasiloxane (D * 4, 9,43) g) and octamethylcyclotetrasiloxane (D4, 129.00 g). Stirring is started and the reactor overhead is oxygenated by a circulation of nitrogen. The receiving flask is cooled by an acetone-carbogiaceous bath. The reaction medium is then heated to 90 ° C. and then, at this temperature, the ground potassium hydroxide (180 mg) is then introduced. The mixture of water (0.886 g) and trimethoxysilane with polyether functions (40.75 g) is poured in. ) whose formula is described below:

via the pouring bulb then begins and lasts 30 minutes. When the addition is complete, the pouring bulb is replaced by a vertical coolant.

The stirring and heating conditions are maintained for 6 hours and during this time, the methanol is collected in the receiving flask.

Phosphoric acid (10% by weight of pure acid, 3,006 g) is then introduced into the reactor and the reaction medium is then heated for 2 hours at the same temperature. The oil thus obtained is devolatilized (150 ° C, 400 Pa, 1 h 30 min). b) The characteristics of the oil obtained are given in Table IV. The structure of the oil was confirmed by nuclear magnetic resonance and steric exclusion chromatography analyzes.

Examples 11 and 12 a) In a reactor, provided with a central mechanical agitation, a temperature probe, a vertical refrigerant and a distillation column provided with a receiving flask and an opening for taking up 1, 3,5,7-tetramethyl 1, 3,5,7-tetrakis (3 (2,2,6,6-tetramethylpypéridinyl 4-oxy) propyl) cyclotetra siloxane (D * 4) is loaded , octamethylcyclotetrasiloxane (D4), trimethoxysilane containing polyether functions, the formula of which is described below:

(MeO) ₃ Si (CH ₂ ) ₃ (OCH ₂ CH ₂ ) ι ₀ OMe polydimethylsiloxane of general formula HO (Me2SiO) gH and crushed potash.

The agitation is started and the sky above the reactor is oxygenated by a circulation of nitrogen. The receiving flask is cooled by an acetone bath- dry ice. The reaction medium is then heated to 150 ° C. The stirring and heating conditions are maintained for 4 hours and during this time, the methanol is collected in the receiving flask.

Phosphoric acid (10% pure acid) is then introduced into the reactor and the reaction medium is then heated for 1 hour at 150 ° C.

The oil thus obtained is devolatilized (150 ° C, 400 Pa, 1 h 30 min).

Loads implemented (g):

The characteristics of the oils obtained are given in Table IV. The structures of the different oils were confirmed by nuclear magnetic resonance and steric exclusion chromatography analyzes.

Example 13 a) The reactor is equipped with a central mechanical agitation, a temperature probe, a vertical cooler and a distillation column provided with a receiving flask and an opening for taking the sample. . Is introduced into the reactor;

- 1, 3,5,7-tetramethyl 1, 3,5,7-tetrakis (3 (2,2,6,6-tetramethylpypéridinyl 4-oxy) propyOcyclotetrasiloxane (D * 4, 10.03 g)

- trimethoxysilane containing polyether functions, the formula of which is described below (26.26 g): (MeO) ₃ Si (CH ₂ ) ₃ (OCH ₂ CH ₂ ) ιoOMe

- the polydimethylsiloxane of general formula HO (Me ₂ SiO) _x H at 1% by weight of silanol functions (121.09 g)

- octamethylcyclotetrasiloxane (D4, 17.91 g) and,

- crushed potash (0.170 g). The reaction medium is stirred and degassed with nitrogen. The receiving flask is cooled by an acetone-dry ice bath. The reaction medium is then heated 150 ° C.

The stirring and heating conditions are maintained for 4 hours and the methanol is collected in the receiving flask. 2.89 g of phosphoric acid (10% pure acid) are then introduced into the reactor and the reaction medium is then heated for 1 hour to 150 ° C. The oil thus obtained is devolatilized (150 ° C, 400 Pa, 1 h 30 min). b) The characteristics of the oil obtained are given in Table IV. The structure of the oil was confirmed by nuclear magnetic resonance and steric exclusion chromatography analyzes.

Example 14 a) The reactor is equipped with a central mechanical agitation, a temperature probe, a vertical coolant, an isobaric pouring bulb and an opening for taking the sample. The following are introduced into the reactor:

- polydimethylsiloxane with polyether functions D (32.75 g),

- 0.5 g of water and,

- trimethoxysilane with polyether functions (6.55 g), the structure of which is described below:

(MeO) ₃ Si (CH2) ₃ (OCH2CH ₂ ) ₁₀ OMe

The reaction medium is stirred and degassed with nitrogen. The reaction medium is then heated 150 ° C. At this temperature, potassium hydroxide is introduced (1.13 g, 15% by weight of pure base). Then the cToctamethylcyclotetrasiloxane mixture (D4, 125.41 g) and 1, 3,5,7-tetramethyl 1, 3,5,7-tetrakis (3 (2,2,6,6-) are introduced by continuous casting over 2 hours. tetramethylpyperidinyl 4-oxy) propyl) cyclotetrasiloxane (D * 4, 9.75 g).

The stirring and heating conditions are then maintained for 4 hours. The medium is neutralized by adding phosphoric acid (10% by weight of pure acid) and the reaction medium is then heated for 1 hour at 150 ° C. The oil thus obtained is devolatilized (150 ° C, 200 Pa, 1.5 h). b) The characteristics of the oil obtained are given in Table IV. The structure of the oil was confirmed by nuclear magnetic resonance and steric exclusion chromatography analyzes.

Example 15 a) The reactor is equipped with a central mechanical stirring, a temperature probe, a vertical coolant, an isobaric pouring bulb and an opening for taking the sample. The following are introduced into the reactor:

- polydimethylsiloxane with polyether functions B (108.02 g)

- trimethoxysilane with polyether functions (8.57 g), the structure of which is described below:

(MeO) ₃ Si (CH ₂ ) ₃ (OCH ₂ CH ₂ ) ₁ oOMe The reaction medium is stirred and degassed with nitrogen. The reaction medium is then heated 150 ° C. At this temperature, the potash (1.667 g, 15% by weight of pure base) and 0.5 g of water are introduced. The mixture of octamethylcyclotetrasiloxane (D4, 148.07 g) and of 1, 3,5,7-tetramethyl 1,3,5,7-tetrakis (3 (2,2,6,6) is introduced by continuous casting over 2 hours. -tetramethylpyperidinyl 4-oxy) propyl) cyclotetrasiloxaπe (D * 4, 11.91 g). The stirring and heating conditions are then maintained for 4 hours. The medium is then neutralized by adding 3.42 g of phosphoric acid (10% by weight of pure acid) and then heated for 1 hour at 150 ° C. The oil thus obtained is devolatilized (150 ° C, 200 Pa, 1.5 h). b) The characteristics of the oil obtained are given in Table IV. The structure of the oil was confirmed by nuclear magnetic resonance and steric exclusion chromatography analyzes.

TESTS

The oils of Examples 1 to 15 and the oils of the prior art are tested in application in the form of an aqueous emulsion and the measurements of hydrophilicity, white index and evaluation of the feel are carried out.

The properties of the fabrics treated with the various emulsions of the oils of Examples 1 to 15 were compared, on the one hand to those of an untreated fabric C1, and on the other hand with those of fabrics treated respectively with the silicone compounds C2 , C3 and the Rhodorsil® 21827 microemulsion.

Compound C2 is a silicone oil marketed under the name Rhodorsil® 21650 by the company Rhône-Poulenc with the general formula:

Compound C3 is a polyether silicone oil sold by the company Osi under the reference L7200 of general formula:

Me ₃ SiO (MeSiO) x (Me ₂ SiO) y SiMe.

(OCH ₂ CH ₂ MOCH, CHCH ₃ ) bOH The Rhodorsil® 21827 micro-emulsion consists of an amine-functional silicone oil sold by the company Rhône-Poulenc.

Emulsions E1 to E17 were prepared using the "phase inversion technique".

The emulsions E1, E2, E3 and E8 are prepared with the oils of Examples 1, 2, 3 and 8 respectively and have the following composition (by weight):

- 20% silicone oil

- 8% cflmbentin T / 060 sold by the company Dr. W. Kolb AG - 0.2% glacial acetic acid

- 0.1% sodium sulfate

- 2% of the monoglutyl ether of diethylene glycol

- 69.7% water.

The emulsions E4, E5, E6, E7 and E9 to E15 are prepared respectively with the oils of Examples 4, 5, 6, 7 and from 9 to 15 and have the following composition (by weight):

- 20% silicone oil

- 8% of Imbentin T / 060 sold by the company Dr. W. Kolb AG

- 0.2% glacial acetic acid

- 71.8% water. The E16 emulsion is prepared from compound C2 and has the following composition

(in weight) :

- 20% Rhodorsil® 21650 oil

- 8% of Synpéronic 13/5 sold by the company HERE

- 0.2% glacial acetic acid - 0.1% sodium sulfate

- 2% of the monoglutyl ether of diethylene glycol

- 69.7% water.

The emulsion E17 is prepared from the compound C3 and has the following composition (by weight): - 20% of silicone polyether L7200

- 80% water

The emulsions E18 to E26 were prepared using the "so-called direct technique". The emulsions Et 8 to E26 prepared with the oils of Examples 1 to 8 and of compound C2 have the following composition (by weight):

- 69.75% water, - 6.45% of Rhodasurf BC-610 marketed by the company Rhône-Poulenc,

- 2.55% of Rhodasurf BC-420 marketed by the company Rhône-Poulenc,

- 0.05% sodium acetate, - 1.20% acetic acid, • 20% silicone oil.

The properties of emulsions E1 to E17 were evaluated from the following three measurements: measurement of non-yellowing, measurement of hydrophilia and touch test.

The properties of the emulsions E18 to E26 were evaluated on the basis of the following two measurements: hydrophonic measurement and touch test.

These evaluations were carried out on textiles treated with 1% by weight of silicone oil.

° Non-yellowing measure:

The fabric used is a white cotton terry cloth. The heat treatment after application is 9 minutes at 150 ° C.

The evaluation of the yellowing is carried out by the measurement, well known in the textile industry, of the degree of white E313 carried out on the spectrophotocolorimeter ACS Sensor II marketed by the company Datacolor with the use of the illuminant D65 reproducing the daylight . ° Touch test:

The fabric used is a cotton terry cloth. After application, the fabric is dried in ambient air for 24 hours. After a heat treatment at 150 ° C for 1 minute 30, the fabric is placed in conditioning for 24 hours (23 ± 2 ° C, 50% ± 5 relative humidity). The softness is evaluated by different testers who are asked to classify the samples from the lowest to the softest. The results are expressed either in soft pleasant touch (AD) or in non-pleasant touch, without softness (NAD).

° Hydrophobic measurement:

The fabric used is a polyester / cotton fabric (50/50), taffeta weave (E1 to E17) or a 100% cotton jersey fabric (E18 to E26).

The heat treatment after application is 5 minutes at 170 ° C. The tissue is left at room temperature for 24 hours. The hydrophobic measurements are made by the Tegewa drop test which measures the absorption time of a drop of water on the surface of the textile. The results obtained are reported in Tables V and VI.

Table I

Table II

Table III

Table IV

Table V

Table VI

Claims

1. A method for conditioning textile materials providing a pleasant feel, good hydrophilicity and an absence of yellowing to said textile materials, in which the textile materials are brought into contact with a composition comprising at least one linear, cyclic or three-dimensional polyorganosiloxane, carrying of substituted amine function (s) and of molecular weight of the order of 5000 to 500,000 grams, preferably of the order of 10,000 to 300,000 grams, characterized by the following points:

The polyorganosiloxane comprises identical or different units of general formula (I):

R _a Xb ^v c ^Si ° 4-frfrc) (I) 2 in which:

(1) a = 0, 1, 2 or 3 b = 0, 1, 2 or 3 c = 0, 1, 2 or 3 a + b + c <3 (2) the symbols R are identical and / or different and 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 hydroxy radical, a radical ethoxy, a methoxy radical or a methyl radical.

(CH ₂ ) _n - (OCH ₂ CH2) _α (OCH ₂ CHCH3) _p - OR ² with 0 <n <10 α and β are completely independent decimal values such as: α ≥ O, β> 0 and 100 x α / (α + β) ≥ 50,

R ² is a hydrogen atom, COR ³ or a linear alkyl radical and,

R ³ is a hydrogen atom or a linear alkyl radical. (4) the symbols V are identical and / or different functional residues and represent a residue containing sterically hindered piperidinyl group (s) chosen from:

For the remains of formula (II)

R ⁴ is a divalent hydrocarbon radical chosen from:

• linear or branched alkylene radicals having 2 to 18 carbon atoms;

* alkylene-cyclohexylene radicals of 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;

* the radicals of formula -R ⁷ - O - R ⁷ in which the identical or different radicals R ⁷ represent alkylene radicals having 1 to 12 carbon atoms; • the radicals of formula -R ⁷ - O - R ⁷ in which the radicals R ⁷ have the meanings indicated above and one of them or both are substituted by one or two group (s) -OH;

• 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;

10 • 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:

in which R ⁴ has the meaning indicated above, R ⁵ and R ⁶

15 have the meanings indicated below and R ¹¹ represents a divalent alkylene radical, linear or branched, having from 1 to 12 carbon atoms, one of the valential bonds (that of R ¹¹ ) being linked to the atom of - NR ¹⁰ -, the other (that of R ⁴ ) being linked to a silicon atom; the radicals R ⁵ are identical or different, chosen from the radicals

20 linear or branched alkyls having 1 to 3 carbon atoms and the phenyl radical; ie radical R ⁶ represents a hydrogen radical or the radical R ⁵ or O *.

For the remains of formula (III):

^ά (III) 'R' ⁴ is chosen from a trivalent group of formula:

-

where m represents a number from 2 to 20, and a trivalent group of formula:

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 with regard to formula (II). (5) the rate of units Q and T being less than or equal to 10% by mole;

2. Method according to any one of the preceding claims, characterized in that at least one of the functional residues X of the polyorganosiloxane is such that:

0 <a≤ 80, 1≤ β≤ 60 and 100 x α / (α + β) ≥ 80.

3. Method according to claim 2, characterized in that at least one of the functional residues X of the polyorganosiloxane is such that α is between 8 and 25 and β is between 0 and 7.

4. Method according to any one of the preceding claims, characterized in that at least one of the functional residues X of the polyorganosiloxane is such that n is equal to 3.

Process according to any one of the preceding claims, characterized in that the polyorganosiloxane used is a polyorganosiloxane of average formula:

in which

(1 ') the symbols R are the same or different and have the meanings given in claim 1;

(2 ') the symbols X are identical or different and have the meanings given in claim 1;

(3 ') the symbols V are the same or different and have the meanings given in claim 1;

(4 ^* ) the symbols Z are identical or different and represent R, X and / or V as defined in claim 1; and

(5 ') x, y, z and w are totally independent decimal values chosen while respecting the pattern rates of (5), (6) and (7) of claim 1 and such that:

- 10.4 <x + y + z + w <3000 - 10 <x <2500

- 0.2 <y <450

- 0.2 <z <450

- 0 <w <300

Method according to claim 5, characterized in that the independent decimal values x, y, z, and w of the polyorganosiloxane are such that: - 100 <x <2000

- 2 <y <20

- 0.8 <z <20

- 0 <w <20

Process according to any one of the preceding claims, characterized in that the composition containing the polyorganosiloxane is in liquid form.

8. Method according to claim 7 characterized in that fa composition containing the polyorganosiloxane in liquid form is an aqueous emulsion.

9. Method according to one of claims 1 to 8, characterized in that said method is implemented on a woven, knitted or non-woven material, said material being based on cotton, polyester, polyamide, viscose, polyacrylate , wool, and / or cellulose acetate.

10. Method ^according to any of claims 1 to 9, characterized in that the quantity of polyorganosiloxane deposited on ia treated textile material corresponds to an amount between 0.1 and 2% by weight based on the weight of the textile material dry treated.

11. Process for the preparation of polyorganosiloxanes of formula (I) used in the process for conditioning textile materials according to any one of claims 1 to 10, characterized in that the process involves redistribution-condensation reactions or redistribution reactions carried out in the presence of compounds comprising at least a first compound functionalized with a V motif and a second compound functionalized with a X motif; said compounds being:

- Or at least one polyorganosiloxane compound, functionalized or not, linear, branched and cyclic and at least one silane having at least one Si-C bond linked to a monovalent organic group with at least one Si-OC bond carrying a hydrocarbon group which can be replaced by an ether-oxygen bond, or

- Either at least two polyorganosiloxane compounds, functionalized or not, linear, branched and cyclic.

12. Process for the preparation of polyorganosiloxanes according to claim 11, characterized in that the silane used has the formula:

ZaSiRs-a (V) in which:

- the symbols Z are identical or different functional residues and have the meanings given above for formula (IV); - the symbols R are identical or different and have the meanings given above for formula (I).

13. Process for the preparation of polyorganosiloxanes according to claim 11 or 12, characterized in that the polyorganosiloxanes used are polydiorgano - cyclic siloxanes having as general formula:

(RZSiO) _s (VO in which:

^• the symbols R are identical and / or different having the meanings given above for formula (I) and, preferably, the symbols R are alkyl radicals;

the symbols Z are identical or different and have the meanings given above for formula (IV) and, preferably, the groups Z are identical.

^• s is an integer between 3 and 10.

14. Process for the preparation of polyorganosiloxanes according to claim 13, characterized in that the symbols R are alkyl radicals, and more particularly methyl radicals.

15. Process for the preparation of polyorganosiloxanes according to claim 11 or 12, characterized in that the polyorganosiloxanes used are functionalized linear polyorganosiloxanes having as general formula:

R

I Zf ^ i-CHSiZ. (VII) ^z in which:

- the symbols R are identical and / or different and have the meanings given above for formula (I) and, preferably, the symbols R are alkyl radicals; - the symbols Z are identical or different and have the meanings given above for formula (IV);

- u is an integer between 2 and 3000.

16. Process for the preparation of polyorganosiloxanes according to claim 15 or 16, characterized in that the symbols R are alkyl, methoxy and / or hydroxy radicals, and more particularly methyl radicals.

17. Process for the preparation of polyorganosiloxanes according to claim 15, characterized in that the compounds defined by formula (VII) are:

RR (R ₂ SiO) _u SiR ₃ (VIII), or Rf ^ KHSiR, OX)

Z "

in which u is an integer between 2 and 3000.

18. Process for the preparation of polyorganosiloxanes according to one of claims 11 to 17, characterized in that one proceeds by casting the functionalized polyorganosiloxanes of formulas (VI) when Z is equal to R or V, and / or compounds of formula (VII) when Z is equal to V on the compounds of formulas (VI) and / or (VII) when Z is equal to X.

19. Process for the preparation of polyorganosiloxanes according to claim 18, characterized in that the casting time of the functionalized polyorganosiloxanes of formulas (VI) and (VII) in the reaction medium is at most equivalent to half the overall heating time of the medium reactional.