EP1225269B1 - Composition for the treatment of fibre materials - Google Patents

Composition for the treatment of fibre materials Download PDF

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Publication number
EP1225269B1
EP1225269B1 EP01101306A EP01101306A EP1225269B1 EP 1225269 B1 EP1225269 B1 EP 1225269B1 EP 01101306 A EP01101306 A EP 01101306A EP 01101306 A EP01101306 A EP 01101306A EP 1225269 B1 EP1225269 B1 EP 1225269B1
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EP
European Patent Office
Prior art keywords
component
composition
diol
acid
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP01101306A
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German (de)
French (fr)
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EP1225269A1 (en
Inventor
Simpert Lüdemann
Jürgen Riedmann
Walter Nassl
Franz Dr. Dirschl
Rolf Dr. Moors
Werner Stechele
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huntsman Textile Effects Germany GmbH
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Ciba Spezialitaetenchemie Pfersee GmbH
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Priority to AT01101306T priority Critical patent/ATE289639T1/en
Priority to DE50105416T priority patent/DE50105416D1/en
Priority to EP01101306A priority patent/EP1225269B1/en
Priority to ES01101306T priority patent/ES2236055T3/en
Publication of EP1225269A1 publication Critical patent/EP1225269A1/en
Application granted granted Critical
Publication of EP1225269B1 publication Critical patent/EP1225269B1/en
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Classifications

    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/165—Ethers
    • D06M13/17—Polyoxyalkyleneglycol ethers
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/144—Alcohols; Metal alcoholates
    • D06M13/148—Polyalcohols, e.g. glycerol or glucose
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/21—Halogenated carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/213—Perfluoroalkyl carboxylic acids; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/10—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing oxygen
    • D06M13/184—Carboxylic acids; Anhydrides, halides or salts thereof
    • D06M13/207—Substituted carboxylic acids, e.g. by hydroxy or keto groups; Anhydrides, halides or salts thereof
    • D06M13/217—Polyoxyalkyleneglycol ethers with a terminal carboxyl group; Anhydrides, halides or salts thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/248—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing sulfur
    • D06M13/256—Sulfonated compounds esters thereof, e.g. sultones
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/244—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus
    • D06M13/282—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing sulfur or phosphorus with compounds containing phosphorus
    • D06M13/292—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof
    • D06M13/298—Mono-, di- or triesters of phosphoric or phosphorous acids; Salts thereof containing halogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/325—Amines
    • D06M13/328—Amines the amino group being bound to an acyclic or cycloaliphatic carbon atom
    • D06M13/33—Amines the amino group being bound to an acyclic or cycloaliphatic carbon atom containing halogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/227—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of hydrocarbons, or reaction products thereof, e.g. afterhalogenated or sulfochlorinated
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/643—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain
    • D06M15/6436—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds containing silicon in the main chain containing amino groups
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
    • D06M2101/02—Natural fibres, other than mineral fibres
    • D06M2101/04—Vegetal fibres
    • D06M2101/06—Vegetal fibres cellulosic
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M2200/00—Functionality of the treatment composition and/or properties imparted to the textile material
    • D06M2200/10—Repellency against liquids
    • D06M2200/11—Oleophobic properties

Definitions

  • the invention relates to an aqueous composition which is suitable for the treatment of fiber materials, especially textiles.
  • Textiles which have been equipped with fluoropolymers without any other additives have the disadvantage that they do not have the desirable for many applications pleasantly soft grip.
  • polymers containing R F can be oil-and water-repellent properties and a certain soil-repellent effect on the textiles in a known manner.
  • the soil release properties ie the removal of soil from the textiles is not attainable to the desired extent. The latter could be due to the inadequate hydrophilicity or wettability of the textiles so finished.
  • the object underlying the present invention was to provide a highly effective To provide a composition for the treatment of fiber materials, which the described disadvantages of known compositions not or only in one considerably reduced level.
  • the composition should be suitable Textiles in addition to oil-repellent properties good hydrophilicity, soft feel and good soil-release properties, and in addition the undesirable effect of a Waschvergrauung to suppress.
  • Under Waschvergrauung here is the phenomenon to understand that textiles after washing have a reduction in whiteness, e.g. conditioned due to impurities in the wash liquor.
  • the composition in the form of a stable aqueous dispersion, which is suitable for the finishing process in the textile finishing operation suitable.
  • the perfluoroalkyl group R F is preferably attached to the olefinic carbon atom and not to the -CH 2 - group.
  • compositions of the type mentioned give textiles oil repellent Properties, good soil release behavior, hydrophilic properties, pleasantly soft feel and little tendency to Waschvergrauung (Wiederanschmutzung the washing process). she Among other things, they are very suitable for finishing textiles that have good hydrophilicity and good soil release is desired, e.g. to the equipment of textiles for sports and leisure purposes, for curtains and for shirt collars and bed linen.
  • the fiber materials which are suitable for the treatment with inventive Compositions are preferably textile fabrics, e.g. tissue or knitted fabric. Particularly advantageous results are achieved on textiles, the whole or partially, e.g. consist of 30 to 100% by weight of cotton.
  • the mixing partner for the Cotton may be another fiber, e.g. a synthetic fiber like polyester or polyamide. Other cellulose fibers than cotton can be well with inventive Treat compositions. Even with pure synthetic fibers such as polyamide or Polyesters can be used according to the invention.
  • compositions according to the invention all mentioned above 4 and in claim 1 Components A) to D) included.
  • Component D) (water) serves the inventive Composition suitable for use in textile finishing operation To bring form; This application is preferably carried out in a conventional padding process.
  • the compositions are either in the form of aqueous solutions or dispersions in front. If the mixture of components A) to C) is not soluble in water (component D)) or self-dispersible, it must for a dispersant or a mixture of dispersants be added. In a preferred embodiment are therefore inventive Compositions in the form of aqueous dispersions, optionally in addition as component E) a dispersant or a mixture of dispersants.
  • Suitable Dispersants are the surface-active agents known to the person skilled in the art Links; especially nonionic and / or anionic dispersants are for the production stable aqueous dispersions suitable.
  • non-ionic dispersants are here, for example ethoxylated alcohols and ethoxylated fatty acids having an alkyl chain length of 8 to To call 24 carbon atoms.
  • At least one such dispersant must be used as component B) always present in compositions of the invention, but it can also be used as a component E) further such surfactants are added, especially if this causes the stability the aqueous dispersion can be improved.
  • Suitable anionic dispersants are the surface-active products also known to those skilled in the art, e.g.
  • Sulfates or carboxylates are particularly suitable anionic dispersants. Particularly suitable anionic dispersants are those given above and in claims 9 and 10 as component G) alkali metal sulfonates. Their additional use represents a preferred embodiment of inventive compositions. You can contribute not only to the stability of the aqueous dispersions, but also as an additional Softening agent act. Preferred herein are the sodium salts of olefin sulfonates, e.g. With a carbon chain length of 8 to 18.
  • compositions according to the invention In addition to water (component D)), all 3 components A), B) and C) must also be present in compositions according to the invention in order to achieve their apex. If component A) (R F -diol) is lacking, the finished textiles have too low an oil-repellent effect and not optimal properties with respect to soil-release behavior and with respect to washing scrubbing. Compositions which, besides water, contain components A) and C) but no component B) are inferior to softness and hydrophilicity according to the invention. On the other hand, sufficient hydrophilicity of the composition is required to achieve good soil release properties. In addition, in the absence of component B), the stability of aqueous dispersions of the compositions may be impaired.
  • component C) is not present, this has a negative effect on the handle of finished textiles, which in this case is not as soft as with the concomitant use of component C).
  • the component C) contributes to increase the hydrophilicity and thus to improve the soil-release properties.
  • Component A) is a diol or a mixture of diols of the formula (I) and / or a product or a mixture of products which are formed by reacting a diol / diol mixture of the formula (I) with an acid [R F -ZX-CH 2 (Y) b] 2 T
  • R F is a perfluorinated alkyl radical having 8 to 24 carbon atoms
  • X is -O- or -S- or a simple chemical bond
  • Y is -CH (OH) -CH 2 -
  • b stands for 0 or 1
  • T is C (CH 2 OH) 2 , N (CHR CH 2 OH or for N (CH R COO ⁇ M ⁇ , in which c is a number from 1 to 4
  • R is hydrogen or an alkyl radical having 1 to 6 carbon atoms and M ⁇ is Na ⁇ , K ⁇ or NH 4 ⁇ .
  • T does not stand for C (CH 2 OH) 2 , b) may not have the value zero, but must have the value 1.
  • a mixture of water and component A) at room temperature has a pH in the range of 6 to 9.
  • component A) was obtained by reacting a diol / diol mixture of the formula (1) with an acid, it is therefore advisable to adjust the pH of component A) so that a mixture of component A) and water pH in the range of 6-9.
  • the pH can be adjusted with bases, particularly suitable for this purpose is ammonia.
  • the acid may be an inorganic strong acid, preferably a halogen-free acid.
  • Particularly suitable acids are aqueous H 3 PO 4 (phosphoric acid) or a polyphosphoric acid.
  • polyphosphoric acid in this context also includes the pyrophosphoric acid H 4 P 2 O 7 and higher-condensed phosphoric acids.
  • compositions according to the invention have a decisive effect on the effects that can be achieved with compositions of the invention.
  • the diols of formula (I) have no polymeric moieties except for the two perfluoroalkyl groups (R F ).
  • Investigations have shown that compositions according to the invention are superior to other compositions containing components B), C) and D), but in which component A) is replaced by a known polyurethane having R F groups or a known polyester with R F groups ,
  • the advantage of compositions according to the invention over the non-inventive compositions mentioned here is above all in excellent hydrophilicity, in the soil-release properties and the low degree of wash-soiling of finished textiles. The reason for this could be the lower hydrophilicity of R F polyurethanes or R F polyesters over component A).
  • Component A) may be a single diol of formula (I) or a mixture of such diols. In the normal case, a mixture is present which is obtained in the preparation of the diols and whose individual representatives differ in the chain length of the radicals R F. Mixtures of compounds which differ in the chain length of R F and / or in the value of a can also be used as component A).
  • component A mixtures which contain both free diols of the formula (I) and additionally reaction products of diols of the formula (I) with acid.
  • preference is given to using phosphoric acid or polyuric acid or a mixture thereof for this reaction.
  • component A Products suitable as component A) are available on the market, for example from Ciba Spezialitätenchemie USA under the name LODYNE. Particularly suitable as component A) are diols of the formula (I) in which Z is (CH 2 X is -O- or -S-, b is 0 and T is C (CH 2 OH) 2 , or reaction products of such diols with acid. Such products suitable for use 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 products mentioned therein are suitable as component A), provided that they fulfill the conditions, those mentioned above and defined by claim 1 of the present invention.
  • component A) Particularly suitable as component A) are products which can be obtained by reacting phosphoric acid or polyphosphoric acid with the preferred diols of the formula (I) mentioned above and in claim 3, in which the radicals R F contain from 8 to 18 carbon atoms, Z for (CH 2 X is -S- and T is C (CH 2 OH) 2 and a is 2 and b is 0 and subsequent adjustment of the pH to 6-9 with ammonia.
  • component A) contains no or negligible amounts of free diols of formula (I)
  • diols of formula (I) are reacted with such amounts of acid that for each equivalent of OH groups of the diols at least one equivalent acidic hydrogen atoms of the acid is used, but preferably an excess of acid.
  • This excess is preferably removed after completion of the reaction until a pH as described above results in from about 6 to 9.
  • Particularly suitable for this is ammonia, for example in the form of an aqueous NH 3 solution.
  • it is also possible to use less than equivalent amounts of acid if it is desired that free diols of the formula (I) are still present in the reaction mixture after the reaction.
  • R F dimes preferably takes place by free-radical addition of perfluoroalkyl iodides (R F -J) to terminally olefinically unsaturated diols, for example allylic unsaturated diols, and subsequent elimination of hydrogen iodide by means of base.
  • R F -J perfluoroalkyl iodides
  • the addition is preferably carried out using an azo compound as a radical initiator and with concomitant use of inorganic salts of sulfur-containing acids, for example Na 2 S 2 O 5 .
  • suitable diols can be obtained by addition of an amino acid, for example alanine or glycine, or an alkali metal or ammonium salt of an amino acid, or a primary amine to allyl glycidyl ether (monoepoxide of diallyl ether) in the molar ratio -NH 2 / ether of about 1: 2, where the amino group adds to the oxirane ring, subsequent addition of R F -J to the remaining allylic double bonds and HJ elimination by means of base.
  • a product useful as component A is LODYNE 2000 (Ciba Specialty Chemicals).
  • Component B) is an ethoxylate of a saturated or unsaturated fatty acid or of a saturated or unsaturated aliphatic alcohol.
  • the underlying fatty acid or alcohol contains 8 to 24 carbon atoms.
  • component B) is a mixture of products which differ in the chain length of the underlying acid or of the underlying alcohol and / or in the degree of ethoxylation.
  • the above statement that the number of carbon atoms is 8 to 24, therefore, refers to their average number, and in smaller amounts, molecules with a slightly higher or lower number of carbon atoms can be included.
  • component B) it is also possible to use mixtures which contain both ethoxylated fatty acids with C 8 to C 24 and also alcohols with C 8 to C 24 .
  • the preferred chain lengths of the fatty acids or aliphatic alcohols underlying the ethoxylates are in the range of 10 to 18 carbon atoms.
  • the degree of ethoxylation, ie the average number of -CH 2 -CH 2 -O units present in component B) is preferably in the range from 6 to 18.
  • Particularly suitable as component B) are ethoxylates of unsaturated or saturated fatty acids having from 10 to 18 ° C. Atoms and average degrees of ethoxylation from 8 to 14.
  • Suitable as component B) products are commercially available and can be obtained by known methods by reacting the corresponding acids or alcohols with ethylene oxide.
  • component B) also includes products in which the terminal OH group remaining after ethoxylation is replaced by an OR group, where R is an alkyl group. Such products can be made by etherifying with ethoxylation an alcohol ROH by known methods. R in this case is preferably a methyl group. However, compounds are preferred for component B) in which the terminal OH group is present as such, that is, was not further reacted.
  • compositions according to the invention may contain, in addition to component B), further surface-active products (component E)), preferably these are non-ionogenic or anion-active species, for example further ethoxylated compounds, including those which do not fall under the definition of component B). However, it must first be examined whether this does not impair the advantageous properties of compositions according to the invention or of textiles finished therewith.
  • Component C) is an oxidized polyolefin wax.
  • Oxidized polypropylene waxes, oxidized ethylene / propylene copolymer waxes or mixtures containing both oxidized polyethylene waxes and oxidized propylene waxes and / or the said oxidized copolymer waxes can be used. Preferably, however, only oxidized polyethylene waxes are used. Oxidized polyolefin waxes are known. Reaction of polyolefins with oxidizing agents produces polar groups in the polymer, for example -COOH groups, which bring about a certain hydrophilicity of the polymer modified in this way.
  • component C) of the compositions of the invention therefore results in hydrophilic properties of the compositions which are important for the soil-release behavior of finished textiles. In addition, it leads to a pleasantly soft feel of the textiles.
  • Particularly suitable as component C) are those oxidized polyolefin waxes, preferably oxidized polyethylene waxes, which can be obtained using known nonionic dispersants in the form of stable aqueous dispersions and which have a melting range between 120.degree. C. and 160.degree.
  • Suitable oxidized waxes based on HDPE which are available in the form of aqueous dispersions in the market.
  • oxidized waxes are available on the market and described in the literature, for example EP-A 641 833 , EP-A 412 324 , US Pat. No. 4,211,815, DE-A 28 24 716, DE-A 19 25 993 and US Pat. No. 3,060 163rd
  • suitable oxidized polyolefin waxes in particular oxidized polyethylene waxes, are apparent from the literature cited in EP-A 412 324.
  • Particularly suitable as component C) are oxidized polyethylene waxes having a density at 20 ° C.
  • component C) in the solid state used and mixed with the other components and homogenized. It however, ready-to-use aqueous dispersions of component C) which are used in the Commercially available and mixed with the other components. If from one oxidized polyolefin wax in solid form and this before mixing Dispersants may be dispersed in water with the other components used, which are known in the art. Examples are ethoxylated linear and / or branched alcohols.
  • compositions according to the invention can be achieved by mixing the individual Components, optionally with the addition of one or more dispersants (Component E)), at room temperature or elevated temperature. It can also be from Water or a mixture of water and component E) and the individual Components A), B) and C) are added in any order.
  • dispersants Component E
  • It can also be from Water or a mixture of water and component E) and the individual Components A), B) and C) are added in any order.
  • the stability of the resulting aqueous dispersion depends on the order of mixing, in these cases, the optimal order is easily determined by experiment. In any case It is advantageous in terms of their application to textile finishing when compositions according to the invention in the form of stable aqueous dispersions.
  • compositions according to the invention additionally contain, as component F), an amino-functional or an amido-functional polyorganosiloxane or a mixture of such polyorganosiloxanes.
  • aminofunctional or amido-functional polyorganosiloxanes are understood as meaning polyorganosiloxanes (silicones) which contain one or more radicals which contain amino groups or amido groups.
  • silicones silicones
  • Such products are available on the market, for example from Wacker Chemie, DE, or from Dow Corning.
  • the amino or amido groups are in this case usually bound via an alkylene group to a respective Si atom, for example via a -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 group.
  • either only one terminal -NH 2 group can be present or several amino groups, for example in the form of radicals of the formula -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH 2 .
  • additional amino groups may be present.
  • Such polyorganosiloxanes are described in EP-A 342 830 and EP-A 342 834 .
  • Aminofunctional polyorganosiloxanes in which no amido groups are present and their preparation are known from the literature, eg EP-A 138192, EP-A 578 144, WO 88/08436 .
  • component F Particularly suitable as component F are polyorganosiloxanes which, in addition to amino groups, also contain radicals bonded to Si atoms in which polyoxyalkylene groups are present, in particular polyoxyethylene groups.
  • Polymers of this type are described in EP-A 578 144, particularly suitable are polymers which are mentioned in this document in claim 1 under Flormel (III). In these polymers, the polyoxyalkylene groups are each bonded via an alkylene bridge to a silicon atom.
  • component F) are polyorganosiloxanes which contain one or more radicals in which secondary amino groups of the formula -NX- are present, where X is the unsubstituted or substituted cyclohexyl radical.
  • component F are linear polyorganosiloxanes whose terminal groups are radicals (CH 3 ) 3 Si-O-. Also in the polysiloxane chain are all bonded to silicon atoms radicals which contain no oxygen atoms and no nitrogen atoms, preferably methyl groups. However, it may also, but less preferred, be a part of the terminal or present in the chain CH 3 groups each by a phenyl group or a long-chain alkyl group, for example a chain length of 2 to 12 carbon atoms, be sets. It is further preferred if more than one functional group, ie more than one oxygen- or nitrogen-containing radical, is bonded to none of the Si atoms of the polyorganosiloxane.
  • component F a component F
  • component F particularly suitable are those amino- or amido-functional polyorganosiloxanes which contain no fluorine atoms, no silicon-hydrogen (Si-H -) bonds, no Si-OH bonds and no Si-OR bonds.
  • compositions according to the invention may additionally contain nitrogen-free polyorganosiloxanes, for example polydimethylsiloxanes. These are also preferably, as described above, not crosslinked and preferably contain no fluorine atoms, no Si-H, no Si-OH and no Si-OR bonds.
  • compositions according to the invention additionally contain as component G) an alkali metal sulfonate, e.g. a Na or K salt of an alkanesulfonic acid with 2 to 18 carbon atoms.
  • alkali metal sulfonate e.g. a Na or K salt of an alkanesulfonic acid with 2 to 18 carbon atoms.
  • Particularly suitable are sodium olefinsulfonates, which in known manner by reacting 1-olefins with gaseous sulfur trioxide and subsequent neutralization can be made with aqueous NaOH.
  • Such products are available in the market.
  • compositions according to the invention are preferably used in the form of aqueous dispersions Treatment of fiber materials, in particular of textilessenngebilen, used and are preferably applied by means of a conventional padding process on the textiles. concentration the padding liquors and process conditions can as in the prior art of the Technique can be selected. If desired, the compositions of the invention or the Foulardfleotten other products are added, as for textile finishing or textile equipment, e.g. Cellulose crosslinkers and / or flame retardants, Biocides, etc. After application via padder, the textiles are dried in a known manner and optionally condensed at elevated temperature.
  • Examples / Formulations Nos. 1, 2 and 6 relate to compositions according to the invention, Examples 3, 4 and 5 represent noninventive comparative examples.
  • Component B is a compound having Component B:
  • the fabrics were dried at 110 ° C to constant weight and then condensed at 150 ° C for 5 minutes.
  • Waschvergrauung note 4 - 5 4-5 3-4 4 4 5 Dry soiling grade 4 4 3 4 4 5 Handle very soft very soft very soft much harder than Example 1 significantly harder than Example 1 slightly harder than Example 1
  • Grade 4 - 5 means that after performing the procedure described below Method on the tissues no or only very small dirt margins remained. Grade 3 - 4 means that there are still distinct dirt marks left.
  • a higher number at the note for the Waschvergrauung means less graying; the grade 4 - 5 means very little, the grade 5 even less graying (practically no more graying), while the grade 3 - 4 means a clear graying. With dry soil, higher numbers mean better grades for the notes.
  • the dry tissue samples are moved in a drum, being in the rotating Drum moving metal balls made sure that dirt brought intensively to the tissues has been.
  • the dry dirt used for this consisted of 5% so-called standard soil (Du Pont) and 95% sea sand.
  • the fabrics were tumbled in the drum for 20 minutes. Then they were treated with clean metal balls again for 5 minutes to only remove loosely adhering dirt.

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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

Die Erfindung betrifft eine wäßrige Zusammensetzung, welche sich zur Behandlung von Fasermaterialien, insbesondere von Textilien, eignet.The invention relates to an aqueous composition which is suitable for the treatment of fiber materials, especially textiles.

Es ist bekannt, Textilien im Rahmen der Textilausrüstung bzw. -veredlung mit Polymeren zu behandeln, welche perfluorierte Reste (RF) enthalten. Den Textilien können hierdurch wasser- und/oder ölabweisende Eigenschaften verliehen werden. Hierfür geeignete Zusammensetzungen sind in der US 4 742 140 und der EP-A 325 918 beschrieben.It is known to treat textiles in textile finishing with polymers containing perfluorinated radicals (R F ). The textiles can thereby be given water- and / or oil-repellent properties. Compositions suitable for this purpose are described in US Pat. No. 4,742,140 and EP-A 325 918 .

Textilien, welche mit Fluorpolymeren ohne sonstige Zusätze ausgerüstet wurden, weisen den Nachteil auf, daß sie nicht den für viele Einsatzgebiete erwünschten angenehm weichen Griff besitzen. Mit RF enthaltenden Polymeren lassen sich zwar in bekannter Weise öl- und wasserabweisende Eigenschaften sowie eine gewisse schmutzabweisende (soil repellent) Wirkung auf den Textilien erzielen. Jedoch ist nicht nur der Griff der nur mit RF-Polymeren behandelten Textilien nicht befriedigend, sondern auch die soil release Eigenschaften, d.h. die Entfernung von Schmutz von den Textilien ist nicht im erwünschten Ausmaß erreichbar. Letzteres könnte an der zu geringen Hydrophilie bzw. Benetzbarkeit der so ausgerüsteten Textilien liegen.Textiles which have been equipped with fluoropolymers without any other additives have the disadvantage that they do not have the desirable for many applications pleasantly soft grip. Although polymers containing R F can be oil-and water-repellent properties and a certain soil-repellent effect on the textiles in a known manner. However, not only is the handle of the textiles treated only with R F polymers not satisfactory, but also the soil release properties, ie the removal of soil from the textiles is not attainable to the desired extent. The latter could be due to the inadequate hydrophilicity or wettability of the textiles so finished.

Wegen der oben genannten bekannten Nachteile wurde bereits versucht, Textilien mit Zusammensetzungen zu behandeln, welche außer RF-Polymeren noch Weichgriffmittel und hydrophitisierende Mittel enthalten. Unter den Produkten, welche hierzu den RF-Polymeren zugemischt wurden, befinden sich auch Polyorganosiloxane, siehe z.B. Textile Chemist and Colorist, Vol 29, No. 9, Seite 26 - 29 (1997), und EP-A 312 949. Gemische von RF-Polymeren und Silikonen besitzen den Nachteil, daß durch den Zusatz von Silikonen die durch die RF-Polymeren vermittelten Eigenschaften des Textils, wie z.B. die ölabweisende Wirkung, abgeschwächt werden. Auch der Versuch, Perfluoralkylgruppen und Siloxangruppen in einem einzigen Copolymer zu vereinigen, siehe z.B. WO 00/05315 und US 3 716 517, konnte die auftretenden Probleme nicht lösen und führte nicht zu optimalen Eigenschaften der Textilien, was ölabweisende Wirkung, soil release-Verhalten und Griff betrifft.Because of the above-mentioned known disadvantages, attempts have already been made to treat textiles with compositions which, in addition to R F polymers, also contain softening agents and hydrophitizing agents. Among the products admixed to the R F polymers there are also polyorganosiloxanes, see eg Textile Chemist and Colorist, Vol. 9, pages 26-29 (1997), and EP-A 312 949. Mixtures of R F polymers and silicones have the disadvantage that the properties of the textile mediated by the R F polymers, such as the oil repellent effect, attenuated. Also, the attempt to combine perfluoroalkyl groups and siloxane groups in a single copolymer, see for example WO 00/05315 and US 3,716,517 , could not solve the problems encountered and did not lead to optimal properties of the textiles, which oil repellency, soil release behavior and Handle concerns.

Auch durch Zusatz von Polyolefinwachsen zu Zusammensetzungen, welche Fluorpolymere ehthalten, siehe EP-A 445 077, können die oben genannten Probleme nicht voll zufriedenstellend gelöst werden.Also, by adding polyolefin waxes to compositions which contain fluoropolymers, see EP-A 445 077, the above-mentioned problems can not be solved completely satisfactorily.

In vielen Fällen tritt bei der Ausrüstung von Textilien mit bekannten Zusammensetzungen außerdem das Problem einer zu ausgeprägten Waschvergrauung auf.In many cases occurs in the finishing of textiles with known compositions In addition, the problem of too pronounced Waschvergrauung on.

Die Aufgabe, welche der vorliegenden Erfindung zugrunde lag, bestand darin, eine hocheffektive Zusammensetzung für die Behandlung von Fasermaterialien zur Verfügung zu stellen, welche die geschilderten Nachteile bekannter Zusammensetzungen nicht oder nur in einem erheblich verringerten Ausmaß aufweist. Insbesondere sollte die Zusammensetzung sich dazu eignen, Textilien neben ölabweisenden Eigenschaften gute Hydrophilie, weichen Griff und gute soil-release-Eigenschaften zu verleihen, und daneben den unerwünschten Effekt einer Waschvergrauung zu unterdrücken. Unter Waschvergrauung ist hierbei das Phänomen zu verstehen, daß Textilien nach Waschvorgängen eine Verringerung des Weißgrads aufweisen, z.B. bedingt durch Verunreinigungen in der Waschflotte. Ferner sollte die Zusammensetzung in Form einer stabilen wäßrigen Dispersion erhältlich sein, die sich für den Ausrüstprozeß im Textilveredlungsbetrieb eignet.The object underlying the present invention was to provide a highly effective To provide a composition for the treatment of fiber materials, which the described disadvantages of known compositions not or only in one considerably reduced level. In particular, the composition should be suitable Textiles in addition to oil-repellent properties good hydrophilicity, soft feel and good soil-release properties, and in addition the undesirable effect of a Waschvergrauung to suppress. Under Waschvergrauung here is the phenomenon to understand that textiles after washing have a reduction in whiteness, e.g. conditioned due to impurities in the wash liquor. Furthermore, the composition in the form of a stable aqueous dispersion, which is suitable for the finishing process in the textile finishing operation suitable.

Die Aufgabe wurde gelöst durch eine Zusammensetzung, welche folgende Komponenten enthält

  • A) ein Diol der Formel (I) [RF-Z-X-CH2 (Y)b]2T oder ein Gemisch solcher Diole und/oder ein Produkt, das entsteht durch Umsetzung eines Diols der Formel (1) mit einer Säure und/oder ein Gemisch solcher Umsetzungsprodukte wobei gegebenenfalls der pH-Wert des Umsetzungsproduktes oder des Gemisches solcher Umsetzungsprodukte auf einen Wert zwischen 6 und 9 eingestellt wird,
  • B) ein Ethoxilat einer gesättigten oder ungesättigten Fettsäure mit 8 bis 24 Kohlenstoffatomen oder ein Ethoxilat eines gesättigten oder ungesättigten aliphatischen Alkohols mit 8 bis 24 Kohlenstoffatomen,
  • C) ein oxidiertes Polyolefinwachs, vorzugsweise ein oxidiertes Polyethylenwachs,
  • D) Wasser
    • wobei
    RF für einen perfluorierten Alkylrest mit 8 bis 24 Kohlenstoffatomen steht,
    X für -O- oder -S- oder eine einfache chemische Bindung steht,
    wobei Z für -CH=CH-CH2- oder für (CH2
    Figure 00030001
    steht, worin a für eine Zahl von 2 bis 6 steht,
    Y für -CH(OH)-CH2 - steht,
    b für 0 oder 1 steht,
    T für C(CH2OH)2, für N (CHR
    Figure 00030002
    CH2OH
    oder für N(CH R COO⊖ M⊕ steht,
    wobei
    c für eine Zahl von 1 bis 4 steht,
    R für Wasserstoff oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen und M⊕ für Na⊕, K⊕ oder NH4 ⊕ steht,
    wobei für den Fall, daß T nicht für C(CH2OH)2 steht, b den Wert 1 besitzt.The object has been achieved by a composition which contains the following components
  • A) a diol of the formula (I) [R F -ZX-CH 2 (Y) b] 2 T or a mixture of such diols and / or a product which is formed by reacting a diol of the formula (1) with an acid and / or a mixture of such reaction products, where appropriate, the pH of the reaction product or of the mixture of such reaction products to a value between 6 and 9 is set,
  • B) an ethoxylate of a saturated or unsaturated fatty acid having 8 to 24 carbon atoms or an ethoxylate of a saturated or unsaturated aliphatic alcohol having 8 to 24 carbon atoms,
  • C) an oxidized polyolefin wax, preferably an oxidized polyethylene wax,
  • D) water
    • in which
    R F is a perfluorinated alkyl radical having 8 to 24 carbon atoms,
    X is -O- or -S- or a simple chemical bond,
    where Z is -CH = CH-CH 2 - or (CH 2
    Figure 00030001
    where a is a number from 2 to 6,
    Y is -CH (OH) -CH 2 -,
    b is 0 or 1,
    T for C (CH 2 OH) 2 , for N (CHR
    Figure 00030002
    CH 2 OH
    or for N (CH R COO ⊖ M ⊕ stands,
    in which
    c is a number from 1 to 4,
    R is hydrogen or an alkyl radical having 1 to 6 carbon atoms and M ⊕ is Na ⊕ , K ⊕ or NH 4 ⊕ ,
    in the event that T is not C (CH 2 OH) 2 , b is 1.

    Wenn Z für -CH=CH-CH2- steht, ist die Perfluoralkylgruppe RF vorzugsweise an das olefinische Kohlenstoffatom gebunden und nicht an die -CH2-Gruppe.When Z is -CH = CH-CH 2 -, the perfluoroalkyl group R F is preferably attached to the olefinic carbon atom and not to the -CH 2 - group.

    Erfindungsgemäße Zusammensetzungen der genannten Art verleihen Textilien ölabweisende Eigenschaften, gutes soil release-Verhalten, hydrophile Eigenschaften, angenehm weichen Griff und geringe Tendenz zur Waschvergrauung (Wiederanschmutzung beim Waschprozeß). Sie eignen sich unter anderem sehr gut zur Ausrüstung von Textilien, bei denen eine gute Hydrophilie und eine gute Fleckauswaschbarkeit (soil release) gewünscht wird, z.B. zur Ausrüstung von Textilien für Sport- und Freizeitzwecke, für Gardinen sowie zur Ausrüstung von Hemdkragen und Bettwäsche. Die Fasermaterialien, welche sich für die Behandlung mit erfindungsgemäßen Zusammensetzungen anbieten, sind vorzugsweise textile Flächengebilde, z.B. Gewebe oder Gewirke. Besonders vorteilhafte Ergebnisse werden auf Textilien erzielt, die ganz oder teilweise, z.B. zu 30 bis 100 Gew% aus Baumwolle bestehen. Der Mischungspartner für die Baumwolle kann hierbei eine andere Faser sein, z.B. eine synthetische Faser wie Polyester oder Polyamid. Auch andere Cellulosefasern als Baumwolle lassen sich gut mit erfindungsgemäßen Zusammensetzungen behandeln. Auch bei reinen Synthesefasern wie Polyamid oder Polyester können erfindungsgemäße Zusammensetzungen verwendet werden.Inventive compositions of the type mentioned give textiles oil repellent Properties, good soil release behavior, hydrophilic properties, pleasantly soft feel and little tendency to Waschvergrauung (Wiederanschmutzung the washing process). she Among other things, they are very suitable for finishing textiles that have good hydrophilicity and good soil release is desired, e.g. to the equipment of textiles for sports and leisure purposes, for curtains and for shirt collars and bed linen. The fiber materials which are suitable for the treatment with inventive Compositions are preferably textile fabrics, e.g. tissue or knitted fabric. Particularly advantageous results are achieved on textiles, the whole or partially, e.g. consist of 30 to 100% by weight of cotton. The mixing partner for the Cotton may be another fiber, e.g. a synthetic fiber like polyester or polyamide. Other cellulose fibers than cotton can be well with inventive Treat compositions. Even with pure synthetic fibers such as polyamide or Polyesters can be used according to the invention.

    Es ist wichtig, daß erfindungsgemäße Zusammensetzungen alle 4 oben und in Anspruch 1 genannten Komponenten A) bis D) enthalten. Komponente D) (Wasser) dient dazu, die erfindungsgemäße Zusammensetzung in eine für die Anwendung im Textilausrüstbetrieb geeignete Form zu bringen; diese Anwendung erfolgt bevorzugt in einem üblichen Foulardverfahren. Hierzu liegen die Zusammensetzungen entweder in Form wäßriger Lösungen oder Dispersionen vor. Falls die Mischung aus den Komponenten A) bis C) nicht in Wasser (Komponente D)) löslich oder selbstdispergierbar ist, so muß hierfür ein Dispergator oder ein Gemisch von Dispergatoren zugesetzt werden. In einer bevorzugten Ausführungsform liegen daher erfindungsgemäße Zusammensetzungen in Form wäßriger Dispersionen vor, die gegebenenfalls zusätzlich als Komponente E) einen Dispergator oder ein Gemisch von Dispergatoren enthalten. Geeignet als Dispergatoren (Komponente E)) sind hierbei die dem Fachmann bekannten oberflächenaktiven Verbindungen; vor allem nichtionogene und/oder anionaktive Dispergatoren sind zur Herstellung stabiler wäßriger Dispersionen geeignet. Als nichtionogene Dispergatoren sind hier beispielsweise ethoxilierte Alkohole und ethoxilierte Fettsäuren mit einer Alkylkettenlänge von 8 bis 24 Kohlenstoffatomen zu nennen. Mindestens ein solcher Dispergator muß als Komponente B) immer in erfindungsgemäßen Zusamensetzungen vorliegen, es können aber auch als Komponente E) weitere solche Tenside zugesetzt werden, vor allem dann, wenn sich dadurch die Stabilität der wäßrigen Dispersion verbessern läßt. Geeignete anionaktive Dispergatoren sind die dem Fachmann ebenfalls bekannten oberflächenaktiven Produkte wie z.B. Sulfate oder Carboxylate. Besonders geeignete anionaktive Dispergatoren sind die oben und in den Ansprüchen 9 und 10 als Komponente G) genannten Alkalimetallsulfonate. Deren zusätzliche Verwendung stellt eine bevorzugte Ausführungsform erfindungsgemäßer Zusammensetzungen dar. Sie können nicht nur zur Stabilität der wäßrigen Dispersionen beitragen, sondern auch als zusätzliche Weichgriffmittel wirken. Bevorzugt hierbei sind die Natriumsalze von Olefinsulfonaten, z.B. mit einer Kohlenstoffkettenlänge von 8 bis 18.It is important that compositions according to the invention all mentioned above 4 and in claim 1 Components A) to D) included. Component D) (water) serves the inventive Composition suitable for use in textile finishing operation To bring form; This application is preferably carried out in a conventional padding process. For this the compositions are either in the form of aqueous solutions or dispersions in front. If the mixture of components A) to C) is not soluble in water (component D)) or self-dispersible, it must for a dispersant or a mixture of dispersants be added. In a preferred embodiment are therefore inventive Compositions in the form of aqueous dispersions, optionally in addition as component E) a dispersant or a mixture of dispersants. Suitable Dispersants (component E)) are the surface-active agents known to the person skilled in the art Links; especially nonionic and / or anionic dispersants are for the production stable aqueous dispersions suitable. As non-ionic dispersants are here, for example ethoxylated alcohols and ethoxylated fatty acids having an alkyl chain length of 8 to To call 24 carbon atoms. At least one such dispersant must be used as component B) always present in compositions of the invention, but it can also be used as a component E) further such surfactants are added, especially if this causes the stability the aqueous dispersion can be improved. Suitable anionic dispersants are the surface-active products also known to those skilled in the art, e.g. Sulfates or carboxylates. Particularly suitable anionic dispersants are those given above and in claims 9 and 10 as component G) alkali metal sulfonates. Their additional use represents a preferred embodiment of inventive compositions. You can contribute not only to the stability of the aqueous dispersions, but also as an additional Softening agent act. Preferred herein are the sodium salts of olefin sulfonates, e.g. With a carbon chain length of 8 to 18.

    Neben Wasser (Komponente D)) müssen auch alle 3 Komponenten A), B) und C) in erfindungsgemäßen Zusammensetzungen vorliegen, um deren Vorfeile zu erzielen.
    Falls Komponente A) (RF-Diol) fehlt, so weisen die ausgerüsteten Textilien eine zu geringe ölabweisende Wirkung und nicht optimale Eigenschaften bezüglich soil-release-Verhalten sowie bezüglich Waschvergrauung auf.
    Zusammensetzungen, welche neben Wasser die Komponenten A) und C), jedoch keine Komponente B) enthalten, sind erfindungsgemäßen Zusammensetzungen bezüglich Weichgriff und Hydrophilie unterlegen. Ausreichende Hydrophilie der Zusammensetzung ist jedoch andererseits erforderlich, um gute soil release-Eigenschaften zu erzielen. Außerdem kann bei Fehlen von Komponente B) die Stabilität wäßriger Dispersionen der Zusammensetzungen beeinträchtigt sein.
    Falls Komponente C) nicht anwesend ist, hat dies negative Auswirkungen auf den Griff ausgerüsteter Textilien, der in diesem Fall nicht so weich ist wie bei Mitverwendung der Komponente C). Außerdem trägt die Komponente C) zur Erhöhung der Hydrophilie und damit zur Verbesserung der soil-release-Eigenschaften bei.    In addition to water (component D)), all 3 components A), B) and C) must also be present in compositions according to the invention in order to achieve their apex.
    If component A) (R F -diol) is lacking, the finished textiles have too low an oil-repellent effect and not optimal properties with respect to soil-release behavior and with respect to washing scrubbing.
    Compositions which, besides water, contain components A) and C) but no component B) are inferior to softness and hydrophilicity according to the invention. On the other hand, sufficient hydrophilicity of the composition is required to achieve good soil release properties. In addition, in the absence of component B), the stability of aqueous dispersions of the compositions may be impaired.
    If component C) is not present, this has a negative effect on the handle of finished textiles, which in this case is not as soft as with the concomitant use of component C). In addition, the component C) contributes to increase the hydrophilicity and thus to improve the soil-release properties.

    Es wurde überraschenderweise gefunden, daß die spezielle Kombination der Komponenten A) bis D) zu hervorragenden Effekten bezüglich der bereits genannten Eigenschaften ausgerüsteter Textilien führt. Ein wesentlicher Einflußfaktor ist hierbei die chemische Natur der Komponente A).
    Komponente A) ist ein Diol oder ein Gemisch von Diolen der Formel (I) und/oder ein Produkt oder ein Gemisch von Produkten, die entstehen durch Umsetzung eines Diols/Diolgemischs der Formel (I) mit einer Säure [RF-Z-X-CH2(Y)b]2T     It has surprisingly been found that the specific combination of components A) to D) leads to excellent effects with respect to the already mentioned properties of finished textiles. An essential influencing factor here is the chemical nature of component A).
    Component A) is a diol or a mixture of diols of the formula (I) and / or a product or a mixture of products which are formed by reacting a diol / diol mixture of the formula (I) with an acid [R F -ZX-CH 2 (Y) b] 2 T

    In dieser Formel (I) steht
    RF für einen perfluorierten Alkylrest mit 8 bis 24 Kohlenstoffatomen,
    X für -O- oder -S- oder eine einfache chemische Bindung,
    Z steht für -CH=CH-CH2- oder für (CH2 , worin a für eine Zahl von 2 bis 6 steht,
    Y steht für -CH(OH) - CH2-,
    b steht für 0 oder 1,
    T steht für C(CH2OH)2, für N(CHR CH2OH
    oder für N (CH R COO⊖ M⊕,
    wobei
    c für eine Zahl von 1 bis 4 steht,
    R für Wasserstoff oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen und M⊕ für Na⊕, K⊕ oder NH4 ⊕ steht.    In this formula (I) stands
    R F is a perfluorinated alkyl radical having 8 to 24 carbon atoms,
    X is -O- or -S- or a simple chemical bond,
    Z is -CH = CH-CH 2 - or (CH 2 in which a is a number from 2 to 6,
    Y is -CH (OH) -CH 2 -,
    b stands for 0 or 1,
    T is C (CH 2 OH) 2 , N (CHR CH 2 OH
    or for N (CH R COO ⊖ M ⊕ ,
    in which
    c is a number from 1 to 4,
    R is hydrogen or an alkyl radical having 1 to 6 carbon atoms and M ⊕ is Na ⊕ , K ⊕ or NH 4 ⊕ .

    Wenn T nicht für C(CH2OH)2 steht, darf b) allerdings nicht den Wert Null, sondern muß den Wert 1 besitzen. If T does not stand for C (CH 2 OH) 2 , b) may not have the value zero, but must have the value 1.

    Für die Verwendung erfindungsgemäßer Zusammensetzung zur Behandlung von Fasermaterialien ist es zweckmäßig, wenn ein Gemisch aus Wasser und Komponente A) bei Raumtemperatur einen pH-Wert im Bereich von 6 bis 9 besitzt. Insbesondere dann, wenn Komponente A) durch Umsetzung eines Diols/Diolgemischs der Formel (1) mit einer Säure erhalten wurde, empfiehlt es sich daher, den pH-Wert von Komponente A) so einzustellen, daß ein Gemisch von Komponente A) und Wasser einen pH-Wert im Bereich von 6 - 9 aufweist. Die Einstellung des pH-Werts kann mit Basen erfolgen, besonders geeignet hierfür ist Ammoniak.
    Falls Diole der Formel (I) mit Säure umgesetzt werden sollen, um Komponente A) zu erhalten, kann als Säure eine anorganische starke Säure verwendet werden, vorzugsweise eine halogenfreie Säure. Besonders geeignet als Säuren sind wäßrige H3PO4 (Phosphorsäure) oder eine Polyphosphorsäure. Der Begriff "Polyphosphorsäure" umfaßt in diesem Zusammenhang auch die Pyrophosphorsäure H4P2O7 sowie höherkondensierte Phosphorsäuren.    For the use of inventive composition for the treatment of fiber materials, it is expedient if a mixture of water and component A) at room temperature has a pH in the range of 6 to 9. In particular, when component A) was obtained by reacting a diol / diol mixture of the formula (1) with an acid, it is therefore advisable to adjust the pH of component A) so that a mixture of component A) and water pH in the range of 6-9. The pH can be adjusted with bases, particularly suitable for this purpose is ammonia.
    If diols of formula (I) are to be reacted with acid to obtain component A), the acid may be an inorganic strong acid, preferably a halogen-free acid. Particularly suitable acids are aqueous H 3 PO 4 (phosphoric acid) or a polyphosphoric acid. The term "polyphosphoric acid" in this context also includes the pyrophosphoric acid H 4 P 2 O 7 and higher-condensed phosphoric acids.

    Durch Untersuchungen wurde festgestellt, daß Komponente A) eine entscheidende Wirkung für die Effekte besitzt, die sich mit erfindungsgemäßen Zusammensetzungen erzielen lassen. Die Diole der Formel (I) besitzen keine polymeren Anteile mit Ausnahme der beiden Perfluoralkylgruppen (RF). Untersuchungen ergaben, daß erfindungsgemäße Zusammensetzungen anderen Zusammensetzungen überlegen sind, welche die Komponenten B), C) und D) enthalten, in denen aber Komponente A) durch ein bekanntes Polyurethan mit RF-Gruppen oder einen bekannten Polyester mit RF-Gruppen ersetzt ist. Der Vorteil erfindungsgemäßer Zusammensetzungen gegenüber den hier genannten nicht-erfindungsgemäßen Zusammensetzungen liegt vor allem in ausgezeichneter Hydrophilie, in den soil-release-Eigenschaften und der geringen Waschvergrauung ausgerüsteter Textilien. Der Grund hierfür könnte in der geringeren Hydrophilie von RF-Polyurethanen oder RF-Polyestern gegenüber Komponente A) liegen.Investigations have shown that component A) has a decisive effect on the effects that can be achieved with compositions of the invention. The diols of formula (I) have no polymeric moieties except for the two perfluoroalkyl groups (R F ). Investigations have shown that compositions according to the invention are superior to other compositions containing components B), C) and D), but in which component A) is replaced by a known polyurethane having R F groups or a known polyester with R F groups , The advantage of compositions according to the invention over the non-inventive compositions mentioned here is above all in excellent hydrophilicity, in the soil-release properties and the low degree of wash-soiling of finished textiles. The reason for this could be the lower hydrophilicity of R F polyurethanes or R F polyesters over component A).

    Komponente A) kann ein einzelnes Diol der Formel (I) sein oder ein Gemisch solcher Diole. Im Normalfall liegt ein Gemisch vor, das bei der Herstellung der Diole anfällt und dessen einzelne Vertreter sich in der Kettenlänge der Reste RF unterscheiden. Auch Gemische von Verbindungen, welche sich in der Kettenlänge von RF und/oder im Wert von a unterscheiden, können als Komponente A) verwendet werden. Als Komponente A) können auch Gemische von Diolen eingesetzt werden, die sich dadurch unterscheiden, daß bei einem Teil der Diole Z für (CH2 steht und bei einem anderen Teil für -CH=CH-CH2-.Analoges gilt, wenn als Komponente A) Umsetzungsprodukte von Diolen der Formel (I) mit Säure verwendet werden. Auch hier liegen im Normalfall Gemische von Verbindungen vor, die sich in der Kettenlänge der Reste RF unterscheiden. Es ist auch möglich, als Komponente A) Gemische einzusetzen, die sowohl freie Diole der Formel (I) enthalten und zusätzlich Umsetzungsprodukte von Diolen der Formel (I) mit Säure. In all den genannten Fällen wird für diese Umsetzung vorzugsweise Phosphorsäure oder Polyphorsäure oder ein Gemisch davon verwendet.Component A) may be a single diol of formula (I) or a mixture of such diols. In the normal case, a mixture is present which is obtained in the preparation of the diols and whose individual representatives differ in the chain length of the radicals R F. Mixtures of compounds which differ in the chain length of R F and / or in the value of a can also be used as component A). As component A) it is also possible to use mixtures of diols which differ in that, for a part of the diols, Z is (CH 2 Analogously, when component A) reaction products of diols of the formula (I) with acid are used, and in another part, -CH =CH-CH 2 -alkyl. Again, there are usually mixtures of compounds which differ in the chain length of the radicals R F. It is also possible to use as component A) mixtures which contain both free diols of the formula (I) and additionally reaction products of diols of the formula (I) with acid. In all the cases mentioned, preference is given to using phosphoric acid or polyuric acid or a mixture thereof for this reaction.

    Als Komponente A) geeignete Produkte sind auf dem Markt erhältlich, z.B. von der Firma Ciba Spezialitätenchemie USA unter dem Namen LODYNE.
    Besonders gut geeignet als Komponente A) sind Diole der Formel (I), bei denen Z für (CH2 steht, X für -O- oder -S- steht, b den Wert 0 besitzt und T für C(CH2OH)2 steht, oder Umsetzungsprodukte solcher Diole mit Säure. Solche als Komponente A) geeignete Produkte und ihre Herstellung sind beschrieben in US 4 946 992, US 5 091 550, US 4 898 981 und US 5 132 445. Alle dort genannten Produkte sind als Komponente A) geeignet, sofern sie die Bedingungen erfüllen, die oben genannt und durch Anspruch 1 der vorliegenden Erfindung festgelegt sind.    Products suitable as component A) are available on the market, for example from Ciba Spezialitätenchemie USA under the name LODYNE.
    Particularly suitable as component A) are diols of the formula (I) in which Z is (CH 2 X is -O- or -S-, b is 0 and T is C (CH 2 OH) 2 , or reaction products of such diols with acid. Such products suitable for use 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 products mentioned therein are suitable as component A), provided that they fulfill the conditions, those mentioned above and defined by claim 1 of the present invention.

    Besonders gut geeignet als Komponente A) sind Produkte, die sich erhalten lassen durch Umsetzung von Phosphorsäure oder Polyphosphorsäure mit den oben und in Anspruch 3 genannten bevorzugten Diolen der Formel (I), in denen die Reste RF 8 bis 18 Kohlenstoffatome enthalten, Z für (CH2 , X für -S- steht und T für C(CH2OH)2 steht und a den Wert 2 und b den Wert 0 besitzt, und nachfolgende Einstellung des pH-Werts mit Ammoniak auf einen Wert von 6 bis 9.Particularly suitable as component A) are products which can be obtained by reacting phosphoric acid or polyphosphoric acid with the preferred diols of the formula (I) mentioned above and in claim 3, in which the radicals R F contain from 8 to 18 carbon atoms, Z for (CH 2 X is -S- and T is C (CH 2 OH) 2 and a is 2 and b is 0 and subsequent adjustment of the pH to 6-9 with ammonia.

    Falls gewünscht wird, daß Komponente A) keine oder unwesentliche Mengen an freien Diolen der Formel (I) enthält, werden Diole der Formel (I) mit solchen Mengen an Säure umgesetzt, daß für jedes Äquivalent an OH-Gruppen der Diole mindestens ein Äquivalent an sauren Wasserstoffatomen der Säure verwendet wird, vorzugsweise jedoch ein Überschuß an Säure. Dieser Überschuß wird nach beendeter Umsetzung vorzugsweise entfernt, bis ein pH-Wert, wie oben beschrieben, von etwa 6 bis 9 resultiert. Besonders geeignet hierfür ist Ammoniak, z.B. in Form einer wäßrigen NH3-Lösung.
    Es kann jedoch auch mit geringeren als äquivalenten Mengen an Säure gearbeitet werden, wenn erwünscht ist, daß nach der Umsetzung noch freie Diole der Formel (I) im Reaktionsgemisch enthalten sind.    If it is desired that component A) contains no or negligible amounts of free diols of formula (I), diols of formula (I) are reacted with such amounts of acid that for each equivalent of OH groups of the diols at least one equivalent acidic hydrogen atoms of the acid is used, but preferably an excess of acid. This excess is preferably removed after completion of the reaction until a pH as described above results in from about 6 to 9. Particularly suitable for this is ammonia, for example in the form of an aqueous NH 3 solution.
    However, it is also possible to use less than equivalent amounts of acid, if it is desired that free diols of the formula (I) are still present in the reaction mixture after the reaction.

    Neben den oben beschriebenen bevorzugten Diolen der Formel (I) existiert eine weitere Gruppe von Diolen der Formel (I), welche als Komponente A) besonders gut geeignet und daher bevorzugt sind. In einer bevorzugten Ausführungsform erfindungsgemäßer Zusammensetzungen ist daher Komponente A) ein Diol oder ein Gemisch von Diolen der Formel (I), worin A) ein Diol der Formel (I) ist, worin

  • Z für -CH=CH-CH2- steht,
  • X für -O- steht,
  • b den Wert 1 besitzt und
  • T für N (CH R COO⊖ M⊕ oder für
  • N (CH R CH2OH steht.
    • In addition to the preferred diols of the formula (I) described above, there is another group of diols of the formula (I) which are particularly suitable as component A) and are therefore preferred. In a preferred embodiment of compositions according to the invention, therefore, component A) is a diol or a mixture of diols of the formula (I) in which A) is a diol of the formula (I) in which
  • Z is -CH = CH-CH 2 -,
  • X is -O-,
  • b has the value 1 and
  • T for N (CH R COO ⊖ M ⊕ or for
  • A.D CH 2 OH is.

    • Im Gegensatz zu den weiter oben genannten Vertretern bevorzugter Diole (bei denen Z für (CH2 und T für C(CH2OH)2 steht), ist es bei der genannten zweiten Gruppe (Z = -CH=CH-CH2- und T = N (CH R COO⊖ M⊕ oder N (CH R CH2OH) zwar auch möglich, an Stelle der freien Diole deren Umsetzungsprodukte mit Säure zu verwenden, jedoch ist dies nicht bevorzugt. Vielmehr werden die Diole dieser zweiten Gruppe bevorzugt in freier Form eingesetzt.
    Ferner ist es bevorzugt, daß M⊕ für NH4 ⊕ steht, wenn T für N (CH R COO⊖ M⊕ steht. Der Wert von c ist eine Zahl von 1 bis 4, bevorzugt 1 oder 2. Alle Reste R in den Einheiten N(CH R stehen unabhängig voneinander für Wasserstoff oder einen Alkylrest mit 1 bis 6 Kohlenstoffatomen, bevorzugt hierbei sind Wasserstoff oder ein linearer Alkylrest, insbesondere Wasserstoff oder CH3.    In contrast to the above-mentioned representatives of preferred diols (in which Z is (CH 2 and T is C (CH 2 OH) 2 ), it is in the said second group (Z = -CH = CH-CH 2 - and T = N (CH R COO ⊖ M ⊕ or N (CH R CH 2 OH), although it is also possible to use their reaction products with acid instead of the free diols, but this is not preferred. Rather, the diols of this second group are preferably used in free form.
    Further, it is preferred that M ⊕ is NH 4 ⊕ when T is N (CH R COO ⊖ M ⊕ stands. The value of c is a number from 1 to 4, preferably 1 or 2. All radicals R in the units N (CH R independently of one another are hydrogen or an alkyl radical having 1 to 6 carbon atoms, preference being given to hydrogen or a linear alkyl radical, in particular hydrogen or CH 3 .

    Diole der bevorzugten Gruppe, bei denen Z = -CH=CH-CH2-, X = -O-, b=1,
    T = N(CH R COO⊖ M⊕ oder N (CH R CH2OH ist, sind beschrieben in US 5 491 261 und US 5 585 517. Ihre Herstellung kann in analoger Weise zu den dort genannten Verfahren erfolgen oder unter analoger Anwendung des Verfahrens der US 5 254 754.
    Die Herstellung gut geeigneter RF-Diote erfolgt vorzugsweise durch radikalische Addition von Perfluoralkyljodiden (RF-J) an endständig olefinisch ungesättigte Diole, z.B. allylisch ungesättigte Diole, und anschließende Eliminierung von Jodwasserstoff mittels Base. Wie in den genannten US-Patentschriften beschrieben, erfolgt die Addition vorzugsweise unter Verwendung einer Azoverbindung als Radikalinitiator und unter Mitverwendung anorganischer Salze schwefelhaltiger Säuren, z.B. Na2 S2O5.
    Besonders gut als Komponente A) geeignete Diole lassen sich erhalten durch Addition einer Aminosäure, z.B. Alanin oder Glycin, oder eines Alkalimetall- oder Ammoniumsalzes einer Aminosäure, oder eines primären Amins an Allylglycidylether (Monoepoxid des Diallylethers) im Molverhältnis -NH2/Ether von etwa 1:2, wobei sich die Aminogruppe an den Oxiranring addiert, nachfolgende Addition von RF-J an die verbleibenden allylischen Doppelbindungen und HJ-Eliminierung mittels Base.
    Ein als Komponente A verwendbares Produkt ist LODYNE 2000 (Ciba Spezialitätenchemie). Dieses Produkt enthält zwar neben RF-Diol und Wasser noch weitere Inhaltsstoffe; es kann aber ohne deren Abtrennung eingesetzt werden. Es ist jedoch darauf zu achten, daß in diesem Fall nur der Anteil an RF-Diol als Komponente A) bei der Ermittlung der unten genannten bevorzugten mengenmäßigen Zusammensetzungen berücksichtigt wird.    Diols of the preferred group in which Z = -CH = CH-CH 2 -, X = -O-, b = 1,
    T = N (CH R COO ⊖ M ⊕ or N (CH R CH 2 OH are described in US 5,491,261 and US 5,585,517 . Their preparation can be carried out in an analogous manner to the processes mentioned there or using analogously the process of US Pat . No. 5,254,754 .
    The preparation of highly suitable R F dimes preferably takes place by free-radical addition of perfluoroalkyl iodides (R F -J) to terminally olefinically unsaturated diols, for example allylic unsaturated diols, and subsequent elimination of hydrogen iodide by means of base. As described in the mentioned US patents, the addition is preferably carried out using an azo compound as a radical initiator and with concomitant use of inorganic salts of sulfur-containing acids, for example Na 2 S 2 O 5 .
    Particularly well as component A) suitable diols can be obtained by addition of an amino acid, for example alanine or glycine, or an alkali metal or ammonium salt of an amino acid, or a primary amine to allyl glycidyl ether (monoepoxide of diallyl ether) in the molar ratio -NH 2 / ether of about 1: 2, where the amino group adds to the oxirane ring, subsequent addition of R F -J to the remaining allylic double bonds and HJ elimination by means of base.
    A product useful as component A is LODYNE 2000 (Ciba Specialty Chemicals). Although this product contains in addition to R F -diol and water other ingredients; but it can be used without their separation. It should be noted, however, that in this case only the proportion of R F -diol as component A) is taken into account in the determination of the below-mentioned preferred quantitative compositions.

    Komponente B) ist ein Ethoxilat einer gesättigten oder ungesättigten Fettsäure oder eines gesättigten oder ungesättigten aliphatischen Alkohols. Die zugrunde liegende Fettsäure oder der zugrunde liegende Alkohol enthält 8 bis 24 Kohlenstoffatome. Im Normalfall ist Komponente B) ein Gemisch von Produkten, die sich in der Kettenlänge der zugrundeliegenden Säure bzw. des zugrundeliegenden Alkohols und/oder im Ethoxilierungsgrad unterscheiden. Die oben genannte Aussage, wonach die Anzahl der Kohlenstoffatome 8 bis 24 beträgt, bezieht sich also auf deren durchschnittliche Anzahl, wobei in kleineren Mengen auch Moleküle mit etwas höherer oder niedrigerer Anzahl von C-Atomen enthalten sein können. Als Komponente B) können auch Gemische eingesetzt werden, die sowohl ethoxilierte Fettsäuren mit C8 bis C24 als auch Alkohole mit C8 bis C24 enthalten. Die bevorzugten Kettenlängen der den Ethoxilaten zugrundeliegenden Fettsäuren oder aliphatischen Alkohole liegen im Bereich von 10 bis 18 Kohlenstoffatomen. Der Ethoxilierungsgrad, d.h. die durchschnittliche Anzahl der in Komponente B) vorliegenden -CH2-CH2-O-Einheiten liegt vorzugsweise im Bereich von 6 bis 18. Besonders gut geeignet als Komponente B) sind Ethoxilate ungesättigter oder gesättigter Fettsäuren mit 10 bis 18 C-Atomen und durchschnittlichen Ethoxilierungsgraden von 8 bis 14.
    Als Komponente B) geeignete Produkte sind im Handel erhältlich und lassen sich nach bekannten Verfahren durch Umsetzung der entsprechenden Säuren oder Alkohole mit Ethylenoxid erhalten.
    Unter die oben genannte Definition von Komponente B) fallen auch Produkte, in denen die nach Ethoxilierung verbleibende endständige OH-Gruppe durch eine OR-Gruppe ersetzt ist, wobei R für eine Alkylgruppe steht. Solche Produkte lassen sich herstellen, indem man nach der Ethoxilierung eine Veretherung mit einem Alkohol ROH nach bekannten Methoden durchführt. R steht in diesem Fall bevorzugt für eine Methylgruppe. Jedoch sind für Komponente B) Verbindungen bevorzugt, in denen die endständige OH-Gruppe als solche vorliegt, also nicht weiter umgesetzt wurde.
    Wie bereits erwähnt, können erfindungsgemäße Zusammensetzungen außer Komponente B) noch weitere oberflächenaktive Produkte enthalten (Komponente E)), vorzugsweise sind diese nichtionogener oder anionaktiver Art, z.B. weitere ethoxilierte Verbindungen, darunter auch solche, die nicht unter die Definition von Komponente B) fallen. Es ist jedoch vorher zu prüfen, ob hierdurch nicht die vorteilhaften Eigenschaften erfindungsgemäßer Zusammensetzungen oder damit ausgerüsteter Textilien verschlechtert werden.     Component B) is an ethoxylate of a saturated or unsaturated fatty acid or of a saturated or unsaturated aliphatic alcohol. The underlying fatty acid or alcohol contains 8 to 24 carbon atoms. In the normal case, component B) is a mixture of products which differ in the chain length of the underlying acid or of the underlying alcohol and / or in the degree of ethoxylation. The above statement that the number of carbon atoms is 8 to 24, therefore, refers to their average number, and in smaller amounts, molecules with a slightly higher or lower number of carbon atoms can be included. As component B) it is also possible to use mixtures which contain both ethoxylated fatty acids with C 8 to C 24 and also alcohols with C 8 to C 24 . The preferred chain lengths of the fatty acids or aliphatic alcohols underlying the ethoxylates are in the range of 10 to 18 carbon atoms. The degree of ethoxylation, ie the average number of -CH 2 -CH 2 -O units present in component B) is preferably in the range from 6 to 18. Particularly suitable as component B) are ethoxylates of unsaturated or saturated fatty acids having from 10 to 18 ° C. Atoms and average degrees of ethoxylation from 8 to 14.
    Suitable as component B) products are commercially available and can be obtained by known methods by reacting the corresponding acids or alcohols with ethylene oxide.
    The above definition of component B) also includes products in which the terminal OH group remaining after ethoxylation is replaced by an OR group, where R is an alkyl group. Such products can be made by etherifying with ethoxylation an alcohol ROH by known methods. R in this case is preferably a methyl group. However, compounds are preferred for component B) in which the terminal OH group is present as such, that is, was not further reacted.
    As already mentioned, compositions according to the invention may contain, in addition to component B), further surface-active products (component E)), preferably these are non-ionogenic or anion-active species, for example further ethoxylated compounds, including those which do not fall under the definition of component B). However, it must first be examined whether this does not impair the advantageous properties of compositions according to the invention or of textiles finished therewith.

    Komponente C) ist ein oxidiertes Polyolefinwachs. Es können oxidierte Polypropylenwachse, oxidierte Ethylen-/Propylen-Copolymerwachse oder Gemische eingesetzt werden, welche sowohl oxidierte Polyethylenwachse als auch oxidierte Propylenwachse und/oder die genannten oxidierten Copolymerwachse enthalten. Vorzugsweise werden jedoch ausschließlich oxidierte Polyethylenwachse verwendet.
    Oxidierte Polyolefinwachse sind bekannt. Durch Umsetzung von Polyolefinen mit Oxidationsmitteln werden polare Gruppen im Polymer erzeugt, z.B. -COOH-Gruppen, welche eine bestimmte Hydrophilie des so modifizierten Polymeren bewirken. Die Komponente C) erfindungsgemäßer Zusammensetzungen führt daher zu hydrophilen Eigenschaften der Zusammensetzungen, welche für das soil-release-Verhalten ausgerüsteter Textilien wichtig sind. Außerdem führt sie zu angenehm weichem Griff der Textilien.
    Als Komponente C) sind insbesondere geeignet solche oxidierte Polyolefinwachse, vorzugsweise oxidierte Polyethylenwachse, welche unter Verwendung bekannter nichtionogener Dispergatoren in Form stabiler wäßriger Dispersionen erhalten werden können und die einen Schmelzbereich zwischen 120°C und 160°C aufweisen. Geeignet sind oxidierte Wachse auf Basis von HDPE, die in Form von wäßrigen Dispersionen auf dem Markt erhältlich sind. Ein Beispiel ist das Produkt Glaswax ® E1 der Ciba Spezialitätenchemie, Basel, dessen Wachskomponente einen Schmelzpunkt im mittleren Bereich besitzt.
    Weitere geeignete oxidierte Wachse sind auf dem Markt erhältlich und in der Literatur beschrieben, z.B. EP-A 641 833, EP-A 412 324, US 4 211 815, DE-A 28 24 716, DE-A 19 25 993 und US 3 060 163.
    Ferner gehen geeignete oxidierte Polyolefinwachse, insbesondere oxidierte Polyethylenwachse aus der in der EP-A 412 324 zitierten Literatur hervor. Besonders gut geeignet als Komponente C) sind oxidierte Polyethylenwachse mit einer Dichte bei 20°C im Bereich von 0,91 bis 1,05 g/cm3, einer Säurezahl von mehr als 5, insbesondere von 10 bis 60, besonders bevorzugt von 20 bis 45 mg KOH/g und einem Schmelzbereich, der zwischen 90 und 160°C, vorzugsweise von 120 bis 160°C liegt.     Component C) is an oxidized polyolefin wax. Oxidized polypropylene waxes, oxidized ethylene / propylene copolymer waxes or mixtures containing both oxidized polyethylene waxes and oxidized propylene waxes and / or the said oxidized copolymer waxes can be used. Preferably, however, only oxidized polyethylene waxes are used.
    Oxidized polyolefin waxes are known. Reaction of polyolefins with oxidizing agents produces polar groups in the polymer, for example -COOH groups, which bring about a certain hydrophilicity of the polymer modified in this way. The component C) of the compositions of the invention therefore results in hydrophilic properties of the compositions which are important for the soil-release behavior of finished textiles. In addition, it leads to a pleasantly soft feel of the textiles.
    Particularly suitable as component C) are those oxidized polyolefin waxes, preferably oxidized polyethylene waxes, which can be obtained using known nonionic dispersants in the form of stable aqueous dispersions and which have a melting range between 120.degree. C. and 160.degree. Suitable oxidized waxes based on HDPE, which are available in the form of aqueous dispersions in the market. An example is the product Glaswax® E1 from Ciba Specialty Chemicals, Basel, whose wax component has a melting point in the middle range.
    Other suitable oxidized waxes are available on the market and described in the literature, for example EP-A 641 833 , EP-A 412 324 , US Pat. No. 4,211,815, DE-A 28 24 716, DE-A 19 25 993 and US Pat. No. 3,060 163rd
    Furthermore, suitable oxidized polyolefin waxes, in particular oxidized polyethylene waxes, are apparent from the literature cited in EP-A 412 324. Particularly suitable as component C) are oxidized polyethylene waxes having a density at 20 ° C. in the range from 0.91 to 1.05 g / cm 3 , an acid number of more than 5, in particular from 10 to 60, particularly preferably from 20 to 45 mg KOH / g and a melting range of between 90 and 160 ° C, preferably from 120 to 160 ° C.

    Zur Herstellung erfindungsgemäßer Zusammensetzungen kann Komponente C) in festem Zustand eingesetzt und mit den übrigen Komponenten vermischt und homogenisiert werden. Es können aber auch fertige wäßrige Dispersionen von Komponente C) verwendet werden, die im Handel erhältlich sind, und mit den übrigen Komponenten vermischt werden. Falls von einem oxidierten Polyolefinwachs in fester Form ausgegangen werden und dieses vor dem Vermischen mit den übrigen Komponenten in Wasser dispergiert werden soll, können hierzu Dispergatoren verwendet werden, die dem Fachmann bekannt sind. Beispiele sind ethoxilierte lineare und/oder verzweigte Alkohole. For the preparation of compositions according to the invention component C) in the solid state used and mixed with the other components and homogenized. It however, ready-to-use aqueous dispersions of component C) which are used in the Commercially available and mixed with the other components. If from one oxidized polyolefin wax in solid form and this before mixing Dispersants may be dispersed in water with the other components used, which are known in the art. Examples are ethoxylated linear and / or branched alcohols.

    Die Herstellung erfindungsgemäßer Zusammensetzungen kann durch Vermischen der einzelnen Komponenten, gegebenenfalls unter Hinzufügen eines oder mehrerer Dispergatoren (Komponente E)), bei Raumtemperatur oder erhöhter Temperatur erfolgen. Es kann auch von Wasser oder einer Mischung von Wasser und Komponente E) ausgegangen und die einzelnen Komponenten A), B) und C) in beliebiger Reihenfolge hinzugefügt werden. In Einzelfällen kann die Stabilität der erhaltenen wäßrigen Dispersion von der Reihenfolge des Mischens abhängen, in diesen Fällen ist die optimale Reihenfolge leicht durch Versuche zu ermitteln. In jedem Fall ist es hinsichtlich ihrer Anwendung für Textilausrüstung von Vorteil, wenn erfindungsgemäße Zusammensetzungen in Form stabiler wäßriger Dispersionen vorliegen.The preparation of compositions according to the invention can be achieved by mixing the individual Components, optionally with the addition of one or more dispersants (Component E)), at room temperature or elevated temperature. It can also be from Water or a mixture of water and component E) and the individual Components A), B) and C) are added in any order. In individual cases can the stability of the resulting aqueous dispersion depends on the order of mixing, in these cases, the optimal order is easily determined by experiment. In any case It is advantageous in terms of their application to textile finishing when compositions according to the invention in the form of stable aqueous dispersions.

    Erfindungsgemäße Zusammensetzungen enthalten die Komponenten A) bis C) vorzugsweise in folgenden Mengenverhältnissen, bezogen auf 100 Gewichtsteile Wasser (Komponente D))

  • Komponente A) 5 bis 20, insbesondere 7 bis 15 Gewichtsteile
  • Komponente B) 5 bis 20, insbesondere 7 bis 15 Gewichtsteile
  • Komponente C) 1 bis 10, insbesondere 2 bis 7 Gewichtsteile
    • Compositions according to the invention comprise components A) to C), preferably in the following proportions, based on 100 parts by weight of water (component D))
  • Component A) 5 to 20, in particular 7 to 15 parts by weight
  • Component B) 5 to 20, in particular 7 to 15 parts by weight
  • Component C) 1 to 10, in particular 2 to 7 parts by weight

    • In einer bevorzugten Ausführungsform enthalten erfindungsgemäße Zusammensetzungen zusätzlich als Komponente F) ein aminofunktionelles oder ein amidofunktionelles Polyorganosiloxan oder ein Gemisch solcher Polyorganosiloxane. Unter aminofunktionellen bzw. amidofunktionellen Polyorganosiloxanen werden in diesem Zusammenhang Polyorganosiloxane (Silikone) verstanden, welche einen oder mehrere Reste enthalten, die Aminogruppen bzw. Amidogruppen enthalten. Solche Produkte sind auf dem Markt erhältlich, z.B. von der Fa. Wacker Chemie, DE, oder von Dow Corning. Die Amino- bzw. Amidogruppen sind hierbei üblicherweise über eine Alkylengruppe an je ein Si-Atom gebunden, z.B. über eine -CH2-CH2- oder -CH2-CH2-CH2-Gruppe. In den an Si gebundenen Resten können entweder nur eine endständige -NH2-Gruppe vorliegen oder mehrere Aminogruppen, z.B. in Form von Resten der Formel -CH2-CH2-CH2-NH-CH2-CH2-NH2. Enthält das Polyorganosiloxan Amidogruppen, so können zusätzlich Aminogruppen vorliegen. Solche Polyorganosiloxane sind in der EP-A 342 830 und der EP-A 342 834 beschrieben.
    Aminofunktionelle Polyorganosiloxane, in welchen keine Amidogruppen vorliegen, sowie ihre Herstellung sind aus der Literatur bekannt, z.B. EP-A 138192, EP-A 578 144, WO 88/08436. Besonders gut geeignet als Komponente F) sind Polyorganosiloxane, welche neben Aminogruppen noch an Si-Atome gebundene Reste enthalten, in denen Polyoxyalkylengruppen vorliegen, insbesondere Polyoxyethylengruppen. Polymere dieser Art sind in der EP-A 578 144 beschrieben, besonders geeignet sind Polymere, die in dieser Schrift in Anspruch 1 unter Flormel (III) genannt sind. In diesen Polymeren sind die Polyoxyalkylengruppen jeweils über eine Alkylenbrücke an ein Siliciumatom gebunden. Geeignet als Komponente F) sind ferner Polyorganosiloxane, welche einen oder mehrere Reste enthalten, in denen sekundäre Aminogruppen der Formel -NX- vorliegen, wobei X für den unsubstituierten oder einen substituierten Cyclohexylrest steht. Weitere geeignete aminofunktionelle Polyorganosiloxane gehen aus der EP-A 659 930 hervor.
    Vorzugsweise werden als Komponente F) lineare Polyorganosiloxane verwendet, deren endständige Gruppen Reste (CH3)3 Si-O- sind. Auch in der Polysiloxankette sind alle an Siliciumatome gebundenen Reste, welche keine Sauerstoffatome und keine Stickstoffatome enthalten, vorzugsweise Methylgruppen. Es kann jedoch auch, was aber weniger bevorzugt ist, ein Teil der endständigen oder der in der Kette anwesenden CH3-Gruppen jeweils durch eine Phenylgruppe oder eine längerkettige Alkylgruppe, z.B. einer Kettenlänge von 2 bis 12 C-Atomen, setzt sein. Ferner ist es bevorzugt, wenn an keines der Si-Atome des Polyorganosiloxans mehr als eine funktionelle Gruppe, d.h. mehr als ein sauerstoff- oder stickstoffhaltiger Rest gebunden ist.    In a preferred embodiment, compositions according to the invention additionally contain, as component F), an amino-functional or an amido-functional polyorganosiloxane or a mixture of such polyorganosiloxanes. In this context, aminofunctional or amido-functional polyorganosiloxanes are understood as meaning polyorganosiloxanes (silicones) which contain one or more radicals which contain amino groups or amido groups. Such products are available on the market, for example from Wacker Chemie, DE, or from Dow Corning. The amino or amido groups are in this case usually bound via an alkylene group to a respective Si atom, for example via a -CH 2 -CH 2 - or -CH 2 -CH 2 -CH 2 group. In the radicals attached to Si, either only one terminal -NH 2 group can be present or several amino groups, for example in the form of radicals of the formula -CH 2 -CH 2 -CH 2 -NH-CH 2 -CH 2 -NH 2 . If the polyorganosiloxane contains amido groups, additional amino groups may be present. Such polyorganosiloxanes are described in EP-A 342 830 and EP-A 342 834 .
    Aminofunctional polyorganosiloxanes in which no amido groups are present and their preparation are known from the literature, eg EP-A 138192, EP-A 578 144, WO 88/08436 . Particularly suitable as component F) are polyorganosiloxanes which, in addition to amino groups, also contain radicals bonded to Si atoms in which polyoxyalkylene groups are present, in particular polyoxyethylene groups. Polymers of this type are described in EP-A 578 144, particularly suitable are polymers which are mentioned in this document in claim 1 under Flormel (III). In these polymers, the polyoxyalkylene groups are each bonded via an alkylene bridge to a silicon atom. Also suitable as component F) are polyorganosiloxanes which contain one or more radicals in which secondary amino groups of the formula -NX- are present, where X is the unsubstituted or substituted cyclohexyl radical. Further suitable amino-functional polyorganosiloxanes are disclosed in EP-A 659 930 .
    Preferably, component F) used are linear polyorganosiloxanes whose terminal groups are radicals (CH 3 ) 3 Si-O-. Also in the polysiloxane chain are all bonded to silicon atoms radicals which contain no oxygen atoms and no nitrogen atoms, preferably methyl groups. However, it may also, but less preferred, be a part of the terminal or present in the chain CH 3 groups each by a phenyl group or a long-chain alkyl group, for example a chain length of 2 to 12 carbon atoms, be sets. It is further preferred if more than one functional group, ie more than one oxygen- or nitrogen-containing radical, is bonded to none of the Si atoms of the polyorganosiloxane.

    Durch den Zusatz einer Komponente F) zu erfindungsgemäßen Zusammensetzungen läßt sich der angenehm weiche Griff ausgerüsteter Textilien noch weiter verbessern. Falls in Komponente F) zusätzlich Polyoxyethyleneinheiten vorliegen, so steigt die Hydrophilie erfindungsgemäßer Zusammensetzungen und auch die Hydrophilie ausgerüsteter Textilien, was Vorteile bezüglich soil-release-Eigenschaften mit sich bringt.
    Als Komponente F) sind besonders geeignet solche amino- oder amidofunktionellen Polyorganosiloxane, die keine Fluoratome, keine Silicium-Wasserstoff (Si-H-)-Bindungen, keine Si-OH- und keine Si-OR-Bindungen enthalten. Ferner sind in diesen bevorzugten Polysiloxanen keine Siliciumatome enthalten, an die 3 oder 4 Sauerstoffatome gebunden sind, die Polysiloxane sind also vorzugsweise nicht quervernetzt, sondern stellen ein lineares Polysiloxangerüst dar. R bedeutet in diesem Zusammenhang einen beliebigen organischen Rest.
    Neben den genannten amino- oder amidofunktionellen Polyorganosiloxanen (Komponente F)) können erfindungsgemäße Zusammensetzungen noch zusätzlich stickstofffreie Polyorganosiloxane, z.B. Polydimethylsiloxane, enthalten. Auch diese sind vorzugsweise, wie oben beschrieben, nicht quervernetzt und enthalten vorzugsweise keine Fluoratome, keine Si-H-, keine Si-OH- und keine Si-OR-Bindungen.    The addition of a component F) to compositions according to the invention makes it possible to further improve the pleasantly soft feel of finished textiles. If polyoxyethylene units are additionally present in component F), the hydrophilicity of compositions according to the invention and also the hydrophilicity of finished textiles increases, which brings advantages in terms of soil-release properties.
    As component F), particularly suitable are those amino- or amido-functional polyorganosiloxanes which contain no fluorine atoms, no silicon-hydrogen (Si-H -) bonds, no Si-OH bonds and no Si-OR bonds. Furthermore, in these preferred polysiloxanes, there are no silicon atoms to which 3 or 4 oxygen atoms are bonded, ie, the polysiloxanes are preferably not crosslinked, but represent a linear polysiloxane backbone. R in this context means any organic radical.
    In addition to the abovementioned amino- or amido-functional polyorganosiloxanes (component F)), compositions according to the invention may additionally contain nitrogen-free polyorganosiloxanes, for example polydimethylsiloxanes. These are also preferably, as described above, not crosslinked and preferably contain no fluorine atoms, no Si-H, no Si-OH and no Si-OR bonds.

    In einer bevorzugten Ausführungsform enthalten erfindungsgemäße Zusammensetzungen zusätzlich als Komponente G) ein Alkalimetallsulfonat, z.B. ein Na- oder K-Salz einer Alkansulfonsäure mit 2 bis 18 Kohlenstoffatomen. Besonders geeignet sind Natriumolefinsulfonate, die in bekannter Art und Weise durch Umsetzung von 1-Olefinen mit gasförmigem Schwefeltrioxid und anschließender Neutralisation mit wäßriger NaOH hergestellt werden können. Solche Produkte sind auf dem Markt erhältlich.In a preferred embodiment, compositions according to the invention additionally contain as component G) an alkali metal sulfonate, e.g. a Na or K salt of an alkanesulfonic acid with 2 to 18 carbon atoms. Particularly suitable are sodium olefinsulfonates, which in known manner by reacting 1-olefins with gaseous sulfur trioxide and subsequent neutralization can be made with aqueous NaOH. Such products are available in the market.

    Vorzugsweise enthalten erfindungsgemäße Zusammensetzungen die Komponenten A) bis C) und E) bis G) in folgenden Mengenverhältnissen, bezogen auf 100 Gewichtsteile Wasser (Komponente D))

  • A) 5 bis 20, vorzugsweise 7 bis 15 Gew.teile
  • B) 5 bis 20, vorzugsweise 7 bis 15 Gew.teile
  • C) 1 bis 10, vorzugsweise 2 bis 7 Gew.teile
  • E) 1 bis 10, vorzugsweise 2 bis 7 Gew.teile
  • F) 0,5 bis 8, vorzugsweise 1 bis 6 Gew.teile
  • G) 0,3 bis 5, vorzugsweise 0,5 bis 3 Gew.teile
    • Compositions according to the invention preferably contain components A) to C) and E) to G) in the following proportions, based on 100 parts by weight of water (component D))
  • A) 5 to 20, preferably 7 to 15 parts by weight
  • B) 5 to 20, preferably 7 to 15 parts by weight
  • C) 1 to 10, preferably 2 to 7 parts by weight
  • E) 1 to 10, preferably 2 to 7 parts by weight
  • F) 0.5 to 8, preferably 1 to 6 parts by weight
  • G) 0.3 to 5, preferably 0.5 to 3 parts by weight

    • Erfindungsgemäße Zusammensetzungen werden bevorzugt in Form wäßriger Dispersionen zur Behandlung von Fasermaterialien, insbesondere von textilen Flächengebilen, verwendet und werden bevorzugt mittels eines üblichen Foulardverfahrens auf die Textilien appliziert. Konzentration der Foulardflotten und Verfahrensbedingungen können wie im bekannten Stand der Technik ausgewählt werden. Falls gewünscht, können den erfindungsgemäßen Zusammensetzungen bzw. den Foulardflotten weitere Produkte zugesetzt werden, wie sie für Textilveredlung bzw. Textilausrüstung bekannt sind, z.B. Cellulosevernetzer und/oder flammhemmende Mittel, Biozide usw. Nach Applikation über Foulard werden die Textilien in bekannter Weise getrocknet und gegebenenfalls bei erhöhter Temperatur kondensiert.Compositions according to the invention are preferably used in the form of aqueous dispersions Treatment of fiber materials, in particular of textile Flächengebilen, used and are preferably applied by means of a conventional padding process on the textiles. concentration the padding liquors and process conditions can as in the prior art of the Technique can be selected. If desired, the compositions of the invention or the Foulardfleotten other products are added, as for textile finishing or textile equipment, e.g. Cellulose crosslinkers and / or flame retardants, Biocides, etc. After application via padder, the textiles are dried in a known manner and optionally condensed at elevated temperature.

    Die Erfindung wird nachfolgend durch Ausführungsbeispiele veranschaulicht.The invention is illustrated below by embodiments.

    Es wurden 6 wäßrige Formulierungen hergestellt. Die nachfolgende Tabelle 1 zeigt deren mengenmäßige Zusammensetzungen (in Gewichtsteilen). Mengenmäßige Zusammensetzungen der untersuchten Formulierungen in Gewichtsteilen Komponente Beispiel Nr. (Formulierung Nr.) 1 2 3 4 5 6 A1 8,0 --- --- 8,0 8,0 8,0 A2 --- 6,0 --- --- ---- --- B 8,0 8,0 8,0 --- 8,0 8,0 C 3,0 3,0 3,0 3,0 --- 3,0 D 75,8 77,8 83,8 84,8 80,0 75,8 E 2,4 2,4 2,4 2,4 2,4 2,4 F 1,8 1,8 1,8 1,8 1,8 --- G 1,0 1,0 1,0 1,0 1,0 1,0 There were prepared 6 aqueous formulations. Table 1 below shows their quantitative compositions (in parts by weight). Quantitative compositions of the tested formulations in parts by weight component Example No. (formulation No.) 1 2 3 4 5 6 A1 8.0 --- --- 8.0 8.0 8.0 A2 --- 6.0 --- --- ---- --- B 8.0 8.0 8.0 --- 8.0 8.0 C 3.0 3.0 3.0 3.0 --- 3.0 D 75.8 77.8 83.8 84.8 80.0 75.8 e 2.4 2.4 2.4 2.4 2.4 2.4 F 1.8 1.8 1.8 1.8 1.8 --- G 1.0 1.0 1.0 1.0 1.0 1.0

    Die Beispiele/Formulierungen Nr. 1, 2 und 6 beziehen sich auf erfindungsgemäße Zusammensetzungen, die Beispiele 3, 4 und 5 stellen nicht-erfindungsgemäße Vergleichsbeispiele dar.Examples / Formulations Nos. 1, 2 and 6 relate to compositions according to the invention, Examples 3, 4 and 5 represent noninventive comparative examples.

    In Tabelle 1 bedeuten:In Table 1, mean: Komponente A1:Component A1:

    Umsetzungsprodukt aus Polyphosphorsäure und einem Diol der Formel (I) gemäß Anspruch 1, worin Z = (CH2 , X = -S-, b = 0, T = C(CH2OH)2, wobei dieses Umsetzungsprodukt in einer mittels Ammoniak neutralisierten Form vorlag.Reaction product of polyphosphoric acid and a diol of formula (I) according to claim 1, wherein Z = (CH 2 , X = -S-, b = 0, T = C (CH 2 OH) 2 , this reaction product being in a form neutralized by ammonia.

    Komponente A2:Component A2:

    Diol der Formel (I) gemäß Anspruch 1, worin Z = -CH=CH-CH2-, X = -O-, b = 1, T = N-CH2-COO⊖ NH4 ⊕ Diol of formula (I) according to claim 1, wherein Z = -CH = CH-CH 2 -, X = -O-, b = 1, T = N-CH 2 -COO ⊖NH 4 ⊕

    Die Mengen der Komponenten A1 bzw. A2 in den Beispielen 1 und 2 waren so gewählt, daß die Formulierungen 1 und 2 in etwa den gleichen Gehalt (in Gewichts%) an Fluor aufwiesen. The amounts of components A1 and A2 in Examples 1 and 2 were chosen so that the Formulations 1 and 2 had approximately the same content (in weight%) of fluorine.

    Komponente B:Component B:

    Kokosfettsäureethoxilat (durchschnittlich etwa 8 bis 12 Mol Ethylenoxid)Coconut fatty acid ethoxylate (average about 8 to 12 moles of ethylene oxide)

    Komponente C:Component C:

    oxidiertes Polyethylenwachs (CAS-Nr. 68441-17-8)oxidised polyethylene wax (CAS No. 68441-17-8)

    Komponente D:Component D:

    Wasserwater

    Komponente E:Component E:

    Gemisch nichtionogener Dispergatoren (Ethoxilate)Mixture of nonionic dispersants (ethoxylates)

    Komponente F:Component F:

    Gemisch zweier aminofunktioneller Polyorganosiloxane, wovon eines Polyoxyethylengruppen enthielt.Mixture of two amino-functional polyorganosiloxanes, of which one polyoxyethylene groups contained.

    Komponente G:Component G:

    NatriumolefinsulfonatNatriumolefinsulfonat

    Die Formulierungen aller 6 Beispiele waren stabile wäßrige Dispersionen.The formulations of all 6 examples were stable aqueous dispersions.

    Mit den Formulierungen 1 bis 6 (entsprechend Beispielen 1 bis 6) wurden jeweils 4 Gewebeproben mittels eines Foulardprozesses ausgerüstet (Flottenkonzentration 45 g/l).With formulations 1 to 6 (corresponding to Examples 1 to 6), 4 tissue samples each were obtained equipped by means of a padding process (liquor concentration 45 g / l).

    Die 4 Gewebe waren:

  • a) 100 % Baumwolle
  • b) Polyester/Baumwolle (65/35)
  • c) 100 % Polyester-Taft
  • d) 100 % Polyamid-Taft
    • The 4 tissues were:
  • a) 100% cotton
  • b) polyester / cotton (65/35)
  • c) 100% polyester taffeta
  • d) 100% polyamide taffeta

    • Die bei Foulardierung erzielten Flottenaufnahmen (Gewichtszunahme nach Abquetschen) waren bei:

  • Gewebe a) 81 %
  • Gewebe b) 74 %
  • Gewebe c) 62%
  • Gewebe d) 79 %
    • The liquor pick-ups achieved during padding (weight increase after squeezing) were at:
  • Fabric a) 81%
  • Fabric b) 74%
  • Tissue c) 62%
  • Fabric d) 79%

    • Nach Foulardierung wurden die Gewebe bei 110°C bis zur Gewichtskonstanz getrocknet und anschließend 5 Minuten bei 150°C kondensiert.After padding, the fabrics were dried at 110 ° C to constant weight and then condensed at 150 ° C for 5 minutes.

    Die Gewebe wurden anschließend bezüglich folgender Parameter beurteilt.

  • Hydrophilie
  • Soil-Release-Verhalten
  • Waschvergrauung
  • Trockenanschmutzung
  • Griffausfall
    • The tissues were then evaluated for the following parameters.
  • hydrophilicity
  • Soil release behavior
  • soil redeposition
  • dry soil
  • handle failure

    • Dabei wurden die in Tabelle 2 aufgeführten Ergebnisse erhalten. Beispiel Nr. (Formulierung Nr.) 1 2 3 4 5 6 Hydrophilie (sec.) Gewebe a) und b) 0 - 1 0 - 1 0 - 1 3-5 3 - 5 0-1 Gewebe c) und d) 2 - 5 5 - 10 2 - 5 5 - 10 5 - 10 2 - 5 Soil-Release Note 4 - 5 4 - 5 3 - 4 3 - 4 3 - 4 5 Waschvergrauung Note 4 - 5 4-5 3-4 4 4 5 Trockenanschmutzung Note 4 4 3 4 4 5 Griff sehr weich sehr weich sehr weich wesentlich härter als Beispiel 1 deutlich härter als Beispiel 1 geringfügig härter als Beispiel 1 The results listed in Table 2 were obtained. Example No. (formulation No.) 1 2 3 4 5 6 Hydrophilicity (sec.) Fabric a) and b) 0 - 1 0 - 1 0 - 1 3-5 3 - 5 0-1 Fabric c) and d) 2 - 5 5 - 10 2 - 5 5 - 10 5 - 10 2 - 5 Soil-release note 4 - 5 4 - 5 3 - 4 3 - 4 3 - 4 5 Waschvergrauung note 4 - 5 4-5 3-4 4 4 5 Dry soiling grade 4 4 3 4 4 5 Handle very soft very soft very soft much harder than Example 1 significantly harder than Example 1 slightly harder than Example 1

    Beim Soil-Release-Verhalten bedeutet Note 4 - 5, daß nach Durchführung der unten beschriebenen Methode auf den Geweben keine oder nur noch sehr geringe Schmutzränder verblieben. Note 3 - 4 bedeutet, daß noch deutliche Schmutzränder verblieben. For Soil Release behavior, Grade 4 - 5 means that after performing the procedure described below Method on the tissues no or only very small dirt margins remained. Grade 3 - 4 means that there are still distinct dirt marks left.

    Eine höhere Zahl bei der Note für die Waschvergrauung bedeutet geringere Vergrauung; die Note 4 - 5 bedeutet sehr geringe, die Note 5 noch geringere Vergrauung (praktisch keine Vergrauung mehr), während die Note 3 - 4 eine deutliche Vergrauung bedeutet.
    Bei der Trockenanschmutzung bedeuten höhere Zahlen für die Noten bessere Werte.    A higher number at the note for the Waschvergrauung means less graying; the grade 4 - 5 means very little, the grade 5 even less graying (practically no more graying), while the grade 3 - 4 means a clear graying.
    With dry soil, higher numbers mean better grades for the notes.

    Die einzelnen Bestimmungen wurden nach folgenden Methoden durchgeführt.The individual determinations were carried out according to the following methods.

    Griff:Handle:

    Es erfolgte eine manuelle BeurteilungThere was a manual assessment

    Hydrophilie:hydrophilicity:

    Die Bestimmung erfolgte durch Messung der Zeit, innerhalb welcher ein auf das Gewebe aufgebrachter Wassertropfen bei 20°C in das Gewebe eindringt. Diese Zeit ist die Zeit (in Sekunden) zwischen Aufbringen des Wassertropfens und demjenigen Zeitpunkt, von dem ab keine weitere Ausbreitung des Tropfens auf dem Gewebe mehr erkennbar ist.The determination was made by measuring the time within which a tissue applied to the tissue Water drops at 20 ° C penetrates into the tissue. This time is the time (in seconds) between application of the water drop and the time from which no further Propagation of the drop on the tissue is more recognizable.

    Soil-Release-Verhalten:Soil release behavior:

    Auf die Gewebemuster wurden verschiedene Arten von Schmutz in Form von räumlich begrenzten Flecken aufgebracht. Unter den geprüften Schmutzarten befanden sich Graphit, Miotoröl, Hautcreme, Pflanzenöl, Mayonnaise, Senf und Rotwein.
    Nach der Applikation der Schmutzflecken wurden die Gewebe an den Applikationszonen 60 Sekunden lang mit einem Gewicht belastet. Nach Entfernen des Gewichts wurden die Gewebe noch 30 Minuten gelagert und dann in einer Haushaltswaschmaschine mit einer wäßrigen Tensidlösung gewaschen. Anschließend wurde visuell beurteilt, inwieweit der Schmutzfleck bei der Wäsche entfernt worden war. Die Ergebnisse wurden in Form von Noten ausgedrückt, wobei höhere Zahlenwerte für die Noten effektivere Schmutzentfernung (= besseres soil-release-Verhalten) bedeuten. Die in Tabelle 2 für das soil-release-Vemalten angegebenen Zahlen stellen Durchschnittswerte aus den unterschiedlichen Geweben und den unterschiedlichen Schmutzarten dar.    Different types of dirt in the form of spatially limited patches were applied to the fabric samples. Among the tested soils were graphite, Miotoröl, skin cream, vegetable oil, mayonnaise, mustard and red wine.
    After application of the stains, the tissues at the application zones were weighted for 60 seconds. After removal of the weight, the tissues were stored for a further 30 minutes and then washed in a household washing machine with an aqueous surfactant solution. It was then visually assessed to what extent the stain on the wash had been removed. The results were expressed in the form of grades, with higher numerical values for the grades meaning more effective soil removal (= better soil-release behavior). The numbers given in Table 2 for soil release painting represent averages of the different tissues and the different soils.

    Waschvergrauung (= Wiederanschmutzung bei Waschvorgängen):Waschvergrauung (= resoiling during washing operations):

    Nach Durchführung des oben beschriebenen Tests auf soil-release-Verhalten wurde an den gewaschenen Gewebeproben der Weißton bzw. eine Graufärbung visuell beurteilt. Hierzu wer den Noten (5 = sehr gut, 1 = sehr schlecht) vergeben. Wie im Fall des soil-release-Verhaltens stellen die in Tabelle 2 für die Waschvergrauung aufgeführten Noten Durchschnittswerte dar.After conducting the above-described test on soil-release behavior was sent to the washed tissue samples, the white tone or a gray color assessed visually. For this purpose who awarded the grades (5 = very good, 1 = very bad). As in the case of soil-release behavior For example, the scores listed in Table 2 for scrubbing are averages.

    Trockenanschmutzung:dry soiling:

    Hierzu werden die trockenen Gewebeproben in einer Trommel bewegt, wobei in der rotierenden Trommel bewegte Metallkugeln dafür sorgten, daß Schmutz intensiv an die Gewebe herangeführt wurde. Der hierzu verwendete Trockenschmutz bestand aus 5 % sog. Standardschmutz (Du Pont) und 95 % Seesand. Die Gewebe wurden 20 Minuten lang in der Trommel bewegt. Anschließend wurden sie mit sauberen Metallkugeln nochmals 5 Minuten behandelt, um nur ganz lose anhaftenden Schmutz zu entfernen. Die Anschmutzung der Gewebe wurde anschließend visuell beurteilt und in Noten ausgedrückt (5 = beste Note).For this, the dry tissue samples are moved in a drum, being in the rotating Drum moving metal balls made sure that dirt brought intensively to the tissues has been. The dry dirt used for this consisted of 5% so-called standard soil (Du Pont) and 95% sea sand. The fabrics were tumbled in the drum for 20 minutes. Then they were treated with clean metal balls again for 5 minutes to only remove loosely adhering dirt. The staining of the tissues was subsequently assessed visually and expressed in notes (5 = best grade).

    Claims (14)

    1. A composition comprising the components A), B), C) and D),
      where component A) is selected from
      a) diols of the formula (I) [RF-Z-X-CH2(Y)b]2T
      b) products formed by reacting a diol of the formula (I) with an acid, where the pH of the reaction product is optionally adjusted to a value between 6 and 9,
      where
      component B) is an ethoxylate of a saturated or unsaturated fatty acid of 8 to 24 carbon atoms or an ethoxylate of a saturated or unsaturated aliphatic alcohol of 8 to 24 carbon atoms,
      where
      component C) is an oxidized polyolefin wax, preferably an oxidized polyethylene wax,
      and where
      component D) is water,
      where
      RF is a perfluorinated alkyl radical of 8 to 24 carbon atoms,
      X is -O- or -S- or a single chemical bond,
      Z is -CH=CH-CH2- or (CH2
      Figure 00230001
      , where a is from 2 to 6,
      Y is -CH(OH)-CH2-,
      b is 0 or 1,
      T is C(CH2OH)2, N(CHR
      Figure 00230002
      CH2OH or N(CHR COO⊖ M⊕,
      where
      c is from 1 to 4,
      R is hydrogen or an alkyl radical of 1 to 6 carbon atoms and M⊕ is Na⊕, K⊕ or NH4 ⊕, with the proviso that when T is not C(CH2OH)2, b is 1.
    2. A composition as claimed in claim 1, where phosphoric acid or polyphosphoric acid is used for the reaction of the diol of the formula (I) with an acid.
    3. A composition as claimed in claim 1 or 2, wherein component A) is a diol of the formula (I)
      where
      Z is (CH2 ,
      X is -O- or -S-,
      b is 0 and
      T is -C(CH2OH)2,
      or wherein component A) is a reaction product of such a diol and an acid.
    4. A composition as claimed in claim 1 or 2, where component A) is a diol of the formula (I)
      where
      Z is -CH=CH-CH2-
      X is -O-,
      b is 1 and
      T is N(CHR COO⊖ M⊕ or N(CHR CH2OH.
    5. A composition as claimed in one or more of claims 1 to 4, in the form of an aqueous dispersion and optionally additionally comprising a component E) which is a dispersant or a mixture of dispersants.
    6. A composition as claimed in one or more of claims 1 to 5, further comprising a component F) which is an amino-functional or an amido-functional polyorganosiloxane.
    7. A composition as claimed in claim 6, wherein component F) contains one or more polyoxyalkylene groups which are each attached to a silicon atom via an alkylene bridge.
    8. A composition as claimed in one or more of claims 1 to 7, which includes no polysiloxane containing fluorine atoms, Si-H bonds, Si-OH bonds, Si-OR bonds and/or containing silicon atoms to which 3 or 4 oxygen atoms are attached, where R is any organic radical.
    9. A composition as claimed in one or more of claims 1 to 8, further comprising a component G) which is an alkali metal sulfonate.
    10. A composition as claimed in claim 9, wherein component G) is a sodium olefinsulfonate.
    11. A composition as claimed in one or more of claims 1 to 10, comprising, based on 100 parts by weight of water (component D)), components A) to C) and E) to G) in the following amount ratios:
      A) 5 to 20 and preferably 7 to 15 parts by weight
      B) 5 to 20 and preferably 7 to 15 parts by weight
      C) 1 to 10 and preferably 2 to 7 parts by weight
      E) 1 to 10 and preferably 2 to 7 parts by weight
      F) 0.5 to 8 and preferably 1 to 6 parts by weight
      G) 0.3 to 5 and preferably 0.5 to 3 parts by weight
    12. The use of a composition as claimed in one or more of claims 1 to 11 for treating fiber materials.
    13. A use as claimed in claim 12, wherein the fiber materials are textile fabrics.
    14. A use as claimed in claim 12 or 13, wherein the fiber materials are wholly or partly cotton.
    EP01101306A 2001-01-20 2001-01-20 Composition for the treatment of fibre materials Expired - Lifetime EP1225269B1 (en)

    Priority Applications (4)

    Application Number Priority Date Filing Date Title
    AT01101306T ATE289639T1 (en) 2001-01-20 2001-01-20 COMPOSITION FOR THE TREATMENT OF FIBER MATERIALS
    DE50105416T DE50105416D1 (en) 2001-01-20 2001-01-20 Composition for the treatment of fiber materials
    EP01101306A EP1225269B1 (en) 2001-01-20 2001-01-20 Composition for the treatment of fibre materials
    ES01101306T ES2236055T3 (en) 2001-01-20 2001-01-20 COMPOSITION FOR THE TREATMENT OF FIBER MATERIALS.

    Applications Claiming Priority (1)

    Application Number Priority Date Filing Date Title
    EP01101306A EP1225269B1 (en) 2001-01-20 2001-01-20 Composition for the treatment of fibre materials

    Publications (2)

    Publication Number Publication Date
    EP1225269A1 EP1225269A1 (en) 2002-07-24
    EP1225269B1 true EP1225269B1 (en) 2005-02-23

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    Application Number Title Priority Date Filing Date
    EP01101306A Expired - Lifetime EP1225269B1 (en) 2001-01-20 2001-01-20 Composition for the treatment of fibre materials

    Country Status (4)

    Country Link
    EP (1) EP1225269B1 (en)
    AT (1) ATE289639T1 (en)
    DE (1) DE50105416D1 (en)
    ES (1) ES2236055T3 (en)

    Cited By (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US7494511B2 (en) 2006-05-08 2009-02-24 E.I. Du Pont De Nemours And Company Hydrophilic stain release agents
    AU2014203168B2 (en) * 2007-05-18 2016-04-21 Invista Technologies S.A R.L. Method and composition for treating fibrous substrates

    Families Citing this family (5)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    MX2007015228A (en) * 2005-06-06 2008-02-22 Invista Tech Sarl Automatically actuated liquid level sensor.
    NZ580818A (en) * 2007-05-18 2012-09-28 Invista Tech Sarl Method and composition for treating fibrous substrates
    EP2302130A1 (en) * 2009-09-26 2011-03-30 Huntsman Textile Effects (Germany) GmbH Compound for making fibre materials oil and/or water resistant
    CN102433741B (en) * 2010-11-16 2013-09-25 南通泰慕士服装有限公司 Sewing-hole resisting treatment process of gray cloth
    DE102013209170A1 (en) * 2013-05-17 2013-09-12 Cht R. Beitlich Gmbh Composition useful e.g. for waterproofing of absorbent materials, comprises silicone polymer, wax and/or fatty acid esters, aminoplast, urea derivatives and/or melamine derivatives, solvent, crosslinking agent, and dispersing auxiliaries

    Family Cites Families (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    DE3737753A1 (en) * 1987-11-06 1989-06-15 Pfersee Chem Fab AQUEOUS EQUIPMENT AND METHOD FOR SOFT HYDROPHOB / OLEOPHOB TREATMENT OF FIBER MATERIALS
    US4946992A (en) * 1988-06-20 1990-08-07 Ciba-Geigy Corporation Heteroatom containing perfluoroalkyl terminated neopentyl glycols and compositions therefrom

    Cited By (2)

    * Cited by examiner, † Cited by third party
    Publication number Priority date Publication date Assignee Title
    US7494511B2 (en) 2006-05-08 2009-02-24 E.I. Du Pont De Nemours And Company Hydrophilic stain release agents
    AU2014203168B2 (en) * 2007-05-18 2016-04-21 Invista Technologies S.A R.L. Method and composition for treating fibrous substrates

    Also Published As

    Publication number Publication date
    DE50105416D1 (en) 2005-03-31
    ATE289639T1 (en) 2005-03-15
    ES2236055T3 (en) 2005-07-16
    EP1225269A1 (en) 2002-07-24

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