AU627461B2

AU627461B2 - Liquid detergent compositions

Info

Publication number: AU627461B2
Application number: AU36269/89A
Authority: AU
Inventors: Guido Clemens Van Den Brom
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1988-06-13
Filing date: 1989-06-09
Publication date: 1992-08-27
Anticipated expiration: 2009-06-09
Also published as: EP0346993A3; CA1334919C; AU3626989A; EP0346993A2; BR8902772A; JPH0234700A

Description

ii

AUSTRALIA

PATENTS ACT 1952 COMPLETE SPECIFICATION Form

(ORIGINAL)

FOR OFFICE USE Short Title: Int. Cl: Application Number: Lodged: Complete Specification-Lodged: Accepted: Lapsed: Published: S 8 S r SPriority: S

S

Related Art: TO BE COMPLETED BY APPLICANT S Name of Applicant:

S

*5 Address of Applicant: UNILEVER PLC UNILEVER HOUSE

BLACKFRIARS

LONDON EC4

ENGLAND

Actual Inventor: Address for Service:

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GRIFFITH HACK CO., 601 St. Kilda Road, MelLourne, Victoria 3004, Ai's--ra 1 4ia Complete Specification for the invention entitled: LIQUID DETERGENT COMPOSITIONS.

Th following statement is a full description of this invention in uding the best method of performing it known to me:- 4 p.- Id 4' c 7141 (R) LIQUID DETERGENT COMPOSITIONS The present invention is concerned with aqueous liquid detergent compositions of the kind in which at least some of the surfactant material forms a structured phase which is capable of suspending solid particulate material.

10 0 0 0 o* 1 0 0 0 *2 *0 S *5 .5

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*e 2 The surfactant material in such compositions usually comprises one or more surfactants which may be soap or non-soap synthetic surfactants. Soap is a particularly useful material since it is capable of a multiplicity of roles. It can be used as a detergent-active agent, as a builder and as a fabric softening agent. Thus, it is a very desirable aim to formulate liquid detergents which are relatively rich in soap. In the case of isotropic liquids containing little or no inorganic builder, it is relatively easy to formulate with high soap levels. It is much more difficult to incorporate large enough quantities in the aqueous structured liquids referred to above.

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j 4 Aqueous structured liquid detergents with solid S suspending capability and containing soap are disclosed in European Patent Specifications EP-A-38 101; EP-A- 86 614; and EP-A-151 884. They are also disclosed in our non-prior published European patent applications EP 301 883 and EP 301 884. However, in none of these has a sufficient amount of soap been incorporated to function as a fabric softening agent and/or as a builder whilst the composition simultaneously contains sufficient non-soap synthetic surfactant to ensure a high level of detergency performance. Further possible disadvantages of the compositions are instability, resulting in more than 2% by volume phase separation 1

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C 7141 (R) 2 after storage for 21 days at 25 0 C, and high viscosity, resulting in non-pourable products.

Thus, according to the present invention, we provide an aqueous liquid detergent composition comprising greater than 7% by weight of non-soap synthetic surfactant material comprising a nonionic detergent of the ethylene oxide condensate type and at least 5% by weight of soap, the composition further comprising electrolyte in a quantity sufficient to cause the soap and the non-soap synthetic surfactant to form a lamellar phase having solid suspending capability, said composition yielding no more than 2% by volume phase separation after storage for 21 days at 25 0 C, said composition having a pH of less than 12.0.

What is especially surprising here is that stable, pourable lamellar-structured liquids can be formulated with the levels of soap and other specified ingredients as claimed herein. As far as we are aware, no compositions matching these quantitative and qualitative requirements have been successfully formulated hitherto.

Such phase separation can manifest itself by the appearance of distinct layers or by the formation of distributed "cracks" containing predominantly aqueous phase-containing dissolved electrolyte. They are also pourable, certainly having a viscosity no more than 6 Pas, preferably no more than 2.5 Pas, most preferably no more than 1.5 Pas, especially 1 Pas or less, these viscosities being measured at a shear rate of 21s 1 The compositions of the present invention require sufficient electrolyte to cause the formation of a l 1 TEY 2 _1 C 7141 (R) 3 lamellar phase by the soap/surfactant to endow solid suspending capability. The selection of the particular Stype(s) and amount of electrolyte to bring this into :i being for a given choice of soap/surfactant is effected using methodology very well known to those skilled in the art. It utilises the particular techniques described in a wide variety of references. One such technique entails conductivity measurements. The detection of the presence of such a lamellar phase is also very well known and may be effected by, for example, optical and electron microscopy or x-ray diffraction, supported by j conductivity measurement.

As used herein, the term electrolyte means any wateroL5 soluble salt. The amount of electrolyte should be o sufficient to cause formation of a lamellar phase by the soap/surfactant to endow solid suspending capability.

SI Preferably, the composition comprises at least 1.0% by weight, more preferably at least 5.0% by weight, most 0 20 preferably at least 17.0% by weight of electrolyte. The electrolyte may also be a detergency builder, such as Sthe inorganic builder sodium tripolyphosphate, or it may be a non-functional electrolyte, such as sodium sulphate or chloride. Preferably, the inorganic builder comprises 1 25 all or part of the electrolyte.

The compositions must also be capable of suspending particulate solids although particularly preferred are ithose systems where such solids are actually in suspension. The solids may be undissolved electrolyte, the same or different from the electrolyte in solution, the latter being saturated in electrolyte. Additionally or alternatively, they may be materials which are substantially insoluble in water alone. Examples of such substantially insoluble materials are aluminosilicate builders and particles of calcite abrasive.

j~ °4 The compositions of the present invention must contain soap. This will usually be an alkali metal soap of a fatty acid, preferably one containing 12 to 18 carbon atoms. Typically, such acids are oleic acid, ricinoleic acid and fatty acids derived from castor oil, rapeseed oil, groundnut oil, coconut oil, palmkernal oil or mixtures thereof. The sodium or potassium soaps of these acids can be used, the potassium soaps being preferred.

The compositions of the present invention must also contain a non-soap synthetic surfactant material which comprises a nonionic detergent of the ethylene oxide condensate type. The non-soap synthetic surfactant material may optionally contain other surfactants selected from any of those known in the art for forming structured liquids and in general may be selected from one or more of anionic, cationic, nonionic, zwitterionic and amphoteric surfactants. However, one preferred combination of non-soap surfactants comprises: S a) a nonionic surfactant and/or polyalkoxylated anionic surfactant; and b) a non-polyalkoxylated anionic surfactant; provided that the total combination contains at least one nonionic detergent of the ethylene oxide condensate type.

Suitable nonionic surfactants of the ethylene oxide condensate type which may be used include in particular the reaction products of compounds having a hydrophobic goup and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl nhenols with ethylene oxide either alone or together with propylene oxide. Specific such nonionic detergent compounds are alkyl (C 6

-C

22 phenols-ethylene oxide condensates, the condensation products of aliphatic (C 8

-C

18 primary or secondary linear or branched alcohols with ethylene oxide, and products made by condensation of ethylene oxide with the reaction products of propylene oxide and ethylene diamine.

Other so-called nonionic detergent compounds not of the ethylene oxide condensate type but which may be used in addition include long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.

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I'y I. 4 i C 7141 (R) The anionic surfactants are usually water-soluble alkali metal salts of organic sulphates and sulphonates having alkyl radicals containing from about 8 to about 22 carbon atoms, the term alkyl being used to include i 5 the alkyl portion of higher acyl radicals. Examples of suitable synthetic anionic detergent compounds are sodium and potassium alkyl sulphates, especially those obtained by sulphating higher (Cg-C 1 8 alcohols L produced, for example, from tallow or coconut oil, S 10 sodium and potassium alkyl (C 9

-C

20 benzene sulphonates, particularly sodium linear secondary alkyl (C 10

-C

15 i benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher i alcohols derived from tallow or coconut oil and :5 synthetic alcohols derived from petroleum; sodium S coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C 8

-C

1 8 fatty alcohol-alkylene S oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut t fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts or fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alphaolefin (C 8

-C

20 with sodium bisulphite and those derived S from reacting paraffins with SO 2 and Cl 2 and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly C 10

C

20 alpha-olefins, with S0 3 and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (C 11

-C

15 alkyl benzene sulphonates and sodium (C 16

-C

18 alkyl sulphates.

The compositions of the present invention preferably also contain a builder in addition to the soap. The non-

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S6 soap builder is preferably present at a level of at i least 5% by weight; the maximum level is preferably A detergency builder is any material which is capable of i reducing the level of free calcium ions in the wash liquor and will preferably provide the composition with other beneficial properties such as the generation of an alkaline pH, and the suspension of soil removed from the fabric. They may be classed as inorganic, organic nonpolymeric and organic polymeric. Generally, we prefer that any inorganic builder comprises all or part of the i electrolyte (provided water-soluble).

S: Examples of phosphorus-containing inorganic detergency o builders include the water-soluble salts, especially alkaline metal pyrophosphates, orthophosphates, j polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include sodium and I potassium tripolyphosphates, phosphates and hexametaphosphates.

Examples of non-phosphorus-containing inorganic detergency builders, when present, include watersoluble alkali metal carbonates, bicarbonates, silicate and crystalline and amorphous alumino silicates.

S, 25 Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates and silicates.

SExamples of organic detergency builders include the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetyl carboxylates and polyhydroxy sulphonates. Specific examples include sodium, potassium, lithium, ammorium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and i 1 1 C 7141 (R) 7 citric acid.

Apart from the ingredients already mentioned, a number of optional ingredients may also be present, such as lather boosters, e.g. alkanolamides, particularly the monoethanolamides derived from palm kernel fatty acids and coconut fatty acids, lather depressants, oxygenreleasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as g sodium sulphate, and, usually present in very minor S amounts, fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides, colourants and 145 fabric softening clay materials.

The pH of the composition is preferably more than more preferably from 7.0 to 12.0, especially preferably less than 11.0, most preferably between 7.0 and a 0 0 The compositions of the present invention may be prepared using the general techniques known in the art 00." of the processing of liquid detergent products. However, the order of addition of components can be important.

25 Thus, a preferred order of addition (with continuous ef mixing) is to add to the water, the soluble electrolytes, then any insoluble material such as aluminosilicates, followed by the actives. The mixtures U are then cooled below 30*C, whereafter any minors and additional ingredients can be added. Finally, if necessary, the pH of the composition can be adjusted, e.g. by the addition of a small quantity of caustic material.

In use, the compositions of the present invention will generally be diluted with water to form a wash liquor C 7141 (R) preferably comprising from 0.1 to 10%, more preferably from 0.5 to 3.0% by weight of said composition. The wash liquor is used for the washing of fabrics, for instance in an automatic washing machine.

The invention will now be illustrated by the following non-limiting Examples.

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S S C S 0 i r, 1 1 Ii C 7141 (R) Ingredient

K-LAS

K-Oleate

CDEA

Neodol 23-6.5 Na-citrate 2 aq.

Na-disil icate Na-carbonate Zeolite 4A 1 4.0 5.5 2.0 3.6 6.8 2.0 2.0 21.6 Examples 1-6 (weights 2 3 2.7 3.4 6.8 7.5 2.0 2.0 3.6 2.4 6.8 6.8 2.0 2.0 2.0 2.0 21.6 21.6 in w/w) 4 3.4 5.5 2.0 4.2 6.8 2.0 2.0 21.6 5 4.0 5.5 2.0 3.6 3.4 2.0 2.0 21.6 6 3.6 4.6 21. 6 *.ft.

0* 0I 0S *0 I 00 02 0 Water viscosity (mPas, 4s-1) 1000 2000 N/A* N/A* 5200 5500 Examples 7-11 0 1 Ingredient Na -LAS Na-OJleate Na-Laurate 25 Synperonic A7 Glycerol Borax

STP

Water Viscosity mPas 21s- 1 7 8.5 5.6 2.0 5.0 3.5 22.0 8 7.

5.

(weights in w/w) 9 5 6.4 4 5.4 .10 6.4 8.1 11 4.3 5.4 3.0 5.0 3.5 22. 0 4.0 5.0 3.5 22.0 4.0 5.0 3.5 22.0 22.0 2730 1660 2490 4640 1390 not available Ii

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.1 MIMMIff_ C 7141 (R) Examples 12-16 (weights in w/w) *.00 0 00 00 00 0000 *0

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0000 00 Se 0

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06 .14 0 04

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0004

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00 Ingredient Na-LAS Na-Oleate K-Oleate Synperonic A7 Glycerol Borax

STP

S CMC Fluorescer Silicone oil Synthetic Amorphous 'L5 Silica Perfume Enzyme Water viscosity 0 (mPas, 21s- 1 12 4.3 8.1 6.0 5.0 3.5 22.0 0.5 13 10. 0 6.0 4.0 4 .85 3.1 15 .0 0.1 0.1 2.0 0.3 0.5 14 10 .0 6.0 4.0 4.85 3.1 15.0 0.1 0.1 0.25 2.0 0.3 C .5 balance 950 15 10 .5 6.0 3.5 4.85 3.1 15 .0 0.1 0.1 0.25 2.0 0.3 0.5 16 10.5 4.85 3.1 15.0 0.1 0.1 0.25 0.3 3230 810 770 1500 Example 17 Na LAS 25 Synperonic A3

STP

K-Oleate NaCl Glycerol Boran Anti-foam Enzyme Fluorescer

SCMC

Water Viscosity approx. 880 mPas at 21s 1

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wt.

4.1 1S. 0 10.0 4 3.10 0.20 0.1 0.1 balance C 7141 (R) Example 18

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0005

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Na LAS Synperonic A3

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K-Oleate PEG 400 Alcosperse 175

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Na 2

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4 Glycerol Borax Anti-foam Enzyme Fluorescer S CMC Water wt.

15.0 10. 0 4.85 3 0.2 0.1 0.1 balance *2 0 25 viscosity approx. 880 mPas at 21s- 1 Raw Material Specification

LAS

CDEA

S CMC

STP

STS

PEG 400 dodecyl benzene suiphonate coconut dief-hanolamide sodium carboxymethyl cellulose sodium tripolyphosphate sodium toluene sulphonate polyethylene glycol, average molecular weight 400 70/3 0 Acrylate/Maleate co-polymer (YIW 20,000 ex ALCO)

CT

2

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13 fatty alcohol alkoxylated with an average of 7 moles of ethylene oxide per molecule.

CT

2

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13 fatty alcohol alkoxylated with an average of 3 moles of ethylene oxide per molecule.

Alcosperse 175 Synperonic A7 Synperonic A3 1 'I I:ii C 7141 (R) Neodol 23-6.5

C

12

-C

13 fatty alcohol alkoxylated with an average of 6.5 moles of ethylene oxide per molecule.

The pH of the compositions of Examples 1-6 was between about 10 and 11; the pH of the compositions of Examples 7-19 was, if necessary, adjusted to a pH of from about 7-8. All compositions were pourable and all yielded less than 2% by volume phase separation after storage at ambient temperature for 2 months. The level of soap in the compositions is sufficient to effect fabric softening and/or a builder effect whilst the r compositions contain sufficient non-soap synthetic surfactant to ensure a high level of detergency performance.

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Claims

1. An aqueous liquid detergent composition comprising more than 7.0% by weight of non-soap synthetic detergent material comprising a nonionic detergent of the ethylene oxide condensate type and at least 5.0% by weight of soap, the composition further comprising electrolyte in a quantity sufficient co cause the soap and the non-soap synthetic surfactant to form a lamellar phase having solid suspending capability, said composition yielding no more than 2% by volume phase separation after storage for 21 days at 25 C, said composition have a pH of less than 12.0. C

2. more A composition according to Claim than 1% by weight of electrolyte. 1, comprising

3. A composition according to Claim 2, comprising more than 5% by weight of electrolyte.

4. A composition according to Claim 3, comprising more than 17% by weight of electrolyte.

A composition according to any of Claims 1-4, also comprising at least 5% by weight of a non-soap builder.

6. A composition according to Claim 5, characterized in that the non-soap builder comprises an inorganic builder.

7. A composition according to Claim 6, characterized in that the inorganic builder comprises all or part of the electrolyte. 7

8. An aqueous liquid detergent composition according to any of Claims 1-5, having a viscosity of no more than 6.0 Pas at a shear rate of 21 s A K .i Li i-i. I- I 2- C 7141 (R)

9. An aqueous liquid detergent composition according to any of Claims 1-6, having a pH between 7.0 and 11.0. Use of an aqueous liquor comprising from 0.1 to by weight of a composition according to any one or more of the preceding Claims for the washing of fabrics. A- .1 S S S S.. DATED THIS 16TH DAY OF JUNE 1992 UNILEVER PLC By its Patent Attorneys: GRIFFITH HACK CO Fellows Institute of Patent Attorneys of Australia 4i