CA2038490A1

CA2038490A1 - Detergent compositions

Info

Publication number: CA2038490A1
Application number: CA002038490A
Authority: CA
Inventors: Jelles V. Boskamp
Original assignee: Individual
Current assignee: Unilever PLC
Priority date: 1990-03-19
Filing date: 1991-03-18
Publication date: 1991-09-20
Also published as: GB9104613D0; EP0448298A1; BR9101075A; ZA912024B; JPH04227692A; CA2038491C; BR9101074A; GB9006171D0; AU7296991A; CA2038491A1

Abstract

A fabric washing detergent composition, preferably particulate, comprises detergent-active compounds and a detergency builder system comprising an aluminosilicate (18-45 wt%) and a citrate (3-18 wt%) in a ratio of 2.5:1-6:1, and is free from solid peroxyacid compounds and peroxybenzoic acid precursors.

Description

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DETERGENT COMPOSITIONS

TECHNICAL FIELD

The present invention relates to detergent compositions, especially particulate deterg0nt compositions, suitable ~or the laundering of fabrics in domestic or commercial w~shin~ machines. The compositions contain a specific combination o~
aluminosilicate and citrate builder salts.

BACKGROUND AND PRIOR ~RT
Detergent compositions for heavy-duty ~abric washing conventionally contain materials - detergency builders to lower the concentra~ion of calcium water hardness ions in the wash liquor and thuæ to give good detergency in hard water as well as in soft wat~r.

Alkali metal alumino~ilicate:ion-~xchangers, especially the crystalli~e sodium aluminosilicate zeolite 4A, are now well-known replac~men ~or the inorganic : . .. . . . .
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- 2 - ~3357 phosphates traditionally u~ed as detergency builders in fabric washing detergen~s. I~ is also well known ~hat zeolites show certain de*iciencies in detergency building, as compared with pho6phates, and that supplementary building power i5 generally desirable. In many zero-phosphate premium detergent powdsrs now on the European market, homo- or copolymers o~ acrylic acid are includ~d for this purpose.

It is also known to include citric acid and/or its salts in detergent compositions, but these compounds are well-known to be poor s~qu~strants of calcium ions and to contribute little to detergency building.

Detergent compositions built with crystalline aluminosilicate (zeolite) and also containing citrates are specifically disclosed in G~ 1 473 201 (Henkel), GB 1 429 143 (Procter & Gamble), GB 1 470 250 ~Procter &
Gamble), EP 1310A (Procter & Gamble), EP 1853A (Procter Gamble), EP 75 796B (Procter ~ Gamble~, GB 2 os5 ~74~
(Colgate-Palmolive), DE 2 336 182C (Lion), EP 234 867A
(Clorox), and also in our cop~nding European Patent Application No. 90 311 672.1 filed on 24 October 1930.
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Water-softening ox detergency building granules based on zeolites and citrates are disclosed in EP 243 908A (Henkel), DE 3 144 297A ~Degussa), EP 22 023A
(Union Carbide), and also in our cope~ding European Patent /
Application No. 90 309 051.2 filed on 17 August 1990 EP 313 143A (Unilever) discloses bleaching detergent compositions containing aluminosilicate (15-40 wt%), citric acid or alkali mekal citrate (1 15 wt%), and a ~olid organic peroxyacid (1-15 wt%). ~P 313 144A (Unilever~ describes and claims bleaching detergent compositions containing .. ....

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~ 3 C3367 aluminosilicate (15-40 wt%)/ citric acid or alkali metal citrate (1-15 wt~), an inorganic peroxy compound (5-35 wt%), and a peroxybenzoic acid bleach precursor (l-10 wt%). Both specifications claim improved cleaning and bleaching performance when a builder system based on æeolite and citrate i~ u~ed in conjunction with th~se specific bleach system The present inventor has now discovered that detergent compositions containi~g aluminosilicate and citrate together in particular amounts and particular proportions can give unexpectadly good detergency, better than that obtained in other amounts and proportions, in the absence of the specific bleach systems disclosed in EP 313 143A and EP 313 144A. Surprisingly, compositions of the invention can give detergency as good as that obtained from compositions built with aluminosilicate/acrylic polymer, despite the known inferiority of citrate to acrylic polymer as a binder of calcium ions.

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~ 4 ~ C3367 DEFINITION OF THE INVENTION

The present invention provides a detergent composition for fabric waE;hing, comprising:

(i) one or more detergent-active c ,,ouJ~ds ~elected from anionic, nonionic, cationic, amphoteric: and zwitterionic detergent-active compound~ and combinations thereof, (ii) a detergency builder system comprising:

(a) a crystalline or a~orphous alkali metal aluminosilicate in an amount of from 18 to 45 wt%
(anhydrous basis), (b) citric acid and/or a salt thereof, in an amount equivalent to from 3 to 18 wt~ of sodium citrate dihydrate, the weight ratio o~ (a) (anhydrous basis) ko (b) (as sodium citrate dihydrate ~quivalent) being within the range of from 2.5:1 to 6:1;

the composition being free from solid peroxyacid compounds and from peroxybenzoic acid precursors.

ThP invention also provides a method of wa6hing fabrics, which includes the step of bringing the fabrics into contact with an aqueous wa~h li~uor containing a detergent composition as defin~d in the previous paragraph.

The invention furth~r provides the use of (x) citric acid or a salt thereo~, in an amount equivalent to ~rom 3 to }8 wt% of sodium citrate dihydrate, a~ a detergency builder in a detergent composition for fabric washing comprising:

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- 5 ~ C3367 (i) one or more detergent-active compounds selected from anionic, nonionic, cationic, amphoteric and zwitterionic detergent-active comp~unds and combinations thereof, (ii) a detergency builder 6ystem comprising (y) a crystalline or amorphous alkali ~etal aluminosilicate, or mixture thereof, in an amount o~ from ~ to 45 wt%
(anhydrous basis), wherein the the weight ratio of (y) (anhydrous basis) to (x~ ~as sodium citrate dihydrate e~uivalent) is within the range o~ from 2.5:1 to 6:1;

the composition being ~ree ~rom solid peroxyacid compounds and from p~ro~ybenzoic acid precursor~.

DETAILED DESCRIPTION OF THE I~V~N'l'lON

The detergent composition of th~ invention contains, as essential component~, a detergent-active compound, and a detergency builder system.

The deter~ent-active com~ound The detergent compositions o~ the invention will contain, as essential ingredients, one or more detergent-active compounds (surfactants) which ~ay be chosen from soap and non-soap anionic, cationic, nonionic, ; amphoteric and zwitterionic detergent-active c~ ~ounds, and mixtures thereo~. Nany ~uitable detergent-active compounds are available and are fully des~rib~d in the literature, ~or exa~ple, in "Surface-Active Agent~ and Detergents", Volumes I and II, by Schwartz, Perry and Berch.
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The preferred deterg~nt-active compounds that can be used are soaps and synthetic non-soap anionic and nonionic compounds.

Anionic surfactant are well-known to those skilled in the art. Examples include alkyl~enzene sulphonat~s, particularly linear alkylbenzene sulphonates having an alkyl C8 C15; primary and secondary alkyl sulphates, particularly C12-ClS primary alkyl 6ulphates;
alkyl ether sulphates; olefin sulphonates; alkyl xylene sulphonates; dialkyl sulphosuccina~es; and fatty acid ester sulphonates. Sodium salts are generally preferred.

Nonionic surfactants that may be used include the primary and secondary alcohol ethoxylates, espeeially the aliphatic Cl~-C15 primary and secondary alcohols ethoxylated with an average of from 3 to 20 moles of ethylene oxide per mole of alcohol; and alkylpolyglycosides.

Preferred detergent-active system6, suitable ~or compositions intended ~or use in automatic fabric washing machines, comprises anionic non-soap surPactant, or nonionic surfactant, or combinations of the two in any ratio, optionally together with soap.
The total a~ount of detergent-active compounds present may suitably lie in the range o~ ~rom 5 to 40 wt%.

30 The detergency builder svstem In the co~positions o~ the invention, the d~tergency builder system comprise~, and preferably con~i~ts essentially of, two components (a) and (b). For 35 convenience, the component (a) will be rePerred to ~ hereinafter as the alu~inosilicate, and the component (b) `. ' . ' ~ : .

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~ 7 - C3367 will be referred to as ~he citrate. All percentag~s of th~
aluminosilicate will be based on the anhydrous material, and all percentages of the citrate will be based on sodium citrate dihydrate equiYalent.

The aluminosilicate (a) The alkali ~etal (preferably ~odium~ aluminosilicate builder may be crystalline or amorphous or a mixture thereof, and has the general formula 0.8-1.5 Na2O.Al2O3.0-8 6 Si2 These materials contain ~ome bound water and are required to have a calcium ion exchange capacity of at least about 50 mg CaO/g. The preferred aluminosilicates contain 1.5-3.5 SiO2 units (in the formula above) and have a particle size of not more than about ~00 ~m, preferably not more than about 20 ~m. Both amorphous and crystalline aluminosilicates can be made readily by reaction between sodium silicate and sodium aluminate, as amply described in ~he li~erature, Cry~talline aluminosilicates (zeolites) are prefer.rad for use in the present invention. Suitable materials are described, ~or ~xample, in GB 1 47~ 201 (Henkel) and GB 1 429 143 tProcter & Gamble). The preferred sodium aluminosilicates of this type are the well-known commercially availabl~ zeolites A and X, and mixtures thereofO

Zeolite A, more e~pecially Type 4A zeolite, i5 especially preferred for use in the present invention, as described in more detail below, 2~3~
- 8 - c3367 ~ lso especially preferred for use in ~he present invention is the novel Yeolite P (maximum aluminium zeolite P, hereinafter zeolite M~P) described and claimed in EP 3~4 070A (~nilever). Zeolite ~AP i~ defin2d as zeolite P having a silicon to aluminium ratio not ex~e~ing 1.33, preferably ~rom 0.9 to 1.33, more preferably ~rom o.s to 1.2. Preferred zeolite MAP has a ~ilicon to aluminium ratio not excee~i n~ 1.15 and has a tetragonally distorted cubic crystal structure. Especially preferr~d zeolite MAP
has a silicon to aluminium ratio not exc~eding 1.07.

Detergency builders and detergent compositions containing zeolite MAP an~ citrate are also the subject of our copending Applic2tion of even date (Case C3367/1) ~ ~' claiming the priority of British Patent Application No. 90 06171.4 filed on 19 March 1990.

Although zeolites contain water of hydration, as mentioned above, for the purposes of the pre~ent invention amounts and percentages of zeolites are expressed in terms of the anhydrous material.

The citrate The second essential builder compon~nt of the compositions of the invention is citric acid or a ~alt thereo~, preferably so~ium citrate. This salt normally exl~ts in the form of the dihydrate, and for the purposes of the present invention amounts and percentages of citrates are expressed in terms of 60dium citrate dihydrate.

It should be understood, however, that the u~e of other wholly and partially neutralised ci ric acid salts, and the free acid itself, in equivalent amount~, is also within the scope of the invention.

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~ 9 ~ C3367 Amounts and ratios Both the amounts and the proportions of the two builder components are important. It has been found that, to obtain detergency ~imilar to that of comparable compositions built with aluminosilicate and acrylic polymer, the aluminosilicate should b~ present in an amount of f.rom 18 to 45 wt~ and the citrate should be present in an amount of from 3 to 1~ wt%
Also importa~t is the proportion of aluminosilioate to citrate. The weight ratio of aluminosilicate to citrate should be within the range of from 2.5:1 to 6:1.

Preferred builder systems In a ~irst preferred embodiment sf the invention, the detergency builder system comprises from 18 to 30 wt%, preferably from 20 to 30 wt%, more preferably ~rom 22 to 28 wt% and most preferably from 24 to 28 wt%, of the alkali metal aluminosilicate; and from 3 to 18 wt~, preferably from 5 to 7 wt~, of the citrate. The alumino~ilicate is preferably zeolite A or zeolite MAP.
The total amount of aluminosilicate plus citrat~ is preferably from 22 to 36 wt%, pre~erably from 28 to 36 wt~.
The ratio of aluminosilicate to citratç is pxeferably from 3:1 to 6:1, more preferably from 4O1 to 5:1.
The first preferred embo~;rent of the invention is especially applicable to compositions containing a bleach system, as described belowO

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In a second preferred embodiment of the invention, the detergency ~uilder system comprises ~rom 35 to 45 wt%, preferably ~rom 37 to 42 wt%, of the alXali metal aluminosilicate and fro~ 9 to 18 wt%, pre~erably from 10 to 15 wt%, of the ci~ra~e. The alurinosilicate is pre~erably zeolite A.

The total amount of alumino~ilicate plus citrat2 is preferably from 50 to 60 wt%, and the ratio of aluminosilicate to ci~rate is preferably form 2.5:1 to 4.5:1.

The second preferred embodiment of the invention is esepcially applicable to compositions that do not contain a bleach system.

Other builder components The composition~ of the invention may be formulated without homo- or copolymers of acrylic acid, for example, polyacrylates or acrylicl~aleic copolymers. Preferr~d compositions are substantially free from such polymers, although compositions containing them are not excluded from the scope of th~ inventisn.

The amount of soluble silicates in the compositions of the invention is pre~erably kept to a relatively low leyel: preferably below 5 wt%, and mor~ preferably below 1 w~.

The co ,~ositions of the invention may advantag~ously contain alkali metal carbonate, to provide alkalinity rath~r than ~or det~rgency building. The amount o~
alkali metal, pre~erably odiu~, carbonate may ~uitably range ~rom 2 to 20 wt~, preferably ~ro~ 5 to ~5 wt%.

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~ C3367 Bleach system Detergent compositions according to the invention may als~ suitably contain a bl~ach sy~tem, proYided that peroxybenzoic acid bleach precursors and solid organic peroxyacids are absent.

The bleach system pre~erably comprises onP or more peroxy bleach compounds, for example, inorganic persalts, which may be employed in conjunction with precursors to improve bleaching action at low wash temperatures. More preferably the bleach system comprises an inorganic persalt optionally in conjunction with a precursor other than a peroxybenzoic acid precursor.
Preferred inorganic persalts are sodium perborate monohydrate and tetrahydrate, and sodium percarbonate.

Preferred bleach precursors are peracetic acid precursors, especially tetraacetylethylene diamine (TAED), and the novel quat~rnary ammonium and phosphonium bleach activators disclosed in US 4 751 015 and US 4 818 426 (Lever Brothers Company), more especially cholyl p-sulphophenyl carbonate (CSPC).
I desired, th~ bleach sy tem ~ay also include a bleach stabiliser (heavy metal sequestrant~.

Compositions cont~ ng a bleach syste~ are preferably in accordance with the ~irst pre~erred embodiment o~ the invention, as described above~

The benefits of the pre~ent invention are, however, also observed with bleach-~ree compositions, and those are preferably in accordance with the ~econd pref~rred ~ ho~ t of the inv~ntion de~cribed above.

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DicarboxYlic acid structurant The invention is especially, but not excl~sively, concerned with detergent compositions in particulate form.

Particulate composi~ions of the invention ~ay advantageously contain a dicarboxylic acid powder structurant. Suitable materials include uccinic acid, adipic acid, glutaric acid and mix~ures ~hereof. The acids may be employed in free acid or in salt (wholly or partially neutrali~ed) form. The dicarboxylic acid is suitably employed in an amount within the range of from 0.5 to 5 wt~.
A commercial mixture of adipic acid ( -Yi 33 wt%), glutaric acid ( ~ 50 wt%) and su~cinic acid ( ~ L 31 wt~ is available from BASF, Ludwig~ha~en, Germany under the trade mark Sokalan DCS, and a si~ilar mixture of sodium salts under the trade mark Sokalan DCN.

Particulate detergent composîtions containing succinates as powder structurants are described and claimed in EP 61 295B (Unilever).
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Other inqredients Other materials tha~ ~ay be present in detergent compositions of the invention include ~luorescers, antiredeposition agents, inorga~ic salts such as ~odium sulphate, enzymes, lather control ag~nt , ~abric softening agents, pigments, coloured peckles, and perf~mes~ ~his list is not in~e~e~ t~ be exhaustive.

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Preparation of the deterqent com~ositionC

Detergent compositions of the invention may be prepared by any suitable method. The particulate detergent compositions which are the preferred embodiment of the invention are suitably prepared by spray drying a slurry of compatible heat-insensitive ingredients, and then spraying on or postdosing those ingredien s unsuitable for processing via the slurry. The skilled detergent formulator will have no diffioulty in deciding which ingredients should be included in the slurry and which should not.

Both the alumlnosilicate and the citraté builder components are suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part of the aluminosilicate to be incorporated post-tower.

The particulate deteryen~ compositions of the invention may be prepared to any suitable bulk density.
Compositions having bulk densities of at least 400 g/l, more preferably at least 500 g/l, are o~ especial interest.

The invention is further illustrated by the following non-limiting Exampl~s, in which parts and percentages are by weight unless otherwise ~tated.

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2~33~ ~9 ~ 14 - C3367 EXAMPLES

Example l. Com~arative Exam~les A - D

Detergent powders co~taining a mixed anionic/~onionic detergent-active system, zeolite 4A, ~odium citrate and a TAED/sodium perborate bleach ~yste~ were prepared, by spray-drying and postdosing, in accordance with the following general formulation:

Linear alkylbenzene sulphonate 9.00 Nonionic surfactant (7E0) 1.00 Nonionic surfactant (3E0) 3.00 Zeolite 4A (anhydrous basis)28.00 Sodium citrate (2 aq basis3 0 - 12~50 (see below) T~ED granules 3.20 Sodium perborate tetrahydrate 17.00 Enzyme (Savinase 6.0T) 0.40 ~luorescer 0.11 25 Sodium carboxymethyl cellulose 0.54 ~ntifoam granuleQ 3.20 Sodium carbonate 11.60 Sodium silicate 0.70 30 Sodium sulphate, moisturebalance The fo~mulations of Example 1 and Comparakive Examples A, B and C contained zeolite/citrate builder systems as follows:

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Example A ~ 1 c Zeolite (a) ~0 2~.0 28.0 28.0 Citrate (b) O 4.0 8.0 12.5 Ratio (a),(b) 7 3.5 2.25 Total (a) + (b3 28.0 32.0 ~6.0 40.5 The deterg~ncy per~ormance of each ~ormulation was compared with that of the ~ollowing control formulation, Comparative Example D, containing zeolite and acrylic/maleic copolymer (Sokalan (Trade ~ark) CP5 ex BASF, Ludwigshafen, Germany):

Linear alkylbenzene sulphonate9.00 : 20 Nonionic surfactant (7EO) 1.00 Nonionic surfactant (3EO) 3.00 Zeolite 4A ~a~hydrous basis) 24.00 ~crylic/maleic copolymer 4.00 TAED granules 2.78 Sodium perborat~ tetrahydrate 15.80 Enzym~ (Savinase 6.0T~ o.40 Fluorescer 0.11 30 Sodium carbo~methyl cellulose 0.54 Antifoam granul2s 3.20 Sodium carbonate 11.60 Sodium silic~te 0~70 : 35 Sodium sulphate, moisture balance . ~ ................ .

~33 Detergencies were assessed by washing five different test cloths in a Siemens Siwamat (Trade ~ark) 660 front-loading automatic washing machine in 40 French hard water (Ca:Mg ratio 7:1) a~ 60C.

The test cloths u~ed were as follows:

(~) oil/silica/ink soil on cotton;
(2) oil/silica/ink soil on polyester/cotton;
(3) Indian ink~olive oil soil on polye6ter/cotton;
(4) proteinaceous (casein) soil on cotton;

(5) proteinaceous (casein) soil on polyester/cotton.

The results, expressed as reflectance differences at 460 nm (~R460) as compared with Comparative Example D, were as follow~:

Test cloth A B 1 C

20 (1) -1.9 0.7 ~1.4 -1.6 (2) -1.9 -0.6 +0.3 -0.5 (3) -4.4 ~1.6 +2.0 -0.1 (4) -0.7 -0.3 0.~ ~.6 (5) -0.7 -0.2 +0.4 ~0.1 These results clearly how the superiority of Example 1 over ths control Comparative Exampl~ D, while Comparative Examples A, B and C were inferior to the - control on all test ~loths.

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- 17 - c3367 Examles 2 and 3 Detergen~ powders containing a mixed anîonic/nonionic detergent-active system, zeolite ~A, 80dium citrate and a TAED/sodium perborate bleach ~ystem were prepared, by spray-drying and postdo~iny, in accordance with the following formulations:

Linear alkylb~nzene sulphonate9.00 9.00 Nonionic surfactant (7EO)1.001.00 Nonionic surfactant (3EO)3.003.00 Zeolite 4A (a~ydrous basis~ (a)28.00 24.00 Sodium citrate (2 aq basis) (b~6.00 6~00 TAED granules 3.20 3.20 20 Sodium perborate tetrahydrate17.00 17.00 Enzyme (Savinase 6.OT) 0.40 0.60 Fluorescer 0.1~ 0.11 Sodium carboxymethyl eellulose0054 0.54 Antifoam granules 3.20 3.20 Sodium carbonate 11.60 11.60 Sodium silicate 0.70 0.70 Sodium sulphate, moisturebalancebalance Ratio (a):(b) 4.67 4.00 To~al (a)~(b) 34.00 30.00 Bo h compositions showed good detergency comparable to that of Comparative Example D.

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~m~le 4 A detergent powder containing a mixed anionic/nonionic detergent-active sys~em, zeolite ~A, ~odium citrate and a TA~D/sodium perborate bleach system and having good detergency and good powder properties was prepared, by spray-dryin~ and postdosing, in accordance with the following formulation:

Linear alkylbenæene sulphonate6.00 Nonionic surfactant (7EO) ~.75 Nonionic surfactant (3EO) 4.25 Soap 1.65 Zeolite 4A (anhydrous basis) (a) 26.00 Sodium citrate (2 aq basis) (b) 6.00 Sokalan DCS (dicarboxylic acids) 1.00 20 Sodium hydroxide 0.67 . TAED granules 2.77 Sodium perborate monohydrate9.50 Enzyme (Savinase 6.OT) O.40 25 Fluorescer 0.20 : Sodium carboxymethyl cellulose0.50 Antifoam granules 1 ~ oo Sodium carbonate 8.40 30 Sodium silicate 0.46 Coloured speckles 0.50 Per~ume 0020 sQdium sulphate ~ moisturebalance 35 Ratio (a):(b) 4,33 Total (a)~(b~ 32~00 - . ' ' : . , ~ . . ~ . .

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19 - c3367 Examples 5 and 6. CQmparative Exam~les E to H

Bleach-fr e det~rgent powder~ containing a higher level of zeolite 4A were prepared, by spray-drying and postdosing, in accordance with the following general formulation:

lo Linear alkylbenzene sulphonate20. 00 Nonionic surfactant (7Eo) 5.00 Soap l.oo Zeolite 4A (anhydrous basis) 42000 15 Sodium citrate (2 aq basis)O - 20. on (see below) Enzyme (SaYinase 6.OT) o.50 Tylose 0.33 Sodium carboxymethyl cellulose 0.60 20 Antifoam granules l.oO
Sodium carbonate g.oo Sodium silicate 0.50 Sodium sulphate and moisture to balance Th~ for~ulations of Exa~ples 5 and 6 and Comparative Examples E to G contained zeolite/citrate builder syst~ms as ~ollows:

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ExamPle E F $ 6 Zeolite (a) 42.0 42.0 42.0 42.0 42.0 Citrate (b) 0 S.0 10.0 15.0 20.0 (a):(b) _ 8.4 4.2 208 2.2 (a) + (b~ 42.0 47.0 52.0 57.0 62.0 The detergency performance o~ each for~ulation was compared with that of a co~ ormulation, Comparative Example H, containing ~2~00 wt~ z~olite 4A and 2.00 wt%
acrylic/maleic copolymer (Sokalan (Trade Mark) CP5 ex BASF, Ludwigshafen, Germany3.

Detergency was measured in a tergotometer in 40 (French) hard water (Ca:Mg ratio 7:1) at 40C and a product dosaye of 3 g/l. C~tton test cloths with proteinaceous (casein) 80il wer~ washed together with a white ballast load. Th~ results, expressad as reflectanc~ differences at 460 nm (~R460) as compared with Comparative ~xample H, Were as follows:

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-1.6 -2.2 +0.4 +0.6 ~0.1 . . , , :: :, . ;. . -. . . . .

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Exa~ples 7 to 9 Detergent powder containing a mixed anionic/nonionic detergent-active system, zeolite HAP, sodium citrate and a S TAED/sodium perborate bleach system wsre prepared to the following formulations (in parts by weight~:

Linear alkylb~nzene sulphonate 7.0Q 7.00 Nonionic surfactant (7E0)3.00 3.00 Nonionic surfactant (3E0)~.00 6.00 Soap 1.50 1.50 Zeolite MAP (anhydrous basiæ) (a)26.00 24.00 Sodium citrate (2 aq basis) (b~ 5.40 5.40 Antifoam granules 2.00 2.00 Sodium carbonate 12.00 12~00 TAED granules 7.00 7.00 Sodium perborate monohydrate 15.00 15.00 Dequest 2047 0.75 0.75 Enzyme (Savinase 6.0~) 0~50 0.50 Fluorescer 0.20 0.20 Sodium carboxymethyl cellulose 0.50 0.50 Ratio (a):(b) 4.80 4.40 Total (a)~(b) (parts)31.40 29.40 .

Example 9 was identical to Example 7 except that the zeolite MAP wa~ replaced by 26.00 parts of zeolite 4A.

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The zeolite MAP was prepared on a pilot scale by the method described in Examples 1 to 3 of EP 384 070A
(Unilever). Its silicon to aluminium ratio was 1.10 and it had a tetragonally distorted cubic crystal structure.
Detergency was measured in a tergotometer in 26 (French) hard water (Ca:~g ratio 4:1) at 60C and ~ product dosage o~ 4 g/l. Test clgths as described below were washed together with a whi~e ballast load. The results, expressed 10 as reflectance differences at 460 nm (~R460), were as follows:

Test cloths (1) oil/silica/ink soil on cotton;

(3) Indian ink/olive oil soil on polyester/cotton;

(6) Indian ink/olive oil soil on cotton.

Test cloth 7 8 9 (1) 2~.6 25.623.6 (3) 16.~ 14.514.1 (6) 25~7 25.622.5 These results show that zeolite MAP/citrate compositions within the invention give even better results than zeolite 4A/citrate compositions.

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Claims

1 A detergent composition for fabric washing, comprising:

(i) one or more detergent-active compounds selected from anionic, nonionic, cationic, amphoteric and zwitterionic detergent-active compounds and combinations thereof, (ii) a detergency builder system comprising:

(a) a crystalline or amorphous alkali metal aluminosilicate, or mixture thereof, in an amount of from 18 to 45 wt% (anhydrous basis), (b) citric acid and/or a salt thereof, in an amount equivalent to from 3 to 18 wt% of sodium citrate dihydrate, the weight ratio of (a) (anhydrous basis) to (b) (as sodium citrate dihydrate equivalent) being within the range of from 2.5:1 to 6:1;

the composition being free from solid peroxyacid compounds and from peroxybenzoic acid precursors.

2 A detergent composition as claimed in claim 1, which contains from 18 to 30 wt% (anhydrous basis) of the aluminosilicate (a) and from 3 to 9 wt% of the citrate (b).

3 A detergent composition ad claimed in claim 2, wherein the aluminosilicate (a) is present in an amount within the range of from 20 to 30 wt% (anhydrous basis).

4 A detergent composition as claimed in claim 2, wherein the aluminosilicate (a) is present in an amount within the range of from 22 to 28 wt% (anhydrous basis).

A detergent composition as claimed in claim 2, wherein the aluminosilicate (a) is present in an amount within the range of from 24 to 28 wt%.

6 A detergent composition as claimed in claim 2, wherein the citrate (b) is present in an amount within the range of from 5 to 7 wt% (sodium citrate dihydrate basis).

7 A detergent composition as claimed in claim 2, wherein the weight ratio of (a) to (b) is within the range of from 3:1 to 6:1.

8 A detergent composition as claimed in claim 2, wherein the weight ratio of (a) to (b) is within the range of from 4:1 to 5:1.

9 A detergent composition as claimed in claim 2, wherein the total amount of (a) (anhydrous basis) plus (b) (as sodium citrate dihydrate equivalent) is within the range of form 22 to 36 wt%.

A detergent composition as claimed in claim 9, wherein the total amount of (a) (anhydrous basis) and (b) (sodium citrate dihydrate basis) is within the range of from 28 to 36 wt%.

11 A detergent composition as claimed in claim 2, wherein the aluminosilicate component (a) is zeolite A.

12 A detergent composition as claimed in claim 2, wherein the aluminosilicate component (a) is maximum aluminium zeolite P.

13 A detergent composition as claimed in claim 2, which comprises a bleach system comprising an inorganic persalt optionally in conjonction with a bleach precursor other than a peroxybenzoic acid precursor.

14 A detergent composition as claimed in claim 13, wherein the persalt comprises sodium perborate tetrahydrate, sodium perborate monohydrate, or sodium percarbonate.

A detergent composition as claimed in claim 13, wherein the bleach system comprises a bleach precursor selected from peracetic acid percursors and cationic bleach percursors.

16 A detergent composition as claimed in claim 13, wherein the bleach system comprises a bleach precursor selected from tetraacetylathylenediamine and cholyl p-sulphophenyl carbonate.

17 A detergent composition as claimed in claim 1, which, contains from 35 to 45 wt% (anhydrous basis) of the aluminosilicate component (a) and from 9 to 18 wt% of the citrate (b).

18 A detergent composition as claimed in claim 17, wherein the aluminosilicate component (a) is present in an amount within the range of from 37 to 42 wt% (anhydrous basis).

19 A detergent composition as claimed in claim 17, wherein the citrate (b) is present in an amount of from 10 to 15 wt%
(sodium citrate dihydrate basis).

A detergent composition as claimed in claim 17, wherein the weight ratio of (a) to (b) is within the range of from 2.5:1 to 4.5:1.

21 A detergent composition as claimed in claim 17, wherein the total amount of (a) (anhydrous basis) and (b) (sodium citrate dihydrate basis) is within the range of from 50 to 60 wt%.

22 A detergent composition as claimed in claim 17, wherein the aluminosilicate (a) is zeolite A.

23 A detergent composition as claimed in claim 17, which does not contain a bleach system.

24 A detergent composition as claimed in claim 1, which is substantially free of homo- or copolymers of acrylic acid.

A detergent composition as claimed in claim 1, which comprises a dicarboxylic acid structurant selected from succinic acid, adipic acid, glutaric acid, and mixtures thereof, in free acid or salt form.

26 A detergent composition as claimed in claim 25, wherein the dicarboxylic acid structurant is present in an amount of from 0.5 to 5 wt%.

27 A detergent composition as claimed in claim 1, which is in particulate form.

28 A method of washing fabrics, which includes the step of bringing the fabrics into contact with an aqueous wash liquor containing a detergent composition as claimed in claim 1.

* * *

29 A detergent composition as claimed in claim 1 and substantially as described herein.