CA1187763A - Detergent additives and detergent compositions containing them - Google Patents

Abstract

ABSTRACT

A detergent composition contains as builder a combination of an aluminosilicate cation-exchange material for example, zeolite A, with an organic precipitant builder having the formula I

(I) wherein:
R1 is C10-C24 alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length;
X is CH, CR2, N or CON;
R2 is C1-C3 alkyl;
Y is hydrogen or a solubilising cation:
n.and m, which may be the same or different, are O or integers from 1 to 4, and Z is COOY or SO3Y.

Preferred organic precipitant builders are the alkyl or alkenyl malonates and succinates. the inorganic phosphate content is desirably less than 10% by weight and zero-phosphate compositions are preferred.

Description

7~
- 1 - C.1302 DETERGE~T ADDITIVES A~D DETERGENT COMPOSITIONS
, CONTAINING_THEM

The present invention relates to additives for detergent compositions, and to detergent compositions containing them. These compositions are particularly, but not essentially, adapted for fabric washing. The invention relates more particularly to substantially phosphate-free detergent compositions.
Fabric washing compositions conventionally contain phosphate detergency builders such as sodium tripolyphosphate. In some circumstances it is thought that the use of phosphates in detergent compositions can lead to environmental problems in wast~ waters. There is therefore a desire to reduce the level of phosphorus, or to eliminate it altogether, in detergent compositions.

Water-insoluble aluminosilicate ion exchange materials have been suggested as al~ernative builders to phosphates;
see, for example, GB 1,473,201 and GB 1,473,202 (Henkel).
It has been found in practice, however, that these aluminosilicate materials, even in large amounts, tend to be undesirably slow in their exchange of cations, especially at low temperatures, resulting in inferior detergency. It has accordingly been suggested that supplementary water-soluble builders should be used in combination with these aluminosilicates to raise the Q5El2E

- ~ - C.1302 detergency to an acceptable level. These supplementary builders are generally materials that are efficient sequestrant builders in their own right, for example, alkali metal tripolyphosphates, nitrilotriaceta~es and poly ~-hydroxyacrylates. High levels of these materials are, however, not generally desirable in detergent compositions for cost or environmental reasons.

We have now discovered that, surprisingly, the de~ergency of aluminosilicate-built detergent products can be substantially boosted by partially replacing the aluminosilicate by an organic precipitant builder having a divalent anion. Replacement of 15 to 30% of the aluminosilicate by such an organic precipitant builder has been found to give detergency results comparable to those obtainable using combinations of zeolite and sodium tripolyphosphate as builders.

It is known that the detergency builder properties of aluminosilicates are enhanced by the addition of watsr soluble complexing agen~s such as sodium tripolyphosphate.
This effect has been explained in terms of the so-called "carrier molecule model": see, for example, P Berth, J. Am. Oil ChPmists' Soc., 55 , 52-53 (1978). The complexing agent is able to take up polvalent water hardness ions (notably Ca2+, but also Mg2~) from solid surfaces (such as the surface of a textile fibre) and pass them on to the aluminosilicate ion-exchanger after transport through the aqueous medium. The complexing agent forms a chelate complex with the hardness ion which on arrival at the surface of the aluminosilicate dissociates.

It is not easy to envisage a similar mechanism with precipitant builders, since these remove hardness ions from the wash liquor by the virtually irreversible formation of a precipitate (insoluble calcium or magnesium aalt).

i3 - 3 C.1302 It is ~hus surprising that aluminosilicate/precipitant combinations can give building properties comparable to those of aluminosilicate/complexing agent combinations.

Attempts have been made to use the commonest organic precipitant builder, soap, as a supplementary builder for zeolites, but detergency benefits have been obtained only at impractically high builder concentrations (8 g/l and above). This is a consequence of the low weight effectiveness of soaps when used as builders; since the soap anion i5 monovalent two moles of soap are consumed by each gram ion of Ca or Mg GB 1,545,801 (Procter & Gamble) discloses a spray-dried granular detergent composition comprising from 1 to 40~ by weight of an organic detergent component: from 3 to 25% by weight of a water-insoluble crystalline aluminosilicate ion-exchange material of the formula:

Nal2~A1~2 siO2~ 12-XH2 w~erein x is an integer of from 20 to 30; from 5 to 35~ by weight of a phosphate build~r; and from 5 to 25% of an alkali metal silicate. The organic detergent component may be inter alia a water-soluble salt of a C6 to C20 ~ -sulphocarboxylic acid.

In a first aspect, the present invention provides a detergent composition comprising:
~a) from about 3 to about 90% by weight of one or more detergent-active agents, and (b) from about 10 to about 97% by weight of a detergent additive consisting essentially of (i) from about 25 to about 97% by weight, based on the detergent additive, of a crystalline or amorphous aluminosilicate cation-exchange material, and 7~i3 - 4 - C.1302 (ii) from about 3~ to about 75~ by weight of an organic precipitant builder having the formula I:

,~ ( CH2 ) nCY
Rl~X (I) (CH2)mz wherein:
Rl is C10-C24 alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length, X is CH, CR2, N or CON;
R2 is Cl-C3 alkyl;
Y is hydrogen or a solubilising cation, preferably alXali metal and especially sodium;
n and m, which may be the same or different, are 0 or integers from 1 to 4; and Z is COOY or SO3Y, with the proviso that if the organic precipitant builder is a C~ to C20C~-sulphocarboxylic acid and the aluminosilicate material is crystalline, the composition contains less than 5~, preferably 3% or less, of inorganic phosphate.

The organic precipitank builder is a water soluble material that reacts with Ca2~ ions, and preferably also with Mg2~ ions, in a 1:1 stoichiometric ratio, to form an insoluble salt. The solubility product of the calcium salt of the organic precipitant builder is preferably less than One preferred group of compounds within the general formula I consists of those in which X is CH, n is zero, and m ls 0 or 1. Thus, according to a first preferred embodiment of the invention, the organic precipitant builder is a compound of the formula II:

'7'7~
- 5 - C.1302 ~, ~ COOY
Rl ~ CH ~ (II) (CH2)p--Z

wherein Rl, Y and Z have the meanings given above, and p is 0 or 1.

Especially preferred classes of compounds within the general formula II are the following~
(i) substituted malonates of the formula III

COOY
~ Rl - CH (III) ~ COOY
- and -(ii) substituted succinates of the formula IV:

~ COOY
Rl - CR (IV) C~I2COOY

Compounds of the formulae III and IV are described, for example, in GB 1,293,753, GB 1,342,247 and GB 1,342,340 (Unilever). Examples of such compounds include disodium dodecyl malonate (C12-AKM), disodium hexadecenyl succinate (C16 1-AKS~, and disodium mixed C15-C18 succinate (C15 18-AKS)~
According to a second preferred embodiment of the invention, the organic precipitant builder is a compound of the formula V:
~ (CH2)VcOOY
1 (V) ( C~2 ) wC~

~L~
- 6 - C.130 or sf the formula VI:
~,,, ( CEI2 ) ~COOY
Rl - CO - N (VI) --(CE12)WCY

wherein Rl and Y have the meanings given above and v and w are each 1 to 4, preferably 1 or 2.

Compounds of the formula V in which v and w are both 1, the N-alkyl iminodiacetates, are of especial in~erest.

Compounds of the formula V in which v and w are both

2, the ~ -iminodipropionates, are known amphoteric surfactants, disclosed, for example, in GB
i,296,793 (General Mills). These materials are also known as lather promoters in soap bars, a for example, in EP 0 025 242 (Procter & Gamble), and as anti-corrosive agents, for exampl~, in US 2,926,10a (General Mills~.
Compounds of the formula V in which v and w are both 1, the iminodiacetates, ha~e also been disclosed, for e~ample, as scum disperqants in soap products, in US 3,630,927 (Monsanto), and as anti-corrosive agents, in US 2,368,604 (Shell). US 3,981,779 (Grace) discloses compounds of bo~h formulae V and VI for use as "chelant-surfactant~" for decreasing the fouling of metals by aqueous sys~ems.

GB 761,384 (California Research Corporation) discloses detergent compositions containing 10 to 50~ by weight of alkylbenzene sulphonate and 5 to 20~ by weigh~ of a water-soluble salt of an N-(C8_Cl8 alkyl)-iminodiacetiC acid, the latter component acting as a foam promoter. Similarly, GB 761,383 (California Research Corporation) discloses combinations of alkyl sulphates and ~-~C8-C18 alkyl)-iminodicarboxylic acids. Other specifications relating to the use of compounds of the formula V in detergent compositions are GB 446,737 and GB 446,813 (I G Farben).

~'7~
- 7 - C.1302 Compounds analogous to those of formula V but having a shorter alkyl chain (C8 or less) are known as sequestrant builders, as in GB 1,383,025~(Chemische Werke Huls), and as rancidity preventers in soaps and non-soap de~ergents, as in GB 574,504 (Unilever).

The aluminosilicate cation exchange material is a crystalline or amorphous material having the general formula:
(Cat2/n O)X A123(si2~y 2 wherein Cat is a cation havîng ~alency n that is exchangeable with calcium (e.g. Na or K ): x is a number from 0.7-1.5; y is a number from 1.3-4, and 7 is such that the bound water content is from 10% to 28~ by weight.

Preferably a crystalline material is used which can be described by the unit cell content:

Nax ~(A1~)X-(si2)y] 2 wherein x and y are integers of at least 6, the ratio of x to y being in the range of 1:1 to 1:2; and z is such that the bound water content is from 10~ to 28~ by weight.

The aluminosilicate preferably has a particle size of from 0.1 to 100 microme~res, ideally between 0.1 and 10 micrometres, and an ion exchange capacity of at least 200 mg CaC03 per gram of aluminosilicate (anhydrous basis).

In a preferred embodiment the water-insoluble aluminosilicate is a crystalline material having the formula described by the unit cell content:

~'7'7~
- ~ - C.1302 Nal2(Alo2)l2 (~io~)l2 2 wherein z is from 20 to 30, preferably about 27.

An example of this material is the commercially available product known as Zeolite type A, which is typically:

~a20.A12O3 2siO2 4-5H2 and is also described by the unit cell content:
12 ~A12)12 (Si2) 12J . ~7H20 .

The detergent COmpQsitiOn of the invention contains from about 10% to about 97~ by weight of the specified detergent additive, preferably from about 12% to about 80%, more preferably from about 15% to about 70%, and especially from about 16% to about 67~.
Since the detergent additive contains from about 25 to about 97% by weight of aluminosilicate, the aluminosilicate content of the detergent composition can range from about 2.5% to about 94%. An aluminosilicate content of from about 10% to about 60%, especially from about 12% to about 55~, is especially preferred.

Similarly, the content of organic precipitant builder can range from about 0.3% to about 73~, a range of from about 1% to about 30%, especially from about 3% to about 17%, being especially preferred.

The detergent compositions of the present invention are preferably substantially free of inorganic phosphate.
This is highly desirable for the environmental reasons mentioned earlier. Compositions according to the invention '7'~
- 9 - C.1302 containing no inorganic phosphate have been found to exhibit detergency properties comparable to those of ~odium tripolyphosphate-built products.

If desired, however, the compositions may contain inorganic phosphate, but preferably at a level not exceeding 10~ based on the whole product. Any phosphate present may, for example, be in the form of alkali metal (preferably sodium) tripolyphosphate, orthophosphate, pyrophosphate or polymeric phosphate.

As previously mentioned, however, the phosphate content must be less than 5%, preferably 3% or less, if ~he organic precipitant builder is a particular ~-sulphocarboxylic acid salt.

~-sulphocaxboxylic acid salts of the formula VII:

~ COOY
R1 - CH (VII) wherein Rl and Y have the meanings given previously, are of interest as organic precipitant builders for use in the present invention, although the previously mentioned malonates and succinates of the formulae III and IV are preferred. Compounds of the formula VII are described, for example, in GB 1,368,736 and GB 1,380,390 (Vnilever).
A typical example is disodium 0~-sulphostearate (C18-SFAS). Blends of compounds of different chain lengths, for example, the ~-sulpho salt of coconut fatty acids (coco-SFAS), or of tallow fatty acids ttallow-SFAS~, or of blended coconut and tallow fatty acids, may also advantageously be used.
In a second aspect, the present invention provides a '7'~i3 - 10 - C.1302 detergent additive consisting essentially of:
(i) from about 25 to about 97% by weight of a crystalline or amorphous aluminosilicate cation-exchange material, and (ii) from about 3 to about 75% by weight of an organic precipitant builder having a polyvalent, preferably divalent, anion, with the proviso that when the aluminosilicate material (i) is crystalline, the organic precipitant builder is not a water-soluble salt of C6 to C20c~-sulphocarboxylic acid.
The organic precipitant builder constitutes from about

3% to about 75~ by weight of the builder mix (detergent additive) of the invention, preferably from about 10% to about 60% and especially from about 15% to about 30%O
The detergent additive of the present invention is an efficient builder system yielding good detergency results when incorporated, with detergent-active materials, in a detergent composition.
Returning now to the first aspect of the invention, the detergent compositions of the invention may if desired contain further non-phosphate builders. The compositions may for example contain organic sequestrant builders in addition to the organic precipitants, for example, as disclosed in our co-pending Canadian Patent Application No.
407,293 of even date (Case C.1303) entitled "Detergent additives and detergent compositions containing them". Organic sequestrant builders are water-soluble materials which form soluble complexes with calcium, preferably with pKCa greater than 3.0, preferably greater than 4.0 and more preferably greater than 4.5. Some sequestrant builders also form complexes with magnesium, preferably with pKMg greater than 4.0 Examples of such materials include alkali metal ~ C.1302 (especially sodium) salts of the following acids:
nitrilotriacetic acid, ethylenediamine tet~acetic acid, polyacrylic acid, poly(CX-hydroxyacrylic) acid, carboxymethyloxymalonic acid, carboxmethyloxysuccinic acid, oxydiacetic acid, oxydisuccinic acid, citric acid, dipicolinic acid and many more. The polyacetal carboxylates disclosed in US 4,144,126 and US 4,146,495 (Monsanto) and the oxidised polysaccharides disclosed in GB
1,330,121, GB 1,330,122 and ÇB 1,330,123 (Unilever) may also advantageously be used.

The detergent composition of the invention necessarily includes from about 3% to about 90% by weight, preferably from about 5% to about 40% by weight, more preferably from about 10% to about 25% by weight, of a synthetic anionic/
nonionic, ampho~eric or zwitterionic detergent compound or mixture thereof. Many suitable detergent-active compounds are commercially available and are fully described in the literature, for ~xample in "Surface Active Agents and Detergents", Volumes I and II, by Scnwartz, Perry and Berch.

The preferred detergent compounds which can be used are synthetic anionic and nonionic compounds. The former are usually wate~ soluble alkali metal salts of organic sulphates and sulphonates ha~ing alXyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include the alkyl portion of higher aryl radicals.
Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (C8-C18) alcohols produced for example from tallow or coconut oil; sodium and potassium alkyl (Cg C20) benzene sulphonates, particularly sodium linear secondary alkyl (C10-Cl5) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from ~'7'7~
- 12 - C.1302 tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty acid monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (Cg-Cl8) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide: sodium and potassium salts of fatty acid amides of methyl taurine; alkane monosulphonate such as those derived by reacting alpha~olefins (C8-C20) with sodium bisulphate and those derived by reacting paraffins with SO2 and C12 and then hydrolysing wi~h a base to produce a random sulphonate: and olein sulphonates, which term is used to describe the material made by reacting olefins, particularly C10-C20 alpha-olefins, with SO3 and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (Cll-C15) alkyl ben7ene sulphonates and sodium (Cl~-C18) alkyl sulphates.
Examples o~ suitable nonionic detergent compounds which may be used include in particular the reaction products of alkylene oxid~s, usually ethylene oxide, with alkyl (C6-C22) phenols, generally 5 to 25 EO, ie 5 to 25 units of ethylene oxide per molecule; the condensation products of aliphatic (C8-C18) primary or secondary linear or branched alcohols with ethylene oxide, generally 6 to 30 EO, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic detergent compounds include long chain tertiary amine oxides, long chain tertiary phosphine oxides and dialkyl sulphoxides.

Mixtures of detergent compounds, for example mixed anionic or mixed anionic and nonionic compounds may be used in the detergent compositions, particularly in the latter ~ 7 7~
- 13 - C.1302 case to provide controlled low sudsing properties~ This is beneficial for compositions intended for use in suds-intolerant automatic washing machines. Anionic and nonionic deteryent compounds are advantageously used together in ratios of from 3:1 to 1.5:1~

Amounts of amphoteric or zwitterionic detergent compounds can also be used in the compositions of the invention but this is not normally desired due to their relatively high cost. If any amphoteric or zwitterionic detergent compounds are used it is generally in small amounts in compositions based on the much more commonly used synthetic anionic and/or nonionic detergent compounds.

15If desired, the composition of the invention may also include soap. The presence of small amounts of soap is beneficial with respect to lather control and detergency.
Soaps which may be used are especially the sodium or less desirably the po~assium, salts of C10-C24 fatty acids.
Soaps based mainly on the longer-chain fatty acids within this range, that is to say, with at least half of the soap having a chain length of C16 or more, are especially preferred. This preferred chain length distribu~ion may be conveniently obtained by using soaps from natural sources such as tallow, palm oil or rapeseed oil, which may be hardened if de~ired, with lesser amounts of other, shorter-chain soaps prepared from nut oils such as coconut oil or palm kernel oil.

30According to a preferred embodiment of the invention, the detergent composition also contains a bleach system.

The bleach system preferably comprises a peroxy bleach compound which is an inorganic persalt, which is preferably used in conjunction with an activator therefor. The persalt may be, for example, sodium perborate ~either the ~ ~ ~'77~
~ C.1302 monohydrate or the tetrahydrate~ or sodium percarbonate.
The activator makes ~he bleaching more effective at lower temperatures, ie in the range from ambient temperature to about 60C, so that such bleach systems are commonly known as low-temperature bleach systems and are well known in the art. The inorganic persalt acts to release active oxygen in solution, and the activator is usually an organic compound having one or more reactive acyl residues, which cause the formation of peracids, the latter providing for a more effective bleaching action at lower temperatures than can be obtained by use of the peroxy bleach compound alone.
The ratio by weight of the peroxy bleach compound to the activator is generally from about 20:1 to abou~
preferably about 15:1 to about 2:1.
The detergent composition of ~he invention preferably contains from about 5~ to about 30% by weight of the peroxy bleach compound, and about 0.1 to about 15% by weight of the activator. The total amount of the bleach system ingredients preferably lies within the range of from 5% to 35% by weight, e~pecially from about 6% to about 30% by weight.

Typical examples of suitable peroxy bleach compounds are alkali metal perborates, both tetrahydrates and monohydrates, alkali metal percarbonates, persilicates and perphosphates, of which sodium perborate is preferred.

Activators for peroxy bleach compounds have been amply described in the literature, including British patents 836,988, 855,735, 907,356, 907,358, 970,950, 1,003,310 and 1,246,339, US patents 3,332,882 and 4,12S,434, Canadian patent 844,481 and South African patent 68/6,344. Specific suitable activators include:
(a) N-diacylated and N,N'-polyacylated amines, such as N,~,M',N'-tetraacetyl methylene diamine and i3 - 15 - C.1302 N,N,~ tetraace~yl ethylene diamine, ~,N-diacetylaniline, N,N-diacetyl-p-toluidine;
1,3-diacylated hydantoins such as, for example, 1,3-diacetyl-5,5-dimethyl hydantoin and 1,3-dipropionyl hydantoin; ~-acetoxy-(N,N')-polyacylmalonamide, for example ~'-acetoxy-(N,N')-diacetylmalonamide;
(b) ~-alkyl-N-sulphonyl carbonamides, for example the compounds N-methyl~N-mesyl-acetamide, N-methyl-~-mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and ~-methyl-~-mesyl-p-methoxybenzamide;
(c) N-acylated cyclic hydrazides, acylated triazones or urazoles, for example monoacetylmaleic acid hydrazide;
(d) 0,N,N-trisùbstituted hydroxylamines, such as 0-benzoyl-N,N-succinyl hydroxylamine, 0-acetyl-~ t ~-succinyl hydroxylamine, 0-p-methoxybenzoyl~N,N-succinyl-hydroxylamine, 0-p-nitrobenzoyl-~,~-succinyl-hydroxylamine and 0,~,N-triacetyl hydroxylamine; 0 ~e) N,N'-diacyl-sulphurylamides, for example N,~'-dimethyl-~,N'-diacetyl-sulphurylamide and N,~'-diethyl-N,~'-dipropionyl sulphurylamide;
tf) Triacylcyanurates, for example triacetyl cyanurate and tribenzoyl cyanurate, (g) Carboxylic acid anhydri~es, such as benzoic anhydride, m-chloro-benzoic anhydride, phthalic anhydride,

4-chloro-phthalic anhydride;
(h) Sugar esters, for example glucose pentaacetate;
(i) 1,3-diacyl-4,5-diacyloxy-imidazolidine, for example 1,3-diformyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-dipropionyloxy-imida7.oline;
(j) Te~raacetylglycoluril and tetrapropionylglycoluril;
(k) Diacylated 2,5-diketopiperazine, such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine and 1,4-dipropionyl-3,6-dimetyl-16 - C.1302 2,5-diketopipera~.ine;
(1~ Acylation product~ of propylenediurea or 2,2-dimethyl-propylenediurea (2,4,6,8-tetraaza-bicyclo-(3,3,1)-nonane-3,7-dione or its 9,9-dimethyl derivative), especially the tetraacetyl- or the tetrapropionyl-propylenediurea or their dimethyl derivatives:
(m) Carbonic acid ester~, for example the sodium salts of p-(ethoxycarbonyloxy)-benzoic acid and p-(propoxy carbonyloxy)-benzenesulphonic acid.
(n) ~-acyloxy-(N,~') polyacyl malonamidesO such as ~acetoxy - (N,N') diacetyl malonamide.

The N-diacylated and N,N'-polyacyla~edamines mentioned under (a) are of special interest, particularly tetra-acetyl-ethylenediamine (TAED).

It is preferred to use ~he activator in granular form, preferably wherein the activa~or is finely divided as described in our Canadian Patent.Application.No. 355,510 Specifically, it is preferred to have an activator of an average particle siza of less than 150 micrometres, which gives significant improvement in bleach efficiency. The ~edimentation losses, when using an activator with an average particle size of less than 150 /um, are substantially decreased. Even better bl.each performance is obtained if the averaye particle size of the activator is less than 100 /um. However, too small a particle ~ize give~ increa-~ed decomposition, dust-formation and handling problems, and although particle sizes below 100 /um can provide for an improved bleaching efficiency, it is d~sirable that the activator should not have more than 20%
by weight of particles with a size of less than 50 /um.
On the other hand, the activator may have a certain amount of particles of a size greater than 150 /um, but it should not contain more than 5% by weight of particles ~ 300 /um, and not more than 20% by weight o~ particles ~.

7~3 - 17 - C.1302 200 /um, preferably > 150 /um. It is to be understood that these particle si~es refer to the activator present in the granulss, and not to the granules themselves. The latter have a particle siæe, the major part of it ranging from 100 to 2000 /um, preferably 250 to 1000 /umO Up to 5% by weight of granules with a particle size of ~ 1700 /um and up to 10~ by weight of granules ~250 /um is tolerable. The granules incorporating the activator, preferably in this finely-divided form, may be obtained by granulatin~ a suitable carrier material, such as sodium tripolyphosphate and/or potassium tripolyphosphate with activator particles of the required size. Other granulation methods, e.g. using organic and/or inorganic granula~ion aids, can also be usefully applied. The granules can be subsequently dried, if required.
Basically, any granulation process is applicable, as long as the granule contains the activator, and as long as the other materials present in thP granule do not negatively affect the activator.

It is particularly preferred to include in the det~rgent compositions a stabiliser for the bleach system, for example ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate. These stabilisers can be used in acid or salts form, especially in calcium, magnesium, ~inc or aluminium salt form, as described in our UK Patent Application ~o 2 048 9~0.
Apart from the components already mentioned, the detergent compositions of the invention can contain any of the conventional additives in the amounts in which such materials are normally employed in fabric washing detergent compositions. Examples of these additives include lather boosters such as alkanolamides, particularly the 7'~
- 18 - C.1302 monoethanolamides derived from palm kernel fatty acids and coconut fatty acids: lather depressants such as alkyl phosphates, silicones, or alkyl phosphonic acids incorporated in petroleum jelly, wax or mineral oil;
anti-redeposition agents such as sodium carboxymethyl-cellulose and cellulose ethers; fabric sof~ening agents;
inorganic salts such as sodium sulphate and sodium carbonate: and, usually present in very minor amounts, fluorescen~ agents, perfumes, enzymes such as proteases and amylases.

It may be desirable to include in the composition an amount of an alkali metal silicate, particularly sodium ortho-, meta- or preferably neutral or alkaline silicate.
The presence of such alkali metal silicates at levels of at least about 1%, and preferably from about 5% to about 15~
by weight of the composition, is advantageous in decreasing ~he corrosion of metal parts in washing machines, besides givin~ processing benefits and generally improved powder properties. ! Th~ more highly alkaline ortho- and meta-silica~es would normally only be used at lower amounts within this range, in admixture with the neutral or alkaline silicates.

The compo~ition of the invention is preferably alkaline, but not too strongly alkaline as this could result in fabric damage and also be hazardous for domestic usage. In practice the composition should desirably give a pH of from about 8.5 to about 11 in use in aqueous wash ~olution. It is preferred in particular for domestic products to have a pH of from about 9.0 to about 10.5 as lower pH's tend to be less effective for optimum detergency building, and more highly alkaline products can be hazardous if misused. The pH is measured at the lowest normal usage concentration of 0.1~ w/v of the product in water of 12H (Ca), (French permanent hardness, calcium ~3'~
- 19 - C.1302 only) at 50C so that a satisfactory degree of alkalinity can be assured in use at all normal product concentrationsO
If necessary, up to 10~ by weight of alkali metal carbonate, preferably sodium carbonate, may be included in order to raise the p~ and to maintain adequate buffer capacity in the presence of acidic soils.

If carbonate or phosphates are present it may be desirable to include in the composition of the invention one or more antideposition agents, to decrease any tendency to form inorganic deposits on washed fabrics. The amount of any such antideposition agent is normally from about OD 1% to about 5% by weight, preferably from about 0.2% to about 1.5% by weight of the composition. The preferred antideposition agents are anionic polyelectrolytes, especially polymeric aliphatic car~oxylates, or organic phosphonates.

The detergent compositions of the invention should desirably be in free-flowing particulate, for example, powdered or granular form, and can be produced by any of the techniques commonly employed in the manufacture of such washing compositions~ fox example, by slurry-making and spray-drying processes. It is preferred that the process used to form the compositions should result in a product having a moisture content of not more than about 12%, more preferably from abou~ 4% to about 10~ by weight.

The detergent compositions of the invention may also be in the form of bars or ~ablets, or in liquid form.

The invention will now be illustrated by the following non-limiting Examples.

tt~

- 20 - C.1302 EXAMPLES

In the Examples that follow, the detergencies of wash liquors incorporating various builder systems were compared by measuring the reflectance of a clay-soiled polyester/
cotton test cloth before and after washing in the Tergotometer. The reflectances were measured using a Carl Zeis~ Elrepho Reflectrometer and the reflectance increase on washing (~R) was taken as a measure of detergency.
EXAMPLES 1 to 3 In each case a wash liquor was prepared using the ingredients stated below in thP concentrations stated below, in 40FH (Ca) or 20F~ (Ca~ water. The wash liquor was allowed to equilibrate for 15 minutes. Test cloth pieces (four pieces per litre, each measuring 76.2 mm x 76.2 mm~ were then added and a 20-minute wash at 80C, pH 10.0 and 55 r.p.m. agitation was carried out, followed by a rinse in water of the same hardness as ~hat of the ~ater used to prepare the wash liquor.

The ingredients and concentrations were as follows:

g/litre Sodium C10-Cl3 linear alkylbenzene0.195 sulphonate 14-C15 alcohol ethoxylate (11 E0)o.og Hardened tallow soap 0.06 Alkaline silicate 0.15 ~7~
- 21 - C.1302 Sodium sulphate 2.00 Detergent additive according to the 0.50-5.00 invention (as specified in Examples) It will be seen that the detergen~ additive according to ~he invention was used at concentrations of from 0.50 to

5.00 g/litre, and the other components of the compositions were used at a constant total concentration of 2.495 g/litre, so that the total concentration ranged from 2.995 to 7.495 g/litre. Thus the percentage o~ the total co~position constituted by the detergent additive of the invention at each concentration of the latter was as follows:

___________________ ____________________ __________ Concentration I -(of detergent¦ (total~ ¦ % detergent additive additiv~ in composition -------_~---_________________________ 050 1 ~-995 1 16.70 1.50 1 3.995 1 37.55 2.00 1 4.495 1 4~.49 2.50 1 40995 1 50.05 3.00 1 5~495 1 54.60 4-00 1 6.495 1 61.59 5.00 1 7.49~ 1 66.71 ________________~____________~______________________ The detergencies of compositions containing two zeolite/precipitant systems according ~o the inven~ion were compared, at various concentrations, with those o~
compositions containing zeolite alone and compositions t-~
- 22 - C.1302 containing zeolite/sodium tripolyphosphate (STP), in 20FH
(Ca2 ) water. The organic precipitants used were disodium dodecyl malonate (C12AKM) and disodium (C15-C18) alkyl succinate ~C15-C18 ~KS), the zeolite was Zeolite A. The results were as follows:

________________________~_~____________ ____________________ Concentration of I Composition of ¦Reflec~ance detergent additive Idetergent additive I ( ~ R) _______________________ 0.50 Izeolite (100~) ¦ 10.7 ¦zeolite (80%)+C12AKM (20%) 1 12-4 ¦zeolite (80%~C15_18AKS(20~)1 11.4 ¦zeolite (80%)+STP(20%) ¦ 13.0 ___________________~___ 1.50 Izeolite (100%) ¦ 17.1 ¦zeolite (80%)+~12AKM (20%) ¦ 21.5 ¦zeolite (80%)~C15_18AKS(20~)1 18.4 ¦zeolite (80%)+STP(20%) 1 22.7 ----___-_________~_____________ 2.00 Izeolite (100~) 1 20.8 Izeolite (80%)+C12AKM (20%) ¦ 25.6 ¦zeolite (80%)+C15_18AXS(20~)1 24.5 Izeolite (80~)+STP(20%) 1 26.7 ------___~___________________ 3.00 Izeolite ~100~) ¦ 25.6 ¦zeolite (80%)-~C12AKM (20%) ¦ 26.6 ¦zeolite (80~)~C15 18AKS(20%)l 26.0 Izeolite ~80%)+STP(20%) 1 27.5 _-________________________~_~__ The detergencies of compositions containing zeolite/
disodium hexadecenyl succinate (C16 1AKS) were compared, at various concentrations, with those of compositions '7~
- 23 - C.1302 containing zeolite alone and ~eoli~e/STP in 40FH(Ca water. The results were as follows:

Concentration of I Composition of ¦ Reflectance detergent additivel detergent additive I ( ~ R) _______.~_____________________________________~______________ 3000 I zeolite ~100%) ¦ 16.0 I zeolite (80%~+C16 1AKS( 20~ ) 18 . 8 I zeolite (80%~+STP(20%) 1 21.8 ____________________~______ ____ ________~___________________ 4-00 I zeolite (100%) 1 20~2 I zeolite (80~)~C16 1AKS(20%) 25.0 I æeolite (80%)+STP(20~) ¦ 25.2 --__-_-__________________________ 5.00 I zeolite (100%~ 1 23.2 ¦ zeolite (80%)+C16 1AKS(20~) 25.4 I zeolite (80~)+STP(20%) 1 25.7 _____ _______________________________________________________ The detergencies of compositions containing another detergent additive according to the inv~ntion were com~ared, at various concentrations, with those of compositions containing zeolite alone and ~eolite/STP, in 40FEl(Ca2 ~ water. The organic precipitant used was disodium ~-sulphostearats (C18-SFAS). The resul~s were as follows:

~'7'~i3 - 24 - C.1302 _ _ ~ _ _ _ _ _ . _ _ _ . ._ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _. _ _ _. _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ .
Concen~ration of I Composition of ¦Reflectance de~ergent additive ¦ detergent additive I ( ~ R) __________________________________________ _______________ 52.50 ¦zeolite (100%) 1 13.4 ~eolite (80~1+Cl8SFAS(20%)1 14.7 ¦zeolite (80%)~STPt~0%) ___________ ______________________________________________ 3.00 Izeolite (100%~ ¦ 15.2 ¦zeolite (80%)^~Cl8SFAS(20%)1 17.5 ¦zeolite (80%)+STP(20%) ¦ 18.3 ______________________ ________________~__________________ 4.00 Izeolite (100%) ¦ 18.6 ¦zeolite (80%)~Cl8SFAS(20~1 21.0 Izeolite (80~)~STP(20%) 1 22.1 _______________~________________________________~_________ 5.00 jzeolite (lO0~) ¦ 21.4 Izeolite (80%)~Cl8SFAS(20~)1 22.6 ¦zeolite (80%)+STP(20%) 1 22.8 -_______________________ _ The detergencies of compositions containing zeolite/
disodium dodecyliminodiacetate (C12 IMA) and ~eolite/disodium tetradecyliminodiacetate (Cl4 IMA) were compared with those of compositions containing zeolite alone and zeolite/STP, at total builder concentrations of 4.0 g/litre in 40FH (Ca ) water. The results were as follows:

'7~ 3 - 25 - C.1302 Composition o~ detergent addltiveRe~lectance ( ~ R) zeolite (100%) 14.0 zeolite (80%) ~ C12 IMA (20~) 15.7 zeolite (80%) ~ C14 IMA (20%~ 1404 zeolite (80~) ~ STP (20%) 17.7 _________________________________________________________ A detergent product was prepared from the following ingredients, the percen~ages being based on the total solids:
%
15 Sodium C10-Cl3 linear alkylbenzene sulphonate 6 Cl~-C15 alcohol ethoxylate (11 EO) 3 Hardened tallow ~oap 5 Sodium silicate Sodium sulphate 3.5 20 Sodium chloride 9.5 Builder (anhydrous basis) 40 The builder systems used were all-zeolite, zeolite/
C15 18AKS, and zeolite/hardened tallow soap.
Detergencies were compared at produc~ dosages o 3.0, 5.0 and 8.0 g/litre, in 35H (Ca2 ) water at 60C and pH
10.0, at a wash duration of 20 minutes in the Tergotometer.
The resul~s were as follows:

7~7~
- 2~ - C.1302 _____________________ _ __ ______________ ______________ Percentage builder Reflectance (~R) for in product product dosages (g/litre) 1 3,0 1 5~0 1 8.0 - __ -___________ ________ 40~ Yeolite ¦ 13.0 ¦ 17.5 ¦ 22.2 35% zeolite ~ 5% C15_18 AKS I - ¦ 19.5 1 23.6 35~ zeolite ~ 5~ hOtallow soap ¦ - ¦ 18.0 ¦ 22.3 30~ zeolite + 10% C15_18 AKS ¦ 13~8 ¦ 19.7 ¦ 24~0 30~ zeolite ~ 10% h.tallow soap 1 12O5 ¦ 18.1 ¦ 22.7 25% zeolite ~ 15% ClS_18 AKS ¦ 14.1 ¦ 20.2 ¦ 24.1 - 15 25% zeolite + 15% h.tallow soap 1 12.1 1 18.4 ¦ 23.5 _________________________________________________________ ***

Claims (26)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE PROPERTY
OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A detergent composition comprising:
(a) from 3 to 90% by weight of one or more detergent-active agents, and (b) from 10 to 97% by weight of a detergent additive consisting essentially of (i) from 25 to 97% by weight, based on the detergent additive, of a crystalline or amorphous aluminosilicate cation-exchange material, and (ii) from 3% to 75% by weight of an organic precipitant builder having the formula I

(I) wherein:
R1 is C10-C24 alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length;
X is CH, CR2, N or CON;
R2 is C1-C3 alkyl;
Y is hydrogen or a solubilising cation:
n and m, which may be the same or different, are O or integers from 1 to 4; and z is COOY or SO3Y;
with the proviso that if the organic precipitant builder is a C6 to C20 .alpha.-sulphocarboxylic acid and the aluminosilicate material is crystalline, the composition contains less than 5% of inorganic phosphate.

2. A detergent composition as claimed in Claim 1, wherein the organic precipitant builder is a compound of the formula II

(II) wherein R1, Y and Z have the meanings given in Claim 1, and p is 0 or 1.

3. A detergent composition as claimed in Claim 2, wherein the organic precipitant builder is a compound of the formula III

(III) wherein R1 and Y have the meanings given in Claim 1.

4. A detergent composition as claimed in Claim 2, wherein the organic precipitant builder is a compound of the formula IV

(IV) wherein R1 and Y have the meanings given in Claim 1.

5. A detergent composition as claimed in Claim 1, wherein the organic precipitant builder is a compound of the formula V

(V) wherein R1 and Y have the meanings given in Claim 1 and v and w are each integers within the range of from 1 to 4.

6. A detergent composition as claimed in Claim l, wherein the organic precipitant builder is a compound of the formula VI

(VI) wherein Rland Y have the meanings given in Claim l and v and w have the meanings given in Claim 5.

7. A detergent composition as claimed in Claim 5 or Claim 6, wherein the organic precipitant builder is a compound of the formula V or of the formula VI, wherein v and w are each l or 2.

8. A detergent composition as claimed in Claim 5 or Claim 6, wherein the organic precipitant builder is a compound of the formula V or of the formula VI, wherein v and w are each 1.

9. A detergent composition as claimed in any one of Claims l to 3, wherein the organic precipitant builder has a calcium salt solubility product of less than 10-8.

10. A detergent composition as claimed in Claim l, wherein the aluminosilicate cation exchange material as a crystalline or amorphous material having the general formula VII

(Cat2/n°) x'A12°3 (si°2)y ZH2° (VII) wherein Cat is a cation having valency n that is exchangeable with calcium (e.g. Na+ or K +); x is a number from 0.7-1.5; y is a number from 1.3-4; and z is such that the bound water content is from 10% to 28% by weight.

11. A detergent composition as claimed in Claim 10, wherein the aluminosilicate cation exchange material is a crystalline material having a unit cell of the formula VIII

Nax (A102)x. (Sio2)y zH20 (VIII) wherein x and y are integers of at least 6, the ration of to y being in the range of l:l to 1:2; and z is such that the bound water content is from 10% to 28% by weight.

12. A detergent composition as claimed in Claim lO, wherein the aluminosilicate cation exchange material is a crystalline material having a unit cell of the formula IX

Na12(A102)12.(sio2)12.zH20 (IX) wherein z is from 20 to 30.

13. A detergent composition as claimed in Claim 12, wherein the aluminosilicate material has a unit cell of the formula IX wherein z is 27.

14. A detergent composition as claimed in any one of Claims l to 3, wherein the aluminosilicate cation-exchange material has a particle size within the range of from 0.1 to 100 /um.

15. A detergent composition as claimed in any one of Claims l to 3, wherein the aluminosilicate cation-exchange material has a particle size within the range of from 0.1 to 10 /um.

16. A detergent composition as claimed in any one of Claims 1 to 3, wherein the aluminosilicate cation-exchange material has an ion exchange capacity of at least 200 mg CaCO3 per gram of anhydrous aluminosilicate.

17. A detergent composition as claimed in any one of Claims 1 to 3, which contains not more than 10% by weight of inorganic phosphate.

18. A detergent composition as claimed in any one of Claims 1 to 3, which contains less than 5% by weight of inorganic phosphate.

19. A detergent composition as claimed in any one of Claims 1 to 3, which contains less than 3% by weight of inorganic phosphate.

20. A detergent composition as claimed in any one of Claims 1 to 3, which contains from 15 to 70% by weight of the detergent additive.

21. A detergent composition as claimed in any one of Claims 1 to 3, which contains from 2.5 to 94% by weight of aluminosilicate cation-exchange material.

22. A detergent composition as claimed in any one of Claims 1 to 3, which contains from 10 to 60% by weight of alumino-silicate cation-exchange material.

23. A detergent composition as claimed in any one of Claims 1 to 3, which contains from 12 to 55% by weight of alumino-silicate cation-exchange material.

22. A detergent composition as claimed in any one of Claims 1 to 3, which contains from 0.3 to 73% by weight of the organic precipitant builder.

25. A detergent composition as claimed in any one of Claims 1 to 3, which contains from 1 to 30% of the organic precipitant builder.

26. A detergent composition as claim in any one of claims l to 3 which contains from 3 to 17% of the organic precipitant builder.