JPH11511799A - Detergent composition - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION                                Detergent composition                                 Background art   The present invention relates to percarbonate bleaches, non-AQA surfactants and bis-alkoxylations. Detergent composition containing quaternary ammonium (bis-AQA) cationic surfactant About.                                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 , Such detergent compositions loosen and remove various types of soils and stains It contains one or more surfactants that aim to do so. Looking at the literature, there are many kinds of fields Combinations of surfactants and surfactants seem to be available to detergent manufacturers In contrast, many of these ingredients are suitable for inexpensive unit cost products such as household laundry detergents. The reality is that it is a specialty chemical that does not. Most of this like laundry detergent Household products may also contain one or more conventional ethoxylated non-ionic and / or sulphated Or are still mainly blending sulfonated anionic surfactants Is a fact. This is probably due to the variety of dirt and stains and It is necessary to formulate a composition that works reasonably well for different fabrics. Would.   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 Mixtures of hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous materials And all of these, to varying degrees, consist of hydrophobic components, It is well known that it is difficult to do. Low levels of hydrophobic stains and residual stains Often remains on the surface of the fabric after washing. In addition to the sequence of washing and wearing, Limited removal of hydrophobic stains increases residual soil and stain buildup, Will take up more particulate dust and yellow the fabric. Ultimately, the fabric is thin It gets dirty and consumers discard it because they can't wear it.   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 In addition, a composition containing both a bis-AQA surfactant and a percarbonate bleach, Demonstrate excellent cleaning performance and white performance for products containing either technology alone 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, used in the present invention Bis-AQA surfactants often have the "daily" fatty / oily hydrophobic nature Significantly improves dirt cleaning. Further, bis-AQA surfactants are alkyl sulfates. Commonly used in detergent compositions such as and alkylbenzene sulfonates Compatible with on-surfactants. The detergent composition is compatible with the anionic surfactant The lack of a common use in the use of previously known cationic surfactants. It was one of the limiting factors. Low level (3 ppm in washings) bis-AQA interface Activators provide the advantages described in the present invention. 5 bis-AQA surfactants Can be formulated over a wide pH range from 12 to 12. Bis-AQA surfactant The agent can be prepared as a 30% (by weight) solution over a pump, and is therefore Easy to handle. Bis-AQA surfactants with a degree of ethoxylation of more than 5 are sometimes It is present in liquid form and can therefore be provided as 100% stock solution. In addition to beneficial handling properties The availability of bis-AQA surfactants as highly concentrated solutions is Is a substantial economic advantage. Bis-AQA surfactants are known in the art. Differs from some cationic surfactants known in It is soluble.   Percarbonate, which supplies peroxide bleach in laundry, is a modern ultra-compact granule wash This is the basic technique of detergent formulation. Peroxide bleach is both hydrophilic and Bleaching effect (eg, produced from peroxide interaction with TEAD) On the other hand, pigments (eg, in particulate stains or beverage stains) Effective in color and helps remove color from organic residues associated with dirt Can also.   Fatty / oily stains are effectively solubilized by bis-AQA and stain in the stains Enables hydrophilic peroxide bleach to gain access to the body (eg, incorporated pigments) , It is thought to improve the decolorization of the stain. The present invention thus provides a hydrophobic fatty / Excellent as it has a significant cleaning effect on both oily stains and hydrophilic colored stains The present invention provides a detergent composition exhibiting an improved cleaning.                                 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 a percarbonate bleach, a non-AQA surfactant, and Effective amount of bis-alkoxylated quaternary ammonium (bis-AQA) cation And / or prepared by combining the surfactants A detergent composition is provided.   (Where R¹Is a linear, branched or substituted C₈-C₁₈Alkyl, alkenyl, ally Alkenyl, ether or glycidyl ether component;^TwoIs C₁ -C_ThreeAn alkyl component;^ThreeAnd R^FourCan vary independently, and hydrogen and Selected from chill and ethyl, X is an anion, and A and A ′ are independently variable And C₁-C_FourAlkoxy, wherein p and q are independently variable And an integer in the range of 1 to 30)                             Detailed description of the invention Percarbonate bleach   The first essential component of the present invention is a percarbonate bleach. Alkali metal or Al Potassium earth metal percarbonates, especially sodium percarbonate, are added to the composition according to the invention. Is a preferred percarbonate. Sodium percarbonate is 2Na_TwoCO_Three・ 3H_TwoO_Two Is an additive compound having the formula and is commercially available as a crystalline solid. Sodium percarbonate is a hydrogen peroxide compound and is commercially available as a crystalline solid. I can do it. Commercial suppliers include Solbay, FMC, Tokai Denka and others. I can do it.   Preferred percarbonate bleaches have an average particle size in the range of 0.5 mm to 1 mm. Comprising less than 10% by weight of the dried particles having less than 0.2 mm, Less than 10% by weight of the particles is greater than 1.250 mm.   The percarbonate comprises between 1% and 50% of the detergent composition, preferably between 1% and 30%. And most preferably at a level between 5% and 20% by weight.   The percarbonate is most preferably in the form of a coating that provides in-product stability. The composition is blended.   Suitable coating materials that provide in-product stability include water-soluble alkali metal sulfates and carbonates. And a mixed salt with a salt. Such coatings can be used in conjunction with the coating process to provide 197 GB-1,46 approved by Interox on March 9, 2007 No. 6,799, previously described. The weight ratio of mixed salt coating material to percarbonate is 1: 200 to 1: 4, more preferably 1:99 to 1: 9, most preferably It ranges from 1:49 to 1:19. Preferably, the mixed salt has the formula: 0.1 to 3, preferably n is 0.3 to 1.0, most preferably n is 0.2 The general formula Na_TwoSO_Four. n. Na_TwoCO_ThreeSodium sulfate with And sodium carbonate.   Silicates (alone or with borate, boric acid or other minerals), waxes, Oils, other coatings containing fatty soaps can also be advantageously used within the present invention. You.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, preferably containing 8 to 14 carbon atoms , Aryl, alkaryl, ether or glycidyl ether components. , R^TwoIs an alkyl group containing from 1 to 3 carbon atoms, preferably methyl;^ThreeAnd And R^FourCan vary independently and include hydrogen (preferred), methyl and ethyl. X^-Chloride, bromide, sulfuric acid Anions such as chill and sulfate, wherein A and A ′ can be varied independently, Each C₁-C_FourAlkoxy, especially ethoxy, propoxy, butoxy and it And p is 1 to 30, preferably 1 to 15, more preferably Or 1 to 8, still more preferably 1 to 4, and q is 1 to 30, preferably Is 1 to 15, more preferably 1 to 8, still more preferably 1 to 4, Most 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 field in the present invention An "effective amount" of a surfactant is defined as directional or significant at a 90% confidence level. To improve the performance of the cleaning composition on at least some of the get soils and stains Means a sufficient amount. Therefore, if the target is a composition containing a specific food stain, And the formulator at least directionally improves the cleaning performance against such stains Use sufficient bis-AQA to Similarly, the composition in which the target contains clay stains In products, formulators at least directionally improve their cleaning performance against such soils. Use enough bis-AQA to improve.   Bis-AQA surfactant achieves at least directional 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 Place If (density is greater than 650 g / l), preferably 0.2% to 5.0% Is converted to the product concentration (weight) of 0.5% to 2.5% bis-AQA surfactant Is done. Based on the usage of 80 g to 100 g / wash load, this is For dry granules (ie "fluffy", density less than 650 g / l) 0.1% to 3.5%, preferably 0.3% to 1.5% bis-AQA field It is converted to the concentration (weight) of the surfactant 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 This is the case for high-concentration (“compact”) granular laundry detergents, based on loading, (Density greater than 650 g / l), 0.25% to 10%, preferably 0% . Converted from 5% to 1.0% bis-AQA surfactant in product concentration (weight) You. Based on the usage rate of 30 g to 40 g / wash load, this is (I.e., "fluffy", with a density less than 650 g / l). Preparation of 25% to 10%, preferably 0.5% to 1% bis-AQA surfactant It is converted to in-product concentration (weight).   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 bis-alkoxylated cationic surfactant in the invention is a nonionic surfactant Mixed surfactant containing, for example, an alkyl sulfate surfactant It has sufficient solubility that can be used in combination with the system. This is a top-loading Automatic washing machines, especially those of the type used in North America, and the conditions of use in Japan Is intended to be used in automatic washing machines of the type used in This can be an important consideration for formulators of certain types of detergent compositions. Typically, this The resulting composition has a composition of from about 25: 1 to about 1:25, preferably from about 20: 1 to about 3: 1. Weight ratio of anionic surfactant to nonionic surfactant. this Is typically about 10: 1 to 1:10, preferably about 5: 1 to about 1: 1. It can be contrasted with a European formulation consisting of a range of anion: nonionic ratios.   Preferred ethoxylated cationic surfactants in the present invention are Akzo Novell® Chemicals Company (Akzo Nobel Chemicals Compa) ny) under the trade name ETHOQUAD. Instead, these materials Has various different reaction mechanisms (where "EO" is -CH_TwoCH_TwoO-YU Ni Can be synthesized by usingMechanism 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. The model for amine alkyl sulfates The ratio is typically 10: 1 to 1: 1.5, preferably 5: 1 to 1: 1.1. , More preferably from 2: 1 to 1: 1. In the product collection step, Substituted amines simply separate from the insoluble aqueous reaction medium as a distinct phase Is done. The second step of this process is performed under conventional reaction conditions . Further ethoxylation and quaternization to yield bis-AQA surfactants are standard It is performed under conditioned 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 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 a toclave, 160 hours under nitrogen at 300-400 psig for 3-4 hours. − Heat to 180 ° C. The mixture was cooled to room temperature and the liquid content of the glass liner was Pour into 250 ml separatory funnel with ml chloroform. Leave the funnel for several minutes. And then separate the mixture. Remove the lower chloroform layer and The product is obtained by evaporating the roform.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 of 50% by weight sodium hydroxide Solution (0.095 mol) and 72 g of distilled H_TwoO in glass autoclave Add to liner. Glass liner with 500ml stainless steel rocking haute Seal in a rabe and 160-1 under 300-400 psig nitrogen for 3-4 hours. Heat to 80 ° C. The mixture was cooled to room temperature and the liquid content of the glass liner was Pour into a 250 ml separatory funnel with 1 liter of chloroform. Enough funnel for a few minutes And then separate the mixture. Remove the lower chloroform layer and remove The product is obtained by evaporating the form. The product is treated with a basic catalyst at 120-130 ° C. React with 1 molar equivalent of ethylene oxide in the absence.   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 according to the invention The degree of alkoxylation described is one-to-one with respect to conventional ethoxylated nonionic surfactants. Understand to report as an average, according to common practice. It is ethoxylated This is because the reaction generally results in a mixture of substances having different degrees of ethoxylation. Obedience Thus, all EO values are reported except as integers (eg, “EO2.5”, “EO3 . 5)) is 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, balance charge Any conventional anion to provide, 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, A preferred type of compound is “coco MeEO2” in the above list in the present invention. Or called "Bis-AQA-I".   Other bis-AQA compounds useful in the present invention include those represented by the following formula: The compound of.   (Where R¹Is C₈-C₁₈Hydrocarbyl, preferably C₈-C₁₄Alkyl Independently, p is 1 to 3, q is 1 to 3, R¹Is C₁-C_ThreeArchi 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 a mixed component of EO and / or Pr and / or i-Pr units And more substituted compounds.   Highly preferred bis-AQA compounds for use in underbuilder formulations Is an integer wherein p and / or q is an integer in the range between 10 and 15 in the above formula It is of the above 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 ("L AS "), primary (" AS ") branched chain and random C_Ten-C₂₀Alkyl sulfate, this formula Wherein x and (y + 1) are at least 7, preferably at least 9 And M is a water-soluble cation, in particular unsaturated salts such as sodium and oleyl sulfate. Sulfate, C₁₂-C₁₈Alpha sulfonated fatty acid ester, C_Ten-C₁₈Sulfation Polyglucoside, C_Ten-C₁₈Alkylalkoxysulfates ("AExS"; especially EO1 -7 ethoxysulfate), and C_Ten-C₁₈Alkyl alkoxy carboxylate EO1-5 ethoxycarboxylate) of the formula CH_Three(CH_Two)_x(CHOSO_Three ^- M⁺) CH_ThreeAnd CH_Three(CH_Two)_y(CHOSO_Three ^-M⁺) CH_TwoCH_ThreeC_Ten-C₁₈ Secondary (2,3) alkyl sulfates. C₁₂-C₁₈Betaine and sulfo Betaine ("sultaine"), C_Ten-C₁₈Amine oxide should also be included in the overall composition. Can be. C_Ten-C₂₀May also be used. If you need high foam, Branched chain C_Ten-C₁₆Soap may be used. Other useful conventional surfactants are Listed in the associated 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 (ARG) 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_FifteenStraight-chain alcohol When 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 Neodol (trade name) 45-9 (available from Medical Company). C₁₄-C_FifteenCondensation product of linear alcohol and 9 moles of ethylene oxide), Neodo l (product name) 23-3 (C₁₂-C₁₃Of linear alcohol with 3 moles of ethylene oxide Condensed product), Neodol (trade name) 45-7 (C₁₄-C_FifteenLinear alcohol and 7 Condensation products with ethylene oxide of a mole) and Neodol (trade name) 45-5 (C_{1 Four} -C_FifteenCondensation product of linear alcohol and 5 mol of ethylene oxide), Procter & Gamble Company (Procter & Gamble Company) Kyro (trade name) EOB (C₁₃-C_Fifteen9 moles of alcohol and alcohol Condensation product with ren), Genapol LA 030 sold by Hoechst or 050 (C₁₂-C₁₄Condensation product of alcohol and 3 or 5 moles of ethylene oxide) No. The preferred range of HLB in these AE nonionic surfactants is , 8 to 11, most preferably 8-10. Propylene oxide and butyl oxide Condensates with ren 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, 2 hydroxy Cypropyl or a mixture thereof,^TwoIs C_5-31Hydrocarbyl , Z is a straight chain hydrocarbyl chain having at least three hydroxyls directly attached to the chain Which is a 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-, -Unlike glucoside or galactoside, Or galactose). The intersaccharide linkage is, for example, one of the additional saccharide units. Positions 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 from 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). Then the additional glycosyl unit is replaced with its own 1-position And the 2-, 3-, 4- and / or 6-position of the preglycosyl unit, preferably Can be linked predominantly to the 2-position.   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. This type of commercially available non- The ionic surfactant includes GAF Corporation (GAF Corporation). on) sold by Igepal (trade name) CO-630 and ROHM & Tri sold by Rohm & Haas Company ton (trade name) X-45, X-114, X-100 and X-102. It is. These surfactants are alkylphenol alkoxylates (e.g., (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.Bleach activator   Bleach activators are a preferred component of the compositions of the present invention. Bleaching activity, if present The amount of the active agent is typically from 0.1% of the bleaching composition comprising the bleach and the bleach activator. 60%, more typically at a level of 0.5% to 40%.   A blend of percarbonate and a peroxide bleach, such as a bleach activator, has a bleaching activity in aqueous solution In-situ generation of the peroxyacid corresponding to the agent (ie, during the cleaning process) You. Various non-limiting examples of activators can be found in Mao et al. On April 10, 1990. Issued U.S. Pat. Nos. 4,915,854 and 4,412,934. Issue. Nonanoyloxybenzenesulfonate (NOBS) and And tetraacetylethylenediamine (TAED) activators are representative, Mixtures thereof can also be used. Other representative useful in the present invention See also US Pat. No. 4,634,551 for bleaches and activators.   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.   A highly preferred activator of the benzoxazine type is 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 (S) on October 8, 1985, which discloses acylcaprolactam. U.S. Pat. No. 4,545,784, issued to Andersen, is incorporated herein by reference. Use and refer to 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. Metal base Other bleaching catalysts include U.S. Pat. No. 4,430,243 and U.S. Pat. , 114, 611. Various complexes to enhance bleaching The use of manganese with ligands is also described in U.S. Pat. No. 4,728,455, Nos. 5,284,944, 5,246,612, 5,256,779, Nos. 5,280,117, 5,274,147, 5,153,161 And 5,227,084.   As a practical matter, and not by way of limitation, the compositions and 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. The present invention The most preferred cobalt catalysts useful in the formula are those in which "OAc" is acetate [Co (NH), wherein “Ty” is an anion_Three)_FiveOAc] with Ty Pentaamine acetate, particularly cobalt pentaamine acetate chloride [C o (NH_Three)_FiveOAc] Cl_Two, And [Co (NH_Three)_FiveOAc] (OAc)_Two, [Co (NH_Three)_FiveOAc] (PF₆)_Two, [Co (NH_Three)_FiveOAc] (SO_Four), [C o (NH_Three)_FiveOAc] (BF_Four)_Two, And [Co (NH_Three)_FiveOAc] (NO_Three)_Two ("PAC" in the present invention).   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. , 810, 410,J. Chem. Ed.(1989),66(12), 1043 -45; Synthesis and characterization of inorganic compounds; L. Jolly (P rentice-Hall; 1970); 461-3;Inorg. Ch em .18 1497-1502 (1979);Inorg. Chem.21, 288 1-2885 (1982);Inorg. Chem.18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960) ;Journal of Physical Chemistry,56, 22- 25 (1952).   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.Additional bleach   The detergent composition in the present invention may optionally contain an additional bleach. Exists In some cases, these additional bleaches are typically used in detergent formulations, especially for fabric laundering. From about 1% to about 30%, more typically from about 5% to about 20% of the composition; Exist.   The bleaching agents used in the present invention are now well known or will become Useful for detergent compositions for hard surface cleaning or other cleaning purposes Any of the agents may be used. These include oxygen bleaches and other bleaches. I can do it. For example, sodium perborate (eg, monohydrate or tetrahydrate) Various perboric acid bleaches 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. Patent No. 4,483,781, filed June 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 U.S. Pat. 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 pyro Sodium phosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide Um. Perborate bleach, persulfate bleach (eg, DuPont) OXONE), which is manufactured commercially by nt), can also be used.   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.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 Aluminosilicates; organic mono-, di-, tri- and tetracarboxylates, especially acids Water, in the form of sodium, potassium or alkanol ammonium salts Oligomeric, including non-surfactant carboxylate, aliphatic and fragrance types Or water-soluble low molecular weight polymer carboxylate; and phytic acid be able to. These builders can be used, for example, with boric acid for pH buffering, with sulfuric acid. Washes containing salts, especially sodium sulfate, and stable surfactants and / or builders Any other fillers or caps that may be important for the engineering of the It may be supplemented by the rear.   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, May 12, 1987 by HP Rieck. Layered silicates such as those described in U.S. Pat. Can be NaSKS-6, sometimes abbreviated as "SKS-6", is Hoechst (Hoe chst), crystalline layered aluminum-free δ-Na_TwoSiO_FiveForm And particularly preferred in granular laundry compositions. Germany DE-A-3 , 417,649 and DE-A-3,742,043 . In the formula, M is sodium or hydrogen and x is 1.9 to 4, preferably Is a number 2 and y is a number from 0 to 20, preferably 0_x O_{2x + 1}・ YH_TwoOther layered silicates, such as those having O, are also contemplated in the present invention. Or in a variant. Layered from Hoechst Silicic acid Salts are also available in the form of α, β and γ layered silicates, NaSKS-5, NaSKS-7. And NaSKS-11. Stabilizers for shrinkage agents and bleaching agents in granules And other silicates, such as magnesium silicate, that can act as components of foam control systems Salts may also be useful.   U.S. Pat. No. 6,27,1995 to Sakaguchi et al. In the formula taught in US Pat. No. 5,427,711, where M is Na and / or K M ′ is Ca and / or Mg, y / x is 0.5 to 2.0, , A general formula xM in the form of an anhydride wherein z / x is from 0.005 to 1.0_TwoO ・ ySiO_TwoA synthetic crystalline ion having a chain structure and composition represented by zM'O 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. In the empirical formula, z and v are small. An integer of at least 6, wherein the molar ratio of z to v is in the range of 1.0 to 0.5; , Where x is an integer from 15 to 264 [M_z(AlO_Two)_z(SiO_Two)_v] XH_Two Those with O are suitable for this purpose. Aluminosilicates are crystalline, amorphous, It may be a natural product or a synthetic derivative. The production method of aluminosilicate is Me U.S. Pat. No. 3,985, issued Oct. 12, 1976 to Krummel et al. , 669. Preferred synthetic crystalline aluminosilicate ion exchange materials are Olite 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_TwoHas O, where x is 20 to 30, especially 27 . Dehydrated zeolites (x = 0-10) may also be used. Preferably, aluminosilicate 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. 3,40 Other known phosphates, such as those of 0,148 and 3,422,137 May also be used and may have desirable anti-scaling 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 Le Succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate Acid salts are also included. Lauryl-succinate is a European publication issued November 5, 1986. It is described in Patent Application No. 86200600.5 / 0,200,263. Fat Fatty acids such as C₁₂-C₁₈Monocarboxylic acid can also be used alone as a surfactant / builder Builder, especially citrate and / or succinate builder In combination with the composition to add builder activity. Appropriate Other polycarboxylates are available from Clutchfield on March 13, 1979 (C U.S. Pat. Nos. 4,144,226 and 19 U.S. Pat. No. 3,308,067 to Diehl, Mar. 7, 67 Issue. US Patent No. 3,723,3 by Diehl See also No.22.   Other types of inorganic builder materials that can be used are of the formula (M_x)_iCa_y( CO_Three)_zWherein x and i are integers from 1 to 15, and y is 1 From 10 to z, z is an integer from 2 to 25, and M_iIs a cation, At least one of them is water-soluble and has the formula Σi = 1-15 (x_iTo M_iAtom of + 2y = 2z is satisfied and the formula has a neutral or “balanced” charge You. In the present invention, these builders are referred to as "Minal Builders". ". Anions other than hydrated water or carbonate balance the overall charge Or as long as it is neutral. The charge or valence effect of these anions The result should be added to the right side of the above equation. Preferably, hydrogen, a water-soluble metal, hydrogen , Boron, ammonium, silicon and mixtures thereof, more preferably sodium Contains lithium, potassium, hydrogen, lithium, ammonium and their mixtures. There are water-soluble cations selected from preferable. Non-limiting examples of non-carbonate anions include chloride, sulfate, fluoride, acid Silicon, hydroxide, silicon dioxide, chromate, nitrate, borate, and mixtures thereof. Including compound And those selected from groups. This type of preference in its simplest form Builder 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_TwoCa_Two(CO_Three)_ThreeAnd And combinations thereof. The builder described in the present invention Particularly preferred materials are Na in any of the crystalline variants._TwoCa (CO_Three)_Twoso is there. Suitable builders of the type defined above may be any one of the following minerals: Or in combination with other natural or synthetic forms. -Include them. Afghanite, Andersonite, A Skroftin Y, Bayerite, Volkalite, Bulbangite, Butzera Light, ash nepheline, carbosernate, carletonite, dabin, donnite Y, Fairchildite, Ferris Light, Flange Night, Gaude Freud, Gay Lasite, Gilbasite, Gregolite, Jarlab skies, Kamforgai Y, Ketter Light, Carnescheid, Lepersonite Gd, Lio Tight, Ma Kquelbait Y, Microsomit, Muroseito, Natrofair chillite, Nirele Light, Lemon Dite Ce, Sacrophanite, Shorockingelite, Show Tight, Slight, Tunisite, Tuscanite, Tricalcite, Visnebai And zemcolite. Preferred mineral forms include nirelate, fairch Rudite and shortite.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 greatest activity across the pH range of 8-12. Can be The preparation of this and similar enzymes is described in Novo, GB 1,243. , 784. Other suitable proteases include A from Novo LCALASE (trade name) and SAVINASE (trade name), and the Netherlands International Bio-Synthetics, Inc. MAXATASE from ionical Bio-Synthetics Inc.) (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. International by Novo Bacillus sp. Described in JP-A-9318140 SP. NCIMB4033 See also high pH protease from 8. Proteases, one or more other enzymes and And enzyme detergents containing reversible protease inhibitors are described in WO 92/92 by Novo. No. 03529. Other preferred proteases include Proctor -International Publication No. by Procter & Gamble No. 9510591. If necessary, reduce adsorption and increase Proteases with increased water splitting are available from Procter & Gamble (Proc. er & Gamble) described in International Publication No. 9507791. Available. Recombinant trypsin-like protea for suitable detergents in the present invention Nose is described in WO 9425583 by Novo.   In more detail, a particularly preferred protease called "Protease D" is , It is a carbonyl hydrolase variant having a non-natural amino acid sequence. this is U.S. patent application Ser. No. 08 / 322,6, both filed on Oct. 13, 1994. No. 76, title of invention, "Protease-containing cleaning composition", Baek (A. Baec) k) and US patent application Ser. No. 08 / 322,677, title of the invention. , "Bleaching Composition Containing Protease Enzymes" by C. Ghosh Bacillus amyloliquefaciens subtilisin nambalin as described in the license application At the position of the carbonyl hydrolase corresponding to position +76, And preferably +99, +101, +103, +104, +107, +123 , +27, +105, +109, +126, +128, +135, +156, + 166, +195, +197, +204, +206, +210, +216, +2 17, +218, +222, +260, +265, and / or +274. In combination with one or more amino acid residue positions corresponding to positions selected from the group The precursor by substituting a plurality of amino acid residues with different amino acids Derived from carbonyl hydrolase.   The purpose of the present invention is not limited to the purpose of automatic dish washing, but is particularly suitable for the purpose. Novel amylases are described, for example, in Novo, UK Patent No. 1,296,839. Α-Amylase, International Bio-Synthetics In (International Bio-Synthetics Inc.) APIDASE (trade name) and Novo's TERMAMYL (trade name) FUNGAMYL (trade name) from Novo is particularly useful. For example, oxidation stable Enzyme engineering for improving stability, such as sex, is well known. For example, J. Biolo technical Chem., Vol. 260, no. 11, June 1985, pp6 See 518-6521. Certain preferred embodiments of the present compositions are directed to automatic dishwashing ties. Stability in detergents such as pumps, and in particular became commercially used in 1993 Oxidation stability as measured against the reference point of TERMAMYL (trade name) good Amylase can be used. These preferred amino acids in the present invention Rases are characterized, at a minimum, by one or more of the following measurable improvements: Share the characteristics of improved stability. That is, for example, when pH 9-10 Stability against hydrogen peroxide / tetraacetylethylenediamine in buffer solution Properties, e.g., thermal stability at common wash temperatures such as about 60 DEG C., e.g. Alkaline stability at a pH of 11 to 11; It is measured against milases. Stability is one of the technical texts that published the technology. Can be used for measurement. For example, as disclosed in International Publication No. WO 942597 See references. Stability improving amylase is available from Novo or Genenka Available from Genencor International. One highly preferred class of amylase in the present invention is one, two or One or more Bacillus amilla, whether or not the Millase strain is a direct precursor Obtained using site-directed mutagenesis from Bacillus α-amylase, in particular. Have in common. Oxidation stability-improved amino acids for the reference amylase shown above Lase is a bleaching detergent composition in the present invention, more preferably chlorine bleaching. Preferred for use with different oxygen bleach detergent compositions. Such preferred amylase (A) WO 94/934 by Novo on February 3, 1994, incorporated above. Amylase according to No. 02597, in a variant, TERMAMYL ( B. known as B.T. position 197 of licheniformis α-amylase or Is B. amyloliquefaciens, B.A. subtilis or B. like stearothermophilus Alanine or methionine residue located at the homologous position variation of similar progenitor amylase Is further modified by a threonine, preferably a variant substituted with threonine. The amylase exemplified, (b) Mitchinson (C. Mitchinson) is 19 Papers presented at the 207th National Meeting of the American Chemical Society, March 13-17, 1994. Genenka International (Gen) encor International)). You. In a dissertation, bleach in automatic dishwashing detergent inactivates alpha-amylase Amylase with improved oxidative stability was obtained from B.A. licheniformis NCIB8 It was pointed out from 061 that Genenka manufactured. Methionine (Met) Probably identified as a residue to be modified. Met is at positions 8, 15, 197 , 256, 304, 366 and 438 at once, the most stable expression mutation Of particular interest are M197L and M197T, including the M197T variant Leads to a specific mutant. Stability is determined by CASCADE (trade name) and SUNLIG It was measured in HT (trade name). (C) Amira particularly preferred in the present invention Sesame directly in the original species, as described in WO 9510603. Amylase mutants having additional denaturation by DURAMYL (trade name) Available from the assignee Novo. Particularly preferred other oxidative stability-improving amillers The company has Genencor International International Publication No. 9418314 by Ional) and International Publication by Novo Japanese Patent Publication No. 9402597 can be mentioned. For example, available Specific sites from known chimeric, hybrid, and simple mutant forms of the milases Any other oxidatively stable amilla, such as that induced by mutagenesis of Can also be used. Other preferred enzyme modifications are available. Novo See International Publication No. 95090909.   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. Both bacterial and fungal types having the appropriate pH are included. March 6, 1984 U.S. Pat. No. 4,435 to Barbesgoard et al. No. 307, from Humicola insolens or Humicola strain DSM1800. Production of a smart fungal cellulase or cellulase 212 belonging to genus aeromonas Fungal, and extracted from the hepatopancreas of the marine mollusk, Dolabella Auricula solander Cellulases are disclosed. Suitable cellulases are described in British Patent No. 2.075. No. 028, British Patent No. 2.095.275 and DE-OS-2.247.8. 32. CAREZYME (brand name) (Novo) is particularly useful is there. See also WO 9117243 by Novo.   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" Obtained from Amano Pharmaceutical Co. Ltd. it can. 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 v from Disynth Co., The Netherlands iscosum 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 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 S Low levels of D96L variants in detergent compositions containing AQA surfactants 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 transferred dyes or pigments from migrating to other substrates present in the wash liquor In addition, for example, it may be used in combination with an oxygen source such as percarbonate, perborate and hydrogen peroxide. No. Known peroxidases include horseradish peroxidase, ligninase, and the like. And haloperoxidases such as chloro- or bromo-peroxidase. I can do it. Peroxidase-containing detergent compositions were prepared by Novo on Oct. 1, 1989. International Publication No. 89099813 on Nov. 9 and International Publication No. 89 by Novo No. 09813. A range of enzyme materials and their means of addition to synthetic detergent compositions include: Countries by International (Genencor International) International Publication No. 9307263 and International Publication No. 9307260, Novo International Patent Publication No. 89086694 and McCarty et al. U.S. Pat. No. 3,553,139, issued Jan. 5, 1971, to U.S. Pat. You. The enzyme is disclosed in United States Patent by Place et al., July 18, 1978. No. 4,101,457, and Hughes on March 26, 1985. And U.S. Pat. No. 4,507,219. Liquid detergent formulation Useful enzyme materials and their addition to such formulations are described in US Pat. No. 4,261,868 to Hora et al. You. Detergent enzymes can be stabilized by various techniques. Enzyme stabilization The technique is described in U.S. Pat. No. 3, August 17, 1971 by Gedge et al. No. 600,319, by Venegas, Oct. 29, 1986. European State Patent Publication No. 199,405 and European Patent Publication No. 200,586. Is illustrated. Enzyme stabilization systems are described, for example, in US Pat. No. 3,519,570. It is also disclosed in the issue. Produces proteases, xylanase and cellulase Useful Bacillus sp. AC13 is published by Novo in WO 9401532. No.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 an enzyme ready to be added to the formulator or detergent, for example. The manufacturer may add it separately. Such stabilizing systems include, for example, calcium ion , Boric acid, propylene glycol, short chain carboxylic acids, boric acid, and mixtures thereof And various safety measures depending on the type and physical form of the detergent composition. Considered to handle the stabilization problem.   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, the matrix corresponding to calcium sulfate or the calcium salt mentioned in the examples is used. Gnesium salts may be used. Calcium and / or magnesium levels Further increases in, for example, promote the lipolytic action of certain types of surfactants Can of course be 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 may be 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 Added to prevent inactivation. Chlorine levels in water are representative Although it is typically in the range of 0.5 ppm to 1.75 ppm and is small, For example, the effective salt in the total volume of water that comes into contact with the enzyme during dishwashing or fabric washing Element can be relatively large and, therefore, the enzyme's safety relative to the chlorine used. Qualitative is sometimes problematic. Chlorine because percarbonate can react with chlorine bleach The use of additional stabilizers to improve the results may improve In general, it may not be important. Suitable chlorine scavenger anions are well known and easy And sulfite, hydrogen sulfite, thiosulfate, iodide It may be a salt containing an ammonium cation with a substance or the like. Carbamate, as Ko 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 likely (e.g., a hydrogen peroxide source), As long as the compound is present in an embodiment comprising the enzyme of the present invention, a separate chlorine scavenger may be used. There is no absolute need to add. Even in these cases, scavengers seek optimal results Only added for. In addition, the formulator is completely compatible with the other reaction components when prescribed. A chemist should avoid using any insoluble enzyme scavengers or stabilizers. Will exercise normal skills. With respect to the use of ammonium salts, these salts Easy to mix with detergent composition, but absorbs water and / or ammonia during storage Tends to be liberated. Therefore, if such materials are present, they will Preferably, US Pat. No. 4,652, Baginski et al. No. 392 is protected in particles.   Polymer stain remover   The composition of the present invention comprises a polymer fouling, hereinafter referred to as "SRA" or "SRA @ s" Contains a remover. SRA ‘s is 0.01% to 10.0% of the composition, typical % From 0.1% to 0.5%, preferably from 0.2% to 3.0% by weight.   Preferred SRA's are typically hydrophobic, such as polyester and nylon. A hydrophilic segment that makes the surface of the hydrophilic fiber hydrophilic, and deposited on the hydrophobic fiber, After the washing and rinsing cycles, the hydrophilic segment remains attached to the fiber. And a hydrophobic segment that acts as an anchor for This is for SRA The stains that occur after the treatment by washing more easily in subsequent washing procedures Can make it possible.   SRA ‘s are available in various forms, for example, charged anions or charged cations (US Pat. No. 4,956,447) and even containing uncharged monomer units. And the structure may be linear, branched or even star. They have a molecular weight A particularly effective encapsulation component to control the physical properties or alter physical or surfactant properties May be included. Structure and charge distribution are applicable to various fiber or fabric types And may be tailored to a variety of detergent or detergent additive products.   Preferred SRA ‘s typically include titanium (IV) alkoxides such as At least one transesterification / oligomerization often involves the use of complex metal catalysts. Oligomeric terephthalates prepared by such processes. These esters, of course, do not form a tightly crosslinked Additional objects that can penetrate the ester structure via two, three, four or more positions It may be manufactured using a mask.   Suitable SRA's include, for example, JJ Scheibel. No. 4,968,451, issued Nov. 6, 1990 and Gosselink. (Gosselink). P. Terephthaloyl and Oxyalkyleneoxy repeating unit oligomer ester backbone And an allyl-derived sulfonated end component covalently linked to the Substantially linear ester oligomer sulfonated products. These Ester oligomers are obtained by (a) ethoxylation of allyl alcohol and (b) The product is treated in a two-step transesterification / oligomerization procedure with dimethyl terephthalic acid (" DMT ") and 1,2-propylene glycol (" PG "), (c ) (B) Can be prepared by reacting the product with sodium metabisulfite in water . Further, suitable SRA's include, for example, poly (ethylene glycol) methyl ether. Esters for polyester, DMT, PG and poly (ethylene glycol) ("PEG") Gosselin, such as those produced by exchange / oligomerization k) et al., U.S. Patent No. 4,711,730, issued December 8, 1987 1,2-propylene / polyoxyethylene terephthalate polyester Ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa Gosselink (Go) such as an oligomer from -8-hydroxyoctanesulfonate U.S. Pat. No. 4,721,580 issued Jan. 26, 1988 to Ssellink). Partial and full anion end-capped oligomeric esters: eg DMT, Me-encapsulated PEG and EG and / or PG, or DMT, EG and // PG, Me-encapsulated PEG and Na-dimethyl-5-sulfoisophthale 198 by Gosselink, manufactured from a combination of luic acids Non-ion-sealing block of U.S. Pat. No. 4,702,857 of Oct. 27, 7 Polyester oligomer compound; Maldonado, Gosselink ( Gosselink et al., U.S. Pat. No. 4,877, Oct. 31, 1989. No. 896, particularly sulfoaroyl-terminated terephthalates. No. The latter is an SRA® useful in both laundry and fabric preparation products. s, one example being optional but preferably, for example, PEG3 M-sulfobenzoic acid monosodium salt, P further added with PEG such as 400 An ester composition produced from G and DMT.   SRA's includes a U.S. Patent by Hays on May 25, 1976 No. 3,959,230 and Basadu on July 8, 1975. r) ethylene terephthalic acid referred to in U.S. Pat. No. 3,893,929 Or propylene terephthalic acid and polyethylene oxide or polypropylene A simple copolymer block with oxide terephthalic acid, from Dow to METHO Cellulose such as hydroxyethercellulose polymer available as CEL Derivatives; and the United States on December 28, 1976 by Nicol et al. C referred to in patent 4,000,093₁-C_FourAlkyl cellulose and C_Four Also included are hydroxyalkyl celluloses. Poly (vinyl ester) hydrophobic Suitable SRA's characterized by a polyalkylene oxide Grafted onto the backbone, eg C₁-C₆Vinyl ester, preferably Graft copolymers of poly (vinyl ester) such as poly (vinyl acetate) No. European patent issued on April 22, 1987 by Kud et al. See request 0 219 048. Commercially available examples include from BASF, Germany SOKALAN SRA ‘s such as SOKALAN HP-22 available Can be Other SRA ‘s are polyoxyethylenes having an average molecular weight of 300-5,000. 90-80% by weight of polyoxyethylenthene derived from tylene glycol Repeating units containing 10-15% by weight ethylene terephthalate with phthalate It is a polyester which has. Commercial examples include DuPont ZELCON 5126 and MILEASE T from ICI.   Other preferred SRAs are terephthaloyl (T), sulfoisophthaloyl (S IP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG ) An empirical formula comprising a unit and preferably terminating at a capping (CAP) (CAP)_Two(EG / PG)_Five(T)_Five(SIP)₁Is an oligomer having Of a sulfoisophthaloyl unit, five terephthaloyl units, preferably Oxyethylene oxy and o in a limiting ratio of about 0.5: 1 to about 10: 1. Xy-1,2-propyleneoxy unit and 2- (2-hydroxyethoxy) ) -Comprising two end-capping units derived from sodium ethanesulfonate Preferably it is a modified isethionate as in the oligomer. The SRA is good Magusuku Is linear sodium dodecylbenzenesulfonate or xylene-, cumene-, Examples, such as members selected from toluene-sulfonates or mixtures thereof For example, 0.5% to 20% by weight of a crystal-reducing stabilizer such as an anionic surfactant. Further comprising an oligomer of All of these stabilizers or denaturing agents may be found in May 1995 Gosselink, Pan, Keret (Ke) issued on the 16th U.S. Pat. No. 5,415,807 to Illett and Hall. Introduced into a synthesis can as taught in Suitable monomers for the above SRA , Na2- (2-hydroxyethoxy) -ethanesulfonate, DMT, Na- Dimethyl 5-sulfoisophthalate, EG and PG.   Yet another group of preferred SRA's is (1) (a) dihydroxysulfonate , At least one unit selected from the group comprising polyhydroxysulfonates Wherein at least trifunctionality forms an ester bond to form a branch Units and Combinations Producing Oligomeric Backbone (b) Terephthalo At least one unit (c) 1,2-oxyalkyleneoxy which is an yl component A backbone comprising at least one non-sulfonated unit that is a 2.) Non-ion sealing units, alkoxylated, preferably ethoxylated isethionates , Alkoxylated propane sulfonate, alkoxylated propane disulfonate, Anionic capping units such as alkoxylated phenol sulfonates, sulfoallo And one or more sealing units selected from yl derivatives and mixtures thereof. It is an oligomer ester. Preferred such esters have the following empirical formula: Is what you do. {(CAP)_x(EG / PG)_{y '}(DEG)_{y "}(PEG)_{y '''}(T)_z(SIP)_{z '} (SEG)_q(B)_m}   (Where CAP, EG / PG, PEG, T and SIP are as defined above. (DEG) represents a di (oxyethylene) oxy unit, and (SEG) represents , Units and related components derived from sulfoethyl ether of glycerin (B) is at least trifunctional so that the ester bond is formed Represents a branch unit formed to produce a branched oligomer backbone, where x is from about 1 About 12, y 'is about 0.5 to about 25, y "is 0 to about 12, y '' 'Is from 0 to about 10, the sum of 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, and the sum of z + z' is about 1 . 5 to about 25, q is about 0.05 to about 12, and m is about 0.01 to X, y ′, y ″, y ″ ′, z, z ′, q and m are the Represents the average number of moles of the corresponding unit per unit, said ester being from about 500 to about 5 With a molecular weight in the range of 2,000)   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 congeners and mixtures thereof and the ethoxylation of allyl alcohol And sulfonated products. Preferred SRA esters of this class include , Na-2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate and And / or Na-2 [2- {2- (2-hydroxyethoxy) -ethoxy} ethoxy [Xy] ethanesulfonate, DMT, Na-2 (2,3-dihydroxypropoxy) D) Ethane sulfonate, EG and PG using the appropriate Ti (IV) catalyst Stele exchange and oligomerization products. This SRA ester is (C AP)_Two(T)_Five(EG / PG)_1.4(SEG)_2.5(B)_0.3Can be expressed as Here, CAP is (Na^+-O_ThreeS [CH_TwoCH_TwoO]_3.5)-And B is glycerin And the molar ratio of EG / PG is the same as that of conventional gas chromatography after hydrolysis. It is about 1.7: 1 as measured by matograph.   Additional classes of SRA's include (I) Violland et al. Yo U.S. Pat. No. 4,201,824 and rice by Lagase et al. Diisocyanate coupling agent referred to in US Pat. No. 4,240,918 Nonionic terephthalate which binds the polymer ester structure using (II) Trimeritate of terminal hydroxyl group by adding melitate to known SRA ‘s S with carboxylate end groups produced by conversion to acid esters RA ‘s. With the proper choice of catalyst, anhydrous trimellitate Rather than by ring opening of the water bond, the independent carboxylic acid of trimellitic anhydride The ester forms a bond at the end of the polymer. Non-ionic or anionic These SRA's have an output as long as they have an esterifiable hydroxyl end group. It can be used as a generating material. U.S. Pat. See 525,524. In addition, additional classes for SRA ‘s include (III) bio See U.S. Patent No. 4,201,824 to Violland et al. Anionic terephthalate-based SRA ‘s, a variant of the urethane binding component, (I V) See U.S. Patent No. 4,579,681 to Ruppert et al. Vinylpyrrolidone, including both nonionic and cationic polymers Poly (vinyl alcohol) with a monomer such as dimethylaminoethyl methacrylate Prolactam) and related copolymers, (V) Lone Poulin Chemii (Rh) one-Poulenc Chemie) EP 279,134. No. 1988, acrylic acid monomer is added to a sulfonated polyester. Added to SOKALAN type from BASF manufactured by A graft polymer wherein the SRA's are similar to known cellulose ethers. Graft polymer claimed to have soil removal and anti-redeposition activity , (VI) BASF EP 457,205 (1991). Acrylic and vinyl acetate such as casein to proteins like casein Ma's Graft, (VII) 1974, Unilever NV No See DE 2,335,044 by Bevan et al. Adipic acid, caprolactam and polyethylene glycol for the treatment of mid fabrics And polyester polyamide SRA's prepared by the condensation of Yes Other SRA's for use in U.S. Patent Nos. 4,240,918, 4,787, No. 989, 4,525,524 and 4,877,896. I have.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 June By Oh and Gosselink, published on 27th of March It is a cationic compound disclosed in state patent application 111,965. Can be used Other clay stain removal / redeposition inhibitors include, but are not limited to, those issued on June 27, 1984. As disclosed in European Patent Application 111,984 by Gosselink. Ethoxylated amine polymer, Gosselink, issued July 4, 1984 elink) disclosed in EP 112,592. And U.S. Pat. No. 4,548,744 aminooxide. Others known in the art Clay soil removal and / or redeposition inhibitors are also utilized in the compositions of the present invention. can do. VanderMeal issued on January 2, 1990 er), US Pat. No. 4,891,160 and issued Nov. 30, 1995. See WO 95/32272 at Row. Another preferred anti- redeposition agent Ips include carboxymethylcellulose (CMC) materials. these Materials are 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 acid / Maleic acid copolymer is disclosed in European Patent Application No. 669, issued December 15, 1982 No. 15, and such polymers including hydroxypropyl acrylate are also described. No. 193,360, issued Sep. 3, 1986. Is a known material. Other useful diacids include maleic acid / acrylic acid / Vinyl alcohol terpolymer. Such materials are, for example, Murray Including 45/45/10 terpolymers of acid / acrylic acid / vinyl alcohol, It is also disclosed in State Patent Publication No. 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. Other enhancements disclosed in this patent Whitening agents include Tinopa available from Ciba-Geigy. l UNPA, Tinopal CBS and Tinopal 5BM; Artic White CC and Artic White CWD, 2- (4-styryl- Phenyl) -2H-naphtho [1,2-d] triazole, 4,4′-bis- ( 1,2,3-triazol-2-yl) -stilbene, 4,4′-bis (styrene Ril) bisphenyl and aminocoumarin. Identification of these brighteners In the example of Is 4-methyl-7-diethyl-amino-coumarin, 1,2-bis (benziimi Dazol-2-yl) ethylene, 1,3-diphenyl-pyrazoline, 2,5-bi S (benzoxazol-2-yl) thiophene, 2-styryl-naphtho [1, 2-d] oxazole and 2- (stilben-4-yl) -2H-naphtho [1 , 2-d] triazole. Hamilton 19 See U.S. Patent No. 3,646,015 issued February 29, 72.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 structure (k). (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 Any of the groups can be linked or can form part of any of the groups described above. Poly The amine oxide unit of the amine N-oxide has a pKa <10, preferably pKa With Ka <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 An alysis, Vol 113, "Modern Methods of Polymer Characterization" Measured by light scattering as described, the disclosure of which is incorporated herein by reference. ). PVPVI copolymer is typically N-vinylimidazole N-vinyl The molar ratio to pyrrolidone is from 1: 1 to 0.2: 1, more preferably 0.8: 1. To 0.3: 1, most preferably 0.6: 1 to 0.4: 1. These The polymer 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 is used and M is a cation such as sodium, the brightener is 4,4'- Bis [(4-amino-6- (N-2-bis-hydroxyethyl) -s-triazine 2-N-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-meth- Tylamino) -s-triazin-2-yl) amino] 2,2′-stilbendisulfur Fonic acid and disodium salt. This particular brightener species is Ciba Geigy (C iba-Geigy Corporation) Commercially sold as BM-GX.   In the above formula, R₁Is anilino and R_TwoIs morpholino and M is na In the case of a cation such as thorium, the brightener is 4,4'-bis [(4-anilino -6-morpholino-s-triazin-2-yl) amino] -2,2'-stilbe And sodium disulfonate. This particular brightener species is Ciba Geigy (C iba-Geigy Corporation) Commercially sold as MS-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 (eg, Tinopal UNPA-GX, T inopal 5BM-GX and / or Tinopal-AMS-GX) By using, when used alone, one of the two detergent composition components Significantly good dye transfer control in aqueous laundry liquors. Without being bound by theory, These brighteners are highly compatible with fabrics in the wash liquor, It is believed that this is due to the relatively fast deposition on the fabric. In the washing liquid The extent to which the brightener is deposited on the fabric in More defined. The wear factor is generally determined by: a) b) washing of the brightener material deposited on the fabric; It is the ratio of the brightener to the initial concentration in the rinsing solution. Brighteners with relatively high wear coefficients In the context of the present invention, it is most appropriate for the control of dye transfer.   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 You can choose from a group that includes, all defined below. It ’s not bound by theory The advantage of these materials, if any, is that washing is partially due to the formation of soluble chelates. It is believed to be due to the excellent ability to remove iron and manganese from the liquor.   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 No. 4,70, Nov. 3, 1987 to Perkins. [S, S] isomers as described in US Pat. No. 4,233.   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 class of foam inhibitors is monocarboxylic fatty acids and their soluble salts. Include. Wayne St. John on September 27, 1960 See U.S. Pat. No. 2,954,347 issued. Used as foam inhibitor Monocarboxylic fatty acids and their salts typically contain 10 to 24 carbon atoms. Having a hydrocarbyl chain of preferably 12 to 18 carbon atoms. To the appropriate salt Are alkali metal salts such as sodium, potassium and lithium salts, ammonium And alkanol ammonium salts.   The detergent composition of the present invention may also contain a non-surfactant foam inhibitor. these For example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (for example, 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. , 933,672, issued March 24, 1987. Ki) et al. in U.S. Pat. No. 4,652,392.   Examples of silicone-based foam inhibitors used in the present invention are: Is a foaming control agent having a foaming suppression amount mainly containing     (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 Shiroki A silicone compound produced by Sun or Silicon resin, and (c) a finely divided filling material, (D) The reaction of the mixture components (a), (b) and (c) is promoted to produce silanolate. A non-aqueous emulsion of a main antifoaming agent, which is a mixture of 2) at least one nonionic silicone surfactant and (3) water at room temperature Polyethylene glycol or polyethylene having a solubility of more than 2% by weight in Copolymer of polypropylene glycol (polypropylene glycol is not used) I). Similar amounts can be used in granular compositions, gels, and the like. 1 U.S. Pat. No. 4,9 by Starch, issued Dec. 18, 990 No. 83,316, Rice by Starch issued January 8, 1991 No. 4,978,471, issued on Feb. 22, 1994, Hube. r) et al., US Pat. No. 5,288,431, to Aizawa et al. U.S. Patent Nos. 4,639,489 and 4,749,740, column 1, See also 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 “foam control amount” allows the formulator of the composition to Or low enough foam detergent to be used in an automatic dishwasher or dishwasher. This indicates that the amount of the foam control agent for controlling foaming can be selected.   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 R Larger amounts may be used. This limit keeps costs to a minimum and reduces effective foaming. Of a practical nature primarily related to smaller amounts of effect on control . Preferably from 0.01% to 1% of a silicone foam inhibitor, more preferably from 0.1 to 1%. Use 25% to 0.5%. As used in the present invention, these weight percentage values Any silica that may be used in combination with the polyorganosiloxane is useful for Any materials that may be used are included. Monostearyl phosphate foam Inhibitors are generally utilized in amounts ranging from 0.1% to 2% by weight of the composition. Charcoal Hydrogen hydride foam inhibitors are typically utilized in amounts ranging from 0.01% to 5.0%. It is. However, more levels can be used. Alcohol foaming inhibitor Is 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) Reference) and are incorporated herein by reference. Chemically these materials Is a polymer having one ethoxy side chain per 7-8 acrylate units. Including acrylate. This side chain has the formula-(CH_TwoCH_TwoO)_m(CH_Two)_nCH_ThreeStuff Where m is 2-3 and n is 6-12. This side chain is Esterified to the relevant "backbone" to form a "comb" polymer structure. Let Although the molecular weight can vary, typically in the range of 2000 to 50,000 is there. Such an alkoxylated polycarboxylate is used in the composition of the present invention. It may contain 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 fine smectite clay and other softeners known in the art. Softening clay is typically present in the composition at a level of 0.5% to 10% by weight. Can be used to impart the benefits of a fabric softener simultaneously with fabric washing. Cle -Softeners are described, for example, by Crisp et al. U.S. Pat. No. 4,375,416 and Harris (H.) issued Sep. 22, 1981. arris et al., US Pat. No. 4,291,071. And a cation softening agent.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%.   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 I Ndan, 5-acetyl-3-isopropyl-1,1,2,6-tetramethylin Dan, 1-dodecanal, 4- (4-hydroxy-4-methylpentyl) -3-cy Clohexene-1-carboxaldehyde, 7-hydroxy-3,7-dimethylo 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-hexamethylcyclopenta-gamma -2-benzopyran, beta-naphthol methyl ether, ambroxane, Decahydro-3a, 6,6,9a-tetramethylnaphtho [2,1b] furan, Dorol, 5- (2,2,3-trimethylcyclopent-3-enyl) -3-me Tylpentan-2-ol, 2-ethyl-4- (2,2,3-trimethyl-3- Cyclopenten-1-yl) -2-buten-1-ol, caryophyllene alcohol , Tricyclodecenyl propionate, tricyclodecenyl acetate, Benzyl lithylate, seryl acetate, and para- (tert-butyl) Clohexyl 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-butylcycline Rohexyl acetate, methyl dihydrojasmonate, beta-naphthol Tyl ether, methyl beta-naphthyl ketone, 2-methyl-2- (para-iso -Propylphenyl) -propionaldehyde, 1,3,4,6,7,8-hexyl Sahydro-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, CaS O_FourWater-soluble magnesium and / or calcium salts such as %-Add at 2% level to add foam or enhance fat removal performance be able to.   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) from 3% to 5% C_13-15Etoki Mixed with proteolytic enzyme containing silylated alcohol (EO7) nonionic surfactant I do. The resulting powder is treated with silicone oil (a variety of silicones in the range 500-12,500). Stir and disperse in corn oil viscosity). The obtained silico Emulsified or otherwise added to the final detergent mother liquor. By this method The above-mentioned enzymes, bleaching agents, bleaching activators, bleaching catalysts, photoactivators, dyes, fluorescent agents Ingredients such as fabric preparations and hydrolyzable surfactants in a liquid laundry detergent composition Can be "protected" for use in detergents, including   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 should be used in 9 or less in use to avoid the smell of impurity amines. It may be formulated to have an effective pH. 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   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 percentages used in the present invention In total, percentages and ratios are expressed as weight percentages unless otherwise specified.   In the following examples, the abbreviated component designations have the following meanings. LAS: Straight chain C₁₂Sodium alkylbenzene sulfonate TAS: Tallow alkyl sodium sulfate C45AS: C₁₄-C_FifteenSodium linear alkyl sulfate CxyEzS: C_1x-C_1ySodium branched alkyl sulfate z mole of ethylene                     Oxide and condensation C45E7: C_14-15Dominant linear primary alcohol average 7 moles ethylene                     Oxide and condensation C25E3: C_12-15Branched primary alcohol average 3 moles of ethyleneoxy                     And condensation C25E5: C_12-15Branched primary alcohol average 5 mol ethyleneoxy                     And condensation Coco EO2: R₁N⁺(CH_Three) (C_TwoH_FourOH)_Two, Where R₁= C₁₂−                     C₁₄ Soap: derived from an 80/20 mixture of tallow oil and coconut oil                     Sodium linear alkyl carboxylate TFAA: C₁₆-C₁₈Alkyl N-methylglucamide TPKFA: C12-C14 head cut fatty acid STPP: anhydrous sodium tripolyphosphate Zeolite A: having a primary particle size in the range of 0.1 to 10 microns                     Chemical formula Na₁₂(AlO_TwoSiO_Two)₁₂・ 27H_TwoO aluminum                     Sodium nosilicate hydrate NaSKS-6: Formula δ-Na_TwoSi_TwoO_FiveCrystalline layered silicate Citric acid: Citric anhydride Carbonate: anhydrous with a particle size between 200 μm and 900 μm                     sodium carbonate Bicarbonate: having a particle size between 400 μm and 1200 μm                     Water sodium bicarbonate Silicate: Amorphous sodium silicate (SiO_Two: Na_TwoO; 2.0 ratio) Sodium sulfate: anhydrous sodium sulfate Citrate: activity with a particle size between 425 μm and 850 μm                     86.4% trisodium citrate dihydrate MA / AA: 1: 4 maleic / acrylic acid copolymer, average molecular weight 7                     0000 CMC: Sodium carboxymethylcellulose Protease: Novo Industries A / S (Novo Industry)                     ries A / S) sold under the trade name Savinase                     Active 4K NPU / g proteolytic enzyme Alcalase: Novo Industries A / S (Novo Industry)                     ries A / S) marketed active 3AU / g protein                     Enzyme Cellulase: Novo Industries A / S (Novo Industry)                     ries A / S) sold under the trade name Carezyme                     Cellulolytic enzyme with an activity of 1000 CEVU / g Amylase: Novo Industries A / S (Novo Industry)                     ries A / S) as trade name Termamy160T                     Active 60KNU / g amylolytic enzyme on sale Lipase: Active 100 sold under the trade name Lipolase                     kLU / g lipolytic enzyme Endolase: Novo Industries A / S (Novo Industry                     riesA / S) Active 3000 EVU / g                     Endoglunase Enzyme PB4: Nominal formula NaBO_Two・ 3H_TwoOH_TwoO_TwoSodium perborate 4                     Hydrate PBI        : Nominal formula 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 DTPMP: Monsanto has the trade name Dequest                     Diethylenetriamine penta sold as 2060                     (Methylene phosphonate) Light activation: sulfonation encapsulated in soluble polymer of bleached dextrin                     Zinc phthalocyanine Brightener 1: 4,4'-bis (2-sulfostyryl) biphenylninato                     Lium Brightener 2: 4,4'-bis (4-amino-6-morpholino-1,3,5                     -Triazin-2-yl) amino) stilbene-2: 2 '                     -Disodium disulfonate HEDP: 1,1-hydroxyethanediphosphonic acid PVNO: polyvinyl pyridine N-oxide PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole SRAI: Oxyethyleneoxy and terephthaloyl backbone                     Sulfobenzoyl end-capped ester having SRA2: Diethoxylated poly (1,2 propylene terephthalate) short                     Chain block polymer silicone defoamer: Shiroki as dispersant                     Polydimethylsilo containing sun-oxyalkylene copolymer                     The ratio of the foam control agent to the dispersant in the xanth foam control agent                     Is from 10: 1 to 100: 1   In the following examples, all levels are stated as% by weight of the composition.                                   Example I   The following detergent formulations according to the invention are prepared. Here, A and C are phosphorus-containing detergents. B 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 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 III   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 IV   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.   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. 2 25,654 (6/16/87), EP 510,762 (10/2 8/92,), European Patent Publication No. 540,089 (5/5/93), European Patent Publication No. 540,090 (5/5/93); U.S. Pat. No. 4,615,820; Patent Publication No. 565,017 (10/13/93), European Patent Publication No. 030,096. No. (5/10/81), which are incorporated herein by reference. Use it. Such a composition is composed of various fine particles suspended in the composition stably. (E.g., a bleaching agent as disclosed above). You. Such non-aqueous compositions comprise a liquid phase and optionally but preferably a solid phase. As described in detail below and as set forth in the cited references. is there. AQA surfactants may be used as described above for the manufacture of other laundry detergent compositions. It is incorporated into the composition in a bell and in a manner.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 of the present invention is mixed with a specific type of non-aqueous liquid diluent. It essentially 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 Which are selected from alkali metal salts of benzene sulfonic acid (referred to in the present invention. (See 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.   Alkyl benzene sulphonate anionic surfactant is 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 Phosphate anionic surfactants generally range from 30% to 65% by weight of the liquid phase. Exists. More preferably, alkyl benzene 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.   The use of this anionic surfactant at these concentrations results in the use of 15 % To 60% by weight, more preferably 20% to 40% by weight of anio in the total composition Corresponding to the surfactant concentration. (B)Non-aqueous liquid diluent   In order to form the liquid phase of the detergent composition, the above-mentioned alkylbenzene sulfonate salt 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.     Alkoxylated alcohol One essential component of the liquid diluent used to form the composition in the present invention Consists of alkoxylated fatty acid family alcohol substances. These substances are themselves It is also a nonionic surfactant. These substances have the general formula R¹(C_mH_2mO)_nOH Is equivalent to Where R¹Is C₈-C₁₆An alkyl group, m is 2 to 4, n ranges from 2 to 12. Preferably, R¹Has 9 to 15 carbon atoms, more preferably Preferably an alkyl group which may be primary or secondary containing 10 to 14 carbon atoms It is. Preferably also, the alkoxylated fatty alcohol is from 2 to 2 per molecule 12 ethylene oxide components, more preferably 3 to 10 ethylene atoms per molecule An ethoxylated material 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-C₁₁N which is primary alcohol e odol 91-10. This type of ethoxylated alcohol is also Shell Chemical Company It is sold under the trade name Dobanol. Dobanol 91-5 is the average Ethoxylated C with 5 moles of ethylene oxide₉-C₁₁Fatty alcohol Dobanol 25-7 has an average of 7 moles per mole of aliphatic alcohol. Ethoxylated C with ethylene oxide₁₂-C_FifteenIt is an aliphatic alcohol.   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 the ethylene oxide per mole A similar ethylene oxide condensation product of a high aliphatic alcohol having 11 groups. A high molecular weight nonionic surfactant such as Neodol 45-11. Like this Products are also available from Shell Chemical Company. pany).   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 When alkoxylated alcohols are used in the composition, 1% to 60% by weight of the composition, Preferably 2% to 40% by weight, most preferably 5% to 25% by weight of the total composition It 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. The term "solvent" refers to the non-solvent of the liquid phase of the composition. Used in the present invention to mean a surface-active carrier or diluent moiety. Departure In the essential and / or optional components of the composition of the present invention, in the "solvent" containing liquid phase Although there are components that can actually be dissolved, fine particles dispersed in the "solvent" -containing liquid phase Some components exist as substances. Thus, the term "solvent" refers to the solvent material That all of the detergent composition components added to the product must be practically soluble. It is not intended.   The non-aqueous organic substance used as a solvent in the present invention is a low-polarity liquid. It is. For the purposes of the present invention, a "low polarity" liquid is one that dissolves sodium percarbonate. The tendency, if any, is very slight. Therefore, like ethanol Should not be used. Non-aqueous liquid detergent composition in the present invention Suitable types of low polarity solvents useful in_Four-C₈Alkylene Recall, alkylene glycol mono-lower alkyl ether, low molecular weight polyethylene Examples include lenglycol, low molecular weight methyl esters 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 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-C₆ Alkyl ethers. Specific examples of such compounds include diethylene Glycol monobutyl ether, tetraethylene glycol monobutyl ether , Dipropylene glycol monoethyl ether and dipropylene glycol Nobutyl ether. Diethylene glycol monobutyl ether and And dipropylene glycol monobutyl ether are particularly preferred. Conversion of this type Compounds are trade names Dowanol, Carbinol and Cellosolve It is sold commercially under   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_ThreeThis is Here, R¹Ranges from 1 to 18. Examples of suitable low molecular weight methyl ethers include , Methyl acetate, methyl propionate, methyl octanoate, Chilled decanoate.   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 Must, of course, 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 1% to 50% by weight of the composition, more preferably 5 to 40%. %, Most preferably from 10% to 30% by weight of the solvent concentration in the total composition. You. 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 a solid phase of particulate material dispersed and suspended in a liquid phase. Generally, such particulate materials are 0.1 to 1500 microns in size. Range. More preferably, such a material is between 5 and 200 in size. In the micron range.   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 may comprise You. 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 sulfonate anionic surfactant and two essential components of 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 Any surfactant in solid particulate form while maintaining shear agitation Essentially all of them range in size from 0.2 to 1,000 microns in size It can be added in the form of a child. After adding any surfactant particles, for example, Organic builders, such as citrates and / or fatty acids, and / or Substantially all particles of an alkali source, such as sodium carbonate, are components of the composition. Can be added while maintaining the mixture under shear stirring. Then, Other solid optional ingredients can be added to the composition at this point. blend The stirring is continued if necessary, and if necessary, the stirring is strengthened at this point. grain A uniform distribution of the child can be formed.   After adding some or all of the above solid material to the stirred mixture, The particles of the preferred peroxide bleach, while again maintaining the mixture under shear stirring, It can be added to the composition. By adding the peroxide bleach material last. After addition of all or most of the other components, and especially alkali After adding the source particles, achieve the necessary stability advantage for peroxide bleach. Can be. If enzyme globules are included, they are preferably added to the non-aqueous liquid mother liquor. Finally add.   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 Or separately forming a premix with a small portion of a non-aqueous low-polar solvent, It may be added as a slurry to the stirred mixture of composition components. These slurs The addition of lee premix is similar to premixes formed in a similar manner. Prior to the addition of peroxide bleach and / or enzyme particles, which may be part of the rally It is desirable to let them go.   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, the effective amount of such a composition is , Preferably added to the water in an automatic washing machine for conventional fabric washing, Form a wash / bleach solution. The aqueous wash / bleach solution thus formed is then , Preferably under agitation, 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 An effective amount of is sufficient to form a composition in an aqueous solution of 500 to 7,000 ppm. Small amounts can be configured. More preferably, 800 to 3,000 ppm The detergent composition of the present invention is formed in an aqueous laundry / bleach solution.                                   Example V   Non-limiting examples of bleach-containing non-aqueous liquids having compositions as described in Table I Prepare laundry detergent. ^*Coco MeEO2. Bis-AQA-1 is a bis-AQA surfactant 2-22 or 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 85 ° F (29 ° C) and once cooled, the remaining Add ingredients. Next, the resulting composition was stirred at 29 ° C. (85 ° F.) for another 1/2 hour. I do.   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.                                   Example VI   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 It can include ingredients that aim to have specific in-use product attributes, such as the benefits of 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, for example, Of the present invention containing a compound, amine oxide, alkyl sulfate and alkyl epoxy sulfate Especially when used in combination with a cleaning mixture comprising a bis-AQA surfactant in Calcium ions, magnesium ions, or add lipolytic performance benefits Mixed ions of calcium / magnesium ions may also be included. Magnesium source Or a calcium source or a mixed Mg / Ca ion source is typically Make up from 0.01% to 4%, preferably from 0.02% to 2% by weight of the composition. This Various water-soluble sources of these ions include, for example, sulfates, chlorides and acetates. I can do it. In addition, these compositions contain nonionic surfactants, especially polyhydroxy Fatty acid amides and alkylpolyglucides May also be included. Preferred are those classes of C₁₂-C₁₄(Coconut al Kill) member. Particularly preferred nonionic surfactants for hand dishwashing are C₁₂ -C₁₄N-methylglycamide. Preferred amine oxides include C₁₂-C₁₄ Dimethylamine oxide. Alkyl sulphate and alkyl sulphate The xy is as described above. Use level for such surfactants in dishwashing liquids Is typically in the range of 3% to 50% of the final composition. Processing of dishwashing liquid composition U.S. Pat. Nos. 5,378,409; 5,376,310; It is described in more detail in various patent publications including 417,893, Quoted and incorporated.   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.   Examples A and B below illustrate the invention with respect to an automatic dishwashing detergent containing granular phosphate. This further exemplifies the invention.                                  Example VII                             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.   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 VII   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, , Where R¹And X is as disclosed above, and the cationic surfactant Has (x + y) or z in the range of 1-5, preferably 1-2, and the other has (X +) in the range of 3-100, preferably 10-20, most preferably 14-16 Formula R with y) or z¹N⁺CH_Three[EO]_x[EO]_yX^-And R¹N⁺(CH_Three)_Two [EO]_zX^-Mixture of ethoxylated cationic surfactants used in the present invention Can be Such compositions may be used individually in the present invention. Ancestry Detergent performance over a wider range of water hardness than surfactants (especially in fabric washing situations) ) Is advantageously improved. Shorter EO cationic surfactants (eg, EO2) In order to improve the cleaning performance of anionic surfactants in soft water, longer EO The cationic surfactant (for example, EO15) has a hardness tolerance of an anionic surfactant. Of anionic surfactants in hard water by acting to improve Improving performance has now been discovered. The traditional wisdom in cleaning technology is that builders Suggests that the performance "window" of anionic surfactants can be optimized . However, to date, this window has been expanded to cover essentially all conditions of water hardness. Incorporation was impossible to achieve.                                   Example IX   The following is the bis-AQA surfactant described in any of the preceding examples, FIG. 3 illustrates a typical non-AQA surfactant mixture that can be used in combination It is not intended to limit the invention. Non-AQ in mixture The proportion of A surfactant is given in parts by weight in the surfactant mixture.Mixture AC       Raw material ratio       AS^*/ LAS 1: 1       AS / LAS 10: 1 (preferably 4: 1)       AS / LAS 1:10 (preferably 1: 4)^* The above-mentioned primary, substantially linear AS surfactant is equivalent to an equivalent amount of secondary AS or Mixed with branched AS, oleyl sulfate, and / or the linear primary AS shown above It can be replaced with these mixtures, including compounds. AS of "tallow" chain length is boiling It is particularly useful under hot water conditions up to the point. "Coconut" AS has a lower wash Suitable for rinsing temperature.   The alkyl sulphate / cationic surfactant mixture described above is a nonionic non- The AQA surfactant is used in a weight ratio of cationic (total) to nonionic 25: 1 to 1: 1. : 5 can be corrected by using them together. The nonionic interface The activator can be any of the conventional types of ethoxylated alcohols or alkyl Knols, alkyl polyglycoxides or polyhydroxy fatty acid amides ( LAS is less preferred), or a mixture of these as described above. Things can also be included.Mixture DF       AS^*/ AES 1: 1       AS / AES 10: 1 (preferably 4: 1)       AS / AES 1:10 (preferably 1: 4)^* Secondary, branched or oleyl AS can be substituted as described above.   The above AS / AES mixture weighs LAS, AS / AES (total) vs. LAS weight. The ratio can be modified in the range of from 1:10 to 10: 1 by using together. The AS / AES mixture or the AS / AES / LAS mixture obtained therefrom Also, the nonionic surfactants described in Mixtures AC were combined with cationic (total) versus Correction by using together non-ionic weight ratio of 25: 1 to 1: 5 Can be.   Any of the above mixtures can be modified by the combined use of amine oxide surfactants. Can be Here, the amine oxide content is from 1% of the total amount of the surfactant mixture. 50%.   In a very preferred combination of the aforementioned non-AOA surfactants, the final laundry detergent set The content in the total composition is from 3% to 60% by weight. The final composition is preferably heavy Contains from 0.25% to 3.5% bis-AQA surfactant in an amount.                                   Example X   This example was added to any of the previous examples of bis-AQA containing detergent compositions. To illustrate, the fragrance formulations (AC) made according to the present invention are illustrated. Mr The various components and levels are described below.   The fragrance composition described above 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 the fragrance or its individual components on the surface Mobility is thus secured.

────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Laura, Kron             Fair Fee, Ohio, USA             Ludo, Lake, Mead, Drive, 5656 (72) Inventor Kevin, Lee, Cott             United States Ohio, Cincinnati,             Bentbrook, Drive, 2920 (72) Inventors Thomas, Anthony, Kryp             United States Ohio, Loveland,             Three, Chimneys, Rain, 599 (72) Inventor John, Downing, Curry             Oxford, Ohio, United States             Road, Stone, Creek, Drive, 95 (72) Inventors Sanjeef, Chris Nadas, Manohar             Fairfay, Ohio, USA             Field, Meadow Lawn, Way, 2014 Bee (72) Inventors Ian, Martin, Dodd             Loughborough, Hollywell, Dora, England             Eve, 47 (72) Inventors Richard, Timothy, Hartshawn             Waira, Northumberland, United Kingdom             M, Dean, Road, 139 (72) Inventors Peter, Robert, Foley             United States Ohio, Cincinnati,             Lytle, Place 1, Apartment             906 (72) Inventor Rinko Katsuta             6-2-1, Minatojima-Nakamachi, Chuo-ku, Kobe City, Hyogo Prefecture             Kobe Park City, Sea 507 (72) Inventor Frank, Andrey, 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) Inventors Kenneth, William, Willman             Fairfay, Ohio, USA             , Williamsburg, Way,             5603 (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 Gizar, 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

Claims (1)

[Claims] 1. Prepared comprising or in combination with a percarbonate bleach, a non-AQA surfactant, and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant represented by the following formula: , Detergent composition. Wherein R ¹ is a linear, branched or substituted C ₈ -C ₁₈ alkyl, alkenyl, aryl, alkaryl, ether or glycidyl ether moiety, R ² is a C ₁ -C ₃ alkyl moiety, R ³ And R ⁴ can be independently varied and selected from hydrogen, methyl and ethyl, X is an anion, A and A ′ can be independently varied and are each C ₁ -C ₄ alkoxy, p and q Can vary independently and are integers ranging from 1 to 30). The composition according to claim 1, which is prepared by mixing a non-AQA surfactant and a bis-AQA surfactant. 3. The composition according to claim 1, wherein the non-AQA surfactant is an anionic surfactant. 4. The composition according to any one of claims 1 to 3, wherein the ratio of bis-AQA to non-AQA surfactant is from 1:15 to 1: 8. 5. Wherein the bis-AQA surfactant has 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 4, wherein the composition is an integer from 1 to 8. 6. Wherein the bis-AQA surfactant has 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 5, wherein the composition is an integer of from 1 to 4. 7. The composition according to any one of claims 1 to 6, wherein the bis-AQA cationic surfactant is one wherein p and / or q is an integer in the range of 10 to 15. 8. The composition according to any one of claims 1 to 7, comprising two or more bis-AQA surfactants, or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant. Stuff. 9. 9. 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. 10. 10. The composition according to any one of the preceding claims, in the form of granules, rods, aqueous or non-aqueous liquids or tablets. 11. A method for removing dirt and stains by bringing dirt and stains into contact with the composition according to any one of claims 1 to 10, or an aqueous medium comprising the detergent composition. 12. 12. The method of claim 11, wherein the bleach sensitive soil is removed from the fabric. 13. The method according to claim 11, wherein the method is performed by an automatic machine. 14． 14. The method according to any one of claims 11 to 13, which is performed by hand. 15. A method of improving the adhesion or persistence of a fragrance or fragrance component on a fabric or other surface comprising contacting the fragrance or fragrance component with the fabric or other surface in the presence of a bis-AQA surfactant . 16. 16. The method of claim 15, wherein the method is performed with a fragrance or fragrance component in combination with a detergent composition comprising bis-AQA.