EP0753569A1

EP0753569A1 - Stable liquid softening through the wash compositions

Info

Publication number: EP0753569A1
Application number: EP95201942A
Authority: EP
Inventors: Serge Gabriel Pierre Roger Cauwberghs; Christel Lauryssen (NMN); Jean-Pol Boutique (Nmn)
Original assignee: Procter and Gamble Co
Current assignee: Procter and Gamble Co
Priority date: 1995-07-14
Filing date: 1995-07-14
Publication date: 1997-01-15
Also published as: BR9609718A; WO1997004065A1; JPH11509258A; MX9800501A

Abstract

The present invention relates to concentrated liquid detergents comprising a clay-softening system and specific modified polyesters.

Description

FIELD OF THE INVENTION

The present invention relates to stable concentrated liquid detergent compositions containing a clay softening system. More in particular, the present invention relates to softening through the wash liquid detergent compositions comprising a clay softening system and specific modified soil release polymers.

BACKGROUND OF THE INVENTION

Liquid detergent compositions providing fabric softening throughout the wash cycle have been described in art. In particular, clays are well known as fabric softening agents through the wash. The relative ability of the softening clays to meet various performance criteria is very much depending on the presence and concentration of adjunct detergent ingredients.
An example of such adjunct detergent ingredient is the presence of soil release polymers.
Said soil release polymers, when used even at low concentrations, interact strongly with the clay, resulting in loss in performance of the soil-release polymer, flocculation of the clay and problems with physical stability of the liquid detergent.
The move towards concentrated liquids make stabilization of soil release polymers in concentrated liquids against physical separation and/or flocculation phenomena even more difficult. Concentrated liquids contain a lower amount of water compared to conventional liquid detergents. This results in an increase in electrolyte and solids levels in these liquid detergent formulas. Another change is the dependence on non-aqueous solvents to aid in the solubilization of detergent components.
It is therefore an object of the present invention to provide a concentrated liquid softening-through-the-wash detergent composition which will remain stable, particularly upon prolonged storage.
It is another object of the present invention to provide a concentrated liquid softening-through-the-wash composition which is capable of providing excellent softening as well as outstanding soil release performance.
The above objectives have been met by a liquid softening-through-the-wash detergent composition comprising a clay softening system in combination with specific modified polyesters. It has now been surprisingly found that the specific modified polyesters according to the present invention are fully compatible with the clay-softening system. This finding allows us to formulate liquid detergent compositions which have both excellent softening and cleaning performance.

SUMMARY OF THE INVENTION

The present invention relates to concentrated liquid detergents comprising a clay-softening system and specific modified polyesters. All percentages, ratios herein are by weight, unless otherwise specified.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to concentrated liquid detergents, in such case, the liquid detergent compositions according to the present invention will contain a lower amount of water, compared to conventional liquid detergents. The level of water in the concentrated liquid detergents of the present invention is less than 50%, preferably less than 40% by weight of the total detergent composition.

Clay softening system

The clay softening system hereof will comprise a fabric softening clay present in an amount of at least 0.5%, preferable from 4% to 30% by weight of the detergent composition. The preferred clays are of the smectite type. Smectite type clays are widely used as fabric softening ingredients in detergent compositions. Most of these clays have a cation exchange capacity of at least 50 meq./100g.
Smectite clays can be described as three-layer expandable materials, consisting of alumino-silicates or magnesium silicates.
There are two distinct classes of smectite-type clays; in the first, aluminium oxide is present in the silicate crystal lattice, in the second class of smectites, magnesium oxide is present in the silicate crystal lattice.
The general formulas of these smectites are A1₂(Si₂0₅)₂(OH)₂ and Mg₃(Si₂O₅) (OH)₂, for the aluminium and magnesium oxide type clay, respectively. The range of the water of hydration can vary with the processing to which the clay has been subjected. Furthermore, atom substitution by iron and magnesium can occur within the crystal lattice of the smectites, while metal cations such as Na⁺, Ca²⁺, as well as H⁺ can be co-present in the water of hydration to provide electrical neutrality.
It is customary to distinguish between clays on the basis of one cation predominantly or exclusively absorbed. For example, a sodium clay is one in which the absorbed cation is predominantly sodium. Such absorbed cations can become involved in equilibrium exchange reactions with cations present in aqueous solutions. In such equilibrium reactions, one equivalent weight of solution cation replaces an equivalent of sodium, for example, and it is customary to measure clay cation exchange capacity in terms of milliequivalents per 100g. of clay (meq/100g.).
The cation exchange capacity of clays can be measured in several ways, including electrodialysis, by exchange with ammonium ion followed by titration, or by a methylene blue procedure, all as set forth in Grimshaw, The Chemistry and Physics of Clays, Interscience Publishers, Inc. pp. 264-265(1971). The cation exchange capacity of a clay mineral relates to such factors as the expandable properties of the clay, the charge of the clay, which in turn, is determinated at least in part by the lattice structure, and the like. The ion exchange capacity of clays varies widely in the range from about 2 meq/100 g. for kaolinites to about 150 meq/100 g., and greater, for certain clays of the montmorillonite variety. Illite clays have an ionexchange capacity somewhere in the lower portion of the range, ca. 26 meq/100 g. for an average illite clay.
It has been determined that illite and kaolinite clays, with their relatively low ion exchange capacities, are not useful in the instant compositions. Indeed such illite and kaolinite clays constitute a major component of clay soils. However, smectites, such as nontronite having an ionexchange capacity of approximately 50 meq/100 g.;saponite, which has an ion exchange capacity greater than 70 meq/100g., have been found to be useful fabric softeners.
The smectite clays commonly used for this purpose herein are all commercially available. Such clays include, for example, montmorillonite, volchonskoite, nontronite, hectorite, saponite, sauconite, and vermiculite. The clays herein are available under commercial names such as "fooler clay" (clay found in a relatively thin vein above the main bentonite or montmorillonite veins in the Black Hills) and various tradenames such as Thixogel #1 (also, "Thixo-Jell") and Gelwhite GP from Georgia Kaolin Co. Elizabeth, New Jersey; Volclay BC and Volclay #325, from American Colloid Co., Skokie, Illinois; Black Hills Bentonite BH 450, from International Minerals and Chemicals; and Veegum Pro and Veegum F, from R.T. Vanderbilt. It is to be recognized that such smectite-type minerals obtained under the foregoing commercial and tradenames can comprise mixtures of the various discrete mineral entitites. Such mixtures of the smectite minerals are suitable for use herein.
Preferred for use herein are the montmorrillonite clays.
Quite suitable are hectorites of natural origin, in the form of particles having the general formula
wherein Me^III is Al, Fe, or B; or y=o; Mⁿ⁺ is a monovalent (n=1) or divalent (n=2) metal ion, for example selected from Na, K, Mg, Ca, Sr.
In the above formula, the value of (x+y) is the layer charge of the hectorite clay.
Such hectorite clays are preferably selected on the basis of their layer charge properties, i.e. at least 50% is in the range of from 0.23 to 0.31.
More suitable are hectorite clays of natural origin having a layer charge distribution such that at least 65% is in the range of from 0.23 to 0.31.
The hectorite clays suitable in the present composition should preferably be sodium clays, for better softening activity.
Sodium clays are either naturally occuring, or are naturally-occuring calcium-clays which have been treated so as to convert them to sodium-clays. If calcium-clays are used in the present compositions, a salt of sodium can be added to the compositions in order to convert the calcium clay to a sodium clay. Preferably, such a salt is sodium carbonate, typically added at levels of up to 5% of the total amount of clay.
Examples of hectorite clays suitable for the present compositions include Bentone EW and Macaloid, from NL Chemicals, N.J., U.S.A., and hectorites from Industrial Mineral Ventures.

Clay-flocculating agents

The clay softening system herein can comprise clay-flocculating agents. The compositions herein may comprise, from 0.05% to 20% by weight of the clay, of flocculating agent, if its molecular weight is 100.000-800.000. Preferred molecular weight of the flocculating agent is 150.000-300.000. Most of these materials are fairly long chain polymers and copolymers derived from such monomers as ethylene oxide, acrylamide, acrylic acid, dimethylamino ethyl methacrylate, vinyl alcohol, vinyl pyrrolidone, ethylene imine. Gums, like guar gum, are suitable as well.
Preferred are polymers of ethylene oxide, acryl amide, or acrylic acid. For proper interaction with the clay particles, the polymers should be fairly long chain, i.e., have a weight average molecular weight of at least 100,000. For sufficient water-solubility the weight average molecular weight of the polymers should not exceed 10 million. Most preferred are polymers having a weight average molecular weight of from 150.000 to 5 million

The modified polyesters

The detergent compositions herein also essentially contain from 0.01 to 2%, preferably from 0.05 to 0.5 by weight of a modified polyester.
Modified polyesters herein are substantially linear end-capped esters having molecular weight ranging from 500 to 5000, preferably from 1000 to 3500; said ester consisting essentially of, on a molar basis :

i) from 1 to 2 moles of two or more types of end-capping units selected from the group consisting of:
- a)ethoxylated or propoxylated hydroxy-ethane and propeanesulfonate end-capping units of the formula (MO₃S)(CH₂)m(CH₂CH₂O)(RO)n-, wherein M is a salt-forming cation such as sodium or tetraalkylammonium, R is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 0 to 4;
- b)sulfoaroyl units of the formula -(0)C(C₆H₄)(SO₃M), wherein M is a salt forming cation;
- c)modified poly(oxyethylene)oxy monoalkyl ether units of the formula XO(CH₂CH₂O)k-, wherein X contains from about 1 to about 4 carbon atoms and k is from about 1 to 100; and
- d)ethoxylated or propoxylated phenolsulfonate end-capping units of the formula NaO₃S(C₆H₄)-(RO)_n-, wherein n is from 1 to 5 and R is ethylene or propylene or a mixture thereof;
ii) from about 0.5 to about 66 moles of units selected from the group consisting of :
- a) oyethyleneoxy units;
- b) oxy-1,2-propyleneoxy units; and
- c) mixtures of a) and b);
iii) from about 1.5 to about 40 moles of terephthaloyl units; and optionally
iv) from 0 to about 26 moles of 5-sulfoisphtholoyl units of the formula -(0)C(C₆H₃)(SO₃M)C(O)-, wherein M is a salt forming cation such as an alkali metal or tetraalkylammonium ion.

These polyesters are described in the Applicants copending application USSN 08/088705.
Preferred polyesters herein are random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol. The target being to obtain is a polymer capped at both end by sulphobenzoate groups, "primarily", in the present context most of said copolymers herein will be end-capped by sulphobenzoate groups. However, some copolymers will be less than fully capped, and therefore their end groups may consist of monoester of ethylene glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.
Most preferred polyesters herein contain about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol, about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic acid, and have a molecular weight of about 3500. The polyesters and their method of preparation are described in detail in EPA 311 342.

Optional detergent ingredients

In another embodiment of the present invention, the liquid detergent composition may comprise one or more of a surfactant selected from a wide range of surfactants.
A typical listing of anionic, nonionic, ampholytic and zwitterionic classes, and species of these surfactants, is given in US Patent 3,664,961 issued to Norris on May 23, 1972.
Highly preferred anionic surfactants include the alkyl sulfate surfactants hereof are water soluble salts or acids of the formula ROSO₃M wherein R preferably is a C₁₀-C₂₄ hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C₁₀-C₁₈ alkyl component, more preferably a C₁₂-C₁₅ alkyl or hydroxyalkyl, and M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or ammonium or substituted ammonium (e.g. monoethanolamine, methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Branched alkylsulfates are especially preferred.
Preferred anionic surfactants include alkyl alkoxylated sulfate surfactants hereof are water soluble salts or acids of the formula RO(A)_mSO3M wherein R is an unsubstituted C₁₀-C₂₄ alkyl or hydroxyalkyl group having a C₁₀-C₂₄ alkyl component, preferably a C₁₂-C₁₈ alkyl or hydroxyalkyl, more preferably C₁₂-C₁₅ alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which can be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted-ammonium cation (e.g. monoethanolamine, methyl-, dimethyl-, and trimethyl ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof, and the like). Alkyl ethoxylated sulfates as well as alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium cations and quaternary ammonium cations such as tetramethyl-ammonium and dimethyl piperdinium cations and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary surfactants are C₁₂-C₁₅ alkyl polyethoxylate (1.0) sulfate (C₁₂-C₁₅E(1.0)M), C₁₂-C₁₅ alkyl polyethoxylate (2.25) sulfate (C₁₂-C₁₅E(2.25)M), C₁₂-C₁₅ alkyl polyethoxylate (3.0) sulfate (C₁₂-C₁₅E(3.0)M), and C₁₂-C₁₅ alkyl polyethoxylate (4.0) sulfate (C₁₂-C₁₅E(4.0)M), wherein M is conveniently selected from sodium and potassium.
Other suitable anionic surfactants to be used are alkyl ester sulfonate surfactants including linear esters of C₈-C₂₀ carboxylic acids (i.e., fatty acids) which are sulfonated with gaseous SO₃ according to "The Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable starting materials would include natural fatty substances as derived from tallow, palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications, comprise alkyl ester sulfonate surfactants of the structural formula :
wherein R³ is a C₈-C₂₀ hydrocarbyl, preferably an alkyl, or combination thereof, R⁴ is a C₁-C₆ hydrocarbyl, preferably an alkyl, or combination thereof, and M is a cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted ammonium cations, such as monoethanolamine, triethanolamine. Preferably, R³ is C₁₀-C₁₆ alkyl, and R⁴ is methyl, ethyl or isopropyl. Especially preferred are the methyl ester sulfonates wherein R³ is C₁₀-C₁₆ alkyl.
Other anionic surfactants useful for detersive purposes can also be included in the laundry detergent compositions of the present invention. These can include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C₉-C₂₀ linear alkylbenzenesulfonates, C₈-C₂₂ primary of secondary alkanesulfonates, C₈-C₂₄ olefinsulfonates, sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline earth metal citrates, e.g., as described in British patent specification No. 1,082,179, C₈-C₂₄ alkylpolyglycolethersulfates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, paraffin sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates, alkyl succinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C₁₂-C₁₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C₆-C₁₂ diesters), sulfates of alkylpolysaccharides such as the sulfates of alkylpolyglucoside (the nonionic nonsulfated compounds being described below), and alkyl polyethoxy carboxylates such as those of the formula RO(CH₂CH₂O)_k-CH₂COO-M+ wherein R is a C₈-C₂₂ alkyl, k is an integer from 0 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tall oil. Further examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein incorporated by reference).
When included therein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 5% to about 25% by weight of such anionic surfactants.
Highly preferred nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula
wherein R¹ is H, or R¹ is C_1-4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R² is C_5-31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative thereof. Preferably, R¹ is methyl, R² is a straight C_11-15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reductive amination reaction.
Other suitable nonionics are amine oxide surfactants. The compositions of the present invention may comprise amine oxide in accordance with the general formula I:

R¹(EO)_x(PO)_y(BO)_zN(O)(CH₂R')₂.qH₂O (I)
In general, it can be seen that the structure (I) provides one long-chain moiety R¹(EO)_x(PO)_y(BO)_z and two short chain moieties, CH₂R'. R' is preferably selected from hydrogen, methyl and -CH₂OH. In general R¹ is a primary or branched hydrocarbyl moiety which can be saturated or unsaturated, preferably, R¹ is a primary alkyl moiety. When $x+y+z = 0$
, R¹ is a hydrocarbyl moiety having chainlength of from about 8 to about 18. When x+y+z is different from 0, R¹ may be somewhat longer, having a chainlength in the range C₁₂-C₂₄. The general formula also encompasses amine oxides wherein $x+y+z = 0$
, R₁ = C₈-C₁₈, R' = H and q = 0-2, preferably 2. These amine oxides are illustrated by C12-14 alkyldimethyl amine oxide,hexadecyl dimethylamine oxide, octadecylamine oxide and their hydrates, especially the dihydrates as disclosed in U.S. Patents 5,075,501 and 5,071,594, incorporated herein by reference.
The invention also encompasses amine oxides wherein x+y+z is different from zero, specifically x+y+z is from about 1 to about 10, R¹ is a primary alkyl group containing 8 to about 24 carbons, preferably from about 12 to about 16 carbon atoms; in these embodiments y + z is preferably 0 and x is preferably from about 1 to about 6, more preferably from about 2 to about 4; EO represents ethyleneoxy; PO represents propyleneoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods, e.g., by the reaction of alkylethoxysulfates with dimethylamine followed by oxidation of the ethoxylated amine with hydrogen peroxide.
Preferred embodiments include dodecyldimethylamine, tetradecyldimethylamineoxidedihydrate,hexadecyldimethylamin eoxidedihydrate and octadecyldimethylamine oxide dihydrate.
Whereas in certain of the preferred embodiments R' = H, there is some latitude with respect to having R' slightly larger than H. Specifically, the invention further encompasses embodiments wherein R' = CH₂OH, such as hexadecylbis(2- hydroxyethyl)amine oxide, tallowbis(2-hydroxyethyl)amine oxide, stearylbis(2-hydroxyethyl)amine oxide and oleylbis(2- hydroxyethyl)amine oxide, dodecyldimethyl(2- hydroxyethyl)amine oxide dihydrate.
Other suitable nonionic surfactants comprises alkyl polyglucoside compounds of general formula

RO (C_nH_2nO)_tZ_x

wherein Z is a moiety derived from glucose; R is a saturated hydrophobic alkyl group that contains from 12 to 18 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.3 to 4, the compounds including less than 10% unreacted fatty alcohol and less than 50% short chain alkyl polyglucosides. Compounds of this type and their use in detergent are disclosed in EP-B 0 070 077, 0 075 996 and 0 094 118.
When included therein, the laundry detergent compositions of the present invention typically comprise nonionic surfactants in the weight ratio of anionic surfactant to nonionic surfactant from 6:1 to 1:3, preferably from 5:1 to 2:1.
Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include the ammonium surfactants such as alkyldimethylammonium halogenides, and those surfactants having the formula :

[R²(OR³)_y][R⁴(OR³)_y]₂R⁵N+X-

wherein R² is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R³ is selected from the group consisting of -CH₂CH₂-, - CH₂CH(CH₃)-, -CH₂CH(CH₂OH)-, -CH₂CH₂CH₂-, and mixtures thereof; each R⁴ is selected from the group consisting of C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, benzyl ring structures formed by joining the two R⁴ groups, -CH₂CHOH-CHOHCOR⁶CHOHCH₂OH wherein R⁶ is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when y is not 0; R⁵ is the same as R⁴ or is an alkyl chain wherein the total number of carbon atoms of R² plus R⁵ is not more than about 18; each y is from 0 to about 10 and the sum of the y values is from 0 to about 15; and X is any compatible anion.
Preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition having the formula :

R₁R₂R₃R₄N⁺X^- (i)

wherein R₁ is C₈-C₁₆ alkyl, each of R₂, R₃ and R₄ is independently C₁-C₄ alkyl, C₁-C₄ hydroxy alkyl, benzyl, and -(C₂H₄0)_xH where x has a value from 1 to 5, and X is an anion. Not more than one of R₂, R₃ or R₄ should be benzyl.
The preferred alkyl chain length for R₁ is C₁₂-C₁₅ particularly where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat or is derived synthetically by olefin build up or OXO alcohols synthesis. Preferred groups for R₂R₃ and R₄ are methyl and hydroxyethyl groups and the anion X may be selected from halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of formulae (i) for use herein are :

coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
octyl or decyl triethyl ammonium chloride;
octyl or decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C_12-15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)₄ ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R₁ is - CH₂-O-C(O)-C_12-14 alkyl and R₂R₃R₄ are methyl).

Other cationic surfactants useful herein are also described in U.S. Patent 4,228,044, Cambre, issued October 14, 1980.
When included therein, the laundry detergent compositions of the present invention typically comprise from 0.5% to about 5%, preferably from about 1% to about 3% by weight of such cationic surfactants.
The compositions according to the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxylates and fatty acids, materials such as ethylenediamine tetraacetate, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediamine tetramethylene phosphonic acid and diethylene triamine pentamethylenephosphonic acid. Though less preferred for obvious environmental reasons, phosphate builders can also be used herein.
Suitable polycarboxylates builders for use herein include citric acid, preferably in the form of a water-soluble salt, derivatives of succinic acid of the formula R-CH(COOH)CH2(COOH) wherein R is C10-20 alkyl or alkenyl, preferably C12-16, or wherein R can be substituted with hydroxyl, sulfo sulfoxyl or sulfone substituents. Specific examples include lauryl succinate , myristyl succinate, palmityl succinate2-dodecenylsuccinate, 2-tetradecenyl succinate. Succinate builders are preferably used in the form of their water-soluble salts, including sodium, potassium, ammonium and alkanolammonium salts.
Other suitable polycarboxylates are oxodisuccinates and mixtures of tartrate monosuccinic and tartrate disuccinic acid such as described in US 4,663,071.
Suitable fatty acid builders for use herein are saturated or unsaturated C10-18 fatty acids, as well as the corresponding soaps. Preferred saturated species have from 12 to 16 carbon atoms in the alkyl chain. The preferred unsaturated fatty acid is oleic acid. Another preferred builder system for liquid compositions is based on dodecenyl succinic acid and citric acid.
Detergency builder salts are normally included in amounts of from 10% to 80% by weight of the composition preferably from 20% to 70% and most usually from 30% to 60% by weight.
Other components used in detergent compositions may be employed, such as enzymes and stabilizers or activators therefore, soil-suspending agents, abrasives, bactericides, tarnish inhibitors, coloring agents, foam control agents, corrosion inhibitors and perfumes. The perfumes, either hydrophobic or hydrophillic can be incorporated in a porous material such as silica. Such a protected system is described in EP 583 512. Especially preferred are combinations with enzyme technologies which also provide a type of color care benefit. Examples are cellulase for color maintenance/ rejuvenation. Other examples are the polymers disclosed in EP 92870017.8 filed January 31,1992 and enzyme oxidation scavengers disclosed in EP 92870018.6 filed January 31, 1992.
Also particulary suitable are amine base catalyst stabilizers disclosed in EP 92870019.4 filed January 31, 1992.
The following examples are meant to exemplify compositions of the present inventions, but are not necessarily meant to limit the scope of the invention.

EXAMPLE I (A/B/C/D)

A stable liquid detergent composition according to the present invention is prepared, having the following compositions :

% by weight of the total detergent composition
	A	B	C	D
Linear alkylbenzene sulfonate	10	15	23	-
Polyhydroxy fatty acid amide	-	5	-	4
Alkyl alkoxylated sulfate	-	-	-	3
Alkyl sulphate	2	2	4	13
C12-C14 dimethyl ammonium chloride	2	2	2	2
Fatty acid	8	8	10	17
Oleic acid	2	2	2	-
Citric acid	2	1	1	1
Diethylenetriamine pentamethylene	1.5	1.5	1.5	1.5
Phosphonic acid
NaOH	5	7	8	7
Propanediol	4	4	4	7
Ethanol	7	7	10	3
Ethoxylated tetraethylene pentamine	0.7	0.7	0.7	0.7
Thermamyl R 300 KNU/g	0.1	0.1	0.1	0.1
Carezyme R 5000 CEVU/g	0.02	0.02	0.02	0.02
Protease 40 mg/g	0.6	0.6	0.6	0.6
Lipolase R 100 KLU/g	0.1	0.1	0.1	0.1
Endoglucanase A 5000 CEVU/g	0.5	0.5	0.5	0.5
Suds supressor (ISOFOL^r)	2.5	2.5	2.5	2.5
Clay	4	4	4	4
Modified soil release polymer	0.3	0.3	0.3	0.3
Minors	up to 100

The above compositions were very good at displaying excellent softening and cleaning performance.

Claims

A concentrated liquid detergent composition comprising a clay softening system characterised in that said composition further comprises a modified polyester, said ester consisting essentially of, on a molar basis :
i) from 1 to 2 moles of two or more types of end-capping units selected from the group consisting of:
a)ethoxylated or propoxylated hydroxy-ethane and propeanesulfonate end-capping units of the formula (MO₃S)(CH₂)m(CH₂CH₂O)(RO)n-, wherein M is a salt-forming cation such as sodium or tetraalkylammonium, R is ethylene or propylene or a mixture thereof, m is 0 or 1, and n is from 0 to 4;

b)sulfoaroyl units of the formula -(0)C(C₆H₄)(SO₃M), wherein M is a salt forming cation;

c)modified poly(oxyethylene)oxy monoalkyl ether units of the formula XO(CH₂CH₂O)k-, wherein X contains from about 1 to about 4 carbon atoms and k is from about 1 to 100; and

d)ethoxylated or propoxylated phenolsulfonate end-capping units of the formula NaO₃S(C₆H₄)-(RO)_n-, wherein n is from 1 to 5 and R is ethylene or propylene or a mixture thereof;

ii) from about 0.5 to about 66 moles of units selected from the group consisting of :
a) oyethyleneoxy units;

b) oxy-1,2-propyleneoxy units; and

c) mixtures of a) and b);

iii) from about 1.5 to about 40 moles of terephthaloyl units; and optionally

iv) from 0 to about 26 moles of 5-sulfoisphtholoyl units of the formula -(0)C(C₆H₃)(SO₃M)C(O)-, wherein M is a salt forming cation such as an alkali metal or tetraalkylammonium ion.
A liquid detergent composition according to claim 1 wherein said esters are random copolymers of dimethyl terephtalate, dimethyl sulfoisophtalate, ethylene glycol and 1-2 propane diol, the end groups consisting primarily of sulphobenzoate and secondarily of mono esters of ethylene glycol and/or propane-diol.
A liquid detergent composition according to claim 1 wherein said ester contain about 46% by weight of dimethyl terephtalic acid, about 16% by weight of propane -1.2 diol, about 10% by weight ethylene glycol, about 13% by weight of dimethyl sulfobenzoid acid and about 15% by weight of sulfoisophtalic acid.
A liquid detergent composition according to claims 1-3 wherein the molecular weight of the modified ester is from 500 to 5000, preferably from 1000 to 3500.
A liquid detergent composition according to claims 1-4 wherein said clay softening system is a smectite type of clay.
A liquid detergent composition according to claims 1-5 wherein the level of water is less than 40% by weight of the total detergent composition.
A liquid detergent composition according to claims 1-6 wherein the modified polyester is present from 0.01 to 2%, preferably from 0.05 to 0.5 % by total weight of the detergent composition.