DE69016449T2 - LIQUID CLEANING AGENTS. - Google Patents

Description

The present invention relates to aqueous liquid cleaning agents containing sufficient detergent material and optionally sufficient dissolved electrolyte for a structure of lamellar droplets dispersed in a continuous aqueous phase.

Lamellar droplets are a special class of surfactant structures that are known from numerous literature sources, for example from H.A. Barnes, "Detergents", Chapter 2, in K. Walters (ed.), "Rheometry: Industrial Applications", J. Wiley & Sons, Letchworth 1980.

Such lamellar dispersions are used to impart such properties as consumer-preferred flow and/or hazy appearance. Many are also capable of suspending particulate solids such as detergent builders or abrasive particles. Examples of such structured liquids without suspended particles are given in US Patent 4,244,840, while examples in which particles are suspended are disclosed in the specifications EP-A-160 342; EP-A-38 101; EP-A-140 452 and also in the above-mentioned US-A-4,244,840. Others are described in European Patent Application EP-A-151 884, in which the lamellar droplets are called "spherulites".

The presence of lamellar droplets in a liquid detergent product can be determined by means known in the art, for example optical techniques, various rheometric measurement techniques, X-ray or neutron scattering and electron microscopy.

The droplets consist of an onion-skin-like configuration of concentric bilayers of surfactant molecules, between which water or electrolyte solution (aqueous phase) is enclosed. Systems in which such droplets are densely packed represent a quite desirable combination of physical stability and solid-suspending properties with usable flow properties.

The viscosity and stability of the product depends on the volume fraction of liquid occupied by the droplets. Generally speaking, if the volume fraction is about 0.6, the droplets are just touching each other (space filling). This allows reasonable stability with acceptable viscosity (i.e. greater than 2.5 Pas, preferably not more than 1 Pas at a shear rate of 21 s-1). This volume fraction also imparts useful solid-suspending properties.

One problem in the formulation of liquid detergents is preventing flocculation. When flocculation occurs between the lamellar droplets at a given volume fraction, the viscosity of the corresponding product increases due to the formation of a network by the liquid. Flocculation can also lead to instability, which manifests itself as phase separation of the product.

It is an object of the invention to minimize flocculation of liquid detergents of the lamellar droplet type. Another object of the present invention is to formulate stable liquid detergents with a relatively high pH and relatively low viscosity.

It has been proposed in GB 1 506 427 to formulate liquid detergent compositions containing 5 essential ingredients in specified relative amounts. The compositions described contain 3 to 12% by weight of an alkylbenzene sulphonate, 2 to 8% by weight of a potassium soap of a C 8-22 fatty acid or polymers thereof and 0.5 to 5% by weight of a non-ionic detergent material, the relative proportions of the active ingredients being within narrowly defined ranges. Compositions of this patent comprise 1 to 25% of an alkali metal tripolyphosphate and 0.1 to 2% of a specific copolymer of maleic anhydride with vinyl methyl ether, ethylene or styrene, partially esterified with the non-ionic detergent. GB 1 589 971 relates to similar compositions in which part of the alkali metal tripolyphosphate is replaced by tetrapotassium pyrophosphate. The pH of the agents exemplified is 12.5, which is generally too low for certain purposes, for example for the industrial cleaning of textiles, the viscosity of the products is 550 mPas or more at 30 s⊃min;¹.

It has now surprisingly been found that stable liquid detergents of the lamellar droplet type can be formulated with a high pH and acceptable viscosity provided that they contain a deflocculant polymer. Suitable deflocculant polymers are, for example, polymers containing a hydrophilic backbone and one or more hydrophobic side chains.

Accordingly, the present invention relates to a cleaning agent comprising a dispersion of lamellar droplets of detergent-active materials in an aqueous continuous phase, the agent comprising a deflocculating polymer selected from the group of:

(i) polymers comprising a hydrophilic backbone and one or more hydrophobic side chains, with the proviso that if the agent comprises 3 to 12% of a potassium alkylbenzene sulfonate, 2 to 8% of a potassium fatty acid soap, 0.5 to 5% of a nonionic surfactant and 1 to 25% of a potassium or sodium tripolyphosphate and/or tetrapotassium pyrophosphate, all percentages are by weight, the weight ratio of the sulfonate to the soap is 1:2 to 6:1, the weight ratio of the sulfonate to the nonionic surfactant is 3:5 to 25:1 and the total amount of sulfonate, soap and nonionic surfactant is 7.5 to 20% by weight, then the deflocculating polymer consists not only of 0.1 to 2% by weight of a partially esterified, neutralized copolymer of maleic anhydride with vinyl methyl ether, ethylene or styrene; and

(ii) polymers consisting of non-ionic monomers and ionic monomers, wherein the ionic monomer constitutes 0.1 to 50 wt.% of the polymer,

the agent having a pH greater than 12.5 and not giving more than 10% by volume of phase separation when stored at 25ºC for 21 days from the date of manufacture.

The compositions of the invention are stable. In the context of the present invention, stability for these systems can be defined in terms of the maximum separation consistent with most manufacturing and retail requirements. That is, stable compositions will give no more than 10%, preferably no more than 5%, most preferably no more than 2% by volume of phase separation, as evidenced by the appearance of 2 or more separate phases after storage at 25°C for 21 days from the time of manufacture.

Agents according to the invention have a pH value of more than 12.5, preferably more than 13.0, particularly preferably more than 13.5. These high pH values make the products according to the invention particularly suitable for producing liquid cleaning agents that are suitable for use in the industrial cleaning of textiles.

Agents according to the invention preferably have a viscosity of less than 2500, in particular less than 1000 mPas at 21 s⁻¹, more preferably less than 750 mPas, most preferably less than 500 mPas, particularly preferably between 100 and 400 mPas at 21 s⁻¹.

Suitable deflocculating polymers for use in the composition of the invention are described, for example, in our pending European Patent Application 89201530.6 (EP 346 995). In general, the hydrophilic backbone of the polymer is predominantly linear (the main chain of the backbone accounts for at least 50%, preferably more than 75%, most preferably more than 90% by weight of the backbone); suitable monomer constituents of the hydrophilic backbone are, for example, unsaturated C₁₋₆ acids, ethers, alcohols, aldehydes, ketones or esters, sugar units, alkoxy units, maleic anhydride and saturated polyalcohols such as glycerol. Examples of suitable monomer units are acrylic acid, methacrylic acid, maleic acid, vinylacetic acid, glucosides, ethylene oxide and glycerol. The hydrophilic framework prepared from the framework components in the absence of hydrophobic side groups is relatively water-soluble at ambient temperatures and at a pH between 10.0 and 15.0. Preferably, the solubility is more than 1 g/l, more preferably more than 5 g/l, most preferably more than 10 g/l. Most preferably, the hydrophilic framework remains soluble at these concentrations in the presence of up to 40 wt.% electrolyte (eg sodium citrate).

Preferably, the hydrophobic side groups are composed of relatively hydrophobic alkoxy groups, for example butylene oxide and/or propylene oxide and/or alkyl or alkenyl chains having 5 to 24 carbon atoms. The hydrophobic groups can be linked to the hydrophilic backbone via relatively hydrophilic bonds, for example a polyethoxy bond.

Preferred polymers are those of the formula:

wherein:

Q2 represents a moiety of formula (Ia):

wherein:

R¹ represents -CO-O-, -O-, -O-CO-, -CH₂-, -CO-NH- or is absent; in particular, it has been found that a -CO-O- bond is more stable at high pH values than a -O-CO- bond.

R² represents 1 to 50 independently selected alkyleneoxy groups, preferably ethylene oxide or propylene oxide groups, or is absent; with the proviso that if R³ is absent and R⁴ represents a hydrogen atom or contains not more than 4 carbon atoms, then R² must contain an alkyleneoxy group, preferably with more than 5 alkyleneoxy groups having at least 3 carbon atoms;

R³ represents a phenylene bond or is not present;

R⁴ represents a hydrogen atom or a C₁₋₂₄-alkyl or C₂₋₂₄-alkenyl group; with the provisos that

a) when R¹ represents -O-CO-, R² and R³ must not be present and R⁴ must contain at least 5 carbon atoms;

b) if R² is not present, R⁴ is not a hydrogen atom and if R³ is also not present, R⁴ must contain at least 5 carbon atoms;

R⁵ represents a hydrogen atom or a group of the formula -COOA⁴;

R⁶ represents a hydrogen atom or a C₁₋₄-alkyl group and

A¹, A², A³ and A⁴ are independently selected from hydrogen atoms, alkali metals, alkaline earth metals, ammonium and amine bases and C₁₋₄ or (C₂H₄O)tH, where t is 1-50 and where the monomer units can be in random order,

Q¹ is a multifunctional monomer that allows the branching of the polymer, whereby the monomers of the polymer can be bonded to Q¹ in any direction and in any order, optionally resulting in a branched polymer, whereby trimethylpropane triacrylate (TMPTA), methylenebisacrylamide or divinyl glycol is preferred for Q¹,

n is at least 1; z and v are 1; and (x + y + p + q + r): z is 4:1 to 1000:1, preferably 6:1 to 250:1, where the monomer units may be arranged in a random manner; and preferably p or q are zero or r is zero;

R⁷ and R⁸ represent -CH₃ or -H;

R⁹⁰ and R¹⁰ represent substituent groups such as amino, amine, amide, sulfonate, sulfate, phosphonate, phosphate, hydroxy, carboxyl and oxide groups, preferably those selected from -SO₃Na, -CO-O-C₂H₄-OSO₃Na, -CO-O-NH- C(CH₃)₂-SO₃Na, -CO-NH₂, -O-CO-CH₃, -OH.

Preferred polymers for use in the agents according to the invention are essentially free of hydrolyzable groups, such as carbonyl groups, for increased polymer stability at high pH values. Particularly preferred polymers for use in agents according to the invention comprise hydrophilic backbones consisting of acid groups, such as acrylic acid, and at least one hydrophobic side chain consisting of 5 to 75 relatively water-insoluble alkoxy groups, such as propoxy units, optionally bonded to the hydrophilic backbone via a polyalkoxy bond consisting of 1 to 10 relatively water-soluble alkoxy groups, such as ethoxy units. Other preferred polymers are copolymers of acidic groups, such as acrylic acid, and α-olefins containing at least 5 carbon atoms. Polymers as in formula IA, wherein R¹ is -CO-O-, are more preferred than polymers wherein R¹ is -O-CO-, due to better stability at higher pH values than the former.

Other polymers for use in the compositions of the invention are described in our co-pending, non-prepublished PCT patent applications WO/91/06622 (published 16 May 1991) and WO/91/06623 (published 16 May 1991) and our co-pending, non-prepublished British patent publication GB 2 237 813 (published 15 May 1991). Of the polymers described in those patent applications, the use of polymers according to our non-prepublished patent application WO/91/06623 (published 16 May 1991) is particularly preferred.

These polymers are composed of non-ionic monomers and ionic monomers, with the ionic monomer making up 0.1 to 50 wt.% of the polymer. Preferred polymers of this type are those of the formula:

wherein: x, z and n are as described above;

- R³ and R⁴ represent a hydrogen atom or C₁₋₄-alkyl;

- R² represents -CO-O-, -O-, -O-CO-, -CH₂-, -CO-NH- or is not present;

- R¹ -C₃H₆-N⁺-(CH₃)₃(Cl⁻), -C₂H₄-OSO₃⁻(Na⁻), -SO₃⁻(Na⁻), -C₂H₄-N⁺(CH₃)₃Cl⁻, -C₂H₄-N⁺(C₂H₆)₃Cl⁻, -CH₂N⁺(CH₃)₃Cl⁻, -CH₂N⁺(C₂H₆)₃Cl⁻ or benzyl-SO₃⊃min;(Na⁺);

- Ra is CH₂, C₂H₄, C₃H₆ or is absent;

- Rb represents 1 to 50 independently selected alkylene oxide groups, preferably ethylene oxide groups, or is not present;

- Rc represents -OH or -H;

and wherein, when R², Ra and R b are not present, Rc is not -H .

Other preferred polymers have the formula:

wherein:

- x = x₁ + x₂

- x, z and n are as defined above

- R¹ represents -CH₂O- or -O-;

- R² represents -CH₂COO⁻Na⁺ or -C₃H₆ON⁻(CH₃)₃Cl⁻

- R³ and R⁴ represent -OH, -CH₂OH, -O(C₃H₆O)p-H, -CH₂-O(C₃H₆O)p-H or -OCH₂COO⁻⁺Na⁺ or -O-C₃H₆ON⁺(CH₃)₃Cl

- R⁵ represents -OH, -NH-CO-CH₃ or -O(C₃H₆O)p-H

- R⁶ represents -OH, -CH₂OH, -CH₂-OCH₃, -O(C₃H₆O)p-H or -CH₂-O-(C₃H₆O)p-H

- p means from 1 to 10.

Preferably, polymers for use in the compositions have a molecular weight (determined as in our co-pending European patent application 346 995) of between 500 and 100,000, more preferably 1,000 to 20,000, most preferably 1,500 to 10,000. Polymers for use in compositions according to the invention can be prepared, for example, using conventional aqueous polymerization processes. Suitable processes are described, for example, in the above-mentioned co-pending European patent application.

Generally, the deflocculant polymer is used in an amount of 0.01 to 5% by weight of the composition, more preferably 0.1 to 3.0%, most preferably 0.25 to 2.0%.

Compositions according to the invention also comprise a detergent material, preferably in an amount of 1 to 70%, based on the weight of the composition, more preferably a proportion of 5 to 40% by weight, most preferably 10 to 35% by weight.

In the case of surfactant mixtures, the exact ratios for each component leading to lamellar structures will depend on the type(s) and amount(s) of electrolytes, as in the case of conventional structured fluids.

In the broadest definition, the detergent material may generally comprise one or more surfactants and may be selected from anionic, cationic, nonionic, zwitterionic and amphoteric forms and (provided that they are compatible with each other) or mixtures thereof. For example, they may be selected from any of the classes, subclasses and specific materials described in "Surface active Agents", Vol. I, by Schwartz & Perry, Interscience 1949 and "Surface active Agents", Vol. II, by Schwartz, Perry & Berch, Interscience 1958 and in the current edition of "McCutcheon's Emulsifiers &Detergents", published by McCutcheon's Division of Manufacturing Confectioners Company or in "Tensid-Taschenbuch", H. Stache, 2nd ed., Carl Hanser Verlag, Munich & Vienna, 1981.

Suitable nonionic surfactants are in particular the reaction products of compounds having a hydrophobic group and a reactive hydrogen atom, for example aliphatic alcohols, acids, amides or alkylphenols with alkylene oxides, in particular ethylene oxide, either individually or with propylene oxide. Characteristic nonionic surfactant compounds are alkyl (C6-C18) primary or secondary linear or branched alcohols with ethylene oxide and products prepared by condensation of ethylene oxide with the reaction products of propylene oxide and ethylenediamine. Other so-called nonionic surfactant compounds are long-chain tertiary amine oxides, long-chain tertiary phosphine oxides and dialkyl sulfoxides.

It is also possible to use salting-resistant active substances, as disclosed for example in EP 328 177, in particular the use of alkyl polyglycoside surfactants, as disclosed for example in EP 70 074. Monoglycosides can also be used.

Preferably, the amounts of non-ionic surfactants are more than 1% by weight of the composition, preferably 2 to 20.0% by weight of the composition, more preferably 5.0 to 19% by weight, particularly preferably 10.0 to 18.0% by weight.

Compositions of the present invention may contain synthetic anionic surfactant ingredients, preferably in combination with the above-mentioned nonionic materials. Suitable anionic surfactants are conventional water-soluble alkali metal salts of organic sulfates and sulfonates having alkyl radicals containing 8 to 22 carbon atoms, the term alkyl used including the alkyl radical of higher acyl radicals. Examples of suitable synthetic anionic surfactant compounds are sodium and potassium alkyl sulfates, in particular those obtainable by sulfonating higher (C8-C18) alcohols, for example from tallow or coconut oil, sodium and potassium alkyl (C9-C20) benzene sulfonates, in particular linear secondary alkyl (C10-C15) benzene sodium sulfonate; sodium alkyl glyceryl ether sulfates, in particular those ethers of higher alcohols derived from tallow or coconut oil and synthetic alcohols derived from petroleum; coconut oil fatty acid monoglyceride sulfates and sulfonates; Sodium and potassium salts of reaction products of sulfuric acid esters of higher (C8-C18) fatty alcohol alkylene oxide, especially ethylene oxide; the reaction products of fatty acids such as coconut fatty acids esterified with isethionic acid and neutralized with sodium hydroxide; sodium and potassium salts of fatty acid amides of methyltaurine; alkane monosulfonates such as those derived by reacting α-olefins (C8-C20) with sodium bisulfite and those derived from the reaction of paraffin with SO2 and Cl2 followed by hydrolysis with a base to produce a randomly sulfonated product; and olefin sulfonates, which term is used to describe the material obtained by reacting olefins, particularly C10-C20 alpha-olefins, with SO3 and then neutralizing and hydrolyzing the reaction product. The preferred anionic surfactant compounds are sodium (C11-C15) alkylbenzenesulfonates, sodium (C16-C18) alkyl sulfates, and primary sodium or potassium (C10-C24) alkyl sulfates.

In general, the proportion of the above-mentioned anionic surfactant materials will amount to 1-15% by weight of the composition. Preferably, however, small particles of these anionic materials are used, for example less than 5%, more preferably less than 3% by weight of the composition, particularly preferably less than 2.5%. In particular, the weight ratio of the above-mentioned synthetic anionic surfactant materials to the non-ionic surfactant materials is less than 1:2, more preferably less than 1:3, particularly preferably 1:4 to 1:10.

It is also possible and sometimes preferred to add an alkali metal soap of a mono- or dicarboxylic acid, in particular a soap of an acid having 12 to 18 carbon atoms, for example oleic acid, ricinoleic acid or fatty acids derived from castor oil, rapeseed oil, peanut oil, coconut oil, palm kernel oil or mixtures thereof. The sodium or potassium soaps of these acids can be used. Preferably the proportion of soaps in the compositions of the invention is 5-35% by weight of the composition, more preferably 10-25%.

The compositions optionally also contain electrolyte in an amount sufficient to give rise to some lamellar structure of the detergent material. Preferably, the compositions contain from 1 to 60%, especially from 10 to 45%, of a salting-out electrolyte. Salting-out electrolyte has been explained in terms of its meaning in the description of EP-A-79 646, i.e. those electrolytes having a lyotropic number of less than 9.5. Optionally, some salting-in electrolyte (as defined in the later parts of the description) may also be included.

In any event, it is preferred that compositions according to the invention containing detergent builder material may contain some or all of the electrolyte. In this connection, it should be noted that some detergent materials, for example soaps, also have builder properties.

Examples of phosphorus-containing inorganic detergent builders are water-soluble salts, in particular alkali metal pyrophosphates, orthophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate builders are sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Phosphonate sequestering builders may also be used. However, it is sometimes preferred to reduce the amount of phosphate builders. In particular, the amount of alkali metal phosphate builders, such as sodium tripolyphosphate, is preferably less than 0.5% by weight of the composition, more preferably less than 0.1%, in particular Preferred compositions of the invention are substantially free of phosphate builder materials.

Examples of non-phosphorus inorganic detergent builders, when present, are water-soluble alkali metal carbonates, bicarbonates, silicates and crystalline and amorphous aluminosilicates. Specific examples are sodium carbonate (with or without calcite seeds), potassium carbonate, sodium and potassium bicarbonates, silicates and zeolites. For high pH compositions according to the invention, the use of silicate builders is preferred as these materials are particularly advantageous due to their buffering capacities at pH values above 12.5.

In connection with inorganic builders, we prefer the addition of electrolytes that promote the solubility of other electrolytes, for example the use of potassium salts to improve the solubility of sodium salts. This can significantly increase the amount of dissolved electrolyte (crystal solution), as described in British Patent Specification GB 1 302 543.

Examples of organic detergent builders, when present, are alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, polyacetylcarboxylates and polyhydroxysulfonates. Specific examples are sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid, mellitic acid, benzenepolycarboxylic acids, CMOS, tartrate monosuccinate, tartrate disuccinate and citric acid.

In connection with organic builders, it is also beneficial to add polymers that are only partially dissolved in the aqueous continuous phase, according to EP-A-301 882. This allows a viscosity reduction (due to the polymer being dissolved) during the addition of a sufficiently high amount for a secondary beneficial effect, in particular builder effect, since partially dissolved, unlike fully dissolved, would not cause instability. Typical amounts are from 0.5 to 4.5 wt.%.

It is also possible to incorporate the inventive Means alternatively or in addition to the partially dissolved polymer, adding another polymer which is substantially completely soluble in the aqueous phase and has an electrolyte resistance of more than 5 g of sodium nitrilotriacetate in 100 ml of a 5 wt.% aqueous solution of the polymer, the second polymer also having a vapor pressure in 20% aqueous solution which is equal to or less than the vapor pressure of a comparative aqueous solution of 2 wt.% or more of polyethylene glycol having an average molecular weight of 6000; and the second polymer having a molecular weight of at least 1000. The use of such polymers is generally described in our EP-A-301 883. Typical concentrations are from 0.5 to 4.5 wt.%.

Particularly preferred compositions according to the invention have a low viscosity (less than 500 mPas at 21 s⊃min;¹) and are substantially free of suspended solids, such as undissolved builder materials. Preferably, the proportion of less soluble builder materials, such as sodium tripolyphosphate, is less than 1%, more preferably less than 0.5%, most preferably less than 1%, and most preferably the builder materials for use in the compositions according to the invention are completely water-soluble.

Preferably, the concentration of non-soap builder materials is 5-40% by weight of the composition, more preferably 5 to 25% by weight of the composition. Particularly preferred is the use of 5-20% by weight of the composition of a silicate builder material, preferably a metasilicate builder material.

Preferred compositions of the invention comprising 5 to 99% by weight water, more preferably 10-50%, most preferably 15 to 40%.

In addition to the components already mentioned, a number of optional components may also be present, for example foam improvers such as alkanolamides, in particular monoethanolamides, derived from palm kernel fatty acids and coconut fatty acids, textile softening agents such as clays, amines and amine oxides, foam inhibitors, 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 in very small quantities, fluorescent agents, perfumes, enzymes such as proteases, amylases and lipases (including Lipolase (registered trademark) from Novo), anti-deposit agents, germicides and colouring agents.

Compositions according to the invention can be prepared by conventional methods for preparing liquid detergents. A preferred method involves dispersing the electrolyte component together with the minor components, excluding the temperature sensitive components, if present, in water at elevated temperature, followed by the addition of the builder material, if present, the deflocculating polymer and the detergent material (optionally as a premix) being added with stirring, followed by the addition of the softening materials, the mixture being cooled and the temperature sensitive minor components, such as enzymes, perfumes, etc., being added.

When using the detergents according to the invention, they are diluted with washing water to form a washing liquor, for example for use in a washing machine. The concentration of liquid detergent in the washing liquor is preferably 0.1 to 10%, more preferably 0.1 to 3% by weight.

The invention will now be explained using the following examples.

The names "Marlon", "Prifac", "Priolene", "Plurafac", "Marlipal", "Synperonic" and "Tinopal" used in the examples are trademarks.

Example I

The following compositions were prepared by adding KOH plus silicate ingredients to ambient temperature water with stirring, followed by addition of the deflocculant polymer. The detergent materials are premixed and then added to the aqueous mixture. Finally, the remaining ingredients are added. The pH value of the product is about 14.0. Component % (weight) ABS (Marlon AS3) Soap (Prifac 9470) Soap (Priolene 6902) Nonionic (Plurafac LF403) Nonionic (Marlipal 13/60) Neutral water glass (100%) KOH (100%) Polymer1) Water Balance 1) Polymer A-11 as described in EP 346 995.

Agent A had a viscosity of 280 mPas at 21 s⁻¹, Agent B of 490 mPas at 21 s⁻¹, Agents C-F had viscosities of about 300 mPas. Agent G (comparison) was unstable (more than 10% phase separation after storage for 3 weeks), no viscosity was measured from this agent. Agents A-F were stable lamellar dispersions of active ingredients on an aqueous basis. The lamellar phase volume of these agents was 0.5 to 0.67.

Example II

The following compositions were prepared as in Example I. Component (wt.%) Plurafac LF403 LAS (Marlon AS3) Oleate Sodium citrate Neutral water glass (34 %) Polymer1) Water Viscosity (mPas at 21 s⊃min;¹) compensation

1) Polymer A-11 as described in EP 346 995

The pH of the products was 14 or more. The performance of the products was tested by washing at 60ºC at a dosage of 5 g/l in the presence of a standard soiled textile AS 9. The following rating was obtained: Medium cleaning rating

Example III

The following remedies were prepared as in the previous examples: Component (wt.%) Surfactants1) Sodium citrate Neutral water glass Polymer2) Polymer3) Water Balance

1) Mixture of Synperonic A7, Marlon AS3 and oleate in a weight ratio of 2.5:1:2.

2) A copolymer of acrylic acid and α-(C₁₂)-olefinic monomers in a molar ratio of 20:1 and a molecular weight of 4800.

3) Polymer A-11, described in EP 346 995.

Agent I had a viscosity of 1680 mPas at 21 s⊃min;1, Agent II had a viscosity of 648 mPas at 21 s⊃min;1

Both agents had a pH of 14 or more.

Example IV

The following remedies were prepared as in the previous examples. Component (wt.%) Nonionic1) Nonionic2) Marlon AS3 Priolene 6903 Priolene 6902 Priolene 6900 Prifac 7904 neutral water glass Tinopal CBSX Polymer3) Polymer4) Water balance

1) Plurafac LF 403

2) Marlipal 013/60

3) Polymer A-11 of EP 346 995

4) Copolymer of acrylic acid and a monomer of the formula

in a molar ratio of 25:1, with a molecular weight of 3100.

The agents had a pH of 14 or more, all formulations were physically stable for more than one month after storage at 37ºC.

Example V

The following formulations were prepared by adding the ingredients in the order listed: Component (wt.%) Water Sodium citrate 2 eq. neutral water glass (34 %) KOH (50 %) Polymer1) (29 %) Polymer2) (25 %) Marlipal 013/60 Priolene 6902 Marlon AS3

1) A copolymer of acrylic acid and α-(C₁₂)-olefinic monomers in a molar ratio of 33:1 and with a molecular weight of 8700.

2) A copolymer of acrylic acid and α-(C₁₂)-olefinic monomers in a molar ratio of 50:1 and with a molecular weight of 7100.

Both agents had a pH value of more than 14.

The viscosity of agent A was 504 mPas at 21 s⁻¹, the viscosity of agent B was 384 mPas at 21 s⁻¹.

Claims (7)

1. A liquid cleaning agent comprising a dispersion of lamellar droplets of detergent materials in an aqueous continuous phase, the agent comprising a deflocculating polymer selected from the group of: (i) polymers comprising a hydrophilic backbone and one or more hydrophobic side chains, with the proviso that if the agent comprises 3 to 12% of a potassium alkylbenzene sulfonate, 2 to 8% of a potassium fatty acid soap, 0.5 to 5% of a nonionic surfactant and 1 to 25% of a potassium or sodium tripolyphosphate and/or tetrapotassium pyrophosphate, all percentages are by weight, the weight ratio of the sulfonate to the soap is 1:2 to 6:1, the weight ratio of the sulfonate to the nonionic surfactant is 3:5 to 25:1 and the total amount of sulfonate, soap and nonionic surfactant is 7.5 to 20% by weight, then the deflocculating polymer consists not only of 0.1 to 2% by weight of a partially esterified, neutralized copolymer of maleic anhydride with vinyl methyl ether, ethylene or styrene; and (ii) polymers consisting of non-ionic monomers and ionic monomers, wherein the ionic monomer constitutes 0.1 to 50 wt.% of the polymer, the agent having a pH greater than 12.5 and not giving more than 10% by volume of phase separation when stored at 25ºC for 21 days from the date of manufacture. 2. Agent according to claim 1 with a pH value of more than 13.0. 3. Agent according to claim 1 having a viscosity of less than 500 mPa s at 21 s⊃min;¹. 4. Agent according to claim 1, comprising 0.01 to 5.0 wt.% of deflocculating polymers. 5. Agent according to claim 1, comprising 5-40 wt.% washing-active materials. 6. Agent according to claim 5, comprising 5.0 to 19.0% nonionic surfactant. 7. A composition according to claim 1 comprising 5 to 20% silicate builder material, the composition being substantially free of phosphate builder materials.