MXPA98007063A - Compositions detergents for washing clothing quecontain sili emulsions - Google Patents

Abstract

The present invention relates to: High performance liquid or granular detergent compositions containing silicone emulsions and selected from among emulsifying surfactants, silicone emulsions preferably having an average particle size of about 20 to about 300 microns. and provide exceptional cleaning and softening benefits

Description

DETERGENT COMPOSITIONS FOR WASHING CLOTHES THAT CONTAIN PE SILICON EMULSIONS CAMPO TECNICQ The present invention relates to granular laundry detergents or high performance liquids containing a silicon emulsion for example poly idimeti 1-si loxane * and surfactants selected to provide exceptional cleaning and softening benefits. The silicone emulsions preferably have an average particle size of about 5 to about 500 microns. Also included herein are methods for cleaning and softening fabrics with the detergent compositions.

BACKGROUND OF THE INVENTION Consumers of laundry cleaning products have regularly preferred that freshly washed clothes be both clean and have a soft feel • this is especially true for laundry items such as linen »bedding» towels and clothes of cotton. Usually. Fabric softening agents have been introduced into the laundry process after the wash cycle. Typically, these fabric softening agents have taken the form of softening compositions that are introduced into the rinse cycle or drying process. Numerous attempts have been made in the past to formulate laundry detergent compositions that have good cleaning properties and are capable of softening textiles and fabrics. This provides convenience to consumers in the sense that laundry detergent and fabric softener do not have to be added to the wash liquor separately. However, such fabric detergent / softener compositions have not been totally satffactory for a variety of reasons including the reduced cleaning ability of the detergent composition and the reduced yield of softening. Without being limited to theory, it is believed that the reduced cleaning capacity is due to the competition problems between the good anionic cleaning surfactants and the cationic fatty agents which are effective conditioning agents. Many formulators in the past have also relied on clays, especially impalpable spectacle clay and similar ingredients to provide smoothing benefit. It is believed that the clays work by depositing a thin layer on the fabric to provide a slippery (or "soft") feel to the touch. Clay softeners in combination with amine and cationic softeners have also been used as disclosed, for example, in the U.S. Patent. 4,375,416. Crisp et al., Issued March 1, 19B3 and the US Patent. 4,291,071 et al., Issued September 22, 1981. However, some problems associated with the use of clays in detergent compositions include an undesirable appearance of the product and a reduced yield of impiety. Thus, the use of cationic conditioners or clays in laundry detergent compositions has not achieved a high level of cleaning performance with acceptable levels of softening. Another material that can provide increased softness is silicone. Typically, in the past, the use of silicone has involved microemulsions of silicone oils. It has been found that emulsions with a particle size of less than 5 microns, usually less than 1 micron, provide unsatisfactory smoothing benefits in conventional detergent compositions. Silicon microemulsions have been disclosed in a number of different publications in laundry detergent compositions. Although these references disclose compositions containing silicone. they do not provide answers to all the problems faced in the inauguration of a totally satisfactory product. The problem of providing detergent compositions that provide smoothing benefits is still unresolved. without the reduction of cleaning level. Another problem is a softening level more difficult than what is desired when including clays, cationic agents or silicone microemulsions in the detergents. Therefore, it is an object of the invention herein to provide a "superior" high performance laundry detergent composition with novel silicone emulsions that provide excellent smoothing benefits. It is another object of the present invention to provide such laundry detergent compositions having good stability and in which the cleaning and softening agents are compatible and provide a combination of superior cleaning and softening benefits. It is another object of the present invention to provide an improved method for cleaning and softening fabrics and text genres. These and other objects will become readily apparent from the detailed description that follows.

PREVIOUS TECHNIQUE Publications that have disclosed the use of silicone in detergent compositions include US Patents. 4.T46.9B2; 5,234,495; 5,254,269; 5,164,100; ,258,451; 4,814,376; 4 »624,794; 4,585, 563; 4 »639» 32l; . 104,555; 5,174,912; 5,302,658: 5,026,489; 5,091,105; ,057,240; 5,041,590; and 4,986,922. see also WO 95/11746; EP 396,457; EP 288,137; and GB 2,206,902.

BRIEF DESCRIPTION OF THE INVENTION In accordance with the present invention, it has now been discovered that high performance detergent compositions which provide very good cleaning and softening properties are surprisingly formed when relatively large silicone emulsions are included in the detergent compositions in relative proportions specified later in the present. The present invention encompasses a high performance laundry detergent composition which includes: a) from about O.IX to about 12%, preferably from about 1 to about 5X "by weight of the composition, of an emulsion silicone; wherein said silicone emulsion includes from about IX to about 90X "preferably from about 20X to approximately BOX" by weight of the Sixtone emulsion "and from about O. IX to about 30X, preferably from about IX to about 10X "by weight of the emulsion, of emulsifier; and wherein said emulsion has an average particle size of from about 5 to about 500 microns, preferably from about 20 to about 300 microns, most preferably from about 50 to about 200 microns; and b) from about IX to about 50X, by weight of the detersive surfactant composition. The emulsifier can be selected from the group consisting of nonionic emulsifier surfactant, anionic emulsifier surfactant, cationic emulsifier surfactant, amine oxide emulsifier surfactant and mixtures thereof; the emulsifier is preferably selected from the group consisting of anionic emulsifying surfactant agent, nonionic emulsifier surfactant and mixtures thereof. It is added to the silicon emulsion to a detergent matrix. These large-size silicone emulsions can be stably suspended in a liquid detergent composition having a relatively high viscosity and a very thinning matrix of the cutting effect. Some examples of the detersive surfactant b) are surface-active agents selected from the non-ionic detersive surfactant, anionic detersive surfactant agent, cationic detersive surfactant, and detersive detersive agent, especially amine oxide detersive surfactants and mixtures thereof. Additional detersive ingredients can be selected from one or more additives selected from detergents, enzymes, brighteners, dirt removers, foam control agents, anti-static agents and dispersing agents. Said additional ingredients are normally present in effective amounts of cleaning. Also disclosed herein is a method for cleaning and softening fabrics that includes contacting said fabrics with an effective amount of a laundry detergent composition that includes: a) from about 0.1X to about 12X, weight of the composition, of a silicone emulsion; wherein said silicone emulsion includes from about IX to about 90X, by weight of the emulsion, of silicone, and from about O. IX to about 30X, by weight of the emulsifier emulsion; and wherein said emulsion has an average particle size of from about 5 to about 500 microns, preferably from about 20 to about 300 microns, and b) from about IX to about 50X, by weight of the composition, of a detersive surfactant. . All percentages and proportions herein are by weight and all cited references are hereby incorporated by reference "unless specifically indicated otherwise.

DETAILED DESCRIPTION OF THE INVENTION Silicones - The silicone additives of this invention can be of the formula: wherein each of R and R2 in each repeating unit "- (Si (Ra.) (Ra) 0) -» is independently selected from alkyl and alkenyl radicals of Cj.o-Cj.oi phenyl, substituted phenyl substituted alkyl or units of -CR ^ RaSi-Ol-; x is from about 50 to about 300,000, preferably from about 100 to about 100,000, most preferably from about 200 to about 50,000, wherein said substituted alkyl or substituted phenyl is substituted with halogen, amino, hydroxyl groups or groups. nitro; wherein said polymer is capped by a hydroxyl, hydrogen or -SiRa group wherein R3 is hydroxyl, hydrogen or methyl. Measurement of particle size - The particle sizes of the silicone emulsion are measured using a particle size analyzer by light scattering »such as a Coulter LS 230. E do, general pyramid to make samples of, size larger The silicone emulsion typically makes mixing silicone fluid with an emulsified surfactant solution with a specific viscosity ratio using a drive mixer for a certain time. In a specific example of this procedure »70X by weight of silicone fluid is mixed» which is composed of 40X of silicone rubber and 60X of dimethicone fluid (350 cst), with 30X by weight of surfactant solution , which is made approximately 25X of alkylsulfate and alkylethoxylate sulfate. After mixing for about one to two hours at a speed of 250 rpm in a peak flask, mixing is stopped and the average particle size is about 250 microns. Also, "Conoidal Systems and Interfaces" by Sydney Ross and Ian D. Morrison. by John Willey & Sons, Inc 1988, and "Emulsion Science" by Philip Sher an, Academic Press, 196B »regarding procedures for making emulsions. Typically, "commercially available silicone emulsions" such as Dow Corning Emulsion 8"and 6E SM2061". they are less than 5 microns, many less than 1 miera. For example. Dow Corning Emulsion 8"contains the 35X 1000 ct (centistoKes) of polydimethylsiloxane fluid and has a particle size of about 0.280 microns.The emulsions herein can also contain water and other solvents is an effective amount to assist in the emulsion Aaen-ta? te a * ve ve ercvna? atiorss - The emulsifiers useful in the silicone emulsions of the present may be selected from the group consisting of non-ionic surfactant surfactant »anionic emulsifier surfactant» agent IO emulsifier surfactant cationic »amine oxide emulsifier surfactant and mixtures thereof. The emulsifying surfactant is present in the emulsion in an amount of about 0.1X to about 30X »preferably from about 0.5X to about 20X, most preferably from about IX to about 10X. in weight of the emulsion. The surfactants suitable for use as emulsifying surfactants will then be considered. Some examples of preferred nonionic emulsifying surfactants include surfactants selected from the group consisting of alkyl phenol, ether, alkylethoxylates, polysorbate surfactants and mixtures thereof. Some examples of preferred anionic emulsifying surfactants include surfactants selected from the group consisting of alkyl sulfate, alkylbenzene sulfonate, alkyl ether sulfate and mixtures thereof. By "emulsifying surfactant" is meant the surfactant added to the silicone noises to form an emulsion. By "detersive surfactant" is meant the surfactant added to the detergent composition for detersive purposes, of the elimination of dirt. Detersive surfactant surfactant - The high performance laundry detergent compositions herein preferably contain detersive surfactants which are selected from nonionic surfactant, anionic detersive surfactant. cationic detersive surfactant. especially quaternary surfactants, suterionic detersive surfactant. amine oxide detersive surfactant and mixtures thereof. Detergent compositions typically contain from about IX to about 50X, preferably from about 15X to about 30X "by weight of the detergent composition, of one or more detersive surfactant components.

Surfactants for efffective purposes Ophthalmology 2. Non-ionic surfactant asante - The anionic surfactants include alkylene carboxymethyl sulphonates (LAS) of primary or "branched chain" or "C10-Ca0" alkylsulfates (AS). the secondary sulfates (2 »3) of ao-Ca .. of the formula CH3 (CHa)" (CHOSO, - "*) CHa and CHa (CHa) and CHOS? _M ^) CHaCHa where xy (y + 1) are integer numbers of at least about 7"preferably at least approximately 9 and M is a cation-solubilizing agent in water" especially sodium "unsaturated sulfates such as olei sulfate the alkylalkoxy sulfates of Cj.oC, .. (" AE, -, S ", especially ethoxysulfates EO 1-7), alkylalcoxycarboxylates of (especially the ethoxy carboxylates of EO 1-5), the ether glycolic esters of C10-C1ß, the alkyl polyols of Cie > - Cxm and its corresponding sulphated polyglycosides, and esters of alpha-sulfonated fatty acids of C? A-Clß. In general terms, anionic surfactants useful in the present invention and U.S. Pat. No. 4.2B5.841. Barrat et al. Issued August 25, 1981"and the U.S. Patent. No. 3,919,678, Laughlin et al., Issued December 30, 1975. The anionic surfactants which are useful include the water-soluble salts, particularly the alkali metal salts, ammonium and alkylolammonium (eg, raonoethanolammonium or triethanolammonium). of organic sulfuric reaction products having in their molecular structure an alkyl group containing from about 10 to about 20 carbon atoms and an ester group of sulfonic acid or sulfuric acid. (The alkyl portion of the aryl groups is included in the term "alkyl"). Some examples of this group of synthetic surfactants are the alkyl sulfates. especially those obtained by sulfating the higher alcohols (B to 18 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil. Other anionic surfactants herein are the water soluble salts of alkylphenol ether ethanol which contain from about 1 to about 4 ethylene oxide units per molecule and from about 8 about 12 carbon atoms in the molecule. the alkyl group. Other anionic surfactants useful herein include the water soluble salts of alpha-sulfonated fatty acid esters containing from about 6 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; the salts are soluble in water of 2-acyloxy-alkene-1-sulphonic acids containing approximately 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane portion; the water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and the Q-alkyloxy-alkan sulphates containing from about 1 to 3 carbon atoms in the alkyl group of about 8 to 20 carbon atoms in the alkane portion. Particularly preferred anionic surfactants herein are the alkyl polyethoxy lato sulfates of the formula. R0 (CaH- »0) MS0 -M- < - wherein R is an alkyl chain having from about 10 to about 22 carbon atoms »saturated or unsaturated» M is a cation which makes the compound soluble in water »especially an alkali metal cation» ammonium or substituted ammonium »and x varies on average from about 1 to about 15. Preferred alkyl sulfate surfactants are the primary and secondary alkyl sulfates of non-ethoxylated C? - m. Under washing conditions with cold water »that is to say» at less than 18.3 ° C »it is preferred that there be a mixture of such ethoxylated and non-ethoxylated alkyl sulphates. Some examples of fatty acids include the capric »lauric» myristic »palmitic» acids stearic »arachidic and behenic. Other examples of fatty acids include palmitoleic acids. oleic linoleic »linoleic and ricinoleic. Nonionic eneionary agent - Conventional non-ionic and amphoteric surfactants include the alkylethoxylates (AE) of C? -C m including the so-called narrow-chain alkyletoxylates and the alkylphenol-Cß-C-alkoxylates (especially ethoxylates) and mixed ethoxy / propoxy). N-alkyl polyhydroxy fatty acids amides of Cxo-Cxß can also be used. Some typical examples include the N-raet lglucamides of C ai-Cxβ. see WO 9 »206» 154. Other surfactants derived from sugars include the fatty acid amides of N-alkoxypol ihydroxy. such as N- (3-etho? ipropyl) glyca ida. The glucamides of C a-Cxm from N-propyl to N-exi or »can be used for reduced foaming. Conventional C10-Cao soaps can also be used. If high foaming is desired, the branched chain Ci0-CAß soaps can be used. Some examples of nonionic surfactants are described in the patent of E.U.A. 4,285,841, Barrat et al., Issued August 25, 1981. Some preferred examples of these surfactants include the ethoxylated alcohols and ethoxylated alkylphenols of the formula R (OCaH ^) nOH, wherein R is selected from the group consisting of aliphatic hydrocarbons containing from about 8 to about 15 carbon atoms and alkylphenyl radicals in which the alkyl groups contain from about 8 to about 12 carbon atoms, and evaluating the n medium is from about 5 to about 15. These agents surfactants are more fully described in the US Patent 4,284,532, Leikhim et al. "Issued August 18, 1981. Ethoxylated alcohols having an average of about 10 to about 15 carbon atoms in alcohol and an average degree of ethoxylation of about 6 to about 12 moles are particularly preferred. of ethylene oxide per mole of alcohol. Mixtures of anionic and nonionic surfactants are especially useful. Other conventional useful surfactants are listed in the common texts, including polyhydroxy fatty acid amides, alkyl glycosides, polyalkyl glycosides. Betaines of C? a-Clß sulfobetainas (ul tainas). Some examples include the N-methylglucads of C x-C m. See WO 9,206,154. Other surfactants derived from sugars include the fatty acid amides of N-alkoxyhydroxy. such as N- (3-methoxypropyl) glucamide of C ^ o-C * ... C-Cxm glucamides from N-propyl to N-exyl can also be used for low foaming.

Cationic Surfactants A class of preferred cationic surfactants are monoalkyl ammonium-quaternary surfactants, although any cationic surfactant useful in detergent compositions is suitable for use herein. Cationic surfactants that can be used herein include quaternary ammonium surfactants of the formula: wherein ñ and R2 are individually selected from the group consisting of C -C ^ alkyl. Hydroxyalkyl of Cx-C ^ »benzyl and - (CaH-0) > < H where x has a value of approximately 2 to 5; X is an anion; and (1) each of R .., and R is a Cβ-Cx alkyl "or (2) Ra is a Cß-Cxß alkyl and R ^ is selected from the group consisting of C-Cxo alquilo alkyl, hydroxyalkyl of C -Cxo. benzyl - (aH ^ O ^ H where x has a value of 2 to 5. Preferred quaternary ammonium surfactants are the chloride, bromide and methylsulfate salts.

Some examples of quaternary ammonium surfactants "monolayer chain alkyl" are those in which each of Rx, Ra and R ^ are methyl and Ra is a Cs-Cxß alkyl "wherein R3 is C3- alkyl. ß and Rl (Ra and R are selected from methyl and hydroxyalkyl groups) Particular preference is given to lauryl trimethylammonium chloride, myristium chloride, trimethylammonium, palothritium chloride, trimethylammonium chloride, coconut trimethylammonium chloride, trimethylammonium methylsulfate, coconut, dimethyl 1-monohydroxy-ethylammonium chloride, dimethyl-1-monohydroxy-coconut-lamonium methylsulfate, etheryl-dimethyl-monohydroxy-ethylammonium chloride »ethanedryl-dimethyl-monohydroxyethylammonium methyl sulfate, dialkyl chloride -dimethyl-ammonium from CXa ~ Cx < # and mixtures thereof ADOGEN ™ is also preferred a lauryltrimethylammonium chloride commercially available from Witco.Water chloride is even more preferred. Trimethyl ammonium chloride and myristium chloride 1 trimethylammonium. Another group of suitable cationic surfactants are the quaternary surfactants of alkanol amide! of the formula: OR II (CHa > "~ Y (CHa)« -X R * wherein R - * - can be C 0-xß alkyl or a substituted or unsubstituted phenyl; R5 * can be an alkyl of - ^. H "or (EO) ^ wherein y is from about 1 to about 5; Y is O or VKR3 ') (R- *); Ra can be H, C- ^ alkyl or (EO) ^, where y is from about 1 to about 5; R-4"if present" can be alkyl of - ^ or (E0). wherein y is from about 1 to about 5 »each n is independently selected from about 1 to about 6» preferably from about 2 to about 4; X is hydroxyl or -N (Rβ) (Rβ) (R "7)" wherein R ". Rβ »R" * are independently selected from alkyl of, -> H »or (EO) -y, wherein y is from about 1 to about 5. Tenaioacti oß of OXÍOO dfi amine - the compositions herein contain also amine oxide surfactants of the formula: RA (EO) X (PO) and (BO) zN (0) (CHaR ') a.qHaO (I) In general it can be seen that the structure (I) provides a long chain portion R * (EO)? (PO) and (BO) z and two short chain portions »CH-, Rr. R 'is preferably selected from hydrogen »methyl and -CHaOH. In general, R is a primary or branched hydrocarbyl portion which may be saturated or unsaturated, preferably R A is a primary alkyl portion. When x + y + z = O »R is a hydrocarbyl portion having a chain length of about 8 to about 18. When x + y + z is different from O» R it may be a little longer »having a length of chain in the range of xa-Ca ^. The general formula also encompasses amine oxides of which x + y + z = O, R * = Cβ-C x β »R 'is H and q is 0-2» preferably 2. These amine oxides are illustrated by alkyldimethylamine oxide of CXa ~ j.- »» oxides of hexadeci 1-dimeti lamina. octadecyl oxide and other hydrates »especially the hydrates described in the patents of E.U.A. 5,075 »501» incorporated herein by reference. The invention also encompasses amine oxides in which x + y + z is different from zero »specifically x + y + z is from about 1 to about 10» RA is a primary alkyl group containing from 8 to about 24 carbons » preferably from about 12 to about 16 carbon atoms; in these embodiments y + z are preferably O and x is preferably from about 1 to about 6 »very preferably from about 2 to about 4» EO represents ethyleneoxy; PO represents propnoxy; and BO represents butyleneoxy. Such amine oxides can be prepared by conventional synthetic methods "for example" by reaction of alkyl ethoxy sulfates with dimethylamine followed by oxidation of ethoxylated amine with hydrogen peroxide. The highly preferred amine oxides herein are solids at room temperature, most preferably have portion points in the range of 30 ° C to 90 ° C. The amine oxides suitable for use herein are made commercially by a number of suppliers "including Akzo Chemie. See compilation of Ethyl Corp; and Procter & Gamble, and the MeCuteheon specialized publication article regarding alternative amine oxide manufacturers. The preferred commercially obtained amine oxides are the solid dihydrate ADMOX 16 and ADMOX 18, ADMOX 12 and especially ADMOX 14 from Ethil Corp. Preferred embodiments include dodecyl oxide Idimeti lamina dihydrate »hexadecyl oxide Idimet lamina dihydrate» octadecyl oxide Idimet Dihydrated film »Hexyltrimethyloxyethylene oxide dimethylamine» tetradecyl dimethylamine dihydrate oxide and mixtures thereof. While in some of the preferred modalities R "is H" there is some freedom with respect to R "slightly greater than H. Specifically, the invention further encompasses embodiments in which R 'is CH-.0H, such as hexadecylbis (2-hydroxyethy1) amine oxide» oxide of such owbis (2-hydroxyethyl) amine »stearate oxide lbis (2-hydroxyethyl) amine» and oleylbis (2-hydroxyeti 1) amine oxide. Metering detergency - The present compositions also optionally contain, but preferably, up to about 50%. very preferably IX to about 40%, most preferably still from about 5% to about 30X, by weight of a builder material. It is not implied, however, »that lower or higher levels of builder are excluded. Builders may optionally be included in the compositions herein to assist in the control of mineral hardness. Both inorganic and organic builders can be used. Detergency builders are typically used in fabric washing compositions to aid in the removal of particulate soils. Detergency builders are disclosed in the U.S. Patent. No. 4.321.1S5 »Smith et al., Issued March 23, 19B2. Preferred detergency builders for use in liquid detergents are described herein in the U.S. Patent. No. 4 »284,532» Leikhim et al., Issued August 18, 1981. Inorganic or phosphorus-containing builders include, but are not limited to, the "alkali metal salts" ammonium and ammonium alkanol polyphosphate moieties ( exemplified by the tripol-osphates »pyrophosphates and bi-polymeric metaphosphates)» phosphonates »phytic acid, silicates» carbonates (including bicarbonates and sesquicarbonates) »sulphates and the ossification. However, phosphate-free detergency builders are required in some places. Importantly, the compositions here perform surprisingly well even in the presence of the so-called "weak" detergency builders (as compared to phosphates) such as citrate, or the so-called "enhanced" situation that can occur with builders. zeolite or stratified silicate. Some examples of silicate builders are alkali metal silicates, particularly those having the Si02: aaO ratio in the 1.6: 1 to 3.2: 1 range and layered silicates such as layered sodium silicate described in US Pat. 4,664 »839, issued May 12, 19B7 to H. P. Rieck NaSKS-6 is the trademark of a crystalline layered silicate distributed by Hoechst (commonly abbreviated herein as" SKS-6"). Unlike other zeolite builders, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has the form of delta-Na3Si morphology of the stratified silicate. It can be prepared by methods such as those described in the German documents DE-A-3,417,649 and DE-A-3 »742» 043 is a highly preferred layered silicate for use herein but can be used herein other such silicates satified. such as those having the general formula NaMSiMOaM + l'yHaO where M is sodium or hydrogen »x is a number from 1.9 to 4» preferably 2, and is a number from 0 to 20, preferably O. Other various layered silicates of Hoechst include NaSKS-5 »NaSKS-7 and NaSKS-11» as the alpha »beta and gamma forms. As indicated above, delta-NaaSiOß (NaS S-6 form) is most preferred for use herein. Other icates may also be useful such as for example magnesium silicate »which can serve as a stabilizing agent for oxygen whiteners as a component of foam control systems. Some examples of carbonate builders are the alkaline and alkaline earth metal carbonates such as those disclosed in German Patent Application 2 2,321,001 published November 15, 1973. The aluminosilicate builders are useful in the present invention. Aluminosilicate builders can be an important detergency builder ingredient in liquid detergent formulations. The aluminosilicate builders include those that have the empirical formula .: M.ÍZAIOa) v3xHa O where z and e are integers of at least 6"the molar ratio of zay are in the range of 1.0 to about 0.5 and x is an integer of about 15 to about 264. The" useful "aluminosilicate ion exchange materials are commercially available . These aluminosilicates may be of crystalline or amorphous structure and may be aluminosilicates which are present in nature or synthetically derived. A method for producing aluminosilicate ion exchange materials is disclosed in the U.S. Patent. 3,985,669 »Kru et al.» Issued October 12, 1976. The preferred "crystalline" synthetic "crystalline" aluminosilicate ion exchange materials useful herein, are obtainable with the designations Zeolite A »Zeolite P (B). Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the ionic exchange material of crystalline aluminosilicate have the formula: Na aC (AI0s;) xa (SiOs) Xa3xHa0 where ? it is from about 20 to about 30, especially from about 27. This material is known as Zeolite A. Dehydrated Zeolites (x = O-10) can also be used herein. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Organic builders suitable for the purposes of the present invention, but are not restricted thereto, are a wide variety of polycarboxylate compounds. As used herein, "polycarboxylate" refers to compounds having a multitude of carboaltylate groups, preferably at least 3 carboxylates. The polycarboxylate builder can generally be added to the composition in acid form but can also be added in the form of a neutralized salt. When used in the form of salt, alkali metals such as sodium, potassium and lithium are preferred, and alkanol ammonium salts are preferred. Included among polycarboxylate builders is a variety of useful material categories. An important category of polycarboxylate builders encompasses ether polycarboxylates, including oxydisuccinate as disclosed in Berg. US Pat. 3 »12B» 287 »issued April 7, 1964, and Lamberti et al. Patent of E.U.A. 3,635,830. issued on January 18, 1972. See also the "TMS / TDS" detergency builders of the U.S. Patent. No. 4,663,071 issued to Bush et al. On May 5, 1987. Suitable ether polycarboxylates also include cyclic compounds, particularly alicyclic compounds, such as those described in U.S. Pat. 3 »923» 679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypol icarboxylates, maleic anhydride copolymers with ethylene or viny lmethyl ether. L-3, 5-trihydroxy-benzene-2,4-6-trisulfonic acid and »carboxymethyl loxysuccinic acid» and various alkali metal salts »ammonium» substituted ammonium acids such as diethylene diamine tetra acetic acid and ethyl triacetic acid »as well as polycarboxylates such as methyl acid »succinic acid, oxydisuccinic acid» polymaleic acid »benzene-l-3,5-tricarboxylic acid. carboxymethyloxysuccinic acid and soluble salts thereof. Citrate builders. for example citric acid and soluble salts thereof (particularly sodium salt), are polycarboxylate builders of particular importance for high performance liquid detergent formulations due to their availability of renewable resources and their biodegradability. Oxydisuccinates are also especially useful in such compositions and combinations. Also suitable in the detergent compositions of the present invention are 3'-3-dicarboxy-4-oxa-1'-6-hexanedioates and the related compounds disclosed in US Pat. 4,566,984 issued on January 28, 1986. Succinic acid builders include the alkyl and alkenyl succinic acids of Cß-Cao and salts thereof. A particularly preferred compound of this type is dodecyl succinic acid. Some specific examples of succinate builders include: lauryl succinate. myristyllysuccinate »pal imitilsucci-nato, 2-dodecenylsuccinate (preferred). 2-pentadecenyl succinate and the like. Laurisuccinates are the preferred builders of this group and are described in European patent application 86200690.5 / 0 »200 >; 263 »published on November 5, 1986. Suitable polycarboxylates are disclosed in the U.S. patent. 4,144,226, Crutchfield et al., Issued March 13, 1969 and the patent of E.U.A. 3 »30B» 067. Diehl, issued on March 7, 1967. See also Diehl patent of E.U.A. 3,723,322. It is also possible to incorporate fatty acids, for example polycarboxylic acids of C a-m, into the compositions "only in combination with the detergency builders" especially citrate builders and / or succinate builders. to provide additional detergency builder activity. Such use of fatty acid will generally result in a decrease in foam formation "and which should be taken into account by the formulator. In situations where phosphorus-based builders can be used, the various alkali metal phosphates can be used, such as the well-known sodium triphosphates, sodium pyrophosphate and sodium orthophosphate. Phosphonate builders such as ethane-1-hydroxy-1-diphosphonate and other known phosphonates can also be used (see, for example, the patents of US patents 3,159,581, 3,213,030, 3,422,021. "3 »400.14ß and 3» 422 »137) Enzymes - Enzymes may be included in the formulations herein for a wide variety of laundry purposes of fabrics, including, for example, the removal of protein-based stains, based on carbohydrates or based on triglycerides, and to avoid the transfer of migratory dyes and the restoration of fabrics The enzymes to be incorporated include proteases, amylas, lipases, cellulases and peroids, as well as mixtures thereof. Other types of enzymes can also be included, they can be of any suitable origin »such as of origin 2B vegetable »animal» bacterial »nicotine and yeast. However, its choice is governed by several factors such as pH activity and / or optimum stability »stability» stability against active detergents »detergency builders» etc. In this regard, bacterial and fungal enzymes are preferred, such as bacterial amylases and proteases and mycotic cellulases. Enzymes are usually incorporated at levels sufficient to provide up to about 5 mg by weight »very typically from about 0.01 mg to about 3 mg of active enzyme per gram of the composition. Stated otherwise, the compositions herein typically comprise from about 0.001% to about 5X, preferably 0.01X-1X by weight of a commercial enzyme preparation. Protease enzymes are usually present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 units of Anson (AU) activity per gram of composition. Suitable examples of proteases are the subtilicins that are obtained from particular strains of B.subtilis and B.1 icheniforms. Another suitable protease is obtained from a strain of Bacillus which has maximum activity throughout the pH regime of 8-12 ° developed by Novo Indudtries 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. The enzymes proteo! Commercially available technologies suitable for removing protein-based stains include those sold under the trademarks ALCALASE and SAVINASE of Novo Industries A / S (Denmark) and MAXATASE of International Bio-Synthetics »Inc. (Netherlands). Other proteases include Protease A (see European Patent Application 130,756 published January 9, 1985) and Protease B (see European Patent Application Serial No. 87303761.8, filed on April 28, 1987 and the European Patent Application. 130,756, Bott et al., Published January 9, 1985). The amides include, for example, α-amylase described in British Patent Specification No. 1,296,839 (Novo), RAPIDASE, International Bio-Synthetic®, Inc. and TERMAMYL. Novo Industries The cellulase usable in the present invention includes both bacterial and fungal cellulase. Preferably »should have an optimum pH of between 5 and 9.5. Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas group. such as Pseudomona stutzeri ATCC 19.154 »as described in British Patent 1,372,034. See also lipases in Japanese Patent Application 53 »204B7, open for public inspection on February 24, 1987. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the registered trademark Lipasa P" Amano " , which henceforth refers to as "Amano-P".

Other commercial lipases include Amano-CES »ex Chromobacter viscosum lipases. v.gr. Chromobacter viscosum var. lipolvctum NRRLB 3673. commercially available from Toyo Jozo Co .. Tagata. Japan; and also the ipases of Chromobacter viscosum from U.S. Boichemical Corp. »E.U.A. and Disoynth Co. »Netherlands» and lipases from ex Pseudomonas gladioli. The LIPOLASE enzyme derived from Humicola lanuginosa and which is commercially available from Novo (see also EPO 341,947) is a preferred lipase for use herein. A wide variety of enzyme materials and means for their incorporation into synthetic detergent compositions are described in the U.S. Patent. 3,553,139 issued January 5, 1971 to McCarty and others. Enzymes are disclosed in the US Patent. 4,101,457 »Place et al., Issued July 18, 1978 and in the U.S. Patent. 4,507,219 »Hughes» both issued on March 26, 19B5. The enzyme materials useful for liquid detergent formulations and their incorporation into such formulations are described in the patent. of E.U.A. 4.261 »868» Time and others »issued on April 14, 1981. Enzymes for detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in the U.S. Patent. 3,600 »319 issued August 7, 1971 to Gedge» and others »and in the European Patent Application Publication No.O 199405. Application No.86200586.5. published on October 29, 1986 »Venegas. Enzyme stabilization systems are also described, for example, in the U.S. Patent. 3,519,570. The enzymes employed herein are typically stabilized by the presence of water-soluble supplies of calcium and / or magnesium ions in the finished compositions that provide said ions to the enzymes. (Calcium ions are in some way generally more effective than magnesium ions and are preferred in the present if only one type of cation is being used). Additional stability can be provided by the presence of several other stabilizers described in the art, especially borate species: see Sverson, E.U.A. 4,537 »706. Typical detergents, especially liquids, comprise from about 1 to about 30, preferably from about 2 to about 20, most preferably from about 5 to about 15 and most preferably from about 8 to about 12 millimoles of ions. of calcium per liter of finished composition. This may somehow vary »depending on the amount of enzyme present and its response to calcium or magnesium ions. The level of calcium or magnesium ions should be selected in such a way that there is always a minimum level available for the enzyme after allowing it to complex with the builders »fatty acids» etc. »in the composition. Any water soluble calcium or magnesium salt can be used as the supply of calcium or magnesium ions "including" but not limited to calcium chloride »calcium sulfate» calcium malate »calcium maleate» calcium hydroxide, calcium formate and calcium acetate and the corresponding magnesium salts. Often a small amount of calcium ions, generally from about 0.05 to about 0.4 millimoles per liter, is also present in the composition due to the calcium present in the enzyme suspension and the water of the formula. In the compositions of the detergent, the formulation may include a sufficient amount of a water-soluble calcium ion supply to provide such an amount in the wash liquor. Alternatively »the hardness of natural water may be sufficient. It should be understood that the aforementioned levels of calcium and / or magnesium ions are sufficient to provide enzyme stability. Additional calcium and / or magnesium ions may be added to the compositions to provide an additional measure of fat removal performance. If used for such purposes, the compositions herein typically should comprise from about 0.05% to about 2% by weight of a water soluble supply calcium or magnesium ions or both. The amount may vary, of course »according to the amount and type of enzyme used in the composition. The composition herein may also optionally contain but preferably several additional stabilizers, especially borate-type stabilizers. Typically, such stabilizers are used in the compositions at levels of from about 0.25X to about 10X, preferably from about 0.5X to about 5X. most preferably from about 0.75X to about 3X by weight boric acid or other borate compound capable of forming boric acid in the composition (calculated based on boric acid). Boric acid is preferred, although other compounds such as boric oxide, borax and other alkali metal borates (eg sodium orthoborate, sodium metaborate and sodium pyroborate and sodium pentaborate) are suitable. Substituted boronic acid (eg, phenyl boronic acid, butanoboronic acid and p-bromophenylboronic acid) can also be used instead of boric acid. Polymeric Efficiency Assayer - Any polymeric soil release agent known to those skilled in the art can be optionally employed in the compositions and methods of this invention. The polymeric soil release agents are characterized by having hydrophilic segments at the same time to hydrophilize the surface of the hydrophobic rows, such as polyester and naylon, and hydrophobic segments, to be deposited on hydrophobic fibers and to remain adhered thereto until the termination of the hydrophobic fibers. the washing and rinsing cycles and »in this way» serve as fixation for the hydrophilic segments.This may be possible that the stains that occur subsequent to the treatment with the soil release agent are more easily cleaned in subsequent washing procedures. Some examples of useful foreign dirt agents useful in a present include loe of the U.S. patent. 4,721,580 »issued on January 26, 1988 to Toßßelink, the patent of the E.U.A. 4,000 * 093 »issued on December 28, 1976 to Nicol and others; European patent application 0 219 048 »published on April 22, 1987 by Kud and others, the patent of E.U.A. 4 »702,857. issued on October 27, 1987 to Goßßelink, the patent of E.U.A. 4,968,451 »issued November 6, 1990 to J.J. Scheibel. Commercially available soil release agents include the SOKALAN type of material "eg, SOKALAN HP-22. obtainable through BASF (West Germany), see also the patent of E.U.A. 3,959,230 of Hays. issued May 25, 1976 and the patent of E.U.A. 3,893,929 of Basadur. Issued July 8, 1975. Some examples of this polymer include a commercially available material ZELCON 5126 (from Dupont) and MILEASE T (from ICI). Other polymeric release agents will include the poly terephthalate ester of the US patent. 4 »711» 730 »issued on December 8, 1987 to Goßselink et al., The algomeric esters of anionic anion ends in the patent of E.U.A. 4,721,580 »issued on January 26, 1988 to Gosßel nk, and the block oligomeric polyester compounds of the U.S. patent. 4,702,857, issued on October 27, 1987 to Gosselink. Preferred polymeric soil release agents also include the soil release agents of the U.S.A. 4, 877,896, issued on October 31, 1989 to Maldonado et al. If used, the soil release agents will generally contain from about O.OIX to about 10.OX "by weight" of the detergent compositions herein typically from about the O.IX to about 5X > preferably from about 0.2X to about 3.0X. Lactate chelants - The detergent compositions of the present invention may also optionally contain one or more iron and manganese chelating agents as an additive builder material. Such chelating agents can be selected from the group consisting of aminocarboxylatos »aminophosphonates» chemically substituted aromatic chelating agents and mixtures thereof all as defined below. Without intending to be limited to theory, it is believed that the benefit of eßtoß materials is due in part to their exceptional ability to remove iron and manganese ions from wash solutions by chelating soluble chelates. Aminocarboxylates useful as optional chelating agents include eti lendiamintetraacetates »N-hydroxyeti lendiaminetroacetate, nitrile-acetates, ethylene di-aminotetrapropionate, triethylenetetraminehexaacetate, ethylene-triaminpentaacetates and ethanoldiglicines» alkali metal salts »ammonium and substituted ammonium thereof and mixtures thereof. same. The onnate aminophones are also suitable for use as chelating agents in the compositions of the invention when at least two levels of total phosphorus are allowed in detergent compositions and include eti lendiaminetetrakis- (methylenephosphonate) or tri-triß (methylene phosphates) and diethylenetriaminpentakis (methylenephosphonate) as DEQUEST. Preferably, these aminophosphonate have no alkyl or alkenyl groups with more than about 6 carbon atoms. The chemically-substituted aromatic chelating agents are also useful in the composition of the precursor. See Patent of U.S.A. 3,812,044 issued May 21, 1974"by Connor et al. Preferred compounds of this type in the acid form are dihydroxydisulfobenzenes, such as l-2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use in the present eß eti lendi aminodisucci nato ("EDDS"), especially the CS, S3 isomer as described in the U.S. Patent. 4,704 »233. November 3, 1987, by Hartman and Per inß. If used, these chelating agents will generally comprise from about O.IX to about 10% by weight of the detergent compositions herein. Most preferably the chelating agents will comprise from about O.IX to about 3.0X by weight of said compositions. Irritation / Clay Syncyty Anti-Rejection Agent - The detergent compositions of the present invention may also optionally contain water soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. The most preferred anti-redeposition and anti-redeposition agent is tetraethylenpentamine etholated. Illustrative ethoxylated amines are further described in the U.S. Patent. 4 »597,898» VanderMeer »issued on July 1, 1986. Another group of preferred clay-dyeing / anti-redeposition agents are the cationic compounds described in European Patent Application 111,965» Oh and GosselinK »published on 27 June 1984. Other agents of the clay anti-redeposition / anti-redeposition that may be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gosselink, published June 27, 1984.; the zwitterionic polymers described in European Patent Application 112,592 »Gosselink, published July 4, 1984; and the amine oxides described in the U.S. Patent. 4 »548» 744 »Connor. issued October 22, 1985. Other clay soil removal and / or anti-redeposition agents known in the art may also be used in the compositions herein. Another type of preferred anti-redeposition agent includes the carboxymethyl cellulose (CMC) matter. These materials are well known in the art. Dietersoree PPTiroericoa - The polymeric dispersing agents can be advantageously used at levels from about O.IX to about 7%, by weight, in the compositions herein, especially in the presence of zeolite and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols. although others known in the art can also be used. It is believed, although it is not intended to limit by the theory that polymeric dispersing agents increase the performance of the global detergency builder when it is used in combination with other detergency builders (including lower molecular weight polycarboxylates) by growth inhibition. of crystals, peptization of dirt release in particles and antiredeposition. Polymeric polycarboxylate materials can be prepared by polymerizing or copying with suitable unsaturated monomer β, preferably in their acid form. The inesaturated monomeric acid β which can be used to form suitable polymeric polycarboxylates include acrylic acid. maleic acid (or maleic anhydride). fumaric acid. itaconic acid »aconitic acid» mesaconic acid »citraconic acid» meti len al nico. The presence of the polymeric polycarboxylates in the precursor or polymeric segments that do not contain carboxylate radicale as well as vinyl ether. styrene ethylene »etc.» is adequate provided that these segments do not constitute more than about 40% in weight. Particularly suitable polycarboxylactosylase can be derived from acrylic acid. Said acrylic acid-based polymers which are useful in the present ion are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form perferably varies from about 2,000 to 10,000, most preferably from about 4,000 to 7,000, and most preferably from about 4,000 to 5,000,000. Water-soluble saltse of said acrylic acid polymers may include, for example, alkali metal salts, ammonium and substituted ammonium. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, U.S. Pat. 3 »308» 067 »issued March 7, 1967. Copolymers based on acrylic ico / maleic acid may also be used as a preferred component of the ds spersor / anti-redeposition agent. Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in the acid form preferably ranges from about 2,000 to 100,000, most preferably from about 5,000 to 75,000 and most preferably from about 7,000 to 65,000. The ratio of the acrylate segments to the maleate loe in said copolymers generally ranges from about 30: 1 to about 1: 1. most preferably around 70:30 to 30:70. Water-soluble saltse of said copolymers of acrylic acid / maleic acid may include, for example, "alkali metal saltse" ammonium and substituate ammonium. The soluble acrylate / ma ate copolymers of this type are known materials which are described in European Patent Application No. 66915. published on December 15, 1982 »as well as in EP 193, 360, published on September 3, 1986. which also describes such polymers comprising hydroxypropyl lacrylate. Other dispersing agents include the terpolymers of maleic / acrylic / vinyl alcohol or vinyl acetate. Said materials are described in EP 193, 360, including, for example, the acrylic / maleic / vinyl alcohol terpolymer 45/45/10. Other polymeric material which may include eε polyethylene glycol (PEG). PEG can exhibit dispersing agent performance and can act as a clay anti-redeposition / anti-redeposition agent. Typical molecular weight scales for this purpose range from about 500 to about 100,000. most preferably from about 1,000 to about 50,000 and most preferably still from about 1,500 to about 10,000.

The dispersing agents of polyaspartate and polyglutamate can also be used, especially in conjunction with zeolite builders. The disperseral agents, such as polyaspartate loe, preferably have a molecular weight (prora.) Of about 10,000. Lighter 11 - Any optical brighteners or brightening or whitening agents known in the art may be incorporated at levels typically from about 0.05% to approximately 1.2X by weight, in the detergent compositions herein. The commercially available optical latents that may be useful in the present invention may be classified into subgroups which include but are not necessarily limited to stilbene, pyrazole, coumarin, carboxylic acid, methinocyanate derivatives, and 5,5-dibenzothiophene dioxide. azoles »5- and 6-membered heterocyclics» and other miscellaneous agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agent". M. Zahradnik »published by John Wi ey & I sounded New York (1982). Specific examples of optical brighteners that are useful in the present compositions are those identified in the U.S. Patent. 4,790,865 issued to Wixon on December 3, 1988. These glossaries include the PHOROWHITE series of brighteners from Verona. Other abri latadores deßcritoe in this reference include Tinopal UNPA. Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD. dieponibleß of Hilton-Daviß. with ßede in Italy; 2- (4-eßtri-phenyl) -2H-naphthol C1.2-d3triazoleβ; 4.4 t-biß (1, 2 »3-triazol-2-2-yl) -elethylbenoe; 4.4 »-bißíeßtril) bißfeniloß» and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin; l »2-bis (-benzimidazol-2-yl) ethylene; L-3-diphenyl-frazoline; 2 »5-biß (benzoxazol-2-yl) thiophene; 2-eßtril-naf-C1.2-diol? Azole; and 2- (stilben-4-yl) -2H-naphtho-Cl »2-d3triazole. See also U.S. Patent. 3,646,015, issued on February 29, 1972 to Hamilton. Here, anionic brighteners are preferred. Suppressors of foams - Compueßtoß to reduce or suppress the formation of foams can be incorporated into the composition of the present invention. The suppression of foams can be of particular importance in the "high concentration cleaning procedure" and in European front-loading washing machines. A wide variety of materials can be used as foam suppressors, and foam suppressors are well known to those skilled in the art. See, for example »Kirk Othmer Encyclopedia of Chemical Technology» 3a. Edition »Volume 7, pages. 430-447 (John Wiley &Sons Inc., 1979). A category of foam suppressant of particular interest includes monocarboxylic fatty acids and soluble saltse to them. See Patent of E.U.A. 2,954,347 »issued on September 27, 1960 to Wayne St. John. The monocarboxylic acids and salts of the same as a foam suppressant typically have hydrocarbyl chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include alkaline earth metal or sodium, potassium and lithium aß ealeß as well as ammonium and alkanolammonium salts. The detergent compositions herein may also contain foam suppressors which are not surface active agents. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic ketones of C m-C? O (v). .gr. »stearone)» etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkylmelamine or di- to tetra-alkyldiaminoprotriazine, formed as a product of cyanuric chloride with two or three molees of a primary or secondary amine containing from 1 to 24 carbon atoms. carbon. oxide of propylene and os atoe of raonoesteari such as ether phosphate of monostearyl alcohol and alkali metal diphosphates (e.g., K. Na and Li) monostearyl and ester phosphates. Hydrocarbons such as paraffin and halogenoparaffins can be used in liquid form. The liquid hydrocarbons will be liquid at room temperature and at atmospheric pressure "and will have a pour point on the scale of about -40 ° C to about 50 ° C. and a minimum boiling point not less than about 110 ° C (atmospheric pressure). The use of waxy hydrocarbons is also known, preferably having a melting point below about 100 ° C. Hydrocarbons constitute a preferred category of foam suppressant for detergent compositions. . The hydrocarbon foam supreßoreß are described, for example, in the patent of US Pat. No. 4,265,779 issued May 5, 1981 to Gandolfo et al. The hydrocarbons »therefore» include saturated or unsaturated aliphatic »alicyclic» aromatic and heterocyclic hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of supreßoreß of eßpuma, is intended to include mixtures of paraffins truee and hydrocarbon-cyclic. Another preferred category of foam suppressors that are not surfactants comprises supreßoreß of silicone foam. This category includes the use of polyorganosi oxane oils such as poly idimeti lsi loxane, dispersions or emulsions of polyorganosi oxano oils or resins, and combinations of polyorganosiloxane with silica particle where the polyorgano loxane eß chemoabsorbed or fused to silica. Silicone foam suppressors are well known in the art and are described, for example, in the U.S. Patent. 4 »265» 779 »issued May 5, 1981 to Gandolfo et al. And European Patent Application No. 89307851.9» published on February 7, 1990 by Starch, M.S.

Another eupreeoreß of silicone foams are described in US Patent 3,455,839 which relates to compositions and processes for the defoaming of aqueous solutions by incorporating them into small amounts of poly idimeti lsi loxane fluids. The mixture of silicone and ßilice ßi lanada are described, for example, in German Patent Application DOS 2,124,526. In the preferred silicone foam suppressant used herein the solvent for a continuous phase is made of certain polyethylene glycols or copolymers of polyethylene propylene glycol or mixtures of the (preferred) 'or poly propylene glycol. The suppressor of primary silicone ese branched / interlaced and preferably non-linear. Dyestuff transfer inhibiting agents - The compositions of the present invention optionally but preferably include one or more effective substances to inhibit the transfer of dye from one fabric to another during the cleaning process. In general, said dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vini-1-imidazole. manganese phthalocyanine »peroxidase and mixtures thereof. If they are used, eßtoß agents typically comprise about 0.01X about 10X by weight of the composition, preferably about 0.01X about 5X. and most preferably about 0.05X approximately 2%. Very specifically, the preferred polyamine N-oxide polymers for ußarße in the precursor contain unidadee having the following structural formula: R-A "-P; wherein P is a polymerizable unit to which a group N-0 may be attached or group N-0 may form part of the polymerizable unit or group N-0 may be attached to both units; A is one of the following structures: -NC (O) - »-C (0> 0-. -S-» -0- »-N = s; x is 0 oi; and R is aliphatic, aliphatic, ethoxylated groups »Aromatic» heterocyclic or alicyclic or any combination thereof at which the nitrogen of the group N-0 can be bound or the group N-0 is part of these groups. The N-oxides of polyamine preferred * doß ßon that loe wherein R eß a heterocyclic group such as pyridine »pyrrole» imidazole »pyrrole ina» piperidine and derivatives thereof The group N-0 can be represented by the following general structures: (R)) < -N- (R, -N- < R > ". I (R,) _ wherein R x »Ra» Ra ßon group β to the "aromatic" heterocyclic or alicyclic phantom or combinations thereof; x »y and z are O or i; and the nitrogen of the group N-0 can be attached or forms part of any of the aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, very preferably still pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures ßon pol ivini loe, pol alkylenes, polyesters. polyethers »polyamide» polides »polyacrylates and mixtures thereof. These polymers include random or block copolymers wherein one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide polymerics typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the group number of amine oxide present in the polyamine oxide polymer may be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of potentialization. Typically, the average molecular weight is within the scale of 500 to 1,000,000; very preferred from 1,000 to 500,000; even more preferred 5'000 to 100'000. The most preferred polyamine N-oxide useful in the detergent compositions herein is the poly-4-vinylated 1-pyridine N-oxide having an average molecular weight of about 500,000 and a ratio of amine to amine N-oxide of about 1: 4. The polymer copolymers of N-v nor 1porro1 idona and N-vinyl imidazole (also known as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth, and other Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization" "whose descriptions are incorporated herein by reference). PVPVI copolymers typically have a molar ratio of N-vini 1 imidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, most preferably from 0.8: 1 to 0.3: 1. most preferably from 0.6: 1 to 0.4: 1. These copolymers can be either linear or branched. The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000"preferably from about 5,000 to about 200,000" and most preferably still from about from 5,000 to approximately 50,000. The PVP are known to those skilled in the art of the detergent field; see »for example» EP-A-262 »897 and EP-A-256,696. incorporated here by reference. Compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000. preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a basis of ppm assorted in wash solutions is from about 2: 1 to about 50: 1. and most preferably from about 3: 1 to about 10: 1. The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If used, the compositions of the preferent will preferably comprise about 0.01X to IX in weight of said optical brighteners. The hryophilic optical brighteners used in the present invention are those which have the structural formula: wherein Rx is selected from anilino »N-2-bis-hydroxyethyl and NH-2-hydroxyethyl» Rase selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-phenylamino. morphine »chlorine and amino; and M eß a ßal-forming cation such as sodium or potassium. When in the previous formula »Rx eß anilino» Ra eß N-2-biß-hydroxyethi and M eß a cation such as sodium, the brightener eß acid 4.4 ».bisC (4-ani 1 ino-6- (N-2 -biß-hydroxyethyl) -ß-triazin-2-yl) amino3-2 »2-t-ethylbendisulfonic acid and disodium ßal. This particular brightener species is commercially marketed under the trade name Tinopal-UNPA-GX by Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of acid 4.4t-bißC (4-anilino). 6- (N-2-hydroxyethyl-N-methylamino) -β-triazin-2-yl) amino3-2 »2» -stilbenedisulfonic acid. Eßta eßpecie de rinillantador particular ße commercially marketed under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the previous formula Rl eß an lino. R2 e morpholino and M eß a cation such as sodium, the brightener is the ßalodium ßal of acid 4 »4, -bieC (4-anil non-6-morphino-β-triazin-2-yl) amino32» 2? e-ethylbenedisulfonic. Eßta eßpecie de rinillantador particular sells coraercimentemente under the trade name Tinopal AMS-GX by Ciba-Geigy Corporation. The species of April specific optical antader selected for use in the present invention provides performance benefits of dye transfer inhibition, particularly effective when used in combination with the agent inhi idoreß. Transfers of selected polymeric dye described above. The combination of said selected polymeric materials (e.g. »PVNO and / or PVPVI) with said ß-selected polyacrylate ß (e.g.» Tinopal UNPA-GX »Tinopal 5BM-GX and / or Tinopal AMS-GX) provides inhibition of Dye transfer is significantly better in aqueous washing solutions than either of these two components of detergent composition when used alone. Without being limited to theory, it is believed that such brighteners work in this manner because they have high affinity for fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the cloth in the wash solution can be defined by a parameter called "depletion coefficient". The coefficient of depletion eß in general as the ratio of a) the polishing material deposited ßobre fabric a b) the concentration of initial rinse in the wash liquor. The open bonding with relatively high depletion coefficients are best suited to inhibit dye transfer in the context of the present invention. Of course, it will be appreciated that the other types of optional composite optical brightener may optionally be present in the compositions of the present to provide benefit of conventional "brightness" to the fabric rather than a true color transfer inhibiting effect. Said ußo eß conventional and well known for detergent formulations. COfflPMeatoa bleaching agents - Bleaching agents and bleach activators - The detergent compositions herein may optionally contain bleaching agents or bleaching compositions containing an agent and one or more bleach activators. When they are present, bleaching agents are typically found at levels from about IX to about 30X »very typically from about 5X to about 20X of the detergent composition» especially for fabric washing. If present, the amount of bleach activators is typically from about 0.1X to about 60X. very typically from about 0.5X to about 40X of the bleaching composition containing the bleaching agent plus the bleach activator. The bleaching agents used herein may be any of the bleaching agents useful for detergent compositions in the cleaning of text. cleaning of hard surfaces or other impieza purposes now known or known later. These include oxygen bleaches as well as other bleaching agents. Perborate bleaches, eg, sodium perborate (e.g., mono and tetrahydrate) can be used herein. Another category of bleaching agent that can be used in-restriction comprises the percarboxylic acid bleaching agents and the saltse thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium ßal of metachloroper-benzoic acid, 4-noni 1-amino-4-oxoperox butyric acid and hyperoxydedecanedioic acid. Said bleaching agents are described in the patent of E.U.A. 4,483,781. Hartman. issued on November 20, 1984, the Patent Application of E.U.A. 740,446, Burnß »et al., Filed June 3, 1985» European Patent Application O, 133 »354 Banks» and others »published on February 20, 1985, the US Patent. 4,412,934 Chung et al., Issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in US Pat. 4,634,551 issued on January 6, 1987 to Bums et al. Also peroxygen bleaching agents can be used. Suitable peroxygen bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Persulfate bleach (v.gr .. OXONE »manufactured commercially by DuPont) can also be used. They may also use mixture of β-binder agent. Loe agents peroxygen bleaches. lobo perboratos. loe percarbonate "etc., preferably combine with bleach activators" which lead to the in situ production in the aqueous solution (ie, during the washing process) of the peroxyacid corresponding to the bleach activator. Various non-limiting examples of activators are described in the U.S. Patent. 4 »9151» 854 issued on April 10, 1990 to Mao and other »and in the patent of E.U.A. 4 »412,934. Nonanoyl oxybenzenesulfonate activators (NOBS) and tetraaceti leti lamina (TAED) are typical and mixtures thereof may also be used, see also E.U.A. 4,634,551 for other typical bleaches and activators useful herein. The activated bleaching agent derived from amide is very preferred with that loe of the formulas: R * N (R > C) 0) R »C (0) L O R ^ -CÍO > N (R ") R * C (0) L wherein R * eß is an alkyl group containing from about 6 to about 12 carbon atoms. Ra is an alkyl containing from 1 to about 6 carbon atoms. RB is H or alkyl, aryl or alkaryl containing about 10 carbon atoms and L is any suitable group. A ßalient group is any group that is displaced from the bleach activator as a result of a nucleophilic attack on the bleach activator by the anhydride of the perhydroly. A preferred leaving group is β-phenylenediane. Preferred examples of bleaching activareß of the above formulas include (6-octanamido-caproyl) oxybenzene-sulfonate "(6-nonanamidocaproyl) oxybenzenesulfonate and mixture thereof as described in the patent of E.U.A. 4,634,551 which is incorporated herein by reference. Another class of bleach activators includes the activators of the benzoyzine type described by Hodge and others in the U.S. Patent. 4,966,723 issued October 30, 1990, which is incorporated herein by reference. Yet another class of preferred bleach activators includes acl 1-lactam activators, especially acylcaprolacta as and aci 1 valerolactams. Highly preferred lactam activators include benzoi-1-caprolactam, octanoylcaprolactam, 3'-5'-trimethyl-1 -hexanoi-caprolactam, nonanoi-1-caprolazamine, decanoyl-caprolactam-undecenoylcaprolactam, benzoyl-alerolactam, octanoyl-valerolactam, decanoi-1-valerolactam, undecenoyl-valero-lactam, nonanoi-1-valerolactam. »5-trimeti-1-hexanoi-1-valerolactam and mixtures thereof, see also US Pat. 4 »545» 784 issued to Sanderßon on October 8, 1985 incorporated in the reference for "describing the acylcaprolactams" including benzo lcaprolactam »adsorbed on sodium perborate. It is also known in the art that bleach agents other than oxygen bleaches agent can be used herein. A type of whitening agent which is not oxygen of particular interest includes photo-bleached bleaching agents such as zinc and / or sulfonated aluminum phthalocytes. see the patent of E.U.A. 4,033,718 issued July 5, 1977 to Holcombe et al. If used, the detergent compositions typically should contain from about 0.025% to about 1.25% by weight of said bleaches, especially sulfonated zinc phthalocyanine.

If desired, the bleaching compounds can be catalyzed by a manganese compound. Such compounds are well known in the art and include, for example, the manganese-based catalysts described in the U.S. Patent. 5,246,621, Patent of E.U.A. 5,244,594; Patent of E.U.A. 5,194,416; Patent of E.U.A. 5,114,606; and European Patent Application Publication Nos. 549,271A1. 549 »272A1, 544.440A2, and 544.490A1. For practical purposes "and not by way of limitation" the compositions and processes herein can be adjusted to provide the order of at least one part per ten million species of bleach catalyst, in the aqueous wash liquor "and preferably will provide from about 0.1 ppm to about 700 ppm »most preferably from about 1 ppm to about 500 ppm» of the catalyst species in the laundry liquor. Organic peroxides »especially Pexi x Diacillo - Illustrated extensively in Kirk Othmer »Encyclopedia of Chemical Technology» Vol. 17. John Wiley and Sons, 1982 on pages 27-90 and especially on pages 63-72 »all incorporated herein by reference. Suitable organic peroxides, especially diacyl peroxides, are also available in "Initiator for Polymer Production", Akzo Chemicals Inc., Product Catalog, Bulletin No. 88-57, incorporated by reference. The diacyl peroxide preferred in the present, whether in pure form or in formulated form for granule, powder or tablet form of the bleaching compositions, constitute solids at 25 ° C, for example, CADETE BPO 78 »powder form of dibenzoyl peroxide »from Akzo The highly preferred organic peroxides» particularly the diacyl peroxides »for said bleaching compositions have melting points above 40 ° C» preferably above 50 ° C. In addition »they prefer the organic peroxide with SADTβ (as defined in the previous Akzo publication) of 35 ° C or greater »preferably 70 ° C or greater Non-limiting example of diacyl peroxides useful herein include di enzoyl peroxide, lauroyl peroxide and dicumyl peroxide. Dibenzoyl peroxide is preferred.In some cases, the diacyl ester bistans available on the market and contain oily substances such as phthalate d. In general it is preferred to use diacyl peroxides which are substantially free of oily phthalates since these can form slides on dishes and glass utensils. Substituted quaternary bleach activators - present Laß composition can optionally also comprise known conventional substituted quaternary bleach activators (QSBA). QSBA's are also illustrated in US Pat. 4,539,130. September 3 1985 and Patent E.U.A. No. 4,283,301. British Patent 1,382,594, published on February 5, 1975, discloses a QSBA's clause, optionally suitable for use herein. The Patent of E.U.A. 4,818,426 issued April 4, 1989, describes another class of QSBA's. See also E.U.A. 5,093,022 issued March 3, 1992 and E.U.A. 4,904,406. Issued on February 27, 1990. Additionally. QSBA's "are described in EP 552,812 A1 published on July 28, 1993" and in EP 540,090 A2"published May 5, 1993. Anti-aesthetic agents - The present compositions may also contain unsightly agents as illustrated in US Pat. 4,861,502. Preferred examples include alkyl-ion pairs anionic surfactants. such as pairs of alkylammonium sulfate ion. If present, antistatic agents are present in an amount of about 0.5X to about 20X "preferably from about IX to about 10X", most preferably from about IX to about 5X "by weight of the detergent composition. In addition, the compositions herein may optionally include one or more other auxiliary detergent materials or other materials to aid or improve the cleaning performance, "treatment of the substrate to be cleaned" or to modify the aesthetics of the detergent composition (for example »perfumes» dyes, dyes, neutralizing agents »pH regulating agents» phase regulators »polyacids» foam regulators »dispersing opacifiers, such as tetraethylenepentamine» antioxidants and bactericides described in the patent of the USA »Barrat and others» issued on August 25, 1981).

Various detergent ingredients used in the present compositions can be subsequently stabilized by absorbing said ingredients on a porous hydrophobic sub-stratum. then coating said ßuvetrato with a hydrophobic coating. Preferably the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous wash liquor "where it performs its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNAT DIO »Degussa) is mixed with a proteolytic enzyme solution containing 3X-5X of ethoxylated nonionic ethoxylated agent of CXa_xß (EO 7). Typically, the enzyme / surfactant solution is 2.5X of the weight of the silica. The resulting powder is digested with stirring in ßil? -con oil (various viscosities of silicone oil can be used in the range of 500-12,500). The resulting silicate oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means »ingredients, such as enzymes, bleaching agents, bleach activators, bleach catalysts, photoactivators, colorants, fluorescedoreß, fabric conditioners and hydrolyzable surfactants mentioned above can be" protected "for use in detergents, including liquid detergent compositions for laundry. The liquid detergent compositions may contain water and other solvents such as vehicles. The low molecular weight primary and secondary alcohols are illustrated by suitable methanol »ethanol» propanol and ß-isopropanol. The preferred β-monohydric alcohols for solubilising surfactant, but polyols such as those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (e.g., 1,3-propanediol) can also be used. ethylene glycol »glycerin and 1,2-propanediol). The compositions may contain from 5% to 90X, typically from 10X to 50X of said vehicles. The detergent compositions of the present preferably will be formulated such that during use in aqueous cleaning operations, the wash water has a pH of between about 6.5 and about 11, preferably between about 7.5 and 10.5. The formulations of products for the automatic washing of tackle preferably have a pH between about 8 and about 11. The laundry products typically have a pH of 9 to 11. The technique for controlling the pH at recommended levels of phosphorus include Regulation of pH, alkalis, acids, etc., and are well known to those skilled in the art. The following examples illustrate compositions according to the invention. All percentages, parts, and relationships used in the foregoing are in lieu to be not specified in a different manner.

EXAMPLE I Liquid laundry detergent compositions containing ßilicon emulsions in suspension formulations are then presented.

EXAMPLE I. { CONTINUATION) The β-silicon emulsions are prepared in any manner known to those skilled in the art. For example * the silicone emulsion of approximately 200 μm is prepared by mixing 70% by weight of silicone fluid consisting of 40X of silicone rubber and 60X of dimethicone fluid (350 cst) with 30X by weight of solution surfactant that consists of 25X of alkylsulfate and alkylethoxy lato-βulfate. The silicone emulsion is combined with the other ingredients and mechanically stirred to ensure a homogeneous product. Each of the above formulas to treat a wad of fabric containing approximately 60X of cotton towel fabrics and poly cotton fabrics * 20X polyester and 20X of other synthetic fabrics. Each bundle is introduced to a washing machine together with approximately 100 grams of liquid detergent containing ßilicón emulsion. The controls for the washing machine are set to provide a wash liquor temperature of 35 ° C with a cold water rinse. The bundles are washed for approximately 14 minutes. Each bundle is then dried in a dryer for about 1 hour. Sixteen weeks of cotton towels were valued in terms of smoothness by a committee of three expert judges "working independently" through a comparison technique for each use of a 4-point scale. The differences were recorded in committee valuation units (psu). the positive performance being much better and the minimum significant difference (LSD) is also calculated at 90X of confidence. As shown above, silicone emulsions with sizes from 60 μm to 200 μm provide significantly better smoothness than silicone-free emulsion control and formula B with an emulsion size of less than 5 μre.

EXAMPLE II Liquid laundry detergents containing silicone emulsions in ißotropic (non-suspension) formulations are presented below.

EXAMPLE II (CONTINUED) The ßilicón emulsion is combined with the other ingredient and then mechanically stirred to obtain a homogeneous product. Each of the above formulas to treat a wad of fabric containing approximately 60X of cotton towel cloth and polycotton fabric, 20X of polyester and 20X of other synthetic fabrics. Each bundle is fed into a washing machine together with approximately 100 grams of liquid detergent containing the silicone emulsion. The controls for the GG washing machine are established to provide a wash liquor temperature of 35 ° C with a cold water rinse. The bundles are washed for approximately 14 minutes. Each bundle is then dried in a dryer for about 1 hour. Sixteen pairs of cotton towels were rated for softness by a committee of three expert judges * working and dependently * through a peer-to-peer comparison technique using a 4-point scale. The difference in the committee valuation unit (psu) was registered, the positive performance being much better and η also calculated the minimum significant difference (LSD) to 90% confidence. As shown above, silicone emulsions with sizes of 80 μm provide significantly better smoothness than the non-silicone emulsion control and formula B with a menoß emulsion size of 0.35 μm.

EXAMPLE III A granular laundry detergent containing silicone emulsions is presented below.

EXAMPLE III (CONTINUED) The silicone emulsion contains the 70X by weight of the silicon fluid consisting of 40X of silicone rubber and 60X of dimethicone fluid (350 cst) and 30% by weight of surfactant solution consisting of 25X of alkyl sulfate and alkyletoxy lato. -bulfate. The silicone emulsion ß can be absorbed on a vehicle, such as polyethylene glycol and mixed with the remaining ingredients.

Claims (10)

NOVELTY OF THE INVENTION CLAIMS

1. A high-performance laundry detergent composition containing: a) from O.IX to 12%, by weight of the composition * of an emulsion; wherein said emulsion contains from IX to 90%, in emulsion oil, from silicon, and from O.IX to 30X, in emulsion oil, from emulsifier; and wherein said emulsion has an average particle size of 5 to 500 microns; and b) from IX to 50X, by weight of said composition, and detersive agent.

2. A detergent composition according to claim 1, further characterized in that said detersive surfactant is selected from the group consisting of nonionic detersive surfactant, anionic detersive surfactant, cationic detective surfactant * zwitterionic detersive surfactant. detersive surfactant agent of amine oxide and mixture thereof.

3. A detergent composition according to claim 2 further comprising an effective amount of cleaning of one or more additives selected from detergency builders, enzymes, brighteners, soil release agents, foam control agents, antistatic agents and agents dispersants; and characterized in that said emulsion has an average particle size of 20 to 300 microns.

4. A detergent composition according to claim 3 * further characterized in that said emulsifier is selected from the group that conßsses in non-ionic emulsifier surfactant, anionic emulsifier surfactant * cationic emulsifier surfactant * amine oxide emulsifier and mixtures thereof »preferably selected from the group consisting of anionic emulsifier surfactant» nonionic emulsifier surfactant and mixtures thereof.

5. A detersive composition according to claim 4 »further characterized in that said emulsifier is a nonionic emulsifier surfactant selected from the group consisting of alkylphenyl polyols, alkyl-ethoxylate. polysorbate surfactant agents and mixtures thereof.

6. A detergent composition according to claim 4 »further characterized in that said emulsifier is an anionic emulsifier surfactant selected from the group consisting of alkyl sulphates. alkylether sulfates »alkyl Ibencensulfonates and mixtures thereof.

7. A detergent composition according to claim 1 »further characterized in that said silicone is polymer of the formula: wherein each of Rx and Ra in each repeating unit »- (Si (Rx) (Ra) 0) -» ß selects independently between alkyl or alkenyl radical of Cx-Cxo. phenyl. ßubstituted alkyl »ßubstituted phenyl or unidadeβ of -CRxRaSi-0-3-? x eß from 50 to 300,000; wherein said substituted alkyl or substituted phenyl is substituted by halogen »amino» hydroxyl groups or nitro groups and wherein said polymer is capped by a hydroxyl group. hydrogen or -SiR3 wherein R is hydro? yl. methyl or hydrogen.

8. A method for cleaning and softening fabrics consisting of putting said fabrics with an effective amount of a laundry detergent composition that contains: a) from 0.1X to 12X "by weight of the composition, of an emulsion; wherein said emulsion contains from IX to 90%. by weight of the emulsion, of silicone. and from O. IX to 30%. in emulsion of the emulsifier, and wherein said emulsion has an average particle size of 5 to 500 microns; and b) from IX to 50X. in excess of said composition, and detersive agent.

9. A detergent composition according to claim 8 »further characterized in that said detersive surfactant is selected from the group consisting of nonionic detersive surfactant» anionic detersive surfactant »cationic detersive surfactant» detersive surfactant zwitteri.ó * nico amine oxide detersive surfactant and mixtures thereof.

10. A method according to claim 9 »further characterized in that said laundry detergent composition also contains an effective amount of cleaning of one or more detersive additives selected from detergency builders» enzymes »brighteners» disease release agents » agentß for foam control »antistatic agents and dispersing agents.