MXPA98009632A - Deterge composition - Google Patents

Abstract

A detergent composition comprising a soil release agent, a non-AQA surfactant and an alkoxylated quaternary ammonium cationic surfactant (AQ)

Description

DETERGENT COMPOSITION TECHNICAL FIELD The present invention relates to a detergent composition comprising a soil release agent, 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, and thus are notoriously difficult to remove. An additional problem is to find in the form of lime soap deposits; the ion salt of insoluble hardness (ie, Ca2 + / Mg2 +) or fatty acids derived from the degradation of triglyceride soils. Lows, levels of hydrophobic soils, residual stains, and lime soap deposits often remain on the surface of the fabric after washing. The successive washing and use coupled with the limited removal of dirt, stains and deposits in the wash culminates in an accumulation in the fabric that also traps dirt in particles leading to yellowing of the fabric. Finally, the cloth acquires a dirty appearance that the consumer perceives as unusable and disposable. 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 discovered that certain alkoxylated quaternary ammonium compounds (AQA) can be used in various detergent compositions to increase the detergency performance in a variety of dirt and stain types, particularly the commonly encountered types of hydrophobic soils. 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, the 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 cationic surfactants to date. 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.

*** 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 soil release agent (SRA), a non-AQA surfactant and an effective amount of an alkoxylated quaternary ammonium cationic surfactant (AQA) of the formula: wherein R is an alkyl portion with alkenyl, aryl, alkanyl, ether or linear, branched or substituted 8-C? _3 alkyl, R 2 is a C 1 -C 3 alkyl portion, R 3 and R 4 can vary independently and are selected from hydrogen , methyl and ethyl, X is an anion, and A is a C1-C alkoxy, p may vary from 2 to 30.

BRIEF DESCRIPTION OF THE INVENTION Dirt releasing agent The known polymeric soil release agents, hereinafter "SRA" or "SRA's", can optionally be employed 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's typically have hydrophilic segments to hydrophilize the surface of the hydrophobic fibers such as polyester and nylon, and the hydrophobic segments to deposit on and remain adhered to the hydrophobic fibers through the completion of the wash and rinse cycles, thus serving as an anchor for the hydrophilic segments. This can make it possible for stains that occur after treatment with the SRA to be cleansed more easily in subsequent washing procedures. SRA's may include a variety of charged, eg, anionic or even cationic species; see the patent of E.U.A. No. 4, 956,447, issued September 11, 1990 to Gosselink et al., As well as monomer uncharged units and their structures which may be linear, branched and even star-shaped. They may include end blocking portions that are especially effective in controlling molecular weight or altering active surface or physical properties. The structures and load distributions can be designed for application to different types of fibers or textiles and for detergent products or various detergent additives. Preferred SRAs 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. Said esters can be manufactured using additional monomers capable of being incorporated into the ester structure through uan, two, three, four or more positions, without, of course, forming a densely intertwined overall structure.

SRA's include: a sulfonated product of a substantially linear ester oligomer composed of an oligomeric ester base structure of terephthaloyl and oxyalkylenoxy repeat units and sulfonated terminal portions derived from allyl covalently bonded to the base structure, for example, as describes in the USA 4,968,451, November 6, 1990 to J.J. Scheibel and E.P. Gosselink: said ester oligomers can be prepared a) by ethoxylating alkyl alcohol, b) by reacting the product of (a) with dimethylterephthalate ("M¿DMT") and 1,2-propylene glycol ("PG") in a transesterification process / two-step oligomerization and c) reacting the product of (b) with sodium metabisulfite in water; the 1,2-propylene / polyoxyethylene terephthalate polyesters of non-ionic blocked ends of the U.S. patent. No. 4,711,730, December 8, 1987 to Gosselink et al., For example those produced by the transesterification / oligomerization of polyethylene glycol methyl ether, DMT, PG and polyethylene glycol ("PEG"); the oligomeric esters of anionic blocked ends partially and completely of the U.S. patent. No. 4,721,580, Jan. 26, 1988, from Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctansulfonate; the non-ionic blocked block polyester oligomeric compounds of the U.S.A. 4,702,857, dated October 27, 1987 from Gosselink, 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-sulfoisophthalate; 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 Gosselink and others, the latter being typical of SRA's useful in both fabric conditioning and laundry products, one example being an ester composition made from the monosodium salt of the acid m-sulfobenzoic, PG and DMT, optionally but preferably further comprising added PG, e.g., PEG 3400. SRA's also include: simple copolymer blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or sodium oxide terephthalate polypropylene, see the US patent 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 derivatives such as the cellulosic hydroxyether polymers available as METHOCEL from Dow; the C1-C4 alkylcelluloses and C4 hydroxyalkylcells of the U.S. patent. No. 4,000,093, of December 28, 1976 to Nicol, and others. Suitable SRAs characterized by hydrophobic polyvinylmethyl ether segments include polyvinyl ether graft copolymers, e.g., C?-Cg vinyl ethers, preferably polyvinylacetate, grafted onto polyalkylene oxide base structures. See European patent application 0 219 048, published on April 22, 1987 by Kud et al. Commercially available examples include SOKALAN SRA's such as SOKALAN HP-22, available from BASF, Germany. Other SRA's are polyesters with repeating units having 10-15% by weight of ethylene terephthalate together with 80-90% by weight of 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)] _, which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1 units , 2-propylene (EG / PG), and which preferably terminates with end blocks (CAP), preferably modified isethionates, as in an oligomer comprising a sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxyl, 2-propylenexi units in a relationship defines, preferably from about 0.5: 1 to about 10: 1, and two end blocking units derived from 2- (2-hydroxyethoxy) -ethanesulfonate. Said SRA preferably comprises from 0.5% to 20% by weight of the oligomer of a crystallinity reduction stabilizer, for example an anionic surfactant such as linear dodecylbenzenesulfonate or a member selected from xylene-, cumen- and toluenesulfonate or mixtures thereof, these stabilizers or modifiers being introduced into the synthesis vessel, all as taught in the US patent No. 5,415,807, Gosselink Pan, Lellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include Na-2 (2-hydroxyethoxy) -ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG. Yet another group of preferred SRA's 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, by of which ester bonds resulting in a branched oligomeric base structure, and combinations thereof, are formed; (b) at least one unit that is a terephthaloyl moiety; and (c) at least one non-sulfonated unit which is a 1,2-oxyalkylenoxy portion; and (2) one or more blocking units selected from non-ionic blocking units, anionic blocking units such as alkoxylated isethionates, preferably ethoxylated, alkoxylated propansulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives, and mixtures thereof. The esters of the empirical formula are preferred:. { (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 are as defined above, (DEG) represents 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, by means of which ester bonds are formed which result in a branched oligomer base structure, x is from about 1 to about 12, and 'is from about 0.5 to about 25, and' ' is from 0 to about 12, and '' 'is from 0 to about 10, and' + y '' + y '' sum in total from about 0.5 to about 25, z is from about 1.5 to about 25, z 'is from about 0 to about 12; z + z 'sum total of about 1.5 to about 25, which is about 0.05 to about 12; m is from about 0.01 to about 10, and x, y ', and' ', and' '', z, z ', q and m represent the average number of moles of the corresponding units per mole of said ester, and said ester has a molecular weight ranging from about 500 to about 5,000. Preferred SEG and CAP monomers for the above esters include sodium 2- (2,3-dihydroxypropoxy) -ethansulfonate ("SEG"), 2-. { 2- (2-hydroxyethoxy) ethoxy} sodium acetate sulfonate ("SE3") and homologues and mixtures thereof, and the products of ethoxylation and sulphonation of allylic alcohol. Preferred SRA esters in this class include the transesterification and oligomerization product of 2-. { 2- (2-hydroxyethoxy) ethoxy} sodium ethane sulfonate and / or 2- [2-. { 2- (2-hydroxyethoxy) ethoxy} sodium ethoxy] ethane sulfonate, DMT, sodium 2- (2,3-dihydroxypropoxy) 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 [CH2CH 0] 3.5) - and B is a glycerin unit, and the mass ratio of EG / PG is about 1.7: 1 measured by conventional gas chromatography after complete hydrolysis. Additional classes of SRA's 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 Lagasse et al., And (II) SRA's with carboxylate end groups made by adding trimethyl anhydride to known SRA's to convert terminal hydroxyl groups to trimethylate esters. With the proper selection of the catalyst, trimethyl anhydride forms bonds to the polymer terminals through a carboxylic acid ester isolated from the trimethyl anhydride instead of opening the anhydride linkage. Either non-ionic or anionic SRAs can be used as starting materials, as long as they have hydroxyl end groups that can be esterified, see E.U.A. No. 4,525,524 Tung and others. Other classes include (III) non-anionic terephthalate-based SRAs 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 dimethylaminethylacrylate, including nonionic and cationic polymers, see E.U.A. 4,579,681, Rupper et al., (V) graft copolymers, in addition to the SOKALAN types of BASF, manufactured by grafting acrylic monomers to sulfonated polyesters. These SRA's have soil release and antiredeposition activity similar to the known cellulose ethers: see EP 279,134 A. 1988 to Rhone Poulenec Chemie. Other classes also include: (VI) vinyl monomer grafts such as acrylic acid and vinyl acetate in proteins such as caseins, see EP 457,205 A to BASF (1991); and (VII) Polyester-polyamide SRA's 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 useful in the U.S. Patents. Nos. 4,240,918, 4,787,989, 4,525,524, and 4,877,896. Other soil release agents include materials with starch base structures with polycarboxylic acid groups grafted thereto. Alkoxylated quaternary ammonium cationic surfactant (AQA) The second essential component of the present invention comprises an effective amount of an AQA surfactant of the formula: wherein R 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; R is an alkyl group containing from 1 to 3 carbon atoms, preferably methyl; R and R may 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., CH2CH2O-), 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 R 1 hydrocarbyl substituent is especially 8-C] o, improves the dissolving speed of laundry granules, especially under cold water conditions, as compared to materials of higher chain length. Accordingly, some formulators may prefer the C3-C12 AQA surfactants. 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% level of confidence, the development of the cleaning composition against at least some of the the dirt and target spots. In this way, in a composition whose objectives include certain food stains, the formulator will use sufficient AQA to improve at least directionally the development of cleaning against such stains. 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 translates into 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) from 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 translates into 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 surfactant AQA in the liquor of Based on the usage 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 d e washing, for dense ("compact") laundry detergents (density above 650 g / 1), this results in a concentration of the AQA surfactant in the product (weight) of 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 AQAanionic / nonionic mixture is in the range 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 surfactants in such compositions . Again, as in the case of 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 the 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 typically will comprise anionic: nomonic ratios on the scale 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 -CH2CH2O-), as follows.

SCHEME 1 R'OH * CH, NH2 H2 / < at Cal0r. R! -N CHí? EXCESS Q & - te-B RÍ-N- (EO) n-: calar CH3 RI-N- (EO) n-H + CH3C1 (= S £ - ~ R-N-- <EO) n-H CH3 cr SCHEME 2 "D__GL_COG0__iMD___" R'BG * SCHEME 3 SCHEME 4 O SbCl * CAT CI-CH2CH2-OH + n _ s ** • Cl- CH2CH2? [EO] n- H R An economic reaction scheme is as follows.

SCHEME 5 Na2S04 + H-O 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.

The reaction pressures are from 3.51 to 70.3 kg / cm2 monometric. A base, preferably sodium hydroxide, may be used to react with HSO4 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 step of recovering the product, 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 an autoclave glass liner were added 156.15 g of sodium dodecylsulfate (0.5415 moles), 81.34 g of 2-methylaminoethanol (1.083 moles), 324.5 g of distilled H2O and 44.3 g. g of 50% by weight sodium hydroxide solution (0.5583 moles of NaOH). The glass liner 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 nitrogen during 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 separated into a lower layer layer, medium turbid layer and clear top layer. The clear top 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 additional salts crystallize. The liquid is filtered under vacuum to remove salts 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 solids and again a clear, colorless liquid is obtained that remains stable. The clear, colorless liquid isolated is the product of the title by NMR analysis and it is > 90% by GC analysis with a typical recovery of > 90% The amine is then ethoxylated in a standard manner. Quaternization with an alkyl halide to form the AQA surfactants herein is a routine. In accordance with the foregoing, the following are non-limiting, specific illustrations of AQA surfactants used herein. It will also be understood that the degree of alkoxylation noted herein for the AQA surfactants is reported as an average, followed by the common tactic for conventional ethoxylated nonionic surfactants. 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.

Disinnation RA E RJ Alkoxylation AQA-1 Cl2 - C14 CH3 CH3 E02 AQA-2 C? O- "Cl6 CH3 CH3 E02 AQA-3 Cl2 CH3 CH3 E02 AQA-4 c14 CH3 CH3 E02-3 AQA-5 c10_c18 CH3 CH3 EO5-8 AQA-6 C12_c14 C H5 CH3 E03-5 AQA- 7 c14_c16 CH3 C3H7 (EO / PrO) 4 AQA-8 c12"c14 CH3 CH3 (PrO) 3 AQA-9 c12-c18 CH3 CH3 EO10 AQA-10 C8-C18 CH3 CH3 E015 AQA -11 C10 C2H5 C2H5 EO3.5 AQA-12 c10 CH3 CH3 E02.5 AQA-13 c10 CH3 CH3 E03.5 AQA-14 c10 C4H9 C4H9 EO30 AQA- 15 C8C14 CH3 CH3 E02 AQA-16 C10 CH3 CH3 EO10 AQA-17 C12c14 C3H9 C3H7 Bu4 AQA- 18 C12c18 CH3 C4H9 E05 AQA-19 c8 CH3 CH3 iPr3 AQA-20 c8 CH3 CH3 E03_7 AQA-21 Cl2 CH3 CH3 E03.5 AQA-22 Cl2 CH3 CH3 EO4.5 Highly preferred AQA compounds for use herein are of the formula; wherein R1 is CQ-Q hydrocarbyl and mixtures thereof, preferably Cß-C, alkyl; c12 'c14 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 (CH2CH20) (EO) units are replaced with butoxy (Bu) isopropoxy [CH (CH3) CH0] and units [CH CH (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 those of the formula wherein p is an integer in the range of between 10 and 15. This compound is particularly useful in hand washing 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 Examples Non-limiting examples of surfactants useful here typically at levels of 1% to 55% by weight include alkylbenzene sulphonates ("LAS") from conventional and branched chain primary alkyl ("AS") alkyl sulphides ("AS") and random, the secondary alkyl sulfates (2,3) of C10-C18 of the formula CH3 (CH2) x (CHOS03"M +) CH3 and CH3 (CH2) and (CHOS03" M +) CH2CH3 where x and (y +1) are integers of at least 7, preferably at least about 9, and M is a cation for solubilization in water, especially sodium, unsaturated sulaphthates such as oleyl sulfate, alkyl alkoxysulfates of C? _o_ci8 ("AEXS", especially ethoxysulfates EO 1-7 ), alkylalkoxycarboxylates of] _o- i8 (especially the ethoxycarboxylates EO 1-5). C12"c18 betaines and sulfobetaines (" sultaines "), amine oxides of C] _Q-c18 'Y similar, can also be included in the overall compositions.Conventional IQ soaps can also be used" C20- If desired high foaming, branched chain C? o_c16 soaps can be used. Other useful conventional surfactants are listed in standard textbooks.

Nonionic Surfactants Examples Non-limiting examples of surfactants useful here typically at levels of 1% to 55% by weight include alkoxylated alcohols (AE) and alkylphenols, polyhydroxy fatty acid amides (PFFAA), alkyl polyglycosides (APG), glycol ether ? o ~ Ci8 * 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 nonionic surfactant of the present invention. The alkyl chain of the aliphatic alcohol may be either 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 commercially available nonionic surfactants of this type include Tergitol ™ 15-S-9 (the linear alcohol condensation product of C] _t_-C? _5 with 9 moles of ethylene oxide), Tergitol ™ 24-L- 6 NMW (the primary alcohol condensation product of C] _2 ~ C14 with 6 moles of ethylene oxide with a limited molecular weight distribution), both marketed by Union Carbide Corporation; Neodol TM 45-9 (the linear condensation product of C14-C15 with 9 moles of ethylene oxide), Neodol ™ 23-3 (the linear alcohol condensation product of Ct_2-C? _3 with 3.0 moles of oxide of ethylene), Neodol ™ 45-5 (the linear condensation product of C14-C15 with 7 moles of ethylene oxide), Neodol ™ 45-5 (the linear condensation product of c14"c15 with 5 moles of ethylene), marketed by Shell Chemical Company, Kyro ™ EOB (the condensation product of C13-C-L5 alcohol with 9 moles of ethylene oxide), marketed by The Procter &Gamble Company, and Genapol LA 050 (the product of condensation of C 2 -Cl 4 alcohol with 5 moles of ethylene oxide) marketed by Hoechst The preferred scale of HLB in these products is 8-11, and most preferred is 8-10 Another class of surfactants Preferred nonionics for use herein are the fatty acid amide surfactants of the formula: R2 - C - N - Z, Rl wherein R 1 is H, or R 1 is hydrocarbyl of Ct__4, 2-hydroxyl, 2-hydroxypropyl or a mixture thereof, R "* is hydrocarbyl of C5_3 ?, and Z is a polyhydroxycarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to the chain, or an alkoxylated derivative of the mimes.

Preferably, Ri is methyl, R_? is a straight alkyl or alkenyl chain of C? _? __? _ 5 ta --- such as cocoalkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose, in an amination reaction reductive Typical examples include the N-methylglucamines of C? 2 ~ c18 and c12"c14- See E.U.A. 5,194,639 and ,298,636. N-alkoxy polyhydroxy fatty 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 alkylpolysaccharides described in the U.S. Patent. 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 substitute the glucoside proportions (optionally the hydrophobic group will adhere at positions 2, 3, 4, etc.). , thus giving a glucose or galactose as opposed to glucoside or galactoside). Intersaccharide bonds can be, eg, between position 1 of the additional saccharide units and positions 2, 3, 4 and / or 6 in the above saccharide units. Preferred alkyl polyglycosides have the formula R20 (CnH nO) t (glycosyl) x wherein R "* is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and meats thereof in which the alkyl groups contain about from 10 to about 18, preferably from about 12 to about 14 carbon atoms, N is 2 or 3, preferably 2; t is from or to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to The glycosyl is preferably derived from glucose.To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first formed and then reacted with glucose, or a source of glucose, to form the glucoside (fixation in the bead 1). The additional glycosyl units can then be adhered between their position 1 position 2, 3, 4 and / or 6 of the above glycosyl units, preferably p redominating the position 2. The condensates of polyethylene oxide, polypropylene, and polybutylene of alkylphenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with condensates of polyethylene oxide being preferred. These compounds include the condensation products of alkylphenols 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 surfactants of this type incubate Igepal ™ CO-630, manufactured by GAF Corporation; and Triton ™ X-45, X-114, X-100 and X-102, all manufactured by Rohm &; Haas Company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkylphenol ethoxylates). The condensation products of ethylene oxide 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 insolubility in water. 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 to the point where the polyoxyethylene content is about 50% of the total product weight of the product. 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 ™ surfactants, 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 properties comprising at least one ester link (ie, -C00-) and at least one cationically charged group. Other suitable anionic surfactants include the quaternary ammonium surfactants selected from N-alkyl or alkenyl surfactants of Cg-C ^ g, preferably Cg-C ^ or wherein the remaining N positions are substituted by methyl, hydroxyethyl or hydroxypropyl groups . Other cationic ester surfactants, including choline ester surfactants, have been described, for example, in U.S. Pat. Nos. 422,8042, 4239660 and 4260529.

Additional Detergent Ingredients The following illustrates several other optional ingredients that can be used in the compositions of this invention, but are not intended to be limited thereto.

Detergency Meters Detergency builders may optionally be included in the compositions herein to help control mineral hardness, especially Ca and / or Mg, hardness in the wash water or to aid in the removal of particulate soils. The surfaces. The detergency builders can operate through a variety of mechanisms including the formation of soluble or insoluble complexes with hardness ions, by ion exchange, and offering a surface more favorable to the precipitation of hardness ions than are the surfaces that have to be cleaned. The level of builder can vary greatly depending on the final use 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 builder. The granulated formulations typically comprise from 10% to 80%, very typically from 15% to 50% by weight, of the builder of the detergent composition. The lower or higher levels of detergency builder are not excluded. For example, a certain detergent additive or formulations with high surfactant content may not have a builder. Suitable builders can be selected from the group consisting of phosphates and polyphosphates, especially the sodium salts; silicates 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, bicarbonates, sesquicarbonates and carbonate minerals other than carbonate or sesquicarbonate; aluminosilicates; organic mono, di, tri and tetracarboxylates especially carboxylates having no water-soluble surface active agent in the form of an acid, sodium, potassium or alkanolammonium salt, as well as oligomeric or water-soluble, olecular polymer polymers including aliphatic and organic types aromatic; and phytic acid. These may be supplemented with borates, for example, for pH regulation purposes, or by sulfates, especially sodium sulfate and any other fillers or vehicles that may be important for engineering detergent compositions containing stable surfactant and / or builder. detergency Mixtures of builders, sometimes referred to as "builders systems", can be used and typically comprise two or more conventional builders, optionally supplemented by chelators, pH regulators or fillers, although the latter materials are considered separately when material quantities are described herein. In terms of relative amounts of surfactant and builder in the detergents herein, preferred builder systems are typically formulated in a weight ratio of surfactant to builder from 60: 1 to 1:80. Certain preferred laundry detergents have said ratio in the range of 0.90: 1.0 to 4.0: 1.0, most preferably 0.95: 1.0 to 3.0: 1.0. P detergent builders often preferred where permitted by law include, but are not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphates illustrated by tripolyphosphates, pyrophosphates, vitreous polymeric metaphosphates and phosphonates. Suitable silicate builders include alkali metal silicates, particularly those liquids and solids having a ratio of SiO2: Na20 in the scale of 1.6: 1 3.2: 1, including particularly for purposes of automatic dishwashing, silicates of 2 solid water relations by PQ Corp. under the trade name BRITESILR, v.gr., BRITESIL H20; and stratified silicates, for example those described in US Patent 4,664,839, May 12, 1987, H. P. Rieck. NaSKS-6, sometimes abbreviated "SKS-6", is a silicate of S-Na2Si? 5 morphology free of crystalline stratified aluminum from Hoechst and is especially preferred in granular laundry compositions. See preparation methods in German Patent DE-A-3,417,649 and DE-A-3,742,043. Other layered silicates such as those having the general formula NaMsix? 2? +? * yH2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, e and is a number from 0 to 20, preferably 0, may also be used or may be used alternately. Hoechst layered silicates also include NaSKS-5, NaSKS-7 and NaSKS-11, as the silicate forms of layers A, β and 6. Other silicates, such as magnesium silicate that can serve as an agent, can also be useful. crisper in granules, as a stabilizing agent for bleaches and as a component of foam control systems. Also suitable here are the crystalline ion exchange materials synthesized or the hydrates thereof having chain structure and a composition represented by the following general formula in acid form: xM20 and Si02. zM'O where M is Na and / or K,, M 'is Ca and / or Mg; y / z is 0.55 to 2.0 and z / 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 earth metal carbonates as is disclosed in German Patent Application No. 2,321,001 published on November 15, 1973, although sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonate minerals such as trona or any convenient sodium carbonate multiple salts and calcium carbonate such as those having the composition 2Na2C03.CaC03 when in anhydrous form and even calcium carbonates including calcite, aragonite and vaterite, especially shapes having surface areas relative to compact calcite may be useful, for example as seeds or for use in synthetic detergent bars. The aluminosilicate builders are especially useful in granular detergents, but can also be incorporated in liquids, pastes or gels. Suitable for the present purposes are those that have the empirical formula: Mz [(ZA102) and] .xH20 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 is a whole from 15 to 264. Aluminosilicates can be crystalline or amorphous, natural or synthetically derived. One method for producing aluminosilicates is in US Patent 3,985,669, Krummel et al. Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are available under the designations Zeolite A, Zeolite P (B), Zeolite X and, to whatever degree it differs from Zeolite P, the so-called Zeolite MAP. Natural types can be used, including clinoptilolite. Zeolite A has the formula: Na] _ [(A102) 12 (SÍO2) i2J? H2 ° where x is around 20 to 30, especially 27. Dehydrated zeolites (x = 0 - 10) can also be use in the present. Preferably, the aluminosilicate has a particle size of about 0.1-10 microns in diameter. Suitable organic builders include water-soluble non-surfactant dicarboxylates and tricarboxylates. Very typically, the builder polyetherboxylates have a plurality of carboxylate groups, preferably at least 3 carboxylates. The carboxylate builders can be formulated in acid, partially neutral, neutral or overbase form. When they are in salt form, the alkali metal salts, such as sodium and potassium, as well as lithium or alkanolammonium are preferred. Polycarboxylate builders include ether polycarboxylates, such as oxydisuccinate, see Berg, U.S. 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 builders of the U.S.A. 4,663,071, issued to Bush and others on May 5, 1987; and other ether carboxylates including cyclic compounds and alicyclic compounds, such as those described in the U.S. Patents. 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-trisulphonic acid, and carboxymethyloxy-succinic acid, various alkali metal, ammonium and ammonium salts. substituted ammonium of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as mellitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof. The 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 its 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 permitted and especially in bar formulations used for hand washing operations, various alkali metal phosphates such as the well-known sodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphate can be used. Phosphonate detergency builders such as ethan-1-hydroxy-1,1-diphosphonate and other known phosphonates, for example, patents 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 detersive surfactants or their short chain homologs also have a builder action. For purposes that have unambiguous formula, when they have surfactant capability, these materials are considered surfactants. Preferred types for builder functionality are illustrated by: 3, 3-dicarboxy-4-oxa-1, 6-hexanediates and the related compounds described in the U.S.A. 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the alkyl and alkenyl succinic acids of C5-C20 and salts thereof. Succinate builders also include: lauryl succinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group, and are described in European patent application 86200690.5 / 0,200,263, published on November 5, 1986.

Fatty acids, e.g., 2-1-20-valent monocarboxylic acids may also be incorporated into the compositions as surfactant / builder materials to provide additional 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. Other types of inorganic builders materials that can be used have the formula (Mx) -_ 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, H ^ are cations, at least one of which is soluble in water and the equation d1 = l-15 (multiplied by the valence of M¿) + 2y = 2z is satisfied in such a way that the formula It has a neutral or "balanced" charge. These builders are known herein as "mineral builders". Hydration waters or anions other than carbonate can be added as long as the overall load is balanced or neutral. The charge or valence effects of said anions must be added to the right side of the previous equation. Preferably, a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon and mixtures thereof, most preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, is present. , sodium and potassium being highly preferred. Non-limiting examples of non-carbonate anions include those selected from the group consisting of 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 Na2Ca (C03) 2, K2Ca (C03) 2, Na2Ca2 (C03) 3, NaKCa (C03) 2, NaKCa2 (C03) 3, K2Ca2 (C03), and combinations thereof. A material espcially. Preferred for the detergency builder described herein is Na2Ca (C03) 2 in any of its crystalline modifications. Suitable detergency builders of the type defined above are further illustrated and include natural or synthetic forms of any or combinations of the following minerals: afghanite, andersonite, ascroftine Y, beierite, borcharite, burbanquita, butscliita, cancrinite, carbocernaite, carletonite, davina , Donnaita Y, Fairchildite, Ferrisurita, Franzinita, Gaudefroita, Gaylusita, Girvasita, Gragorita, Jouravskita, Kamfaugita, Ketnerite, Kanesita, L.epersonitaGd, Lyotita, MckelveitaY, Microsomite, Mroseita, Natrofaircildita, Nyerereita, RemonditaCe, Sacrofanita, Scrockingerita, Sortita, surita, tunisita, tuscanita, tyrolita, visnevita, and zemkorita. The mineral forms include nyererita, faircildita and sortita.

*** The preferred amide derivative bleach activators are those of the formulas: R1N (R5) C) 0) R2C (0) LO R - C (0) N (R5) R2C (0) L wherein R is an alkyl group containing from about 6 to about 12 carbon atoms, R2 is an alkylene containing from 1 to about 6 carbon atoms, R 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 perhydrolysis anion. A preferred residual group is phenylsulfonate. Preferred examples of bleach activators of the above formulas include (6-octanamido-caproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate and mixtures thereof as described in the patent of E.U.A. 4,634,551 which is incorporated herein by reference. Another class of bleach activators includes activators of the benzoxazine type described by Hodge et al. In the U.S. Patent. 4,966,723 issued October 30, 1990, which is incorporated herein by reference. A highly preferred bleach activator of the benzoxazine type is: Yet another class of preferred bleach activators includes acyl-lactam activators, especially acylcaprolactams and acylvalerolactams of the formulas: wherein R is H or an alkyl, aplo or alkaryl group containing from 1 to about 12 carbon atoms. Highly preferred lactam activators include benzoylcaprolactam, octanoylcaprolactam, 3, 5, 5-trimethyl-hexanoylcaprolactam, nonanoylcaprolactam, decanoylcaprolactam, undecenoylcaprolactam, benzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam, undecenoylvalerolactam, nonanoylvalerolactam, 3,5,5-trimethylhexanoylvalerolactam and mixtures thereof. 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.

Bleach catalyst Bleach catalysts are preferred components of compositions of the present invention which, in addition to the photobleach, comprise an oxygen-liberating bleaching agent. Bleach catalysts are well known in the art and include, for example, the manganese-based catalysts described in the U.S.A. No. 5,246,621, patent of E.U.A. No. 5,244,594, patent of E.U.A. No. 5,114,606 and you are from pat. European pub. Nos. 549,271A1, 549,272A1, 544,440A2 and 544,490A1. Preferred examples of these catalysts include Mn 2 (u-0) 3 (1,4, 7-trimethyl-1,4,7-triazacyclononane) 2- (PFg) 2, MnIu 2 (u-0) i (u-OAc) 2 (1,4, 7-trimethyl-1,4,7-triazacyclonono-nano) 2- (CIO 4) 2, MnIV 4 (u-0) g (1,4,7-triazacyclononane) 4- (CIO 4) 2, Mn ^ j n1 ^ (u-0) 1 (u-OAc) 2 (1,4, 7-trimethyl-1,4, 7-triazacyclo-nonane) - (CIO4) 3, MnIV (1, 4, 7- trimethyl-l, 4,7-triazacyclononane) - (0CH3) 3 (PFg) and mixtures thereof. Other metal-based catalysts include those described in the U.S.A. 4,430,243 and patent of E.U.A. 5,114,611. The use of manganese with several complex ligands to improve bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161 and 5,227,084. As a practical matter, and not by way of limitation, the compositions and methods herein can be adjusted to provide in the order of at least one part per ten million of the active bleach catalyst species in the aqueous wash liquor, and will preferably provide about 0.1 ppm to about 700 ppm, most preferably about 1 ppm to about 500 ppm of the catalyst species in the wash liquor. Cobalt bleach catalysts useful herein are known being described for example together with their base hydrolysis rates in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes", Adv. Inorq. Bioinor Mech. , (1983), 2, pages 1-94. The most preferred cobalt catalysts useful herein are cobalt pentaaminoacetate salts having the formula [Co (NH3) _ 5OAC] Ty, wherein OAc represents an acetate portion, and especially cobalt pentaaminoacetate chloride, [Co ( NH3) 50Ac] Cl; as well as [Co (NH3) 50Ac] (OAc) 2); [C (NH3) 50Ac] (PFg) 2; [Co (NH3) 50Ac] (S04); [Co (NH3) 5OAc] (BF4) 2; and [Co (NH3) 5OAc] (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, .L. Jolly (Prentice-Hall, 1970), pp. 461-3; Inorq. Chem. 18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and Journal of Physical 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 species of active bleach catalyst in the aqueous wash medium, and preferably provide from 0.01 ppm to 25 ppm, most preferably from 0.05 ppm to 10 ppm, and most preferably still from 0.1 ppm to 5 ppm of the bleach catalyst species in the wash solution. To obtain such levels in the washing solution of an automatic dishwashing process and the typical dishwashing automatic washing compositions herein will comprise from 0.0005% to 0.2%, most preferably from 0.004% to 0.08%, of bleach catalyst, especially manganese or cobalt catalysts, by weight of the cleaning compositions.

Enzymes Enzymes may be included in the present detergent compositions for a variety of purposes, including the removal of protein-based, carbohydrate-based or triglyceride-based stains from surfaces such as textiles or tableware, for the prevention of the transfer of migratory dye, for example in the washing of clothes and for the restoration of the fabric. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases and mixtures thereof of any suitable origin, for example of vegetable, animal, bacterial, fungal and yeast origin. Preferred selections are influenced by factors such as pH activity and / or stability optima, thermostability and stability to active detergents, builders and the like. In this regard, bacterial or fungal enzymes, such as bacterial amylases and proteases and fungal cellulases, are preferred. The term "detersive enzyme", as used "agui", means any enzyme that has a beneficial effect of cleaning, stain removal or any other beneficial effect in a laundry detergent, hard surface cleaning or personal care composition. Detersive enzymes that are preferred are hydrolases such as proteases and amylases. Enzymes that are preferred for laundry purposes include, but are not limited to, proteases, cellulases and peroxidases. The amylases and / or proteases for automatic dishwashing are widely preferred, including both commercially available types and improved types, which, while becoming increasingly compatible due to successive improvements, still have some degree of susceptibility to deactivation of the bleach. Enzymes are normally incorporated in detergent or detergent additive compositions at levels sufficient to provide an "effective cleaning amount". The term "effective cleaning amount" refers to any amount capable of producing a cleaning, stain removal, dirt removal, whiteness, deodorizing or freshness enhancing effect on substrates such as fabrics, tableware and the like. In practical terms for current commercial preparations, typical amounts are from about 5 mg by weight, more typically about 0.01 mg to about 3 mg, of active enzyme per gram of composition. Stated otherwise, the compositions herein will typically consist of from about 0.001% to about 5%, preferably 0.01% -1% by weight of a commercial enzyme preparation. Protease enzymes are 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, 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 thereby improve splashes / films or other results. final. Higher active levels in highly concentrated detergent formulations may also be desirable. Suitable examples of proteases are the subtilisins that are obtained from particular strains of B. subtilis and B. licheniforms. Other suitable proteases 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 Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme 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., The Netherlands; 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 that comprise 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 __ Gamble. When desired, a protease having decreased adsorption and increased hydrolysis is available as described in WO 9507791 to Procter __ Gamble. A recombinant trypsin-like protease for detergents suitable herein is as described in WO 9425583 to Novo. In more detail, a particularly preferred protease, called "protease D" is a variant of carbonyl hydrolase having an amino acid sequence that is not found in nature, which is derived from a precursor carbonyl hydrolase by substituting a different amino acid for a plurality of amino acid residues at a position in said carbonyl hydrolase equivalent to the +76 position, preferably also in combination with one or more amino acid residue positions equivalent 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 Bacillus ayloliquefaciens subtilisin numbering as described in the patent applications of A. Baeck et al., Entitled " Protease-Containing Cleaning Compositions "which has a US serial number No. 08 / 322,676, and C. Ghosh et al., "Bleaching Compositions Comprising Protease Enzymes", which has the serial number of E.U. No. 08 / 322,677, both filed October 13, 1994. Suitable amylases herein, 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 detergents such as those used for automatic dishwashing, especially improved oxidative stability as measured against a TERMAMYLR reference point in commercial use in 1993. These Preferred amylases herein share the characteristics of being "improved stability" amylases, characterized, to 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 temperatures such as about 60 ° C; or alkaline stability, e.g., at a pH of about 8 to about 11, measured against the amylase of the reference point identified above. Stability can be measured using any of the technical tests described in the art. See, for example, the references described in WO 9402597. The improved stability amylases can be obtained from Novo or from Genencor International A class of amylases highly preferred herein has the common property of being derived using site-directed mutagenesis. one or more of the Bacillus amylases, especially the Bacillus amylases, regardless of whether one, two or multiple strains of amylases are the immediate precursors.It is preferred to use the oxidative amylases of improved stability vs. the above-identified reference amylase, especially in the bleaching compositions, most preferably oxygenated bleaching, other than chlorine bleaching, of the present invention Said preferred amylases include a) an amylase according to WO 9402597, Novo, Feb. 3, 1994 incorporated above, as it is further illustrated by a mutant in which it is substituted, using alanine or threonine, preferably threonine, the methionine residue located at position 197 of alpha-amylase of B. lichemiformis, known as TERMAMYL, or the variation of the homologous position of a similar progeny amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus; b) improved stability amylases as described by Genencor International in a document entitled "Oxidatively Resistant alpha-Amylases", presented at the 207 American Chemical Society National Meeting, March 13-17, 1944, by C. Mitchinson. There it is mentioned that the bleaches in automatic dishwashing detergents inactivate alpha-amylases, but that oxidative amylases of improved stability have been made by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as the residue most likely to be modified. The Met was substituted, one at a time, in positions 8, 15, 197, 256, 304, 366 and 438 carrying specific mutants, 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 such as those described in WO 9510603 A and available from the Novo transferee, such as DURAMYL. 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 known chimeric, hybrid or simple mutant progenitor forms of available amylases. Other modifications of enzyme that are preferred are also accessible. See WO 9509909 to Novo. Other amlase enzymes include those described in WO 95/26397 and in the co-pending Application by nOVO nORDISK pct / dk96 / 00056. Specific amylase enzymes for use in the detergent compositions of the present invention amylase characterized by having a specific activity of at least 25% more than the specific activity of Termamyl at a temperature of 25 ° C to 55 ° C and a value of pH on a scale of 1 to 10, as measured by the Phadebas A-amylase activity test. (Said Phadebas® Á-amylase test is described on pages 9-10, WO 95/26397). Also included herein are α-amylases that are at least 80% homologous to the amino acid sequences shown in the SEQ ID listing in the references, these enzymes are preferably incorporated in laundry detergent compositions at a level of 0.00018% to 0.060% of pure enzyme by weight of the total composition, most preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition. Cellulases that can be used herein include both bacterial and fungal cellulases, preferably at 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 the strain DSM 1800 of Humicola insolens or Humicola, or a cellulase-producing fungus 212 belonging to the genus Aeromonas, and the cellulase extracted from the hepatopancreas of a marine mollusk Dolabella Auricular Solander. Suitable cellulases are also described in GB-A-2,075,028; GB-A-2, 095, 275 and DE-OS-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 Pseudomonas stutzeri ATCC 19,154 as described in GB 1,372,034. Also see lipases in Japanese Patent Application 53,20487, open to public inspection on February 24, 1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the tradename Lipase P "Amano," or "Amano-P." Other suitable commercial lipases include Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacter viscosum var. lipoliticum NRRLB 3673, from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp, E.U.A. and Disoynth Co., Holland and lipases ex Pseudomonas gJLadioli. The LIPOLASER enzyme derived from Humicola lanuginosa and commercially available from Novo, see also EP 341,947, is a preferred lipase for use herein. Variants of lipase and amylase stabilized against proxidase enzymes are described in WO 9414951 A by Novo. See also WO 9505249 and RD 94359044. Despite the large number of publications about lipase enzymes, only lipase derived from Hu icola lanuginosa and produced in Aspergillus oryzae as host has so far been found to have wide application as an additive for washing products of fabrics, 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 the native Humicola lanuginosa lipase improves the efficiency of butter spot removal by a factor of 4.4 over the wild-type lipase (enzymes compared in an amount ranging from 0.075 to 2.5 mg of protein per liter). The research description No. 35944 published on March 10, 1994 by Novo Nordisk discloses that the lipase variant (D96L) 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 on fabrics by using low levels of D96L variant in detergent compositions containing AQA surfactants in the manner described herein, especially when D96L is used at levels in the range of 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 sources, eg, percarbonate, perborate, hydrogen peroxide, etc., for "bleaching in solution" or to avoid the transfer of dyes or pigments removed from the substrates during the washing operations to other substrates in the washing solution. Known peroxidase enzymes include horseradish peroxidase, ligninase and haloperoperoxidase such as chloroperoxidase and bromoperoxidase. Peroxidase-containing detergent compositions 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 incorporation 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. Additionally, enzymes are described in the U.S. patent. 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 incorporation into such formulations are described in US Pat. 4,261,868, Hora et 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, August 7, 1971 to Gedge et al., And EP 199,405 and EP 200,586, October 29, 1986, Venegas. Enzyme stabilization systems are also described, for example, in E.U. 3,519,570. A Bacillus sp. Useful AC13 which gives proteases, xylanases and cellulases is described in WO 9401532 A to Novo.

Enzyme stabilization system The compositions containing enzymes herein may comprise from 0.001% to 10%, preferably from 0. 005% to 8%, most preferably 0.01% to 6% by weight of an enzyme stabilization system. 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 enzymes ready for detergents. Said enzyme stabilization systems may, for example, comprise calcium ion, boric acid, propylene glycol, short chain carboxylic acids, boronic acids and mixtures thereof, and are designed to satisfy 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 about 1 to about 30, preferably about 2 to about 20, most preferably about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, although variation is possible depending of factors that include the multiplicity, type and levels of enzymes incorporated. Preference is given to using water-soluble calcium or magnesium salts, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate; very generally, calcium sulfate or the magnesium salts corresponding to the exemplified calcium salts can be used. Further increased levels of calcium and / or magnesium may of course be useful, for example to promote the fat-cutting action of certain types of surfactant.

Another approach to stabilization is through the use of borate species. See Severson, E.U. 4,537,706. Borate stabilizers, when used, may be at levels of at 10% or more of the composition, although more typically levels of from about 3% by weight of boric acid or other borate compounds such as borax or orthoborate are suitable for the use of liquid detergents. Substituted boric acids such as phenylboronic acid, butanboronic acid, p-bromophenylboronic acid or the like, may be used in place of boric acid and reduced levels of total boron may be possible in the detergent compositions by the use of said substituted boron derivatives. The stabilization systems of certain cleaning compositions may also comprise from 0 to 10%, preferably from 0.01% to 6% by weight, of chlorine bleach scavengers, added to prevent the chlorine bleach species present in many water sources from attacking and inactivating the enzymes, 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, it can be relatively large; consequently, the stability of the enzyme to chlorine during use is sometimes problematic. Since percarbonate or perborate, which have the ability to react with chlorine bleach, may be present in some of the present compositions in amounts independent of the stabilization system, the use of additional stabilizers against chlorine may, very generally, not be essential, although improved results can be obtained from its use. Suitable chlorine scavenging anions are widely known and readily available, and, if used, may be salts containing ammonium cations with sulfite, bisulfite, thiosulfite, thiosulfate, iodide, etc. Likewise, antioxidants such as carbamate, ascorbate, etc., organic amines such as ethylenediaminetetraacetic acid (EDTA) or an alkali metal salt thereof, monoethanolamine (MEA) and mixtures thereof can be used. Likewise, special enzyme inhibition systems can be incorporated so that the different enzymes have maximum compatibility. If desired, other conventional sweepers such as bisulfate, nitrate, chloride, hydrogen peroxide sources such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate can be used. , formate, lactate, malate, tartrate, salicylate, etc. and mixtures thereof. In general, since the chlorine sweeping function can be carried out by separately listed ingredients under better recognized functions (eg, hydrogen peroxide sources), there is no absolute requirement to add a separate chlorine scavenger unless a compound that performs that function to the desired degree is absent in an embodiment of the invention that contains enzymes; Even in that case, the sweeper is added only for optimal results. Moreover, the formulator will exercise a normal chemical ability by avoiding the use of any enzyme scavenger or stabilizer that is primarily incompatible, as formulated, with other reactive ingredients, if used. In connection with the use of ammonium salts, said salts can be simply mixed with the detergent composition, but are prone to adsorb water and / or release ammonia during storage. Accordingly, such materials, if present, are desirably protected in a particle such as that described in E.U. 4,652,392, Baginski et al.

Polymeric dispersion agents Polymeric dispersion agents can be advantageously used at levels of 0.1% to 7%, by weight, in the compositions herein, especially in the presence of zeolite builders and / or layered silicate builders. Suitable polymeric dispersing agents include polymeric polycarboxylates and polyethylene glycols, although others known in the art may also be used. It is believed, although not intended to be limited by theory, that polymer dispersion agents increase the performance of the overall detergency builder, when used in combination with other 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 copolyzing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids which can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic. The presence of the polymeric polycarboxylates in the present or polymeric segments, 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. Said acrylic acid-based polymers which are useful herein are the water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form perferably varies from about 2,000 to 10,000, most preferably from about 4,000 to 7,000 and most preferably from about 4,000 to 5,000. The water-soluble salts of said acrylic acid polymers can include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble polymers of this type are known materials. The use of polyacrylates of this type in detergent compositions has been described, for example, in Diehl, U.S. Pat. 3,308,067, issued March 7, 1967. Copolymers based on acrylic / maleic acid may also be used as a preferred component of the dispersing / anti-redeposition agent. Such materials include the water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of said copolymers in the acid form preferably ranges from about 2,000 to 100,000, more preferably from 5,000 to 75,000 and most preferably from 7,000 to 65,000. The ratio of the 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 salts of said acrylic acid / maleic acid copolymers may include, for example, the alkali metal, ammonium and substituted ammonium salts. Soluble acrylate / maleate copolymers of this type are known materials which are described in European patent application No. 66915, published on December 15, 1982, as well as in EP 193,360, published on September 3, 1986, which also describes 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). The PEG can exhibit dispersing agent performance and can act as a clay dirt removal / anti-redeposition agent. Typical molecular weight scales for these purposes range 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 polyaspartate and polyglutamate, especially in conjunction with zeolite builders, can also be used. Dispersing agents such as those of polyaspartate preferably have a molecular weight (avg.) Of 10,000.

Clay soil remover / anti-redeposition agents The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay dirt removal and anti-redeposition properties. Granular detergent compositions containing these compounds 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. Exemplary ethoxylated amines are more fully described in the U.S.A. 4,597,898, VanderMeer, issued July 1, 1986. Another group of clay soil removal / anti-redeposition agents are the cationic compounds described in European Patent Application 111,965, Oh and Gosselink, published June 27, 1984. Other clay soil removers / anti-redeposition agents that can be used include the ethoxylated amine polymers described in European Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers described in European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides described in the U.S.A. No. 4,548,744, Connor, issued October 22, 1985. Other clay removers 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 (CMC) materials. These materials are well known in the art.

Brightener Any optical brighteners or other brightener or whitening agents known in the art can be incorporated at levels typically from 0.01% to 1.2% by weight, in the detergent compositions herein. Commercial optical brighteners that may be useful in the present invention may be classified into subgroups including, but not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methinocyanin, dibenzotifen-5-dioxide, azole, heterocyclic 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 U.S. patent. 4,790,856 issued to Wixon on December 15, 1988. These brighteners include the PHORWHITE series of brighteners from Verona. Other brighteners described in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM; available from Ciba-Geigy; Artic White CC and Artic White CWD, available from Hilton-Davis, located in Italy; 2- (4-styryl-phenyl) -2H-naphthol [1,2-d] triazoles; 4,4'-bis- (1, 2, 3-triazol-2-yl) -stilbenes; 4,4'-bis (styryl) bisphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethylaminocoumarin; 1, 2-bis (-benzimidazol-2-yl-ethylene; 1,3-diphenylpyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-styryl-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. Generally, said dye transfer inhibiting agents include polyvinyl pyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidases and mixtures thereof. If used, these 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 preferred polyamine N-oxide polymers 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 be part of the polymerizable unit or the N-O group can be attached to both units; A is one of the following structures: -NC (O) -, -C (0) 0-, -S-, - O-, -N =; x is O or 1; and R is aliphatic, aliphatic, ethoxylated, aromatic, heterocyclic or alicyclic groups or any combination thereof to which the nitrogen of the N-O group can be attached or the N-O group is part of these groups. Preferred polyamine N-oxides are those wherein R 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: wherein R] _, 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 aforementioned groups. The amine oxide unit of the polyamine N-oxides has a pKa < 10, preferably pKa < 7, very preferably still pKa < 6. Any polymer base structure can be used as long as the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric base structures are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. These polymers include random or block copolymers wherein one type of monomer is an amine N-oxide and the other type of monomer is an N-oxide. The amine N-oxide 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 present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Polyamine oxides 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. This preferred class of materials can be referred to as "PVNO". 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 Polymer copolymers of N-vinylporrolidone and N-vinylimidazole (also known as "PVPVI") are also preferred for use herein. Preferably, the PVPVI has an average molecular weight in the range of 5,000 to 1,000,000, most preferably 5,000 to 200,000 and most preferably even 10,000 to 20,000. (The average molecular weight scale is determined by light scattering as described in Barth, and other Chemical Analysis, Vol. 113. "Modern Methods of Polymer Characterization", the descriptions of which are incorporated herein by reference). PVPVI 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. These copolymers can be either linear or branched. The compositions of the present invention may also employ a polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 5,000 to about 400,000, preferably from about 5,000 to about 200,000, and most preferably still from about 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. The PVP-containing compositions may also contain polyethylene glycol ("PEG") having an average molecular weight of from about 500 to about 100,000, preferably from about 1,000 to about 10,000. Preferably, the ratio of PEG to PVP on a basis of ppm assorted in wash solutions is from about 2: 1 to about 50: 1, and most preferably from about 3: 1 to about 10: 1. The detergent compositions herein may also optionally contain from about 0.005% to 5% by weight of certain types of hydrophilic optical brighteners that also provide a dye transfer inhibiting action. If used, the compositions herein will preferably comprise from 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; R 2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphino, chloro and amino; and M is a salt-forming cation such as sodium or potassium. When in the above formula, R? _ Is anilino, R2 is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is acid 4,4 ', bis [(4-anilino-6- (N -2-bis-hydroxyethyl) -s-triazin-2-yl) amino] -2,2'-styrylisulfonic acid and disodium salt. 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 compositions herein.

When in the above formula R1 is anilino, R2 is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is the disodium salt of 4,4'-bis [4- anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino] -2,2 '-stilbenedisulfonic acid. This particular brightener species is commercially marketed 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 sodium, the brightener is the sodium salt of 4,4 '-bis [(4-anilino-6-morphino-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 Corporation. The specific optical brightener species selected for use in the present invention provides speci? Cally effective dye transfer inhibition performance benefits when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of said selected polymeric materials (e.g., PVNO and / or PVPVI) with said selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX and / or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than either of these detergent composition components when used alone. Without being limited to the theory, it is believed that such brighteners work in this way because they have high affinity for fabrics in the wash solution and therefore they deposit relatively quickly on these fabrics. The degree to which the brighteners are deposited on the fabrics in the wash solution can be defined by a parameter called "exhaustion coefficient". The depletion coefficient 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 optical brightener compounds may optionally be present in the compositions herein to provide conventional "brightness" benefits to the fabrics, rather than a true dye transfer inhibiting effect. Said use is conventional and well known for detergent formulations.

Chelating Agents The detergent compositions herein may also optionally contain one or more iron and / or manganese chelating agents. Such chelating agents can be selected from the group consisting of aminocarboxylates, aminophosphates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, all as defined below. Without intending 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 solutions through the formation of soluble chelates. Aminocarboxylates useful as optional chelating agents include ethylenediaminetetracetates, N-hydroxyethyl-ethylenediaminetriacetates, nitrilotriacetates, ethylenediamono-tetraproprionates, triethylenetetraaminohexacetates, diethylenetriaminopentaacetates and ethanoldiglicines, alkali metal, ammonium and substituted ammonium salts 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 allowed in the detergent compositions and include ethylenediaminetetrakis- (methylenephosphonates) as DEQUEST. Preferably, these aminophosphonates do not contain alkyl or alkenyl groups with more than about 6 carbon atoms. Polyfunctionally substituted aromatic chelating agents are also useful in the compositions herein. See the patent of E.U.A. 3,812,044 issued May 21, 1974 to Connor et al. Preferred compounds of this type in acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene. A preferred biodegradable chelator for use herein is ethylenediamine disuccinate ("EDDS"), especially the isomer [S, S,] as described in U.S. Pat. 4,704,223 issued on 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 of 0. 1% to 3.0% by weight of said compositions.

Foam suppressors Compounds for reducing or suppressing foaming can be incorporated into the compositions of the present invention. The suppression 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 suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of Chemical Technology, 3a. Edition, Volume 7, pages. 430-447 (John Wiley S_ Sons, Inc., 1979). A category of foam suppressant of particular interest includes monocarboxylic fatty acids and soluble salts thereto. See the patent of E.U.A. 2,954,347, issued September 27, 1960 to Wayne St. John. The monocarboxylic fatty acids and salts thereof used as a foam suppressant typically have hydrocarbyl 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, as well as ammonium and alkanolammonium salts. The detergent compositions herein may also contain suds suppressants that are not surfactants. These include, for example: high molecular weight hydrocarbons such as paraffin, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, C18-C40 aliphatic ketones (e.g., stearone), etc. Other foam inhibitors include N-alkylated aminotriazines such as tri- to hexa-alkylmelamines or di- to tetra-alkyldiaminocrotriazines formed as cyanuric chloride products with two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms. . propylene oxide and monostearyl phosphates such as monostearyl alcohol phosphate ester and alkali metal (eg, K, Na and Li) diphosphates, monostearyl phosphates and ester phosphates. Hydrocarbons such as paraffin and halogenoparaffins can be used in liquid form. The liquid hydrocarbons will be liquid at room temperature and at atmospheric pressure, and will have a pour point on the scale of about -40 ° C to about 50 ° C, and a minimum boiling point 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. Hydrocarbons constitute a preferred category of foam suppressant for detergent compositions. The hydrocarbon foam suppressors are described, for example, in U.S. Patent No. 4,265,779, issued May 5, 1981 to Gandolfo et al. The hydrocarbons, therefore, include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in the discussion of suds suppressors, is intended to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred category of foam suppressors that are not surfactants comprise silicone foam suppressors. This category includes the use of poiorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles wherein the polyorganosiloxane is chemisorbed or fused onto the silica. Silicone foam suppressors are well known in the art and are described, for example, in the U.S.A. 4,265,779, issued May 5, 1981 to Gandolfo et al. And in European patent application No. 89307851, published on February 7, 1990 by Starch, M.S. Other silicone foam suppressors are described in U.S. Patent 3,455,839, which relates to compositions and processes for the defoaming of aqueous solutions by incorporating thereto small amounts of polydimethylsiloxane fluids. Mixtures of silicone and silanated silica are described, for example, in German patent application DOS 2,124,526. Silicone foam scavengers and foam controlling agents in granular detergent compositions are described in U.S. Patent 3,933,672, Bartolotta et al., And in U.S. Patent 4,652,392, Baginski et al., Issued March 24, 1987. illustrative silicone-based foam suppressant for use herein is a foaming suppressant amount of a foaming controlling agent consisting essentially of: (i) polydimethylsiloxane fluid having a viscosity of from about 20 cs to about 1,500 cs a 25 ° C; (ii) about 5 to about 50 parts per 100 parts by weight of (i) siloxane resin composed of (CH3) 3SiO? / 2 units of SiO2 units in a ratio of (CH3) 3SiO? / 2 units to Si02 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 phase is made of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The primary silicone foam suppressor is branched / interlaced and non-linear. To illustrate this point further, typical liquid laundry detergent compositions with optionally controlled foams 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 weight percent of said foam suppressant. silicone, comprising (1) a non-aqueous emulsion of a primary foaming antifouling agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin-producing silicone compound, (c) a finely divided filler material and (d) a catalyst for promoting the reaction of blend components (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 solubility in water at room temperature of more than about 2% by weight; and without polypropylene glycol. Similar amounts can be used in granular 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 and others in column 1, row 46 to column 4, row 35. The silicone foam suppressant of the present preferably comprises polyethylene glycol and a polyethylene glycol / polypropylene glycol copolymer, all having a lower average molecular weight of about 1,000, preferably between about 100 and 800. The polyethylene glycol and polyethylene / polypropylene copolymers herein have a solubility in water at room temperature other than about 2% by weight, preferably more than about 5% by weight. The preferred solvent herein is polyethylene glycol having an average molecular weight of 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 silicone foam suppressors and used 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 foam suppressors useful herein contain the secondary alcohols (e.g., 2-alkylalkanols) and mixtures of said alcohols with silicone oils, such as the silicones described in US Pat. Nos. 4,798,679, 4,075,118 and EP 150,872. Secondary alcohols include alkyl alcohols of Cg-Ct_g having a chain of C? _-C? _g. 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 trade name ISALCHEM 123 from Enichem. Mixed foam suppressors typically comprise alcohol + silicone blends at a weight ratio of 1: 5 to 5: 1. For any detergent compositions to be used in automatic washing machines, the foams should not be formed to the extent that they overflow from the washing machine. The foam suppressors, when used, are preferably present in an amount of foam suppression. By "foam suppression amount" is meant that the formulator of the composition can select an amount of this foam controlling agent that will sufficiently control the foams 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% foam suppressant. When used as suds suppressors, the monocarboxylic fatty acids, and salts thereof, will typically be present in amounts of about 5% by weight of the detergent composition. Preferably, about 0.5% to about 3% of the fatty monocarboxylate foam suppressant is used. Silicone foam suppressors are typically used in amounts of about 2.0%, by weight, of the detergent composition, although higher amounts may be used. This upper limit is practical in nature, mainly due to the interest of keeping costs reduced to a minimum and the effectiveness of lower quantities to effectively control foaming.

Preferably from about 0.01% to about 1% silicone foam suppressant is used, most preferably from about 0.25% to about 0.5%. As used herein, these values in percent by weight include any silica that can be used in combination with polyorganosiloxane, as well as any auxiliary materials that can be used. The monostearyl phosphate foam suppressors are generally used in amounts ranging from about 0.01% to about 02% by weight of the composition. The hydrocarbon 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 such as those prepared from polyacrylates are useful herein to provide fat removal performance. Such materials are described in WO 91/08281 and PCT 90/01815 on page 4 and subsequent, incorporated herein 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 - (CH CH20) m (CH2) nCH3 where m is 2-3 and n is 6-12. The side chains are ester linked to the "base structure" of polyacrylate to provide a "comb" type polymer structure. The molecular weight may vary, but is typically on the scale of 2000 to 50,000. Said alkoxylated polycarboxylates may 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 clays 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% by weight in the compositions herein to provide softening benefits concurrently with the cleaning of fabrics. Clay-based softeners can be used in combination with amine and cationic softeners as described, for example, in the U.S. patent. 4,375,416, Crisp et al., March 1, 1983 and in the patent of E.U.A. 4,291,071, Harris et al., Issued September 22, 1981.

Perfumes The perfumes and perfumery ingredients useful in the present compositions and processes comprise a wide variety of natural and synthetic chemical ingredients, including but not limited to aldehydes, cerones, esters. Also included are various natural extracts and natural essences which may comprise complex mixtures of ingredients, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam essence, sandalwood oil, pine oil, cedar . The finished perfumes may comprise extremely complex mixtures of said 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-1,1-dimethyl indane; para-hydroxy-phenyl-butanone; benzophenone; methyl beta-naphthyl ketone; 6-acetyl-l, 1, 2, 3, 3, 5-hexamethyl indan; 5-acetyl-3-isopropyl-1,1,2,6-tetramethyl indan; 1-dodecanal, 4- (4-hydroxy-4-methylpentyl) -3-cyclohexane-1-carboxaldehyde; 7-hydroxy-3,7-dimethylocatanal; 10-undecen-l-al; iso-hexenylcyclohexyl carboxaldehyde; formyltriciclodecane; condensation products of hydroxy-citronellal and methylanthranilate, condensation products of hydroxy-citronellal 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-iso-propylphenyl) -propionaldehyde; coumarin; gamma-decaiactone; Cyclopentadecanolide; l6-hydroxy-9-hexadecenoic acid lactone; 1, 3, 4, 6, 7, 8-hexahydro-4, 6, 6, 7, 8, 8-hexamethylcyclo-penta-gamma-2-benzopyran; methyl ether of beta-naphthol; ambroxane; dodecahydro-3a, 6, 6, 9a-tetramethylnaphthol [2; lb] furan; cedrol, 5- (2,2,3-trimethylcyclopent-3-endyl) -3-methylpentan-2-ol; 2-ethyl-4- (2,2,3-trimethyl-3-cyclopenten-1-yl) -2-buten-1-ol; caryophyllene alcohol; tricyclodecenyl propionate; tricyclodece-nylacetate; benzylsalicylate; Cryrilacetate; and para- (tert-butyl) cyclohexylacetate. Particularly preferred perfume materials are those that provide the greatest odor improvements in finished product compositions containing cellulases. These perfumes include but are not limited to: hexyl cinnamic aldehyde; 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde; 7-acetyl-1,2,3,4,5,6,7,8-octahydro-l, 1,6,7-tetramethylnaphthalene; benzyl salicylate: 7-acetyl-l, 1, 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-benzopyran; dodecahydro3a, 6,6,9a-tetramethylnaphtho [2, lb] furan; anisaldehyde; coumarin; cedrol; vanillin; Cyclopentadecanolide; tricyclodecenylacetate; and tricyclodecenyl propionate. Other perfume materials include essential oils, resinoids and resins from a variety of sources including, but not limited to: Peruvian balm, olibanu resinoids, stretches, lavender resin, nutmeg, cassia oil, benzoin resin, corundum and lavender. Other chemical perfume compositions include phenylethyl alcohol, terpineol, 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 compositions herein, including other active ingredients, vehicles, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions , etc. If high foam formation is desired, foam boosters such as C ^ Q-Ci alkanolamides can be incorporated into the compositions, typically at levels of 1% -10%. The monoethanol and diethanolamides of C? O_ci4 illustrate a typical class of such foam boosters. The use of said foam boosters with high foaming adjunct surfactants such as oxides of. amine, betaines and sultaines mentioned above is also advantageous. If desired, soluble magnesium salts such as MgCl 2, gS 4 and the like can be added, typically at levels of 0.1% -2%, to provide additional foam and to improve the fat removal performance. Various detersive ingredients employed in the present compositions can be further stabilized by absorbing said ingredients on a porous hydrophobic substrate, then coating said substrate with a hydrophobic coating. Preferably, the detersive ingredient is mixed with a surfactant before being absorbed into the porous substrate. During use, the detersive ingredient is released from the substrate in the aqueous wash liquor, where it performs its intended detersive function. To illustrate this technique in more detail, a porous hydrophobic silica (trade name SIPERNAT DIO, Degussa) is mixed with a proteolytic enzyme solution containing 3% -5% nonionic ethoxylated alcohol surfactant of C? 3 _] _ 5 ( EO 7). Typically, the enzyme / surfactant solution is 2.5X the weight of the silica. The resulting powder is dispersed with agitation in silicone oil (various viscosities of silicone oil can be used in the range of 500-12,500). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this means, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, colorants, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including liquid detergent compositions for laundry. The liquid detergent compositions may contain water and other solvents such as vehicles. The low molecular weight primary and secondary alcohols 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 (e.g., 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 herein 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. Techniques for controlling pH at recommended levels of use include the use of pH, alkali, acid regulators, etc., and are well known to those skilled in the art.

Granule Manufacturing The addition of alkoxylated cationic compounds of this invention in a degrading mixture, followed by conventional spray drying, helps to remove any residual, potentially short-smelling, short-chain amine contaminants. In case the formulator wishes to prepare a miscible particle containing the alkoxylated cationic compounds to be used for example, in a high density granular detergent, it is preferred that the particulate composition is not highly alkaline. Methods 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 such as boric acid, citric acid or the like, or an appropriate pH regulator, to the particle. In an alternative mode, the prospective problems associated with bad odors of amine can be covered by the use of 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 identifications of abbreviated components have the following meanings: linear C] _2 sodium alkylbenzene sulfonate. TAS Sodium tallow alkyl sulphate. C45AS Sodium C14-C15 linear alkyl sulfate.

CxyzS Branched alkylsulfate of C - (_? - C? _ Sodium with z moles of ethylene oxide C45E7 A predominantly linear primary alcohol of C14-C.5 condensed with an average of 7 moles of ethylene oxide C25E3 A branched primary alcohol of C] _2-Ci5 condensed with an average of 3 moles of ethylene oxide C25E5 A branched primary alcohol of? 2-Ci5 condensed with an average of 5 moles of ethylene oxide COCOE02 R! .N + (CH3 ) (C2H4OH) 2 with R = C12-C14 Linear sodium alkylcarboxylate soap derived from a mixture of 80/20 tallow and coconut oil.

TFAA Alkyl-N-methylglucamide of C? _g-Ct_8 TPKFA Fatty acids cut in the upper part of Ct_2-Ct_4. STPP Anhydrous sodium tripolyphosphate. Zeolite A Hydrated sodium aluminosilicate of the formula Na ^ 2 (A10 Si02)] _2.27H20 having an average particle size on the scale of 1 to 10 microns. NaSKS-6 Crystalline layered silicate of the formula S-Na2Si2? 5. Citric acid Anhydrous citric acid. Carbonate Anhydrous sodium carbonate with a particle size between 200 micras and 900 micras.

Bicarbonate Anhydrous sodium bicarbonate with particle size distribution 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 microns and 850 microns. MA / AA Copolymer of maleic / acrylic acid 1: 4, average molecular weight of 70,000. CMC Carboxymethylcellulose sodium.

Protease Proteolytic enzyme of 4KNPU / g of activity sold by Novo Industries A / S under the trade name Savinase Alcalasa 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 Endolasa Enzyme endoglucanase of 3000 CEVU / g of activity sold by Novo Industries A / S PB4 Tebohydrate of sodium perborate tetrahydrate of formula NaB02.3H2O.H2? 2 • PBl Bleach of anhydrous sodium perborate of nominal formula NaB? 2-H202. Percarbonate Sodium percarbonate of nominal formula 2Na2C03.3H202. NOBS Nonanoiloxybenzenesulfonate in the form of sodium salt. TAED Tetraacetylethylenediamine. DTPMP Diethylenetriaminepentamethylenephosphonic acid, marketed by Monsanto under the trade name Dequest 2060. Phthalocyanine bleach of encapsulated sulfonated zinc photoactivated in dextrin-soluble bleaching polymer Brightening 1 4,4 '-bis (2-sulfostyril) biphenyl Brightener 2 4,4' -bis (4-anilino) -6-morpholino) -1,3,5-triazino-2-yl) amino) stilben-2: 2'-disulfonate. HEDP 1, 1-hydroxyethanediphosphonic acid PVNO N-oxide poly-4-vinylpyridine. PVPVI Copolymer of polyvinylpyrrolidone and vinylimidazole SRA1 Esters blocked at the ends with sulfobenzoyl having an oxyethyleneoxy and terphthaloyl base structure SRA2 Poly (1,2 propylene terephthalate) short block polymer. Foam controller of polydimethylsi-silicone loxane with siloxane-acial-chileno copolymer as a dispersing agent with a ratio of foam to dispersing agent ratio from 10: 1 to 100: 1. In the following examples all levels are given in% by weight of 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. ABC 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 CCooccooMMeeEE0022 ** 11..55 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 DDTTPPMMPP 00..44 0.4 0.2 Spray C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone antifoam 0.3 0.3 0.3 PPeerrffuummee 00..33 0.3 0.3 Dry additives Carbonate 6.0 13.0 15.0 PB4 .. 0.0 4.0 10.0 PBl 4.0 0.0 0 Percarbonate ... .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 AQA surfactants herein.

EXAMPLE II The following detergent formulations containing nil bleaches are of particular use in washing color laundry. "D E F Zeolite Blown Powder A 15.0 15.0 2.5 Sodium Sulphate 0.0 5.0 1.0 LAS 2.0 2.0 - CoCoMeE02 * 1.0 1.0 1.5 DTPMP 0.4 0.5 - CMC 0.4 0.4 - MA / AA 4.0 4.0 - 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 MA / AA - - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - 8.0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI / PVNO 0.5 0.5 0.5 Alcalase 0.5 0.3 0.9 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 55..00 5.0 5.0 Dry additives Sodium sulphate 0.0 9.0 0.0 The rest (Moisture and various components ) for: 100.0 100.0 100.0 Density (g / liter) The surfactant AQA-1 (CocoMeE02) of the example may be replaced by an equivalent amount of any surfactant AQA-2 to AQA-22 or other AQA surfactants herein.

EXAMPLE III The following detergent formulations, according to the present invention are prepared: H Powder blowing Zeolite A 30.0 22.0 6.0 Sodium 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 Silicate - 1.0 5.0 Soap - - 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0 DTPMP _ 0.4 0.4 Spray C45E7 1.0 1.0 1.0 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 Cellulase 0.1 0.1 0.1 NOBS 6.1 4.5 PBl 1.0 5.0 6.0 Sodium Sulfate 6.0 The rest (Moisture and various components) for: 100 100 100 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 AQA surfactants herein.

EXAMPLE IV The following detergent formulations containing a high density and bleach, according to the present invention are prepared: K Powder blowing 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 Bicarbonate - 3.0 - Carbonate 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 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0 The rest (Moisture and various components) for: 100.0 100.0 100.0 Density (g / liter) 850 850 850 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 AQA surfactants herein.

EXAMPLE V The following high density detergent formulations according to the present invention are prepared: MN Blown Powder Zeolite A 2.5 2.5 Sodium Sulfate 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 Percarbonate 15.0 15.0 SRA 1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Amylase 0.6 0.6 Silicone antifoam 5.0 5.0 Brightener 1, 0.2 0.2 Brightener 2 0.2 The rest (moisture and To: 100 100 various components Density (gl / liter) 850 850 * The AQA surfactant (CocoMeE02) of the example can be replaced by an equivalent amount of any of the surfactants from AQA-2 to AQA-22 or other AQA surfactants in The present invention, any of the granular detergent compositions provided herein can be tableted using known tabletting methods to provide detergent tablets. Examples A and B further illustrate the invention herein with respect to a laundry bar.

EXAMPLE VI Ingredient% (by weight) Scale (% by weight) A B Ci2-Ci8 sulfate 15.75 13.50 0-25 LAS 6.75 0-25 Na2C03 15.00 3.00 1-20 DTPP1 0.70 0.70 0.2-1.0 Bentonite Clay 10.0 0-20 Sokolan CP-52 0.40 1.00 0-2.5 AQA-l3 2.0 0.5 0.15-3.0 TSPP 5.00 0 0-10 STPP 5.00 15.0 0-25 Zeolite 1.25 1.25 0-25 Sodium Laurate 9.00 0-15 SRA-1 0.30 0.30 0-1.0 Protease enzyme 0.12 0-0.6 Enzyme amylase 0.12 0-0.6 Enzyme lipase 0.10 0.0.6 Enzyme cellulase 0.15 0-0.3 The -i residue4 - "- Sodium diethylenetriaminepentaphosphonate Sokolan CP-5 is maleic acid acrylic copolymer 3AQA-1 can be replaced by an equivalent amount of surfactants from AQA, AQA2 to AQA-22 or others AQA surfactants of the present.

The remainder comprises water (2% to 8%, including water of hydration), sodium sulfate, sodium carbonate and other minor ingredients.

EXAMPLE VII The following hand wash detergent formulations, according to the present invention, are prepared by mixing the ingredients in the weight percentage amounts as indicated below:.

A B C D LAS 15.0 12.0 15.0 12.0 TFAA 1.0 2.0 1.0 2.0 C25E5 4.0 2.0 4.0 2.0 AQA-9 * 2.0 3.0 3.0 2.0 STPP 25.0 25.0 15.0 15.0 MA / AA 3.0 3.0 3.0 3.0 CMC 0.4 0.4 0.4 0.4 DTPMP 1.0 1.6 1.6 1.6 Carbonate 2.0 2.0 5.0 5.0 Bicarbonate - - 2.0 2.0 Silicate 7.0 7.0 7.0 7.0 Protease 1.0 - 1.0 1.0 Amylase 0.4 0.4 0.4 - Lipase 0.12 0.12 - 0.12 Brightener 0.3 0.3 0.3 0.3 photoactivated Sulphate 2.2 2.2 2.2 2.2 PBl 4.0 5.4 4.0 2.3 NOBS 2.6 3.1 2.5 1.7 SRA 1 0.3 0.3 0.7 0.3 Brightener 1 0.15 0.15 0.15 0.15 The rest comp. 100.0 100.0 100.0 100.0 div. / water for 100 The AQA-9 *; it can be replaced by any AQA surfactant described herein. Preferred AQA surfactants for use in this example are those with 10 to 15 ethoxy groups; for example AQA-10, AQA-16. The above examples illustrate the present invention when relating to laundry compositions but are not intended to be limited thereto.

EXAMPLE VIII Ingredient% (by weight) Scale (% by weight) AQA-1 * 2.0 0.15-3 C12-C13 ammonium alkyl sulfate 7.0 2-35 Ethoxy (1) C12-C1 sulfate 20.5 5-35 Cocoamine oxide 2.6 2-5 Betaine / Tetronic 704R 0.87-0. .10 0-2 (mixture) Ethoxylated alcohol of CßEn 5.0 2-10 Ammonium xylene sulphonate 4.0 1-6 Ethanol 4.0 0-7 Ammonium citrate 0.06 0-1.0 Magnesium chloride 3.3 0-4.0 Calcium chloride 2.5 0-4.0 Ammonium sulphate 0.08 0-4.0 Peroxide hydrogen 200 ppm 0-300 ppm Perfume 0.18 0-0.5 Maxatase Protease? 0.50 0-1.0 Water and minor components The remainder * Can be replaced by A AQQ'AA - 22 - AQA - 22 or other AQA surfactants herein. ** Cocoalkylbetaine. The following example further illustrates the invention with respect to hard surface cleaners.

EXAMPLE IX Ingredient% (by weight) Ratio (% by weight) AQA-1- * 2.0 0.25-5 3- (N-dodecyl-N, N-dimethyl) 2-hydroxy-propane-1-sulfonate 2.0 1-5 Octylpolyethoxylate (2.5) 1.1 1-5 Octylpolyethoxylate (6.0) 2.9 1- 5 Butoxipropoxypropanol 5.0 0-10 Succinic acid 10.0 2-12 Sodium Cumensulfonate 4.2 1-5 SRA 2 0.2 0.2 Water, pH regulators and minor components The res: t? pH 3.0 * Can be replaced by AQA2-10 or other AQA surfactant herein. The following example further illustrates the invention with respect to hard surface cleaning gel or bar.

EXAMPLE X Ingredient% (by weight) Ratio (% by weight) AQA-1 * 1 .5 1.0-3.0 Coconut soap, Na ** 80 .0 70-99 Methylglucamide from c12_ 14 4. .0 0-10 Carboxymethylcellulose 2., 0 0-5 SRA 1 0. .4 0.12 Perfume 0., 1 Optional Moisture and minor components The rest * Can be replaced by AQA2-10 or other AQA surfactant herein.

** The soap may be replaced in whole or in part by surfactants such as Ci2-c14 alkyl sulfates or C12-C-I6 alkylcyto-sulfates. The following examples A and B further illustrate the invention herein with respect to an automatic dishwashing detergent containing granulated phosphate.

EXAMPLE XI % by weight of active material Ingredients AB STPP (anhydrous) 1 31 26 Sodium carbonate 22 32 Silicate (% Si02) 9 7 Surfactant (non-ionic) 3 1.5 NaDCC 2 whitener 2 AQA-1 * 0.5 1.0 Sodium perborate 5 TAED 1.5 Savinase (Au / g ) 0.04 Termamyl (Amu / g) 425 Sulfate 25 25 Perfume / minor components up to 100% up to 100% - • Sodium tripolyphosphate Sodium dichlorocyanurate * The surfactant of AQA-1 can be replaced by AQA-2 to AQA-22.

EXAMPLE XII The following illustrates mixtures of AQA surfactants which can replace the AQA surfactants listed in any of the above examples. As described above, such mixtures can be used to provide a spectrum of performance benefits and / or to provide cleaning compositions that are useful over a wide variety of conditions of use. Preferably, the AQA surfactants in said mixtures differ by at least 1.5, preferably 2.5-20, total EO units. 'The ratio scales (by weight) for such mixtures with typically 10: 1-1: 10. Non-limiting examples of said mixtures are the following. Components Relationship (by weight) 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 Mixtures of the AQA surfactants herein with the corresponding cationic surfactants containing only an ethoxylated chain can also be used. Thus, for example, mixtures of ethoxylated cationic surfactants of the formula R ^ + CH; -. [EO] x [EO] yX ~ and RV1"(CH3) 2 [EO] ZX ~, where R1 and X are as described above and where one of the cationic has (x + y) oz on the scale of 1-5 preferably 1-2 and the other has (x + y) oz on the scale of 3-100, preferably 10-20, most preferably 14-16, can be used herein Said compositions advantageously provide detergency performance improved (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 shorter EO cationics (e.g., E02) they improve the cleaning performance of anionic surfactants in soft water, while the higher EO cationic ones (for example, E015) act to improve the hardness tolerance of anionic surfactants, thereby improving the cleaning performance of anionic surfactants in hard water. Conventional knowledge in the detergency technique suggests that builders can optimize the "window" performance of anionic surfactants. However, until now it has been impossible to achieve the expansion of the window to essentially cover all water hardness conditions.

EXAMPLE XIII This example illustrates the perfume formulations (A-C) made in accordance with the invention for incorporation into any of the above examples of detergent compositions containing AQA. The various ingredients and levels are established later. (% by weight) Perfume ingredient A B C Hexyl cinnamic aldehyde 10.0 - 5.0 Propionaldehyde of 2-methyl-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, 1,6, 7-tetramethyl Benzyl salicylate 5.0 6-hexamethyltetralin from 10.0 5.0 10.0 7-acetyl-l, l, 3,4,4 Para- (tert-butyl) acetate 5.0 5.0 cyclohexyl Methyldihydro jasmonate - 5.0 Methyl beta-naphthyl ether - 0.5 Methyl beta-naphthyl ketone - 0.5 2-methyl-2- (para-iso-propylphenyl) - - 2.0 propionaldehyde 1, 3,4, 6, 7, 8-hexahydro-4, 6, 6, 7, - 9.5 8, 8-hexamethyl-cyclopenta-gamma-2-benzopyran Dodecahydro- 3a-6, 6, 9a-tetramethylnaph - - 0.1 [2, lb] furan Anisaldehyde - - 0.5 Coumarina - - 5.0 Cedro1 - - 0.5 Vanilina - - 5.0 Cyclopentadecanolide 3.0 - 10.0 Tricyclodecenyl acetate - - 2.0 Labdanum resin - - 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 Acetate Orange oil - • 5.0 cold-pressed Bencil Acetate 2.0 2.0 - Orange terpenes - 10.0 - Eugenol - 1.0 - Diethylphthalate - 9.5 - Lemon oil pressed in cold - - 10.0 Total 100.0 100.0 100.0 The above perfume compositions are mixed or sprayed (typically at levels up to about 2% by weight of the total detergent composition) of any AQA surfactant containing cleaning compositions (including bleaches) described in the present. The improved deposition and / or retention of the perfume or individual components thereof on the surface that are cleaned (or bleached) is safe in this way. ***

Claims (9)

NOVELTY OF THE INVENTION CLAIMS

1. A composition comprising or prepared by the combination of an aluminosilicate soil release agent, a non-AQA surfactant and an effective amount of. an alkoxylated quaternary ammonium cationic surfactant (AQA) of the formula: wherein r is an alkyl, alkenyl, aryl, alkaryl, ether or branched or substituted C3-C18 glycrylic ether moiety, R is an alkyl moiety of C? _C3, R and R4 can independently vary and are selected from hydrogen, methyl and ethyl, X is an anion, A is C1-C4 alkoxy and p is an integer in the range of 2 to 30.

2. A composition according to claim 1, further characterized in that the soil release agent is a ester blocked at its ends with sulfobenzoyl, with a polyethylene terephthaloyl copolymer blocked at its sulfonated ends, with 5 sulfoisophthaloyl units.

3. - A composition according to any of claims 1 to 2, which is prepared by mixing the non-AQA surfactant and the AQA surfactant.

4. - A composition according to any of claims 1 to 3, further characterized in that the non-AQA surfactant is an anionic surfactant.

5. A composition according to any of claims 1 to 4, further characterized in that the weight ratio of surfactant AQA to non-AQA is from 1:15 to 1: 8.

6. - A composition according to any of claims 1 to 5, further characterized in that said AQA surfactant of the formula in the R is alkyl of c8"c18 'R is methyl, A is an ethoxy or propoxy group and p is an integer from 2 to 8. 1. - A composition according to any of claims 1 to 6, further characterized in that said AQA surfactant of the formula in R is alkyl of c8"c18 'R is methyl, A is an ethoxy or propoxy group and p is an integer from 2 to 4. 8. A detergent composition according to any of claims 1 to 7 further characterized in that the cationic surfactant formula of AQA is such that p is an integer in the scale of 10, to 15. 9. A detergent composition according to any of claims 1 to 8 comprising 2 or more AQA surfactants, or a mixture of AQA surfactant and a monoethoxylated cationic surfactant. 10. - A detergent composition according to any of claims 1 to 9 comprising 2 or more non-AQA surfactants and a mixture of two or more AQA surfactants. 11. A composition according to any of claims 1 to 10 in granular, bar, aqueous or liquid non-aqueous or tablet form. 12. - A method for removing dirt and stains by contacting said soils and stains with a detergent composition, or an aqueous medium comprising said detergent composition according to any of claims 1 to 11. 13. - A method of conformance with the reinvidication 12 to remove sensitive dirt from the detergent builder on fabrics. 14. - A method according to any of claims 12 or 13 that is driven in an automatic machine. 15. A method according to any of claims 12 to 14 that is driven manually. 16. - A method according to any of claims 12 to 15, further characterized in that it comprises a mixture of two or more surfactants of AQA, or a mixture of surfactant AQA and a cationic monoethoxylated surfactant. 1

7. - A method according to any of claims 12 to 16, further characterized in that it comprises a mixture of two or more surfactants of AQA, or a mixture of surfactant AQA and a cationic monoethoxylated surfactant. 1

8. A method for increasing the deposition or substantivity of perfume or perfume ingredients on fabrics or other surface, comprising contacting said surfaces with a perfume or perfume ingredient in the presence of an AQA surfactant. 1

9. - A method according to claim 18 which is conducted using a perfume or perfume ingredient in combination with a detergent composition comprising an AQA.