NZ201211A - Detergent additives and compositions - Google Patents

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 <CHEM> 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 zerophosphate compositions are preferred.

Description

New Zealand Paient Spedficaiion for Paient Number £01 211 ?, 01 ? 1 r-'l ' Priority Date(s): . 15. 7.7.

Complete Specification Filed: Clsss: .C\\T?.?].k<P. fre-AUG'MSS' Publication Date: P.O. Journal, No: ,. 73 NEW ZEALAND ' PATENTS ACT, 1953 •9 JUL 1982 No.: mm', Date: COMPLETE SPECIFICATION DETERGENT ADDITIVES AND DETERGENT COMPOSITIONS CONTAINING THEM J(/We, UNILEVER PLC a British company of Unilever House, Blackfriars, London EC4, England, hereby declare the invention for which K/ we pray that a patent may be granted to rit&/us, and the method by which it is to be performed, to be particularly described in and by the following statement: - - 1 - (followed by page la) / I -u- \ 20121 1 eri^ea- DETERGENT ADDITIVES AND DETERGENT COMPOSITIONS 'CONTAINING THEM The present invention relates to additives for 5 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 15 environmental problems in waste 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 20 have been suggested as alternative 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, 25 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 Q5E12E 2 01 2J^1 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, nitrilotriacetates and poly-0(-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 detergency 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 water-soluble complexing agents 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 Chemists' Soc. , 5_5 , 52-53 (1978). The complexing agent is able to take up polvalent water 2+ 2+ hardness ions (notably Ca , but also Mg ) 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 salt). 20121 1 &r±3trr~ It is thus 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 10 effectiveness of soaps when used as builders; since the soap anion is monovalent two moles of soap are consumed by each gram ion of Ca^+ or Mg^+.

GB 1,545,801 (Procter & Gamble) discloses a 15 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[A102-Si02jl2'xH2° wherein x is an integer of from 20 to 30; from 5 to 35% by weight of a phosphate builder; and from 5 to 25% of an alkali metal silicate. The organic detergent component may 25 be inter alia a water-soluble salt of a Cg to Cjq o<-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 35 detergent additive, of a crystalline or amorphous aluminosilicate cation-exchange material, and 2012lfN°' C.1302 (ii) from about 3% to about 75% by weight of an organic precipitant builder having the formula I: (CH_) COOY 2 n Rj-X (I) ^(CH,) Z z m wherein: R^ is cio~C24 alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length; 10 X is CH, CR2, N or CON; R2 is C^-C3 alkyl; Y is hydrogen or a solubilising cation, preferably alkali metal and especially sodium; n and which may be the same or different, are 0 or 15 integers from 1 to 4; and Z is COOY or S03Y, with the proviso that if the organic precipitant builder is an 0C-sulphocarboxylic acid salt and the 20 aluminosilicate material is crystalline, the composition contains less than 5%, preferably 3% or less, of inorganic phosphate.

The organic precipitant builder is a water-soluble 2+ material that reacts with Ca ions, and preferably also 2+ with Mg ions, in a 1:1 stoichiometric ratio, to form an insoluble salt. The solubility product of the calcium salt of 10' of the organic precipitant builder is preferably less than ,-8 One preferred group of compounds within the general formula I consists of those in which X is CH, n is zero, and m is 0 or 1. Thus, according to a first preferred embodiment of the invention, the organic precipitant 35 builder is a compound of the formula II: - 5 - ^ C. 1302 cooy rx - ch_ (ii) (CH.) -Z 2 p wherein R^, 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 rx - ch_ (iii) ^-COOY - and - (ii) substituted succinates of the formula IVs cooy Rx " CH_ (IV) ch2cooy 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 (C^2-AKM), disodium hexadecenyl succinate (C.,. ,-AKS), and disodium mixed C, c-C, Q 16:1 15 18 succinate (C^_^g-AKS).

According to a second preferred embodiment of the invention, the organic precipitant builder is a compound of the formula V: ^(ch_) cooy 2 v Rx - N (V) (ch2)wcooy 1 6 or of the formula VI (ch2)vcooy R 1 CO - N (VI) (ch2)wcooy wherein R^^ 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 10 1, the N-alkyl iminodiacetates, are of especial interest.

Compounds of the formula V in which v and w are both 2, the jG -iminodipropionates, are known amphoteric surfactants, disclosed, for example, in GB 15 1,296,793 (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 example, in US 2,926,108 (General Mills). Compounds of the formula V in which v and w are both 1, the 20 iminodiacetates, have also been disclosed, for example, as scum dispersants 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 both formulae V and VI for use as "chelant-surfactants" for 25 decreasing the fouling of metals by aqueous systems.

GB 761,384 (California Research Corporation) discloses detergent compositions containing 10 to 50% by weight of alkylbenzene sulphonate and 5 to 20% by weight of a water-30 soluble salt of an N-(Cg_c^g alkyl)-iminodiacetic acid, the latter component acting as a foam promoter. Similarly, GB 761,383 (California Research Corporation) discloses combinations of alkyl sulphates and N-(Cg-C^g alkyl)-iminodicarboxylic acids. Other specifications relating to 35 the use of compounds of the formula V in detergent compositions are GB 446,737 and GB 446,813 (I G Farben). ^ ■;; ' - 7 - e^-tae-2- Compounds analogous to those of formula V but having a shorter alkyl chain (Cg or less) are known as sequestrant builders, as in GB 1,383,025 (Chemische Werke Hiils), and as rancidity preventers in soaps and non-soap detergents, as in GB 574,504 (Unilever).

The aluminosilicate cation exchange material is a crystalline or amorphous material having the general formula: (Cat2/n °)x-A1203^Si02^y*zH20 wherein Cat is a cation having valency n that is *|* exchangeable with calcium (e.g. Na or K ); x is a 15 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.

Preferably a crystalline material is used which can be 20 described by the unit cell content: Na x r<A102)x.(Si02)l zHjO wherein x and y are integers of at least 6, the ratio of x 25 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 micrometres, ideally between 0.1 and 10 30 micrometres, and an ion exchange capacity of at least 200 mg CaCO^ 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: 2 012 11 8 C.1302 "a12(Al°2)12 * ^^°2^12* zH2° 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: Na20.A1203.2Si02."4.5H20 and is also described by the unit cell content: Na 12 [(A102>12.<Si02)JJ 27H20.

The detergent composition 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 25 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 30 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. 35 This is highly desirable for the environmental reasons mentioned earlier. Compositions according to the invention 2 0 f 2 1 1 C. 1302 containing no inorganic phosphate have been found to exhibit detergency properties comparable to those of sodium 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, 10 pyrophosphate or polymeric phosphate.

As previously mentioned, however, the phosphate content must be less than 5%, preferably 3% or less, if the organic precipitant builder is a particular 15 0(-sulphocarboxylic acid salt. <X-sulphocarboxylic acid salts of the formula VII: COOY ^ - CH (VII) SO3Y wherein and Y have the meanings given previously, are of interest as organic precipitant builders for use in 25 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 (Unilever). A typical example is disodium OC-sulphostearate 30 (C^g-SFAS). Blends of compounds of different chain lengths, for example, the OC-sulpho salt of coconut fatty acids (coco-SFAS), or of tallow fatty acids (tallow-SFAS), or of blended coconut and tallow fatty acids, may also advantageously be used.

In a second aspect, the present invention provides a 201211 aoU - 10 - C—±3&2- 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 a Cg to C2q O^-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%.

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 25 addition to the organic precipitants, for example, as disclosed in our New Zealand Patent Specification No. 201212 entitled "Detergent additives and detergent compositions containing them". Organic sequestrant builders are water-soluble materials which form soluble complexes with calcium, preferably with PK£a 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 greater than 4.0.

Examples of such materials include alkali metal 201 (especially sodium) salts of the following acids: nitrilotriacetic acid, ethylenediamine tetracetic acid, polyacrylic acid, poly((X-hydroxyacrylic) acid, carboxymethyloxymalonic acid, carboxmethyloxysuccinic acid, 5 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 GB 1,330,123 (Unilever) may 10 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 15 about 10% to about 25% by weight, of a synthetic anionic, nonionic, amphoteric or zwitterionic detergent compound or mixture thereof. Many suitable detergent-active compounds are commercially available and are fully described in the literature, for example in "Surface Active Agents and 20 Detergents", Volumes I and II, by Schwartz, Perry and Berch.

The preferred detergent compounds which can be used are synthetic anionic and nonionic compounds. The former 25 are usually water soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term allcyl being used to include the alkyl portion of higher aryl radicals. Examples of suitable synthetic anionic detergent compounds 30 are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (cg"~ci8^ alcohols produced for example from tallow or coconut oil; sodium and potassium alkyl (C9-C2o^ benzene sulphonates, particularly sodium linear secondary alkyl (cio~C15^ 35 benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from € ^ f f; L; ( L - 12 - JS^-±StrZ~ 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 (C9-Cig) fatty 5 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 10 monosulphonates such as those derived by reacting alpha-olefins (Cg-^Q) with sodium bisulphate and those derived by reacting paraffins with SC>2 and Cl2 and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the 15 material made by reacting olefins, particularly c^o~^20 alpha-olefins, with SO^ and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium alkyl benzene sulphonates and sodium (ci6~cig) alkyl sulphates.

Examples of suitable nonionic detergent compounds which may be used include in particular the reaction products of alkylene oxides, usually ethylene oxide, with alkyl (C6~C22^ phenols, generally 5 to 25 EO, ie 5 to 25 25 units of ethylene oxide per molecule; the condensation products of aliphatic (cg~cig) 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 30 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 35 anionic or mixed anionic and nonionic compounds may be used in the detergent compositions, particularly in the latter ■u % f ' i. - 13 - CTT502" case to provide controlled low sudsing properties. This is beneficial for compositions intended for use in suds-intolerant automatic washing machines. Anionic and nonionic detergent compounds are advantageously used 5 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 10 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.

If 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 potassium, salts of c-lq~C24 fatty acids. 20 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 or more, are especially preferred. This preferred chain length distribution may be conveniently obtained by using soaps from natural sources 25 such as tallow, palm oil or rapeseed oil, which may be hardened if desired, with lesser amounts of other, shorter-chain soaps prepared from nut oils such as coconut oil or palm kernel oil.

According 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 35 used in conjunction with an activator therefor. The persalt may be, for example, sodium perborate (either the 201211 -e, 1302 monohydrate or the tetrahydrate) or sodium percarbonate. The activator makes the bleaching more effective at lower temperatures, ie in the range from ambient temperature to about 60°C, so that such bleach systems are commonly known 5 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 10 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 about 1:1, preferably about 15:1 to about 2:1.

The detergent composition of the 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 20 ingredients preferably lies within the range of from 5% to 35% by weight, especially from about 6% to about 30% by weight.

Typical examples of suitable peroxy bleach compounds 25 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 30 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 4,128,494, and Canadian patent 844,481. Specific suitable activators include: (a) N-diacylated and N,N1-polyacylated amines, such as N,N,N',N"-tetraacetyl methylene diamine and - 15 - er-3rsxnr N,N,N',N'-tetraacetyl ethylene diamine, N,N-diacetylaniline, N,N-diacetyl-p-toluidine; 1,3-diacylated hydantoins such as, for example, 1,3-diacetyl-5,5-dimethyl hydantoin and 5 1,3-dipropionyl hydantoin; OC-acetoxy-(N,N')- polyacylmalonamide, for example OC-acetoxy-(N,N')-diacetylmalonamide; (b) N-alkyl-N-sulphonyl carbonamides, for example the compounds N-methyl-N-mesyl-acetamide, N-methyl-N- mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide; (c) N-acylated cyclic hydrazides, acylated triazones or urazoles, for example monoacetylmaleic acid hydrazide; (d) 0,N,N-trisubstituted hydroxylamines, such as 15 0-benzoyl-N,N-succinyl hydroxylamine, O-acety1-N,N-succinyl hydroxylamine, O-p-methoxybenzoyl-N,N-succinyl-hydroxylamine, O-p-nitrobenzoyl-N,N-succinyl-hydroxylamine and 0,N,N-triacetyl hydroxylamine; 20 (e) N,N'-diacyl-sulphurylamides, for example N,N'- . dimethyl-N,N"-diacetyl-sulphurylamide and N,N'-diethyl-N,N'-dipropionyl sulphurylamide; (f) Triacylcyanurates, for example triacetyl cyanurate and tribenzoyl cyanurate; (g) Carboxylic acid anhydrides, 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 30 1,3-diformyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-diacetoxy-imidazolidine, 1,3-diacetyl-4,5-dipropionyloxy-imidazoline; (j) Tetraacetylglycoluril and tetrapropionylglycoluril; (k) Diacylated 2,5-diketopiperazine, such as 1,4-diacetyl-35 2,5-diketopiperazine, 1,4-dipropionyl-2,5- diketopiperazine and 1,4-dipropionyl-3,6-dimetyl- t - 16 - e^±3&2- sfl C' ;N L . ■r //. V 7 "ST<2 2,5-dilcetopiperazine; (1) Acylation products 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), 5 especially the tetraacetyl- or the tetrapropionyl- propylenediurea or their dimethyl derivatives; (m) Carbonic acid esters, for example the sodium salts of p-(ethoxycarbonyloxy)-benzoic acid and p-(propoxy-carbonyloxy)-benzenesulphonic acid. 10 (n) °C-acyloxy-(N,N') polyacyl malonamides, such as °C-acetoxy - (N,N' ) diacetyl malonamide.

The Nrdiacylated and N,N'-polyacylatedamines mentioned under (a) are of special interest, particularly N,N,N',N'-15 tetra-acetyl-ethylenediamine (TAED).

It is preferred to use the activator in granular form, preferably wherein the activator is finely divided as BrHi'Sh £bi4o-nt "3pec>\ -KOCvK'ca^, No. a OS3 , described in our UK 'Patent Application No.—80 21979.

Specifically, it is preferred to have an activator of an average particle size of less than 150 micrometres, which gives significant improvement in bleach efficiency. The sedimentation losses, when using an activator with an average particle size of less than 150 ^um, are substantially decreased. Even better bleach performance is obtained if the average particle size of the activator is less than 100 ^um. However, too small a particle size gives increased decomposition, dust-formation and handling problems, and although particle sizes below 100 ^um can provide for an improved bleaching efficiency, it is desirable that the activator should not have more than 20% by weight of particles with a size of less than 50 ^urn.

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 yum, and not more than 20% by weight of particles - 17 - -&rl302 ^>200 ^um, preferably 150 ^urn. It is to be understood that these particle sizes refer to the activator present in the granules, and not to the granules themselves. The latter have a particle size, the major 5 part of it ranging from 100 to 2000 ^um, preferably 250 to 1000 ^um. 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 10 finely-divided form, may be obtained by granulating 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 15 granulation 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 the granule do not negatively 20 affect the activator.

It is particularly preferred to include in the detergent compositions a stabiliser for the bleach system, for example ethylene diamine tetramethylene 25 phosphonate and diethylene triamine pentamethylene phosphonate. These stabilisers can be used in acid or salts form, especially in calcium, magnesium, zinc or aluminium salt form, as described in our UK Patent Application No 2 048 930.

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 35 compositions. Examples of these additives include lather boosters such as alkanolamides, particularly the V / C7X3UT 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; 5 anti-redeposition agents such as sodium carboxymethyl- cellulose and cellulose ethers; fabric softening agents; inorganic salts such as sodium sulphate and sodium carbonate; and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases 10 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. 15 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 the corrosion of metal parts in washing machines, besides giving processing benefits and generally improved powder 20 properties. The more highly alkaline ortho- and meta-silicates would normally only be used at lower amounts within this range, in admixture with the neutral or alkaline silicates.

The composition 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 30 solution. 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 35 normal usage concentration of 0.1% w/v of the product in water of 12°H (Ca), (French permanent hardness, calcium tfTl / I'.

J - - . J J 11302- only) at 50°C so that a satisfactory degree of alkalinity can be assured in use at all normal product concentrations. If necessary, up to 10% by weight of alkali metal carbonate, preferably sodium carbonate, may be included in 5 order to raise the pH 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 10 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 0.1% to about 5% by weight, preferably from about 0.2% to about 1.5% by weight of the composition. The preferred 15 antideposition agents are anionic polyelectrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.

The detergent compositions of the invention should 20 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, for example, by slurry-making and spray-drying processes. It is preferred that the process 25 used to form the compositions should result in a product having a moisture content of not more than about 12%, more preferably from about 4% to about 10% by weight.

The detergent compositions of the invention may also 30 be in the form of bars or tablets, or in liquid form.

The invention will now be illustrated by the following non-limiting Examples. 201211 - 20 - e-rrroT" EXAMPLES In the Examples that follow, the detergencies of wash liquors incorporating various builder systems were compared 5 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 Zeiss Elrepho Reflectrometer and the reflectance increase on washing (AR) 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 the concentrations stated 15 below, in 40°FH (Ca) or 20°FH (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 80°C, pH 10.0 and 55 r.p.m. agitation was carried out, followed 20 by a rinse in water of the same hardness as that of the water used to prepare the wash liquor.

The ingredients and concentrations were as follows: g/litre Sodium c^o~C13 li-near alkylbenzene 0.195 sulphonate C14"c15 alcohol ethoxylate (11 EO) 0.09 Hardened tallow soap 0.06 Alkaline silicate 0.15 - 21 - xrrriUT' Sodium sulphate 2.00 Detergent additive according to the 0.50-5.00 invention (as specified in Examples) It will be seen that the detergent additive according to the 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 10 g/litre, so that the total concentration ranged from 2.995 to 7.495 g/litre. Thus the percentage of the total composition constituted by the detergent additive of the invention at each concentration of the latter was as follows: Concentration (of detergent I (total) additive) 1 1 1 % detergent additive 1 in composition 0.50 I 2.995 1 16.70 1.50 I 3.995 1 37.55 2.00 | 4.495 1 44.49 2.50 1 4.995 1 50.05 3.00 1 .495 1 54.60 4.00 1 6.495 1 61.59 .00 1 1 7.495 1 66.71 1 EXAMPLE 1 The detergencies of compositions containing two zeolite/precipitant systems according to the invention were 35 compared, at various concentrations, with those of compositions containing zeolite alone and compositions 201211 - 22 - &rt3&2- containing zeolite/sodium tripolyphosphate (STP), in 20°FH 2+ (Ca ) water. The organic precipitants used were disodium dodecyl malonate (C^2AKM) an<^ disodium (C^g-C1g) alkyl succinate (ci5~cig AKS); the 5 zeolite was Zeolite A. The results were as follows: Concentration of Composition of Reflectance detergent additive detergent additive ( A R) 0.50 zeolite 100%) .7 zeolite 80%)+C12AKM (20%) 12.4 zeolite 80%)+C15_18AKS(20%) 11.4 zeolite 80%)+STP(20%) 13.0 1.50 zeolite 100%) 17.1 zeolite 80%)+C12AKM (20%) 21.5 zeolite 80%)+c15_18AKS(20%) 18.4 zeolite 80%)+STP(20%) 22.7 2.00 zeolite 100%) .8 zeolite 80%)+C12AKM (20%) .6 zeolite 80%)+C15_18AKS(20%) 24.5 zeolite 80%)+STP(20%) 26.7 3.00 zeolite 100%) .6 zeolite 80%)+C12AKM (20%) 26.6 zeolite 80%)+C15_18AKS(20%) 26.0 zeolite 80%)+STP(20%) 27.5 EXAMPLE 2 The detergencies of compositions containing zeolite/ disodium hexadecenyl succinate (C^g_^AKS) were compared, at various concentrations, with those of compositions 201211 containing zeolite alone and zeolite/STP in 40°FH(Ca"''~r) water. The results were as follows: 6.1302 2+, Concentration of I Composition of detergent additive! detergent additive Reflectance ( A R) 3 .00 zeolite (100%) 1 16.0 zeolite (80% )+C, g. . AKS (20%) 16:1 1 18.8 zeolite (80%)+STP(20%) | 21.8 4 .00 zeolite (100%) I .2 zeolite (80% )+C. g. .AKS(20%) lb: l | .0 zeolite (80%)+STP(20%) 1 .2 .00 zeolite (100%) 1 23.2 zeolite (80% )+C.. g. .AKS (20%) 16:1 I .4 zeolite (80%)+STP(20%) 1 .7 EXAMPLE 3 The detergencies of compositions containing another detergent additive according to the invention were compared, at various concentrations, with those of compositions containing zeolite alone and zeolite/STP, in 2+ 40°FH(Ca ) water. The organic precipitant used was disodium 0<-sulphostearate (C^g-SFAS). The results were as follows: /? V j " Gnri^ea- Concentration of Composition of Reflectance detergent additive detergent additive ( A R) 2.50 zeolite (100%) 13.4 zeolite (80%)+C1QSFAS(20%) 14.7 zeolite (80%)+STP(20%) - 3.00 zeolite (100%) .2 zeolite (80%)+C18SFAS(20%) 17.5 zeolite (80%)+STP(20%) 18.3 4.00 zeolite (100%) 18.6 zeolite (80%)+C18SFAS(20%) 21.0 zeolite (80%)+STP(20%) 22.1 .00 zeolite (100%) 21.4 ' zeolite (80%)+C18SFAS(20%) 22.6 zeolite (80%)+STP(20%) 22.8 EXAMPLE 4 The detergencies of compositions containing zeolite/ disodium dodecyliminodiacetate (C^ IMA) and zeolite/disodium tetradecyliminodiacetate (C^ IMA) were compared with those of compositions containing zeolite alone and zeolite/STP, at total builder concentrations of 2+ 4.0 g/litre in 40°FH (Ca ) water. The results were as 30 follows: 2 012 11 C~-±302- Composition of detergent, additive Reflectance (AR) zeolite (100%) 14.0 zeolite (80%) + C12 IMA (20%) 15.7 zeolite (80%) + C14 IMA (20%) 14.4 zeolite (80%) + STP (20%) 17.7 EXAMPLE 5 A detergent product was prepared from the following ingredients, the percentages being based on the total solids: % Sodium ciq~C13 linear alXylbenzene sulphonate 6 C14~C15 alcohol ethoxylate (11 EO) 3 Hardened tallow soap 5 Sodium silicate 6 Sodium sulphate 3.5 Sodium chloride 9.5 Builder (anhydrous basis) 40 The builder systems used were all-zeolite, zeolite/ Ci5_i8AKS, and zeolite/hardened tallow soap. 25 Detergencies were compared at product dosages of 3.0, 5.0 and 8.0 g/litre, in 35°H (Ca^+) water at 60°C and pH 10.0, at a wash duration of 20 minutes in the Tergotometer. The results were as follows:

Claims (28)

- 26 - -erT5tT2r Percentage builder in product Reflectance (&R) for 1 3. 0 5. 0 8 .0 40% zeolite 13. 0 17. 5 22 .2 35% zeolite + 5% C15_18 AKS 19. 5 23 .6 35% zeolite + 5% li. tallow soap 18. 0 22 .3 30% zeolite + 10» C15_18 AKS 13. 8 19. 7 24 .0 30% zeolite + 10% h.tallow soap 12. 5 18. 1 22 .7 25% zeolite + 15% C15_18 AKS 14. 1 20. 2 24 .1 25% zeolite + 15% h.tallow soap 12. 1 18. 4 23 .5 10 15 *** - 27 - 201211° * n C 1 m? (T ) GB- WHAT t/WF CLAIM iS: crarMs

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 ^(CH„) COOY 2 n Rx-x (I) I ^(ch9) z 2 m wherein: is Ci0-C24 alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length; X is CH, CR2, N or CON; R2 is Ci-C3 alkyl; Y is hydrogen or a solubilising cation: n and which may be the same or different, are O or integers from 1 to 4; and Z is COOY or S03Y; with the proviso that if the organic precipitant builder is an c<-sulphocarboxylic acid salt 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 - 28 - ~O2kQL)I 2 COOY Rx CH_ (II) (CH,) -Z 2 p wherein R^, 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 COOY R-L — CH_ (III) COOY wherein R^ 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 COOY Rj^ — CH_ (IV) ch2cooy wherein R^ 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 (CH2)vC00Y (V) (CH_) COOY 2 w wherein R^ and Y have the meanings given in Claim 1 and v and w are each integers within the range of from 1 to 4. - 29 - 2C121Hcu*ii C . 1302(L) OB

6. A detergent composition as claimed in Claim 1, wherein the organic precipitant builder is a compound of the formula VI (CH2) COOY - CO - N (VI) (CH.) COOY 2 w wherein and Y have the meanings given in Claim 1 and v and w have the meaninos aiven 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 1 or 2.

8. A detergent composition as claimed in Claim 7, wherein the organic precipitant builder is a compound of the I 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 1 to 8, wherein the organic precipitant builder has a — 8 calcium salt solubility product of less than 10

10. A detergent composition as claimed in any one of Claims 1 to 9, wherein the aluminosilicate cation-exchange material is a crystalline or amorphous material having the general formula VII (Cat2/n0)x-A12°3(Si02)y,zH20 (VII) wherein Cat is a cation having valency n that is exchangeable with calcium 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 weiaht. 201214°^ - 30 - £.1302(L) Ci3

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 Na (A10,) .(SiO_) zH-0 (VIII) 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.

12. A detergent composition as claimed in Claim 11, wherein the aluminosilicate cation-exchange material is a crystalline material having a unit cell of the formula IX Na12(A102)12.(Si02)12.zH20 (IX) wherein z is from 20 to 30. i

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 1 to 13, 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 Claim 14, 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 15, wherein the aluminosilicate cation-exchange material has an ion exchange capacity of at least 200 mg CaCO^ per gram of anhydrous aluminosilicate. - 31 - '8 2 1 e-rir3tT2 (L) GB

17. A detergent composition as claimed in any one of Claims 1 to 16, which contains not more than 10% by weight of inorganic phosphate.

18. A detergent composition as claimed in Claim 17, which contains less than 5% by weight of inorganic phosphate.

19. A detergent composition as claimed in Claim 18, which contains less than 3% by weight of inorganic phosphate.

20. A detergent composition as claimed in any one of Claims 1 to 19, 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 20, which contains from 2.5 to 94% by weight of aluminosilicate cation-exchange material.

22. A detergent composition as claimed in Claim 21, which contains from 10 to 60% by weight of aluminosilicate cation-exchange material.

23. A detergent composition as claimed in Claim 22, which contains from 12 to 55% by weight of aluminosilicate cation-exchange material.

24. A detergent composition as claimed in any one of Claims 1 to 23, which contains from 0.3 to 73% by weight of the organic precipitant builder.

25. A detergent composition as claimed in Claim 24, which contains from 1 to 30% of the organic precipitant builder.

26. A detergent composition as claimed in Claim 25, which contains from 3 to 17% of the organic precipitant builder.

27. A detergent composition as claimed in Claim 1, substantially as described in any one of the Examples herein.

28. A detergent additive for use in a detergent composition as claimed in any one of Claims 1 to 27, which consists essentially of (i) from 25 to 97% by weight of a crystalline or amorphous aluminosilicate cation-exchange material, and (ii) from 3 to 75% by weight of an organic precipitant builder having a polyvalent anion, with the proviso that when the aluminosilicate material (i) is crystalline, the organic precipitant builder is not a water-soluble salt of a C^-C20 (X- sulphocarboxylic acid. fjUL PATENT QFRG -9JUL1982