DE69727983T2 - A DETERGENT COMPOSITION - Google Patents

Abstract

The present invention relates to detergent compositions comprising anionic mid-branched surfactant compounds and a bleaching system comprising a hydrophobic and a hydrophilic bleach precursor. The compositions are particularly useful as solid laundry detergent compositions.

Description

technical area

The The present invention relates to detergent compositions which are anionic mid-branched surfactant compounds and a bleach system comprising a hydrophobic and a hydrophilic bleach precursor. The compositions are as solid laundry detergent compositions especially useful.

background the invention

In front recently a particular new type of anionic mid-chain branched Surfactants have been developed. These surfactants are in the same time pending Applications WO 97/38557, WO 97/39090, WO 97/38956, WO 97/34597 and WO 97/38972 described.

It it has been found that this mid-chain branched surfactants are excellent surfactants, in particular for use in laundry products, especially under washing conditions of cool or cold water, even as low as 20 ° C-5 ° C. It is also been found that the Combination of two or more of these mid-chain branches Surfactants can provide a surfactant mixture which has an even higher surface activity and a better solubility in water at low temperature.

A Component, which is traditionally used in most cleaning products is present, is a bleach. Different bleaching systems are been developed in recent decades, such as bleaching systems based on organic peroxyacids. The organic peroxyacids are often by the in situ perhydrolysis of organic peroxyacid bleach precursor compounds (Bleach activators).

however is well known that a Variety of other detergent ingredients commonly found in a detergent, not always (completely) bleach compatible are, for example, certain surfactants, perfumes and enzymes. These ingredients can react with the bleach, resulting in a reduction in performance resulting in both the bleaching agent and these ingredients. It is therefore desirable To formulate cleansers containing as little bleach as include, to get excellent bleaching performance, and the detergents to formulate with bleach-compatible ingredients.

It it has now been established that these medium-chain branched surfactants are very pale compatible. Besides that is been found that with Detergent compositions comprising these mid-chain branched Surfactants and a mixed bleaching system comprising hydrophobic and hydrophilic bleach precursors, a excellent bleaching and cleaning performance is achieved, even when small amounts of bleach are used. It is surprising has been found that hydrophilic and hydrophobic, bleachable and non-bleachable stains and / or Pollutions are removed more effectively. Without a theory to be bound, it is believed that this is due to the excellent Stain and dirt removal by the mid-chain branching Surfactant is due, which gives access to the remaining bleachable spots and Dirt from the hydrophobic and hydrophilic bleach facilitates and allows these Bleach these remaining bleachable stains very effective bleaching. Another additional Advantage is that through reducing the amount of bleach which is good for Bleaching performance is required, the simplicity of the formulation can be improved and the formulation costs are reduced can.

Summary of the invention

• a) mindestens 0,5, vorzugsweise mindestens 5, mehr bevorzugt mindestens 10 Gew.-% der Zusammensetzung eines Tensidsystems, umfassend eine oder mehrere längeralkylkettige, mittelkettigverzweigte Tensidverbindungen der Formel: Ab-X-B worin:
• (I) A^b eine hydrophobe mittelkettigverzweigte Alkyleinheit mit insgesamt 9 bis 22 Kohlenstoffen, vorzugsweise 12 bis 18, in der Einheit ist, mit: (1) einer Längsten linearen Kohlenstoffkette, gebunden an die -X-B-Einheit im Bereich von 8 bis 21 Kohlenstoffatomen; (2) einer oder mehreren C₁-C₃-Alkyleinheiten, welche von dieser längsten linearen Kohlenstoffkette abzweigen; (3) wobei mindestens eine der abzweigenden Alkyleinheiten direkt an einen Kohlenstoff der längsten linearen Kohlenstoffkette gebunden ist an einer Position innerhalb des Bereiches des Position 2-Kohlenstoffs, gezählt vom Position 1-Kohlenstoff (#1), welcher an die -X-B-Einheit gebunden ist, zu der Position des endständigen Kohlenstoffs minus 2 Kohlenstoffen (der (ω-2)-Kohlenstoff); und (4) wobei, wenn mehr als eine dieser Verbindungen vorliegt, die durchschnittliche Gesamtanzahl an Kohlenstoffatomen in den A^b-X-Einheiten in der obigen Formel innerhalb des Bereichs von größer als 14,5 bis 18, vorzugsweise 15 bis 17, liegt;
• (II) B eine hydrophile Einheit ist, gewählt aus Sulfaten, Sulfonaten,Aminoxiden, Polyoxyalkylen, vorzugsweise Polyoxyethylen und Polyoxypropylen, alkoxylierten Sulfaten, Polyhydroxyeinheiten, Phosphatestern, Glycerinsulfonaten, Polygluconaten, Polyphosphatestern, Phosphonaten, Sulfosuccinaten, Sulfosuccaminaten, polyalkoxylierten Carboxylaten, Glucamiden, Taurinaten, Sarcosinaten, Glycinaten, Isethionaten, Dialkanolamiden, Monoalkanolamiden, Monoalkanolamidsulfaten, Diglykolamiden, Diglykolamid sulfaten, Glycerinestern, Glycerinestersulfaten, Glycerinethern, Glycerinethersulfaten, Polyglycerinethern, Polyglycerinethersulfaten, Sorbitanestern, polyalkoxylierten Sorbitanestern, Ammonioalkansulfonaten, Amidopropylbetainen, allcylierten Quats, alkylierten/polyhydroxyalkylierten Quats, alkylierten Quats, allcylierten/polyhydroxylierten Oxypropylquats, Imidazolinen, 2-yl-Succinaten, sulfonierten Alkylestern und sulfonierten Fettsäuren; und
• (III) X aus -CH₂- und -C(O)- gewählt ist; und
• b) mindestens 0,5 Gew.-% der Zusammensetzung eines Bleichsystems, umfassend
• (I) einen hydrophoben Bleichvorläufer; und
• (II) einen hydrophilen Bleichvorläufer.

The invention relates to detergent compositions comprising

• a) at least 0.5, preferably at least 5, more preferably at least 10% by weight of the composition of a surfactant system comprising one or more longer alkyl chain, mid-chain branched surfactant compounds of the formula: A b XB wherein:
• (I) A ^{b is} a hydrophobic mid-chain branched alkyl moiety having a total of 9 to 22 carbons, preferably 12 to 18, in the moiety, having: (1) a longest linear carbon chain attached to -XB unit in the range of 8 to 21 carbon atoms; (2) one or more C ₁ -C ₃ alkyl moieties branching from this longest linear carbon chain; (3) wherein at least one of the branching alkyl moieties is bonded directly to a carbon of the longest linear carbon chain at a position within the region of the position 2 carbon counted from the position 1 carbon (# 1) attached to the -XB moiety is to the position of the terminal carbon minus 2 carbons (the (ω-2) carbon); and (4) when more than one of these compounds is present, the average total number of carbon atoms in the A ^b -X units in the above formula is within the range of greater than 14.5 to 18, preferably 15 to 17;
• (II) B is a hydrophilic unit selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, preferably polyoxyethylene and polyoxypropylene, alkoxylated sulfates, polyhydroxy units, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccinates, polyalkoxylated carboxylates, glucamides, taurinates, sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalkanolamide sulfates, diglycolamides, Diglykolamid sulfates, allcylierten Glycerinestern, Glycerinestersulfaten, glycerol ethers, glycerol ether, polyglycerol ethers Polyglycerinethersulfaten, sorbitan esters, polyalkoxylated sorbitan esters, ammonioalkanesulfonates, amidopropyl betaines, allcylierten quats, alkyated / polyhydroxyalkylated quats, alkylated quats, / polyhydroxylated oxypropyl quats, imidazolines, 2-yl succinates, sulfonated alkyl esters and sulfonated fatty acids; and
• (III) X is selected from -CH ₂ - and -C (O) -; and
• b) at least 0.5% by weight of the composition of a bleaching system comprising
• (I) a hydrophobic bleach precursor; and
• (II) a hydrophilic bleach precursor.

Full Description of the invention

 Containing surfactant system mid-chain branched surfactant compounds

The Detergent compositions according to the invention include at least 0.5, preferably at least 5, more preferably at least 10% by weight of the composition of a surfactant system comprising längeralkylkettige, mid-chain branched surfactant compounds selected from the group consisting from surfactant compounds having the formula defined above.

worin die Gesamtanzahl an Kohlenstoffatomen in der verzweigten primären Alkyleinheit dieser Formel (einschließlich der R-, R¹- und R²-Verzweigung) 13 bis 19 beträgt; R, R¹ und R² jeweils unabhängig gewählt sind aus Wasserstoff und C₁-C₃-Alkyl (vorzugsweise Methyl), mit der Maßgabe, daß R, R¹ und R² nicht alle Wasserstoff sind, und, wenn z 0 ist, mindestens R oder R¹ nicht Wasserstoff ist; w eine ganze Zahl von 0 bis 13 ist; x eine ganze Zahl von 0 bis 13 ist; y eine ganze Zahl von 0 bis 13 ist; z eine ganze Zahl von 0 bis 13 ist; und w+x+y+z 7 bis 13 ist.Preferred surfactant systems herein include longer alkyl chain, mid-chain branched surfactant compounds of the above formula wherein the A ^b moiety is a branched primary alkyl moiety of the formula:

wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula (including the R, R ¹ and R ² branch) is 13 to 19; R, R ¹ and R ^{2 are} each independently selected from hydrogen and C ₁ -C ₃ alkyl (preferably methyl), with the proviso that R, R ¹ and R ^{2 are} not all hydrogen, and when z is 0, at least R or R ^{1 is} not hydrogen; w is an integer from 0 to 13; x is an integer of 0 to 13; y is an integer of 0 to 13; z is an integer of 0 to 13; and w + x + y + z is 7 to 13.

In general, for the mid-chain branched surfactant compounds of the surfactant system, certain branching points (eg, the position along the chain of R, R ¹ and / or R ² units in the above formula) are preferred over other branching points along the backbone of the surfactant. The following formula illustrates the mid-chain branching region (ie, where the branching points occur), the preferred mid-chain branching region, and the more preferred mid-chain branching region for monomethyl-branched A ^b alkyl moieties which are useful in the present invention.

It should be noted that for the monomethyl substituted surfactants, these ranges are the two exclude terminal carbon atoms of the chain and the carbon atom immediately adjacent to the -XB group.

The following formula illustrates the mid-chain branching region, the preferred mid-chain branching region, and the more preferred mid-chain branching region for dimethyl-substituted A ^b alkyl moieties which are useful in the present invention.

Preferred are surfactant compounds wherein in the above formula the A ^b moiety has no quaternary substituted carbon atoms (ie, 4 carbon atoms directly attached to a carbon atom).

The most preferred mid-chain branched surfactant compounds for use in the detergent compositions herein are mid-chain branched primary Alkyl sulfonate and more preferably alkyl sulfate surfactants. It should Of course be that for the purpose the invention may be preferred that the surfactant system is a mixture from two or more mid-chain branched primary alkyl sulfate or sulfonate surfactants.

preferred mid-chain branched primary Alkyl sulfate surfactants correspond to the formula

These Surfactants have a linear primary alkyl sulfate chain backbone (i.e. the longest linear carbon chain containing the sulfated carbon atom includes) which preferably comprises 12 to 19 carbon atoms, and their branched primary Alkyl units preferably comprise a total of at least 14 and preferably not more than 20 carbon atoms. In the surfactant system, comprising more than one of these sulfate surfactants, the average Total number of carbon atoms for the branched primary alkyl moieties preferably within the range of greater than 14.5 to 17.5. consequently comprises the surfactant system preferably at least one branched primary alkyl sulfate surfactant compound with a longest linear carbon chain of not less than 12 carbon atoms or not more than 19 carbon atoms, and the total number of Carbon atoms, including of branching, must be at least 14, and still the average total on carbon atoms for the branched primary Alkyleinheit within the range of greater than 14.5 to 17.5.

R, R ¹ and R ² are each independently selected from hydrogen and a C ₁ -C ₃ alkyl group (preferably hydrogen or C ₁ -C ₂ alkyl, more preferably hydrogen or methyl, and most preferably methyl), provided that R, R ¹ and R ^{2 are} not all hydrogen. Furthermore, when z is 1, at least R or R ^{1 is} not hydrogen.

worin R³, R⁴, R⁵ und R⁶ unabhängig Wasserstoff, C₁-C₂₂-Alkylen, verzweigtes C₄-C₂₂-Alkylen, C₁-C₆-Alkanol, C₁-C₂₂-Alkenylen, verzweigtes C₄-C₂₂-Alkenylen und Mischungen hiervon sind. Bevorzugte Kationen sind Ammonium (R³, R⁴, R⁵ und R⁶ entsprechen Wasserstoff), Natrium, Kalium, Mono-, Di- und Trialkanolammonium und Mischungen hiervon. In den erfindungsgemäßen Monoalkanolammoniumverbindungen entspricht R³ C₁-C₆-Alkanol, und entsprechen R⁴, R⁵ und R⁶ Wasserstoff; in den erfindungsgemäßen Dialkanolammoniumverbindungen entsprechen R³ und R⁴ C₁-C₆-Alkanol, und entsprechen R⁵ und R⁶ Wasserstoff; in den erfindungsgemäßen Trialkanolammoniumverbindungen entsprechen R³, R⁴ und R⁵ C₁-C₆-Alkanol, und entspricht R⁶ Wasserstoff. Bevorzugte Alkanolammoniumsalze der vorliegenden Erfindung sind die quaternären Mono, Di- und Triammoniumverbindungen der Formeln: M is hydrogen or a salt-forming cation, depending on the synthetic method. Examples of salt-forming cations are lithium, sodium, potassium, calcium, magnesium and quaternary alkylamines of the formula

in which R ³ , R ⁴ , R ⁵ and R ^{6 are} each independently hydrogen, C ₁ -C ₂₂ -alkylene, branched C ₄ -C ₂₂ -alkylene, C ₁ -C ₆ -alkanol, C ₁ -C ₂₂ -alkenylene, branched C ₄ -C ₂₂ alkenylene and mixtures thereof. Preferred cations are ammonium (R ³ , R ⁴ , R ⁵ and R ⁶ are hydrogen), sodium, potassium, mono-, di- and trialkanolammonium and mixtures thereof. In the monoalkanolammonium compounds according to the invention, R ³ corresponds C ₁ -C ₆ alkanol, and R ⁴ , R ⁵ and R ^{6 are} hydrogen; in the dialkanolammonium compounds according to the invention R ³ and R ⁴ correspond to C ₁ -C ₆ -alkanol, and R ⁵ and R ⁶ correspond to hydrogen; in the trialkanolammonium compounds according to the invention, R ³ , R ⁴ and R ⁵ correspond to C ₁ -C ₆ -alkanol and R ⁶ corresponds to hydrogen. Preferred alkanolammonium salts of the present invention are the quaternary mono, di and triammonium compounds of the formulas:

Preferably M is sodium, potassium and the above-mentioned C ₂ alkanolammonium salts; most preferred is sodium.

Under Further referring to the above formula, w is an integer of 0 to 13; x is an integer from 0 to 13; Y is an integer from 0 to 13; z is an integer of at least 1; and w + x + y + z is one integer from 8 to 14.

A preferred mittelkettigverzweigtes primary alkyl sulfate surfactant is a primary alkyl sulfate surfactant with a total C16 carbons having 13 carbon atoms in the backbone and 1, 2 or 3 branching units (ie, R, R ¹ and / or R ²⁾ has a total of 3 carbon atoms, (thus, the total number of carbon atoms is at least 16). Preferred branching units may be a propyl branching unit or three methyl branching units.

worin die Gesamtanzahl an Kohlenstoffatomen, einschließlich der Verzweigung, 15 bis 18 beträgt, und worin, wenn mehr als eines dieser Sulfate vorhanden ist, die durchschnittliche Gesamtanzahl an Kohlenstoffatomen in den verzweigten primären Alkylgruppen mit der obigen Formel innerhalb des Bereichs von größer als 14,5 bis etwa 17,5 liegt; R¹ und R² jeweils unabhängig Wasserstoff oder C₁-C₃-Alkyl sind; M ein wasserlösliches Kation ist; x 0 bis 11 ist; y 0 bis 11 ist; z mindestens 2 ist; und x+y+z 9 bis 13 ist, vorausgesetzt, daß R¹ und R² nicht beide Wasserstoff sind.Another preferred surfactant system for use in the present invention comprises one or more branched primary alkyl sulfate of the formula

wherein the total number of carbon atoms, including the branching, is from 15 to 18, and wherein, when more than one of these sulfates is present, the average total number of carbon atoms in the branched primary alkyl groups having the above formula is within the range greater than 14.5 to about 17.5; R ¹ and R ^{2 are} each independently hydrogen or C ₁ -C ₃ alkyl; M is a water-soluble cation; x is 0 to 11; y is 0 to 11; z is at least 2; and x + y + z is 9 to 13, provided that R ¹ and R ^{2 are} not both hydrogen.

Preferably, the surfactant system comprises at least 20% by weight of the system, more preferably at least 60%, even more preferably at least 90% by weight of the system of a mid-chain branched primary alkyl sulfate, wherein preferably R 'and R ^{2 are} independently hydrogen or methyl are provided that R 'and R ^{2 are} not both hydrogen; x + y is 8, 9 or 10, and z is at least 2, whereby the average total number of carbon atoms in these sulfate surfactants is preferably 15 to 17, more preferably 16-17.

oder Mischungen hiervon umfassen; worin M ein oder mehrere Kationen bedeutet; a, b, d und e ganze Zahlen sind, a+b 10 bis 16 ist, d+e 8 bis 14 ist, und wobei weiterhin wenn a+b=10, a eine ganze Zahl von 2 bis 9 ist und b eine ganze Zahl von 1 bis 8 ist; wenn a+b=11, a eine ganze Zahl von 2 bis 10 ist und b eine ganze Zahl von 1 bis 9 ist; wenn a+b=12, a eine ganze Zahl von 2 bis 11 ist und b eine ganze Zahl von 1 bis 10 ist; wenn a+b=13, a eine ganze Zahl von 2 bis 12 ist und b eine ganze Zahl von 1 bis 11 ist; wenn a+b=14. a eine ganze Zahl von 2 bis 13 ist und b eine ganze Zahl von 1 bis 12 ist; wenn a+b=15, a eine ganze Zahl von 2 bis 14 ist und b eine ganze Zahl von 1 bis 13 ist; wenn a+b=16, a eine ganze Zahl von 2 bis 15 ist und b eine ganze Zahl von 1 bis 14 ist; wenn d+e=8, d eine ganze Zahl von 2 bis 7 ist und e eine ganze Zahl von 1 bis 6 ist; wenn d+e=9, d eine ganze Zahl von 2 bis 8 ist und e eine ganze Zahl von 1 bis 7 ist; wenn d+e=10, d eine ganze Zahl von 2 bis 9 ist und e eine ganze Zahl von 1 bis 8 ist; wenn d+e=11, d eine ganze Zahl von 2 bis 10 ist und e eine ganze Zahl von 1 bis 9 ist; wenn d+e=12, d eine ganze Zahl von 2 bis 11 ist und e eine ganze Zahl von 1 bis 10 ist; wenn d+e=13, d eine ganze Zahl von 2 bis 12 ist und e eine ganze Zahl von 1 bis 11 ist; wenn d+e=14, d eine ganze Zahl von 2 bis 13 ist und e eine ganze Zahl von 1 bis 12 ist; wobei, wenn mehr als eines dieser Sulfat-Tenside in dem Tensidsystem vorliegt, die durchschnittliche Gesamtanzahl an Kohlenstoffatomen in den verzweigten primären Alkyleinheiten der obigen Formeln innerhalb des Bereichs von größer als 14,5 bis 17,5 liegt.Further preferred surfactant systems are those which contain at least about 20, more preferably at least 60, even more preferably at least 90% by weight of the system of one or more mid-chain branched alkyl sulfates of the formula:

or mixtures thereof; wherein M represents one or more cations; a, b, d and e are integers, a + b is 10 to 16, d + e is 8 to 14, and further when a + b = 10, a is an integer from 2 to 9 and b is an integer Number is from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; if a + b = 14. a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; if a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein, when more than one of these sulfate surfactants is present in the surfactant system, the average total number of carbon atoms in the branched primary alkyl moieties of the above formulas is within the range of greater than 14.5 to 17.5.

preferred Monomethyl-branched primary Alkyl sulfates are chosen from the group consisting of: 3-methyl pentadecanol sulfate, 4-methyl pentadecanol sulfate, 5-methyl pentadecanol sulfate, 6-methyl pentadecanol sulfate, 7-methyl pentadecanol sulfate, 8-methyl pentadecanol sulfate, 9-methyl pentadecanol sulfate, 10-methyl pentadecanol sulfate, 11-methyl pentadecanol sulfate, 12-methyl pentadecanol sulfate, 13-methyl pentadecanol sulfate, 3-methylhexadecanol sulphate, 4-methylhexadecanol sulphate, 5-methylhexadecanol sulphate, 6-methylhexadecanol sulphate, 7-methylhexadecanol sulphate, 8-methylhexadecanol sulphate, 9-methylhexadecanol sulphate, 10-methylhexadecanol sulphate, 11-methylhexadecanol sulphate, 12-methylhexadecanol sulfate, 13-methylhexadecanol sulfate, 14-methylhexadecanol sulfate and mixtures thereof.

preferred Dimethyl-branched primary Alkyl sulfates are chosen from the group consisting of: 2,3-methyltetradecanol sulfate, 2,4-methyltetradecanol sulfate, 2,5-Methyltetradecanolsuifat, 2,6-methyltetradecanol sulfate, 2,7-methyltetradecanol sulfate, 2,8-methyltetradecanol sulfate, 2,9-methyltetradecanol sulfate, 2,10-methyltetradecanol sulfate, 2,11-methyltetradecanol sulfate, 2,12-methyl tetradecanol sulfate, 2,3-methyl pentadecanol sulfate, 2,4-methyl pentadecanol sulfate, 2,5-methyl pentadecanol sulfate, 2,6-methyl pentadecanol sulfate, 2,7-methyl pentadecanol sulfate, 2,8-methyl pentadecanol sulfate, 2,9-methyl pentadecanol sulfate, 2,10-methyl pentadecanol sulfate, 2,11-methyl pentadecanol sulfate, 2,12-methyl pentadecanol sulfate, 2,13-methyl pentadecanol sulfate and mixtures thereof.

6-Methylpentadecylsulfat mit der Formel

7-Methylpentadecylsulfat mit der Formel

8-Methylpentadecylsulfat mit der Formel

Methylpentadecylsulfat mit der Formel

14-Methylpentadecylsulfat mit der Formel

worin M vorzugsweise Natrium ist.The following branched primary alkyl sulfates comprising 16 carbon atoms and having one branching unit are examples of preferred branched surfactants useful in the compositions of the present invention: 5-methylpentadecyl sulfate having the formula

6-methylpentadecyl sulfate of the formula

7-methylpentadecyl sulfate of the formula

8-methylpentadecyl sulfate of the formula

Methylpentadecyl sulfate with the formula

14-methylpentadecyl sulfate with the formula

wherein M is preferably sodium.

2,0-Methylpentadecylsulfat mit der Formel

2,7-Methylpentadecylsulfat mit der Formel

2,8-Methylpentadecylsulfat mit der Formel

2,9-Methylpentadecylsulfat mit der Formel

2,10-Methylpentadecylsulfat mit der Formel

The following branched primary alkyl sulfates comprising 17 carbon atoms and having two branching units are examples of preferred branched surfactants according to the present invention: 2,5-dimethylpentadecyl sulfate having the formula

2.0-methylpentadecyl sulfate of the formula

2,7-methylpentadecyl sulfate of the formula

2,8-methylpentadecyl sulfate of the formula

2,9-Methylpentadecylsulfate with the formula

2,10-Methylpentadecylsulfate with the formula

bleaching system

The used according to the invention Bleaching system a hydrophobic and a hydrophilic bleach precursor.

The Bleaching system is in a proportion of at least 0.5 wt .-% of Composition, preferably 0.5 to 45 wt .-%, more preferably 1 to 30% by weight, most preferably 1.5 to 25% by weight of the detergent compositions in front.

worin L eine Abgangsgruppe ist, und X im wesentlichen irgendeine Funktionalität ist, welche für die vorliegende Erfindung festlegt, ob der Vorläufer hydrophob oder hydrophil ist, und welche derart ist, daß bei der Perhydrolyse die Struktur der erzeugten Peroxysäure

Preferably, the bleach precursors are peroxyacid bleach precursors which can be represented as

wherein L is a leaving group and X is essentially any functionality which determines for the present invention whether the precursor is hydrophobic or hydrophilic, and which is such that upon perhydrolysis the structure of the peroxyacid produced

The used according to the invention hydrophobic bleaching agent a group X containing at least 6 carbon atoms. The Hydrophilic bleaching agent of the present invention comprises a Group X, which contains less than 6 carbon atoms.

Preferably, the bleaching system used in the present invention contains a hydrogen peroxide source and a hydrophilic and a hydrophobic (organic peroxyacid) bleach precursor compound. The generation of the organic peroxyacid occurs by an in situ reaction of the precursors with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. Preferred perhydrate bleaching agents are metal perborates and metal percarbonates, especially the sodium salts. The perborate may be mono- or tetrahydrated. Sodium percarbonate has the formula 2Na ₂ CO ₃ .3H ₂ O ₂ and is commercially available as a crystalline solid. Potassium or sodium peroxymonopersulfate are other optional inorganic perhydrate salts for use in the detergent compositions herein.

The inorganic perhydrate bleaches are preferably in one Proportion of 1 to 40% by weight, more preferably 3 to 35% by weight, most preferably 5 to 20% by weight of the detergent composition.

leaving groups

The Leaving group, hereinafter L group, must be sufficiently reactive, so that the perhydrolysis reaction within the optimal time Frame (e.g., a wash cycle) can take place. However, if L too is reactive, it becomes difficult to use this activator in a bleaching composition.

und Mischungen hiervon, worin R¹ eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R³ eine Alkylkette mit 1 bis 8 Kohlenstoffatomen ist, R⁴ H oder R³ ist, und Y H oder eine solubilisierende Gruppe ist. Irgendeiner der Reste R', R³ und R⁴ kann durch im wesentlichen irgendeine funktionelle Gruppe, einschließlich zum Beispiel Alkyl-, Hydroxy-, Alkoxy-, Halogen-, Amin-, Nitrosyl-, Amid- und Ammonium- oder Alkylammoniumgruppen, substituiert sein.Preferred L groups are selected from the group _; consisting of:

and mixtures thereof, wherein R ^{1 is} an alkyl, aryl or alkaryl group of 1 to 14 carbon atoms, R ^{3 is} an alkyl chain of 1 to 8 carbon atoms, R ^{4 is} H or R ³ , and Y is H or a solubilizing group. Any of R ', R ³ and R ⁴ may be substituted by substantially any functional group including, for example, alkyl, hydroxy, alkoxy, halogen, amine, nitrosyl, amide, and ammonium or alkyl ammonium groups ,

The preferred solubilizing groups are -SO ₃ ^- M ^+, -CO ₂ ^- M ^+, -SO ₄ ^- M ^+, -N ⁺ (R ³⁾ ₄ X ^- and O <- N (R ³⁾ _3, and at the most preferably -SO ₃ ^- M ⁺ and -CO ₂ ^- M ⁺ , wherein R ^{3 is} an alkyl chain of 1 to 4 carbon atoms, M is a cation which provides the solubility of the bleach activator, and X is an anion which is suitable for the Solubility of the bleach activator provides. Preferably, M is an alkali metal, ammonium or substituted ammonium cation, with sodium and potassium being most preferred, and X is a halide, hydroxide, methylsulfate or acetate anion.

Preferred hydrophilic and hydrophobic precursors

Suitable bleach precursors typically contain one or more N- or O-acyl groups, which precursors may be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides. Lactams and acylated derivatives of imidazoles and oximes. Examples of more useful Materials within these classes are disclosed in GB-A-1586789. Suitable esters are disclosed in GB-A-836988, 864798, 1147871 and 2143231 and EP-A-0170386.

Alkyl bleach precursor

Alkyl percarboxylic acid bleach precursors are preferred precursors for use herein. They form percarboxylic acids in perhydrolysis. Preferred precursors of this type see peracetic acid during perhydrolysis.

Preference is given to phenyl esters of C _14-22 alkanoic or alkenoic acids, esters of hydroxylamine, geminal diesters of lower alkanoic acids and Gem idols, such as those described in EP-A-0125781, especially 1,1,5-Triacetoxypent-4-ene and 1,1,5,5-tetraacetoxypentane and the corresponding butene and butane compounds, ethylidene benzoate acetate and bis (ethylidene acetate) adipate and enol ester, for example as described in EP-A-0140648 and EP-A-0092932.

Preferred imide-type alkyl percarboxylic acid precursor compounds include the N, N, N ¹ , N ¹ -tetraacetylated alkylenediamines wherein the alkylene group contains from 1 to 6 carbon atoms; especially those compounds wherein the alkylene group contains 1, 2 and 6 carbon atoms. Tetraacetylethylenediamine (TAED, a hydrophilic precursor) is especially preferred.

Other particularly preferred allcyl percarboxylic acid precursors include sodium acetoxybenzenesulfonate (ABS) and pentaacetylglucose, dodecanolyloxybenzenesulphonate sodium salt, Dodecanoyloxybenzenesulfonate sodium salt (DOBS), benzoyloxybenzenesulfonate sodium salt (BOBS), more preferably sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate (iso-NOBS) and more preferably sodium nonanoyloxybenzenesulfonate (NOBS) (which hydrophobic precursors are a.

Amide-substituted alkyl peroxyacid precursors

worin R¹ eine Alkylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R² eine Alkylengruppe mit 1 bis 14 Kohlenstoffatomen ist, und R⁵ H oder eine Alkylgruppe mit 1 bis 10 Kohlen stoffatomen ist, und L im wesentlichen irgendeine Abgangsgruppe sein kann. Amid-substituierte Bleichaktivatorverbindungen dieses Typs sind in EP-A-0170386 beschrieben.Amide-substituted alkyl peroxyacid precursors are preferred precursors herein. They include those of the following general formulas:

wherein R ^{1 is} an alkyl group having 1 to 14 carbon atoms, R ^{2 is} an alkylene group having 1 to 14 carbon atoms, and R ^{5 is} H or an alkyl group having 1 to 10 carbon atoms, and L may be substantially any leaving group. Amide-substituted bleach activator compounds of this type are described in EP-A-0170386.

Perbenzoic acid precursor

Perbenzoic acid precursors are other preferred precursors here in. You see perbenzoic acid during perhydrolysis. Suitable O-acylated perbenzoic acid precursor compounds shut down the substituted and unsubstituted benzoyloxybenzenesulfonates and the benzoylation products of sorbitol, glucose and all saccharides with benzoylating agents and those of the imide type, including N-benzoylsuccinimide, Tetrabenzoylethylenediamine and the N-benzoyl-substituted ureas one. Suitable perbenzoic acid precursors of Close imidazole type N-benzoylimidazole and N-benzoylbenzimidazole. Other useful N-acyl groups containing perbenzoic acid precursors include N-benzoylpyrrolidone, Dibenzoyltaurine and benzoylpyroglutamic acid.

Especially preferred hydrophobic precursors are (6-octanamidocaproyl) oxybenzenesulfonate, (6-decanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, decanoyloxybenzenesulfonate sodium salt and benzoyloxybenzenesulfonate nitrate.

Organic peroxyacid precursors of Benzoxazintype

worin R₁ H, Alkyl, Alkaryl, Aryl oder Arylalkyl ist.Also suitable are benzoxazine type precursors as disclosed, for example, in EP-A-332,294 and EP-A-482,807, especially those of the formula:

wherein R _{1 is} H, alkyl, alkaryl, aryl or arylalkyl.

Additional detergent components

The Detergent compositions according to the invention can also additional Detergent components included. The exact nature of this extra Components and the admixture parts thereof depend on the physical form of the composition and the exact type of the washing process, for which it is to be used off.

The Compositions of the invention preferably contain one or more additional detergent components, chosen from additional Surfactants, additional Bleaching agents, bleach catalysts, alkalinity sources, builders, organic polymeric compounds, additional Enzymes, suds suppressors, Lime soap dispersants, soil suspending and anti redeposition agents and corrosion inhibitors.

extra surfactant

The Detergent compositions according to the invention preferably contain an additional surfactant, chosen from additional anionic, nonionic, cationic, ampholytic, amphoteric and zwitterionic surfactants and mixtures thereof.

A typical listing of anionic, nonionic, ampholytic and zwitterionic classes and species of these surfactants is disclosed in U.S. Patent 3,929,678, issued to Laughlin and Heuring on December 30, 1975, specified. Further examples are in "Surface Active Agents and Detergents" (Volumes I and II, by Schwartz, Perry and Berch). A listing of suitable cationic surfactants is disclosed in U.S. Patent 4,29,217 issued to Murphy on March 31, 1981.

If present are ampholytic, amphoteric and zwitterionic surfactants generally in combination with one or more anionic and / or nonionic surfactants.

anionic surfactant

The Detergent compositions according to the invention preferably comprise an additional one anionic surfactant. In essence, any anionic Surfactant, which for Cleaning purposes useful are included in the detergent composition. These can Salts (including for Example sodium. Potassium, ammonium and substituted ammonium salts, such as mono-, di- and triethanolamine salts) of the anionic sulphate, Include sulfonate, carboxylate and sarcosinate surfactants. Anionic sulfate surfactants are favored.

Other anionic surfactants include the isethionates such as the acyl isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (particularly saturated and unsaturated C ₁₂ -C ₁₈ monoesters), diesters of sulfosuccinate (especially saturated and unsaturated C ₆ C ₁₄ diester) and N-acyl sarcosinates. Resin acids and hydrogenated resin acids are also suitable, such as rosin and hydrogenated rosin, as well as resin acids and hydrogenated resin acids present or derived from tall oil.

anionic Sulfate surfactant

Anionic sulfate surfactants suitable for use herein include the linear and branched, primary and secondary alkyl sulfates, alkyl ethoxy sulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C ₅ -C ₁₇ acyl-N- (C ₁ -C ₄ alkynyl) - and -N- (C ₁ -C ₂ -hydroxyalkyl) -glucamine sulfates and sulfates of alkyl polysaccharides, such as the sulfates of alkyl polyglucoside (the nonionic, non-sulfated compounds described herein).

Alkyl sulfate surfactants are preferably selected from linear and branched primary C ₁₀ -C ₁₈ alkyl sulfates, more preferably branched chain C ₁₁ -C ₁₅ alkyl sulfates and linear chain C ₁₂ -C ₁₄ alkyl sulfates.

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting of the C ₁₀ -C ₁₈ alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C ₁₁ -C ₁₈ , most preferably a C ₁₁ -C ₁₅ alkyl sulfate which has been ethoxylated with 0.5 to 7, preferably 1 to 5, moles of ethylene oxide per molecule.

One particularly preferred aspect of the invention relates to the use mixtures of the preferred alkyl sulfate and alkyl ethoxy sulfate surfactants. Such mixtures are disclosed in PCT Patent Application No. WO 93/18124 been revealed.

anionic Sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of linear C ₅ -C ₂₀ alkyl benzene sulfonates, alkyl ester sulfonates, C ₅ -C ₂₂ primary or secondary alkane sulfonates, C ₆ -C ₂₄ olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, Fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates and any mixtures thereof.

anionic Carboxylate surfactant

suitable anionic carboxylate surfactants include the alkyl ethoxy carboxylates, the alkylpolyethoxypolycarboxylate surfactants and the soaps ('alkylcarboxyls'), especially certain secondary Soaps as described herein.

Suitable alkyl ethoxy carboxylates include those of the formula RO (CH ₂ -CH ₂ O) _x CH ₂ COO ^- M ⁺ , wherein R is a C ₆ to C ₁₈ alkyl group, x ranges from 0 to 10, and the ethoxylate distribution is such in that, on a weight basis, the amount of material wherein x is 0 is less than 20%, and M is a cation. Suitable alkylpolyethoxypolycarboxylate surfactants include those of the formula RO- (CHR ₁ -CHR ₂ -O) -R ₃ wherein R is a C ₆ to C ₁₈ alkyl group, x is 1 to 25, R ₁ and R ₂ are selected from the group consisting of hydrogen, methyl acid residue, succinic acid residue, hydroxysuccinic acid residue and mixtures thereof, and R _{3 is} selected from the group consisting of hydrogen, substituted or unsubstituted hydrocarbon of between 1 and 8 carbon atoms, and mixtures thereof.

suitable Close soap surfactants, the secondary ones Soap surfactants containing a carboxy moiety containing a secondary one Carbon is connected. Preferred secondary soap surfactants for use herein are water-soluble Representative, elected from the group consisting of the water-soluble salts of 2-methyl-1-undecanoic acid, 2-ethyl-1-decanoic acid, 2-propyl-1-nonanoic acid, 2-butyl-1-octanoic acid and 2-pentyl-1-heptanoic acid. Certain soaps can also as suds suppressor be included.

Alkali-Surfactant

Other suitable anionic surfactants are the alkali metal sarcosinates of the formula R-CON (R ¹ ) CH ₂ COOM, wherein R is a linear or branched C ₅ -C ₁₇ alkyl or alkenyl group, R ^{1 is} a C ₁ -C ₄ alkyl group and M is an alkali metal ion. Preferred examples are the myristyl and Oleoylmethylsarcosinate in the form of their sodium salts.

Alkoxylated nonionic surfactant

in the Some are alkoxylated nonionic surfactants suitable herein. The ethoxylated and propoxylated, nonionic Surfactants are preferred. The nonionic surfactant is preferably in a relationship to the surfactant system comprising the present invention mid-chain branched surfactants, from 10: 1 to 1:10, more preferred 5: 1 to 1:10, more preferably 1: 1 to 1:10 before. Preferred alkoxylated Surfactants can from the classes of nonionic condensates of alkylphenols; nonionic ethoxylated alcohols; nonionic ethoxylated / propoxylated Fatty alcohols; nonionic ethoxylate / propoxylate condensates with Propylene glycol; and the nonionic ethoxylate condensation products be selected with propylene oxide / ethylenediamine adducts.

Nonionic alkoxylated Alcohol surfactant

The Condensation products of aliphatic alcohols with 1 to 25 moles Alkylene oxide, especially ethylene oxide and / or propylene oxide, are for Use suitable herein. The alkyl chain of the aliphatic alcohol can be either straight or branched, primary or secondary and contains generally 6 to 22 carbon atoms. Particularly preferred the condensation products of alcohols having an alkyl group containing 8 to 20 carbon atoms, more preferably 9 to 15 carbon atoms, with 3 to 12 moles of ethylene oxide per mole of alcohol.

Nonionic polyhydroxy fatty acid amide surfactant

Polyhydroxy fatty acid amides suitable for use herein are those having the structural formula R ² CONR ¹ Z wherein: R ^{1 is} H, C ₁ -C ₄ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl, ethoxy, propoxy or a mixture thereof, preferably C ₁ C ₄ alkyl, more preferably C ₁ or C ₂ alkyl, most preferably C ₁ alkyl (ie, methyl); and R _{2 is} C ₅ -C ₃₁ hydrocarbyl, preferably straight chain C ₅ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₄ -C ₁₇ alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain wherein at least 3 hydroxyl groups are attached directly to the chain, or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably, Z is a glycityl.

Nonionic fatty acid amide surfactant

Suitable fatty acid amide surfactants include those of the formula R ⁶ CON (R ⁷ ) ₂ , wherein R ^{6 is} an alkyl group of 7 to 21, preferably 9 to 17, carbon atoms, and each R ^{7 is} selected from the group consisting of hydrogen, C ₁ -C ₄ -alkyl, C ₁ -C ₄ -hydroxyalkyl and - (C ₂ H ₄ O) _x H, wherein x is in the range of 1 to 3.

Nonionic alkyl polysaccharide surfactant

suitable Alkyl polysaccharides for use herein are described in U.S. Patent 4,565,647, Llenado, issued January 21, 1966, discloses and has a hydrophobic Group containing 6 to 30 carbon atoms, and a hydrophilic one Polysaccharide group, e.g. a polyglycoside containing 1.3 to 10 Saccharide units, on.

Preferred alkyl polyglycosides have the formula R ² O (C _n H _2n O) _t (glycosyl) _x wherein R ^{2 is} selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof wherein the alkyl groups contain from 10 to 16 carbon atoms; n is 2 or 3; t is 0 to 10, and x is 1.3 to 6. The glycosyl is preferably derived from glucose.

Amphoteric surfactant

suitable Amphoteric surfactants for use herein include the amine oxide surfactants and the alkyl amphocarboxylic acids.

Suitable amine oxides include the compounds of the formula R ³ (OR ⁴ ) _x N ⁰ (R ⁵ ) ₂ wherein R ^{3 is} selected from an alkyl, hydroxyalkyl, acylamidopropoyl and alkylphenyl group, or mixtures thereof containing 8 to 26 carbon atoms; R ^{4 is} an alkylene or hydroxyalkylene group having 2 to 3 carbon atoms or mixtures thereof; x is 0 to 5, preferably 0 to 3; and each R ^{5 is} an alkyl or hydroxyalkyl group having 1 to 3 carbon atoms or a polyethylene oxide group having 1 to 3 ethylene oxide groups. Preference is given to C ₁₀ -C ₁₈ -alkyldimethylamine oxide and C ₁₀ -C ₁₈ -acylamidoalkyldimethylamine oxide.

One suitable example for an alkylamphodicarboxylic acid is Miranol (TM) C2M Conc., manufactured by Miranol, Inc., Dayton, NJ.

Zwitterionic surfactant

Zwitterionic surfactants may also be included in the detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic, secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonic compounds. Betaine and sultaine surfactants are exemplary zwitterionic surfactants for use herein.

Suitable betaines are the compounds of the formula R (R ') ₂ N ⁺ R ² COO ^- , wherein R is a C ₆ -C ₁₈ hydrocarbyl group, each R ^{1 is} typically a C ₁ -C ₃ alkyl, and R ^{2 is} a C ₁ -C ₃ hydrocarbyl group. Preferred betaines are C _12-18 dimethylammonium hexanoate and the C _10-18 acylamidopropane (or ethane) dimethyl (or diethyl) betaines. Complex betaine surfactants are also suitable for use herein.

canonical surfactants

Additional cationic surfactants may also be used in the detergent compositions herein. Suitable cationic surfactants include the quaternary ammonium surfactants selected from mono C ₆ -C ₁₆ , preferably C ₆ -C _10, N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are methyl, hydroxyethyl, or hydroxypropyl groups.

alkalinity

In the detergent compositions of the invention is preferably an alkalinity system present for optimal performance for the to achieve cationic ester surfactant. The alkalinity system comprises Components, which capable are alkalinity species in solution provided. With alkalinity species is meant herein: carbonate, bicarbonate, hydroxide, the various Silicate anions, percarbonate, perborates, perphosphates, persulphate and persilicate.

Such alkalinity can for example, when alkali salts. chosen out Salts of alkali metal or alkaline earth metal carbonate, bicarbonate, hydroxide or silicate, including crystalline layered silicate, and percarbonate, perborate, perphosphate, persulfate and persilicate salts, as described above, and any mixtures thereof, in water solved become.

Examples for carbonates are the alkaline earth and alkali metal carbonates, including sodium carbonate and sesquicarbonate, and any mixtures thereof with ultrafine Calcium carbonate, such as that disclosed in German Patent Application No. 2,321,001, released on November 15, 1973.

Suitable silicates include the water-soluble sodium silicates having a SiO ₂ : Na ₂ O ratio of 1.0 to 2.8, with ratios of 1.6 to 2.0 being preferred, and a ratio of 2.0 being most preferred , The silicates may be in the form of either an anhydrous salt or a hydrated salt. Sodium silicate with a SiO ₂ : Na ₂ O ratio of 2.0 is the most preferred silicate.

Preferred crystalline gale silicates for use herein have the general formula NaMSi _x O _{2x + 1} . yH ₂ O wherein M is sodium or hydrogen, x is a number from 1.9 to 4, and Y is a number from 0 to 20. Crystalline layered sodium silicates of this type are disclosed in EP-A-0164514 and processes for their preparation are disclosed in DE-A-3417649 and DE-A-3742043. Here, x in the above general formula preferably has a value of 2, 3 or 4 and is preferably 2. The most preferred material is δ-Na ₂ Si ₂ O ₂ , which is available from Hoechst AG as NaSKS-6.

Water-soluble builder compound

The Detergent compositions according to the invention preferably contain a water-soluble builder compound which typically in a proportion of 1 to 80 wt.%, preferably 1.0 to 70% by weight, most preferably 20 to 60% by weight of the composition is present.

suitable water-soluble Close builder compounds the water-soluble monomeric polycarboxylates or their acid forms; homopolymers or copolymers polycarboxylic or their salts, wherein the polycarboxylic acid has at least two carboxyl radicals comprises which are separated from each other by not more than 2 carbon atoms are; borates; Phosphate; and mixtures of any of the foregoing Species.

Of the Carboxylate or polycarboxylate builder may be of the monomeric or be oligomeric type, although monomeric polycarboxylates in general for cost and performance reasons to be favoured.

suitable Carboxylates containing a carboxy group. close the water-soluble Salts of lactic acid and glycolic acid and ether derivatives thereof. Polycarboxylates with two carboxy groups shut down the water-soluble Salts of succinic acid, malonic, (Ethylenedioxy) diacetic acid, maleic acid, diglycolic, Tartaric acid, tartronic and fumaric acid as well as the ether carboxylates and the sulfinyl carboxylates. polycarboxylates with three carboxy groups especially water-soluble Citrates, aconitrates and citraconates as well as succinate derivatives, such as the carboxymethyloxysuccinates described in the British patent No. 1,379,241; Lactoxysuccinates described in the British patent No. 1,389,732; and aminosuccinates described in the Dutch Application 7205873; and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylates, described in British Patent No. 1,387,447.

polycarboxylates with four carboxy groups Oxydisuccinates disclosed in British Patent No. 1,261,829; 1,1,2,2-ethane; 1,1,3,3-propane; and 1,1,2,3-propane tetracarboxylates one. Polycarboxylates having sulfo substituents include Sulfosuccinate derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Patent No. 3,936,448; and the sulfonated, pyrolyzed citrates described in British Patent No. 1,439,000. Preferred polycarboxylates are hydroxycarboxylates with up to three carboxy groups per molecule, more preferably citrates.

The parent acids the monomeric or oligomeric polycarboxylate complexing agent or Mixtures thereof with their salts, e.g. Citric acid or Citrate / citric acid mixtures, are considered useful builder components also considered.

Borate builders and builders containing borate-forming materials, the borate under detergent storage or washing conditions useful water-soluble Builder herein.

suitable examples for water-soluble Phosphate builders are the alkali metal tripolyphosphates; Sodium-, Potassium and ammonium pyrophosphate; Sodium and potassium and ammonium pyrophosphate; Sodium and potassium orthophosphate; Sodium polymetaphosphate, wherein the degree of polymerization ranges from about 6 to 21; and salts of Phytic acid.

Partially soluble or insoluble builder compound

The Detergent compositions according to the invention can a partially soluble or insoluble Builder compound containing, which is typically in one part from 1 to 80% by weight, preferably 10 to 70% by weight, most preferably From 20% to 60% by weight of the composition.

Examples for the most part water Close builder the sodium aluminosilicates.

Suitable aluminosilicate zeolites have the unit cell formula Na ₂ [(AlO ₂ ) _Z (SiO ₂ ) _y ]. xH ₂ O, wherein z and y are at least 6; the molar ratio of z to y is 1.0 to 0.5, and x is at least 5, preferably 7.5 to 276 and more preferably 10 to 264. The aluminosilicate materials are in hydrated form and are preferably crystalline, containing from 10 to 28%, more preferably from 18 to 22%; Water in bound form.

The aluminosilicate zeolites may be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, and mixtures thereof. Zeolite A has the formula Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]. xH ₂ O where x is 20 to 30, especially 27. Zeolite X has the formula Na ₈₆ [(AlO ₂ ) ₈₆ (SiO ₂ ) ₁₀₆ ]. 276 xH ₂ O.

Pre-formed organic peroxy

The Detergent compositions or the bleaching system may be used in addition to the bleach precursors one preformed organic peroxyacid typically present in a proportion of from 1 to 15% by weight, more preferably 1 to 10% by weight, of the composition.

worin R¹ eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 14 Kohlenstoffatomen ist, R² eine Alkylen-, Arylen- oder Alkarylengruppe mit 1 bis 14 Kohlenstoffatomen ist, und R⁵ H oder eine Alkyl-, Aryl- oder Alkarylgruppe mit 1 bis 10 Kohlenstoffatomen ist. Amidsubstituierte organische Peroxysäureverbindungen dieses Typs sind in EP-A-0170386 beschrieben.A preferred class of organic peroxyacid compounds are the amide-substituted compounds of the following general formulas:

wherein R ^{1 is} an alkyl, aryl or alkaryl group having 1 to 14 carbon atoms, R ^{2 is} an alkylene, arylene or alkarylene group having 1 to 14 carbon atoms, and R ^{5 is} H or an alkyl, aryl or alkaryl group with 1 to 10 carbon atoms. Amide substituted organic peroxyacid compounds of this type are described in EP-A-0170386.

Other organic peroxyacids shut down Diacyl and tetraacyl peroxides, especially diperoxydodecanedioic acid, diperoxytetradecanedioic acid and Diperoxyhexadecanedioc. Mono- and diperazelaic acid, mono- and diperbrassylic acid and N-phthaloylaminoperoxycaproic acid are also suitable herein.

Other suitable organic peroxyacids shut down Diperoxyalkandisäuren with more than 7 carbon atoms, such as diperoxydodecanedioic acid (DPDA), diperoxytetradecanedioc and diperoxyhexadecanedioic acid. Mono- and diperazelaic acid. Mono- and diperbrassylic acid and N-phthaloylaminoperoxycaproic acid (PAP), nonanoylamidoperoxoadipic acid (NAPAA), Decanoyl or Dodecanoylamidoperoxysäuren and Hexansulfenoylperoxypropionsäure are also suitable herein.

worin: R gewählt ist aus der Gruppe, bestehend aus C₁-C₁₂-Alkylen, C₅-C₁₂-Cycloalkylen, C₆-C₁₂-Arylen und Restkombinationen hiervon; R¹ und R² unabhängig gewählt sind aus der Gruppe, bestehend aus H, C₁-C₁₆-Alkyl- und C₆-C₁₂-Arylresten und einem Rest, welcher einen C₃-C₁₂-Ring zusammen mit R³ und beiden Stickstoffatomen bilden kann; R³ gewählt ist aus der Gruppe, bestehend aus C₁-C₁₂-Alkylen-, C₅-C₁₂-Cycloalkylen- und C₁-C₁₂-Arylenresten; n und n' jeweils eine ganze Zahl sind, welche derart gewählt ist, daß die Summe davon 1 ist; m und m' jeweils eine ganze Zahl sind, welche derart gewählt ist, daß die Summe davon 1 ist; und M gewählt ist aus der Gruppe, bestehend aus H, Alkalimetall, Erdalkalimetall, Ammonium, Alkanolammoniumkationen und Resten und Kombinationen hiervon.Other suitable organic peroxyacids include diaminoperoxyacids, disclosed in WO 95/03275, having the following general formula:

wherein: R is selected from the group consisting of C ₁ -C ₁₂ alkylene, C ₅ -C ₁₂ cycloalkylene, C ₆ -C ₁₂ arylene and residual combinations thereof; R ¹ and R ^{2 are} independently selected from the group consisting of H, C ₁ -C ₁₆ alkyl and C ₆ -C ₁₂ aryl radicals and a radical having a C ₃ -C ₁₂ ring together with R ³ and can form both nitrogen atoms; R ^{3 is} selected from the group consisting of C ₁ -C ₁₂ alkylene, C ₅ -C ₁₂ cycloalkylene and C ₁ -C ₁₂ arylene radicals; n and n 'are each an integer selected such that the sum of them is 1; m and m 'are each an integer selected such that the sum thereof is 1; and M is selected from the group consisting of H, alkali metal, alkaline earth metal, ammonium, alkanolammonium cations and radicals and combinations thereof.

worin X Wasserstoff oder einen kompatiblen Substituenten bedeutet, Ar eine Arylgruppe ist, R (CH₂)_n bedeutet, worin n = 2 oder 3, und Y und Z jeweils unabhängig einen Substituenten bedeuten, gewählt aus Wasserstoff oder einer Alkyl- oder Aryl- oder Alkarylgruppe oder einer Arylgruppe, substituiert mit einen kompatiblen Substituenten, vorausgesetzt, daß mindestens eines von Y und Z nicht Wasserstoff ist, falls n = 3. Der Substituent X an dem Benzolkern ist vorzugsweise ein Wasserstoffatom oder ein meta- oder para-Substituent, gewählt aus der Gruppe, umfassend ein Halogen, typischerweise, ein Chloratom, oder einige andere nicht-freigesetzte, nicht-störende Spezies, wie eine Alkylgruppe, geeigneterweise bis zu C6, zum Beispiel eine Methyl-, Ethyl- oder Propylgruppe. Alternativ kann X einen sekundären Amidopercarbonsäure-Substituenten der Formel

bedeuten, worin R, Y_; Z und n wie oben definiert sind. MOOC-R¹CO-NR²-R³-NR⁴-CO-R⁵COOOM worin R¹ gewählt ist aus der Gruppe, bestehend aus C₁-C₁₂-Alkylen-, C₅-C₁₂-Cycloalkylen, C₆-C₁₂-Arylen und Restkombinationen hiervon; ROther suitable organic peroxyacids include the amido peroxyacids disclosed in WO 95/16673 having the general structure:

wherein X is hydrogen or a compatible substituent, Ar is an aryl group, R is (CH ₂ ) _n , where n = 2 or 3, and Y and Z are each independently a substituent selected from hydrogen or an alkyl or aryl or Alkaryl group or an aryl group substituted with a compatible substituent, provided that at least one of Y and Z is not hydrogen, if n = 3. The substituent X on the benzene nucleus is preferably a hydrogen atom or a meta or para substituent selected from the group comprising a halogen, typically a chlorine atom, or some other non-released non-interfering species such as an alkyl group, suitably up to C6, for example a methyl, ethyl or propyl group. Alternatively, X may be a secondary amido-percarboxylic acid substituent of the formula

where R, Y _; Z and n are as defined above. MOOC-R ¹ CO-NR ² -R ³ -NR ⁴ -CO-R ⁵ COOOM wherein R ^{1 is} selected from the group consisting of C ₁ -C ₁₂ alkylene, C ₅ -C ₁₂ cycloalkylene, C ₆ -C ₁₂ arylene and residual combinations thereof; R

It can be especially useful be the preformed peracid and the cationic surfactant before admixing with any other components of the detergent composition mix together.

Cationic peroxyacid precursors

cationic Peroxyacid precursors may be suitable additional Components of the detergent compositions or bleach systems herein be. They produce cationic peroxyacids during perhydrolysis.

typically, are cationic peroxyacid precursors by Substituting the Peroxysäureteils a suitable peroxyacid precursor compound by a positively charged functional group, such as an ammonium or alkylammonium group, preferably an ethyl or methylammonium group, educated. Cationic peroxyacid precursors are present typically in the solid detergent compositions as a salt with a suitable anion, such as a halide ion.

The such cationically-substituted peroxyacid precursor compound may be a perbenzoic acid precursor compound or a substituted derivative thereof as described above be. Alternatively, the peroxyacid precursor compound may be an alkyl percarboxylic acid precursor compound or an amide-substituted alkyl peroxyacid precursor, as described below, be.

cationic Peroxyacid precursors are in U.S. Patent 4,904,406; 4,751,015; 4,966,451; 4,397,757; 5,269,962; 5,127,852; 5,093,022; and 5,106,526; GB 1,382,594; EP 475,512, 458,396 and 264,292; and JP 67-318,332.

Examples preferred cationic peroxyacid precursors in WO 95/28463, WO 96/06914, EP 0699745 and WO 96/06913.

suitable cationic peroxyacid precursors include any the ammonium- or alkylammonium-substituted alkyl- or benzoyloxybenzenesulfonates, N-acylated caprolactams and monobenzoyl tetraacetyl glucose benzoyl peroxides one. Preferred cationic peroxyacid precursors of the class of N-acylated caprolactams shut down the trialkylammoniummethylenebenzoylcaprolactams and the trialkylammoniummethylene-alkylcaprolactams one.

bleach catalyst

The Compositions optionally contain a transition metal-containing Bleach catalyst. A suitable bleach catalyst type is a Catalyst system comprising a heavy metal cation with a defined pale catalytic activity, such as copper, iron or manganese cations, an additional metal cation with a low or no bleach catalytic activity, such as zinc or aluminum cations, and define a sequestering agent stability constants for the catalytic and additional Metal cations, especially ethylenediaminetetraacetic acid, ethylenediaminetetra (methylenephosphonic acid) and water-soluble Salts thereof. Such catalysts are disclosed in U.S. Patent 4,430,243.

Other bleach catalyst types include the manganese-based complexes disclosed in U.S. Patent 5,246,621 and U.S. Patent 5,244,594. Preferred examples of these catalysts include Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO) ₃ (u-OAc) ₂ ( 1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ - (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4,7-triazacyclononane) ₄ (ClO ₄ ) ₂ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₃ and mixtures thereof. Others are described in European Patent Application Publication No. 549,272. Other ligands suitable for use herein include 1,5,9-trimethyl-1,5,9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-1,4,7-triazacyclononart, 1,2 , 4,7-tetramethyl-1,4,7-triazacyclononane and mixtures thereof.

For examples of suitable bleach catalysts cf. U.S. Patent 4,246,612 and U.S. Patent 5,227,084. See also U.S. Patent 5,194,416 which discloses mononuclear manganese (IV) complexes such as Mn- (1,4,7-trimethyl-1,4,7-triazacyclo nonane) (OCH ₃ ) ₃ - (PF ₆ ). Yet another type of bleach catalyst, as disclosed in U.S. Patent 5,114,606, is a water-soluble complex of manganese (III) and / or - (IV) with a ligand containing a non-carboxylate polyhydroxyl compound having at least three consecutive C-OH groups is.

Other examples include binuclear Mn complexed with tetra-Nzähnigen and bi-Nzähnigen ligands, including N ₄ Mn ^III ₂ (uO) ₂ Mn ^IV N ₄₎ ⁺ and [Bipy ₂ Mn ^III - (uO) ₂ Mn ^IV -bipy ₂ ] - (ClO ₄ ) ₃ , a.

Further suitable bleach catalysts are described, for example, in European Patent Application No. 408,131 (cobalt complex catalysts), European Patent Applications Publication Nos. 384,503 and 306,089 (metalloporphyrin catalysts), in US Pat US 4,728,455 (Manganese / multidentate ligand catalyst), in US 4,711,748 and European Patent Application Publication No. 224,952 (absorbed manganese on an aluminosilicate catalyst), in U.S. Pat US 4,601,845 (Aluminosilicate support with manganese and zinc or magnesium salt), US 4,626,373 (Manganese / ligand catalyst), US 4,119,557 (Iron (III) complex catalyst), German Patent Specification 2,054,019 (cobalt chelate catalyst), Canadian Patent 866,191 (transition metal-containing salts), in US 4,430,243 (Chelators with manganese cations and non-catalytic metal cations) and in US 4,728,455 (Manganese gluconate catalysts) described.

Heavy Metal ion sequestrants

The Detergent compositions according to the invention preferably contain as an optional component a heavy metal ion sequestering agent. With heavy metal ion sequestrants herein are components which are effective in sequestering heavy metal ions (Chelate). These components can also be a calcium and Magnesium chelation capacity but preferably they show selectivity for binding heavy metal ions such as iron, manganese and copper.

Heavy Metal ion sequestrants are generally in a proportion of 0.005 to 20 wt .-%, preferably 0.1 to 10 wt%, more preferably 0.25 to 7.5 wt% and most preferably 0.5 to 5 wt .-% of the compositions before.

suitable Heavy metal ion sequestrants for use herein include organic phosphonates, such as the aminoalkylene poly (alkylene phosphonates), alkali metal ethane 1-hydroxy diphosphonates and nitrilotrimethylene phosphonates.

From the above species are diethylene triamine penta (methylene phosphonate), Ethylenediaminetri (methylenephosphonate), hexamethylenediamine tetra (methylenephosphonate) and hydroxyethylene-1,1-diphosphonate are preferred.

Other suitable heavy metal ion sequestrants for use to conclude here nitrilotriacetic and polyaminocarboxylic acids such as ethylenediaminetetraacetic acid, Ethylenetriaminepentaacetic acid, ethylenediamine disuccinic acid, ethylenediamine diglutaric acid, 2-hydroxypropylenediamine disuccinic acid or any Salts thereof. Particular preference is given to ethylenediamine-N, N'-disuccinic acid (EDDS) or the alkali metal, alkaline earth metal, ammonium or substituted Ammonium salts thereof, or mixtures thereof.

Further suitable heavy metal ion sequestrants for use herein are iminodiacetic acid derivatives such as 2-hydroxyethyldiacetic acid or glyceryliminodiacetic acid, which are described in EP-A-317,542 and EP-A-399,133. The iminodiacetic acid N-2-hydroxypropylsulfonsäure- and Aspartic acid N-carboxymethyl-N-2-hydroxypropyl-3-sulfonic acid sequestrants described in EP-A-516,102 are also suitable herein. The β-alanine-N, N'-diacetic acid, aspartic acid-N, N'-diacetic acid, aspartic acid-N-monoacetic acid and Iminodisuccinic sequestrant described in EP-A-509,382 are also suitable.

EP-A-476,257 describes suitable amino-based sequestering agents. EP-A-510,331 describes suitable Sequestrant derived from collagen, keratin or casein are. EP-A-528,859 describes a suitable alkyliminodiacetic acid sequestering agent. dipicolinic and 2-phosphonobutane-1,2,4-tricarboxylic acid are also suitable. Glycinamide-N, N'-disuccinic acid (GADS), Ethylenediamine-N, N'-diglutaric acid (EDDG) and 2-hydroxypropylenediamine-N, N'-disuccinic acid (HPDDS) are also suitable.

enzyme

One another preferred ingredient used in the detergent compositions useful is, is one or more additional Enzymes.

preferred additional Close enzyme materials the commercially available Lipases, cutinases, amylases, neutral and alkaline proteases, Cellulases, endoiases, esterases, pectinases, lactases and peroxidases which conventionally be incorporated into detergent compositions. Suitable enzymes are in the US patents 3,519,570 and 3,533,139.

preferred commercially available Close Protease Enzymes under the trade names Alcalase, Savinase, Primase, Durazym and Esperase sold by Novo Industries A / S (Denmark) under the trade names Maxatase, Maxacal and Maxapem by Gist-Brocades sold by Genencor International and sold under the trade name Opticlean and Optimase by Solvay Enzymen sold one. The protease enzyme can be used in the compositions according to the invention in a proportion of 0.0001 to 4% active enzyme, based on the Weight of the composition to be included.

preferred Close amylases for example α-amylases one obtained from a particular strain of B. licheniformis be, in more detail described in GB-1,269,839 (Novo). Preferred commercially available Close amylases for example, under the trade name Rapidase by Gist-Brocades sold under the trade names Termamyl and BAN Novo Industries A / S sold one. The amylase enzyme can be found in the composition according to the invention in a proportion of 0.0001 to 2% active enzyme, based on the Weight of the composition to be included.

One lipolytic enzyme may be present in proportions of the active lipolytic Enzyme from 0.0001 to 2% by weight, preferably from 0.001 to 1% by weight, most preferably from 0.001 to 0.5% by weight of the compositions available.

The Lipase can be fungal or bacterial in origin and becomes a Example from a lipase-producing strain of Humicola sp. Thermomyces sp. or Pseudomonas sp., including Pseudomonas pseudoalcaligenes or Pseudomonas fluorescens. Lipases from chemical or Genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which in the given European Patent EP-B-0218272 is described.

A Another preferred lipase herein is by cloning the gene Humicola lanuginosa and expression of the gene in Aspergillus oryza as a host, as in European Patent Application EP-A-0258 068, and is commercially available from Novo Industri A / S, Bagsvaerd, Denmark, available under the trade name Lipolase. This lipase is too in U.S. Patent 4,810,414, Huge-Jensen et al., issued March 7, 1989, described.

organic polymeric compound

organic Polymeric compounds are preferred additional components of the detergent compositions of the present invention and are preferably as components of any particulate components in which they may be effective, for example, to the particulate components to connect with each other. With organic polymeric compound herein essentially any polymeric organic compound meant, usually as a dispersant and anti redeposition and soil suspending agent is used in detergent compositions, including any the high molecular weight organic polymeric compounds, which are described herein as a clay flocculating agent.

The Organic polymeric compound is typically in the detergent compositions of the invention in a proportion of 0.1 to 30% by weight, preferably 0.5 to 15% by weight, most preferably 1 to 10% by weight of the compositions included.

Examples of organic polymeric compounds include the water-soluble, organic, homo- or copolymers polycarboxylic acids or their salts, wherein the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of the latter type are disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2,000-5,000 and their copolymers with maleic anhydride, such copolymers having a molecular weight of 20,000 to 100,000, especially 40,000 to 80,000.

The Polyamino compounds are useful herein, including the from aspartic acid derived, such as those described in EP-A-305282, EP-A-305283 and EP-A-351629 are.

Terpolymers containing monomeric units _; selected from maleic acid, acrylic acid, polyaspartic acid and vinyl alcohol, especially those having an average molecular weight of 5,000 to 10,000, are also suitable herein.

Other organic polymeric compounds suitable for incorporation in the detergent compositions suitable herein Cellulose derivatives such as methylcellulose, carboxymethylcellulose, hydroxypropylmethylcellulose and hydroxyethyl cellulose.

Further useful organic polymeric compounds are the polyethylene glycols, especially those having a molecular weight of 1,000-10,000, more preferably 2,000 to 8,000, and most preferably about 4,000.

Suds suppressing system

The Detergent compositions according to the invention when used in machine-based compositions Washing formulated, preferably a suds suppressing system, which in a proportion of 0.01 to 15 wt .-%, preferably 0.05 to 10% by weight, most preferably 0.1 to 5% by weight of the composition is present.

suitable Foam suppression systems for use herein comprise essentially any known antifoam compound, including for example, silicone antifoam compounds and 2-alkylalkanol antifoam compounds.

With Antifoam compound is herein any compound or one Meant mixture of compounds which are thereby effective that she the foaming or the foaming caused by a solution of a Detergent composition, especially during the movement of the solution, suppress.

Especially preferred antifoam compounds for use herein are silicone antifoam compounds, which is defined herein as any antifoam compounds which include a silicone component. Such silicone antifoam compounds typically also contain a silica component. The term "silicone" as used herein and Generally used in industry includes a variety of relatively high molecular weight polymers, which siloxane units and Hydrocarbyl groups of different types included. Preferred silicone antifoam compounds the siloxanes, especially the polydimethylsiloxanes, are trimethylsilyl endblocking units have.

Other suitable antifoam compounds include the monocarboxylic fatty acids and soluble Salts thereof. These materials are disclosed in U.S. Patent 2,954,347. issued on September 27, 1960 to Wayne St. John. The Monocarboxylic fatty acids and salts thereof for use as suds suppressors are typically Hydrocarbyl chains having 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include Alkali metal salts such as sodium, potassium and lithium salts, as well as Ammonium and alkanolammonium salts.

Other suitable antifoam compounds include, for example, high molecular weight fatty esters (eg, fatty acid triglycerides); Fatty acid esters of monohydric alcohols; aliphatic C ₁₈ -C ₄₀ ketones (eg stearone); N-alkylated aminotriazines, such as tri- to hexaalkylmelamines or di- to tetraalkyldiaminochlorotriazines, which are formed as products of cyanuric chloride having two or three moles of a primary or secondary amine containing 1 to 24 carbon atoms; propylene oxide; bis stearic acid amide and monostearyldialkali metal phosphates (eg, sodium, potassium or lithium) and phosphate esters.

One preferred foam suppression system comprises

• (a) an antifoam compound, preferably a silicone antifoam compound, most preferably a silicone antifoam compound, comprehensive in combination
• (I) polydimethylsiloxane in a proportion of 50 to 99 wt .-%, preferably 75 to 95 wt .-%, of the silic con antifoam compound; and
• (ii) silica in a proportion of 1 to 50% by weight, preferably 5 to 25% by weight of the silicone / silica antifoam compound; in which the silica / silicone antifoam compound in a proportion of 5 to 50% by weight, preferably 10 to 40% by weight;
• (b) a dispersant compound, most preferably comprising a comb-like Silicone-glycol copolymer having a polyoxyalkylene content of 72-78% and a relationship of ethylene oxide to propylene oxide of 1: 0.9 to 1: 1.1, in one portion from 0.5 to 10% by weight, preferably from 1 to 10% by weight; being a special preferred comb-like Silicone glycol copolymer of this type DCO544 is commercially available available from Dow Corning under the trade name DCO544; and
• (c) an inert carrier fluid compound, most preferably comprising a C ₁₆ -C ₁₈ ethoxylated alcohol having a degree of ethoxylation of from 5 to 50, preferably from 8 to 15, in a proportion of from 5 to 80% by weight, preferably from 10 to 70% by weight .-%.

One particularly preferred particulate Suds suppressing system is described in EP-A-0210731 and comprises a silicone antifoam compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C, wherein the organic carrier material a monoester of glycerin and a fatty acid having from 12 to 20 carbon atoms comprising carbon chain. EP-A-0210721 other preferred particulate Foam suppression systems, wherein the organic carrier material a fatty acid or an alcohol containing from 12 to 20 carbon atoms Carbon chain or a mixture thereof having a melting point from 45 ° C up to 80 ° C is.

Clay softening

The Detergent compositions can a clay softening system. comprising a clay mineral compound and optionally a clay flocculating agent.

The Clay mineral compound is preferably a smectite clay compound. Smectite clays are disclosed in U.S. Patent Nos. 3,862,058, 3,948,790, U.S. Pat. 3,954,632 and 4,062,647. European Patent Nos. EP-A-299,575 and EP-A-313,146 in the name of the Procter & Gamble Company describe suitable organic polymeric clay flocculants.

Polymeric dye transfer inhibiting agents

The detergent compositions herein may also contain from 0.01% to 10% by weight, preferably from 0.05% to 0.5% by weight _; to polymeric dye transfer inhibiting agents. The polymeric dye transfer inhibiting agents are preferably selected from polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers or combinations thereof.

a) polyamine N-oxide polymers

R aliphatische, ethoxylierte aliphatische, aromatische. heterocyclische oder alicyclische Gruppen oder irgendeine Kombination hiervon darstellt, woran der Stickstoff der N-O-Gruppe gebunden sein kann, oder worin der Stickstoff der N-O-Gruppe ein Teil dieser Gruppen ist.Polyamine N-oxide polymers suitable for use herein contain units having the following structural formula:

R aliphatic, ethoxylated aliphatic, aromatic. heterocyclic or alicyclic groups, or any combination thereof, to which the nitrogen of the NO group may be attached, or wherein the nitrogen of the NO group is a part of these groups.

worin R₁, R₂ und R₃ aliphatische Gruppen, aromatische. heterocyclische oder alicyclische Gruppen oder Kombinationen hiervon sind, x und/oder Y und/oder z 0 oder 1 ist, und worin der Stickstoff der N-O-Gruppe gebunden sein kann, oder worin der Stickstoff der N-O-Gruppe einen Teil dieser Gruppen bildet. Die N-O-Gruppe kann Teil der polymerisierbaren Einheit (P) sein oder kann an das polymere Grundgerüst gebunden sein, oder eine Kombination aus beidem.The NO group can be represented by the following general structures:

wherein R ₁ , R ₂ and R _{3 are} aliphatic groups, aromatic. heterocyclic or alicyclic groups or combinations thereof, x and / or Y and / or z is 0 or 1, and wherein the nitrogen of the NO group may be bonded, or wherein the nitrogen of the NO group forms part of these groups. The NO group may be part of the polymerizable unit (P) or may be attached to the polymeric backbone, or a combination of both.

suitable Polyamine N-oxides wherein the N-O group forms part of the polymerizable Unit comprise polyamine N-oxides wherein R is aliphatic, aromatic, alicyclic or heterocyclic groups is selected. A class of polyamine N-oxides comprises the group of polyamine N-oxides, wherein the nitrogen of the N-O group forms part of the R group. Preferred polyamine N-oxides are those in which R is a heterocyclic group, such as pyrridine, pyrrole, Imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives hereof.

Other suitable polyamine N-oxides are the polyamine oxides wherein the N-O group is attached to the polymerizable Unit is bound. A preferred class of these polyamine N-oxides comprises the polyamine N-oxides of the general formula (I) in which R is an aromatic, heterocyclic or alicyclic group; where the nitrogen the N-functional group is part of the R group. Examples of these classes are polyamine oxides wherein R is a heterocyclic Compound such as pyrridine, pyrrole, imidazole and derivatives thereof.

The Polyamine N-oxides can be obtained in virtually any degree of polymerization. The degree of polymerization is not crucial; with the proviso that the material has the desired water solubility and Possesses dye suspension force. Typically, this is the average Molecular weight in the range of 500 to 1,000,000.

b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole

Suitable herein are copolymers of N-vinylimidazole and N-vinylpyrrolidone with an average molecular weight of 5,000 up to 50,000. The preferred copolymers have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2.

c) polyvinylpyrrolidone

The Detergent compositions herein can also be a polyvinylpyrrolidone ("PVP") with an average Use molecular weight of 2,500 to 400,000. Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada, under the product designations PVP K-15 (viscosity molecular weight 10,000), PVP K-30 (average molecular weight 40,000), PVP K-60 (average molecular weight 160,000) and PVP K-90 (average molecular weight 360,000) available. PVP K-15 is also available from ISP Corporation.

Other suitable polyvinylpyrrolidones, which are commercially available from BASF Corporation available are close Solcalan HP-165 and Sokalan HP-12.

d) Polyvinyloxazolidone

The Detergent compositions herein may also include polyvinyloxazolidones as polymeric dye transfer inhibiting agents use. The Polyvinyloxazolidone have an average Molecular weight from 2,500 to 400,000.

e) polyvinylimidazole

The detergent compositions herein can also use polyvinylimidazole as a polymeric dye transfer inhibitor. The polyvinylimidazoles preferably have an average Molecular weight from 2,500 to 400,000.

Optical brightener

The Detergent compositions herein also optionally contain about 0.005 to 5% by weight of certain types of hydrophilic optical Brighteners.

worin R₁ aus Anilino, N-2-Bis-hydroxyethyl und NH-2-Hydroxyethyl gewählt ist; R₂ aus N-2-Bis-hydroxyethyl, N-2-Hydroxyethyl-N-methylamino, Morphilino, Chlor und Amino gewählt ist; und M ein salzbildendes Kation ist, wie Natrium oder Kalium.Hydrophilic optical brighteners useful herein include those of the structural formula:

wherein R _{1 is selected} from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R _{2 is selected} from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation, such as sodium or potassium.

In the above formula, when R _{1 is} anilino, R _{2 is} N-2-bis-hydroxyethyl, and M is a cation such as sodium, then the brightener is 4,4'-bis [(4-anilino-6- (N-2 -bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid or the disodium salt. This particular brightener species is sold commercially under the tradename Tinopal-UNPA-GX by Giba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions herein.

In the above formula, when R _{1 is} anilino, R _{2 is} N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, then the brightener is 4,4'-bis - [(4-anilino-6 - (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2'-stilbenedisulfonic acid or the disodium salt. This particular brightener species is sold commercially under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation.

In the above formula, when R _{1 is} anilino, R _{2 is} morphilino and M is a cation such as sodium, then the brightener is 4,4'-bis - [(4-anilino-6-morphilino-s-triazin-2-yl ) - amino] -2,2'-stilbenedisulfonic acid or the sodium salt. This particular brightener species is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation.

cationic Fabric softening agents

cationic Teatil softening agents can also included in the compositions of the invention be. Suitable cationic teatil softening agents include water tertiary Amines or dilange-chain amide materials as in GB-A-1 514 276 and EP-B-0 011 340.

cationic Fabric softening agents are typically in total proportions of 0.5 to 15 wt%, usually 1 to 5 wt%, included.

Other optional components

Other optionally components which are included in the compositions of the invention are suitable, close Dyes and filler salts with sodium sulfate being a preferred filler salt.

pH of the compositions

The present compositions preferably have a pH measured as a 1% solution in distilled water, of at least 8.5, preferably 9.0 to 12.5, most preferably 9.5 to 11.0.

Form of the Compositions The compositions of the invention may take a variety of physical, preferably solid forms, including granular, tablet and bar forms, ha ben.

in the general can Granular detergent compositions according to the invention by a variety of methods, including dry blending, spray drying, Agglomeration and granulation.

The mid-chain branched surfactant system herein, preferably with additional Surfactants, is preferably in granular compositions in the form of surfactant agglomerate particles, preferably not comprising the bleach precursors, which may take the form of flakes, prills, marumes, noodles or ribbons, but preferably have the form of granules. The most preferred Way to process the particles is through the agglomeration of Powders (e.g., aluminosilicate, carbonate) with highly active surfactant pastes and controlling the particle size of the resulting Agglomerates within specified limits. Such a procedure involves mixing an effective amount of powder with one highly active surfactant paste in one or more agglomeration devices, such as a pan agglomerator, a Z-blade mixer or more preferred a pipe mixer, such as that of Schugi (Holland) BV, 29 Chroomstraat 8211 AS, Lelystad, The Netherlands, and the brothers Lodige Maschinenbau GmbH, D-4790 Paderborn 1, Elsenerstraße 7-9, PO Box 2050, Germany. Most preferred is one High shear mixer such as a Lodige CB (trade name) used.

A highly active surfactant paste comprising from 50% to 95% by weight, preferably From 70% to 85% by weight of the surfactants, including the mid-chain branched Surfactants, is typically used. The paste can be in the agglomerator be pumped at a temperature which is sufficient to a pumpable one viscosity which is low enough to break down to avoid the anionic surfactants used. A processing temperature the paste of 50 ° C up to 80 ° C is typical.

The Bleaching precursors according to the invention are preferably dry to the detergent base or agglomerates added.

The mean particle size of the components of granular compositions according to the invention should preferably be such that not more than 5% of the particles greater than 1.7 mm in diameter and not more than 5% of the particles are smaller than 0.15 mm in diameter.

Of the Term mean particle size, like is defined herein by sieving a sample of the composition into a series of fractions (typically 5 fractions) with one Series calculated by Tyler-Sieben. The ones obtained in this way Weight fractions are applied against the mesh size of the sieves. As mean particle size. becomes the mesh size through which 50% by weight of the sample passes would.

The bulk density the granular detergent compositions of the invention is typically a bulk density of at least 300 g / liter, more preferably 330 g / liter to 1,200 g / liter, stronger preferably 380 g / liter to 850 g / liter. The bulk density is determined with the help of a simple funnel and a cup-shaped device, which consists of a conical funnel, immovable on a base attached and at its lower end with a flap is provided to the emptying of the contents of the funnel into one axially aligned, cylindrical Cup, which is located under the funnel to allow. The funnel is 130 mm high and has at its respective upper and lower end have an inner diameter of 130 mm and 40 mm, respectively. He is so attached that himself the lower end 140 mm above the surface the base area located. The cup has a total height of 90 mm, an interior height of 87 mm and an inner diameter of 84 mm. Its nominal volume is 500 ml.

to execution In a measurement, the funnel is filled by hand pouring with powder, which flap will be opened and you leave the powder overflow the cup. Of the filled Cup is taken out of the cream, and excess powder is removed from the Cup removed by a puller, e.g. a knife over the slide on top of it. Of the filled Cup is then weighed and that obtained for the weight of the powder Value is duplicated to the bulk density in g / liter. If necessary, repeat measurements carried out.

The Compositions of the invention can also in or in combination with bleach additive compositions, for example, comprising a chlorine bleach, as mentioned above become.

However, since the preferred detergent compositions of the invention are solid, most are The chlorine-based liquid bleach will be unsuitable for these detergent compositions, and only granular or powdery chlorine-based bleaches will be suitable.

alternative can the detergent compositions are formulated to be compatible with Chlorine-based bleaching agents are compatible, thereby ensuring will that one Chlorine-based bleach to the detergent composition the consumer at the beginning or during the washing process can be added.

The Chlorine-based bleaches include a hypochlorite species which is formed in aqueous solution. The hypochlorination is represented chemically by the formula OCl.

Such Bleaching agents which give a hypochlorite species in aqueous solution, shut down All-alkali metal and alkaline earth metal hypochlorites, hypochlorite addition products, Chloramines, chlorimines, chloramides and chlorimines. specific examples for Close connections of this type Sodium hypochlorite, potassium hypochlorite, monobasic calcium hypochlorite, dibasic magnesium hypochlorite, chlorinated trisodium phosphate dodecahydrate, Potassium dichloroisocyanurate, sodium dichloroisocyanurate, sodium dichlorocyanurate dihydrate, trichlorocyanuric, 1,3-dichloro-5,5-dimethylhydantoin, N-chlorosulfamide, chloramine T, Dichloramine T, chloramine B and dichloramine B. A preferred one Bleaching agent for use in the compositions according to the invention is sodium hypochlorite, Potassium hypochlorite or a mixture thereof. A preferred bleaching agent chlorine-based can be triclosan (trade name).

The most of the hypochlorite bleaches described above are available in solid or concentrated form and are used during the Preparation of the compositions of the invention dissolved in water. Some of the above materials are available as aqueous solutions.

Laundry process

Machinery Washing procedures herein typically involve treating dirty laundry with an aqueous washing solution, wherein an effective amount of a detergent composition of the invention for machine washing clothes solved or dispensed, in a washing machine. With an effective Amount of the detergent composition is 40 g to 300 g of product, solved or dispersed in a washing solution with a volume of 5 to 65 liters ,. meant what typical product dosages ments and wash solution volumes which are ordinary in conventional Method for machine washing can be used.

Under A preferred aspect of the application is a dispensing device used in the washing process. The dispensing device is filled with the detergent product and is used to put the product directly into the drum of the washing machine before beginning the wash cycle. Your volume should be be that way can hold a sufficient amount of the detergent product as they do normally used in the washing process.

As soon as the washing machine with laundry is loaded, the dispensing device, which is the detergent product contains placed in the drum. At the beginning of the wash cycle of the washing machine is Water is introduced into the drum and the drum rotates periodically. The dispensing device should be designed to hold the Inclusion of the dry detergent product, but then the release of this product during the wash cycle in response on their movement, when the drum turns, and also as one Result of their contact with the wash water allowed.

Around to allow the release of the detergent product during washing the device may comprise a series of openings through which the product can pass through. In another embodiment, the device be made of a material which permeable to liquids, but for the solid product impermeable is what the release of the dissolved Product allowed. Preferably, the detergent product is initially the wash cycle quickly released, thereby temporarily localized high concentrations of the product in the drum of the washing machine at this stage of the Washer be provided.

Preferred dispensing devices are reusable and constructed in such a manner that the integrity of the container is maintained both in the dry state and during the wash cycle. Particularly preferred dispensing devices for use with the composition of the present invention have been described in the following patents: GB-B-2,157,717, GB-B-2; 157,718, EP-A-0201376, EP-A-0288345 and EP-A-0288346. An article by J. Bland, published in "Manufacturing Chemist", November 1989, pages 41-46, also describes particularly preferred dispensing devices for use with granular detergent products which correspond to a type commonly known as "granulette". Another preferred dispensing device for use with the compositions of the invention is disclosed in PCT Patent Application No. WO 94/11562.

Especially preferred dispensing devices are in the European patent applications with the publication numbers 0343069 and 0343070. The latter application discloses a device comprising a flexible sleeve in the form of a bag, which from a support ring which has an opening defined, with the opening adapted in this way is that in the bag a sufficient amount of the product for one Wash cycle can be included in a washing process. A part of the washing medium flows through the opening in the bag, triggers the product, and the solution flows then out of the opening in the washing medium. The support ring is provided with a cover to the outlet of the moistened, undissolved product to prevent this device being typically radially extending Including walls that from a center reinforcement in a spoke wheel assembly or similar structure in which the Walls one spiral Own form, extend.

In another embodiment, the dispensing device may be a flexible container, eg a bag or a bag. The bag may be a fibrous construction coated with a water-proofing protective material to retain the contents as disclosed in published European Patent Application No. 0018678. Alternatively, it may be formed from a water-insoluble synthetic polymeric material provided with an edge seal or closure designed to rupture in aqueous media, as disclosed in published European Patent Applications Nos. 001100, 001101, 001102 and 0011968 is disclosed. A suitable form of water-fragile closure comprises a water-soluble adhesive attached to one edge of a bag made of a water-impermeable adhesive _; polymeric film is formed as polyethylene or polypropylene, is distributed and this edge seals.

Packaging for the compositions

Commercially available bleach composition embodiments may be packaged in any suitable container, including those made from paper, cardboard, plastic materials, and any suitable composites. A preferred packaging design is in EP 0634485 described.

Used in the examples Abbreviations

LAS:

Lineares Natrium-C₁₂-alkylbenzolsulfonat

TAS:

Natriumtalgalkylsulfat

C45AS:

Lineares Natrium-C₁₄-C₁₅-alkylsulfat

MES:

Sulfomethylester einer C₁₈-Fettsäure

CayEzS:

Verzweigtes Natrium-C_1x-C_1y-alkylsulfat, kondensiert mit z Molen Ethylenoxid

MBAS_x,y:

Mittelkettigverzweigtes Natriumalkylsulfat mit durchschnittlich x Kohlenstoffatomen, wovon y Kohlenstoffatome in (einer) Verzweigungseinheiten) umfaßt sind

C₄₈SAS.

Sekundäres Natrium-C₁₄-C₁₈-alkoholsulfat

SADE2S:

Natrium-C₁₄-C₂₂-alkyldisulfat der Formel 2-(R).C₄H₇-1,4-(SO₄ ^-)₂, worin R = C₁₀0C₁₈, kondensiert mit z Molen Ethylenoxid

C45E7:

Ein überwiegend linearer primärer C_14–15-Alkohol, kondensiert im Durchschnitt mit 7 Molen Ethylenoxid

CxyEz:

Ein verzweigter primärer C_1x-C_1y-Alkohol, kondensiert im Durchschnitt mit z Molen Ethylenoxid

QASII:

R₂.N⁺(CH₃)₂(C₂H₄OH) mit R₂ = 50%–60% C₉; 40%–50% C₁₁

QASIV:

R₁.N⁺(CH₃)₂(C₂H₄OH) mit R₁ = C₁₂-C₁₄

QASV:

R²O(C₂H₄O)_x(Glycosyl)₂, worin R² eine C₈-C₁₀-Alkylgruppe ist; t 2 bis 8 ist

Seife:

Lineares Natriumalkylcarboxylat, abgeleitet aus einer 80/20-Mischung von Talg- und Kokosnußölen

TFAA:

C₁₆-C₁₈-Alkyl-N-methylglucamid

TPKFA:

Herausdestillierte Gesamtfraktion von C₁₂-C₁₄-Fettsäuren

STPP:

Wasserfreies Natriumtripolyphosphat

Zeolith A:

Hydratisiertes Natriumaluminosilicat der Formel Na₁₂(AlO₂SiO₂)₁₂. 27H₂O, mit einer primären Teilchengröße im Bereich von 0,1 bis 10 μm

NaSKS-6:

Kristallines Schichtsilicat der Formel δ-Na₂Si₂O₅

Citronensäure:

Wasserfreie Citronensäure

Carbonat:

Wasserfreies Natriumcarbonat mit einer Teilchengröße zwischen 200 μm und 900 μm

Bicarbonat:

Wasserfreies Natriumbicarbonat mit einer Teilchengrößenverteilung zwischen 400 μm und 1.200 μm

Silicat:

Amorphes Natriumsilicat (SiO₂:Na₂O; Verhältnis = 2,0)

Natriumsulfat:

Wasserfreies Natriumsulfat

Citrat:

Trinatriumcitratdihydrat mit einer Aktivität von 86,4% bei einer Teilchengrößenverteilung zwischen 425 μm und 850 μm

MA/AA:

Copolymer von Malein/Acrylsäure (1:4), durchschnittliches Molelculargewicht etwa 70.000

CMC:

Natriumcarboxymethylcellulose

Protease:

Proteolytisches Enzym mit einer Aktivität von 4 KNPU/g, vertrieben durch Novo Industries A/S unter dem Handelsnamen Savinase

Alcalase:

Proteolytisches Enzym mit einer Aktivität von 3 AU/g, vertrieben durch Novo Industries A/S

Cellulase:

Cellulytisches Enzym mit einer Aktivität von 1.000 CEVU/g, vertrieben durch Novo Industries A/S unter dem Handelsnamen Carezyme

Amylase:

Amylolytisches Enzym mit einer Aktivität von 60 KNU/g, vertrieben durch Novo Industries A/S unter dem Handelsnamen Termamyl 60T

Lipase:

Lipolytisches Enzym mit einer Aktivität von 100 KLU/g, vertrieben durch Novo Industries A/S unter dem Handelsnamen Lipolase

Endolase:

Endoglucanaseenzym mit einer Aktivität von 3.000 CEVU/g, vertrieben durch Novo Industries A/S

PB4:

Natriumperborattetrahydrat der nominalen Formel NaBO₂.3H₂O.H₂O₂

PB1:

Wasserfreies Natriumperborat-Bleichmittel der nominalen Formel NaBO₂.H₂O₂

Percarbonat:

Natriumpercarbonat der nominalen Formel 2Na₂CO₃.3H₂O₂

NAC-OBS:

(Nonanamidocaproyl)oxybenzolsulfonat in Form des Natriumsalzes

NOBS:

Nonanoyloxybenzolsulfonat in Form des Natriumsalzes

LOBS:

Dodecanoyloxybenzolsulfonat in Form des Natriumsalzes

DOBS:

Decanoyloxybenzolsulfonat in Form des Natriumsalzes

DPDA:

Diperoxydodecandisäure

PAP:

N-Phthaloylamidoperoxycapronsäure

NAPAA:

Nonanoylamidoperoxoadipinsäure

NACA:

6-Nonylamino-6-oxo-capronsäure

TAED:

Tetraacetylethylendiamin

DTPMP:

Diethylentriaminpenta(methylenphosphonsäure), vertrieben durch Monsanto unter dem Handelsnamen Dequest 2060

Licht- aktiviertes Bleichmittel:

Sulfoniertes Zink- oder Aluminiumphthalocyanin, eingekapselt

Aufheller 1:

Dinatrium-4,4'-bis(2-sulfostyryl)biphenyl

Aufheller 2:

Dinatrium-4,4'-bis(4-anilino-6-morpholino-1,3,5-triazin-2-yl)amino)-stilben-2,2'-disulfonat

HEDP:

1,1-Hydroxyethandiphosphonsäure

PVNO:

Polyvinylpyrridin-N-oxid

PVPVI:

Copolymer von Polyvinylpyrrolidon und Vinylimidazol

QEA:

Bis((C₂H₅O)(C₂H₂O)_n)(CH₃)-N⁺-C₆H₁₂-N⁺-(CH₃)bis((C₂H₂O)(C₂H₄O)_n), worin n = 20 bis 30

SRP 1:

Sulfobenzoyl-endverkappte Ester mit einem Oxyethylenoxy- und Terephthaloyl-Grundgerüst

SRP 2:

Kurzes diethoxyliertes Poly(1,2-propylenterephthalat)-Blockpolymer

Silicon-Antischaummittel:

Polydimethylsiloxan-Schaumkontrollmittel mit einem Siloxan Oxyalkylen-Copolymer als Dispergiermittel mit einem Verhältnis von Schaumkontrollmittel zu dem Dispergiermittel von 10:1 bis 100:1

In the detergent compositions, the abbreviated component designations have the following meanings:

READ:

Linear sodium C ₁₂ alkyl benzene sulfonate

TAS:

Natriumtalgalkylsulfat

C45AS:

Linear sodium C ₁₄ -C ₁₅ alkyl sulfate

MES:

Sulfomethyl ester of a C ₁₈ fatty acid

CayEzS:

Branched sodium C ₁ -C ₁ -alkyl sulfate condensed with z moles of ethylene oxide

MBAS _{x, y} :

Mid-chain branched sodium alkyl sulfate having an average of x carbon atoms, of which y are carbon atoms in branching unit (s)

C ₄₈ SAS.

Secondary sodium C ₁₄ -C ₁₈ alcohol sulfate

SADE2S:

Sodium C ₁₄ -C ₂₂ alkyl disulfate of the formula 2- (R) .C ₄ H ₇ -1,4- (SO ₄ ^- ) ₂ , wherein R = C ₁₀ 0C ₁₈ , condensed with z moles of ethylene oxide

C45E7:

A predominantly linear C _14-15 primary alcohol condenses on average with 7 moles of ethylene oxide

CxyEz:

A branched primary C "_x" C "_1y" alcohol condenses on average with z moles of ethylene oxide

QASII:

R ₂ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) with R ₂ = 50% -60% C ₉ ; 40% -50% C ₁₁

QASIV:

R ₁ .N ⁺ (CH ₃ ) ₂ (C ₂ H ₄ OH) with R ₁ = C ₁₂ -C ₁₄

QASV:

R ² O (C ₂ H ₄ O) _x (glycosyl) ₂ , wherein R ^{2 is} a C ₈ -C ₁₀ alkyl group; t is 2 to 8

Soap:

Linear sodium alkyl carboxylate derived from an 80/20 blend of tallow and coconut oils

TFAA:

C ₁₆ -C ₁₈ -alkyl-N-methylglucamide

TPKFA:

Distilled total fraction of C ₁₂ -C ₁₄ fatty acids

STPP:

Anhydrous sodium tripolyphosphate

Zeolite A:

Hydrated sodium aluminosilicate of formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ . 27H ₂ O, having a primary particle size in the range of 0.1 to 10 microns

NaSKS-6:

Crystalline layered silicate of the formula δ-Na ₂ Si ₂ O ₅

citric acid:

Anhydrous citric acid

carbonate:

Anhydrous sodium carbonate with a particle size between 200 microns and 900 microns

bicarbonate

Anhydrous sodium bicarbonate with a particle size distribution between 400 μm and 1200 μm

Silicate:

Amorphous sodium silicate (SiO ₂ : Na ₂ O, ratio = 2.0)

Sodium sulfate:

Anhydrous sodium sulfate

citrate:

Trisodium citrate dihydrate with an activity of 86.4% with a particle size distribution between 425 microns and 850 microns

MA / AA:

Copolymer of maleic / acrylic acid (1: 4), average molecular weight about 70,000

CMC:

sodium

protease:

Proteolytic enzyme with an activity of 4 KNPU / g, marketed by Novo Industries A / S under the trade name Savinase

Alcalase:

Proteolytic enzyme with an activity of 3 AU / g, marketed by Novo Industries A / S

cellulase:

Cellulytic enzyme with activity of 1000 CEVU / g sold by Novo Industries A / S under the trade name Carezyme

amylase:

Amylolytic enzyme with an activity of 60 KNU / g sold by Novo Industries A / S under the trade name Termamyl 60T

lipase:

Lipolytic enzyme with an activity of 100 KLU / g, marketed by Novo Industries A / S under the trade name Lipolase

Endolase®:

Endoglucanase enzyme with an activity of 3000 CEVU / g sold by Novo Industries A / S

PB4:

Sodium perborate tetrahydrate of nominal formula NaBO ₂ .3H ₂ OH ₂ O ₂

PB1:

Anhydrous sodium perborate bleach of nominal formula NaBO ₂ .H ₂ O ₂

percarbonate:

Sodium percarbonate of nominal formula 2Na ₂ CO ₃ .3H ₂ O ₂

NAC-OBS:

(Nonanamidocaproyl) oxybenzenesulfonate in the form of the sodium salt

NOBS:

Nonanoyloxybenzenesulfonate in the form of the sodium salt

LOBS:

Dodecanoyloxybenzenesulfonate in the form of the sodium salt

DOBS:

Decanoyloxybenzenesulfonate in the form of the sodium salt

DPDA:

diperoxydodecanedioc

PAP:

N-phthaloyl

NAPAA:

Nonanoylamidoperoxoadipinsäure

NACA:

6-nonylamino-6-oxo-caproic acid

TAED:

tetraacetylethylenediamine

DTPMP:

Diethylenetriaminepenta (methylenephosphonic acid), marketed by Monsanto under the tradename Dequest 2060

Light-activated bleach:

Sulfonated zinc or aluminum phthalocyanine encapsulated

Brightener 1:

Disodium 4,4'-bis (2-sulphostyryl) biphenyl

Brightener 2:

Disodium 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) amino) stilbene-2,2'-disulfonate

HEDP:

1,1-hydroxyethane

PVNO

Polyvinylpyridine-N-oxide

PVPVI:

Copolymer of polyvinylpyrrolidone and vinylimidazole

QEA:

Bis ((C ₂ H ₅ O) (C ₂ H ₂ O) _n ) (CH ₃ ) -N ⁺ C ₆ H ₁₂ -N ⁺ - (CH ₃ ) to ((C ₂ H ₂ O) (C ₂ H ₄ O) _n ), where n = 20 to 30

SRP 1:

Sulfobenzoyl end-capped esters with an oxyethyleneoxy and terephthaloyl backbone

SRP 2:

Short diethoxylated poly (1,2-propylene terephthalate) block polymer

Silicone anti-foaming agents:

Polydimethylsiloxane foam control agent comprising a siloxane-oxyalkylene copolymer dispersant with a ratio of foam control agent to dispersant of 10: 1 to 100: 1

In In the following examples, all parts are by weight Composition or as% by weight of the composition, if indicated, cited.

example 1

The following high density granular laundry detergent compositions A to F of particular use under European machine wash conditions were made in accordance with the invention:

Example 2

The following granular Laundry detergent compositions G to I with a bulk density of 750 g / liter are compositions according to the invention:

Example 3

The The following are detergent formulations according to the invention, wherein J is a phosphorus-containing detergent composition, No zeolite-containing detergent composition is, and L is a compact detergent composition is:

Example 4

The The following are detergent formulations according to the invention:

Example 5

The The following are detergent formulations according to the invention:

Example 6

sThe The following are high density and bleach-containing detergent formulations of the invention:

Example 7

The The following are highly compressed detergent formulations according to the invention:

Example 8

The following granular Detergent formulations are examples of the present invention:

Example 9

Example 10

The following laundry detergent compositions AQ to AT are made in accordance with the invention:

Example 11

The following laundry detergent compositions AU to AY are made in accordance with the invention:

Example 12

The following laundry detergent compositions AZ to Ee are prepared in accordance with the invention:

Claims (10)

A detergent composition comprising a) at least 0.5, preferably at least 5, more preferably at least 10% by weight of the composition of a surfactant system comprising one or more longer alkyl chain mid-chain branched surfactant compounds of the formula: A b XB wherein: (I) ^{Ab is} a hydrophobic, mid-chain branched alkyl moiety having a total of 9 to 22 carbons in the moiety, preferably 12 to 18, with: (1) a longest linear carbon chain attached to the -XB moiety in Range of 8 to 21 carbons; (2) one or more C ₁ -C ₃ alkyl moieties branching from this longest linear carbon chain; (3) at least one of the branching alkyl moieties is bonded directly to a carbon of the longest linear carbon chain at a position within the region of the position 2 carbon counted from position 1 carbon (# 1) attached to the -XB moiety to the position of the terminal carbon minus 2 carbons, (the (ω-2) carbon); and (4) when more than one of these compounds is present, the average total number of carbon atoms in the Ab-X units of the above formula is within the range of from 14.5 to 18, preferably 15 to 17; (II) B is a hydrophilic unit selected from sulfates, sulfonates, amine oxides, polyoxyalkylene, preferably polyoxyethylene and polyoxypropylene, alkoxylated sulfates, polyhydroxy units, phosphate esters, glycerol sulfonates, polygluconates, polyphosphate esters, phosphonates, sulfosuccinates, sulfosuccinates, polyalkoxylated carboxylates, glucamides, taurinates, Sarcosinates, glycinates, isethionates, dialkanolamides, monoalkanolamides, monoalcanolamide sulfates, diglycolamides, diglycolamide sulfates, glycerol esters, glycerol ester sulfates, glycerol ethers, glycerol ether sulfates, polyglycerol ethers, polyglycerol ether sulfates, sorbitan esters, polyalkoxylated sorbitan esters, ammonium alkanesulfonates, amidopropyl betaines, alkylated quats, alkylated / polyhydroxyalkylated quats, alkylated quats, alkylated / polyhydroxylated oxypropyl quats, imidazolines, 2-yl succinates, sulfonated alkyl esters and sulfonated fatty acids; and (III) X is selected from -CH ₂ - and -C (O) -; and b) at least 0.5% by weight of the composition of a bleaching system comprising (I) a hydrophobic bleach precursor; and (II) a hydrophilic bleach precursor. A detergent composition according to claim 1 wherein the surfactant compounds of surfactant system a) are of the above formula wherein the A ^b moiety is a branched primary alkyl moiety having the formula:

wherein the total number of carbon atoms in the branched primary alkyl moiety of this formula, including the R, R ¹ and R ² branches, is from 13 to 19; R, R1 and R2 are each independently selected from hydrogen and C ₁ -C ₃ alkyl, preferably methyl, with the proviso that R, R ¹ and R ^{2 are} not all hydrogen and when z is 0, at least R or R ^{1 is} not hydrogen; w is an integer from 0 to 13; x is an integer of 0 to 13; y is an integer of 0 to 13; z is an integer of 0 to 13; and w + x + y + z is 7 to 13. A detergent composition according to any preceding claim wherein the surfactant system a) contains at least about 20% by weight of the system, more preferably at least 90% by weight of one or more mid-chain branched alkyl sulfates of the formula:

or mixtures thereof; wherein M represents one or more cations; a, b, d and e are integers, a + b is 10 to 16, d + e is 8 to 14, and further when a + b = 10, a is an integer from 2 to 9 and b is an integer Number is from 1 to 8; when a + b = 11, a is an integer from 2 to 10 and b is an integer from 1 to 9; when a + b = 12, a is an integer from 2 to 11 and b is an integer from 1 to 10; when a + b = 13, a is an integer from 2 to 12 and b is an integer from 1 to 11; when a + b = 14, a is an integer from 2 to 13 and b is an integer from 1 to 12; when a + b = 15, a is an integer from 2 to 14 and b is an integer from 1 to 13; when a + b = 16, a is an integer from 2 to 15 and b is an integer from 1 to 14; when d + e = 8, d is an integer from 2 to 7 and e is an integer from 1 to 6; when d + e = 9, d is an integer from 2 to 8 and e is an integer from 1 to 7; when d + e = 10, d is an integer from 2 to 9 and e is an integer from 1 to 8; when d + e = 11, d is an integer from 2 to 10 and e is an integer from 1 to 9; when d + e = 12, d is an integer from 2 to 11 and e is an integer from 1 to 10; when d + e = 13, d is an integer from 2 to 12 and e is an integer from 1 to 11; when d + e = 14, d is an integer from 2 to 13 and e is an integer from 1 to 12; wherein when more than one of these sulfate surfactants is present in the surfactant system, the average total number of carbon atoms in the branched primary alkyl moieties is 14.5 to 17.5. A detergent composition according to any preceding claim, wherein the surfactant compounds of the surfactant system a) comprise an A ^b -X unit having 16 to 18 carbon atoms and B is a sulfate group. A detergent composition, wherein the hydrophobic bleach precursor corresponds to the formula

wherein R ^{1 is} an aryl or alkaryl group having 1 to 4 carbon atoms, R ^{2 is} an alkylene, arylene and alkarylene group having 1 to 14 carbon atoms, and R 5 is H or an alkyl, aryl or alkaryl group having 1 to 10 carbon atoms and L may be essentially any leaving group. A detergent composition according to at least one preceding Claim wherein the hydrophobic bleach precursor is selected from the group consisting of comprising (6-octanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, decanoyloxy-benzenesulfonate sodium salt, Benzoyloxy-benzenesulfonate sodium salt, sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate and Sodium nonanoyl, decanoyl or dodecanoyloxybenzene sulfonate. A detergent composition according to at least one preceding Claim, wherein the hydrophilic bleach precursor is TAED. A detergent composition according to at least one preceding Claim, wherein the bleach system is an inorganic perhydrate salt preferably a perborate or percarbonate salt, preferably in a proportion of 3 to 25% by weight of the composition. A detergent composition according to any preceding claim wherein a nonionic surfactant, preferably a C ₉ -C ₁₅ primary alcohol ethoxylate having from 3 to 12 moles of ethylene oxide per mole of alcohol, in a ratio to the surfactant system a) of from 10: 1 to 1:10, preferably 1: 1 to 1:10. A detergent composition according to at least one preceding Claim in the form of a solid laundry detergent composition.