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EP2814929B1 - Moyen de lavage et de nettoyage protégeant les couleurs - Google Patents

Moyen de lavage et de nettoyage protégeant les couleurs Download PDF

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Publication number
EP2814929B1
EP2814929B1 EP13704412.9A EP13704412A EP2814929B1 EP 2814929 B1 EP2814929 B1 EP 2814929B1 EP 13704412 A EP13704412 A EP 13704412A EP 2814929 B1 EP2814929 B1 EP 2814929B1
Authority
EP
European Patent Office
Prior art keywords
groups
polyamide
polyamide fibers
fibers
alkanediyl
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.)
Not-in-force
Application number
EP13704412.9A
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German (de)
English (en)
Other versions
EP2814929A1 (fr
Inventor
Roland Ettl
Evgueni Klimov
Christian Schmidt
Markus Brym
Birgit GLÜSEN
Mareile Job
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Priority to EP13704412.9A priority Critical patent/EP2814929B1/fr
Publication of EP2814929A1 publication Critical patent/EP2814929A1/fr
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Publication of EP2814929B1 publication Critical patent/EP2814929B1/fr
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
    • C11D17/049—Cleaning or scouring pads; Wipes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/32—Amides; Substituted amides
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3719—Polyamides or polyimides
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/58—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products
    • D01F6/60—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolycondensation products from polyamides
    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
    • D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
    • D04H1/4326—Condensation or reaction polymers
    • D04H1/4334—Polyamides

Definitions

  • the present invention relates to the use of fibers of water-insoluble polyamides as color transfer inhibiting agents in the washing and / or cleaning of textiles and detergents or cleaners containing such fibers.
  • Detergents and cleaners in addition to the indispensable for the washing and cleaning process ingredients such as surfactants and builders usually other ingredients that can be summarized under the term washing aids and include as different drug groups such as foam regulators, grayness inhibitors, bleach, bleach activators and enzymes.
  • auxiliaries also include substances which are intended to prevent dyed textile fabrics from causing a changed color impression after washing.
  • This Farbindrucksver Sung washed, that is, cleaner, textiles may be based on the fact that dye components are removed by the Waschregulatingmoi cleaning process from the textile (“fade”), on the other hand, from different colored textiles detached dyes on the textile reflected (“discoloration"). The same applies to cleaning hard surfaces.
  • the discoloration aspect may also play a role in undyed laundry items when washed together with colored laundry items.
  • detergents especially if they are provided as so-called color or colored laundry detergents for colored textiles, contain active ingredients which prevent the detachment of dyes from the textile or At least the deposition of detached, located in the wash liquor to avoid dyes on textiles.
  • many of the commonly used - usually water-soluble - polymers have such a high affinity for dyes that they draw them more from the dyed fiber, so that it comes in their use to color loss.
  • some conventional dye transfer inhibitors perform only with some classes of dyes and can not prevent the transfer of other dye classes.
  • the international patent application WO 2009/124908 describes the use of particulate water-insoluble polymers, including polyamide, to prevent the transfer of textile dyes of dyed textiles to undyed or differently colored textiles in their common washing in particular surfactant-containing aqueous solutions. From the international patent application WO 2009/127587 It is known that porous polyamide particles with a certain particle diameter and particle diameter distribution, specific surface area, oil absorption capacity and crystallinity avoid the transfer of textile dyes from dyed textiles to non-dyed or other-colored textiles when they are washed together in particular surfactant-containing aqueous solutions.
  • An object of the invention is therefore the use of fibers consisting of water-insoluble polyamide, whose average diameter (number average) is not more than 2 microns, to avoid the transfer of textile dyes of dyed textiles on undyed or differently colored textiles in their common washing in particular surfactant-containing aqueous Solutions.
  • the invention also relates to the aforementioned polyamide fibers per se, insofar as these have basic amino groups and optionally carboxyl groups, wherein on average the content of amino groups outweighs the content of carboxyl groups. Furthermore, the invention relates to fabrics containing these polyamide fibers and in particular consist of these.
  • water-insoluble is understood as meaning polyamides whose solubility in water is below 3 g / l, preferably below 1 g / l and in particular below 0.1 g / l at 25 ° C.
  • fiber refers to a macroscopically homogeneous and generally flexible body having a high length to width ratio and a small cross section. Fibers are also understood to mean filaments and filament-like structures which are distinguished by a particularly long length. A general overview of fibers is in the ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING, Vol. 6, pp. 647-755 and pp. 802-839, John Wiley and Sons, New York, (1986 ) to find.
  • the average diameter (number average) of the polyamide fibers according to the invention or used in the invention, which are in particular nano- and / or mesofibers, is preferably in the range of 1 nm to 1500 nm, particularly preferably in the range of 10 nm to 1000 nm, in particular in the range of 20 nm to 500 nm and especially in the range of 50 nm to 250 nm.
  • Nanofibers or mesofibers are understood here to mean fibers whose diameter is at least not more than 800 nm and generally not more than 500 nm.
  • the ratio of length to diameter of the polyamide fibers is generally greater than 10, in particular greater than 50 and is generally in the range of 10 to 100,000, preferably in the range of 50 to 50,000 and more preferably in the range of 100 to 10,000.
  • the polyamide fibers can be used in the form of a sheet.
  • the sheet is a non-woven or woven fabric.
  • a fleece is understood as meaning a fabric which contains fibers which are arranged spatially relative to one another completely or predominantly in random form.
  • the nonwovens and wovens may contain one or more groups of polyamide fibers which differ in the dimensions of the fibers, in particular their average diameter, with respect to the polyamides constituting the fibers, in particular their average molecular weights and the nature and the ratio of the monomers which they are constructed, and / or the fact of whether one or more of the polyamide are present in the fibers.
  • the webs and fabrics may be constructed solely of the polyamide fibers of the invention or additionally contain conventional fibers known to those skilled in the art. For example, it is possible that they are composed of a mixture of conventional fibers and the polyamide fibers.
  • the nonwoven webs and webs may contain other components other than fibers which a person skilled in the art would, if appropriate, consider as part of conventional webs and fabrics.
  • the sheet consists of a flat carrier on which the polyamide fibers of the invention are arranged.
  • the carrier may consist of any material known to those skilled in the art, which can be brought into a flat shape.
  • the backing may be a conventional type of woven or nonwoven fabric, or a solid surface such as a glass sheet, or a polymer-containing or polymer-containing film using as polymers, for example, polypropylene, polyester, polyamide, or cellulose can be.
  • the polyamide fibers can be arranged in any desired manner on the flat support, for example in the form of the previously described nonwovens or woven fabrics.
  • the weight fraction of the polyamide fibers is typically in the range from 1 to 60%, preferably in the range from 3 to 40% and in particular in the range from 5 to 24%.
  • the polyamide fibers according to the invention or used according to the invention have a BET surface area in the range of normally 0.01 g / m 2 to 200 g / m 2 , preferably in the range from 1 to 100 g / m 2 , more preferably in the range from 3 to 70 g / m 2 and in particular in the range from 5 to 50 g / m 2 .
  • the polyamides from which the polyamide fibers according to the invention or inventively used are formed generally have a number average molecular weight (M n ) in the range of 500 g / mol to 100000 g / mol, preferably from 500 g / mol to 75000 g / mol and in particular from 1000 g / mol to 50,000 g / mol.
  • the weight-average molecular weight (M w ) is usually in the range from 1000 g / mol to 300000 g / mol, preferably from 1500 g / mol to 150000 g / mol and in particular from 2000 g / mol to 100000 g / mol.
  • the polydispersity index M w / M n characterizing the molecular weight distribution is typically a number in the range of 1 to 10, preferably in the range of 1.5 to 5 and in particular in the range of 2 to 4.
  • the polyamides which form the polyamide fibers used according to the invention or according to the invention generally have at least 40 mmol / kg, preferably at least 50 mmol / kg, more preferably at least 75 mmol / kg and in particular at least 100 mmol / kg of basic amino groups.
  • Basic amino groups are understood as meaning those which can be determined by titration with aqueous hydrochloric acid solution.
  • the polyamides which form the polyamide fibers used according to the invention or according to the invention usually have less than 150, preferably less than 100 mmol / kg, in particular less than 50 mmol / kg and especially less than 40 mmol / kg of free carboxyl groups. Accordingly, the polyamides have amino groups and optionally carboxyl groups preferably in such numbers that the content of amino groups outweighs the content of carboxyl groups on average.
  • the polyamides forming polyamides have a content of carboxyl groups which is less than 100 meq / kg and at least 5 meq / kg and in particular at least 10 meq / kg below the content of amino groups, with respect to the content of amino groups the units of measurement meq / kg and mmol / kg are synonymous.
  • the ratio of terminal amino groups to terminal carboxyl groups of the polyamides is generally at least 0.8, preferably at least 1, more preferably at least 1.2, in particular at least 1.5 and is typically in the range of 0.8 to 2, preferably in the range of 1.2 to 1.9 and in particular in the range of 1 , 5 to 1.8.
  • the polyamides which form the polyamide fibers used according to the invention or according to the invention consist essentially of aliphatic and optionally cycloaliphatic and / or aromatic structural units, and preferably of aliphatic and optionally cycloaliphatic structural units.
  • the monomer units of which the polyamides are preferably constructed therefore comprise substantially either those derived from aliphatic or cycloaliphatic diamines and aliphatic or cycloaliphatic dicarboxylic acids or those derived from ⁇ -aminocarboxylic acids or their lactams.
  • bifunctional monomer units there may additionally be those which are derived from monomers having further amino or carboxyl groups, such as, for example, triamines or diaminocarboxylic acids.
  • Another suitable size for characterizing the polyamides is the molar ratio of amino to carboxyl groups, including the derivatized amino and carboxyl groups capable of amide formation, in the entirety of the monomers underlying the polyamides.
  • this molar ratio is in the range of 0.8: 1 to 15: 1, preferably in the range of 1: 1 to 12: 1, and more preferably in the range of 1.05: 1 to 10: 1.
  • the polyamides forming polyamide fibers may be present as linear or branched polymers, which may optionally be additionally crosslinked.
  • the polyamides are branched.
  • the branching points are preferably nitrogen atoms of a tertiary amino group or a doubly substituted amide group.
  • the degree of branching of the polyamides, if branched, is typically in the range of 0.05 mol / kg to 15 mol / kg, preferably in the range of 0.1 mol / kg to 7.5 mol / kg and especially in the range of 0 , 2 mol / kg to 4 mol / kg.
  • the polyamides are linear.
  • the polyamides are crosslinked.
  • the polyamides forming the polyamide fibers are preferably prepared from monomers which are aliphatic and optionally cycloaliphatic and / or aromatic monomers. It follows that the polyamides consist essentially of aliphatic repeat units and optionally cycloaliphatic and / or aromatic repeat units. This is to be understood that the molecular moieties of the polyamides which connect the functional groups, for example amino groups and in particular carboxamide groups, to one another are aliphatic, cycloaliphatic and / or aromatic.
  • preferred polyamides are composed essentially of repeating units of the formulas Ia and / or Ib; if appropriate, they additionally comprise branching units of the formulas II and / or II ', in which
  • A is selected from alkanediyl radicals having 2 to 20 carbon atoms, in which 1, 2, 3, 4 or 5 non-adjacent CH 2 groups may be replaced by a corresponding number of NH groups, and / or in which 2 linked together CH 2 - Groups may be replaced together by a C 5 -C 7 -cycloalkanediyl group, and groups of the formula (A'-O) p -A ', wherein A' is C 2 -C 4 alkanediyl, and p is an integer in the Range of 1 to 20, wherein the repeating units A'-O may be the same or different, A 'is selected from Alkandiylresten having 2 to 20 C-atoms, wherein 1, 2, 3, 4 or 5 non-adjacent CH 2 groups may be replaced by a corresponding number of NH groups, and / or in which 2 CH 2 groups linked together may be replaced by a C 5 -C 7 -cycloalkanediyl group, B
  • the repeat units Ia and Ib are generally based on the polymerization of diamines and dicarboxylic acids or aminocarboxylic acids or their lactams, while the repeating units II and II ', if present, usually on a polymerization in the presence of amino compounds having one secondary and two primary amino groups or with one tertiary and three primary amino groups
  • alkanediyl radical having 2 to 20 carbon atoms refers to a bivalent group derived from a straight-chain or branched C 2 -C 20 alkane, such as methylene, 1,2-ethanediyl, 1,2-propanediyl , 1,3-propanediyl, 1,2-butanediyl, 1,3-butanediyl, 1,4-butanediyl, 2-methyl-1,2-propanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,9 Nonanediyl, 1,12-dodecanediyl.
  • C 5 -C 7 cycloalkanediyl group refers to a bivalent group derived from a cycloalkane having 5 to 7 C atoms, such as 1,2-cyclopentanediyl, 1,3-cyclopentanediyl, 1,2- Cyclohexanediyl, 1,3-cyclohexanediyl, 1,4-cyclohexanediyl or 1,4-cycloheptanediyl.
  • the radical A is preferably selected from C 2 -C 10 -alkanediyl, C 5 -C 20 -alkanediyl in which 1, 2, 3 or 4 non-adjacent CH 2 groups are each replaced by NH groups and Groups of the formula (A'-O) p -A 'wherein A' is 1,2-ethanediyl, 1,2-propanediyl, 1,3-propanediyl or 1,4-butanediyl and p is an integer in the range of 1 until 10 stands.
  • the radicals A from the group of C 2 -C 10 -alkanediyls are preferably selected from C 2 -C 8 -alkanediyl, especially 1,2-ethanediyl, 1,2-propanediyl, 1,3-propanediyl, 1 , 3-butanediyl, 1,4-butanediyl, 2-methyl-1,2-propanediyl, 1,5-pentanediyl, 1,6-hexanediyl, 1,7-heptanediyl, 1,6-heptanediyl and 1,8-octanediyl , particularly preferably 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl and 1,7-heptanediyl and in particular the radicals A from the group of the C 2 -C 10 -alkanediyls are
  • radicals A from the group of C 5 -C 20 -alkanediyls which in each case have NH groups instead of 1, 2, 3 or 4 non-adjacent CH 2 groups, are in particular selected from radicals of the formula [(C 2 -C 8 ) alkanediyl-NH] o - (C 3 -C 8 ) alkanediyl wherein the alkanediyl units are independently selected and o is an integer in the range of from 1 to 10 and preferably from 1 to 6.
  • radicals A are selected from radicals of the formula [(C 2 -C 6 ) -alkanediyl-NH] o - (C 3 -C 6 ) -alkanediyl, where o is 1, 2 or 3, more preferably under (C 2 -C 6 ) alkanediyl-NH- (C 3 -C 6 ) alkanediyl, for example 1,6-hexanediyl-NH-1,6-hexanediyl or 1,3-propanediyl-NH-1,3-propanediyl, and (C 2 -C 6 ) alkanediyl-NH] 2 - (C 3 -C 6 ) alkanediyl, for example 1,3-propanediyl-NH-1,2-ethanediyl-NH-1,3-propanediyl.
  • a of the formula (A'-O) p -A ' are in particular selected from (1,2-propanediyl-O) q -1,2-propanediyl, (1,2-ethanediyl-O) q -1 , 2-ethanediyl, wherein each q is 3, 4, 5, 6, 7 or 8, and (C 2 -C 6 ) alkanediyl-O - [(C 2 -C 6 ) alkanediyl-O] r - (C 2 -C 6) alkanediyl, where r is 1, 2, 3 or 4.
  • radicals A are independent preferably selected from one another for the rest A as preferred radicals.
  • the polyamides may also contain repeating units which differ from those of the formula Ia in that the unit -NH-A-NH- is substituted by a divalent heterocyclyl radical having at least 2 nitrogen atoms in the ring and an optional (C 1 -C 10 ) -Aminoalkyl substituent, is replaced.
  • heterocyclyl refers herein to a 5- or 6-membered monocyclic or an 8- to 10-membered bicyclic heterocyclic radical of the 2 nitrogen atoms and optionally 1 or 2 further heteroatoms selected from N, O and S as ring atoms, wherein the heterocyclic The residue may be saturated, partially saturated or aromatic.
  • the heterocyclic radical is attached either via two ring nitrogen atoms or via a ring nitrogen atom and the nitrogen atom of the optional aminoalkyl group.
  • the heterocyclic radical is therefore preferably derived from heterocycles containing either two secondary amino groups or, if substituted with an aminoalkyl group, a secondary amino group. Examples of such heterocycles are imidazole, pyrazole, triazole, tetrazole, benzimidazole, purine and piperazine.
  • the said one bivalent heterocyclyl-containing repeating units are preferably selected from monocyclic saturated and partially saturated 5- or 6-membered monocyclic heterocycles with 2 nitrogens, such as piperazine, and monocyclic partially saturated and aromatic 5- or 6-membered monocyclic heterocycles having 2 nitrogen atoms, the with a (C 1 -C 10 ) -aminoalkyl group N-substituted, such as N- (3-aminopropyl) imidazole.
  • the radical B is preferably selected from a covalent bond and C 1 -C 10 -alkanediyl.
  • B is selected from C 1 -C 7 alkanediyl, especially methylene, 1,2-ethanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,3-butanediyl, 1,4-butanediyl, 2-methyl 1,2-propanediyl, 1,5-pentanediyl, 1,6-hexanediyl and 1,7-heptanediyl, more preferably 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl and 1,6- hexanediyl.
  • B is 1,4-butanediyl.
  • the radical B ' is preferably selected from C 4 -C 10 -alkanediyl.
  • B ' is selected from C 4 -C 6 alkanediyl, especially 1,4-butanediyl, 1,5-pentanediyl and 1,6-hexanediyl, and more preferably B' is 1,5-pentanediyl.
  • B can also be selected from the group of the bivalent C 6 -C 14 -arylene radicals, ie the group of C 6 -C 14 -arylenediols which are bivalent mono - or polycyclic aromatic hydrocarbons.
  • the C 6 -C 14 -arylenediyls may be unsubstituted or have 1 or 2 substituents which are C 1 -C 4 -alkyl, C * 1 -C 4 -alkoxy and SO 3 H, in particular C 1 -C 2 -alkyl , C 1 -C 2 alkoxy and SO 3 H are selected.
  • Radicals B from the group of C 6 -C 14 -arylenediyls are preferably selected from C 6 -C 10 -arylenediyl, especially 1,3-phenylene, 1,4-phenylene, 1,4-naphthylene, 1,3-naphthylene , 1,5-naphthylene, 2,6-naphthylene, 2,7-naphthylene and 1,6-naphthylene, which are unsubstituted or have 1 or 2 substituents selected from methyl, ethyl, methoxy and SO 3 H.
  • the polyamide fibers according to the invention comprise at least one polyamide, which is composed essentially of repeating units of the formula Ia, wherein the radicals A are preferably C 4 -C 7 alkanediyl, especially 1,6-hexanediyl, and Radicals B are preferably C 2 -C 5 -alkanediyl, especially 1,4-butanediyl.
  • the polyamide fibers according to the invention comprise at least one polyamide which is composed essentially of repeating units of the formula Ib, where the radicals B 'are preferably C 4 -C 6 -alkanediyl, especially 1,5-pentanediyl.
  • the polyamide fibers according to the invention comprise at least both a polyamide, which is composed essentially of repeating units la, and a polyamide, the is constructed essentially of repeating units Ib, wherein the radicals A, B and B 'preferably have the meanings mentioned in the preceding preferred embodiments.
  • the polyamide fibers preferably include both PA 6.6 and PA 6, or consist, according to a particularly preferred embodiment, of PA 6.6 and PA 6.
  • the polyamides which form the polyamide fibers can be prepared by the processes known from the prior art for the preparation of polyamides and oligoamides. Particularly suitable for this purpose are polycondensation reactions of monomers which contain primary or secondary amino groups or isocyanate groups and / or carboxyl groups or amide-forming groups derived therefrom.
  • the monomers M2 and M3 taken together are referred to as amide-forming compounds.
  • Aliphatic and optionally cycloaliphatic and / or aromatic di- and triamines having two or three, in particular two, primary amino groups are used in particular as monomers M1.
  • monomers M1 selected from diamines of the formula VI H 2 NA-NH 2 (V1) wherein the bivalent radical A has the meanings described herein, in particular the meanings mentioned herein as preferred.
  • Particularly preferred monomers M1 are diamines V1, wherein A is 1,4-butanediyl, 1,5-pentanediyl, 1,6-hexanediyl or 1,7-heptanediyl and especially 1,6-hexanediyl.
  • These preferred monomers M1 are therefore 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane or 1,7-diaminoheptane and especially 1,6-diaminohexane.
  • monomers having at least two amino groups for the preparation of the polyamides are also the previously described heterocycles which are either two secondary amine groups, or, if they are substituted by a (C 1 -C 10 ) -aminoalkyl group, a secondary amino group contain.
  • heterocycles are referred to as monomers M1 '.
  • Preferred monomers M1 ' are saturated and partially saturated 6-membered rings containing two secondary amino groups as ring members, in particular piperazine, and aromatic 5- or 6-membered rings having one secondary and one tertiary amino group and one N-linked (C 1 - C 6 ) -Aminoalkyl group, in particular the N- (C 1 -C 6 ) -aminoalkyl-substituted derivatives of imidazole, pyrazole, triazole, tetrazole, benzimidazole, purine and piperazine, especially N- (3-aminopropyl) imidazole.
  • Aliphatic and optionally cycloaliphatic and / or aromatic dicarboxylic acids and their amide-forming derivatives are used in particular as monomers M2.
  • the amide-forming derivatives are in particular the abovementioned dicarboxylic acids in which one or both carboxyl groups are replaced by ester groups, nitrile groups, carboxylic anhydride groups and carboxylic acid halide groups, preferably carboxylic acid chloride groups.
  • monomers M2 selected from dicarboxylic acids of the formula V2, HOOC-B-COOH (V2) and their amide-forming derivatives wherein B is selected from a covalent bond, alkanediyl radicals having from 1 to 20 carbon atoms, in which 2 mutually linked CH 2 groups may be replaced together by a C 5 -C 7 cycloalkanediyl group, and arylene which is unsubstituted or has 1, 2 or 3 substituents selected from C 1 -C 4 alkyl, C 1 -C 4 alkoxy and SO 3 H.
  • B is selected from a covalent bond, alkanediyl radicals having from 1 to 20 carbon atoms, in which 2 mutually linked CH 2 groups may be replaced together by a C 5 -C 7 cycloalkanediyl group, and arylene which is unsubstituted or has 1, 2 or 3 substituents selected from C 1 -C 4 alkyl, C 1 -C 4 alk
  • Particularly preferred monomers M2 are dicarboxylic acids V2 and their amide-forming derivatives in which B is selected from a covalent bond and C 1 -C 10 -alkanediyl, in particular C 1 -C 7 -alkanediyl, especially methylene, 1,2-ethanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,3-butanediyl, 1,4-butanediyl, 2-methyl-1,2-propanediyl, 1,5-pentanediyl, 1,6-hexanediyl and 1,7- Heptanediyl, more preferably 1,3-propanediyl, 1,4-butanediyl, 1,5-pentanediyl and 1,6-hexanediyl.
  • Particularly preferred monomers are dicarboxylic acids V2 and their amide-forming derivatives where B is 1,4-
  • monomers M3 in particular aliphatic ⁇ -aminocarboxylic acids having 4, 5 or 6 carbon atoms and their lactams are used.
  • Preferred monomers M3 are 4-aminobutanoic acid, 5-aminopentanoic acid and 6-aminohexanoic acid and also their lactams pyrrolidin-2-one, piperidin-2-one and ⁇ -caprolactam.
  • Particularly preferred monomers M3 are 6-aminohexanoic acid, pyrrolidin-2-one, piperidin-2-one and ⁇ -caprolactam, and especially ⁇ -caprolactam.
  • polyamides forming the polyamide fibers according to the invention or to be used according to the invention are preferably obtainable by reacting at least one monomer M3, or alternatively by reacting monomers comprising at least one amino compound having 2 primary amino groups and at least one amide-forming compound selected from dicarboxylic acids, their amide-forming derivatives and lactams is selected.
  • the at least one amino compound having 2 primary amino groups is preferably reacted with at least one dicarboxylic acid, in particular selected from dicarboxylic acids of the formula V2 or an amide-forming derivative thereof.
  • the at least one amino compound, based on 1 mol of the at least one dicarboxylic acid is generally present in an amount of at least 1 mol, preferably of at least 1.05 mol, in particular of more than 1.1 mol and more preferably of more than 1.25 Mol used.
  • the reactions according to the above preferred embodiment are preferably carried out with one or two different and most preferably with a dicarboxylic acid or an amide-forming derivative thereof. If the reactions with two different dicarboxylic acids or amide-forming derivatives are carried out, the molar ratio is usually in the range of 20: 1 to 1: 1, preferably in the range of 15: 1 to 1: 1 and in particular in the range of 10: 1 to 1: 1.
  • the dicarboxylic acids are preferably selected from adipic acid or an amide-forming adipic acid derivative and mixtures thereof with another dicarboxylic acid V2 different from it or its amide-forming derivative.
  • the at least one amino compound having 2 primary amino groups preferably selected from monomers M1 and more preferably from diamines of the formula V1, reacted with at least one amide-forming compound selected from monomers M3, in particular from lactams of aliphatic ⁇ -aminocarboxylic acids with 4 , 5 or 6 carbon atoms, and their mixtures with monomers M2.
  • the at least one monomer M3, based on 1 mole of the at least one amino compound is preferably used in an amount of more than 3 mol, in particular of more than 6 mol and more preferably of more than 12 mol.
  • the monomers M3 are preferably selected from the lactams of aliphatic ⁇ - (C 4 -C 6 ) aminocarboxylic acids and mixtures thereof with one or more dicarboxylic acids or their amide-forming derivatives.
  • the at least one monomer M3 is caprolactam. If the reactions according to the above preferred embodiment are carried out with a lactam and one or more dicarboxylic acids or their amide-forming derivatives, the molar ratio of lactam to dicarboxylic acids or dicarboxylic acid derivatives is generally in the range from 20: 1 to 1:10, preferably in the range from 15: 1 to 1: 5, and more preferably in the range of 10: 1 to 1: 2.
  • monomer M1 diamine of formula V1
  • amide-forming derivative of a dicarboxylic acid monomer M2, monomer M3 and lactam have the meanings defined above and in particular the meanings mentioned as preferred.
  • the reactions according to the latter two preferred embodiments are preferably carried out with an amino compound having 2 primary amino groups, or with two or more different, especially two different amino compounds having 2 primary amino groups.
  • the second and all further amino compounds are preferably selected from monomers M1.
  • the molar ratio of the two amino compounds is usually in the range from 20: 1 to 1: 1, preferably in the range from 15: 1 to 1: 1 and in particular in the range of 10: 1 to 1: 1. If the reactions are carried out with more than two different amino compounds having 2 primary amino groups, the molar ratio of an amino compound to the sum of all other amino compounds is usually in the range from 1:30 to 1: 1, preferably in the range from 1:20 to 1: 1 and in particular in the range of 1:15 to 1: 2.
  • the amino compounds having 2 primary amino groups are preferably selected from 1,6-diaminohexane and mixtures thereof with at least one further, different diamine V1. Particularly preferred are the amino compounds having 2 primary amino groups selected from 1,6-diaminohexane and mixtures thereof with another, different diamine V1. These reactions can also be carried out in the presence of at least one triamine having three primary amino groups.
  • Preferred triamines are selected from compounds of the formulas V3 and V4, N- (V-NH 2 ) 3 (V 3 ), in which V is a bivalent aliphatic radical and in particular C 2 -C 10 -alkanediyl, W is hydrogen or an aliphatic radical and in particular hydrogen or C 1 -C 6 -alkyl, T is C 2 -C 4 -alkanediyl in particular for 1,2-ethanediyl, 1,2-propanediyl, 1,3-propanediyl, 1,2-butanediyl, 1,3-butanediyl, 1,4-butanediyl or 2-methyl-1,2-propanediyl and especially is 1,2-ethanediyl or 1,2-propanediyl, n and k are independently 0, 1, 2, 3 or 4 and in particular 0 or 1, and m is an integer in the range of 1 to 20 and in particular from 3 to 8 stands.
  • the molar ratio of the at least one triamine to the at least one amino compound having two primary amino groups is generally in the range from 1: 1 to 1:50, preferably in the range from 1: 3 to 1:30 and especially in the range of 1:10 to 1:25.
  • At least one triamine having three primary amino groups is used in the reactions, preferably only one such triamine is used in combination with one or two, in particular an amino compound having 2 primary amino groups.
  • the reactions to the polyamides which form the polyamide fibers used according to the invention or according to the invention can be carried out analogously to known processes of the prior art by polycondensation of the bivalent monomers, as described, for example, in "Technische Polymere, Chapter 4: Polyamides", eds. L. Bottenbruch and R. Binsack, 1998, Hanser (Munich, Vienna).
  • the reaction conditions naturally depend on the type and functionality of the monomers used.
  • a suitable method for the preparation of the polyamides is the thermal polycondensation.
  • a monomer mixture which preferably comprises dicarboxylic acids and diamines, at relatively high temperatures, for example in the range of 180 to 350 ° C, in particular from 220 ° C to 300 ° C and generally elevated pressures of 0.8 to 30 bar, in particular 5 to 20 bar, reacted.
  • the reaction can be carried out in bulk, in solution or in suspension.
  • the reaction is carried out in a suitable solvent for the reaction.
  • dicarboxylic acids and diamines in particular water is suitable as a solvent.
  • the proportion of water in the reaction mixture is usually from 20 to 80, in particular from 30 to 60 percent by mass, with respect to the monomer weight. If a high proportion of water is used for the reaction, which may optionally also be above the upper range limits given above, the polyamides can be obtained in aqueous dispersion in the present case. Such a primary dispersion can be fed directly to one of the spinning processes explained below for the preparation of the polyamide fibers according to the invention. If the monomer mixture comprises lactams and diamines, the preparation of the polyamides preferably takes place by means of hydrolytic polycondensation, which likewise preferably takes place in a temperature range from 180 to 350 ° C., in particular from 220 ° C. to 300 ° C.
  • the polycondensation reaction is preferably carried out in solution and optionally in the presence of a catalyst.
  • the work-up of the crude products obtained in the abovementioned processes is usually carried out by drying and then grinding to a powder or by dissolving it in a moderately polar organic solvent such as, for example, phenols, cresols and benzyl alcohol, the solvent possibly already having regard to its suitability for the fiber spinning process which is to be used subsequently is selected.
  • a moderately polar organic solvent such as, for example, phenols, cresols and benzyl alcohol
  • the solvent possibly already having regard to its suitability for the fiber spinning process which is to be used subsequently is selected.
  • the abovementioned solutions in organic solvents can be obtained by precipitation with very polar Solvent, such as methanol, water or acetone, and then dispersing in water, further processed.
  • a solution of the polyamides to be used in the spinning process in an organic solvent such as formic acid may also be prepared from the above-mentioned dried and ground raw product or the aforementioned precipitate.
  • the polyamides thus obtained in the form of a solution in organic solvent or an aqueous dispersion can be used directly in fiber spinning processes.
  • the weight-average particle diameter of the polyamides present in aqueous dispersion can be determined by methods known from the prior art, such as sieve analysis or light scattering, and is typically in the range from 1 nm to 50 .mu.m, preferably in the range from 10 nm to 25 .mu.m, and in particular in the range of 20 nm to 10 ⁇ m.
  • Another suitable method for producing fabrics constructed from fibers is the rotor spinning or centrifuge spinning process.
  • the starting material is introduced as a solution or finely divided dispersion in a field with gravitational forces.
  • This is the fluidized Fiber raw material placed in a container and the container set in rotation, wherein the fiber raw material is discharged by centripetal or centrifugal forces from the container in the form of fibers.
  • the fibers can then be removed by gas flow and combined to form sheets.
  • the preparation of the polyamide fibers according to the invention or of the invention and of the fabrics containing such fibers according to the invention or used according to the invention can be carried out in any manner known to the person skilled in the art.
  • the above-mentioned electrospinning and rotor spinning processes are particularly suitable.
  • the electrospinning process with which the polyamide fibers of the invention can generally be obtained directly in the form of sheetlike structures according to the invention or used in accordance with the invention has proven particularly suitable.
  • the polymer threads formed during the electrospinning process are deposited on one of the aforementioned flat carriers or on a treadmill, for example on a polypropylene substrate, wherein a fabric is formed by mixing and intermingling the polymer threads.
  • polyamide fibers according to the invention or those used according to the invention and to the invention or according to the invention used fabric produced by electrospinning which correspond to one of the following two variants.
  • Variant 1 The formulation in the form of a solution, a colloidal dispersion or a melt of a polyamide or polyamide mixture is placed in an electric field having a thickness of generally between 0.01 to 10 kV / cm, preferably between 1 and 6 kV / cm and in particular between 2 and 4 kV / cm, by being squeezed out of one or more cannulas under low pressure. As soon as the electrical forces exceed the surface tension of the drops at the cannula tip (s), the mass transport takes place in the form of a jet on the opposite electrode. The optionally present solvent evaporates in Eisenelektroden Hurm and the solid of the formulation is then in the form of fibers on the counter electrode. Spinning can be done in both vertical directions (bottom to top and top to bottom) and in horizontal direction.
  • Variant 2 This variant is carried out with a system comprising a cylinder or a roller, such as the system "Nanospider” Elmarco (Czech Republic).
  • the formulation in the form of a solution, a dispersion or a melt of a polyamide or polyamide mixture is either in a container in which a metal roller rotates permanently, or is metered onto the roller by means of a separate device.
  • the roll can be smooth, structured or provided with metal wires.
  • the roll surface is at least partially permanently covered with a portion of the formulation.
  • the electric field between the roller and the counter electrode which is usually located above the roller, causes the formulation located on the roller initially liquid jets are formed, which then on the way to the counter electrode, by evaporation of the solvent or Cooling the melt, solidify to polyamide fibers.
  • the desired polyamide fibers contained fabric is formed on a flat support (eg., Polypropylene, polyester or cellulose), which is located between the two electrodes or passes between the two electrodes.
  • the electric field generally has the strength specified in Variant 1. Particularly preferably, the electric field here also has a thickness of about 2 kV / cm to 4 kV / cm. Spinning can be done in both vertical directions (bottom to top and top to bottom) and in horizontal direction.
  • the fibrous webs obtained by the methods of variants 1 and 2 may be treated at temperatures above the melting temperature or glass transition temperature to join the fibers at the cross points. If a formulation in the form of a dispersion is used, the above-mentioned optional process step can also be used to join the juxtapositions of polyamide particles or short polyamide fibers, which are initially formed by electrospinning from the jets, to give polyamide fibers according to the invention.
  • the polyamide fibers can be added separately to the wash solution, for example as part of a wash additive, as part of a manual or mechanical washing or cleaning process. They are preferably brought into contact with the textile as part of a pretreatment agent in a step preceding the actual washing process, or are furthermore preferably introduced into the washing or cleaning solution as a constituent of a washing or cleaning agent.
  • An object of the invention is the use of water-insoluble polyamide fibers whose mean diameter is not more than 2 ⁇ m as additives in laundry detergent compositions.
  • the polyamide and the fibers thereof have the aforementioned properties, in particular the properties mentioned as preferred or particularly preferred.
  • the use of such polyamide fibers in a laundry pre-treatment step is possible, in which case the polyamide-containing pretreatment agent is preferably not washed out, but remains on the subsequently to be washed textile and passes together with this in the wash liquor.
  • Another object of the invention is therefore a color-protective washing, washing additive, laundry pre-treatment or cleaning agent containing a dye transfer inhibitor in the form of previously described, consisting of water-insoluble polyamide fibers whose average diameter is not more than 2 microns, in addition to conventional with this component compatible ingredients.
  • An agent according to the invention preferably contains 0.05% by weight to 20% by weight, in particular from 0.1% by weight to 5% by weight of the polyamide fibers.
  • the incorporation into the respective formulation takes place in a manner known per se, wherein the polyamide fibers can be used in the form of the unbonded fibers or in the form of the inventive fabrics.
  • the unbound fibers usually remain in the wash liquor and are separated from the textiles to be washed by being discharged with the wash liquor.
  • the polyamide fibers contribute to both aspects of color constancy mentioned at the outset, that is, they reduce both discoloration and fading, although the effect of preventing staining, especially when washing white textiles, is most pronounced.
  • Another object of the invention is therefore the use of fibers consisting of water-insoluble polyamide whose average diameter is not more than 2 microns, to avoid the change in the color impression of textiles in their washing in particular surfactant-containing aqueous solutions. By changing the color impression is by no means the difference between dirty and clean textile to understand, but the color difference between each clean textile before and after the washing process.
  • Another object of the invention is a process for washing dyed textiles in surfactant-containing aqueous solutions, which is characterized in that one uses a surfactant-containing aqueous solution containing the previously described, consisting of water-insoluble polyamide fibers whose average diameter is not more than 2 microns is, contains.
  • the concentration of the polyamide fibers in the surfactant-containing aqueous solution is preferably 0.025 g / l to 5 g / l, in particular 0.2 g / l to 2.5 g / l.
  • an agent according to the invention may, in addition to the abovementioned dye-transfer-inhibiting active ingredient, additionally comprise a known dye transfer inhibitor, then preferably in amounts of from 0.01% by weight to 5% by weight, in particular from 0.1% by weight to 1% by weight.
  • a known dye transfer inhibitor which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof.
  • enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water.
  • polyvinylpyrrolidone preferably has an average molar mass in the range from 10,000 g / mol to 60,000 g / mol, in particular in the range from 25,000 g / mol to 50,000 g / mol.
  • copolymers preference is given to those of vinylpyrrolidone and vinylimidazole in a molar ratio of 5: 1 to 1: 1 with an average molar mass in the range from 5,000 g / mol to 50,000 g / mol, in particular 10,000 g / mol to 20,000 g / mol ,
  • compositions according to the invention may in principle contain, in addition to the active ingredient used in accordance with the invention, all known ingredients customary in such compositions.
  • the agents according to the invention may in particular be builders, surface-active surfactants, bleaches based on organic and / or inorganic peroxygen compounds, bleach activators, water-miscible organic solvents, enzymes, sequestering agents, electrolytes, pH regulators and other auxiliaries, such as optical brighteners, grayness inhibitors, foam regulators and colorants Contain fragrances.
  • the polyamide fibers to a flat support, in particular a water-insoluble cloth, or to introduce them, optionally with further customary ingredients of detergents or cleaners, into a bag of water-insoluble but water-permeable material, or from the fibrous form Polyamide a particular sheet-like fabric, such as a fabric or a nonwoven, or other shaped body such as a ball or a cube to produce, and it as an additive or as part of an additive in the Use washing or cleaning process.
  • the fibrous polyamide or a composition containing the same can be introduced in portions into a water-soluble material, for example a polyvinyl alcohol film, in the washing or cleaning process.
  • compositions according to the invention may comprise one or more surfactants, in particular anionic surfactants, nonionic surfactants and mixtures thereof, but also cationic, zwitterionic and amphoteric surfactants.
  • Suitable nonionic surfactants are in particular alkyl glycosides and ethoxylation and / or propoxylation of alkyl glycosides or linear or branched alcohols each having 12 to 18 carbon atoms in the alkyl moiety and 3 to 20, preferably 4 to 10 alkyl ether groups. Also suitable are ethoxylation and / or propoxylation products of N-alkylamines, vicinal diols, fatty acid esters and fatty acid amides which correspond to said long-chain alcohol derivatives with respect to the alkyl moiety and of alkylphenols having 5 to 12 carbon atoms in the alkyl radical.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • EO ethylene oxide
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 -alcohols with 3 EO or 4 EO, C 9 -C 11 -alcohols with 7 EO, C 13 -C 15 -alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 -alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C 12 -C 14 -alcohol with 3 EO and C 12 -C 18 -alcohol with 7 EO.
  • the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols containing more than 12 EO can also be used become. Examples include (tallow) fatty alcohols with 14 EO, 16 EO, 20 EO, 25 EO, 30 EO or 40 EO.
  • agents for use in mechanical processes usually extremely low-foam compounds are used. These include, preferably, C 12 -C 18 -alkylpolyethylene glycol-polypropylene glycol ethers having in each case up to 8 mol of ethylene oxide and propylene oxide units in the molecule.
  • low-foam nonionic surfactants such as, for example, C 12 -C 18 -alkyl polyethylene glycol-polybutylene glycol ethers having in each case up to 8 mol of ethylene oxide and butylene oxide units in the molecule and end-capped alkylpolyalkylene glycol mixed ethers.
  • hydroxyl-containing alkoxylated alcohols as described in the European patent application EP 0 300 305 are described, so-called Hydroxymischether.
  • the nonionic surfactants also include alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, in particular 2-methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is a Glykoseiki with 5 or 6 C-atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is an arbitrary number - which, as a variable to be determined analytically, may also assume fractional values - between 1 and 10; preferably x is 1.2 to 1.4.
  • R 1 CO is an aliphatic acyl radical having 6 to 22 carbon atoms
  • R 2 is hydrogen, an alkyl or hydroxyalkyl radical having 1 to 4 carbon atoms
  • [Z] is a linear or branched polyhydroxyalkyl radical having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the polyhydroxy fatty acid amides are preferably derived from reducing sugars having 5 or 6 carbon atoms, in particular from glucose.
  • the group of polyhydroxy fatty acid amides also includes compounds of the formula given below, in the R 3 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 4 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms and R 5 is a linear, branched or cyclic alkyl radical or a Aryl radical or an oxy-alkyl radical having 1 to 8 carbon atoms, wherein C 1 -C 4 alkyl or phenyl radicals are preferred, and [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this group.
  • [Z] is also obtained here preferably by reductive amination of a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • a sugar such as glucose, fructose, maltose, lactose, galactose, mannose or xylose.
  • the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides, for example by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants, in particular together with alkoxylated fatty alcohols and / or alkyl glycosides, are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl ester.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • nonionic surfactants are so-called gemini surfactants. These are generally understood as meaning those compounds which have two hydrophilic groups per molecule. These groups are usually separated by a so-called “spacer”. This spacer is typically a carbon chain that should be long enough for the hydrophilic groups to be spaced sufficiently apart for them to act independently of each other. Such surfactants are generally characterized by an unusually low critical micelle concentration and the ability to greatly reduce the surface tension of the water. In exceptional cases, the term gemini surfactants is not only used to describe such "dimers”, but also understood according to "trimeric" surfactants.
  • Suitable gemini surfactants are, for example, sulfated hydroxy mixed ethers or dimer alcohol bis and trimer alcohol tris sulfates and ether sulfates.
  • End-capped dimeric and trimeric mixed ethers are characterized in particular by their bi- and multi-functionality.
  • the end-capped surfactants mentioned have good wetting properties and are low foaming, so that they are particularly suitable for use in machine washing or cleaning processes.
  • gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides.
  • sulfuric acid monoesters of straight-chain or branched C 7 -C 21 -alcohols ethoxylated with from 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9 -C 11 -alcohols having on average 3.5 mol of ethylene oxide (EO) or C 12 - C 18 -fatty alcohols with 1 to 4 EO.
  • EO ethylene oxide
  • the preferred anionic surfactants also include the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters, and the monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
  • Preferred sulfosuccinates contain C 8 to C 18 fatty alcohol residues or mixtures of these.
  • Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which by themselves are nonionic surfactants.
  • Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
  • alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
  • Suitable further anionic surfactants are fatty acid derivatives of amino acids, for example N-methyltaurine (Tauride) and / or N-methylglycine (sarcosides).
  • sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate.
  • anionic surfactants are particularly soaps into consideration.
  • Particularly suitable are saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, stearic acid, hydrogenated erucic acid and behenic acid and, in particular, soap mixtures derived from natural fatty acids, for example coconut, palm kernel or tallow fatty acids. Together with these soaps or as a substitute for soaps, it is also possible to use the known alkenylsuccinic acid salts.
  • the anionic surfactants may be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
  • the anionic surfactants are preferably present in the form of their sodium or potassium salts, in particular in the form of the sodium salts.
  • Suitable cationic surfactants are mono- and di- (C 7 -C 25 -alkyl) dimethylammonium compounds and esterquats, in particular quaternary esterified mono-, di- and trialkanolamines which have been esterified with C 8 -C 22 -carboxylic acids.
  • Suitable amphoteric surfactants are, for example, alkylbetaines, alkylamidbetaines, aminopropionates, aminoglycinates and amphoteric imidazolium compounds.
  • Surfactants are present in detergents according to the invention in proportions of preferably from 5% by weight to 50% by weight, in particular from 8% by weight to 30% by weight.
  • An agent according to the invention preferably contains at least one water-soluble and / or water-insoluble, organic and / or inorganic builder.
  • the water-soluble organic builder substances include polycarboxylic acids, in particular citric acid and sugar acids, monomeric and polymeric aminopolycarboxylic acids, in particular methylglycinediacetic acid, nitrilotriacetic acid and ethylenediaminetetraacetic acid and polyaspartic acid, polyphosphonic acids, in particular aminotris (methylenephosphonic acid), ethylenediaminetetrakis (methylenephosphonic acid) and 1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds such as dextrin and also polymeric (poly) carboxylic acids, in particular the polycarboxylates obtainable by oxidation of polysaccharides or dextrins, polymeric acrylic acids, methacrylic acids, maleic acids and copolymers thereof, which may also contain polymerized small amounts of polyme
  • the molecular weight of the homopolymers of unsaturated carboxylic acids is generally between 3,000 g / mol and 200,000 g / mol, that of the copolymers between 2,000 g / mol and 200,000 g / mol, preferably 30,000 g / mol to 120,000 g / mol, in each case based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of 30,000 g / mol to 100,000 g / mol.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Suitable, though less preferred Compounds of this class are copolymers of acrylic acid or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the proportion of the acid is at least 50% by weight.
  • Terpolymers which contain two unsaturated acids and / or salts thereof as monomers and also vinyl alcohol and / or an esterified vinyl alcohol or a carbohydrate as the third monomer may be used as water-soluble organic builder substances, the first acidic monomer being selected from a monoethylenically unsaturated C 3 - C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid, derived and the second acidic monomer is a derivative of a C 4 -C 8 dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid substituted in the 2-position with an alkyl or aryl radical.
  • the first acidic monomer being selected from a monoethylenically unsaturated C 3 - C 8 carboxylic acid and preferably from a C 3 -C 4 monocarboxylic acid, in particular from (meth) acrylic acid, derived and
  • the organic builder substances can be used, in particular for the preparation of liquid agents, in the form of aqueous solutions, preferably in the form of 30 to 50 percent by weight aqueous solutions. All of the acids mentioned are generally used in the form of their water-soluble salts, in particular their alkali metal salts.
  • Such organic builders may, if desired, be included in the compositions in amounts of up to 40% by weight, in particular up to 25% by weight, and preferably from 1% by weight to 8% by weight. Quantities close to the stated upper limit are preferably used in paste-form or liquid, in particular water-containing, agents according to the invention.
  • Suitable water-soluble inorganic builder materials are, in particular, alkali metal silicates, alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • alkali metal silicates alkali metal carbonates and alkali metal phosphates, which may be in the form of their alkaline, neutral or acidic sodium or potassium salts.
  • examples of these are trisodium phosphate, tetrasodium diphosphate, disodium dihydrogen diphosphate, pentasodium triphosphate, so-called sodium hexametaphosphate, oligomeric trisodium phosphate with degrees of oligomerization of from 5 to 1000, in particular from 5 to 50, and the corresponding potassium salts or mixtures of sodium and potassium salts.
  • Crystalline or amorphous alkali metal aluminosilicates in amounts of up to 50% by weight, preferably not more than 40% by weight, and in liquid agents, in particular from 1% by weight to 5% by weight, are particularly suitable as water-insoluble, water-dispersible inorganic builder materials.
  • these are the crystalline sodium aluminosilicates in detergent grade, especially zeolite A, P and optionally X, alone or in mixtures, for example in the form of a co-crystallizate from zeolites A and X (Vegobond® AX, a commercial product of Condea Augusta SpA). Amounts near the above upper limit are preferably used in solid, particulate agents.
  • suitable aluminosilicates have no particles with a particle size greater than 30 .mu.m and preferably consist of at least 80% by weight of particles having a size of less than 10 .mu.m.
  • Their calcium binding capacity is usually in the range of 100 to 200 mg CaO per gram.
  • Suitable substitutes or partial substitutes for the said aluminosilicate are crystalline alkali silicates which may be present alone or in a mixture with amorphous silicates.
  • the alkali metal silicates useful as builders in the compositions according to the invention preferably have a molar ratio of alkali metal oxide to SiO 2 below 0.95, in particular from 1: 1.1 to 1:12, and may be present in amorphous or crystalline form.
  • Preferred alkali metal silicates are the sodium silicates, in particular the amorphous sodium silicates, with a molar ratio of Na 2 O: SiO 2 of 1: 2 to 1: 2.8.
  • the crystalline silicates which may be present alone or in admixture with amorphous silicates, are crystalline layer silicates with the general formula Na 2 Si x O y are used 2x + 1 H 2 O, in which x, the so-called module, a number from 1.9 to 22, in particular 1.9 to 4 and y is a number from 0 to 33 and preferred values for x are 2, 3 or 4.
  • Preferred crystalline phyllosilicates are those in which x in the abovementioned general formula assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates (Na 2 Si 2 O 5 y H 2 O) are preferred.
  • amorphous alkali silicates can be used in inventive compositions.
  • a crystalline sodium layer silicate with a modulus of 2 to 3 is used, as can be prepared from sand and soda.
  • Crystalline sodium silicates with a modulus in the range from 1.9 to 3.5 are used in a further preferred embodiment of compositions according to the invention.
  • Crystalline layer-form silicates of formula (I) given above are sold by Clariant GmbH under the trade name Na-SKS, eg.
  • Na-SKS-1 Na 2 Si 22 O 45 xH 2 O, Kenyaite
  • Na-SKS-2 Na 2 Si 14 O 29 xH 2 O, magadiite
  • Na-SKS-3 Na 2 Si 8 O 17 xH 2 O
  • Na-SKS-4 Na 2 Si 4 O 9 xH 2 O, Makatite
  • Na-SKS-5 ⁇ -Na 2 Si 2 O 5
  • Na-SKS-7 ⁇ -Na 2 Si 2 O 5 , Natrosilit
  • Na-SKS-9 NaHSi 2 O 5 3H 2 O
  • Na-SKS-10 NaHSi 2 O 5 3H 2 O, kanemite
  • Na-SKS-11 t-Na 2 Si 2 O 5
  • Na-SKS-13 NaHSi 2 O 5
  • Na-SKS-6 ⁇ - Na 2 Si 2 O 5
  • composition according to the invention a granular compound of crystalline phyllosilicate and citrate, of crystalline phyllosilicate and of the above-mentioned (co-) polymeric polycarboxylic acid, or of alkali silicate and alkali metal carbonate, as it is commercially available, for example, under the name Nabion® 15 ,
  • Builder substances are preferably present in the compositions according to the invention in amounts of up to 75% by weight, in particular 5% by weight to 50% by weight.
  • suitable peroxygen compounds are in particular organic peracids or pers acid salts of organic acids, such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration.
  • organic peracids or pers acid salts of organic acids such as phthalimidopercaproic acid, perbenzoic acid or salts of diperdodecanedioic acid, hydrogen peroxide and under the washing conditions hydrogen peroxide donating inorganic salts, which include perborate, percarbonate, persilicate and / or persulfate Caroat belong into consideration.
  • solid peroxygen compounds are to be used, they can be used in the form of powders or granules, which can also be enveloped in a manner known in principle.
  • an agent according to the invention contains peroxygen compounds, they are present in amounts of preferably up to 50% by weight, in particular from 5% by weight to 30% by weight.
  • bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzolsulfonat (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy-2,5-dihydrofuran and enol esters,
  • TAED
  • hydrophilic substituted acyl acetals and the acyl lactams are also preferably used.
  • Combinations of conventional bleach activators can also be used.
  • Such bleach activators can, in particular in the presence of the abovementioned hydrogen peroxide-producing bleach, in the usual amount range, preferably in amounts of from 0.5 wt .-% to 10 wt .-%, in particular 1 wt .-% to 8 wt .-%, based on However, total agent, be included, missing when using percarboxylic acid as the sole bleach, preferably completely.
  • sulfone imines and / or bleach-enhancing transition metal salts or transition metal complexes may also be present as so-called bleach catalysts.
  • Suitable enzymes which can be used in the compositions are those from the class of amylases, proteases, lipases, cutinases, pullulanases, hemicellulases, cellulases, oxidases, laccases and peroxidases and mixtures thereof. Particularly suitable are from fungi or bacteria, such as Bacillus subtilis, Bacillus licheniformis, Bacillus lentus, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes, Pseudomonas cepacia or Coprinus cinereus derived enzymatic agents.
  • the enzymes may be adsorbed to carriers and / or embedded in encapsulants to protect against premature inactivation. They are preferably present in the detergents or cleaners according to the invention in amounts of up to 5% by weight, in particular from 0.2% by weight to 4% by weight. If the agent of the invention contains protease, it preferably has a proteolytic activity in the range of about 100 PE / g to about 10,000 PE / g, in particular 300 PE / g to 8000 PE / g. If several enzymes are to be used in the agent according to the invention, this can be achieved by incorporation of the two or more separate or in a known manner separately formulated enzymes or be carried out by two or more enzymes synthesized together in a granule.
  • organic solvents which can be used in addition to water include alcohols having 1 to 4 C atoms, in particular methanol, ethanol, isopropanol and tert-butanol, diols having 2 to 4 C -Atomen, in particular ethylene glycol and propylene glycol, and mixtures thereof and derived from the classes of compounds mentioned ether.
  • Such water-miscible solvents are preferably present in the compositions according to the invention in amounts of not more than 30% by weight, in particular from 6% by weight to 20% by weight.
  • the compositions according to the invention can contain system- and environmentally compatible acids, in particular citric acid, acetic acid, tartaric acid, malic acid, lactic acid, glycolic acid, succinic acid, glutaric acid and / or adipic acid. but also mineral acids, in particular sulfuric acid, or bases, in particular ammonium or alkali metal hydroxides.
  • Such pH regulators are present in the compositions according to the invention in amounts of preferably not more than 20% by weight, in particular from 1.2% by weight to 17% by weight.
  • Graying inhibitors have the task of keeping suspended from the textile fiber dirt suspended in the fleet.
  • Water-soluble colloids of mostly organic nature are suitable for this purpose, for example starch, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or of cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • water-soluble polyamides containing acidic groups are suitable for this purpose.
  • starch derivatives can be used, for example aldehyde starches.
  • cellulose ethers such as carboxymethylcellulose (Na salt), methylcellulose, hydroxyalkylcellulose and mixed ethers, such as methylhydroxyethylcellulose, methylhydroxypropylcellulose, methylcarboxymethylcellulose and mixtures thereof, for example in amounts of from 0.1 to 5% by weight, based on the compositions.
  • Detergents according to the invention may contain, for example, derivatives of diaminostilbenedisulfonic acid or their alkali metal salts as optical brighteners, although they are preferably free of optical brighteners for use as color detergents.
  • Suitable salts are, for example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulphonic acid or compounds of similar construction which, instead of the morpholino Group carry a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group.
  • brighteners of the substituted diphenylstyrene type may be present, for example, the alkali salts of 4,4'-bis (2-sulfostyryl) -diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) -diphenyl, or 4 - (4-chlorostyryl) -4 '- (2-sulfostyryl).
  • Mixtures of the aforementioned optical brightener can be used.
  • foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant foam inhibitors are, for example, organopolysiloxanes and mixtures thereof with microfine, optionally silanized silica and paraffins, waxes, microcrystalline waxes and mixtures thereof with silanated silicic acid or bis-fatty acid alkylenediamides. It is also advantageous to use mixtures of various foam inhibitors, for example those of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone- and / or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. In particular, mixtures of paraffins and bistearylethylenediamide are preferred.
  • compositions according to the invention presents no difficulties and can be carried out in a known manner, for example by spray-drying or granulation, enzymes and possibly other thermally sensitive ingredients such as, for example, bleaching agents optionally being added separately later.
  • a process comprising an extrusion step is preferred.
  • compositions according to the invention in tablet form which are single-phase or multiphase, monochrome or multicolor and in particular from a layer or from can consist of several, in particular of two layers
  • a tablet produced in this way has a weight of 10 g to 50 g, in particular 15 g up to 40 g.
  • the spatial form of the tablets is arbitrary and can be round, oval or angular, with intermediate forms are also possible. Corners and edges are advantageously rounded. Round tablets preferably have a diameter of 30 mm to 40 mm.
  • the size of rectangular or cuboid-shaped tablets, which are introduced predominantly via the metering device, for example the dishwasher, is dependent on the geometry and the volume of this metering device.
  • Exemplary preferred embodiments have a base area of (20 to 30 mm) x (34 to 40 mm), in particular of 26x36 mm or 24x38 mm.
  • Liquid or pasty compositions of the invention in the form of conventional solvents, in particular water, containing solutions are usually prepared by simply mixing the ingredients that can be added in bulk or as a solution in an automatic mixer.
  • the accurately weighed sample was dissolved in a phenol / methanol mixture and titrated potentiometrically with hydrochloric acid solution (0.02 N).
  • the number of titratable amino groups was calculated from the consumption up to the inflection point of the titration curve and a corresponding blank value of the pure solvent.
  • the BET method determinations were carried out with the Autosorb Automated Gas Sorption (Quantachrome) apparatus using nitrogen as the adsorbate.
  • the activation temperature was in the range of 80 to 120 ° C and the adsorption of nitrogen was at its boiling point (77 K).
  • the preparation of the polyamide particles was carried out by Kryomahlung the dried in vacuo at 80 ° C for 3 days polymers A, B, C and D in a laboratory centrifugal mill.
  • the mean particle size (weight average particle diameter) of the polyamide powder obtained was about 220 ⁇ m.
  • the average particle size of the porous particles of the polymer E was determined to be 26 ⁇ m, the BET surface area was 9 m 2 / g.
  • a solution of 6.02 g of polymer A in 264 g of formic acid (98-100%, p.a.) was used (2.2 wt .-% solution).
  • the polymer A used had a proportion of AEG of 87 mmol / kg and a proportion of CEG of 48 meq / kg.
  • the solution of the polymer A was spun with the Nanospider apparatus from Elmarco according to the aforementioned variant 2.
  • the solution used was in a container in which a spinning electrode (roller) permanently rotated.
  • the spinning electrode in this case was an electrode based on metal wires. Part of the formulation was consistently on the surface of the wires.
  • the electric field between the roller and the counter electrode above the roller caused that first liquid jets formed from the formulation, which then auf loose or solidify existing solvent the way to the counter electrode.
  • the desired fleece of polyamide nanofibres was formed on a polypropylene support, which passed between the two electrodes.
  • a nonwoven fabric consisting of polymer A was produced on the polypropylene support. Electron microscopic analysis of the web revealed that it was composed of fibers with a mean diameter of 160 ⁇ 30 nm.
  • the solution of the polymer was spun with the Nanospider apparatus of Elmarco according to the aforementioned variant 2.
  • the solution used was in a container in which a spinning electrode (roller) permanently rotated.
  • the spinning electrode in this case was an electrode based on metal wires. Part of the formulation was consistently on the surface of the wires.
  • the electric field between the roller and the counter electrode above the roller caused the formulation to form liquid jets, which then lose or solidify the solvent present on the way to the counter electrode.
  • the desired fleece of polyamide nanofibres was formed on a polypropylene support, which passed between the two electrodes.
  • a non-woven consisting of the corresponding polymer was produced on the polypropylene support. Electron microscopic analysis of the nonwoven showed that in both cases it was composed of fibers with an average diameter of 140 ⁇ 40 nm.
  • the mixture was spun with the Elmarco Nanospider apparatus as previously described.
  • FC nonwoven fabric
  • the solution of polymer E was spun with the Nanospider apparatus from Elmarco according to variant 2 above.
  • the solution used was in a container in which a spinning electrode (roller) permanently rotated.
  • the spinning electrode in this case was an electrode based on metal wires. Part of the formulation was consistently on the surface of the wires.
  • the electric field between the roller and the counter electrode above the roller caused the formulation to form liquid jets, which then lose or solidify the solvent present on the way to the counter electrode.
  • the desired fleece of polyamide nanofibres was formed on a polypropylene support, which passed between the two electrodes.
  • a non-woven made of polymer E was produced on the polypropylene support. Electron microscopic analysis of the web revealed that it was composed of fibers with a mean diameter of 135 ⁇ 35 nm.
  • wash liquor was produced to which the color textiles listed in the table below were added and with the white textile pieces (6 cm x 16 cm) made of cotton (Krefelder standard) or polyamide (EMPA 406 ) were treated at 60 ° C for 30 minutes.
  • otherwise identical wash liquors containing, in addition to the agent W1, the polyamide fiber webs FA, FB, FC, FD or FE prepared as described above (each 2.5 g / l) or, for comparison, the particulate polyamides A, B, C prepared as described above , D or E in the same amount, tested under the same conditions.

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Claims (14)

  1. Agent de lavage, d'adoucissement, de prétraitement du linge ou de nettoyage contenant un inhibiteur de transfert de colorant se présentant sous la forme de fibres de polyamides insolubles dans l'eau dont le diamètre moyen ne dépasse pas 2 µm, en plus des ingrédients classiques compatibles avec cette composition.
  2. Agent selon la revendication 1, caractérisé en ce qu'il contient de 0,05% en poids à 20% en poids, en particulier de 0,1% en poids à 5% en poids, de fibres de polyamides.
  3. Utilisation de fibres de polyamides insolubles dans l'eau dont le diamètre moyen ne dépasse pas 2 µm, comme additifs dans des compositions d'agent de lavage pour textiles.
  4. Utilisation de fibres de polyamides insolubles dans l'eau dont le diamètre moyen ne dépasse pas 2 µm, pour empêcher le transfert de colorants de textiles de textiles teints vers des textiles non teints ou de couleurs différentes lorsqu'ils sont lavés conjointement en particulier dans des solutions aqueuses contenant des agents tensioactifs, ou pour empêcher la modification de la perception des couleurs des textiles quand ils sont lavés en particulier dans des solutions aqueuses contenant des agents tensioactifs.
  5. Procédé de lavage de tissus teints dans des solutions aqueuses contenant un agent tensioactif, caractérisé en ce qu'on utilise une solution aqueuse, contenant un agent tensioactif, qui contient des fibres de polyamides insolubles dans l'eau dont le diamètre moyen ne dépasse pas 2 µm.
  6. Agent, utilisation ou procédé selon l'une des revendications précédentes, dans lequel les fibres de polyamides se présentent sous la forme d'un produit en nappe, en particulier un non-tissé ou un tissu.
  7. Agent, utilisation ou procédé selon l'une des revendications précédentes, dans lequel les fibres de polyamides présentent au moins une, en particulier au moins 2, 3 ou 4, des caractéristiques suivantes i) à iv) :
    i) le diamètre moyen des fibres de polyamides est dans la gamme de 10 nm à 1000 nm ;
    ii) les fibres de polyamides ont une surface BET dans la gamme de 0,5 à 50 g/m2 ;
    iii) les polyamides formant les fibres de polyamides comportent des groupes amino et le cas échéant des groupes carboxyle et ont une teneur en groupes amino d'au moins 40 mmol/kg ;
    iv) lés polyamides formant les fibres de polyamides comportent des groupes amino et éventuellement des groupes carboxyle et ont une teneur en groupes carboxyle qui est inférieure à 100 meq/kg, au moins 10 méq/kg étant au-dessus de la teneur en groupes amino.
  8. Agent, utilisation ou procédé selon l'une des revendications précédentes, dans lequel les polyamides des fibres de polyamides sont choisis parmi les polymères qui sont essentiellement constitués des unités de répétition suivantes la et Ib,
    Figure imgb0015
    Figure imgb0016
     dans lesquelles
    A est choisi parmi les résidus alcanediyle ayant 2 à 20 atomes de carbone, dans lesquels 1, 2, 3, 4 ou 5 groupes CH2 non adjacents peuvent être remplacés par un nombre correspondant de groupes NH et/ou dans lesquels deux groupes CH2 combinés l'un à l'autre peuvent être remplacés conjointement par un groupe cycloalcanediyle en C5 à C7, et des groupes de la formule (A'O)P-A' dans lesquels A' représente un alcanediyle en C2 à C4, et p est un nombre entier dans la gamme allant de 1 à 20, les unités de répétition A'-O pouvant être identiques ou différentes,
    B est choisi parmi une liaison covalente, des résidus alcanediyle ayant 1 à 20 atomes de carbone, dans lesquels deux groupes CH2 peuvent être remplacés conjointement par un groupe cycloalcanediyle en C5 à C7, et
    B' est choisi parmi des résidus alcandiyle ayant 4 à 20 atomes de carbone.
  9. Agent, utilisation ou procédé selon l'une des revendications précédentes, dans lequel les polyamides des fibres de polyamides sont obtenus par réaction
    a) d'au moins un composé amino qui comporte 2 groupes amino primaires, choisis en particulier parmi les composés de la formule V1,

            H2N-A-NH2     (V1)

    dans laquelle A est choisi parmi des résidus alcanediyle ayant 2 à 20 atomes de carbone, dans lesquels 1, 2, 3, 4 ou 5 groupes CH2 non adjacents peuvent être remplacés par un nombre correspondant de groupes NH, et/ou dans lesquels deux groupe CH2 combinés l'un à l'autre peuvent être remplacés conjointement par un groupe cycloalcanediyle en C5 à C7, et des groupes de la formule (A"-O)p-A" dans laquelle A" représente un alcanediyle en C2 à C4 et p est un nombre entier dans la gamme allant de 1 à 20, les unités de répétition A"-O pouvant être identiques ou différentes, avec
    b) au moins un composé formant un amide, qui est choisi parmi les acides dicarboxyliques, les dérivés formant des amides et les lactames, choisis en particulier parmi les acides dicarboxyliques de la formule V2

            HOOC-B-COOH     (V2)

    et de leurs dérivés formant des amides, dans laquelle
    B est choisi parmi une liaison covalente et des résidus alcanediyle ayant 1 à 20 atomes de carbone, dans lesquels deux groupes CH2 combinés l'un à l'autre peuvent être remplacés conjointement par un cycloalcanediyle en C5 à C7.
  10. Fibres de polyamides insolubles dans l'eau, qui comportent des groupes amino et éventuellement des groupes carboxyle, la teneur en groupes amino étant en moyenne prédominante par rapport à la teneur en groupes carboxyle, dans lequel le diamètre moyen des fibres de polyamides ne dépassant pas 2 µm.
  11. Fibre de polyamides selon la revendication 10, dans laquelle les polyamides des fibres de polyamides sont choisis parmi les polymères qui sont essentiellement constitués des unités de répétition suivante la et Ib,
    Figure imgb0017
    Figure imgb0018
     dans lesquelles
    A est choisi parmi les résidus alcanediyle ayant 2 à 20 atomes de carbone, dans lesquels 1, 2, 3, 4 ou 5 groupes CH2 non adjacents peuvent être remplacés par un nombre correspondant de groupes NH et/ou dans lesquels deux groupes CH2 combinés l'un à l'autre peuvent être remplacés conjointement par un groupe cycloalcanediyle en C5 à C7, et des groupes de la formule (A'O)P-A' dans lesquels A' représente un alcanediyle en C2 à C4, et p est un nombre entier dans la gamme allant de 1 à 20, les unités de répétition A'-O pouvant être identiques ou différentes,
    B est choisi parmi une liaison covalente, des résidus alcanediyle ayant 1 à 20 atomes de carbone, dans lesquels deux groupes CH2 peuvent être remplacés conjointement par un groupe cycloalcanediyle en C5 à C7, et
    B' est choisi parmi des résidus alcanediyle ayant 4 à 20 atomes de carbone.
  12. Fibres de polyamides selon la revendication 10, dans lesquelles les polyamides des fibres de polyamides sont obtenus par réaction
    a) d'au moins un composé amino qui comporte 2 groupes amino primaires, choisis en particulier parmi les composés de la formule V1,

            H2N-A-NH2     (V1)

    dans laquelle A est choisi parmi des résidus alcanediyle ayant 2 à 20 atomes de carbone, dans lesquels 1, 2, 3, 4 ou 5 groupes CH2 non adjacents peuvent être remplacés par un nombre correspondant de groupes NH, et/ou dans lesquels deux groupe CH2 combinés l'un à l'autre peuvent être remplacés conjointement par un groupe cycloalcanediyle en C5 à C7, et des groupes de la formule (A"-O)p-A" dans laquelle A" représente un alcanediyle en C2 à C4 et p est un nombre entier dans la gamme allant de 1 à 20, les unités de répétition A"-O pouvant être identiques ou différentes,
    avec
    b) au moins un composé formant un amide, qui est choisi parmi les acides dicarboxyliques, les dérivés formant des amides et les lactames, choisis en particulier parmi les acides dicarboxyliques de la formule V2

            HOOC-B-COOH     (V2)

    et de leurs dérivés formant des amides, dans laquelle
    B est choisi parmi une liaison covalente et des résidus alcanediyle ayant 1 à 20 atomes de carbone, dans lesquels deux groupes CH2 combinés l'un à l'autre peuvent être remplacés conjointement par un cycloalcanediyle en C5 à C7.
  13. Fibres de polyamides selon l'une des revendications 10 à 12, qui présentent au moins une, en particulier au moins 2, 3 ou 4, des caractéristiques suivantes i) à iv) :
    i) le diamètre moyen des fibres de polyamides est dans la gamme de 10 nm à 1000 nm ;
    ii) les fibres de polyamides ont une surface BET dans la gamme de 0,5 à 50 g/m2 ;
    iii) les polyamides formant les fibres de polyamides comportent des groupes amino et le cas échéant des groupes carboxyle et ont une teneur en groupes amino d'au moins 40 mmol/kg ;
    iv) les polyamides formant les fibres de polyamides comportent des groupes amino et éventuellement des groupes carboxyle et ont une teneur en groupes carboxyle qui est inférieure à 100 meq/kg, au moins 10 méq/kg étant au-dessus de la teneur en groupes amino.
  14. Produit en nappe contenant les fibres de polyamides selon l'une des revendications 10 à 13, se présentant en particulier sous la forme d'un non-tissé ou d'un tissu ou disposé un support plat.
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WO2013120815A1 (fr) 2013-08-22
EP2814929A1 (fr) 2014-12-24
US20140349906A1 (en) 2014-11-27
KR20140114076A (ko) 2014-09-25

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