Technical Field of the Invention

The present invention relates to detergent compositions comprising a surfactant which provides suds supressing benefits.

Background of the Invention

There is a wide choice of surfactants currently available to the detergent manufacturer when considering formulating detergent compositions in order to achieve the desired performance benefits.

A particularly desirable performance benefit for detergent compositions is good greasy and oily soil removal over a wide spectrum of temperatures. In order to achieve such desired performance benefits, detergent manufacturers frequently have found it necessary to increase the total amount of surfactants incorporated into detergent compositions. As a result the compositions have also tended to become more compact. This is also in line with current trends to produce more compact formulations to reduce the environmental impact. Cationic surfactants, especially in combination with anionic surfactants, have been found to provide these desired cleaning benefits, particularly with respect to greasy and oily soil removal and are thus a desirable component of detergent formulations.

The sudsing profile of a detergent composition is also an important factor to be considered by the detergent manufacturer. It is generally considered that high sudsing is not a desirable feature of a laundry detergent composition for laundering conducted in automatic washing machines. However, high levels of surfactant in a detergent composition usually results in an increase in the sudsing of the detergent composition. This problem is particularly acute if the surfactant system comprises high levels of anionic surfactant. Thus, in order to control the suds profile, such compositions require the addition of a suds suppressor. However, the suds suppressors currently available are generally expensive and also

provide no other performance benefit to the composition other than suds suppression. Therefore, it is desirable that their presence is minimised.

Thus, it is an aim of the present invention to provide a surfactant system which provides the dual performance benefits of excellent cleaning performance and providing suds suppression.

It has now been found that this objective can be achieved by the use of certain branched hydrolysable cationic compounds and detergent compositions as described herein. The cationic compounds of the present invention readily hydrolyse in the wash liquor and these hydrolysis products then act as suds suppressors. The hydrolysis products can thus act to suppress the sudsing produced by other surfactants which may be preferred components of the detergent composition. Of particular benefit is that the hydrolysis products tend to be formed in the latter stages of the washing process, when sudsing is at its greatest and suds suppression is most required. Furthermore, another advantage of the presence of the suds suppressing hydrolysis products, is that the amount of additional suds suppressor required in the formulation is reduced. Thus, the cationic compounds of the present invention have a dual function as a component of a surfactant system providing improved cleaning and as precursors of suds suppression agents in detergent compositions.

A further advantage of the cationic compounds of the present invention is that they are also low sudsing compounds per se.

Cationic surfactants have been described in the art in detergent compositions to provide fabric care benefits and enhanced cleaning. See for example US 4 239 660, US 4 259 217, US 4 260 529, US 4 228 042, EP 021 491 and EP 000 234. Branched cationic species for softening have been disclosed in DE 3402 146.

Summary of the Invention

One aspect of the present invention relates to a novel compound according to the formula:

R 1-

CH— (R ₃ ) _a -χ-(R v — ₍ γ) _c -<R - Q _e M

5

R

2

wherein Ri and R2 are independently a C4 to Cj2 hydrocarbyl, and wherein c is 1 or 0, provided that where c is 1 , X and Y are independently selected from

— O — C— O — , — C — O and — o — C*-— , and where c is

O

II

0, X is O C O _f R^ and R4 are independently Ci to C4 hydrocarbyl or a benzyl group, a and b are independently from 0 to 4, R5 is a C\ to C9 hydrocarbyl or Ci to C9 polyalkylene oxide having an average degree of polymerization of from 1 to 9, d is 0 to 2, Q is a cationic group, e is 1 or 2, M is an anion providing electrical neutrality and mixtures of any of the foregoing compounds.

The present invention also relates to detergent composition comprising at least 0.1 % of a compound as hereinbefore defined and at least 0.1 % of a detergent ingredient selected from surfactants, builders and chelants and mixtures thereof.

In another aspect of the present invention there is provided a detergent composition comprising an anionic surfactant and a compound according to the formula: R

CH— (R ₃ ) _a -χ-(R ₄ ) _b — _(γ)c -(R^ _QeM

R

2 wherein Ri and R2 are independently C4 to C12 hydrocarbyl, X and Y are independently selected from

O O 0

II II II

— O— C— O — , — C — O and — o — C _c is 0 or 1, R3 and R4 are independently Ci to C4 hydrocarbyl or a benzyl group a and b

are independently from 0 to 4, R5 is a Ci to C9 hydrocarbyl or Ci to C9 polyalkylene oxide having an average degree of polymerization of from 1 to 9, d is 0 to 2, Q is an cationic group, e is 1 or 2, M is an anion providing electrical neutrality and mixtures thereof.

The present invention also relates to a method of washing fabrics comprising contacting said fabrics with an aqueous solution comprising at least 0.005% compound hereinbefore defined according to the present invention or at least 0.1 % of a detergent composition according to the present invention.

All percentages, ratios and parts as used herein are by weight unless otherwise specified.

Detailed Description of the Invention

The compound

The present invention relates to a compound which provides the dual benefits both of improved surfactancy particularly with respect to oily and greasy soil removal and of suds suppression.

According to the present invention said compound is according to the formula:

wherein R\ and R2 are independently C4 to C12 _» preferably Cβ to Ci2, more preferably C to CJO hydrocarbyl, selected from alkyl, alkenyl and alkylaryl groups and which may be branched or linear. Preferably Ri and R2 are independently alkyl groups.

In a preferred embodiment of the compounds of the present invention the sum of the carbon chain lengths of Ri and R2 is from 10 to 18, more preferably from 12 to 18 and the difference in said carbon chain lengths of Ri and R2 is 4 or less, preferably 3 or less, most preferably 2 or less. In a most preferred embodiment Ri and R2 are independently C to Cio linear alkyl groups and most preferably have the same number of carbon atoms.

According to the present invention c is 1 or 0, provided that where c is 1 , X and Y are independently selected from

O O O

11 11 II

— O — C— O — , — C — O and — O — C _an d _wne re c is 0,

O

II X i _s o— c — 0.

According to the present invention R3 and R4 are independently Cj to C4, preferably linear C\ to C2 hydrocarbyl or a benzyl group.

Preferably only R3 or R4 comprises a benzyl group, a and b are independently from 0 to 4, preferably from 1 to 2.

R5 is a Ci to Ci8, preferably a Ci to C9 group selected from alkyls, alkenyls, alkylaryls, and polyalkylene oxide, preferably ethylene or propylene having an average degree of polymerization of from 1 to 9. d is 0 to 2.

According to the present invention Q is any cationic group and e is 1 or 2. Suitable cationic groups for use herein may be selected from:

π

N(+) — , wherein p is from 1 to 12

m (C ₂ H O) _p H

N(+) — , wherein p is from 1 to 12

IV ^(C ₂ ^H Λ ^H

and mixtures thereof.

Preferably said cationic group is selected from I, II, III and IV, preferably I, III and IV, most preferably I and III. These cationic groups have R groups which are Ci to C4 hydrocarbyl or hydroxyhydrocarbyls, optionally interrupted by aryl groups.

According to the present invention, if e is equal to two, cationic components containing two cationic charge centres are formed. An example of a

A preferred type of cationic group for use herein are the alkoxylated alkyl quaternaries. Examples of such groups are given below:

wherein each p is from 1 to 12, preferably from 1 to 10 (with the total ethylene oxide groups in a molecule not exceeding about 13). It is preferred that these compounds contain no more than a total of about 10, preferably no more than about 7, ethylene oxide groups in order to obtain the best removal of greasy and oily soils.

The compositions of the present invention are preferably substantially free of cationic compounds containing about 13 or more ethylene oxide groups. These compounds tend to be relatively non-biodegradable, do not enhance the cleaning or fabric conditioning benefits provided by the compositions and may, in some circumstances, decrease the overall laundering performance provided by them. It is to be noted that polyethoxylated cationic surfactants having relatively low levels of ethoxylation, such as those described above, exhibit better biodegradability characteristics and may be advantageously included in the compositions of the present invention.

According to the present invention M is a counter ion and may be any anion which results in the compound becoming water dispersible. The counterions are present in an appropriate number to give electrical neutrality. Suitable anions may be selected from halides, sulphates and nitrates and are preferably chloride, bromide, iodide and methyl sulphate and mixtures thereof.

Another aspect of the present invention relates to a detergent composition comprising an anionic surfactant and a compound according to the formula: R

CH— (R ₃ ) _a -X-(R ₄ ) _b — (Y) _c -Oy _j - QeM

R

2 wherein R\ and R2 are independently C4 to Cj2 hydrocarbyl, X and Y are independently selected from

0 0 0

II II

— o— c— o — , — c — 0 0 - — and — o — C — c is 0 or 1, R3 and R4 are independently Ci to C4 hydrocarbyl or a benzyl group a and b are independently from 0 to 4, R5 is a C\ to C9 hydrocarbyl or Ci to C9 polyalkylene oxide having an average degree of polymerization of from 1 to 9, d is 0 to 2, Q is an cationic group, e is 1 or 2, M is an anion providing electrical neutrality and mixtures thereof.

Preferably R and R2 are Ctj to Ci2, selected from alkyl, alkenyl and alkylaryl groups and which may be branched or linear. Most preferably Ri and R2 are independently alkyl groups. In a preferred embodiment of this aspect of the present invention, the sum of the carbon chain lengths of Rj and R2 is from 10 to 18, more preferably from 12 to 18 and the difference in said carbon chain lengths of Ri and R2 is 4 or less, preferably 3 or less, most preferably 2 or less. In a most preferred embodiment of this aspect of the present invention Ri and R2 have the same number of carbon atoms.

R3 and R4 are preferably linear Ci to C2 hydrocarbyl or a benzyl group. More preferably only R3 or R4 comprises a benzyl group, a and b are preferably from 1 to 2. R5 is preferably a Ci to C9 group selected from alkyls, alkenyls, alkylaryls, and polyalkylene oxide, preferably propylene or ethylene having an average degree of polymerization of from 1 to 9. Q is preferably selected from one of the cationic groups I to VI, preferably I, III and IV, most preferably I and III.

Particularly preferred compounds for use in anionic detergent compositions of this aspect of the present invention are the choline ester derivatives having the following formula:

R ₂

CH,

as well as those compounds in which the ester linkage in the above formula is replaced with a reverse ester linkage.

Other preferred cationic compounds for use in anionic detergent compositions of this aspect of the present invention are betaine ester derivatives having the formula:

O CH, ι +

CH- CH ₂ — O CH- ^■ N — M

R

2 CH ₃ as well as those compounds in which the ester linkage in the above formula is replaced with a reverse ester.

Detergent compositions

According to the present invention another aspect of of the present invention is a detergent composition comprising at least 0.1 % , preferably from 0.5% to 40%, most preferably from 0.5% to 20% of said compound and at least 0.1 %, preferably from 0.3% to 99.9% of a detergent ingredient selected from surfactants, builders, chelants and mixtures thereof.

Detersive Surfactants

Surfactants suitable for use herein include the conventional Cιj-Ci8 alkyl benzene sulphonates ("LAS") and primary, branched-chain and random C10-C20 alkyl sulphates ("AS"), the C10-C18 secondary (2,3) alkyl sulphates of the formula CH3(CH2) _x (CHOSθ3 ^' M ⁺ ) CH3 and CH3 (CH2) _y (CHOSθ3 ^' M ⁺ ) CH2CH3 where x and (y + 1) are integers of at least about 7, preferably at least about 9, and M is a water-solubilizing cation, especially sodium, unsaturated sulphates such as oleyl sulphate, the C10-C18 alkyl alkoxy sulphates ("AE _X S"; especially EO 1-7 ethoxy sulphates), Cifj-Cis alkyl alkoxy carboxylates (especially the EO 1-5 ethoxycarboxylates), the Cιrj-18 glycerol ethers, the Cifj-Cis alkyl polyglycosides and their corresponding sulphated polyglycosides, and C12-C18 alpha-sulphonated fatty acid esters. According to the present invention the detergent composition comprises from 1 % to 80%, preferably from 1 % to 60%, more preferably from 1 % to 40% of an anionic surfactant.

If desired, the conventional nonionic and amphoteric surfactants such as the C12-C18 alkyl ethoxylates ("AE") including the so-called

narrow peaked alkyl ethoxylates and C6-C12 alkyl phenol alkoxy lates (especially ethoxylates and mixed ethoxy/propoxy), C12-C18 betaines and sulphobetaines ("sultaines"), C10-C18 amine oxides, and the like, can also be included in the overall compositions. The C10-C18 N-alkyl polyhydroxy fatty acid amides can also be used. Typical examples include the C12-C18 N-methylglucamides. See WO 9,206,154. Other sugar- derived surfactants include the N-alkoxy polyhydroxy fatty acid amides, such as C10-C18 N-(3-methoxypropyl) glucamide. The N-propyl through N-hexyl C12-C18 glucamides can be used for low sudsing. C10-C20 conventional soaps may also be used. If high sudsing is desired, the branched-chain soaps may be used. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants such as linear cationic surfactants are listed in standard texts.

According to the present invention the detergent compositions preferably comprise from 1 % to 80%, preferably from 1 % to 60%, most preferably from 5% to 40% of surfactant. Preferred surfactants for use herein are linear alkyl benzene sulphonate, alkyl sulphates, alkyl alkoxylated nonionic surfactants or mixtures thereof.

Builders

Detergent builders can optionally be included in the compositions herein to assist in controlling mineral hardness. Inorganic as well as organic builders can be used. Builders are typically used in fabric laundering compositions to assist in the removal of paniculate soils.

The level of builder can vary widely depending upon the end use of the composition and its desired physical form. When present, the compositions will typically comprise at least 1 % builder. Liquid formulations typically comprise from 5% to 50%, more typically about 5% to about 30%, by weight, of detergent builder. Granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% by weight, of the detergent builder. Lower or higher levels of builder, however, are not meant to be excluded.

12

Inorganic or P-containing detergent builders include, but are not limited to, the alkali metal, ammonium and alkanolammonium salts of polyphosphates (exemplified by the tripolyphosphates, pyrophosphates, orthophosphates and glassy polymeric meta-phosphates), phosphonates, phytic acid, silicates, carbonates (including bicarbonates and sesquicarbonates), sulphates, and aluminosilicates (see, for example, U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137).

However, non-phosphate builders are required in some locales. Importantly, the compositions herein function surprisingly well even in the presence of the so-called "weak" builders (as compared with phosphates) such as citrate, or in the so-called "underbuilt" situation that may occur with zeolite or layered silicate builders.

Examples of silicate builders are the alkali metal silicates, particularly those having a Siθ2:Na2θ ratio in the range 1.6:1 to 3.2:1 and layered silicates, such as the layered sodium silicates described in U.S. Patent 4,664,839, issued May 12, 1987 to H. P. Rieck. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, the Na SKS-6 silicate builder does not contain aluminum. NaSKS-6 has the delta-Na2S.2θ5 morphology form of layered silicate. It can be prepared by methods such as those described in German DE-A-3, 417,649 and DE- A-3,742,043. SKS-6 is a highly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi _x θ2χ+ l*yH2θ wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 can be used herein. Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11, as the alpha, beta and gamma forms. As noted above, the delta-Na2Si2θ5 (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful such as for example magnesium silicate, which can serve as a crispening agent in granular formulations, as a stabilizing agent for oxygen bleaches, and as a component of suds control systems.

Examples of carbonate builders are the alkaline earth and alkali metal carbonates as disclosed in German Patent Application No. 2,321,001 published on November 15, 1973.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most currently marketed heavy duty granular detergent compositions, and can also be a significant builder ingredient in liquid detergent formulations. Aluminosilicate builders include those having the empirical formula:

M _z [(Siθ2) _w (zAlθ2)y]-xH ₂ 0 wherein w, z and y are integers of at least 6, the molar ratio of z to y is in the range from 1.0 to about 0.5, and x is an integer from about 15 to about 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates can be crystalline or amorphous in structure and can be naturally-occurring aluminosilicates or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel, et al, issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In an especially preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula:

Nai2[(Alθ2)l2(Siθ2)l2]-xH ₂ 0 wherein x is from about 20 to about 30, especially about 27. This material is known as Zeolite A. Dehydrated zeolites (x = 0 - 10) may also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the present invention include, but are not restricted to, a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a plurality of carboxylate groups, preferably at least 3 carboxylates. Polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a

neutralized salt. When utilized in salt form, alkali metals, such as sodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categories of useful materials. One important category of polycarboxylate builders encompasses the ether polycarboxylates, including oxydisuccinate, as disclosed in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al, U.S. Patent 3,635,830, issued January 18, 1972. See also "TMS/TDS" builders of U.S. Patent 4,663,071, issued to Bush et al, on May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether, 1, 3, 5-trihydroxy benzene-2, 4, 6-trisulphonic acid, and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediamine tetraacetic acid and nitrilotriacetic acid, as well as polycarboxylates such as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for heavy duty liquid detergent formulations due to their availability from renewable resources and their biodegradability. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also especially useful in such compositions and combinations.

Also suitable in the detergent compositions of the present invention are the 3,3-dicarboxy-4-oxa-l,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C5-C20 alkyl and alkenyl succinic acids and salts thereof. A particularly preferred compound of this

type is dodecenylsuccinic acid. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2- dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Laurylsuccinates are the preferred builders of this group, and are described in European Patent Application 86200690.5/0,200,263, published November 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Patent

4,144,226, Crutchfield et al, issued March 13, 1979 and in U.S. Patent

3,308,067, Diehl, issued March 7, 1967. See also Diehl U.S. Patent 3,723,322.

Fatty acids, e.g., Ci2-Cj8 monocarboxylic acids, can also be incorporated into the compositions alone, or in combination with the aforesaid builders, especially citrate and/or the succinate builders, to provide additional builder activity. Such use of fatty acids will generally result in a diminution of sudsing, which should be taken into account by the formulator.

C eatin Agents

The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents can be selected from the group consisting of amino carboxylates, amino phosphonates, poly functionally-substituted aromatic chelating agents and mixtures therein, all as hereinafter defined. Without intending to be bound by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from washing solutions by formation of soluble chelates.

Amino carboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethylethylenediaminetriacetates, nitrilotriacetates, ethylenediamine tetraproprionates, triethylenetetraamine hexacetates, diethylenetriaminepentaacetates, and ethanoldiglycines, alkali metal, ammonium, and substituted ammonium salts therein and mixtures therein.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the invention when at lease low levels of total phosphorus are permitted in detergent compositions, and include ethylenediaminetetrakis (methylenephosphonates) as DEQUEST. Preferred, these amino phosphonates to not contain alkyl or alkenyl groups with more than about 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents are also useful in the compositions herein. See U.S. Patent 3,812,044, issued May 21, 1974, to Connor et al. Preferred compounds of. this type in acid form are dihydroxydisulfobenzenes such as l,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the [S,S] isomer as described in U.S. Patent 4,704,233, November 3, 1987, to Hartman and Perkins.

If utilized, these chelating agents will generally comprise from 0.1 % to 10% by weight of the detergent compositions herein, more preferably, from 0.1 % to 3.0% by weight of such compositions.

Bleaching Compounds - Bleaching Agents and Bleach Activators

The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing a bleaching agent and one or more bleach activators. When present, bleaching agents will typically be at levels of from 1 % to 30%, more typically from 5% to 20%, of the detergent composition, especially for fabric laundering. If present, the amount of bleach activators will typically be from 0.1 % to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent-plus-bleach activator.

The bleaching agents used herein can be any of the bleaching agents useful for detergent compositions in textile cleaning, hard surface cleaning, or other cleaning purposes that are now known or become known. These include oxygen bleaches as well as other bleaching agents.

Peroxygen bleaching agents can also be used. Suitable peroxygen bleaching compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by DuPont) can also be used.

A preferred percarbonate bleach comprises dry particles having an average particle size in the range from about 500 micrometers to about 1,000 micrometers, not more than about 10% by weight of said particles being smaller than about 200 micrometers and not more than about 10% by weight of said particles being larger than about 1,250 micrometers. Optionally, the percarbonate can be coated with silicate, borate or water- soluble surfactants. Percarbonate is available from various commercial sources such as FMC, Solvay and Tokai Denka.

Another category of bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application 740,446, Burns et al, filed June 3, 1985, European Patent Application 0,133,354, Banks et al, published February 20, 1985, and U.S. Patent 4,412,934, Chung et al, issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in U.S. Patent 4,634,551, issued January 6, 1987 to Burns et al.

Mixtures of bleaching agents can also be used. Peroxygen bleaching agents, the perborates, e.g., sodium perborate (e.g., mono- or tetra-hydrate) , the percarbonates, etc., are preferably combined with bleach activators, which lead to the in situ production in aqueous solution (i.e., during the washing process) of the peroxy acid corresponding to the bleach activator. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al,

and U.S. Patent 4,412,934. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine (TAED) activators are typical, and mixtures thereof can also be used. See also U.S. 4,634,551 for other typical bleaches and activators useful herein.

Highly preferred amido-derived bleach activators are those of the formulae:

RlN(R5)C(0)R2C(0)L or R1C(0)N(R*5)R2C(0)L wherein R is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R5 is H or alkyl, aryl, or alkaryl containing from about 1 to about 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a consequence of the nucleophilic attack on the bleach activator by the perhydrolysis anion. A preferred leaving group is phenyl sulfonate.

Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate, (6- nonanamidocaproyl)- oxybenzenesulfonate, (6-decanamido- caproyl)oxybenzenesulfonate, and mixtures thereof as described in U.S. Patent 4,634,551 , incorporated herein by reference.

wherein R" is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5- trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate.

Bleaching agents other than oxygen bleaching agents are also known in the art and can be utilized herein. One type of non-oxygen bleaching agent of particular interest includes photoactivated bleaching agents such as the sulfonated zinc and/or aluminum phthalocyanines. See U.S. Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will typically contain from 0.025% to 1.25%, by weight, of such bleaches, especially sulfonate zinc phthalocyanine.

If desired, the bleaching compounds can be catalyzed by means of a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat. 5,114,606; and European Pat. App. Pub. Nos. 549,271 Al, 549.272A1, 544,440A2, and 544,490A1; Preferred examples of these catalysts include Mn^ 2( ^u "0 3 l ,4,7-trimethyl-l ,4,7-triazacyclononane)2(PF6)2, Mnm2(u-0)ι(u-OAc)2(l,4,7-trimethyl-l,4,7-triazacyclononane) 2- (Clθ4)2, Mn ^IV 4(u-0)6(l,4,7-triazacyclononane)4(Clθ4)4, Mn^lMn^ (u-0)ι(u-OAc)2-(l,4,7-trimethyl-l,4,7-triazacyclononane)2(C lθ4)3, Mn ^IV (l,4,7-trimethyl-l,4,7-triazacyclononane)- (OCH3)3(PF6), and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243 and U.S. Pat. 5,114,611. The use of

manganese with various complex ligands to enhance bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; 5,227,084;

According to the present invention the detergent composition may comprise any other ingredients commonly employed in conventional detergent compositions such as soaps, polymeric soil release agents, anti- redeposition agents, polymeric dispersing agents, suds suppressors, dye transfer inhibitors, perfumes, softeners, brighteners, enzymes and enzyme stabilisers.

The detergent compositions of the present invention may be in granular, liquid or gel form or bar form. Preferably the compositions are granular. The detergent compositions may be prepared by combining the ingredients in the required amounts in any suitable order by conventional means. When formulated as free following particles i.e in powdered or granulated form any conventional technique employed in the manufacture of detergent compositions may be used. To prevent premature hydrolysis of the compounds of the present invention in the formulation prior to washing, the maintenance of elevated temperatures under alkaline aqueous conditions should be avoided. Consequently, dry-mixing, agglomeration, granulation and extrusion techniques are preferable means of producing free flowing particle compositions.

According to the present invention the cationic compounds can be synthesised by methods known in the art.

Example I: Synthesis of Cj^-Cj^ branched guerbet betaine ester

C14/18 H29/37 OH + CI CH2 CO CI ->Ci4/i8 H29/37 O CO CH2 CI+ H C1

lOOg (0.42 mole) of a C14-C18 Guerbet alcohol blend was placed in a 500ml conical flask fitted with a magnetic stirrer and dropping funnel and equipped with calcium chloride drying tubes to prevent ingress of moisture. With stirring, at 20°C, 47.5g (0.42 mole) of chloroacetyl chloride was added over 15 minutes via the dropping funnel. The

resulting reaction mixture was stirred, at 20°C, for 18 hours, completeness of reaction being confirmed by infra-red spectroscopy (disappearance of both alcohol hydroxyl, singlet 3300cm~l, and acid chloride carbonyl, singlet 1820cm ^_ l). The product was dissolved in diethyl ether and transferred to a separating funnel where it was washed with water, aqueous sodium bicarbonate solution and water again. The ethereal solution was dried over anhydrous sodium sulphate, filtered and the ether removed by means of a rotary vacuum evaporator. This yielded 120g of intermediate Guerbet chloroacetate.

CC14/18 H29 37 O CO CH ₂ CI + N(CH ₃ ) ₃ -»Cι ₄ l8 H29/37 O CO CH2 N(CH3)3 CI

85g (0.27 mole) of Guerbet chloroacetate and lOOmls of acetone were placed in a 500ml round bottomed flask fitted with a -60 °C (carbon dioxide/acetone) reflux condenser, magnetic stirrer and dropping funnel and equipped with calcium chloride drying tubes to prevent ingress of moisture. The flask was cooled to -5°C by means of a carbon dioxide/acetone cold bath and, with stirring, 65g (1.1 moles) of precooled (-20 °C) trimethylamine was quickly added via the dropping funnel. The reaction mixture was stirred at -5°C for 6 hours and then allowed to warm to 20°C. The condenser and dropping funnel were removed, the flask was stoppered and then allowed to stand at 20°C for 72 hours. The resulting cloudy solution was clarified by gravity filtration through a Whatman No.54 paper and then the acetone and excess trimethylamine removed by means of a rotary vacuum evaporator. This yielded 89g of product which was 95.2% pure by Cat SO3 titration. Mass spectroscopy analysis identified the chainlength distribution of Ri and R2 as 21 % as C7, C7, 20% as C7, C8, and Cs, C7, 35% as C7, C9, and C9,C7, 13% as C8,C9 and C9, Cs, and 10% as C9.C9,

Example II: Synthesis of l-rø-f /V- imethylethanolammonium-methyn benzovloxyl 2-butvl-octanvl

Preparation of 4-chloromethylbenzoyl chloride

Thionyl chloride (0.75 mol, 5.5 ml) and a few drops of dimethylformamide were added to a solution of 4-chloromethylbenzoic acid (0.05 mol, 8.53 g) in dry toluene (100 ml). The mixture was stirred at room temperature for 10 minutes and then at 70°C for three hours, at the end of which the solution became completely clear and a green solid was deposited on the walls of the 250 ml round-bottom flask. The solution was filtered and concentrated under vacuum, yielding 4- chloromethylbenzoyl chloride as a yellow solid, which was used in the next step without further purification.

Preparation of l-r(4-chloromethynbenzoynf2-butylVoctanyl

4-chloromethylbenzoyl chloride previously obtained (0.1 mol, 8ml) was mixed with dichloromethane (100 ml), in a 250 ml conical flask, cooled on a cold water-bath. To this solution was added dropwise a mixture of 2-butyl-octanol (0.12 mol, 26.6 ml), pyridine (0.12 mol, 9.7 ml) in dichloromethane (25 ml), the total addition time being 30 minutes. The reaction mixture was left to stir for 16 hours at room temperature after which the white precipitate of pyridinium chloride was filtered off and the reaction mixture was washed with distilled water (3x150 ml), dried over MgS04 and the solvent removed under reduced pressure, yielding l-[(4-chloromethyl)benzoyloxy](2-butyl)-octanyl as a colourless oil which was subsequently dried under vacuum.

Preparation of l-M- /V-dimethylethanolammonium-methyn benzovloxvl

2-butyl-oςtaπyl

N,N-dimethylethanolamine (0.12 mol, 13.3 ml) was mixed with a solution of l-[4-chloromethylbenzoyloxy]2-butyl-octanyl (0.12 mol, 40.7 g) in chloroform (150 ml), and the reaction mixture was left to stir for 48 hours at room temperature. After removal of the solvent, the oil recovered was added dropwise to some petroleum spirit (40-60°C) on contact with which a white precipitate forms. The latter was filtered off and carefully stirred with ether (150 ml) for an hour, filtered again and dried under vaccuum, yielding l-[4-(N,N-dimethylethanolammonium- methyl)benzoyloxy]2-butyl-octanyl as a white gum.

Example III: Synthesis of Cjfi branched guerbet choline ester

Preparation of 2-n-hexyldecanoyl chloride

RCOOH + SOC12 —* ^* RCOC1 + HC1 + SO2 where R = C8HπCH(C6Hi3)-

Thionyl chloride (50g, 0.42 mole) was placed in a 250ml round bottomed flask fitted with a magnetic stirrer, dropping funnel and reflux water condenser and equipped with calcium chloride drying tubes to prevent ingress of moisture. With stirring, at 20°C, 2-n-hexyldecanoic acid (50g, 0.195 mole) was added over 30 minutes via the dropping funnel. The resulting reaction mixture was heated to 40°C, by means of an oil bath, and stirred at that temperature for 3 hours, completeness of reaction being confirmed by infra-red spectroscopy. Excess thionyl chloride and residual, by-product gases were removed by means of a rotary vacuum evaporator to yield 53g of liquid product.

Preparation of 2-dimethylaminoethyl (^-n-hexyldecanoate)

R COC1 + 2 (CH3)2 CH2CH2OH — * ^* R COO CH2CH2 N(CH3)2

+ R COO CH2CH2 N(CH3)2 HC1

N,N-dimethylethanolamine (34.4g, 0.386 mole) and 100ml of diethyl ether were placed in a 500ml round bottomed flask fitted with a magnetic stirrer, dropping funnel and reflux condenser and equipped with calcium chloride tubes to prevent ingress of moisture. With stirring, at 20°C, 2-n-hexyldecanoyl chloride (53g, 0.193 mole) was added over 30 minutes via the dropping funnel. The resulting suspension was heated to reflux, by means of an oil bath, and stirred at that temperature for 2 hours. After cooling to 20°C, by-product hydrochloride was removed by filtration and then the ether was removed by means of a rotary vacuum evaporator to yield 63g of liquid product. The product was characterised by infra-red and proton nuclear magnetic resorance spectroscopy; NMR indicated a purity of 100%.

Preparation of N-r2- 2 -n-hexyldecanoyloxy) ethyll N.N.N-trimethyl ammonium bromide

53g (0.162 mole) of 2-dimethylaminoethyl (2 -n-hexyldecanoate) and 100ml of acetone were placed in a 500ml round bottomed flask fitted with a -60°C (carbon dioxide/acetone) reflux condenser, magnetic stirrer and dropping funnel and equipped with calcium chloride drying tubes to prevent ingress of moisture. The flask was cooled to 0°C by means of an ice bath and, with stirring, 38g (0.4 mole) of precooled (0°C) methyl bromide was quickly added via the dropping funnel. The reaction mixture was stirred at 0°C for 3 hours and then, with continued stirring, a further 18g (0.19 mole) of precooled (0°C) methyl bromide was quickly added via the dropping funnel. The condenser and dropping funnel were removed from the flask which was then stoppered and allowed to stand, at 20°C, for 72 hours.

The resulting cloudy solution was clarified by gravity filtration through a Whatman No54 paper and then the acetone and excess methyl bromide removed by means of a rotary vacuum evaporator. This yielded 65g of solid product which was characterised by proton NMR spectroscopy and shown to be 98.6% pure by CatS03 titration.

Example IV: Synthesis of C\ branched guerbet choline carbonate ester

Preparation of Isofol 16lM Chloroformate

R-OH + COC/ ► ROCC/ + HC7 II

O

50g (0.207 mole) of Isofol 16™ Guerbet alcohol blend (Mul.Wt.taken as 242) and lOOmls of toluene were placed in a 500ml round bottomed flask fitted with a Dean & Stark receiver, magnetic stirrer and thermomantle. With stirring, the system was brought to reflux and traces of moisture were removed via the Dean & Stark receiver. The flask was allowed to cool to 20°C, the thermomantle and Dean & Stark receiver were removed and then it was fitted with a dropping funnel and equipped with calcium chloride tubes to prevent ingress of moisture. The flask was cooled to 0°C by means of an ice bath and, with stirring, 150mls of a 20% w/v solution of phosgene in toluene (0.30 mole of phosgene) was added over 30 minutes. The resulting reaction mixture was allowed to warm to 20°C and stirred at that temperature for 2 hours.

The dropping funnel was removed from the flask which was then stoppered and allowed to stand, at 20 °C, for 18 hours. The toluene and residual phosgene and hydrogen chloride were removed by means of a rotary vacuum evaporator to yield 63g of liquid product. The product was characterised by infra-red spectroscopy (chloroformate carbonyl, singlet 1780 cm-1).

Preparation of Isofol 16 Amino Carbonate Ester

ROCQ +2 (CH ₃ ) ₂ N CH ₂ CH ₂ OH ► ROCOCH ₂ CH ₂ N(CH ₃ ) ₂

O o

© 0

⁺ (CH ₃ ) ₂ N CH ₂ CH ₂ OHCl H

12g of N,N-dimethylethanolamine (0.135 mole) and 100ml of diethyl ether were placed in a 250ml round bottomed flask fitted with a magnetic stirrer, dropping funnel and reflux condenser and equipped with

calcium chloride tubes to prevent ingress of moisture. With stirring, at 20°C, 20g of Isofol 16 chloroformate (0.066 mole) was added over 30 minutes via the dropping funnel. The resulting suspension was heated to reflux, by means of an oil bath, and stirred at that temperature for 1 1/2 hours. After cooling to 20°C, by-product hydrochloride was removed by filtration and then the ether was removed by means of a rotary vacuum evaporator to yield 21.5g (93%) of liquid product. The product was characterised by proton nuclear magnetic resonance spectroscopy.

Preparation of Isofol 16 Chlorine Carbonate Ester

® ©

ROCOCH ₂ CH ₂ N(CH ₃ ) ₂ + CH ₃ Br ► ROCOCH ₂ CH ₂ N(CH ₃ ) ₃ Br

0 0

20g of Isofol 16 amino carbonate ester (0.056 mole) and 100ml acetone were placed in a 500ml round bottomed flask fitted with a -60 °C (carbon dioxide/acetone) reflux condenser, magnetic stirrer and dropping funnel and equipped with calcium chloride drying tubes to prevent ingress of moisture. The flask was cooled to 0°C by means of an ice bath and, with stirring, 16g of precooled (0°C) methyl bromide (0.169 mole) was quickly added via the dropping funnel. The reaction mixture was stirred at 0°C for 2 hours and then, with continued stirring, a further 9g of precooled (0°C) methyl bromide (0.095 mole) were quickly added via the dropping funnel. The condenser and dropping funnel were removed from the flask which was then stoppered and allowed to stand, at 20° C, for 72 hours. The acetone and excess methyl bromide were removed from the cloudy reaction solution by means of a rotary vacuum evaporator. This yielded 25g of solid product which was characterised by proton NMR spectroscopy and shown to be 83% pure by Cat SO3 titration.

Examples

According to the present invention granular detergent compositions are prepared by combining the listed ingredients in the amounts indicated below.

Composition 1 2 3

Zeolite A 30 22 6

Na2 sulphate 19 16 7

Carboxylated polymer 3 3 6

LAS 10 9 20

45AS 8 7 7

AE7 1 1 1

Soap - - 2 cationic compound* 4 3 2

Na2 silicate - 1 5

Na2 carbonate 8 16 20 brightener 0.2 0.2 0.2

DTPMP - 0.4 0.4

PVP 0.5 0.5 0.5

Savinase™ 4KNPU/g 1 1 1

LipolaseTM lOOLU/g 0.4 0.4 0.4

NOBS - 6.1 4.5

PBi 1 0.5 6

Balance 100 100 100

Cationic compound* according to Example II

Composition 4 5

Zeolite A 23 23

Na2 citrate 5

Na2S04 - 8

LAS 6.5 8

TAS 2 2

C14/18 betaine ester * 1.5 1.5

45AE7 2 2

45AE3 2

DTPMP 0.4 0.4

CMC 0.4 0.4

Carboxylated polymer 4 2

Na2 silicate 3 3

Na2 carbonate 16 23

Na bicarbonate - 3

TAED 6 2

PBi 6 2

SavinaseT 1 1

4KNPU/g

LipolaseTM 1(X)LU/1 0.4 0.4

TermamylTM 0.6 0.6

60KNU/g

CarezymeTM 0.6 0.6

Silicone antifoam 4 4 granule

Perfume 0.3 0.3

Balance 100 100

*C14/18 betaine ester according to Example I

Composition 6 7 8

Zeolite A 25 30 13

SKS6 - 12

Na2 citrate 10 8

DTPMP 0.4 0.5

CMC 0.4 0.4 0.5

Carboxylated polymer 4 4 5

45AS - 9

LAS 7.5 6.5

TAS 3 2

C16 choline ester* 1.5 1.5 2

AE7 4 4 4

AE3 2 2 2

Na2 silicate 4 4

Na2 carbonate 17 12 14

Na bicarbonate 7 3 5

PVP 0.5 0.5 0.5

SavinaseTM 4 KNPU/g 1 1 1.3

LipolaseTM 100 LU/1 0.4 0.4 0.4

TermamylTMfSOKNU/ 0.6 0.6 0.6 a

& CarezymeT 0.6 0.6 0.6

Silicone antifoam 4 4 4 granule

Na2 sulphate - 14

Perfume 0.3 0.3 0.5

Balance 100 100 100

*Ci6 choline ester according to Example III

Composition 9 10

STPP 24

Zeolite A - 24

Na2 sulphate 12 9

Carboxylated polymer 2 4

LAS 4 6

TAS 2

AE7 2.5 2.5

AE3 2.5 2.5

Cationic compound* 2 2

CMC 1 1

Brightener 0.2 0.2

DTPMP 0.4 0.4

Soap 1 1

Silicone suds 0.2 0.2 suppressor

Na2 silicate 7 3

Na2 carbonate 6 13

PB4 18 18

PBi 4 4

TAED 3 3

Zinc phthalocyanine 0.02 0.02 encapsulate

SavinaseTM 1 1

4KNPU/g

LipolaseTM \QQ _L U/1 0.4 0.4

Perfume 0.3 0.3

Balance 100 100

*cationic compound according to Example IV