AU672747B2 - Detergent compositions - Google Patents

Description

-~xf bnl- 1 i: OPI DATE 30/12/92 AOJP DATE 11/02/93 APPLN. ID 17610/92 IIHHl iii PCT NUMBER PCT/GB92/00943 111111111111111111111111111 i i 11 AU9217610 INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 5 (1I) International Publication Number: WO 92/20772 CUD 17/00, 1/75 Al (43) International Publication Date: 26 November 1992 (26.11.92) (21) International Application Number: PCT/GB92/00943 (81) Designated States: AT, AT (European patelt), AU, BB, BE (European patent), BF (OAPI patent), BG, BJ (OAPI (22) International Filing Date: 22 May 1992 (22.05.92) patent), BR, CA, CF (OAPI patent), CG (OAPI patent), CH, CH (European patent), CI (OAPI patent), CM Priority data: (OAPI patent), CS, DE, DE (European patent), DK, 9111219.3 24 May 1991 (24.05.91) GB DK (European patent), ES, ES (Europeain patent), FI, 9202884.4 12 February 1992 (12.02.92) GB FR (European patent), GA (OAPI patent), GB, GB (European patent), GN (OAPI patent), GR (European pa- (71) Applicant (for all designated States except US): IMPERIAL tent), HU, IT (European patent), JP, KP, KR, LK, LU, CHEMICAL INDUSTRIES PLC [GB/GB]; Imperial LU (European patent), MC (European patent), MG, ML Chemical House, Millbank, London SWIP 3JF (OAPI patent), MN, MR (OAPI patent), MW, NL, NL (European patent), NO, PL, RO, RU, SD, SE, SE (Euro- (72) Inventor; and pean patent), SN (OAPI patent), TD (OAPI patent), TG Inventor/Applicant Cfor US only): HEPWORTH, Paul [GB/ (OAPI patent), US.

GB]; 13 Bankside Close, Upper Poppleton, York YO2 6LH Published With international search report.

(74) Agents: LOCKE, Timothy, John et al.; ICI Group Patents Services Department, P.O. Box 6, Shire Park, Bessemer Road, Welwyn Garden City, Hertfordshire AL7 IHD

(GB).

672 74 7 (54) Title: DETERGENT COMPOSITIONS (57) Abstract Liquid detergent compositions containing amine oxides, solid builders and otpionally bleaches and specified water levels are highly stable. Compositions containing an amine oxide, a builder and a polyalkylene glycol confer easy-iron properties on fabrics.

ii WO 92/20772 PC/GB92/00943 DETERGENT COMPOSITIONS THIS INVENTION relates to detergent compositions.

Detergent compositions are known which comprise a suspension of a builder in an organic liquid which comprises a surfactant.

Non-aqueous compositions of this type of good stability are described in European Patents Nos 30096 and 120,659.

It is however difficult to exclude water completely from detergents, and it is desirable that their water-sensitivity should be reduced.

It is believed that a reduction in water sensitivity may aid the dispensibility of such materials ie they may make them easier to introduce into a wash liquid.

Detergent compositions may be introduced into a washing machine by placing them in a unit through which water is passed to carry the detergent with the water into a washing zone.

Compositions of low dispensibility may produce solid deposits which remain in the unit. In some cases detergents are placed in containers which are introduced into the washing zone. If the container has restricted access solid deposits may be left in it especially if it was not dry when the detergent was placed in it.

It is believed that dispensibility is improved, especially in the latter case, if the water sensitivity of the composition is reduced.

Surprisingly we have found that small quantities of water can be tolerated in such compositions providing that an amine oxide is present. In general the quantity of water should be at most 5 preferably less than 3 and more preferably less than 2 moles per mole for example 0.5 to 1.9 moles of amine oxide and is preferably 1.0 to 1.7 moles of water per mole of amine oxide. By water is meant water which is n;t aIcluded as water of !i crystallisation of solids, which is irrelevant in this context.

Whilst anhydrous amine oxides are known, in general they are available commercially as aqueous solutions which may contain for example 65% by weight of water. Clearly such solutions are unsuitable for the present purpose and according to one form of this invention means are provided by which they may be converted into a composition useful for inclusion .n liquid laundry detergent compositions'.

SUBSTITUTE SHEET

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WO 92/20772 PCrIGB92/00943 This invention comprises a liquid detergent composition which comprises: i) a liquid organic phase which comprises an amine oxide; ii) a solid builder; iii) at most 5 and preferably less than 2 for example 0.5 to less than 2 and preferably 1.0 to 1.7 moles of water (other than water of crystallisation of any solid present) per mole of amine oxide.

The builder may suitably be water soluble and if desired a bleach may be present.

The invention also comprises a composition suitable for inclusion in a liquid detergent which comprises: i an amine oxide; ii a polyalkylene glycol, which preferably comprises ethylene glycol residues and optionally propylene glycol residues and more preferably polyethylene glycol; and iii at most 5 and preferably less than 2 moles, for Ecample to less than 2 moles and preferably 1 to 1.7 moles of water per mole of the amine oxide.

This composition enables liquid laundry detergents of good stability and easy-iron properties to be produced by the addition of a suitable builder. The weight ratio of polyalkylene glycol to amine oxide is suitably 0.5 to 1 to 2:1.

This composition may be produced by distilling an aqueous solution of an amine oxide in the presence of the polyalkylene glycol, preferably polyethylene glycol, preferably under reduced pressure at a temperature of 40 to 80 0 C and preferably 65 to 75 0

C.

We have surprisingly found that the presence of the polyalkylene glycol serves to reduce the problem of gel formation which occurs and impedes distillation of an aqueous solution of an amine oxide if it is distilled as such.

We have found that when used together with a builder, polyethylene glycol and preferably another non ionic surfactant amine oxides appear to leave fabrics which have been laundered in them easy to iron.

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l,1 WO 92/20772 PC/GB92/00943 3 This invention therefore also comprises a detergent composition for example a laundry detergent composition which comprises: i an amine oxide; ii a builder; iii a polyalkylene glycol, having a molecular weight of 100 to 1500 preferably polyethylene glycol, and preferably a non ionic surfactant other than an amine oxide and preferably a bleach.

In many parts of the world it is desirable to reduce the concentrations of phosphates in waste water for environmental reasons. The use of phosphates and particularly condensed phosphates for example sodium tripolyphosphate in detergents has been common for many years but in some cases is now restricted by law for environmental reasons. It is, therefore, desirable to formulate detergent compositions of good performance which are free from phosphates.

This invention also comprises detergent compositions which are free from phosphates and which are suitably laundry detergent compositions which comprise: 1) An amine oxide 2) A hydroxy carboxylic acid containing 2 to 6 COOH groups and 1 to 5 OH groups and 3) A polycarboxylic acid comprising at least 10 and preferably at least 100 for example 150 to 2000 and preferably 200 to 1000 COOH groups and which contain at most 5 and preferably less than 2 moles of water per mole of amine oxide (excluding any present as water of crystallisation).

The polycarboxylic acid may be a polyacrylic acid for example a maleinised polyacrylic acid or is more preferably carboxy methyl cellulose which suitably has 100 to 1000 for example 100 to 500 combined glucose units per molecule and suitably has a degree of substitution (proportion of OH groups which have been converted to carboxy methyl form) of 35 to 85% and preferably 45 to The hydroxycarboxylic acid may be for example a tartrate or preferably a citrate.

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WO 92/20772 PCI'/GB92/00943 The composition suitably comprises 2 to 10% by weight of component above and preferably comprises 3 to 9% and more preferably 5 to 8% thereof. It suitably comprises 20 to 50% and preferably 25 to 40% by weight of zomponent above.

The composition is preferably substantially neutral or alkaline in reaction and it is preferred that acidic substances be neutralised with ammonium, substituted ammonium or preferably alkali metal ions. It is preferred that at least one part by weight of component 3 be present per eight parts by weight of component 2.

It is preferred that liquid compositions should comprise to 70% and preferably 30 to 60% for example 40 to 60% by weight of total solids. The solids preferably comprise a builder which may be present in an amount of 25 to 60% by weight of the total composition. A bleach for example a perborate or percarbonate of an alkali metal for example sodium may be present in an amount of 0 to 25% for example 1 to 20% and preferably 5 to 20% by weight of the total composition. Optionally a polycarboxylic acid comprising at least 10 and preferably at least 100 for 150 to 2000 and preferably 200 to 1000 COOH groups which is suitably carboxymethyl cellulose may also be present.

The liquid phase suitably comprises a polyalkylene glycol, preferably polyethylene glycol which is for example 5 to 55% by weight of the total composition and which is preferably 10 to by weight of the total composition and a non ionic surfactant which is suitably 5 to 25% and preferably 7 to 20% by weight of the total composition. The amine oxide is preferably 5 to 100% and more preferably 5 to 50% of the organic matter of the liquid phase by weight.

L 30 The builder may be for example a condensed phosphate, a silicate or a zeolite or a hydroxycarboxylic acid containing 2 to 6 -COOH groups and 1 to 5 -OH groups which may be citric or tartaric acid. It is preferred however that it be a condensed phosphate which may be an alkali metal, preferably sodium, salt for example sodium tripolyphosphate.

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i; "ci r WO 92/20772 PCr/GB92/00943 The molecular weight of the polyethylene glycol may be 100 to 1500 and is suitably 150 to 500.

It is preferred that compositions according to the invention be formulated as pourable liquids. To this end it is preferred that the liquid detergent composition should comprise a dispersion of solids in a liquid medium. The solids may be of average particle size at most 10 micro metres. The composition suitably has a pour point of less than 10 0 C. The pour point may be measured by ASTM test method designation D97-66 approved in 1971. It is desirable that at least 90% of the particles should have particle sizes less than 10 micro metres in diameter. The average particle sizes may be determined by either the number average method or the weight average method. A range of 1.2 to 8 micro metres is preferred.

The surfactant component of the composition may comprise for example a non ionic surfactant. It is suitably an alkylene oxide derivative, the alkylene oxide preferably being ethylene and/or propylene oxide. It may very suitably be a product of reaction of J an amine, alkyl phenol or alkanol with ethylene and/or propylene oxide. The alkyl group in the alkyl phenol may be straight chain or branched chain and may contain from 6 to 20 carbon atoms for example six to twelve carbon atoms. The alkanol may contain 6 to carbon atoms and preferably 10 to 16 carbon atom. The alkanol is preferably a primary or secondary alkanol having a linear or mono branched alkyl chain. Suitably the non ionic surfactant comprises a chain of 1 to 10, preferably 3 to 8 alkylene glycol residues, it being understood that this is an average value.

The surfactant may consist essentially of an amine oxide which preferably comprises an alkyl group having 10 to 18 carbon atoms and preferably 12 to 16 carbon atoms and 2 other groups selected individually from the C 1 to C 3 alkyl or hydroxyalkyl group. The composition may if desired comprise two or more non ionic surfactants. The pour point may be adjusted by varying the liquid phase composition, for example, by including surfactants and/or polyethylene glycol of low pour point. Suitably, 10 to and preferably 15 to 30% by weight of surfactant is present. The surfactant may alternatively be anionic or cationic.

L*1 i iL 1 1 *p WO 92/20772 PCT/GB92/00943 6 Such anionic or cationic surfactants may be of known type for example the anionic detergents may be soaps, alkylbenzene or olefine sulphonates, alcohol sulphates or alcohol alkoxylate sulphates; the cationic surfactants are suitably di-C 0 22 and preferably di-C6- 1 8 alkyl,. di-lower alkyl mmonium salts or hydroxides for example chlorides or sulphates or for example fabric softeners of the C10 16 alkyl, di lower alkyl (for example methyl), s'stituted ethyl ammonium salts. The substituent on the ethyl group may be an -OOCR group where R is a C1322 alkyl group, and the anion of the salt may be a RSO 4 group where R is lower alkyl for example methyl. The lower alkyl groups are suitably methyl groups.

It is preferred that a polyalkylene glycol, for example a polyethylene/polypropylene glycol or preferably a polyethylene glycol should be present. This contributes to the effectiveness of the compositions in washing fabrics and is of favourable biodegradability. Polyalkylene glycols of average molecular weight 100 to 400 and preferably 150 to 300 are preferred as they tend to reduce the pour point of liquid compositions thus making 1 20 them more easily usable in a cold environment. Suitably 10 to and preferably 25 to 45% by weight of polyalkylene glycol is present.

Very suitably the composition comprises a bleach which is suitably a perborate or percarbonate of an alkali metal. If desired bleach activators may be incorporated. Suitably 1 and preferably 2 15% by weight of bleach is present.

The composition may also contain additives conventionally found in detergent compositions, for example optical brighteners, ethylene diamine tetra acetic acid, dyes, perfumes and/or enzymes.

In compositions according to the invention the dispersion of the solids in the non-ionic surfactant is remarkably stable Sespecially if the particle size of the solids is at most 10 micro meters. If the solids separate at all then the resulting phase is usually loosely flocculated and is readily redispersible while if the relative amounts of the solids, polyethylene glyclol and SWO 92/20772 PCT/GB92/00943 7 surfactant in the composition are correctly chosen there is little phase separation as the liquid fills the space between the loosely packed solid particles.

Compositions according to the invention may suitably be made by a process which comprises milling ingredients together.

The percentages by weight given herein are based on the total weight of the composition unless the context requires otherwise.

EXAMPLE 1 Dehydration of Alkyl Dimethyl Amine Oxide The following procedure produces a 50% w/w solution of an amine oxide having an alkyl group of chain distribution 70%- C12, 27%- C14 and C16 and two methyl groups substituted on its nitrogen atom (DMAO) in polyethylene glycol (MW200) (PEG 200).

1 equivalent of PEG200 is added to 4 equivalents of DMAO in aqueous solution. (Approx 33% by weight DMAO).

The water is removed by distillation at reduced pressure in a Quickfit flask fitted with a N 2 bleed to bottom and a 2 foot froth disengagement column or a splash head, then via a water condenser to a collection vessel and vacuum control.

The boiler is charged at no more than 1/3 to 1/2 fill (to give froth space). The contents are agitated at 100 rpm with a strirrer paddle and a nitrogen bleed introduced. A vacuum is applied and the nitrogen bleed adjusted to maintain a minimum flow. When the vacuum is established the temperature is slowly increased to 60-75 0 C. Frothing can be controlled by fine adjustment of the vacuum or optionally a silicon antifoam at a level of 0..05 to 0.1 equivalents can be added to the reaction mixture.

When the theoretical water has been removed, the water content of the boiler is measured.

Distillation conditions, scale, 12 hours, 50 mm Hg at 60 0

C

500ml scale, 3 hours, 45 mm Hg at 75 0

C.

Under these conditions, but making a 60% DMAO composition (less PEG 200 being added) the product is a solid at room temperature, the 50% Amine Oxide material being a liquid.

L WO 92/20772 PCr/GB92/00943 8 w/w 50% w/w Amine Oxide 6i.0 Amine Oxide 50.0 Free Amine 0.7 Free Amine 0.6 3.5 HO2 PEG 200 35.0 PEG 200 44.5 EXAMPLE 2 Formulation A was produced as follows: The liquid components were mixed and seven parts by weight mixed with the enzyme and bentonite and the remainder was mixed with the other solid components with a homogeniser and the product milled to a mean particle size of 3 micrometers (weight average).

The two mixtures were then mixed together using homogeniser.

Formulation B was produced as follows: The components other than the enzyme were mixed using a homogeniser and milled to a weight average particle size of 3 micrometers. The enzyme was then added and mixed in 'sing a homogeniser.

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A

Sodium Citrate Sodium Tripolyphosphate Sodium Carbonate Carboxymethyl cellulose Sodium Disilicate "Leukophor" DUK optical Brightener Enzyme (Protease and amylase) "Synperonic" A3 "Synperonic" 87K Polyethylene glyclol, molecular weight 200 (PEG 200) DMAO (as 100%) Sodium perborate monohydrate Tetra acetyl ethylene diaxnine Bentonite Clay Water 37% 5% 1% 2% 0.3% 0.3% 2.5% 7% 32% 10% Formulation

B

2 7 1% 0.3% 0.3% 1.3% 3.8% 36% 3% 0.75% Commercial product sold as "Courlose" A610, degree of substitution 0.5 to 0.7 molecular weight believed to be 60,000 to 100,000.

it I if 4 9>? 7 WO 92/20772 PCMiGB92/00943 I0 "Synperonic" A3 and "Synperonic" 87K are the products of condensing respectively an average of 3 moles ethylene oxide and seven moles of a mixture of 92% ethylene oxide and 8% propylene oxide with a mixture of two parts C 13 primary alkanol to one part

C

15 primary alkanol, both having some 2-methyl branching.

The above percentages are all by weight.

The formulations were tested as laundry detergents as follows: The performance of formulations A and B was comnared with that of a comnercial detergent as follows. The wash tests were carried out using a Zanussi FL1030 washing machine run at 400C and 600C in water with 90 ppm Ca hardness. Standard cloths from EMPA or Krefeld were used to assess the performance of each product.

The machine was filled with four test pieces (10xlOcm) of each different type of test cloth together with 2 kg of clean cloth a,ballast for each wash. Each test cloth was measured in ten different places to assess the increase in reflectance of each cloth. The dose levels of detergent were 60g for formulations A and B and 180g of the commercial product per load.

The results were as foll-ws: Formulation

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Cloth 40 0

C

EMPA 101 37.8 KREFELD 10C 46.7 EMPA 104 38.6 KREFELD 20C 55.3 EMPA 1,11 (Blood) 77.1 EMPA 112 (Cocoa) 25.1 EMPA 114 (Red Wine) 31.7 KRFELD 10K (Coffee) 56.2 The numerical values given reflectance after washing.

600C 50.4 52.2 53.1 59.6 78.9 47.8 35.6 59.9 are the 400C 40.0 28.8 37.4 31.5 34.9 49.1 66.9 600C 51.0 43.9 52.4 54.2 49.8 47.6 67.2 72.3 Commercial 400C 600C 29.5 45.9 33.7 49.7 27.9 46.8 31.0 49.1 77.7 80.9 28.3 51.4 41.0 43.9 56.6 61.4 percentage increase in The above results show good performances copaed with the i PCT/GB92/00943 WO 92/20772 11 use of three time the weight of a commercial product.

Easy Iron Properties After using Formulation A for a fortnight, 27 out of 29 people answered yes to the question "Did the clothes handle well during ironing?" A foriulation substan ially equivalent to formulation A but modified for greater consuzr r appeal may be made up as follows: Synperonic A3 Synperonic 87K PEG 200 DMAO (as 100%) Sodium Carbonate "Courlose" A610 Sodium Disilicate Sodium Tripolyphosphate Ethylene diamine tetra-acetic acid Optical Brightener Blue Colouring Silicone Antifoam Bentonite Clay TiO 2 Fragrance Protease and Amylase Enzymes Weight kg/te 23.828 2.4 71.567 7.2 320.452 32.1 97.447 9.7 47.958 4.8 9.967 18.954 1.9 366.261 36.6 2.002 0.2 2.998 0.3 0.029 0.0 0.588 0.1 28.956 2.9 2.492 0.2 3.000 0.3 3.000 0.3 999.500 100.0 j i i i I i I ij WO 92/20772 PCT/GB92/00943 12 EXAMPLE 3 Liquid suspensions comprising the ingredients of the following Table and which comprised about 50% solids were made up. Formulation C was milled to a mean particle size of 3 micrometres by weight average. The other formulations were made by mixing solid pre-ground particles with liquid components the size of the particles not having been determined.

Formulation Formulation Formulation A B C "Dequest" 2016D Phosphonate Builder Sodium Citrate 32% 32% 32% Sodium Carbonate 10% Carboxymethyl Cellulose 6% b% 2% Sodium Disilicate 1% 1% 1% "Tinopal" CBS-X Optical Brightener 0.2% 0.2% 0.2% Enzyme (Protease and amylase) 0.3% 0.3% 0.3% "Synperonic" A3 3.75% 3.75% 3.75% f "Synperonic" 87K 11.25% 11.25% 11.25% Polyethylene glycol, Molecular weight 200 25.5% 25.5% 34.5% Tetra acetyl ethylene diamine 3% "Synprolam" 35DMQ 10% 10% Sodium Perborate Monohydrate 7% Conmercial Product sold as "Courlose" A161, degreq of substitution 0.5 to 0.7 molecular weight believed to be 60,000 to 100,000.

"Synperonic" A3 and "Synperonic 87K are the products of condensing respectively an average of 3 moles ethylene oxide and seven moles of a mixture of 92% ethylene oxide and 8% propylene oxide with a mi:ture of two parts C 13 primary alkanol to one part

C

15 primary alkanol, both having some 2-methyl branching, and "Synprolam" 35DMG is an amine oxide having an alkyl group corresponding to the said mixture of C13 and C 15 alkanols and two methyl groups substituted on its nitrogen atom.

The above percentages are all by weight.

W. 92/20772 PC/GB92/00943 13 The formulations were tested as laundry detergents as follows: The performance of formulations A, B and C was -ompared with that of a commercial detergent as follows. The wash tests were carried out using Miele W451 washing machines run at 40°C and in hard water (360C French specification hardness).

Standard cloths from EMPA or Krefeld were used to assess the performance of each product. Three machines were filled with four test pieces (lOxlQcm) of each different type of test cloth together with 2 kg of clean cloth as ballast for each wash. Each test cloth was measured in twelve different places to assess the increase in reflectance of each cloth. The dose levels of the detergent were 60g for formulations A, B and C and 180g of the commercial product per load.

The results were as follows: I I' I I I Formulation A B I C ICommercial SI I I ICloth 140°C 160°C 40°C 160°C 140°C 160°C 140°C I I I I I EMPA101 134.7 130.5 132.8 132.7 124.5 122.1 119.8 1 18.91 IKREFELD O10C 141.1 153.2 135.9 156.4 129.2 146 142.4 55.31 |EMPA 104 146.5 142.4 146.9 142.8 118.8 119.5 117.1 17.51 IKREFELD 20C 139.8 (50.2 152.4 149.7 119.3 120.7 129.5 46.31 JEMPA 111 167.2 167.8 123.9 154.9 178.3 176.3 174.2 73.71 JEMPA 112 140.8 145.6 140.3 135.6 139.8 143.7 138.6 37.21 JEMPA 114 (21.7 131.2 131.3 j5.0 126.4 (29.3 133.2 40.31 IKREFELD 101C149.3 (53.3 152.8 J65.8 151.8 153 153,2 57.11 JKREFELD AS12136.9 136.6 143.7 144.8 I I 149 43.81 IKREFELD PC12146.4 (43.2 150.8 (51.4 I I 144.9 42.11 III I I I I I I it a 1; r WO 92/20772 PCf/GB92/00943 14 The numerical values given are the percentage increase in reflectance after washing.I The above results show good performances compared with the use of three times the weight of a commercial product.

The commercial product contained about one third by weight of water and the comparison oin a total chemicals content is thus at a ratio of about one to two.

EXAMPLE 4 Two liquid detergent compositions comprising solids suspended in liquids of the following composition were tested as follows: A B w/w w/w Sodium Tripolyphosphate 36.7 40.15 Bentonite Clay 2.9 Sodium Carbonate 4.8 5.00 Sodium Silicate 1.9 2.00 Carboxymethyl Cellulose 1.0 1.00 Sodium Ethylene Diamine Tetraacetate 0.2 0.2 Optical Brightener 0.3 0.3 Enzymes 0.3 0.3 Titanium Dioxide 0.25 0.25 Synperonic A3 2.4 2.4 Synperonic 87K 7.2 Polyethylene Glycol Molecular Wgt 200 32.0 40.0 Dimethyl Cocoamine Oxide 9.8 NIL Perfume 0.25 0.8 Water was then added to both compositions in amounts of 1%, 2.5% and 3% by weight.

is r~ jf -t SWO 92/20772 PCI/GB92/00943 The viscosity after 45 minutes and (where shown) one day at 0 C is shown below: -Fl: ii Added Water 0.0% Viscosity (Poise) min day 48.0 50.8 60.2 90.4 70.9 800,000.0 Viscosity (Poise) 45 min di 46.0 70.8 139.0 304.0 706,000.0 These data show that the amine oxide containing composition was more resistant to degradation by water.

Compositions A and B were also tested for dispensibility in a commercial Zanussi washing machine with a draw dispenser. times more residue was left in the tray at the commencement of the washing process in the case of composition B than in the case of composition A.

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Claims (10)

16- THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS: 1. A liquid detergent composition which includes i) a liquid organic phase which includes an amine oxide surfactant; and ii) a solid phase which includes a builder; from 0.5 to 5 moles of water being present per mole of amine oxide excluding any water present as water of crystallation of any solid present. 2. A composition as claimed in claim 1 in which the amount of water present is from 0.5 to less than 2 moles of water per mole of amine oxide. 3. A composition as claimed in claim 2 in which the amount of water present is from 1.0 to 1.7 moles of water per mole of amine oxide. 4. A composition as claimed in any one of claims 1 to 3 in which the amount of surfactant present is from 10 to 50% by weight of the composition. I' 5. A composition as claimed in any one of claims 1 to 4 in which the amount of amine oxide present is from 5 to 100% by weight of the surfactant in the composition. 6. A composition as claimed in any one of claims 1 to 5 which additionally Sincludes at least one polyalkylene glycol. 25 7. A composition as claimed in claim 6 in which the weight ratio of Spolyalyklene glycol to amine oxide is from 0.5:1 to 2:1. 8. A composition as claimed in either claim 6 or claim 7 in which the amount of polyalkylene glycol present is from 5 to 55% by weight of the composition. (YA j. C;\WINWORD\SIMONE\NODELETEI1761OC92.DOC 1/ -17- 9. A composition as claimed in any one of claims 6 to 8 wherein the polyalkylene glycol is polyethylene glycol having an average molecular weight of from 150 to 500. 10. A composition as claimed in any one of claims 1 to 9 in which the solids including the builder are from 25 to 70% by weight of the composition. 11. A composition as claimed in any one of claims 1 to 10 in which the solids are of weight average particle size at most 10 micrometers. 12. A composition as claimed in any one of claims 1 to 11 which includes as a builder a condensed phosphate, a zeolite, a silicate or a hydroxycarboxylic acid containing 2 to 6 COOH groups and 1 to 5 OH groups. 13. A composition as claimed in claim 12 wherein the condensed phosphate is a condensed alkali metal phosphate. 14. A composition as claimed in either claim 12 or claim 13 in which the hydroxycarboxylic acid is citric or tartaric acid. A composition as claimed in any one of claims 1 to 14 which further includes a polycarboxylic acid having at least 10 COOH groups. 16. A liquid detergent composition as claimed in any one of claims 1 to 11 25 which is substantially free from phosphates which includes i) a liquid organic phase which includes an amine oxide; and ii) a solid phase which includes a builder, including at least one hydroxycarboxylic acid containing 2 to 6 COOH groups and 1 to 5 OH groups, and a polycarboxylic acid having at least 10 COOH groups; from 0,5 to 5 moles of water being present per mole of amine oxide excluding any water present as water of crystallation of any solid present. SC:WI\NWLORD\SIMONENODELETE17lGOC92.DOC C~' Pi 1 i I I 1 I I *r C (I I, i a i 1~ L._ i -18-

17. A composition as claimed in claim 16 in which the hydroxycarboxylic acid is citric or tartaric acid.

18. A composition as claimed in either claim 16 or claim 17 which additionally includes as a builder a zeolite and/or a silicate.

19. A liquid detergent composition as claimed in any one of claims 1 to which includes i) a liquid organic phase which includes an amine oxide and a polyalkylene glycol; and ii) a solid phase which includes as a builder a condensed phosphate; from 0.5 to 5 moles of water being present per mole of amine oxide excluding any water present as water of crystallation of any solid present.

20. A composition as claimed in any one of claims 1 to 19 which further includes a bleach.

21. A composition as claimed in any one of claims 1 to 20 which further includes an enzyme.

22. A detergent composition as claimed in any one of claims 1 to 21 in the form of a pourable liquid which composition is a dispersion of solids in a liquid medium in which: i) the solids are of weight average particle size at most 25 micrometers; ii) the liquid medium includes an amine oxide surfactant and a *a i polyalkylene glycol having a molecular weight of 100 to 1500; and iii) the solids include a builder; in which from 0.2 to 5 moles of water are present per mole of amine oxide excluding any water present as water of crystallation of any solid present. A I SC C:\WINWORDLSIMONENODELE176ll 0C2DOC ^roQ ii i if I it v .a ii A f;P-_b .S 19-

23. A pourable liquid detergent composition as claimed in claim 22 in which the polyalkylene glycol has a molecular weight of 150 to 500 and in which less than 2 moles of water are present per mole of amine oxide excluding any water present as water of crystallation of any solid present.

24. A composition according to any one of claims 1, 16, 19 or 22 as substantially hereinbefore described with reference to any one of the examples. DATED: 1 August, 1996 j PHILLIPS, ORMONDE FITZPATRICK Attorneys for: IMPERIAL CHEMICAL INDUSTRIES, PLC I i SC C:\WINWORD\SIMONE\NODELETE1761OC92DMOC ,~t~o Az INTERNATIONAL SEARCH REPORT international Appication N.. PCT/G8 92/00~943 I: CLASSIFICATION OF SUsjEcTMATr= (If several classification symabols apply, indicate all)(' According to international 'atent Clasuification or to bath Natioa Classifiction and IPC Int.Cl. 5 C11017/00; C1101/75 U. FIELDS SEARCHED Minimum Documentation Serched 7 Classification system Classification Symbols Int..C1. 5 Clio Documentation Searched other than Minimum Documentation to the Extent that such Documents are Includted In the Fields Searchedl MD. DOCUMENTS CONSIDERED TO BE RELEVANT9 Category 0 Citation of Document, 1 with Indication, where appropriate, of the e'ele~t passages 1 2 Relevat to Clm No. 1 3 X USA,4 264 466 CARLETON ET AL.) 28 April 1,4-8,11. 1981 see column 4, line 35 column 10, line 31; claims X tJS,A,4 874 537 PETERSON ET AL.) 17 October 1,4,6,7, 1989 11 see column~ 3, line 22 column 4, line 4; claims 1-7 A EP,A,O 120 659. (IMPERIAL CHEMICAL INDUSTRIES) 3 1,3,4, October 1984 6-9,11 cited in thd\application see claims 1-8 A EP,A,O 425 149 (IMPERIAL CHEMICAL INDUSTRIES) 2 1,3,4, May 1991 6-9,11 see page 3, line 3 line 48; claims; example 6 0 Special categories of cited documents 10 Tr later document published after the international filing date A' datmnt efiingthegenral tatof he rt hic isnotor priority date ad ote In conflict with the application but W dcunside o te ora tate ofeleeance ic I cited to undersand the principle or thenry underlying the consderd tobe artcula Maan"Irnventin 'E earlier document but published on or after the international "r document of patiamla relmacte; the clalo Invention filing date cano: be considered novel or cannot be considered to. IV document which my throw doubts on priority delam(s) or 0lvw an Inventive step which Is cited to establish the publication date of another document of partilar relevance; the claimed Invention citation or other special taioo (as specified) otb considered to !avolve an inventive step when the document referring to an oral disclosure, us*, hlbitioo or document is combined with one or more other such docu- other means maots such combination being obvious to a person skilled document published prior to the international filing date bu In the am. later than the priority date claimed documeat member of the tame pat family IV. CERTIFICAION Date of the Actual Complation of the International Search Date of Mailing of this International Search Report AUGUST 1992 2 7.89 International Searching Auhty Sigature of Authorized Officere EVJ1OPEAN PATEN4T OFFICE SERBETSOGLOUA. relear ASAM I 4mm 4janI 138 V A I y Ii PCT/GB 92/00943 International Application No HI. DOCUMENTS CONSIDERED TO BE RELEVANT (CONTINUED FROM THE SECOND SHEET) Category Citation of Document, with indication, where appropriate, of the relevant passages Relevant to Claim No. US,A,4 276 205 FERRY) 30 June 1981 sae column 7, line 1 column 10, line claims 1-3,19,22 US,A,3 281 368 ZIMMERER ET AL.) 25 October 1966 see column 4, line 12 line 52; claims WO,A,9 113 139 (UNILEVER) 5 September 1991 see page 6, line 15 page 7, line 21; claims WO,A,9 118 079 (ETHYL CORP.) 28 November 1991 see page 6, line 7 line 27; claims 1-7; example 1 1,3-8,11 1,3-7,11 1,5-7,11 2,5,10 ^l FOm ICTIISAI0 "O t l |J0 11i1 U) ANNEX THE INTERNATIONAL SEARCH REPORT, ON INTERNATIONAL PATENT APPLICATION NO.~ 9200943 SA 59604 TIsk annex lists the patent faraily munbers relating to the patent documents cited in the above-nentiolled international search report. e Mhembhers awe as contained in the Euzropean~ Patent Office EDP file on The European Patent office is in no way Diame for them partim, ars which are merelY given for the Pa'rPoqr of infb'mati@. 20/08/92 Paadoant Publicatin Patent fAWAlY Publication ct inU searhmV re t date member s)da US-A-4264466 28-04-81 AT-T- CA-A- EP-A, B JP-A- 10011 1148830 0034387 56159297 15-11-84

28-06-83 26-08-81 08-12-81 US-A-4874537 17-10-89 AU-A- 3673289 05-04-90 EP-A- 0361646 04-04-90 JP-A- 2093000 03-04-90 EP-A-0120659 03-10-84 AU-B- 570035 03-03-88 AU-A- 2604384 04-10-84 CA-A- 1221891 19-05-87 JP-A- 59189198 26-10-84 US-A- 4615820 07-10-86 EP-A-0425149 02-05-91 AU-A- 6461690 26-04-91 JP-A- 3167297 19-07-91 US-A-4276205 30-06-81 None US-A-3281368 BE-A- 651634 10-02-65 DE-A- 1518086 06-11-69 FR-A- GB-A- NL-A- U S-A- 1450374 1018774 286242 3202714 WO-A-9113139 05-09-91 AU-A- 7344191 18-09-91 EP-A- 0444858 04-09-91 WO-A-9118079 28-11-91 US-A- 5120469 09-06-92 US-A- 5055232 08-10-91 US-A- 5055614 08-10-91 SFor mer detelk about thin mm m Ofihia Journal of the Erpeam at offic, No. 12/32 (I it if Ii