CZ20021612A3 - Detergent composition containing zwitterion polyamines - Google Patents

Abstract

The present invention relates to laundry detergent composition comprising: from about 0.01 %, most preferably from about 3 % to about 50 %, most preferably to about 7 % by weight, of a hydrophobically modified polyamine having formula (I): wherein R is C5-C20 linear or branched alkylene, and mixtures thereof; R<1> is an alkyleneoxy unit having the formula: -(R<2>O)x-R3 wherein R<2> is C2-C4 linear or branched alkylene, and mixtures thereof; R<3> is hydrogen, C1-C22 alkyl, C7-C22 alkylenearyl, an anionic unit, and mixtures thereof; x is from about 15 to about 30; Q is a hydrophobic quaternizing unit selected from the group consisting of C8-C30 linear or branched alkyl, C6-C30 cycloalkyl, C7-C30 substituted or unsubstituted alkylenearyl, and mixtures thereof; X is an anion present in sufficient amount to provide electronic neutrality; n is from 0 to 4, from about 0.01 % by weight, of surfactant; the balance carriers and adjunct ingredients.

Description

The present invention relates to laundry detergent compositions containing one or more hydrophobically modified _and polyamines providing improved cleaning properties, inter alia, clay cleaning. The invention also relates to methods for removing hydrophilic soils from clothing.

BACKGROUND OF THE INVENTION ·

For fabrics, especially clothing, contamination can occur with various substances ranging from hydrophobic stains (fat, oil) to hydrophilic stains (clay). The intensity of cleaning required to remove said foreign matter depends primarily on the amount of impurity present and the degree of contact of the foreign matter with the fabric fibers. Grass stains usually result from direct abrasive contact with plant matter, which results in highly penetrating soiling. Clay stains, although in some cases with less force, include another type of removal problem associated with the high charge associated with the clay itself. This ^high% surface charge density may act repulsively to certain laundry additive compositions, inter alia for dispersing clay, thus preventing any appreciable peptization and dispersion of the clay into the wash liquor.

As such, the surfactant is not the only component sufficient to remove undesirable soil and soil stains. In fact, most surfactants in water have a surprisingly low removal effect on dirt due to clay. On • ·

different types of stains also do not all the same surfactants. In addition to the surfactants, polyamine dispersants for hydrophilic impurities are added to the laundry detergent compositions to separate clay impurities from the fabric surface and to provide sufficient

In stabilizing the removed particles in solution to minimize. the possibility of their repositioning on the fabric. However, unless there is an initial separation of clay from the soiled fabric, the solution does not contain any particles that would bind to the dispersant and keep it suspended.

There is a continuing need in the art for detergent compositions for laundry, which effectively disintegrates and removes soil and other hydrophilic impurities from the fabric into which they have penetrated. In addition, for increasing concentrations of hydrophilic impurities in the wash liquid, a surfactant system capable of functioning under conditions of increased loading of the impurities is required. There is also a long-term need for an active clay-contaminant which is optimized for particular detergent compositions such as, among other things, granular or liquid compositions, to suit the surfactant system used. Furthermore, there is a long-term need for a method for removing hydrophilic stains from fabrics, by which hydrophilic stains would be effectively peptized, dispersed and suspended in the wash fluid:

SUMMARY OF THE INVENTION

The present inventors have surprisingly found that detergent compositions comprising fully quaternized polyethoxylated polyamines, wherein said polyethoxy units are terminated with anionic units and the polyamine skeleton contains relatively hydrophobic spacer groups, said polyamines can be hydrophobically modified by selecting certain quaternized units to achieve enhanced soil removal performance from clothes. The detergent compositions of the invention are particularly effective for the removal of clay and other hydrophilic ^- soils from fabrics. When used with a suitable surfactant system, the hydrophobically modified polyamines of the present invention allow the removal of stains that have been believed to degrade the fabric, especially the cellulose-containing fabric.

A first aspect of the invention is a laundry detergent composition comprising:

A) from about 0.01%, preferably from about 0.1%, even more preferably from about 1%, most preferably from about 3% to about 50%, preferably to about 20%, even more preferably to about 10%, most preferably to about 7% by weight of a hydrophobically modified polyamine having the formula:

- R ¹ I (R ^ -R- -tf-R] -S (R ‘) 2 X * Q Q Q - ->

wherein R is a straight or branched C ₅ -C ₂₀ alkylene group and mixtures thereof; R ¹ represents an alkyleneoxy unit having the general formula:

- (R ² O) _x -R ³ wherein • R ² is C ₂ -C ₄ alkylene group with straight -or branched alkylene, and mixtures thereof; ^R3 is an anionic unit, and mixtures thereof; x is about 15 to about 30; Q represents a hydrophobic quaternizing unit which means a group selected from the group consisting of straight-chain or branched C ₈ -C ₃ oalkyl, C 6 -C ₃₀ cycloalkyl, substituted or unsubstituted C ₇ -C ₃₀ alkylenaryl and mixtures thereof; X represents an anion in an amount sufficient to provide electroneutrality; n is 0 to 4;

B) from about 0.01% by weight of a surfactant system comprising one or more surfactants selected from the group consisting of:

i) 0% to 100% by weight of one or more anionic surfactants;

ii) 0% to about 100% by weight of one or more non-ionic surfactants;

iii) optionally 0.1% to about 80% by weight of one or more cationic surfactants;

iv) optionally 0.1% to about 80% by weight of one or more zwitterionic surfactants;

v) optionally 0.1% to about 80% by weight of one or more ampholytic surfactants;

vi) mixtures thereof; .

C) replenishment of carriers and auxiliaries.

The invention also relates to a method of cleaning fabrics, said method comprising the step of contacting a fabric-containing article, preferably a garment, with an aqueous solution of a detergent composition comprising a hydrophobically modified polyamine of the invention.

Said and other objects, features and advantages of the invention will be apparent to those skilled in the art from the following detailed description and from the appended claims. All percentages, ratios and proportions herein are by weight unless otherwise indicated. All temperature data are in degrees Celsius (° C) unless otherwise indicated. All references are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

The invention relates to hydrophobically modified quaternized zwitterionic polyamines suitable for use in laundry detergent compositions. The hydrophobically modified zwitterionic polyamines of the invention provide improved soil removal and dirt removal effects.

Surprisingly, it has been found that the hydrophobically modified quaternary zwitterionic polyamines have enhanced efficiency when used on fabrics contaminated with body fluids, sweat, etc. Without being bound by specific theory, it is believed that the hydrophobically modified quaternary zwitterionic polyamines of the invention have unexpectedly balanced properties that allow said compounds penetrate the fabric where they dissolve the greasy and oily stains, while maintaining water solubility and the ability to form a suspension of particulate impurities in the fluid needed to directly remove impurities from the fabric and thereby prevent re-establishment on the fabric. In addition, the hydrophobically modified zwitterionic polyamines of the invention enhance the cleaning performance of high soap and phosphate cleaning systems. '

When used in laundry detergent compositions, zwitterionic polyamines are effective in an amount of from about 0.01%, preferably from about 0.1%, even more preferably from about 1%, most preferably from about 3% to about 50%, preferably to about 20%, even more preferably up to about 10%, most preferably up to about 7%, based on said detergent composition.

• ť

Hydrophobically modified quaternary zwitterionic polyamines

For purposes of the present invention, the term hydrophobically modified refers to the reaction product of a linear polyamine containing 2 to 5 nitrogen atoms, wherein each nitrogen atom has a hydrogen atom on the skeleton replaced by a polyalkyleneoxy group containing at least about 15 alkylenoxy units terminated by anionic group with at least one equivalent per atom wherein said quaternizing agent comprises a linear alkyl moiety of at least 8 carbon atoms, a cyclic alkyl moiety having at least 6 carbon atoms, an alkylenaryl moiety, inter alia benzyl having at least 7 carbon atoms, or mixtures thereof.

For the purposes of the present invention, the term polyamine means an amine skeleton containing less than 6 nitrogen atoms and no branching whereas amines containing more than 5 nitrogen atoms for the purposes of the present invention are referred to as oligomeric amines (oligoamines) or polymerized amines (polyalkylenimines or polyalkylenimines).

Hydrophobically modified zwitterionic polyamines according to • · • 9 · 9 ·

The X 'of the invention have the general formula:

Wherein R is a straight chained or branched C6-C20 alkylene group and mixtures thereof; in one embodiment of the invention R is a straight chain C8-C10 alkylene group, in another embodiment R is In a further embodiment, each of the R units is a hexylene unit, usually a linear hexylene unit.

R ¹ represents a polyalkyleneoxy unit having terminal anion of the general vzdrce:

- (R ² O) _X -R ³ where R ² represents a C ² -C ⁴ straight or branched chain alkylene group and mixtures thereof. The term straight or branched chain used in connection with R ² means any straight or branched alkylene unit; branched chain having a total of 2 to 4 carbon atoms. In one embodiment of the invention, R ² is ethylene, 1,2-propylene, and mixtures thereof; in yet another embodiment of the invention, each R ² unit is an ethylene unit. In one embodiment of the invention which is preferred in terms of bleaching effects, the composition of the invention comprises hydrophobically modified zwitterionic polyamines formed first of 1-6, preferably 1-3 alkyleneoxy units in the form of 1,2-propyleneoxy units and subsequently in amounts up to a given number of ethyleneoxy units .

R ³ is an anionic capping unit, and mixtures of these units. The term anionic terminal unit and mixtures thereof

Units means that R ³ may be one type of anionic unit or each R ³ may be a different anionic terminal unit, or R ³ may be a mixture of anionic units. Examples of, but not limited to, anionic units that are included in one embodiment of the invention are anionic units selected from the group consisting of:

a) - (CH ₂ ) _f CO ₂ M;

b) -C (O) (CH ₂ ) _f CO ₂ M;

c) - (CH ₂ ) _f PO ₃ M;

d) - (CH ₂ ) _f OPO ₃ M;

e) - (CH ₂ ) _f SO ₃ M;

f) -CH ₂ (CHSO ₃ M) (CH 2) fSO ₃ M;

g) -CH ₂ (CHSO ₂ M) (CH ₂ ) _f SO ₃ M;

h) -C (O) CH ₂ CH (SO ₃ M) CO ₂ M; ·

i) -C (O) CH ₂ CH (CO ₂ M) NHCH (CO ₂ M) CH ₂ CO ₂ M;

j) and mixtures thereof;

wherein M is hydrogen or a cation providing electroneutrality. For the purposes of the invention, all M units attached to the hydrophobically modified zwitterionic polyamine, surfactant or adjuvant may be either a hydrogen atom or a cation depending on. isolated form or relative pH of the system in which the compound is contained. Examples of preferred cations that are not limited to said cations include sodium, potassium, ammonium, and mixtures thereof. The index f is in the range of 0 to about 10, in one embodiment of the invention said index is in the range of 0 to 2.

The index x, which indicates the mean number of alkyleneoxy units attached to the scaffold nitrogen, is from about 15 to about 30, preferably from about 15 to 25, even more preferably from 18 to 23, and most preferably 99 to 99.

9 9 9 ·

9 9 9 9

999 9 9 99 ··

* The number of alkyleneoxy units is 20. When ethoxylating the zwitterionic polyamine, only the mean ethoxylation value or the statistical distribution of the alkyleneoxy units can be ascertained. Therefore, the mean value may vary from embodiment to embodiment depending on how well or precisely the alkoxylation of the zwitterionic polyamine is performed.

Q znamená.hydrofobní quaternizing unit and each unit Q independently represents C ₃ -C-O-alkyl straight or branched chain C ₃ -C ₆ ocykloalkylovou group, C7 · C3oalkylenarylovou substituted or unsubstituted, and mixtures thereof; in one embodiment of the invention Q is a hydrophobic quaternizing unit selected from the group consisting of a C 7 -C 30 substituted or unsubstituted alkylenearyl group, and mixtures thereof; preferably it is selected from the group consisting of benzyl, substituted benzyl, naphthyl, substituted naphthyl and mixtures thereof. In the description of the invention, the formulas:

or

correspond to the meaning of naphthyl whether the unit is substituted at the α or β position. The index w stands for 0 to 20. Other alkylenaryl units are formed in addition to the benzyl group by groups of the formula:

wherein the index z is 1 to 24.

For purposes of the invention, the term substituted applied to alkylene aryl units suitable as Q units includes those units containing one or more straight or branched chain C 1 -C 12 alkyl groups wherein the total number of carbon atoms including those in the aromatic ring does not exceed 30.

An example of a substituted alkylenaryl unit of a unit of the invention, without being limited to said unit, is a group of the formula:

which is 3,5-di-tert-butylbenzyl.

The index n represents the number of secondary nitrogen atoms in the skeleton. The index n ‘denotes 0 to 4, preferably 0 to 2.

X is an anion contained in an amount sufficient to maintain electroneutrality. Examples of anions include, but are not limited to, chlorine, bromine, iodine, methyl sulfate, and mixtures thereof.

An example of a preferred hydrophobically modified zwitterionic polyamine of the invention is a compound of the formula:

• · ♦ ♦

I * * ·

0 #.

• · »0 · ♦ 0 ♦

0

00 ··

wherein X is a water-soluble anion selected from the group consisting of chlorine, bromine, iodine, methyl sulfate and mixtures thereof.

Surface active system

The detergent compositions of the invention comprise from about 0.01%, preferably from about 1%, even more preferably from about 5%, most preferably from 10% to about 80%, preferably to about 50%, even more preferably to about 30% by weight of the surfactant system. wherein said surfactant system comprises one or more surfactants selected from the group consisting of:

i) 0% to 100% by weight of one or more anionic surfactants;

ii) 0% to about 100% by weight of one or more nonionic surfactants;

iii) optionally 0.1% to about 80% by weight of one or more cationic surfactants;

iv) optionally 0.1% to about 80% by weight of one or more zwitterionic surfactants;

v) optionally 0.1% to about 80% by weight of one;

0 0

0 · • 0

000 ·

0 »

0 ♦ 0 · · t »

0 0 00 00 ·· more ampholytic surfactants;

vi) mixtures thereof;

A preferred surfactant system of the invention comprises from about 0.01% by weight of one or more surfactants selected from the group consisting of:

(i) from 1% to about 100% by weight of an anionic surfactant selected from the group consisting of:

(a) linear alkylbenzene sulphonates; , '

(b) 'Arylsulfonate surfactants with a branched internal chain, of the general formula:

SO3M 'where A represents an alkyl unit with side chains within a chain of the general formula:

IRR ^{1 !} II I ^CH 3 (CH _{2) x} CH (CH _{2) y} CH (CH _{2) z} - wherein R @ a R @ ¹ each independently represent hydrogen, Ci-C3 alkyl a- mixtures thereof with the proviso that the total number of carbon atoms in said alkyl the unit is 6 to 18 and at least one of R ¹ and R ^{1 is} not hydrogen; x is an integer from 0 to 13; y is an integer from 0 to 13; z is 0 or 1; R ² represents hydrogen, Ci-C ₃ alkyl and mixtures thereof; M 'means a water-soluble cation having a charge sufficient to achieve this

4 • ·

4 · · 4

4 4 4 4

4 4 4 «

4 4 4 4 4

4 4 ·· • 4 ·· • 444 electroneutrality;

c) branched alkyl sulfate surfactants of the general formula:

WITH

CH ₃ CH ₂ (CH ₂ ) _m CH ₂ OSO ₃ M;

or of the general formula:

CH ₃ CH ₂ (CH ₂ ) _m CH ₂ (OCH ₂ CH ₂ ) _y OSO ₃ M;

(d) alkylsulfate surfactants branched within the chain of the formula:

RRR ² III, CH ₃ CH ₂ (CH 2) _w CH (CH 2) _x CH (CH 2) _y CH (CH ₂ ) _from OSO ₃ M _j or the general formula:

RR ¹ R ² !

III í

CH ₃ CH ₂ (CH 2) _w CH (CH 2) _{) (} CH (CH 2) _y CH (CH 2) _z (OR ³ ) _in OSO ₃ M where R and R ¹ and R ² each independently represent hydrogen, C 1 -C 2 _{3 is} an alkyl group and mixtures thereof, with the proviso that the total number of carbon atoms in said surfactant 14 to 20 and at least one of R ¹ and R ¹ and R ^{2 is} not hydrogen; w is an integer from 0 to 13; 13; 'y is an integer from 0 to .13; z is an integer of at least 1 with the proviso that w + x + y + z is from 8 to 14 and the total number of carbon atoms in a surfactant is from 14 to 20; R ³ represents a group from the group consisting of ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene and mixtures thereof, the mean index m being at least about 0.01; · 4 · · 4 ··· · · ·

• 4 · ·

a soluble cation having a charge sufficient to achieve electroneutrality;

ii) from 0% to 100% by weight of one or more nonionic surfactants;

iii) optionally from 0.1% to about 80% by weight, of one or more cationic surfactants;

iv) optionally 0.1% to about 80% by weight of one or more zwitterionic surfactants;

v) optionally 0.1% to about 80% by weight of one or more ampholytic surfactants;

vi) mixtures thereof; .

Depending on the embodiment of the invention, it is possible to select one or more categories of surfactants, however, at least one anionic or nonionic surfactant is required. More than one type of surfactant may be selected within each surfactant category.

Examples of surfactants suitable for use in the present invention include, but are not limited to:

a) C 11 -C 18 alkylbenzene sulfonates (LAS);

b) primary C 10 -C 20 branched and randomly selected alkyl sulfates (AS);

· * * 9.. 9. 9

4 · 9449

c) secondary Ci -Ci8 ₀ (2,3) alkyl sulfates of the formula:

OSOýNT

CH ₃ (CH 2> _x (CH) CH 3 or

OSO-fM

CH ₃ (CH ₂ ) y (CH) CH ₂ CH 3 wherein x and (y + 1) are integers from at least 7, preferably at least 9; said surfactants are disclosed in US Patent 3,234,258 to Morris, issued Feb. 8, 1996; U.S. Patent 5,075,041 to Lutz, issued December 24, 1991; U.S. Patent 5,349,101 to Lutz et al., issued Sep. 20, 1994; and US Patent 5,389,277 to Prieto, issued Feb. 14, 1995, all of which are incorporated herein by reference;

d) Cio ^- Ci8alkylalkoxysulfáty (AE _x S) wherein x is preferably

1-7; . .

e) C 10 -C 18 alkylalkoxycarbonates preferably containing 1-5 ethoxy units;

wf) C 12 -C ₁₈ alkyl ethoxylates, C ₆ -C ₁₂ alkylphenol alkoxylates wherein the alkoxylate units form a mixture of ethyleneoxy and propyleneoxy units, with C ₁₂ -C ₁₈ alcohol block copolymers. and

C 6 -C 12 alkylphenol with ethylene oxide / propylene oxide such as Pluronic ® ex BASF, among others, disclosed in U.S. Patent 3,929,678 to Laughlin et al., Issued December 3, 1975, which is incorporated herein by reference;

g) alkyl polysaccharides disclosed in U.S. Patent 4,565,647 to Llenado, which is incorporated herein by reference;

(h) polyhydroxy fatty acid amides of the general formula:

* · • φ * φ ·· φφ · φ

ί wherein R represents a radical from the group consisting _of C ₇ -C ₂ ialkyl straight chain C ₇ -C ₂ ialkyl straight chain C ₇ -C ₂ ialkenyl straight chain C ₇ -C ₂ xalkenyl branched alkylene, and mixtures thereof .

R ¹ represents an ethylene group; R ² is C ₃ -C ₄ alkyl with Kupino straight chain, C ₃ -C ₄ alkyl group with a branched chain, and mixtures thereof; preferably R ² is 1,2propylenovou group. Nonionic surfactants which contain mixtures of R ¹ R ² units preferably contain from about 4 to about 12 ethylene units in combination with about 1 to 4 1,2 propylene units. Said units may be alternated or combined in any suitable combination. Preferably, the ratio of R ¹ units to R ² units is from about 4: 1 to about 8: 1. Preferably, the R ² units (i.e., 1,2-propylene) are attached to the nitrogen atom and then the remainder of the chain of 4 to 8 ethylene units is attached.

R ³ represents a radical from the group consisting of hydrogen, _Ci-C4 straight chain alkyl, C ₃ -C ₄ branched alkyl, and mixtures thereof; preferably hydrogen or methyl, more preferably hydrogen.

R ⁴ is hydrogen, straight chain C 1 -C 4 alkyl, branched C 3 -C 4 alkyl, and mixtures thereof; is preferably hydrogen. When the index m is 2, then the index n must be equal to 0 and the ^R4 unit has no meaning and is replaced by a moiety - [(R ¹ 0) x (R ² 0) _y R ^3].

• 9 999 *

9 · • 9 * ♦ • Φ · 9 φ Φ 4 9

9 9 9 9 · * · »

ΦΦ ··

9 9 9 9

Φ «»

9 9 • 9 ·

Φ Φ ΦΦ Φ Φ

M is 1 or 2, n is 0 or 1, provided that when m is 1 n is 1; and when m is 2 n is 0; preferably m is lan is 1 resulting in a single unit [(R ^x O) x (R ² O) y R ³ ] and the nitrogen contains a group R ⁴ . The index x is in the range of 0 to 50, preferably about 3 to 25, even more preferably about 3 to 10. The index y is 0 to about 10, preferably means 0, but if not 0, y is in the range of 1 to about 4. Preferably all alkyleneoxy units are ethyleneoxy units. It will be apparent to those skilled in the art that for the ethoxylated polyoxyalkylenalkylamide surfactants, the mean values of the x and y indexes are given, and that the actual values may be in the range of several values depending on the manner of alkoxylation of the amides.

Suitable compositions for preparing the polyoxyalkylene alkylamide surfactants of the invention are described in Surfactant Science Series, Editor Martin Schick, Vol. 1, Chapter 8 (1967) and Vol.XIX, Chapter 1 (1987), which is incorporated herein by reference. Branched-chain alkyl sulphates

The surfactant system of the invention may comprise an in-chain branched alkyl sulphate and / or an in-chain branched alkyl sulphate. Since the use of alkylsulfate or alkoxysulfate surfactants with in-chain branched chains is not necessary when an arylsulfonate surfactant with in-chain branched chains is used, the surfactant system need not contain / i.e. contain 0% of the surfactants active system in an amount of from 0.01%, preferably from about 0.1%, even more preferably from% by weight, about 30% by weight, about 1% to about 100%, preferably to about preferably about 60%, most preferably based on surfactant system. If the in-chain branched chain alkylsulfate surfactant or the in-chain branched chain alkyl-alkoxysulfate surfactant constitutes 100% of said surfactant system, then said surfactant constitutes up to 60% of the final laundry detergent composition.

. The internally branched chain alkyl surfactant compositions of the present invention have the general formula:

s RR ¹ R ² III ·} • CH ₃ CH ₂ (CH _{2) w} CH (CH2) ₃ I: H (CH2) y (CH _{2) 2 QSOjM>} alkyl alkoxy sulfates have the formula:

RR ¹ R ²

CH ₃ CH ₂ (CH ₂ ) _w CH (CH 2) _x CH (CH ₂ ) _y CH (CH ₂ ) _z (OR ³ ) _m OSO ³ M ₎ wherein R, R ¹ -and R ² each independently represent hydrogen, C 1 -C 3 alkyl a group and mixtures thereof; with the proviso that at least one of R, R ¹ and R ^{2 is} not hydrogen; preferably R, R ¹ and R ² are methyl; preferably one of R, R ¹ and R ² is methyl and the others are hydrogen. The total number of carbon atoms in the alkyl sulfate and alkylalkoxysulfate surfactants with the in-chain branched chain is 14 to 20; w is an integer from 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; with the proviso that w + x + y + z is in the range of 8 to 14 and the total number of carbon atoms in the surfactant is 14 to 20; R ³ represents a straight or branched C ¹ -C ₄ alkylene group, preferably an ethylene group, 1,219;

ΦΦ

443 4 • ·

Φ · • Φ φ

4 »•

··

ΦΦ »

4444 propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene and mixtures thereof. However, a preferred embodiment of the invention includes an embodiment comprising 1 to 3 units wherein R ³ is 1,2-propylene, 1,3-propylene or mixtures thereof with successive units, to the desired number wherein R ³ is ethylene units. In another preferred embodiment, the R ³ units comprise randomly selected ethylene and 1,2-propylene units. The mean index m is at least about 0.01. When the index m is low, the surfactant system comprises predominantly alkyl sulfates with a small proportion of an alkyl alkoxy sulfate surfactant. The alkyl chain may also contain a number of tertiary carbon atoms, but this embodiment is not desired.

M represents a cation, preferably hydrogen, a water-soluble cation and mixtures thereof. Examples of water-soluble cations include, but are not limited to, sodium, potassium, lithium, ammonium, alkylammonium, and mixtures thereof.

Preferred alkyl sulfate and alkylalkoxysulfate surfactants with a chain branched within the chain are substantially linear. Substantially linear for the purposes of this invention means alkyl units containing a single branched unit or chemical reaction products comprising a mixture of linear (straight chain) alkyl units and alkyl units containing a single branched unit. The term chemical reaction products refers to a mixture obtained by a process in which it is desirable to prepare primarily linear alkyl units, but also to form branched alkyl units. When combined with the definitions of R ¹ , R ¹ and R ² , where one is methyl and the other is hydrogen, the preferred alkyl sulfate and alkylalkoxy sulfate sulfate surfactant is a chain-linked surfactant. · Branched within the chain, it contains one branch consisting of a methyl group that is not in the α, β position or next to the last carbon atom. Typically, said branched chains are mixtures of isomers.

Preferred examples of alkylsulfate alkoxyalkylsulfate surfactants with a chain branched within the chain are shown below.

8-methylenedecyl sulfate:

3-Methylenedecyl sulfate:

SO3M

3-Methyltridecyl sulfate:

SO3M

8-methyltridecyl sulphate:

Arylsulfonates containing an internally branched chain

The surfactant systems of the invention may comprise an arylsulfonate surfactant comprising an internally branched chain. Since the use of arylsulfonate surfactants with in-chain branched chains is not necessary when using alkyl sulfate and / or alkylalkoxysulfate surfactants with in-chain branched chains, the surfactant system need not contain these compositions, i.e., contains 0% if so in the surfactant system in an amount of from 0.01%, preferably from about 0.1%, even more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% % by weight of the surfactant system. If the internally branched chain arylsulfonate surfactant constitutes 100% of said surfactant system, then said surfactant constitutes up to 60% of the final laundry detergent composition.

Arylsulfonates containing a branched chain have the general formula:

wherein A is an internally branched chain alkyl unit having the general formula:

CHaCCH ^ hich CHfCH ^ ^ - wherein R and R ¹ each independently represents a group of · hydrogen, _Ci-C3 alkyl, and mixtures thereof, with the proviso that at least one of E and R ¹ is not hydrogen; preferably at least one of R and ^R1 represents a methyl group; and wherein the total number of carbon atoms in said alkyl unit is 6-18

the alkyl chain may also contain some tertiary carbon atoms, but this embodiment is not desirable.

The value of x is an integer from 0 to 13. The value of y is 0 to 13. The value of z is either 0 or 1, preferably 0.

R ² represents hydrogen, _Ci-C3 alkyl, and mixtures thereof. Preferably, R ² is hydrogen.

M 'is a water-soluble cation with a charge sufficient to achieve electronutrality, preferably hydrogen, a water-soluble cation and mixtures thereof. Examples of water-soluble cations include, but are not limited to, sodium, potassium, lithium, ammonium, alkylammonium, and mixtures thereof.

In one embodiment of the invention, the arylsulfonate internally branched surfactants are substantially linear aryl surfactants. Substantially linear aryl means, for the purposes of the present invention, an alkyl unit linked to an aryl unit, wherein said alkyl unit comprises a single branched unit, but a substantially linear aryl surfactant is considered to be a straight chain alkyl unit although the mixture comprises a straight chain alkyl unit. containing an aryl unit attached to a carbon atom at the 2-position of the alkyl chain. Preferred alkyl units do not contain a branched methyl group on the second carbon atom relative to the last carbon atom. Typically, the branched chains are mixtures of isomers. However, in the case of the intra-branched arylsulfonates, the relative position of the aryl group is of key importance for the function of the surfactant. Preferably, the aryl moiety is attached to a second carbon of the branched alkyl chain as shown below.

• · · · · · · · · · ·

According to one or more embodiments of the invention, the intra-branched arylsulfonates of the invention comprise a mixture of branched-chain compounds. R ¹ preferably represents methylovou'skupinu subscript x is 0, sulfate group is due to the branched alkyl substituent in the .PAR (1.4), leading to 2-phenyl arylsulfonátům represented by the general formula:

The 2-phenyl arylsulfonates are prepared as a mixture with the 3-phenyl arylsulfonates represented by the general formula:

The intrinsically branched arylsulfonates of the present invention as surfactants can be modified by varying the ratio of the 2-phenyl isomer to the 3-phenyl isomer in the final surfactant composition. A suitable means for characterizing the relative amounts of the isomers contained is the 2/3 phenyl index defined in this specification as 100 times the amount of the 2-phenyl isomer divided by the amount of the 3-phenyl isomer contained. Any suitable means, including but not limited to NMR means, may be used to determine the relative amounts of isomers present. A preferred 2/3 phenyl index is at least about 275, which corresponds to a 2.75-fold greater proportion of the 2-phenyl isomer over the 3-phenyl isomer in the surfactant composition. A preferred 2/3 phenyl index of the invention is from about 275, more preferably from about 350, most preferably from about 500 to about 10,000, preferably to about 1200, even more preferably to about 700.

It will be apparent to those skilled in the art that the chain-branched surfactants of the present invention will be a mixture of isomers and the composition will vary depending upon the method of preparation of the surfactants selected. For example, the following mixture is considered to be a branched arylsulfonate. Sodium para- (7-methylnonan-2-yl) benzenesulfonate, sodium para- (6-methylnonan-2-yl) benzenesulfonate, sodium para- (7-methylethylan-3-yl) benzenesulfonate, sodium para- ( 7-methyldecan-2-yl) benzenesulfonate, sodium para- (7-methylnonanyl) benzenesulfonate.

Preparations

The compositions of the invention may be in any form, inter alia in liquid form, in the form of granules, as a paste. Depending on the specific form of the laundry composition, as well as the intended use, various surfactants and additive combinations are used.

The heavy duty granular composition of the invention comprises:

a) a hydrophobically modified polyamine in an amount of from about 0.01%, preferably from about 0.1%, even more preferably from 1%, most preferably from 3% to about 20%, preferably to about 10%, even more preferably to about 7% by weight; and ··

I 9 · 9 9 9 9 999 9999

b) a surfactant system in an amount of from about 0.01% by weight, preferably from about 0.1%, even more preferably from about 1% to about 60%, preferably to about 30% by weight of the composition, wherein said surfactant system contains:

i) a surfactant in an amount of from 0.01%, preferably from about 0.1%, even more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% wherein said surfactant is selected from the group consisting of alkyl sulfate surfactants, alkoxysulfate surfactants, alkylsulfate surfactants with an in-chain branched chain, alkoxysulfate surfactants with an in-chain branched chain, arylsulfonate surfactants with an in-branched chain chains and mixtures thereof;

ii) optionally and preferably one or more anionic surfactants in an amount of from 0.01%, preferably from about 0.1%, even more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably up to about 30% by weight;

iii) optionally one or more non-ionic surfactants in an amount of from 0.01%, preferably from about 0.1%, even more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about about 60%, most preferably up to about 30% by weight;

HDG laundry detergent compositions typically contain other anionic surfactants. For this, zwitterionic polyamines having a plurality of ♦ ·

anion units rather than skeletal cation units. The resulting overall charge then attenuates the negative interaction of the surfactant molecules with zwitterionic polymers active on hydrophilic impurities.

In contrast, heavy duty liquid (HDL) compositions include:

a) a zwitterionic polyamine in an amount of from about 0.01%, preferably from about 0.1%, even more preferably from 1%, most preferably from 3%, to about 20%, preferably to about 10%, even more preferably to about 5% by weight, wherein said polyamine comprises less or the same number of anions than the number of scaffold quaternary nitrogen units; and

b) a surfactant system in an amount of from about 0.01% by weight, preferably from about 0.1%, even more preferably from about 1% to about 60%, preferably to about 30% by weight, of said composition, wherein said surfactant -system contains:

i) a surfactant in an amount of from 0.01%, preferably from about 0.1%, even more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably to about 30% % by weight, wherein said surfactant is selected from the group consisting of intra-chain branched alkyl sulfate surfactants, intra-chain branched alkoxysulfate surfactants, an in-chain branched arylsulfonate surfactant, and mixtures thereof;

ii) preferably one or more non-ionic surfactants

Active agents in an amount of from 0.01%, preferably from about 0.1%, even more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60% most preferably up to about 60% by weight, wherein said nonionic surfactants are selected from the group consisting of alcohols, alcohol ethoxylates, polyoxyalkylenalkylamides, and mixtures thereof.

iii) optionally one or more nonionic surfactants in an amount of from 0.01%, preferably from about 0.1%, even more preferably from about 1% to about 100%, preferably to about 80% by weight, preferably to about 60%, most preferably up to about 30% by weight.

HDL laundry detergent compositions typically comprise an additional minor amount of anionic surfactant and other nonionic surfactants.

For this purpose, zwitterionic polyamines having the same number of anionic units as the cationic units or having a greater number of cationic skeletal units than the number of anionic units are used.

Bleaching system

The hydrophobically modified polyamine-containing laundry detergent compositions of the invention may optionally contain a bleaching system. Bleaching systems typically comprise a bleaching agent (hydrogen peroxide source) and an initiator or catalyst.

Preferred laundry detergent compositions of the invention which contain a bleaching system include:

a) a hydrophobically modified polyamine according to the invention

00

0 »• 0 0 • 000 • 9 · · · 0 0 0 0 • 0 · * ·· ·· · * ¹ in an amount of 0.01% by weight;

(b) a surfactant system in an amount of from about 0.01% by weight, comprising:

λ

(i) a surfactant system containing one; or. _t more anionic surfactants in an amount of 0% to 100% by weight;

(Ii) a surfactant system comprising one or more nonionic surfactants in an amount of 0% to 0%;

100% by weight;

iii) a surfactant system comprising one or more cationic surfactants in an amount of 0.1% to 80% by weight;

iv) optionally a surfactant system comprising one or more zwitterionic surfactants in an amount of 0.1% to 80% by weight;

(V) optionally a surfactant system comprising one or more ampholytic surfactants

in an amount of 0.1% to 80% by weight; or vi) mixtures thereof;

c) a peroxygen bleach system in an amount of from about 1%, preferably from about 5% to about 80%, preferably to about 50% by weight based on the weight of the detergent composition, comprising:

(i) source of hydrogen peroxide in an amount of approximately 40% by weight;

4 4 4

4,444 • 4 4

··

4 4 4 · ·

4 4 · ·

44444 preferably from about 50%, preferably to about 95%, based on bleaching, even more preferably from about 60 even more preferably to about 80% to about 100%, by weight of the system;

ii) optionally a bleach activator in an amount of from about 0.1%, preferably from about 0.5% to about 60%, preferably to about 40% by weight based on the weight of the bleaching system;

iii) optionally a bleach catalyst comprising a transition metal in an amount of from about 1 ppb (0.0000001%), more preferably from about 100 ppb (0.00001%), even more preferably from about 500 ppb (0.00005%), and even more preferably from about 1 ppm (0.0001%) to about 99.9%, even more preferably to about 50%, even more preferably to about 5%, even more preferably to about 500 ppm (0.05%) by weight of the composition;

iv) optionally pre-formulated peroxygen bleach in an amount of from about 0.1% by weight; and

(d) additional carriers and other additives.

Bleaching agents - hydrogen peroxide sources are described in detail in Kirk Othmer's Encyclopedia of Chemical Technology,

4th Edition (1992, John Wiley & Sons), Vol.4, pp. 271-300 (Bleaching Agents (Survey)) wherein said work is incorporated by reference, and includes various forms of sodium perborate and sodium percarbonate, including coated and modified forms.

Sources of hydrogen peroxide suitable for use in the compositions of the invention include, but are not limited to, perborates, percarbonates, perphosphates, persulfates, and mixtures thereof. Preferred sources of hydrogen peroxide

9 ·

9 9 • 4 · 99 • 9 9 ·

9 · 9

9 9 9 ** 9999 include sodium perborate monohydrate, sodium perborate tetrahydrate, sodium percarbonate and sodium persulfate, even more preferred are sodium perborate monohydrate, sodium perborate tetrahydrate and sodium percarbonate. When a hydrogen peroxide source is used, the amount thereof is from about 40%, preferably from about 50%, even more preferably from about 60% to about 100%, preferably to about 95%, even more preferably to about 80% by weight of the bleaching system. . In embodiments in which the bleach-forming composition is first wetted, it may comprise from 5% to 99% of a hydrogen peroxide source.

Preferred percarbonate bleach comprises dry particles having an average particle size ranging from about 500 microns to about 1000 microns, with at most about 10% by weight of the particles being less than about 200 microns and at most about 10% by weight of said particles being greater than about 1250 microns. Optionally, the percarbonate may be provided with a silicate, borate or water-soluble surfactant.

Bleach activators

Preferably, the source of hydrogen peroxide (peroxygen bleach component) in the composition is combined with an activator (peracid precursor). The amount of activator is from about 0.01%, preferably from about 0.5%, even more preferably from about 1% to about 15%, preferably to about 10%, even more preferably to about 8% by weight of the composition. Bleach activators also make up about 0.1% to 60% by weight of the bleach system. If the above bleach system comprises 60% by weight of activator (maximum amount), and said composition (bleaching composition, detergent or the like) contains 15% by weight of said activator (maximum weight).

said composition will contain 25% by weight of the bleaching system (60% bleach activator, 40% hydrogen peroxide source). However, the above ratio of activator to hydrogen peroxide source of 60:40 is not limited to the stated value.

The molar ratio of the peroxygen bleach compound (such as AvO) to the bleach activator of the invention generally ranges from at least 1: 1, preferably from about 20: 1, even more preferably from about 10: 1 to about 1: 1, preferably about 3: 1.

Preferred activators are selected from the group of tetracetyl ethylene diamine (TAED), benzoylcaprolactam (BzCl), 4-nitrobenzoylcaprolactam, 3-chlorobenzoylcaprolactam, benzolyoxybenzensulfonát (BOBS), nonanoyloxybenzenesulphonate (NOBS), phenyl benzoate (PhBz) dekanoyloxybenzensulfonát (C ₀ OBS), benzoylvalerolactam (BZVL octanoyloxybenzene sulfonate (Cg-OBS), hydrolyzable peroxyester and mixtures thereof, most preferably benzoylcaprolactam and benzoylvalerolactam. Particularly preferred bleach activators for a pH range of about 8 to about 9.5 are those containing a leaving group OBS and VL.

Preferred hydrophobic bleach activators include, but are not limited to, nonanoyloxybenzenesulfonate (NOBS), 4- [N-nonanoyl) aminohexanoyloxy] benzenesulfonate sodium, an example of which is described in US Pat. No. 5,523,434, dodecanoyloxybenzenesulfonate (LOBS), or C12-C12- 10-undecenoyloxybenzenesulfonate (UDOBS or Cu-OBS with unsaturated bond at position 10); and decanoyloxybenzoic acid (DOBA).

Preferred bleach activators are those disclosed in U.S. Patent No. 5,698,504 to Christie et al., Issued December 16.

1997; No. 5,695,679 to Christie et al., issued Dec. 9, 1997; No. 5,686,401 to Willey et al

November 11, 1997; No. 5,686,014 to Hartshorn et al., issued Nov. 11, 1997; No. 5,405,412, Willey et al., issued April 11, 1995; No. 5,405,413, Willey et al., issued Nov. 11, 1997; No. 5,130,045 to Mitchel et al. July 14, 1992; and U.S. Pat. No. 4,412,934 to Chung et al., And U.S. patent application Ser. No. 08 / 709,072 and 08 / 064,564; acyl lactam activators described in U. S. 5, 698.504,. U. S. 5, 698,504 and U. S. No. 5,686,014, each of which is incorporated herein by reference, which are particularly suitable for use herein, particularly acyl caprolactams (see, e.g., WO 94-28102A) and the acylvalerolactams described in US 5,503,639 by Willey et al. April 1996, which are also incorporated herein by reference.

The compositions may also comprise quaternary substituted bleach activators. The present cleaning compositions preferably comprise a quaternary substituted bleach activator (QSBA) or a quaternary-substituted peroxyacid (QSP); more preferably, said first component. Structures depicting preferred QSBAs are further described in U. S. 5,686,015. Willey et al., issued Nov. 11, 1997; No. 5,654,421, Taylor et al., issued Aug. 5, 1997; No. 5,460,747 to Gossélink et al., issued Oct. 24, 1995; No. 5,584,888 to Miracle et al., issued Oct. 17, 1996; and U.S. 5,578,136 to Taylor et al., issued Nov. 26, 1996, all of which are incorporated herein by reference.

Particularly preferred bleach activators suitable for use in the present invention are the amide substituted compounds described in U.S. 5,698,504, U.S. 5,686,014 and 5,686,014, all of which are cited above. Examples of such preferred bleach activators include (6-octanamido caproyl) oxybenzerisulfonate, (6-nonanamido caproyl) oxybenzenesulfonate, (6-decanamido caproyl) oxybenzenesulfonate, and mixtures thereof.

Other suitable activators are described in U.S.5,698,504,

US5,695,679, US5,686,014, all of which are cited above and in US4,966,723 to Hodge et al., Issued Oct. 30, 1990, comprising benzoxazine-type activators containing a C6H4 ring to which it is coupled at the 1,2-position by condensation -C (O) OC (R ¹ ) = N-.

Depending on the type of activator and the precision of the process, good bleaching results can be obtained with bleaching systems having a pH of from about 6 to about 13, preferably from about 9.0 to about 10.5, when in use. For example, activators containing electron withdrawing groups are typically used for pH regions close to neutral or subneutral. Alkaline and buffering agents can be used to provide the desired pH.

Bleach catalysts containing transition metals

The detergent compositions of the present invention optionally comprise bleach systems which contain one or more bleach catalysts. Selected bleach catalysts such as, but not limited to, 5,12-dimethyl-1,5,8,12-tetrazabicyclo [6.6.2] hexadecananganium (II) chloride can be used in bleach systems in which it is not necessary to use a hydrogen peroxide source or a peroxygen bleach. Said compositions comprise from about 1 ppb (0.0000001%), more preferably from about 100 ppb (0.00001%), even more preferably from about 500 ppb (0.00005%), and even more preferably from about 1 ppm (0.0001) %) to about 99.9%, more preferably to about 50%, even more preferably to about 5%, even more preferably to about 500%

Ppm (0.05%) of a transition metal catalyst based on the weight of the composition.

Examples of suitable manganese-based catalysts are described in U.S. 5,576,282 to Miracle et al., Issued Nov. 19, 1996; U.S. 5,246,621 Favre et al., Issued Sep. 21, 1993; U.S. 5,244,594 Favre et al., Issued September 14, 1993;

U.S. 5,194,416 to Jureler et al., Issued Mar. 16, 1993; U.S. 5,114,606 van Vliet et al., Issued May 19, 1992;

U.S. 4,430,243, Bragg, issued Feb. 7, 1984; U.S. 5,114,611, van Kralingen, issued May 19, 1992; U.S. 4,728,455, Rerek, issued Mar. 1, 1988; U.S. 5,284,944, Madison, issued Feb. 8, 1994; U.S. 5,246,612 van Dijk et al., Issued September 21, 1993;

5,256 _{out of} 779, authors Kerschner and sp.,. issued October 26th 1993; 5,280,117, authors Kerschner and sp., issued January 18th 1994; 5,274,147, authors Kerschner and sp., issued December 28th

1993; U.S. 5,153,161, Kerschner et al., Issued Oct. 6, 1992; and U.S. 5,227,084 to Martens et al., issued July 13, 1993; and in European Published Patent Applications Nos. 549,271 A1, 549,272 A1, 544,440 A2 and 544,490 A1.

Examples of suitable cobalt-based catalysts include, but are not limited to, those described in U.S. 5,597,936 Perkins et al., Issued Jan. 28, 1997; U.S. 5, 595,967 to Miracle et al., Issued Jan. 21, 1997;

U.S. 5,703,030 Perkins et al., Issued Dec. 30, 1997; U.S. Patent 4,810,410 to Diakun et al., Issued Mar. 7, 1989; in M. L. Tobe's Base Hydrolysis of Transition-Metal Complexes, Adv. Inorg. Bioinorg. Moss. , (1983), 2, pp. 1-94;

Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W. L. Jolly (PrenticeHall; 1970), pp.461-3; Inorg Chem., 18, 1497-1502 (1979); Inorg Chem., 18, 1497-1502 (1979); Inorg. Chem., 21, 2881-2885

4 ♦ · 4 4 · 4 4 ·

1444 (1982); Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and in the Journal of Physical Chemistry, 56, 22-25 (1952).

Further examples of a preferred macrocyclic ligand forming bleach catalysts are described in WO 98/39406 A1, published Sep. 11, 1998, which is incorporated herein by reference. Suitable examples of said bleach catalysts include:

dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanmanganium (II), diaqua-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanmanganium (II) hexafluorophosphate, aquahydroxy-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanemanganium (III) hexafluorophosphate, diaquá-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanmanganium (II) tetrafluoroborate, dichloro-5,12-dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanmanganium (III) hexafluorophosphate, dichloro-5,12-dibutyl-1,5 , 8,12-tetraazabicyclo [6.6.2] hexadecanmanganium (II), dichloro-5,12-dibenzyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecanmanganium (II), dichloro-5-butyl-12 -methyl-1,5,8,12-tetraazabicyclo [6.6.2] -hexadecanmanganium (II), dichloro-5-octyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] -hexadecanmanganium (II) ( (II), dichloro-5-butyl-12-methyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane-manganese (II).

Prepared bleaching agents and 9 9999

The bleaching systems of the invention may further comprise one or more bleaching compositions already prepared in an amount of from 0.1%, preferably from 1%, even more preferably from 5% to about 10%, preferably to about 7% by weight. The bleaching compositions prepared generally have the general formula:

HO-O-C-R-Y wherein R is C 1 -C ₂ alkylene, C ₁ -C ₂₂ substituted alkylene, C ₆ -C ₂₂ substituted phenylene and mixtures thereof, Y is hydrogen, halogen, alkyl , aryl, -C (O) OH, -C (O) OOH ', and mixtures thereof.

Organic peroxycarboxylic acids suitable for use in the invention may contain one or more peroxy groups and may be either aliphatic or aromatic. If it is an aliphatic organic peroxyacid, the unsubstituted acid 'has the general formula: Ό.

HO - O - C - (CH 2) n - Y wherein Y may be hydrogen, methyl, methyl chloride, carboxylate, peroxycarboxylate; and n is an integer from 1 to 20.

When it is an aromatic organic peroxyacid, the unsubstituted acid has the general formula:

· ¹¹

HO-O-G- ( ^of 7-Y wherein Y may be hydrogen, alkyl, haloalkyl, carboxylate, peroxycarboxylate and mixtures thereof).

• · * * * * * *

Typical monoperoxycarboxylic acids suitable for use herein include alkylperoxycarboxylic and arylperoxycarboxylic acids such as:

i) perbenzoic acid and in the ring substituted peroxybenzoic acid such as peroxy-o-naphthoic acid;

ii) aliphatic, substituted aliphatic and arylalkyl monoperoxyacids such as peroxylauric acid, peroxystearic acid and N, N-phthaloylaminoperoxycaproic acid (PAP).

Typical diperoxycarboxylic acids suitable for use herein include alkyldiperoxycarboxylic and arylperoxycarboxylic acids such as:

iii) 1,12-diperoxydodecanedioic acid;

iv) 1,9-diperoxyazelaic acid;

(v) diperoxybrassylic acid, diperoxybasic acid and diperoxyisophthalic acid;

vi) 2-decyldiperoxybutane-1,4-dioic acid;

vii) 4,4'-sulfonylbisperoxybenzoic acid

An example of a highly preferred, but not limited to, bleaching composition is 6-nonylamino-6-oxoperoxycaproic acid (NAPAA) disclosed in US Patent No. 4,634,551 to Bruns' et al., Issued Jan. 6, 1987, which is incorporated herein by reference. description by reference.

«0.

• 0 0 *

0 0 0 • 0 000

0 · ·· · 0 »

0.0 ♦ ·

0 0 0

0 0 * · »• 0 ·· ♦ 0« 0

0 ♦

0 ·

0 0

0 · 0000

Similar to the peroxide bleaching compositions described above, the compositions of the invention may also comprise a bleaching agent of the chlorine-containing type. Such compositions are well known in the art and include, for example, sodium dichloroisocyanurate (NaDCC). However, chlorine-type bleaching agents are less preferred in enzyme-containing compositions.

> ·

Auxiliary additives

The laundry compositions of the invention may contain other adjuvants such as, but not limited to, builders, optical brighteners, soil release polymers, dye transfer agents, dispersants, enzymes, antifoams, pigments, perfumes, dyes, saline fillers, hydrotropic agents, photoactivators, fluorescent agents, fabric conditioners, hydrolyzable surfactants, preservatives, antioxidants, chelating agents, stabilizers, anti-shrinkage agents, anti-wrinkle agents, germicides, fungicides, anticorrosive additives, and mixtures thereof.

Enzymes

As used herein, the term enzyme or cleaning enzymes means any enzyme having the ability to clean, stain, wash, hard surface or other cleaning compositions or compositions described above. In the compositions of the invention, the enzymes are generally present in an amount of from 0.0001%, more preferably from 0.0005%, most preferably from 0.001% to 2%, preferably up to 0.1%, even more preferably up to 0.02%

9 • · · 9

9 ·

9 10 »« 9 ·

T * t *

9 9 9

9 ···

9 * ··

9 9 9 • · ♦ ·

9

9 · 9 · »by weight calculated as pure enzymes. Preferably the enzymes are hydrolases such as amylases and lipases. Preferred enzymes for wet scrubbing purposes include, but are not limited to, proteases, cellulases, lipases, and peroxidases.

Proteasy

The liquid detergent compositions of the invention preferably further comprise at least 0.001% by weight of a protease enzyme.

However, an effective amount of a protease is an amount sufficient for use in a liquid laundry composition as described below. The term effective amount means an amount having an improved effect on cleaning, stain removal, dirt removal, bleaching, odor removal or freshness of substrates such as fabric.

In practice, for commercially available formulations, up to about 5 mg, more usually 0.01 to 3 mg, of active enzyme per gram of detergent composition is meant. In other words, said compositions usually comprise from 0.001% to 5%, preferably 0.01% to 1%, of a commercially available enzyme preparation. According to the invention, the protease enzymes are usually contained in commercially available formulations in an amount providing an activity of 0.005 to 0.1 Anson units (AU) per 1 g of the composition.

Preferred liquid laundry detergent compositions of the invention comprise modified protease enzymes derived from Bacillus amyloliquefaciens or Bacillus lentus. For the purposes of the present invention, protease enzymes derived from

B. amyloliquefaciens are hereinafter referred to as subtilisin BNN as well as protease A and B. lentus-derived protease enzymes are hereinafter referred to as subtilisin 309. For the purposes of this invention, the numbering of subtilisin from Bacillus amyloliquefaciens is described in the patent application of A. Baecka et al. ., entitled * · • · «• · • · • · ·· ···· * w **» ** • · · · · · * ⁹ • · · · · · · • ·· ·· «· t · * • 4 · * ** *

Proteasé-Containing Cleaning Compositions with U.S. Serial No. 08 / 322,676 uses both the subtilisin BPN and subtilisin 309 amino acid sequences as numbering.

Bacillus amyloliquefaciens subtilisin-BPN 'enzyme derivatives

A preferred protease enzyme for use according to the invention is a variant of protease A (BPN ⁷ ) which is a non-naturally occurring carbonyl hydrolase variant having different proteolytic activity, stability, substrate specificity, pH-profile and / or activity characteristics compared to the precursor carbonyl hydrolase from variant amino acid sequence derived. Said variant BPN 'is described in EP 130,756 A, January 9, 1985.

Proteasa B

A preferred protease enzyme for use in the present invention is protease B. Protease B is a non-naturally occurring variant of carbonyl hydrolase having a different proteolytic activity, stability, substrate specificity, pH-profile and / or activity characteristic compared to the precursor carbonyl hydrolase from which the amino acid sequence is different. derived. Said protease B is a variant of BPN 'in which tyrosine at position +217 is replaced by leucine and is described in EP 303,761 A, April 28, 1987 and EP 130,756 A, January 9, 1985.

Proteasa C

A preferred protease enzyme for use in the present invention is protease C '. Protease C is a variant of an alkaline serine protease derived from Bacillus, wherein at position 27 the lysine is replaced by arginine, the tyrosine at position 104 is replaced by valine, the serine is at position 123 replaced by asparagine and alanine at position 274 replaced by threonine. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637 published May 16, 1991.

Genetically modified variants, in particular protease C, are also described.

Proteasa D

A preferred protease enzyme for use in the present invention is protease D. Protease D is a carbonyl hydrolase variant derived from Bacillus lentus subtilisin and is described in WO 95/10615 published April 20, 1995 by Genencor International.

Another preferred protease enzyme suitable for combination with the modified polyamines of the invention is ALCALASE® from Novo. Another suitable protease is obtained from the genus Bacillus, has an activity in the pH range of 8-12 and has been developed and sold in the form of ESPERASE® by Novo Industries A / S, Denmark, hereinafter abbreviated to Novo. The preparation of said enzyme and analogous enzymes is described in GB 1,243,784, Novo. Other suitable proteases include SAVINASE® from Novo and MAXATASE® from International Inc, The Netherlands. See also high pH protease from Bacillus species, NCIMB 40338 described in WO 9318140 A to Novo. Enzyme detergents containing a protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 9203529 to Novo. Other preferred proteases include the enzymes described in WO 9510591 A to Procter & Gamble. If desired, a protease with reduced adsorption and increased hydrolysis according to WO 9507791 from Procter & Gamble is available. Trypsin-like proteases of recombinant origin suitable for detergents according to the invention are described in WO 9425583 to Novo.

Other particularly suitable proteases are described in PCT Patent Application Nos. PCT / US98 / 22588, PCT / US98 / 22482 and PCT / US98 / 22486, all of which were filed October 23, 1998 by

Procter & Gamble.

Also suitable for the purposes of the invention are the proteases described in patent applications 251,446 and WO 91/06637, the BLAP® protease described in WO91 / 02792 and variants thereof described in WO 95/23221.

See also high pH protease from Bacillus NCIMB 40338, which is described in WO 93/18140 A to Novo. Enzymatic detergent compositions comprising a protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. If desired, a protease with reduced adsorption and increased hydrolysis according to WO 95/07791 to Procter & Gamble is available. Trypsin-like proteases of recombinant origin suitable for the detergents of the invention are described in WO 94/25583 to Novo. Other suitable proteases are described in EP 516 200 of Unilever.

Commercially available proteases suitable for use in the present invention are known under the proprietary names ESPERASE®, ALCALASE®, DURAZYM®, SAVINASE®, EVERLASE® and KANNASE®, all from Novo Nordisk A / S, Denmark, as well as MAXATASE®, MAXACAL®, PROPERASE® and MAXAPEM® all from Genencor International (formerly Gist-Brocades of the Netherlands). A preferred protease for use in the present invention is the protease enzyme described in U.S. Pat

WO99 / 20771 published April 29, 1999.

• 4444 ··· 4 4

In addition to the protease enzymes described above, the following enzymes are suitable for use in the liquid detergent compositions of the invention.

Other enzymes

In addition to the proteases, the detergent compositions of the invention may contain other enzymes for a variety of reasons, including removal of protein, carbohydrate or triglyceride impurities from surfaces such as textile products, and to prevent delamination, for example, in laundry and fabric recovery. Suitable enzymes include amylases, lipases, cellulases, peroxidases, and mixtures thereof, which may be of any suitable origin, such as vegetable, animal, bacterial, from fungi and yeast. Factors such as pH-dependency of activity and / or optimum stability, thermostability, and stability to active detergent compositions, activating agents, and the like affect the choice. In the above aspects, enzymes of bacterial origin and fungal enzymes such as bacterial amylases and fungal cellulases are preferred.

Amylases suitable for use in the present invention include, for example, α-amylases described in GB 1,296,839 to Novo; RAPIDASE®, International Bio-Synthetics Inc, and TERMAMYL®, Novo. FUNGAMYL® from Novo is particularly preferred. Processing of enzymes to improve stability, e.g., oxidation stability, is known. See, e.g., J. Biological Chem., Vol.260, No. 11, June 1985, pp.6518-6521 and WO 9402597 to Novo, issued Feb. 3, 1994, and WO 9509909 to Novo.

Cellulases suitable for use in the present invention include both cellulases of bacterial origin and fungal-derived cellulases, preferably cellulases having an optimum pH of between 5 and 9.5.

U.S. Pat. No. 4,435,307 to Barbesgoard et al., Issued Mar. 6, 1984, discloses suitable fungal cellulases derived from Humicola insolens or from Humicula DSM 1800 or cellulase 212-producing sponges belonging to the genus Aeromonas, and cellulase extracted from hepatopancreatus mollusc. auricola solander. Suitable cellulases are also described in GB-A2.075.028; GB-A-2.095.275 and DE-OS-2.274.832. A particularly suitable enzyme is CAREZYME® (Novo). See also WO 9117243 to Novo.

Suitable lipases for use in detergents include enzymes produced by Pseudomonas family microorganisms such as Pseudomonas stutzeri ATCC 19.154 as described in GB 1,372,034. See also lipases described in Japanese Patent Application 53,20487, published Feb. 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan under the tradename Lipasa P Amano or Amano-P. Other suitable commercially available lipases include Amano-CES, lipases ex. Chromobacter viscosum e.g. Chromobacter lipasum var. lipolyticum'NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.s.Biochemical Corp.,

And Disoynth Co., The Nederlands, and lipases ex. Pseudomonas gladioli. For use according to the invention, LIPOLASA® derived from Humicola lanuginosa, commercially available from Novo, is also preferred, see also EP 341,947. Variant lipase and amylases stabilized against peroxidase enzymes are described in WO 9414951 A to Novo. See also WO 9205249 and RD 94359044.

Enzymes, cutinases suitable for use herein are described in WO 8809367 to Genencor.

Peroxidases can be used in combination with oxygen sources, • Φ φφ Φ · φ · ·· * · | · Φ Φ φ · ΦΦ ΦΦ ·

I Φ φ φ · · · perox atd φ φ φ s>>> s ♦ Φ Φ Φ s s s s φ «« «« «« «« «« «« «« «« «« «« « or pigment removed from the substrates to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase and haloperoxidases such as chloro- or bromo-peroxidase. Peroxidase-containing detergent compositions are described in WO 89099813 A of Oct. 19, 1989 to Novo and in WO 8909813 A to Novo.

Various enzymes and compositions for incorporating them into synthetic detergent compositions are also described in WO 9307263 A and WO 9307260 A by Genencor International, WO 8908694 A by Novo and in US 3,553,139 by McCarty et al., Issued Jan. 5, 1971. Enzymes are also described in US 4,101,457 to Placha et al. issued July 18, 1978 and in US4,507,219, Hughes, issued March 26, 1985. Enzymatic compositions suitable for liquid detergent compositions and methods for incorporating them into said compositions are described in US4,261,868, Hora et al., issued April 14, 1981. Enzymes when used according to the invention it is possible to stabilize in various ways. Methods of enzyme stabilization and examples of said stabilization are described in U. S. 3, 600, 319 by Gedge et al., Issued Aug. 17, 1971; in EP 199,405 and EP 200,586 of Oct. 29, 1986, Venegas. Enzyme stabilization systems are described, for example, in U.S. Patent 3,519,570. A suitable Bacillus of the type AC13 providing professions, xylanases and cellulases is described in WO 9401532 to Novo.

Enzyme stabilizing systems

Enzyme-containing compositions, including but not limited to, liquid compositions of the invention may contain from about 0.001%, preferably from about 0.005%, even more preferably from about

• · ··· ·

0.01% to about 10%, preferably up to about 8%, even more preferably up to about 6% by weight of the enzyme stabilizing system. Said enzyme stabilizing system may be any stabilizing system. compatible with cleaning system. Said system may naturally be provided by other active ingredients, or may be incorporated into the composition, or may be part of an enzymatic composition intended for laundry detergent compositions.

Said stabilizing systems may, for example, comprise calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boron acids, and mixtures thereof, and are proposed to solve stability problems depending on the type and physical form of the detergent composition.

One approach to enzyme stabilization involves the use of water-soluble sources of calcium and / or magnesium ions available to the enzymes. Generally, calcium ions are more effective than magnesium ions, even if only one type of cation is used. Conventional detergent compositions, particularly liquid, contain from about 1 to about 30, preferably from about 2 to about 20, even more preferably from about 8 to about 12 millimoles of calcium ions per liter of the final detergent composition, although some variations are possible depending on factors including the number, type and concentration of the enzymes used. Water-soluble salts of calcium or magnesium are preferably used, which include, for example, calcium chloride, calcium hydroxide, calcium formate, calcium maleate, calcium maleate, calcium hydroxide and calcium acetate; more generally, calcium sulfate or magnesium salts corresponding to the examples of calcium salts may be used. Further increases in calcium and / or magnesium concentrations may also be useful, for example, to promote the disruptive effect of certain types of surfactant on fat impurities.

Another stabilization approach involves the use of borate • 9

stabilizers disclosed in US 4,537,70-6, Severson, issued Aug. 27, 1985. When borate stabilizers are used, their concentrations in the composition are typically up to 10% or more, more usually up to about 3% by weight, in the form of boric acid or other boron compounds such as is borax or boroborate which are suitable for liquid detergent compositions. Substituted boric acids such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or the like may be used in place of boric acid, whereby a total reduction of boron concentration in the detergent compositions can be achieved using these derivatives.

The stabilization systems of certain cleaning compositions may further comprise from 0, preferably from about 0.01% to about 10%, preferably to about 6%, by weight, of a chlorine quencher that is added to prevent chlorine additives contained in many water sources to act and inactivated enzymes, especially under alkaline conditions. Although chlorine concentrations in water may be low, usually in the range of about 0.5 ppm to about 1.75 ppm, the total available chlorine in the total volume of water that can contact the enzyme, for example, during washing may be quite large; Accordingly, the stability of the enzyme to chlorine may be problematic in use in some cases. Since perborate and percarbonate have the ability to react with chlorine compositions, and some compositions of the invention may contain them in amounts calculated separately for the stabilizing system, the use of other chlorine protection agents may not generally be necessary although improved results may be obtained . Suitable anionic flame retardants are generally known and readily available, and may include salts of ammonium cation with sulphite, bisulphite, thiosulphite, thiosulphate, iodide, etc. when used. Similarly, antioxidants may be used.

Such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts, monoethanolamine (MEA), and mixtures thereof.

Furthermore, it is possible to incorporate a separate enzyme inhibition system to make the various enzymes as compatible as possible. Other suitable quenchers that may be used include hydrogen sulphate, nitrate, chloride, hydrogen peroxide sources such as perborate tetrahydrate, perborate monohydrate and sodium percarbonate as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate , tartrate, salicylate, etc., and mixtures thereof. In general, since the function of a chlorine quencher can be accomplished by additives included for other reasons (eg, a source of hydrogen peroxide), it is not an absolute necessity to add a separate chlorine quencher if the compound is a compound enabling this function is an embodiment of the invention comprising an enzyme present in sufficient quantity; if the quencher is still added, it is only for better results. In addition, it is based on general chemical experience to avoid the use of a chlorine quencher or stabilizer which is considerably incompatible in processing with other reactants. As for the ammonium salts, they can be simply mixed with the detergent composition but are susceptible to water absorption and / or ammonia release during storage. Accordingly, it is desirable to protect said compositions, when used, in a manner such as that described in U.S. Pat. No. 4,652,392 to Baginski et al., Issued Mar. 24, 1987.

Builders.

The detergent compositions of the present invention for washing preferably contain one or more activating ingredients or activating systems. When such compositions are included, the compositions comprise at least about 1% of the activating additive, »»

999 more preferably from about 10% to about 80%, preferably to about 50%, even more preferably to about 30% by weight.

The concentration of the activating additive can vary widely depending on the end use and the desired physical form. If present, the compositions typically contain at least about 1% of an activating additive. The compositions typically contain from about 5% to about 50%, more usually about 5% to about 30% by weight of the activating additive. Granular formulations generally comprise from about 10% to about 80%, more usually from about 15% to about 50% by weight of the detergent builder. However, these values do not mean that values higher or lower are excluded.

Inorganic β-containing detergent builders include, but are not limited to, alkali metal salts, ammonium and alkanolammonium salts of polyphosphates (e.g., tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates), phosphonates, phytic acid, silicates, carbonates (including hydrogen carbonates and sesquicarbonates), sulfates and aluminosilicates. However, non-phosphate activating agents are required in certain areas. Importantly, the compositions of the invention surprisingly also work in the presence of so-called weak activating agents (as compared to phosphate) or in a so-called underdose condition, which may occur when zeolite or layered silicate activating agents are used.

Examples of silicate builders include alkali metal silicates, especially silicates having a SiO ₂ : Na ₂ O ratio of 1.6: 1 and 3.2: 1, and layered silicates such as the layered sodium silicates described in US 4,664,839, Rieck, issued Mar. '. NaSKS-6 is a trade name for Hoechst Crystalline Layered Silicate (commonly abbreviated

9 9 99 9 9 9 9 9 9 9 9 9 9 9

I 9 9 <

»9 9 9 ► 9 9 1

9 9 9 on SKS-6). Unlike zeolite builders NaSKS6 does not contain aluminum: NaSKS6 has the delta-Na ₂ SiO5 morphology form of layered silicate. Said component can be prepared by the methods described in DE-A3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferred layered silicate for use in the present invention, but other layered silicates such as silicates of the formula NaMSi _x O _2x + i + may also be used. yH ₂ O, where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably is 2, and y is a number from 0 to 20, preferably when used according to the invention is 0. Various other layered silicates from Hoechst include NaSKS -5, NaSKS-7 and NaSKS-11, in alpha, beta and gamma forms. As described above, deltaNa ₂ SiO ₅ (NaSKS-6 form) is most preferred for use herein. Other silicates may also be suitable, such as magnesium silicate, which acts as a brittleness enhancing agent in granular formulations and as a stabilizer for oxygen bleaching agents, and as a component of antifoam systems.

Examples of carbonate builders include alkali earth and alkali metal carbonates and are described in German Patent Application No. 2,231,001 published November 15, 1973.

Aluminosilicate activating agents are suitable for use herein. Aluminosilicate builders are very important agents found in most commercially available heavy duty granular detergent compositions, but can also form a significant builder in liquid formulations. Aluminosilicate builders have an empirical general formula:

[M ₂ (zA 102 ₂ ) _y ]. xH ₂ O

9

9999 • t · • · · · ··· ···

99 · · <

Wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of from 1.0 to about 0.5 and x is an integer of from about 15 to about 264.

Suitable aluminosilicate ion-exchange agents are commercially available. Said aluminosilicates may have a crystalline or amorphous structure and may be naturally occurring aluminosilicates or may be of synthetic origin. A process for preparing aluminosilicate ion-exchange compositions is disclosed in US 3,985,669 to Krummel et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion-exchange compositions suitable for use in the present invention are commercially available under the designation Zeolite A, Zeolite P (B). ), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion-exchange composition of the formula:

Nai2 [(AlO2) 12 (S1O2) 12] • XH2O where x is a number from about 20 to about 30, especially about 27. This composition is known as Zeolite A. Dehydrated zeolites may also be used (x = 0-10) . The particle size of the aluminosilicate is preferably in the range of about 0.1-10 microns.

Organic detergent builders for purposes of the invention include, but are not limited to, various polycarboxylate compounds. The term polycarboxylate as used herein means compounds having multiple carboxylate groups, preferably at least 3 carboxylate groups. The polycarboxylate builders may be added to the composition in the form of an acid, but may also be added in the form of a neutralized salt. When used in salt form,

44

4 4

4 4 4 • 4>

4 4 4

44 • 4

4 »44

4 4 4 4

4,444 • 4 4

44

44

4 4 4

4 · 44

Alkali metal salts such as sodium, potassium or lithium salts or alkanolammonium salts are preferred.

Polycarboxylate builders include various categories of suitable formulations. One significant category of polycarboxylate activating agents includes ether polycarboxylates comprising the oxydisuccinate disclosed in US3,128,287 Berg, issued April 7, 1964 and US3,635,830 by Lamberti et al., Issued January 18, 1972. See also TMS / TDS activating agents of US4,663,071. Bush et al., Issued May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, especially alicyclic compounds such as those disclosed in US3,923,679 by Rapko, issued Dec. 2, 1975; No. 4,158,635 to Crutchfield et al., issued Jun. 19, 1979; No. 4,120,874 to Crutchfield et al., issued Oct. 17, 1978; and U.S. Patent No. 4,102,903 to Crutchfield et al., issued Jul. 25, 1978.

Other suitable detergent builders include etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, various alkali metal salts, ammonium and substituted ammonium with polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid as well as polycarboxylates such as melitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1 ', 3,5-tricarboxylic acid, carboxymethylsuccinic acid and their soluble salts.

Of particular importance for heavy-duty liquid detergent compositions are polycarboxylate builders. &Lt; tb &gt; &lt; tb &gt; Comprising citrate activating agents such as citric acid and its water-soluble salts (especially sodium salt), and this is due to their availability from renewable sources and their biolodegradability. Citrates can also be used in granular compositions, particularly in combination with zeolite and / or layered silicate activating agents. Oxydisuccinates are also particularly useful in the compositions and combinations.

Also suitable for the detergent compositions of the invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and related compounds described in US 4,566,984, Bush, issued Jan. 28, 1986. Suitable activating compositions comprising succinic acid derivatives include C 5 -C 20 alkylated and alkenylated succinic acids and their salts. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate builders include: lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferably), 2-pentadecenyl succinate, and the like. In this class of activating additives, lauryl succinates are preferred, and are described in European Patent Application 86200690.5 / 0.200263 published. November 5, 1986.

Other suitable polycarboxylates are described in U.S. Patent 4,144,226 to Crutchfield et al., Issued March 13, 1979 and U.S. Patent 3,308,067 to Diehl, issued March 7, 1967. See also Diehl's U.S. Patent No. 3, 723,322.

It is also possible to incorporate fatty acids such as C 12 -C 18 carboxylic acids into the compositions of the invention, either alone or in combination with the aforementioned activating ingredients, in particular citrate and / or succinate activating ingredients, to provide better activating activity.

4 4 4 «« 9 · 4 · 4 44

The use of said fatty acids generally leads to a decrease in foaming which is necessary in the choice of the composition.

Where it is possible to use phosphorous-based activating agents, and in particular for hand wash bar formulations, various alkali metal phosphates such as commonly known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate may be used. It is also possible to use phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see, for example, US Patent Nos. 3, 159,581; 3,213, 030; 3, 422, 021; 3, 400,148 and 3,422,137).

Dispersants

A description of other suitable polyalkyleneimine dispersants which may optionally be combined with the bleach-stable dispersants of the present invention can be found in the following patents: U.S. Pat. European Patent Application 111,965 Oh and Gosselink, published June 27, 1984; European Patent Application 111,984, Gosselink, published Jun. 27, 1984; European Patent Application 112,592, Gosselink, published Jul. 4, 1984; U.S. 4,548,744, Connor, issued Oct. 22, 1985; and U.S. 5,565,145 to Watson et al., issued Oct. 15, 1996; However, any clay / soil dispersant dispersant or anti-redeposition agent may be used in the laundry compositions of the invention.

In addition, polymeric dispersants including polymeric polycarboxylates and polyethylene glycols are suitable for use in the present invention. Polymeric polycarboxylate compositions can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, citraconic acid, and methylenemalonic acid. The content of polymeric polycarboxylates or monomeric segments containing no carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc. is suitably adjusted for use according to the invention such that said segments do not comprise more than about 40% by weight.

Particularly suitable polymeric polycarboxylates are derived from acrylic acid. Said acrylic acid-based polymers are suitable for use according to the invention in the form of water-soluble salts of acrylic acid polymers. The average molecular weight of said polymers in acid form is preferably in the range of from about 2000 to about 10.00, more preferably from about 4000 to about 7000. and most preferably from about 4000 to 5000. The water-soluble salts of said acrylic acid polymers may include, for example, alkali salts. metals, ammonium and substituted ammonium. Soluble polymers of this type are known compositions. The use of polyacrylates of this type in detergent compositions is described, for example, in U.S. Patent 3,308,067, Diehl, issued March 7, 1967.

Acrylic / maleic copolymers may be used as the preferred component in the dispersing / antiredeposition agent. Said compositions include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in acid form is preferably in the range of from about 2000, preferably from about 5000, more

0 0

0 0 *

more preferably from about 7000 to about 100,000, more preferably to about 75,000 and most preferably to 65,000. The ratio of acrylate and maleate segments in said copolymers is generally in the range of about 30: 1 to about 1: 1, more preferably from about 10: 1 to 2 - 1. Water-soluble salts of said acrylic / maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known formulations as described in European Patent Application, No. 6,615, published December 15, 1982, and also in EP 193,360 published September 3, 1986, in which said hydroxypropyl acrylate-containing polymers are also described. Still other suitable dispersants include raspberry / acrylic acid / vinyl alcohol thermopolymers. Said compositions such as the acrylic acid / maleic acid / vinyl alcohol 45/45/10 terpolymer are also described in EP 193,360.

Another polymeric material that can be used is polyethylene glycol (PEG). PEG may exhibit dispersant effects, and may also act as an antiredeposition agent to remove soil particles. Typical molecular weights for the above purpose are in the range of from about 500 to about 100,000, preferably from about 1000 to about 50,000, even more preferably from about 1500 to about 10,000.

Dispersants including polyaspartate and polyglutamate may also be used, particularly in conjunction with zeolite builders. Dispersants such as polyaspartate preferably have a molecular weight (mean) of about

000

Means releasing dirt

The compositions of the invention may optionally contain one or more soil release agents. When used, the content of soil release agents in the composition is from about 0.01%, preferably from about 0.1%, even more preferably from about 0.2% to about 10%, preferably to about 5%, even more preferably to about 3%. % by weight. The polymeric soil release compositions are characterized in that they have both hydrophilic segments hydrophilizing the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments adhering to and adhering to the hydrophobic fibers until the wash cycle is completed, thereby also anchoring the hydrophilic segments. This makes it easier to remove stains remaining after treatment with the debris release agent in subsequent wash cycles.

Suitable polymers as soil release agents are described in the following patents, all of which are incorporated herein by reference. U.S. 5,843,878 Gosselink et al., Issued December 1, 1998; U.S. Pat. No. 5,834,412, Rohrbaugh et al., Issued Nov. 10, 1998; U.S. Pat. 5,728,671, Rohrbaugh et al., Issued Mar. 17, 1998; U.S. 5,691,298, Gosselink et al., Issued Nov. 25, 1997; No. 5,599,782, Pan et al., Issued Feb. 4, 1997; U.S. 5,415,807, Gosselink et al., Issued May 16, 1995; U.S. 5,182,043 Morral et al., Issued Jan. 26, 1993;

U.S. 4,956,447, Gosselink et al., Issued September 11, 1990;

U.S. 4,976,879, Maldonado et al., Issued Dec. 11, 1990;

No. 4,968,451, Scheibel et al., Issued Nov. 6, 1990;

U.S.4,925,577, Borcher, Sr. &amp; et al., issued May 15, 1990;

No. 4,861,512 ', Gosselink et al., Issued Aug. 29, 1989;

No. 4,877,896, Maldonado et al., Issued Oct. 31, 1989;

U.S. 4,771,730, Gosselink et al., Issued October 27, 1987;

U.S. 4,711,730, Gosselink et al., Issued Dec. 8, 1987;

U.S. 4,721,580, Gosselink, issued Jan. 26, 1988;

• · · · · · · · · · · · · · · · · · · · · · · · · · · ·

1976;

and European

U.S. 4,000,093, Nicol et al., Issued Dec. 28

No. 3,959,230, Hayes, issued May 25, 1976;

No. 3,893,929, Besadur, issued July 8, 1975;

Patent Application 0 219 048, published April 22, 1987 by Kud et al.

Other suitable soil release compositions are described in U.S. Pat. Nos. 4,201,824 to Voilland et al .; U.S. 4,240,918 to Lagasse et al .; No. 4,525,524 to Tung et al .;

U.S. Patent No. 4,579,681 to Ruppert sp .; U.S.4,220,918; U.S.4,787,989; EP 279,134 A, 1988 to Rhone-Poulenc Chemie; EP 457,205 A to BASF (1991); and DE 2,335,044 by Unilever N.V., 1974; all of which are incorporated herein by reference.

Method of use.

The invention further relates to a method of removing hydrophobic impurities among other body greasy impurities, sweat impurities and other fabric impurities, preferably from clothing, said method comprising contacting a fabric to be cleaned with an aqueous solution containing at least 0.01% by weight of a laundry detergent composition comprising:

A) from about 0.01% by weight of a hydrophobically modified polyamine of the formula:

R ¹ (R 'h-R- [li] -R] -S (R') ₂ QQQ

X * wherein R represents a straight-chain or straight-branched C 5 -C 6 alkylene group and mixtures thereof; ^{R1-represents} alkyleneoxy having the formula:

- (R ² O) _X -R ³ wherein R ² represents a C ² -C ⁴ straight-chain or branched alkylene group and mixtures thereof; ^R3 is an anionic unit, and mixtures thereof; x is about 15 to about 30; Q is a hydrophobic quaternizing unit which is selected from the group consisting of straight or branched chain C ₈ -C ₃₀ alkyl, C ₆ -C ₃ ocycloalkyl, substituted or unsubstituted C ₇ -C ₃ oalkylenaryl, and mixtures thereof; X is an anion in an amount sufficient to provide electroneutrality; n represents 0 'to 4; ·

B) from about 0.01% by weight of a surfactant system comprising one or more surfactants selected from the group consisting of:

i) 0% to 100% by weight of one or more anionic surfactants;

ii) 0% to about 100% by weight of one or more non-ionic surfactants;

iii) optionally 0.1% to about 80% by weight of one or more cationic surfactants;

iv) optionally 0.1% to about 80% by weight of one or more zwitterionic surfactants;

v) optionally 0.1% to about 80% by weight of one or more ampholytic surfactants;

• knows) mixtures thereof;

(C) additional carriers and excipients.

Preferably, the aqueous solution comprises at least about 0.01% (100 ppm), preferably at least about 1% (1000 ppm) by weight of said laundry detergent composition.

The compositions of the invention can be prepared by any suitable method, examples, but not limited to, are described in the following patents: U.S. 5,691,297, Nassano et al., Issued Nov. 11, 1997; U.S. 5,574,005, Welch et al., Issued Nov. 12, 1996; U.S. 5,569,645, Dinniwell et al., Issued Oct. 29, 1996; No. 5,565,422, Del Greco, et al., Issued Oct. 15, 1996; U.S. 5,516,448, Capeci et al., Issued May 14, 1996; No. 5,489,939, Capeci-a sp., Issued Feb. 6, 1996; No. 5,486,303, Capeci et al., Issued Jan. 23, 1996, all of which are incorporated herein by reference.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

Synthesis of ethoxylated (E20) bis (hexamethylene) triamintribenzylquaternary-ammonium bromide

Ethoxylation of bis (hexamethylene) triamine to an average E20 value of NH - Ethoxylation is carried out in a 2 gallon (7.6 L) stainless steel autoclave equipped with a thermostat for controlling and measuring the temperature, a pressure gauge, an inlet for. vacuum and purging with inert gas and an inlet for introducing ethylene oxide as a liquid. A ~ 20 lb (9 kg) ethylene oxide (ARC) cylinder fitted with an ethylene oxide pump for autoclave is placed on the scale to monitor the amount of ethylene oxide pumped.

Then, 362 g of bis (hexamethylene) triamine (BHMT) (molecular weight 215 (Aldrich), 1.68 mol, 5.04 mol of nitrogen, 8.4 mol of ethoxylated sites (NH)) are introduced into the autoclave. The autoclave was then sealed and purged with air (applying a vacuum of 28 Hg and then pressurized with nitrogen to 250 psia and then releasing the valve to atmospheric pressure). The contents of the autoclave are then heated under vacuum at 80 ° C. After about 1 hour, nitrogen was re-introduced into the autoclave under a pressure of about 250 psia while cooling the autoclave to about 105 ° C. Ethylene oxide is then gradually added to the autoclave following the additions while monitoring the autoclave pressure, temperature and ethylene oxide flow rate. Then the ethylene oxide supply pump is turned off and the autoclave is cooled to reduce any temperature rise resulting from the exothermic reaction. The temperature is then maintained between 100 and 110 ° C while the pressure is allowed to rise gradually during the reaction. Once a total of 370 g of ethylene oxide (8.4 mol) was added to the autoclave, the temperature was raised to 110 ° C and the autoclave content was stirred for a further 2 hours. At this point, vacuum is again applied to remove any unreacted ethylene oxide residues.

The vacuum was then applied continuously while the autoclave was cooled to 50 ° C and 181.5 g of a 25% solution of sodium methoxide in methanol (0.84 moles were added to achieve a 10% catalyst content relative to the ethoxylated functional groups). when the methoxide solution is removed from the autoclave under vacuum and the autoclave thermostat temperature is set to 100 ° C. A device measuring the energy consumed by the stirrer is used to monitor the reaction. The stirrer energy is monitored simultaneously with temperature and pressure. The required energy values for the ballhole and the temperature •

they gradually increase with the removal of methanol from the autoclave and with an increase in the viscosity of the mixture, which stabilizes in about 1.5 hours, indicating that most of the methanol has already been removed. The mixture was then further heated and stirred under vacuum for an additional 30 minutes.

The vacuum is then removed and the autoclave is cooled to 105 ° C while being charged with 250 psia nitrogen and then vented to room pressure. Then, in the same manner as described above, ethylene oxide is successively introduced into the autoclave while closely monitoring the pressure, autoclave temperature and ethylene oxide flow rate into the autoclave while maintaining a temperature in the range of 100-110 ° C, limiting any temperature increase during the exothermic reaction. After addition of 4180 g of ethylene oxide (95 moles corresponding to a total of 20 moles of ethylene oxide per mole of ethoxylated sites in the BHMT), the temperature was raised to -110 ° C and the mixture was stirred for an additional two hours.

The reaction mixture was then transferred to a three-necked round-bottomed flask. 22 1 purged with nitrogen. The strongly alkaline catalyst was neutralized by the slow addition of 80.7 g of methanesulfonic acid (0.84 mol) with heating (100 ° C) and mechanical stirring. The reaction mixture is then freed of residual ethylene oxide and deodorized by introducing an inert gas (argon or nitrogen) into the mixture by frit for gas dispersing while stirring and heating the mixture at 120 ° C for 1 hour. The final reaction product is then slightly cooled and stored in a glass vessel under nitrogen.

BHMT E20 quenching to 90 mol%: (3 moles N per mol polymer) - Into a weighed 1000 ml three-necked round bottom flask equipped with argon inlet, condenser, addition funnel, thermometer, mechanical stirrer and argon outlet (via bubbler) is introduced in an argon atmosphere of BHMT

• ·

EO 2 O (522.8 g, 0.333 mol of N, 98% activity, m / w 4615). The contents of the flask are then heated at 80 ° C until melting. Then, benzyl bromide (61.6 g, 0.36 mol, Aldrich, molecular weight 171.04) was added slowly to the molten ΒΗΜΤO 2 O via addition funnel over 10 minutes. The reaction is carried out for 6 hours at 80 ° C with stirring. Then the reaction mixture is dissolved in 500 g of water, the pH is adjusted to > 7 with NaOH 1 mol and transferred to a plastic container for storage]

Sulfation of ΒΗΜΤE20 'to 90% - The reaction mixture prepared in the quaternization step is cooled to 5 ° C in an argon atmosphere using an ice bath (ΒΗΜΤE20, 90 + mol% quart., 0.59 mol OH). Chlorosulfonic acid (72 g, 0.61 mol, 99%, molar mass 116.52) was then slowly added via addition funnel. The reaction mixture is then maintained at a temperature not exceeding 10 ° C. The ice bath was then removed and the reaction mixture was allowed to warm to room temperature. After 6 hours, the reaction is complete. Then the reaction mixture was recooled to 5 ° C and sodium methoxide (264 g, 1.22 mol, Aldrich, 25% solution in methanol, mp 54.02) was added slowly and rapidly with stirring. The temperature of the reaction mixture is maintained at a value not exceeding 10 ° C. The reaction mixture was then transferred to a one neck round bottom flask. Purified water (1300 mL) and dichloromethane, methanol were added to the reaction mixture, and some of the water was distilled off on a rotary evaporator at 50 ° C.

The clear, light yellow solution is transferred to a storage vessel. The pH of the final product is verified and adjusted to 99 with 1 M NaOH or 1 M HCl as necessary.

Examples of the compositions of the invention, without being limited thereto, are given in the table below.

• Φ ·· • φ · · ·

Table 1% by weight

component 2 3. 4 5 C 14 -C ₁₅ alkylE1. Osulfate 22.5 22.5 22.5 22.5 linear alkylbenzenesulfonate 3.0 3.0 3.0 3.0 Cioamidopropyl DMA 1.5 1.5 1,5 · 1.5 C ₁₂ -C ₁₄ alkyl E7; 0 3, 0 3.0 3.0 3.0 citric acid 2,5 ' 2.5 2.5 2.5 CI2 ^- Ci8alkyl-fatty acid 3.5 3.5 3.5 3.5 rapeseed oil fatty acid 5, 0 5, 0 5.0 5.0 proteasa 0, 8 1.57 1.57 1, 57 amylasa 0, 055 0,088 0, 088 0,088 celulasa 0,188 · 0,055 0,055 0,055 lipolasa 0.06 - - - mannanasa 0.007 0,0033 0,0033 0,0033 sodium metaborate 2; 0. 2/5 2.5 2.5 Ca-formate / CaCl2 0.02 0.10 0.10 0.10 modified polyamine ¹⁷ bleach catalyst ²⁷ 0,035 0,034 0, 034 0, 034 hydrophobic · dispersing agent ³⁷ 0, 65 0.76 0.76 0, 76 prostř. releasing dirt ⁴⁷ 0.147 - - - prostř. releasing dirt ⁵⁷ 0.10 0.10 0.10 anti-foaming additive 0, 60 0, 60 0, 60 0.60 water and minor components q.s. q.s. q.s. q.s.

1 / Hydrophobically modified polyamine according to Example 1.

2 / 1,5-Bis (hydroxymethylene) -3,7-dimethyl-2,4-bis (2-pyridyl) -3,7-diazabicyclo [3.3.1] nonan-9-ol-manganese (II) dichloride. I / 2H2O.

3 / ΙΕΙ 189 Ε15-18 according to U.S. Patent 4, -597,898, Vander-Meer, issued July 1, 1986

4 / A soil release agent according to U.S. Patent 4,702,857, Gosselink, issued October 27, 1987.

5 / A soil release agent according to U.S. Patent 4,968,451, Scheibel et al., Issued Nov. 6, 1990.

The examples below are examples of compositions containing a bleaching aid.

Table 2% by weight

component 6. 7 8 9 sodium-C 11 -C 13 alkylbenzenesulfonate 13.3 13.7 10.4 11.1 sodium-C ₁₄ -C ₁₅ alcohol sulfate 3.9 4.0 4,5 11.2 sodium-C 14 -C ₁₅ alcohol ethoxylate (0.5) sulfate 2,0 2,0 sodium-C 14 -C 15 alcohol-ethoxylate (6, 5) 0, 5 0.5 0.5 1.0 tallow fatty acid - - - 1.1 sodium tripolyphosphate - 41.0 - - Zeolite A hydrate (size 0,1- 10pm). 26.3 21.3 28.0 sodium carbonate 23.9 12.4 25.2 16.1 sodium polyacrylate (45%) 3.4 - 2/7 3.4 sodium silicate (NaO / SiO ₂ ratio 1: 6) (46%) 2.4 6, 4 2.1 2, 6 sodium sulfate 10.5 10.9 ^; 8.2 15.0 sodium perborate 1.0 1.0 5.0 - poles (ethylene glycol), M _r ~ 4000 (50%) 1.7 0.4 1.0 1.1

% by weight

Table 2 (continued)

component 6 7 8 9 citric acid - 3.0 - bleach catalyst ¹⁷ 0,035 0.030 0,034 0,028 bleach catalyst ²⁷ - - 5.9 - dirt release agent ³⁷ 0.10 0.10 0.10 polyamine ⁴⁷ anti-foaming additive 0, 60 0.60 0.60 0, 60 Water and minor ingredients ⁵⁷ q.s. q.s. q.s. q.s.

1 / 1,5-Bis (hydroxymethylene) -3,7-dimethyl-2,4-bis (2-pyridyl) -3,7-diazabicyclo [3.3.1] nonan-9-ol-manganese (II) dichloride .1 / 2H ₂ O.

2) Sodium p-hydroxybenzenesulfonate nonyl ester.

3 / A soil release composition according to U.S. Patent 5,415,807, Gosselink et al., Issued May 16, 1995.

4) Hydrophobically modified polyamine according to Example 1.

5 / In addition to 100%, where minor components include, for example, optical brighteners, perfumes, impurity dispersing agents, chelating agents, dye transfer inhibiting agents, additional water and fillers including CaCC> 3, talc, silicates, etc.

The examples below are examples of bleaching systems according to the invention without a source of hydrogen peroxide.

Table 3% by weight

component 10 11 12 13 sodium-C 1 -C 6 alkylbenzenesulfonate 13.3 13, 7 10.4. 11, 1 sodium-C ₁₄ '-C ₁₅ alkphol sulfate 3.9 4.0 4,5 11.2 sodium-C ₁₄ -C ₁₅ alcohol ethoxylate (0.5) sulfate 2,0 2,0 ngtrium-C14_C ₁₅ alcohol ethoxylate (6,5) 0.5 0,5- 0, 5 1.0 tallow fatty acid - - - 1.1 sodium tripolyphosphate - 41.0 - - Zeolite A, hydrate velikost (size 0,1- 10pm) 26, 3 21.3 28.0 sodium carbonate 23.9 12.4 25.2 16.1 sodium polyacrylate (45%) 3.4 - 2.7 3.4 Sodium silicate (NaO / SiO ₂ ratio 1: 6) (46%) 2.4 6.4 2.1 2.6 sodium sulfate 10.5 10, 9 WHAT 15, 0 poles (ethylene glycol), M _r -4000 (50%) 1.7 0.4 1.0 1.1 citric acid - - 3.0 - bleach catalyst ¹⁷ 0,10- 0.07 0,035 0,028 hydrophobically modified polyamine ²⁷ a hydrophobic dispersant ⁵⁷ 0, 65 0.76 0.76 0.76 release agent ⁶⁷ 0.147 0.10 0.10 0.10 anti-foaming additive 0.60 0.60 0.60 0, 60 water and minor ingredients ⁷⁷ q.s. q.s. q.s. q.s.

1,1,5-bis (hydroxymethylene) -3,7-dimethyl-2,4-bis (2-pyridyl) -3,7-diazabicyclo [3.3.1] nonan-9-ol-manganese (II) dichloride .1 / 2H ₂ O.

2) Hydrophobically modified polyamine according to Example 1.

3 / Potassium sulphite *

♦ ».

»· · · · · ·

4 / ΙΕΙ 189 Ε15-18 according to U.S. Patent 4,597,898, Vander-Meer, issued July 1, 1986.

6 / A soil release composition according to U.S. Patent 5,415,807, Gosselink et al., Issued May 16, 1995.

7 / To 100% addition, where minor components include, for example, optical brighteners, perfumes, dirt dispersing agents, chelating agents dye transfer inhibiting agents, additional water and fillers including CaCO ₃ , talc, silicates, etc. ·

The compositions of the invention can be prepared by any suitable method, examples, but not limited to, of which are described in the following U.S. Patents 5,691,297, Nassano et al., Issued Nov. 11, 1997; U.S. 5,574,005, Welch et al., Issued Nov. 12, 1996; U.S. 5,569,645, Dinniwell et al., Issued Oct. 29, 1996; No. 5,565,422, Del Greco et al., Issued October 15, 1996; U.S. 5,516,448, Capeci et al., Issued May 14, 1996; No. 5,489,392, Capeci et al., Issued Feb. 6, 1996; No. 5,486,303, Capeci et al., Issued Jan. 23, 1996, all of which are incorporated herein by reference.

Claims (10)

A detergent composition for washing, comprising: A) from 0.01% to 50% by weight of a hydrophobically modified polyamine of the formula:. R ¹ (R ') ₂ R ~ R ~ _[N-R] ^ _(R i χ · _h QQQ wherein R is a Cs-Cžoalkylenovou group with straight or branched alkylene, and mixtures thereof; R ¹ is alkyleneoxy having the formula: - (R ²⁰ ) _X- R ³ wherein R ² represents a C ² -C 4 alkylene group, straight or branched, and mixtures thereof; ^R3 is an anionic unit, and mixtures thereof; x is 15 to 30; Q is a hydrophobic quaternizing unit selected from the group consisting of _C8-C30 alkyl, straight or branched chain C ₃ -C ₆ Ocycloalkyl, substituted or unsubstituted C7-C3oalkylenaryl and mixtures thereof; X represents an anion in an amount sufficient to provide electron neutrality; n is 0 to 4; B) from 0.01% to 60% by weight of a surfactant system comprising one or more surfactants selected from the group consisting of: · * *;;;; »:» ..:. ..:. »::. · · · · · · · · · * · ···· · <·· ^w i) 0% to 100% by weight of one or more anionic surfactants; ii) 0% to 100% by weight of one or more nonionic surfactants; iii) optionally 0.1% to 80% by weight of one or more cationic surfactants; iv) optionally 0.1% to 80% by weight of one or more zwitterionic surfactants; v) optionally 0.1% to 80% by weight of one or more ampholytic surfactants; vi) mixtures thereof; C) Carriers and auxiliaries in addition to the required amount. 2. The composition of claim 1 wherein R is hexylene; R ² is ethylene, 1,2-propylene and mixtures thereof. Composition according to claim 1 or 2, characterized in that R ³ is selected from the group consisting of: a) - (CH ₂ ) f CO ₂ M; b) -C (O) (CH ₂ ) f CO ₂ M; c) - (CH ₂ ) _f PO ₃ M; d) - (CH ₂ ) _f OPO ₃ M; e) - (CH ₂ ) _f SO ₃ M; f) -CH ₂ (CHSO ₃ M) (CH _{2) 3} M .fSO; g) -CH ₂ (CHSO ₂ M) (CH ₂ ) _f SO ₃ M; h) -c (O) CH ₂ CH (SO ₃ M) ω ₂ m; i) -C (O) CH ₂ CH (CO ₂ M) NHCH (CO ₂ M) CH ₂ CO ₂ M; j) and mixtures thereof; Wherein M is hydrogen or an electroneutrality cation. The composition of any one of claims 1-3, wherein the index x is 15 to 25. A composition according to any one of claims 1-4, wherein Q is A straight chain C ₁₂ -C ₁₈ alkyl group, a C ₇ -C ₁₂ alkylenaryl group which is substituted or unsubstituted, and mixtures thereof. Composition according to any one of claims 1-5, characterized in that the hydrophobically modified polyamine has the general formula: wherein M represents a water-soluble cation; X is a water-soluble anion selected from the group consisting of chlorine, bromine, iodine, methyl sulfate, and mixtures thereof. The composition of any one of claims 1-6, wherein said surfactant system comprises from 0.01% to 100% by weight of one or more surfactants. Φί / Ζζ selected from the group consisting of: (i) 1% to. 80% by weight of an anionic surfactant selected from the group consisting of: (a) linear alkylbenzene sulphonates; (b) arylsulfonate surfactants with a branched chain within the chain of the general formula: Wherein A represents an alkyl unit with a chain branched within the chain of the general formula: RR * ^CH 3 ( ^CH 2 X 5 H (CH 2) y a (CH 2) z - wherein R and R ¹ each independently represent hydrogen, C 1 -C 3 alkyl and mixtures thereof, provided that the total carbon atoms of said alkyl unit are 6 to 18 and at least one of R and R ^{1 is} not hydrogen; x is an integer from 0 to 13; y is an integer from 0 to 13; z is 0 or 1; R ² is hydrogen, C 1 -C 3 alkyl and mixtures thereof; a water-soluble cation having a charge sufficient to achieve neutrality; c) branched alkyl sulfate surfactants of the general formula: CH ₃ CH ₂ (CH ₂ ) _m CH ₂ OSO ₃ M; 7ko0oO2 - / <£ / 2 ··. ··. ♦ ** · ♦ or the general formula: CH ₃ CH ₂ (CH ₂ ) _m CH ₂ (OCH ₂ CH ₂ ) _y OSO ₃ M; (d) Alkyl sulphate surfactants with a chain branched within the chain of the general formula: or.General formula: where R and R ¹ . and R ² each independently represents hydrogen, A C 1 -C ₃ alkyl group and mixtures thereof with the proviso that the total number of carbon atoms in said (surfactant is 14 to 20 and at least one of R ¹ and R ¹ and R ^{2 is} not hydrogen; w is an integer from 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; with the proviso that w + x + y + z is 8 to 14 and the total number of carbon atoms in the surfactant is 14 to 20; R ³ is ethylene, 1,2-propylene, 1,3-propylene, 1,2-butylene, 1,4-butylene and mixtures thereof; the mean index m is at least about 0.01; M is hydrogen, a water-soluble cation having a charge sufficient to achieve electroneutrality; and mixtures thereof ii) from 0% to 100% by weight of one or more non-ionic surfactants; iii) optionally from 0.1% to about 80% by weight of one or more cationic surfactants; iv) optionally 0.1% to about 80% by weight of one or more zwitterionic surfactants; . v) optionally 0.1% to about 80% by weight of one or more ampholytic surfactants; vi) mixtures thereof; The composition of any one of claims 1-7, further comprising an amount of from 1% by weight of a peroxygen bleach system comprising: a. i) a source of hydrogen peroxide in an amount of about 40% by weight of the bleaching system; ii) optionally a bleach activator in an amount of from about 0.1% by weight based on the weight of the bleach system; iii) optionally a bleach catalyst comprising a transition metal in an amount of about 1 ppb relative to the composition; iv) optionally prepared peroxygen bleach in an amount of about 0.1% by weight. 9. A detergent composition for washing comprising: (A) from 0,01% by weight of hydrophobically modified polyamine of the following formula: ·· ·· **. «** · · *« '. ·. *. »·: ·· ·.:.: ^· '·: · *:: · ·. · ·· ·· ···· .. ^r where Μ is a water soluble cation; X is a water-soluble anion selected from the group consisting of chlorine, bromine, iodine, methyl sulfate, and mixtures thereof. B) from 0.01% to 60% by weight of a surfactant system comprising one or more surfactants selected from the group consisting of: i) 0% to 100% by weight of one or more anionic surfactants; ii) 0% to 100% by weight of one or more non-ionic surfactants; iii) optionally from 0.1% to 80% by weight of one or more cationic surfactants; iv) optionally 0.1% to 80% by weight of one or more zwitterionic surfactants; v) optionally from 0.1% to 80% by weight of one or more ampholytic surfactants; vi) mixtures thereof; C) Carriers and auxiliaries in addition to the required amount. 10. A method of cleaning a fabric comprising the step of contacting a fabric article with an aqueous solution comprising at least 0.1% by weight of a composition comprising: A) from 0.01% to 50% by weight of a hydrophobically modified polyamine of the formula: R ¹ Q Q Q X 'wherein R. represents a straight chained or branched C ₅ -C ₂ oalkylene group and mixtures thereof; R ¹ 'means an alkyleneoxy unit having the general formula: - (R ² O) _x -R ³ wherein R ² represents a C ₂ -C ₄ straight-chain or branched alkylene group and mixtures thereof; R ³ represents an anionic unit selected from the group consisting of: a) - (CH ₂ ) _f CO ₂ M; b) -C (O) (CH ₂ ) _f CO ₂ M; c) - (CH ₂ ) _f PO ₃ M; d) - (CH ₂ ) _£ OOP ₃ M; . e) - (CH ₂ ) fSO ₃ M; f) -CH ₂ (CHSO ₃ M) (CH ₂ ) _f SO ₃ M; g) -CH ₂ (CHSO ₂ M) _(CH2) - _f SO ₃ M; h) -C (O) CH ₂ CH (SO ₃ M) CO ₂ M; i) -C (O) CH ₂ CH (CO ₂ M) NHCH (CO ₂ M) CH ₂ CO ₂ M; j) and mixtures thereof; wherein the index f is 0 to 10; M is hydrogen or a cation providing electroneutrality; x is 15 to 30; Q is a hydrophobic quaternizing unit which is a group selected from the group consisting of straight or straight C ₈ -C ₃₀ alkyl; - / <£ / yy ···························· Branched-chain, C ₆ -C ₃₀ cycloalkyl, substituted or unsubstituted C 7 -C ₃₀ alkylenaryl, and mixtures thereof; X represents an anion in an amount sufficient to provide electroneutrality; n is 0 to 4; B) from 0.01% to 60% by weight of a surfactant. a system comprising one or more surfactants selected from the group consisting of: i) 0% to 100% by weight of one or more anionic surfactants; ii) 0% to 100% by weight of one or more non-ionic surfactants; iii) optionally 0.1% to 80% by weight of one or more cationic surfactants; iv) optionally 0.1% to 80% by weight of one or more zwitterionic surfactants; v) optionally 0.1% to 80% by weight of one or more ampholytic surfactants; vi) mixtures thereof; »» C) Carriers and auxiliaries in addition to the required amount.