EP0346993A2

EP0346993A2 - Liquid detergent compositions

Info

Publication number: EP0346993A2
Application number: EP19890201528
Authority: EP
Inventors: Guido Clemens Van Den Brom
Original assignee: Unilever PLC
Current assignee: Unilever PLC
Priority date: 1988-06-13
Filing date: 1989-06-12
Publication date: 1989-12-20
Also published as: CA1334919C; BR8902772A; JPH0234700A; AU627461B2; EP0346993A3; AU3626989A

Abstract

An aqueous liquid detergent composition comprising greater than 7% by weight of non-soap synthetic surfactant 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 weight by volume phase separation after storage for 21 days at 25°C, said composition having a pH of less than 12.0.

Description

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.
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.
Aqueous structured liquid detergents with solid 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 after storage for 21 days at 25°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 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°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.
Thus, the compositions of the present invention are stable, preferably yielding no more than 2% by volume phase separation after storage for 21 days at 25°C.
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 lamellar phase by the soap/surfactant to endow solid suspending capability. The selection of the particular type(s) and amount of electrolyte to bring this into 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 conductivity measurement.
As used herein, the term electrolyte means any water-soluble salt. The amount of electrolyte should be sufficient to cause formation of a lamellar phase by the soap/surfactant to endow solid suspending capability. Preferably, the composition comprises at least 1.0% by weight, more preferably at least 5.0% by weight, most preferably at least 17.0% by weight of electrolyte. The electrolyte may also be a detergency builder, such as the inorganic builder sodium tripolyphosphate, or it may be a non-functional electrolyte, such as sodium sulphate or chloride. Preferably, the inorganic builder comprises all or part of the electrolyte.
The compositions must also be capable of suspending particulate solids although particularly preferred are those 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.
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. This may be 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 :

a) a nonionic surfactant and/or polyalkoxylated anionic surfactant; and
b) a non-polyalkoxylated anionic surfactant.

Suitable nonionic surfactants which may be used include in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkyl phenols with alkylene oxides, especially ethylene oxide either alone or with propylene oxide. Specific nonionic detergent compounds are alkyl (C₆-C₂₂) phenols-ethylene oxide condensates, the condensation products of aliphatic (C₈-C₁₈) 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 include long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulphoxides.
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 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 (C₈-C₁₈) alcohols produced, for example, from tallow or coconut oil, sodium and potassium alkyl (C₉-C₂₀) benzene sulphonates, particularly sodium linear secondary alkyl (C₁₀-C₁₅) benzene sulphonates; sodium alkyl glyceryl ether sulphates, especially those ethers of the higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; sodium coconut oil fatty monoglyceride sulphates and sulphonates; sodium and potassium salts of sulphuric acid esters of higher (C₈-C₁₈) fatty alcohol-alkylene oxide, particularly ethylene oxide, reaction products; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralised with sodium hydroxide; sodium and potassium salts or fatty acid amides of methyl taurine; alkane monosulphonates such as those derived by reacting alpha-olefin (C₈-C₂₀) with sodium bisulphite and those derived from reacting paraffins with SO₂ and Cl₂ and then hydrolysing with a base to produce a random sulphonate; and olefin sulphonates, which term is used to describe the material made by reacting olefins, particularly C₁₀-C₂₀ alpha-olefins, with SO₃ and then neutralising and hydrolysing the reaction product. The preferred anionic detergent compounds are sodium (C₁₁-C₁₅) alkyl benzene sulphonates and sodium (C₁₆-C₁₈) alkyl sulphates.
The compositions of the present invention preferably also contain a builder in addition to the soap. The non- soap builder is preferably present at a level of at least 5% by weight; the maximum level is preferably 30%. A detergency builder is any material which is capable of 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 non-polymeric and organic polymeric. Generally, we prefer that any inorganic builder comprises all or part of the electrolyte (provided water-soluble).
Examples of phosphorus-containing inorganic detergency builders include the water-soluble salts, especially alkaline metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates.
Examples of non-phosphorus-containing inorganic detergency builders, when present, include water-soluble alkali metal carbonates, bicarbonates, silicate and crystalline and amorphous alumino silicates. Specific examples include sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates and silicates.
Examples 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, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and 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, oxygen-releasing bleaching agents such as sodium perborate and sodium percarbonate, peracid bleach precursors, chlorine-releasing bleaching agents such as trichloroisocyanuric acid, inorganic salts such as sodium sulphate, and, usually present in very minor amounts, fluorescent agents, perfumes, enzymes such as proteases and amylases, germicides, colourants and fabric softening clay materials.
The pH of the composition is preferably more than 7.0, more preferably from 7.0 to 12.0, especially preferably less than 11.0, most preferably between 7.0 and 8.0.
The compositions of the present invention may be prepared using the general techniques known in the art of the processing of liquid detergent products. However, the order of addition of components can be important. Thus, a preferred order of addition (with continuous mixing) is to add to the water, the soluble electrolytes, then any insoluble material such as aluminosilicates, followed by the actives. The mixtures 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 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.

Examples 1-6
	(weights in w/w)
Ingredient	1	2	3	4	5	6
K-LAS	4.0	2.7	3.4	3.4	4.0	4.0
K-Oleate	5.5	6.8	7.5	5.5	5.5	5.5
CDEA	2.0	2.0	2.0	2.0	2.0	2.0
Neodol 23-6.5	3.6	3.6	2.4	4.2	3.6	3.6
Na-citrate 2 aq.	6.8	6.8	6.8	6.8	3.4	4.6
Na-disilicate	2.0	2.0	2.0	2.0	2.0	2.0
Na-carbonate	2.0	2.0	2.0	2.0	2.0	2.0
Zeolite 4A	21.6	21.6	21.6	21.6	21.6	21.6
Water	balance
Viscosity (mPas, 4s⁻¹)	1000	2000	N/A*	N/A*	5200	5500

* not available

Examples 7-11
	(weights in w/w)
Ingredient	7	8	9	10	11
Na-LAS	8.5	7.5	6.4	6.4	4.3
Na-Oleate	-	5.4	5.4	8.1	5.4
Na-Laurate	5.6	-	-	-	-
Synperonic A7	2.0	3.0	4.0	4.0	6.0
Glycerol	5.0	5.0	5.0	5.0	5.0
Borax	3.5	3.5	3.5	3.5	3.5
STP	22.0	22.0	22.0	22.0	22.0
Water	balance
Viscosity mPas 21s⁻¹)	2730	1660	2490	4640	1390

Examples 12-16
	(weights in w/w)
Ingredient	12	13	14	15	16
Na-LAS	4.3	10.0	10.0	10.5	10.5
Na-Oleate	8.1	-	-	-	-
K-Oleate	-	6.0	6.0	6.0	5.5
Synperonic A7	6.0	4.0	4.0	3.5	4.0
Glycerol	5.0	4.85	4.85	4.85	4.85
Borax	3.5	3.1	3.1	3.1	3.1
STP	22.0	15.0	15.0	15.0	15.0
SCMC	-	0.1	0.1	0.1	0.1
Fluorescer	-	0.1	0.1	0.1	0.1
Silicone Oil	-	-	0.25	0.25	0.25
Synthetic Amorphous Silica	-	2.0	2.0	2.0	2.0
Perfume	-	0.3	0.3	0.3	0.3
Enzyme	0.5	0.5	0.5	0.5	0.5
Water	balance
Viscosity (mPas, 21s⁻¹)	3230	810	950	770	1500

Example 17
	wt.%
NaLAS	4.1
Synperonic A3	3.0
STP	15.0
K-Oleate	10.0
NaCl	2.0
Glycerol	4.85
Borax	3.10
Anti-foam	0.20
Enzyme	0.5
Fluorescer	0.1
SCMC	0.1
Water	balance
Viscosity approx. 880 mPas at 21s⁻¹

Example 18
	wt.%
NaLAS	6.0
Synperonic A3	4.0
STP	15.0
K-Oleate	10.0
PEG 400	3.0
Alcosperse 175	1.0
STS	0.5
Na₂SO₄	0.5
Glycerol	4.85
Borax	3.10
Anti-foam	0.2
Enzyme	0.5
Fluorescer	0.1
SCMC	0.1
Water	balance
Viscosity approx. 880 mPas at 21s⁻¹

Raw Material Specification
LAS -	dodecyl benzene sulphonate
CDEA -	coconut diethanolamide
SCMC -	sodium carboxymethyl cellulose
STP -	sodium tripolyphosphate
STS -	sodium toluene sulphonate
PEG 400 -	polyethylene glycol, average molecular weight 400
Alcosperse 175 -	70/30 Acrylate/Maleate co-polymer (MW 20,000 ex ALCO)
Synperonic A7 -	C₁₂-C₁₃ fatty alcohol alkoxylated with an average of 7 moles of ethylene oxide per molecule.
Synperonic A3 -	C₁₂-C₁₃ fatty alcohol alkoxylated with an average of 3 moles of ethylene oxide per molecule.
Neodol 23-6.5 -	C₁₂-C₁₃ 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 compositions contain sufficient non-soap synthetic surfactant to ensure a high level of detergency performance.

Claims

1. An aqueous liquid detergent composition comprising more than 7.0% by weight of non-soap synthetic detergent and at least 5.0% 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°C, said composition having a pH of less than 12.0.

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

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.

5. A composition according to 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.

8. An aqueous liquid detergent composition according to Claims 1-5, having a viscosity of no more than 6.0 Pas at a shear rate of 21 s⁻¹.

9. An aqueous liquid detergent composition according to Claims 1-6, having a pH between 7.0 and 11.0.

10. Use of an aqueous liquor comprising from 0.1 to 10% by weight of a composition according to one or more of the preceding Claims for the washing of fabrics.