EP2430137B1 - Agent de lavage ou de nettoyage protégeant les couleurs - Google Patents

Agent de lavage ou de nettoyage protégeant les couleurs Download PDF

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Publication number
EP2430137B1
EP2430137B1 EP10716362.8A EP10716362A EP2430137B1 EP 2430137 B1 EP2430137 B1 EP 2430137B1 EP 10716362 A EP10716362 A EP 10716362A EP 2430137 B1 EP2430137 B1 EP 2430137B1
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Prior art keywords
benzoxazine
compounds
polymer
general formula
carbon atoms
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EP10716362.8A
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German (de)
English (en)
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EP2430137A1 (fr
Inventor
Paula Barreleiro
Thomas Eiting
Andreas Taden
Siglinde Erpenbach
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
    • C11D3/3776—Heterocyclic compounds, e.g. lactam

Definitions

  • the present invention relates to the use of polymers which are accessible by polymerization of benzoxazines, as dye transfer inhibiting agents in the washing and / or cleaning of textiles and detergents or cleaners containing such color transfer inhibiting polymers.
  • 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 color impression change washed, i. cleaner, textiles can be based on the fact that dye components are removed by the Waschregulatingmoi cleaning process from the textile ("fading"), on the other hand, from other colored textiles detached dyes on the textile precipitate (“discoloration").
  • the discoloration aspect may also play a role in undyed laundry items when washed together with colored laundry items.
  • detergents In order to avoid these undesirable side effects of removing dirt from textiles by treatment with usually surfactant-containing aqueous systems, 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.
  • 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 polymers have such a high affinity for dyes that they draw more of them from the dyed fiber, resulting in loss of color when used. The same applies to cleaning hard surfaces.
  • Polybenzoxazine compounds as additives for electrolytic membranes are made EP 1760110 known.
  • benzoxazine (co) polymers lead to unexpectedly high color transfer inhibition when used in detergents or cleaners. Particularly pronounced is the prevention of dyeing of white or other colored fabrics by washed out of textiles dyes. It is conceivable that the benzoxazine (co) polymers defined below are applied to the textiles during washing and thereby effectively prevent the dyes from being removed from the textiles and, secondly, they have a repellent effect on dye molecules already present in the liquor.
  • the invention relates to the use of polymers which are obtainable by polymerization of benzoxazine monomers, to avoid the transfer of textile dyes of dyed textiles to undyed or differently colored textiles in their common washing in particular surfactant-containing aqueous solutions.
  • the benzoxazine (co) polymers used according to the invention can be obtained in a basically known manner by polymerization of benzoxazines.
  • the benzoxazine compounds which can be used to prepare the benzoxazine (co) polymers used in the present invention are polymerizable monomers comprising at least one benzoxazine group.
  • Preferred monomers may preferably comprise up to four benzoxazine groups, it being possible to use both individual monomers and mixtures of two or more monomers for the preparation of benzoxazine (co) polymers used according to the invention.
  • Polymerization of the polymerizable benzoxazine compound (to the benzoxazine polymer) or mixture of various polymerizable benzoxazine compounds (to the benzoxazine copolymer) can be accomplished by methods known in the art, for example, at elevated temperatures according to a self-initiating mechanism (thermal polymerization) or by addition of cationic initiators .
  • Suitable cationic initiators are, for example, Lewis acids or other cationic initiators, for example metal halides, organometallic reagents, such as metalloporphyrins, methyl tosylates, methyltriflates or trifluorosulphonic acids.
  • basic reagents can be used to initiate the polymerization of the polymerizable benzoxazine compound or the mixture of various polymerizable benzoxazine compounds.
  • Suitable basic reagents may for example be selected from imidazole or imidazole derivatives.
  • the thermal polymerization is carried out usually at temperatures of 150 ° C to 300 ° C, in particular at temperatures of 160 ° C to 220 ° C. By using the above-mentioned initiators and / or other reagents, the polymerization temperature may also be lower.
  • the polymerization process is based essentially on the thermally-induced ring opening of the oxazine ring of a benzoxazine system
  • R in each repeating unit is independently selected from hydrogen and methyl.
  • the divalent organic compound groups R 1 in formula (I) and / or R 6 in formula (II) preferably comprise 2 to 50, particularly preferably 2 to 25 and in particular 2 to 20 carbon atoms. Furthermore, the divalent organic compound groups R 1 and R 6 may each be selected from linear or branched, optionally substituted alkylene groups comprising 1 to 15 carbon atoms, wherein the alkylene groups are optionally interrupted by at least one heteroatom selected from oxygen, sulfur or nitrogen.
  • the term "interrupted" is understood as meaning that in a divalent alkylene group at least one non-terminal carbon atom of the group mentioned is replaced by a heteroatom, the heteroatom preferably being selected from -SS-- (sulfur), --O-- (oxygen), and --NR a - (nitrogen), wherein R a is in particular hydrogen or a linear or branched, optionally substituted alkyl groups having 1 to 15 carbon atoms.
  • the divalent organic linking groups R 1 and / or R 6 are selected from alkylene groups comprising 2 to 8 C atoms.
  • R 1 and / or R 6 is selected from linear alkylene groups comprising from 2 to 6, especially 2 or 3, carbon atoms, such as ethylene, propylene, butylene, pentylene and hexylene groups.
  • R 1 in formula (I) and / or R 6 in formula (II) may be a covalent bond.
  • the divalent organic linking groups R 1 and / or R 6 may comprise at least one arylene group and / or at least one biphenylene group, each preferably containing from 6 to 12 carbon atoms.
  • the arylene groups and biphenylene groups may be substituted or unsubstituted, suitable substituents being selected, for example, from alkyl, alkenyl, halogen, amine, thiol, carboxyl and hydroxyl groups.
  • at least one carbon atom of the aromatic ring system of said groups can be replaced by a heteroatom, wherein the heteroatom is preferably selected from oxygen, nitrogen and sulfur.
  • radicals R 2 and R 5 in formula (I) and formula (II) are preferably each hydrogen and methyl.
  • the radical A in formula (II) represents a hydroxyl group or a nitrogen-containing heterocycle.
  • nitrogen-containing heterocycle is understood in particular to mean those ring systems which contain 3 to 8 ring atoms, preferably 5 to 6 ring atoms, where the ring system comprises at least one nitrogen atom and at least two carbon atoms.
  • Said nitrogen-containing heterocycle can have a saturated, unsaturated or aromatic structure and, in addition to the abovementioned atoms, also comprise further heteroatoms, for example sulfur and / or oxygen atoms.
  • the nitrogen-containing heterocycle is linked to the nitrogen atom of the oxazine ring of the benzoxazine structure via the divalent compound group R 6 according to formula (II).
  • the divalent linking group R 6 may be linked to any nitrogen or carbon ring atom of the nitrogen-containing heterocycle by R 6 formally replacing a hydrogen atom covalently linked to a nitrogen or carbon ring atom.
  • nitrogen-containing heterocycles are selected, for example, from 5-membered nitrogen-containing heterocycles, such as imidazoles, imidazolidones, tetrazoles, oxazoles, pyrroles, pyrrolidines and pyrazoles or 6-membered nitrogen-containing heterocycles, such as piperidines, piperidones, piperazines, pyridines, diazines and morpholines.
  • 5-membered nitrogen-containing heterocycles such as imidazoles, imidazolidones, tetrazoles, oxazoles, pyrroles, pyrrolidines and pyrazoles
  • 6-membered nitrogen-containing heterocycles such as piperidines, piperidones, piperazines, pyridines, diazines and morpholines.
  • the polymerizable benzoxazine compounds of the general formula (I) are selected from compounds of the general formula (III) where x is a number between 0 and 1000 and y is a number between 0 and 1000, with the proviso that x + y ⁇ 2, where Z, R 2 , Y and q are each as defined above in formula (I).
  • x + y is ⁇ 3, more preferably ⁇ 4, and most preferably ⁇ 5.
  • n and / or x + y therefore takes as the lower limit a value of at least 3, 4, 6, 10, 12, 14, 16, 18, 20, 25, 30, 35, 40, 50, 60, 80, 100, 150 or 200.
  • a useful upper limit for n and / or x + y in the benzoxazine compounds of the general formula (I) or (III) according to the invention is preferably at a value of at most 10,000, 2000, 1800, 1600, 1400, 1200, 1000, 800, 600 or 400.
  • the benzoxazine compounds of the general formula (II) are selected from compounds of the general formula (IV) and / or from compounds of the general formula (V) wherein R 7 and R 8 are each independently selected from hydrogen, halogen, linear or branched, optionally substituted alkyl groups, alkenyl groups and aryl groups, wherein c, B, R 5 and R 6 are each as defined above in formula (II).
  • R 7 and R 8 in formula (IV) are independently selected from hydrogen, methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl and iso-butyl, where R 7 and R 8 are in particular hydrogen or methyl.
  • benzoxazine compounds of the general formula (IV) are selected from the following benzoxazine compounds: wherein c, B, R 5 , R 6 , R 7 and R 8 are as defined above.
  • the illustrated benzoxazine compounds bearing an imidazole ring as a nitrogen-containing heterocycle can be obtained, for example, by the reaction of a phenolic compound with an aldehyde such as formaldehyde and an aminoalkylimidazole compound.
  • Suitable phenolic compounds can be selected, for example, from mono- or biphenolic compounds such as phenol, bisphenol A, bisphenol F, bisphenol S or thiodiphenol.
  • aldehyde in addition to formaldehyde and paraformaldehyde trioxane or polyoxymethylene or any mixtures thereof may be used.
  • preferred aminoalkylimidazole compounds have a primary amino group and can be selected, for example, from compounds of general formula (VI) wherein R 6 , R 7 and R 3 are as defined above.
  • 1-aminoalkylimidazole compounds of the general formula (VII) or 2-aminoalkylimidazole compounds of the general formula (VIII) suitable for the preparation of the corresponding benzoxazine compounds, wherein R 6 , R 7 and R 8 are as defined above.
  • Suitable 1-aminoalkylimidazole compounds of general formula (VII) are known in the art and are commercially available. Examples are about 1- (3-aminopropyl) imidazole, available under the trade name Lupragen® API from BASF SE, 3-imidazol-1-yl-2-methyl-propylamine (Chem Pacific), 2-methyl-1H-imidazole-1-propanamine, (3B Scientific Corporation), 3-imidazole 1-yl-2-hydroxypropylamine (Ambinter, Paris Collection), 1- (4-aminobutyl) imidazole (Ambinter, Paris), 2-ethyl-1H-imidazole-1-propanamine (ChemBridge Corp.).
  • 2-Aminoalkylimidazole compounds of the general formula (VIII) are also known from the prior art.
  • the preparation can be carried out by means of common organic synthesis methods.
  • a practical synthesis is, for example, in Tetrahedron 2005, Vol. 61, at pages 11148-11155 described.
  • the illustrated benzoxazine compounds bearing a free hydroxyl group can be prepared by reacting a phenolic compound with an aldehyde such as formaldehyde and an aminoalcohol.
  • the reaction time can vary from a few minutes to a few hours.
  • Suitable amino alcohols such as 2-aminoethanol, 3-amino-1-propanol, amino-2-propanol, 4-amino-1-butanol, 2-amino-1-butanol, 4-amino-2-butanol, 5-amino 1-pentanol, 6-amino-1-hexanol, 7-amino-1-heptanol, 3-amino-1,2-propanediol, 2- (2-aminoethoxy) ethanol and 2-amino-1,3-propanediol are commercially available and can be obtained, for example, from Sigma-Aldrich or Tokyo Chemical Industry.
  • the polymerizable benzoxazine compounds can be used both alone and in any combination possible to prepare the benzoxazine (co) polymer used in the present invention.
  • the weight ratio of the at least one polymerizable benzoxazine compound of the general formula (I) to the at least one polymerizable benzoxazine compound of the general formula (II) is preferably between 10: 1 and 1:10, particularly preferably between 5: 1 and 1: 5 and in particular between 2: 1 and 1: 2, wherein a weight ratio of 1: 1 may be particularly useful.
  • the weight ratio of the at least one polymerizable benzoxazine compound of the general formula (I) to the at least one polymerizable benzoxazine compound of the general formula (IV) is preferably between 10: 1 and 1:10, particularly preferably between 5: 1 and 1: 5 and in particular between 2: 1 and 1: 2, wherein a weight ratio of 1: 1 may be particularly useful.
  • the weight ratio of the at least one polymerizable benzoxazine compound of the general formula (I) to the at least one polymerizable benzoxazine compound of the general formula (V) is preferably between 10: 1 and 1:10, particularly preferably between 5: 1 and 1: 5 and in particular between 2: 1 and 1: 2, wherein a weight ratio of 1: 1 may be particularly useful.
  • the proportion of the polymerizable benzoxazine compound of the general formula (I) in the total amount of the polymerizable benzoxazine compounds is preferably from 5 to 90% by weight, particularly preferably from 10 to 80% by weight and very particularly preferably from 25 to 50% by weight.
  • the proportion of the polymerizable benzoxazine compound of the general formula (IV) is preferably 5 to 90 wt .-%, particularly preferably 10 to 80 wt .-% and very particularly preferably 25 to 50 wt .-% and the proportion of the polymerizable benzoxazine compound of the general formula (IV) is preferably 5 to 90 wt .-%, particularly preferably 10 to 80 wt .-% and most preferably 25 to 50 wt. -%, in each case based on the total amount of polymerizable benzoxazine compounds.
  • B-IXX general formula
  • benzoxazine compounds are furthermore compounds of the general formula (B-XX) to (B-XXII), wherein R 1 ' and R 4' are as defined above and R 3 and R 2 ' are defined as R 1' .
  • the benzoxazine compounds shown are commercially available and are described, inter alia, by Huntsman Advanced Materials; Georgia-Pacific Resins, Inc. and Shikoku Chemicals Corporation, Chiba, Japan. Regardless, the benzoxazine compounds may also be obtained by reacting a phenolic compound such as bisphenol A, bisphenol F, bisphenol S or thiophenol with an aldehyde such as formaldehyde in the presence of a primary amine. Suitable manufacturing methods are used, for example, in U.S. Patent 5,543,516 , in particular in Examples 1 to 19 in columns 10 to 14 discloses, wherein the reaction time of the corresponding reaction, depending on the concentration, reactivity and reaction temperature may last from a few minutes to a few hours.
  • the benzoxazine (co) polymer used according to the invention has a linear or branched structure. Linear structures are preferred for their high water solubility and good interaction with a variety of surfaces.
  • the weight-average molecular weight "M w " of the benzoxazine (co) polymers used according to the invention is preferably between 500 and 100,000 g / mol, particularly preferably between 1,000 and 100,000 g / mol and very particularly preferably between 3,000 and 50,000 g / mol.
  • the weight-average molecular weight can be determined by gel permeation chromatography (GPC) using polystyrene as standard.
  • the benzoxazine (co) polymers obtainable by polymerization from the benzoxazine compounds are used as such according to the invention as color transfer inhibitors.
  • the alkylation can be carried out in a manner known per se.
  • the benzoxazine (co) polymer is introduced either as a pure substance or as a solution or as a dispersion or emulsion and mixed with the respective alkylating agent or a mixture of different alkylating agents.
  • the reaction can be carried out in alcoholic solution, for example in ethanol or isopropanol, it also being possible to work in the presence of inert emulsifiers or dispersants.
  • the particular reaction conditions and the amount of alkylating agent are preferably chosen so that at least 5% of all nitrogen atoms, based on the total number of nitrogen atoms in the benzoxazine (co) polymer, are converted into permanently quaternary nitrogen atoms.
  • Suitable alkylating agents in this context are preferably alkyl halides, dialkyl sulfates, dialkyl carbonates and alkylene oxides, such as, for example, ethylene oxide - the latter in the presence of dialkyl phosphates.
  • the alkylation is carried out with methyl iodide and / or dialkyl sulfates.
  • Benzoxazine (co) polymer with permanently quaternary nitrogen atoms are referred to in the context of the present invention as cationic benzoxazine (co) polymers.
  • the desired color transfer inhibiting effect occurs except in the washing process in the narrower sense, if one brings the above-defined polymers which are accessible by polymerization of benzoxazines in a Wambasenach aspects Kunststoff, for example as part of a fabric softener, in contact with the textile and the textile thus treated in the next washing process, which can be carried out with a polymer containing the polymer used according to the invention or one which is free of it, in the presence of different colored laundry washes.
  • Another object of the invention is therefore a color-protective cleaning, washing or laundry aftertreatment agent containing a dye transfer inhibitor in the form of a polymer as defined above.
  • An agent according to the invention preferably contains from 0.01% by weight to 10% by weight, in particular from 0.1% by weight to 1% by weight, of said polymer.
  • the polymers used in the present invention contribute to both of the above-mentioned aspects of color constancy, 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 a corresponding polymer to prevent 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 a polymer as defined above.
  • a surfactant-containing aqueous solution containing a polymer as defined above.
  • the color transfer inhibiting effect of polymers used according to the invention in the washing of textiles made of cotton, wherein the type of textile refers to the white or undyed textile.
  • the color transfer inhibiting effect of polymers used according to the invention is particularly pronounced in the washing of textiles dyed with direct, reactive or acid dyeings.
  • An inventive composition can, in addition to the polymer, which is accessible by polymerization of benzoxazines, if desired, additionally a known dye transfer inhibitor, this then preferably in amounts of 0.01 wt .-% to 5 wt .-%, in particular 0.1 wt. % to 1 wt .-%, which in a preferred embodiment of the invention is a polymer of vinylpyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer thereof.
  • N-polyvinylpyrrolidones N-vinylimidazole / N-vinylpyrrolidone copolymers
  • polyvinyloxazolidones copolymers based on vinyl monomers and carboxamides
  • pyrrolidone-containing polyesters and polyamides grafted polyamidoamines and polyethyleneimines
  • polymers containing amide groups from secondary amines polyamine-N-oxide polymers
  • Polyvinyl alcohols and copolymers based on acrylamidoalkenylsulfonic acids it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water.
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine
  • a mediator compound for the peroxidase for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine
  • the above-mentioned polymeric color transfer inhibiting agents being additionally used can.
  • the copolymers useful as additional color transfer inhibiting agents those of vinylpyrrolidone and vinylimidazole in the molar ratio of 5: 1 to 1: 1 are preferred.
  • the detergents 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 agents.
  • 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.
  • 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
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • 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 -alkyle 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 narrowed Homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 EO can also be used. 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 -Alkylpolyethylenglykolpolypropylenglykolether each with at 8 mol ethylene oxide and propylene oxide in the molecule.
  • 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.
  • polyhydroxy fatty acid amides of the formula in which R 11 CO is an aliphatic acyl radical having 6 to 22 carbon atoms, R 12 represents hydrogen, an alkyl or hydroxyalkyl having 1 to 4 carbon atoms and [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 in the R 13 is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 14 is a linear, branched or cyclic alkylene radical or an arylene radical having 2 to 8 carbon atoms
  • R 15 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
  • [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 not only such "dimer”, but also corresponding to "trimeric” surfactants understood.
  • 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 are by themselves 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.
  • Cationic surfactants which are used in particular in inventive laundry aftertreatment agents are preferably selected from esterquats and / or quaternary ammonium compounds (QAV) according to general formula (R I ) (R II ) (R III ) (R IV ) N + X - in which R I to R IV are identical or different C 1-22 -alkyl radicals, C 7-28 -arylalkyl radicals or heterocyclic radicals, where two or, in the case of an aromatic incorporation as in pyridine, even three radicals together with the nitrogen atom are the heterocycle , eg a pyridinium or imidazolinium compound, and X - represents halide ions, sulfate ions, hydroxide ions or similar anions.
  • QAV quaternary ammonium compounds
  • QACs can be prepared by reacting tertiary amines with alkylating agents, such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • alkylating agents such as, for example, methyl chloride, benzyl chloride, dimethyl sulfate, dodecyl bromide, but also ethylene oxide.
  • the alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary
  • Candidate QACs are, for example, benzalkonium chloride (N alkyl-N, N dimethyl-benzylammonium chloride), benzalkone B (m, p-dichlorobenzyl-dimethyl-C 12 -alkylammonium chloride, benzoxonium chloride (benzyl-dodecyl-bis (2-hydroxyethyl) -ammonium chloride ) Cetrimonium bromide (N-hexadecyl-N, N-trimethyl-ammonium bromide), Benzetonium chloride (N, N-dimethyl-N [2- [2- [2- [p- (1,1,3,3-tetramethyl-butyl) -phenoxy] -ethoxy] -ethyl ] benzylammonium chloride), dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride, didecyldimethyl
  • Esterquats are here compounds of the general formula, in which R 6 is an alkyl or alkenyl radical having 12 to 22 carbon atoms and 0, 1, 2 or 3 double bonds, R 7 and R 8 are independently H, OH or O (CO) R 6 , s, t and u are each independently of the other the value 1, 2 or 3 and X - is an anion, in particular halide, methosulfate, methophosphate or phosphate and mixtures of these. Preference is given to compounds which contain the group O (CO) R 6 for R 7 and an alkyl radical having 16 to 18 carbon atoms for R 6 . Particularly preferred are compounds in which R 8 is also OH.
  • Examples of compounds of the abovementioned formula are methyl N- (2-hydroxyethyl) -N, N-di (tallowacyl oxyethyl) ammonium methosulfate, bis (palmitoyl) ethyl hydroxyethyl, methyl ammonium methosulfate or methyl N , N-bis (acyloxyethyl) -N- (2-hydroxyethyl) ammonium methosulfate.
  • the acyl groups whose corresponding fatty acids have an iodine number between 5 and 80, preferably between 10 and 60 and in particular between 15 and 45 and / or which have a cis / trans isomer ratio (in mols %) of greater than 30: 70, preferably greater than 50:50 and in particular greater than 70:30.
  • Commercial examples are sold by Stepan under the trade name Stepantex® ® methylhydroxyalkyldialkoyloxyalkylammonium or those known under the trade name Dehyquart® ® products from Cognis Germany GmbH or the known under the name Rewoquat ® products by manufacturer Goldschmidt-Witco.
  • Surfactants are present in inventive compositions in proportions of preferably 5 wt .-% to 50 wt .-%, in particular from 8 wt .-% to 30 wt .-%.
  • 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 and 200,000, of the copolymers between 2,000 and 200,000, preferably 30,000 to 120,000, each based on the free acid.
  • a particularly preferred acrylic acid-maleic acid copolymer has a molecular weight of from 30,000 to 100,000.
  • Commercially available products are, for example, Sokalan® CP 5, CP 10 and PA 30 from BASF.
  • Suitable, although less preferred, compounds of this class are copolymers of acrylic or methacrylic acid with vinyl ethers, such as vinylmethyl ethers, vinyl esters, ethylene, propylene and styrene, in which the acid content is at least 50% by weight.
  • the first acidic monomer or its salt is derived 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.
  • the second acidic monomer or its salt may be a derivative of a C 4 -C 8 -dicarboxylic acid, with maleic acid being particularly preferred, and / or a derivative of an allylsulfonic acid which is substituted in the 2-position by an alkyl or aryl radical.
  • Such polymers generally have a molecular weight between 1,000 and 200,000.
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or vinyl acetate.
  • 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.
  • organic builder substances may be present 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.
  • 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 of Na 2 Si x O used 2x + 1 ⁇ y H 2 O in which x, known as the modulus, an integer of 1, 9 to 22, especially 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 practically anhydrous crystalline alkali silicates of the abovementioned general formula in which x is a number from 1.9 to 2.1, 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 layered silicates of the above Formula (I) are marketed 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) or Na-SKS-4 (Na 2 Si 4 O 9 ⁇ xH 2 O, makatite).
  • 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 , natrosilite
  • 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, such as, for example, commercially available under the name Nabion® 15, is used ,
  • 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.
  • 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, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (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 ester
  • 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 carried out by incorporation of the two or more separate or in a known manner separately prepared enzymes or by two or more enzymes formulated 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.
  • compositions of the invention system and environmentally acceptable 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.
  • environmentally acceptable 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.
  • 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.
  • inventive compositions having an increased bulk density in particular in the range from 650 g / l to 950 g / l, a process comprising an extrusion step is preferred.
  • compositions according to the invention in tablet form, which may be monophasic or multiphase, monochromatic or multicolor and in particular consist of one or more layers, in particular two layers
  • the procedure is preferably such that all constituents - if appropriate one per layer - in one Mixer mixed together and the mixture by means of conventional tablet presses, such as eccentric or rotary presses, pressed with compressive forces in the range of about 50 to 100 kN, preferably at 60 to 70 kN.
  • 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 according to the invention in the form of customary solvent-containing solutions are generally prepared by simply mixing the ingredients, which can be added in bulk or as a solution in an automatic mixer.
  • Example 1.1 Under the conditions described in Example 1.1, paraformaldehyde, p-cresol and ethanolamine were reacted. 328.6 g of the corresponding polymerizable benzoxazine compound B-box III were obtained.
  • benzoxazine (co) polymers were prepared in the composition shown in Table 1.
  • Table 1 Proportion of the respective polymerizable benzoxazine compounds on the benzoxazine (co) polymer polymer Weight fraction of the respective polymerizable benzoxazine compounds in% B-Box I-1.2 B-Box I-1.1 B-Box II B-Box III 1 100 2 100 3 100 4 100 5 30 70 6 50 50 7 30 70 8th 50 50 9 30 70 10 50 11 70 30 12 50 13 30 35 35 14 50 25 25 15 30 35 35 16 50 25 25;
  • Example 3 Alkylation of benzoxazine (co) polymers to prepare cationic benzoxazine (co) polymers
  • NMR spectroscopic methods have shown that at least 5% of all nitrogen atoms, based on the total number of nitrogen atoms in the cationic benzoxazine (co) polymer mentioned above, are in the form of permanent quaternary nitrogen atoms.
  • compositions of compositions E according to the invention and those of a comparative example C 1 Table 2: Formulation [wt .-%] e V1 C 12-18 fatty alcohol with 7 EO 10 10 Na-C 12-18 fatty alcohol with 7 EO sulphate 14.5 14.5 C 12-18 fatty acid 5 5 citric acid 3 3 Na-phosphonate 1 1 Benzoxazine (co) polymer (from Example 2 or 3) 0.1 - polyvinylpyrrolidone - 0.1 caustic soda 4.5 4.5 propylene glycol 9 9 boric acid 1 1 Silicone antifoam 0.1 0.1 water Ad 100 Ad 100 Ad 100 Ad 100
  • compositions E according to the invention which contained a benzoxazine (co) polymer prepared in Examples 2 and 3, showed better ink transfer-inhibiting properties in washing experiments than Comparative Formulation V1.

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Claims (12)

  1. Utilisation de polymères que l'on obtient par polymérisation de monomères de benzoxazine pour éviter le transfert de colorants textiles à partir de textiles colorés sur des textiles non colorés ou colorés autrement, lors de leur lessive commune en particulier dans des solutions aqueuses contenant des agents tensioactifs.
  2. Utilisation de polymères que l'on obtient par polymérisation de monomères de benzoxazine pour éviter la modification de l'impression de couleur laissée par des textiles lors de la lessive de ces derniers dans en particulier des solutions aqueuses contenant des agents tensioactifs.
  3. Agent de nettoyage, de lavage ou de traitement ultérieur du linge, contenant un inhibiteur du transfert des couleurs sous la forme d'un polymère que l'on obtient par polymérisation de monomères de benzoxazine.
  4. Agent selon la revendication 3, caractérisé en ce qu'il contient de 0,01 % en poids à 10 % en poids, en particulier de 0,1 % en poids à 1 % en poids du polymère.
  5. Agent selon la revendication 3 ou 4, caractérisé en ce qu'il contient en outre un polymère choisi parmi la vinylpyrrolidone, le vinylimidazole, un N-oxyde de vinylpyridine ou un de leurs copolymères.
  6. Procédé pour le lavage de textiles dans des solutions aqueuses contenant des agents tensioactifs, caractérisé en ce qu'on met en oeuvre une solution aqueuse contenant des agents tensioactifs, qui contient un polymère que l'on obtient par polymérisation de monomères de benzoxazine.
  7. Procédé selon la revendication 6, caractérisé en ce qu'on amène le polymère, dans une étape de traitement ultérieur du linge, par exemple sous la forme d'un constituant d'un agent adoucissant, en contact avec le textile, et on lave le textile ainsi traité, au cours de la phase de lavage suivante qui peut être mise en oeuvre avec un agent contenant un polymère utilisé conformément à l'invention ou avec un agent qui est exempt dudit polymère, en présence de pièces de linge d'autres couleurs.
  8. Agent, utilisation ou procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que l'on obtient le polymère par polymérisation de composés de benzoxazine choisis parmi des composés répondant à la formule générale (I) ou parmi des composés répondant à la formule générale (II) ou parmi des mélanges desdits composés :
    Figure imgb0045
    Figure imgb0046
    dans lesquelles q représente un nombre entier de 1 à 4 ;
    n représente un nombre de 2 à 20.000 ;
    R, dans chaque unité de répétition, est choisi de manière respectivement indépendante parmi un atome d'hydrogène ou des groupes alkyle linéaires ou ramifiés, facultativement substitués qui comprennent de 1 à 8 atomes de carbone ;
    Z est choisi parmi un atome d'hydrogène (pour q = 1), un groupe alkyle (pour q = 1), un groupe alkylène (pour q = 2 à 4), un groupe carbonyle (pour q = 2), un atome d'oxygène (pour q = 2), un atome de soufre (pour q = 2), un groupe sulfoxyde (pour q = 2), un groupe sulfone (pour q = 2) et une liaison covalente directe (pour q = 2) ;
    R1 représente une liaison covalente ou un groupe de liaison divalent qui comprend de 1 à 100 atomes de carbone ;
    R2 est choisi parmi un atome d'hydrogène, un atome d'halogène, un groupe alkyle et un groupe alcényle ou bien R2 représente un résidu divalent qui, à partir de la structure de benzoxazine, forme une structure correspondante de naphtoxazine ;
    Y est choisi parmi des groupes alkyle linéaires ou ramifiés, facultativement substitués, qui comprennent de 1 à 15 atomes de carbone, des résidus cycloaliphatiques qui contiennent de manière facultative un ou plusieurs hétéroatomes, des résidus aryle qui contiennent de manière facultative un ou plusieurs hétéroatomes, et un groupe -(C=O)R3, R3 étant choisi parmi des groupes alkyle linéaires ou ramifiés, facultativement substitués comprenant de 1 à 15 atomes de carbone, et un groupe X-R4, X étant choisi parmi un atome de soufre, un atome d'oxygène et un groupe NH, et R4 étant choisi parmi des groupes alkyle linéaires ou ramifiés, facultativement substitués comprenant de 1 à 15 atomes de carbone ;
    c représente un nombre entier de 1 à 4 ;
    B est choisi parmi un atome d'hydrogène (pour c = 1), un groupe alkyle (pour c = 1), un groupe alkylène (pour c = 2 à 4), un groupe carbonyle (pour c = 2), un atome d'oxygène (pour c = 2), un atome de soufre (pour c = 2), un groupe sulfoxyde (pour c = 2), un groupe sulfone (pour c = 2) et une liaison covalente directe (pour c = 2), A représente un groupe hydroxyle ou un hétérocycle azoté ;
    R5 est choisi parmi un atome d'hydrogène, un atome d'halogène, un groupe alkyle et un groupe alcényle ou bien R5 représente un résidu divalent qui, à partir de la structure de benzoxazine, forme une structure correspondante de naphtoxazine et R6 représente une liaison covalente ou un groupe de liaison divalent qui comprend de 1 à 100 atomes de carbone.
  9. Agent, utilisation ou procédé selon la revendication 8, caractérisé en ce que les composés de benzoxazine répondant à la formule générale (I) sont choisis parmi des composés répondant à la formule générale (III)
    Figure imgb0047
     dans laquelle x représente un nombre entre 0 et 1000 et y représente un nombre entre 0 et 1000, avec cette mesure que x+y ≥ 2, Z, R2, Y et q étant chaque fois tels que définis dans la formule (I).
  10. Agent, utilisation ou procédé selon la revendication 8, caractérisé en ce que les composés de benzoxazine répondant à la formule générale (II) sont choisis parmi des composés répondant à la formule générale (IV) et/ou parmi des composés répondant à la formule générale (V) :
    Figure imgb0048
    Figure imgb0049
     dans lesquelles R7 et R8 sont choisis chaque fois de manière respectivement indépendante parmi un atome d'hydrogène, un atome d'halogène, des groupes alkyle, alcényle et aryle linéaires ou ramifiés, facultativement substitués, c, B, R5 et R6 étant chaque fois définis comme indiqué ci-dessus dans la formule (II).
  11. Agent, utilisation ou procédé selon l'une quelconque des revendications 1 à 10, caractérisé en ce que le poids moléculaire moyen en poids « Mw » des (co)polymères de benzoxazine se situe entre 500 et 100.000 g/mol.
  12. Agent, utilisation ou procédé selon l'une quelconque des revendications 1 à 11, caractérisé en ce que, en ce qui concerne le (co)polymère de benzoxazine, il s'agit d'un (co)polymère cationique de benzoxazine que l'on peut obtenir via une mise en réaction avec au moins un agent d'alkylation.
EP10716362.8A 2009-05-12 2010-05-06 Agent de lavage ou de nettoyage protégeant les couleurs Not-in-force EP2430137B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102009003034A DE102009003034A1 (de) 2009-05-12 2009-05-12 Farbschützendes Wasch-oder Reinigungsmittel
PCT/EP2010/056175 WO2010130624A1 (fr) 2009-05-12 2010-05-06 Agent de lavage ou de nettoyage protégeant les couleurs

Publications (2)

Publication Number Publication Date
EP2430137A1 EP2430137A1 (fr) 2012-03-21
EP2430137B1 true EP2430137B1 (fr) 2014-11-12

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EP10716362.8A Not-in-force EP2430137B1 (fr) 2009-05-12 2010-05-06 Agent de lavage ou de nettoyage protégeant les couleurs

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US (1) US8580726B2 (fr)
EP (1) EP2430137B1 (fr)
DE (1) DE102009003034A1 (fr)
WO (1) WO2010130624A1 (fr)

Families Citing this family (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20130139327A1 (en) * 2010-08-03 2013-06-06 Henkel Ag & Co. Kgaa Textile treatment composition for removal of deodorant stains
US20130111675A1 (en) * 2011-11-03 2013-05-09 Ecolab Usa Inc. Sustainable laundry sour compositions with iron control
WO2015112341A1 (fr) 2014-01-22 2015-07-30 The Procter & Gamble Company Composition de traitement de textile
EP3097172A1 (fr) 2014-01-22 2016-11-30 The Procter & Gamble Company Procédé de traitement de surfaces textiles
WO2015112339A1 (fr) 2014-01-22 2015-07-30 The Procter & Gamble Company Composition de traitement de textile
EP3097174A1 (fr) 2014-01-22 2016-11-30 The Procter & Gamble Company Procédé de traitement de surfaces textiles
JP2018501331A (ja) 2014-11-17 2018-01-18 ザ プロクター アンド ギャンブル カンパニー 有益剤送達組成物
WO2016176280A1 (fr) 2015-04-29 2016-11-03 The Procter & Gamble Company Procédé de traitement d'un tissu
DK3088505T3 (da) 2015-04-29 2020-08-03 Procter & Gamble Fremgangsmåde til behandling af et tekstilstof
CN107820515A (zh) 2015-04-29 2018-03-20 宝洁公司 洗涤剂组合物
US20160319224A1 (en) 2015-04-29 2016-11-03 The Procter & Gamble Company Method of treating a fabric
EP3088504B1 (fr) 2015-04-29 2021-07-21 The Procter & Gamble Company Procédé de traitement d'un textile
CN108291180A (zh) 2015-11-26 2018-07-17 宝洁公司 包含蛋白酶和经包封的脂肪酶的液体洗涤剂组合物
EP4112707A1 (fr) 2021-06-30 2023-01-04 The Procter & Gamble Company Traitement des tissus
CA3234192A1 (fr) 2022-07-11 2024-01-18 Ming Tang Composition de detergent a lessive contenant un copolymere greffe et une matiere premiere de parfum
WO2024011343A1 (fr) 2022-07-11 2024-01-18 The Procter & Gamble Company Composition de détergent à lessive contenant un copolymère greffé d'oxyde de polyalkylène et un polymère inhibiteur de transfert de colorants
WO2024011345A1 (fr) 2022-07-11 2024-01-18 The Procter & Gamble Company Composition de détergent à lessive contenant un copolymère greffé et un agent bénéfique
WO2022214113A2 (fr) 2022-07-11 2022-10-13 The Procter & Gamble Company Composition de détergent de lessive contenant un copolymère greffé et un polymère inhibiteur de transfert de colorant
EP4306628A1 (fr) 2022-07-11 2024-01-17 The Procter & Gamble Company Composition de détergent pour le lavage du linge contenant deux copolymères greffés

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT330930B (de) 1973-04-13 1976-07-26 Henkel & Cie Gmbh Verfahren zur herstellung von festen, schuttfahigen wasch- oder reinigungsmitteln mit einem gehalt an calcium bindenden substanzen
DE3434820A1 (de) 1984-09-22 1986-04-03 Bayer Ag, 5090 Leverkusen Alterungsbestaendige polyamidlegierungen
CN1066194C (zh) * 1994-04-07 2001-05-23 普罗格特-甘布尔公司 含有漂白活化剂和漂白催化剂的漂白组合物
US5755992A (en) * 1994-04-13 1998-05-26 The Procter & Gamble Company Detergents containing a surfactant and a delayed release peroxyacid bleach system
US5543516A (en) 1994-05-18 1996-08-06 Edison Polymer Innovation Corporation Process for preparation of benzoxazine compounds in solventless systems
EP2218748B1 (fr) * 2005-09-03 2012-10-10 Samsung SDI Co., Ltd. Composé polybenzoxazine, membrane électrolyte contenant ce composé et cellule de combustion employant ce membrane électrolyte
DE102009003032A1 (de) * 2009-05-12 2010-11-18 Henkel Ag & Co. Kgaa Kationische Benzoxazin(co)polymere

Also Published As

Publication number Publication date
US20120047664A1 (en) 2012-03-01
DE102009003034A1 (de) 2010-11-18
EP2430137A1 (fr) 2012-03-21
US8580726B2 (en) 2013-11-12
WO2010130624A1 (fr) 2010-11-18

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