ES2236055T3 - COMPOSITION FOR THE TREATMENT OF FIBER MATERIALS. - Google Patents

Abstract

The composition of a medium to treat fiber materials, and especially for finishing textiles, has a diol with perfluoroalkyl groups or a conversion product of such a diol with an acid. It also contains an ethoxylated fatty acid or alcohol, and an oxidized polyolefin wax. The textile finishing medium contains: (A) a diol with the formulation (RF-Z-X-CH2(Y)b)2T, or a mixture of such diols and/or a conversion product of the diol with an acid and/or a mixtures of conversion products with adjustment of the pH value if necessary to 6-9; (B) an ethoxylate of a saturated or unsaturated fatty acid, or an ethoxylate of a saturated or unsaturated aliphatic alcohol with 8-24 carbon atoms; (C) an oxidized polyolefin wax and preferably polyethylene wax; and (D) water. RF = perflourated alkyl residue with 8-24 carbon atoms X = -O- or -S- or a simple chemical compound Z = -CH=CH-CH2- or (CH2)a a = 2-6 Y = -CH(OH)-CH2- b = 0 or 1 T = C(CH2OH)2 for N(CHR)c, CH2OH or N(CHR)c as COO- M+ c = 1-4 R = hydrogen or an alkyl reside with 1-6 carbon atoms, and M+ = Na+, K+ or NH4+. In the event that T is not for C(CH2OH)2 then b has a value of 1. Phosphor acid or polyphosphor acid is used for the diol conversion. The (A) component of the formula for the diol can have Z as (CH2)a with X for -O- or -S-, b has a value of 0 and T is for C(CH2OH)2, or it is a conversion product of the diol with an acid. The (A) component of the diol formula can have Z for -CH=CH-CH2-, X for -O- and b with a value of 1, and T for N(CHR)c, COO- M+ or CH2OH. The composition is a watery dispersion, with a dispersion agent or a mixture of dispersion agents as an additional component (E). An additional component (F) is a polyorganosiloxane with an amino or amido function, or one or more polyoxyalkylene groups, bonded to each Si atom by an alkylene bridge. The composition is free of polysiloxane where there are fluoro atoms, SiH compounds, SiOH compounds and/or SiOR compounds, where R is a suitable organic residue, and in silicon atoms bonded to 3 or 4 oxygen atoms. An additional component (G) is an alkali metal sulfonate or a sodium olefin sulfonate. The component proportions as parts by weight, in relation to 100 parts by weight of water (component D) are A: 5-20 and preferably 7-15; B: 5-20 and preferably 7-15; C: 1-10 and preferably 2-7; E: 1-10 and preferably 2-7; F: 0.5-8.0 and preferably 1-6; G: 0.3-5.0 and preferably 0.5-3.0.

Description

Composition for the treatment of materials fibers

The invention relates to an aqueous composition, which is appropriate for the treatment of fiber materials, in particular fabrics.

It is already known, the treatment of tissues in the textile finishing frame or respectively ennobling, with polymers, which contain perfluorinated radicals (RF). From this way, repellent properties can be communicated to the tissues to water and / or oil repellent. Regarding this, they are described suitable compositions in US 4,742,140 and the patent EP-A 325 918.

The finished fabrics with fluorpolymers without special additives have the disadvantage that they do not have the Soft touch that is desirable for many fields of employment. With polymers containing RF can be achieved so known oil and water repellent properties as well as a certain soil repellent action on soil tissues. However, it is not only unsatisfactory the touch of tissues treated only with RF polymers but also the release properties of dirt, that is, the removal of dirt from tissues is not achieved as far as desired. This could be caused by the low character hydrophilic or respectively due to the poor wettability of finished fabrics this way.

Because of the known disadvantages cited, tissue treatment with compositions has been tested, which contain in addition to the RF polymers, softening agents and hydrophilizing agents. Among the products that were mixed with the RF polymers for this purpose are polyorganosiloxanes, see p. eg, Textile Chemist and Colorist , Vol 29, No. 9, pages 26-29 (1997) , and EP-A 312 949. Mixtures of R_ {F} -polymers and silicones have the disadvantage that by adding silicones the tissue properties reported by the RF-polymers, such as p. eg, the oil-repellent action, they weaken. Nor does the assay of unifying perfluoralkyl groups and siloxane groups into a single copolymer, see p. e.g., patents WO 00/05315 and US 3 716 517, was able to solve the problem and did not lead to optimal tissue properties in regard to oil-repellent action, dirt removal behavior, and touch.

Nor by adding waxes from polyolefin to the compositions containing the fluorpolymers, see patent EP-A 445 077, can be solved from all satisfactorily the problems mentioned above.

In many cases, when finishing fabrics with known compositions, the problem of a pronounced graying with washing.

The objective that the present invention was proposed achieve, was to make available to the technique a highly effective composition for the treatment of materials fibers, which will not present the described disadvantages of known compositions, or present them only in one considerably reduced measure. In particular, the composition should be able to communicate to the tissues next to good oil repellent properties, a good hydrophilic character, a soft touch and good dirt removal properties, and next to this, prevent the unwanted effect of a crush on the washed. With the term "wash grating", the phenomenon that occurs when the tissues after the processes of Washing show a decrease in the degree of whiteness, e.g. eg due to the impurities of the wash bath. In addition, the composition it should be obtainable in the form of a stable aqueous dispersion, that was suitable for the finishing process in the finishing factory textiles

The objective was achieved through a composition with the following components:

A) A diol of formula (I)

(I) [R_ {F} - Z - X - CH 2} (Y) b] 2 T

or a mixture of said diols and / or a product obtained by reacting a diol of formula (I) with an acid and / or a mixture of said reaction product, in where eventually the pH value of the reaction product or of the mixture of said reaction product, is adjusted to a value between 6 and 9.

B) An ethoxylate of a saturated or no acid grade saturate, from 8 to 24 carbon atoms or an ethoxylate of an alcohol saturated or unsaturated aliphatic of 8 to 24 carbon atoms.

C) An oxidized polyolefin wax, of preferably an oxidized polyethylene wax,

D) Water

where

R F represents a perfluorinated alkyl radical from 8 to 24 carbon atoms,

X represents a -O- or -S- or a chemical bond simple,

where Z represents -CH = CH-CH 2 - or - (- CH 2 -) a -, in where a represents a number from 2 to 6,

And represents -CH (OH) -CH2 -,

b represents 0 or 1,

T represents C (CH 2 OH) 2, represents N - (- CHR -) c - CH 2 OH

or represents N - (- CHR -) c - COO ^ {\ ominus} M ^ {\ oplus},

where

c represents a number from 1 to 4,

R represents hydrogen or an alkyl radical of 1 at 6 carbon atoms and M ^ \ oplus represents Na ^ \ oplus, K ^ {\ oplus} or NH_ {4} ^ {\ oplus},

where in case T does not represent C (CH 2 OH) 2, b has the value 1.

When Z represents -CH = CH-CH2 -, the perfluoralkyl group RF it is preferably attached to the olefinic carbon atom and not to the group -CH_ {2} -.

Compositions according to the invention of the type mentioned they communicate to the tissues oil repellent properties, good behavior to the removal of dirt, properties hydrophilic, a pleasant soft touch and little tendency to cracking due to washing (new fouling in the process of washed). They are very appropriate for finishing fabrics, for which a good hydrophilic character and good washability is desired stains (removal of dirt), p. eg for finishing of fabrics for sportswear and leisure time, for curtains, as well as for finishing shirt collars and bedding. The fiber materials that are used for treatment with compositions according to the invention are preferably structures flat, p. eg, fabrics or knitwear. Results especially advantageous are obtained on tissues that are completely or partially p. For example, they consist of 30 to 100% by weight of cotton. The other Cotton blend component may be another fiber p. eg one synthetic fiber such as polyester or polyamide. Also others Cellulosic fibers such as cotton can be treated well with Compositions according to the invention. Also in the case of fibers Pure synthetics such as polyamide or polyester can be used the compositions according to the invention.

It is important that the compositions according to the invention contain the 4 components A) to D) cited above and also in claim 1. Component D) (water) serves to converting the composition according to the invention in a suitable form for application in the textile finishing factory; is application takes place preferably with a usual procedure of foulardado. For this the compositions are in the form of aqueous solutions or dispersions. In case the mixture of Components A) to C) is not soluble or self-dispersible in water (component D), a dispersant or mixture of dispersants In a preferred embodiment there are compositions according to the invention in the form of aqueous dispersions, which eventually also contain as component E) a dispersant or mixture of dispersants. They are appropriate as dispersants (component E) known surfactant compounds by the expert; mainly non-ionic dispersants and / or anionics are appropriate for obtaining dispersions more stable aqueous. As non-ionic dispersants they should be mentioned by example ethoxylated alcohols and ethoxylated fatty acids with a alkyl chain length of 8 to 24 carbon atoms. For the less such a dispersant must always be present as component B) in the compositions according to the invention, and can also added as component E) other surfactants, mainly when the stability of the aqueous dispersion Appropriate active anion dispersants are the surfactant products also known to those skilled in the art as p. eg, sulfates or carboxylates. Anionative dispersants particularly suitable are alkali metal sulphonates since cited above and in claims 9 and 10 as a component G). Your additional employment represents a preferred form of execution of the compositions according to the invention. They can contribute not only to the stability of the aqueous dispersions but that they can also act as additional agents to communicate a Soft touch. In this regard, sodium salts of the olefin sulfonates, e.g. eg, with a chain length of 8 to 18 carbon atoms

Together with the water (component D)) they must also be present all the other 3 components A), B) and C) in the compositions according to the invention, to achieve all advantages. In the event that component A) is missing (diol R_), finished fabrics have an oil repellent action too small and have no optimal properties with respect to behavior to the elimination of the dirt, as well as with respect to the wash grating.

The compositions that together with the water, contain components A) and C), but do not contain any component B), are lower compositions according to the invention regarding soft touch and hydrophilic character. However it is a sufficient hydrophilic character of the composition, to achieve good removal properties of the dirt. In addition, when component B) is missing, the stability of the aqueous dispersions of the compositions.

In case the component C) is not present, this has negative effects on tissue touch finishes, which is not as smooth in this case as with employment component set C). In addition, component C) contributes to increase the hydrophilic character and with it the improvement of dirt removal properties.

It was surprisingly discovered that the special combination of components A) to D) leads to magnificent effects regarding the aforementioned properties of the finished fabrics. A essential influencing factor is in this respect the chemical nature of component A).

Component A) is a diol or a mixture of diols of formula (I) and / or a product or a mixture of products, which are obtained by reacting a diol / mixture of diols of formula (I) with an acid

(I) [R_ {F} - Z - X - CH 2} - (- Y -) b -] 2 T

In this formula (I):

R F represents a perfluorinated alkyl radical from 8 to 24 carbon atoms,

X represents -O- or -S- or a chemical bond simple,

Z represents -CH = CH-CH2 - or - (- CH 2 -) a -, where a represents a number from 2 to 6,

And represents -CH (OH) -CH2 -,

b represents 0 or 1,

T represents

C (CH 2 OH) 2, \ N - (- CHR -) c -CH2OH \ or \ N - (- CHR -) c -COO ^ \ \ ominus M ^ {\ oplus},

in where

c is a number from 1 to 4,

R represents hydrogen or an alkyl radical of 1 at 6 carbon atoms and M ^ \ oplus represents Na ^ \ oplus, K ^ {\ oplus} or NH_ {4} ^ {\ oplus}.

When T is not C (CH 2 OH) 2 , b must not in any case have the value zero but must have the value 1.

For the use of the composition according to the invention for the treatment of fiber materials, is convenient that the mixture of water and component A) has, to room temperature, a pH value in the range of 6 to 9. In in particular, when component A) was obtained by reaction of a diol / mixture of diols of formula (I) with an acid, recommends adjusting the pH value of component A) in such a way that a mixture of component A) and water has a pH value of 6-9. The adjustment of the pH value can be achieved with bases, ammonia being particularly suitable.

In case the diols of formula (I) must react with acid, to obtain component A), it can be used as acid a strong inorganic acid, preferably an acid halogen free. Particularly suitable as acids are the H 3 PO 4 (phosphoric acid) aqueous or a polyphosphoric acid. The term "polyphosphoric acid" also includes in this regard pyrophosphoric acid H 4 P 2 O 7 as well as acids phosphoric of higher condensation.

Through the corresponding investigations it was found that component A) had a decisive action for the effects that can be achieved with the compositions according to the invention. The diols of formula (I) do not contain any proportion of polymers with the exception of the two perfluoralkyl groups (RF). The investigations resulted in the compositions according to the invention being superior to other compositions, which contain components B), C) and D), in which, however, component A) is substituted by a known polyurethane with groups R_ { F} or a known polyester with RF groups. The advantage of the compositions according to the invention over the compositions here called non-according-to-the-invention lies mainly in a magnificent hydrophilic character, in dirt removal properties and in the poor washing of finished fabrics. The cause of this could be the small hydrophilic character of the R_ {F} -polyurethanes or R_ {F} -polyesters compared to the
component A).

Component A) can be a unique diol of formula (I) or a mixture of said diols. In the normal case there is a mixture that produces the diols and whose individual representative differs in chain length of the radicals R_ {F}. Also the mixtures of compounds the which differ in the length of the chain of R_ {F} and / or in the value of a, can be used as components A). As a component A) mixtures of diols can also be used which they differ in that on the one hand the Z diols are represented by - (- CH 2 -) a - and then by -CH = CH-CH2 -. Similarly, it is valid when component A) the reaction products of the diols of formula (I) with an acid. There are also normal mixtures of compounds, which differ from the radicals RF in the chain length It is also possible to use as component A) mixtures containing both the free diols of the formula (I) and additionally the reaction products of the diols of formula (I) with the acid. In all the cases mentioned it is used for this preferably phosphoric acid or polyphosphoric acid reaction or a mixture thereof.

As component A) they are appropriate products that can be purchased commercially, e.g. eg, in the firm Ciba Spezialitätenchemie USA, with the name of LODYNE.

Particularly suitable as component A) are the diols of the formula (I) in which Z represents - (- CH 2 -) a -,
X represents -O- or -S-, b represents the value 0 and T represents C (CH 2 OH) 2, or the reaction products of said diols with an acid. These appropriate products as component A) and their preparation are described in US 4 946 992, US 5 091 550, US 4 898 981 and US 5 132 445. All the products cited therein are appropriate as component A), as long as they satisfy the conditions cited above, which are set in claim 1 of the present invention.

They are particularly appropriate as a component A), the products that can be obtained by the reaction of phosphoric or polyphosphoric acid with the preferred diols of formula (I) cited above and in claim 3, wherein R F radicals contain from 8 to 18 carbon atoms, Z represents - (- CH 2 -) a -, X represents -S- and T represents C (CH 2 OH) 2, and a has the value 2 and b the value 0, and the subsequent adjustment of the pH value with ammonia is a value from 6 to 9.

In case it is desired that component A) does not contain free diols of formula (I), or contain them in amounts invaluable, the diols of formula (I) react with such amounts of acid, which for each equivalent in OH groups of diols, at least one equivalent of hydrogen atoms is used acid acid, although preferably however, a excess acid This excess is preferably removed once The reaction is over, until a pH value results as described above, from about 6 to 9. It is particularly appropriate for this ammonia, p. eg, in the form of a solution aqueous NH3.

You can also work with more quantities smaller than equivalent amounts of acid, when desired that after the reaction diols are still free formula (I) in the reaction mixture.

Together with the preferred diols described in formula (I) there is another group of diols of formula (I) which are particularly suitable as component A) and therefore They are preferred. In a preferred form of execution of the compositions according to the invention, component A) is a diol or a mixture of diols of formula (I) wherein A) is a diol of formula (I), where

Z represents -CH = CH-CH2 -,

X represents -O-,

b has the value 1, and

T represents N - (- CHR -) c -COO ^ \ \ ominus M ^ {\ oplus} or N - (- CHR -) c -CH 2 OH.

Contrary to the representatives cited above, of the preferred diols (in which Z represents - (- CH 2 -) a - and T represents C (CH 2 OH) 2), it is also possible to use in the so-called second group (Z = -CH = CH-CH2 - and T = N-
(-CHR -) c -COO ^ {\ ominus} M ^ {\ oplus} or N - (- CHR -) c -CH2 OH), instead of the free diols, their acid reaction products, although this is not preferred. It is much more preferred to use the diols of this second group in free form.

It is further preferred that M ^ {\ oplus} represents NH_ {4} ^ {\ oplus} when T represents N - (- CHR -) c -COO ^ \ \ ominus M ^ {\ oplus}. He value of c is a number from 1 to 4, preferably 1 or 2. All R radicals in the units N - (- CHR -) c - represent, independently of each other, hydrogen or an alkyl radical of 1 to 6 carbon atoms, hydrogen or a linear alkyl radical, in particular hydrogen or CH 3.

Diols of the preferred group, in which Z = -CH = CH-CH 2 -, X = -O-, b = 1, T = N - (- CHR -) c - COO ^ ominus M ^ {\ oplus} or N - (- CHR -) c
-CH 2 OH, are described in US Patent 5 491 261 and US 5 585 517. Their obtaining can be achieved analogously to the process mentioned therein or by analogous use of the procedure of US Patent 5 254 754.

Obtaining R_ {F} -diols appropriate takes place preferably by the radical addition of perfluoralkyl iodides (RF-I) in non-diols saturated olefinic terminals, e.g. eg, unsaturated diols allylics, and the subsequent elimination of hydroiodic acid by one base. As described in the cited US patents, the addition takes place preferably using an azo compound as radical initiator and together with the use of salts inorganic sulfur-containing acids, e.g. eg Na 2 S 2 O 5.

Particularly suitable diols such as component A), can be obtained by adding an amino acid, e.g. eg, alanine or glycine, or an alkali metal or ammonium salt of an amino acid or a primary amine, in allyl glycidic ether (diallyl ether monoepoxide) in the molar ratio -NH2 / ether of about 1: 2 where the amino group is added to the ring of oxirane, subsequent addition of RF -I to the remaining allylic double bonds and elimination of HI by means of a base.

A product that can be used as component A is the LODYNE 2000 (Ciba Spezialitätenchemie).

This product still contains next to R_-F diol and water other substances constituents; however, it can be used without the need for separate them. It should be taken into account however, that in this case should be considered as component A), only the part of R_ {F} -diol, when relationships are established weights of the preferred compositions cited below.

Component B) is an ethoxylate of a saturated or unsaturated fatty acid or a saturated or unsaturated aliphatic alcohol. Fundamental fatty acid or fundamental alcohol contains 8 to 24 carbon atoms. In the normal case component B) is a mixture of products that differ in the length of the chain of the fundamental acid or respectively of the fundamental alcohol and / or in the degree of ethoxylation. The aforementioned statement that the number of carbon atoms is 8 to 24, also refers to the average number, where smaller amounts may also contain molecules with a somewhat higher or lower number of C atoms. As component B) mixtures containing both ethoxylated fatty acids of 8 to 24 carbon atoms as well as alcohols of 8 to 24 carbon atoms can also be used. Preferred chain lengths of fatty acids or aliphatic alcohols that serve as the basis for ethoxylates are in the range of 10 to 18 carbon atoms. The degree of ethoxylation, that is, the average number of units -CH_ {2} -CH2 -O- that exist in component B), is preferably in the range of 6 to 18. They are particularly very suitable as component B) ethoxylates of unsaturated or saturated fatty acids of 10 to 18 carbon atoms and average degrees of ethoxylation of
8 to 14.

Appropriate products as component B), may acquired in commerce and can also be obtained according to procedures already known by reacting the corresponding acids or alcohols with ethylene oxide.

Under the above-mentioned definition of component B) those products are also included in the which the terminal OH group that remains after ethoxylation, is substituted by an OR group, where R represents a group I rent. These products can be obtained, after the ethoxylation an etherification with an alcohol ROH according to methods already known. R represents in this case preferably a methyl group. However, for component B) compounds are preferred in the which the terminal OH group exists as such, that is, it has not reacted

As already mentioned, the compositions according to invention may contain in addition to component B) other products surfactants (component E)), preferably these are of the type no ionic or active anion, p. eg, other ethoxylated compounds, among which are also those that do not fall within the definition of component B). However, it must be checked beforehand, if with this does not deteriorate the advantageous properties of the compositions according to the invention or fabrics finished with she.

Component C) is an oxidized polyolefin wax. Oxidized polypropylene waxes, oxidized ethylene / propylene copolymer waxes, or mixtures, which contain both oxidized polyethylene waxes and also oxidized propylene waxes and / or said oxidized copolymer waxes, can be used. Preferably, oxidized polyethylene waxes are used exclusively.

Oxidized polyolefin waxes are already known. By reacting polyolefins with agents Oxidants originate polar groups in the polymer, e.g. eg groups -COOH, which communicate a certain hydrophilic character to the polymers thus modified. Component C) of the compositions according to the invention therefore communicates hydrophilic properties to the compositions which are important for behavior of dirt removal from finished fabrics. further They communicate a nice and soft touch to textiles.

As component C) they are particularly suitable those oxides of oxidized polyolefins, preferably waxes of oxidized polyethylene, which with the use of known non-ionic dispersants can be obtained in the form of dispersions aqueous, and have a melting range between 120ºC and 160ºC. Oxidized HDPE-based waxes are appropriate, which can Obtained commercially in the form of aqueous dispersions. A example is the product Glaswax® E1 from Ciba Spezialitätenchemie, Basel, whose wax component has a melting point in the middle margin

Other suitable oxidized waxes can be obtained in commerce and are described in the literature, p. eg EP-A 641 833, EP-A 412 324, US4 211 815, DE-A 28 24 716, DE-A 19 25 993 and US 3 060 163.

In addition, it should be noted as appropriate, waxes oxidized polyolefins, in particular oxidized polyethylene waxes of the literature cited in patent EP-A 412 324

Very particularly appropriate as component C) are oxidized polyethylene waxes with a density at 20 ° C in the margin of 0.91 to 1.05 g / cm3, an acid number greater than 5, in particularly from 10 to 60, particularly preferred from 20 to 45 mg KOH / g and a melting range that is between 90 and 160 ° C, preferably from 120 to 160 ° C.

To obtain compositions according to the invention, component C) can be used in solid state, mixing with the rest of the components and homogenizing. They can however, prepared aqueous dispersions of the component are used C), which can be purchased commercially, mixing with the other components In case of starting a polyolefin wax oxidized in solid form, which before mixing with the rest of components must be dispersed in water, can be used for this dispersants that are already known to the expert. Examples are the linear and / or branched ethoxylated alcohols.

Obtaining compositions according to the invention can be achieved by mixing the individual components, if any with the addition of one or more dispersants (component E)), at temperature ambient or high temperature. It can also start from water or a mixture of water and component E), and add the components individual A), B) and C) in a random order. In isolated cases, The stability of the aqueous dispersion obtained depends on the order in which the mixing has been made, in these cases you can The optimal order is easily determined by several tests. In In any case, it is advantageous as regards its application in the fabric finishing, that the compositions according to the invention are present in the form of stable aqueous dispersions.

The compositions according to the invention contain components A) to C) preferably in the following relationship of quantities, referred to 100 parts by weight of water (component D))

Component A) 5 to 20, in particular 7 to 15 parts in weigh

Component B) 5 to 20, in particular 7 to 15 parts in weigh

Component C) 1 to 10, in particular 2 to 7 parts in weigh

In a preferred embodiment the compositions according to the invention additionally contain as component F) a polyorganosiloxane with an amino function or a amido function, or a mixture of said polyorganosiloxanes. Between the aminofunctional or amido polyorganosiloxanes functional, are included in this regard polyorganosiloxanes (silicones), which contain one or more radicals, which in turn contain amino groups or respectively Amido groups These products can be obtained commercially, e.g. eg, from Wacker Chemie, DE, or Dow Corning. The amino or respectively amido groups are usually linked by an alkylene group each to an Si atom, e.g. eg by a group -CH_ {2} -CH_ {2} - or -CH_ {2} -CH_ {2} -CH_ {2} -. In the radicals attached to Si may be present or only one -NH2 terminal group or several amino groups p. eg, in the form of formula radicals -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH 2. In case the polyorganosiloxane contains amido groups, they can additionally there are amino groups. These polyorganosiloxanes are described in patents EP-A 342 830 and EP-A 342 834.

The amino functional polyorganosiloxanes in which does not exist any amido group, as well as its obtaining, are already known in the literature, p. e.g., EP-A 138 192, EP-A 578 144, WO 88/08436. Very particularly appropriate as component F) are polyorganosiloxanes, which next to amino groups still contain radicals attached to Si atoms, in which there are polyoxyalkylene groups, particularly polyoxyethylene groups. Polymers of this type are described in EP-A 578 144, are polymers particularly appropriate, which are mentioned in this document in claim 1, with the formula (III). In these polymers polyoxyalkylene groups are in each case by means of a alkylene bridge attached to a silicon atom. Are appropriate as component F) in addition, polyorganosiloxanes, which contain one or more radicals, in which amino groups are present secondary, of formula -NX- where X represents a radical unsubstituted or substituted cyclohexyl. Other polyorganosiloxanes Appropriate amino functionalities are described in the patent EP-A 659 930.

Preferably they are used as component F) linear polyorganosiloxanes, whose terminal groups are radical (CH 3) 3 Si-O-. Also in the polysiloxane chains are all radicals attached to atoms of silicon, which does not contain any oxygen atom or any nitrogen atom, preferably, methyl groups. Can also happen, which is less preferred, than a part of the groups -CH_ {3} terminals or that are in the chain, can be each time substituted with a phenyl group or an alkyl group of long chain, p. eg, a chain length of 2 to 12 atoms of carbon. It is also preferred when none of the Si atoms of the polyorganosiloxane is linked more than one functional group, it is that is, more than one radical containing oxygen or nitrogen.

By adding a component F) to the compositions according to the invention can be further improved the Nice soft touch of the finished fabrics. In the case that in component F) there are also polyoxyethylene units, it increases the hydrophilic character of the compositions according to the invention and also the hydrophilic character of the finished fabrics, which brings advantages over the elimination properties of dirt.

As component F) they are particularly appropriate said amino or amidofunctional polyorganosiloxanes that do not have no fluorine atom, no union silicon-hydrogen (Si-H), none Si-OH junction and no Si-OR junction. In addition, no preferred content is contained in these preferred polysiloxanes. silicon atom, to which 3 or 4 oxygen atoms are attached, the polysiloxanes are not preferably cross-linked They represent a linear polysiloxane framework. R means to In this respect, any organic radical.

Together with the so-called polyorganosiloxanes (component F)) amino or amidofunctional, the compositions according to invention may still additionally contain polyorganosiloxanes nitrogen free, p. eg, polydimethylsiloxanes. Neither do these, as described above, they are preferably crosslinked, and preferably they contain no fluorine atom, no union Si-H, no Si-OH and none Yes-OR.

In a preferred embodiment, the compositions according to the invention additionally contain as component G) an alkali metal sulphonate, e.g. eg, a salt of Na or K of an alkanesulfonic acid of 2 to 18 carbon atoms. They are particularly suitable are sodium olefin sulfonates, which can be obtained in a known manner and manner by reaction of 1 olefin with sulfur trioxide in the form of gas and subsequent neutralization with aqueous NaOH. These products can be obtained at trade.

Preferably the compositions according to the invention contain components A) to C) and E) to G) in the following ratios of quantities, referred to 100 parts by weight of water (component D)).

A) from 5 to 20, preferably 7 to 15, parts in weight

B) from 5 to 20, preferably 7 to 15, parts in weight

C) from 1 to 10, preferably 2 to 7, parts in weight

E) from 1 to 10, preferably 2 to 7, parts in weight

F) 0.5 to 8, preferably 1 to 6 parts in weight

G) from 0.3 to 5, preferably 0.5 to 3 parts in weight

The compositions according to the invention are used preferably in the form of aqueous dispersions for treatment of fiber materials, in particular of textile structures flat and preferably applied by a procedure of current foulardado on the tissues. The concentration of the bathroom of Standard and procedure conditions can be chosen according to the current state of the art. If desired, they can be added to the compositions according to the invention or respectively the baths of foulardado, other products already known in the finish or ennobled textile, p. eg, cellulose crosslinking agents and / or agents flame retardants, biocides, etc. After application in the foulard, the tissues are dried in a known manner and eventually condense at high temperature.

The invention is illustrated below by Examples of different forms of execution.

6 aqueous formulations were prepared. The board following shows its quantitative compositions (in parts in weight).

TABLE 1 Quantitative compositions of the formulations investigated, in parts by weight

one

Examples / formulations Nos 1, 2 and 6 are refer to the compositions according to the invention, examples 3, 4 and 5 represent comparative examples unrelated to the invention.

In table 1, they mean:

Component A1:

Product of reaction of polyphosphoric acid with a diol of formula (I) according to the claim 1, wherein Z = - (- CH 2 -) a -, X = -S-, b = 0, T = C (CH 2 OH) 2, where this product reaction is in a form neutralized with ammonia.

Component A2:

Formula Diol (I) according to claim 1, wherein Z = -CH = CH-CH2 -, X = -O-, b = 1, T = N-CH2 -COO ^ {\ ominus} NH_ {4} \ oplus}.

The amounts of components A1 or A2 respectively in examples 1 and 2, they chose so that formulations 1 and 2 had approximately the same content (in% by weight) of fluorine.

Component B:

Ethoxylate coconut fatty acids (average of approximately 8 to 12 moles of ethylene oxide)

Component C:

Wax oxidized polyethylene (CAS No. 68441-17-8)

Component D:

Water

Component E:

Mix of nonionic dispersants (ethoxylates)

Component F:

Mix of two aminofunctional polyorganosiloxanes of which one contains polyoxyethylene groups.

Component G:

Olefinsulfonate of sodium.

The formulations of all 6 examples were stable in aqueous dispersions.

With formulations 1 to 6 (corresponding to Examples 1 to 6) were finished with each of them, 4 samples of fabric by a fouling procedure (concentration of bath 45 g / liter).

The 4 tissues were:

a) cotton 100%

b) Polyester / Cotton (65/35)

c) taffeta of 100% polyester

d) taffeta of 100% polyamide

Bath absorptions produced in the Foulardado (absorption by weight after squeezing) were:

Fabric a) 81%

Fabric b) 74%

Fabric c) 62%

Fabric d) 79%

After the fouling, the tissues were dried 110 ° C to constant weight and then condensed 5 minutes at 150 ° C.

The tissues were evaluated below with respect to to the following parameters:

Character hydrophilic

Behavior to dirt removal

Grating by washed

Soiling by drying

Touch

In this respect the results were obtained set out in table 2.

TABLE 2

3

In the case of the behavior to the elimination of dirt, score 4-5 means that after of the execution of the method described below, it is not left over tissues no edge of dirt or in any case very small. The note 3-4 means that there are still clear edges of dirt.

A high number in the score for the wash grating means smaller grating; the score 4-5 means a crushing very small, the score 5 means a crush even more small (virtually no graying) while scoring 3-4 means clear grating.

Individual determinations were made according to the following methods.

Touch

A manual determination was made

Hydrophilic character

The determination was made by measuring the time during which a drop of water applied on the tissue to 20ºC penetrates inside. This time is the time (in seconds) that elapses between the application of the drop of water and the moment to from which it is observed that the drop no longer spreads over the tissue.

Dirt removal behavior

They are applied on the different tissue sample dirt classes in the form of spatially limited spots. Among the types of dirt tested are graphite, motor oil, skin creams, vegetable oil, mayonnaise, Mustard and red wine.

After the application of the spots of dirt, a weight was applied to the fabric in the stained areas for 60 seconds After removing the weight, the tissues are stored for about 30 minutes and then washed in a Domestic washing machine with an aqueous solution of a detergent. Then it was observed visually to what extent the stain of dirt had been removed with washing. The results are expressed in the form of a score where numerical values higher mean the most effective elimination scores of dirt (= better behavior to eliminate dirt). The numbers indicated in table 2 for the dirt removal behavior represent the average values from different tissues and different types of dirt.

Crushing by washing (= new fouling in the process of washed)

After the execution of the test described further above about the behavior to the removal of dirt is visually ruled in the washed tissue samples the tone of whiteness or gray color respectively. To do this assigned scores (5 = very good, 1 = very bad). As in the case from behavior to dirt removal, scores listed in table 2 for washing graying They represent average values.

Drying fouling

To do this, the samples are set in motion. dried tissue inside a rotating drum, in which there are some moving metal balls that deal with Actively transport dirt to tissues. Dry dirt used for it is made up of 5% of the so-called dirt standard (Du Pont) and 95% marine sand. The tissues moved for 20 minutes in the hype. Then they were treated 5 minutes more with clean metal balls, to remove adherent dirt That was completely loose. The fouling of the tissues is then visually ruled expressing it in the form of a score (5 = the best score).

Claims (14)

1. Composition containing components A), B), C) and D), where component A), is chosen from

to)

  diols of formula (I)

(I) [R_ {F} - Z-X- CH2} - (- Y -) b -] 2 T

b)

products that are formed by reaction of a diol of formula (I) with an acid where eventually the pH value of the product reaction is set to a value between 6 and 9,

where component B) is an ethoxylate of an acid saturated or unsaturated fat, 8 to 24 carbon atoms or a ethoxylate of a saturated or unsaturated aliphatic alcohol, from 8 to 24 carbon atoms, where component C) is a polyolefin wax oxidized, preferably an oxidized polyethylene wax, and where component D) is water, where R F represents a perfluorinated alkyl radical from 8 to 24 carbon atoms, X represents a -O- or -S- or a chemical bond simple, where Z represents -CH = CH-CH 2 - or - (- CH 2 -) a -, where a represents a number from 2 to 6, And represents -CH (OH) -CH2 -, b represents 0 or 1, T represents C (CH 2 OH) 2, represents N - (- CHR -) c - CH 2 OH or represents N - (- CHR -) c -COO ^ M \ {\ oplus}, where c represents a number from 1 to 4, R represents hydrogen or an alkyl radical of 1 at 6 carbon atoms and M ^ \ oplus represents Na ^ \ oplus, K ^ {\ oplus} or NH_ {4} ^ {\ oplus}, where in case T does not represent C (CH 2 OH) 2, b has the value 1. 2. Composition according to claim 1, characterized in that the reaction of the diol of formula (I) with acid is used with phosphoric acid or polyphosphoric acid. 3. Composition according to claim 1 or 2, characterized in that component A) is a diol of formula (I), wherein Z represents - (- CH 2 -) a -, X represents -O- or -S-, b has the value 0 and T represents -C (CH 2 OH) 2, or because component A) is a product of reaction of one of such diols and an acid. 4. Composition according to claim 1 or 2, characterized in that component A) is a diol of formula (I), wherein Z represents -CH = CH-CH2 -, X represents -O-, b has the value 1, and T represents N - (- CHR -) c -COO ^ \ \ ominus M ^ {\ oplus} or N - (- CHR -) c -CH 2 OH. 5. Composition according to one or more of claims 1 to 4, characterized in that it is in the form of an aqueous dispersion and optionally additionally contains as component E) a dispersant or a mixture of dispersants. 6. Composition according to one or more of claims 1 to 5, characterized in that it additionally contains as component F) an amino functional or amidofunctional polyorganosiloxane. 7. Composition according to claim 6, characterized in that the component F) contains one or more polyoxyalkylene groups, which by means of an alkylene bridge are each linked to a Si atom. Composition according to one or more of claims 1 to 7, characterized in that it does not contain any polysiloxane, in which fluorine atoms, Si-H bonds, Si-OH bonds, Si-OR bonds, and / or are present in the which are present silicon atoms to which 3 or 4 oxygen atoms are attached, where R represents any organic radical. 9. Composition according to one or more of claims 1 to 8, characterized in that it additionally contains as component G) an alkali metal sulphonate. 10. Composition according to claim 9, characterized in that component G) is a sodium olefin sulfonate. Composition according to one or more of claims 1 to 10, characterized in that referring to 100 parts by weight of water (component D)) contains components A) to C) and E) to G) in the following quantity ratios: A) 5 to 20, preferably 7 to 15 parts in weight B) 5 to 20, preferably 7 to 15 parts in weight C) 1 to 10, preferably 2 to 7 parts in weight E) 1 to 10, preferably 2 to 7 parts in weight F) 0.5 to 8, preferably 1 to 6 parts in weight G) 0.3 to 5, preferably 0.5 to 3 parts in weight 12. Use of a composition according to one or more of claims 1 to 11, for the treatment of materials of fibers 13. Use according to claim 12, characterized in that the fiber materials are flat textile structures. 14. Use according to claim 12 or 13, characterized in that the fiber materials consist entirely or partially of cotton.