JPH11510554A - Detergent composition - Google Patents

Abstract

  (57) [Summary] A detergent composition comprising an enzyme, a non-AQA surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant.

Description

DETAILED DESCRIPTION OF THE INVENTION                                Detergent composition                                 Technical field   The present invention relates to an enzyme, a non-AQA surfactant and a bis-alkoxylated quaternary ammonium. The present invention relates to a detergent composition containing a sodium (bis-AQA) cationic surfactant.                                Background of the Invention   Laundry detergent formulations and other cleaning compositions pose significant challenges. Modern compositions are required to remove various stains and stains from various substrates Because. Therefore, laundry detergents, hard surface cleaners, shampoos and other -Sonal cleaning compositions, hand dishwashing detergents, and detergent compositions suitable for automatic dishwashers All require the proper selection and combination of ingredients to work effectively. In general These detergent compositions release and remove various types of stains and stains It contains one or more surfactants that aim to do so. Looking at the literature, there is a wide variety Surfactants and combinations of surfactants seem to be available to detergent manufacturers On the other hand, many of these ingredients are inexpensive unit cost products like household laundry detergents. The reality is that it is a specialty chemical that is not suitable for. Most saws like laundry detergent The household product comprises one or more conventional ethoxylated nonionic and / or sulfuric acid. Or sulfonated anionic surfactants are still mainly compounded It is true that This is probably due to the variety of dirt, stains, and It is necessary to formulate a composition that works reasonably well for various fabrics Will.   Different types of stains, such as dirt, greasy / greasy stains and certain food stains Rapid and efficient removal of stains and stains can be a difficult problem. These stains Including a mixture of triglycerides, lipids, complex polysaccharides, inorganic salts and protein substances All of these are more or less composed of hydrophobic components, so it is necessary to remove them. The difficulties are well known. Low level of hydrophobic stains and residual stains after washing Often remains on the surface of the fabric. In addition to the continuous washing and wearing, hydrophobic in washing The limited removal of soil stains increases the accumulation of residual stains and stains, which Incorporate additional dust in the fabric to yellow the fabric. Ultimately, the fabric is not dingy Therefore, consumers feel that they cannot wear it and throw it away.   According to the literature, various nitrogen-containing cationic surfactants are available in various cleaning compositions. And useful. Typically, an amino, amide, quaternary ammonium or These substances, in the form of imidazolinium compounds, can be used for specialized applications. Often aimed at. For example, various amino and quaternary ammonium surfactants Agents have been proposed for shampoo compositions and are said to be good for hair styling. That Other nitrogen-containing surfactants provide fabric softening and antistatic benefits Used in some laundry detergents. However, in most cases, Commercial use is limited by the obstacles encountered in large-scale production of these compounds. Have been. A further limitation is that ionic interactions with cationic surfactants The possibility of precipitation of the anionic active component of the detergent composition caused. Said above Nonionic and anionic surfactants are still present in current laundry compositions It is the main surfactant component.   Certain bis-alkoxylated quaternary ammonium (bis-AQA) compounds are generally Increases cleaning performance on the variety of soils and stain types encountered, especially hydrophobic soil types It has now been discovered that various detergent compositions can be used to proceed. Surprising Alternatively, a composition containing an enzyme and a bis-AQA surfactant is used in either technical unit. In addition to exhibiting excellent cleaning and white performance for products including Germany, Improving local care has now been discovered.   The bis-AQA surfactants of the present invention are based on previously known cationic surfactants. Provides substantial benefits to formulators over agents. For example, the screws used in the present invention -AQA surfactant removes frequently occurring "daily" fatty / oily hydrophobic stains Greatly improves cleaning. Further, the bis-AQA surfactant is an alkyl sulfate. Commonly used in detergent compositions such as and alkyl benzene sulfonates Compatible with on-surfactants. Detergent compositions are compatible with anionic surfactants Lack of a cation generally limits the use of cationic surfactants to date Was a factor. Low levels of bis-AQA surfactant (3 ppm in the wash liquor) Produces the advantages described in the present invention. Bis-AQA surfactants comprise 5 to 12 It can be formulated over a wide pH range. Bis-AQA surfactants are Can be prepared as a 30% (by weight) solution over the pump Can handle. Bis-AQA surfactants with a degree of ethoxylation of more than 5 are sometimes present in liquid form. And therefore can be provided as close to 100% material. In addition to beneficial handling properties, high The availability of bis-AQA surfactant as a concentrated solution means that transportation costs A substantial economic advantage. Bis-AQA surfactants are known in the art. Unlike some known cationic surfactants, it is compatible with various flavoring ingredients. is there. One aspect of the invention is the use of lipase enzymes in combination with AQA detergents. And to provide a means for improving the removal of greasy / greasy soils. fat Soil / oily soils consist of a mixture of substances, including triglycerides. Contamination before washing During clothing storage, triglycerides in soil are converted to fatty acids by the action of bacteria. Be transformed into The lipase enzyme removes any remaining triglycerides from the fatty acids by washing. It can be used to convert to The fatty acids in the soil are (Eg, Mg²⁺And Ca²⁺Ion) to interact with the insoluble fatty acid Produces gnesium / calcium salt or lime soap. Lime soap, washing solution From the ground, forming a layer of lime soap on the fabric. Repeated washing will result in fine particles The dust on the fabric, preventing the removal of dirt and removing dirt on the fabric after washing. Accumulate lime soap deposits that enhance residue retention. Old / worn cotton fabric Or other problems in the disintegration of the skin surrounding the fibers of other cellulosic fabrics. Exists. Gelatin / amorphous cellulose that decomposes and takes in dust Glue "is generated. In addition, the glue may be a fatty / oily hydrophobic stain (eg, Acts as an ideal substrate for adhesion / retention of collars and pillowcases). Remaining When repeatedly wearing / washing the accumulation of stains, lime soap accumulates and dust accumulates in it. It is taken in and leads to yellowing of the fabric. Eventually, the fabric becomes dingy and worn by consumers Often feels impossible and throws away.   Detergent composition containing bis-AQA surfactant and lipase enzyme, Demonstrates excellent cleaning performance and whiteness performance for products including the technology alone. Now found. These advantages include: (1) Bis-AQA reduces the production of lime soap; (2) (bis- Fatty acids effectively emerge from the soil (by AQA), maximizing lipase activity (soil High levels of fatty acids in the medium inhibit lipase action) It is believed that there is.   Surprisingly, bis-AQA surfactants and cellulolytic enzymes (eg, And / or endoglucanase). Demonstrates excellent cleaning performance and whiteness performance for products containing only one of these components Has now been discovered. These advantages are due to the fact that bis-AQA surfactants It appears to be the result of penetrating dirt effectively. This, in turn, around the fiber Cellulose that breaks down some amorphous cellulose glue (which binds dirt to the fabric) Enhances the access of the protease. Dust captured as glue dissolves Is removed and whiteness is restored. In addition to the benefits of washing, combined cellulose degradation / The bis-AQA system is a cationic It also offers the benefits of flexibility and fabric care over either the system or the enzyme alone.   Detergent containing a combination of bis-AQA surfactant and amylase enzyme in the present invention The composition has excellent detergency and whiteness over compositions containing either technique alone Performance has now been further discovered. These benefits are around the fiber It seems to be the result of improving the dissolution of the residual “glue”. Improving the approach of amylase to sensitive soil components by hydration). Glue melts The whiteness is restored and the captured particulate dust is removed / removed. The decolorizing action of other laundry activators is exerted.                                 Background art   A. Mehreteab and Lopresto (FJ Lop) U.S. Pat. No. 5,441,541 issued Aug. 15, 1995. No. relates to anionic / cationic surfactant mixtures. Murphy (AP . Murphy), Smith (RJM Smith) and Brooks (M. P. Brooks), UK 2,040,99, issued on September 3, 1980. No. 0 relates to ethoxylated cationic surfactants in laundry detergents.                                Summary of the Invention   The present invention provides an enzyme, a non-AQA surfactant and an effective amount of a bioactive agent represented by the following formula: Including s-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant Provide a detergent composition having or prepared by using them in combination . (Where R¹Is a linear, branched or substituted C₈-C₁₈Alkyl, alkenyl, aryl , An alkaryl, ether or glycidyl ether component;^TwoIs C₁− C_ThreeAn alkyl component;^ThreeAnd R^FourCan vary independently, and hydrogen and methyl And X is an anion, and A and A 'are independently variable With each other, C₁-C_FourAlkoxy, wherein p and q can be independently varied And an integer in the range of 1 to 30)                             Detailed description of the invention enzyme   The composition of the present invention contains an enzyme as an essential component. Enzymes are used for various purposes Can be added to the present detergent composition. Its purpose is to transfer effluent dyes in the washing of fabrics. Remove proteins, carbohydrates or triglycerides from the substrate to prevent dyeing and to restore the fabric. Removal of stains due to cerides. Suitable enzymes include plants, animals, Amylase, a protease of any suitable origin, such as bacterial, fungal and yeast origin And lipases, cellulases, peroxidases, and mixtures thereof. It is. Preferred choices include pH activity and / or stability optima, thermal stability, and And active detergents and builder stability. In this regard Such as bacterial amylase, bacterial protease and fungal cellulase. Bacterial or fungal enzymes are preferred.   The term "cleaning enzyme" as used in the present invention refers to laundry compositions, hard surface cleaning compositions Effect, stain removal effect or its effect on the product or personal care detergent composition Any enzyme having other beneficial effects is meant. Preferred cleaning enzymes are protein Hydrolytic enzymes such as ase, amylase and lipase. For washing purpose Preferred enzymes are proteases, cellulases, lipases and peroxidases But not limited to them. Very good for automatic dishwashing Is an amylase and / or a protease.   Enzymes are usually present in detergent compositions or detergents at levels sufficient to provide a "wash effective amount". Is added to the additive additive composition. The term "cleaning effective amount" refers to a substrate such as a cloth or dish. Washing effect, stain removing effect, stain removing effect, whitening effect, deodorizing effect or freshness on Any amount capable of producing an improving effect is meant. For current commercial products In practical terms, typical amounts are up to 5 mg, more typically 0.01 mg to 3 mg active enzyme / gram of detergent composition. In other words, in the present invention, The composition is typically from 0.001% to 5%, preferably from 0.01% to 1%. Contains by weight commercial enzyme products. Protease enzymes are usually from 0.005 to 0 . Enough to provide 1 AU (activity per gram of composition, Anson unit) It is present in these commercial products at a reasonable level. Specific washing, such as in automatic dishwashing In the case of chemicals, minimizing the total amount of non-catalytically active substances will help Increased the active enzyme content of commercial products to improve other end results May be desirable. High activity levels, but also highly concentrated detergent formulations Things may be desirable in things.   Suitable examples of proteases are described in subtilis and B. licheniformis specific It is a subtilisin obtained from a strain. One suitable protease is Denmer Novo Industries A / S (Hereinafter referred to as “Novo”) developed and sold as ESPERASE (trade name) Obtained from a strain of Bacillus having the highest activity across the pH range of 8-12. It is. The preparation of this and similar enzymes is described in Novo, UK Patent 1,243, No. 784. Other suitable proteases include AL from Novo CALASE (trade name) and SAVINASE (trade name), and the Netherlands International Bio-Synthetics, Inc. ionical Bio-Synthetics Inc. MAXATASE from) (Product name). In addition, the European Patent Publication published Jan. 9, 1985 Protease A disclosed in No. 130,756, Europe on Apr. 28, 1987. Patent publication No. 303,761 and European patent publication January 9, 1985. No. 130,756. You. Bacillus sp. SP described in WO 9318140 by Novo . See also high pH protease from NCIMB 40338. Protease, 1 type These enzymes and enzyme detergents, including reversible protease inhibitors, are International Patent Publication No. 9203529. Other preferred proteins Aase includes Procter & Gamble International Publication No. 9510591. Necessary place In this case, proteases that have reduced adsorption and increased hydrolysis International Publication No. 95077 by Gamble (Procter & Gamble) Available as described in No. 91. Recombination for a suitable detergent in the present invention Trypsin-like proteases are described in WO 9425583 by Novo. It is listed.   In more detail, a particularly preferred protease called "Protease D" Are carbonyl hydrolase variants with non-natural amino acid sequences. This No. 08/322, filed October 13, 1994, both of which are incorporated herein by reference. No. 676, entitled "Protease-Containing Cleaning Composition", Baek (A. eck) and U.S. patent application Ser. No. 08 / 322,677, By the name "Cleaning composition containing protease enzymes" by G. Ghosh Number of Bacillus amyloliquefaciens subtilisin as described in patent application According to the ring, at the position of said carbonyl hydrolase corresponding to position +76 Preferably, +99, +101, +103, +104, +107, +1 23, +27, +105, +109, +126, +128, +135, +156 , +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274 In combination with one or more amino acid residue positions corresponding to positions selected from the group comprising Substituting multiple amino acid residues with different amino acids And is derived from the precursor carbonyl hydrolase.   Although not limited to the purpose of an automatic dishwasher, it is particularly suitable for that purpose in the present invention. Novel amylases include, for example, those described in GB 1,296,839 by Novo. Α-Amylase listed, International Bio-Synthetics Inc. (International Bio-Synthetics Inc.) RAPIDASE (trade name) and Novo TERMAMYL (trade name) FUNGAMYL (trade name) from Novo is particularly useful. For example, oxidation Enzyme engineering for improving stability, such as stability, is well known. For example, J. Bio logical Chem. Vol. 260, no. 11, June 1985, See pp6518-6521. Certain preferred embodiments of the present compositions are Stability in detergents such as wash types, especially as used commercially in 1993 Oxidation stability as measured against the reference point of TERMAMYL (trade name) Amylase with improved properties can be used. These preferences in the present invention. New amylase is characterized by, at a minimum, one or more of the following measurable improvements: They share the characteristic of "stability improvement". That is, for example, pH 9- 10 against hydrogen peroxide / tetraacetylethylenediamine in buffer Oxidation stability, e.g., thermal stability at common laundering temperatures such as about 60 <0> C, e.g. The alkali stability at a pH of 8 to 11, all of which are indicated above. Measured against reference point amylase. Stability is a technical text that has published the technology Can be measured using any of For example, see International Publication No. 9402597. See the indicated references. Stability improving amylase is available from Novo or Genenka I Obtained from Genencor International it can. One class of highly preferred amylase in the present invention is one, two or more. Or one or more Bacill, regardless of whether the multiamylase strain is a direct precursor or not. us amylase, especially Bacillus α-amilla In common with the use of site-directed mutagenesis from lyase. Shown above The improved oxidative stability amylase with respect to the standard amylase, For bleaching detergent compositions, more preferably for oxygen bleaching detergent compositions different from chlorine bleaching It is preferable to have. Such preferred amylases include (a) 1 Amirror from Novo WO 94402597 by Novo on Feb. 3, 994 Which, in a variant, is known as B. cerevisiae, known as TERMAMYL (trade name). li position 197 of cheniformis α-amylase; amyloliquefaciens, B . subtilis or B. Homologues of similar progenitor amylase such as stearothermophilus Alanine or threonine, preferably a An amylase further exemplified by a variant substituted with onine, (b) C. Mitchinson, March 13-17, 1994, No. 20 Paper presented at the 7th National Meeting of the American Chemical Society At Genencor International ionical). In the dissertation Bleach in automatic dishwashing detergents deactivates alpha-amylase, but Amylase with improved qualitative properties from licheniformis NCIB 8061 It was noted that Nenka made it. Methionine (Met) is probably denatured Residues to be identified. Met is at positions 8, 15, 197, 256, 30 4,366 and 438 at once, the most stable expression variant, M19 Particularly important particular variants, M197L and M197T, including the 7T variant, Lead. Stability is determined by CASCADE (trade name) and SUNLIGHT (trade name) It was measured in. (C) Particularly preferred amylase in the present invention include international Additional metamorphosis in the direct species, as described in Publication No. 9510603 Amylase mutants, and the assignee Novo as DURAMYL (trade name). Available from Particularly preferred other oxidative stability Improved amylase includes Genencor I International Publication No. WO 9418314 and Novo Described in International Patent Publication No. 9402597. For example Known chimeric, hybrid, and simple mutant forms of amylase available Any other ammonium oxide, such as that induced by site-directed mutagenesis Qualitative improving amylase can also be used. Other preferred enzyme modifications available it can. See WO95050909 by Novo.   Other amylases include those described in WO 95/26397. And PCT / DK96 / 000 co-pending by Novo Nordisk 56. Specific agents used in the detergent composition of the present invention Amylase was assayed using a Padebas (trade name) α-amylase activity assay. Measured temperature range from 25 ° C to 55 ° C and pH value in the range from 8 to 10 At least 25% higher than the specific activity of Termamyl (trade name) Α-amylase that is characterized by ebas (trade name) α-amylase activity assay is described in WO 95/26. 397, pages 9-10). Also included in the present invention are references At least having the amino acid sequence shown in the SEQ ID list in the literature It is an α-amylase with 80% homology. These enzymes are preferably used in whole compositions 0.00018% to 0.060% by weight of pure enzyme, more preferably the total composition From 0.00024% to 0.048% by weight of pure enzyme in laundry detergent compositions Is added.   Cellulases that can be used in the present invention preferably have a maximum between 5 and 9.5. Bacterial and fungal types with appropriate pH are included. March 6, 1984 U.S. Pat. No. 4,435,3 by Barbesgoard et al. 07 is Humicola insolens, Humicola strain DSM1800 or genus Appropriate fungal cellulases from fungi producing cellulases 212 belonging to aeromonas Extracted from the hepatopancreas of the marine mollusk Dolabella Auricula Solander Disclosed. Suitable cellulases are described in GB 2,075,028, Also disclosed in British Patent 2,095,275 and DE-OS-2,247,832 It is shown. CAREZYME (trade name) and CELLUZYME (trade name) ) (Novo) is particularly useful. Novo International Publication No. 9117243 reference.   Suitable lipases for detergent applications are disclosed in GB 1,372,034. Pseudomonas stutzeri ATCC 19.154 Examples include those produced by microorganisms. Japanese Patent Application No. 53-February 24, 1978 See also lipase at 20487. This lipase is lipase P "Amono" Amano Pharmaceutical, located in Nagoya, Japan, under the brand name of "Amono-P" Tikaru (Amano Pharmaceutical Co. Ltd.) I can do it. Other suitable commercial lipases include Amano-CES, for example, Japan Viscosum var. From Toyo Brewery located in Tagata, Japan. lipolyticum Lipase ex Chromobacter viscosum such as NRRLB3663, Uye, USA Biochemical Corp. (U.S. Biochemical Corp.) And Chromobacter from Disynth Co., The Netherlands viscosum lipase; and the lipase exPseudomonas gladioli. Europe Novo derived from Humicola lanuginosa found in State Publication No. 341,947 The LIPOLASE® enzyme commercially available from Is a preferred lipase. Stabilized against peroxidase enzymes Lipase and amylase variants are described in WO 94414951 by Novo. No. International Publication Nos. WO 9205249 and RD943590 See also 44.   Despite the large number of publications on lipase enzymes, Humicola lanuginosa Lipase derived from Aspergillus oryzae as a host Mi has been widely used as an additive in fabric laundry products. This is before Obtained from Novo Nordisk under the trade name Lipolase (trade name) Wear. Novo Nordisk to optimize Lipolase stain removal performance Produced a number of variants. It is described in WO 92/052496. As noted, the native D96L mutant of Humicola lanuginosa lipase was Improves the lard stain removal efficiency 4.4 times compared to Pase (enzyme from 0.075 2.5 mg protein / liter range). Novo Nordisk Research Publication No. issued March 10, 1994, 35944 is a ripper Ze mutant (D96L) in an amount of 0.001 to 100 mg (5-500,000 LU / liter). (Tle) Lipase mutant / washing liquid can be added in an amount corresponding to liter It is disclosed that there is. The present invention specifically relates to D96L from 50 LU to 8500 LU / When used at levels in the range of liters of washing liquid, the method disclosed in the present invention provides Low levels of D96L mutations in detergent compositions containing su-AQA surfactant The use of the body provides the advantage of improving the whiteness maintenance of the fabric.   Cutinase enzymes suitable for use in the present invention are internationally available from Genenka. It is described in Japanese Unexamined Patent Publication No. 8809367.   Peroxidase enzymes are removed from the substrate for "solution bleaching" or during washing To prevent dyes or pigments from being transferred to other substrates present in the wash liquor. For example, even when used in combination with an oxygen source such as percarbonate, perborate, hydrogen peroxide, etc. Good. Known peroxidases include horseradish peroxidase, ligninase, And haloperoxidases such as chloro- or bromo-peroxidase No. Peroxidase-containing detergent compositions were obtained from Novo, October 1989. International Patent Publication No. 89099813 on Nov. 19 and International Publication No. No. 8909813.   A range of enzyme materials and their means of adding to synthetic detergent compositions are ・ By International (Genencor International) International Publication Nos. 9307263 and 9307260, International Patent Publication No. WO 8990894 and McCarty Et al., U.S. Pat. No. 3,553,139, issued Jan. 5, 1971, ing. The enzyme was purchased from the United States by Place et al., July 18, 1978. No. 4,101,457, and Hugh on March 26, 1985. es) in U.S. Pat. No. 4,507,219. Liquid detergent Useful enzyme materials for formulations and their addition to such formulations are described in April 1981. No. 4,261,868 to Hora et al. ing. Detergent enzymes can be stabilized by various techniques. Enzyme cheap The stabilization technique is described in US Pat. 3,600,319, by Venegas, October 2, 1986. EP-A-199,405 and EP-A-200,586 on the 9th And is exemplified. Enzyme stabilization systems are described, for example, in US Pat. No. 3,519. 570. Protease, xylanase and cellulase Useful Bacillus sp. AC13 is published by Novo in International Publication No. 940 No. 1532.Bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant   The second essential component of the present invention comprises an effective amount of a bis-AQA surfactant represented by the following formula: Contains sexual agents. (Where R¹Has 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably Straight-chain, branched or substituted alkyl, alkenyl containing from 8 to 14 carbon atoms An aryl, alkaryl, ether or glycidyl ether component; R^TwoIs an alkyl group containing from 1 to 3 carbon atoms, preferably methyl;^Threeand R^FourCan vary independently and include hydrogen (preferred), methyl and ethyl Selected from the group^-Chloride, bromide, methyl sulfate And anions such as sulfates, where A and A 'can vary independently and Each C₁-C_FourAlkoxy, especially ethoxy, propoxy, butoxy and their Wherein p is 1 to 30, preferably 1 to 15, and more preferably Is from 1 to 8, even more preferably from 1 to 4, and q is from 1 to 30, preferably 1 to 15, more preferably 1 to 8, still more preferably 1 to 4, most preferably Also preferably, p and q are 1.)   Hydrocarbyl substituent R¹Is C₈-C₁₂, Especially C₈-C_TenBis-AQA The compound increases the dissolution rate of laundry granules, especially under cold water conditions, compared to long chain substances. You. Therefore, C₈-C₁₂Bis-AQA surfactants are preferred by some formulators Sometimes. Bis-AQA interface used to prepare a final laundry detergent composition The level of activator is 0.1% to 5%, typically 0.45% to 2.5% by weight Range. The weight ratio of bis-AQA to percarbonate bleach was 1:10. 0 to 5: 1, preferably 1:60 to 2: 1, most preferably 1:20 to 1 : 1 range.   The present invention is directed to improving the performance of cleaning compositions containing other optional components. An "effective amount" of the bis-AQA surfactant is used. Bis-AQA herein An "effective amount" of surfactant is directly or significantly at a 90% confidence level. -Improve the performance of the cleaning composition against at least some of the soil and stains Means a sufficient amount. Therefore, if the target is a composition containing a specific food stain, The formulator must at least directly improve the cleaning performance against such stains. Use sufficient bis-AQA. Similarly, if the target contains clay stains In products, formulators at least directly increase the cleaning performance against such soils. Use sufficient bis-AQA to improve.   Bis-AQA surfactant achieves at least a direct improvement in cleaning performance May be used in combination with other detersive surfactants at levels effective for No. In the context of a fabric laundry composition, such "use level" is a measure of dirt and stains. Not only the type and intensity, but also the washing water temperature, washing water volume and washing machine type. Can be changed.   For example, a top-mounted vertical axis U using 45 to 83 liters of water in the washing bath . S. Type automatic washing machine, 10 to 14 minutes washing cycle and 10 to 50 ° C In washing water temperature, 2 ppm to 50 ppm, preferably 5 ppm to 25 pp Preferably, m of the bis-AQA surfactant is contained in the wash water. From 50ml Based on the usage rate of 150 ml / wash load, this is a heavy duty liquid wash In the case of rinses, 0.1% to 3.2%, preferably 0.3% to 1.5% -Converted to the concentration (weight) of AQA surfactant in the product. 60g to 95g / wash Based on the usage rate of the rinsing load, this is a high concentration ("compact") granular laundry detergent (Density greater than 650 g / l), 0.2% to 5.0%, preferred Or 0.5% to 2.5% bis-AQA surfactant concentration in the product (weight) Converted. Based on the usage rate of 80 g to 100 g / wash load, this Spray-dried granules (ie "fluffy", density less than 650 g / l) 0.1% to 3.5%, preferably 0.3% to 1.5% of bis-AQ It is converted to the concentration (weight) of the surfactant A in the product.   For example, top-loading horizontal axis Europe with 8 to 15 liters of water in the washing bath Type automatic washing machine, 10 to 60 minute washing cycle and 30 ° C to 95 ° C washing water At temperature, 13 ppm to 900 ppm, preferably 16 ppm to 390 p Preferably, pm of the bis-AQA surfactant is contained in the wash water. 45ml Based on usage rates of 270 ml / wash load, this is a heavy duty liquid 0.4% to 2.64%, preferably 0.55% to 1.1% for laundry detergent Of the bis-AQA surfactant in the product (weight). From 40g to 21 Based on the usage of 0 g / wash load, this is a high concentration (“compact”) granule For laundry detergents (density greater than 650 g / l), from 0.5% to 3.5 %, Preferably 0.7% to 1.5% of the bis-AQA surfactant in the product ( Weight). Based on the usage rate of 140g to 400g / washing load, This is because the spray-dried granules (ie, "fluffy", having a density of 650 g / liter) 0.13% to 1.8%, preferably 0.18% to 0.7% It is converted to the product concentration (weight) of 6% bis-AQA surfactant.   For example, top-loading vertical axis days using 26 to 52 liters of water in the washing bath This type of automatic washing machine, 8 to 15 minute washing cycle and 5 to 25 ° C washing water temperature In 1.67 ppm to 66.67 ppm, preferably 3 ppm to 6 p Preferably, pm of the bis-AQA surfactant is contained in the wash water. 20ml Based on the usage rate of 30ml / wash load, this is a heavy duty liquid wash 0.25% to 10%, preferably 1.5% to 2% of bis-A for rinsing It is converted to the concentration (weight) of the QA surfactant in the product. 18g to 35g / washing load Based on the load, the use of high-density (“compact”) granular laundry detergents If (density is greater than 650 g / l), preferably 0.25% to 10% Is converted to the product concentration (weight) of 0.5% to 1.0% bis-AQA surfactant Is done. Based on the usage rate of 30 g to 40 g / wash load, this is spray drying For granules (ie "fluffy", density less than 650 g / l) , 0.25% to 10%, preferably 0.5% to 1% bis-AQA field It is converted to the concentration (weight) of the surfactant in the product.   As can be seen from the above description, the screws used in the washing situation of the machine washing -The amount of AQA surfactant will vary depending on the user's habits and practices, and the type of washing machine. Can be. However, in this context, prior to one of the bis-AQA surfactants The advantage that was not observed was that other surfactants (generally anionic Or an anion / non-ionic mixture). To improve performance at least directionally over a range of stains and stains. It is possible. This means that various cationic surfactants can be used at the stoichiometric level. Or other groups in the art for use with or near anionic surfactants It is distinguished from adult. Generally, in the practice of the present invention, in a laundry composition The weight ratio of bis-AQA: anionic surfactant is 1:70 to 1: 2, preferably. Or 1:40 to 1: 6, preferably 1:30 to 1: 6, most preferably 1 : 15 to 1: 8. Both anionic and nonionic surfactants Bis-AQA: mixed anion / non-ionic weight ratio in the containing laundry composition Ranges from 1:80 to 1: 2, preferably from 1:50 to 1: 8.   Anionic surfactants, optional nonionic surfactants and betaines, salts And various other cleaning compositions containing special surfactants such as amine oxides, The method of the present invention may be formulated using an effective amount of a bis-AQA surfactant. it can. Such compositions include hand dishwashing products (especially in liquid or gel form), hard surfaces Detergents, shampoos, personal wash bars, wash bars, etc. Not limited. Differences in the habits and practices of users of these compositions are extremely small From about 0.25% to about 5%, preferably from about 0.45% to about 2% by weight of bis- It is sufficient to add the AQA surfactant into such a composition. Again, granules And the bis-AQA present in such compositions as in the case of liquid laundry compositions The weight ratio of surfactant to other surfactants is small. That is, the anionic system Less than stoichiometric for surfactants. Preferably, such a cleaning composition comprises It consists of the bis-AQA / surfactant ratio just described in the case of the machine laundry composition.   In contrast to other cationic surfactants known in the art, the present invention The bis-alkoxylated cationic surfactant in Ming is a nonionic surfactant. Mixed interfaces containing very little and, for example, alkyl sulfate surfactants It has sufficient solubility that can be used in combination with the activator system. This is the upper Self-contained automatic washing machines, especially those used in North America, and Japanese It was previously intended to be used in automatic washing machines of the type used in This can be an important consideration for the formulator of the type of detergent composition being used. Typically Such compositions may have a composition of from about 25: 1 to about 1:25, preferably from about 20: 1 to about Has a weight ratio of anionic surfactant to nonionic surfactant in the range of 3: 1 . This is typically from about 10: 1 to 1:10, preferably from about 5: 1 to about 1: 1. This can be contrasted with a European formulation comprising an anion: non-ion ratio in the range of 1: 1.   Preferred ethoxylated cationic surfactants in the present invention are Akzo Novell ・ Chemicals Company (Akzo Nobel Chemicals Comp) any) under the trade name ETHOQUAD. Instead, these materials The charge can be based on a variety of different reaction mechanisms (where “EO” is —CH_TwoCH_TwoO- (Representing a unit).   Mechanism 1   Mechanism 2   Mechanism 3   Mechanism 4             The economic reaction mechanism is as follows.   Mechanism 5   The following parameters summarize optional and preferred reaction conditions for mechanism 5 is there. Step 1 of the reaction is preferably performed in an aqueous medium. The reaction temperature is Typically, it is in the range of 140-200 ° C. Reaction pressure is 50-1000 psi g. A basic catalyst, preferably sodium hydroxide, can be used. Anti The molar ratio of the reactants is amino: alkyl sulfate = 2: 1 to 1: 1. The reaction is good Preferably C₈-C₁₄This is performed using an alkyl sulfate sodium salt. Ethoxylation And the quaternization step is performed using conventional conditions and reactions.   In some cases, the reaction mechanism 5 is sufficient to allow a gel to form in the aqueous reaction medium. This produces a soluble product. The required product can be recovered from the gel, but will be described later An alternative two-step synthesizer 6 may be more desirable in commercial environments. You. The first step in the mechanism 6 is performed similarly to the mechanism 5. Second step (Ethoxylation) preferably results in ethylene oxide and a quaternary surfactant The reaction is performed using an acid such as HCl. As shown below, chlorohydrin, That is, chloroethanol also reacts to produce bishydroxyethyl derivatives be able to.   For the reaction mechanism 6, the following parameters are optional and related to the first step: It summarizes the preferred reaction conditions. The first step is preferably an aqueous medium Done throughout the body. Reaction temperatures are typically in the range of 100-230 ° C. Anti The reaction pressure is 50-1000 psig. Base, preferably sodium hydroxide HSO formed during the reaction using_FourAnd can be reacted. Or excess It is also possible to react with an acid using an amine. Amine alkyl sulfate The molar ratio to the typical is 10: 1 to 1: 1.5, preferably 5: 1 to 1 : 1.1, more preferably 2: 1 to 1: 1. In the product collection step , The required substituted amine is simply a distinct phase from the insoluble aqueous reaction medium. Purely separated. The second step in this process is to run under conventional reaction conditions. Done. Further ethoxylation to produce bis-AQA surfactant and quaternary The conversion is carried out under standard reaction conditions.   Mechanism 7 optionally comprises ethylene oxide under standard ethoxylation conditions but without catalyst. To achieve monoethoxylation.   The following mechanism illustrates these additional reaction mechanisms, where "EO" is -CH_TwoCH_TwoRepresents the O-unit. In this reaction, an inorganic base, an organic base or Is the HSO formed using any of the excess amine reactants_FourNeutralize.   Mechanism 6   Mechanism 7   The following further describes some of the above reactions, merely for the benefit of the formulator, It is not intended to limit the reaction.Synthetic A Preparation of N, N-bis (2-hydroxyethyl) dodecylamine   19.86 g of sodium dodecyl sulfate (0.06921 mol), 14.55 g of diethanolamine (0.1348 mol), 7.6 g of 50% by weight sodium hydroxide. Thorium solution (0.095 mol) and 72 g of distilled H_TwoO for glass haute Add to lay liner. Glass liner with 500ml stainless steel rocking Sealed in an autoclave for 3-4 hours under 300-400 psig of nitrogen. Heat to 0-180 ° C. Cool the mixture to room temperature and remove the liquid contents of the glass liner. Pour into a 250 ml separatory funnel with 80 ml chloroform. Minutes of funnel Shake well for a while, then allow the mixture to separate. Remove the lower chloroform layer, The product is obtained by evaporating the chloroform.Synthetic B Preparation of N, N-bis (2-hydroxyethyl) dodecylamine   One mole of sodium dodecyl sulfate is prepared in the manner described in Synthesis A in the presence of a base. React with 1 mol of ethanolamine. The resulting 2-hydroxyethyl dodecyl Recover amine and react with 1-chloroethanol to prepare title compound .Synthetic C Preparation of N, N-bis (2-hydroxyethyl) dodecylamine   19.86 g of sodium dodecyl sulfate (0.06921 mol), 21.37 g ethanolamine (0.3460 mol), 7.6 g 50% by weight sodium hydroxide Solution (0.095 mol) and 72 g of distilled H_TwoO for glass autoclave Add to briner. Glass liner with 500ml stainless steel rocking Seal in toclave, 3-4 hours, 300-400 psig nitrogen Heat to 160-180 ° C underneath. Cool the mixture to room temperature and remove the liquid in the glass liner. Pour the contents together with 80 ml of chloroform into a 250 ml separatory funnel. Low The mixture is shaken well for several minutes, after which the mixture is allowed to separate. The lower chloroform layer Withdraw and evaporate the chloroform to obtain the product. Smell the product at 120-130 ° C To react with 1 molar equivalent of ethylene oxide in the absence of a basic catalyst to give the final product obtain.   Further ethoxylation of the bis-substituted amine prepared in the above synthesis in a standard manner can do. Quaternized with an alkyl halide, the bis-A Generating a QA surfactant is a routine procedure.   The following is the bis-AQA surfactant used in the present invention according to the above description. 5 is a non-limiting specific example of a sex agent. Bis-AQA surfactant herein The degree of alkoxylation described in the above, with respect to the conventional ethoxylated nonionic surfactant Understand common practice and report as an average. this is, Because the ethoxylation reaction generally produces a mixture of substances with different degrees of ethoxylation It is. Therefore, all EO values are reported except as integers (eg, "EO2.5 , "EO3.5") are not uncommon.   ^*Ethoxy optionally terminated with methyl or ethyl   A highly preferred bis-AQA compound for use in the present invention has the formula: Is what is done. (Where R¹Is C₈-C₁₈Hydrocarbyl and their mixed components, preferably C₈ , C_Ten, C₁₂, C₁₄Alkyl and their mixed components, X, provide charge balance. Any conventional anion, preferably chloride)   With respect to the general structure of the bis-AQA surfactant described above, the preferred compound And R¹Coconut (C₁₂-C₁₄Alkyl) fraction derived from fatty acids,^TwoBut Chill, ApR^ThreeAnd A'qR^FourAre monoethoxy, Preferred types of compounds are referred to herein as “CocoMeEO2” in the list above. "Or" bis-AQA-1 ".   Other bis-AQA compounds useful in the present invention include those represented by the following formula: Including. (Where R¹Is C₈-C₁₈Hydrocarbyl, preferably C₈-C₁₄Alkyl Independently p is 1 to 3, q is 1 to 3, R¹Is C₁-C_ThreeAlkyl , Preferably methyl, and X is an anion, especially chloride or bromide )   Other compounds of the type described above include ethoxy (CH_TwoCH_TwoO) Unit (E O) is butoxy (Bu) isopropoxy [CH (CH_Three) CH_TwoO] and [CH_Two CH (CH_ThreeO)] unit (i-Pr) or n-propoxy unit (pr ) Or mixed components of EO and / or Pr and / or i-Pr units And a compound substituted by   Highly preferred bis-AQA compounds for use in underbuilder formulations The object is where p and / or q are integers in the range between 10 and 15 It is of the formula. This compound is particularly useful in hand laundry detergent compositions.Non-AQA cleaning surfactant   In addition to the bis-AQA surfactant, the composition of the present invention preferably comprises a non-AQA It further contains a detersive surfactant. Non-AQA detersive surfactants essentially include: Any anionic, nonionic, or additional cationic surfactant may be included .Anionic surfactant   Anionic interfaces useful in the present invention, typically at a level of 1% to 55% by weight Non-limiting examples of activators include conventional C₁₁-C₁₈Alkylbenzene sulfonate (" LAS "), first (" AS ") branched chain and random C_Ten-C₂₀Alkylsulf , Formula CH_Three(CH_Two)_x(CHOSO_Three ^-M⁺) CH_ThreeAnd CH_Three(CH_Two)_y( CHOSO_Three ^-M⁺) CH_TwoCH_ThreeC_Ten-C₁₈Second (2,3) alkyl sulfate Wherein x and (y + 1) are at least 7, preferably at least 9 And M is a water-soluble cation, especially sodium, such as oleyl sulfate. Unsaturated sulfate, C₁₂-C₁₈Alpha-sulfonated fatty acid ester, C_Ten− C₁₈Sulfated polyglucoside, C_Ten-C₁₈Alkyl alkoxy sulfate ("A ExS "; especially EO1-7 ethoxysulfate), and C_Ten-C₁₈Alkyl Alkoxy carbonates (especially EO1-5 ethoxy carbonate) are listed. I can do it. C₁₂-C₁₈Betaine and sulfobetaine ("sultaine"), C_Ten -C₁₈An amine oxide can also be included in the overall composition. C_Ten-C₂₀Conventional Soaps may also be used. If high foaming is required, the branched chain C_Ten-C₁₆Use soap You may. Other useful traditional surfactants are listed in the standard text .Nonionic surfactant   Nonionic interfaces useful in the present invention, typically at a level of 1% to 55% by weight Non-limiting examples of activators include alkoxylated alcohols (AE), alkyl phenols , Polyhydroxy fatty acid amide (PFAA), alkyl polyglycoside (AR G) and C_Ten-C₁₈Glycerol ether.   More specifically, primary and secondary aliphatic alcohols and 1-25 moles of ethylene oxide The product (AE) condensed with a resin is used as the nonionic surfactant in the present invention. Suitable for The alkyl chain of the aliphatic alcohol may be linear or branched, primary or The second can be any and generally contains from 8 to 22 carbon atoms. The preferred ones are Alkyl groups containing from 8 to 20 carbon atoms, more preferably from 10 to 18 carbon atoms. 1 to 10 moles, preferably 2 to 10 moles per mole of alcohol and alcohol 7, most preferably a condensation product with 2 to 5 ethylene oxides. This type of Examples of commercially available nonionic surfactants include Union Carbide Co. Sold by Union Carbide Corporation Tergitol (trade name) 15-S-9 (C₁₁-C_FifteenLinear alcohol and Product condensed with 9 moles of ethylene oxide) and Tergitol (trade name) 24- L-6 (C₁₂-C₁₄A condensation product of primary alcohol and 6 moles of ethylene oxide. And a narrow molecular weight distribution), Shell Chemical Company (Shell Ch) Neodol (trade name) 45- sold by Chemical Company) 9 (C₁₄-C_FifteenCondensation product of linear alcohol and 9 mol of ethylene oxide), Neo dol (trade name) 23-3 (C₁₂-C₁₃Linear alcohol and 3 moles of ethylene oxide And Neodol (trade name) 45-7 (C₁₄-C_FifteenStraight-chain alcohol And Neodol (trade name) 45-5 (C₁₄-C_FifteenCondensation product of linear alcohol and 5 mol of ethylene oxide), Proctor -& Gamble Company (Procter & Gamble Company) Sold by Kyro (brand name) EOB (C₁₃-C_FifteenAlcohol and 9 moles of acid Condensation product with ethylene fluoride), Genapol LA 03 sold by Hoechst 0 or 050 (C₁₂-C₁₄Condensation of alcohol with 3 or 5 moles of ethylene oxide Product). HLB preference in these AE nonionic surfactants The preferred range is 8 to 11, most preferably 8-10. Propylene oxide and Condensates with butylene oxide may also be used.   Another class of preferred nonionic surfactants for use in the present invention is It is a polyhydroxy fatty acid amide surfactant represented by the formula. (Where R¹Is H, C_1-4Hydrocarbyl, 2-hydroxyethyl, 2hydroxy Propyl or a mixture thereof,^TwoIs C_5-31Hydrocarbyl, Z is a linear hydrocarbyl chain having at least three hydroxyls directly attached to the chain Polyhydroxyhydrocarbyl or an alkoxylated derivative thereof)   Preferably, R¹Is methyl and R^TwoIs linear C_11-15Alkyl, C_15-17Archi An alkenyl chain such as coconut alkyl or a mixture thereof, In the reductive amination reaction, glucose, fructose, maltose, It is derived from reducing sugars such as glucose. A typical example is C₁₂-C₁₈And C₁₂-C₁₄ N-methylglucamide is exemplified. U.S. Patent No. 5,194,639 and See U.S. Patent No. 5,298,636. N-alkoxy polyhydroxy fatty acids Amides can also be used. See U.S. Patent No. 5,489,393.   U.S. Pat. No. 4,411,211, 1986 issued to Llenado. No. 6,565,647, such as those disclosed in US Pat. Hydrophilic groups containing 0 to 16 carbon atoms and 1 such as, for example, polyglycosides . 3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7 sugars Alkyl polysaccharides having a polysaccharide hydrophilic group containing a saccharide unit are also used in the present invention. It is useful as an ionic surfactant. Any reduction containing 5 or 6 carbon atoms Sugar can also be used. For example, the glucose, galactose and galactosyl components , The glucosyl moiety can be substituted (optionally, the hydrophobic groups can be 2-, 3-, 4- -At the same position, glucose is different from glucoside or galactoside. Or produce galactose). For example, an inter-saccharide bond may be added to an additional saccharide unit. One position and 2-, 3-, 4- and / or 6-positions in the prosaccharide unit Between.   Preferred alkyl polyglycosides are those represented by the following formula:                        R^TwoO (C_nH_2nO)_t(glycosyl)_x (Where R^TwoIs alkyl, alkylphenyl, hydroxyalkyl, hydroxy Selected from groups containing alkyl phenyl and mixtures thereof, in which alkyl The radical contains 10 to 18, preferably 12 to 14 carbon atoms and n is 2 or 3, preferably 2, t is 0 to 10, preferably 0, and x is 1.3 10, preferably 1.3 to 3, most preferably 1.3 to 2.7)   Glycosyl is preferably derived from glucose. Prepare these compounds To produce alcohol or alkylpolyethoxy alcohol first, Reacting it with glucose or a glucose source to produce glucosides (Attached at 1-position). Thereafter, the additional glycosyl unit is replaced by its own 1-position Position and 2-, 3-, 4- and / or 6-position of the pre-glycosyl unit, preferred Or predominantly between the two positions.   Alkylphenol polyethylene, polypropylene and polybutylene oxy Sid condensates are also used as the surfactant-based nonionic surfactant of the present invention. Suitably, polyethylene oxide condensates are preferred. These compounds include linear or Represents 6 to 14 carbon atoms in any of the branched structures, preferably 8 to 14 Alkylene oxides of alkylphenols having alkyl groups containing carbon atoms And condensation products of In a preferred embodiment, the ethylene oxide is 2 To 25 moles, more preferably 3 to 15 moles of ethylene oxide mole / alkyl Phenol is present in an amount equal to moles. Commercially available of this type Non-ionic surfactants include GAF Corporation (GAF Corporation) ION) sold by Igepal (trade name) CO-630 and ROHMUAN Sold by Dohas Company (Rohm & Haas Company) Triton (trade name) X-45, X-114, X-100 and X-102 No. These surfactants are alkylphenol alkoxylates (eg, (For example, alkylphenol ethoxylate).   For the condensation of ethylene oxide with propylene oxide and propylene glycol Condensation products with hydrophobic bases formed from Suitable for use as a surfactant. The hydrophobic portion of these compounds is preferably Has a molecular weight of 1500 to 1800 and is water-insoluble. To this hydrophobic part The addition of the polyoxyethylene component tends to increase the water solubility of the molecule as a whole. And the liquid properties of the product correspond to condensation with up to 40 moles of ethylene oxide, Retained to the point where the polyoxyethylene content is 50% of the total weight of the condensation product . Examples of compounds of this type include certain commercially available products sold by BASF. Pluronic (trade name).   Ethylene oxide, resulting from the reaction of propylene oxide with ethylenediamine The product condensed with the product is also a nonionic surfactant-based nonionic surfactant according to the present invention. Suitable for use as an activator. The hydrophobic component of these products is ethylene diamine From the reaction product of propylene oxide and excess propylene oxide, generally from 2500 It has a molecular weight of 3000. The hydrophobic component contains 40% to 80% by weight of the condensed product. % Polyoxyethylene and has a molecular weight of 5,000 to 11,000 To a certain extent with ethylene oxide. This type of nonionic surfactant Examples include certain commercially available Tetronic (sold by BASF) Trade name) compounds.Additional cationic surfactant   Suitable cationic surfactants are preferably at least one ester (such as That is, a surfactant containing a -COO-) bond and at least one cationically charged group It is a water-dispersible compound having the properties of a surfactant.   Other suitable cationic surfactants include Mono C₆-C₁₆, Preferably C₆− C_TenQuaternary amines selected from N-alkyl or alkenyl ammonium surfactants Ammonium surfactants. In this case, the remaining N positions are methyl, Substituted by a roxyethyl or hydroxypropyl group. Choline ester world Other suitable cationic ester surfactants, including surfactants, include, for example, rice Nos. 4,228,042, 4,239,660 and 4,260, No. 529.Optional detergent ingredients   In the following, various optional other ingredients that may be used in the composition of the present invention are described. Although described, it is not intended to limit the ingredients.Enzyme stabilization system   The enzyme-containing liquid composition of the present invention is preferably used in an amount of about 0.001% to about 1%. 0%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to It also contains about 6% by weight of the enzyme stabilizing system. Enzyme stabilization systems are compatible with detergent enzymes. Any stabilizing system may be used. These systems can be internalized by other compound activators Or the manufacturer of the enzyme in a state where it can be added to the formulator or detergent, for example. May be added separately. Such stabilizing systems include, for example, calcium ions, boron Acids, propylene glycol, short chain carboxylic acids, boric acid, and mixtures thereof. And various stabilization questions depending on the type and physical form of the detergent composition. The subject is considered to be processed.   One approach to stabilization is to use calcium and calcium in the final composition. And / or use a water-soluble source of such ions to provide magnesium ions to the enzyme. Is Rukoto. Calcium ions are generally more effective than magnesium ions Yes, the use of only one type of cation is preferred in the present invention. Typical The detergent composition, in particular the liquid composition, may have a concentration of from 1 to 30 per liter of the final detergent composition. From 2 to 20, more preferably from 8 to 12 mmol of calcium ions. However, it may vary depending on factors including the multiplicity, type and level of enzyme to be added. Is possible. Preferably, for example, calcium chloride, calcium hydroxide, ants Calcium acid, calcium malate, calcium maleate, calcium hydroxide And water-soluble calcium or magnesium salts, including calcium acetate You. More generally, it corresponds to calcium sulfate or the calcium salts mentioned in the examples. Magnesium salt may be used. Calcium and / or magnesium Further increases in the bell, for example, promote the lipolytic effect of certain types of surfactants Of course useful for.   Another approach for stabilization is by using boric acid species. C See U.S. Patent No. 4,537,706 to Severson. Bo When using an acid stabilizer, the boric acid stabilizer may comprise up to 10% or more of the composition. It may be a level. However, more typically, boric acid levels up to about 3% by weight Alternatively, sodium borate or another borate compound such as orthoborate may be used as a solution. Suitable for detergent applications. Phenyl borate, butane borate or para-broborate Substituted boric acid, such as mophenyl, can be used in place of boric acid and can be used in detergent compositions. Reducing the level of total boron in the system is due to the use of these substituted boron derivatives. It is possible.   Certain cleaning composition stabilizing systems, such as automatic dishwashing compositions, have 0-10%, Preferably, it may further comprise from 0.01% to 6% by weight of a chlorine bleach scavenger, , Chlorine-bleaching species present in many water supplies attacked enzymes, especially under alkaline conditions R It is added to prevent deactivation. Chlorine levels in water are typical Although it is in the range of 0.5 ppm to 1.75 ppm and is small, For example, available chlorine in the total volume of water that contacts the enzyme during dishwashing or fabric washing Can be relatively large, and therefore the stability of the enzyme to the chlorine used Sex is sometimes problematic. Because percarbonate can react with chlorine bleach, On the other hand, the use of additional stabilizers may improve There are things that are not important. Suitable chlorine scavenger anions are well known and readily available. Available and, if used, sulfite, hydrogen sulfite, thiosulfate, iodide Or a salt containing an ammonium cation. Carbamate, Asco Antioxidants such as rubate, ethylenediaminetetraacetic acid (EDTA) or Such as alkali metal salts, monoethanolamine (MEA) and mixtures thereof Organic amines can be used as well. Similarly, special enzyme suppression systems are Element can be added to have maximum compatibility. Bisulfite, nitrate , Chloride; sodium perborate tetrahydrate, sodium perborate monohydrate and percarbonate Sources of hydrogen peroxide such as sodium, phosphates, condensed phosphates, acetates, benzoates, Enoate, formate, lactate, malate, tartrate, salicylate, etc. and it Other conventional scavengers, such as mixtures thereof, can be used if desired. one In general, the function of the chlorine scavenger has been replaced by another designated component in the recognized better function. More possible (eg, a hydrogen peroxide source) to achieve the required functionality As long as the compound to be present is present in the embodiment containing the enzyme of the present invention, a separate chlorine scavenger There is no absolute need to add. Even in these cases, scavengers seek optimal results. Added only for In addition, the formulator has no Chemists should avoid using any incompatible enzyme scavengers or stabilizers. Will exercise their normal workmanship. Regarding the use of ammonium salts, these salts Is easily mixed with the detergent composition, but absorbs water during storage and / or D It tends to release a. Therefore, if such materials are present, they are preferably No. 4,652,392 to Baginski et al. Protected within particles such asbleach   The detergent composition of the present invention may optionally contain a bleaching agent. Bleach present If so, especially for fabric laundering, typically from about 1% to about 30% of the detergent composition. %, More typically at a level of about 5% to about 20%. For use in the present invention The bleaching agents used are now well known or will become known for fabric cleaning purposes, hard surface cleaning Any of the bleaching agents useful for detergent compositions for purposes or other cleaning purposes It may be. These include oxygen bleaches and other bleaches. For example, a perborate drift such as sodium perborate (eg, monohydrate or tetrahydrate). Whitening agents can be used in the present invention.   Another type of bleach that can be used without limitation is percarboxylic acid bleach and Including its salts. A suitable example of this class of bleach is magnesium monoperoxy. Ciphthalate hexahydrate; metachloroperbenzoic acid, 4-nonylamino-4-oxo Magnesium salts of peroxybutyric acid and diperoxide decandioic acid . Such bleaches are available from Hartma, published November 20, 1984. n) U.S. Pat. No. 4,483,781, filed Jun. 3, 1985 U.S. Patent Application No. 740,446 to Burns et al., February 2, 1985. European Patent Application No. 0,133,354 issued by Bank et al. And U.S. Pat. No. 4,4 by Chung et al., Issued Nov. 1, 1983. No. 12,934. Highly preferred bleaches include Burns (Bu) No. 4,634,551 issued Jan. 6, 1987 to Rns et al. 6-nonylamino-6-oxoperoxycaproic acid as described in It is.   Peroxide bleaches can also be used. Suitable peroxide bleaching compounds include carbonic acid Sodium peroxyhydrate and equivalent "percarbonate" bleach, sodium pyrophosphate Lium peroxy hydrate, urea peroxy hydrate, sodium peroxide You. Persulfate bleach (e.g., commercially manufactured by DuPont) OXONE) can also be used.   Preferred percarbonate bleaches have a flatness ranging from 500 microns to 1000 microns. Dry particles having a uniform particle size, wherein 10% by weight or less of the particles are 200 Less than 10% by weight of the particles, less than Contains dry particles. Optionally, the percarbonate is a silicate, borate or water-soluble surfactant Can be coated. Percarbonates are available in various trades such as FMC, Solvay and Tokai Electrification. Available from commercial suppliers.   Bleaches other than oxygen bleaches are also known in the art, and in the present invention Can be used. One class of non-oxygen bleaches of particular interest is sulfone Light-activated bleaches such as zinc and / or aluminum phthalocyanine Can be Published July 5, 1977 to Holcombe et al. See U.S. Pat. No. 4,033,718. If this is used, the detergent composition will Typically, 0.025% to 1.25% by weight of these bleaches, especially sulfonic acids Contains zinc phthalocyanine.   Mixtures of bleach can also be used.Bleach activator   Bleach activators are a preferred component of oxygen bleaches containing detergent compositions. bleaching If an activator is present, it is typically a bleaching composition comprising a bleach and a bleach activator. Present at a level of 0.1% to 60% of the composition, more typically 0.5% to 40% I do.   Peroxide bleaches, perborates, etc., preferably correspond to the bleach activator in aqueous solution. In-situ production of peroxy acids or peracids (i.e. during the cleaning process) Used in combination with a bleach activator. Various non-limiting examples of activators are available from Mao et al. U.S. Pat. No. 4,915,854, issued Apr. 10, 1990 and the United States It is disclosed in Japanese Patent No. 4,412,934. Nonanoyloxybenzenesul Phonate (NOBS) and tetraacetylethylenediamine (TAED) activity The agents are representative, and mixtures thereof can also be used. In the present invention Other representative bleaching agents and activators useful are described in U.S. Pat. 551.   Highly preferred amide-derived bleach activators are of the formula       R¹N (R^Five) C (O) R^TwoC (O) L or R¹C (O) N (R^Five) R^TwoC (O) L (Where R¹Is an alkyl group containing 6 to 12 carbon atoms, R^TwoHas 1 to 6 carbon atoms Including alkylene, R^FiveIs H or alkyl, aryl containing 1 to 10 carbon atoms Or alkaryl and L are any suitable leaving groups)   The leaving group is the result of a nucleophilic attack on the bleach activator by the perhydrolytic anion. And any group that is displaced from the bleach activator. Preferred leaving groups are sulf Phenyl phonate.   Preferred examples of bleach activators of the above formula include those described in U.S. Pat. No. 4,634,551. (6-Octanoic acid amide-caproyl) oxybenzenesulfone as described G, (6-nonanoamidocaproyl) oxybenzenesulfonate, (6-de Canoamido-caproyl) oxybenzenesulfonate and mixtures thereof Which is incorporated herein by reference.   Another class of bleach activators includes U.S. Pat. Benzooxy disclosed by Hodge et al. Sagin-type activators are mentioned and this patent is incorporated herein by reference. Benzoxa Highly preferred activators of the gin type are of the formula:   Yet another class of preferred bleach activators includes acyllactam activators, especially And acyl valerolactams of the formula (Where R⁶Is H or an alkyl, aryl containing 1 to 12 carbon atoms or An alkoxyaryl or alkaryl group)   Highly preferred lactam activators include benzoylcaprolactam, octanoy Lcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nona Noircaprolactam, Decanoylcaprolactam, Undecenoylcaprolact Tom, benzoylvalerolactam, octanoylvalerolactam, decanoylva Reloractam, undecenoylvalerolactam, nonanoylvalerolactam, 3 , 5,5-trimethylhexanoylvalerolactam and mixtures thereof Can be Including benzoylcaprolactam adsorbed in sodium perborate Sanderson on October 8, 1985, discloses acylcaprolactam US Pat. No. 4,545,784 issued to (Sanderson). Quoted and incorporated in the book, see also this.Bleaching catalyst   A bleach catalyst is an optional component of the composition of the present invention. If necessary, add bleaching compound Catalysis can be exerted by magnesium compounds. These compounds Are known in the art and include, for example, US Pat. No. 6,621, U.S. Pat. No. 5,244,594, U.S. Pat. No. 5,194,41. No. 6, U.S. Pat. No. 5,114,606, European Patent Application 549,271 A1,5. 49,272A1, 544,440A2 and 544,490A1. Magnesium based catalysts are mentioned. Preferred examples of these catalysts include Mn IV_Two(U-O)_Three(1,4,7-trimethyl-1,4,7-triazacyclononane )_Two(PF₆)_Two, MnIII_Two(U-O)₁(U-OAc)_Two(1,4,7-trimethyl 1,4,7-triazacyclononane)_Two(ClO_Four)_Two, MnIV_Four(U-O)₆ (1,4,7-triazacyclononane)_Four(ClO_Four)_Four, MnIIIMnIV_Four(U- O)₁(U-OAc)_Two(1,4,7-trimethyl-1,4,7-triazacyclo Nonan)_Two(ClO_Four)_Three, MnIV (1,4,7-trimethyl-1,4,7-tri Azacyclononane)-(OCH_Three)_Three(PF₆) And mixtures thereof You. Other metal-based bleaching catalysts include U.S. Pat. No. 4,430,243 and And US Pat. No. 5,114,611. Strengthen bleaching The use of manganese with various complexing ligands is also described in US Pat. No. 8,455, No. 5,284,944, No. 5,246,612, No. 5,25 No. 6,779, No. 5,280,117, No. 5,274,147, No. 5,15 Nos. 3,161 and 5,227,084.   As a practical matter, and not by way of limitation, the compositions and The process comprises at least a part-per-million active bleach catalyst in aqueous laundry liquor. Species, preferably 0.1 ppm to 700 ppm, more preferably 1 ppm Can be adjusted to yield from 500 ppm of catalytic species in the wash water.   Cobalt bleach catalysts useful in the present invention are known and are described, for example, by Tove (M. L. Tobe), “Base hydrolysis of transition metal complexes” Adv. Inorg. Bio inorg. Mech. (1983), 2, pp. 1-94. Departure Most preferred cobalt catalysts useful in the literature are of the formula [Co (NH_Three)_FiveOAc] T Cobalt pentaamine acetate having y (where “OAc” represents an acetate component) And "Ty" is an anion), especially cobalt pentaamine acetic chloride [ Co (NH_Three)_FiveOAc] Cl_Two, And [Co (NH_Three)_FiveOAc] (OAc)_Two , [Co (NH_Three)_FiveOAc] (PF₆)_Two, [Co (NH_Three)_FiveOAc] (SO_Four) , [Co (NH_Three)_FiveOAc] (BF_Four)_Two, And [Co (NH_Three)_FiveOAc] (N O_Three)_Two("PAC" herein).   These cobalt catalysts are described, for example, in Tobe's articles and references. U.S. Pat. No. 4, issued to Diakun et al. On Mar. 7, 1989. No., 810,410, J.A. Chem. Ed. (1989), 66 (12), 10 43-45; Synthesis and characterization of inorganic compounds; L. Jolly (Prentice-Hall; 1970); 461-3; Inorg. Chem. 18, 1497-1502 (1979); Inorg. Chem. 2 1, 2881-2885 (1982); Inorg. Chem. 18, 2023 -2025 (1979); Inorg. Synthesis, 173-176 ( 1960); Journal of Physical Chemistry, 5 6, 22-25 (1952). It is.   As a practical matter, and not by way of limitation, the automatic dishwashing composition of the present invention The object and the cleaning process are at least 100 parts-per-million in aqueous cleaning media. Activated bleach catalyst species, preferably from 0.01 ppm to 25 ppm, more preferably From 0.05 ppm to 10 ppm, most preferably from 0.1 ppm to 5 ppm It can be adjusted to produce bleaching catalyst species in the wash water. Automatic dish washer pro In order to obtain such a level in the washing water of Seth, a typical automatic dish washer according to the present invention was used. The composition may comprise from 0.0005% to 0.2% of the cleaning composition, more preferably 0.0% to 0.2%. Contains from 0.4% to 0.08% by weight of bleach catalyst, especially manganese or cobalt catalyst I do.builder   Detergent builders are, for example, particularly suitable for the Ca and / or Mg mineral hardness in the wash water. Book to assist in control or to remove particulate soil from surfaces It can be optionally, but preferably, added to the composition of the invention. building Can form various soluble or insoluble complexes with hardness ions. Precipitation of hardness ions through the mechanism, by ion exchange and from the surface of the object to be cleaned By creating a surface that is convenient for Builder's Les The bell can vary greatly depending on the end use of the composition and its physical form. building Detergents typically contain at least 1% builder. Liquid formulation , Typically from 5% to 50%, more typically from 5% to 35% builder Including. Granular formulations typically comprise from 10% to 80% of the detergent composition, more typically Typically, it contains 15% to 50% by weight of the builder. However, higher than this of the builder Neither levels nor low levels are excluded. For example, certain detergent additives or high The surfactant formulation may not be builder.   Suitable builders in the present invention are phosphates and polyphosphates, especially sodium Salt; including water-soluble form and hydrated solid form, and a chain structure, a layer structure or a three-dimensional structure Having an amorphous solid form or an unstructured liquid form; carbonates , Bicarbonates, tricarbonates, and carbonates other than sodium carbonate or tricarbonate Stuff; Aluminosilicates; organic mono-, di-, tri- and tetracarboxylates, especially acids, Water soluble in the form of thorium, potassium or alkanol ammonium salts Oligomeric or non-surfactant carboxylate, including aliphatic and perfume types Selecting from the group comprising water soluble low molecular weight polymer carboxylate; and phytic acid Can be. These builders are, for example, sulfates with boric acid for pH buffering purposes, In particular, a detergent composition containing sodium sulfate and a stable surfactant and / or builder Any other fillers or carriers that may be important for the engineering of the product May be supplemented by   A builder mixture sometimes called a "builder system" can be used, and these Mixtures, typically with a chelating agent, pH buffer or filler. In addition, two or more conventional builders can be blended. However, the optional supplement When the amounts of each material in the present invention are written out, they are generally counted separately. In this detergent With respect to the relative amounts of surfactant and builder, preferred builder systems are typically The formulation is formulated with a weight ratio of surfactant to builder of 60: 1 to 1:80. Certain preferred laundry detergents have the ratio from 0.90: 1.0 to 4.0: 1.0, more preferably Is preferably 0.95: 1.0 to 3.0: 1.0.   P-containing detergent builders, which are often preferred where permitted by law, include Alkaline polyphosphoric acid represented by phosphites, pyrophosphates and vitreous polymer metaphosphates Potassium metal salts, ammonium salts and alkanol ammonium salts; Honate, but not limited to.   Suitable silicate builders include PQ Corp., for example, BRITESIL H2 Sold under the brand name BRITESIL (trade name) such as O, especially automatic dishes Alkali metal silicates, including solid hydrous (2-ratio) silicates for washing purposes, especially 1.6 SiO in the range of 1: 1 to 3.2: 1_Two: Na_TwoLiquid and solid forms with O ratio And, for example, 1987 by HP Rieck. Layered silicates such as those described in U.S. Pat. No. 4,664,839, May 12, Salts. NaSKS-6, sometimes abbreviated as "SKS-6", is a hex Crystalline layered aluminum-free δ-Na sold by Hoechst_Two SiO_FiveIt is a silicate in form and is particularly preferred in granular laundry compositions. Germany Keys in DE-A-3,417,649 and DE-A-3,742,043 See manufacturing method. Formula NaMSi_xO_{2x + 1}・ YH_TwoO (where M is sodium or water X is a number from 1.9 to 4, preferably 2, and y is 0 to 20, preferably Or other layered silicates such as those having a number of 0) in the present invention. , Or variations. From Hoechst Layered silicates are also available as α, β and γ layered silicates in the form of NaSKS-5, NaS KS-7 and NaSKS-11. For shrinkage agents and bleaching agents in granules Its like magnesium silicate can act as a stabilizer and a component of the foam control system Other silicates may be useful.   U.S. Pat. No. 6,27,1995 to Sakaguchi et al. General formula xM in the form of an anhydride taught in US Pat. No. 5,427,711_TwoO ・ y SiO_TwoZM'O (where M is Na and / or K and M 'is Ca and And / or Mg, y / x is from 0.5 to 2.0, and z / x is 0.005 From 1.0 to 1.0) having a chain structure and composition represented by Exchange materials or hydrates thereof are also suitable for use in the present invention.   Suitable carbonate builders include German Patent Application No. 15/15/1973. Alkaline earth metal carbonates and alkalis as disclosed in US Pat. No. 2,321,001 Metal carbonates. However, sodium bicarbonate, sodium carbonate, tricarbonate Sodium, and composition 2Na_TwoCO_Three・ CaCO_ThreeCharcoal such as those with anhydrides Sodium or calcium carbonate trona or any convenient multiple salt Large surface area compared to other carbonate materials, especially compressed calcite Even calcium carbonate containing calcite, aragonite and vaterite types Are also useful, for example, as seeds or for use in detergent bars. In some cases.   Aluminosilicate builders are particularly useful in granular detergents, It can also be added to a paste or gel. The empirical formula [M_z(AlO_Two)_z(SiO_Two )_v] XH_TwoOz, where and v is an integer of at least 6, and Where the molar ratio ranges from 1.0 to 0.5 and x is an integer from 15 to 264. Are suitable for this purpose. Aluminosilicates are crystalline, amorphous, natural It may be a product or a synthetic derivative. Aluminosilicate production method is Krummel (Krummel) et al., US Pat. No. 3,985, October 12, 1976. No. 669. A preferred synthetic crystalline aluminosilicate ion exchange material is Zeo Light A, zeolite P (B), zeolite X and so-called zeolite MAP (Different from zeolite P to some extent). Clinopti Natural types, including olites, may be used. Zeolite A has the formula Na₁₂[(AlO_Two )₁₂(SiO_Two)₁₂] XH_TwoO, wherein x is from 20 to 30, especially 27. You. Dehydrated zeolites (x = 0-10) may also be used. Preferably, aluminosilicate The salt has a particle size of 0.1-10 microns in diameter.   Suitable organic detergent builders include water-soluble non-surfactant dicarboxylates and tricarboxylic acids. A polycarboxylate compound containing a carboxylate is exemplified. More typical builders The polycarboxylate comprises a plurality of carboxylate groups, preferably at least 3 Having a carboxylate of Carboxylate builder is acid, partially neutral, neutral Or it can be formulated in overbased form. When in the form of salt, nato Alkali metal salts or alkanols such as lithium, potassium and lithium Preference is given to ammonium salts. April 7, 1964 for polycarboxylate builders U.S. Patent No. 3,128,287 to Berg, January 1972 US Patent No. 3,635,8 to Lamberti et al. Polycarboxylic acid ethers such as oxydisuccinates referred to in US Pat. U.S. Pat. No. 4,633,071 to Bush et al. "TMS / TDS" builder and U.S. Pat. No. 3,923,679, No. 835,163, No. 4,158,635, No. 4,120,874, No. 4, Others, including cyclic and alicyclic compounds, such as those described in US Pat. Of polycarboxylic acid ethers.   Other suitable builders are hydroxypolycarboxylic acid ethers, anhydrous maleic Copolymer of ethylene and vinyl or methyl ether, 1,3,5-trihydr Roxybenzene-2,4,6-trisulfonic acid, carboxymethyloxysuccinate Acids; various types of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid. Lucali metal, ammonium and substituted ammonium salts; melitic acid, succinic acid, Polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxy Succinic acid, and their soluble salts.   Citrate salts, such as citric acid and its soluble salts, are available from renewable resources. For performance and biodegradability, for example, important for heavy duty liquid detergents It is a carboxylate builder. Citrates, especially also zeolites and / or layers It can be used in a granular composition in combination with a silicate. Oxydisuccinate Are also particularly useful in such compositions and combinations.   Where permitted, and especially for bar-shaped formulations used for hand washing Sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate Alkali metal phosphates, such as calcium, can be used. Ethane-hydroxy-1, Phosphate builders such as 1-diphosphate and, for example, US Pat. No. 9,581, No. 3,213,030, No. 3,422,021, No. 3, Other known phosphorous, such as those of 400,148 and 3,422,137. Acid salts can also be used and may have desirable anti-scale properties.   Certain detersive surfactants or their short-chain homologs also have a builder effect. If they have a surface-active ability for the purpose of explaining a clear formulation, these Are counted as cleaning surfactants. Preferred type for builder function U.S. Pat. No. 4,566, issued to Bush on January 28, 1986. , 984,3,3-dicarboxy-4-oxa-1,6-hexane Illustrated by geoates and related compounds. Succinate builders include C_Five -C₂₀Alkyl and alkenyl succinic acids and their salts are mentioned. Ko Succinate builders include lauryl succinate, myristyl succinate, palmitic Succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate Succinates are also included. Lauryl-succinate was issued on November 5, 1986. It is described in European Patent Application No. 86200600.5 / 0,200,263. . Fatty acids such as C₁₂-C₁₈Monocarboxylic acid is also a surfactant / builder alone As builder or builder described above, especially citrate and / or succinate In combination with the rudder, it can be incorporated into the composition to add builder activity. Suitable Other polycarboxylates are available from Clutch Field on March 13, 1979 U.S. Patent No. 4,144,226 to Crutchfield et al., And U.S. Pat. No. 3,308,0 by Diehl, Mar. 7, 1967. No. 67. U.S. Patent No. 3,723 to Diehl , 322.   Other types of inorganic builder materials that can be used are of the formula (M_x)_iCa_y( CO_Three)_zIt has. (Where x and i are integers from 1 to 15, y is an integer from 1 to 10; z is an integer from 2 to 25;_iIs a cation At least one of which is water-soluble and has the formula Σi = 1-15 (x_iTo M_i + 2y = 2z is satisfied and the equation is neutral or “balanced” charge Having). In the present invention, these builders are referred to as “Minal Build”. ders ". Anions other than water or carbonate of hydrates have an overall charge May be added as long as is balanced or neutral. The charge of these anions or The valence effect should be added to the right side of the above equation. Preferably, hydrogen, water-soluble gold Genus, hydrogen, boron, ammonium, silicon and mixtures thereof, more preferably Or sodium, potassium, hydrogen, lithium, ammonium and their mixtures A water-soluble cation selected from the group containing components, sodium and potassium Is highly preferred. Non-limiting examples of non-carbonate anions include chloride, sulfate, fluoride. Oxides, hydroxides, silicon dioxide, chromates, nitrates, borates and Those selected from groups containing these mixtures are included. Took the simplest form A preferred builder of this type is Na_TwoCa (CO_Three)_Two, K_TwoCa (CO_Three)_Two, Na_TwoCa_Two(CO_Three)_Three, NaKCa (CO_Three)_Two, NaKCa_Two(CO_Three)_Three, K_TwoC a_Two(CO_Three)_ThreeAnd combinations thereof. In the present invention A particularly preferred material for the disclosed builder is Na in any of the crystal variants._Two Ca (CO_Three)_TwoIt is. Suitable builders of the type defined above are Further exemplified by any one or combination of natural or synthetic forms. Is included. Afghanite, Andersonite, Ashcrov Chin Y, Bayerite, Volcalite, Bulbangite, Butzlight, Ash Kaseki, Carbosernate, Calletonite, Dabin, Donnite Y, Fairch Rudite, ferris light, frangunite, gaudefreit, gaylasite , Gilbasite, Gregolite, Jarlab Skye, Kamforgaite Y, Tatterlight, Carnescheid, Lepersonite Gd, Riotite, Mckelbe Site Y, microsomit, muroseit, natrofair chillite, nirelate, Mondite Ce, Sacrophanite, Shorockingelite, Shortite, Slight, Tunisite, Tuscanite, Tricalcite, Screw Nebite and zemcolite. Preferred mineral forms include nirelate, And hair tightite.Polymer stain remover   Known polymer stain removers, hereinafter referred to as "SRA" or "SRA's", It can be optionally used in the present detergent composition. When used, SRA ‘s is generally Preferably, 0.01% to 10.0% of the composition, typically 0.1% to 0.5%, Or from 0.2% to 3.0% by weight.   Preferred SRAs are typically hydrophobic fibers such as polyester and nylon. A hydrophilic segment that hydrophilizes the surface of fibers, and is deposited on hydrophobic fibers and washed And after the end of the rinsing cycle, the And a hydrophobic segment acting as an anchor. This is due to SRA To make it easier to wash stains that occur after processing in subsequent washing procedures Enable.   SRA can be of various types, for example, charged anions or charged cations (US Pat. , 956,447) and may contain uncharged monomer units. The structure can be straight, branched or even star. They are controlled by molecular weight. Contains encapsulating ingredients that are particularly effective at altering control or physical or surfactant properties May be. The structure and charge distribution can be adapted to different fiber or fabric types. And may be adapted to various detergent or detergent additive products.   Preferred SRAs typically include a gold such as a titanium (IV) alkoxide. Involves at least one transesterification / oligomerization, often using a genus catalyst Oligomeric terephthalates prepared by the process. This Such esters, of course, can form 1,2 without forming a tightly crosslinked overall structure. Additional monomers capable of penetrating the ester structure via three, four or more positions To It may also be manufactured using.   Suitable SRAs include, for example, those described by JJ Scheibel. U.S. Pat. No. 4,968,451, Nov. 6, 1990 and Gosselink (G. osselink). P. Terephthaloyl and o as described in Oligomer ester backbone of xyalkyleneoxy repeating unit and Consists of an allyl-derived sulfonated end component covalently linked to this backbone Substantially linear ester oligomer sulfonated products are included. These es Teroligomers are (a) ethoxylated allyl alcohols, (b) products of (a) Was converted to dimethyl terephthalic acid (“DM T)) and 1,2 pyropyrene glycol ("PG"), (c) ( b) by reacting the product of b) with sodium metabisulfite in water Wear. Further, suitable SRA ‘s include, for example, poly (ethylene glycol) methyl Of diether, DMT, PG and poly (ethylene glycol) ("PEG") Gosselink, such as that produced by transesterification / oligomerization link, et al., U.S. Patent No. 4,711,730, issued December 8, 1987. Non-ionic end-blocked 1,2-propylene / polyoxyethylene terephthalic acid poly Esters; ethylene glycol ("EG"), PG, DMT and Na-3,6 Oligomeric gossells from dioxa-8-hydroxyoctanesulfonate U.S. Pat. No. 4,72, Jan. 26, 1988 to Gosselink No. 1,580 partially and fully anionic end-capped oligomeric esters: for example , DMT, Me-encapsulated PEG and EG and / or PG, or DMT, EG and / or PG, Me-encapsulated PEG and Na-dimethyl-5-sulfo Gosselink, produced from a combination of isophthalic acids U.S. Pat. No. 4,702,857 issued Oct. 27, 1987 to the non-ion-sealed Blocking block polyester oligomer compound; Maldonado 1989 by Maldonado, Gosselink et al. US Pat. No. 4,877,896, Oct. 31, 2010, particularly sulfoallo Il-terminated terephthalic acid esters. The latter includes laundry products and cloth Representative of SRAs useful in both ground preparation products, one example is optionally There is preferably, but not limited to, an m-source further added with PEG such as PEG 3400, for example. Ester composition produced from rusobenzoic acid monosodium salt, PG and DMT Things.   SRA includes U.S. Patent No. 3 by Hays, May 25, 1976. No. 959, 230 and Basadur on July 8, 1975. Ethylene terephthalic acid also referred to in U.S. Pat. Is propylene terephthalic acid and polyethylene oxide or polypropylene oxy A simple copolymer block with doterephthalic acid, from Dow to METHOCE Cellulose induction such as hydroxyethercellulose polymer available as L Conductors; and U.S. Patent to Dec. 28, 1976 by Nicol et al. C1-C4 alkylcellulose and C4 referenced in 4,000,093 Also included are hydroxyalkyl celluloses. Poly (vinyl ester) hydrophobic segment Suitable SRAs characterized by the For example, C1-C6 vinyl ester, preferably poly A graft copolymer of poly (vinyl ester) such as (vinyl acetate) Can be European Patent Application 0, issued April 22, 1987 by Kud et al.  See 219 048. Commercially available examples include those obtained from BASF, Germany And SOKALAN SRA such as SOKALAN HP-22. Other SRAs are polyoxyethylene glycols having an average molecular weight of 300-5,000. 90-80% by weight of polyoxyethylene terephthalate derived from polyester With repeating units containing 10-15% by weight ethylene terephthalate with It is an ester. Commercial examples include ZELCO from DuPont. N5126 and MILEASE T from ICI.   Other preferred SRAs are terephthaloyl (T), sulfoisophthaloyl ( SIP), oxyethyleneoxy and oxy-1,2-propylene (EG / P G) Experiments involving units and preferably terminated with capping (CAP) Formula (CAP)_Two(EG / PG)_Five(T)_Five(SIP)₁An oligomer having One sulfoisophthaloyl unit, five terephthaloyl units, preferably Is an oxyethyleneoxy and a limiting ratio of about 0.5: 1 to about 10: 1 Oxy-1,2-propyleneoxy unit and 2- (2-hydroxyethoxy) B) including two end-capping units derived from sodium ethanesulfonate. Preferred is the modified isethionate salt, as in the case of the oligomer. The SRA is: Preferably, linear sodium dodecylbenzenesulfonate or xylene, A member selected from men-, toluene-sulfonate or a mixture thereof. 0.5% to 2% of a crystal-reducing stabilizer such as an anionic surfactant. It further comprises 0% by weight of the oligomer. These stabilizers or denaturants are all 199 Gosselink, Pan, Ke published on May 16, 5 U.S. Patent No. 5,41 to Kellett and Hall It is introduced into a synthesis can as taught in US Pat. No. 5,807. Appropriate for the above SRA Examples of such monomers include Na2- (2-hydroxyethoxy) -ethanesulfonate, D MT, Na-dimethyl 5-sulfoisophthalate, EG and PG You.   Yet another group of preferred SRAs is (1) (a) dihydroxysulfonate, At least one unit selected from the group comprising rehydroxysulfonates Therefore, the ester bond is formed by being at least trifunctional, and Sesame backbone producing units and combinations thereof (b) Terephthaloyl At least one unit (c) which is a component A backbone containing at least one non-sulfonated unit that is Ion sealing unit, alkoxylated, preferably ethoxylated isethionate, Alkoxylated propane sulfonate, alkoxylated propane disulfonate, alcohol Anionic capping units such as coxylated phenol sulfonates, sulfoaroyl And one or more sealing units selected from derivatives and mixtures thereof. Sesame ester. Preferred such esters are those of the empirical formula {(CAP)_x (EG / PG)_{y '}(DEG)_{y ''}(DEG)_{y '''}(T)_z(SIP)_{z '}(SEG)_q (B)_m}belongs to. Where CAP, EG / PG, PEG, T and SI P is as defined above, and (DEG) is di (oxyethylene) oxyunit (SEG) is a unit derived from the sulfoethyl ether of glycerin. Represents a knit and associated component units, wherein (B) is at least trifunctional Resulting in a branched oligomer backbone, forming an ester bond. Represents knit, x is from about 1 to about 12, y 'is from about 0.5 to about 25, y ″ is from 0 to about 12, y ″ is from 0 to about 10, and y ′ + y ″ +  y '' 'is from about 0.5 to about 25, z is from about 1.5 to about 25, z 'is from 0 to about 12, the sum of z + z' is from about 1.5 to about 25, and q is about From 0.05 to about 12, m from about 0.01 to about 10, x, y ', y' , Y '', z, z ', q and m are the corresponding units per mole of the ester. Where the ester is a molecule in the range of about 500 to about 5,000. Quantity).   Preferred SEG and CAP monomers for the above esters include Na-2- (2-, 3-, dihydroxypropoxy) ethanesulfonate ("SEG"), Na-2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate (" SE3 "), its homologs and mixtures thereof and allyl alcohol Ethoxylated and sulfonated products. Preferred SRA for this class The esters include Na-2- {2- (2-hydroxyethoxy) ethoxy} ethanes Rufonate and / or Na-2 [2- {2- (2-hydroxyethoxy)- Ethoxy} ethoxy] ethanesulfonate, DMT, Na-2 (2,3-dihydrogen Roxypropoxy) ethanesulfonates, suitable Ti (IV) of EG and PG Catalytic transesterification and oligomerization products. This SRA Steal (CAP)_Two(T)_Five(EG / PG)_1.4(SEG)_2.5(B)_0.13And table Where CAP is (Na^+-O_ThreeS [CH_TwoCH_TwoO]_3.5)- , B are units derived from glycerin, and the molar ratio of EG / PG Later, it is about 1.7: 1 as measured by conventional gas chromatography).   Additional classes of SRA include (I) by Bioland et al. U.S. Pat. No. 4,201,824 and the United States by Lagase et al. The diisocyanate coupling agent referred to in Patent 4,240,918 Nonionic terephthalate that binds the polymer ester structure using (II) Add a melitate to a known SRA to remove terminal hydroxyl groups SRA with carboxylate end groups produced by conversion to stel Is mentioned. With the proper choice of catalyst, the anhydrous trimellitate can form an anhydrous bond. An independent carboxylic acid ester of trimellitate anhydride rather than by ring opening Form a bond at the end of the polymer. S, either nonionic or anionic RA is a starting material as long as it has an esterifiable hydroxyl end group. Can be used. U.S. Pat. No. 4,525,52 to Tung et al. See No. 4. Additional classes of SRA include (III) Bioland (Viol land) et al., U.S. Pat. No. 4,201,824. Anion terephthalate-based SRA of the combined component variant, (IV) rapert (Rup No. 4,579,681 to Pert et al. Vinylpyrrolidone and / or both non-ionic and cationic polymers Poly (vinyl caprolact) with monomers such as dimethylaminoethyl methacrylate Tam) and related copolymers, (V) Rhone- Poulenc Chemie) EP 279.134, 19 Graft acrylic acid monomer onto sulfonated polyester, see 88 Grafted to a SOKALAN type from BASF produced by the method A polymer whose SRA has a soil removal activity similar to known cellulose ethers. And (VI) BA, a graft polymer claimed to have anti-redeposition activity Casey, referred to SF No. 457,205 (1991). Grafting of vinyl monomers such as acrylic acid and vinyl acetate onto proteins such as (VII), 1974, Unilever NV, Beran (B) evan) et al., DE 2,335,044, in particular polyamide fabrics Of adipic acid, caprolactam and polyethylene glycol for the treatment of And polyester polyamide SRA prepared by Other useful SRA is disclosed in U.S. Patent Nos. 4,240,918, 4,787,989, Nos. 525,524 and 4,877,896.Clay soil removal / anti-deposition agent   The composition of the present invention comprises a water-soluble ethoxide having clay stain removal and redeposition prevention properties. A xylated amine may optionally also be included. Granule detergent composition containing these compounds Typically contains 0.01% to 10% by weight of a water-soluble ethoxylate amine. Have. Liquid detergent compositions typically contain from 0.01% to 5%.   The most preferred soil removal and redeposition inhibitor is ethoxylated tetraethylene pen. This is Tamin. Examples of ethoxylated amines can be found in Vandemee, published July 1, 1986. Further described in U.S. Pat. No. 4,597,898 to VanderMeer. Have been. Another group of preferred clay soil removal-redeposition inhibitors is 1984 By Oh and Gosselink, issued June 27 It is a cationic compound disclosed in European Patent Application 111,965. Can be used Issued June 27, 1984 for other possible clay stain removal / redeposition inhibitors In European Patent Application 111,984 by Gosselink Ethoxylated amine polymer, Gosselink, published July 4, 1984 (Gos sell, zwitterionic poly disclosed in EP 112,592. And US Patent issued by Connor on Oct. 22, 1985. No. 4,548,744 aminooxide. Its known in the art Other clay soil removal and / or redeposition inhibitors are also useful in the compositions of the present invention. Can be used. VanderMir issued on January 2, 1990 (VanderM) eer), US Pat. No. 4,891,160 and Nov. 30, 1995. See published WO 95/32272. Another of the preferred redeposition inhibitors Types include carboxymethylcellulose (CMC) materials. these Are well known in the art.Polymer dispersant   Polymeric dispersants are particularly useful in the presence of zeolites and / or layered silicate builders. In the presence, it is advantageously available in compositions of the invention at levels of 0.1% to 7% by weight. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols. Call. However, other materials known in the art may also be used. Can be. While not intending to be limited by theory, polymeric dispersants may When used in combination with builders (including low molecular weight polycarboxylates) By suppressing crystal growth and preventing solidification and re-deposition of the removed particulate matter, overall It is believed to enhance detergent builder performance.   The polymeric polycarboxylate material is suitably unsaturated, preferably in the acid form. It can be prepared by polymerizing or copolymerizing a monomer. Suitable for polymerization Unsaturated monomeric acids that can produce high molecular weight polycarboxylates include: Crylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aquo Knit acid, mesaconic acid, citraconic acid and methylene malonic acid. Bi Carboxylate radicals such as nil methyl ether, styrene, ethylene, etc. The present invention does not contain a high molecular weight polycarboxylate or monomer segment. The presence is appropriate as long as such segments do not constitute more than 40% by weight. .   Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Wear. Such acrylic acid-based polymers useful in the present invention are polymerized acrylics. It is a water-soluble salt of luic acid. The average molecular weight of these polymers in the acid form is preferred. 2,000 to 10,000, more preferably 4,000 to 7,000, Most preferably, it is in the range of 4,000 to 5,000. Such acrylic acid po Water-soluble salts of Lima include, for example, alkali metal salts, ammonium salts and substituted anions. Monium salts can be included. This type of soluble polymer is a known material . The use of polyacrylates of this type in detergent compositions is e.g. U.S. Pat. No. 3,308,06 issued to Diehl on March 7, 2007. No. 7.   Acrylic / maleic acid based copolymers are also preferred as dispersing / redeposition inhibitors It may be used as a component. These materials include copolyacrylic acid and maleic acid. Water-soluble salts. The average molecular weight of these polymers in acid form is favorable. Preferably from 2,000 to 10,000, more preferably from 5,000 to 7,50 0, most preferably in the range of 7,000 to 65,000. Such a copoly The ratio of acrylic acid to maleic acid in the polymer is generally between 30: 1 and 1: 1. : 1, more preferably from 10: 1 to 2: 1. Such acrylic acid / The water-soluble salts of the maleic acid copolymer include, for example, alkali metal salts and ammonium salts. And substituted ammonium salts. This type of soluble acrylic Lulic acid / maleic acid copolymer is described in European Patent Application No. 6 issued December 15, 1982. No. 6915, and also such polymers, including hydroxypropyl acrylate. No. 193,360, issued Sep. 3, 1986. It is a well-known material. Other useful diacids include maleic acid / acrylic acid. Luic acid / vinyl alcohol terpolymer. Such materials are, for example, Including 45/45/10 terpolymer of oleic / acrylic / vinyl alcohol And EP-A-193,360.   Another polymeric material that can be included is polyethylene glycol (PEG) is there. PEG exhibits dispersant performance and also removes clay stains and prevents redeposition. Also acts as. A typical molecular weight range for these purposes is 500 to 1 00,000, preferably 1,000 to 50,000, more preferably 1.5 It ranges from 00 to 10,000.   Polyaspartate and polyglutamate dispersants are also particularly suitable for zeolite builders. May be used in combination with-. Dispersants such as polyaspartate are preferably 10 It has a molecular weight (average) of 2,000.Whitening agent   Any optical brightener known in the art, other brighteners or white The agent is typically present at a level of 0.01% to 1.2% by weight of the detergent in the present invention. It can be added to the composition. Commercial optical enhancements that may be useful in the present invention Whitening agents include stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanine, Benzothiophene-5,5-dioxide, azole, 5- and 6-membered heterocycles And other miscellaneous agents, but are not necessarily limited to Group. Examples of such brighteners are described in John Whiley & Son M.s., published by New York (1982). To Zahrdnik Published in "Production and Use of Optical Brighteners".   A specific example of an optical brightener useful in the present composition is described on December 13, 1988. Specified in U.S. Patent No. 4,790,856 issued to Wixon. It was done. These brighteners include brighteners from Verona PHORHHITE series. The patent disclosed in this patent specification Other brighteners include Tin available from Ciba-Geigy. opal UNPA, Tinopal CBS and Tinopal 5BM; A rt White CC and Art White CWD, 2- (4-s Tyryl-phenyl) -2H-naphtho [1,2-d] triazole, 4,4'-b is- (1,2,3-triazol-2-yl) -stilbene, 4,4'-bi s (styryl) bisphenyl and aminocoumarin. These brightening Particular examples of agents include 4-methyl-7-diethyl-amino-coumarin, 1,2-bi S (benzimidazol-2-yl) ethylene, 1,3-diphenyl-pyrazoli , 2,5-bis (benzoxazol-2-yl) thiophene, 2-styryl -Naphtho [1,2-d] oxazole and 2- (stilben-4-yl) -2 H-naphtho [1,2-d] triazole is exemplified. Hamilton US Pat. No. 3,646,015 issued Feb. 29, 1972 to Ton). See.Transfer dye inhibitor   The composition of the present invention has a dye transfer from one fabric to another during the cleaning process. One or more materials that may be effective in suppressing the formation of the organic solvent may also be added. Generally, these Examples of the dye transfer inhibitor include polyvinylpyrrolidone polymer and polyamine N-oxide polymer. A copolymer of N-vinylpyrrolidone and N-vinylimidazole, manganese lid Russianin, peroxidase and mixtures thereof. These rolls If a dye inhibitor is used, typically from 0.01% to 10% by weight of the composition is preferred. Or 0.01% to 5%, more preferably 0.05% to 2%.   More specifically, preferred polyamine N-oxides for use in the present invention Lima comprises units having the structural formula R-Ax-P, where P is a polymerizable unit. Knitted, this unit can have an N-O group attached, or the N-O group can be polymerized Can form part of a simple unit, or the NO group can be attached to both units; A is one of NC (O)-, -C (O) O-, -S-, -O-, -N = , X is 0 or 1, and R is aliphatic, ethoxylated aliphatic, fragrance, heterocyclic, An alicyclic group or any combination thereof, to which the nitrogen of the NO group is bonded. Or the NO group is part of these groups. Preferred polyamine NO Oxides are those in which R is pyridine, pyrrole, imidazole, pyrrolidine, piperidine or And heterocyclic groups such as derivatives thereof.   The NO group can be represented by the following general structural formula. (Where R₁, R_Two, R_ThreeIs an aliphatic, fragrance, heterocyclic, alicyclic group or their X, y and z are 0 or 1, and the nitrogen of the NO group is Or can form part of any of the groups described above. Polia The amine oxide unit of the min N-oxide has a pKa <10, preferably pK a <7, more preferably pKa <6).   The formed amine oxide polymer is water-soluble and has dye transfer inhibiting properties Any polymer backbone can be used. The right polymer backbone Examples of polyvinyl, polyalkylene, polyester, polyether, polyamide , Polyimide, polyacrylate and mixtures thereof. These poly One monomer species is an amine N-oxide and the other monomer species is N-oxide. -Random or block copolymers which are oxides. Amine NO The oxide polymer typically has a ratio of amine to amine N-oxide of 10: 1. From 1,000,000. However, in polyamine oxide polymers The number of amine oxide groups present depends on the appropriate copolymerization or the appropriate degree of N-oxidation. Can be obtained. Polyamine oxides are obtained at almost any degree of polymerization be able to. Typically, the average molecular weight is between 500 and 1,000,000, Preferably from 1,000 to 500,000, most preferably from 5,000 to 1 It is in the range of 00,000. This preferred material grade is referred to as "PVNO" be able to.   Most preferred polyamine N-oxy useful in detergent compositions in the present invention Has an average molecular weight of 50,000 and a ratio of amine to amine N-oxide 1: 4 poly (4-vinylpyridine-N-oxide).   Copolymer of N-vinylpyrrolidone and N-vinylimidazole polymer (grade and (Referred to as "PVPVI") are also preferred for use in the present invention. Preferred Preferably, PVPVI is from 5,000 to 1,000,000, more preferably 50,000. Average from 00 to 200,000, most preferably from 10,000 to 20,000 Have a molecular weight range (average molecular weight ranges are described by Barth et al., Chemical Analysis, Vol 113 "Polymer Characterization Measured by light scattering as described in Modern Methods of Incorporated by reference to the invention). PVPVI copolymer is typically N-vinyl alcohol. The molar ratio of midazole to N-vinylpyrrolidone is 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 may be either linear or branched.   The composition of the present invention may have a molecular weight of 5,000 to 400,000, preferably 5,000. Average molecular weight of 200,000, more preferably 5,000 to 50,000. Polyvinylpyrrolidone (PVP) may also be used. PVP is used in the detergent field. It is known to the trader. For example, European Patent Publication No. 26, incorporated herein by reference. See 2,897 and EP-A-256,696. Contains PVP The composition of the present invention comprises from 500 to 100,000, preferably from 1,000 to 10, Polyethylene glycol (PEG) having an average molecular weight of 000 may also be included. . Preferably, the ratio of PEG to PVP added to the washing liquor on a ppm basis is From 2: 1 to 50: 1, more preferably from 3: 1 to 10: 1.   The detergent composition of the present invention has a discoloration inhibiting effect of 0.005% to 5% by weight. % Of a specific type of hydrophilic optical brightener may also optionally be included. If you use The composition in the present invention preferably comprises from 0.01% to 1% by weight of such an optical Contains brightener.   Hydrophilic optical brighteners useful in the present invention are those having the following structural formula . (Where R₁Are anilino, N-2-bis-hydroxyethyl and NH-2-H Selected from droxyethyl, R_TwoIs N-2-bis-hydroxyethyl, N-2- From hydroxyethyl-N-methylamino, morpholino, chloro and amino And M is a salt-forming cation such as sodium or potassium).   In the above formula, R₁Is anilino and R_TwoIs N-2-bis-hydroxyd When chill and M is a cation such as sodium, the brightener is 4,4'- Bis [(4-amino-6- (N-2-bis-hydroxyethyl) -s-triazine 2--2-yl) amino] -2,2-stilbene disulfonic acid and disodium Salt. This particular brightener species is Ciba-Geigy Co. commercial under the trade name Tinopal-UNPA-GX Is sold. Tinopal-UNPA-GX is a detergent composition of the present invention. Are preferred hydrophilic optical brighteners.   In the above formula, R₁Is anilino and R_TwoIs N-2-hydroxyethyl- Whitening when N-2-methylamino and M is a cation such as sodium The agent is 4,4'-bis [(4-amino-6- (N-2-hydroxyethyl-N- Methylamino) -s-triazin-2-yl) amino] 2,2'-stilbene Sulfonic acid and disodium salt. This particular brightener species is Ciba Geigy Trade name Tinopa by (Ciba-Geigy Corporation) Commercially sold as 1-5BM-GX.   In the above formula, R₁Is anilino and R_TwoIs morpholino and M is na If it is a cation such as thorium, the brightener is 4,4'-bis [(4-anili No-6-morpholino-s-triazin-2-yl) amino] -2,2'-styrene Rubendisulfonate sodium salt. This particular brightener species is Ciba Geigy Trade name Tinopa by (Ciba-Geigy Corporation) Commercially sold as 1-AMS-GX.   The particular optical brightener species selected for use in the present invention is selected from those selected above. When used in combination with a polymeric dye transfer inhibitor, it has the advantage of particularly effective dye transfer control performance. You. Such selected polymeric materials (eg, PVNO and / or PVPVI) ) With such selected optical brighteners (e.g., Tinopal UNPA-GX, (Tinopal 5BM-GX and / or Tinopal-AMS-GX) When used alone, one of the two detergent composition components is provided when used alone Equipped with significantly better control of dye transfer in aqueous laundry liquors. Must be bound by theory For example, these brighteners are highly compatible with fabrics in It is believed that this is due to the relatively fast deposition on these fabrics. Washing The degree to which the brightener is deposited on the fabric in the liquid is a parameter called the "wear coefficient". Data. The attrition coefficient is generally determined by: a) b) of the brightener material deposited on the fabric; ) The ratio to the initial concentration of the brightener in the washing liquid. Brightener with relatively high wear coefficient Is most appropriate for controlling dye transfer in the context of the present invention.   Of course, the other conventional optical brightener species of the compound, not the true transfer inhibition effect Can be optionally used in the composition to provide the traditional "whitening" benefits of the fabric. It is expected that can be. These uses are conventional and require detergent delivery. It is known to the union.Chelating agent   The detergent composition according to the invention comprises one or more iron and / or manganese chelates An agent may optionally be included. Such chelators are aminocarboxylates , Aminophosphonates, polyfunctionally substituted perfume chelating agents and mixtures thereof And all are defined below. By the bounds of theory If not, the benefits of these materials would be partially due to the formation of soluble chelates. Possibly due to the excellent ability to remove iron and manganese from the rinse .   Aminocarboxylates useful as any chelating agent include ethylene dia Mintetraacetate, N-hydroxyethylethylenediaminetriacetate , Nitrilotriacetate, ethylenediaminetetrapropionate, triethyl Lentetraamine hexaacetate, diethylenetriaminepentaacetate, And their ethanol diglycine, alkali metal, ammonium, Ammonium salts and mixtures thereof.   Aminophosphates also have at least low levels of total phosphorus in the detergent composition. Where permitted, suitable for use as a chelating agent in the compositions of the present invention; Aminophosphates include ethylenediaminetetrakis as DEQUEST (Methylene phosphonate). Alkyl with more than 6 carbon atoms is also Those aminophosphonates which do not contain a alkenyl group are preferred.   Multifunctionally substituted perfume chelating agents are also useful in the compositions of the present invention. U.S. Pat. No. 3, issued to Connor et al. On May 21, 1974. See 812,044. Preferred compounds of this type in the acid form include 1 Dihydroxydisulfo such as 2,2-dihydroxy-3,5-disulfobenzene It is benzene.   A preferred biodegradable chelating agent for use in the present invention is ethylene diamine. Disuccinate ("EDDS"), especially Hartman and U.S. Pat. No. 4, November 3, 1987 to Perkins. [S, S] isomers as described in US Pat.   The composition of the present invention may be used as a chelating agent or a zeolite or a layered sheet. As a useful co-builder with an insoluble builder, such as Methylglycine diacetate (MGDA) salt (or acid form) may also be included.   If utilized, these chelating agents generally comprise the detergent compositions of the present invention. From 0.1% to 15% by weight. More preferably, if used, clean Toning agents contain from 0.1% to 3.0% by weight of such compositions.Foaming inhibitor   Compounds for reducing or inhibiting foam formation may be added to the compositions of the present invention. it can. Foam control is disclosed in U.S. Patent Nos. 4,489,455 and 4,489,5. The so-called "high concentration cleaning process" as described in No. 74 and front charging Of particular importance in style European style washing machines.   Various materials may be used as foam inhibitors, which are known to those skilled in the art. You. For example, Kirk-Othmer Dictionary of Chemistry, Third Edition, Vol. 7, pp. 430-47 ( John Wiley & Sons, Inc. 1979). Of particular interest One type of foam control agent is monocarboxylic fatty acids and their soluble salts. Is included. Wayne St. John on September 27, 1960 See U.S. Pat. No. 2,954,347 issued to U.S. Pat. Used as foam inhibitor The monocarboxylic fatty acids and salts thereof typically have 10 to 24 carbon atoms. It has a hydrocarbyl chain of atoms, preferably 12 to 18 carbon atoms. Suitable salt Include alkali metal salts such as sodium, potassium and lithium salts, ammonia And alkanol ammonium salts.   The detergent composition of the present invention may also contain a non-surfactant foam inhibitor. these Include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg, Fatty acid triglyceride), fatty acid ester of monohydric alcohol, aliphatic C₁₈-C₄₀ Ketone (eg, stearone) and the like. Other foam control agents include -To N-alkylated aminotriazines such as hexa-alkylmelamines; Is the primary or secondary cyanuric chloride containing 2 or 3 moles of 1 to 24 carbon atoms. Di-tetra-alkyldiamine chloride formed as a product with diamine Liazine; propylene oxide; monostearyl alcohol phosphate ester And monostearyl dialkali metal (eg, K, Na, and Li) phos Monostearyl phosphates such as phosphate and phosphate esters include Can be Hydrocarbons such as paraffins and haloparaffins are available in liquid form. Liquid hydrocarbons are liquids at room temperature and atmospheric pressure, and in the range of -40 ° C and 50 ° C. And a minimum boiling point (atmospheric pressure) of 110 ° C. or higher. Preferably the melting point is 10 It is also known to utilize waxy hydrocarbons below 0 ° C. Hydrocarbons, detergent composition It constitutes a preferred type of foam inhibitor for the product. For example, hydrocarbon foam inhibitors For example, the United States issued May 5, 1981 to Gandolfo et al. It is described in Japanese Patent No. 4,265,779. Thus, hydrocarbons have 12 Aliphatic, cycloaliphatic, fragrance and heterocyclic, saturated or unsaturated, having from 70 to 70 carbon atoms And saturated hydrocarbons. The "paraffin" used in this discussion of foam inhibitors The term `` quine '' is intended to include a mixture of true paraffins and cyclic hydrocarbons. Is intended.   Another preferred class of non-surfactant foam inhibitors include silicone foam inhibitors. Can be This class includes polyorganosiloxanes such as polydimethylsiloxane Oils, dispersions or emulsions of polyorganosiloxane oils or resins, and Polyorganosiloxane in which polyorganosiloxane is chemisorbed or fused onto silica Utilization of a combination of siloxane and silica particles. Silicone foam inhibitor Are known in the art, for example, Gandolfo o) et al., US Pat. No. 4,265,779, issued May 5, 1981; Issued on February 7, 1990 by Starch and Starch (MS). It is disclosed in European Patent Application No. 89307851.9.   For other silicone foam inhibitors, add a small amount of polydimethylsiloxane liquid. U.S. Pat. No. 455,839.   Mixtures of silicone and silanized silica are described, for example, in German Patent Application DOS2 , 124, 526. Silicone defoamer in granular detergent composition and And Foam control agents are disclosed in Bartolotta et al., US Pat. No. 933,672, published on March 24, 1987 in Baginski. i) et al. in U.S. Pat. No. 4,652,392.   Examples of silicone-based foam inhibitors used in the present invention are practically A foam control agent having a foam suppressing amount including the following.   (I) about 20 cs. From about 1,500 cs. Having a viscosity of Chill siloxane liquid.   (Ii) from about 0.6: 1 to about 1.2: 1 of (CH_Three) 3SiO_1/2Unit: Si O_TwoIn unit ratio, (CH_Three)_ThreeSiO_1/2Unit and SiO_TwoUnit and About 5 to about 50 parts by weight / 100 parts of the siloxane resin containing (i)   (Iii) from about 1 to about 20 parts by weight of solid silica gel / 100 parts of (i)   In the preferred silicone foam inhibitor used in the present invention, for the continuous phase Solvent is a specific polyethylene glycol, polyethylene-polypropylene glycol Cole copolymer, their mixtures (preferred) or polypropylene bricol Consists of The primary silicone foam control agent is a branched / crosslinked one, preferably a linear is not.   To further illustrate this point, a representative liquid laundry detergent composition with controlled foaming is: About 0.001 to about 1, preferably about 0.1 to about 0.7, most preferably about 0 . From about 0.5% to about 0.5% by weight of the silicone foam inhibitor. The foaming inhibitors for cones are (1) (a) polyorganosiloxane and (b) resinous Siloxane compound produced from siloxane or silicone resin, and (c) finely divided filling Promotes the reaction of the materials with (d) mixture components (a), (b) and (c) A non-aqueous emulsion of a primary antifoaming agent which is a mixture of (2) at least one nonionic silicone surfactant; and (3) Polyethylene glycol having a solubility in water at room temperature of more than 2% by weight Or a copolymer of polyethylene-polypropylene glycol (polypropylene glycol) Call is not used). Similar amounts may be used in granular compositions, gels, etc. Can be. Rice by Starch issued on December 18, 1990 No. 4,983,316, Starch (Star) issued on Jan. 8, 1991. ch) U.S. Pat. No. 4,978,471, issued Feb. 22, 1994. U.S. Pat. No. 5,288,431 to Huber et al., Aizawa. Nos. 4,639,489 and 4,749,74 by Zawa) et al. See also No. 0, column 1, line 46 to column 4, line 35.   The silicone foam control agents in the present invention are preferably all about 1,000 Polyethylene having an average molecular weight of less than about 100, preferably between about 100 and 800 Glycol and polyethylene / polypropylene glycol copolymers. Polyethylene glycol and polyethylene / polypropylene according to the present invention The recall copolymer is present in water at room temperature in excess of about 2% by weight, preferably about 5% It has a solubility of more than%.   Preferred solvents in the present invention are less than about 1,000, more preferably 100 and less. Poly, having an average molecular weight between 800 and most preferably between 200 and 400 Ethylene glycol, and polyethylene / polypropylene glycol, preferred Is a copolymer of PPG200 / PEG300. Between about 1: 1 and 1:10 Polyethylene glycol: polyethylene, most preferably between 1: 3 and 1: 6. The weight ratio of the copolymer of propylene glycol to polypropylene glycol is preferred.   The preferred silicone foam inhibitor used in the present invention has a molecular weight of 4, especially. Contains no 000 polypropylene. They are also preferably PLURON Block copolymer of ethylenoxide and propylene oxide, such as IC L101 Does not include Lima.   Other foam inhibitors useful in the present invention are secondary alcohols (e.g., 2- Alkyl alkanols) and such alcohols and US Pat. 679,4,075,118 and EP 150.872. And mixtures with sea corn oils such as the disclosed silicones. Secondary alcohol Is C₁-C₁₆C with a chain₆-C₁₆Alkyl alcohol is mentioned. preferable The alcohol is 2-butyl octanol and has the trade name ISOFIL 12. Available from Condea. Mixtures of secondary alcohols are trade names Available as ISALCHEM from Enichem. Mixed foaming Inhibitors typically comprise alcohol and silicone in a weight ratio of 1: 5 to 5: 1. Of mixtures.   For any detergent composition used in automatic washing machines or automatic dishwashers Even the extent to which foaming overflows the washing machine or adversely affects the washing mechanism of the dishwasher Should not occur. When used, the foaming inhibitor is preferably used in the form of “foaming suppressing amount. ]. The “foaming suppression amount” allows the formulator of the composition to sufficiently control foaming. By selecting the amount of this foam control agent to control, the automatic washing machine or automatic dish washer It is intended to be a low foam laundry detergent or dish detergent used in the above.   The compositions according to the invention generally comprise from 0% to 10% of a foam control agent. Foaming When used as inhibitors, monocarboxylic fatty acids and their salts are typically Are present in amounts up to 5% by weight of the detergent composition. Preferably, 0.5 to 3% Fatty acid monocarboxylate foam inhibitors are utilized. Silicone foam inhibitor , Typically utilized in amounts up to 2.0% by weight of the detergent composition. However, it is Larger amounts may be used. This upper limit keeps costs to a minimum and effective foaming Of a practical nature primarily related to smaller effects on the control of You. Preferably 0.01% to 1% of a silicone foam inhibitor, more preferably 0% to 1%. . Use 25% to 0.5%. When used in the present invention, these weight percentages The rate values are based on any silica that may be used in combination with the polyorganosiloxane. , Any materials that may be utilized. Monostearyl phosphate Foam inhibitors are generally utilized in amounts ranging from 0.1% to 2% by weight of the composition. . Hydrocarbon foam inhibitors are typically used in amounts ranging from 0.01% to 5.0%. Used. However, more levels can be used. Alcohol foaming suppression The additives are typically used at 0.2% -3% by weight of the final composition.Alkoxylated polycarboxylate   Alkoxylated polycarboxylates, such as those prepared from polyacrylates G is useful in the present invention to add fat removal performance. These materials International Publication No. 91/08281 and PCT 90/01815 (4 pages or less) ) And are incorporated herein by reference. Chemically, these materials The polystyrene has one ethoxy side chain per 7-8 acrylate units. Contains acrylate. This side chain has the formula-(CH_TwoCH_TwoO)_m(CH_Two)_nCH_ThreeNomo Where m is 2-3 and n is 6-12. This side chain is Ester-linked to the acrylate "backbone", resulting in a "comb" polymer structure Let it. The molecular weight can vary, but typically ranges from 2000 to 50,000 It is. Such an alkoxylated polycarboxylate is used in the composition of the present invention. From 0.05% to 10% by weight.Fabric softener   Various fabric softeners during washing, especially storms issued December 13, 1977 ( U.S. Pat. No. 4,062 to Storm) and Nirschl. No. 647, and other smectite clays known in the art. Softening clays typically have a level of 0.5% to 10% by weight in the composition. Can be used to impart the benefits of a fabric softener at the same time as fabric washing. K Laye softeners are available, for example, on March 1, 1983 (Crisp). U.S. Patent No. 4,375,416 to Crisp et al. And September 22, 1981. Published in US Pat. No. 4,291,071 issued to Harris et al. It can be used in combination with amines and cationic softeners as indicated.Fragrance   Fragrances and perfume ingredients useful in the present compositions and processes include Aldehi. Various natural and synthetic compounds including, but not limited to, Chemical components. Orange oil, lemon oil, rose extract, lavender, ja Of ko, patchouli, balsam essence, sandalwood oil, pine oil, cedar Includes a variety of natural extracts and essences that can combine complex mixtures of similar ingredients Can be Final fragrances can incorporate extremely complex mixtures of these components. Wear. The final fragrance is typically from 0.01% of the detergent composition of the present invention. 2% by weight, with the individual perfume ingredients ranging from 0.0001% to 9% of the final perfume composition. 0% can be included.   Non-limiting examples of fragrance ingredients useful in the present invention include 7-acetyl-1,2 , 3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaph Taren, ionone methyl, ionone gamma methyl, methyl sedron, methyl di Hydrojasmonate, methyl 1,6,10-trimethyl-2,5,9-cyclo Dodecatrien-1-ylketone, 7-acetyl-1,1,3,4,4,6-he Xamethyltetralin, 4-acetyl-6-tert-butyl-1,1-dimethyl Ruindane, para-hydroxy-phenyl-butanone, benzophenone, methyl Beta naphthyl ketone, 6-acetyl-1,1,2,3,3,5-hexamethyl Indan, 5-acetyl-3-isopropyl-1,1,2,6-tetramethyli Ndan, 1-dodecanal, 4- (4-hydroxy-4-methylpentyl) -3- Cyclohexene-1-carboxaldehyde, 7-hydroxy-3,7-dimethyl Oh Kutanal, 10-undecene-1-al, iso-hexenyl-cyclohexyl Carboxaldehyde, formyl tricyclodecane, hydroxycitronellal Product of hydroxycitronellal with methyl anthranilate, India Condensation products with phenylacetaldehyde and indole, 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde , Ethyl vanillin, heliotropin, hexylcinnamaldehyde, amylcin Namaldehyde, 2-methyl-2- (para-iso-propylphenyl) -propyl Onaldehyde, coumarin, decalactone gamma, cyclopentadecanolide, 1 6-hydroxy-9-hexadecenoic acid lactone, 1,3,4,6,7,8 -Hexahydro-4,6,6,7,8,8-hexamethylcyclopentagun Ma-2-benzopyran, beta-naphthol methyl ether, ambroxane, Dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1b] furan, Cedrol, 5- (2,2,3-trimethylcyclopent-3-enyl) -3- Methylpentan-2-ol, 2-ethyl-4- (2,2,3-trimethyl-3 -Cyclopenten-1-yl) -2-buten-1-ol, caryophyllenal Coal, tricyclodecenyl propionate, tricyclodecenyl acetate, Benzyl salicylate, seryl acetate, and para- (tert-butyl) Cyclohexyl acetate is mentioned.   Particularly preferred perfume materials are most preferred in final product compositions containing cellulases. It brings great incense improvement. These flavoring agents include hexylcinnamal Dehyde, 2-methyl-3- (para-tert-butylphenyl) -propiona Aldehyde, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1 , 1,6,7-Tetramethylnaphthalene, benzyl salicylate, 7-acetyl- 1,1,3,4,4,6-hexamethyltetralin, para-tert-butyloxy Clohexyl acetate, methyl dihydrojasmonate, beta-naphthol Met Toluene, methyl beta-naphthyl ketone, 2-methyl-2- (para-iso- Propylphenyl) -propionaldehyde, 1,3,4,6,7,8-hexa Hydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma-2 -Benzopyran, dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2 , 1b] furan, anisaldehyde, coumarin, cedrol, vanillin, cyclo Pentadecanolide, tricyclodecenyl acetate and tricyclodecenylpi Onate, but not limited thereto.   Other flavoring materials include essential oils, resinoids; Nam Resinoid, Stylax, Radanam Resin, Nikuzuku, Cassia Oil, Ben Various types including, but not limited to, zoin resins, cilantro and lavandin And resins from sources. Another flavoring chemical is phenylethyl alcohol. Rucol, terpineol, linalool, linalyl acetate, geraniol, nero 2- (1,1-dimethylethyl) -cyclohexanol acetate, acetate acetate And eugenol. Carrier like diethyl phthalate It can be used in the final perfume composition.Other ingredients   Various other ingredients useful in detergent compositions are incorporated into the compositions of the present invention. Can be added. They include other active ingredients, carriers, hydrotrols , Processing aids, dyes, pigments, solvents for liquid formulations, solid fillers for rod compositions, etc. Is mentioned. If high foaming is required, C_Ten-C₁₆Foaming like alkanolamide Enhancers can be included in the composition, typically at a level of 1% to 10%. C_Ten-C₁₄Monoethanol and diethanolamine are two of these foam enhancers. This is an example of a typical class. The amine oxide, betaine and Use these foam enhancers with any of the high foaming surfactants like sultein It is also advantageous to do so. If necessary, MgCl_Two, MgSO_Four, CaCl_Two, CaSO_FourWater-soluble magnesium and / or calcium salts such as Added at 0.1% -2% level to add foam and enhance fat removal performance Can be   The various cleaning components optionally used in the present composition are based on a porous hydrophobic substrate. Further stabilization by absorbing the components and then coating the substrate with a hydrophobic coating can do. Preferably, the cleaning components are interfacial before being absorbed by the porous substrate. Mix with activator. In use, the cleaning components are released from the substrate into the aqueous laundry liquor. Therefore, the intended cleaning function is realized.   In order to explain this method in more detail, porous hydrophobic silica (trade name: SIPER) NAT D10, DeGussa) with 3% to 5% C_13-15Et Mixed with proteolytic enzymes containing xylated alcohol (EO7) nonionic surfactant Combine. Typically, the enzyme / detergent solution is 2.5 times the weight of the silica . The obtained powder is treated with silicone oil (various silicones in the range of 500-12,500). Oil viscosity can be used) with stirring. The obtained silicone Emulsify the oil dispersion or otherwise add to the final detergent mother liquor. By this method , The aforementioned enzymes, bleach, bleach activator, bleach catalyst, photoactivator, dye, fluorescent agent, cloth Ingredients such as ground preparations and hydrolyzable surfactants, including liquid laundry detergent compositions. Can be "protected" for use in detergents.   Liquid cleaning compositions may contain water or other solvents as a carrier. Meta Low, typified by ethanol, propanol and isopropanol A primary or secondary alcohol of molecular weight is suitable. Monohydric alcohol is a surfactant Is preferred to solubilize but 2 to 6 carbon atoms and 2 to 6 hydroxy groups Polyols such as those containing (eg, 1,3-propanediol, ethylene glycol) Recall, glycerin and 1,2 propanediol) can also be used. The composition comprises from 5% to 90%, typically 10% to 50% of such a carrier. May be included.   The detergent composition of the present invention is preferably used during aqueous washing operations, The pH of the wash water is between 6.5 and 11, preferably between 7.5 and 10.5. To be prescribed. The product formulation for liquid dishwashing is preferably pH 6.8 and 9. It is between 0. Laundry products typically have a pH of 9-11. Recommended usage level Methods for controlling pH include the use of buffers, alkalis, acids, etc. It is known to those skilled in the art.Production of granules   The bis-alkoxylated cationic surfactant of the present invention is added to the detergent mixture and After conventional spray drying, no residual potentially odorous short-chain amine contaminants Promotes removal. Formulators, for example, alkoxylated for high-density granular detergents If you want to prepare mixable particles containing a cationic surfactant, It is preferred that the child composition is not a strong alkali. High density (greater than 650 g / l) A process for preparing granules is described in US Pat. No. 5,366,652. . These particles have an effective p during use to avoid the odor of the impurity amines. You may prescribe so that H may be set to 9 or less. This is a small amount such as boric acid, citric acid, etc. Can be achieved by adding an acid source or a suitable pH buffer to the particles. You. In another aspect, the present invention relates to anticipated problems associated with amine odors. As disclosed above, masking can be achieved through the use of flavoring agents.                                    An example   In the following examples, the abbreviations for the various components used in the compositions are as follows: It has the following meaning: LAS C11.5 Alkylbenzene Sulfonate Anion with Average Chain Length Surfactants, preferably sodium salts. AS C₁₄-C_FifteenPrimary alkyl sulfate anion system of average chain length Surfactants, preferably sodium salts. NI C12-C15 ethoxylation with an average degree of EO9 ethoxylation Alcohol (non-ionic surfactant). SKS-6 layered silicate, Hoechst, sold. Copolymer Acrylic / maleic acid copolymer, sodium salt. Zeolite 1-10 micron zeolite A. PEG 4000 polyethylene glycol, average molecular weight 4000. NOBS Nonanoyloxybenzenesulfonate bleach activator. PB-1 Sodium perborate monohydrate. Protease Proteolytic detergent enzyme as disclosed above, BIOSAM3 . Contains 0. Amylase Starch degrading detergent enzyme. SRA-1 stain remover, methylcellulose, molecular weight about 13,000, degree of substitution 1.8-1.9. SRA-2 Stain remover according to US Patent No. 5,415,807. Brightener X Tinopal (trade name) CBS-X; distyrylbiphenyl Disulfonates; Ciba-Geigy. Brightener Y Tinopal (trade name) UNPA-GX; Sinauryl chloride ( Cynauric / diamidostilbenes; Ciba-Gei gy). Foam control agent Silica / silicone foam inhibitor. The following examples are illustrative of the present invention, but limit the scope of this specification or define them separately. It is not intended to do so. All the terms used in this specification Parts, percentages and ratios are expressed as weight percentages unless otherwise specified. Condyle The granular detergents in Examples A and B are as follows.                                 Example A Input amount-20g / 30L^* The example AQA1 (coco MeEO2) surfactant has an equivalent amount of surfactant AQA-2 To any of AQA-22 or other AQA surfactants in the present invention It may be replaced more.                                   Example B ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.   The following are examples of various stains and stains using compositions within the scope of the present invention. 2 illustrates laboratory procedures and test results. As can be seen from the data, an overall wash Improvements in cleanliness have been achieved at various stains and stains on various fabrics.                               Performance test procedure Sample preparation Preparation of a sample basically includes the following steps. 1. Preparation of premix LAS + AS. 2. Preparation of premix LAS + AS + cation. 3. Preparation of stock nonionic (AE) surfactant. 4. Preparation of builder solution. 5. Preparation of granules.Surfactant: ^*(Actual weight depends on percent activity) Product Preparation Procedure for Performance TestingStep I The individual surfactants are weighed and mixed according to the following procedure. Weigh 1.78.85 grams of LAS. Weigh 2.34.55 grams of AS into the same beaker. 3.498.10 ml of distilled water is added to the LAS & AS mixture. 4. Thoroughly dissolve LAS and AS at 40 ° C. for about 30 minutes until completely dissolved Pre-mix while heating.Step II 1.01.9 grams of cations were weighed and contained the LAS + AS premix solution. Into the same beaker. 2. The total volume of the solution is now 500 ml. This 500 ml surfactant mixture is sufficient for 5 washes. This stock solution 100 ml of the liquid is used for one washing. 49 liters of water in this 100 ml solution The addition of running water results in a corresponding wash concentration for each surfactant.Step III 1. Weigh 19.44 grams of AE separately. 2. Add 900 ml of distilled water to the AE. 3. This 900 ml solution is sufficient for 18 washes. 4.50 ml of this solution are used for one wash.Step IV Silicate: 148.32 grams per 900 ml of distilled water. 50 ml of this solution Used for one wash. Copolymer: 92.88 grams per 900 ml of distilled water. 50 ml of this solution Used for one wash. Granules: Weigh each granule component separately in the same beaker.Order of addition to washing machine The ingredients are added in the following order with stirring. 1. Silicate (2.0R) 2. Copolymer (as above) 3. Granules     The stirring is stopped here (to avoid foaming during the addition of the surfactant). 4. LAS + AS + cation solution 5. AE solution     Stir for 15 seconds     Hardness: No extra hardness is added in addition to tap water hardness.     Load: Typically, 2.4 kg of laundry having the following configuration is used.           Cotton dress shirt (1)           Worn out T-shirts (from panelists (3)           Large T-shirt (11)           DKPE T-shirt (1)           P / C shorts (2)           Cotton shorts (1) PKPE is a double knit polyester. DMO is a dirty motor oil.   The following test results I are based on a book using a mixture of Coco MeEO2 and LAS / AS. 1 shows the performance of a composition according to the invention. Test result II is compared with Coco MeEO2 / LAS And Coco MeEO10^*And the performance using LAS / AS. In the test , The performance is different dirt type, namely dirt, builder sensitive dirt, bleach sensitive Dirt, surfactant-sensitive dirt and socks^*Measured against. In the present invention According to the term "bis", "EO10" is an average of 10E in the molecule. O units, typically about 5 units per chain (but not limited to) Has two poly-EO chains.                                Test result I Premix of Coco MeEO2 cation and LAS & AS (overall anion system)                                Test result I            Premix of Coco MeEO2 cation and LAS alone                                Test result II          Premix of Coco MeEO10 cation with LAS + AS                                Test result II           Premix of Coco MeEO10 cation and LAS aloneDirt After wearing color 0.17 False collar -0.52 Cufflinks 0.19 Darkened -0.17 Stain (average) -0.08 Clay C / D -0.34 Clay DKPE 0.09 Builder sensitive dirt (average) -0.13 Spinach 0.06 Coffee 0.08 Bleach sensitive stain (average) 0.07 Meat sauce -0.20 Curry -0.38 Bacon oil -0.33 DMO -0.33 Surfactant sensitive soil (average) -0.31 Average (including socks) -0.11 Socks (front) 0.42S Socks (after) 0.64S Socks (Delta) 0.22   The following examples are illustrative of the invention, but limit the scope of the invention or define it separately. It is not intended to do so. All the terms used in this specification Parts, percentages and ratios are expressed as weight percentages unless otherwise specified. Less than In the examples below, the abbreviated component designations have the following meanings. LAS: Linear C₁₂Sodium alkylbenzene sulfonate TAS: Tallow alkyl sulfate sodium C45AS: C₁₄-C_FifteenSodium linear alkyl sulfate CxyEzS: C₁x-C₁y-branched sodium alkyl sulfate               Condensation with z moles of ethylene oxide C45E7: C_14-15Dominant linear primary alcohol             Condensed with an average of 7 moles of ethylene oxide C25E3: C_12-15Branched primary alcohol             Condensation with an average of 3 moles of ethylene oxide C25E5: C_12-15Branched primary alcohol             Condensation with an average of 5 moles of ethylene oxide Coco EO2: R₁N⁺(CH_Three) (C_TwoH_FourOH)_Two, Where R₁= C₁₂-C₁₄ Soap: straight chain alkyl derived from an 80/20 mixture of tallow oil and coconut oil Sodium lecarboxylate TFAA: C₁₆-C₁₈Alkyl N-methylglucamide TPKFA: C₁₂-C₁₄Uncut whole cut fatty acids STPP: anhydrous sodium tripolyphosphate Zeolite A: Formula Na having a primary particle size in the range of 0.1 to 10 microns₁₂ (AlO_TwoSiO_Two)₁₂・ 27H_TwoO sodium aluminosilicate hydrate NaSK S-6: Formula δ-Na_TwoSi_TwoO_FiveCrystalline layered silicate Citric acid: Citric anhydride Carbonate: anhydrous sodium carbonate having a particle size between 200 μm and 900 μm M Bicarbonate: anhydrous bicarbonate having a particle size between 400 and 1200 μm thorium Silicate: amorphous sodium silicate (SiO_Two: Na_TwoO; 2.0 ratio) Sodium sulfate: anhydrous sodium sulfate Citrate: activity 86.4 with particle size between 425 μm and 850 μm % Trisodium citrate dihydrate MA / AA: 1: 4 maleic / acrylic acid copolymer             Average molecular weight 70,000 CMC: Sodium carboxymethylcellulose Protease: Novo Industries A / S (Novo Industry es A / S) sold under the trade name Savinase Active 4KNPU / g protease Alcalase: Novo Industries A / S (Novo Industries) es A / S) marketed active 3AU / g protease Cellulase: Novo Industries A / S (Novo Industries) s A / S) active 1000 CEV sold under the trade name Carezyme U / g cellulolytic enzyme Amylase: Novo Industries A / S (Novo Industries) s A / S) active 60KN sold under the trade name Termamy 160T U / g amylolytic enzyme Lipase: Novo Industries A / S (Novo Industries) A / S) with an activity of 100 kLU / g sold under the trade name Lipolase Lipolytic enzyme Endolase: Novo Industries A / S (Novo Industries) es A / S) endoglunase (E) with an activity of 3000 EVU / g ndoglunase) enzyme PB4: Nominal NaBO_Two・ 3H_TwoOH_TwoO_TwoSodium perborate tetrahydrate PB1: Nominal NaBO_Two・ H_TwoO_TwoAnhydrous sodium perborate bleach Percarbonate: Nominal formula 2Na_TwoCO_Three・ 3H_TwoO_TwoSodium percarbonate NOBS: Nonanoyloxybenzene sulfate in the form of sodium salt TAED: Tetraacetylethylenediamine NACA-OBS: Sulfonic acid (6-nonanamidocaproyl) oxybenzene DTPMT: Monsanto trade name Dequest 2060 Diethylene triamine penta (methylene phosphonate) sold as Co catalyst: pentaamine acetate cobalt (III) salt Mn catalyst: described in U.S. Patent Nos. 5,246,621 and 5,244,594. Mn as listed^IV _Two(M-O)_Three(1,4,7-trimethyl-1,4,7- Triazacyclononane)_Two-(PF6)_Two Photoactivation: sulfonated zinc phthalo encapsulated in soluble polymer of bleached dextrin Cyanine Brightener 1: 4,4'-bis (2-sulfostyryl) biphenyl disodium Brightener 2: 4,4'-bis (4-amino-6-morpholino-1,3,5-tria Zin-2-yl) amino) stilbene-2: 2'-disulfonate disodium HEDP: 1,1-hydroxyethanediphosphonic acid PVNO: polyvinyl pyridine N-oxide PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole SRA1: Sulfate with oxyethyleneoxy and terephthaloyl backbone Ruphobenzoyl end-blocking ester SRA2: Diethoxylated poly (1,2 propylene terephthalate) short chain block Polymer Silicone antifoam: contains siloxane-oxyalkylene copolymer as dispersant A polydimethylsiloxane foam control agent, wherein the ratio of the foam control agent to the dispersant is 1 0: 1 to 100: 1   In the following examples, all levels are stated as% by weight of the composition.                                   Example 1   The following detergent formulations according to the invention are prepared. Here, A and C are phosphorus-containing detergents. Wherein C is a zeolite-containing detergent composition. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                   Example II   The following bleach-free detergent compositions are particularly useful in washing colored garments. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                  Example III   The following detergent formulations according to the invention are prepared. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                   Example IV   The following high density, bleach-containing detergent formulations according to the present invention are prepared. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                   Example V   The following high-density detergent formulations according to the invention are prepared. ^*An example bis-AQA-1 (coco MeEO2) surfactant is the surfactant bis-A Any of QA-2 to bis-AQA-22 or other bis in the present invention -It may be replaced by an equivalent amount of the AQA surfactant.                                   Example VI   The following liquid detergent formulations according to the invention are prepared. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.   Any of the granular detergent compositions provided in the present invention can be used to form a cleaning tablet. Tablets may be formed using known tableting methods.   Heavy duty liquid detergent compositions comprising a non-aqueous carrier medium, especially for fabric laundering The manufacture of the compositions intended for is carried out in the manner disclosed in detail hereinafter. Can be. In a variation, such a non-aqueous composition is disclosed in US Pat. No. 3,570, No. 4,767,558, No. 4,772,413, No. 4,88 9,652, 4,892,673; British Patent 2,158,838; US Patent Nos. 2,195,125; UK Patent No. 2,195,649; U.S. Patents No. 4,988,462, US Pat. No. 5,266,233, European Patent Publication No. 225,654 (6/16/87), EP-A-510,762. (10/28/92,), EP 540,089 (5/5/93). ), EP-A-540,090 (5/5/93), U.S. Pat. 15,820, EP-A-565,017 (10/13/93), Prepared according to the disclosure of EP-A-030,096 (5/10/81) And these are incorporated herein by reference. These compositions are stable Various particulate cleaning components suspended in the composition (e.g., as disclosed above). Bleaching agent). Accordingly, such non-aqueous compositions include It comprises the liquid phase and optionally but preferably the solid phase, all of which are described in detail hereinafter. And as described in the cited document. AQA surfactant is used for other washing Formulated in the composition at the level and manner described above for the manufacture of the rinse composition Is done.Liquid phase   The liquid phase generally comprises from 35% to 99% by weight of the detergent composition according to the invention. You. More preferably, the liquid phase comprises from 50% to 95% by weight of the composition. most Preferably, the liquid phase comprises from 45% to 75% by weight of the composition according to the invention. . The liquid phase of the detergent composition in the present invention is mixed with a specific type of non-aqueous liquid diluent. It also contains relatively high concentrations of certain types of anionic surfactants. (A)Essential anionic surfactant   Anionic surfactants essentially used as an essential component of the non-aqueous liquid phase are Alkyl groups containing 10 to 16 carbon atoms in a linear or branched configuration Selected from alkali metal salts of benzene sulfonic acid (referred to in the present invention by U.S. Pat. Nos. 2,220,099 and 2,477,383 which are incorporated herein by reference). . Particularly preferred are linear alkyl groups having an alkyl group having an average carbon number of 11 to 14. Rukylbene sulfonic acid (LAS) sodium and potassium. C₁₁− C₁₄Sodium LAS is particularly preferred.   Alkylbenzenesulfonate anionic surfactants are the second essential component of the non-aqueous phase. It is dissolved in the non-aqueous liquid diluent that makes up the sucrose component. Proper phase stability and satisfaction Alkylbensene sulfo to form the systematic liquid phase required for Nate anionic surfactants generally range from 30% to 65% by weight of the liquid phase. Exists. More preferably, alkylbensene sulfonate anionic surfactant The agents make up from 35% to 50% by weight of the non-aqueous liquid phase of the composition according to the invention. Using these anionic surfactants at these concentrations, 15% of the composition To 60% by weight, more preferably 20% to 40% by weight of anions in the total composition Corresponds to the system surfactant concentration. (B)Non-aqueous liquid diluent   In order to form a liquid phase of the detergent composition, the above-mentioned alkylbenzene sulfonate is used. The nonionic surfactant is mixed with a non-aqueous liquid diluent containing two essential components. These two components are a liquid alkoxylated material and a non-aqueous, low-polarity organic solvent. i)Alkoxylated alcohol   One essential component of the liquid diluent used to form the composition in the present invention is The portion consists of an alkoxylated fatty acid alcohol material. These substances are themselves It is also a body nonionic surfactant. Such substances have the general formula R¹(C_mH_2mO)_nO H. Where R¹Is C₈-C₁₆An alkyl group, m is 2 to 4 , N ranges from 2 to 12. Preferably, R¹Is 9 to 15 carbon atoms, and Primary or secondary alkyl, preferably containing 10 to 14 carbon atoms Group. Preferably also, the alkoxylated fatty alcohol has two or less per molecule. And 12 ethylene oxide components, more preferably 3 to 10 ethylene oxide molecules per molecule. An ethoxylated substance containing an oxide component.   The alkoxylated fatty alcohol component of the liquid diluent has a hydrophilicity ranging from 3 to 17 Often have a lipophilic balance (HLB). More preferably, the substance The HLB ranges from 6 to 15, most preferably 8 to 15.   A useful as one of the essential components of the non-aqueous liquid diluent in the composition of the present invention. Examples of alkoxylated fatty alcohols include alcohols of 12 to 15 carbon atoms And those containing 7 moles of ethylene oxide. Like this The material is Shell Chemical Company. pany) with the trade names Neodol 25-7 and Neodol 23-6.3. And sell them commercially. Other useful Neodols include 5 moles of ethyl Having an average of 11 carbon atoms in the alkyl chain with the oxide Neodol 1-5, an aliphatic alcohol, containing 9 moles of ethylene oxide Ethoxylated C₁₂-C₁₃Neodol 23-9, a primary alcohol Ethoxylated C with moles of ethylene oxide₉-C₁₁Primary alcohol Neodol 91-10. This type of ethoxylated alcohol Also see Shell Chemical Company any) under the trade name Dobanol. Dobanol 91- 5 is an ethoxylated C having an average of 5 moles of ethylene oxide₉-C₁₁Aliphatic al And Dobanol 25-7 is an average per mole of aliphatic alcohol. Ethoxylated C having an average of 7 moles of ethylene oxide₁₂-C_FifteenWith fatty alcohol is there.   Other examples of suitable ethoxylated alcohols include Union Carbide Co. Union Carbide Corporation is commercial Tergitol, both ethoxylated linear secondary alcohols sold to 15-S-7 and Tergitol 15-S-9. The former is 7 C with moles of ethylene oxide₁₁To C_FifteenMixed ethanol of linear secondary alkanol Xylated product, the latter being a similar product but with 9 moles of ethylenoxide It was a response.   Other types of ethoxylated alcohols useful in the composition are high aliphatic The alcohol is of 14-15 carbon atoms and Neodol 45-11 (model A similar effect of a high aliphatic alcohol having 11 ethylene oxide groups per A high molecular weight nonionic surfactant (such as a ethylene oxide condensation product). This The product is also sold by Shell Chemical C. market).   Used essentially as part of the liquid diluent in the non-aqueous composition in the present invention The alkoxylated alcohol component generally ranges from 1% to 60% of the liquid phase composition. Exists. More preferably, the alkoxylated alcohol component comprises from 5% to 4% of the liquid phase. Make up 0%. Most preferably, the essentially utilized alkoxylated alcohol The components make up from 5% to 30% of the detergent composition liquid phase. These concentrations in the liquid phase Utilizing an alkoxylated alcohol in 1% to 60% by weight of the composition, More preferably 2% to 40% by weight, most preferably 5% to 25% by weight of the whole set Corresponds to the alkoxylated alcohol concentration in the product. ii)Non-aqueous low polar organic solvent   The second essential component of the liquid diluent which forms part of the liquid phase of the detergent composition in the present invention The fraction consists of a non-aqueous, low-polarity organic solvent. As used herein, the term "solvent" refers to the group It refers to the non-surfactant carrier or diluted portion of the liquid phase of the product. Set in the present invention The essential and / or optional components of the product will actually dissolve in the "solvent" containing liquid phase But present as particulate matter dispersed in the liquid phase containing the solvent Some components do. Thus, the term "solvent" refers to a solvent substance added to the composition. It is also intended to make all of the ingredients of the detergent composition actually soluble. There is no.   The non-aqueous organic substance used as a solvent in the present invention is a low-polarity liquid. For the purposes of the present invention, a "low polarity" liquid is a negligible, One of the preferred types of particulate material used in the composition in which Tend to dissolve chloride bleach, sodium perborate or sodium percarbonate Things. Therefore, highly polar solvents such as ethanol should not be used. No. Suitable types of low polar solvents useful in the non-aqueous liquid detergent composition of the present invention Ip has non-vicinal C_Four-C₈Alkylene glycol, alkylene glycol Lower alkyl ether, low molecular weight polyethylene glycol, low molecular weight methyl ether Stels and amides.   Another preferred type of non-aqueous, low-polarity solvent for the composition in the present invention is Null C_Four-C₈Branched or straight chain alkylene glycols are mentioned. This type of Substances include hexylene glycol (4-methyl-2,4-pentanediol), 1,6-hexanediol, 1,3-butylene glycol and 1,4-butylene Glycol. Hexin glycol is most preferred.   Another preferred type of non-aqueous low polarity solvent used in the present invention includes mono- -, Di-, tri- or tetra-C_Two-C_ThreeAlkylene glycol mono C_Two-C₆A Alkyl ether. Specific examples of such compounds include diethylene glycol. Recohol monobutyl ether, tetraethylene glycol monobutyl ether, Dipropylene glycol monoethyl ether and dipropylene glycol mono Butyl ether. Diethylene glycol monobutyl ether and Dipropylene glycol monobutyl ether is particularly preferred. Compounds of this type The products are available under the trade names Dowanol, Carbinol and Cellosolve. Originally sold commercially.   Another preferred type of non-aqueous low-polar organic solvent useful in the present invention includes low Molecular weight polyethylene glycol (PEG). These substances are few Both have a molecular weight of 150. P with a molecular weight ranging from 200 to 600 EGs are most preferred.   Yet another preferred type of non-aqueous low polarity solvent is low molecular weight methyl ether. No. Such substances have the general formula R¹—C (O) —OCH_ThreeIs the expression Medium, R¹Ranges from 1 to 18. Examples of suitable low molecular weight methyl ethers include: Methyl acetate, methyl propionate, methyl octanoate, and methyl Ludodecanoate.   The non-aqueous low-polar organic solvent used in the liquid detergent composition of the present invention With other composition components used, for example bleach and / or activators Of course, it is desirable that they be compatible and non-reactive. Such solvent components Is generally utilized in an amount of 1% to 70% by weight of the liquid phase. More preferably, non- The aqueous low-polar organic solvent comprises from 10% to 60% by weight of the liquid phase, most preferably of the composition. Make up from 20% to 50% by weight of the liquid phase. At these concentrations in the liquid phase Dissolution With the use of a medium, 1% to 50% by weight of the composition, more preferably 5 to 40% by weight %, Most preferably from 10% to 30% by weight of the solvent concentration in the total composition. iii)Ratio of alkoxylated alcohol to solvent   The ratio of alkoxylated alcohol to organic solvent in the liquid diluent will ultimately be It can be used to change the flow characteristics of the resulting detergent composition. Generally, The weight ratio of alkoxylated alcohol to organic solvent ranges from 50: 1 to 1:50. It is an enclosure. More preferably, this ratio ranges from 3: 1 to 1: 3. iv)Liquid diluent concentration   Similar to the concentration of the alkylbenzene sulfonate anionic surfactant mixture, The amount of total liquid diluent in the non-aqueous liquid phase in the present invention depends on the type of other composition components. And the amount and composition characteristics required. Generally, liquid diluents are used in the present invention. Make up from 35% to 70% of the non-aqueous liquid phase of the composition. More preferably, liquid The diluent comprises 50% to 65% of the non-aqueous liquid phase. This is 15% of the composition 70% by weight, more preferably 20% to 50% by weight of the non-aqueous liquid in the total composition Corresponds to diluent concentration.Solid phase   The non-aqueous detergent composition of the present invention comprises 1% to 65% by weight, more preferably 5% by weight. % To 50% by weight of the solid phase of the particulate material dispersed and suspended in the liquid phase. You. Generally, such particulate materials are 0.1 to 1500 micron in size. Ron's range. More preferably, such a material is 5 to 2 in size. Range of 00 microns.   The particulate material used in the present invention is a non-aqueous liquid of the composition in a particulate form. One or more types of detergent composition components that are substantially insoluble in the phase can be included. The types of particulate materials that can be used are described in detail as follows.Preparation and use of the composition   The non-aqueous liquid detergent composition of the present invention is essential in any convenient order. And optional components are mixed, and the obtained component mixture is mixed, for example, by stirring. To form the phase stable composition of the present invention. Such a composition In a typical process for preparing the ingredients, the essential components and certain preferred optional components are The minutes are formulated in a particular order and under particular conditions.   In the first step of these typical preparation processes, the alkylbenzene Mixture of a sulfonate anionic surfactant and two essential components of a non-aqueous diluent Is formed by heating a blend of these materials to a temperature of 30 ° C to 100 ° C. Is done.   In the second step, the heated mixture formed as described above is left for 2 minutes. For 20 hours at a temperature of 40 ° C. to 100 ° C. under shear stirring. Duty If desired, a vacuum can be applied to the mixture at this point. This second step is It acts to completely dissolve the anionic surfactant in the non-aqueous liquid phase.   In a third step, this liquid phase formulation of the material is cooled to a temperature between 0 ° C and 35 ° C. Be rejected. This cooling step adds the particulate material of the detergent composition of the present invention. Form a systematic surfactant-containing liquid base that can be added or dispersed Act like so.   Particulate material is a liquid-based material that maintains the particulate material under conditions of shear agitation. And in the fourth step by mixing. Two or more types of fine When adding particulate materials, it is preferred to adhere to a particular order of addition. For example While maintaining shear agitation, essentially any interface in solid particulate form The activator can also be added in the form of particles ranging in size from 0.2 to 1,000 microns. After the addition of optional surfactant particles, for example, citrate and / or fatty acid-like Organic builder and / or fruit of an alkali source such as, for example, sodium carbonate. quality In general, all particles continue to maintain this mixture of composition components under shear agitation. Can be added. Next, any other solid components are assembled at this point. It can be added to the composition. Continue stirring the mixture, stirring if necessary at this point. Enhanced agitation can form a uniform dispersion of insoluble solid particulates in the liquid phase .   After stirring some or all of the solid material described above and adding it to the mixture, it is highly preferred. New peroxide bleach particles, again maintaining the mixture under shear stirring Can be added to the product. By adding the peroxide bleach material last, Or after adding all or most of the other ingredients, and especially the alkali source granules After adding the particles, it is possible to realize the necessary stability advantage for peroxide bleach. it can. If formulating enzyme globules, they should be added to the mother liquor, preferably in a non-aqueous liquid. To be added.   As a final process step, after all the particulate material has been added, Continue stirring the mixture for a period of time sufficient to form a composition with temperature and phase stability properties I do. This often requires 1 to 30 minutes of stirring.   As a variation of the composition preparation procedure described above, a small portion of one or more A stirred mixture of one or more solid components as a slurry of mixed particles May be added. Therefore, particles of organic builder material and / or inorganic alkali Source particles and / or bleach activator particles and an alkoxylated alcohol and / or Alternatively, a separate premix with a small fraction of the non-aqueous Together, they may be added as a slurry to the stirred mixture of composition components. like this The addition of the slurry premix used is a premix formed in a similar manner by itself. Of certain peroxide bleach and / or enzyme particles as part of It is desirable to precede the addition.   The composition of the present invention prepared as described above is an aqueous wash for fabric laundering and bleaching. Can be used to form a rinsing solution. Generally, an effective amount of the composition is preferred. Or added to water in a conventional automatic washing machine for fabric washing to form an aqueous washing / bleaching solution. Form. The aqueous wash / bleach solution thus formed is then preferably agitated. Below, it comes in contact with the fabric to be washed and bleached.   Liquid laundry composition according to the invention which is added to water to form an aqueous laundry / bleach solution Is effective to form a composition of 500 to 7,000 ppm in aqueous solution. Can comprise a small amount. More preferably, 800 to 3,000 pp m of the detergent composition of the present invention is formed in an aqueous wash / bleach solution.                                  Example VII Non-limiting example of a bleach-containing non-aqueous liquid wash having a composition as described in Table I Prepare a rinse. ^*Coco MeEO2. Bis-AQA-1 is a bis-AQA surfactant 2-22 or Alternatively, it may be replaced by another bis-AQA surfactant in the present invention.   Bis-AQA and LAS, then hexylene at 130 ° F. for 1/2 hour at 54 ° C. Preparation of composition by mixing glycol and ethoxylated alcohol together I do. The mixture is then cooled to 29 ° C (85 ° F) and the remaining ingredients are added. . Next, the resulting composition is stirred at 29 ° C. (85 ° F.) for another 1/2 hour.   The resulting composition has excellent stain and stain when used in normal fabric washing operations. It is a stable, anhydrous, heavy-duty, liquid laundry detergent with removal performance.   Examples A and B below further illustrate the invention in the present invention with respect to bar-shaped laundry soaps. It is proof.                                  Example VIII ¹: Sodium diethylene triamine penta (phosphonate)^Two : Sokolan CP-52 is a maleic / acrylic copolymer.^Three : Bis-AQA-1 is obtained from an equivalent of bis-AQA surfactant, bis-AQA2. Bis-AQA-22 or other bis-AQA surfactant in the present invention May be replaced.^Four : Water (2% to 8% including water of hydration), sodium sulfate, calcium carbonate And other minor components.                                   Example IX   The present invention is achieved by mixing together the components in weight percentages as indicated below. The following hand laundry detergent formulation is prepared. AQA-9^*Placement with any of the AQA surfactants described in the present invention. May be replaced. Preferred AQA surfactants for use in this example include, for example, Having 10 to 15 ethoxy groups such as AQA-10 and AQA-16 You.   While the above example illustrates the present invention for a fabric laundry composition, The example below is intended to illustrate another type of cleaning composition according to the present invention. However, it is not intended to limit the invention.   Modern high performance hand dishwashing compositions have lipolytic ability, high foaming, mildness and skin feel Can include ingredients designed to bring the benefits of a particular product attribute Wear. Such components for use with the bis-AQA surfactant in the present invention Include, for example, amine oxide surfactants, betaines and / or sultaines Surfactants, alkyl sulfate and alkyl sulfate epoxy surfactants, liquid carriers A, especially water and natural oils such as water / propylene glycol mixtures and lemon oil. I can do it. Further, preferred liquid and / or gel hand dishwashing compositions are Ion, magnesium ion or mixed calcium / magnesium ion It may also include cations, such as amine oxides, alkyl sulfates and Including bis-AQA surfactant of the present invention containing alkyl sulphate sulfate Magnesium adds to the benefits of lipolytic performance, especially when used in conjunction with a wash mixture The source of calcium or calcium or the source of mixed Mg / Ca ions is typically From 0.01% to 4%, preferably from 0.02% to 2% by weight of the composition It becomes. Various water-soluble sources of these ions include, for example, sulfates, chlorides and Acetate. In addition, these compositions contain nonionic surfactants, especially poly Hydroxy fatty acid amides and alkylpolyglucas (polyglucas) ide) species. Preferred are those classes of C₁₂-C₁₄(Here Nut alkyl) members. Nonionic surfactants especially preferred for hand dishwashing liquids The activating agent is C₁₂-C₁₄N-methylglycamide. Preferred amine oxides include , C₁₂-C₁₄Dimethylamine oxide. Alkyl sulfate and sulfuric acid Lucyl ethoxy is as described above. For such surfactants in dishwashing liquid Use levels typically range from 3% to 50% of the final composition. Dishwashing liquid The formulation of the composition is described in U.S. Patent Nos. 5,378,409, 5,376,310 and others. And various patent publications, including 5,417,893. , Incorporated herein by reference.   Modern automatic dishwashing detergents are a source of hypochlorite, perborate, percarbonate or persulfate Bleaching agents such as bleaching agents, proteases, lipases and amylases or their Enzymes, such as mixtures, rinsing aids, especially nonionic surfactants; Builders, including sulfate builders, low foaming detergents, especially ethylene oxide An oxide / propylene oxide condensate may be included. Such compositions are Expressively, they exist in the form of granules or gels. When used in the form of a gel, Various gelling agents known in the literature can be used.   The following examples further illustrate the invention in the present invention with respect to hand dishwashing liquids. .                                   Example X ^*Bis-AQA-2 to Bis-AQA-22 or other bis in the present invention -It may be replaced by an AQA surfactant.^** Cocoalkyl betaine   Examples A and B below illustrate the invention with respect to an automatic dishwashing detergent containing granular phosphate. This further exemplifies the invention.                                   Example XI                             Wt% active material ¹: Sodium tripolyphosphate^Two : Sodium dichlorocyanurate^* Bis-AQA-1 surfactants are converted from bis-AQA-2 to bis-AQA-22. It may be replaced more.                                  Example XII   The following examples enhance the level of liquid-gel automatic dishwashing detergent or stain removal benefits This further exemplifies the invention herein with respect to other detergents used.                             Wt% active material ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of bis-AQA -2 to bis-AQA-22 or other bis-A in the present invention It may be replaced by a QA surfactant.   Various gelling agents, such as CMC and clay, can vary in amount depending on the formulator's needs. It can be used in compositions to provide a degree of viscosity or rigidity.                                  Example XIII   The following replaces the bis-AQA surfactant described in any of the above examples FIG. 1 illustrates a mixture of bis-AQA surfactants that can be used. Above As disclosed, such mixtures have a range of performance advantages, And / or to provide a useful cleaning composition over a variety of conditions of use. Can be Preferably, the bis-AQA surfactant in such a mixture is All EO units differ by at least 1.5, preferably 2.5-20. This The ratio range (weight) for such mixtures is typically 10: 1-1: 10. You. Non-limiting examples of such mixtures are as follows.component                                                     Ratio (weight) Bis-AQA-1 + Bis-AQA-5 1: 1 Bis-AQA-1 + Bis-AQA-10 1: 1 Bis-AQA-1 + Bis-AQA-15 1: 2 Bis-AQA-1 + Bis-AQA-5 + Bis-AQA-20 1: 1: 1 Bis-AQA-2 + Bis-AQA-5 3: 1 Bis-AQA-5 + Bis-AQA-15 1.5: 1 Bis-AQA-1 + Bis-AQA-20 1: 3   Bis-AQA surfactants according to the invention comprise a pair comprising only a single ethoxylated chain. Mixtures with the corresponding cationic surfactants can also be used. So, for example, , Formula R¹N⁺CH_Three[EO]_x[EO]_yX^-And R¹N⁺(CH_Three)_Two[EO]_zX^-Of et Mixtures of xylated cationic surfactants can be used in the present invention. (Where R¹And X are as disclosed above, and one of the cationic surfactants Has (x + y) or z in the range 1-5, preferably 1-2, and the other has 3-1. 00, preferably in the range of 10-20, most preferably in the range of 14-16 to (x + y). Or z). Such compositions are individually provided by the cationic surfactant of the present invention. Detergent performance over a wide range of water hardness (especially for fabric washing) Is advantageously improved. Shorter EO cationic surfactants (eg, EO 2) improves the cleaning performance of anionic surfactants in soft water, while longer EO cationic surfactants (eg EO15) are the hardness of anionic surfactants Acts to improve the tolerance, thereby allowing the anionic surfactant in hard water to It has now been discovered to improve cleaning performance. The traditional wisdom in cleaning technology is building Can optimize the performance "window" of anionic surfactants It suggests. But until now, expanding this window, essentially everything It was not achievable to include the conditions of water hardness.Example XIV   This example was added to any of the previous examples of bis-AQA containing detergent compositions. To illustrate, the perfume formulation (AC) made according to the present invention is illustrated. Mr The various components and levels are described below.   The above-mentioned perfume composition contains the bis-AQA surfactant disclosed in the present invention. Mixed or sprayed with any of the cleaning (including bleaching) compositions (Typically, at levels up to about 2% by weight of the total detergent composition). To be cleaned (or Bleaching) improved adhesion and / or preservation of perfume or its individual components on the surface Mobility is thus secured.

────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventors André, Cesar, Beck             Belgian Bey 2820, Bon Heiden, P             Sestene Wake, 273 (72) Inventor Kaori Minamikawa             1-26-46 Hyogo Prefecture Himeji City (72) Inventors Richard, Timothy, Hartshawn             Waira, Northumberland, United Kingdom             M, Dean, Road, 139 (72) Inventor Jones, Linda, Ann, Speed             Newcastle, UK, UK, UK             Inn, Gosforth, Mayfield, B             Mode, 21 (72) Inventor Rinko Katsuta             6-2-1, Minatojima-Nakamachi, Chuo-ku, Kobe City, Hyogo Prefecture             Kobe Park City, Sea 507 (72) Inventor Frank, Andoy, Kubitok             United States Ohio, Cincinnati,             Richwood, Avenue, 1103 (72) Inventor Mark, Cyan-Quen, Mao             2-23-13 Sumiyoshi Honcho, Higashinada Ward, Kobe City, Hyogo Prefecture (72) Michael, Alan, John, Moss             Stockholm, Northumberland, United Kingdom             Sfield, Painshawfield,             Road, 13 (72) Inventor Masaru Murata             6-5-A3, Yumabacho, Nishinomiya City, Hyogo Prefecture (72) Inventor Ryohei Otani             7-19 Uedanakamachi, Nishinomiya City, Hyogo Prefecture (72) Inventors Layan, Keshaf, Panandadaikar             United States Ohio, West, Chi             Esther, Oregon, Pass, 6484 (72) Inventor Kakumanu, Pramod             United States Ohio, West, Chi             Esther, Kingfisher, Rain,             7986 (72) Inventors Kizar, Mohammed, Kang, Sarnaik             Higashi-Nada-ku, Koyo-cho, Kobe City, Hyogo Prefecture             ―302 (72) Inventors Christian, Arthur, Jax, Ka             Miel, Toen             Belgian Bae 9120, Haasdonk, Bae             Quitohustrato, 4 (72) Inventor Kevin, Lee, Cott             United States Ohio, Cincinnati,             Bentbrook, Drive, 2920 (72) Inventors Kenneth, William, Wilman             Fairfay, Ohio, USA             , Williamsburg, Way,             5603 (72) Inventor Laura, Kron             Fairfay, Ohio, USA             Field, lake, mead, drive, 5656 (72) Inventor Thomas, Anthony, Creep             United States Ohio, Loveland,             Three, Chimneys, Rain, 599 (72) Inventor John, Downing, Curry             Oxford, Ohio, United States             Road, Stone, Creek, Drive, 95 (72) Inventors Peter, Robert, Foley             United States Ohio, Cincinnati,             Lytle, Place 1, Apartment             906 (72) Inventor Ian, Martin, Dodd             Loughborough, Hollywell, Dora, England             Eve, 47 (72) Inventors Sanjeef, Chris Nadas, Manohar             Fairfay, Ohio, USA             Field, meadow loan, way, 2014             ー (72) Inventor Mitsuyo Okamoto             8-16-204, Kusu-cho, Ashiya-shi, Hyogo

Claims (1)

[Claims] 1. Comprising an enzyme, a non-AQA surfactant, and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant represented by the following formula, or prepared in combination: Detergent composition. Wherein R ¹ is a linear, branched or substituted C ₈ -C ₁₈ alkyl, alkenyl, aryl, alkaryl, ether or glycidyl ether component, R ² is a C ₁ -C ₃ alkyl component, R ³ And R ⁴ are independently variable and are selected from hydrogen, methyl and ethyl, X is an anion, A and A ′ are independently variable and are each C ₁ -C ₄ alkoxy, p and q Can vary independently and are integers ranging from 1 to 30). The composition of claim 1, wherein the enzyme is selected from the group comprising lipase. 3. The composition according to claim 1, wherein the enzyme is a protease. 4. The composition according to any one of claims 1 to 3, wherein the enzyme is cellulase. 5. The composition according to any one of claims 1 to 4, wherein the enzyme is endoglucanase. 6. The composition according to any one of claims 1 to 5, wherein the enzyme is an amylase. 7. The composition according to any one of claims 1 to 6, wherein the enzyme is peroxidase. 8. The composition according to any one of claims 1 to 7, further comprising an enzyme stabilizing compound. 9. 9. The composition according to any one of claims 1 to 8, prepared by mixing a non-AQA surfactant and an AQA surfactant. 10. The composition according to claim 1, wherein the non-AQA surfactant is an anionic surfactant. 11. A composition according to any one of the preceding claims, wherein the ratio of bis-AQA to non-AQA surfactant is from 1:15 to 1: 8. 12. The bis-AQA surfactant is represented by the formula wherein R ¹ is C ₈ -C ₁₈ alkyl, R ² is methyl, A and A ′ are ethoxy or propoxy groups, and p and q are each 1 The composition according to any one of claims 1 to 11, wherein the composition is of an integer from to 8. 13. The bis-AQA surfactant is represented by the formula wherein R ¹ is C ₈ -C ₁₈ alkyl, R ² is methyl, A and A ′ are ethoxy or propoxy groups, and p and q are each 1 The composition according to any one of claims 1 to 12, wherein the composition is of an integer from to 4. 14． 14. The composition according to any one of claims 1 to 13, wherein the bis-AQA cationic surfactant has the formula wherein p and / or q is an integer in the range of 10 to 15. 15. The composition according to any one of claims 1 to 14, comprising two or more bis-AQA surfactants, or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant. Stuff. 16. 16. The composition according to any one of the preceding claims, comprising two or more non-AQA surfactants and a mixture of two or more bis-AQA surfactants. 17． 17. The composition according to any of the preceding claims, substantially free of bleach. 18. 18. The composition according to any one of claims 1 to 17, which is in the form of a granule, a stick, an aqueous liquid, a non-aqueous liquid or a tablet. 19. A method for removing dirt and stains, wherein the dirt and stains are contacted with the detergent composition according to any one of claims 1 to 18 or an aqueous medium comprising the detergent composition. 20. 20. The method of claim 19, wherein the enzyme sensitive soil, fatty / oily soil or surfactant sensitive soil is released from the fabric. 21. 21. The method of any one of claims 19 or 20, which is performed by hand. 22. 22. The method according to any one of claims 19 to 21, performed in an automatic machine. 23. A method for improving the deposition or persistence of a fragrance or fragrance component on a fabric or other surface, comprising contacting said surface with a fragrance or fragrance component in the presence of a bis-AQA surfactant . 24. 24. The method of claim 23, wherein the method is performed with a fragrance or fragrance component in combination with a detergent composition comprising bis-AQA.