NZ201212A

NZ201212A - Detergent additives and compositions

Info

Publication number: NZ201212A
Application number: NZ201212A
Authority: NZ
Inventors: R V Scowen; T Stirling; G J Welch
Original assignee: Unilever Plc
Priority date: 1981-07-15
Filing date: 1982-07-09
Publication date: 1985-08-16
Also published as: ATE15499T1; EP0070190A1; JPS6116315B2; BR8204091A; JPS5823897A; JPS5823896A; ZA825005B; ZA825006B; DK314782A; ATE16818T1; EP0070190B1; AU8598582A; EP0070192B1; NO822434L; DE3267784D1; EP0070192B2; NZ201213A; JPH045720B2; BR8204092A; AU8598482A

Abstract

A ternary builder system for detergent compositions comprises 25 to 97% by weight of an aluminosilicate cation-exchange material such as Zeolite A and 3 to 75% by weight, in total, of ( i) a soap containing at least 60% by weight of saturated material, and (ii) nitrilotriacetic acid or a water-soluble salt thereof, at a (i):(ii) ratio of 10:1 to 1:10, the proportion of soap in the ternary mix being at least 12%. The builder mix is advantageously used in detergent compositions containing less than 10% inorganic phosphate, and gives good results in zero-phosphate compositions.

Description

New Zealand Paient Spedficaiion for Paient Number £01 212 2012 12 Priority Datc(s): J&"7&J.

Complete Specification Filed: Class: Pubflootlon Data: K P. M» Sfl P. (3. Journal, No: .....

NO DRAWINGS NEW ZEALAND PATENTS ACT, 1953 No.: Date: COMPLETE SPECIFICATION DETERGENT ADDITIVES AND DETERGENT COMPOSITIONS CONTAINING THEM f * 9 JUL l%2 IH We, UNILEVER PLC a British company of Unilever House, Blackfriars, London EC4, England hereby declare the invention for which we pray that a patent may be granted to me/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) 2012 12 - 1 cl~ C. 1303- DETERGENT ADDITIVES AND DETERGENT COMPOGITIONO CONTAINING THEM The present invention relates to additives for detergent compositions, and to detergent compositions 5 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 10 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 waste waters. There is therefore a desire to reduce the level of phosphorus, or to eliminate 15 it altogether, in detergent compositions.

Water-insoluble aluminosilicate ion exchange materials 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 20 aluminosilicate materials, even in large amounts, tend to be undesirably slow in their exchange of cations, __A£E-2-itf 2012 12 — 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 5 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 PQly-tX-hydroxyacrylates. High levels of these materials 10 are, however, not generally desirable in detergent compositions for cost or environmental reasons.

We have now discovered that surprisingly good detergency results are obtained by using, in combination with an aluminosilicate builder, relatively small amounts 15 of both an organic sequestrant builder and of an organic precipitant builder. The detergency results obtained using ternary systems of this type have surprisingly been found to be better than would have been expected from consideration of the results obtained using the 20 corresponding binary aluminosilicate/sequestrant and aluminosilicate/precipitant systems, so that decreased amounts of the supplementary builders can be used, giving cost savings and environmental advantages.

It is known that the detergency builder properties of 25 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. , 5fj , 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 2012 12 - 3 - *€-r±3tT3 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 5 precipitant builders, since these remove hardness ions from the wash liquor by the virtually irreversible formation of a precipitate (insoluble calcium or magnesium salt).

It is thus unexpected that addition of a precipitant builder and an aluminosilicate/sequestrant system gives a 10 substantial improvement in detergency builder properties.

The present invention accordingly provides, in a first aspect, a detergent additive consisting essentially of: (a) from about 25% to about 97% by weight of a crystalline or amorphous aluminosilicate cation-exchange material, 15 (b) from about 3% to about 75% by weight, in total, of (i) an organic precipitant builder having a polyvalent anion, which builder forms an insoluble calcium salt, and (ii) an organic builder which forms a soluble complex 20 with calcium, the weight ratio of (i) to (ii) being from about 10:1 to about 1:10.

The organic precipitant builder is preferably one having a divalent anion.

The aluminosilicate cation exchange material is a crystalline or amorphous material having the general formula: (Cat2/n °'x-A1203(S102)y-ZH2° 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 7 0 1 ?. 1 2 - 4 - C.1303- 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: Kax[(A102)x.(Si02)y]ZH20 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 10 from 0.1 to 100 micrometres, ideally between 0.1 and 10 micrometres, and an ion exchange capacity of at least 200 mg CaCOg per gram of aluminosilicate (anhydrous basis).

In a preferred embodiment the water-insoluble aluminosilicate is a crystalline material having the 15 formula described by the unit cell content: Nai2(A102)i2*(Si°2)i2- 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 20 typically: Na20.Al203.2Si02.~4.5H20 and is also described by the unit cell content: Ha12C(A102)12-<Sl02)12]-27H2°- The organic precipitant builder is a water-soluble material which forms an insoluble calcium salt and which has a polyvalent, preferably divalent, anion. Materials 2 012 12 - 5 - C. 1303" having a divalent anion are substantially more weight- effective as builders than are soaps; only one mole is 2+ 2+ consumed by each gram ion of Ca or Mg hardness ions, as compared with two moles of soap.

The solubility product of the calcium salt of the organic precipitant builder having a divalent anion is —8 preferably less than 10 Advantageously the organic precipitant builder is a compound of the formula Is X is CH, CR2, N or CON; R2 is C^-C^ alkyl; Y is hydrogen or a solubilisirig cation, preferably alkali metal and especially sodium; n and nw_ which may be the same or different, are 0 or integers from 1 to 4; and Z is COOY or S03Y. definition 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 builder is a compound of the formula II.

(I) wherein: R^ is cio~C24 alkyl or alkenyl, or an arylalkyl or alkylaryl group of equivalent chain length; One preferred group of compounds within this COOY (II) 2012 12 - 6 - cT±3G3- wherein . 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: - ch COOY 'COOY (III) (ii) substituted succinates of the formula IV: Rx - CH.

COOY ch2cooy (IV) - and - (iii) C>(-sulphofatty acid salts of the formula V: COOY so3y (v) 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^-AKM), disodium hexadecenyl succinate (Cir n-AKS), and disodium mixed C..c-C,0 lb: JL is lb succinate (C^^_^g-AKS).

Compounds of the formula V are described, for example, 25 in GB 1,368,736 and GB 1,380,390 (Unilever). A typical example is disodium o<-sulphostearate (C^g-SFAS).

Blends of compounds of different chain lengths, for example n- rr ■ - < h .' t - 7 - C.1303 I /v the g^-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.

According to a second preferred embodiment of the 5 invention, the organic precipitant builder is a compound of the formula VI: .(ch2)vcooy Rx - N (VI) or of the formula VII: (ch-) cooy 2 w .(CH,,) COOY 2 v Rx - CO - N'T (VII) '(CH,) COOY z w wherein and Y have the meanings given above and v .and 15 w are each 1 to 4, preferably 1 or 2.

Compounds of the formula VI in which v and w are both 1, the N-alkyl iminodiacetates, are of especial interest.

Compounds of the formula VI in which v and w are both 2, the /2> -iminodipropionates, are known amphoteric 20 surfactants, disclosed, for example, in GB 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). 25 Compounds of the formula VI in which v and w are both 1, the 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 30 formulae VI and VII for use as "chelant-surfactants" for decreasing the fouling of metals by aqueous systems. 2 012 12 - 8 - CrT3T73~~ 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-soluble salt of an N-(Cg-Clg alkyl)-iminodiacetic acid, 5 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 the use of compounds of the formula VI in detergent 10 compositions are GB 446,737 and GB 446,813 (I G Farben). Compounds analogous to those of formula VI but having a shorter alkyl chain (Cg 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 detergents, 15 as in GB 574,504 (Unilever).

The organic sequestrant builder is a water-soluble material which forms soluble complexes with calcium, preferably with pKCa greater than 3.0, preferably greater than 4.0 and more preferably greater than 4.5. 20 Advantageously the sequestrant builder also forms complexes with magnesium, preferably with P^Mg greater than 4.0.

Examples of suitable materials include alkali metal (especially sodium) salts of the following acids: 25 nitrilotriacetic acid, ethylenediamine tetracetic acid, polyacrylic acid, poly( -hydroxyacrylic) acid, carboxymethyloxymaIonic acid, carboxymethyloxysuccinic acid, oxydiacetic acid, oxydisuccinic acid, citric acid, dipicolinic acid and many more. The polyacetal 30 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 also advantageously be used.

C.1303 201212 Alkali metal salts of nitrilotriacetic acid (NTA), especially the trisodium salt, are, however, the preferred organic sequestrants used according to the present invention. The use of NTA salts in combination with 5 precipitant builders having a divalent anion is especially preferred.

The nitrilotriacetic acid compounds preferably used according to the present invention are known sequestering agents and may be represented by the following structural 10 formula N=(CH2COOX) wherein X, as before is hydrogen or a solubilizing cation. These compounds further contain C-bonded substituents of an inert and innoxious nature such as alkyl, eg methyl or 15 ethyl, or haloalkyl, eg chloromethyl. The nature of said compounds is not particularly critical with the implicit* limitation that such substituents be devoid of any tendency to deleteriously affect the desirable properties of the nitrilotriacetic acid compound.

Preferred compounds falling within the ambit of the above-described definition and formula are nitrilotriacetic acid, trisodium nitrilotriacetate monohydrate, tripotassium nitrilotriacetate, disodium nitrilotriacetate and dipotassium nitrilotriacetate.

The organic precipitant builder and the organic sequestrant builder together constitute 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 20% to about 50%. The ratio of 30 precipitant to sequestrant is from 10si to 1:10, preferably from 3:1 to 1:3 and desirably from 3:1 to 1:1. fv »r ^ fy * ■' i<*. - 10 - -CTT3XJT 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.

Accordingly, in a second aspect the present invention provides a detergent composition comprising from about 3 to about 90% by weight of at least one synthetic detergent-active material, and from about 10 to about 97% by weight of a detergent additive as previously defined.

The detergent composition of the invention contains from about 10% to about 97% by weight of the detergent additive of the invention, preferably from about 10% to about 80%. more preferably from about 25% to about 70%, and especially from about 28% 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 17% to about 47%, is preferred.

Similarly, the content of organic builders (precipitant plus sequestrant) can range from about 0.3% to about 73%, a range of from about 5% to about 40%. especially from about 7% to about 27%, being preferred.

The preferred range for the content of the precipitant builder is from about 3% to about 20%, especially from about 5% to about 10%; for the sequestrant builder the preferred range is from about 1% to about 15%, especially from about 2% to about 10%.

The detergent compositions of the present invention are preferably substantially free of inorganic phosphate. 2012 12 - 11 - C. 1303' This is highly desirable for the environmental reasons mentioned earlier. Compositions according to the invention containing no inorganic phosphate have been found to exhibit detergency properties comparable to those of sodium 5 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; a level below 5% is advantageous, and a level below 3% is especially 10 preferred. Any phosphate present may, for example, be in the form of alkali metal (preferably sodium) tripolyphosphate, orthophosphate, pyrophosphate or polymeric phosphate.

The detergent composition of the invention necessarily 15 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, amphoteric or zwitterionic detergent compound or mixture thereof. Many suitable detergent-active compounds 20 are commercially available and are fully described in the literature, for example in "Surface Active Agents and Detergents", Volumes I and II, by Schwartz, Perry and Berch.

The preferred detergent compounds which can be used 25 are synthetic anionic and nonionic compounds. The former 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 alkyl being used to include the alkyl portion of higher aryl radicals. 30 Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (cg~cig) alcohols produced for example from tallow or coconut oil; sodium and 201212 g.1303- potassium alkyl (C9~C2o^ benzene sulphonates, particularly sodium linear secondary alkyl (cio~ci5) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from 5 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'C^g) fatty alcohol-alkylene oxide, particularly ethylene oxide, 10 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 monosulphonates such as those derived by reacting 15 alpha-olefins (Cg-C20^ with sodium bisulphate and those derived by reacting paraffins with S02 and Cl2 and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly ciq~C20 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 (cig~cig) alkyl sulphates.

Examples of suitable nonionic detergent compounds 25 which may be used include in particular the reaction products of alkylene oxides, usually ethylene oxide, with alkyl P^enols» generally 5 to 25 EO, ie 5 to units of ethylene oxide per molecule; the condensation products of aliphatic (cg~cig) primary or secondary 30 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 35 chain tertiary phosphine oxides and dialkyl sulphoxides. 2012 12 - 13 - C.1303 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 case to provide controlled low sudsing properties. This is 5 beneficial for compositions intended for use in suds-intolerant automatic washing machines. Anionic and nonionic detergent compounds are advantageously used together in ratios of from 3:1 to 1.5:1.

Amounts of amphoteric or zwitterionic detergent 10 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 15 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 20 desirably the potassium, salts of cio~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 or more, are especially preferred. This preferred chain length distribution may be 25 conveniently obtained by using soaps from natural sources 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.

C.1303 201212 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 5 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 as low-temperature bleach systems and are well known in the 10 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 15 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 20 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, especially from about 6% to about 30% by 25 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 peroxybleach 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 ©§ C^vL, 246,339, US patents 3,332,882 and 4,128,494, and Canadian f'l tx. y t - 15 - C.1303 201212 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 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 I,3-dipropionyl hydantoin; 0C-acetoxy-(N,N')-10 polyacylmalonamide, for example 0^-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 0-benzoyl-N,N-succinyl hydroxylamine, 0-acetyl-N,N-succinyl hydroxylamine, O-p-methoxybenzoy1-N,N-succiny1-hydroxylamine, O-p-nitrobenzoyl-N,N-succinyl-hydroxylamine and 0,N,N-triacetyl hydroxylamine; (e) N,N'-diacyl-sulphurylamides, for example N,N'-25 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 30 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, \ \ A. ' t 1,3-diacetyl-4,5-dipropionyloxy-imidazoline; (j) Tetraacetylglycoluril and tetrapropionylglycoluril; (k) Diacylated 2,5-diketopiperazine, such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropiony1-2,5-5 diketopiperazine and 1,4-dipropionyl-3,6-dimetyl- 2,5-diketopiperazine; (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), 10 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. 15 (n) CX-acyloxy-(N,N') polyacyl malonamides, such as c<-acetoxy-(N,N') diacetyl malonamide.

The N-diacylated and N,N'-polyacylatedamines mentioned under (a) are of special interest, particularly N,N,N',N'-tetra-acetyl-ethylenediamine (TAED). 7-S2 It is preferred to use the activator in granular form, preferably wherein the activator is finely divided as Gr/'Ksh |?a-fen+ SpetS^«+Vo^ Ho. SL o53 , described in our UK Patent Application No»—80 21079.

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% G-ri"3^3~ 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 5 J> 300 ^um, and not more than 20% by weight of particles ^ 200 ^um, preferably ^>150 ^um. 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 10 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 ^uxn and up to 10% by weight of granules 250 ^um is tolerable. The granules incorporating the activator, preferably in this 15 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 20 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 25 affect the activator.

It is particularly preferred to include in the detergent compositions a stabiliser for the bleach system, for example ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene 30 phosphonate. These stabilisers can be used in acid or salt form, especially in calcium, magnesium, zinc or aluminium salt form, as described in our UK Patent Application No. 2 048 930. 201212 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 5 compositions. Examples of these additives include lather boosters such as alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids? lather depressants such as alkyl phosphates, silicones, or alkyl phosphonic acids 10 incorporated in petroleum jelly, wax or mineral oil? 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, 15 fluorescent 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. 20 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 25 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 30 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 solution. It is preferred in particular for domestic 2012 12 - 19 - -erirstrr' 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 5 normal usage concentration of 0.1% w/v of the product in water of 12°H (Ca), (French permanent hardness, calcium 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 10 carbonate, preferably sodium carbonate, may be included in 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 15 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 20 antideposition agents are anionic polyelectrolytes, especially polymeric aliphatic carboxylates, or organic phosphonates.

The detergent compositions of the invention should desirably be in free-flowing particulate, for example, 2 5 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 used to form the compositions should result in a product 30 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 be in the form of bars or tablets, or in liquid form.

C. 1303- The invention will now be illustrated by the following non-limiting Examples. 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 Zeiss Elrepho Reflectometer and the reflectance increase on 10 washing (Ar) was taken as a measure of detergency.

In each case a wash liquor was prepared using the ingredients stated below in the concentrations stated below, in 40°FH (Ca) or 20°FH (Ca) water. The wash liquor was allowed to equilibrate for 15 minutes. Test cloth 15 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 rpm agitation was carried out, followed 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: EXAMPLES In the Examples that follow, the detergencies of wash g/litre Sodium C^q C^^ linear alkylbenzene 0.195 sulphonate C^^-C^^ alcohol ethoxylate (11 EO) 0.09 Hardened tallow soap 0.06 Alkaline silicate 0.15 2012 12 g/litre Sodium sulphate 2.00 Detergent additive according to the invention (as specified in Examples) 1.00-5.00 It will be seen that the detergent additive according to the invention was used at concentrations of from 1.00 to 5.00 g/litre, and the other components of the composition were used at a constant total concentration of 2.495 g/litre, so that the total concentration ranged from 3.495 10 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 % detergent additive in composition (of detergent I additive ) I (total) 1.00 I 3.495 28.61 1.50 1 3 .995 37.55 2.00 I 4.495 44.49 2.50 1 4.995 50.05 3.00 I .495 54.60 4.00 1 6.495 61.59 .00 1 1 7.495 66.71 All percentages given in the Examples are by weight and are based on the anhydrous materials.

C7T353 EXAMPLE 1 The detergencies of compositions containing a ternary builder system (detergent additive) according to the invention were compared at two different concentrations and 5 water hardnesses, with those of control compositions containing single or binary builder systems. The aluminosilicate used was zeolite A, the organic precipitant was disodium dodecylmalonate (C^AKM), an(j the organic sequestrant was trisodium nitrilotriacetate (NTA). The 10 results were as follows: Reflectance A.R In 20°FH Ca In 406FH Ca water water Concentration, g/1 1.0 1.5 2.5 4.0 Detergent additive 60% zeolite/25% C^ AKM/15% NTA 22.6 26.0 25.4 28.5 85% zeolite 15%/NTA 18.5 24.5 20.1 26.7 75% zeolite/25% C^ AKM 17.4 24.0 21.2 25.8 100% zeolite 16.4 20.8 16.5 25.0 EXAMPLE 2 A similar procedure to that of Example 1 was carried out using the organic sequestrant trisodium carboxymethyloxysuccinate (CMOS) instead of NTA. The 5 results were as follows: Reflectance AR In 20°FH Ca water In 40 °FH Ca water Concentration, g/1 1.0 2.0 4.0 .0 Detergent additive 60% zeolite/25% C AKM/15% CMOS 12 18.5 26.9 85% zeolite/15% CMOS 16.8 23.5 26.5 27.0 24.1 24.7 75% zeolite/25% C12AKM 17.4 26.1 .8 26.6 100% zeolite 16.4 25.1 .0 25.8 EXAMPLE 3 A similar procedure to that of Example 1 was carried out using the organic sequestrant poly (o^-hydroxy acrylate) (PHAC) instead of NTA. The tests at 2.5 g/l and 2+ in 40° FH (Ca ) water were carried out using a different test cloth, one with a predominantly fatty soil. The results were as follows: 1212 Reflectance Ar In 40 °FH Ca water Concentration, g/l Detergent additive (fatty test cloth) 2.5 60% zeolite/25% C AKM/15% PHAC 12 85% zeolite/15% PHAC 75% zeolite/25% C AKM 12 29.1 28.1 28.0 In 40 °FH Ca water (clay-soiled test cloth ) 3.0 28.0 25.6 24.1 100% zeolite 26.6 19.8 EXAMPLE 4 A similar procedure to that of Example 1 was carried out using as organic sequestrant a polyacrylate (Versicol E7) instead of NTA. The tests were carried out at 3.0 g/l 2+ and in 40°FH (Ca ) water, and the results were as follows s Detergent additive Reflectance AR 60% zeolite/25% C^ AKM/15% polyacrylate 25.3 85% zeolite/15% polyacrylate 22.0 2 01212 - 25 - C.1303 " Detergent additive Reflectance AR 75% zeolite/25% C^ AKM 24.1 100% zeolite 19.8 EXAMPLE 5 A similar procedure to that of Example 1 was carried out using as organic sequestrant tetrasodium ethylenediamine-tetraacetate (EDTA) instead of NTA, at 3.0 2 + g/l and in 40° FH (Ca ) water. The results were as 10 follows: Detergent additive Reflectance AR 60% zeolite/25% C^ AKM/15% EDTA 26.3 85% zeolite/15% EDTA 22.6 75% zeolite/25% C^ AKM 24.1 100% zeolite 19.8 EXAMPLE 6 A similar procedure to that of Example 1 was carried out using as organic sequestrant tetrasodium oxydisuccinate (ODS) instead of NTA, at 3.0 g/l and in 40° FH (Ca^+) water. The results were as follows: C.1JUS Detergent additive Reflectance AR 60% zeolite/25% AKM/15% ODS 24.9 85% zeolite/15% ODS 23.4 75% zeolite/25% C.^ AKM 24.1 100% zeolite 19.8 EXAMPLE 7 A similar procedure to that of Example 1 was carried 10 out using as organic sequestrant instead of NTA, an oxidised starch as described in GB 1,330,121. The tests 2+ were carried out at 3.0 g/l in 40° FH (Ca ) water and the results were as follows: Detergent additive Reflectance AR 60% zeolite/25% C^ AKM/15% oxidised starch 25.2 85% zeolite/15% oxidised starch 21.1 75% zeolite/25% C^ 25 AKM 24.1 100% zeolite 19.8 y ^ i 7 1i 7 C.1303 EXAMPLE 8 A similar procedure to that of Example 1 was carried out using as organic precipitant, instead of AKM, disodium hexadecenyl succinate (C16 AKS). The tests were 5 carried out in 40° FH (Ca^+) water and the results were as follows: Reflectance AR Concentration, g/l 2.0 2.5 4.0 Detergent additive 60% zeolite/25% C AKS/15% NTA 16 19.5 85% zeolite/15% NTA 15.9 .9 21.2 27.2 25.0 75% zeolite/25% C AKS 16 16.2 .3 24.5 100% zeolite 14.6 17.3 23.0 EXAMPLE 9 A similar procedure to that of Example 1 was carried out using, as organic precipitant, instead of C^ AKM, disodium C><-sulphostearate (C1Q SFAS). The tests were 2+ carried out in 40° FH (Ca ) water and the results were as follows: C J 11 I , J r-~) / / Reflectance AR Concentration, g/l 2.5 3.0 4.0 Detergent additive 60% zeolite/25% C^g 5 SFAS/15% NTA 22.7 24.8 27.1 85% zeolite/15% NTA 21.2 23.5 25.0 75% zeolite/25% C^g SFAS 19.6 21.5 23.4 100% zeolite 17.2 19.5 23.0 EXAMPLE 10 A similar procedure to that of Example 1 was carried out using, as organic precipitant, instead of C^AKM, disodium hexadecyliminodiacetate (C^glMA). The tests were carried out at a total builder concentration of 4 g/ 2+ litre in 40°FH (Ca ) water. Tests were carried out using both a clay-soiled test cloth and a test cloth soiled with a mixture of organic and particulate soils. The results were as follows:

Claims

201212 - 29 - C.1303 " Detergent additive 100% zeolite 90% zeolite/10% NTA 80% zeolite/20% C16IMA 70% zeolite/20% C16IMA/ 10% NTA 70% zeolite/30% C 16 IMA 10 60% zeolite/30% C16IMA/ 10% NTA 80% zeolite/20% STP Reflectance ( A R) Clay-soiled test cloth Mixed-soil test cloth 14.0 16.5 13.6 31.5 32.9 31.1 17.3 15.0 33.5 not tested 18.0 17.4 not tested 34.1 CT1303 (L) GD— 30 what -ffWE CLAIM IS- CLAIMS

1. A detergent additive consisting essentially of: (a) from 25% to 97% by weight of a crystalline or amorphous aluminosilicate cation-exchange material, (b) from 3% to 75% by weight, in total, of (i) an organic precipitant builder having a polyvalent anion, which builder forms an insoluble calcium salt, and (ii) an organic sequestrant builder which forms a soluble complex with calcium, the weight ratio of (i) to (ii) being from 10:1 to 1:10.

2. A detergent additive as claimed in Claim 1, wherein the organic precipitant builder has a divalent anion.

3. A detergent additive as claimed in Claim 2, wherein the solubility product of the calcium salt of the organic _8 divalent precipitant builder is less than 10

4. A detergent additive as claimed in Claim 2 or Claim 3, wherein the organic precipitant builder is a compound of the formula I wherein R.^ 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 m_j_ which may be the same or different, are 0 or integers from 1 to 4; and Z is COOY or S03Y. (I) AvEZvJ 'O - 31 - U.IJUJ(L) GB——

5. A detergent additive as claimed in Claim 4, wherein the organic precipitant builder is a compound of the formula II ■ cooy - CH (II) <CH2'p-Z wherein , Y and Z have the meanings given in Claim 4, and p is 0 or 1.

6. A detergent additive as claimed in Claim 5, wherein the organic precipitant builder is a compound of the formula iii z COOY R2 - CH (III) COOY wherein R^ and Y have the meanings given in Claim 4,

7. A detergent additive as claimed in Claim 5, wherein the organic precipitant builder is a compound of the formula IV COOY rx - ch (iv) ch2cooy wherein R^ and y have the meanings given in Claim 4.

8. A detergent additive as claimed in Claim 5, wherein the organic precipitant builder is a compound of the formula V ^ cooy r^ - ch (v) •so3y wherein R^ an(j y have the meanings given in Claim 4. 11 // J - 32 - -e-ri303(L"7 GB

9. A detergent additive as claimed in Claim 4, wherein the organic precipitant builder is a compound of the formula VI ^(CH0) COOY ^— 2 v R^ - N (VI) (CH0 ) COOY £ w wherein R^ and Y have the meanings given in Claim 4, and v and w are each integers within the range of from 1 to 4.

10. A detergent additive as claimed in Claim 4, wherein the organic precipitant builder is a compound of the formula VII ^(CH») COOY 2 v Rx - CO - N (VII) "^(CH0) COOY z w wherein R^ and Y have the meanings given in Claim 4, and v and w are each integers withih the range of from 1 to 4.

11. A detergent additive as claimed in Claim 9 or Claim 10, wherein the organic precipitant builder is a compound of the formula VI or of the formula VII, wherein v and w are each 1 or 2.

12. A detergent additive as claimed in Claim 11, wherein the organic precipitant builder is a compound of the formula VI or of the formula VII, wherein v and w are both 1.

13. A detergent additive as claimed in any one of Claims 1 to 12, wherein the organic sequestrant builder is a compound which forms with calcium ions a soluble complex with pK^a greater than 3.0. 33 C.1303(L) GB 201212

14. A detergent additive as claimed in Claim 13, wherein the organic sequestrant builder is a compound which forms with calcium ions a soluble complex with pKCa greater than 4.5.

15. A detergent additive as claimed in any one of Claims 1 to 14, wherein the organic sequestrant builder is an alkali metal salt of an organic carboxylic acid having three or more carboxyl groups.

16. A detergent additive as claimed in Claim 15, wherein the organic sequestrant builder is an alkali metal salt of nitrilotriacetic acid.

17. A detergent additive as claimed in Claim 15, wherein the organic sequestrant builder is selected from alkali metal salts of ethylenediaminetetraacetic acid, polyacrylic acid, poly( -hydroxyacrylic) acid, carboxymethyloxymalonic acid, carboxymethyloxysuccinic acid, oxydiacetic acid, oxydisuccinic acid, citric acid, dipicolinic acid, polyacetal carboxylates and oxidised polysaccharides.

18. A detergent additive as claimed in any one of Claims 1 to 17, wherein the aluminosilicate cation-exchange material is a crystalline or amorphous material having the general formula VIII. wherein Cat is a cation having valency n that is exchangeable with calcium; x is a number from 0.7-1.5; ^ is a number from 1.3-4; and is such that the bound water content is from 10% to 28% by weight. (Cat2/n°)x-A1203(Si02)yzH2° (VIII) - 34 - C.1303(L) GB 201212

19. A detergent additive as claimed in Claim 18, wherein the aluminosilicate cation-exchange material is a crystalline material having a unit cell of the formula IX Nax (A102)x.(Si02)y zH20 (IX) wherein x and ^ are integers of at least 6, the ratio of x to ^ 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.

20. A detergent additive as claimed in Claim 19, wherein the aluminosilicate cation-exchange material is a crystalline material having a unit cell of the formula X Na12(A102)12.(Si02)12.zH20 (x) wherein z is from 20 to 30.

21. A detergent additive as claimed in Claim 20. wherein the aluminosilicate cation-exchange material has a unit cell of the formula X wherein z is 27.

22. A detergent additive as claimed in any one of Claims 1 to 21, wherein the aluminosilicate cation-exchange material has a particle size within the range of from 0.1 to 100 ^um.

23. A detergent additive as claimed in Claim 22, wherein the aluminosilicate cation-exchange material has a particle size within the range of from 0.1 to 10 ^urn.

24. A detergent additive as claimed in any one of Claims 1 to 23, wherein the aluminosilicate cation-exchange material has an ion-exchange capacity of at least 200 mg CaCO. gram of anhydrous aluminosilicate. 201212 - 35 - e-rl303(L) GB-

25. A detergent additive as claimed in any one of Claims 1 to 24, which contains from 10 to 60% by weight, in total, of the organic precipitant builder and the organic sequestrant builder.

26. A detergent additive as claimed in Claim 25, which contains from 20 to 50% by weight, in total, of the organic precipitant builder and the organic sequestrant builder.

27. A detergent additive as claimed in any one of Claims 1 to 26, wherein the weight ratio of the organic precipitant builder to the organic sequestrant builder is from 3:1 to 1:3.

28. A detergent additive as claimed in Claim 27, wherein the weight ratio of the organic precipitant builder to the organic sequestrant builder is from 3:1 to 1:1.

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

30. A detergent composition which comprises from 3 to 90% by weight of at least one synthetic detergent-active material and from 10 to 97% by weight of a detergent additive as claimed in any one of Claims 1 to 29.

31. A detergent composition as claimed in Claim 30, which contains from 10 to 80% by weight of the detergent additive as claimed in any one of Claims 1 to 29.

32. A detergent composition as claimed in Claim 31, which contains from 25 to 70% by weight of the detergent additive as claimed in any one of Claims 1 to 29. - 36 - 20121 C.1303(L) GB—

33. A detergent composition as claimed in Claim 32, which contains from 28 to 67% by weight of the detergent additive as claimed in any one of Claims 1 to 29.

34. A detergent composition as claimed in any one of Claims 30 to 33, which contains from 10 to 60% by weight of the aluminosilicate cation-exchange material.

35. A detergent composition as claimed in Claim 34, which contains from 17 to 47% by weight of the aluminosilicate cation-exchange material.

36. A detergent composition as claimed in any one of Claims 30 to 35, which contains, in total, from 5 to 40% by weight of the organic precipitant and sequestrant builders.

37. A detergent composition as claimed in Claim 36, which contains, in total, from 7 to 27% by weight of the organic precipitant and sequestrant builders.

38. A detergent composition as claimed in any one of Claims 30 to 37, which contains from 3 to 20% by weight of the organic precipitant builder.

39. A detergent composition as claimed in Claim 38, which contains from 5 to 10% by weight of the organic precipitant builder.

40. A detergent composition as claimed in any one of Claims 30 to 39, which contains from 1 to 15% by weight of the organic sequestrant builder.

41. A detergent composition as claimed in Claim 40, which contains from 2 to 10% by weight of the organic sequestrant builder. 201212 37 G-v-i^e-3-fir-}—

42. A detergent composition as claimed in any one of Claims 30 to 41, which contains not more than 10% by weight of inorganic phosphate.

43. A detergent composition as claimed in Claim 42, whi'ch contains less than 5% by weight of inorganic phosphate.

44. A detergent composition as claimed in Claim 43, which contains less than 3% by weight of inorganic phosphate.

45. A detergent composition as claimed in Claim 30, substantially as described in any one of the Examples herein.