EP0964912B1 - Detergent and cleaning agent formulation with a bleaching system and a mixture of amines and complexing agents - Google Patents

Description

The present invention relates to a new detergent and cleaning agent formulation with a bleaching system and one Mixture of largely biodegradable amines and Heavy metal ions complexing complexing agents. Farther The invention relates to the use of the above Mixture of amines and complexing agents for efficient stabilization of the bleaching system based on hydrogen peroxide, peroxo compounds and / or peracids in detergent and cleaning agent formulations.

That for the bleaching effect in the usual perborate or percarbonate containing Textile detergent formulations responsible for hydrogen peroxide is quickly decomposed by traces of heavy metals. This Heavy metal ions, especially iron, copper and manganese ions, are in tap water (caused by tap corrosion or Corrosion damage in the washing machine), in the dirt of the laundry or in the detergent raw materials, usually even more water-soluble Shape, present. They reduce the efficiency of the Bleaching system through unselective decomposition of the released Hydrogen peroxides can and through transfer of oxygen radicals cause additional fiber damage to the fabric. Sodium perborate / sodium percarbonate can also be present oxidatively destroy optical brighteners from traces of heavy metals, Cause color shifts or impair fluorescence. By effectively complexing the heavy metal ions this can be prevented.

From US-A 2 544 649 (1) it is known to use aqueous solutions of Alkali metal hydroxide by adding triethanolamine and ethylenediaminetetraacetic acid or their salts before the precipitation of iron compounds to protect. It will not be a technical application specified for the alkali metal hydroxide solutions described.

DE-A 32 10 004 (2) describes a means for dissolving insoluble substances Iron (III) compounds in highly alkaline textile treatment fleets described which is a water soluble Hydroxycarbonyl compound e.g. Glucose, as a reducing agent, a special complexing agent complexing iron (II) ions, e.g. Contains gluconic acid and triethanolamine. Other usual Complexing agents such as aminopolycarboxylic acids are considered for designated purpose is no longer sufficiently effective.

WO-A 94/29421 (3) relates to the use of glycine-N, N-diacetic acid derivatives, e.g. α-alanine-N, N-diacetic acid and their Alkali metal, ammonium and substituted ammonium salts, as biodegradable complexing agents for alkaline earth and heavy metal ions, for example in detergent and cleaning agent formulations. These glycine-N, N-diacetic acid derivatives can also be used as organic amine salts with trialkylamines or trialkanolamines be used.

EP-A-0 036 691 describes bleaching detergent compositions, the alkanolamines or nitrilotriacetic acid (NTA) included.

The object of the present invention was to make it harmless of disruptive heavy metal ions in bleach containing Detergent and cleaning agent formulations improve as well the complexing agents usually used alone for this purpose, in particular Aminocarboxylates, in this function as in need of improvement have highlighted.

(A) biologisch weitgehend abbaubaren aliphatischen oder alicyclischen Aminen mit 1 bis 12 C-Atomen, welche zusätzlich Hydroxylgruppen tragen können, und

(B) auf Schwermetallionen komplexierend wirkenden Komplexbildnern,

wobei das Gew.-Verhältnis A:B von 1:20 bis 20:1, insbesondere von 1:5 bis 5:1, beträgt, enthält.Accordingly, a detergent and cleaning agent formulation has been found which, in addition to other conventional constituents, comprises a bleaching system based on hydrogen peroxide, peroxo compounds and / or peracids and a mixture of

(A) largely biodegradable aliphatic or alicyclic amines having 1 to 12 carbon atoms, which can additionally carry hydroxyl groups, and

(B) complexing agents which have a complexing action on heavy metal ions,

wherein the weight ratio A: B is from 1:20 to 20: 1, in particular from 1: 5 to 5: 1.

In particular come as aliphatic or alicyclic amines A. tertiary amines with 3 to 12 carbon atoms. alicyclic Amines A are those with saturated cyclic structures, e.g. Cyclohexylamine, N, N-dimethylcyclohexylamine, azacyclohexane or N-methyl-azacyclohexane. However, tertiary are particularly preferred aliphatic amines such as trialkylamines with 1 to 4 carbon atoms per alkyl radical, e.g. Trimethylamine, triethylamine, tri-n-propylamine, Triisopropylamine or tri-n-butylamine, and especially trialkanolamines with a total of 6 to 9 carbon atoms, e.g. triethanolamine, Tri-n-propanolamine or triisopropanolamine. It can too Mixtures of the amines A mentioned are used.

in der M für Wasserstoff, Alkalimetall, beispielsweise Natrium oder Kalium, oder unsubstituiertes Ammonium steht.In principle, all conventional complexing agents which have a complexing or chelating action on heavy metal ions are suitable as complexing agents B. These complexing agents should be water-soluble or at least partially water-soluble - be it in the form of free acids or their salts such as alkali metal salts - in order to be sufficiently effective in the washing and cleaning liquors. However, aminocarboxylates are preferably used, in particular those having one or more groupings of the formula

in which M represents hydrogen, alkali metal, for example sodium or potassium, or unsubstituted ammonium.

• Ethylendiamin-N,N,N',N'-tetraessigsäure ("EDTA") und deren Alkalimetall- und Ammoniumsalze;
• Nitrilotriessigsäure ("NTA") und deren Alkalimetall- und Ammoniumsalze;
• Aminodicarbonsäure-N,N-diessigsäuren und deren Alkalimetall- und Ammoniumsalze der Formel
  
  z.B. Asparaginsäure-N,N-diessigsäure ("ASDA", n = 1) oder Glutaminsäure-N,N-diessigsäure (n = 2);
• β-Alanin-N,N-diessigsäure ("β-ADA") und deren Alkalimetall- und Ammoniumsalze;
• Iminodiessigsäure ("IDA") und deren Alkalimetall- und Ammoniumsalze;
• Alkyl- und Hydroxyalkyliminodiessigsäuren und deren Alkalimetall- und Ammoniumsalze, z.B. Methyliminodiessigsäure ("MIDA") oder 2-Hydroxyethyliminodiessigsäure ("HEIDA");
• Glycin-N,N-diessigsäure-Derivate und deren Alkalimetall- und Ammoniumsalze der Formel
  
  (R¹ = C₁- bis C₃₀-Alkyl oder C₂- bis C₃₀-Alkenyl), z.B. α-Alanin-N,N-diessigsäure ("α-ADA") oder Glycin-N,N-diessigsäure-Derivate mit C₅- bis C₂₀-, insbesondere C₇- bis C₁₅-Alkyl- oder Alkenylresten R¹ (derartige Systeme werden in (3) beschrieben);
• Hydroxamsäuren und Hydroxamsäureether der allgemeinen Formeln I und II
  
  in denen

  Z¹ und Z²

  für die Gruppen -NH-OY, -NR²-OY oder -OX stehen,
  wobei bei (I) mindestens einer der Reste Z¹ oder Z² und bei (II) der Rest Z¹ für -NH-OY oder -NR²-OY steht und

  R²

  C₁- bis C₁₈-Alkyl bezeichnet,

  X

  Wasserstoff, Alkalimetall oder Ammonium bezeichnet und

  Y

  Wasserstoff, Alkalimetall, Ammonium oder C₁- bis C₁₈-Alkyl bedeutet, und

  L

  für ein C₁- bis C₁₀₀-Brückenglied steht, welches noch sauerstoff- und stickstoffunktionelle Gruppen tragen kann,

  wie sie in der WO-A 94/24096 beschrieben werden, z.B. N,N-Bis(carboxymethyl)-3-aminopropiohydroxamsäure, D,L-Asparaginsäure-N-propiohydroxamsäure, Epoxybernsteinsäure-bishydroxamsäure, Weinsäure-bis-hydroxamsäure, Citronensäuretris-hydroxamsäure, D-Gluconsäurehydroxamsäure, D-Glucoheptonsäurehydroxamsäure oder N,N-Bis(carboxymethyl)-2-aminoacethydroxamsäure;
• Phenolderivate der allgemeinen Formel III und IV
  
  in denen

  R³

  C₆- bis C₂₀-Alkyl oder -Alkenyl, welches durch ein oder mehrere nicht benachbarte Sauerstoffatome unterbrochen sein kann, oder eine Gruppe der Formel -O-CO-R⁷, -CO-O-R⁷, -NH-CO-R⁷, -NR⁸-CO-R⁷, -CO-NH-R⁷, -CO-NR⁸-R⁷, -NH-SO₂-R⁷, -NR⁸-SO₂-R⁷, -SO₂-NH-R⁷ oder -SO₂-NR⁸-R⁷ bedeutet, wobei R⁷ für C₆- bis C₂₀-Alkyl oder -Alkenyl, welches durch ein oder mehrere nicht benachbarte Sauerstoffatome unterbrochen sein kann, und R⁸ für C₁- bis C₄-Alkyl steht,

  R⁴ und R⁵

  Wasserstoff oder eine Gruppe der Formel -CH₂-N(CH₂COOM)₂, in der M für Wasserstoff, Alkalimetall oder Ammonium steht, bezeichnet, wobei mindestens einer der Reste R⁴ oder R⁵ eine Gruppe der Formel -CH₂-N(CH₂COOM)₂ bezeichnen muß, und

  R⁶

  für eine Gruppe der Formel -CO-O-R⁷, -CO-NH-R⁷ oder CO-NR⁸-R⁷ steht,

  wie sie in der WO-A 95/06095 beschrieben sind, z.B. 2,6-Bis(amino-N,N-diessigsäure-methyl)-4-iso-dedecylphenol-Tetranatriumsalz;
• Trisäuren der allgemeinen Formel V
  
  in der

  X¹ bis X³

  unabhängig voneinander Carbonsäuregruppen der Formel COOM, Sulfonsäuregruppen der Formel SO₃M oder Phosphonsäuregruppen der Formel PO₃M₂ bedeuten, wobei

  M

  für Wasserstoff, Alkalimetall oder Ammonium steht,

  A¹ bis A³

  unabhängig voneinander 1,2-Alkylen mit 2 bis 18 C-Atomen bezeichnen,

  R⁹ bis R¹¹

  unabhängig voneinander C₁- bis C₈-Alkylen bedeuten und

  x, y und z

  unabhängig voneinander für eine Zahl von 0 bis 10 stehen, wobei die Summe x+y+z größer oder gleich 1 sein muß,

  wie sie in der WO-A 96/22964 beschrieben sind, z.B. 5-Amino-3-oxa-pentacarbonsäure-N-N-diessigsäure, 8-Amino-3,6-dioxa-octancarbonsäure-N,N-diessigsäure oder das Oxidationsprodukt eines Umsetzungsproduktes von Triethanolamin mit 4 oder 8 mol Ethylenoxid, hergestellt durch Oxidation in wäßriger Natronlauge mit einem Cu/ZrO₂-Katalysator;
• Hydroxyalkylaminocarbonsäuren der allgemeinen Formel VI
  
  in der

  R¹²

  Wasserstoff, einen C₁- bis C₁₄-Alkylrest oder eine Gruppierung der Formel -CHR¹⁴-CH(OH) -R¹³ oder - (CH₂)_m-COOM wobei m für eine Zahl von 1 bis 4 steht, bezeichnet,

  R¹³ und R¹⁴

  unabhängig voneinander Wasserstoff, einen Phenylrest oder einen Alkyl- oder Alkenylrest, der zusätzlich Phenoxygruppen, Carbonsäure-C₁- bis C₄-alkylester-Gruppierungen oder von Triglyceriden auf der Basis von ungesättigten C₁₀- bis C₂₂-Fettsäuren abgeleitete Ester-Gruppierungen tragen und durch nicht benachbarte Sauerstoffatome unterbrochen sein kann, bedeuten, wobei die Summe der C-Atome aus beiden Resten R¹³ und R¹⁴ mindestens 4 betragen muß,

  A⁴

  für eine lineare oder verzweigte C₁- bis C₆-Alkylengruppe, die zusätzlich eine Hydroxylgruppe und/oder eine Gruppe der Formel COOM tragen kann, steht, wobei R¹² und A⁴ zusammen mit dem N-Atom einen fünf- oder sechsgliedrigen Ring bilden können, und

  M

  Wasserstoff, Alkalimetall oder Ammonium bezeichnet,

  wie sie in der WO-A 96/19557 beschrieben sind, z.B. die Umsetzungsprodukte aus Sarkosin und 1,2-Epoxyoctan, Sarkosin und 2-Ethylhexylglycidylether, Sarkosin und Styroloxid sowie Sarkosin und 2,3-Epoxypropyl-phenylether;
• Bis(dicarbonsäure)diaminoalkylen-Derivate der allgemeinen Formel VII
  
  in der

  B

  eine 1,2-Ethylen-, 1,3-Propylen- oder 2-Hydroxy-1,3-propylengruppe bezeichnet,

  M

  für Wasserstoff, Alkalimetall oder Ammonium steht und

  p und q

  unabhängig voneinander die Zahlen 1 oder 2 bedeuten,

  wie Ethylendiaminosuccinat ("EDDS"), (2-Hydroxypropylen)-1,3-diaminosuccinat ("HPDDS") und Ethylendiaminoglutamat ("EDDG") oder deren Alkalimetall- und Ammoniumsalze;
• Hexan-1,3,6-tricarbonsäure oder deren Alkalimetall- und Ammoniumsalze;
• Serin-N,N-diessigsäure ("SDA") oder deren Alkalimetall- und Ammoniumsalze;
• Isoserin-N,N-diessigsäure ("ISDA") oder deren Alkalimetallund Ammoniumsalze;
• 2-Methyl- und 2-Hydroxymethyl-serin-N,N-diessigsäure oder deren Alkalimetall- und Ammoniumsalze.

Typical complexing agents B are the following:

• Ethylenediamine-N, N, N ', N'-tetraacetic acid ("EDTA") and their alkali metal and ammonium salts;
• Nitrilotriacetic acid ("NTA") and its alkali metal and ammonium salts;
• Aminodicarboxylic acid N, N-diacetic acids and their alkali metal and ammonium salts of the formula
  
  for example aspartic acid N, N-diacetic acid ("ASDA", n = 1) or glutamic acid-N, N-diacetic acid (n = 2);
• β-alanine-N, N-diacetic acid ("β-ADA") and their alkali metal and ammonium salts;
• Iminodiacetic acid ("IDA") and its alkali metal and ammonium salts;
• Alkyl and hydroxyalkyliminodiacetic acids and their alkali metal and ammonium salts, for example methyliminodiacetic acid ("MIDA") or 2-hydroxyethyliminodiacetic acid ("HEIDA");
• Glycine-N, N-diacetic acid derivatives and their alkali metal and ammonium salts of the formula
  
  (R ¹ = C ₁ to C ₃₀ alkyl or C ₂ to C ₃₀ alkenyl), for example α-alanine-N, N-diacetic acid (“α-ADA”) or glycine-N, N-diacetic acid derivatives with C ₅ - to C ₂₀ -, in particular C ₇ - to C ₁₅ -alkyl or alkenyl radicals R ¹ (such systems are described in (3));
• Hydroxamic acids and hydroxamic acid ethers of the general formulas I and II
  
  in which

  Z ¹ and Z ²

  represent the groups -NH-OY, -NR ² -OY or -OX,
  where in (I) at least one of Z ¹ or Z ² and in (II) Z ^{1 is} -NH-OY or -NR ² -OY and

  R ²

  Denotes C ₁ - to C ₁₈ -alkyl,

  X

  Denotes hydrogen, alkali metal or ammonium and

  Y

  Is hydrogen, alkali metal, ammonium or C ₁ - to C ₁₈ -alkyl, and

  L

  represents a C ₁ to C ₁₀₀ bridge member which can still carry oxygen and nitrogen functional groups,

  as described in WO-A 94/24096, for example N, N-bis (carboxymethyl) -3-aminopropiohydroxamic acid, D, L-aspartic acid-N-propiohydroxamic acid, epoxysuccinic acid-bishydroxamic acid, tartaric acid-bis-hydroxamic acid, citric acid tris-hydroxamic acid , D-gluconic acid hydroxamic acid, D-glucoheptonic acid hydroxamic acid or N, N-bis (carboxymethyl) -2-aminoacethydroxamic acid;
• Phenol derivatives of the general formula III and IV
  
  in which

  R ³

  C ₆ to C ₂₀ alkyl or alkenyl, which can be interrupted by one or more non-adjacent oxygen atoms, or a group of the formula -O-CO-R ⁷ , -CO-OR ⁷ , -NH-CO-R ⁷ , -NR ⁸ -CO-R ⁷ , -CO-NH-R ⁷ , -CO-NR ⁸ -R ⁷ , -NH-SO ₂ -R ⁷ , -NR ⁸ -SO ₂ -R ⁷ , -SO ₂ - NH-R ⁷ or -SO ₂ -NR ⁸ -R ⁷ , where R ^{7 is} C ₆ -C ₂₀ -alkyl or alkenyl, which can be interrupted by one or more non-adjacent oxygen atoms, and R ^{8 is} C ₁ - until C ₄ alkyl,

  R ⁴ and R ⁵

  Denotes hydrogen or a group of the formula -CH ₂ -N (CH ₂ COOM) ₂ , in which M represents hydrogen, alkali metal or ammonium, where at least one of the radicals R ⁴ or R ⁵ denotes a group of the formula -CH ₂ -N (CH ₂ COOM) ₂ , and

  R ⁶

  represents a group of the formula -CO-OR ⁷ , -CO-NH-R ⁷ or CO-NR ⁸ -R ⁷ ,

  as described in WO-A 95/06095, for example 2,6-bis (amino-N, N-diacetic acid-methyl) -4-iso-dedecylphenol tetrasodium salt;
• Triacids of the general formula V
  
  in the

  X ¹ to X ³

  independently of one another are carboxylic acid groups of the formula COOM, sulfonic acid groups of the formula SO ₃ M or phosphonic acid groups of the formula PO ₃ M ₂ , where

  M

  represents hydrogen, alkali metal or ammonium,

  A ¹ to A ³

  independently denote 1,2-alkylene with 2 to 18 carbon atoms,

  R ⁹ to R ¹¹

  independently of one another are C ₁ -C ₈ -alkylene and

  x, y and z

  independently of one another represent a number from 0 to 10, where the sum x + y + z must be greater than or equal to 1,

  as described in WO-A 96/22964, for example 5-amino-3-oxapentacarboxylic acid-NN-diacetic acid, 8-amino-3,6-dioxa-octane carboxylic acid-N, N-diacetic acid or the oxidation product of a reaction product of triethanolamine with 4 or 8 mol of ethylene oxide, prepared by oxidation in aqueous sodium hydroxide solution with a Cu / ZrO ₂ catalyst;
• Hydroxyalkylaminocarboxylic acids of the general formula VI
  
  in the

  R ¹²

  Hydrogen, a C ₁ - to C ₁₄ -alkyl radical or a grouping of the formula -CHR ¹⁴ -CH (OH) -R ¹³ or - (CH ₂ ) _m -COOM where m stands for a number from 1 to 4,

  R ¹³ and R ¹⁴

  independently of one another hydrogen, a phenyl radical or an alkyl or alkenyl radical which additionally carry phenoxy groups, carboxylic acid C ₁ -C ₄ -alkyl ester groups or ester groups derived from triglycerides based on unsaturated C ₁₀ -C ₂₂ -fatty acids and can be interrupted by non-adjacent oxygen atoms, where the sum of the C atoms from both radicals R ¹³ and R ¹⁴ must be at least 4,

  A ⁴

  represents a linear or branched C ₁ - to C ₆ -alkylene group which can additionally carry a hydroxyl group and / or a group of the formula COOM, where R ¹² and A ⁴ together with the N atom form a five- or six-membered ring can, and

  M

  Denotes hydrogen, alkali metal or ammonium,

  as described in WO-A 96/19557, for example the reaction products of sarcosine and 1,2-epoxyoctane, sarcosine and 2-ethylhexylglycidyl ether, sarcosine and styrene oxide as well as sarcosine and 2,3-epoxypropylphenyl ether;
• Bis (dicarboxylic acid) diaminoalkylene derivatives of the general formula VII
  
  in the

  B

  denotes a 1,2-ethylene, 1,3-propylene or 2-hydroxy-1,3-propylene group,

  M

  represents hydrogen, alkali metal or ammonium and

  p and q

  independently of one another represent the numbers 1 or 2,

  such as ethylenediaminosuccinate ("EDDS"), (2-hydroxypropylene) -1,3-diaminosuccinate ("HPDDS") and ethylenediaminoglutamate ("EDDG") or their alkali metal and ammonium salts;
• Hexane-1,3,6-tricarboxylic acid or its alkali metal and ammonium salts;
• Serine-N, N-diacetic acid ("SDA") or its alkali metal and ammonium salts;
• Isoserine-N, N-diacetic acid ("ISDA") or its alkali metal and ammonium salts;
• 2-methyl and 2-hydroxymethyl-serine-N, N-diacetic acid or its alkali metal and ammonium salts.

Mixtures of the complexing agents B mentioned can also be used become.

The mixture mentioned from the amines A and the complexing agents B lies in the washing and cleaning agent formulation according to the invention usually in an amount of 0.1 to 10 wt .-%, in particular 0.2 to 3% by weight, based on the total amount of the formulation, in front.

Of particular interest is a textile detergent formulation containing bleach, which the said mixture of the Amines A and the complexing agents B in the sense of the present Invention contains.

Textile detergent formulations usually contain bleaching systems from bleach activators, bleaching agents in the form of hydrogen peroxide, Peroxo compounds and / or peracids and optionally Bleaching catalysts and bleach stabilizers as well furthermore nonionic and / or anionic surfactants, calcium and / or Compounds sequestering magnesium ions (builders, Builder, Cobuilder) and a number of other common ones Aids. Sequestering as calcium and / or magnesium ions Connections usually become representatives from the group of zeolites, silicates, alkali metal phosphates, polycarboxylates and aminopolycarboxylates used, individually or in mixtures.

Bleach activators are usually in amounts of 0.1 to 10% by weight, in particular 0.5 to 7 wt .-%, bleaching agents in amounts of 0.5 to 40% by weight, in particular 5 to 30% by weight, nonionic and / or anionic surfactants in amounts of 0.5 to 50 wt .-%, in particular 5 to 30 wt .-%, and calcium and / or magnesium ions sequestering Compounds in amounts of 5 to 85 wt .-%, in particular 10 to 70% by weight, based in each case on the total amount of the formulation, in front.

In principle, zeolites and silicates can be used as inorganic ion exchangers be designated. Suitable zeolites (aluminosilicates) are in particular those of the types A, P, X, B, HS and MAP in their Sodium form or in forms in which sodium is partially against others Cations such as Li, K, Ca, Mg or ammonium are exchanged. Such zeolites are described, for example, in EP-A 038 591, EP-A 021 491, EP-A 087 035, US-A 4 604 224, GB-A 2 013 259, EP-A 522 726, EP-A 384 070 and WO-A 94/24 251.

Suitable amorphous or crystalline silicates, in particular Layered silicates are mainly amorphous and crystalline Disilicates such as the layered silicate SKS-6 (manufacturer Fa. Maximum). The silicates can be in the form of their alkali metal, alkaline earth metal or ammonium salts can be used. Preferably Na, Li and Mg silicates are used.

In particular, trisodium polyphosphate is used as the alkali metal phosphate into consideration, which is also an inorganic ion exchanger can be viewed.

• C₄- bis C₂₀-Di-, -Tri- und -Tetracarbonsäuren wie z.B. Bernsteinsäure, Propantricarbonsäure, Butantetracarbonsäure, Cyclopentantetracarbonsäure und Alkyl- und Alkenylbernsteinsäuren mit C₂- bis C₁₆-Alkyl- bzw. -Alkenyl-Resten;
• C₄- bis C₂₀-Hydroxycarbonsäuren wie z.B. Äpfelsäure, Weinsäure, Gluconsäure, Glucarsäure, Citronensäure, Lactobionsäure und Saccharosemono-, -di- und -tricarbonsäure.

Suitable low molecular weight polycarboxylates and aminopolycarboxylates as builders are in particular:

• C ₄ to C ₂₀ di, tri and tetracarboxylic acids such as succinic acid, propane tricarboxylic acid, butane tetracarboxylic acid, cyclopentane tetracarboxylic acid and alkyl and alkenyl succinic acids with C ₂ to C ₁₆ alkyl or alkenyl radicals;
• C ₄ to C ₂₀ hydroxycarboxylic acids such as malic acid, tartaric acid, gluconic acid, glucaric acid, citric acid, lactobionic acid and sucrose mono-, di- and tricarboxylic acid.

• Oligomaleinsäuren, wie sie beispielsweise in EP-A 451 508 und EP-A 396 303 beschrieben sind;
• Co- und Terpolymere ungesättigter C₄- bis C₈-Dicarbonsäuren, wobei als Comonomere monoethylenisch ungesättigte Monomere
• aus der Gruppe (i) in Mengen von bis zu 95 Gew.-%,
• aus der Gruppe (ii) in Mengen von bis zu 60 Gew.-%,
• aus der Gruppe (iii) in Mengen von bis zu 20 Gew.-%
einpolymerisiert enthalten sein können.

Suitable oligomeric or polymeric polycarboxylates and aminopolycarboxylates as builders are in particular:

• Oligomaleic acids as described, for example, in EP-A 451 508 and EP-A 396 303;
• Copolymers and terpolymers of unsaturated C ₄ to C ₈ dicarboxylic acids, with monoethylenically unsaturated monomers as comonomers
• from group (i) in amounts of up to 95% by weight,
• from group (ii) in amounts of up to 60% by weight,
• from group (iii) in amounts of up to 20% by weight
polymerized may be included.

Examples of suitable unsaturated C ₄ to C ₈ dicarboxylic acids are maleic acid, fumaric acid, itaconic acid and citraconic acid. Maleic acid is preferred.

Group (i) includes monoethylenically unsaturated C ₃ -C ₈ -monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid. From group (i), preference is given to using acrylic acid and methacrylic acid.

Group (ii) includes monoethylenically unsaturated C ₂ to C ₂₂ olefins, vinyl alkyl ethers with C ₁ to C ₈ alkyl groups, styrene, vinyl esters of C ₁ to C ₈ carboxylic acids, (meth) acrylamide and vinyl pyrrolidone. From group (ii), preference is given to using C ₂ -C ₆ -olefins, vinyl alkyl ethers having C ₁ -C ₄ -alkyl groups, vinyl acetate and vinyl propionate.

Group (iii) includes (meth) acrylic esters of C ₁ to C ₈ alcohols, (meth) acrylonitrile, (meth) acrylamides of C ₁ to C ₈ amines, N-vinylformamide and vinylimidazole.

If the polymers of group (ii) polymerize vinyl esters contain, they can also partially or completely to vinyl alcohol structural units be hydrolyzed. Suitable co and Terpolymers are known, for example, from US Pat. No. 3,887,806 and DE-A 43 13 909 known.

• Copolymere von Maleinsäure und Acrylsäure im Gewichtsverhältnis 10:90 bis 95:5, insbesondere solche im Gewichtsverhältnis 30:70 bis 90:10, insbesondere mit Molmassen von 1.000 bis 150.000;
• Terpolymere aus Maleinsäure, Acrylsäure und einem Vinylester einer C₁- bis C₃-Carbonsäure im Gewichtsverhältnis 10 (Maleinsäure) : 90 (Acrylsäure + Vinylester) bis 95 (Maleinsäure) : 5 (Acrylsäure + Vinylester), wobei das Gewichtsverhältnis von Acrylsäure zu Vinylester im Bereich von 20:80 bis 80:20 variieren kann;
• Terpolymere aus Maleinsäure, Acrylsäure und Vinylacetat oder Vinylpropionat im Gewichtsverhältnis 20 (Maleinsäure) : 80 (Acrylsäure + Vinylester) bis 90 (Maleinsäure) : 10 (Acrylsäure + Vinylester), wobei das Gewichtsverhältnis von Acrylsäure zum Vinylester im Bereich von 30:70 bis 70:30 variieren kann;
• Copolymere von Maleinsäure mit C₂- bis C₈-Olefinen im Molverhältnis 40:60 bis 80:20, wobei Copolymere von Maleinsäure mit Ethylen, Propylen oder Isobutan im Molverhältnis von ca. 50:50 besonders bevorzugt sind.

As copolymers of dicarboxylic acids, the following are particularly suitable as builders:

• Copolymers of maleic acid and acrylic acid in a weight ratio of 10:90 to 95: 5, in particular those in a weight ratio of 30:70 to 90:10, in particular with molecular weights of 1,000 to 150,000;
• Terpolymers of maleic acid, acrylic acid and a vinyl ester of a C ₁ to C ₃ carboxylic acid in a weight ratio of 10 (maleic acid): 90 (acrylic acid + vinyl ester) to 95 (maleic acid): 5 (acrylic acid + vinyl ester), the weight ratio of acrylic acid to vinyl ester can vary in the range from 20:80 to 80:20;
• Terpolymers of maleic acid, acrylic acid and vinyl acetate or vinyl propionate in a weight ratio of 20 (maleic acid): 80 (acrylic acid + vinyl ester) to 90 (maleic acid): 10 (acrylic acid + vinyl ester), the weight ratio of acrylic acid to vinyl ester in the range from 30:70 to 70 : 30 may vary;
• Copolymers of maleic acid with C ₂ to C ₈ olefins in a molar ratio of 40:60 to 80:20, copolymers of maleic acid with ethylene, propylene or isobutane in a molar ratio of about 50:50 being particularly preferred.

Graft polymers of unsaturated carboxylic acids on low molecular weight Carbohydrates or hydrogenated carbohydrates, cf. US-A 5 227 446, DE-A 44 15 623 and DE-A 43 13 909 also come as builders into consideration. Suitable unsaturated carboxylic acids are here, for example, maleic acid, fumaric acid, itaconic acid, Citraconic acid, acrylic acid, methacrylic acid, crotonic acid and vinyl acetic acid as well as mixtures of acrylic acid and maleic acid, the in amounts of 40 to 95 wt .-%, based on the to be grafted Component to be grafted on.

For modification, up to 30% by weight, based on the component to be grafted, further monoethylenically unsaturated Monomers are present in copolymerized form. Suitable modifying Monomers are the above group monomers (ii) and (iii).

Degraded polysaccharides such as acidic or enzymatically degraded starches, inulins or cellulose, reduced (hydrogenated or hydrogenated aminated) degraded polysaccharides such as mannitol, sorbitol, aminosorbitol and glucamine and polyalkylene glycols with molecular weights of up to M _w = 5,000 such as polyethylene glycols are suitable as grafting bases. Ethylene oxide / propylene oxide or ethylene oxide / butylene oxide block copolymers, statistical ethylene oxide / propylene oxide or ethylene oxide / butylene oxide copolymers or alkoxylated mono- or polybasic C ₁ to C ₂₂ alcohols, cf. US-A 4 746 456.

Grafted mined or mined from this group are preferred reduced starches and grafted polyethylene oxides are used, wherein 20 to 80 wt .-% monomers based on the graft component be used in the graft polymerization. to Grafting is preferably a mixture of maleic acid and Acrylic acid used in a weight ratio of 90:10 to 10:90.

Examples of possible builders are polyglyoxylic acids described in EP-B 001 004, US-A 5 399 286, DE-A 41 06 355 and EP-A 656 914. The end groups of the polyglyoxylic acids can be different Have structures.

Polyamidocarboxylic acids and modified polyamidocarboxylic acids as possible builders are known for example from EP-A 454 126, EP-B 511 037, WO-A 94/01486 and EP-A 581 452.

The aminopolycarboxylates used are preferably also polyaspartic acid or cocondensates of aspartic acid with further amino acids, C ₄ to C ₂₅ mono- or dicarboxylic acids and / or C ₄ to C ₂₅ mono- or diamines. Particularly preferred are prepared in phosphorus-containing acids, with C ₆ - to C ₂₂ used modified mono- or diamines, polyaspartic acids - to C ₂₂ -mono- or -dicarboxylic acids or with C. ₆

Condensation products of citric acid with hydroxycarboxylic acids or polyhydroxy compounds as builders are e.g. known from WO-A 93/22362 and WO-A 92/16493. Such carboxyl groups Condensates usually have molecular weights of up to 10,000, preferably up to 5,000.

Particularly preferred as builders in the invention Textile detergent formulation of the above Substance classes zeolite A, zeolite P, zeolite X, layered silicates such as SKS-6, trisodium polyphosphate, acrylic acid / maleic acid copolymers (in particular those with a molecular weight of 10,000 to 100,000), polyaspartic acid, Citric acid, nitrilotriacetic acid, methylglycinediacetic acid and mixtures thereof are used.

Of particular interest as mixtures are those made from zeolites and polyaspartic acid, zeolites and oligomaleic acids, zeolites and acrylic acid / maleic acid copolymers, trisodium polyphosphate and layered silicates, trisodium polyphosphate and acrylic acid / maleic acid copolymers, Zeolites and trisodium polyphosphate as well as from zeolites, layered silicates and acrylic acid / maleic acid copolymers as the respective main components of the Builder component.

Bleach activators are primarily compounds of the following Substance classes into consideration:

Polyacylated sugars or sugar derivatives with C ₁ - to C ₁₀ -acyl residues, preferably acetyl, propionyl, octanoyl, nonanoyl or benzoyl residues, in particular acetyl residues, can be used as bleach activators. Mono or disaccharides and their reduced or oxidized derivatives can be used as sugar or sugar derivatives, preferably glucose, mannose, fructose, sucrose, xylose or lactose. Particularly suitable bleach activators of this class of substances are, for example, pentaacetylglucose, xylose tetraacetate, 1-benzoyl-2,3,4,6-tetraacetylglucose and 1-octanoyl-2,3,4,6-tetraacetylglucose.

O-acyl oxime esters can also be used as bleach activators such as. O-acetylacetone oxime, O-benzoylacetone oxime, bis (propylimino) carbonate or bis (cyclohexylimino) carbonate. Such acylated Oximes and oxime esters are described, for example, in US Pat EP-A 028 432 and EP-A 267 046.

N-Acylcaprolactams can also be used as bleach activators such as N-acetylcaprolactam, N-benzoylcaprolactam, N-octanoylcaprolactam or carbonyl biscaprolactam.

• N-diacylierte und N,N'-tetracylierte Amine, z.B. N,N,N',N'-Tetraacetylmethylendiamin und -ethylendiamin (TAED), N,N-Diacetylanilin, N,N-Diacetyl-p-toluidin oder 1,3-diacylierte Hydantoine wie 1,3-Diacetyl-5,5-dimethylhydantoin;
• N-Alkyl-N-sulfonyl-carbonamide, z.B. N-Methyl-N-mesyl-acetamid oder N-Methyl-N-mesyl-benzamid;
• N-acylierte cyclische Hydrazide, acylierte Triazole oder Urazole, z.B. Monoacetyl-maleinsäurehydrazid;
• O,N,N-trisubstituierte Hydroxylamine, z.B. O-Benzoyl-N,N-succinylhydroxylamin, O-Acetyl-N,N-succinyl-hyroxylamin oder O,N,N-Triacetalhydroxylamin;
• N,N'-Diacyl-sulfurylamide, z.B. N,N'-Dimethyl-N,N'-diacetylsulfurylamid oder N,N' -Diethyl-N,N'-dipropionyl-sulfurylamid;
• Triacylcyanurate, z.B. Triacetylcyanurat oder Tribenzoylcyanurat;
• Carbonsäureanhydride, z.B. Benzoesäureanhydrid, m-Chlorbenzoesäureanhydrid oder Phthalsäureanhydrid;
• 1,3-Diacyl-4,5-diacyloxy-imidazoline, z.B. 1,3-Diacetyl-4,5-diacetoxyimidazolin;
• Tetraacetylglycoluril und Tetrapropionylglycoluril;
• diacylierte 2,5-Diketopiperazine, z.B. 1,4-Diacetyl-2,5-diketopiperazin;
• Acylierungsprodukte von Propylendiharnstoff und 2,2-Dimethylpropylendiharnstoff, z.B. Tetraacetylpropylendiharnstoff;
• α-Acyloxy-polyacyl-malonamide, z.B. α-Acetoxy-N,N'-diacetylmalonamid;
• Diacyl-dioxohexahydro-1,3,5-triazine, z.B. 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin.

Can also be used as bleach activators

• N-diacylated and N, N'-tetracylated amines, for example N, N, N ', N'-tetraacetylmethylene diamine and ethylenediamine (TAED), N, N-diacetylaniline, N, N-diacetyl-p-toluidine or 1,3 -diacylated hydantoins such as 1,3-diacetyl-5,5-dimethylhydantoin;
• N-alkyl-N-sulfonyl-carbonamides, for example N-methyl-N-mesyl-acetamide or N-methyl-N-mesyl-benzamide;
• N-acylated cyclic hydrazides, acylated triazoles or urazoles, for example monoacetyl-maleic acid hydrazide;
• O, N, N-trisubstituted hydroxylamines, for example O-benzoyl-N, N-succinylhydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine or O, N, N-triacetalhydroxylamine;
• N, N'-diacylsulfurylamide, for example N, N'-dimethyl-N, N'-diacetylsulfurylamide or N, N '-diethyl-N, N'-dipropionylsulfurylamide;
• Triacyl cyanurates, for example triacetyl cyanurate or tribenzoyl cyanurate;
• Carboxylic anhydrides, for example benzoic anhydride, m-chlorobenzoic anhydride or phthalic anhydride;
• 1,3-diacyl-4,5-diacyloxy-imidazolines, for example 1,3-diacetyl-4,5-diacetoxyimidazoline;
• Tetraacetylglycoluril and tetrapropionylglycoluril;
• diacylated 2,5-diketopiperazines, for example 1,4-diacetyl-2,5-diketopiperazine;
• Acylation products of propylene diurea and 2,2-dimethylpropylene diurea, for example tetraacetyl propylene diurea;
• α-acyloxy-polyacyl-malonamides, for example α-acetoxy-N, N'-diacetylmalonamide;
• Diacyl-dioxohexahydro-1,3,5-triazines, e.g. 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine.

Also suitable as bleach activators are 2-alkyl or 2-aryl- (4H) -3,1-benzoxazin-4-one, as for example in the EP-B 332 294 and EP-B 502 013 are described. In particular are 2-phenyl- (4H) -3,1-benzoxazin-4-one and 2-methyl- (4H) -3,1-benzoxazin-4-one usable.

Mainly active oxygen releasing agents come as bleaching agents inorganic peroxo compounds into consideration. such Peroxo compounds are, in particular, alkali metal perborates such as Sodium perborate tetrahydrate and sodium perborate monohydrate, also alkali metal carbonate perhydrates such as sodium carbonate perhydrate ("Sodium percarbonate") and hydrogen peroxide.

Mostly in addition to these inorganic peroxo compounds, the bleaching system of the detergent formulation can contain inorganic or organic peracids, especially percarboxylic acids, for example C ₁ - to C ₁₂ -percarboxylic acids, C ₈ - to C ₁₆ -dipercarboxylic acids, imidopercaproic acids or aryldipercaproic acids. Preferred examples of usable acids are peracetic acid, linear or branched octanoic, nonanoic, decanoic or dodecane monoperacids, decanoic and dodecanediperic acid, mono- and diperphthalic acids, isophthalic acids and terephthalic acids, phthalimidopercaproic acid and terephthaloyl diamidopercaproic acid. These percarboxylic acids can be used as free acids or as salts of the acids, preferably alkali or alkaline earth metal salts.

Other components of the bleaching system of the invention Textile detergent formulation can be bleaching catalysts and / or Be bleach stabilizers.

Quaternized imines are usually used as bleaching catalysts or sulfonimines used, such as in US-A 5 360 568, US-A 5 360 569 and EP-A 453 003 are described, as well as manganese complexes, as described for example in WO-A 94/21777 are described. Other usable metal-containing Bleaching catalysts are described in EP-A 458 397, EP-A 458 398 and EP-A 549 272. Bleaching catalysts are usually used in amounts of up to 1% by weight, in particular 0.01 to 0.5% by weight, based on the detergent formulation used.

Bleach stabilizers are additives that are used in bleaching adsorb, bind or complex disturbing traces of heavy metals can. In particular, this becomes the usual complexing agent in the form of the acids or as partially or fully neutralized Alkali metal salts in amounts of up to 1% by weight, in particular 0.01 to 0.5% by weight, based on the detergent formulation, used.

Common nonionic or anionic surfactants can be used as surfactants used alone or mixtures thereof.

Suitable anionic surfactants are, for example, fatty alcohol sulfates of fatty alcohols having 8 to 22, preferably 10 to 18 carbon atoms, for example C ₉ to C ₁₁ alcohol sulfates, C ₁₂ to C ₁₃ alcohol sulfates, cetyl sulfate, myristyl sulfate, palmityl sulfate, stearyl sulfate and tallow fatty alcohol sulfate.

Other suitable anionic surfactants are sulfated ethoxylated C ₈ to C ₂₂ alcohols (alkyl ether sulfates) or their soluble salts. Compounds of this type are prepared, for example, by first alkoxylating a C ₈ to C ₂₂ , preferably a C ₁₀ to C ₁₈ alcohol, for example a fatty alcohol, and then sulfating the alkoxylation product. Ethylene oxide is preferably used for the alkoxylation, 2 to 50, preferably 3 to 20, moles of ethylene oxide being used per mole of fatty alcohol. However, the alkoxylation of the alcohols can also be carried out using propylene oxide alone and, if appropriate, butylene oxide. Alkoxylated C ₈ to C ₂₂ alcohols which contain ethylene oxide and propylene oxide or ethylene oxide and butylene oxide are also suitable. The alkoxylated C ₈ or to C ₂₂ alcohols can contain the ethylene oxide, propylene oxide and butylene oxide units in the form of blocks or in statistical distribution.

Other suitable anionic surfactants are alkane sulfonates such as C ₈ to C ₂₄ , preferably C ₁₀ to C ₁₈ alkane sulfonates, and soaps such as the salts of C ₈ to C ₂₄ carboxylic acids.

Further suitable anionic surfactants are C ₉ to C ₂₀ linear alkylbenzenesulfonates (LAS).

Further suitable anionic surfactants are N-acyl sarcosinates with aliphatic saturated or unsaturated C ₈ to C ₂₅ acyl residues, preferably C ₁₀ to C ₂₀ acyl residues, for example N-oleoylsarcosinate.

The anionic surfactants become the detergent formulation preferably added in the form of salts. Suitable cations in these salts are alkali metal ions such as sodium, potassium and lithium and ammonium ions.

Of the anionic surfactants mentioned are linear alkylbenzenesulfonates and fatty alcohol sulfates of particular interest.

Examples of suitable nonionic surfactants are alkoxylated C ₈ to C ₂₂ alcohols, such as fatty alcohol alkoxylates or oxo alcohol alkoxylates. The alkoxylation can be carried out using ethylene oxide, propylene oxide and / or butylene oxide. All alkoxylated alcohols which contain at least two molecules of an alkylene oxide mentioned above can be used as the surfactant. Here too, block polymers of ethylene oxide, propylene oxide and / or butylene oxide come into consideration or addition products which contain the alkylene oxides mentioned in a statistical distribution. As a rule, 2 to 50, preferably 3 to 20, mol of at least one alkylene oxide are used per mol of alcohol. Preferably used as the alkylene oxide is ethylene oxide. The alcohols preferably have 10 to 18 carbon atoms.

Another class of suitable nonionic surfactants are alkylphenol ethoxylates with C ₆ to C ₁₄ alkyl chains and 5 to 30 moles of ethylene oxide units.

Another class of nonionic surfactants are alkyl polyglucosides with 8 to 22, preferably 10 to 18 carbon atoms, in the Alkyl chain. These compounds usually contain 1 to 20, preferably 1.1 to 5 glucoside units.

wobei R¹⁵ C₆- bis C₂₂-Alkyl, R¹⁶ H oder C₁- bis C₄-Alkyl und R¹⁷ ein Polyhydroxyalkyl-Rest mit 5 bis 12 C-Atomen und mindestens 3 Hydroxygruppen ist. Vorzugsweise ist R¹⁵ C₁₀- bis C₁₈-Alkyl, R¹⁶ Methyl und R¹⁷ ein C₅- oder C₆-Rest. Beispielsweise erhält man derartige Verbindungen durch die Acylierung von reduzierend aminierten Zuckern mit Säurechloriden von C₁₀- bis C₁₈-Carbonsäuren.Another class of nonionic surfactants are N-alkyl glucamides of general structure VIII or IX

where R ^{15 is} C ₆ to C ₂₂ alkyl, R ¹⁶ H or C ₁ to C ₄ alkyl and R ^{17 is} a polyhydroxyalkyl radical having 5 to 12 C atoms and at least 3 hydroxy groups. R ¹⁵ is preferably C ₁₀ to C ₁₈ alkyl, R ^{16 is} methyl and R ^{17 is} a C ₅ or C ₆ radical. For example, such compounds are obtained by the acylation of reducing aminated sugars with acid chlorides of C ₁₀ to C ₁₈ carboxylic acids.

The textile detergent formulation according to the invention preferably contains as nonionic surfactants with 3 to 12 moles of ethylene oxide ethoxylated C ₁₀ to C ₁₆ alcohols, in particular ethoxylated fatty alcohols and / or ethoxylated oxo alcohols.

The textile detergent formulation according to the invention can be used as an additional component usual graying inhibitors and / or Soil release polymers in the usual amounts for this (about 0.1 up to 2% by weight).

• Polyester aus Polyethylenoxiden mit Ethylenglycol und/oder Propylenglycol und aromatischen Dicarbonsäuren oder aromatischen und aliphatischen Dicarbonsäuren;
• Polyester aus einseitig endgruppenverschlossenen Polyethylenoxiden mit zwei- und/oder mehrwertigen Alkoholen und Dicarbonsäure.

Suitable soil release polymers and / or graying inhibitors for detergents are, for example:

• Polyesters of polyethylene oxides with ethylene glycol and / or propylene glycol and aromatic dicarboxylic acids or aromatic and aliphatic dicarboxylic acids;
• Polyester made of polyethylene oxides which are end group-capped with di- and / or polyhydric alcohols and dicarboxylic acid.

Such polyesters are known, for example from US-A 3 557 039, GB-A 1 154 730, EP-A 185 427, EP-A 241 984, EP-A 241 985, EP-A 272 033 and US-A 5 142 020.

Other suitable soil release polymers are amphiphilic grafters Copolymers of vinyl and / or acrylic esters on polyalkylene oxides (see US-A 4 746 456, US-A 4 846 995, DE-A 37 11 299, US-A 4 904 408, US-A 4 846 994 and US-A 4 849 126) or modified Celluloses such as Methyl cellulose, hydroxypropyl cellulose or carboxymethyl cellulose.

As a further additional component, the invention Textile detergent formulation usual color transfer inhibitors in the usual amounts for this (about 0.1 to 2% by weight) contain.

Color transfer inhibitors are, for example, homo- and Copolymers of vinyl pyrrolidone, vinyl imidazole, vinyl oxazolidone and 4-vinylpyridine-N-oxide with molecular weights of 15,000 to 100,000 and cross-linked, finely divided polymers based on of these monomers used. The use mentioned here Polymers is known, cf. DE-B 22 32 353, DE-A 28 14 287, DE-A 28 14 329 and DE-A 43 16 023.

As a further additional component, the invention Textile detergent formulation usual enzymes (usually in ready-made form) in the usual quantities (approx. 0.1 up to 3% by weight).

Suitable enzymes are primarily proteases, lipases, amylases, Cellulases and peroxidases; preferably be used for detergents optimized enzymes effective in the alkaline medium. Enzymes which are particularly preferred are those which are effective against bleaching agents are stable.

Examples of suitable proteases are alkalase, savinase, Durazym and Esperase (Novo), Maxatase (Int. Bio-Synthetics Inc.), FN-base (Genencor) and Opticlean (MCK). Examples of suitable lipases are Lipolase and Lipolase Ultra (Novo). Examples of suitable cellulases are Carezyme and Celluzyme (Novo). Examples of suitable amylases are termamyl and Duramyl (Novo).

As a further additional component, the invention Textile detergent formulation usual optical brighteners in the usual quantities included for this.

Dinatrium-4,4'-bis(2-diethanolamino-4-anilino-s-triazin-6-ylamino)stilben-2,2'-disulfonat,

Dinatrium-4,4'-bis(2-morpholino-4-anilino-s-triazin-6-ylamino) stilben-2,2'-disulfonat,

Dinatrium-4,4'-bis(2,4-dianilino-s-triazin-6-ylamino)stilben-2,2'-disulfonat,

Mononatrium-4',4''-bis(2,4-dianilino-s-triazin-6-ylamino)stilben-2-sulfonat,

Dinatrium-4,4'-bis(2-anilino-4(N-methyl-N-2-hydroxyethylamino)-striazin-6-ylamino)stilben-2,2'-sulfonat,

Dinatrium-4,4'-bis(4-phenyl-2,1,3-triazol-2-yl)stilben-2,2'-disulfonat,

Dinatrium-4,4'-bis(2-anilino-4(1-methyl-2-hydroxyethylamino)-striazin-6-ylamino)stilben-2,2'-disulfonat und

Natrium-2(stilbyl-4''(naphtho-1',2',4,5)-1,2,3-triazol)-2-sulfonat.

Examples of common anionic optical brighteners are:

Disodium 4,4'-bis (2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate,

Disodium 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate,

Disodium 4,4'-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate,

Monosodium 4 ', 4''- bis- (2,4-dianilino-s-triazin-6-ylamino) stilbene-2-sulfonate,

Disodium 4,4'-bis (2-anilino-4 (N-methyl-N-2-hydroxyethylamino) -s-triazine-6-ylamino) stilbene-2,2'-sulfonate,

Disodium 4,4'-bis (4-phenyl-2,1,3-triazol-2-yl) stilbene-2,2'-disulfonate,

Disodium 4,4'-bis (2-anilino-4 (1-methyl-2-hydroxyethylamino) striazin-6-ylamino) stilbene 2,2'-disulfonate and

Sodium-2 (stilbyl-4 '' (naphtho-1 ', 2', 4,5) -1,2,3-triazol) -2-sulfonate.

Furthermore, the textile detergent formulation according to the invention alkaline additives, especially sodium carbonate and / or Sodium bicarbonate, in amounts of up to 40% by weight, in particular 1 to 25 wt .-%, and adjusting agents, in particular Alkali metal sulfates such as sodium sulfate, in amounts of up to 60% by weight, in particular 1 to 30% by weight, contain.

Further additives to the textile detergent formulation according to the invention can be: foam dampers, corrosion inhibitors, clays, Bactericides, phosphonates, abrasives, dyes and encapsulated and unencapsulated perfumes.

The textile detergent formulation according to the invention is preferably in powder or granulate form with a bulk density from 200 to 1,100 g / l. However, they are also liquid formulations possible.

The textile detergent formulation according to the invention can Bleach activators included so that they are pure Components or as pre-assembled with suitable additives Components distributed in the powder or granule of the detergent are included, or so that the bleach activators as pure components or as pre-assembled with suitable additives Components as from the other detergent ingredients separated powder or granules are present. The Incorporation of the bleach activators as separate powder or Granules, in particular as pre-assembled with suitable additives Product, allows the gentle production of Detergents with particularly good bleach activator stability.

Non-compacted powder or granular detergents have a low bulk density, usually from 200 to 600 g / l. You can use a phosphate-based builder system contain, be reduced in phosphate or be free of phosphate.

Compositions in% by weight of non-compacted powder or granular detergents for the purposes of the present invention:

Phosphate-based heavy-duty detergents have the following composition, for example: 15 to 60% Phosphate, preferably trisodium polyphosphate 5 to 35% surfactants 0.5 to 6% Bleach activators 5 to 25% inorganic peroxo compounds as bleach 5 to 50% Adjusting agent, preferably sodium sulfate ad 100 other ingredients.

Detergents of this type are usually with 4 to 15 g / l dosed.

For example, low-phosphate heavy-duty detergents have the following composition: 0.5 to 40% Phosphate, preferably trisodium polyphosphate 2 to 20% Zeolites, layered silicates, polycarboxylates or aminopolycarboxylates or mixtures thereof 5 to 35% surfactants 0.5 to 6% Bleach activators 5 to 25% inorganic peroxo compounds as bleach 5 to 50% Adjusting agent, preferably sodium sulfate ad 100 other ingredients.

Detergents of this type are usually with 4 to 15 g / l dosed.

Phosphate-free heavy duty detergents have the following composition, for example: 15 to 70% Zeolites, layered silicates, polycarboxylates or aminopolycarboxylates or mixtures thereof 5 to 35% surfactants 0.5 to 6% Bleach activators 5 to 25% inorganic peroxo compounds as bleach 5 to 50% Adjusting agent, preferably sodium sulfate ad 100 other ingredients.

Detergents of this type are usually with 4 to 15 g / l dosed.

Compact detergents usually have a high bulk density from 550 to 1,100 g / l. You can build a system based on it possess of phosphate, be reduced in phosphate or be free of phosphate.

Compositions in% by weight of compacted powder or granular detergents for the purposes of the present invention:

Phosphate-based compact detergents have the following composition, for example: 10 to 60% Phosphate, preferably trisodium polyphosphate 5 to 35% surfactants 0.5 to 6% Bleach activators 10 to 25% inorganic peroxo compounds as bleach ad 100 other ingredients.

Detergents of this type are usually with 2.5 to 7 g / l dosed.

Phosphate-reduced compact detergents have the following composition, for example: 2 to 40% Phosphate, preferably trisodium polyphosphate 2 to 20% Zeolites, layered silicates, polycarboxylates or aminopolycarboxylates or mixtures thereof 5 to 35% surfactants 0.5 to 6% Bleach activators 10 to 25% inorganic peroxo compounds as bleach ad 100 other ingredients.

Detergents of this type are usually with 2.5 to 7 g / l dosed.

Phosphate-free compact detergents have the following composition, for example: 15 to 70% Zeolites, layered silicates, polycarboxylates or aminopolycarboxylates or mixtures thereof 5 to 35% surfactants 0.5 to 6% Bleach activators 10 to 25% inorganic peroxo compounds as bleach ad 100 other ingredients.

Detergents of this type are usually with 2.5 to 7 g / l dosed.

A) biologisch weitgehend abbaubaren aliphatischen oder alicyclischen Aminen mit 1 bis 12 C-Atomen, welche zusätzlich Hydroxylgruppen tragen können, und

B) auf Schwermetallionen komplexierend wirkenden Komplexbildnern

im Gew.-Verhältnis A:B von 1:20 bis 20:1, insbesondere von 1:5 bis 5:1, zur effizienten Stabilisierung des Bleichsystems auf Basis von Wasserstoffperoxid, Peroxoverbindungen und/oder Persäuren in Wasch- und Reinigungsmittel-Formulierungen.The use of the aforementioned mixture of the amines A and the complexing agents B in detergent and cleaning agent formulations containing bleach, in particular textile detergent formulations, leads to an effective stabilization of the bleaching system. The present invention therefore also relates to the use of a mixture of

A) largely biodegradable aliphatic or alicyclic amines having 1 to 12 carbon atoms, which can additionally carry hydroxyl groups, and

B) complexing agents having a complexing action on heavy metal ions

in a weight ratio A: B of 1:20 to 20: 1, in particular from 1: 5 to 5: 1, for efficient stabilization of the bleaching system based on hydrogen peroxide, peroxo compounds and / or peracids in detergent and cleaning agent formulations.

For an efficient stabilization of the bleaching system in the sense It is important in the present invention that the amines A at least partially in free, i.e. not protonated form alongside the other components of the formulation in the aqueous washing or detergent fleet. It is an advantage if the total amount of amines A to the total amount of proton donating Groups (e.g. COOM) in complexing agents B in non-stoichiometric Relationship stands; a stoichiometric excess Amines A to the proton donating groups in B are preferred in particular from 10 to 300%, especially from 50 to 150%.

The following examples are intended to illustrate the invention without restricting them. The efficiency of the Bleach stabilization according to the invention in a conventional Textile detergent formulation made clear.

Examples

A zeolite-containing model detergent formulation (Formulation A) was mixed with the amounts of complexing agents and heavy metal ions given below. In formulation A, bleach activators were not added because they have no influence on bleach stabilization. The stabilizing effect of the complexing agent after storage of the heavy metal-containing washing liquor at elevated temperature for one hour was determined by titration of the hydrogen peroxide still present in the liquor with potassium permanganate. Without the addition of a complexing agent, the hydrogen peroxide content had dropped to about 20% of the initial value after storage at 60 ° C. for one hour. Formulation A (in% by weight): Dedecylbenzolsulfonsäure sodium salt 12.5 C ₁₃ / C ₁₅ oxo alcohol, reacted with 7 moles of ethylene oxide 4.7 Soap 2.8 Zeolite A 25.0 sodium 12.0 magnesium silicate 1.0 sodium disilicate 4.5 Acrylic acid / maleic acid copolymer, MW = 70,000 5.0 Sodium perborate 4-hydrate 20.0 sodium sulphate 12.5 x complexing x 100 test conditions: Dosage: 6 g / l of formulation A Water hardness: 2.5 mmol Ca / Mg 3/1 (14 ° dH) pH of the wash liquor: 10.9 The washing liquor is stored at 60 ° C. for 1 hour Metal salt additives: 8.33 ppm iron (III) chloride 0.83 ppm manganese (II) sulfate 0.84 ppm copper (II) sulfate test results: Addition to formulation A Quantity x
(in% by weight) stöchiometr. Excess amine to COONa
(in %) H ₂ O ₂ stabilization
(in% of the initial value) Example 1:
Mixture of NTA (as tri-Na salt monohydrate) and triethanolamine in a weight ratio of 25:75 1.0 84 57.5 Example 2:
Mixture of EDTA (as di-sodium salt dihydrate) and triisopropanolamine in a weight ratio of 25:75 1.0 95 54.8 Example 3:
Mixture of α-ADA (as tri-Na salt monohydrate) and triethanolamine in a weight ratio of 25:75 1.0 94 56.7 Example 4:
Mixture of IDA (as di-Na salt monohydrate) and triethanolamine in a weight ratio of 20:80 1.0 75 55.6 For comparison: No addition 0 20.5 Example A:
NTA, EDTA, α-ADA or IDA (as in Ex. 1-4) each alone 0.25 21-24 Example B
Triethanolamine alone 0.75 40.6 Example C
NTA, EDTA, α-ADA or IDA (as in Ex. 1-4) each alone 1.0 33-36 Example D
Triethanolamine alone 1.0 42.0

It is clearly evident from the test results above that when the mixture of amines A and complexing agents B is used, the stability of the H ₂ O ₂ -containing formulation increases. In comparative examples A and B, the proportionate amounts of complexing agent or triethanolamine (with regard to Examples 1-3) were used individually. In comparative examples C and D, complexing agents or triethanolamine were used individually in each case in the same quantity to form the mixture from Examples 1-4. In all comparisons, the effectiveness of the mixture of complexing agents and amines was not achieved.

Claims (8)

1. A detergent formulation comprising, as well as further, customary ingredients, a bleaching system based on hydrogen peroxide, peroxo compounds and/or peracids and also a mixture comprising

   (A) substantially biodegradable aliphatic or alicyclic amines having from 1 to 12 carbon atoms with or without hydroxyl substitution, and

   (B) complexing agents for heavy metal ions,

   the weight ratio of A:B being within the range from 1:20 to 20:1, especially within the range from 1:5 to 5:1.
2. A detergent formulation as claimed in claim 1, containing the mixture comprising the amines A and the complexing agents B in an amount from 0.1 to 10 % by weight, especially from 0.2 to 3 % by weight, based on the total amount of the formulation.
3. A laundry detergent formulation as recited in claim 1 or 2.
4. A detergent formulation as claimed in any of claims 1 to 3, wherein amines A are selected from trialkanolamines having from 6 to 9 carbon atoms.
5. A detergent formulation as claimed in any of claims 1 to 4, wherein complexing agents B are selected from aminocarboxylates.
6. A detergent formulation as claimed in claim 5, wherein complexing agents B are selected from aminocarboxylates having one or more groups of the formula

   

   where M is hydrogen, an alkali metal or unsubstituted ammonium.
7. The use of a mixture comprising

   (A) substantially biodegradable aliphatic or alicyclic amines having from 1 to 12 carbon atoms with or without hydroxyl substitution, and

   (B) complexing agents for heavy metal ions,

   the weight ratio of A:B being within the range from 1:20 to 20:1, especially within the range from 1:5 to 5:1, for efficient stabilization of the bleaching system based on hydrogen peroxide, peroxo compounds and/or peracids in detergent formulations.
8. A process for efficient stabilization of the bleaching system based on hydrogen peroxide, peroxo compounds and/or peracids in detergent formulations, which comprises mixing a mixture comprising

   (A) substantially biodegradable aliphatic or alicyclic amines having from 1 to 12 carbon atoms with or without hydroxyl substitution, and

   (B) complexing agents for heavy metal ions,

   the weight ratio of A:B being within the range from 1:20 to 20:1, especially within the range from 1:5 to 5:1, with the bleaching system and further, customary ingredients of detergent formulations.