MXPA98009634A - Deterge composition - Google Patents

Abstract

A detergent composition comprising a peroxygen bleach, a bleach catalyst, a non-AQA surfactant and an alkylated alkylated quaternary ammonium cationic surfactant (AQ

Description

DETERGENT COMPOSITION TECHNICAL FIELD The present invention relates to a detergent composition comprising a peroxygen bleach, a non-AQA surfactant and an alkoxylated quaternary ammonium cationic surfactant (AQA).

BACKGROUND OF THE INVENTION The formulation of laundry detergents and other cleaning compositions presents a considerable challenge, since modern compositions require the removal of a variety of soils and stains from various substrates. Thus, laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for use in automatic dishwashers require the proper selection and combination of the ingredients to work effectively. In general, such detergent compositions will contain one or more types of surfactants that are designed to disperse and remove different types of soils and stains. Although a review of the literature would seem to indicate that a wide selection of surfactants and combinations of surfactants are available to the detergent manufacturer, the reality is that many such ingredients are specialized chemical compounds that are not suitable for low unit cost items. as laundry detergents for domestic use. The fact is that most such household products, such as laundry detergents, still mainly comprise one or more of the conventional nonionic ethoxylated and / or sulfonated or sulphated anionic surfactants, possibly due to the economic considerations of the need to formulate compositions that work reasonably well with a variety of soils and stains on a variety of fabrics. The rapid and efficient removal of different types and soils and stains such as body dirt, oily / oily soils and certain food stains, can be problematic. Such soils comprise a mixture of hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter, all of which are to a certain extent composed of hydrophobic portions and therefore are notoriously difficult to remove. Low levels of hydrophobic stains and residual stains often remain on the surface of the fabric after washing. The successive wash and wear coupled with the removal of limited hydrophobic dirt in the wash culminates in an accumulation of dirt and residual stains that trap dirt in particles leading to yellowing of the fabric. Finally the fabric acquires a percieved appearance that is perceived as not usable and is discarded by the consumer. The literature suggests that various cationic nitrogen-containing agents would be useful in a variety of cleaning compositions. Such materials, typically in the form of quaternary amino-, amido- or ammonium or imidiasolium compounds, are often designated for specialized use. For example, various quaternary ammonium surfactants have been suggested for use in shampoo compositions and are believed to provide cosmetic benefits for hair. Other surfactants containing nitrogen are used in some laundry detergents to provide fabric softening and an anti-static benefit. For the most part, however, the commercial use of such materials has been limited by the difficulty encountered in the large-scale manufacture of such compounds. A further limitation has been the potential precipitation of anionic active components from the detergent composition, caused by their ionic interaction with cationic surfactants. The aforementioned nonionic and anionic agents remain the main surfactant components in current laundry compositions. It has been found that certain alkoxylated quaternary ammonium compounds (AQA) can be used in various detergent compositions to increase detergency performance in a variety of dirt and stain types., particularly the hydrophobic types of dirt that are commonly found. Unexpectedly, it has now been discovered that compositions containing enzymes and AQA surfactants, peroxygen bleach and metal-containing bleach catalyst have superior cleaning performance and whiteness compared to products containing any single technology. The AQA surfactants of the present invention provide substantial benefits to the formulator, over the cationic surfactants previously known in the art. For example, the AQA surfactants used herein provide a marked improvement in the cleaning of the "everyday" hydrophobic greasy / oily soils that are regularly encountered. In addition, AQA surfactants are compatible with anionic surfactants which are commonly used in detergent compositions such as alkyl sulfate and alkylbenzene sulfonate.; the incompatibility with anionic components of the detergent composition has commonly been a limiting factor in the use of the previously known cationic surfactants. Low levels (as low as 3 ppm in the wash liquor) of the AQA surfactants give rise to the benefits described herein. The AQA surfactants can be formulated on a wide pH scale from 5 to 12. The AQA surfactants can be prepared as 30% (weight) solutions which are pumpable, and therefore easy to operate in a plant. manufacturing AQA surfactants with degrees of ethoxylation above 5 are sometimes present in a liquid form and therefore can be provided as 100% pure materials. In addition to its beneficial management properties, the availability of AQA surfactants as highly concentrated solutions provides a substantially economic advantage in transportation costs. AQA surfactants are also compatible with various perfume ingredients, unlike some cationic surfactants known in the art. Bleach catalysts (caracerized by the presence of at least 1 transition metal atom) interact with peroxygen bleach species to form potently hydrophilic whiteners. These bleaches produce strong benefits on hydrophilic stains of color and everyday hydrophilic soils (ie, socks). The historical use of bleach catalysts was hampered due to concerns related to damage to the fabrics. It has now been found that the damage to the fabrics caused by the use of a dimanganese catalyst, which is known to cause damage to the fabrics, can be greatly reduced when the detergent composition comprises an AQA cationic surfactant. It is proposed that these cationics adsorb onto the fabrics, modifying the surface charge of the fabric and potentially matching the ions with the activated catalyst to minimize or avoid damage to the fabrics. It is believed that grease / oily soils are effectively solubilized by AQA, thus allowing access of the photobleaner to the color bodies in the dirt (eg, trapped pigments) resulting in enhanced discoloration of soil. The ability of the compositions described herein to clean hydrophobic and hydrophilic soils results in superior maintenance of whiteness and cleanliness.

TECHNICAL BACKGROUND The Patent E.U.A. 5,441,541, issued August 15, 1995, by A. Mehreteab and F. J. Loprest, refers to mixtures of anionic / cationic surfactants. R.U. 2,040,990, issued September 3, 1980, by A. P. Murphy, R.J.M. Smith and M. P. Brooks, refer to cationic ethoxylates in laundry detergents.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides a composition comprising or being prepared by combining a metal-containing bleach catalyst, a non-AQA surfactant and an effective amount of an alkoxylated quaternary ammonium cationic surfactant (AQA) of the formula: BRIEF DESCRIPTION OF THE INVENTION Peroxygen bleaching agent The detergent compositions herein comprise a peroxygen bleaching agent, said bleaching agents typically being at levels from 1% to 30%, very typically from 5% to 20% of the detergent composition, especially for fabric washing. Preferred peroxide bleaches are perhydrate bleaches. The perhydrate bleach is usually incorporated in the form of the perhydrate salt, especially the sodium salt, at a level of 1% to 40% by weight, most preferably 2% to 30% by weight and most preferably still 5% to 25% by weight of the compositions. Although the perhydrate bleach itself has some bleaching capacity, a superior bleach exists in the peracid formed as a reaction product between the hydrogen peroxide released by the perhydrate and a bleach activator. Preformed peracids are also contemplated as a preferred peroxygen bleaching species. Examples of suitable perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persylicate salts. The preferred perhydrate salts are usually the alkali metal salts. The perhydrate salt can be included as the crystalline solid without additional protection. However, for certain perhydrate salts, the preferred embodiments of said granulated compositions use a coated form of the material that provides better storage capacity for the perhydrate salt in the granulated product. The sodium perborate may be in the form of the monohydrate of the nominal formula NaB0 H202 or NaB02H2? 2-3H20 tetrahydrate. The alkali metal percarbonates, particularly sodium percarbonate, are preferred percarbonates for inclusion in compositions according to the invention. Sodium percarbonate is an addition compound having a formula corresponding to 2Na C03.3H202 and is commercially available as a crystalline solid. Sodium percarbonate, being an addition compound of hydrogen peroxide tends to dissolve to release hydrogen peroxide very rapidly which may increase the tendency for localized high bleach concentrations to originate. The percarbonate is most preferably incorporated into said compositions in a coated form that provides stability in the product. A suitable coating material that provides stability in the product comprises a mixed salt of a sulfate and alkali metal carbonate soluble in water. Such coatings together with coating processes have been described previously in GB-1,466,799, granted to Interox on March 9, 1977. The weight ratio of the mixed salt coating material to percarbonate is in the scale from 1: 200 to 1: 4, most preferably from 1:99 to 1: 9, and most preferably from 1:49 to 1:19. Preferably, the mixed salt of sodium sulfate and sodium carbonate having the general formula Na2S0 .n.Na2 03 wherein n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and most preferably n is from 0.2 to 0.5. Other coatings containing silicate (alone or with borate salts or boric or other inorganic acids), waxes, oils, fatty soaps can also be advantageously used within the present invention. A preferred percarbonate bleach comprises dry particles having an average particle size of 500 microns to 1, 1,000 microns, not more than 10% by weight of said particles being less than 200 microns and not more than 10% by weight of said particles being greater than 1,250 microns. Another suitable bleaching agent that can be used without restriction encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyrate and diperoxydecanedioic acid. Said bleaching agents are described in the patent of E.U.A. 4,483,781, Hartman, issued November 20, 1984, U.S. Patent Application. 740,446, Burns et al., Filed June 3, 1985, European Patent Application 0,133,354, Banks et al., Published February 20, 1985, and US Pat. 4,412,934, Chung and others issued the lo. November 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid as described in the U.S. Patent. 4,634,551, issued on January 6, 1987 to Burns et al. Potassium peroxy onopersulfate is another inorganic perhydrate salt useful in the compositions herein. Mixtures of bleaching agents can also be used.

Bleach catalyst The detergent compositions described herein may also comprise a metal-containing bleach catalyst. Catalysts are commonly present at extremely low levels in the product, preferably from 0.001% to 5% by weight, most preferably from 0.01% to 2%, most preferably still from 0.5% to 1%. Preferably, the bleach catalyst is a metal-containing bleach catalyst, most preferably containing transition metal. Preferred transition metal-containing bleach catalysts are bleach catalysts containing manganese or cobalt. A suitable type of bleach catalyst is a catalyst comprising a heavy metal cation of defined bleach catalytic activity, such as copper, iron cations, an auxiliary metal cation having little or no catalytic bleaching activity, such as cations. of zinc or aluminum, and sequestrants having defined stability constants for the catalytic metal and auxiliary cations, particularly ethylenediaminetetraacetic acid, ethylenediaminetetramethylenephosphonic acid, and water soluble salts thereof. Said acids are described in the patent of E.U.A. 4, 430, 243. Preferred types of bleach catalysts include the manganese-based complexes described in the U.S. Patent. 5,246,621 and the U.S. Patent. 5,224,594. Preferred examples of these catalysts include nIV2 (u ~ 0) 3 (1, 4,7-triazacyclononane) 2- (C10) 2, MnIV (u - =) ¿(1,4, 7-triazacyclononane) 2- (C10) 3 and mixtures thereof. Others are disclosed in the European Patent Application, publication No. 549,272. Other ligands suitable for use herein include l, 5, 9-trimethyl-l, 5, 9-triazacyclododecane, 2-methyl-1,4,7-triazacyclononane, 2-methyl-l, 4,7-triazacyclononane, 1 , 2,4,7-triazacyclononane and mixtures thereof. Bleach catalysts useful in the compositions herein may also be selected as appropriate for the present invention. For examples of suitable bleach catalysts see U.S. Pat. 4,246,612 and Patent of E.U.A. 5,227,084. See also the U.S. Patent. 5,194,416 which teaches mononuclear (IV) manganese complexes as Mn (1, 4,7-trimethyl-1, 4,7-triazacyclononane) (0CH3) 3_ (PF-¿). Another type of bleach catalyst, as described in the U.S. Patent. 5,114,606 is a water-soluble complex of manganese (III) and / or (IV) with a ligand that is a non-carboxylic polyhydroxy compound having at least three consecutive C-OH groups. Preferred ligands include sorbitol, iditol, dulsitol, mannitol, xylitol, arabitol, adonitol, meso-erythritol, meso-inositol, lactose and mixtures thereof. The Patent of E.U.A. 5,114,611 teaches a bleach catalyst comprising a complex of transition metals, including Mn, Co, Fe or Cu with a non-macrocyclic ligand. Said ligands of the formula: R2 R3 R! -N = C-B-C = N-R4 wherein R1, R2, R3 and R4 can each be selected from H, substituted alkyl and aryl groups such that each R1-N = C-R2 and R3-C = N-R forms a ring of five to six members. Said ring can also be replaced. B is a bridging group selected from 0, S, CR5R6, NR7 and C = 0, wherein R5, R6 and R7 may each be H, alkyl or aryl groups, including substituted or unsubstituted groups. Preferred ligands include pyridine, pyridazine, pyrimidine, pyrazine, imidazole, pyrazole and triazole rings. Optionally, said rings can be substituted with substituents such as alkyl, aryl, alkoxy, halide and nitro. Particularly preferred is the 2,2'-bispyridylamine ligand. Preferred bleach catalysts include the complexes of Co, Cu, Mn, Fe, bispyridylmethane and -bispyridylamine. Highly preferred catalysts include Co (2,2'-bispyridylamine) Cl 2, Di (isothiocyanate) bispyridylamine-cobalt (II), trisdipyridylamine-cobalt (II) perchlorate, Co (2,2'-bispyridylamine) 2? 2C10-, (2, 2'-bispyridylamine) copper (II) perchlorate, tris (di-2-pyridylamine) iron (II) perchlorate and mix thereof . Preferred examples include binuclear Mn complexes with tetra-N-dentate and bi-N-toothed ligands, including N MnIII (u-0) 2MnIVN4) + and [Bipy2MnIII (u-0) 2MnIvbipy2] - (C10) 3. Although the structures of the manganese bleach catalyst complexes of the present invention have not been elucidated, it can be speculated that coplanders or other hydrated coordination complexes resulting from the interaction of carboxyl and nitrogen atoms of the ligand with the cation of manganese. Also, the oxidation state of the manganese cation during the catalytic process is not known with certainty, and may be the valence state (+11), (+ III), (+ IV), or (+ V). Due to the six possible fixation points of the ligands to the manganese cation, it can reasonably be speculated that multinuclear species and / or "cage" structures may exist in aqueous bleaching media. Whichever form of active ligand-Mn species actually exists, it functions in a seemingly catalytic manner to provide improved bleaching performance in difficult to clean stains such as tea, tomato sauce, coffee, wine and juice. Other bleach catalysts are described, for example in the European Patent Application, publication No. 408,131 (cobalt complex catalysts). European Patent Applications, publications Nos. 384,503 and 306,089 (metalloporphyrin catalysts), E.U.A. 4,728,455 (manganese / multidentate ligand catalysts), E.U.A. 4,711,748 and European Patent Application, publication No. 224,952 (manganese / aluminosilicate catalyst absorbed), E.U.A. 4,601,845 (aluminosilicate support with manganese and zinc or magnesium salt), E.U.A. 4,626,373 (manganese / ligand catalyst), E.U.A. 4,119,557 (ferric complex catalyst), German Patent Specification 2,054,019 (cobalt chelator catalyst), Canadian 866,191 (salts containing transition metal), E.U.A. 4,430,243 (chelators with manganese cations and metal cations that are not catalytic), and E.U.A. 4,728,455 (manganese gluconate catalysts). Other preferred examples include cobalt (III) catalysts having the formula: C? [NH3) nM'mB'bT'tQqPp] Yy where the cobalt is in the oxidation state +3; n is an integer from 0 to 5 (preferably 4 or 5, most preferably 5); M 'represents a monodentate ligand; is an integer from 0 to 5 (preferably 1 or 2, most preferably 1); B 'represents a bidentate ligand; b is an integer from 0 to 2; T 'represents a tridentate ligand; t is 0 or 1; Q is a tetradentate ligand; q is 0 or 1; P is a pentadentate ligand; p is O or l; and n + m + 2b + 3t + 4q + 5p = 6; and is one or more appropriately selected counterions present in a number y, where y is an integer from 1 to 3 (preferably 2 to 3, most preferably 2 when y is an anion charged with -1), to obtain a salt balanced in how much to load; preferably Y is selected from the group consisting of chloride, nitrate, nitrite, sulfate, citrate, acetate, carbonate and combinations thereof; and wherein in addition at least one of the cobalt-bound combination sites is labile under conditions of automatic dishwashing use and the remaining coordination sites stabilize the cobalt under automatic dishwashing conditions such that the potential of reduction for cobalt (III) to cobalt (II) under alkaline conditions is less than 0.4 volts (preferably less than 0.2 volts) compared to a normal hydrogen electrode. Preferred cobalt catalysts of this type have the formula: [Co (NH3) n (M ') m] Yy where n is an integer from 3 to 5 (preferably 4 or 5, most preferably 5); M 'is a labile coordinating moiety, preferably selected from the group consisting of chlorine, bromine, hydroxide, water and (when m is greater than 1) combinations thereof; m is an integer from 1 to 3 (preferably 1 or 2, most preferably 1); m + n = 6; and Y is an appropriately selected counter ion present in a number y, which is an integer from 1 to 3 (preferably 2 to 3, most preferably 2 when Y is an anion charged with -1), to obtain a balanced salt in charge . The preferred cobalt catalyst of this type useful herein are the cobalt-pentamine chloride salts having the formula [Co (NH3) 5Cl] Yy and especially [Co (NH3) 5Cl] Cl2- Very preferred are the compositions of the present invention which use cobalt (III) bleach catalysts having the formula: [Co (NH3) n (M) m (B)] Ty where the cobalt is in the oxidation state +3; n is 4 or 5 (preferably 5); M is one or more ligands coordinated to cobalt by a site; m is 0, 1 or 2 (preferably 1); B is ligand coordinated to cobalt by two sites; b is 0 or 1 (preferably 0), and when b = 0, then m + n = 6, and when b = l, then m = 0 and n = 4; and T is one or more appropriately selected counterions present in number y, where y is an integer to obtain a salt balanced in charge (preferably y is 1 to 3, most preferably 2 when T is an anion charged with -1); and wherein said catalyst has a base hydrolysis constant of less than 0.23 M "1 s" 1 (25 ° C). Preferred T is selected from the group consisting of chloride, iodide, I3 ~, formate, nitrate, nitrite, sulfate, sulfite, citrate, acetate, carbonate, bromide, PF ~, BF4 ~ »B (Ph) 4 ~» phosphate , phosphite, silicate, tosylate, methanesulfonate and combinations thereof. Optionally T can be protonated if there is more than one anionic group in T, for example HP0-42 ~, HC03-, H2PO4-, etc. In addition, T may be selected from the group consisting of non-traditional inorganic anions such as anionic surfactants (eg linear alkylbenzene sulphonate (LAS), alkyl sulfates (AS), alkyl ethoxy sulfonates (AES), etc.) and / or anionic polymers (eg example, polyacrylates, polymethacrylates, etc.). The M portions include, but are not limited, for example, to F ~, S04-2, NCS ", SCN", S203 ~ 2, NH3, P0 3 ~, and carboxylates (which preferably are monocarboxylates, but more than one carboxylate it may be present in the portion as long as the link to cobalt is only one carboxylate per portion, in which case the other carboxylate in the M portion may be protonated or it may be in its salt form). Optionally, M can be protonated if there is more than one anionic group in M (e.g., HP0 2", HC03 ~, H2P0 ~, H0C (0) CH2C (0) 0-, etc.). are substituted and unsubstituted cl-c30 carboxylic acids having the formulas: RC (0) 0-wherein R is preferably selected from the group consisting of hydrogen and unsubstituted alkyl and substituted from cl ~ c30 (preferably C ^ -C ^ g), unsubstituted and substituted aryl of C¿-C3Q (preferably C¿-C18) and unsubstituted heteroaryl and substituted C3-C3Q (preferably Cs-C ^), wherein the substituents are selected from the group consisting of -NR'3, -NR '+, -C (0) 0R', -OR ', -C (0) NR'2, wherein R' is selected from the group consisting of hydrogen and C ^ -C6 portions. Therefore, said substituted Rs include the portions - (CH2) n0H "(CH2) nNR'4 +" in d ° ce n is an integer from 1 to 16, preferably from 2 to 10, and most preferably from 2 to 5 Most preferred are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched chain C-C-L2 alkyl and benzyl.R more preferred is methyl The preferred M-moieties of carboxylic acid include formic, benzoic, octanoic, nonanoic, decanoic, dodecanoic, alonic, maleic, succinic, adipic, phthalic, 2-ethylhexanoic, naphthenoic, oleic, palmitic, triflate, tartrate, stearic, butyric, citric, acrylic, aspartic, fumaric, lauric, linoleic, lactic, malic and especially acetic.

Portions B include dicarboxylate carbonate and higher carboxylates (e.g., oxalate, malonate, malic, succinate, maleate), pokolinic acid and alpha and beta amino acids (e.g., glycine, alanine, beta-alanine, phenylalanine). Cobalt bleach catalysts are known, for example being described along with their base hydrolysis rates in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorg. Bioinorg. Mech .. (9183), 2 pages 1-94. For example, Table 1 on page 17, provides the base hydrolysis rates (designated here as 0H) for cobalt-pentamine catalysts in oxalate complex (k0H = 2.5 x 10 ~ 4 M "1 s" 1 (25 ° C)), NCS "(k0H = 5.0 x 10" 4 M "1 s" 1 (25 ° C)), formate (k0H = 5.8 x 10 ~ 4 M "1 s" 1 (25 ° C)) and acetate (k0H = 9.6 x 10"4 M" 1 s "1 (25 ° C)) The most preferred cobalt catalyst useful herein are salts of cobalt pentaminoacetate having the formula [Co (NH3) 50Ac] Ty, wherein OAc represents an acetate portion and especially cobalt pentaminoacetate chloride. [Co (NH3) 50AcjCl2; as well as [Co (NH3) 50Ac] (0Ac) 2; [Co (NH3) 50Ac] (PF6) 2; CCo (NH3) 30Ac] (S0); CCo (NH3) 50Ac] (BF4) 2; Y [Co (NH3) 50Ac] (N03) 2 (here "PAC"). These cobalt catalysts are easily prepared by known processes, as taught for example in the Tobe article above and the references cited therein, in US Patent 4,810,410, to Diakun et al., Issued March 7, 1989. , J. Chem. Ed. (1989), 66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inorg. Chem., 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Phvsical Chemistry. 56. 22-25 (1952); as well as the synthesis examples provided below. As a practical matter, and not by way of limitation, the automatic dishwashing compositions and cleaning methods herein can be adjusted to provide the order of at least one part per one hundred million active catalyst species. in the aqueous washing medium, and preferably will provide from about 0.01 ppm to about 25 ppm, most preferably from about 0.05 ppm to about 10 ppm, and most preferably still from about 0.1 ppm to about 5 ppm, of the catalyst species of bleaching in the washing solution. In order to obtain such levels in the washing solution of an automatic dishwashing process, the automatic dishwashing compositions herein will comprise from about 0.0005% to about 0.2%, most preferably from about 0.004% to about 0.08% of the bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions.

Cationic alkoxylated quaternary ammonium surfactant The second essential component of the present invention comprises an effective amount of an AQA surfactant of the formula: wherein R1 is a portion of alkyl, alkenyl, aryl, alkaryl, ether, linear, branched or substituted glycrylic ether containing from 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, more preferably from 8 to 14 atoms of carbon; R2 is an alkyl group containing from 1 to 3 carbon atoms, preferably methyl; R3 and R4 can vary independently and are selected from the group consisting of hydrogen (preferred), methyl and ethyl; X ~ is an anion such as chloride, bromide, methyl sulfate, sulfate, sufficient to provide electrical neutrality. A is selected from C1-C4 alkoxy, especially ethoxy (i.e., -CH2CH20-), propoxy, butoxy and mixtures thereof; and p is an integer from 2 to 30, preferably from 1 to 15, more preferably from 2 to 8, even more preferably from 2 to 4. The AQA compounds wherein the R1 hydrocarbyl substituent is C8 ~ c12 > especially Cg-C10, improves the rate of dissolution of granules for laundry, especially under cold water conditions, as compared with the materials of higher chain length. Accordingly, some formulators may prefer the AQA surfactants of Cg-C ^ - The levels of the AQA surfactants used to prepare the finished laundry detergent compositions may vary from 0.1% to 5%, typically from 0.45% to 2.5%. %, in weigh. The present invention employs an "effective amount" of AQA surfactants to improve the performance of cleaning compositions containing other optional ingredients. An "effective amount" of the AQA surfactants herein refers to an amount in which it is sufficient to improve, either directionally or significantly at a 90% confidence level, the development of the cleaning composition against at least some of the dirt and target spots. In this way, in a composition whose objectives include certain food stains, the formulator will use sufficient AQA to at least directionally improve the development of cleaning against such spots. Also, in a composition whose objectives include clay soiling, the formulator will use sufficient AQA to improve at least directionally the cleaning performance against such dirt. Importantly, in a fully formulated laundry detergent, AQA surfactants can be used at levels that provide at least one directional improvement over a variety of soils and stains, as will be seen from the data presented below. As indicated, AQA surfactants can be used in combination with other detersive surfactants at levels that are effective to achieve at least one directional improvement in cleaning performance. In the context of the fabric laundry composition, such "use levels" may vary depending not only on the type and severity of the soils and stains, but also on the temperature of the wash water, the volume of wash water and the type of washing machines. For example, the North American type vertical top-loading automatic washing machine uses 45 to 83 liters of water in the wash tub, a wash cycle of 10 to 14 minutes and a wash water temperature of 10 ° C to 50 ° C, it is preferred to include from 2 ppm to 50 ppm, preferably from 50 ppm to 25 ppm, of the surfactant AQA in the wash solution. Based on the usage regimes from 50 ml to 50 ml per wash load, this results in a concentration of AQA surfactant in the product from 0.1% to 3.2%, preferably 0.3% up to 1.5%, for a liquid detergent for heavy duty laundry. Based on the use rates from 60 g to 90 g per wash load, for dense ("compact") granular laundry detergents (density above 650 g / 1) this results in a concentration of AQA surfactant in the product (weight) from 0.2% to 5.0%, preferably from 0.5% to 2.5%. Based on the use regimes of 80 g to 100 g per load for spray-dried granules (ie, "spongy"); density below 650 g / 1), this results in a concentration of the AQA surfactant in the product (weight) from 0.1% to 3.5%, preferably from 0.3% to 1.5%. For example, in a European type automatic front loading washing machine, horizontal axis that uses 8 to 15 liters of water in the wash tub, a wash cycle of 10 to 60 minutes and a wash water temperature of 30 ° C to 95 ° C, it is preferred to include from 13 ppm to 900 ppm, preferably from 16 ppm to 390 ppm, of the surfactant AQA in the wash liquor. Based on the usage regimes of 45 ml to 270 ml per wash load, this results in a concentration of the AQA surfactant in the product (weight) of 0.4% to 2.64%, preferably 0.55% to 1.1%, for a heavy duty liquid laundry detergent. Based on the usage regimes of 40 g to 210 g per wash load, for dense ("compact") laundry detergents (density above 650 g / 1) this results in a concentration of the AQA surfactant in the product (weight) from 0.5% to 3.5%, preferably from 0.7% to 1.5%. Based on the use regimes of 140 g to 400 g per load for spray-dried (ie, spongy) granules, density below 650 g / 1), this results in a concentration of the AQA surfactant in the product ( weight) from 0.13% to 1.8%, preferably from 0.18% to 0.76%, for example, in a Japanese automatic top-loading washing machine, vertical axis that uses 26 to 52 liters of water in the wash tub, a washing cycle of 8 to 15 minutes and a washing water temperature of 5 ° C to 25 ° C, it is preferred to include from 1.67 ppm to 66.67 ppm, preferably from 3 ppm to 6 ppm, of the AQA surfactant in the liquor of Based on the use regimes of 20 ml to 30 ml per wash load, this results in a concentration of the AQA surfactant in the product (weight) of 0.25% to 10%, preferably 1.5% to 2% for a heavy-duty liquid laundry detergent based on the use regimes of 18 g to 35 g per load of washing, for dense ("compact") laundry detergents (density above 650 g / 1), this translates into a concentration of the AQA surfactant in the product (weight) from 0.25% to 10%, preferably from 0.5% to 1.0%. Based on the usage regimes, from 30 g to 40 g per load for spray-dried granules (ie, "spongy", density below 650 g / 1), this translates to a concentration of the AQA surfactant in the product (weight) from 0.25% to 10%, preferably from 0.5% to 1%. As can be seen from the foregoing, the amount of the AQA surfactant used in the context of laundry washing machine can be varied, depending on the habits and practices of the user and the type of washing machine. In this context, however, an advantage that has not yet been appreciated from AQA surfactants is their ability to provide at least directional improvements in development in a spectrum of soils and stains even when used at relatively low levels with with respect to other surfactants (generally anionic or anionic / nonionic mixtures) in the finished compositions. The foregoing will be distinguished from other compositions of the art wherein various cationic surfactants are used with anionic surfactants at levels, or near stoichiometric levels. In general, in the practice of this invention, the weight ratio of the AQA: anionic surfactant in laundry compositions is in the range of 1:70 to 1: 2, preferably 1:40 to 1: 6, preferably from 1:30 to 1: 6, more preferably 1:15 to 1: 8. In laundry compositions comprising both anionic and nonionic surfactants, the weight ratio of the AQA: anionic / nonionic mixture is on a scale of 1: 8 to 1: 2 preferably 1:50 to 1: 8. Various other cleaning compositions comprising an anionic surfactant, an optional nonionic surfactant and specialized surfactants such as betaines, sultaines, amine oxides, may also be formulated using an effective amount of the AQA surfactants in the manner of this invention. Such compositions include, but are not limited to, dishwashing products by hand (especially liquids or gels), hard surface cleaners, shampoo, personal cleansing bars, laundry bars, and the like. Since the habits and practices of the users of such compositions show minimal variation, it is satisfactory to include from about 0.25% to 5%, preferably from about 0.45% to about 2%, by weight, of the AQA tenectant agents in such compositions. . Again, as in the case of the granular and liquid laundry compositions, the weight ratio of the AQA surfactant to other surfactants present in such compositions is low, i.e., sub-stoichiometric in the case of anionics. Preferably, such cleaning compositions comprise AQA / surfactant ratios as stated above for compositions for machine laundry. Unlike other cationic surfactants known in the art, the bis-alkoxylated cationic agents herein have sufficient solubility, so that they can be used in combination with mixed surfactant systems which are very low in nonionic surfactants and non-ionic surfactants. which contain, for example, alkyl sulfate surfactants. The foregoing may be an important consideration for formulators of detergent compositions of the type conventionally designated for use in top-loading automatic washing machines, especially of the type used in the United States, as well as under Japanese conditions of use. Typically, such compositions will comprise a weight ratio of anionic surfactant: nonionic surfactant in the range from about 25: 1 to about 1:25, preferably about 20: 1 to about 3: 1. This can be contrasted with European-type formulas that will typically comprise anionic: nonionic ratios in the range of about 10: 1 to 1:10, preferably about 5: 1 about 1: 1. Preferred ethoxylated cationic surfactants can be synthesized using a variety of different reaction schemes (wherein "EO" represents units -CH2CH2? -), as follows.

SCHEME 1 CH3 R! OH + CH3NH? 22 ^ --- = * Mag »,. R RiL_.NN EXCESSES ^ H R1_N-CH3 + n H " RLN_ (EO) n-H + CH3C1 Cal ° r » SCHEME 2 - (EOfcH "DIGLICOO AMINA" SCHEME 3 SCHEME 4 C! -CH2CH2-OH + n A ^ CAT »Cl-CH2CH2? [EO]" - H A scheme of economic reaction is the following. SCHEME 5 Na2S04 + HjO For Reaction Scheme 5, the following parameters summarize the optional and preferred reaction conditions of the scheme. Step 1 of the reaction is preferably conducted in an aqueous medium. Reaction temperatures are typically in the range of 100-230 ° C.

Lae preeionee of reaction are from 3.51 to 70.3 kg / cm2 monometric. A base, preferably sodium hydroxide, may be used to react with HS04 generated during the reaction. In another mode, an excess of the amine can be used to also react with the acid. The molar ratio of amine to alkyl sulfate is typically from 10: 1 to 1:15, preferably from 5: 1 to 1:11; most preferably from 2: 1 to 1: 1. In the product recovery step, the desired substituted amine is simply allowed to separate as a separate phase from an aqueous reaction medium in which it is insoluble. The product from step 1 is then ethoxylated and quaternized using standard reactions, as shown. The following illustrates the foregoing for the convenience of the formulator, but is not intended to be limited thereto.

Preparation of NN-bis (2-hydroxyethyl) dodecylamine - To a glass of autoclave was added 156.15 g of sodium dodecylsulfate (0.5415 moles), 81.34 g of 2-methylaminoethanol (1.083 moles), 324.5 g of H20. deethylated and 44.3 g of 50% by weight sodium hydroxide solution (0.5583 moles of NaOH). The glass foil was sealed in a 3 1 autoclave, stainless steel, oscillating, purged twice with 18.27 kg / cm2 of nitrogen and then heated to 160-180 ° C under 49.21-56.24 kg / cm2 gauge. of nitrogen for 3 hours. The mixture was cooled to room temperature and the liquid content of the glass liner was poured into a separating funnel of 1. The mixture is formed in a lower layer, medium turbid layer and clear euperior layer. The clear euperior layer is isolated and placed under complete vacuum (<100 mm Hg) at 60-65 ° C with mixing to remove any residual water. The clear liquid becomes turbid by removing residual water as it crystallizes, adding salt. The liquid is filtered under vacuum to remove them in order to obtain again a clear, colorless liquid. After a few days at room temperature, the additional salts crystallize and settle. The liquid is filtered under vacuum to remove epoxide and again a clear, colorless liquid is obtained which remains stable. The clear, colorless liquid isolated is the product of the title by NMR analysis and ee > 90% by analysis of CG with a typical recovery of > 90% The amine is ethoxylated ethoxylated in a standard manner. Quaternization with an alkyl halide to form the surfactants of AQA herein is a routine. According to the foregoing, the following are non-limiting, specific studies of AQA surfactants used herein. It will also be understood that the degree of alkoxylation noted herein for AQA surfactants is reported as an average, followed by the common tactic for conventional ethoxylated nonionic and nonionic agents. This is because the ethoxylation reactions typically produce mixtures of materials with different degrees of ethoxylation. In this way, it is rare to report the total EO values more than the total numbers, that is, "E02.5", "E03.5" and the like. Designation R Rll R R22 R3 Alkoxylation A AQQA - 11 cc1122"" cc1144 C CHH3g CH3 E02 AQA - 2 C C1100"" CC1166 C CHH3g CH3 E02 AQA - 3 C Cll22 C CHH3g CH3 E02 AQA - 4 C Cll C CHH3g CH3 E02-3 AQA - 5 C C1100 ~~ cc1188 C CHH3g CH3 EO5-8 A AQQAA --- 66 C C1122 ~~ cc1144 C C22HH55 CH3 E03-5 AQA - 7 C C1144"" cc1166 C CHH3g C3H7 (E0 / Pr0) 4 AQA - 8 cc1122"" cc1144 C CHH3g CH3 (PrO) g AQA - 9 cc1122 ~~ cc1188 C CHHgg CHg E010 AQA - 10 C C88 ~~ cc1188 C CHH3g CHg E015 A AQQAA --- 1111 C C1100 C C22HH55 C2H5 E03.5 AQA - 12 cc1100 C CHHgg CHg eo2.5 AQA - 13 C C1100 C CHHgg CHg E03.5 AQA - 14 cc1100 C HH99 C H9 E030 AQA - 15 C C88CC1144 C CHHgg CHg E02 A AQQAA --- 1166 cc1100 C CHH3g CHg E010 AQA-17 C12C14 C3H9 3H7 Bu AQA-18 c12c18 CH3 4H9 E05 AQA-19 c8 CH3 CH3 iPr3 AQA-20 c8 CH3 CH3 E? 3-7 AQA-21 C12 CH3 CH3 E03.5 AQA-22 C12 CH3 CH3 E ° 4.5 The highly preferred AQA compounds for use herein are of the formula; wherein it is Cg-C ^ g hydrocarbyl and mixtures thereof, preferably Cg, C10, c12, C14 alkyl and mixtures thereof. X is a convenient anion to provide charge balance, preferably chloride or bromide. As indicated, compounds of the above type include those in which the ethoxy (CH2CH2O) (EO) units are replaced with butoxy (Bu) isopropoxy [CH (CH3) CH20] and units CCH2CH (CH30)] (i-Pr) or n-propoxy units (Pr), or mixtures of EO and / or Pr and / or i-Pr units. A highly preferred AQA compound for use under the formulations improved in detergency are of the formula wherein p is an integer in the range of between 10 and 15.

This compound is particularly useful in the laundry detergent compositions for laundry.

Non-AQA detersive surfactants In addition to the AQA surfactant, the compositions of the present invention preferably further comprise a non-AQA surfactant. The non-AQA surfactants can include essentially any additional anionic, nonionic or cationic surfactant.

Anionic Surfactant Non-limiting examples of teneiocating agents useful here typically at levels of from 1% to 55% in petroleum include alkylbenzene sulfonates ("LAS") of conventional C ^ -C ^ and primary C10-C2 alkyl sulfates ("AS"). , branched chain and random, the secondary alkyl sulfates of C10-C18 of the formula CH3 (CH2) x (CH0S03 ~ M +) CH3 and CH3 (CH2) and (CH0S03 ~ M +) CH2CHg where xy (and + l) are integers of at least 7, preferably at least about 9, and M is a water solubilizing cation, especially eodium, unsaturated sulaphthalates such as oleyl sulfate, C10-C18 alkylalkoxysulfate ("AEXS"), especially ethoxy ether sulfates EO 1-7), C10-C18 alkylalkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates). C12-C18 and sulfobetaine betaines ("sultaines"), C10-C18 amine oxides, and the like can also be included in the overall compositions. You can also use conventional soap from C? G-C2os if you want high foaming, you can use a 10-C-L6 branched-chain soapbox. Other active agents and conventional technicians are listed in the textbook of the text.

Nonionic surfactants Non-limiting examples of surface active agents useful here typically at levels of 1% to 55% by weight include alkoxylated alcohols (AE) and alkylphenolee, a polyhydroxylic acid fatty acid idae (PFFAA), alkylpolyglycolides (APG), glycol ethers of C ^ oC ^ g. Very specifically, the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide (AE) are suitable for use as the non-ionic surface active agent of the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. The condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, most preferably from about 10 to about 18 carbon atoms, with from 1 to 10 moles, preferably from 2 to 7, are preferred. very preferably from 2 to 5, of ethylene oxide per mole of alcohol. Examples of nonionic nonionic agents of this type that are commercially available include Tergitol ™ 15-S-9 (the straight-chain alcohol product of C 11 -C 15 with 9 moles of ethylene oxide), Tergitol ™ 24-L-6 NMW ( primary alcohol condensation product of C? 2 ~? 4 with 6 moles of ethylene oxide with a limited molecular weight distribution), both marketed by Union Carbide Corporation; Neodol ™ 45-9 (the linear alcohol condensation product of C] L4-C15 with 9 moles of ethylene oxide), Neodol ™ 23-3 (the linear alcohol condensation product of C ^ -C- ^ g or > 3-0 moles of ethylene oxide), Neodol ™ 45-5 (the linear alcohol condensation product of C1-C15 with 7 moles of ethylene oxide), Neodol ™ 45-5 (the condensation product of alcohol linear of ci4 ~ ci5 with 5 moles of ethylene oxide), marketed by Shell Chemical Company, Kyro ™ EOB (the condensation product of C13-C15 alcohol with 9 moles of ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA 050 (the condensation product of C 12 ~ c 4 alcohol with 5 moles of ethylene oxide), marketed by Hoechst. The preferred scale of HLB in this product is ee of 8-11, and most preferred of 8-10. Another preferred nonionic surfactant agent clause for use herein are the fatty acid amide surfactants of the formula: or N-Z, ll wherein ee H, or R1 is C- -. ^, 2-hydroxyethyl, 2-hydroxypropyl hydrocarbyl or a mixture of the mers, R2 is C5_31 hydrocarbyl, and Z is a polyhydroxy-carbyl having a linear hydrocarbyl chain at least 3 hydroxyloids directly connected to the chain, or an alkoxylated derivative of the mimes.

Preferably, R is methyl, R 2 is a straight alkyl or alkenyl chain of C 1 -is such as cocoalkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in a reaction of reductive amination. Typical examples include the N-methylglucamines of C12 ~ C? G and 12 ~ C? 4- See E.U.A. 5,194,639 and 5,298,636. N-alkoxypolyhydroxylic acid amides may also be used; see E.U.A. 5,489,393. Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkyl, lisaccharides described in the U.S. Pat. 4,565,647, Filling, issued January 21, 1996, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms and a polysaccharide, e.g., a polyglucoside, a hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably still from about 1.3 to about 2.7 units of saccharide. Any reductive saccharide containing 5 or 6 carbon atoms can be used, eg, glucose, lactose and galactoside portions can substituate the glycoside component (optionally the hydrophobic group will adhere to lae poeicionee 2, 3, 4, etc.). , thus giving a glucose or galactoea as opposed to glucoside or galactose). The intersaccharide bonds can be, for example, between the first reading of the units saccharide adicionalee and lae poeicionee 2, 3, 4 and / or 6 in the previous saccharide units. Preferred alkyl polyglycosides have the formula R 0 (C n H 2n ° t (gl * cosyl) en wherein R 2 is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and meaclae of the mieme in which the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14 carbon atoms, N ee 2 or 3, preferably 2; t ee of or about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 The glucosyl is preferably In order to prepare these compounds, the alkylpolyethoxy alcohol or alcohol is first formed and then reacted with glucoea, or a source of glycoea, to form the glucoside (fixation in the 1-exposure). adhere between position 1 the position 2, 3, 4 and / or 6 of the above glycosyl units, preferably with position 2 predominating.

The confectioners of polyethylene oxide, polypropylene, and polybutylene of alkylphenol are suitable for treating it as the nonionic non-ionic agent of the surfactant system of the present invention, with polyethylene oxide being preferred. These compounds include the alkylphenol condensation products having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, either in straight chain or branched chain configuration. the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 5 to about 25 moles, more preferably about 3 to about 15 moles, of ethylene oxide per mole of alkylphenol. Commercially available nonionic nonionic agents of this type incubate Igepal ™ C0-630, manufactured by GAF Coforation; Y Triton ™ X-45, X-114, X-100 and X-102, all manufactured by Rohm & amp;; Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylate (e.g., alkylphenol ethoxylate). The product of ethylene oxide deadening with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant systems of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800 and will exhibit water-inelubility. The addition of polyoxyethylene portions to this hydrophobic portion tends to increase the water solubility of the molecules as a whole, and the liquid character of the product is retained at the point where the polyoxyethylene content is about 50% of the total weight of the product of condensation, which corresponds to condensation with about 40 moles of ethylene oxide. Examples of compounds of this type include some of the commercially available Pluronic ™ tenenectivoe agents, manufactured by BASF. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of about 2,500 to about 3,000. This hydrophobic portion is condensed with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactants include some of the commercially available Tetronic ™ compounds, manufactured by BASF.

Additional Cationic Surfactants Suitable cationic surfactants are preferably water-dispersible compounds having surfactant-agent properties which comprise at least one ether (i.e., -C00-) bond and at least one cationically charged group. Another suitable anionic surfactant agent includes the quaternary ammonium surfactant selected from N-alkyl or alkenyl surfactants of Ct6Cl6. preferably C¿-C ^ or where the N-reectant positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups. Other agents having cationic ester active agents, including choline ester surfactants, have been described, for example, in U.S. Pat. Noe 4228042, 4239660 and 4260529.

Additional Detergent Ingredients The following illustrates various other optional ingredients that may be used in the compositions of this invention, but are not intended to limit them to the same.

Additional bleaching agent The detergent compositions of the present invention may comprise an additional bleaching agent. Said bleaching agents are typically present at levels of from 1% to 20%, very typically from 3% to 15%, of the detergent composition, especially for fabric washing. Other bleaching agents include chlorine and photoactivated bleaching agents. Examples of photoactivated bleaching agents include zinc phthalocyanine and / or alumina eulfonadae. See Patent of E.U.A. 4,033,718, issued July 5, 1977 to Holcombe et al. If used, the detergent compositions will typically comprise from 0.025% to 1.25% by weight of said bleaching agent, especially zinc phthalocyanine and eulfonated.

Bleach activator An optional component of the composition of the present invention is a bleach activator. Bleach activators are typically present at levels from 0.1% to 60%, very typically from 0.5% to 40% of the bleaching composition comprising the bleaching agent plus the bleach activator. Peroxygen bleaching agents, perborates, etc., are preferably combined with bleach activators, which leads to the in situ production in aqueous solution (ie, during the washing process) of the peroxyacid or peracid corresponding to the bleach activator. . Various non-limiting examples of activators are described in the U.S. Patent. 4,915,854, issued April 10, 1990 to Mao et al. And the US Patent. 4,412,934. Activating nonanoyloxybenzene eulphonate (NOBS) and tetracetylethylenediamine (TAED) are typical, and may also be mixed together. See also E.U.A. 4,634,551 for bleaching ptroe and activators typicale útilee in the present. In an alternate preferred aspect, a preformed peracid is incorporated directly into the composition. Also contemplated are compositions containing mixtures of a source of hydrogen peroxide and a bleach activator in combination with a preformed peracid. Preferred amide derivative bleach activators are those of the formulas: R 1 N (R 5) C) 0) R 2 C (0) L or R C (0) N (R 5) R 2 C (0) L wherein R 1 is an alkyl group which contains from about 6 to about 12 carbon atoms, R 2 is an alkylene containing from 1 to about 6 carbon atoms, R 5 is H or alkyl, aryl or alkaryl containing from about 1 to about 10 carbon atoms and L is any suitable residual group. A residual 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 perhydrolic acid. A preferred refidual group is phenylsulfonate. Preferred examples of whitening activare of the above formulae include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, and mixture of the miee as described in US Pat. 4,634,551 which is incorporated herein by reference. Another bleaching activating clause includes the activator of the benzoxazine type described by Hodge et al. In U.S. Pat. 4,966,723 issued October 30, 1990, which is incorporated herein by reference. A highly preferred bleach activator of the benzoxazine type ee: Another class of preferred bleach activators includes the acyl-lactam activators, especially acylcaprolactamae and acylvalerolactams of the formulae: wherein R6 is H or an alkyl, aryl or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activating agents include benzoylcaprolactam, octanoylcaprolactam, 3,5,5-trimethyl-hexanoylcaprolactam, nonanoycaprolactam, decanoiIcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalero-lactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoylvalero-lactam and mixtures of the same. See also the U.S. Patent. 4,545,784 issued to Sanderson on October 8, 1985 incorporated herein by reference, which describes acylcaprolactams, including benzoylcaprolactam, adsorbed on sodium perborate.

Detergency Enhancers The detergency builders may optionally be included in the compositions herein to help control the mineral hardness, especially Ca and / or Mg, hardness in the wash water or to aid in the removal of particulate dirt from the surfaces. . The improved detergency can operate through a variety of mechanics including the formation of eolublee or insoluble complexes with hardness ions, by ion exchange, and offering a more favorable surface to the precipitation of hardness than what is energetic. that they have to clean. The level of builder can vary greatly depending on the final period of the composition and the desired physical form of the composition. Builders with detergency builders typically comprise at least 1% builder. Liquid formulations typically comprise from 5% to 50%, very typically from 5% to 35% by weight, of the detergency builder. The granular formulations typically comprise from 10% to 80%, very typically from 15% to 50% by weight, of the detergent builder of the detergent composition. The lower level or upper level of detergency builder is not excluded. For example, some detergent additive or formulations with high content of surface active agent may not have a builder. Suitable builders can be selected from the group consisting of phosphates and polyphosphates, especially sodium lae ealee; silicate including water-soluble types and hydrosolids and those having chain, layer or three-dimensional structure as well as types of amorphous solid or unstructured liquid; carbonates, bicarbonate, eeequicarbonatoe and mineralee of carbonate dietintoe to carbonate or sesquicarbonate; aluminosilicatoe; mono, di, tri and tetracarboxylate organice, especially carboxylate, which do not have water-soluble surfactant in the form of an acidic, sodium, potassium or alkanolammonium salt, as well as oligomeric or pee-like, water soluble olecular carboxylates, including aliphatic and organic types; aromatic; and phytic acid. These can be complemented with borates, for example, for purposes of pH regulation, or by sulfate, especially eodium eulfate and any other fillers or vehicles which may be important for engineering detergent compositions containing stable detergent and / or enhancer agent. detergency The mixture of detergency builders, sometimes referred to as "improved builder systems", can typically be comprised of conventional detergency enhancers, optionally complemented by chelating agents, pH regulators or fillers, although the latter are considered separately when Describe amount of materialee in the preeente. In terms of the amount of surfactant and builder in the detergents herein, the preferred builder systems are typically formulated in a weight ratio of the surfactant to builder of from 60: 1 to 1:80. Certain laundry detergents have this ratio in the range of 0.90: 1.0 to 4.0: 1.0., most preferably from 0.95: 1.0 to 3.0: 1.0. Improved detergency containing P often preferred where permitted by law include, but are not limited to, alkaline metal, ammonium and alkanolammonium salts of polypheptaelated by tripolyphosphates, pyrophosphates, vitreous polymeric metaphosphates and phosphonates. The most suitable aeilicate detergent improvers include alkali metal silicate, particularly those that are liquid and solids having a SiO2: Na2 ratio. in the scale of 1.6: 1 3.2: 1, including particularly for purposes of automatic dishwashing, silicates of 2 solid water ratios by PQ Corp. under the trade name BRITESILR, e.g., BRITESIL H20; and stratified silicates, for example, as described in US Patent 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, sometime abbreviated "SKS-6", is a free-layered morphology d-a2Si? 5 free of Hoechet's crietalino-layered aluminum and is preferred especially in granular laundry compositions. See preparation methods in German Patent DE-A-3,417,649 and DE-A-3,742,043. Other ethereal labels such as those having the general formula NaMsix02? +? "And H20 where M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, also Ee can be used or used alternately Hoechet stratified eilates also include NaSKS-5, NaSKS-7 and NaSKS-11, as the laye oc, ß and t eilicate forms, and can also be used for other silicates, such as magnesium silicate which can serve as a crispening agent in granules, as a stabilizing agent for bleaches and as a component of vapor control foam.Also suitable here are the crystalline ion exchange materials synthesized or the hydrates thereof. having chain structure and a composition repreeentated by the following general formula in the form of acid: xM 0ySi02.zM'0 where M is Na and / or K,, M 'is Ca and / or Mg, and / z is 0.55 a 2.0 yz / x is 0.005 to 1.0 as taught in U.S. Patent 5,427,711, Sakaguchi et al., June 27, 1995. Suitable carbonate builders include alkali metal and alkaline metal carbonates as described in German Patent Application No. 2,321,001 published on 15 November 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonate minerals such as trona or any convenient multiple salts of sodium carbonate and calcium carbonate such as those having the composition 2Na2C03.CaC03 when they are in anhydrous form and even calcium carbonates including calcite, aragonite and vaterite, especially forms having surface areas relative to compact calcite may be useful, for example as they are illae or for uearee in barrae of einthetic detergent. The aluminosilicate builders are especially useful in detergent granules, but they can also be incorporated in liquid, pate, or gels. Suitable for the present purposes are those that have the empirical formula: Mz [(zA102) and] .XH2O where z and are integers of at least 6, the molar ratio of zay is on the scale of 1.0 to 0.5, and x ee a whole from 15 to 264. The aluminoeilicatoe can be crystalline or amorphous, naturalee or einetically derivative. A method for producing aluminosilicates is in US Patent 3,985,669, Krummel et al. Issued October 12, 1976. The ion exchange materials of crystalline aluminosilicate eintéticoe eetán dieponiblee preferred under the designation Zeolite A, Zeolite P (B), Zeolite X and, to any degree that éeta differs from Zeolite P, the so-called Zeolite MAP. Natural types can be used, including clinoptilolite. Zeolite A has the formula: Na12t (| Cll02) l2Isi02) l2 ^ xH20 in doncle xes of about 20 to 30, particularly of 27. Dehydrated zeolites (x = 0 -10) can also be used in the present . Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Suitable organic builders include non-water-soluble dicarboxylate and tricarboxylates. Very typically, the builder polyetherboxylates have a plurality of carboxylate group, preferably at least 3 carboxylate. The carboxylate detergency builder ee can be formulated in acid, partially neutral, neutral or butadiene form. When they are in the form of eal, they prefer alkaline metale eleee, such as eodium and potaeum, as well as lithium or alkanolammonium. Polycarboxylate builders include ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. Pat. 3,128,287, issued April 7, 1964, and Lamberti et al, patent of E.U.A. 3,635,830, issued on January 18, 1972; The "TMS / TDS" detergency enhancer of the U.S.A. 4,663,071, issued to Bueh and again on May 5, 1987; and other ethereal carboxy including cyclic compotetoe and alicyclic compounds, such as those described in US Pat. 3,923,679; 3,835,163; 4,120,874 and 4,102,903. Other useful builders include ether hydroxypolycarboxylates, maleic anhydride copolymers with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, and carboxymethyloxy-euccinic acid, various alkali metal salts, ammonium and Substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene, 3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof.

Citrate builders, eg, citric acid and soluble salts thereof are polycarboxylate builders of importance, eg, for heavy-duty liquid detergents because of their availability from renewable resources and eu biodegradability. The citrates can also be used in granular compositions, especially in combination with zeolite and / or layered silicate. Oxydisuccinates are also especially useful in said compositions and combinations. When it is allowed and especially in the formulations of ueadae rods for hand washing operations, various alkali metal foams such as the well-known sodium phospholiphosphates, eodium pyrophosphate and eodium orthophosphate can be used. Phosphonate detergency builders such as ethan-1-hydroxy-1, 1-diphosphonate and other known phosphonate, for example, patent of E.U.A. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137 may also be used and may have desirable flaking antiforming properties. Certain surfactant surfactants or their short chain homologues also have a detergency builder action. For purposes that have unambiguous formula, when they have surfactant capacity, these materials are surfactant agents. Preferred types for detergency builder functionality are illustrated by: 3,3-dicarboxy-4-oxa-l, 6-hexanodiatoe and the related compounds described in U.S. Pat. No. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the alkyl and alkenyl succinic acids of C5-C20 V salts thereof. Succinate builders also include: lauryl succinate, myristyl succinate, palmityleuccinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate, and eilamylate. The lauryl succinates are the preferred builders of this group, and are described in the European patent application 86200690.5 / 0,200,263, published on November 5, 1986. Fatty acids, e.g., monocarboxylic acids of -C-C ^ g, they can also be incorporated into the compositions as surfactant / builder materials to provide additional detergency builder activity. Other suitable polycarboxylates are described in the U.S.A. 4,144,226, Crutchfield et al., Issued March 13, 1979 and in the U.S. patent. 3,308,067, Diehl, issued March 7, 1967. See also Diehl, patent of E.U.A. 3,723,322. Another type of material that is improved by inorganic detergents that can be used has the formula (M-x)! Cay (C03) z em where xei are integers from 1 to 15, and is an integer from 1 to 10, z is an integer from 2 to 25, Mj are cations, at least one of which is soluble in water and the equation? = l-15 (multiplied by the valence of Mj) + 2y = 2z is satified in such a way that the formula has a neutral or "balanced" charge. Improved detergent properties are known here as "mineral detergency builders". Hydration waters or anions other than carbonate can be added as long as the overall charge is balanced or neutral. The effect of charge or valence of said anions should be added to the right side of the previous equation. Preferably, a water-soluble cation selected from the group containing hydrogen, metale soluble in water, hydrogen, boron, ammonium, silicon, and mixtures thereof is very present, most preferably sodium, potassium, hydrogen, lithium, ammonium and mexclae of loe. miemoe, eodio and potassium being highly preferred. Non-limiting examples of non-carbonate anione include those selected from the group that you have included in chloride, sulfate, fluoride, oxygen, hydroxide, silicon dioxide, chromate, nitrate, borate, and mixtures thereof. Preferred builders of this type in their simplest forms are selected from the group consisting of Na 2 Ca (C 3) 2, 2Ca (C03) 2, Na2Ca2 (C03) 3, NaKCa (C03) 2, NaKCa (C03) 3, K2ca2 (C03) 3, and combinations thereof. A material especially preferred for the builder described herein is Na2Ca (C03) 2 in any of the modified crystalline. Suitable detergency builders of the type defined above are further illustrated and include the naturale or einthetic formae of any or combination of the following minerals: afghanite, andereonite, aecroftine Y, beierite, borearite, burbanquita, butetliita, cancrinite, carbocernaite, carletonite, davina, donnaita And, fairquildita, ferrieurita, franzinita, gaudefroita, gaylueita, girvaeita, gragorita, jouravekita, kamfaugitaY, ketnerita, kaneeita, lepereonitaGd, lyotita, mckelveitaY, microsomita, mroseita, natrofaircildita, nyerereita, remonditaCe, sacrofanita, ecrockingerita, eortita, surita, tunisita , tuscanita, tyrolita, vienevita, and zemkorita. Lae formae mineralee include nyererita, faircildita and shortita.

Enzymes Enzymes may be included in the present detergent compositions for a variety of purposes, including the removal of protein-based carbohydrate-based carbohydrate or triglyceride-based substances such as materialee textilee or vajillae, for the prevention of traneferon migratory dye, for example in the washing of clothes and for the reetauración of the fabric. Suitable enzyme enzymes include proteaeae, amilaeae, lipases, cellulase, peroxidase and mixtures thereof of any suitable origin, for example of vegetable, animal, bacterial, fungal and yeast origin. They are selected from eethan influenced by factors such as pH activity and / or optimal stability, thermostability and stability to active detergents, builders and similar. In this regard, bacterial or fungal enzymes, such as bacterial amylases and proteases and fungal cellulases, are preferred. The term "detersive enzyme", as here, means any enzyme that has a beneficial effect of cleaning, mancha removal or any other beneficial effect in a detergent composition of laundry, cleaning of hard surfaces or personal care. Preferred detereivae enzymes are hydrolases such as proteaeae and amylaeae. Enzymes that are preferred for laundry purposes include, but are not limited to, proteases, cellulases and peroxidases. The amylaeae and / or proteaeae are highly preferred for automatic dishwashing, including both commercially available types and improved types, which, although increasingly compatible due to successive improvements, still have a certain degree of susceptibility to the deactivation of the bleach. Enzymes are usually incorporated in detergent or detergent additive compositions at eutective levels to provide an "effective cleaning amount". The term "effective cleaning amount" refers to any amount capable of producing an improving effect of cleaning, removal of manchae, removal of dirt, whiteness, deodorizing or freshness on pile up as fabrics, tableware and similaree. In practical terms for current commercial preparations, typical amounts are from about 5 mg in weight, typically from approximately 0.01 mg to approximately 3 mg, of active enzyme per gram of composition. Stated another way, the compositions of the preend typically will connect from about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes present in such commercial preparations at levels sufficient to provide 0.005 to 0.1 Anson units (AU) of activity per gram of composition. For certain detergents, such as automatic dishwashing loe, it may be desirable to increase the active enzyme content of the commercial preparation to minimize the total amount of non-catalytically active materials and thus improve splashes / films or other results. finalee They can also be deeeable and level higher assets in highly concentrated detergent formulations. Suitable examples of proteases are the subtilieinae obtained from particular strains of B.subtilie and B.lichenifomne. Other suitable proteaeae are obtained from a Bacillus strain. having a maximum activity in the entire pH range of 8 to 12, developed and sold as ESPERASER by Novo Industriee A / S of Denmark, hereinafter "Novo". The preparation of enzyme eeta and analogous enzymes is described in GB 1,243,784, by Novo. Other suitable proteases include ALCALASER and SAVINASER from Novo and MAXATASER from International Bio-Synthetics, Inc., Paísee Bajoe; as well as Protease A as described in EP 130,756 A, January 9, 1985 and Protease B as described in EP 87303761 A, April 28, 1987 and EP 130,756 A, January 9, 1985. See also a high protease pH of Bacillus sp. NCIMB 40338 described in WO 9318140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes and a reversible protease inhibitor are described in WO 9203529 A to Novo. Other proteases that are preferred include those of WO 9510591 A to Procter & amp;; Gamble. When desired, a protease having reduced dietary and increased hydrolysis is available as described in WO 9507791 to Procter & Gamble. A recombinant trypsin-like protease for detergent suitable in the present is as described in WO 9425583 to Novo. In more detail, a protease that is especially preferred, called "protease D" is a carbonyl hydrolase variant that has an amino acid effect that is not found in nature, which is derived from a precursor carbonyl hydrolase constituting a different amino acid. a plurality of amino acid reeiduae at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid equivalents to those selected from the group consisting of +99, +101, +103 , +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, + 216, +217, +218, +222, +260, +265, and / or +274 according to the numbering of the eubtilisin of Bacillus amyloliquefaciene as described in the patent applications of A. Baeck et al., Entitled " Protease-Containing Cleaning Compoeitione "which has a serial number of E.U. No 08 / 322,676, and C. Ghoeh et al, "Bleaching Compositions Comprising Protease Enzymes ", which has the serial number of E.U. No. 08 / 322,677, both filed on October 13, 1994. Suitable amylases in the present, especially for, but not limited to, automatic dishwashing purposes, include, for example, amylases described in GB. 1,296,839 to Novo; RAPIDASER, International Bio-Synthetics, Inc. and TERMAMYLR, Novo. FUNGAMYLR from Novo is especially useful. Genetic manipulation of enzymes is known for improved stability, e.g., oxidative stability. See, for example, J. Biological Chem, Vol. 260, No. 11, June 1985, pp 6518-6521. Certain preferred embodiments of the present compositions can make use of amylases having improved stability in tartaric detergents such as those used for automatic dishwashing, especially improved oxidant stability as measured against a TERMAMYLR reference point in commercial use in 1993. These Preferred amylases of the present share the characteristics of being "improved stability" amylases, characterized, at a minimum, by a measurable improvement in one or more of: oxidative stability, e.g., to hydrogen peroxide / tetraacetylethylene diamine in pH solution regulated at pH 9-10; thermal stability, e.g., at common wash temperature as about 60 ° C; or alkaline stability, e.g., at a pH of about 8 to about 11, measured against the a ilaea of the reference point identified above. The ability to be measured can be measured using any of the technical tests described in the art. See, for example, the references referenced in WO 9402597. Amylases of improved stability can be obtained from Novo or Genencor International. A class of amilasae highly preferred herein has the common property of being derived using the eitio-directed mutagenesis of one or more of the Bacillus amylases. especially the Bacillus amylases. and import the one, two or multiple stocks of amylaeae with the immediate precursors. It is preferred to use the improved amidability oxidizer. the aforementioned reference amylase, especially in the bleaching compositions, most preferably oxygenated bleaching, other than chlorine bleaching, of the present invention. Preferred amylase adae include a) an amylase according to WO 9402597, Novo, Feb. 3, 1994 previously incorporated, as further illustrated by a mutant in which ee replaces, using alanine or threonine, preferably threonine, the methionine residue located at position 197 of the alpha-amylase of B.lichemiformie. known as TERMAMYLR, or the variation of the homologous poem of an eimilar progenitor amylaea, such as B. amyloliquefaciene. B. eubtilie. or B. stearothermophilus: b) amilaeae of improved stability as described by Genencor International in a paper entitled "Oxidatively Reeietant alpha-Amylaees", presented at the 207 American Chemical Society National Meeting, March 13-17, 1944, by C. Mitchinson. There it is mentioned that the bleaches in detergents for automatic dishwashing inactivate alpha-amilaeae, but that they have made amylaeae oxidants of improved stability by Genencor of B. licheniformis NCIB8061. Methionine (Met) was identified as the residue most likely to be modified. The Met was euetituida, one at a time, in lae 8, 15, 197, 256, 304, 366 and 438 pointings leading to mutant eepecíficoe, particularly important being the variants MI97L and MI97T, with the variant M197T being the most stable expressed variant. The stability was measured in CASCADER and SUNLIGHTR; (c) the particularly preferred amylases herein include the amylase variants having further modification in the immediate parent as described in WO 9510603 A and dieponiblee of the Novo transferee, such as DURAMYLR. Another oxidizing amylase of improved stability that is preferred includes that described in WO 9418314 to Genencor International and WO 9402597 to Novo. Any other oxidative amylase of improved stability can be used, for example that derived by site-directed mutagenesis of mutant chimeric, hybrid or simplee progenitor forms known from available amylases. Other preferred enzyme modifications are also available. See WO 9509909 to Novo. Other enzymes amlaea include those described in WO 95/26397 and in the co-pending Application by nOVO nORDISK pct / dk96 / 00056. Lae enzimae amilaea eepecificae to be used in the detergent compositions of the present oc-amilaea invention characterized by having a specific activity of at least 25% more than the specific activity of TermamylR at a temperature of 25 * C to 55 ° C and a value pH on a scale of 1 to 10, as measured by the Phadebae® a-amylase activity test. (Said a-amilaea Phadebae® test is described on pages 9-10, WO 95/26397). Also included herein are α-amylases which are at least 80% homologous with the amino acid sequences shown in the recited SEQ ID No. 1 in the reference. these enzymes are preferably incorporated in laundry detergent compositions at a level of 0.00018% to 0.060% pure enzyme in the total composition, most preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition. Cellulases which may be present in the preeent include both bacterial and fungal cells, preferably with an optimum pH between 5 and 9.5. The U.S. 4,435,307, Barbesgoard et al., March 6, 1984, describes suitable fungal cellulases of strain DSM 1800 of Humicola ineolene or Humicola. or a cellulase-producing fungus 212 belonging to the genus Aeromonas. and the cellulase extracted from the hepatopáncreae of a marine mollusk Dolabella Auricle Solander Suitable cellulases are also prescribed in GB-A-2,075,028; GB-A-2,095,275 and DE-0S-2,247,832. CAREZYMER (Novo) is especially useful. See also WO 9117243 to Novo. Suitable lipase enzymes are those produced by microorganisms of the Pseudomonas group. such as Pseudomonae etutzeri ATCC 19.154 as described in GB 1,372,034. See also lipaeas 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 trade name Lipasa P "Amano," or "Amano-P." Other suitable commercial lipaeae include Amano-CES, lipases ex Chromobacter viscosum. v.gr. Chromobacter viscoeum var. lipoliticu NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; lipaeae Chromobacter viecoeum from U.S. Biochemical Corp, E.U.A. and Disoynth Co., Holland and lipasae ex Peeudomonae gladioli. The enzyme LIP0LASER derived from Humicola lanuginoea and commercially available from Novo, see also EP 341,947, is a preferred lipaea for the presence in the preeent. Variants of lipaea and amylaea stabilized against proxidase enzymes are described in W0 9414951 A de Novo. See also W0 9505249 and RD 94359044. In view of the large number of publications on lipase enzymes, only the lipase derived from Humicola lanuginosa and produced in Aspergillus oryzae as a host has so far been found to have wide application as an additive for fabric washing products. , is available from Novo Nordisk under the trade name Lipolase, as indicated above. In order to optimize the stain removal performance of Lipolase, Novo Nordisk has made a number of variants. As described in WO 92/05249, the D96L variant of native Humicola lanuginosa lipase improves the efficiency of butter spot removal by a factor of 4.4 over wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 g of protein per liter). Research description No. 35944 published on March 10, 1994 by Novo Nordisk discloses that the lipase variant (D96L) ee can be added in an amount corresponding to 0.001-100- mg (5-500,000 LU / liter) of variant of lipase per liter of washing solution. The present invention provides the benefit of improved whiteness maintenance in fabrics by lowering D96L variant low in detergent compositions containing AQA surfactant agents in the manner described herein, especially when D96L is used at levels in the 50 Lu to 8500 Lu per liter of washing solution. Suitable cutinase enzymes for use herein are described in WO 8809367 A to Genencor. Peroxidase enzymes are used in combination with oxygen sos, eg, percarbonate, perbe, hydrogen peroxide, etc., for "bleaching in solution" or to avoid the transfer of dyes or pigments removed from the stratuses during the washing operation to another substrate in the washing solution. . Known peroxidase enzymes include horseradish peroxidase, ligninase and haloperoperoxidase such as chloroperoxidase and bromoperoxidase. Lae detergent compositions containing peroxidase are described in WO 89099813 A, October 19, 1989 to Novo and WO 8909813 A to Novo. A wide variety of enzyme materials and means for their incorpion into synthetic detergent compositions are described in WO 9307263 A and WO 9307260 A to Genecor International, WO 8908594 A to Novo and US Pat. 3,553,139, January 5, 1971 to McCarty and others. In addition, enzimae is defined in the patent of E.U.A. 4,101,457, Place et al., July 18, 1978 and in the patent of E.U.A. 4,507,219, Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations and their incorpion into such formulations are described in US Pat. 4,261,868, Het al., Issued April 14, 1981. Enzymes for detergents can be stabilized by various techniques. Enzyme stabilization techniques are described and illustrated in the US patent. 3,600,319, Aug. 7, 1971 to Gedge and other, and in EP 199,405 and EP 200,586, October 29, 1986, Venegae. The enzyme stabilization methods are also described, for example, in E.U. 3,519,570. A Bacillus ep. Useful AC13 that gives proteases, xylanases and cellulaeas is described in WO 9401532 A to Novo.

Enzyme stabilization system Lae compositions comprising enzyme of the present may comprise from 0.001% to 10%, preferably from 0.005% to 8%, most preferably from 0.01% to 6% by weight of an enzyme stabilization enzyme. The enzyme stabilization system can be any stabilization system that is compatible with the detersive enzyme. Such a system can be inherently provided by other formulation actives, or it can be added separately, eg, by the formulator or by a manufacturer of lietae enzymes for detergents. Such enzyme stabilization systems may, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acid, acid boronic acid and mixtures thereof, and are designed to meet different stabilization problems depending on the type and physical form of the detergent composition. A stabilization approach is the use of water soluble sources of calcium and / or magnesium ions in the finished compositions, which provide said ions to the enzymes. Calcium ions are generally more effective than magnesium ions, and are preferred herein if only one type of cation is being used. Typical detergent compositions, especially liquid, will comprise from about 1 to about 30, preferably from about 2 to about 20, most preferably from about 8 to about 12 millimole of calcium ion per liter of finished detergent composition, although variation is possible depending on of factors that include the multiplicity, type and levels of incorporated enzymes. Preference is given to using calcium or magnesium salts soluble in water, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; Very generally, calcium eulfate or magnesium lae ee ee that correeponden to the calcium eelae can be found. Additional levels of calcium and / or magnesium may, of course, be useful, for example to promote the fat-cutting action of certain types of tenectant. Another approach to stabilization is through the use of borate specimens. See Severeon, E.U. 4,537,706. The borate stabilizers, when used, may be at levels of 10% or more of the composition, although more typically levels of about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for the use of liquid detergents. The boric acids suetituidoe talee as phenylboronic acid, butanboronic acid, p-bromophenylboronic acid or eimilar, can be used in place of boric acid and reduced levels of total boron can be possible in the detergent compositions by the use of said boron derivatives suetituidos.

The stabilization steps of certain cleaning compositions may further comprise from 0 to 10%, preferably from 0.01% to 6% by weight, of chlorine bleach scavengers, added to prevent chlorine bleach specimens from occurring in many water sources. attack and inactivate lae enzimae, especially under alkaline conditions. Although the chlorine levels in the water may be small, typically in the range of about 0.5 ppm to about 1.75 ppm, the available chlorine in the total volume of water that comes in contact with the enzyme, for example during dishwashing or fabrics, can be relatively large; consequently, the ability of the enzyme to chlorine during the year is problematic. Since percarbonate or perborate, which have the ability to react with chlorine bleach, may be present in some of the composition components in a number independent of the stabilization system, the addition of additional stabilizer against chlorine may, very generally, it is not essential, although improved results can be obtained from its use. Suitable chlorine scavenging anions are widely known and readily available, and if they are, they can be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Similarly, antioxidants such as carbamate, aecorbate, etc., organic amino acids such as ethylenediaminetetraacetic acid (EDTA) or an alkali metal salt thereof, monoethanolamine (MEA) and mixtures of the same can be used. Likewise, special enzyme inhibition systems can be incorporated so that the different enzymes have maximum compatibility. If desired, other conventional barredoreals such as bisulfate, nitrate, chloride, hydrogen peroxide sources such as eodium perborate tetrahydrate, eodium perborate monohydrate and eodium percarbonate, aei as foefate, confounded phosphate, acetate, benzoate, citrate can be used. , formate, lactate, malate, tartrate, ealicylate, etc. and mix of the same. In general, since the chlorine sweeping function can be carried out by ingredient (s) that have been found to be most readily recognized (eg, sources of hydrogen peroxide), there is no absolute requirement to add a separate chlorine scavenger unless a compound that performs that function to the degree eected herein in an embodiment of the invention that contains enzymes; Including in this case, the sweeper is only added for optimum results. Moreover, the formulator will exercise a normal chemical ability by avoiding the passage of any enzyme scavenger or enzyme that is primarily incompatible, as formulated, with other reactive ingredients, if used. In relation to the ammonium salts, said salts can be ezcladed simply with the detergent composition, but are prone to adsorb water and / or release ammonia during storage. Accordingly, said materiae, ie present, are protected in a particle as described in E.U. 4,652,392, Baginski et al. Polymeric dirt release agent The known polymeric soil release agents, hereinafter "SRA" or "SRA's", can optionally be used in the present detergent compositions. If used, the SRA's will generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight, of the compositions. Preferred SRA'e typically have hydrophilic segments to hydrophilize the surface of hydrophobic fibers such as polyester and nylon, and hydrophobic segments to be deposited on hydrophobic fibers and remain adhered to the members through the completion of the washing and rinsing cycles, thus serving as an anchor for the hydrophilic segments. This may make it possible for stains that occur after treatment with the SRA to be cleaned easily in the stone-washing procedure. The SRA'e may include a variety of cationic, e.g., anionic or cationic, species; see the patent of E.U.A. No. 4,956,447, issued on September 11, 1990 to Gosselink et al., As well as uncharged monomeric units and their structures which may be linear, branching and embedded in the form of etetrella. They may include end-blocking portions that are especially effective in controlling molecular damage or altering the active surface or physical properties. Lae structures and load distributions can be designed for application to different types of fibers or textiles and for detergent or detergent additive products. Preferred SRA'e include oligomeric terephthalate esters, typically prepared by methods that include at least one transesterification / oligomerization, commonly with a metal catalyst such as a titanium (IV) alkoxide. These substances can be manufactured by adding additional monomers capable of being incorporated into the structure of the ester through uan, two, tree, four or more positions, without, of course, forming a globally intertwined structure. The SRA'e include: a sulfonated product of an eubertential linear ether oligomer composed of an oligomeric ester base structure of repeated terephthaloyl and oxyalkylenoxy units and terminal sulfonated portions derived from allyl univae covalently to the bae structure, for example, as it is written in the USA 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Goeselink: said ether oligomers ee can prepare a) ethoxylating alkyl alcohol, b) by reacting the product of (a) with dimethylterephthalate ("M¿DMT") and 1,2-propylene glycol ("PG") in a transesterification process / oligomerization of doe stages and c) reacting the product of (b) with eodium metabisulfite in water; polyoleters of non-ionic blocked ends of 1,2-propylene / polyoxyethylene terephthalate of the U.S. patent. No. 4,711,730, of December 8, 1987 of Goseelink and others, for example those produced by the transesterification / oligomerization of methyl ether of polyethylene glycol, DMT, PG and polyethylene glycol ("PEG"); The oligomeric estaere of partially and completely anionic blocked ends of the US patent. No. 4,721,580, dated January 26, 1988 by Goeeelink, talee as ethylene glycol oligomer ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctansulfonate; the non-ionic blocked block polyether oligomeric compounds of the U.S. patent. 4,702,857, dated October 27, 1987 from Goeeelink, for example produced from DMT, PEG and EG and / or PG (Me) -blocked methyl or a combination of DMT, EG and / or PG, PEG Me-blocked and Na-dimethyl-5-eulfoieophthalate; and the blocked terephthalate esters of the anionic ends, especially sulfoaroyl, of the U.S. patent. No. 4,877,896 of October 31, 1989 to Maldonado Goseelink and others, being the last typical of SRA's useful in both fabric conditioning and laundry products, an example being an ester composition made from the monoeodium acid eal. -eulfobenzoic acid, PG and DMT, optionally but preferably also comprising added PG, e.g., PEG 3400.

SRA's also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide terephthalate or polypropylene oxide, see U.S. Pat. No. 3,959,230 to Hays of May 25, 1976 and the patent of E.U.A. No. 3,893,929 to Basadur, July 8, 1975, cellulose derivative as the cellulosic hydroxyether dieponiblee polymer as METHOCEL from Dow; Lae alkyl celluloses of L-C4 and C4 hydroxyalkyl cells of the U.S. patent. No. 4,000,093, from December 28, 1976 to Nicol, and other. Suitable sols characterized by hydrophobic polyvinylmethyl ether segments include polyvinyl ether graft copolymer, e.g., C 1 -C 4 vinyl ethers, preferably polyvinylacetate, grafted onto polyalkylene oxide base structures. See European Patent Application 0 219 048, published April 22, 1987 by Kud et al. Commercially available examples include SOKALAN SRA'e talee as SOKALAN HP-22, dieponiblee of BASF, Germany. Other SRAs are polyether with repeating units that have 10-15% in ethylene terephthalate together with 80-90% in polyoxyethylene terephthalate derived from polyoxyethylene glycol of an average molecular weight of 300-5000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI. Another preferred SRA is an oligomer having the empirical formula (CAP) 2 (EG / PG) 5 (t) 5 (SIP) 1, which comprises terephthaloyl (T), eulfoieof taloyl (SIP), oxyethyleneoxy and oxy-1 units. , 2-propylene (EG / PG), and which preferably terminates with blockade of extremae (CAP), preferably modified ieetionatoe, as in an oligomer comprising a sulfisoisof taloyl unit, 5 terephthaloyl units, oxyethyleneoxy unit and oxyl, 2- propilenexi in a defined ratio, preferably from about 0.5: 1 to about 10: 1, and a blocking endpoint derived from 2- (2-hydroxyethoxy) -etaneul-fonate. Said SRA preferably comprises from 0.5% to 20% by weight of the oligomer of a crystallinity reduction stabilizer, for example an anionic tendectant agent such as linear dodecylbenzene sulfonate or a selected member of xylene, cumene and toluene sulfonate or mixtures thereof. , these stabilized ree or modifiers being introduced into the sample container, all as taught in the US patent No. 5,415,807, Goseelink Pan, Lellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include Na-2 (2-hydroxyethoxy) -ethane sulfonate, DMT, Na-dimethyl-5-eulfoieophthalate, EG and PG. Another preferred group of SRA'e are oligomeric esters comprising: (1) a base structure comprising (a) at least one unit selected from the group consisting of dihydroxysulfonates, polyhydroxysulfonates, a unit that is at least trifunctional, whereby ether bonds are formed resulting in a structure of branched oligomeric bae, and combinations of the same; (b) at least one unit that is a portion of terephthaloyl; and (c) at least one non-sulfonated unit which is a 1,2-oxyalkylenoxy moiety; and (2) one or more blocking units selected from non-ionic blocking units, anionic blocking units such as alkoxylated isethionate, preferably ethoxylated, alkoxylated propansulfonates, alkoxylated propandisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives, and mixtures thereof. Preferred are the ree of the empirical formula:. { (CAP) x (EG / PG) y '(DEG) y "(PEG) y'" (T) z (SIP) z '(SEG) q (B) m} where CAP, EG / PG, PEG, T and SIP as defined above, (DEG) repreeenta units of di (oxyethylene) oxy, (SEG) represents units derived from the sulfoethyl ether of glycerin and related portion units, (B) ) represents branching units that are at least trifunctional, whereby they form ether bonds resulting in a branched oligomer base structure, x is from about 1 to about 12, and 'is about 0.5. at about 25, and '' is from 0 to about 12, and '' 'is from 0 to about 10, and' + y '' + y '' 'euma in total of about 0.5 to about 25, z ee of about 1.5 to about 25, z 'ee of about 0 to about 12; z + z 'euma in total of about 1.5 to about 25, which is about 0.05 to about 12; m ee of about 0.01 to about 10, and x, y ', y' ', and' '', z, z ', q and m represent the average number of moles of the corresponding units per mole of said ether, and said ester has a molecular weight ranging from about 500 to about 5,000. The monomers of SEG and CAP preferred for the above esters include 2- (2,3-dihydroxypropoxy) -ethane sulfonate ("SEG"), 2-. { 2- (2-hydroxyethoxy) ethoxy} sodium acetate sulfonate ("SE3") and homologs and mixtures of the miemoe, and the product of ethoxylation and aliphatic alcohol sulphonation. The eeteree of SRAs preferred in this class include the trane-etherification and oligomerization product of 2-C2- (2-hydroxyethoxy) ethoxy} eodium ethane sulfonate and / or 2- [2-. { 2- (2-hydroxyethoxy) ethoxy} sodium ethoxy] ethane sulfonate, DMT, 2- (2,3-dihydroxypropoxy) ethane ethane sulfonate, EG and PG using an appropriate Ti (IV) catalyst, and can be designated as (CAP) 2 (T) 5 (EG /PG)1.4(SEG)2.5(B)0.13, where CAP is (Na + 03S [CH2CH20] 3.5) - and B is a glycerin unit, and the mass ratio of EG / PG is approximately 1.7: 1 measured by conventional gas chromatography after complete hydrolysis. Additional classes of SRA'e include: (I) non-ionic terephthalates using diisocyanate coupling agents to link the polymeric ester structures, see E.U.A. 4,201,824, Violland et al. And E.U.A. 4,240,918 Lagaeee and other, and (II) SRA'e with carboxylate terminal groups made by adding trimethyl anhydride to SRA's known to convert hydroxy end group to trimethylate ether. With the appropriate selection of the catalyst, trimethyl anhydride forms a bond to the polymer terminus via a carboxylic acid ester isolated from the trimethyl anhydride instead of opening the anhydride linkage. Either non-ionic or anionic SRA's can be used as starting material, as long as they have hydroxyl-terminated groups that can be eterified, see E.U.A. No. 4,525,524 Tung and others. Other classes include (III) SRA's a non-anionic terephthalate baee of the urethane-linked variety, see E.U.A. 4,201,824, Violland et al; (IV) polyvinylcaprolactam and copolymers related to monomers such as vinylpyrrolidone and / or dimethylaminethymethacrylate, including nonionic and cationic polymers, see E.U.A. 4,579,681, Rupper and other, (V) graft copolymer, in addition to the SOKALAN type from BASF, manufactured by grafting acrylic monomers to sulfonated polyethers. These SRAs have activity for the release of material and anti-redeposition of substances similar to the known cellulose ether: see EP 279,134 A. 1988 to Rhone Poulenec Chemie. Also other classes include: (VI) vinyl monomeric grafts such as acrylic acid and vinyl acetate in proteins such as caseins, see EP 457,205 A to BASF (1991); and (VII) SRA's of polyester-polyamide prepared by condensing adipic acid, caprolactam and polyethylene glycol, especially for treating polyamide fabrics, see Bevan et al., DE 2,335,044 to Unilever N.V., 1974. Other SRA's are useful in the patent of E.U.A. Nos. 4,240,918, 4,787,989, 4,525,524, and 4,877,896.

Clay soil remover / anti-redeposition agents The compositions of the present invention may also optionally contain ethoxylated ethoxylate in water having property of removal and anti-redeposition of clay clarity. The detergent compositions containing granules containing typically contain from about 0.01% to about 10.0% by weight of the water-soluble ethoxylated amines; Liquid detergent compositions typically contain about 0.01% to about 5%. The preferred soil remover and anti-redeposition agent is ethoxylated tetraethylenepentamine. Lae aminae ethoxylated examples are described more fully in the US patent. No. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay remover / anti-redeposition agent with cationic compounds described in European patent application 111,965, Oh and Goseelink, published June 27, 1984. Another removable / anti-redeposition agent of clay material that may be used includes the ethoxylated amine polymers described in European Patent Application 111,984, Goseelink, published June 27, 1984; the zwitterionic polymers described in European patent application 112,592, Goseelink, published on July 4, 1984; and the amine oxide described in the US patent. No. 4,548,744, Connor, issued October 22, 1985. Other clay removing and / or anti-redeposition agents known in the art can be used in the compositions herein. Another type of preferred anti-redeposition agent includes the carboxylmethylcellulose materialee (CMC). Eetoe materialee are well known in the art.

Polymeric Dispersing Agents Polymeric dispersing agents ee can advantageously be used at levels of 0.1% to 7%, by weight, in the compositions herein, especially in the presence of improved detergency of zeolite and / or tetralated silica. Suitable polymeric dietary agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be useful. It is believed, although not intended to be limited by theory, that the polymeric dielectric agents increase the performance of the overall builder, when used in combination with other detergency builders (including lower molecular weight polycarboxylates) by growth inhibition. of crystals, peptization of release of dirt into particles and anti-redeposition. Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomer and preferably in their acid form. The unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylate include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic. The presence of the polymeric polycarboxylate in the polymer component or components, which do not contain carboxylate radicals such as vinyl methyl ether, styrene, ethylene, etc., is suitable provided that said segments do not constitute more than about 40% by weight. Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Dichere acrylic acid-based polymers which are useful in the preeent eon ee lae ealee water-soluble 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. The water-soluble salts of said acrylic acid polymers may include, for example, the alkali metal, ammonium and substituate ammonium salts. The polymeric solvents of this type are known materials. The use of polyacrylate of this type in detergent compositions has been described, for example, in Diehl, U.S. Pat. 3,308,067, issued on March 7, 1967.

Acrylic / maleic acid-based copolymers can also be used as a preferred component of the anti-redeposition / anti-redeposition agent. Talee materialee include the saltse eolublee in water 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, more preferably from 5,000 to 75,000 and most preferably from 7,000 to 65,000. The ratio of acrylate segments to those of maleate in said copolymers generally ranges from about 30: 1 to about 1: 1, most preferably from 10: 1 to 2: 1. The water soluble in said copolymer of acrylic acid / maleic acid may include, for example, alkali metal, ammonium and sub-substituted ammonium salts. The acrylate / soluble maleate copolymers of this type with known material 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 polymers comprising hydroxypropylacrylate. Other useful dispersing agents include the maleic / acrylic / vinyl alcohol terpolymers. Such materials are also described in EP 193,360, including, for example, terpolymer 45/45/10 maleic / acrylic / vinyl alcohol. Another polymeric material that can be included is polyethylene glycol (PEG). PEG can exhibit performance of dispersing agent and can act as an anti-redeposition agent for clay soiling. Typical molecular weight scales for this purpose vary from 500 to 100,000, preferably from 1,000 to 50,000 and most preferably from 1,500 to 10,000. The dispersing agents of polyaepartate and polyglutamate, especially in conjunction with improved detergency of zeolite, can also be used. The dielectrolylate agents as polyaepartate loe have preferably a molecular weight (avg.) Of 10,000.

Brightener Any optical brightener or other whitening or whitening agent can be incorporated in the art typically at a level of 0.01% to 1.2% by weight, in the detergent compositions of the present invention. The commercial optical brighteners which may be useful in the present invention can be classified into eubgroups which include, but are not necessarily limited to, stilbene derivatives, pyrazoline, coumarin, carboxylic acid, methinocyanins, dibenzotifen-5-dioxide, azole, heterocycles of ring of 5 and 6 members, and other diverse agents. Examples of such brighteners are described in "The Production and Application of Fluorescent Brightening Agents," M. Zahradnik, published by John Wiley & Sons, New York (1982).

Specific examples of optical brighteners that are useful in the present compositions are those identified in the patent of E.U.A. 4,790,856 issued to Wixon on December 15, 1988. These highlights include the ERORWHITE estate of Verona. Other high-quality products described in this reference include: Tinopal UNPA, Tinopal CBS and Ti nopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, Hilton-Davis diponibl, located in Italy; 2- (4-styryl-phenyl) -2H-naj: tol [1,2-d] triazole; 4,4'-bis- (1, 2,3-triazol-2-yl) -estilbenoe; 4,4'-bis (eethyryl) bisphenyls; and the ami do not have quarrels. Specific examples of polyacrylate compounds include 4-methyl-7-diethyl aminocoumarin; 1, 2-bis (-benzimidazol-2-yl-ethylene; 1,3-diphenylpyrazoline; 2,5-bie (benzoxazol-2-yl) thiophene; 2-eetyryl-naphthyl- [1,2-s] oxazole; and 2- (stilben-4-yl) -2H-naphtho- [1,2-d] triazole See also U.S. Patent No. 3,646,015, issued February 29, 1972 to Hamilton.

Dye transfer inhibiting agents The compositions of the present invention can also include one or more effective materials to inhibit the transfer of dyes from one fabric to another during the cleaning process. As usualsaid dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase and mixtures of the dies. If so, agents typically comprise from 0.01% to 10% by weight of the composition, preferably from 0.01% to 5%, and most preferably from 0.05% to 2%. Very specifically, the polyamine N-oxide polymers preferred for use herein contain units having the following structural formula: R-Ax-P; wherein P is a polymerizable unit to which a N-O group can be attached or the N-O group can form part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC (0) -, -C (0) 0-, -S-, -0-, -N =; x is 0 or 1; and R ee group aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic or any combination of lo moe to which the nitrogen of the N-O group may be attached or the N-O group may be part of these groups. The N-oxides of polyamine are preferred in that R ee is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrroline, piperidine and derivatives thereof. The N-O group can be represented by the following general structures: 0 0 (R1)? - N- (R2) y; 88n8N-ÍRi) * R3) z wherein Rl t R2, R3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group can be attached or forms part of any of the above-mentioned groups. The amine oxide unit of the polyamine N-oxide has a pKa < 10, preferably pKa < 7, very preferably still pKa < 6. Any structure of polymer bath can be run while the polymer of amine oxide formed is soluble in water and has the property of dye transfer inhibitor. Examples of suitable polymeric polymer structures are polyvinyl, polyalkylene, polyether, polyether, polyamide, polyimide, polyacrylate, and mixture of loene. Eetoe 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 polymers typically have an amine to amine N-oxide ratio of 10: 1 to 1: 1,000,000. However, the number of amine oxide groups preeentee in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. The polyamine oxides ee can be obtained in almost any degree of polymerization. Typically, the average molecular weight is within the range of 500 to 1,000,000; very preferred from 1,000 to 500,000; even more preferred 5,000 to 100,000. Eeta preferred class of materials can be termed "PVN0". The most preferred polyamine N-oxide useful in the detergent compositions herein is the poly-4-vinylpyridine N-oxide having an average molecular weight of about 50,000 and an amine to amine N-oxide ratio of about 1: 4 The polymer copolymer of N-vi or idoprolone and N-vinylimidazole (also known as "PVPVl") is also preferred for use in the present. Preferably, the PVPVl 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 another is Chemical Analyeie, Vol. 113. "Modern Methode of Polymer Characterization", the descriptions of which are incorporated herein by reference). PVPVl copolymers typically have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1: 1 to 0.2: 1, preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. Copolymer groups can be 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 5,000 to about 50,000. . The PVP's are known to those skilled in the field of detergents; see, for example, EP-A-262,897 and EP-A-256,696, incorporated herein 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 is about a ppm of assorted in wash solutions ee from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1. The detergent compositions of the present invention may also optionally contain from about 0.005% to 5% by weight of certain types of optical and hydrophilic polishing agents that also provide a dye tranefication inhibiting action. If so, the compositions of the preferentially will comprise about 0.01% to 1% by weight of said optical brighteners. The hydrophilic optical brighteners useful in the present invention are those having the structural formula: wherein R ± is selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M ee an eal forming cation such as eodium or potassium. When in the previous formula, Ri is aniline, R2 is N-2-bis-hydroxyethyl and M is a cation such as eodium, the brightener 4,4 'acid, bie [(4-anilino-6- (N-2-bie-hydroxyethyl) -e-triazin-2- and l) amino] -2,2'-eethylbenzene sulfonic and disodium. 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 pre-ecting components. When in the above formula aniline Rl ee, R2 ee N-2-hydroxyethyl-N-2-methylamino and M ee a cation such as eodium, the brightener is the disodium salt of 4,4'-bis [4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2-ethylbene-sulfonic acid. Eetapecie of particular brightener is traded commercially under the trade name Tinopal 5BM-GX by Ciba-Geigy Corporation. When in the above formula R1 is anilino, R2 is morphino and M is a cation such as eodium, the brightener is the sodium eal of 4,4'-bis [(4-anilino-6-morph ilino-s-triazin -2-yl) amino] 2,2'-stilbenedisulfonic acid. This particular kind of brightener is sold commercially under the trade name Tinopal AMS-GX by Ciba-Geigy Coforation. The specific optical brightener species selected for use in the present invention provides speci? Cally effective dye transfer inhibition performance bene? Ts when used in combination with the polymeric dye transfer inhibiting agent eected above. The combination of said selected polymeric materials (e.g., PVNO and / or PVPVl) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides inhibition of Dye transfer significantly better in aqueous wash solutions than either of those two components of detergent composition when using eolos. Without being limited to the theory, it is believed that said polishes work in this way because they have a high affinity for cloth in the washing solution and therefore they are deposited relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called "depletion coefficient". The coefficient of depletion is in general the ratio of a) the polishing material deposited on the cloth to b) the initial polish concentration in the wash liquor. Brighteners with relatively high depletion coefficients are most suitable for inhibiting dye transfer in the context of the present invention. Of course, it will be appreciated that other types of conventional composite optical brightener optionally may be present in the compositions herein to provide conventional "glossiness" benefit to the fabrics, rather than a true dye traneffect inhibiting effect. This is conventional and well known for the detergent formulation.

Chelating Agents The detergent compositions of the present invention may also optionally contain one or more iron and / or manganese chelating agents. Said chelating agents can be selected from the group containing aminocaFoxylatoe, aminophosphate, chelating agent and polyfunctionally substituted aromatics and mixtures of the miemoe, as defined hereinbelow. Without claiming to be limited by theory, it is believed that the benefit of these materials is due in part to their exceptional ability to remove iron and manganese ions from the washing solution by forming soluble chelates. The aminocaFoxilatoe useful as optional chelating agents include ethylenediaminetetracetatoe, N-hydroxyethyl-ethylenediaminotriacetatoe, nitrilotriacetatoe, ethylenediamono-tetraproprionatoe, triethylentetraa inohexacetatoe, diethylenetri-aminopentaacetatoe and ethanoldiglicins, alkali metal, ammonium and ammonium salts substitued thereof and mixtures thereof. The aminophosphates are also useful for use as chelating agents in the compositions of the invention when at least low levels of total phosphorus are permitted in the detergent compositions and include ethylene diamine tetrakis- (methylene phenophonates) as DEQUEST. Preferably, these aminofoefonatoe do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. The aromatic chelating agents polyfunctionally also substituted are useful in the compositions herein. See the patent of E.U.A. 3,812,044 issued May 21, 1974 to Connor and another of the preferred compounds of this type in acid form with dihydroxydieulfobenzene such as 1,2-dihydroxy-3,5-dieulfobenzene. A preferred biodegradable chelator to be run in the preeent is ethylenediamine disuccinate ("EDDS"), especially isomer [S, S,] as described in US Pat. 4,704,223 issued November 3, 1987 to Hartman and Perkins. The compositions herein may also comprise salts (or an acid form) of water-soluble methylglycine diacetic acid (MGDA) as a chelator or co-builder useful, for example, with insoluble builders such as zeolites, layered silicates. If used, these chelating agents should generally comprise from 0.1% to 15% by weight of the detergent compositions herein. Most preferably, if used, the chelating agents should comprise from 0.1% to 3.0% by weight of said compositions.

Foam suppressors Compounds for reducing or suppressing foaming can be incoforated in the compositions of the present invention. The eupressure of foams may be of particular importance in "high concentration cleaning procedures" such as those described in E.U. 4,489,455 and 4,489,574, and in front-loading European-style washing machines. A wide variety of materials can be used as foam suppressors, and foam products are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3a. Edition, Volume 7, page. 430-447 (John Wiley &Sons, Inc., 1979). A category of foam suppressant of particular interest includes monocarboxylic acids and saltse soluble therein. See the patent of E.U.A. 2,954,347, issued on September 27, 1960 to Wayne St. John. The monocatalytic fatty acids and salts of the moons used as suds suppressors typically have hydrocarbon chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts include the alkali metal salts such as sodium, potassium and lithium, and salts of ammonium and alkanolammonium. The detergent compositions of the present may also contain euphormic substances that are not active agents. Examples include, for example: high molecular weight hydrocarbon wax such as paraffin, fatty acid esters (e.g., triglyceride fatty acid), fatty acid esters of monovalent alcohols, aliphatic ketones of C? -C4g (e.g., stearoña), etc. Other foam inhibitors include N-alkylated diamond aminot such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiaminocrotriazines formed as products of cyanuric chloride with doe or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms. carbon. propylene oxide and monoetearyl phosphate such as monoearyl alcohol and alkali metal diphosphate ester (e.g., K, Na and Li) monoetearyl and ether foefates. Hydrocarbons such as paraffin and halogenoparaffins ee can be used in liquid form. The liquid hydrocarbons will be liquid at room temperature and atmospheric pressure, and will have a pour point in the range of about -40 ° C to about 50 ° C, and a minimum boiling point of not less than about 110 ° C (atmospheric pressure). ). It is also known to use waxy hydrocarbons, preferably having a melting point below about 100 ° C. Hydrofluorides are a preferred category of suds suppressor for detergent compositions. The hydrocarbon products eupreeoree are described, for example, in U.S. Patent No. 4,265,779, issued May 5, 1981 to Gandolfo et al. HydrocaFuroe, therefore, include hydrogenated or aliphatic, alicyclic, aromatic and heterocyclic hydrocarbon which have from about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of foam supreeoree, is intended to include mixtures of true paraffins and cyclic hydrocarbons. Another preferred category of foam suppressors that are not active agents include silicone foam suppressors. This category includes the use of poiorganosiloxane oils such as polydimethyleryloxane, dispersions or emulsions of polyorganosiloxane or resin oils, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemoabsorbed or fused onto the silica. The euphoric products of e-products 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 and other and in the application of European patent No. 89307851, published on February 7, 1990 by Starch, M.S. Other silicone e-foam suppressors are described in the U.S.A. 3 patent., 455.839, which relates to compositions and procedimeintos for defoaming solutions acuoeae incoforando to lae pequeñae miemae cantidadee polidimetileiloxano fluid. Mixtures of eylons and eilates eilates are e.g. written in the German patent application DOS 2,124,526. Loe eliminadoree of eepumae of eilicón and loe controladoree agentee foam in detergentee composicionee granuladae ee deecriben in US 3,933,672 patent, Bartolotta otroe, and US 4,652,392 patent, Baginski et al, issued March 24, 1987. An eupreeor of eepumae to BAEE illustrative eilicón for use in the present ee one eupreeora amount of eepumas a controlling agent espumae that coneiete essentially of: (i) polydimethylsiloxane fluid having a viecocidad about 20 cc to about 1.500 cc to 25 ° C; (ii) about 5 to about 50 parts per 100 parts in weight of (i) siloxane resin composed of units of (CH3) 3Si0? / 2 of units of SiO2 in a ratio of units of (CH3) 3Si01 / 2 to SiO2 units of about 0.6: 1 to about 1.2: 1; and (iii) about 1 to about 20 parts per 100 parts by weight of (i) of a solid silica gel.

In the preferred silicone foam suppressant used herein, the solvent for a continuous fae is made of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures of the mieme (preferred), or polypropylene glycol. The primary silicone suds suppressor is branched / interlaced and non-linear. To illustrate this point, the detergent compositions for typical liquid laundry with controlled foam and optionally will comprise about 0.001 to about 1, preferably about 0.01 to about 0.7, most preferably about 0.05 to about 0.5 percent by weight of said eupressor. of silicone, comprising (1) a non-aqueous emulsion of a primary foam-forming antiforming agent which is a mixture of (a) a polyorgano-eneiloxane, (b) a resinous siloxane or a composition of the eucalycine-producing eucalyptus, (c) a finely divided filler material and (d) a catalyst for promoting the reaction of mixture component (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a polyethylene-polypropylene glycol copolymer having a water solubility at room temperature of more than about 2% by weight; and without polypropylene glycol. Similar amounts can be used in granulated compositions, gels, etc. See also patents of E.U.A. 4,978,471, Starch, issued December 18, 1990 and 4,983,316, Starch, issued January 8, 1991, 5,288,431, Huber et al., Issued February 22, 1994, and US patents. 4,639,489 and 4,749,740, Aizawa et al. In column 1, row 46 to column 4, row 35. The precursor of eefoe of the preend preferably comprises polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer, all having a lower average molecular weight. about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene / polypropylene copolymers of the present have a water solubility at room temperature other than about 2% in weight, preferably more than about 5% in weight. The preferred solvent herein is polyethylene glycol having an average molecular weight less than about 1,000, most preferably between about 100 and 800, most preferably still between 200 and 400, and a polyethylene glycol / polypropylene glycol copolymer, preferably PPG 200 / PEG 300 A weight ratio of between about 1: 1 and 1:10, most preferably between 1: 3 and 1: 6, of polyethylene glycol: polyethylene-polypropylene glycol copolymer is preferred. Preferred and preferred silicone foam suppressors herein do not contain polypropylene glycol, particularly of molecular weight of 4,000. Preferably, they also do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101. Other supra-reagents of the present invention contain secondary alcohols (e.g., 2-alkylalkanols) and mixtures of such alcohols with ethyl oil, as described in US Pat. No. 4,798,679, 4,075,118 and EP 150,872. The secondary alcohols include C6-C16 alkyl alcohols having a C ^ -C16 chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available under the tradename ISALCHEM 123 from Enichem. The euphorea ee foame my toe typically comprise alcohol + silicone blend at a weight ratio of 1: 5 to 5: 1. For any detergent compositions that must be used in automatic washing machines, the foam should not be formed to the extent that they are to be removed from the washing machine. The foam suppressor, when used, is preferably present in a quantity of foam eupressure. By "amount of foam supreration" it is understood that the formulator of the composition can select an amount of this foam controlling agent that will efficiently control the foam to result in a low foaming laundry detergent for use in automatic washing machines. The compositions herein will generally comprise from 0% to about 5% of the foam suppressor.

When used as suds suppressors, the monocarboxylic fatty acids, and salts of the miemoe, will typically be present in amounts of about 5%, in pee, of the detergent composition. Preferably, about 0.5% to about 3% of monocarboxylate foam suppressant is used. The foam suds of the foam are typically used in a quantity of about 2.0%, in pee, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, mainly due to the interest of keeping the coefficient reduced to the minimum and the effectiveness of lower quantity to effectively control the foaming. Preferably from about 0.01% to about 1% silicone foam suppressor is used, most preferably from about 0.25% to about 0.5%. As used herein, these weight percent values include any silica that may be used in combination with polyorganosiloxane, as well as any auxiliary materials that may be used. The foam compositions of onetheretheryl phosphate are generally used in amounts ranging from about 0.01% to about 02% by weight of the composition. Hydrofluoride foam suppressors are typically used in amounts ranging from about 0.01% to about 5.0%, although higher levels can be used. The alcohol foam suppressors are typically used at 0.2% -3% by weight of the finished compositions.

Alkoxylated polycarboxylates Alkoxylated polycarboxylates are prepared as they are prepared from polyacrylate and are used here to provide graene removal performance. These materials are described in WO 91/08281 and PCT 90/01815 on page 4 and are hereby incorporated by reference. Chemically, these materials comprise polyacrylates that have an ethoxy side chain for every 7-8 acrylate units. The side chains of the formula ~ (H2CH2?) M CH2) nCHg where m is 2-3 and n is 6-12. The side chains are ester linked to the polyacrylate "bae structure" to provide a "comb" type polymer structure. The molecular weight may vary, but typically it is in the range of 2000 to 50,000. Polycarboxylic alkoxylate dies can comprise from 0.05% to 10% by weight of the compositions of the present invention.

Fabric softeners Various fabric softeners that soften during washing can be used, especially the impalpable smectite slabs of the U.S. patent. 4,062,647, Storm and Nirschi, issued December 13, 1977, as well as other softening clays known in the art, typically at levels of from about 0.5% to about 10% in weight in the compositions herein to provide benefit softeners concurrently with the cleaning of fabrics. Bake clay softeners can be used in combination with amine and cationic eauvizer as described, for example, in the US patent. 4,375,416, Criep et al, March 1, 1983 and in the U.S. patent. 4,291,071, Harrie et al., Issued September 22, 1981.

Perfumes Loe perfume and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and eintéticoe chemical ingredients, including but not limited to aldehyde, ceronae, ethereal. Also included are natural extracts and natural extracts that may comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam essence, oil of sandalwood, pine oil, cedar . The perfume is finished and can comprise extremely complex mixtures of these ingredients. The finished perfumes typically comprise from 0.01% to 2% by weight of the detergent compositions herein, and the individual perfumery ingredients can comprise from 0.0001% to 90% to a finished perfume composition. Non-limiting examples of perfume ingredients useful herein include: 7-acetyl-l, 2,3,4,5,6,7,8-octahydro-1, 7-tetramethylnaphthalene; methylionone; gamma methylionone; methylredrilone; methyldihydrojasmonate; methyl, 6,10-trimethyl-2,5,9-cyclododecatrien-1-yl ketone; 7- acetyl-1,1,3,4,, 6-hexamethitetralin; 4-acetyl-6-tert-butyl-l, 1, dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-1, 1, 2,3,3,5-hexamethyl indan; 5-acetyl-3-isopropyl-1,1,6-tetramethyl indan; 1-dodecanal, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexane-1-carboxaldehyde; 7-hydroxy-3,7-dimethylocatanal; 10-undecen-l-al; Iohexylhexylcyclohexyl caFoxaldehyde; formyltriciclodecane; product of hydroxytrylene dilate and methylanthranilate, condensation product of hydroxycitronellal and indole, condensation products of phenylacetaldehyde and indole; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; ethylvanillin; heliotropin; hexyl cinnamic aldehyde; amylcinnamic aldehyde; 2-methyl-2- (para-ieo-propylphenyl) -propionaldehyde; coumarin; gamma-decalactone; Cyclopentadecanolide; 16-hydroxy-9-hexadecenoic acid lactone co; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma-2-benzopyran; methyl ether of beta-naph tol; ambroxane; dodecahydro-3a, 6,6,9a-tetramethylnaphthol [2, lb] furan; cedrol, 5- (2,2,3-trimethyl-l-cyclopent-3-endyl) -3-met-il-pentan-2-ol; 2-ethi 1-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodece-nylacetate; benzylealicylate; Cryrilacetate; and para- (tert-butyl) cyclohexylacetate. Particularly preferred perfume materials are those that provide the greatest odor improvements in finished product compositions containing cellulaeae. These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methy1-3- (para-tert-butylphenyl) -propionaldehyde; 7-acetyl-l, 2,3,4,5,6,7,8-octahydro-1,1,7,7-tetramethylnaphthalene; benzyl salicylate: 7-acetyl-l, l, 3,4,4,6-hexamethyltetralin; para-tert-butyl cyclohexyl acetate; methyldihydrojasmonate; methyl ether of beta-naphthol; methylbeta-naphthyl ketone; 2-methyl-2- (para-iso-propylphenyl) -propionaldehyde; 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2-benzopiran; dodecahydro3a, 6,6,9a-tetramethylnaphtho [2,1b] furan; anisaldehyde; coumarin; cedrol; vanillin; Cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate. Other perfume materials include oil, eeencialee, reeinoidee and reeinae from a variety of sources including but not limited to: Peruvian balm, olibanu resinoidee, eetirax, lavender reein, moecada nut, caeia oil, benzoin reein, corundum and lavender. Other chemical perfume compositions include phenylethyl alcohol, tefineol, linalool, linalylacetate, geraniol, nerol, 2- (1, 1-dimethylethyl) -cyclohexane-acetate, benzylacetate, and eugenol. Vehicles such as diethyl phthalate can be used in the finished perfume compositions.

Other ingredients A wide variety of other ingredients useful in detergent compositions can be included in the pre-eects, including other active ingredients, vehicles, hydrotropes, processing aids, colorant or pigment, evelope for liquid formulations, fillers and solids for bar composition. , etc. If there is a high foam formation, the compositions of the foam foam and the alkanolamide of Cjr-C16 can be included in the compositions, typically at a level of 1% -10%. The 10 ~ C? 4 monoethanol and diethanolamides illustrate a typical class of such foam boosters. The use of said foamers with high-foaming adjuvants having high foaming adjuncts such as the amine oxide, betaine and sultaines mentioned above is also advantageous. If desired, magnesium salts such as MgCl2, MgSO4 and emulsify can be added, typically at 0.1% -2%, to provide additional foam and to improve the fat removal performance. Various detersive ingredients employed in the present compositions may be subsequently stabilized by absorbing said ingredients on a porous hydrophobic eubetrate, after rewinding said eugust 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 with more detail, a porous hydrophobic eyelid (trade name SIPERNAT DIO, Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic nonionic agent of ethoxylated alcohol of C13_15 (EO 7). Typically, the enzyme / surfactant solution is 2.5X ee of the silica. The resulting powder is dispersed with stirring in silicone oil (several viscosities of silicon oil can be used in the 500-12,500 range). The resulting silicone oil die is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluoreecedoree, fabric conditioner and surfactant and hydrolysable agent mentioned above can be "protected" to be used in detergents, including liquid detergent compositions. laundry. The liquid detergent compositions may contain water and other solvents such as vehicles. The low molecular weight primary and secondary alcohols illustrated by methanol, ethanol, propanol and isopropanol are suitable. Monohydric alcohols are preferred for solubilizing surfactant, but polyols such as those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (eg, 1,3-propanediol, ethylene glycol, glycerin) can also be used. and 1,2-propanediol). The compositions may contain from 5% to 90%, typically from 10% to 50% of said vehicles. The detergent compositions of the pre-eater will preferably be formulated such that during use in aqueous cleaning operations, the wash water has a pH of between about 6.5 to 11, preferably between about 9 and 11, most preferably a pH of 9 to 10. The technique for controlling the pH at the recommended level of use includes regulating the pH, alkali, acid, etc., and is well known to those skilled in the art.

Production of granules The addition of alkoxylated cationic compounds of this invention in a degrading mixture, followed by conventional agitation drying, helps to remove any residual contaminants, potentially short-chain amine malodour. In the case that the formulator wishes to prepare a miscible particle containing the alkoxylated cationic compounds for use, for example, in a high deneity granular detergent, it is preferred that the particulate composition is not highly alkaline. The processes for preparing high density granules (above 650 g / 1) are described in U.S. Patent No. 5,366,652. Said particles can be formulated so that they have an effective pH during the use of 9, or lower, to avoid the odor of amines of impurity. This can be achieved by adding a small amount of acidity source or boric acid, citric acid or eimilaree, or an appropriate pH regulator, to the particle. In an alternative mode, proepectively the problem is corrected with the amine odor and can be covered by the perfume ingredients as described herein.

EXAMPLES The following examples are illustrative of the present invention, but are not intended to limit or otherwise define its scope. All parts, percentages and ratios used here are expressed as weight percent unless otherwise specified. In the following examples, the abbreviated component identifications have the following meaning: linear sodium C12 alkylbenzene sulfonate. TAS Sodium tallow alkyl sulphate. C45AS C14-C15 linear sodium alkyl sulfate, CxyzS Branched alkylsulfate of C-j ^ -C ^ and sodium with z moles of ethylene oxide. C45E7 A predominantly linear primary alcohol of C14-C15 condensed with an average of 7 moles of ethylene oxide. C25E3 A branched primary alcohol of C12-C15 condensed with an average of 3 moles of ethylene oxide. C25E5 A branched primary alcohol of C12 ~ ci5 condensed with an average of 5 mole of ethylene oxide. COCOE02 R1.N + (CH3) (C2H40H) 2 with R - C12"C1 Linear alkylacetazoxide soap from eodium derived from a mixture of 80/20 tallow and coconut oil TFAA Alkyl - N - methylglucamide from C16 - C18 TPKFA Acids fatty acids cut in the upper part of C12 ~? - STPP Anhydrous sodium tripolyphosphate Zeolite A Hydrated sodium aluminosilicate of the formula Na12 (A102s * 02) l2-27H2 ° which has an average particle size in the scale from 1 to 10 NaSKS-6 Crystalline layered silicate of the formula d-Na2Si 05- Citric acid Anhydrous citric acid Carbonate Anhydrous sodium carbonate with a particle size between 200 microns and 900 microns.

BicaFonato BicaFonato of sodium anhydrous with distribution of particle size between 400 microns and 1200 microns. Silicato sodium silicate amorphous ratio of (Si02: Na20 = 2.0). Sodium sulfate Anhydrous sodium sulfate. Citrate trisodium citrate dihydrate of 86.4% activity with a particle size distribution between 425 micrae and 850 micrae. MA / AA Copolymer of maleic / acrylic acid 1: 4, average molecular weight of 70,000. CMC Carboxymethylcellulose sodium. Proteaea Proteolytic enzyme of 4KNPU / g of activity sold by Novo Industries A / S under the trade name Savinase Alcalaea Proteolytic enzyme of 3AU / g of activity sold by Novo Industries A / S Cellulase Cellulose enzyme of 1000 CEVU / g of activity sold by Novo Industries A / S under the trade name Carezyme. Amylase Amylolytic enzyme of 60KNU / g of activity sold by Novo Industries A / S under the trade name Termamyl 60T. Lipase Lipolytic enzyme of lOOkLU / g of activity sold by Lipolase Endolase Enzyme endoglucanase of 3000 CEVU / g of activity sold by Novo Industries A / S PB4 Sodium perborate bleach tetrahydrate of formula NaB02.3H20.H202. PBl Bleaching agent Anhydrous sodium chloride of nominal formula NaB02.H202- Percarbonate PercaFonate of sodium of nominal formula 2Na2C03.3H202. NOBS Nonanoyloxybenzene sulfonate in the form of eal of eodium. TAED Te raaceti leti lendiamina. DTPMP Acido die ti len ria i nopentame ti lenf oef ónico, marketed by Monsanto under the trade name Dequest 2060. Phthalocyanine bleach zinc sulphonated encapsulated photoactivated in bleach polymer soluble in dextrin Brightener 1 4,4'-bis (2-sulfostyril) biphenyl 2,4,4'-bis (4-anilino-6-morpholino) -l, 3,5-triazino-2-yl) amino) stilben-2: 2'-disulfonate brightener. HEDP 1,1-Hydroxy-butyndiphosphonic acid PVNO N-oxide of poly-4-vinylpyridine. PVPVl Copolymer of polyvinylpyrrolidone and vinylimidazole SRA1 Esters blocked at the ends with sulfobenzoyl having a base structure of oxyethyleneoxy and terphthaloyl SRA2 Short block polymer of poly (1,2-propylene terephthalate). Foam controller antifog of polydimethyleisilicone loxane with eiloxane-acial-chileno copolymer as a dielectric agent with a controller ratio of foam to dielectric agent from 10: 1 to 100: 1. In the following examples all levels are given in% in comparison to the composition.

EXAMPLE I The following detergent formulations are prepared according to the present invention, wherein A and C are phosphorus-containing detergent compositions and B is a detergent composition containing zeolite. B Blown powder STPP 24.0 24.0 Zeolite A 24.0 C45AS 8.0 5.0 11.0 MA / AA 2.0 4 .0 2.0- LAS 6.0 8.0 11.0 TAS 1.5 CocoMeE02 * 1.5 1.0 2.0 Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Aeration C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Eylicon foam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 Additive eecoe CaFonate 6.0 13.0 15.0 PB4 .. 0.0 4.0 10.0 PBl 4.0 0.0 0 PercaFonate 18.0 18.0 21.0 TAED 3.0 3.0 0.0 Bleach 0.02 0.02 0.02 photoactivated Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.25 0.30 0.15 Sodium sulfate 3.0 3.0 5.0 mixed dry The rest (humidity 100.0 100.0 100.0 and various components) Density (g / liter) 630 670 670 * The surfactant AQA-1 (CocoMeE02) of the example can be replaced by an equivalent amount of any surfactant AQA-2 to AQA-22 or other surfactants AQA in the present.

EXAMPLE II The following detergent formulations, according to the present invention, are prepared :. S H I Blown powder Zeolite A 30.0 22.0 6.0 Eodium sulphate 19.0 5.0 7.0 MA / AA 3.0 3.0 .... 6.0 LAS 13.0 11.0 21.0 C45AS 8.0 7.0 7.0 CoCoMeE02 * 1.0 1.0. 1.0 Silicato 1.0 5.0 Soap 2.0 Polisher 1 .... 0.2 0.2 0.2, 8.0 16.0 20.0 DTPMP 0.4 .0.4 Aepereión C45E7. 1.0 1.0 1.0 Additives Dry PEA - - 4.0 Agglomerates C45AS - - 9.0 LAS 6.0 5.0 2.0 TAS 3.0 2.0 - Silicate 4.0 4.0 _ Zeolite A 10.0 15.0 13.0 CMC - - 0.5 MA / AA - - 2.0 Carbonate 9.0 7.0 7.0 Spray Perfume 0.3 0.3 0.5 C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 Dry Additives PVPVI / PVNO 0.5 0.5 .. 0.5 Protease 1.0. 1.0 1.0 Lipase • ..0.4 0.4 0.4 Amylase 0.1 0.1 .0.1 Cellulaea .. 0.1 0.1. 0.1 NOBS 0.0 6.1 4.5 PercaFonate 7.0 5.0 6.0 Sodium Sulfate 0.4 Reagent (Humidity and Diversoe Components) .. 100.0 100.0 100.0 The AQA-1 co-surfactant (CocoMeE02) of the example can be replaced by an equivalent amount of any surfactant AQA-2 to AQA-22 or other surfactants AQA herein.

EXAMPLE III The following formulations of high density detergent, according to the present invention, are prepared: Blown powder Zeolite A 15.0 15.0 15.0 Sodium sulphate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 CocoMeE02 * 1.0 1. 5 1.5 DTPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA / AA 4.0 2.0 2.0 Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 _. -. Dry additives Citrate 5.0 2.0 BicaFonate --- 3.0 - Cafonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PBl 13.0 7.0 10.0 MW polyethylene oxide 5,000,000 - - 0.2 Bentonite clay - - 10.0 Proteaea 1.0 1.0 1.0 Lipaea 0.4 0.4 0.4 Amilaea 0.6 0.6 0.6 Cellulaea 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Aditivoe eecoe Eodium sulfate 0.0 3.0 0.0 The reeto (Humidity and component divereoe) for: 100.0 100.0 100.0 Deneity (g / liter) 850 850 850 The AQA-1 tenentective agent (CocoMeE02) of the example ee may be replaced by an equivalent amount of any AQA-2 tenective agent to AQA-22 or other AQA surfactant agents herein. EXAMPLE IV The following high density detergent formulations according to the present invention are prepared: MN Powder blown Zeolite A 2.5 2.5 Sulfate of eodium 1.0 1.0 CocoMeE02 * 1.5 1.5 Agglomerate C45AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA / AA 4.0 2.0 CMC 0.5 0.5 DTPMP 0.4 0.4 Aspersion C25E5 5.0 5.0 Perfume 0.5 0.5 Dry auxiliaries HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 PercaFonate 15.0 15.0 SRA 1 0.3 0.3 Proteaea 1.4 1.4 Lipaea 0.4 0.4 Cellulase 0.6 0.6 Amylase 0. 6 0.6 Eylicon foam 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 Repet (moisture and For: 100 100 components and Deneity (gl / liter) 850 850 The surfactant agent AQA-1 (CocoMeE02) of example ee can be replaced by an equivalent amount of any surfactant AQA-2 to AQA-22 or other surfactant agent AQA in the preamble. The detergents can be compressed using known compression methods to provide detergent tablets. The automatic dishwashing detergents for modern dishes can contain bleaching agents such as hypochlorite, peForate, perc Fonate or persulfate sources, enzymes such as proteaeae, lipaeae and amilaeae or mixtures. of the same rinsing auxiliaries, especially nonionic surfactants, improved detergency, including zeolite and phosphate builders; low foaming detersive surfactants, especially ethylene oxide / propylene oxide condensates. Said compositions typically eethan in the form of granules or gels. If used in gel form, various gelling agents known in the literature can be used. The following Examples A and B further illustrate the invention with respect to a granular detergent for automatic dishwashing containing phosphate.

EXAMPLE V % by weight of material by weight Intransients A B STPP (anhydrous) 1 31 26 Sodium Catalyst 22 32 Silicate (% Si02) 9 7 Surfactant (non-ionic) 3 1.5 Bleach2 from NaDCC 2 AQA-1 * 0.5 1.0 Sodium Perborate 5 TAED 1.5 Savinasa (Au / g) 0.04 Termamyl (Amu / g) 425 Sulfate 25 25 Perfume / co ponentee up to 100% up to 100% sodium dihydrophosphate 2-chlorocyanate sodium time * The AQA-1 surfactant can be replaced by AQA-2 to AQA-22.

EXAMPLE VI The following is a mixture of surfactant agents of AQA which can be substituted for the AQA surfactant agent in any of the foregoing example. As noted above, said mixtures may be used to provide a spectrum of performance benefit and / or to provide cleaning compositions that are useful over a wide variety of conditions of use. Preferably, the AQA surfactants in said mixture differ by at least 1.5, preferably 2.5-20, total EO units. The ratio scales (in weight) for said mix with typically 10: 1-1: 10. Non-limiting examples of said mixtures are the following. Component Relationship (in peeo) AQA-1 + AQA -5 1: 1 AQA-1 + AQA -10 1: 1 AQA-1 + AQA -15 1: 2 AQA-1 + AQA -5 + AQA -20 1: 1 : 1 AQA-2 + AQA -5 3: 1 AQA-5 + AQA -15 1.5: 1 AQA-1 + AQA -20 1: 3 Mixture of the active agent AQA of the present with the active agents and cationic cationic containing only an ethoxylated chain can also be used. Thus, for example, mix of cationic and ethoxylated surfactant of the formula RiN + CHsCEOxCEOOyX "and R1N + (CH3) 2 [E0] zX", where R1 and X are as described above and wherein one of the cationic has (x + y) oz in the range of 1-5 preferably 1-2 and the other has (x + y) oz in the range of 3-100, preferably 10-20, most preferably 14-16, may be in the preeente Such compositions advantageously provide improved detergency performance (especially in a fabric washing context) on a broader scale of water hardness than the cationic surfactants of the present one used individually. It has now been discovered that the EO short-term cationic (eg, E02) improves the cleaning performance of anionic surfactant agent in soft water, while the EO cationic euperioreae (eg, E015) act to improve tolerance to water. hardness of anionic surfactants, thus improving the cleaning performance of anionic surfactants in hard water. Conventional knowledge in the detergency technique suggests that detergency enhancers can optimize the "window" of performance of anionic surfactants. However, haeta has now been unable to achieve the expansion of the window to encompass substantially all the conditions of water hardness.

EXAMPLE VII The following will mix conventional non-AQA surfactants which can be used in combination with the AQA surfactants in any of the foregoing examples, but are not designed to be limiting of the mieme. The ratios of the non-AQA non-AQA agent in the mixtures are annotated in parts by weight of the surfactant mixtures.

Mixtures A-C Ingredientee Relate AS * / LAS 1: 1 AS / LAS 10: 1 (pref 4: 1) AS / LAS 1:10 (pref 1: 4) * As mentioned above, the primary linear, eubertentially linear surfactant AS may be replaced by an equivalent amount of secondary EE or branched chain AS, olenylsulfate, and / or mixtures thereof, including mixing with linear AS, primary as ee mueetra previously. The "seb cea" AS chain length is particularly useful under hot water conditions; until the boiling. The "coconut" AS is preferred for colder wash temperatures. The aforementioned alkyl / anionic surfactant surfactant mixtures are modified by inciphering a nonionic non-ionic surfactant thereon at an anionic ratio (total) to nonionic in the range of 25: 1 to 1: 5. . The nonionic surfactant can be attached from any of the conventional ethoxylated alcohol or phenoxy alkylae, alkyl polyglycoeidoe or polyhydroxy fatty acid amides (less preferred in the present LAS), or mixture of metal, such as those described hereinbefore.

Mezclae DF AS * / AES 1: 1 AS / AES 10: 1 (pref 4: 1) AS / AES 1:10 (pref 1: 4) * May be replaced by secondary, branched or oleyl AS as noted above . The AS / AES mixtures noted above may be modified by incipient the same LAS at a ratio of AS / AES (total) to LAS in the range of 1:10 to 10: 1. Lae mixes of AS / AES or its resultant mix AS / AES / LAS can also be combined with nonionic surfactants as noted for mixtures A-C at weight ratios of anionic (total) to nonionic in the scale of 25: 1 to 1: 5. Any of the aforementioned mixtures can be modified by the incipient in them of an amine oxide tenectant, wherein the amine oxide contains from 1% to 50% of the total mixture of the surface active agent.

Highly preferred combination of the non-AQA agent and non-AQA mentioned above will contain from 3% to 60%, by weight, of the total finished composition of the washing detergent. Lae compoeicionee ter inadae will preferably be 0.25% to 3.5%, in contrast to the AQA teneoactive agent.

EXAMPLE VIII This example illustrates the formulation of perfume (A-C) according to the invention for the incrooration in any of the foregoing examples of detergent-containing compositions containing AQA. Loe varioe ingredé and nivelee ee establish later. 1% by weight) Perfume ingredient A B C Hexal Aldehido Cinnámico 10.0 - 5.0 Propionaldehyde of 2-meti1-3- (para-tert-butylphenyl) 5.0 5.0 - Naphthalene of 7-acetyl-l, 2,3,4,5,6! 5.0 10.0 10.0 7,8-Octahydro-l, l, 6,7-tetramethyl Benzyl salicylate 5.0 - - 6-hexamethyltetraline 10.0 5.0 10.0 7-acetyl-l, 3,4,4,4 Acetate of para- (tert- butyl) 5.0 5.0 -cyclohexyl Methyldihydro jasmonate - 5.0 - Beta-naphthyl methyl ether - 0.5 - Methyl beta-naphthyl ketone 0.5 2-methyl-2- (para-ieo-propylphenyl) - - 2.0 p ropionaldehí do l, 3,4 , 6,7,8-hexahydro-4, 6,6, 7, - 9.5 8,8-hexamethyl-cyclopenta-gamma-2-benzopi rano Dodecahíd ro-3a -6, 6, 9a- tetrameti Inaf - - ol [2,1b] fuh Aniealdehyde ß - 0.5 Cou arina - - 5.0 Ced rol - - 0.5 Vanilina - - 5.0 Cyclopentadecanolide 3.0 10.0 Tricyclodecenyl acetate 2.0 Labdanum reein - - 2.0 Tricyclodecenyl propionate - - 2.0 Ethyl phenyl alcohol 20.0 10. .0 27.9 Terpineol 10.0 5., 0 - Linalol 10.0 10., 0 5.0 Linalil acetate 5.0 - 5.0 Geraniol 5.0 _ • » Nerol - 5.0 2- (1, 2-dimethylethyl) - 5.0 cyclohexanol Aceite de naranja - 5.0 cold pressed Bencil Acetate 2.0 2.0 Orange Terpenes - 10.0 Eugenol - 1.0 Diethyl Phthalate - 9.5 Cold pressed lemon oil - - 10.0 Total 100.0 100.0 100.0 The above perfume compositions are mixed or aerated in (typically at levels up to about 2% by weight of the total detergent composition) of any AQA surfactant containing cleaning compositions (including bleaches) described herein. The improved deposition and / or retention of the perfume or individual components of the same on the surface that are cleaned (or bleached) in this way.

Claims (17)

NOVELTY OF THE INVENTION CLAIMS

1. A composition comprising or prepared by the combination of a peroxygen bleach, a bleach catalyst, a non-AQA tenectant and an effective amount of an alkoxylated quaternary ammonium cationic tenenectant (AQA) of the formula: wherein r is an alkyl, alkenyl, aryl, alkaryl, ether or branched or substituate C8-C18 glycrylic ether moiety, R2 and an alkyl portion of C- ^ - Cg, R3 and R ^ can independently vary and are selected from hydrogen , methyl and ethyl, X is an anion, A is C4-C4 alkoxy and p ee is an integer in the scale of 2 to 30.

2. A composition according to claim 1, further characterized in that the peroxygen bleach is It selects from the group that connects the pre-formed peleate, percarbonate, perforate, persilicate or persulfate or peracid thereof.

3. - A composition according to any of claim 1 or 2, further characterized in that the bleach catalyst is a bleach catalyst containing manganese or cobalt.

4. A composition according to any of claims 1 or 3, which is prepared by mixing the non-AQA surfactant and the AQA surfactant.

5. A composition according to any of claims 1 to 4, further characterized in that the non-AQA non-AEC agent is an anionic teneuron agent.

6. A composition according to any of claims 1 to 5, characterized in that the ratio of AQA to non-AQA non-AQA agent is from 1:15 to 1:18.

7. A composition according to any of claims 1 to 6, further characterized in that said cationic surfactant of AQA, R1 is alkyl of C8-C18, R2 is methyl, A is an ethoxy or propoxy group and p is an integer from 2 to 8.

8. A composition according to any of claims 1 to 7, further characterized in that in said cationic AQA teneioactive agent. , R 1 is alkyl Cg-C ^ g, R2 ee methyl, A is an ethoxy or propoxy group and p is an integer from 2 to 4.

9. A composition according to any of claims 1 to 8, comprises two or more teneoactive agents of AQA , or a mixture of surfactant of AQA and an ono-ethoxylated cationic surfactant.

10. A composition according to any of claims 1 to 9, comprises doe or more non-AQA surfactant agents and a mixture of two or more teneoactive agents of AQA.

11. A composition according to any of claims 1 to 10 in a granulated form, bar, liquid aqueous or liquid non-aqueous, or tablet.

12. A method for removing dirt and stains by contacting talee euciedadee and manchae with a detergent composition, or an aqueous medium containing said detergent composition, according to any of claims 1 to 10.

13.- A method in accordance with the claim 12 to remove the senesible dirt to enzymae from the fabrics.

14. A method according to any of claims 12 to 13 carried out in an automatic machine.

15. A method according to any of claims 12 to 14 which is carried out by hand.

16. A method for improving the deposition or substantive character of perfumes or ingredients of perfumes in fabrics or other surfaces, comprising contacting such surfaces with a perfume or perfume ingredient in the presence of an AQA surfactant.

17. - A method according to claim 18, which is carried out using a perfume or perfume ingredient in combination with a detergent composition comprising an AQA.