WO1997012953A1

WO1997012953A1 - Detergent composition containing particulate zeolite builder and lubricant therefor

Info

Publication number: WO1997012953A1
Application number: PCT/US1996/014858
Authority: WO
Inventors: Jonathan Richard Clare
Original assignee: The Procter & Gamble Company
Priority date: 1995-09-30
Filing date: 1996-09-13
Publication date: 1997-04-10
Also published as: GB9520024D0; BR9610730A; EP0964907A4; CA2233594A1; EP0964907A1

Abstract

A detergent composition is provided which contains a zeolite builder having a particle size, d50, of less than 1.0 micrometres; and an agent capable of acting as a lubricant for the particulate zeolite builder thereby reducing any abrasive contact of the builder with fabrics when employed in a method of washing laundry.

Description

DETERGENT COMPOSITION CONTAINING PARTICULATE ZEOLITE BUILDER AND LUBRICANT THEREFOR.

The present invention relates to a detergent composition comprising both a particulate zeolite component having a small particle size as a sequestering agent for water hardness and an agent capable of reducing the abrasive contact of said particulate zeolite with laundry fabrics, when employed in a laundry washing method.

Detergent compositions for fabric washing conventionally contain detergency builders which lower the concentration of calcium and magnesium water hardness ions in the wash liquor and thereby provide good detergency effect in both hard and soft water.

Conventionally, inorganic phosphates, such as sodium tripolyphosphate, have been used as builders for laundry detergents. More recently, alkali metal aluminosilicate ion-exchangers, particularly crystalline sodium aluminosilicate zeolite A, have been proposed as replacements for the inorganic phosphates.

For example, EP 21 491 A (Procter & Gamble) discloses detergent compositions containing a building system which includes zeolite A, X or P (B) or a mixture thereof. EP 384070 A (Unilever) discloses specific zeolite P materials having an especially low silicon to aluminium ratio not greater than 1.33 (hereinafter referred to as zeolite MAP) and describes its use as a detergency builder, optionally with cobuilders.

The Applicants have now surprisingly found that a problem may occur when a water insoluble zeolite having a small particle size, is used as a detergency builder. The problem has been found to be particularly pronounced when the zeolite builder is zeolite MAP.

The choice of a small particle size for a zeolite MAP component, that is to say particles having a particle size, measured as a d50 value, of up to 1.0 micrometres has previously been taught to be preferred in the art, as represented, for example, by EP 384070 A. The small particle size can enhance the capacity of the builder to absorb liquid components, which can be advantageous in the preparation of high active zeolite agglomerate particles containing liquid detergent components.

The problem relates to the aforementioned detergent compositions having a marked incompatibility with printed fabrics, particularly printed cotton fabrics. In particular, it has been found that the use of detergent compositions containing small particle size zeolite tends to lead to the removal of printed pigment from a printed fabric surface.

The Applicant has surprisingly found that this problem can be ameliorated by the use in the detergent composition of a lubricating agent which is capable of forming a partial or complete lubricant coating on the zeolite particles, thereby reducing their abrasive affect on the surface of the printed cotton fabrics which they come into contact with as the wash proceeds.

The present invention is thus based on the unexpected finding that the printed fabric care profile of a detergent composition comprising an insoluble zeolite of small particle size and a 'small particle zeolite lubricating agent' is superior to that of comparable compositions not containing the zeolite lubricating agent.

This finding allows the formulation of detergent compositions providing both excellent cleaning and printed fabric care properties on fabrics, especially cotton fabrics.

Whilst the prior art, as represented for example by European Patent Aplications, EP 384070 A, EP 448297 A, EP 522726 A, EP 533392 A, EP 544492 A, EP 552053 A, and EP 552054 A has envisaged the use of various detergent components in combination with zeolite in laundry detergent compositions, none of these prior art documents specifically disclose the use of a lubricating agent with a small particle size zeolite component. Furthermore, none of these prior art documents provides any teaching relating to the small particle size zeolite specific printed fabric care problem addressed by the current invention, nor of any solution thereto involving the use of a zeolite particle lubricating agent.

Thus, the present invention provides a detergent composition suitable for use in a method of washing soiled fabrics containing

(a) a surfactant selected from anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds and mixtiures thereof;

(b) a particulate zeolite builder having a particle size, d50, of less than 1.0 micrometres; and

(c) an agent capable of acting as a lubricant for the particulate zeolite builder thereby reducing any abrasive contact ofthe zeolite builder with said fabrics when employed in said method of washing.

In a preferrred embodiment of the invention the zeolite builder comprises zeolite P having a silcon to aluminium ratio of not greater than 1.33 (zeolite MAP).

In a further preferred embodiment the detergent composition according to the invention is formulated to be especially useful in the laundering of coloured fabrics and preferably is free of bleach. According to another aspect of the invention, the composition is substantially free of an optical brightener.

According to another aspect ofthe present invention there is provided the use of a detergent composition containing a particulate zeolite builder having a particle size, d5Q, of less than 1.0 micrometres in a method of washing printed fabrics, particularly printed cotton fabrics, wherein said composition contains an agent capable of acting as a lubricant for said particulate zeolite builder thereby reducing the abrasive contact ofthe zeolite builder with said printed fabrics.

Surfactant

The detergent composition according to the invention contains as an essential component a surfactant selected from anionics, nonionics, zwitterionics, ampholytics and cationics.

The surfactant is preferably present in the detergent compositions at a level of from 1% to 50%, preferably from 3% to 30%, most preferably from 5% to 20% by weight ofthe compositions.

Many suitable detergent-active compounds are available and fully described in the literature (for example "Surface Active Agents and Detergents" Volumes I and II by Schwartz, Perry and Berch).

Examples of suitable additional anionic surfactants include anionic sulfates, olefin sulphonates, alkyl xylene sulphonates, dialkylsulphosuccinates, and fatty acid ester sulphonates. Sodium salts are generally preferred.

Anionic sulfate surfactant

Anionic sulfate surfactants suitable for use herein include the linear and branched primary alkyl sulfates, alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, the C5-C17 acyl-N- (C1-C4 alkyl) and -N-(Cι-C2 hydroxyalkyi) glucamine sulfates, and sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described herein).

Alkyl ethoxysulfate surfactants are preferably selected from the group consisting ofthe C6-C18 alkyl sulfates which have been ethoxylated with from 0.5 to 20 moles of ethylene oxide per molecule. More preferably, the alkyl ethoxysulfate surfactant is a C6-C18 alkyl sulfate which has been ethoxylated with from 0.5 to 20, preferably from 0.5 to 5, moles of ethylene oxide per molecule.

Anionic sulfonate surfactant

Anionic sulfonate surfactants suitable for use herein include the salts of C5-C20 linear alkylbenzene sulfonates, alkyl ester sulfonates, C6-C22 primary or secondary alkane sulfonates, C6-C24 olefin sulfonates, sulfonated polycarboxylic acids, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof.

Nonionic surfactant

The nonionic surfactant is preferably a hydrophobic nonionic surfactant, particularly an alkoxylated nonionic surfactant, having a hydrophilic lipophilic balance (hlb) value of < 9.5, more preferably < 10.5.

Examples of suitable hydrophobic alkoxylated nonionic surfactants include alkoxylated adducts of fatty alcohols containing an average of less than 5 alkylene oxide groups per molecule.

The alkylene oxide residues may, for example, be ethylene oxide residues or mixtures thereof with propylene oxide residues.

Preferred alkylene oxide adducts of fatty alcohols useful in the present invention can suitably be chosen from those ofthe general formula:

R-0-(C_nH₂nO)yH

wherein R is an alkyl or alkenyl group having at least 10 carbon atoms, most preferably from 10 to 22 carbon atoms, y is from 0.5 to 3.5 and n is 2 or 3.

Preferred nonionic surfactants include primary Cj 1-C15 aliphatic alcohols condensed with an average of no more than five ethylene oxide groups per mole of alcohol, having an ethylene oxide content of less than 50% by weight, preferably from 25% to less than 50% by weight.

A particularly preferred aliphatic alcohol ethoxylated is a primary alcohol having an average of 12 to 15 carbon atoms in the alkyl chain condensed with an average of three ethoxy groups per mole of alcohol.

Specific examples of suitable alkoxylated adducts of fatty alcohols are Synperonic A3 (ex ICI), which is a C13-C15 alcohol with about three ethylene oxide groups per molecule and Empilan KB3 (ex Marchon), which is lauric alcohol 3EO.

Another class of nonionic sufactants comprises alkyl polygiucoside compounds of general formula

RO(C_nH_2nO)tZ_x

wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent compositions are disclosed in EP-B 0070074, 0070077, 0075996 and 00941 18.

Zeolite builder

The second essential component ofthe detergent compositions ofthe present invention is an aluminosilicate zeolite builder, optionally in conjunction with one or more cobuilders. Such aluminosilicate zeolite builders are generally water-insoluble.

The zeolite builder is typically present at a level of from 1% to 80%, more preferably from 15% to 40% by weight ofthe compositions.

Suitable aluminosilicate zeolites have the unit cell formula Na_z[(Alθ2)_z(Siθ2)y]. XH2O wherein z and y are at least 6; the molar ratio of z to y is from 1.2 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilicate material are in hydrated form and are preferably crystalline, containing from 10% to 28%, more preferably from 18% to 22% water in bound form.

The aluminosilicate zeolites can be naturally occurring materials, but are preferably synthetically derived. Synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite MAP, Zeolite HS and mixtures thereof.

Zeolite A has the formula

Na ₁₂ [A10₂) 12 (Si0₂)l2]. XH2O

wherein x is from 20 to 30, especially 27. Zeolite X has the formula Na86 [(AlO₂)86(SiO₂)i06]. 276 H₂0.

Zeolite MAP is described in EP 384070A (Unilever). It is defined as an alkali metal alumino-silicate ofthe zeolite P type having a silicon to aluminium ratio not greater than 1.33, preferably within the range from 0.9 to 1.33 and more preferably within the range of from 0.9 to 1.2.

Of particular interest is zeolite MAP having a silicon to aluminium ratio not greater than 1.15 and, more particularly, not greater than 1.07.

Zeolite P having a Si.Al ratio of 1.33 or less may be prepared by the O 97/12953 PC17US96/14858

following steps:

(i) mixing together a sodium aluminate having a mole ratio Na2θ:Al2U3 within the range of from 1.4 to 2.0 and a sodium silicate having a mole ratio Siθ2:Na2θ within the range of from 0.8 to 3.4 with vigorous stirring at a temperature within the range of from 25 °C to boiling point usually 95°C, to give a gel having the following composition; AI2O3: (1.75-3.5) SiC>2 : (2.3-7.5) Na2θ :P (80-450)H2θ;

(ii) ageing the gel composition for 0.5 to 10 hours, preferably 2 to 5 hours, at a temperature within the range of from 70°C to boiling point, usually to 95°C, with sufficient stirring to maintain any solids present in suspension;

(iii) separating the crystalline sodium aluminosilicate thus formed, washing to a pH within the range of from 10 to 12.5, and drying, preferably at a temperature not exceeding 150°C, to a moisture content of not less than 5 wt.%.

Preferred drying methods are spray-drying and flash-drying. It appears that oven drying at too high a temperature may adversely affect the calcium binding capacity ofthe product under certain circumstances.

Commercial sodium metasilicate pentahydrate dissolved in water and commercial sodium silicate solution (waterglass) are both suitable silica sources for the production of zeolite P in accordance with the invention. The reactants may be added together in any order either rapidly or slowly. Rapid addition at ambient temperature, and slow addition at elevated temperature (90-95°C) both give the desired product. Vigorous stirring ofthe gel during the addition ofthe reactants, and at least moderate stirring during the subsequent ageing step, however, appear to be essential for the formation of pure zeolite P. In the absence of stirring, various mixtures of crystalline and amoφhous materials may be obtained.

Zeolite MAP generally has a calcium binding capacity of at least 150 mg CaO per g of anhydrous aluminosilcate, as measured by the standard method described in GB 1473201 (Henkel). The calcium binding capacity is normally 160 mg CaO/g and may be as high 170 mg CaO/g.

Although zeolite MAP like other zeolites contains water of hydration, for the purposes ofthe present invention amounts and percentages of zeolite are expressed in terms ofthe notional anhydrous material.

The amount of water present in hydrated zeolite MAP at ambient temperature and humidity is generally about 20 wt.%.

The zeolite builder used in the present invention has a particle size d5o of less than 1.0 micrometres, preferably from 0.05 to 0.9 micrometres, most preferably from 0.2 to 0.7 micrometres. The d50 value indicates that 50% by weight of the particles have a diameter smaller than that figure. The particle size may be determined by conventional analytical techniques such as, for example, microscopic determination utilizing a scanning electron microscope or by means of a laser granulometer.

Zeolite builder having the required particle size according to the present invention can be prepared by the conventional techniques as described above while adopting one or more ofthe following steps:-

a) decreasing crystallisation time;

b) decreasing the size ofthe seed crystals used to produce the zeolite;

c) screening the zeolite product to remove coarse material. An article by D. Vucelic, published in Progr Colloid Polymer Science, 1994, Volume 95, pages 14 - 38 describes methods for the synthesis of zeolite particles, and in particular how to influence the particle size characteristics of the zeolites by modification of the synthesis process steps.

Lubricant

The detergent compositions contain as an essential component an agent capable 'in use' of acting as a lubricant for the zeolite particles, thereby reducing the abrasive effect associated with the contact ofthe particles with any fabrics, particularly printed cotton fabrics, in the wash. The agent therefore acts such as to reduce the frictional forces which can arise when the zeolite particles contact any fabric in the wash. One mechanism for such reduction of abrasive frictional contact is for the lubricant 'in use' to partially or completely coat the zeolite particles.

The lubricant should moreover not significantly compromise the ability ofthe zeolite to provide builder capacity to a wash solution, and is most preferably water soluble. Biodegradable lubricants are preferred.

The zeolite particle lubricant is preferably present at a level of from 0.05% to 50%, more preferably from 1% to 20% by weight ofthe detergent composition.

Preferably, the level of incorporation ofthe lubricant will be selected to be such as to reduce the level of abrasive contact to an acceptable level. A low lubricant to zeolite ratio is preferred from a cost standpoint. In particular, the weight ratio of lubricant to zeolite should be less than 1 :3, preferably less than 1 :5, more preferably less than 1 :7. Suitable zeolite lubricants are preferably polymers which are nonionic in character, particularly those containing a plurality of glycol components. In particular, fatty alcohol poly(ethylene glycol) ethers of molecular weights of from 400 to 5000 are suitable herein. WO 93/16159 describes particularly suitable fatty alcohol poly (ethylene glycol) ethers which contain from 4 to 7 glycol units. DE 4124247 A similarly describes suitable fatty alcohol poly (ethylene glycol) ethers. DE 3401861 A describes suitable alkylphenol polyglycol ethers. DE 344431 1 A describes suitable isotridecyl polyglycol ethers.

Particulate zeolite colubricants which are based on alcohol ethoxylates, especially those having at least a proportion of branched carbon chains, are also suitable herein, particularly when present in combination with the hereinbefore described glycol containing lubricants. The degree of carbon chain branching is preferably at least 10% by weight, more preferably at least 20% by weight. US 5298185 A describes suitable oxo alcohol ethoxylates and their use in detergent compositions in combination with polyethylene glycols.

Additional detergent components

The detergent composition according to the invention may contain other detergent components such as cobuilders, bleaches, fluorescers, antiredeposition agents, inorganic salts such as sodium sulphate, other enzymes, lather control agents, fabric softening agents, pigments, coloured speckles and perfumes.

Cobuilder

In addition to zeolite, the detergent compositions may contain an organic or inorganic cobuilder.

Suitable organic cobuilders can be monomeric or polymeric carboxylates such as citrates or polymers of acrylic, methacrylic and/or maleic acids in neutralised form. Suitable inorganic cobuilders include carbonates and amorphous and crystalline layered silicates.

Suitable crystalline layered silicates have the composition:

NaMSi_xθ2χ+l . _yH2θ

where M is sodium or hydrogen, preferably sodium; x is a number from 1.9 to 4; and y is a number from 0 to 20. Such materials are described in US Patents No. 4664839; No. 4728443 and No. 4820439 (Hoechst AG). Especially preferred are compounds in which x = 2 and y = O. The synthetic material is commercially available from Hoechst AG as δ -Na2 Si2θ5 (SKS6) and is described in US Patent No. 4664830.

The total amount of detergency builder in the granular composition typically ranges from 10 to 80 wt.%, more preferably from 15 to 60 wt% and most preferably from 10 to 45 wt.%.

In a highly preferred aspect the level of carbonate builder, that is of inorganic compound capable of releasing carbonate ions into a wash solution, is less than 7% by weight, preferably less than 4% by weight of the detergent composition. High levels of carbonate have been found to further exacerbate the printed cotton fabric abrasion problem. Most preferably the detergent composition is free from carbonate builder.

Bleach

Detergent compositions according to the invention may also contain a bleach system. Where present, this preferably comprises one or more peroxy bleach compounds, for example, inorganic persalts or organic peroxyacids, which may be employed in conjunction with bleach precursors to improve bleaching action at low temperatures.

The bleach system preferably comprises a peroxy bleach compound, preferably an inorganic persalt, optionally in conjunction with a peroxyacid bleach precursor. Suitable persalts include sodium perborate monohydrate and tetrahydrate and sodium percarbonate, with sodium percarbonate being most preferred.

Preferred bleach precursors are peracetic acid precursors, such as tetraacetylethylene diamine (TAED); peroxybenzoic acid precursors.

In one preferred aspect, the detergent compositions are free of bleach and of particular utility in the washing of loads containing brightly coloured fabrics.

Low pH/alkalinitv detergent compositions

Preferred detergent compositions according to the invention are characterised by having a pH measured as a 1% solution of the detergent composition in distilled water at 25°C of < 10.5, preferably < 10.4, most preferably < 10.3.

It has been found that compositions having a low level of reserve alkalinity are advantageous in that they have a further reduced tendency to cause the removal of printed pigment from printed cotton fabrics. Reserve alkalinity is expressed as g of NaOH per 100 g of composition as determined by acid titration of a sample, as 1% solution in distilled water to a pH of 9.5. Preferred values of reserve alkalinity are < 8.0 g preferably < 5.0 g, most preferably < 3.0 g NaOH per lOOg of composition.

Physical form

The detergent composition according to the invention may be of any physical type, for example powders, liquids and gels. However, granular and liquid compositions are preferred.

Making process

The detergent compositions ofthe invention may be prepared by any suitable method. The particulate detergent compositions are suitably prepared by any tower (spray-drying) or non-tower process.

In processes based around a spray-drying tower, a base powder is first prepared by spray-drying a slurry and then other components unsuitable for processing via the slurry can be sprayed on or admixed (postdosed).

The zeolite builder is suitable for inclusion in the slurry, although it may be advantageous for processing reasons for part ofthe zeolite builder to be incorporated post-tower. The crystalline layered silicate, where this is employed, is also incorporated via a non-tower process and is preferably postdosed.

Alternatively, particulate detergent compositions in accordance with the invention may be prepared by wholly non-tower processes such as granulation.

The granular detergent compositions ofthe invention may be prepared to any suitable bulk density. The compositions preferably have a bulk density of at least 400 g/l preferably at least 550 g/l, most preferably at least 700 g/l and, with particular preference at least 800 g l-

The benefits ofthe present invention are particularly evident in powders of high bulk density, for example, of 700 g/l or above. Such powders may be prepared either by post-tower densification of spray- dried powder, or by wholly non-tower methods such as dry mixing and granulation; in both cases a high-speed mixer/granulator may advantageously be used. Processes using high-speed mixer/granulators are disclosed, for example, in EP340 013 A, EP 367 339A, EP 390 251 A and EP 420 317A (Unilever).

The detergent composition ofthe invention may be formulated as a liquid detergent composition which may be aqueous or anhydrous. The term "liquid" used herein includes pasty viscous formulations such as gels. The liquid detergent composition generally has a pH of from 6.5 to 10.5.

The total amount of detergency builder in the liquid composition is preferably from 5 to 70% ofthe total liquid composition.

Illustrative compositions according to the present invention are presented in the following Examples. In the detergent compositions, the abbreviated component identifications have the following meanings:

24AS : Sodium alkyl sulfate surfactant containing predominantly C \ 2 and C 14 alkyl chains

TAS Sodium alkyl sulfate surfactant containing predominantly C 16 - Cj 8 alkyl chains derived from tallow oil.

24AE3S C12-C14 alkyl ethoxysulfate containing an average of three ethoxy groups per mole

35E3 A C i3_i 5 alcohol having 10% alkyl chain branching condensed with an average of 3 moles of ethylene oxide

25E3 A C12-C15 alcohol having 30% alkyl chain branching condensed with an average of 3 moles of ethylene oxide

PEG 1 A C 12-C 15 primary fatty alcohol condensed with an average of 5 moles of ethylene glycol

PEG 2 A C12-C15 alkylphenol condensed with an average of 5 moles of ethylene glycol

Carbonate Anhydrous sodium carbonate

Perborate Sodium perborate tetrahydrate

Percarbonate Sodium percarbonate

TAED Tetra acetyl ethylene diamine

Silicate Amorphous Sodium Silicate (Siθ2:Na2θ ratio normally follows)

SKS6 Crystalline layered silicate available from Hoechst AG as SKS6 (tradename) Zeolite MAP Hydrated sodium aluminosilicate zeolite MAP having a silicon to aluminium ratio of 1.07 having a particle size, expressed as a d5Q value, of 0.7 micrometres

Zeolite A Hydrated sodium aluminosilicate zeolite A having a particle size, expressed as a d5o value, of 0.6 micrometres

MA/AA Copolymer of 1 :4 maleic/acryiic acid, average molecular weight about 80,000.

Alcalase Proteolytic enzyme sold under the tradename Alcalase by Novo Industries A S (approx 1 % enzyme activity by weight)

BSA Amylolytic enzyme sold under the tradename LEI 7 by Novo Industries A/S (approx 1% enzyme activity)

Example 1

The following granular laundry detergent compositions were prepared (parts by weight) in accordance with the invention.

A B C D E

24AS 7.6 6.5 4.8 6.8 -

TAS - - - - 8.6

24AE3S 2.4 - 1.2 1.7 -

25E3 3.26 - - - 6.3

35E3 - 5.0 5.0 5.0 -

Zeolite MAP 20.0 25.0 25.0 - 16.0

Zeolite A - - - 25.0 15.0

PEG 1 2.0 - 3.0 - 2.0

PEG 2 - 3.0 - 2.0 1.0

SKS6 7.0 5.0 10.0 - -

Carbonate 5.0 3.0 - - -

MA/AA 4.25 4.25 4.25 4.25 2.0

Perborate - 16.0 - 16.0 20.0

Percarbonate 20.0 - 20.0 - -

TAED 5.0 5.0 5.0 5.0 6.7

Alcalase 0.2 0.5 0.3 0.2 0.1

BSA - - 0.1 - -

Protease 0.04 0.08 - 0.05 0.05

Silicate (2.0 4.0 - - 4.0 3.0 ratio)

Water and miscellaneous (Including suds suppressor, sodium sulphate, perfume) to balance

The detergent compositions A to E according to the invention, which comprise a zeolite particle lubricant (i.e. PEG 1 or PEG 2), show good results in stain removal and lower printed cotton fabric damage as compared with a composition comprising no zeolite particle lubricant.

Claims

CLAIMS:

1. A detergent composition suitable for use in a method of washing soiled fabrics containing

(a) a surfactant selected from anionic, cationic, nonionic, amphoteric and zwitterionic detergent active compounds and mixtures thereof;

(b) a particulate zeolite builder having a particle size, d5o, of less than 1.0 micrometers; and

2. A detergent composition according to claim 1, wherein the zeolite builder has a particle size ά$Q of from 0.05 to 0.9 micrometres.

3. A detergent composition according to either of claims 1 or 2, wherein the zeolite builder comprises zeolite P having a silicone to aluminium ratio of not greater than 1.33 (zeolite MAP).

4. A detergent composition according to claim 3, wherein the zeolite MAP has a silicon to aluminium ratio not greater than 1.15.

5. A detergent composition according to any one of claims 1 to 4, which comprises from 1 to 80% by weight ofthe zeolite builder.

6. A detergent composition according to any of claims 1 to 5, which comprises lubricant at a weight ratio of lubricant to zeolite builder of less than 1 :3.

7. A detergent composition according to any of claims 1 to 6, wherein the lubricant is a nonionic polymeric compound containing a plurality of glycol components.

8. A detergent composition according to any of claim 7, wherein the lubricant comprises a fatty alcohol poly(ethylene glycol) ether having a molecular weight of from 400 to 5000.

9. A detergent composition according to claim 8 wherein the composition comprises a fatty alcohol ethoxylate as a colubricant.

10. A detergent composition according to claim 9, wherein the fatty alcohol ethoxylate has a degree of carbon chain branching of at least 10% by weight.

1 1. The use of a detergent composition containing a particulate zeolite builder having a particle size, d5o, of less than 1.0 micrometres in a method of washing printed fabrics, particularly printed cotton fabrics, wherein said composition contains an agent capable of acting as a lubricant for said particulate zeolite builder thereby reducing the abrasive contact ofthe zeolite builder with said printed fabrics.