EP0100125B1 - Flüssige Reinigungsmittelzusammensetzungen, eine Koazervatmischung aus Alkylcellulose enthaltend und Carboxymethylcellulose und Verfahren zu deren Herstellung - Google Patents

Flüssige Reinigungsmittelzusammensetzungen, eine Koazervatmischung aus Alkylcellulose enthaltend und Carboxymethylcellulose und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0100125B1
EP0100125B1 EP83201070A EP83201070A EP0100125B1 EP 0100125 B1 EP0100125 B1 EP 0100125B1 EP 83201070 A EP83201070 A EP 83201070A EP 83201070 A EP83201070 A EP 83201070A EP 0100125 B1 EP0100125 B1 EP 0100125B1
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EP
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Prior art keywords
weight
composition
anionic
nonionic
coacervate
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EP83201070A
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English (en)
French (fr)
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EP0100125A3 (en
EP0100125A2 (de
Inventor
Jean Wevers
Barry Stoddart
Christian Barrat
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Procter and Gamble Co
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Procter and Gamble Co
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Priority to AT83201070T priority Critical patent/ATE39126T1/de
Publication of EP0100125A2 publication Critical patent/EP0100125A2/de
Publication of EP0100125A3 publication Critical patent/EP0100125A3/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/83—Mixtures of non-ionic with anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0026—Structured liquid compositions, e.g. liquid crystalline phases or network containing non-Newtonian phase
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/22—Carbohydrates or derivatives thereof
    • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
    • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/38—Products with no well-defined composition, e.g. natural products
    • C11D3/386—Preparations containing enzymes, e.g. protease or amylase
    • C11D3/38618—Protease or amylase in liquid compositions only
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • C11D1/143—Sulfonic acid esters
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • This invention relates to aqueous homogeneous liquid detergent compositions comprising surface-active agents and a mixture, in additive level, of alkylcellulose and carboxymethylcellulose.
  • the invention herein relates to concentrated homogeneous compositions comprising a coacervate mixture of known anti-redeposition agents in combination with high levels of anionic and nonionic surface-active agents.
  • the mixture of anti-redeposition agents is present as a coacervate capable of forming, in combination with the surfactants, a network of loosely associated droplets.
  • This tridimensional network provides means for stably and homogeneously suspending detergent components/additives which otherwise could not be incorporated, particularly ingredients which are substantially insoluble in the liquid matrix.
  • compositions herein are especially beneficial in several respects.
  • the claimed compositions exhibit the benefits attached to the utilization of anti-redeposition agents.
  • the tridimensional network provides a "honey comb-" or "wine cellar-” like structure, i.e, means for incorporating desirable detergent additives which up to now could not be compatibly incorporated into the like compositions because of phase separation, sedimentation, flocculation, coalescence or other known phenomena which can destablize the like liquid compositions.
  • the compositions herein do not require highly viscous and/or thixotropic consistencies with a view to stabilize the cellulose ether coacervate.
  • alkylcellulose and carboxymethylcellulose are well known in detergents and has found widespread commercial application, particularly in granular detergents, in an anti-redeposition functionality.
  • incorporation of these cellulose ethers in liquid detergents is subject to considerable difficulties.
  • the solubilization of anti-redeposition agents in liquid detergents is virtually impossible in presence of anionic surface-active agents.
  • stable cellulose ether dispersions require frequently high product viscosities with or without thixotropic properties. It is understood that product viscosity serves as a means to provide homogeneous dispersions as a result of decreased phase separation.
  • Dispersion stability can allegedly also be obtained from using mixtures of anionic and nonionic cellulose ethers.
  • This approach in fact, aims at providing equilibrium between ascending and descending tendencies of the nonionic and anionic particles respectively.
  • the latter approach is disclosed in FR-A-1 192 968.
  • Phosphate built, highly alkaline, liquid detergent compositions are disclosed containing mixtures of different cellulose ether derivatives.
  • the '638 technology requires an excess of methylcellulose over carboxymethylcellulose.
  • U.S. Patent 3,328,305 patented June 27, 1967, relates to a process for preparing detergent formulations containing separately prewetted cellulose ethers.
  • the prewetting step is carried out with fatty acids which are liquid at ambient temperatures.
  • German Patent Application 24 02 225 discloses pourable, substantially non-aqueous, fluid masses having plastic Bingham-properties. Dispersed particulate solids are suspended in the fluid compositions with the aid of a fibrous tridimensional network. Fatty acid soaps constitute the network structure which network can serve to suspend particulate materials such as inorganic abrasives, or pigments.
  • US-Patent 3,523,088 pertains to an antiredeposition agent and detergent compositions containing same.
  • the antiredeposition agent is represented by a mixture of alkali metal carboxymethylcellulose and hydroxypropylcellulose.
  • the prior art has, as of yet, not suggested means for effectively using mixtures of anionic and nonionic cellulose ethers, having a coacervate network structure, in liquid detergents.
  • the art is non-suggestive of formulating stable liquid detergents containing cellulose ethers having a low viscosity without thixotropic properties.
  • the art is silent with respect to advantageously utilizing a cellulose ether coacervate network structure for stably incorporating ingredients which otherwise would be difficulty incorporatable, e.g., ingredients which are normally insoluble in the matrix.
  • a coacervate is in general an aggregate of colloidal droplets, held together by basic colloidal forces, frequently termed primary coacervate.
  • network herein stands for a coacervate network; it is a particular coacervate wherein colloidal isotropic droplets, having generally a diameter below 10 microns, are loosely associated into a three-dimensional network.
  • colloidal isotropic droplets having generally a diameter below 10 microns
  • This invention relates to aqueous homogeneous concentrated liquid detergents containing a coacervate of carboxymethyl cellulose and a mixture of anionic and nonionic surface-active agents.
  • the invention more specifically relates to homogeneous liquid detergent compositions containing:-
  • compositions of this invention have a pH measured "as is" at 20°C of from 6.0-10.
  • compositions herein comprise at least 5% by weight, calculated on the total detergent composition, of non-soap anionic surface-active agents.
  • the coacervate network provides storage stability and consequently an approch for beneficially utilizing the known anti-redeposition properties of the AC and CMC in liquid detergents. Additionally, the tridimensional coacervate network can serve to stably incorporate all kinds of detergent additives which up to now could not be effectively incorporated into the like composition because of known incompatibility to the general liquid system.
  • the preferred alkylcellulose for use herein is methylcellulose.
  • compositions of this invention comprise as a first essential component from 0.1 % to 3%, preferably from 0.5% to 1.5%, of a coacervate of a nonionic C i -C 4 alkyl, possibly hydroxylated, cellulose and an anionic carboxymethyl cellulose.
  • the nonionic C 1 -C 4 alkyl, possibly hydroxylated, cellulose is represented by methylcellulose.
  • the latter ingredient has normally a degree of substitution (DS) ranging from 0.5 to 2.8, preferably from 1.4 to 2.2. It is further characterized by a degree of polymerization (DP) between 50-1000, preferably between 150-300.
  • DS degree of substitution
  • DP degree of polymerization
  • suitable nonionic C l -C 4 alkyl cellulose for use herein include: methylcellulose DS 1.7; DP 200; ethylcellulose DS 1.5; DP 200; methylhydroxyethylcellulose DS 2.1; DP 200; and methylhydroxypropylcellulose DS 1.7; DP 200.
  • the DS indicates the number of substituted alkyl groups per anhydro-glucose unit.
  • the DP expresses the number of anhydro-glucose units present in the polymer molecule.
  • the anionic carboxymethylcellulose is represented by one having a DS ranging from 0.3 to 1.5, preferably from 0.6 to 0.9, and a DP in the range from 50-1000, preferably from 200-400.
  • Carboxymethylcellulose is eminently well-known in the detergent art.
  • the carboxymethylcellulose is preferably used as a salt with conventional cation such as sodium, potassium, amines, or substituted amines.
  • a typical example of a suitable carboxymethylcellulose is the sodium salt having a DS of 0.7 and a DP of 250.
  • the weight ratio of the alkylcellulose to carboxymethylcellulose is normally in the range from 4:1 to 1:6, preferably from 1:1 to 1:3.
  • a second essential ingredient for use in the compositions herein is represented by a mixture of anionic and nonionic surface-active agents.
  • This mixture is used in an amount of more than 20%, preferably in a level from 25% to 60%.
  • the nonionic surface-active agent represents more than 3% (of the total detergent composition) whereas the weight ratio of anionic to nonionic surface-active agents is in the range from 1 to 1 to 8 to 1, preferably from 1:1 to 4:1.
  • the non-soap anionic surface-active agent shall represent at least 5%, preferably more than 8%, of the total detergent composition.
  • Suitable anionic surface-active agents are usually selected from the group of sulfonates, sulfates, and carboxylates/soaps. These anionic detergents are eminently well-known in the detergent arts and have found wide-spread commercial application.
  • Preferred anionicwater-soluble sulfonate or sulfate surfactants have in their molecular structure an alkyl radical containing from 8 to 22 carbon atoms.
  • Examples of preferred anionic surfactant are the reaction products obtained by sulfating C 8 C l8 fatty alcohols derived from tallow and coconut oil; alkylbenzene sulfonates wherein the alkyl group contains from 8 to 15 carbon atoms; sodium alkylglyceryl ether sulfonates; ether sulfates of fatty alcohols derived from tallow and coconut oils; coconut fatty acid monoglyceride sulfates and sulfonates; and water-soluble salts of paraffin sulfonates having from 8 to 22 carbon atoms in the alkyl chain.
  • Sulfonated olefin surfactants as more fully described in e.g. U.S.
  • Patent Specification 3.332.880 incorporated herein by reference, can also be used.
  • the neutralizing cation for the anionic synthetic sulfonates and/or sulfates is represented by conventional cations which are widely used in detergent technology such as sodium, potassium, amines and substituted amines.
  • a preferred anionic surfactant component herein is represented by the water-soluble salts of an alkylbenzene sulfonic acid having from 10 to 13 carbon atoms in the alkyl group.
  • Preferred are the sodium, potassium and substituted amine, such as triethanolamine, salts.
  • Another preferred anionic surface-active agent is a sulfated C '2 -C '4 fatty alcohol, possibly with a degree of ethoxylation in the range from 1-4, in combination with alkylbenzene sulfonates in a weight ratio of 3:1 to 1:3.
  • Still another preferred anionic surfactant is a paraffin sulfonate having from 12 to 20, preferably from 14 to 18 carbon atoms in the alkyl chain.
  • the paraffin sulfonate can beneficially be used in combination with C,,-C 13 alkylbenzene sulfonate in e.g. a weight ratio of 1:3 to 3:1.
  • the anionic surface-active agent is usually represented by the salts of fatty acids having from 10 to 24, preferably 12 to 18, carbon atoms.
  • Suitable soap surface-active agents can originate from saturated and unsaturated fatty acids.
  • Suitable unsaturated fatty acid species include: palmitoleic, oleic, linoleic, linolenic and ricinoleic acid.
  • Highly preferred for use herein are fatty acids having from 16 to 18 carbon atoms and which are comprised of at least 30% of unsaturated species.
  • Other preferred fatty acids are represented by a mixture of saturated C 10 ⁇ C 14 (coconut) fatty acids and oleic acid in a ratio (weight) of from 2:1 to 1:3.
  • the nonionic surface-active agents are frequently ethoxylated. All ethoxylated nonionic surfactants which are known to be suitable for use in detergent application can be used in the compositions of this invention.
  • suitable nonionics include polyethoxylates derived from primary and secondary aliphatic alcohols having from 8 to 24 carbon atoms, and having a HLB (hydrophilic-lipophilic balance) in the range from 9 to 15. These ethoxylates frequently contain from 2 to 14 moles of ethylene oxide per mole of hydrophobic moiety.
  • the alkyl chain (hydrophobic moiety) can be represented by linear or branched fatty alcohols.
  • a preferred class of nonionic ethoxylates is represented by the condensation product of a fatty alcohol having from 12 to 15 carbon atoms and from 4 to 10 moles of ethylene oxide per mole of fatty alcohol.
  • Suitable species of this class of ethoxylates include: the condensation product of C '2 -C '5 oxo-alcohols and 7 moles of ethylene oxide per mole of alcohol; the condensation product of narrow cut C 14 ⁇ C 15 oxo-alcohols and 7 or 9 moles of ethylene oxide per mole of fatty (oxo) alcohol; the condensation product of a narrow cut C 12 ⁇ C 13 fatty (oxo) alcohol and 6.5 moles of ethylene oxide per mole of fatty alcohol; and the conddensation products of a C 'O -C '4 coconut fatty alcohol with a degree of ethoxylation (moles EO/mole fatty alcohol) in the range from 5 to 8.
  • the fatty oxo alcohols while mainly linar can have, depending upon the processing conditions and raw material olefins, a certain degree of branching, particularly short chain such as methyl branching.
  • a degree of branching in the range from 15% to 50% (weight %) is frequently found in commercial oxo-alcohols.
  • Preferred nonionic ethoxlated components can also be represented by a mixture of 2 separately ethoxylated nonionic surface-active-agents having a different degree of ethoxylation.
  • the nonionic ethoxylate can be represented by mixtures of a first ethoxylated surfactant containing from 3 to 7 moles of ethylene oxide per mole of hydrophobic moiety and a second ethoxylated species having from 8 to 14 moles of ethylene oxide per mole of hydrophobic moiety.
  • a preferred nonionic ethoxylated mixture contains a lower ethoxylate which is the condensation product of a C 12 ⁇ C 15 oxo-alcohol, with up to 50% (wt) branching, and from about 3 to 7 moles of ethylene oxide per mole of fatty oxo-alcohol, and a higher ethoxylate which is the condensation product of a C 16 ⁇ C 19 oxo-alcohol with more than 50% (wt) branching and from 8 to 14 moles of ethylene oxide per mole of branched oxo-alcohol.
  • nonionic and anionic surface-active agents are essential with a view to produce the coacervate network. It is believed that the anionic surfactant aids in the formation of a primary coacervate whereas the mixed non-soap anionic+nonionic surface-active agents promote the formation of a tridimensional network structure, usually starting from the primary coacervate.
  • the formation of the coacervate network can easliy be ascertained e.g. by microscopic, particularly dark-field, examination of the composition.
  • the network can be seen as a filamentous arrangement of aggregated droplets.
  • the coacervate network formation will occur provided water is used in a level in the range of from 10% to 50%.
  • This formulation parameter is expressed in the weight ratio of the total ingredients to water as being in the range of from 1:1 to 9:1.
  • total ingredient stands for the sum of all substances inclusive of surface-active agents, soaps, solvents, hydrotropes and organic and inorganic neutralizing agents.
  • the pH can have an adverse impact on the formation of the coacervate network. Under highly alkaline conditions e.g. pH above 10 the network formation can become more difficult, particularly if inorganic bases such as sodium or potassium hydroxide are used for pH adjustment.
  • inorganic bases such as sodium or potassium hydroxide are used for pH adjustment.
  • organic bases such as amines or substituted amines, is less damaging in this respect and some coacervate network formation can occur even under conditions of high alkalinity e.g. around pH 11.
  • compositions of this invention have a pH, measured "as is” and at 20°C, in the range from 6.0 to 10.
  • a preferred aspect of this invention relates to liquid detergent compositions which are essentially free of conventional water-soluble polyphosphate builders, having a pH in the range from 7 to 9 ("as is" -20°C).
  • water-soluble qualifies the dissolution of the particular polyphosphate in the total liquid detergent. More than subadditive levels, e.g. above 2%, of composition-soluble polyphosphates can inhibit the formation of the coacervate network because of excessive alkalinity and increase of ionic strength. It is understood that composition-insoluble polyphosphate salts can be stably incorporated with the aid of the wine cellar structure as explained hereinafter.
  • compositions of this invention can be prepared by a variety of mixing techniques whereby the formation of the coacervate network can easily be ascertained.
  • the non-soap anionic surface-active agents are added, under mixing, to an aqueous solution of the nonionic and anionic cellulose ethers, preferably at a temperature in the range from 15°C to 30°C.
  • the resulting solution contains the primary coacervate droplets.
  • the remainder of the anionic surfactants is thereafter added, under mixing, to the solution containing the primary coacervate.
  • the nonionic surface-active agents are subsequently added under mixing.
  • the pH of the solution throughout the mixing sequence shall be maintained above 6, usually in the range from 7 to 9. pH adjustments are made at the end of the sequence.
  • Solvents, pH regulating agents and other additives and optional ingredients can be added after the primary coacervate is formed or at the end of the mixing operation.
  • Conventional minor additives inclusive of dyes, perfumes, brightners, can frequently be added at the end of the mixing process, i.e., after the addition of the nonionic surface-active agents.
  • compositions of this invention can contain, in addition to the essential ingredients described hereinbefore, a series of conventional liquid detergent composition additives in the art established levels for their known functionality.
  • Detergent enzymes generally aid and augment the removal of specific stains.
  • Suitable enzymes can be represented by proteases, amylases, lipases, glucose oxidases or mixtures thereof.
  • Proteases and/or amylases are preferred in the claimed liquid concentrated compositions. They are frequently employed in a level from 0.01 % to 1 %. Mixtures of proteases and amylases can usually contain from 0.05% to 0.8% proteases and from 0.001 % to 0.2% alpha-amylases.
  • Another preferred additive is represented by a polyacid or mixture of polyacids in an amount from 0.05% to 2%.
  • Preferred polyacid species for use herein can be represented by organo-phosphonic acids, particularly alkylenepolyamino-polyalkylene phosphonic acids such as-ethylene diamine tetramethylenephosphonic acid, hexamethylene diaminetetramethylenephosphonic acid, diethylene triaminepentamethylene-phosphonic acid, and aminotrimethylenephosphonic acid or the salts thereof. These organophosphonic acids/salts are preferably used in an amount from 0.1 %-0.8%.
  • a non-phosphonated polyacid suitable for use include ethylenediaminetetraacetic acid and diethylene triamine pentaacetic acid.
  • the beneficial utilization of the claimed compositions under various usage conditions can require the utilization of a suds regulant.
  • a suds regulant While generally all detergent suds regulants can be utilized preferred for use herein are alkylated polysiloxanes, such as dimethylpolysiloxane also frequently termed silicone, self emulsifiable silicones as e.g. known from German Patent Application DE-OS 26 46 057.
  • the silicones are frequently used in a level not exceeding 0.5%, most preferably between 0.01 % and 0.2%.
  • opacifiers it can also be desirable to utilise opacifiers inasmuch as they contribute to create a uniform appearance of the concentrated liquid detergent compositions.
  • suitable opacifiers include: polystyrene commercially known as Lytron 621 0 manufactured by Monsanto Chemical Corporation. The opacifiers are frequently used in an amount from 0.3% to 1.5%.
  • compositions herein can also contain conventional antioxidants for their known utility, frequently radical scavengers, in the art established levels i.e. 0.001% to 0.25% (by reference to total composition). These antioxidants can be introduced in conjunction with the fatty acid, especially the unsaturated fatty acid. While many suitable antioxidants are readily known and available for that purpose especially preferred for use in the compositions herein are: 2,6 ditertiary butyl-p-cresol, more commonly known as butylated hydroxytoluene, BHT, and 2-tertiarybutyl-4-hydroxyanisole or 3-tertiarybutyl-4-hydroxyanisole more commonly known as BHA or butylated hydroxyanisole. Other suitable antioxidants are: 4,4'thiobis(6-tert-butyl-m-cresol) and 2-methyl-4,6-dinonyl phenol.
  • compositions herein can comprise additive levels, usually below 5%, of co-surface-active agents such as: nonionics other than ethoxylated species, zwitterionics, semipolar nonionics; and cationic surface-active agents.
  • suitable semipolar nonionics include amine oxides, phosphone oxides and sulfoxides containing at least one C 12 -C 14 alkyl group.
  • coconutalkyldimethyl amine oxide in a level of from 0.2 to 2% can be particularly useful inasmuch as, in addition to detergency, it can provide soil release properties.
  • Cationic surfactants can also be utilized beneficially in the compositions herein, usually in a level in the range from 0.5% to 4%.
  • Suitable cationic surfactant species include C 10 ⁇ C 16 alkyl trimethylammonium salts.
  • compositions herein can also contain as an optional ingredient from 0.0001% to 0.2% of a photoactivator.
  • Suitable photoactivators are described in European Patent No. 0 026 744, granted May 5, 1982.
  • Suitable incrustation/decrustation inhibitors can be added to improve the appearance of used soiled textiles. They are frequently used in levels ranging from 0.5% to 2%.
  • a well-known example of such a "crustation” inhibitor is a copolymer containing maleic acid and (meth)-acrylic acid monomers, as more fully described in European Patent Application 82.200602.9.
  • compositions herein can also contain additive levels (0.01% ⁇ 0.3%) of particular aminosilanes with a view to improve machine compatibility, particularly in relation to enamel-coated surfaces.
  • Suitable amino-silanes are disclosed in EP ⁇ A ⁇ 0.075.988.
  • Suitable enzyme stablizers for use herein include short chain carboxylic acid, most preferably salts of formic acid, in levels of 0.1% to 3%, and subadditive levels of water-soluble Ca-salts. The utilization of these stabilizers is described in U.S. Patent 4.287.082 of September 1, 1981.
  • compositions can further contain composition-soluble detergent builders.
  • Organic detergent, usually sequestering, builders are preferred although low levels of inorganic builders can be used provided they are soluble in the total detergent.
  • suitable organic detergent builders include monomeric polycarboxylates such as citric acid; carboxymethyloxysuccinic acid; nitrilotriacetic alkali metal, salts thereof.
  • Polymeric carboxylate builders inclusive of polyacrylate and polyhydroxyacrylate can also be used.
  • the optional builder component can be used in the claimed compositions in levels from 2% to 10%.
  • the claimed compositions can contain a series of useful detergent additives which could up to now not be used effectively in the like liquid detergent compositions because of insufficient storage stability, deactivation, flocculation, sedimentation and other phenomena which were known to adversely affect their effectiveness.
  • the like additives are usually employed in levels of from 1 % to 10%, preferably 2% ⁇ 6%.
  • ingredients which can be stably incorporated in the claimed compositions with the aid of the coacervate network include water-insoluble ingredients and composition-insoluble ingredients which have a non-negligible water-solubility.
  • water-insoluble and composition-insoluble as used herein stand for solubilities below 0.1% in water and the composition respectively.
  • These ingredients shall have a particle size in the range from 1 ⁇ ⁇ meter to 100 u- meters preferably from 1-20 u- meters.
  • Water-insoluble ingredients can be represented by inorganic builders such as Zeolite A having the formula Na l2 (AlO 2 ⁇ SiO 2 ) 12 ⁇ 27H 2 O; Zeolite X: Na 86 (AlO 2 ) 86 (SiO 2 ) 106 ⁇ 264H 2 0; and Zeolite P(B): Na 6 (AlO 2 ) 6 (SiO 2 ) 10 ⁇ 15H 2 0. These zeolites have frequently primary particle sizes of from 1-6 ⁇ ⁇ meters.
  • insoluble additives are suds depressors such as hydrophobic silica, microcrystalline waxes, and fabric treatment/softening agents such as smectite clays.
  • Composition-insoluble ingredients can also include inorganic builders such as salts of pyrophosphates, anti-corrosion agents e.g. sodium aluminate, particularly upon use of this aluminate in neutral to mildly alkaline compositions, oxygen-bleach activators such as tetra-acetylethylene diamine (TAED), oxygen bleaches, e.g., the alkaline earth metal salts of perborates, antibactericides, immobilized enzymes and homopolymeric and copolymeric additives such as polycarboxylates having sequestrant and anti-redeposition functionalities.
  • inorganic builders such as salts of pyrophosphates, anti-corrosion agents e.g. sodium aluminate, particularly upon use of this aluminate in neutral to mildly alkaline compositions, oxygen-bleach activators such as tetra-acetylethylene diamine (TAED), oxygen bleaches, e.g., the alkaline earth metal salts of
  • composition-insoluble ingredients that can be stably incorporated herein includes coated, especially micro-encapsulated, additives such as enzymes, bactericidal agents, bleaches and activators therefore, perfumes, dyes, suds regulant anti-corrosion agents and more in general any kind of desirable additives which heretofore were not compatible with concentrated liquid detergent compositions.
  • additives such as enzymes, bactericidal agents, bleaches and activators therefore, perfumes, dyes, suds regulant anti-corrosion agents and more in general any kind of desirable additives which heretofore were not compatible with concentrated liquid detergent compositions.
  • liquid detergents were prepared by mixing the individual ingredients in the listed proportions thereby using the method set forth in Claim 10.
  • compositions in accordance with this invention demonstrate the benefits derived from the compositions in accordance with this invention vs. closely related prior art compositions.
  • the results high-light the claim criticalities -Composition A absence of AC; Composition B absence of nonionic ethoxylate; Composition C ratio total ingredients: water below 1:1.
  • compositions which contain the coacervate network exhibit excellent storage stability characteristics.

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Claims (10)

1. Eine wässerige, homogene, flüssige Reinigungsmittelzusammensetzung, enthaltend anionische grenzflächenaktive Mittel, nichtionische grenzflächenaktive Mittel, Carboxymethylcellulose und gegebenenfalls herkömmliche Bestandteile für derartige Zusammensetzungen, dadurch gekennzeichnet, daß sie:-
0,1 Gew-% bis 3 Gew.-% eines Koazervats von gegebenenfalls hydroxylierter C1―C4-Alkylcellulose (AC) und Carboxymethylcellulose (CMC) in einem Gewichtsverhältnis von CMC:AC von 6:1 bis 1:4;
mehr als 20 Gew.-% eines Gemisches der anionischen und der nichtionischen grenzflächenaktiven Mittel, wobei das nichtionische grenzflächenaktive Mittel mehr als 3 Gew.-% darstellt, und wobei das Gewichtsverhältnis von anionischem grenzflächenaktivem Mittel zu nichtionischem grenzflächenaktivem Mittel im bereich von 1:1 bis 8:1 liegt; und
mehr als 10 Gew.-% Wasser enthält, wobei das Gewichtsverhältnis der gesamten Bestandteile zu Wasser 1:1 bis 9:1 beträgt.
2. Die Zusammensetzung nach Anspruch 1, wobei das Gewichtsverhältnis von CMC zu AC im Bereich von 3:1 bis 1:1 liegt.
3. Die Zusammensetzung nach Anspruch 1, welche einen pH-Wert, gemessen "so wie sie ist" bei 20°C, von 6,0 bis 10 aufweist.
4. Die Zusammensetzung nach Anspruch 1, wobei das AC-CMC-Koazervat 0,5 Gew.-% bis 1,5 Gew.-% ausmacht.
5. Die Zusammensetzung nach Anspruch 1, wobei wenigstens 5 Gew.-%, berechnet auf Basis der Reinigungsmittelzusammensetzung, des anionischen grenzflächenaktiven Mittels durch ein anionisches Nichtseifen-grenzflächenaktives Mittel repräsentiert wird.
6. Die Zusammensetzung nach Anspruch 1, wobei das Verhältnis der anionischen zu nichtionischen grenzflächenaktiven Mitteln im Verhältnisbereich von 1:1 bis 4:1 liegt.
7. Die Zusammensetzung nach den Ansprüchen 1 und 5, wobei das Gemisch der anionischen und der nichtionischen grenzflächenaktiven Mittel 25 Gew.-% bis 60 Gew.-% darstellt, und wobei das nichtionische grenzflächenaktive Mittel ein ethoxyliertes, nichtionisches grenzflächenaktives Mittel ist, das eine Hydrophil-Lipophil-Bilanz (HLB) im Bereich von 9 bis 15 hat, und das anionische Nichtseifengrenzflächenaktive Mittel ein C,o-C,3-Alkylbenzolsulfonat ist.
8. Die Zusammensetzung nach Anspruch 1, enthaltend ein dreidimensionales Koazervatnetzwerk und 1 Gew.-% bis 10 Gew.-% von in der Zusammensetzung unlöslichen Reinigungsmittelzusätzen mit einer Teilchengröße im Bereich von 1 um bis 100 um.
9. Die Zusammensetzung nach Anspruch 1, enthaltend zusätzlich:
0,01 Gew.-% bis 1 Gew.-% eines Gemisches von Proteasen und a-Amylasen;
0,05 Gew.-% bis 2 Gew.-% einer Polysäure;
bis zu 5 Gew.-% an nichtionischen, semipolaren nichtionischen und kationischen kogrenzflächenaktiven Mitteln; und
0,1 Gew.-% bis 3 Gew.-% an Salzen der Ameisensäure.
10. Ein Verfahren zur Herstellung der wässerigen, homogenen, flüssigen Reinigungsmittelzusammensetzung nach den Ansprüchen 1, 5 und 8, umfassend die folgenden Stufen:-
Zugeben des anionischen Nichtseifen-grenzflächenaktiven Mittels zu einer wässerigen Lösung des Gemisches aus gegebenenfalls hydroxylierter C1-C4-Alkylcellulose und Carboxymethylcellulose, um dabei unter Mischen ein primäres Koazervat zu bilden; gefolgt vom
Zugeben der übrigen anionischen grenzflächenaktiven Mittel unter Mischen; und anschließend
Zugeben der nichtionischen grenzflächenaktiven Mittel unter Mischen, um dabei ein Koazervatnetzwerk zu bilden; mit der weiteren Maßgabe, daß während der Mischvorgänge der pH-Wert über 6,0 gehalten wird.
EP83201070A 1982-07-27 1983-07-20 Flüssige Reinigungsmittelzusammensetzungen, eine Koazervatmischung aus Alkylcellulose enthaltend und Carboxymethylcellulose und Verfahren zu deren Herstellung Expired EP0100125B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT83201070T ATE39126T1 (de) 1982-07-27 1983-07-20 Fluessige reinigungsmittelzusammensetzungen, eine koazervatmischung aus alkylcellulose enthaltend und carboxymethylcellulose und verfahren zu deren herstellung.

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GB8221726 1982-07-27
GB8221726 1982-07-27

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EP0100125A2 EP0100125A2 (de) 1984-02-08
EP0100125A3 EP0100125A3 (en) 1986-09-10
EP0100125B1 true EP0100125B1 (de) 1988-12-07

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EP (1) EP0100125B1 (de)
JP (1) JPH0713237B2 (de)
AT (1) ATE39126T1 (de)
CA (1) CA1217107A (de)
DE (1) DE3378637D1 (de)
GR (1) GR78636B (de)
IE (1) IE55461B1 (de)

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ATE39126T1 (de) 1988-12-15
GR78636B (de) 1984-09-27
JPS5985000A (ja) 1984-05-16
EP0100125A3 (en) 1986-09-10
JPH0713237B2 (ja) 1995-02-15
EP0100125A2 (de) 1984-02-08
IE55461B1 (en) 1990-09-26
DE3378637D1 (en) 1989-01-12
CA1217107A (en) 1987-01-27
IE831758L (en) 1984-01-27

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