EP2430137B1 - Color-protecting washing or cleaning agent - Google Patents

Description

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. Such 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 Waschbeziehungsweise 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. 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. However, 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.

Surprisingly, it has now been found that 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. Also, 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

• wobei q eine ganze Zahl von 1 bis 4 ist, n eine Zahl von 2 bis 20000, vorzugsweise von 3 bis 10000, besonders bevorzugt von 4 bis 8000 und insbesondere von 5 bis 7000 ist,
• R in jeder Wiederholungseinheit unabhängig voneinander ausgewählt wird aus Wasserstoff oder linearen oder verzweigten, gegebenenfalls substituierten Alkylgruppen, die 1 bis 8 Kohlenstoffatome umfassen,
• Z ausgewählt wird aus Wasserstoff (für q = 1), Alkyl (für q = 1), Alkylen (für q = 2 bis 4), Carbonyl (für q = 2), Sauerstoff (für q = 2), Schwefel (für q = 2), Sulfoxid (für q = 2), Sulfon (für q = 2) und einer direkten, kovalenten Bindung (für q = 2),
• R¹ für eine kovalente Bindung steht oder eine divalente Verbindungsgruppe ist, die 1 bis 100 Kohlenstoffatome umfasst,
• R² ausgewählt wird aus Wasserstoff, Halogen, Alkyl und Alkenyl oder R² ein divalenter Rest ist, der aus der Benzoxazin-Struktur eine entsprechende Naphthoxazin-Struktur macht,
• Y ausgewählt wird aus linearen oder verzweigten, gegebenenfalls substituierten Alkylgruppen, die 1 bis 15 Kohlenstoffatomen umfassen, cycloaliphatischen Resten, die gegebenenfalls ein oder mehrere Heteroatome enthalten, Arylresten, die gegebenenfalls ein oder mehrere Heteroatome enthalten, und -(C=O)R³, wobei R³ aus linearen oder verzweigten, gegebenenfalls substituierten Alkylgruppen mit die 1 bis 15 Kohlenstoffatomen und X-R⁴ ausgewählt wird, wobei X aus S, O, und NH ausgewählt wird und R⁴ aus linearen oder verzweigten, gegebenenfalls substituierten Alkylgruppen mit 1 bis 15 Kohlenstoffatomen ausgewählt wird,
• c eine ganze Zahl von 1 bis 4 ist,
• B ausgewählt wird aus Wasserstoff (für c = 1), Alkyl (für c = 1), Alkylen (für c = 2 bis 4), Carbonyl (für c = 2), Sauerstoff (für c = 2), Schwefel (für c = 2), Sulfoxid (für c = 2), Sulfon (für c = 2) und einer direkten, kovalenten Bindung (für c = 2), A eine Hydroxylgruppe oder ein stickstoffhaltiger Heterozyklus ist,
• R⁵ ausgewählt wird aus Wasserstoff, Halogen, Alkyl und Alkenyl oder R⁵ ein divalenter Rest ist, der aus der Benzoxazin-Struktur eine entsprechende Naphthoxazin-Struktur macht und R⁶ für eine kovalente Bindung steht oder eine divalente Verbindungsgruppe ist, die 1 bis 100 Kohlenstoffatome umfasst.

In a particular embodiment of the present invention, the polymerizable benzoxazine compound is selected from compounds of the general formula (I) or from compounds of the general formula (II) or mixtures of these,

• where q is an integer from 1 to 4, n is a number from 2 to 20,000, preferably from 3 to 10,000, particularly preferably from 4 to 8,000 and in particular from 5 to 7,000,
• R in each repeating unit is independently selected from hydrogen or linear or branched, optionally substituted alkyl groups comprising from 1 to 8 carbon atoms,
• Z is selected from hydrogen (for q = 1), alkyl (for q = 1), alkylene (for q = 2 to 4), carbonyl (for q = 2), oxygen (for q = 2), sulfur (for q = 2), sulfoxide (for q = 2), sulfone (for q = 2) and a direct, covalent bond (for q = 2),
• R ^{1 is} a covalent bond or is a divalent linking group comprising 1 to 100 carbon atoms,
• R ^{2 is} selected from hydrogen, halogen, alkyl and alkenyl or R ^{2 is} a divalent radical which turns the benzoxazine structure into a corresponding naphthoxazine structure,
• Y is selected from linear or branched, optionally substituted alkyl groups comprising 1 to 15 carbon atoms, cycloaliphatic radicals optionally containing one or more heteroatoms, aryl radicals optionally containing one or more heteroatoms, and - (C = O) R ³ , wherein R is selected from linear or branched, optionally substituted alkyl groups having 1 to 15 carbon atoms and XR ^{4 3,} wherein X is selected from S, O, and NH and ^R4 is selected from linear or branched, optionally substituted alkyl groups having 1 to 15 carbon atoms is selected
• c is an integer from 1 to 4,
• B is selected from hydrogen (for c = 1), alkyl (for c = 1), alkylene (for c = 2 to 4), carbonyl (for c = 2), oxygen (for c = 2), sulfur (for c = 2), sulfoxide (for c = 2), sulfone (for c = 2) and a direct, covalent bond (for c = 2), A is a hydroxyl group or a nitrogen-containing heterocycle,
• R ^{5 is} selected from hydrogen, halogen, alkyl and alkenyl, or R ^{5 is} a divalent radical which makes a corresponding naphthoxazine structure from the benzoxazine structure and R ^{6 is} a covalent bond or is a divalent linking group containing 1 to 100 Carbon atoms.

In one embodiment of the invention, in formula (I), 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. In the context of the present invention, 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. Preferably, the divalent organic linking groups R ¹ and / or R ⁶ are selected from alkylene groups comprising 2 to 8 C atoms. In a preferred embodiment, 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. Alternatively, R ¹ in formula (I) and / or R ⁶ in formula (II) may be a covalent bond.

In addition, 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. Furthermore, 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.

The 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. For the purposes of the present invention, the term "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. Particularly preferred 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.

wobei x eine Zahl zwischen 0 und 1000 und y eine Zahl zwischen 0 und 1000 ist, mit der Maßgabe, dass x+y ≥ 2 ist, wobei Z, R², Y und q jeweils wie oben in Formel (I) definiert sind. Vorzugsweise ist x+y ≥ 3, besonders bevorzugt ≥ 4 und ganz besonders bevorzugt ≥ 5.In a preferred embodiment of the invention, 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). Preferably, x + y is ≥ 3, more preferably ≥ 4, and most preferably ≥ 5.

Depending on the application profile, it may be expedient to adapt the number of alkylene oxide units of the alkylene oxide chain in the polymerizable benzoxazine compound of the general formula (I) and (III). In certain embodiments of the invention, 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.

wobei R⁷ und R⁸ jeweils unabhängig voneinander ausgewählt werden aus Wasserstoff, Halogen, linearen oder verzweigten, gegebenenfalls substituierten Alkylgruppen, Alkenylgruppen und Arylgruppen, wobei c, B, R⁵ und R⁶ jeweils wie oben in Formel (II) definiert sind.In a further preferred embodiment of the invention, 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).

In a further embodiment of the invention, 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.

wobei c, B, R⁵, R⁶, R⁷ und R⁸ wie oben definiert sind.Particularly preferred 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.

Specific benzoxazine compounds of the general formula (IV) can be selected by way of example from the following compounds:

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. As aldehyde in addition to formaldehyde and paraformaldehyde, trioxane or polyoxymethylene or any mixtures thereof may be used.

wobei R⁶, R⁷ und R³ wie oben definiert sind.In particular, 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.

oder 2-Aminoalkylimidazol-Verbindungen der allgemeinen Formel (VIII)

zur Herstellung der entsprechenden Benzoxazin-Verbindungen geeignet, wobei R⁶, R⁷ und R⁸ wie oben definiert sind.In particular, 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 (ChemPacific), 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.). In addition to the use of commercially available 1-Aminoalkylimidazol compounds of the general formula (VII), these can also be prepared by conventional methods of organic synthesis, such as by a method which in the Houben-Weyl, Methods of Organic Chemistry Vol. E 16d, Georg Thieme Verlag Stuttgart, 1992 on pages 755 ff , is described.

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.

Specific benzoxazine compounds of the general formula (V) can be selected by way of example from the following compounds:

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.

• mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (I), vorzugsweise mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (III) und
• mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (II) umfasst.

In one embodiment of the invention, therefore, a mixture is prepared for the preparation of the benzoxazine (co) polymer used in the invention

• at least one polymerizable benzoxazine compound of the general formula (I), preferably at least one polymerizable benzoxazine compound of the general formula (III) and
• at least one polymerizable benzoxazine compound of the general formula (II).

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.

• mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (I), vorzugsweise mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (III) und
• mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (IV) umfasst.

In a specific embodiment of the present invention, a mixture is prepared for the preparation of the benzoxazine (co) polymer used in the invention

• at least one polymerizable benzoxazine compound of the general formula (I), preferably at least one polymerizable benzoxazine compound of the general formula (III) and
• at least one polymerizable benzoxazine compound of the general formula (IV).

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.

• mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (I), vorzugsweise mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (III) und
• mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (V) umfasst.

In a further specific embodiment of the present invention, a mixture is prepared for the preparation of the benzoxazine (co) polymer used in the invention

• at least one polymerizable benzoxazine compound of the general formula (I), preferably at least one polymerizable benzoxazine compound of the general formula (III) and
• at least one polymerizable benzoxazine compound of the general formula (V).

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.

• mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (I), vorzugsweise mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (III),
• mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (IV) und
• mindestens eine polymerisierbare Benzoxazin-Verbindung der allgemeinen Formel (II) umfasst.

In a further preferred embodiment of the present invention, a mixture is prepared for the preparation of the benzoxazine (co) polymer used in the invention

• at least one polymerizable benzoxazine compound of the general formula (I), preferably at least one polymerizable benzoxazine compound of the general formula (III),
• at least one polymerizable benzoxazine compound of the general formula (IV) and
• at least one polymerizable benzoxazine compound of the general formula (II).

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.

In addition, it may be advantageous to use, in addition to the polymerizable benzoxazine compounds already described, further polymerizable benzoxazine compounds for the preparation of the benzoxazine (co) polymer used according to the invention, which differ from the abovementioned polymerizable benzoxazine compounds.

wobei o' eine ganze Zahl zwischen 1 und 4 ist, X' ausgewählt wird aus der Gruppe bestehend aus Alkyl (für o' = 1), Alkylen (für o' = 2 bis 4), Sauerstoff (für o' = 2), Thiol (für o' = 1), Schwefel (für o' = 2), Sulfoxid (für o' = 2), Sulfon (für o' = 2) und einer direkten, kovalenten Bindung (für o' = 2), R¹ ausgewählt wird aus der Gruppe bestehend aus Wasserstoff, Alkyl, Alkenyl und Aryl und R^4' ausgewählt wird aus der Gruppe bestehend aus Wasserstoff, Halogen, Alkyl und Alkenyl, oder R^4' ein divalenter Rest ist, der aus der Benzoxazin-Struktur eine entsprechende Naphthoxazin-Struktur macht.Suitable benzoxazine compounds are preferably described by formula (B-XVIII),

where o 'is an integer between 1 and 4, X' is selected from the group consisting of alkyl (for o '= 1), alkylene (for o' = 2 to 4), oxygen (for o '= 2), Thiol (for o '= 1), sulfur (for o' = 2), sulfoxide (for o '= 2), sulfone (for o' = 2) and a direct, covalent bond (for o '= 2), R ^{1 is} selected from the group consisting of hydrogen, alkyl, alkenyl and aryl; and R ^{4 'is} selected from the group consisting of hydrogen, halogen, alkyl and alkenyl, or R ^{4' is} a divalent radical selected from the benzoxazine structure corresponding naphthoxazine structure makes.

wobei p' = 2 ist und Y' ausgewählt wird aus der Gruppe bestehend aus Biphenyl, Diphenylmethan, Diphenylisopropan, Diphenylsulfid, Diphenylsulfoxid, Diphenylsulfon, Diphenylketon und R^4' ausgewählt wird aus der Gruppe bestehend aus Wasserstoff, Halogen, Alkyl und Alkenyl, oder R^4' ein divalenter Rest ist, der aus der Benzoxazin-Struktur eine entsprechende Naphthoxazin-Struktur macht.Preferred benzoxazine compounds are furthermore compounds of the general formula (B-IXX),

wherein p '= 2 and Y' is selected from the group consisting of biphenyl, diphenylmethane, diphenylisopropane, diphenylsulfide, diphenylsulfoxide, diphenylsulfone, diphenyl ketone and R ^{4 'is} selected from the group consisting of hydrogen, halogen, alkyl and alkenyl, or R ^{4 'is} a divalent radical which turns the benzoxazine structure into a corresponding naphthoxazine structure.

wobei R^1' und R^4' wie oben definiert sind und R³ sowie R^2' wie R^1' definiert sind.Also preferred 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.

Depending on the choice of the benzoxazine compounds, 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. Can be used also the cationic benzoxazine (co) polymers obtainable from them by reaction with at least one alkylating agent. The alkylation can be carried out in a manner known per se. For this purpose, 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. In particular, the particular reaction conditions and the amount of alkylating agent to be chosen so that at least 10%, or at least 15%, or at least 20%, or at least 25%, or at least 30%, or at least 35%, or at least 35%, or at least 40%, or at least 45%, or at least 50%, or at least 55%, or at least 60%, or at least 65%, or at least 70%, or at least 75%, or at least 80%, or at least 85%, or At least 90%, or at least 95% of all nitrogen atoms are converted into permanent 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. Preferably, 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 Wächsenachbehandlungsschritt, 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. In such a method, it is possible to wash white or undyed textiles together with the dyed textile without the white or undyed textile being dyed. Particularly pronounced is 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. In addition, 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. Useful are both 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. However, it is also possible to use enzymatic systems comprising a peroxidase and hydrogen peroxide or a substance which produces hydrogen peroxide in water. The addition of a mediator compound for the peroxidase, for example an acetosyringone, a phenol derivative or a phenotiazine or phenoxazine, is preferred in this case, with the above-mentioned polymeric color transfer inhibiting agents being additionally used can. Among 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, which may be in the form of homogeneous solutions or suspensions, especially in powdered solids, in densified particle form, 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.

The 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.

in der R¹¹CO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R¹² für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Vorzugsweise leiten sich die Polyhydroxyfettsäureamide von reduzierenden Zuckern mit 5 oder 6 Kohlenstoffatomen, insbesondere von der Glucose ab. Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel

in der R¹³ für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R¹⁴ für einen linearen, verzweigten oder cyclischen Alkylenrest oder einen Arylenrest mit 2 bis 8 Kohlenstoffatomen und R¹⁵ für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C₁-C₄-Alkyl- oder Phenylreste bevorzugt sind, und [Z] für einen linearen Polyhydroxyalkylrest, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes steht. [Z] wird auch hier vorzugsweise durch reduktive Aminierung eines Zuckers wie Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose erhalten. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden. Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden, insbesondere zusammen mit alkoxylierten Fettalkoholen und/oder Alkylglykosiden, eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester. Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon. Als weitere Tenside kommen sogenannte Gemini-Tenside in Betracht. Hierunter werden im Allgemeinen solche Verbindungen verstanden, die zwei hydrophile Gruppen pro Molekül besitzen. Diese Gruppen sind in der Regel durch einen sogenannten "Spacer" voneinander getrennt. Dieser Spacer ist in der Regel eine Kohlenstoffkette, die lang genug sein sollte, dass die hydrophilen Gruppen einen ausreichenden Abstand haben, damit sie unabhängig voneinander agieren können. Derartige Tenside zeichnen sich im Allgemeinen durch eine ungewöhnlich geringe kritische Micellkonzentration und die Fähigkeit, die Oberflächenspannung des Wassers stark zu reduzieren, aus. In Ausnahmefällen werden unter dem Ausdruck Gemini-Tenside nicht nur derartig "dimere", sondern auch entsprechend "trimere" Tenside verstanden. Geeignete Gemini-Tenside sind beispielsweise sulfatierte Hydroxymischether oder Dimeralkohol-bis- und Trimeralkohol-tris-sulfate und -ethersulfate. Endgruppenverschlossene dimere und trimere Mischether zeichnen sich insbesondere durch ihre Bi- und Multifunktionalität aus. So besitzen die genannten endgruppenverschlossenen Tenside gute Netzeigenschaften und sind dabei schaumarm, so dass sie sich insbesondere für den Einsatz in maschinellen Wasch- oder Reinigungsverfahren eignen. Eingesetzt werden können aber auch Gemini-Polyhydroxyfettsäureamide oder Poly-Polyhydroxyfettsäureamide. Geeignet sind auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C₇-C₂₁-Alkohole, wie 2-Methylverzweigte C₉-C₁₁-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C₁₂-C₁₈-Fettalkohole mit 1 bis 4 EO. Zu den bevorzugten Aniontensiden gehören auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobernsteinsäureester bezeichnet werden, und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C₈- bis C₁₈-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen. Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen. Als weitere anionische Tenside kommen Fettsäure-Derivate von Aminosäuren, beispielsweise von N-Methyltaurin (Tauride) und/oder von N-Methylglycin (Sarkoside) in Betracht. Insbesondere bevorzugt sind dabei die Sarkoside beziehungsweise die Sarkosinate und hier vor allem Sarkosinate von höheren und gegebenenfalls einfach oder mehrfach ungesättigten Fettsäuren wie Oleylsarkosinat. Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind insbesondere gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierten Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, zum Beispiel Kokos-, Palmkern- oder Talgfettsäuren, abgeleitete Seifengemische. Zusammen mit diesen Seifen oder als Ersatzmittel für Seifen können auch die bekannten Alkenylbernsteinsäuresalze eingesetzt werden.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. In particular, however, 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). In addition to these nonionic surfactants, 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. In particular, 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. One can also use other known low-foaming nonionic surfactants such as C ₁₂ -C ₁₈ alkyl polyethylene glycol polybutylene each having up to 8 moles of ethylene oxide and butylene oxide units in the molecule and end-capped Alkylpolyalkylenglykolmischether. Also particularly preferred are the hydroxyl-containing alkoxylated alcohols, so-called hydroxy mixed ethers. 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 Glykoseeinheit 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. Also suitable are 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 and 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, 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. 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. Another class of preferred 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. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof. Other suitable 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. Thus, 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. However, it is also possible to use gemini-polyhydroxy fatty acid amides or poly-polyhydroxy fatty acid amides. Also suitable are the 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. 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. 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. Likewise, it is also possible to use 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). Particularly preferred are the sarcosides or the sarcosinates and here especially sarcosinates of higher and optionally monounsaturated or polyunsaturated fatty acids such as oleyl sarcosinate. As further 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, including soaps, 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. 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. The alkylation of tertiary amines with a long alkyl radical and two methyl groups succeeds particularly easily, and the quaternization of tertiary amines with two long radicals and one methyl group can be carried out with the aid of methyl chloride under mild conditions. Amines which have three long alkyl radicals or hydroxy-substituted alkyl radicals are less reactive and are quaternized, for example, with dimethyl sulfate. 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- [p- (1,1,3,3-tetramethyl-butyl) -phenoxy] -ethoxy] -ethyl ] benzylammonium chloride), dialkyldimethylammonium chlorides such as di-n-decyldimethylammonium chloride, didecyldimethylammonium bromide, dioctyldimethylammonium chloride, 1-cetylpyridinium chloride and thiazoline iodide, and mixtures thereof. Preferred QACs are the benzalkonium chlorides having C ₈ -C ₂₂ -alkyl radicals, in particular C ₁₂ -C ₁₄ -alkyl-benzyl-dimethylammonium chloride.

verstanden werden, in der R⁶ für einen Alkyl- oder Alkenylrest mit 12 bis 22 Kohlenstoffatomen und 0, 1, 2 oder 3 Doppelbindungen, R⁷ und R⁸ unabhängig voneinander für H, OH oder O(CO)R⁶, s, t und u jeweils unabhängig voneinander für den Wert 1, 2 oder 3 und X^- für ein Anion, insbesondere Halogenid, Methosulfat, Methophosphat oder Phosphat sowie Mischungen aus diesen, steht. Bevorzugt sind Verbindungen, die für R⁷ die Gruppe O(CO)R⁶ und für R⁶ einen Alkylrest mit 16 bis 18 Kohlenstoffatomen enthalten. Besonders bevorzugt sind Verbindungen, bei denen R⁸ zudem für OH steht. Beispiele für Verbindungen der genannten Formel sind Methyl-N-(2-hydroxyethyl)-N,N-di(talgacyl-oxyethyl)ammonium-methosulfat, Bis-(palmitoyl)-ethyl-hydroxyethyl-methyl-ammonium-methosulfat oder Methyl-N,N-bis(acyloxyethyl)-N-(2-hydroxyethyl)ammonium-methosulfat. Werden quarternierte Verbindungen eingesetzt, die ungesättigte Gruppen aufweisen, sind die Acylgruppen bevorzugt, deren korrespondierende Fettsäuren eine Jodzahl zwischen 5 und 80, vorzugsweise zwischen 10 und 60 und insbesondere zwischen 15 und 45 aufweisen und/oder die ein cis/trans-Isomerenverhältnis (in Mol-%) von größer als 30 : 70, vorzugsweise größer als 50 : 50 und insbesondere größer als 70 : 30 haben. Handelsübliche Beispiele sind die von der Firma Stepan unter dem Warenzeichen Stepantex^® vertriebenen Methylhydroxyalkyldialkoyloxyalkylammoniummethosulfate oder die unter dem Handelsnamen Dehyquart^® bekannten Produkte der Firma Cognis Deutschland GmbH beziehungsweise die unter der Bezeichnung Rewoquat^® bekannten Produkte des Herstellers Goldschmidt-Witco.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. If quaternized compounds having unsaturated groups are used, 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 polymerizable substances without carboxylic acid functionality. 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. It is also possible to use 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 as water-soluble organic builder substances. 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.

If desired, such 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. 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. used. Among these, preferred are the detergent grade crystalline sodium aluminosilicates, particularly zeolite A, P and optionally X, alone or in mixtures, for example in the form of a cocrystal of 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. In particular, 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, according to the information of the German Patent DE 24 12 837 can be determined, 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 β- and δ-sodium disilicates (Na ₂ Si ₂ O ₅ y H ₂ O) are preferred. Also prepared from 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. In a further preferred embodiment of the composition according to the invention, 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). Of these, especially Na-SKS-5 (α-Na ₂ Si ₂ O ₅ ), Na-SKS-7 (β-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₎ and Na-SKS-13 (NaHSi ₂ O ₅ ), but especially Na-SKS-6 (δ-Na ₂ Si ₂ O ₅ ). In a preferred embodiment of the 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.

As for the use in agents according to the invention 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. If 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. If 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. The addition of small amounts of known bleach stabilizers such as phosphonates, borates or metaborates and metasilicates and magnesium salts such as magnesium sulfate may be useful.

As 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. Preference is given to 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, as well as acetylated sorbitol and mannitol or their described Mixtures (SORMAN), acylated sugar derivatives, in particular pentaacetylglucose (PAG), pentaacetylfruktose, tetraacetylxylose and octaacetyllactose as well as acetylated, optionally N-alkylated glucamine and gluconolactone, and / or N-acylated lactams, for example N-benzoylcaprolactam. The 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.

In addition to the conventional bleach activators or in their place, 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.

Among the solvents according to the invention, in particular when they are in liquid or pasty form, 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.

To establish a desired, by the mixture of the other components not automatically resulting pH value, the 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. 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. Also, water-soluble polyamides containing acidic groups are suitable for this purpose. Furthermore, other than the above-mentioned starch derivatives can be used, for example aldehyde starches. Preference is given to using 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. Further, 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.

In particular, when used in mechanical processes, it may be advantageous to add conventional foam inhibitors to the compositions. As 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.

The preparation of solid 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. For the preparation of 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.

For the preparation of 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. Particularly in the case of multilayer tablets, it may be advantageous if at least one layer is pre-compressed. This is preferably carried out at pressing forces between 5 and 20 kN, in particular at 10 to 15 kN. This gives fracture-resistant, yet sufficiently rapidly soluble tablets under application conditions with fracture and flexural strengths of normally 100 to 200 N, but preferably above 150 N. Preferably, 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. In particular, 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.

Examples Example 1: Preparation of polymerizable benzoxazine compounds using Jeffamines

The following describes the preparation of various polymerizable benzoxazine compounds of the formula (B-Box-I)

1.1. Preparation of a Polymerizable Benzoxazine Compound Using Jeffamine M2070 (PO / EO 10/31); Designation (B-Box-I-1.1)

Approach: 9.38 g Paraformaldehyde (96%) 0.30 mol in 50 ml of ethyl acetate 309,9g Jeffamine M2070 (Huntsman) 0.15 mol in 200 m of ethyl acetate 16.22 g p-cresol 0.15 mol in 50 ml of ethyl acetate

Paraformaldehyde was introduced into ethyl acetate and the p-cresol, likewise dissolved in ethyl acetate, was added dropwise within 10 minutes. Then Jeffamine M-2070 was added over 30 minutes, keeping the temperature below 10 ° C. After 10 minutes of stirring, the reaction mixture was refluxed for 6 hours. After cooling, the reaction mixture was filtered and the solvent and water formed were removed in vacuo. This gave 318.90 g of the corresponding polymerizable benzoxazine compound B-Box-I-1.1.

1.2 Preparation of a Polymerizable Benzoxazine Compound Using Jeffamine M1000 (PO / EO 3/19), Designation (B-Box-I-1.2)

Approach: 18.7 g Paraformaldehyde (96%) 0.60 mol in 50 ml of ethyl acetate 312.9 g Jeffamine M1000 (Huntsman) 0.30 mol in 250 m of ethyl acetate 32.44 g p-cresol 0.30 mol in 60ml ethyl acetate

Under the conditions described in Example 1.1, paraformaldehyde, p-cresol and Jeffamin M-100 were reacted. This gave 352.57 g of the corresponding polymerizable benzoxazine compound B-Box-I-1.2.

1.2 Preparation of a polymerizable benzoxazine compounds using N- (3-aminopropyl) imidazole

Ansatz: 78,20 g Paraformaldehyd (96%ig) 2,50 mol in 100 ml Essigsäureethylester 157,5 g N-(3-Aminopropyl)-imidazol (Lupragen®API) 1,25 mol in 10 ml Essigsäureethylester 135,17 g p-Kresol 1,25 mol in 100 ml Essigsäureethylester The following is a description of the preparation of a polymerizable benzoxazine compound of the formula (B-Box-II):

Approach: 78.20 g Paraformaldehyde (96%) 2.50 mol in 100 ml of ethyl acetate 157.5 g N- (3-aminopropyl) -imidazole (Lupragen®API) 1.25 mol in 10 ml of ethyl acetate 135.17 g p-cresol 1.25 mol in 100 ml of ethyl acetate

Paraformaldehyde, p-cresol and Lupragen® API (BASF SE) were reacted under the conditions described in Example 1.1. 322.74 g of the corresponding polymerizable benzoxazine compound B-Box-II were obtained.

1.3 Preparation of a polymerizable benzoxazine compounds using ethanolamine

Ansatz: 106,35 g Paraformaldehyd (96%ig) 3,40 mol in 100 ml Essigsäureethylester 103,87 g Ethanolamin 1,70 mol in 30 ml Essigsäureethylester 183,84 g p-Kresol 1,70 mol in 80 ml Essigsäureethylester The following is a description of the preparation of a polymerizable benzoxazine compound of the formula (B-Box-III):

Approach: 106.35 g Paraformaldehyde (96%) 3.40 mol in 100 ml of ethyl acetate 103.87 g ethanolamine 1.70 mol in 30 ml of ethyl acetate 183.84 g p-cresol 1.70 mol in 80 ml of ethyl acetate

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.

Example 2: Polymerization for the preparation of non-cationic benzoxazine (co) polymers

The polymerizable benzoxazine compounds described above were thermally cured as mixtures or alone in a drying oven with air circulation in moldings at 180 ° C within 2 h. Subsequently, the samples were removed from the moldings and cooled to room temperature. Thereby, 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 50 11 70 30 12 50 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 3.1 Alkylation of the non-cationic benzoxazine (co) polymer 3 with dimethyl sulfate to produce the cationic benzoxazine (co) polymer alk-3

28.0 g of the benzoxazine (co) polymer 3 from Example 2 (100 wt .-% B-Box-II) in 60 ml of ethanol were added slowly while stirring with 26.3 g of dimethyl sulfate. After 10 minutes of stirring, the reaction mixture was refluxed for 3.5 hours. Subsequently, the reaction mixture was stirred for 4 days at 22 ° C under a nitrogen atmosphere and then poured onto 600 ml of diethyl ether. The precipitate was separated and dried for 24 h at 80 ° C in a vacuum oven. 48.7 g of the cationic benzoxazine (co) polymer alk-3 were obtained. 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.

3.2 Alkylation of benzoxazine (co) polymer 8 with methyl iodide to produce the cationic benzoxazine (co) polymer alk-8

5.0 g of the non-cationic benzoxazine (co) polymer 8 from Example 2 (50% by weight of B-box 1.2 and 50% by weight of B-box III) in 6 ml of ethanol were added slowly with stirring while stirring Solution of 6.86 g of methyl iodide in 4 ml of ethanol. Subsequently, the reaction mixture was stirred for 24 hours at 22 ° C under a nitrogen atmosphere and then poured onto 60 ml of diethyl ether. The precipitate was separated and dried for 24 h at 120 ° C in a vacuum oven. This gave 5.2 g of the cationic benzoxazine (co) polymer alk-8. By NMR spectroscopic methods it was shown that at least 5% of all nitrogen atoms, based on the total number of nitrogen atoms in o.g. cationic benzoxazine (co) polymer, in the form of permanent quaternary nitrogen atoms.

3.3 Alkylation of benzoxazine (co) polymer 11 with dimethyl sulfate to prepare the cationic benzoxazine (co) polymer alk-11

10.6 g of the benzoxazine (co) polymer 11 from Example 2 (70 wt .-% B-box 1.2 and 30 wt .-% B-Box-II) in 10 ml of ethanol were added slowly with 1.9 g with stirring added. After 10 minutes of stirring, the reaction mixture was refluxed for 3.5 hours. Subsequently, the reaction mixture was stirred for 24 hours at 22 ° C under a nitrogen atmosphere and then poured onto 100 ml of diethyl ether. The precipitate was separated and dried for 24 h at 80 ° C in a vacuum oven. The cationic benzoxazine (co) polymer alk-11 was obtained. By NMR spectroscopic methods it was shown that at least 5% of all nitrogen atoms, based on the total number of nitrogen atoms in o.g. cationic benzoxazine (co) polymer, in the form of permanent quaternary nitrogen atoms.

Example 4: Color transfer inhibition

The following table shows the 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

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.

Claims (12)

1. Use of polymers, obtainable by polymerizing benzoxazine monomers, to avoid the transfer of textile dyes from dyed textiles onto un-dyed or differently colored textiles when they are washed together in, in particular surfactant-containing aqueous solutions.
2. Use of polymers, obtainable by polymerizing benzoxazine monomers, to avoid the modification of the color impression of textiles when they are washed in, in particular surfactant-containing aqueous solutions.
3. Cleaning, washing or fabric conditioning agents, comprising a color transfer inhibitor in the form of a polymer, obtainable by polymerizing benzoxazine monomers.
4. The agent according to claim 3, comprising 0.01 wt.% to 10 wt.%, in particular 0.1 wt.% to 1 wt.%, of the polymer.
5. The agent according to claim 3 or 4, additionally comprising a polymer of vinyl pyrrolidone, vinylimidazole, vinylpyridine-N-oxide or a copolymer of these.
6. A process for washing textiles in surfactant-containing aqueous solutions, wherein a surfactant-containing aqueous solution is employed that comprises a polymer, obtained by polymerizing benzoxazine monomers.
7. The process according to claim 6, wherein the polymer, for example as a component of a fabric softener, is brought into contact with the textile in a fabric conditioning step, and the thus-treated textile is washed in the presence of differently colored washing articles in the next washing operation, which can be carried out with an agent that comprises the polymer used according to the invention , or that is exempt from it.
8. The agent, use or process according to one of the preceding claims, wherein the polymer is obtainable by polymerizing benzoxazine compounds, selected from compounds of the general Formula (I) or from compounds of the general Formula (II) or from mixtures of them,

   

   

   wherein q is a whole number from 1 to 4,

   n is a number from 2 to 20 000,

   R in each repeat unit is selected independently of each other from hydrogen or linear or branched, optionally substituted alkyl groups that comprise 1 to 8 carbon atoms,

   Z is selected from hydrogen (for q = 1), alkyl (for q = 1), alkylene (for q = 2 to 4), carbonyl (for q = 2), oxygen (for q = 2), sulfur (for q = 2), sulfoxide (for q = 2), sulfone (for q = 2) and a direct, covalent bond (for q = 2),

   R¹ stands for a covalent bond or a divalent linking group that contains 1 to 100 carbon atoms,

   R² is selected from hydrogen, halogen, alkyl and alkenyl, or R² is a divalent group that makes a corresponding naphthoxazine structure from the benzoxazine structure,

   Y is selected from linear or branched, optionally substituted alkyl groups that contain 1 to 15 carbon atoms, cycloaliphatic groups that optionally comprise one or more heteroatoms, aryl groups that optionally comprise one or more heteroatoms, and -(C=O)R³, wherein R³ is selected from linear or branched, optionally substituted alkyl groups containing 1 to 15 carbon atoms and X-R⁴, wherein X is selected from S, O, and NH and R⁴ is selected from linear or branched, optionally substituted alkyl groups containing 1 to 15 carbon atoms,

   c is a whole number from 1 to 4,

   B is selected from hydrogen (for c = 1), alkyl (for c = 1), alkylene (for c = 2 to 4), carbonyl (for c = 2), oxygen (for c = 2), sulfur (for c = 2), sulfoxide (for c = 2), sulfone (for c = 2) and a direct, covalent bond (for c = 2), A is a hydroxyl group or a nitrogen-containing heterocycle,

   R⁵ is selected from hydrogen, halogen, alkyl and alkenyl, or R⁵ is a divalent group that makes a corresponding naphthoxazine structure from the benzoxazine structure and R⁶ stands for a covalent bond or is a divalent linking group that contains 1 to 100 carbon atoms.
9. The agent, use or process according to claim 8, wherein the benzoxazine compounds of the general Formula (I) are selected from compounds of the general Formula (III),

   

   wherein x is a number between 0 and 1000 and y is a number between 0 and 1000, with the proviso that x+y ≥ 2, wherein Z, R², Y and q are each defined as in Formula (I).
10. The agent, use or process according to claim 8, wherein the benzoxazine compounds of the general Formula (II) are selected from compounds of the general Formula (IV) and/or compounds of the general Formula (V),

    

    

    wherein R⁷ and R⁸ each independently of one another are selected from hydrogen, halogen, linear or branched, optionally substituted alkyl groups, alkenyl groups and aryl groups, wherein c, B, R⁵ and R⁶ are each as defined above as in Formula (II).
11. The agent, use or process according to one of claims 1 to 10, wherein the weight average molecular weight "M_w" of the benzoxazine (co)polymer is between 500 and 100 000 g/mol.
12. The agent, use or process according to one of claims 1 to 11, wherein the benzoxazine (co)polymer is a cationic benzoxazine (co)polymer obtainable by reaction with at least one alkylation agent.