AND STABLE AQUEOUS DETERGENT FOR LAUNDRY THAT HAS IMPROVED SOFTENING PROPERTIESTECHNICAL FIELDThe present invention relates to compositions ofThe liquid detergent compositions are stable, heavy-duty laundry detergents, which provide exceptional cleaning as well as mildness and anti-static benefits.The detergent compositions herein are substantially clear and isotropic and comprise an anionic and anionic surfactant component. a quaternary ammonium fabric softening agent The ammonium surfactant component comprises cheilsulphates + polyethoxides and limited amount of alkylenebenzenefona * or < -,.
BACKGROUND OF THE INVENTIONNumerous attempts have been made to formulate laundry detergent compositions having good cleansing properties together with fabric softening properties in order to avoid the need to use a textile mop product added to the rinse in addition to the usual laundry rate. Since cleaning by inclusion includes the removal of material from the textile surface and textile softness usually includes the accumulation of material on the same surface, these intense ones have typically involved a compromise in the formulation between the performance of the cleaning and the cleaning. smoothness. Cationic surfactants, including quaternary ammonium surfactants, have been known as additives useful in laundry detergent compositions for the purpose of providing washed fabrics with a static control benefit (see for example U.S. Patent No. 3,951,879, Uixon, issued on April 20, 1976, and U.S. Patent No. 3,959,157, Tnarnorato, issued on April 25, 1976, both of which are incorporated herein), a benefit of cloth softness ( see, for example, U.S. Patent No. 3,607,763, Sal ent et al., issued September 21, 1971, U.S. Patent No. 3,644,203, Lambert i et al., issued February 22, 1972, and U.S. Patent No. 3,537,993, Co ard. and others, issued November 3, 1970, all of which are incorporated herein by reference), or a sanitation benefit (see, for example, U.S. Patent No. 2,742.43 4, Kopp, issued April 17, 1956, U.S. Patent No. 3,539,520, Cantor et al., Issued November 10, 1970, and U.S. Patent No. 3,965,026, Lancz, issued December 22, 1976, all of which they are incorporated into the present reference). Attempts to formulate aqueous heavy duty laundry detergent compositions containing ionic surfactants and a quaternary ammonium fabric softening agent or lauryl methylphenium chloride and which provide softness through static control and washing benefits have resulted in deficient physical product characteristics including separate phases or have resulted in poor performance of fabric cleaning. It has now been found that detergent compositions < Aqueous heavy-duty liquids containing certain unique surfactants and a quaternary ammonium fabric softening agent provide softness through washing and anti-static benefits, excellent cleaning performance, and attractive product characteristics, ie they are substantially clear, isotropic and of stable phase. It has been found that by limiting the level of alkenyl sulfonate in aqueous detergent compositions containing the polyethoxy side-sulfate, the unpleasant precipitates of the formation in the detergent product are prevented or inhibited and superior performance is promoted (face-to-face cleaning, softness through of washing and antistatic benefits). Therefore, an object of the present invention is to provide an aqueous laundry detergent composition that is heavy duty and substantially clear and substantially provides excellent cleaning and gentleness through the washing and antistatic benefits.
BRIEF DESCRIPTION OF THE INVENTIONThe present invention encompasses heavy-duty, isotropic, aqueous, substantially clear laundry liquid laundry detergent compositions comprising, by weight of the composition: (a) from about 10 to 40% of an ammonium surfactant component comprising, by weight of the compound: i.0 (i) from about 5 to 40% of polyethoxylated alkyl sulfates wherein the alkyl group contains from 10 to 22 carbon atoms and the polyoxyethylate chain contains from 1 to 15 ethylene oxide entities; and 15 (n) not more than about 5% of alkylbenzene, ulphates; (b) from about 1 to about 10% of a quaternary ammonium fabric softening agent having the formula (R 1 Ri / NX (-) / R 3 2 TG wherein Ri and R 2 are individually selected from the group consists of Ci-C alkyl, hydroxyalkyl of C1-C4, benc lo, and - (C2r-U0), cH where x has a value of 2 to 5, X is an anion, and (1) R3 and R4 are each an alkyl of Ca-C? Io (2) R3 is a C8-C2 alkyl and R * is selected from the group consisting of C1-C10 alkyl, hydroxyalkyl of C1 -C10, benzyl and ~ (C2H.; 0)? H where x has a value of 2 to 5.
DETAILED DESCRIPTION OF THE INVENTIONIn accordance with the present invention, it has now been found that an entangleable heavy duty aqueous liquid detergent composition is formed surprisingly when certain anionic surfactants and a quaternary ammonium softening agent are combined in relative proportions specified hereinafter. The composition is substantially clear and isotropic and provides remarkable cleanliness and smoothness through the washing benefits. As used in the present, -? The term "isotropic" indicates a single continuous phase, for example a liquid. A suspension or liquid having suspended crystals, precipitates or more than one liquid or liquid crystalline phase would not fall within the scope thereof. As used herein, the term "substantially clear" means statically clear, transparent or translucent. The liquid detergent compositions for lav < The heavy-duty workings herein contain an anionic surfactant component and a quaternary ammonium fabric softening agent as essential ingredients.
Anionic surfactant component The detergent compositions herein comprise from about 10 to 40%, preferably from about 15 to 25% by weight of the detergent composition, of an ammonium surfactant component. The ammonium surfactant component contains polyoxylated alkylsulphonates, and may contain other ammonium surfactants without soap, or mixtures thereof. srnos. The ammonium surfactant component should not contain more than about 5% alkylbenzene sulphonates. Generally speaking, ammonia tensives useful herein are disclosed in U.S. Patent No. 4,285,841, Barrat et al., Issued August 25, 1981, and in U.S. Patent No. 3,919, (578, Laughlin et al. , issued December 30, 1975, both of which are incorporated herein by reference, Useful ammonium surfactants include Water-soluble salts, particularly those of alkali metal, ammonium salts and alkyl laron (for example monoethanolamome or triethanolamome), of organic sulfur reaction products having in their molecular structure an alkyl group containing from 10 to 20 carbon atoms api xunately and an ester group of sulfonic acid or sulfuric acid. the term "alkyl" is the alkyl portion of the groups aplo.) Examples of this group of synthetic surfactants are the alkylsulfates, especially those obtained by sulfation d. and higher alcohols (Cß-Ciß carbon atoms) such as those produced by reduction of tallow glycerides or coconut oil. Other anionic surfactants herein are the water soluble salts of paraffin sulphonates containing from about 8 to about 24 carbon atoms.(preferably 12 to 18); alkylglyceryl ether sulfonates, especially those ethers of the. Cß-Ciß coholes (for example sebum derivatives and coconut oil); ethylene oxide ether alkyl phenolsulphates containing from about .1 to about 4 about ethylene oxide units per molecule and from about 8 to about 12 carbon atoms in the alkyl group. And ether of ethylene oxide alkyl sulfates containing from about 1 to about 4 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group. Other anionic surfactants useful herein include the water soluble salts in the esters of α-sulfonated fatty acids containing from about 6 to about 20 carbon atoms in the fatty acid group and from about 1 to about 10 atoms of carbon approximately in the. ester group; water-soluble salts of 2-acyloxy-alkane-1-yl-phonic acids, containing from about 2 to about 9 arbono atoms approximately in the acyl group and from about 9 to about 23 carbon atoms in the entity alkane; water soluble salts olefmsulfonates containing from about 12 to about 24 carbon atoms; and ß-alkyloxyalkanesulfonates, which contain from about 1 to about 3 carbon atoms in the alkyl group and from about 8 to about 20 carbon atoms approximately in the alkane range. Ammonium surfactants in particular preferred herein are the polyoxylated alkyl sulfates of formula R0 (C2H "0) X 03-I + wherein R is an alkyl chain having from about 10 to about 22 carbon atoms,, aturated or unsaturated, and the most linear portion of the alkyl chain is about 15 carbon atoms or less - on the average, M is a cation that makes the compound soluble in water, especially an alkali metal, an ammonium cation or substituted ammonium, and x is about about 15 approximately. The ammonium surfactant component of the present compositions comprises from about 5 to about 40, preferably from about 7 to about 36%, most preferably from about 10 to about 25% by weight of the detergent composition, from 1-methylpolyethoxy. sulfate as described above. Other preferred ammonium surfactants are the non-ethoxylated C12-C15 primary alkylsulphones and secondaries. Under conditions of washing with cold water, it is less than about 18.3 ° C, it is preferred that there be a mixture of these ethoxylated and non-ethoxylated alkylsulphates. Mixtures of the alkyl sulfates with the paraffin sulphonates described above, ersulfonates with quilgliceplicos and esters of a-sulphonated fatty acids are also preferred. The ammonium surfactant component herein should comprise no more than about 5%, preferably less than about 3%, most preferably less than about 1% alkyl benzene sulfonates. Most preferably, the detergent compositions herein "do not contain alkylbenzene sulfonates. These include alkylbenzene sulphonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight or branched chain configuration, for example those of the type described in US Pat. Nos. 2,220,099 and 2,477,383. Especially problematic are the alkylbenzene sulphonates of < vd 'linear straight line in which the average number of atoms ^ carbon in the alkyl group is from 11 to 14 approximately. While not intending to be limited by theory, it is believed that the quaternary ammonium agent (a cationic surfactant) and ammonium surfactants typically contain ion pair complexes in aqueous solutions. The ion pairs formed between the cationic surfactants described and the alkylbenzenesulfonate salts have low solubility and are precipitated with a separate solid salt. This is not only a negative effect on the performance of the piece, but also avoids its use in isotropic liquid detergents. On the other hand, the ion pairs formed by the described cationic surfactants and the polyethoxylated alkyl sulphonates are more soluble in the present liquid detergent composition. This allows the formulation of isotropic liquid detergents wherein the cationic agent provides softness, antistatic and cleaning performance, and the cleaning performance of the alkylpoloethoxylate is not deteriorated.
Quaternary ammonium fabric softening agent The compositions herein also contain from about 1 to about 1.0%, preferably from about 2 to about 7%, most preferably from about 3 to about 5% by weight of a softening agent. quaternary ammonium fabric of the formula: (+) ü Ri \ / NX (-) / \ R3 2wherein Ri and R2 are individually selected from the group consisting of C1-C4 alkyl, hydroxyalkyl of C1-C4, benzyl, and - (C2r-0) XH wherein x has a value of 2 to 5; X is an anion; and (1) R3 and 4 are each a Cß-C alquilo alkyl or (2) R «is a C alquilo-C22 alquilo alkyl and 3 is selected from the group consisting of C 1 -C 10 alkyl, C 1 -C 10 hydroxyalkyl, benzyl, and - (C2H4?)? H wherein x has a value of 2 to 5. Of the foregoing, the alkyl quaternary ammonium surfactants of a long chain are preferred wherein the above formula Ri, R2 and R3 are each one ethyl and RA is an alkyl of Cß-Ciß- The agents < The most preferred quaternary ammonium salts are the chloride, bromide and alkyltrirnetium salts of Ce-Cie of methyl sulfate, and the Cs-Ciß alkyldihydroxyethyl-methylammonium salts. Of the above, laupltrimethylarnium chloride, myristylpyrimidium chloride and chloride and di ammonium coconut rnethyl sulfate are particularly preferred. ADOGFN 12TM a chloride latent lt pmet ilarnomo available cornercLally do Uitco, is a preferred softening agent herein. Another class of preferred quaternary ammonium surfactant agents are chlorides or methyl alkyldisulfates and di-C-ary lamomo; particularly preferred is the quil d methylar chloride or d? -Ci 2 -C 14 chloride. This kind of materials is particularly suited to provide antistatic benefits to fabrics. Materials that have two alkyl chain lengths longer than C14 such as alkyldimethiiar chloride or di-Ciß-Ciß, which are commonly used in fabric softeners added to the rinse, are not included in the invention, since they do not produce isotropic liquid detergents when combined with the above-described ammonium surfactants. A preferred embodiment of the invention herein comprises the detergent composition wherein the weight ratio of the ammonium surfactant component to the quaternary ammonium softening agent is about 3; 1 approximately 20: 1.
Fatty acid The compositions of the present invention may optionally contain from about 1 to about 10%, preferably from about 2 to about 7%, most preferably from about 3 to about 5% by weight., of a fatty acid containing from about 8 to about 20 carbon atoms. The fatty acid may also contain from about 1 to about 10 units of ethylene oxide in the hydrocarbon chain. Suitable fatty acids are those saturated and / or more saturated and can be obtained from natural sources such as vegetable or animal esters (for example, palm kernel oil, palm oil, coconut oil, babassu oil, safflower oil, wood pulp oil, castor oil, tallow and fish oils, fats and mixtures thereof), or synthetically prepared (for example by oxidation of petroleum or by hydrogenation of carbon onoxide by the Fisher Tropsch method). Examples of saturated fatty acids suitable for use in-oppositions of this invention include capric acid,^ rich, myristic, palrnitic, stearic, arachidic and behenic. Suitable unsaturated fatty acid species include: palmitinoleic, oleic, linoleic, linolenic and risinoleic acid. Examples of preferred fatty acids are the C 12 fatty acids, saturated C 12 -C 14 fatty acids, and saturated or unsaturated C 12 to C 1 fatty acids, and mixtures thereof. In the detergent compositions present, the weight ratio of the quaternary ammonium softening agent to fatty acid is preferably from about 1: 3 to about 3: 1, most preferably about 1: 1.5 about 1.5: 1, most preferably about 1: 1.5. :1.
Optional components The compositions of the present invention also preferably contain up to about 30%, preferably from about 1 to about 20%, most preferably from about 2 to about 10% by weight of an ethoxylated nonionic surfactant. These materials are described in U.S. Patent No. 4,285,841, Barrat et al., Issued August 25, 1981, incorporated herein by reference. The ethoxylated alcohols are preferred to the ethoxylated alkylphenols of the formula R (0C2Hü) n0H, wherein R is selected from the group consisting of aliphatic hydrocarbon radicals containing from about 8 to about 15 carbon atoms and alkyl phenyl radicals or in which the groups alkyl contains from about 8 to about 12 carbon atoms, and the average value of n is from about 5 to about 15. These surfactants are more fully described in U.S. Patent No. 4,284,532, Lei lirn others, issued August 18, 1981, incorporated herein by reference. Particularly preferred are the ethoxylated alcohols having an average of about 10 to about 15 carbon atoms in the alcohol and an average degree of ethoxylation of about 6 to about 12 moles of ethylene oxide per mole of alcohol. The addition of the ethoxylated nonionic surfactant to the compositions of the invention herein is helpful in providing physical stability to the detergent product, i.e. avoiding phase separation and precipitation. This is particularly true for compositions containing high levels of quaternary ammonium agent and / or low levels of ammonium surfactant. Therefore, a preferred embodiment of the present invention comprises at least about 2% of the nonionic surfactant in the detergent composition. The compositions herein also preferably contain up to about 30%, preferably from about 1 to about 20%, most preferably from about 1 to about 10% by weight of a builder material. Although all types of detergent compositions known in the art can be used in the present composition, the type and level of improver should be selected so that the final composition will have an initial pH of from about 7.0 to about 9.0 at a concentration of about approximately 10% by weight and water at 20 ° C. Detergency builders are described in U.S. Patent No. 4,321,165, Smith et al., Issued March 23, 1982, incorporated herein. In the preferred liquid detergent compositions present, the improver preferably represents from about 1 to about 20%, most preferably from about 3 to about 10% by weight of the composition. Preferred improvers for use in the present liquid improvers are described in U.S. Patent No. 4,284,532, eil-him et al., Issued August 18, 1981, incorporated herein by reference. A particularly preferred improver is citric acid. Enzymes can be included in the formulations present for a wide variety of laundry purposes of fabrics, including the removal of protein based, carbohydrate-based or protein-based stains, for example and for fabric renewal. Enzymes to be incorporated include proteases, amylases, lipases, and cellulases, as mixtures thereof. Other types of enzymes can also be included. They can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast origin, however, their choice is determined by several factors such as optimum pH-activity and / or stability, thermostability, stability against active detergents, inejaradores etc. In this regard, bacterial or fungal enzymes, such as bacterial lases and proteases - fungal cellulases, are preferred. Particularly preferred compositions herein contain from 0.05% to 2% by weight approximately of detersive enzymes, especially the alases, proteases and mixtures thereof, of the well-known type for detergent formulators. Enzymes are normally incorporated at levels sufficient to provide up to about 5 mg by weight, more typically from 0.01 mg to about 3 mg of active enzyme per gram of the composition. Stated otherwise, the present compositions typically comprise from 0.001% to about 5%, preferably n.01% -1% in either or a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition. Suitable examples of proteases are the subtiiisins that are obtained from particular strains of B. substilis and B. lichenifor s. Another suitable protease is obtained from a b.'cillus strain, which has maximum activity across the entire pH range of 8 to 12, developed and sold by Novo Industries A / S, under the trademark ESPERASE. The preparation of this enzyme and analogous enzymes is described in British Patent Specification No. 1,243,784 of Novo. Suitable proteolytic enzymes for removing protein-based stains that are commercially available include those sold under the brands ALCALASE and SAVTNASE by Novo dustries A / S (Denmark) and MAXATASE by International Bio-Synthetics, Inc. (The Netherlands). Other proteases include Protease A (see European Patent Application 130,756, published January 9, 1985) and Proteaea B (See European Patent Application No. 87303761.8, filed April 28, 1987, and European Patent Application No. 130,756 et al., Published January 9, 1985). The methods include, for example, those described in British Patent Specification No. 1,296,839, "Novo, RAPIDASE, Alternative Natural Bio-Synthetics, Tnc, and TERMAMYL, Novo Industries. The cellulase useful in the present invention includes both bacterial and fungal cellulase. Preferably, they have an optimum pH of between 5 and 9.5. Suitable cellulasees are described in US Patent No. 4,435,307 Barbesgoard et al. Issued March 6, 1984, which describes fungal cellulase produced from Hurnicola insolens and Hu icola strain DSM1800, or a cellulase from production 212 of fungus that .. . ß belongs to the genus of aeroonas, and cellulase extracted from the hepatopancreas of a marine mollusk (Dolabella Auricle Solander). Suitable cellulases are also described in GB-A- ^ .075.028; GB-A-2,095,275 and DE-OS-2,247,832 CAREZYME (Novo), is especially useful. Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudornonas group such as Pseudomonas stutzeri ATCC 19.154,It is not described in British Patent 1,372,034. See also lipases in Japanese Patent Application 53,20487, open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd. Nagoya, Japan, under the trademark Lipase P "Amano", hereby forward referred to as"Arnano-P". Other commercial lipases include Arnano-CES, lipases ex Chrornobacter viscosum, p. ex. Chromobacter viscosum, ar. lipolyticu NRRLB 3573, commercially available from ToyoJozo Co., T ata, 3a? An; and also Chromobacter viscosum lipases from U.S. Biochemistry Corp. E.U.A. and Diosynth Co.,Holland. The commercially available and commercially available Hurnicola enzyme from Novo (See also EPO 341,947) is a preferred lipase for use herein. A broad scale of enzyme materials and means for their incorporation into synthetic detergent compositions are also described in US Patent No. 3,553,139 issued January 5, 1971 to McCarty et al. Also the enzymes are described in North American Patent No.^, 101,457 Place et al., Issued July 18, 1978 and in US Patent No. 4,507,219 Hughes, issued March 26, 1985 both. Useful enzyme materials for liquid detergent formulations, and their incorporation into such formulations are described in U.S. Patent 4,261,868, Hora et al., Issued April 14, 1981. Enzyme stabilization techniques are described and exemplified in US Patent 3,600,319, issued on August 17, 71 for Gegde, and others and in the publication of European Patent Application No. 0 199 405 Application No. 86200586.5 published on October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in U.S. Patent No. 3,519,570. The enzymes employed herein can be stabilized with the presence of water-soluble calcium and / or nagnesium ion sources in the finished compositions which provide such ions to the enzymes. (Calcium ions are generally somewhat more effective than magnesium ions and are preferred here if only one type of cation is used). Additional stability can be provided with the presence of other different stabilizers described in the art, especially, borate species. See Severson, North American Patent No. 4,537,706. Typical detergents, especially liquids, comprise from about 1 to about 30, preferably from about 2 to about 20, preferably from about 5 to about 15, and most preferably from about 12 to about, preferably, mmole of calcium ion per nitro of the misprinted composition. This may vary a bit, depending on the amount of enzyme present and its response to calcium or magnesium lotions. The level of calcium or magnesium ions should be selected so that there is always a minimum level available for the enzyme, after allowing complex formation with enhancers, fatty acids, etc., in the composition. Any calcium or magnesium salt soluble in water may be used as the source of calcium or magnesium ions, including, but not limited to, calcium chloride, calcium sulfate, calcium alato, calcium maleate, calcium hydroxide, calcium formate and calcium acetate and the corresponding magnesium salts. A small amount of calcium ion, generally from 0.05 to 0.4 mmol / l, is also frequently present in the composition due to the calcium in the enzi suspension attacks and the water formula. In solid detergent compositions the formulation may include a sufficient amount of a water soluble calcium ion source to provide such amounts in the wash liquor. As an alternative, the natural hardness of the water may be sufficient. It is understood that the above levels of calcium and / or magnesium ions are sufficient to provide enzymatic stability. More calcium and / or magnesium ion can be added to the compositions to provide an additional provision of fat removal performance. Thus, as a proposition the present compositions will typically comprise from about 0.05% to about 2% by weight of a source of water soluble calcium or magnesium ions, or both. The amount may, of course, vary with the amount and type of enzyme used in the composition. The compositions herein may also contain nationally, but preferably different, additional stabilizers, especially borate-type stabilizers. v epically, such stabilizers will be used at levels in the compositions of from about 0.25 to about 1.0%, preferably from about 0.5 to about 5%, most preferably from about 0.75 to about 4% by weight of boric acid or other compound of borato capable of fonnar >; boric oxide in the composition (calculated on the basis of noric acid). Boric acid is preferred, although other compounds are suitable such as boric oxide, borax and other alkali metal borates (eg ortho-, meta- and sodium pyroborate and sodium pentaborate). Substituted boric acids (eg, phenylboronic acid, butanoboric acid, and p-bromo phenylboronic acid) may also be used in place of boric acid. Other preferred components for use in'> Liquid moieties herein are the neutralizing agents, regulating agents, phase regulators, hydrotropes, polyacids, suds regulators, opacifiers, antioxidants, bactericides, colorants, perfumes, and brighteners, described in US Patent No.77, 285, 841, Bar et al., Issued August 25, 1981, incorporated herein by reference. Preferred neutralization agents to be used herein are organic bases, especially tnetanolamine and monoethanolarnine, which result in better detergency performance than inorganic bases such as sodium and potassium hydroxide. The following non-limiting examples illustrate the compositions of the present invention. All percentages, - "rates and proportions used herein are by weight unless otherwise specified.
EXAMPLE ILiquid heavy duty laundry detergent compositions are prepared by mixing the ingredients listed in the stated proportions:Component Weight%? 1 0. 1 To the polyethoxylated sodium sulphite (C12-C15) (2.5) 18.0 18.0 18.0 18.0Lauryl Pyrilamine Chloride - 5.0 5.0 5.0 Polyethoxylated (C12-C13) Alkene (9) 2.0 2.0 2.0 2.0Alkyl (C12) glucosamide 5.0 5.0 5.0 5.0Citric acid 3.0 3.0 3.0 3.0Fatty acid of alkyl (C12-C14) 2.0 2.0 2.0 2.0 e't nol 3.7 3.7 3.7 3.7 Propanodiol 8.0 8.0 8.0 8.0 Monoethanolamine 1.1 1.1 1.1 1.1 Boric acid 3.5 3.5 3.5 3.5Ethoxylated tetraethylene pentamine (15-18) 1 1..22 1.2 1.2 1.2 Sodium ensulfate 3.0 3.0 3.0 3.0 Enzyme Protease 0.9 0.9 0.9 0.9 Enzyme Lipase 0.1 0.1 0.1 0.1.Fnzirna Celulasa 0.08 0.08 - 0.08Sodium hydroxide - for pH 8.0 - Water, perfume and minor ingredients Adjust to 100-Four cotton towel samples (mixture of 86% cotton and 14% polyester) were washed in normal laundry loads in automatic clothes washers. Each charge uses 0.48 cups (123 g) of one of the above detergent compositions providing approximately 1900 ppm of the detergent composition to the water wash solution. The water was washed at 35 ° C and the hardness of water was 6 grams / 3.78 1 (3: 1 Ca ++: Mg ++). After a normal washing cycle (washing, rinsing and squeezing), the loads were dried in normal electric clothes dryers. For each load, four cotton towel samples were used. Mix 86% cotton 14% polyester. For smoothness graduations; 4 loads were washed for each of the compositions, and the softness gradations were averaged. The samples were manually graded by three expert graders. A rating scale of -4 to +4 panel scoring units (psu) is used with +4 psu indicating much more softness advantage, 0 indicating no difference, and -4 psu indicating much less softness advantage. The results for each of the compositions were averaged and the composition A was assigned a relative value of 0. The results are as follows:SMOOTHNESSB vs A C vs A D vs A +0.9 psu +0.9 psu +0.9 psuThese differences in softness are statistically significant in a confidence interval of 90%. The test shows that the compositions B, C and D of the invention provide increased fabric softness benefits against composition A of the prior art which does not contain cationic softening agents. In addition, the benefit in softness is not related to the presence of the cellulase enzyme, and is observable even in the absence of fatty acid. The compositions B, C and D are clear isotropic compositions, do not exhibit precipitation of components after a prolonged period, and provide good unsightly benefits. In tests comparing the stain removal performance of composition A against compositions similar to composition B (compositions of the present invention), the compositions are considered to be on average equal for the removal of 10 different types. of spots. In some grease / oil stains (such as makeup stains and dirty engine oil) the compositions of the invention are considered to be better than the reference composition A.
EXAMPLE IIHeavy-duty liquid laundry detergent compositions were prepared by mixing the ingredients listed in the stated proportions:"'" •• - component Weight% E 1 2 • / Lauriltri Etüammonium Chloride 5.0 5.0 5.0C12 alkylbenzene sulphonic acid "7.2 1.8.0Alkyl (C12-C15) polyethoxylated (2.5) 18 8..00 10.8 - Alkyl (C12-C13) polyethoxylated (9) 0. 2.0 2.0Citric acid 3.0 3.0 3.0 n '- the fat of alkyl -i-Cu) 2.0 2.0 2.0Ethanol 3.7 3.7 3.7Propanodiol 8.0 8.0 8.0 Monoethanol ina 1.1 1.1 1.1Boric acid 3.5 3.5 3.5 Ethoxylated xetraethylenepentamine (15-18) 11..22 1.2 1.2Sodium Curnenosulfate 3.0 3.0 3.0Protease Enzyme 0.9 0.9 0.9Enzyme Lipase 0.1 0.1 0.1Cellulase Enzyme 0.08 0.08 0.8Sodium hydroxide -pa ra pH 8. 0 Water, perfume and minor ingredients the restAppearance of the Clear Composition White Separation after a day at tempera- thin of viscous phases atmosphereThe composition E of the present invention, which contains lauryl alkyltrimethylamide chloride and does not contain alkylbenzenesulonic acid, is clear and stable for several months in storage at room temperature. The"Reference compositions 1 and 2, which contain alkylbenzene-phonic acid, have undesirable physical properties (phase separation or high viscosity) after one day only.