JPH11511794A - Detergent composition - Google Patents

Abstract

  (57) [Summary] A detergent composition comprising an aluminosilicate, 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 comprises an aluminosilicate builder, a non-AQA surfactant, -Alkoxylated quaternary ammonium (bis-AQA) cationic surfactant. And a detergent composition comprising:                                Background of the Invention   Laundry detergent formulations and other cleaning compositions pose significant challenges. Modern compositions require removal of 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 advantageously remove and remove various types of soils and stains. It contains one or more surfactants that aim to be. Looking at the literature, there is a rich variety of Surfactants and combinations of surfactants seem to be available to detergent manufacturers On the other hand, many of these ingredients have become inexpensive unit cost products such as household laundry detergents. The reality is that they are unsuitable specialty chemicals. Most of this like laundry detergent Household products comprising one or more conventional ethoxylated nonionic and / or sulfated products Or still keeps mainly sulfonated anionic surfactants That is the fact. This is probably due to the variety of stains and stains and Because it is necessary to formulate a composition that works reasonably well for a variety of fabrics There will be.   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.   Detergent builders have a mineral hardness, especially Ca in the wash water.²⁺And / or Mg²⁺Io To help control air flow or to remove particulate soil from surfaces. Used in the composition described in the present invention. The builder must be soluble in hardness ions. Or ion exchange through a variety of mechanisms, including forming insoluble complexes. , And to produce a surface more favorable for precipitation of hardness ions than the surface of the object to be cleaned Can act. Recently, there are environmental benefits as well as economic benefits. The development of synthetic builder compounds is gaining momentum. These builder materials Typically, it is inorganic and insoluble / partially soluble. Insoluble / partially soluble inorganic plastic A particular problem associated with the use of ruder is the problem of washing substrates, such as washed fabrics. Form insoluble complexes with hardness ions that can be deposited on the surface to form That is, the material taken up on the surface of the washed fabric and wrapped in the skin, or Is to leave a layer of material encased in the hull.   Building wrapped in dirt, stains and skin in laundry, in addition to the sequence of washing and wearing The limited removal of dust material increases the accumulation on the fabric, and these accumulations Take in more dust and yellow the fabric. Eventually, the fabric becomes dingy However, consumers feel that they cannot wear it and throw it away.   According to the literature, various nitrogen-containing cationic surfactants are available in various cleaning compositions. And useful. Typically, an amino, amide, quaternary ammonium or These substances, in the form of imidazolinium compounds, can be used for specialized applications. Often aimed at. For example, various amino and quaternary ammonium surfactants Agents have been proposed for shampoo compositions and are said to be good for hair styling. That Other nitrogen-containing surfactants provide fabric softening and antistatic benefits Used in some laundry detergents. However, in most cases, Commercial use is limited by the obstacles encountered in large-scale production of these compounds. Have been. A further limitation is that ionic interactions with cationic surfactants The possibility of precipitation of the anionic active component of the detergent composition caused. Said above Nonionic and anionic surfactants are still present in current laundry compositions It is the main surfactant component.   Certain bis-alkoxylated quaternary ammonium (bis-AQA) compounds are generally Improves cleaning performance on the various types of stains and stains encountered, especially hydrophobic stains It has now been discovered that it can be used in a variety of detergent compositions to do so. The present invention Of the bis-AQA surfactants were previously known in the art. Provides substantial benefits to formulators over surfactants. For example, in the present invention, Bis-AQA surfactants used in the field are often associated with "daily" fatty / Greatly improves the cleaning of oily hydrophobic stains. Further, bis-AQA surfactants Commonly used in detergent compositions such as alkyl sulfates and alkyl benzene sulfonates It has an affinity for anionic surfactants. Detergent composition has anionic surfactant The incompatibility with surfactants has generally been a factor in the use of cationic surfactants to date. Was a limiting factor. Low level (3 ppm in laundry liquor) bis-AQA surfactant The agent provides the advantages described in the present invention. Bis-AQA surfactants are 5 to 1 It can be formulated over two broad pH ranges. Bis-AQA surfactant , Can be prepared as a 30% (by weight) solution over the pump, thus easily at the manufacturing plant Can handle. Bis-AQA surfactants with a degree of ethoxylation of more than 5 are sometimes liquid And thus can be provided as a 100% stock solution. In addition to beneficial handling properties Availability of bis-AQA surfactant as a highly concentrated solution means that transportation costs A substantial economic advantage.   Further, it contains both a bis-AQA surfactant and an aluminosilicate builder. The composition has excellent cleaning performance and whiteness for products containing either technology alone It has now been discovered that it works. In particular, high levels of inorganic and insoluble or partially soluble Dissolved builders are used to increase the level of residual crusted material remaining on the washed substrate. It has been found that it can be used in the compositions of the present invention without addition. Al Insoluble inorganic builders such as minosilicate builders are composed of discrete units It is considered that some surfaces thereof are negatively charged. Positively charged head glue Bis-AQA having a hydrophilic surface is composed of two charged hydrophilic surfactants around inorganic particles. By interacting with these surfaces by forming a layer, builder residues from the fabric Floatable inorganic particles / dirt / stain, and effective dissolution of inorganic particles in washing water Bring about.   The present invention thus comprises an aluminosilicate builder and a bis-AQA surfactant. Demonstrates effective cleaning of daily, especially hydrophobic stains using a detergent composition A detergent composition is provided.                                 Background art   A. Mehreteab and Lopresto (FJ Lop) U.S. Pat. No. 5,441,541 issued Aug. 15, 1995. No. relates to anionic / cationic surfactant mixtures. Murphy (AP . Murphy), Smith (RJM Smith) and Brooks (M. P. Brooks), UK 2,040,99, issued on September 3, 1980. No. 0 relates to ethoxylated cationic surfactants in laundry detergents.                                Summary of the Invention   The present invention provides an aluminosilicate builder, a non-AQA surfactant, and An effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) Prepared by combining or combining thione surfactants A detergent composition to be 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 Aluminosilicate builder   The first essential component of the composition of the present invention is an aluminosilicate builder. Aluminum Silosilicate builders are particularly useful in granular detergents, It can also be blended into rutile-like materials.   Suitable aluminosilicates include aluminosilicate zeolites having the following unit cell formula: G.                 Na_z[(AlO_Two)_z(SiO_Two)_y] XH_TwoO   Wherein z and y are integers of at least 6, and the molar ratio of z to y is 1 . X ranges from 0 to 0.5 and x is at least 5, preferably 7.5 to 276 , More preferably 10 to 264)   The aluminosilicate material may be crystalline or amorphous, Preferably, it is crystalline and is 10% to 28%, more preferably 18% Is a hydrate containing water in a 22% bound form.   Aluminosilicate zeolites may be naturally occurring materials, but are preferred. Or a synthetic derivative. Preferred synthetic crystalline aluminosilicate ion exchange materials are Zeolite A, zeolite B, zeolite P (or zeolite MAP), zeolite Available under Olite X, Zeolite HS and mixtures thereof.   Zeolite A has the following formula:              Na₁₂[AlO_Two)₁₂(SiO_Two)₁₂] XH_TwoO (Where x is from 20 to 30, especially 27. Dehydrated zeolite (x = 0) is also used May be. Zeolite X, a preferred aluminosilicate, has the formula Na₈₆[(AlO_Two)₈₆ (SiO_Two)₁₀₆] · 276H_TwoIt has O. Opened in European Patent Publication No. 384,070 The zeolite MAP as shown is also a preferred aluminosilicate building in the present invention. Dar. Preferably, the aluminosilicate is 0.1 to 10 micron in diameter. Ron particle size)   Aluminosilicate builders typically comprise 1% to 80% by weight of the composition, Or from 10% to 80% by weight, most preferably from 15% to 50% by weight Or at a level of 60% by weight.Bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant   Another essential component of the present invention is an effective amount of bis-AQA surfactant represented by the following formula: Agent.   (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 Base Selected from X^-Chloride, bromide, methyl sulphate sufficient to provide electrical neutrality , Sulfate and the like, and A and A ′ can be independently varied, Each C₁-C_FourAlkoxy, especially ethoxy, propoxy, butoxy and their Selected from mixed components, wherein p is from 1 to 30, preferably from 1 to 15, more preferably 1 to 8, even more preferably 1 to 4, and q is 1 to 30, preferably 1 To 15, more preferably 1 to 8, still more preferably 1 to 4, most preferably 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 the case for high concentration (“compact”) granular laundry detergents. If (density is greater than 650 g / l), 0.2% to 5.0%, preferably 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 interface It is converted to the concentration (weight) of the activator 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 wash In the case of detergents (density greater than 650 g / l), 0.5% to 3.5%, Preferably, 0.7-1.5% bis-AQA surfactant concentration in the product (weight ). Based on usage rate of 140g to 400g / wash load, this Are spray-dried granules (ie, "fluffy", having a density less than 650 g / liter) ), 0.13% to 1.8%, preferably 0.18% to 0.76% It is converted into the concentration (weight) of bis-AQA surfactant in the product.   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 surface Agents, shampoos, personal wash bars and wash bars, but are not limited thereto. Not determined. The differences between the habits and practices of the 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-A It is sufficient to add a QA surfactant to such a composition. Again, the granules and And the bis-AQA field present in such compositions, as in liquid laundry compositions. The weight ratio of surfactant to other surfactants is small. That is, the anionic interface Less than stoichiometric for activators. Preferably, such a cleaning composition comprises a machine In the case of laundry compositions, it consists of the bis-AQA / surfactant ratio just described.   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 Company) y) and can be obtained under the trade name ETHOQUAD. Instead, these materials , Various different reaction mechanisms (where "EO" is -CH_TwoCH_TwoO-Uni (Representing a set).Mechanism 1 Mechanism 2 Mechanism 3 Mechanism 4           The economic reaction mechanism is as follows.Mechanism 5   The following parameters summarize optional and preferred reaction conditions for mechanism 5 is there. Step 1 of the reaction is preferably performed in an aqueous medium. The reaction temperature is Typically, it is in the range of 140-200 ° C. Reaction pressure is 50-1000 psi g. A basic catalyst, preferably sodium hydroxide, can be used. Anti The molar ratio of the reactants is amino: alkyl sulfate = 2: 1 to 1: 1. The reaction is good Preferably C₈-C₁₄This is performed using an alkyl sulfate sodium salt. Ethoxylation And the quaternization step is performed using conventional conditions and reactions.   In some cases, the reaction mechanism 5 is sufficient to allow a gel to form in the aqueous reaction medium. This produces a soluble product. The required product can be recovered from the gel, but will be described later An alternative two-step synthesizer 6 may be more desirable in commercial environments. You. The first step in the mechanism 6 is performed similarly to the mechanism 5. Second step (Ethoxylation) preferably results in ethylene oxide and a quaternary surfactant The reaction is performed using an acid such as HCl. As shown below, chlorohydrin, That is, chloroethanol also reacts to produce bishydroxyethyl derivatives be able to.   For the reaction mechanism 6, the following parameters are optional and related to the first step: It summarizes the preferred reaction conditions. The first step is preferably an aqueous medium Done throughout the body. Reaction temperatures are typically in the range of 100-230 ° C. Anti The reaction pressure is 50-1000 psig. Base, preferably sodium hydroxide HSO formed during the reaction using_FourAnd can be reacted. Or excess It is also possible to react with an acid using an amine. 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 sodium dodecyl sulfate (0.06921 mol), 14.55 g Diethanolamine (0.1348 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 And sealed under a nitrogen atmosphere 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 “cocoMeEO2” in the above list in the present invention. Or "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.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 Wherein x and (y + 1) are at least 7, preferably at least 9 M is an integer, and M is a water-soluble cation, particularly an unsaturated salt such as sodium or oleyl sulfate. Sulfate, C₁₂-C₁₈Alpha-sulfonated fatty acid ester, C_Ten-C₁₈Sulfation Polyglucoside, C_Ten-C₁₈Alkylalkoxy sulfates ("AExS"; especially EO 1-7 ethoxysulfate), and C_Ten-C₁₈Alkyl alkoxy carboxylate Formula CH (especially EO1-5 ethoxycarboxylate)_Three(CH_Two)_x(CHOS O_Three ^-M⁺) CH_ThreeAnd CH_Three(CH_Two)_y(CHOSO_Three ^-M⁺) CH_TwoCH_ThreeC_Ten− C₁₈Secondary (2,3) alkyl sulfates. C₁₂-C₁₈Betaine and Su Luhobetaine ("sultaine"), C_Ten-C₁₈Amine oxide is also included in the overall composition Can be C_Ten-C₂₀May also be used. Don't need high foam From the chain C_Ten-C₁₆Soap may be used. Other useful conventional surfactants Are listed in the standard text.Nonionic surfactant   Nonionic interfaces useful in the present invention, typically at a level of 1% to 55% by weight Non-limiting examples of activators include alkoxylated alcohols (AE), alkyl phenols , Polyhydroxy fatty acid amide (PFAA), alkyl polyglycoside (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_FifteenLinear alcohol and Product condensed with 9 moles of ethylene oxide) and Tergitol (trade name) 24- L-6 (C₁₂-C₁₄A condensation product of primary alcohol and 6 moles of ethylene oxide. And a narrow molecular weight distribution), Shell Chemical Company (Shell Chem) Neodol (trade name) 45-9 (C_{1 Four} -C_FifteenCondensation product of linear alcohol with 9 moles of ethylene oxide), Neodol ( Product name) 23-3 (C₁₂-C₁₃Condensation of linear alcohol with 3 moles of ethylene oxide Product), Neodol (trade name) 45-7 (C₁₄-C_FifteenLinear alcohol and 7 mol And Neodol (trade name) 45-5 (C₁₄− C_FifteenCondensation product of linear alcohol and 5 mol of ethylene oxide), Procter & Gya Sold by Promter & Gamble Company Kyro (brand name) EOB (C₁₃-C_Fifteen9 moles of alcohol and alcohol Condensation product with benzene), Genapol LA 030 or 0 sold by Hoechst 50 (C₁₂-C₁₄Alcohol 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, Reacts with glucose, fructose, maltose, Derived from reducing sugars such as toose. A typical example is C₁₂-C₁₈And C₁₂− C₁₄N-methylglucamide is exemplified. U.S. Pat. No. 5,194,639 and And U.S. Patent No. 5,298,636. N-alkoxy polyhydroxy fat Acid 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 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 & Tr sold by Haas Company (Rohm & Haas Company) iton (trade name) X-45, X-114, X-100 and X-102 Can be These surfactants are alkylphenol alkoxylates (eg, , 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.Additional builders   Additional builders may be added to the compositions described in the present invention. Additional The builder may be present at a level of at least 1%. Liquid formulations are typical Contains from 5% to 50%, more typically from 5% to 35% of builders, The ratio may include additional builders. Granular compositions typically comprise a detergent composition. Contains 10% to 80%, more typically 15% to 50% by weight of the builder , The ratio may include additional builders. Lower or higher It does not exclude levels.   Mixed builder systems comprising two or more builders are contemplated in the present invention. mixture Builder systems are optionally supplemented with chelating agents, pH buffers or fillers. However, these latter materials are generally used when writing out the amount of each material in the present invention. Separately. Regarding the relative amounts of surfactant and builder in the detergent, New builder systems typically have a surfactant to builder weight ratio of 60: Formulated from 1 to 1:80. Certain preferred laundry detergents have the ratio 0.90: 1.0 to 4.0: 1.0, more preferably 0.95: 1.0 to 3.0: 1. It is in the range of 0.   Suitable additional builders in the present invention are phosphates and polyphosphates, especially Having a chain, layer or three-dimensional structure, including lithium salts, water-soluble and hydrous forms Silicates, including and including amorphous solid or non-structural liquid forms; carbonates, bicarbonates , Tricarbonate, and carbonate minerals other than sodium carbonate or tricarbonate, organic Mono, di, tri and tetracarboxylates, especially acids, sodium, potassium or Is a non-surfactant carboxylate in the form of an alkanol ammonium salt, a fat Or water soluble low molecular weight polymeric carboxylic acids containing aromatic and perfume types It can be selected from the group comprising salts, and phytic acid. These are, for example, pH Buffer Borates, sulfates, especially sodium sulfate, and stable surfactants and Any other that may be important for the engineering of detergent compositions containing builder and / or builder These fillers or carriers may also supplement.   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 (Ho echst), crystalline layered aluminum-free δ-Na_TwoSiO_Fiveform Silicates, and are particularly preferred in granular laundry compositions. Germany DE-A- 3,417,649 and DE-A-3,742,043. Teru. In the formula, M is sodium or hydrogen and x is from 1.9 to 4, preferably Or a number of 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 Silicates are also available in the form of α, β and γ layered silicates, NaSKS-5, NaSKS -7 and NaSKS-11. Granule stability against shrinkage and bleaching agents Other agents, such as magnesium silicate, that can act as Silicates 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.   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 Succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate Citrates are also included. Lauryl-succinate is a European publication issued on November 5, 1986. No. 86200690.5 / 0,200,263. Fatty acids such as C₁₂-C₁₈Monocarboxylic acids can also be used alone with surfactants / builders. Builder, especially citrate and / or succinate building In addition to the above, it can be added to the composition to add builder activity. Appropriate Other polycarboxylates are available from Clutch Field on March 13, 1979 ( U.S. Pat. Nos. 4,144,226 to Crutchfield et al. U.S. Pat. No. 3,308,06 issued to Diehl on March 7, 967. No. 7. U.S. Patent No. 3,723, by Diehl See also No. 322.   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, the formula has a neutral or “balanced” charge . These builders are referred to in the present invention as "Minal Builders" Called. Anions other than water or carbonate of hydrates have an overall charge balance Middle You may add as long as it is a nature. The charge or valence effect of these anions is It should be added to the right side of the above equation. Preferably, hydrogen, water-soluble metal, hydrogen, boron , Ammonium, silicon and their mixtures, more preferably sodium Containing potassium, potassium, hydrogen, lithium, ammonium and mixtures thereof Water-soluble cations are present, sodium and potassium are highly preferred No. Non-limiting examples of non-carbonate anions include chloride, sulfate, fluoride, oxygen, water Oxides, silicon dioxide, chromates, nitrates, borates and mixtures thereof And those selected from the groups containing. The simplest form of this type A good builder is Na_TwoCa (CO_Three)_Two, K_TwoCa (CO_Three)_Two, Na_TwoCa_Two(C O_Three)_Three, NaKCa (CO_Three)_Two, NaKCa_Two(CO_Three)_Three, K_TwoCa_Two(CO_Three)_Three And combinations thereof. Builder described in the present invention Particularly preferred materials with respect to Na_TwoCa (CO_Three)_Two It is. Suitable builders of the type defined above include any one of the following minerals: Or in combination with other natural or synthetic forms. Ruder includes them. That is, Afghanite and Andersonite , Ashcroftin Y, Bayerite, Volkalite, Bulbangite, Tourite, ash nepheline, carbosernate, carletonite, dabin, donnite Y, Fairchildite, Ferris Light, Flange Knight, Gaudefruit, ・ Gairasite, Gilbasite, Gregolite, Jarlab Skeet, Kamfo -Gaite Y, Ketter Light, Carnescheid, Lepersonite Gd, Rio Thai G, McKelbait Y, Microsomit, Muroseito, Natrofairtildite, Nirelate, Lemon Dite Ce, Sacrophanite, Shorockingelite, Shortite, Slight, Tunisite, Tuscanite, Tricalcite, Screw Nebite and zemcolite. Preferred mineral forms include nirelate, And hair tightite.bleach   The detergent composition of the present invention may optionally contain a bleaching agent. If there Such bleaching agents, especially for fabric laundering, typically comprise about 1% of the detergent composition. To about 30%, more typically from about 5% to about 20%.   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. Pat. No. 4,483,781, filed Jun. 3, 1985 U.S. Patent Application No. 740,446 to Burns et al., February 2, 1985. European Patent Application No. 0,133,354 issued by Bank et al. And U.S. Pat. No. 4,4 by Chung et al., Issued Nov. 1, 1983. No. 12,934. Highly preferred bleaches include Burns (Bu) No. 4,634,551 issued Jan. 6, 1987 to Rns et al. 6-nonylamino-6-oxoperoxycaproic acid as described in It is.   Peroxide bleaches can also be used. Suitable peroxide bleaching compounds include carbonic acid Sodium peroxyhydrate and equivalent "percarbonate" bleach, sodium pyrophosphate Lium peroxy hydrate, urea peroxy hydrate, sodium peroxide You. Persulfate bleach (e.g., commercially manufactured by DuPont) OXONE) can also be used.   Preferred percarbonate bleaches have a range of 500 microns to 1,000 microns. Dry particles having an average particle size of less than 10% by weight of the particles Less than cron, less than 10% by weight of the particles are greater than 1,250 microns . Optionally, the percarbonate can be coated with a silicate, borate or water-soluble surfactant. Percarbonates are available from various commercial suppliers, such as FMC, Solvay and Tokai Electrification. Available from   Bleaches other than oxygen bleaches are also known in the art, and in the present invention Can be used. One class of non-oxygen bleaches of particular interest is sulfone Light-activated bleaches such as zinc and / or aluminum phthalocyanine Can be Published July 5, 1977 to Holcombe et al. See U.S. Pat. No. 4,033,718. If this is used, the detergent composition will Typically, 0.025% to 1.25% by weight of these bleaches, especially sulfonic acids Contains zinc phthalocyanine.   Mixtures of bleach can also be used.Bleach activator   Bleach activators are preferred components of the composition when oxygen bleaches are present. Existence When present, the amount of bleach activator is typically the amount of bleach and bleach At a level of 0.1% to 60% of the composition, more typically 0.5% to 40% .   The mixture of peroxide bleach and bleach activator corresponded to the bleach activator in aqueous solution The peroxyacid is produced in situ (ie, during the washing process). Activator Various non-limiting examples are described in Mao et al., US Pat. Nos. 4,915,854 and U.S. Pat. No. 4,412,934. ing. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetate Tylethylenediamine (TAED) activators are representative and their mixtures Things can also be used. Other representative bleaches useful in the present invention and See also US Pat. No. 4,634,551 for 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. 6, No. 621, US Pat. No. 5,244,594, US Pat. No. 5,194,416. No. 5,114,606, European Patent Application 549,271 A1,549. , 272A1, 544, 440A2 and 544, 490A1. Nesium based catalysts are mentioned. Preferred examples of these catalysts include MnIV_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-triazacyclonona N)_Two(ClO_Four)_Three, MnIV (1,4,7-trimethyl-1,4,7-triaza Cyclononane)-(OCH3)_Three(PF₆) And mixtures thereof. Other metal-based bleach catalysts include U.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. Enhances bleaching The use of manganese with various complex ligands has also been described in US Pat. No. 4,728, No. 455, No. 5,284,944, No. 5,246,612, No. 5,256. No. 779, No. 5,280,117, No. 5,274,147, No. 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 ー [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), [ Co (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 .181497-1502 (1979);Inorg. Chem.21, 2881-2885 (1982);Inorg. Chem.18, 2023-2 025 (1979); Inorg. Synthesis, 173-176 (19) 60);Journal of Physical Chemistry,56, Easily prepared by known procedures such as the teachings of J. 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.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%. Heavy Contains% by volume commercial enzyme product. Protease enzymes are usually from 0.005 to 0. Enough to provide 1 AU (activity per gram of composition, Anson unit) At a high level in these commercial products. Specific detergents, such as in automatic dishwashing In case of minimizing the total amount of non-catalytically active substances, Increase the active enzyme content of commercial products to improve other end results It may be desirable. High activity levels, but also highly concentrated detergent formulations May be desirable.   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 (ional Bio-Synthetics Inc.) Product name). In addition, European Patent Publication No. Protease A disclosed in U.S. Pat. Patent Publication No. 303,761 and European Patent Publication No. No. 130,756. International Public by Novo Bacillus sp. NCIMB 40338 described in Japanese Unexamined Patent Publication No. 9318140. See also high pH protease from. Proteases, one or more other enzymes and Enzyme detergents containing reversible protease inhibitors are described in Novo WO 920 No. 3529. Other preferred proteases include Proctor Ann International Publication No. 951 by DeGamble (Procter & Gamble) No. 0591. If necessary, reduce adsorption and hydrolyze Protease & Gamble (Procter & Gambling)  Gamble), as described in International Publication No. 9507791. Wear. The recombinant trypsin-like protease for a suitable detergent in the present invention is: It is described in WO 9425583 by Novo.   In more detail, a particularly preferred protease called "Protease D" Are carbonyl hydrolase variants with non-natural amino acid sequences. This No. 08/322, filed October 13, 1994, both of which are incorporated herein by reference. No. 676, entitled "Protease-Containing Cleaning Composition", Baek (A. eck) and U.S. patent application Ser. No. 08 / 322,677, By the name "Cleaning composition containing protease enzymes" by G. Ghosh Number of Bacillus amyloliquefaciens subtilisin as described in patent application According to the ring, at the position of said carbonyl hydrolase corresponding to position +76 Preferably, +99, +101, +103, +104, +107, +1 23, +27, +105, +109, +126, +128, +135, +156 , +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and / or +274 In combination with one or more amino acid residue positions corresponding to positions selected from the group comprising By substituting different amino acids for multiple amino acid residues Derived from precursor 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.) R 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) Improved amylase can be used. These preferred elements in the present invention are Millases are characterized, at a minimum, by one or more of the following measurable improvements: Share the characteristics of improved stability. That is, for example, to pH 9-10 Oxide against hydrogen peroxide / tetraacetylethylenediamine in buffer in solution Qualitative, e.g., thermal stability at common wash temperatures such as about 60 <0> C, e.g. Alkaline stability at a pH of from 11 to 11 Measured for amylase. Stability depends on the technical text that published the technology It can be measured using this. For example, it is disclosed in International Publication No. 9402597. See References. Stability improving amylase is available from Novo or Genenka Available from National (Genencor International) . One class of highly preferred amylases in the present invention is one, two or more. One or more Bacillus amylase strains, whether or not the amylase strain is a direct precursor Enzymes, particularly using site-directed mutagenesis from Bacillus α-amylase. Have in common. Oxidation stability improvement for the standard amylase shown above Millase is a bleaching detergent composition in the present invention, more preferably chlorine bleaching. Is preferred for use in different oxygen bleach detergent compositions. These preferred amillers In addition, (a) Novo International Publication No. 9 by Novo, Feb. 3, 1994, incorporated above. Amylase according to EP-A-402597, which in a variant is TERMAMYL (quotient B. known as "product name" position 197 of licheniformis α-amylase, or B. amyloliquefaciens, B.A. subtilis or B. kind like stearothermophilus Alanine or methionine residue located at homologous position variation of similar progenitor amylase Further examples are given by mutants substituted with threonine, preferably threonine. Amylase shown, (b) C. Mitchinson 199 A paper presented at the 207th National Meeting of the American Chemical Society on March 13-17, 2004 Genenka International (Gene) amylase as described by Ncor International) Is mentioned. In the dissertation, the bleach in automatic dishwashing detergents was Alpha-Amira Amylase that inactivates but has improved oxidative stability. licheniformis NCIB8061 pointed out that it was manufactured by Genenka. Methionine (M et) were identified as likely residues to be modified. Met is at position 8, 1 5, 197, 256, 304, 366 and 438 at once, most stable M197L and M197T containing the M197T mutant, which is a novel expression mutant Leads to particular variants of particular interest. Stability is determined by CASCADE (trade name) and S Measured at UNLIGHT (trade name). (C) Particularly preferred in the present invention New amylase may be directly used as described in WO 9510603. Amylase variants with additional alterations in the original species are mentioned, and DURAMYL ( (Brand name) from the assignee Novo. Other oxidation stability modifications that are particularly preferred Good amylase includes Genencor In International Publication No. 9418314 and Novo Described in International Publication No. 9402597. For example, Known chimeric, hybrid and simple mutant forms of amylase available Any other oxidative stability, as induced by site-directed mutagenesis Sex improving amylase can also be used. Other preferred enzyme modifications are available Wear. By Novo See WO95050909.   Other amylases include those described in WO 95/26397. And PCT / DK96 / 000 co-pending by Novo Nordisk 56. Specific agents used in the detergent composition of the present invention Amylase was assayed using a Padebas (trade name) α-amylase activity assay. Measured temperature range from 25 ° C to 55 ° C and pH value in the range from 8 to 10 At least 25% higher than the specific activity of Termamyl (trade name) Α-amylase that is characterized by ebas (trade name) α-amylase activity assay is described in WO 95/26. 397, pages 9-10). Also included in the present invention are references At least having the amino acid sequence shown in the SEQ ID list in the literature It is an α-amylase with 80% homology. These enzymes are preferably used in whole compositions 0.00018% to 0.060% by weight of pure enzyme, more preferably the total composition From 0.00024% to 0.048% by weight of pure enzyme in laundry detergent compositions Is added.   Cellulases that can be used in the present invention preferably have a maximum between 5 and 9.5. Bacterial and fungal types with appropriate pH are included. March 6, 1984 U.S. Pat. No. 4,435,3 by Barbesgoard et al. 07 is Humicola insolens, Humicola strain DSM1800 or genusaero Appropriate fungal cellulases and fungi from cellulase 212 producing fungi belonging to monas Cellular extracted from the hepatopancreas of the western mollusc, Dolabella Auricula Solander Disclose. Suitable cellulases are described in GB 2,075,028, Also disclosed in National Patent No. 2,095,275 and DE-OS-2,247,832 Have been. CAREZYME (trade name) and CELLUZYME (trade name) (Novo) is particularly useful. See also WO 9117243 by Novo Teru.   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 is from Humicola insolens or Humicola strain DSM1800. Suitable fungal cellulase or cellulase 212 belonging to genus aeromonas Extracted from the hepatopancreas of fungi and marine molluscs, Dolabella Auricula solander The disclosed cellulase is disclosed. Suitable cellulases are described in GB 2.07 5.028, UK Patent No. 2.095.275 and DE-OS-2.247 . 832 is also disclosed. CAREZYME (trade name) (Novo) is especially It is for. See also WO 9117243 by Novo.   Suitable lipases for detergent applications are disclosed in GB 1,372,034. Pseudomonas groups as shown, such as Pseudomonas stutzeri ATCC 19.154 And those produced by the microorganisms. Japanese Patent Application No. 53, February 24, 1978 See also lipase at -20487. This lipase is lipase P "Amono" Or Amano Pharmash, located in Nagoya, Japan, under the trade name "Amono-P" (Amano Pharmaceutical Co. Ltd.) I can do it. Other suitable commercial lipases include Amano-CES, for example, Japan Chromobacter viscosum var. From Toyo Brewery located in Tagata, Japan. lipolyticum Lipase exChromobacter viscosum such as NRRLB3663, U.S.A. Biochemical Corp. (US Biochemical Corp.) And Chromobacter v. From Disynth Co., The Netherlands. and lipase exPseudomonas gladioli. Europe Derived from Humicola lanuginosa found in State Publication No. 341,947, LIPOLASE (TM) enzyme, commercially available from It is a preferred lipase to use. Stabilized against peroxidase enzymes Lipase and amylase variants have been described by Novo in WO 941495. No. 1. WO 9205249 and RD 94359 See also 044.   Despite the large number of publications on lipase enzymes, Humicola lanuginosa Lipase derived from Aspergillus oryzae as a host Only one has heretofore been widely used as an additive for fabric laundry products. this is, Obtained from Novo Nordisk under the trade name Lipolase (trade name) as described above it can. Novo Nordis to optimize Lipolase stain removal performance Ku produced a number of variants. It is described in WO 92/052496. As noted, the native Humicola lanuginosa lipase D96L mutant is wild-type. Improves lard stain removal efficiency 4.4-fold compared to lipase (0.075 enzyme Compared in amounts ranging from 2.5 mg protein / liter). Novo Nordisk Research Publication No. published on Mar. 10, 1994 by No. 35944 is Lipa 0.001-100 mg (5-500,000 LU / Liter) Can be added in the amount corresponding to lipase mutant / washing liquid liter Is disclosed. The present invention specifically relates to D96L from 50 LU to 8500 LU. When used at a level in the range of / liter of washing liquid, the method disclosed in the present invention Low level of D96L change in detergent compositions containing bis-AQA surfactant The use of variants 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 Haloperoxidases such as chloro- or bromo-peroxidase include It is. The peroxidase-containing detergent composition was prepared by Novo on Oct. 19, 1989. International Publication No. 89099813 and International Publication No. 8909 by Novo. No. 813. A range of enzyme materials and their means of addition to synthetic detergent compositions include: By International (Genencor International) WO 9307263 and WO 9307260, Novo International Patent Publication No. WO 89908694 and McCarty Also disclosed in U.S. Pat. No. 3,553,139 issued Jan. 5, 1971, I have. The enzyme was purchased from Place et al. No. 4,101,457, and Hughe on March 26, 1985. s) is further disclosed in U.S. Patent No. 4,507,219. Liquid detergent distribution Useful enzyme materials for compounds and their addition to such formulations are described in US Pat. U.S. Pat. No. 4,261,868 to Hora et al. I have. Detergent enzymes can be stabilized by various techniques. Enzyme stability The conversion procedure is described in U.S. Pat. No. 3, August 17,1971 by Gedge et al. No. 6,600,319, by Venegas, Oct. 29, 1986. European Patent Publication No. 199,405 and Japanese Patent Publication No. 200,586 It is disclosed and illustrated. Enzyme stabilization systems are described, for example, in US Pat. No. 3,519, No. 570 is also disclosed. Protease, xylanase and cellulase The resulting useful Bacillus sp. AC13 is published by Novo in WO 94015 No. 32.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, it corresponds to calcium sulfate or the calcium salts mentioned in the examples. Magnesium salt may be used. Calcium and / or magnesium Further increases in the bell, for example, promote the lipolytic effect of certain types of surfactants 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 An antioxidant such as corbate, ethylenediaminetetraacetic acid (EDTA) or Such as its alkali metal salts, monoethanolamine (MEA) and mixtures thereof Organic amines can be used as well. Similarly, special enzyme suppression systems Enzymes can be added for maximum compatibility. Bisulfite, nitric acid Salts, chlorides; sodium perborate tetrahydrate, sodium perborate monohydrate and percarbonate Hydrogen peroxide sources such as sodium acid, phosphates, condensed phosphates, acetates, benzoates, Citrate, formate, lactate, malate, tartrate, salicylate, etc. These Other conventional scavengers such as mixtures of can be used if desired. General In some cases, the function of the chlorine scavenger may be (E.g. a hydrogen peroxide source) to achieve the required function to the extent necessary. As long as the compound is present in embodiments containing the enzyme of the invention, a separate chlorine scavenger may be added. There is no absolute need to add. Even in these cases, scavengers seek optimal results It is added for protection. In addition, the formulator is completely compatible with other Chemists are advised to avoid the use of any non- Will exercise regular skills. Regarding the use of ammonium salts, these salts may be washed Can be easily mixed with the agent composition, but absorbs water and / or removes ammonia during storage. Tends to be liberated. Therefore, if such materials are present, they are preferred. More preferably, U.S. Patent No. 4,652,3, to Baginski et al. Protected in particles such as those described in No. 92.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 ) By reacting the product of (b) with sodium metabisulfite in water. Can be manufactured. Further, suitable SRA ‘s include, for example, poly (ethylene glycol) Methyl ether, DMT, PG and poly (ethylene glycol) ("PEG") Gosselink, such as that produced by transesterification / oligomerization of elink) et al., U.S. Pat. No. 4,711,730, issued Dec. 8, 1987. Of non-ionic end-blocked 1,2-propylene / polyoxyethylene terephthalic acid Ester; ethylene glycol ("EG"), PG, DMT and Na-3,6- Dioxa-8 -Gosselink as oligomer from hydroxyoctane sulfonate (Goss elink) U.S. Pat. No. 4,721,580, Jan. 26, 1988. Partially and fully anionic end-capped oligomeric esters: eg DMT, Me -Encapsulated PEG and EG and / or PG, or DMT, EG and / or Or PG, Me-encapsulated PEG and Na-dimethyl-5-sulfoisophthalic acid 1987 by Gosselink, manufactured from a combination of Non-ion-sealing block poly of US Pat. No. 4,702,857 of Oct. 27. Ester oligomeric compounds; Maldonado, Gosselink (Go) U.S. Pat. No. 4,877,8, issued Oct. 31, 1989 to Ssellink et al. No. 96, especially sulfoaroyl-terminated terephthalate esters Can be The latter is an SRA ‘s useful in both laundry and fabric preparation products. Representative, one example is optional but preferably, for example, PEG340 M-sulfobenzoic acid monosodium salt, PG and And an ester composition produced from 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 Available SOKALAN SRA ‘s, such as SOKALANH P-22 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 ZELCON5126 and MILEASET 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 Preferably, sodium linear dodecylbenzenesulfonate or xylene, Or a member selected from toluene-sulfonate or a mixture thereof. For example, 0.5% to 20% of a crystal-reducing stabilizer such as an anionic surfactant. It further comprises a weight percent of the oligomer. These stabilizers or denaturants are all 1995 Gosselink, Pan, Kellet issued on May 16, 2011 U.S. Pat. No. 5,415,8 to Kellett and Hall. No. 07 is introduced into the synthesis can as taught. Appropriate things for the above SRA To Is 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 derived from the sulfoethyl ether of glycerin and related components (B) is an ester bond by being at least trifunctional. Represents a branching unit that forms a branched oligomer backbone, where x is about 1 To about 12, y ′ is from about 0.5 to about 25, and y ″ is from 0 to about 12. Y ′ ″ is from 0 to about 10, and the sum of y ′ + y ″ + y ″ ″ is from about 0.5 to about 25. Where z is from about 1.5 to about 25, z 'is from 0 to about 12, and z + z' The total is from about 1.5 to about 25, q is from about 0.05 to about 12, and m is about 0.5. 01 to about 10 And x, y ′, y ″, y ″ ′, z, z ′, q and m are the molar equivalents of the ester. Represents the average number of moles of each corresponding unit, wherein the ester is from about 500 to about 5,0 With a molecular weight in the range of 00)   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 homologues and their mixtures and the ethoxylation and 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] C] ethanesulfonate, DMT, Na-2 (2,3-dihydroxypropoxy ) Ethane sulfonate, EG and PG using suitable Ti (IV) catalyst Tell exchange and oligomerization products. This SRA ester is (CA P)_Two(T)_Five(EG / PG)_1.4(SEG)_2.5(B)_0.13Can be expressed as Where 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. No. 4,201,824 and by Lagase et al. Diisocyanate coupling, see U.S. Pat. No. 4,240,918. Nonionic terephthalate that binds the polymer ester structure using an agent, (II) anhydrous Add limellitic acid salt to known SRA's to trim terminal hydroxyl groups. With carboxylate end groups produced by conversion to tonic esters SRA ‘s. With the proper choice of catalyst, trimellitic anhydride is Independent carboxylic acid of trimellitic anhydride, not by ring opening of the anhydride bond of 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) viola See U.S. Pat. No. 4,201,824 to Violland et al. Anionic terephthalate-based SRA ‘s, a variant of a urethane binding component, (IV) See U.S. Pat. No. 4,579,681 to Rupert et al. Vinylpyrrolidone and / or both nonionic and cationic polymers Or poly (vinylcap) with a monomer such as dimethylaminoethyl methacrylate Lactam) and related copolymers, (V) Lone Phulan Chemii (Rho) Ne-Poulenc Chemie) EP 279,134. Graph of acrylic acid monomer to sulfonated polyester, referenced in 1988 Added to the SOKALAN type from BASF manufactured by A raft polymer whose SRA's are similar in fouling to known cellulose ethers. A graft polymer which is claimed to have removal and anti-redeposition activity, (VI) See BASF European Patent Publication No. 457,205 (1991). Of vinyl monomers, such as acrylic acid and vinyl acetate, to proteins, such as casein Graft, (VII) 1974, Vera, Unilever NV See DE 2,335,044 by Bevan et al. Adipic acid, caprolactam and polyethylene glycol for the treatment of fabrics And polyester polyamide SRA's prepared by the condensation of useful Other SRA's are disclosed in U.S. Patent Nos. 4,240,918 and 4,787,9. Nos. 89, 4,525,524 and 4,877,896. You.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: Crilic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconi And citric acid, mesaconic acid, citraconic acid and methylenemalonic acid. Vini Containing carboxylate radicals such as methyl ether, styrene, ethylene, etc. The presence of the high molecular weight polycarboxylate or monomer segment in the present invention. Currently, it is appropriate unless such segments 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 Examples of 4-methyl-7-diethyl-amino-coumarin, 1,2-bis (ben (Zimidazol-2-yl) ethylene, 1,3-diphenyl-pyrazoline, 2, 5-bis (benzoxazol-2-yl) thiophene, 2-styryl-naphtho [1,2-d] oxazole and 2- (stilben-4-yl) -2H-naph [1,2-d] triazole. Hamilton See U.S. Pat. No. 3,646,015, issued Feb. 29, 1972.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 A combination wherein 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 "PVPVL") is also preferred for use in the present invention. Has a PVPVI of 5,000 to 1,000,000, more preferably 5,000. Average min from 0 to 200,000, most preferably 10,000 to 20,000 (Average molecular weight ranges are described by Barth et al., Chemical An. alysis, Vol 113, "Modern Methods of Polymer Characterization" To 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) When used in combination, one of the two detergent composition components is provided when used alone. It has significantly better dye transfer control in aqueous washing liquid. If not bound by theory These brighteners are highly compatible with fabrics in laundry liquors, This is believed to be the reason for the relatively fast deposition on the fabric. Washing liquid The degree to which the brightener is deposited on the fabric is a parameter called the "consumption coefficient". Can be defined by The wear factor is generally determined by: a) b) the brightener material deposited on the fabric; This is the ratio of the whitening agent in the washing liquid to the initial concentration. Brighteners with relatively high wear coefficients In the context of the present invention, it is most appropriate for the control of transfer dyeing.   Of course, the other conventional optical brightener species of the compound, not the true transfer inhibition effect Can be optionally used in the composition to provide the traditional "whitening" benefits of the fabric. It is expected that can be. These uses are conventional and require detergent delivery. It is known to the union.Chelating agent   The detergent composition according to the invention comprises one or more iron and / or manganese chelates An agent may optionally be included. Such chelators are aminocarboxylates , Aminophosphonates, polyfunctionally substituted perfume chelating agents and mixtures thereof And all are defined below. By the bounds of theory If not, the benefits of these materials would be partially due to the formation of soluble chelates. It is believed to be due to the excellent ability to remove iron and manganese from the rinse.   Aminocarboxylates useful as any chelating agent include ethylene dia Mintetraacetate, N-hydroxyethylethylenediaminetriacetate , Nitrilotriacetate, ethylenediaminetetrapropionate, triethyl Les Tetraamine hexaacetate, diethylene triamine pentaacetate, In addition to their ethanol diglycine, alkali metal, ammonium, substituted Monium 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 type of foam control agent is monocarboxylic fatty acids and their soluble salts. Is included. Wayne St. John on September 27, 1960 See U.S. Pat. No. 2,954,347 issued to U.S. Pat. Used as foam inhibitor The monocarboxylic fatty acids and salts thereof typically have 10 to 24 carbon atoms. It has a hydrocarbyl chain of atoms, preferably 12 to 18 carbon atoms. Suitable salt Include alkali metal salts such as sodium, potassium and lithium salts, ammonia And alkanol ammonium salts.   The detergent composition of the present invention may also contain a non-surfactant foam inhibitor. these 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. k i) 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 Methyl siloxane liquid.     (Ii) from about 0.6: 1 to about 1.2: 1 of (CH_Three) 3SiO_1/2Unit: S iO_TwoIn unit ratio, (CH_Three)_ThreeSiO_1/2Unit and SiO_TwoUnit and From about 5 to about 50 parts by weight / 100 parts of a 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 A silicone compound produced from siloxane or silicone resin, and (c) a finely divided filler. To promote the reaction of (d) mixture components (a), (b) and (c) Non-aqueous emulsion of the main antifoaming agent, which is a mixture of And (2) at least one nonionic silicone surfactant, and (3) at room temperature. Polyethylene glycol or poly having a solubility in water of more than 2% by weight Ethylene-polypropylene glycol copolymer (polypropylene glycol is Not used). Similar amounts can be used in granular compositions, gels, etc. You. 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 Or a copolymer of PPG200 / PEG3000. About 1: 1 and 1:10 Polyethylene glycol: polyethylene, most preferably between 1: 3 and 1: 6 The weight ratio of the copolymer of len-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. Open Including mixtures with the indicated silicone-like sea corn oil. Secondary alcohol , C₁-C₁₆C with a chain₆-C₁₆Alkyl alcohol is mentioned. Preferred a Rucol is 2-butyloctanol, trade name ISOFIL 12 Available from Condea. The mixture of secondary alcohols is trade name I Available as SALCHEM from Enichem. Mixed foaming suppression The agent is typically a 1: 5 to 5: 1 weight ratio of alcohol to silicone. Contains 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 Larger amounts may be used. This upper limit keeps costs to a minimum and effective foaming Of a practical nature primarily related to smaller effects on the control of You. Preferably 0.01% to 1% of a silicone foam inhibitor, more preferably 0% to 1%. . Use 25% to 0.5%. As used in the present invention, these weight percentages Values include any silica that may be used in conjunction with the polyorganosiloxane, Any materials that may be utilized are included. Derived from monostearyl phosphate Suds suppressors are generally utilized in amounts ranging from 0.1% to 2% by weight of the composition. Charring Hydrogen foam inhibitors are typically utilized in amounts ranging from 0.01% to 5.0%. You. However, more levels can be used. Alcohol foam inhibitor , Typically from 0.2% to 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, and other smectite clays known in the art. Softening clays typically have a level of 0.5% to 10% by weight in the composition. Can be used to impart the benefits of a fabric softener at the same time as fabric washing. K Ray softeners are described, for example, by Crisp et al. U.S. Pat. No. 4,375,416 and Harris, issued Sep. 22, 1981 Harris et al., US Pat. No. 4,291,071. It can be used in combination with min and cationic softeners.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 Indan, 5-acetyl-3-isopropyl-1,1,2,6-tetramethyli Ndan, 1-dodecanal, 4- (4-hydroxy-4-methylpentyl) -3- Cyclohexene-1-carboxaldehyde, 7-hydroxy-3,7-dimethyl Octanal, 10-undecene-1-al, iso-hexenyl-cyclohexyl Lucarboxaldehyde, formyl tricyclodecane, hydroxycitroneller Product of methyl anthranilate with hydroxycitronellal Condensation products of 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-butyloxy Clohexyl acetate, methyl dihydrojasmonate, beta-naphthol Methyl ether, methyl beta-naphthyl ketone, 2-methyl-2- (para So-propylphenyl) -propionaldehyde, 1,3,4,6,7,8- Xahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma- 2-benzopyran, dodecahydro-3a, 6,6,9a-tetramethylnaphtho [ 2, 1b] Furan, anisaldehyde, coumarin, cedrol, vanillin, cyclope Nantadecanolide, tricyclodecenyl acetate and tricyclodecenyl pio But not limited to.   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, nerol , 2- (1,1-dimethylethyl) -cyclohexanol acetate, ben acetate Jill and eugenol. Carriers such as diethyl phthalate It can be used in a flavoring 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. Typically, the enzyme / detergent solution is 2.5 times the weight of the silica. The obtained powder is treated with silicone oil (various silicones in the range of 500-12,500). (Oil viscosity can be used) with stirring to disperse. The obtained silicone oil Emulsify the dispersion or otherwise add to the final detergent mother liquor. By this method, Enzymes, bleach, bleach activator, bleach catalyst, photoactivator, dye, fluorescent agent, fabric Ingredients such as preparations and hydrolyzable surfactants, including liquid laundry detergent compositions Can be "protected" for use in detergents.   Liquid cleaning compositions may contain water or other solvents as a carrier. Meta Low, typified by ethanol, propanol and isopropanol A primary or secondary alcohol of molecular weight is suitable. Monohydric alcohol is a surfactant Is preferred to solubilize but 2 to 6 carbon atoms and 2 to 6 hydroxy groups Polyols such as those containing (eg, 1,3-propanediol, ethylene glycol) Recall, glycerin and 1,2 propanediol) can also be used. The composition comprises from 5% to 90%, typically 10% to 50% of such a carrier. May be included.   The detergent composition of the present invention is preferably used during aqueous washing operations, The pH of the wash water is between 6.5 and 11, preferably between 7.5 and 10.5. To be prescribed. The product formulation for liquid dishwashing is preferably pH 6.8 and 9. It is between 0. Laundry products typically have a pH of 9-11. Recommended usage level Methods for controlling pH include the use of buffers, alkalis, acids, etc. It is known to those skilled in the art.Production of granules   The bis-alkoxylated cationic surfactant of the present invention is added to the detergent mixture and After conventional spray drying, no residual potentially odorous short-chain amine contaminants Promotes removal. Formulators, for example, alkoxylated for high-density granular detergents If you want to prepare mixable particles containing a cationic surfactant, It is preferred that the child composition is not a strong alkali. High density (greater than 650 g / l) A process for preparing granules is described in US Pat. No. 5,366,652. . These particles 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.   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. Condyle The granular detergents in Examples A and B are as follows.                                   Example A ^*The example AQA1 (coco MeEO2) surfactant has an equivalent amount of surfactant AQA-2 To any of AQA-22 or other AQA surfactants in the present invention It may be replaced more.                                   Example B ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.   The following are examples of various stains and stains using compositions within the scope of the present invention. 2 illustrates laboratory procedures and test results. As can be seen from the data, an overall wash Improvements in cleanliness have been achieved at various stains and stains on various fabrics.                               Performance test procedure Sample preparation Preparation of a sample basically includes the following steps. 1. Preparation of premix LAS + AS. 2. Preparation of premix LAS + AS + cation. 3. Preparation of stock nonionic (AE) surfactant. 4. Preparation of builder solution. 5. Preparation of granules.Surfactant: ^*(Actual weight depends on percent activity) Product Preparation Procedure for Performance TestingStep I; The individual surfactants are weighed and mixed according to the following procedure. Weigh 1.78.85 grams of LAS. Weigh 2.34.55 grams of AS into the same beaker. 3.498.10 ml of distilled water is added to the LAS & AS mixture. 4. Thoroughly dissolve LAS and AS at 40 ° C. for about 30 minutes until completely dissolved Pre-mix while heating.Step II; 1.9 grams of cation are weighed and the same containing LAS + AS premix solution Put in beaker. 2. The total volume of the solution is now 500 ml.   This 500 ml surfactant mixture is sufficient for 5 washes. This stock 100 ml of the solution is used for one washing. 49 liters of this 100 ml solution The addition of tap water results in a corresponding wash concentration for each surfactant.Step III; 1. Weigh 19.44 grams of AE separately. 2. Add 900 ml of distilled water to the AE. 3. This 900 ml solution is sufficient for 18 washes. 4. 50 ml of this solution is used for one washing.Step IV; Silicate: 148.32 grams per 900 ml of distilled water. 50 ml of this solution Used for washing multiple times. Copolymer: 92.88 grams per 900 ml of distilled water. 50 ml of this solution Used for washing multiple times. Granules: Weigh each granule component separately in the same beaker.Order of addition to washing machine The ingredients are added in the following order with stirring. 1. Silicate (2.0R) 2. Copolymer (as above) 3. Granules     The stirring is stopped here (to avoid foaming during the addition of the surfactant). 4. LAS + AS + cation solution 5. AE solution     Stir for 15 seconds     Hardness: No extra hardness is added in addition to tap water hardness.     Load: Typically, 2.4 kg of laundry having the following configuration is used.         Cotton dress shirt (1)         Worn out T-shirts (from panelists (3)         Large T-shirt (11)         DKPET-shirt (1)         P / C shorts (2)         Cotton shorts (1) PKPE is a double knit polyester. DMO is a dirty motor oil.   The following test results I are based on a book using a mixture of Coco MeEO2 and LAS / AS. 1 shows the performance of a composition according to the invention. Test result II is compared with Coco MeEO2 / LAS And Coco MeEO10^*And the performance using LAS / AS. In the test , The performance is different dirt type, namely dirt, builder sensitive dirt, bleach sensitive Dirt, surfactant-sensitive dirt and socks^*Measured against. In the present invention According to the term "bis", "EO10" is an average of 10E in the molecule. O units, typically about 5 units per chain (but not limited to) Has two poly-EO chains.                                Test result I Premix of Coco MeEO2 cation and LAS & AS (overall anion system)                                Test result I            Premix of Coco MeEO2 cation and LAS alone                                Test result II          Premix of Coco MeEO10 cation with LAS + AS                                Test result II           Premix of Coco MeEO10 cation and LAS alone Dirt After wearing color 0.17 False collar -0.52 Cufflinks 0.19 Darkened -0.17 Stain (average) -0.08 Clay C / D -0.34 Clay DKPE 0.09 Builder sensitive dirt (average) -0.13 Spinach 0.06 Coffee 0.08 Bleach sensitive stain (average) 0.07 Meat sauce -0.20 Curry -0.38 Bacon oil -0.33 DMO -0.33 Surfactant sensitive soil (average) -0.31 Average (including socks) -0.11 Socks (front) 0.42S Socks (after) 0.64S Socks (Delta) 0.22                                    An example In the following examples, the abbreviated component designations have the following meanings. LAS: Linear C₁₂Sodium alkylbenzene sulfonate TAS: Tallow alkyl sodium sulfate C45AS: C₁₄-C_FifteenSodium linear alkyl sulfate CxyEzS: C₁x-C₁Ethyl y-branched sodium alkylsulfate zmol                   And condensation C45E7: C_14-15Dominant linear primary alcohols with an average of 7 moles of ethylene oxide                   Oxide and condensation C25E3: C_12-15Branched primary alcohol average 3 mol ethylene oxide                   And condensation C25E5: C_12-15Branched primary alcohol average 5 mol                   Of ethylene with ethylene oxide 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: Formula with primary particle size ranging from 0.1 to 10 microns                   Na₁₂(AlO_TwoSiO_Two)₁₂・ 27H_TwoO aluminosilicate                   Thorium hydrate NaSKS-6: Formula δ-Na_TwoSi_TwoO_FiveCrystalline layered silicate Citric acid: Citric anhydride Carbonate: anhydrous carbon having a particle size between 200 μm and 900 μm                   Sodium acid Bicarbonate: anhydrous with a particle size between 400 μm and 1200 μm                   Sodium bicarbonate Silicate: amorphous sodium silicate (SiO_Two: Na_TwoO; 2.0 ratio) Sodium sulfate: anhydrous sodium sulfate Citrate: activity 8 with a particle size between 425 μm and 850 μm                   6.4% trisodium citrate dihydrate MA / AA: 1: 4 maleic acid / acrylic acid copolymer average molecular weight 70,                   000 CMC: Sodium carboxymethylcellulose Protease: Novo Industries A / S (Novo Industries)                   is A / S) sold under the trade name Savinase                   Active 4K NPU / g proteolytic enzyme Alcalase: Novo Industries A / S (Novo Industries)                   is A / S) proteolytic enzyme with an active 3 AU / g                   Elementary Cellulase: Novo Industries A / S (Novo Industries)                   is A / S) sold under the trade name Carezyme                   Cellulase Degrading Enzyme with 1000 CEVU / g Activity Amylase: Novo Industries A / S (Novo Industries)                   ies A / S) sold under the trade name Termamy160T                   Active 60KNU / g amylolytic enzyme Lipase: Novo Industries A / S (Novo Industries)                   is A / S) sold under the trade name Lipolase                   Lipolytic enzyme having an activity of 100 kLU / g Endolase: Novo Industries A / S (Novo Industries)                   ies A / S) sells 3000 EVU / g of active                   Endoglunase enzyme PB4: Nominal formula NaBO_Two・ 3H_TwoOH_TwoO_TwoSodium perborate 4 water                   Japanese PB1: Nominal NaBO_Two・ H_TwoO_TwoAnhydrous sodium perborate bleach Percarbonate: Nominal formula 2Na_TwoCO_Three・ 3H_TwoO_TwoSodium percarbonate NOBS: Nonanoyloxybenzene sulfate in the form of sodium salt TAED: Tetraacetylethylenediamine DTPMP: Monsanto has the trade name Dequest2                   060 sold as diethylene triamine penta (me                   Tylene phosphonate) Photoactivation: Sulfonated subunit encapsulated in soluble polymer of bleached dextrin                   Lead phthalocyanine Brightener 1: 4,4'-bis (2-sulfostyryl) biphenyldinatriu                   M Brightener 2: 4,4'-bis (4-amino-6-morpholino-1,3,5-                   Triazin-2-yl) amino) stilbene-2: 2'-dis                   Disodium sulfonate HEDP: 1,1-hydroxyethanediphosphonic acid PVNO: polyvinyl pyridine N-oxide PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole SRA1: Oxyethyleneoxy and terephthaloyl backbone                   Having sulfobenzoyl end-blocking ester SRA2: Diethoxylated poly (1,2 propylene terephthalate) short chain                   Block polymer Silicone defoamer: contains siloxane-oxyalkylene copolymer as dispersant                     A polydimethylsiloxane foam control agent, before the foam control agent.                     With a ratio to the dispersant of from 10: 1 to 100: 1   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. Less than In the examples below, all levels are stated as weight percent of the composition.                                   Example I   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 II   The following bleach-free detergent compositions are particularly useful in washing colored garments. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                   Example III   The following detergent formulations according to the invention are prepared. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                   Example IV   The following high density, bleach-containing detergent formulations according to the present invention are prepared. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                   Example V   The following high-density detergent formulations according to the invention are prepared. ^*An example bis-AQA-1 (coco MeEO2) surfactant is the surfactant bis-A Any of QA-2 to bis-AQA-22 or other bis in the present invention -It may be replaced by an equivalent amount of the AQA surfactant. Any of the granular detergent compositions provided in the present invention may be any known detergent-forming tablets. May be made into a tablet using the tableting method described above.   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; No. 2,195,125, United Kingdom Patent No. 2,195,649, U.S. Pat. No. 4,988,462; U.S. Pat. No. 5,266,233; 5,654 (6/16/87), EP 510,762 (10/28 / 92,), European Patent Publication No. 540,089 (5/5/93), European Patent Publication No. 5 No. 40,090 (5/5/93), US Pat. No. 4,615,820, European Patent Publication No. 565,017 (10/13/93), EP 030,096 ( 5/10/81), which are incorporated herein by reference. To use. Such a composition is composed of various particulate washings stably suspended in the composition. A cleaning component (eg, a bleaching agent as disclosed above) can be included. Such non-aqueous compositions comprise a liquid phase and optionally, but preferably, a solid phase. All as described in detail below and in the cited references. . AQA surfactants may be used at the levels described above for the manufacture of other laundry detergent compositions. And in a manner incorporated into the composition.Liquid phase The liquid phase generally comprises from 35% to 99% by weight of the detergent composition according to the invention. . More preferably, the liquid phase comprises from 50% to 95% by weight of the composition. Most favorable 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 according to the invention is mixed with a specific type of non-aqueous liquid diluent. It also contains relatively high concentrations of certain types of anionic surfactants. (A)Essential anionic surfactant   Anionic surfactants essentially used as an essential component of the non-aqueous liquid phase are Alkyl groups containing 10 to 16 carbon atoms in a linear or branched configuration 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. Using these anionic surfactants at these concentrations, 15% of the composition To 60% by weight, more preferably 20% to 40% by weight of anions in the total composition Corresponds to the system surfactant concentration. (B)Non-aqueous liquid diluent   In order to form 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. i)Alkoxylated alcohol   One essential component of the liquid diluent used to form the composition in the present invention is The portion consists of an alkoxylated fatty acid alcohol material. These substances are themselves It is also a body nonionic surfactant. 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 eodol 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 liquid phase of the composition Used in the present invention to mean non-surfactant carrier or diluent moiety. Book In the essential and / or optional components of the composition according to the invention, the "solvent" -containing liquid phase Fine particles dispersed in the "solvent" -containing liquid phase while some components are actually soluble Some components are present as solid substances. Thus, the term "solvent" refers to a solvent substance All of the detergent composition components added to the composition must be practically soluble. It is not intended to be   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 defined as a composition according to the present invention. One of the preferred types of particulate materials used in , Even if it tends to dissolve sodium perborate or sodium percarbonate It is slight. Therefore, you should use a considerably polar solvent such as ethanol. is not. Suitable low-polarity solvents useful in the non-aqueous liquid detergent composition of the present invention. Non-vicinal C_Four-C₈Alkylene glycol, alkylene glyco Mono-lower alkyl ether, low molecular weight polyethylene glycol, low molecular weight Examples include tyl 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-C₆A Alkyl ether. Specific examples of such compounds include diethylene glycol. Recohol monobutyl ether, tetraethylene glycol monobutyl ether, Dipropylene glycol monoethyl ether and dipropylene glycol mono Butyl ether. Diethylene glycol monobutyl ether and Dipropylene glycol monobutyl ether is particularly preferred. Compounds of this type The products are available under the trade names Dowanol, Carbinol and Cellosolve. Originally sold commercially.   Another preferred type of non-aqueous low-polar organic solvent useful in the present invention includes low Molecular weight polyethylene glycol (PEG). These substances are few Both have a molecular weight of 150. P with a molecular weight ranging from 200 to 600 EGs are most preferred.   Yet another preferred type of non-aqueous low polarity solvent is low molecular weight methyl ether. No. Such substances have the general formula R¹—C (O) —OCH_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- aqueous The low polar organic solvent may comprise from 10% to 60% by weight of the liquid phase, most preferably the liquid phase of the composition. From 20% to 50% by weight. At these concentrations in the liquid phase, this organic solvent With the use of a medium, 1% to 50% by weight of the composition, more preferably 5 to 40% by weight %, Most preferably from 10% to 30% by weight of the solvent concentration in the total composition. iii)Ratio of alkoxylated alcohol to solvent   The ratio of alkoxylated alcohol to organic solvent in the liquid diluent will ultimately be It can be used to change the flow characteristics of the resulting detergent composition. Generally, The weight ratio of alkoxylated alcohol to organic solvent ranges from 50: 1 to 1:50. It is an enclosure. More preferably, this ratio ranges from 3: 1 to 1: 3. iv)Liquid diluent concentration   Similar to the concentration of the alkylbenzene sulfonate anionic surfactant mixture, The amount of total liquid diluent in the non-aqueous liquid phase in the present invention depends on the type of other composition components. And the amount and composition characteristics required. Generally, liquid diluents are used in the present invention. Make up from 35% to 70% of the non-aqueous liquid phase of the composition. More preferably, liquid The diluent comprises 50% to 65% of the non-aqueous liquid phase. This is 15% of the composition 70% by weight, more preferably 20% to 50% by weight of the non-aqueous liquid in the total composition Corresponds to diluent concentration.Solid phase   The non-aqueous detergent composition of the present invention comprises 1% to 65% by weight, more preferably 5% by weight. % To 50% by weight of 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 of 0 ° C. to 35 ° C. Is done. This cooling step includes adding the particulate material of the detergent composition of the present invention. To form a systematic surfactant-containing liquid base that can be dispersed or dispersed. Act like   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 Virtually all particles of an alkali source, such as sodium carbonate, The mixture can be added while keeping it under shear stirring. Then, other The solid optional components of can be added to the composition at this point. Of the mixture Continue stirring and, if necessary, increase stirring at this point to remove insoluble solid particles in the liquid phase. 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 One or more solid components into a stirred mixture as a slurry of mixed particles It may be added. Thus, particles of organic builder material and / or inorganic alkali The source particles and / or the bleach activator particles with the alkoxylated alcohol and / or Alternatively, separately form a premix with a small portion of the non-aqueous It may be added as a slurry to the stirred mixture of the constituent components. Such a slurry -The addition of the premix is based on a premix slurry formed in a similar manner by itself. Prior to the addition of peroxide bleach and / or enzyme particles, which may be part of the It is desirable to make it.   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 Is an effective amount to form a composition in an aqueous solution of 500 to 70000 ppm. A sufficient amount can be constituted. More preferably, 800 to 3,000 pp m of the detergent composition of the present invention is formed in an aqueous wash / bleach solution.                                   Example VI   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 Alternatively, it may be replaced by another bis-AQA surfactant in the present invention. Bis-AQA and LAS at 130 ° F. for 1/2 hour, then hexileng The composition is prepared by mixing together the recall and the ethoxylated alcohol You. The mixture is then cooled to 85 ° F (29 ° C) and, once cooled, the remaining components Add a minute. Next, the resulting composition is stirred for an additional 1/2 hour at 29 ° C (85 ° F). You.   The resulting composition has excellent stain and stain when used in normal fabric washing operations. It is a stable, anhydrous, heavy-duty, liquid laundry detergent with removal performance.   Examples A and B below further illustrate the invention in the present invention with respect to bar-like laundry soaps. It is proof.                                   Example VII ¹: Sodium diethylene triamine penta (phosphonate)^Two : Sokolan CP-52 is a maleic / acrylic copolymer.^Three : Bis-AQA-1 is obtained from an equivalent of bis-AQA surfactant, bis-AQA2. Bis-AQA-22 or other bis-AQA surfactant in the present invention May be replaced.^Four : Water (2% to 8% including water of hydration), sodium sulfate, calcium carbonate And other secondary components.   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 automatic dishwashing detergents contain a source of hypochlorite, perborate, percarbonate or persulfate. Bleaching agents such as whitening agents, proteases, lipases and amylases or mixtures thereof Enzymes, rinse aids, especially nonionic surfactants; zeolites and phos Builders, including fate builders, low foaming detergents, especially ethylene oxide A sid / propylene oxide condensate may be included. Such compositions are representative Typically, it exists in the form of granules or gels. When used in the form of a gel, the statement Various gelling agents known in the art can be used.                                  Example VIII   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, , In the formula, R¹And X are as disclosed above, wherein the cationic surfactant One has (x + y) or z in the range of 1-5, preferably 1-2, and the other has 3 (X + y) in the range of -100, preferably 10-20, most preferably 14-16. ) Or a formula R with z¹N⁺CH_Three[EO]_x[EO]_yX^-And R¹N⁺(CH_Three)_Two[E O]_zX^-A mixture of ethoxylated cationic surfactants is used in the present invention. Can be. Such compositions may be used individually in the cationic system of the present invention. 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. Inclusion was not achievable.

──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3/50 C11D 3/50 (72) Inventor Laura, Clon Fairfield, Lake, Mead, Drive, 5656 (Ohio, USA) 72) Inventor Peter, Robert, Foley, Ohio, USA, Cincinnati, Lytle, Place 1, Apartment, 906 (72) Inventor Thomas, Anthony, Kryp, Ohio, United States, Loveland, Three, Chimneys, Rain, 599 (72) Inventor John, Downing, Curry Oxford, Stone, Creek, Drive, Ohio, USA 95 (72) Inventor Kenneth, William, Willman America Country Ohio, Fairfield, Williamsburg, Way, 5603 (72) Inventor Ian, Martin, Dodd England Loughborough, Hollywell, Drive, 47 (72) Inventor Christian, Arthur, Jax, Kamiel, Toen Beiss 9120, Haasdonk, Bequitostraat, Belgium, 4 (72) Inventor Michael, Alan, John, Moss Northumberland, Stocksfield, Painshawfield, Rhodes, United Kingdom, 13 (72) Inventor Noriko Katsuta 6-2-1, Minatojima-Nakamachi, Chuo-ku, Kobe-shi, Hyogo Kobe Park City, Sea 507 (72) Inventor Frank, Andrey, Kubitok, United States of America Ohio, Cincinnati, Richwood, Avenue, 1103 (72) Inventor Mark, Cyan ―Quen, Mao Departure from 23-23-13 (72) at Sumiyoshi Honcho, Higashinada Ward, Kobe City, Hyogo Prefecture Who Masaru Murata Nishinomiya, Hyogo Prefecture Yuba-cho, 6-5- Rays 3 (72) inventor Kizaru, Mohammed, cans, Sarunaiku Kobe, Hyogo Prefecture Higashi-Nada Ward Koyochonaka 5-1-523 -302

Claims (1)

[Claims] 1. Prepared comprising or in combination with an aluminosilicate builder, 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 of claim 1, comprising an additional builder. 3. The composition of claim 2, wherein the additional builder is selected from the group consisting of a mineral builder, a layered silicate builder, or a phosphate builder. 4. The composition according to any one of claims 1 to 3, which is prepared by mixing a non-AQA surfactant and a bis-AQA surfactant. 5. The composition according to any one of claims 1 to 4, wherein the non-AQA surfactant is an anionic surfactant. 6. The composition according to any of the preceding claims, wherein the weight ratio of bis-AQA to non-AQA surfactant is from 1:15 to 1: 8. 7. 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 6, wherein the composition is an integer from 1 to 8. 8. 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 7, wherein the composition is an integer of from 1 to 4. 9. 9. The composition according to any one of claims 1 to 8, comprising two or more bis-AQA surfactants or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant. Stuff. 10. 10. 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. 11. The composition according to claim 1, which is in the form of a granule, a stick, an aqueous liquid, a non-aqueous liquid or a tablet. 12. The composition according to any one of claims 1 to 11, wherein the composition is substantially free of a bleaching component. 13. 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 12 or an aqueous medium comprising the detergent composition. 14． 14. The method according to claim 13, wherein an ethoxylated polyamine is used. 15. 15. A method according to claim 13 or claim 14 wherein builder sensitive soil is removed from the fabric. 16. The method according to any one of claims 13 to 15, which is performed by an automatic machine. 17． The method according to any one of claims 13 to 16, which is performed by hand. 18. 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 . 19. 19. The method according to claim 18, wherein the method is performed using a fragrance or fragrance component in combination with a detergent composition comprising bis-AQA.