JPH11512146A - Detergent composition - Google Patents

Abstract

  (57) [Summary] A soil dispersant polymer, a non-bis AQA surfactant, and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant, and the weight ratio of bis-AQA to the soil dispersant polymer is: A detergent composition which is in the range of 1:11 to 1:14.

Description

DETAILED DESCRIPTION OF THE INVENTION                                Detergent composition                                 Technical field   The present invention relates to soil dispersant polymers, non-AQA surfactants and bis-alkoxylations. A detergent composition containing a quaternary ammonium (bis-AQA) cationic surfactant. I do.                                 Background art   Modern compositions are capable of removing various stains and stains from a wide variety of substrates. As needed, the formulation of laundry detergents and other cleaning compositions has considerable Present an assignment. Thus, laundry detergents, hard surface cleaners, shampoos and And other personal cleansing compositions, used in hand dishwashing detergents and automatic dishwashers Detergent compositions that are suitable for use all have the proper choice of ingredients to function effectively. And require a combination. Generally, such detergent compositions are of different types One or more surfactants designed to loosen and remove stains and stains Will contain. Reviewing the literature, a broad selection of surfactants and surfactants Although combinations may have been shown to be available to detergent manufacturers, many Special ingredients are not suitable for low unit cost products such as laundry detergents for home use The reality is that it is a chemical. In fact, most such homes like laundry detergent The product used is probably due to economic considerations and various stains and stains and various fabrics Due to the need to formulate compositions that work reasonably well, Ethoxylated nonionic surfactants and / or sulfated or sulfonated anionic surfactants It remains composed of one or more of the on-surfactants.   Different types of stains such as body stains, grease / oil stains, certain food stains and Quick and efficient removal of stains can be problematic. Such stains Of hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous materials It is well known that they contain compounds and are thus difficult to remove. Additional problem is lime Insoluble fatty acids derived from the decomposition of soap deposits and triglyceride stains Hardness ion salt (for example, Ca²⁺/ Mg²⁺). Small amount of hydrophobic stain , Residual stains and lime soap deposits often appear on the surface of the fabric (fabric) after washing. Remains on the surface. Combines with limited removal of dirt, stains and deposits in the cleaning solution Continual cleaning and wear eventually accumulates on the fabric, Means that the particle stains are further trapped and the fabric becomes yellowish. After all, fabric is a consumer A dingy appearance that is considered unwearable and should be discarded by Take on.   In the literature, various nitrogen-containing cationic surfactants are available in various cleaning compositions. It has been suggested that it would be useful. Such substances (typically amino, In the form of quaternary ammonium or imidazolinium compounds) For example, it is designed for special uses. For example, various amino and quaternary ammonium Surfactants have been suggested for use in shampoo compositions and cosmetics It is said to give the above benefits to hair. Other nitrogen-containing surfactants are fabric soft May be used in laundry detergents to provide antioxidant and antistatic benefits . However, in most cases, the commercial use of such materials is Has been limited by the difficulties encountered in large-scale production of such compounds. even more The limitation is the detergent set caused by ionic interactions with cationic surfactants Potential precipitation of the anionic active component of the product. The nonionic surfactant and And anionic surfactants remain the main component of surfactants in today's laundry compositions .   Certain bis-alkoxylated quaternary ammonium (bis-AQA) compounds are commonly used. Various stains and stain types commonly encountered, especially hydrophobic stains and lime soap deposits Found to be usable in a variety of detergent compositions to enhance the detergency performance above Was. The bis-AQA surfactants of the present invention are more effective than known cationic surfactants. Provides qualitative benefits to prescribers. For example, the bis-AQA surfactant used here The agent is prominent in the cleaning of "daily" grease / oil hydrophobic dirt that is normally encountered Give improvement. Further, bis-AQA surfactants are commonly used in detergent compositions. Anionic surfactants such as alkyl sulfates and alkyl benzenes Compatible with rufonate. Incompatibility with the anionic component of the detergent composition is usually To date, it has been a limiting factor in the use of cationic surfactants. Small amount ( Bis-AQA surfactants (as high as 3 ppm in the wash liquor) have the benefits described herein. give. Bis-AQA surfactants are formulated over a wide pH range of 5-12 it can. Bis-AQA surfactants can be pumped and handled at manufacturing plants It can be prepared as an easy 30% (weight) solution. Has a degree of ethoxylation greater than 5 Bis-AQA surfactants are sometimes present in liquid form and are therefore 100% Can be given as a substance. In addition to beneficial handling properties, as a highly concentrated solution The availability of bis-AQA surfactants offers substantial economic advantages in shipping costs .   Further, there is no composition containing a soil dispersant polymer and a bis-AQA surfactant. Additional superior cleaning and cleaning compared to products containing any of these technologies alone And whiteness performance. Especially clay / mud dirt There is an increase in detergency performance on dirt found in dirt and socks. The polymer dispersant is For crystal growth suppression, particle dirt release peptization, redeposition prevention and dirt solubilization Therefore, the total cleaning power is increased. Without wishing to be limited by theory, bis-AQA The benefits of the dirt dispersant polymer system are that (1) AQA acts on the stain surface to Minimizes the formation and lifts the calcium soap present, thereby improving (2) AQA provides solubilization to deep soils On the other hand, the polymer acts as a “greasing shuttle” to solubilize AQA This is believed to be the result of removing the fractions and dispersing them in the washing solution.   A. Maleate and F.I. J. Issued on August 15, 1995 to Loprest U.S. Pat. No. 5,441,541 discloses an anionic surfactant / cationic interface. It relates to an activator mixture. A. P. Murphy, R.A. J. M. Smith and M.S. P . British Patent No. 2,040,990 issued to Brooks on September 3, 1980 The book relates to ethoxylated cationic surfactants in laundry detergents.   None of the existing technologies provide all of the advantages and benefits of the present invention .                                Disclosure of the invention   The present invention relates to a soil dispersant polymer, a non-AQA surfactant and a compound of the formula (Where R¹Is linear, branched or substituted C₈~ C₁₈Alkyl, alkenyl, aryl , An alkanyl, ether or glycityl ether moiety;^TwoIs C₁~ C_Three An alkyl moiety;^ThreeAnd R^FourCan be independently varied and hydrogen, methyl and X is an anion, A and A 'can be independently varied and each is C₁~ C_FourAlkoxy, wherein p and q can vary independently and are in the range of 1 to 30 Is an integer of An effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cation field Compositions prepared by including or combining surfactants (bis-AQA vs. soil) Wherein the weight ratio of the dispersant polymer is in the range of about 1:11 to about 1:14). .   These features, aspects and advantages of the present invention and other features, aspects and aspects And advantages will be apparent to one of ordinary skill in the art from reading the present disclosure.                      BEST MODE FOR CARRYING OUT THE INVENTION   The specification particularly points out and distinctly claims the invention without departing from the spirit and scope of the invention. It is believed that the invention will be better understood from the following description.   All percentages are by weight of the total composition unless otherwise indicated. All ratios Percentages are weight ratios unless otherwise indicated. "Include" used here is the final result Means that other steps and other ingredients that do not affect the water content can be added. This Include the terms “consisting of” and “consisting essentially of”.   All references are incorporated herein by reference. The citation of the literature is It is not an admission that it is considered a decision regarding the availability of the claimed invention as prior art.   Surprisingly, a certain proportion of soil dispersant polymer and bis-AQA surfactant Compositions containing, compared to products containing either technology alone Has been found to be capable of providing excellent cleaning and whiteness performance. Was. In particular, there is an increase in detergency performance for clay / mud soil and soil on socks . This surprising benefit is due to the weight ratio of bis-AQA to soil dispersant polymer of about 1:11. From about 1:14, preferably from about 1:12 to about 1:13. Is.Soil dispersant polymer   The composition of the present invention comprises a soil dispersant polymer. The dirt dispersant polymer is the composition of the present invention. 5-20% by weight, preferably 10-15% by weight, more preferably 13-14% by weight It is present in an amount of% by weight. Preferred dispersants for use herein include high molecular weight polymers Carboxylate.   The polymeric polycarboxylate material is a suitable unsaturated monomer (preferably in acid form) Can be produced by polymerizing or copolymerizing Suitable polymeric polycarboxy Unsaturated monomeric acids that can be polymerized to produce the Formic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesa Conic acid, citraconic acid and methylene malonic acid. Vinyl methyl ether Monomer seg that does not contain carboxylate groups such as ter, styrene, ethylene That the polymer is present in the polymeric polycarboxylates of the present invention. It is preferred if the pigment does not constitute more than 40% by weight.   Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. here Such acrylic acid based polymers that are useful in It is a water-soluble salt of luic acid. The average molecular weight of such polymers in the acid form is preferably 2 20,000 to 10,000, more preferably 4,000 to 7,000, most preferred 4,000 to 5,000. With such a water-soluble salt of acrylic acid polymer Thus, for example, alkali metal salts, ammonium salts and substituted ammonium salts Can be mentioned. Such soluble polymers are known substances. This kind of po The use of acrylates in detergent compositions has been described, for example, on March 7, 1967. Row's Deal is disclosed in U.S. Pat. No. 3,308,067.   Acrylic / maleic acid based copolymers are also preferred soil dispersants. May be used. Such materials include copolymers of acrylic acid and maleic acid. And water-soluble salts of coalescing. The average molecular weight of such copolymers in the acid form is preferred. 2,000 to 100,000, more preferably 5,000 to 75,000 , Most preferably from 7,000 to 65,000. In such a copolymer, The ratio of acrylate segment to maleate segment is generally from 30: 1. It will be 1: 1, more preferably 10: 1 to 2: 1. Such acrylic acid / As the water-soluble salt of the maleic acid copolymer, for example, alkali metal salts, ammonium And substituted ammonium salts. This kind of soluble acryle The salt / maleate copolymer is disclosed in European Patent Application No. 6/15/15/1982. No. 6915 and EP 193,360 published Sep. 3, 1986. book (Such polymers containing hydroxypropyl acrylate are also described) Is a substance. Still other useful dispersants include maleic acid / acrylic acid / vinyl Alcohol terpolymer. Such substances, for example, acrylic acid A 45/45/10 terpolymer of maleic acid / maleic acid / vinyl alcohol is also EP 1 93,360.Bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant   The second essential component of the present invention has the formula (Where R¹Is carbon number 8-18, preferably carbon number 8-16, most preferably carbon Linear, branched or substituted alkyl, alkenyl, aryl, alka having a prime number of 8 to 14 Reel, ether, glycityl ether moiety;^TwoIs an alkyl group having 1 to 3 carbon atoms. A kill group, preferably methyl;^ThreeAnd R^FourCan change independently and hydrogen (preferably X) selected from the group consisting of methyl and ethyl;^-Gives electrical neutrality Enough chloride, bromide, methyl sulfate, sulfate, etc. A and A 'can vary independently and each has C₁-C_FourAlkoxy, especially d Selected from toxic, propoxy, butoxy and mixtures thereof; , Preferably 1 to 15, more preferably 1 to 8, more preferably 1 to 4, q is 1 to 30, preferably 1 to 15, more preferably 1 to 8, and even more preferably 1 -4, most preferably both p and q are 1) An effective amount of a bis-AQA surfactant.   Hydrocarbyl substituent R¹Is C₈~ C₁₂, Especially C₈~ C_TenBis-AQA The compound has a faster dissolution rate of detergent granules compared to longer chain length materials, especially under cold water conditions. Increase the degree. Therefore, C₈~ C₁₂Bis-AQA surfactants are available from formulators May be preferred. Bis-AQ used to prepare finished laundry detergent compositions The amount of the surfactant A is 0.3 to 4% by weight, preferably 0.5 to 2% by weight, more preferably Preferably it can be 0.8-1.2% by weight. As already mentioned, screw-AQ The weight ratio of A to soil dispersant polymer is from about 1:11 to about 1:14, preferably about 1: 1. : 12 to about 1:13.   The weight ratio of bis-AQA to percarbonate bleach was 1: 100 to 5: 1, Preferably within the range of 1:60 to 2: 1, most preferably 1:20 to 1: 1. is there.   The present invention is directed to improving the performance of cleaning compositions containing other optional ingredients. An "effective amount" of the bis-AQA surfactant is used. Where the “effective amount” of the screw -AQA surfactant is a cleansing agent for at least some of the target stains and stains. 90% confidence in the performance of leaning compositions, directionally or significantly Means an amount that is sufficient to improve with either. In this way, the target In compositions that include food stains, the prescriber may have a Use sufficient bis-AQA to improve leaning performance at least directionally Will be. Similarly, in compositions where the target comprises clay soil, the prescriber To at least directionally improve the cleaning performance against such stains. Sufficient bis-AQA will be used.   Bis-AQA surfactant achieves at least directional improvement in cleaning performance May be used in combination with other detergent surfactants in amounts effective to do so. Cloth laundry composition In the field, such "consumption" depends only on the type and intensity of stains and stains. However, it can be changed according to the washing water temperature, the washing water capacity and the type of washing machine.   For example, 45-83 liters of water in a wash bath, a wash cycle of 10-14 minutes and Top-loaded vertical axis US type automatic washing machine using wash water temperature of 10 ° C to 50 ° C The bis-AQA surfactant is preferably 2 ppm to 50 ppm, more preferably 5 ppm to 2 ppm. It is preferable to add 5 ppm to the cleaning solution. 50ml to 150ml per washing load Based on the usage rate, this is the case for heavy duty liquid laundry detergents The concentration (by weight) of the bis-AQA surfactant in the product is 0.1% to 3.2%, preferably It is converted to 0.3% to 1.5%. Use rate of 60g to 95g per washing load ("Compact") granular laundry detergent (density higher than 650 g / l) In the case of), this means that the bis-AQA surfactant concentration in the product (by weight) is 0.2%. To 5.0%, preferably 0.5% to 2.5%. 80g per load Based on a usage rate of 100 g, the spray-dried granules (ie, "fluffy", (Density less than 650 g / l), this is the product of the bis-AQA surfactant The concentration (weight) is converted to 0.1% to 3.5%, preferably 0.3% to 1.5%. .   For example, 8 to 15 liters of water in a washing bath, 10 to 60 minutes of washing cycle and washing A front-mounted horizontal axis European type washing machine with a water purification temperature of 30 ° C to 95 ° C The amount of the bis-AQA surfactant is 13 ppm to 900 ppm, preferably 16 pp. It is preferable to add m to 390 ppm to the cleaning liquid. 45 ml per washing load Based on a usage rate of 270 ml, this is the same for heavy duty liquid laundry detergents. In the case, the concentration of bis-AQA surfactant in the product (weight) is 0.4% to 2.64%, Preferably, it is converted to 0.55% to 1.1%. 40 g to 210 per washing load g ("compact") granular laundry detergent (650 g / g) In the case of densities higher than 1, this is the product concentration of the bis-AQA surfactant in the product ( (Weight) 0.5% to 3.5%, preferably 0.7% to 1.5%. load Spray dried granules (i.e., " "Fluffy", with a density of less than 650 g / l) Surfactant concentration in the product (weight) 0.13% to 1.8%, preferably 0.18% to Converted to 0.76%.   For example, 26-52 liters of water in a washing bath, 8-15 minutes of washing cycle and washing Top-loading vertical axis Japanese type automatic washing machine using water purification temperature 5 ℃ ~ 25 ℃ , Bis-AQA surfactant 1.67 ppm to 66.67 ppm, preferably 3 p It is preferable to mix pm to 6 ppm in the cleaning liquid. 20ml-3 per washing load Based on 0 ml usage rate, this is the case for heavy duty liquid laundry detergent Has a bis-AQA surfactant concentration in the product of 0.25% to 10% by weight, preferably Or 1.5% to 2%. Usage rate of 18g to 35g per washing load ("Compact") granular laundry detergent (density higher than 650 g / l) In the case of) this is the product concentration of bis-AQA surfactant in the product (weight) 0.25 % To 10%, preferably 0.5% to 1.0%. 30g per load Based on a 40 g use rate, the spray-dried granules (ie, "fluffy", dense (Less than 650 g / l), this is the concentration of bis-AQA surfactant in the product. The degree (weight) is converted to 0.25% to 10%, preferably 0.5% to 1%.   As can be seen from the above, the bis-AQA interface used in the field of machine washing and laundering The amount of activator may vary depending on user habits and practices, and the type of washing machine. Wear. However, in the art, one of the previously recognized bis-AQA surfactants has been identified. An advantage that has not been noted is that other surfactants in the finished composition (typically anionic surfactants) Or relatively small amounts with respect to anionic / nonionic surfactant mixtures) At least directional modification of performance over a wide range of dirt and stains, even when used Ability to give good. This means that various cationic surfactants can be stoichiometric or Should be distinguished from other compositions in the vicinity in combination with anionic surfactants. You. Generally, in the practice of the present invention, a bis-AQA counter anion in a laundry composition The weight ratio of surfactants is from 1:70 to 1: 2, preferably from 1:40 to 1: 6, Preferably in the range of 1:30 to 1: 6, most preferably in the range of 1:15 to 1: 8 is there. Laundry compositions containing both anionic and nonionic surfactants The weight of bis-AQA versus mixed anionic surfactant / nonionic surfactant The ratio is in the range from 1:80 to 1: 2, preferably 1:50 to 1: 8.   Anionic surfactant, optional nonionic surfactant and betaine, sultaine And various other cleaning compositions containing special surfactants such as amine oxides Alternatively, an effective amount of a bis-AQA surfactant can be formulated using the method of the present invention. This Compositions such as, but not limited to, hand dishwashing products (especially liquids or gels), Hard surface cleaner, shampoo, personal cleansing solid, laundry solid And the like. Variations in the habits and practices of users of such compositions About 0.25 to about 5% by weight of bis-AQA surfactant, Alternatively, about 0.45 to about 2% by weight may be satisfactory in such compositions. Again, as in granular and liquid laundry compositions, it is present in such compositions The weight ratio of bis-AQA surfactant to other surfactants depends on the anionic surfactant Low, ie, sub-stoichiometric. Preferably such cleaning The composition is a bis-AQA / surfactant as previously described for a machine laundry composition. Including ratio.   In contrast to other cationic surfactants known in the art, the bis-alkoxys of the present invention Since cationic surfactants have sufficient solubility, all nonionic surfactants Mixed surfactants containing less and for example alkyl sulphate surfactants Can be used with the system. This is especially true under North American and Japanese operating conditions. Types of detergent compositions usually designed for use in several types of top-loading automatic washing machines This can be an important consideration of the prescriber of the product. Typically, like this A suitable composition has a weight ratio of anionic to nonionic surfactant of about 25: 1. It will include about 1:25, preferably about 20: 1 to about 3: 1. This is Typically, the ratio of anionic surfactant to nonionic surfactant is about 10: 1 to 1:10, In contrast to European formulations which will preferably comprise from about 5: 1 to about 1: 1 There is. Preferred ethoxylated cationic surfactants of the present invention are Akzo Nove Available from Le Chemicals Company under the trade name ETHOQUAD . Alternatively, such materials can be synthesized using a variety of different reaction schemes as follows: ("EO" is -CH_TwoCH_TwoO-unit).Scheme 1 Scheme 2 Scheme 3 Scheme 4             The economic reaction scheme is as follows.Scheme 5   The following parameters summarize any preferred reaction conditions of Scheme 5. Anti The corresponding step 1 is preferably performed in an aqueous medium. The reaction temperature is typically 14 It is in the range of 0 to 200 ° C. Reaction pressure is 50-1000 psig. salt A base catalyst, preferably sodium hydroxide, can be used. The reactant molar ratio is 2: 1 to 1: 1 alkyl to alkyl sulfate. The reaction is preferably carried out at C₈ ~ C₁₄This is performed using the sodium salt of an alkyl sulfate. Ethoxylation step and fourth The grading step is performed using normal conditions and reactants.   Under some circumstances, Reaction Scheme 5 shows that the aqueous reaction is sufficient to prepare the gel. Produce a product that is soluble in the reaction medium. The desired product can be recovered from the gel, The following alternative two-step synthesis scheme 6 may be more desirable under commercial circumstances . The first step in Scheme 6 is performed in the same manner as in Scheme 5. The second step (Etoki Is preferably carried out using an acid such as ethylene oxide and HCl. This gives a quaternary surfactant. As shown below, Chloroethanol is reacted to give the desired bishydroxyethyl derivative Can also be given.   In the case of Reaction Scheme 6, the following parameters are optional for the first step: Summarize the reaction conditions. The first step is preferably performed in an aqueous medium. Reaction temperature Is typically in the range of 100-230 ° C. The reaction pressure is 50-100 0 psig. A base, preferably sodium hydroxide, is generated during the reaction HSO_FourOr excess amine can be reacted with an acid Can also be used for The molar ratio of amine to alkyl sulfate is typically 10: 1 to 1: 5, preferably 5: 1 to 1: 1.1, more preferably 2: 1 From 1: 1. In the product recovery step, the desired substituted amine is simply As a separate phase from the neutral reaction medium (in which the desired substituted amine is insoluble) Let it. The second step of the method is performed under normal reaction conditions. Screw-AQ Further ethoxylation and quaternization to provide the A surfactant is performed using standard reaction conditions. Perform under the condition.   Scheme 7 optionally employs standard ethoxy to achieve monoethoxylation. Can be carried out using ethylene oxide under silicidation conditions (but without catalyst) You.   The following illustrates these additional reaction schemes ("EO" is -CH_Two CH_TwoO-unit). In this reaction, an inorganic base, an organic base or excess Any of the amine reactants of_FourUsed to neutralize .Scheme 6 Scheme 7   The following merely further illustrate some of the above reactions for the convenience of the formulator, It is not intended to be limiting.Synthetic A Production of N, N-bis (2-hydroxyethyl) dodecylamine   19.96 g of sodium dodecyl sulfate (0.2 g) was added to a glass autoclave liner. 06921 mol), 14.55 g (0.1384 mol) of diethanolamine, 5 7.6 g (0.095 mol) of 0% by weight sodium hydroxide solution and distilled H_TwoO7 Add 2 g. Glass liner in 500ml stainless steel rocking autoclave And heated to 160-180 ° C. under 300-400 psig nitrogen for 3-4 hours I do. The mixture was cooled to room temperature and the liquid content of the glass liner was washed with chloroform 80. Pour along with ml into a 250 ml separatory funnel. Shake the funnel well for several minutes, then mix Separate objects. Discharge the lower layer of chloroform and evaporate chloroform to form Get things.Synthetic B Production of N, N-bis (2-hydroxyethyl) dodecylamine   One mole of sodium dodecyl sulfate was prepared by the method described in Synthesis A in the presence of a base in the presence of ethanol. Reaction with 1 mol of amine. The obtained 2-hydroxyethyl dodecylamine Is recovered and reacted with 1-chloroethanol to produce the title compound.Synthetic C Production of N, N-bis (2-hydroxyethyl) dodecylamine   19.96 g of sodium dodecyl sulfate (0.2 g) was added to a glass autoclave liner. 06921 mol), ethanolamine 21.37 g (0.3460 mol), 50 7.6 g (0.095 mol) by weight of sodium hydroxide solution and distilled H_TwoO72 Add g. Glass liner in 500ml stainless steel rocking autoclave Seal and heat to 160-180 ° C. under 300-400 psig nitrogen for 3-4 hours You. The mixture was cooled to room temperature and the liquid content of the glass liner was washed with 80 ml of chloroform. Into a 250 ml separatory funnel. Shake the funnel well for a few minutes, then Allow the mixture to separate. Drain the lower layer of chloroform and evaporate the chloroform Obtain the product. The product is then heated at 120-130 ° C. in the absence of a base catalyst. React with one molar equivalent of ethylene oxide to produce the desired end product.   The bis-substituted amine prepared in the above synthesis can be further ethoxylated by standard methods. Book Quaternization with alkyl halides to produce inventive bis-AQA surfactants Is conventional.   As noted above, the following are non-limiting of the bis-AQA surfactants used herein. This is a specific example. Alkoxy described herein in the case of bis-AQA surfactant Degree of silicification is a common practice for normal ethoxylated nonionic surfactants. Therefore, it should be understood that it is reported as an average. This is because the ethoxylation reaction Typically, a mixture of substances having different degrees of ethoxylation is prepared. This , The total EO value other than an integer, for example, “EO2.5”, “EO3.5” It is not uncommon to report. ^★Ethoxy (optionally end-capped with methyl or ethyl)   Highly preferred bis-AQA compounds for use herein are of the formula (Where R¹Is C₈~ C₁₈Hydrocarbyl and mixtures thereof, preferably C₈ , C_Ten, C₁₂, C₁₄Alkyl and mixtures thereof, where X is the charge balance A convenient anion to give, preferably chloride) Having. Regarding the general bis-AQA structure, in a preferred compound, R¹Is coconut (C₁₂~ C₁₄Alkyl) fraction derived from fatty acids,^TwoIs methyl And ApR^ThreeAnd A'qR^FourAre monoethoxy, so this preferred type Are listed herein as "CocoMeEO2" or "Bis-AQ". A-1 ".   Other bis-AQA surfactants useful herein include those of the formula (Where R¹Is C₈~ C₁₈Hydrocarbyl, preferably C₈~ C₁₄Alkyl Independently p is 1-3, q is 1-3, R^TwoIs C₁~ C_ThreeAlkyl, preferred Or X is an anion, especially chloride or bromide) Compounds.   Other compounds of the above class include ethoxy (CH_TwoCH_TwoO) Unit (EO) is Toxic (Bu), isopropoxy [CH (CH_Three) CH_TwoO] and [CH_TwoCH (CH_ThreeO] unit (i-Pr) or n-propoxy unit (Pr), or EO And / or Pr and / or i-Pr mixtures. I can do it.   Highly preferred bis-A for use in under built formulations The QA compound has a formula wherein p and / or q is an integer in the range of 10-15. You. This compound is particularly useful in laundry hand-wash detergent compositions.Non-AQA detergent surfactant   In addition to the bis-AQA surfactant, the composition of the present invention preferably comprises a non-AQA It further contains a surfactant. Non-AQA surfactants include essentially any anion Surfactants, nonionic surfactants or additional cationic surfactants may also be mentioned. No.Anionic surfactant   Non-limiting examples of anionic surfactants useful herein, typically in amounts of 1 to 55% by weight As usual C₁₁~ C₁₈Alkylbenzenesulfonate ("LAS") and And primary ("AS"), branched and random C_Ten~ C₂₀Alkyno sulfate , The formula CH_Three(CH_Two)_x(CHOSO_Three ^-M⁺) CH_ThreeAnd CH_Three(CH_Two)_y(CH OSO_Three ^-M⁺) CH_TwoCH_ThreeWherein x and (y + 1) are at least 7, preferably Or an integer of at least 9 and M is a water-solubilizing cation, especially sodium) C_Ten~ C₁₈Secondary (2,3) alkino sulfates, unsaturated sulfates, eg For example, oleino sulfate, C₁₂~ C₁₈α-sulfonated fatty acid ester, C_Ten ~ C₁₈Sulfated polyglycoside, C_Ten~ C₁₈Alkyl alkoxy sulfate (" AE_xS "; especially EO1-7 ethoxysulfate), and C_Ten~ C₁₈Archi Alkoxycarboxylate (especially EO1-5 ethoxycarboxylate) No. C₁₂~ C₁₈Betaine and sulfobetaine ("sultaine"), C_Ten ~ C₁₈Amine oxide can also be included in the total composition. Normal C_Ten~ C₂₀Soap, May be used. If high foaming properties are desired, the branched C_Ten~ C₁₆Soap used You may. Other commonly useful surfactants are described in the standard text.Nonionic surfactant   Non-limiting examples of nonionic surfactants useful herein, typically in amounts of 1 to 55% by weight Include alkoxylated alcohols (AE) and alkyl phenols, polyphenols Droxy fatty acid amide (PFAA), alkyl polyglycoside (APG), C_Ten ~ C₁₈Glycerol ether.   More specifically, primary and secondary aliphatic alcohols and ethylene oxide 1 The condensate (AE) with 25 moles is used as a nonionic surfactant in the present invention. It is suitable for. The alkyl chain of the aliphatic alcohol may be linear or branched primary or It can be secondary and generally has from 8 to 22 carbon atoms. 8 carbon atoms 20, more preferably an alcohol having an alkyl group having 10 to 18 carbon atoms and an alcohol 1 to 10 moles, preferably 2 to 7 moles, most preferably 2 to 1 mole per mole of coal Condensates with 5 moles of ethylene oxide are preferred. Commercial non-ionic field of this kind Examples of surfactants include those marketed by Union Carbide Corporation Tergitol^TM) 15-S-9 (C₁₁~ C_FifteenLinear alcohol Condensation product of ethylene and 9 moles of ethylene oxide) and tertitol^TM24-L-6N MW (C with narrow molecular weight distribution₁₂~ C₁₄Primary alcohol and ethylene oxide Condensate with 6 mol); commercially available from Shell Chemical Company Odol (Neodol^TM) 45-9 (C₁₄~ C_FifteenLinear alcohol and ethylene oxide Condensate with 9 mol), neodol^TM23-3 (C₁₂~ C₁₃Linear alcohol and ethyl Condensate with 3 mol of lenoxide), neodol^TM45-7 (C₁₄~ C_FifteenLinear Al Condensation product of coal and 7 mol of ethylene oxide) and neodol^TM45-5 (C₁₄ ~ C_FifteenCondensation product of linear alcohol and 5 mol of ethylene oxide), The Procta -Kilo marketed by End Gambling Company^TM) E OB (C₁₃~ C_FifteenCondensate of alcohol and 9 moles of ethylene oxide), and Genapol LAO3O or O5O (commercially available from Kist) C₁₂~ C₁₄Condensates of alcohols with 3 or 5 moles of ethylene oxide) It is. The preferred range of HLB in these AE nonionic surfactants is 8-11. , Most preferably 8 to 10. Propylene oxide and butylene oxide And a condensate thereof may also be used.   Another type of nonionic surfactant preferred for use herein is of the formula (Where R¹Is H or C_{1 ~Four}Hydrocarbyl, 2-hydroxyethyl, 2- Hydroxypropyl or a mixture thereof;^TwoIs C_{Five ~ 31}Hydrocarbyl And Z is a linear hydro hydride having at least three hydroxyls directly attached to the chain. Polyhydroxyhydrocarbyl having carbyl chain, or alkoxylation thereof Conductor) Is a polyhydroxy fatty acid amide surfactant. Preferably, R¹Is methyl Yes, R^TwoIs C_{11 ~ 15}Alkyl or C_Fifteen~ C₁₇Alkyl or alkenyl straight chain For example, coconut alkyl or a mixture thereof, wherein Z is a reductive amination residue. In the reaction, reducing sugars such as glucose, fructose, maltose, lactose Derived from A typical example is C₁₂~ C₁₈And C₁₂~ C₁₄N-methyl gluka Mido. U.S. Patent Nos. 5,194,639 and 5,298 636. N-alkoxy polyhydroxy fatty acid amides can also be used. Wear. See U.S. Pat. No. 5,489,393.   Further, a hydrophobic group having 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, and 1.3 to Contains 10, preferably 1.3-3, most preferably 1.3-2.7 saccharide units Polysaccharides (eg, polyglycosides) alkyl polysaccharides having a hydrophilic group, for example, No. 4,565,647 to Lenado, issued Jan. 21, 1986. The disclosure is useful in the present invention as a nonionic surfactant. 5 carbon atoms or 6 can be used, for example, glucosyl in place of the glucosyl moiety. , Galactose and galactosyl moieties can be used (optionally hydrophobic The groups are linked at the 2-, 3-, 4-, etc. position, thus forming a glucoside or galactoside. Gives glucose or galactose as opposed to sid). Intersugar linkage Can be, for example, position 1 of the additional sugar unit and positions 2, 3, 4, and / or on the previous sugar unit. Or sixth place.   Preferred alkyl polyglycosides have the formula                   R^TwoO (C_nH_2nO)_t(Glycosyl)_x (Where R^TwoIs alkyl, alkylphenyl, hydroxylalkyl, hydroxy Selected from the group consisting of silalkylphenyl, and mixtures thereof, and The alkyl group has 10 to 18, preferably 12 to 14 carbon atoms; Or 3, preferably 2; t is 0-10, preferably 0; x is 1.3 -10, preferably 1.3-3, most preferably 1.3-2.7) Having. Glycosyl is preferably derived from glucose. These compounds First produce alcohol or alkyl polyethoxy alcohol for production And then react with glucose or a glucose source to produce glucosides. (Bond at position 1). Additional glycosyl units are then added to their 1-position and the previous glycosyl. The 2-, 3-, 4- and / or 6-position of the cosyl unit, preferably mainly 2 Can be combined between   Polyethylene oxide condensate of alkylphenol, polypropylene oxide Condensates and polybutylene oxide condensates are also nonionics of the surfactant systems of the present invention. Suitable for use as surfactants, polyethylene oxide condensates are preferred. New These compounds include 6-14 compounds in either a linear or branched configuration. Having an alkyl group having, preferably, 8 to 14 carbon atoms A condensate of a kill phenol and an alkylene oxide is exemplified. In a preferred embodiment In this case, ethylene oxide is used in an amount of 2 to 25 moles per mole of alkylphenol. , More preferably in an amount equal to 3 to 15 moles. Commercial non-ion of this kind As a surfactant, Igepar commercially available from GAF Corporation was used. Le (Igepal^TM) By CO-630 and ROHM End Haas Company Triton (Triton^TM) X-45, X-114, X-100, And X-102. These surfactants are usually alkylphenol Alkoxylate (eg, alkylphenol ethoxylate).   Hydrophobicity formed by condensation of propylene oxide with propylene glycol Condensates of the ionic base with ethylene oxide are also useful in the present invention as additional nonionic surfactants. It is suitable for use as. The hydrophobic portion of these compounds is preferably It has a molecular weight of 1500 to 1800 and will be water insoluble. The port to this hydrophobic part The addition of a loxyethylene moiety tends to increase the water solubility of the molecule as a whole And the liquid properties of the product are such that the polyoxyethylene content is 50% of the total weight of the condensate (Corresponding to condensation with up to 40 moles of ethylene oxide). Examples of such compounds include commercially available products marketed by BASF Pluronic^TM) Certain surfactants.   Ethylene and products from the reaction of propylene oxide with ethylenediamine The condensate with the oxide is also a nonionic surfactant of the nonionic surfactant system of the present invention. It is suitable for use. The hydrophobic part of these products is ethylenediamine And an excess of propylene oxide, generally having a molecular weight of 2500 ~ 3000. This hydrophobic part is formed by a condensation product of polyoxyethylene 40-80. Ethylene to the extent that it contains by weight and has a molecular weight of 5,000 to 11,000. Condenses with oxides. An example of this type of nonionic surfactant is BASF Commercially available Tetronic^TMSome) compound Things.Additional cationic surfactant   Suitable cationic surfactants are preferably at least one ester (ie, , -COO-) bond and at least one positively charged group. To It is a water-dispersible compound.   Other suitable cationic surfactants include Mono C₆~ C₁₆, Preferably C₆~ C_Ten N-alkyl or alkenyl ammonium surfactant (the remaining N-position is methyl , Substituted with a hydroxyethyl or hydroxypropyl group) Ammonium surfactants. Other goodies, including choline ester surfactants Suitable cationic ester surfactants are described, for example, in US Pat. No. 4,228,042. Nos. 4,239,660 and 4,260,529. You.Optional detergent ingredients   The following are illustrative of various other optional ingredients that may be used in the compositions of the present invention. But do not try to limit it.builder   The detersive builder is optionally, but preferably, for example, minerals in the wash water. To help control material hardness, especially Ca and / or Mg hardness, Can be incorporated into the composition to facilitate removal of particulate soil from the surface. builder Produces a soluble or insoluble complex with hardness ions, for example, by various mechanisms. The surface of the article to be cleaned. It can be operated by providing a surface that is convenient for ion precipitation. Builder amount , Can vary widely depending on the end use and physical form of the composition. Builder detergent Typically contains at least 1% of a builder. Liquid formulations are typically 5% to 50%, more typically 5% to 35%. Granular formulations are typical Has a builder of from 10 to 80%, more typically from 15 to 50% by weight of the detergent composition. Including Less or more builders are not excluded. For example, a certain detergent Additives or high surfactant formulations may be free of builders.   Suitable builders here are phosphates and polyphosphates, especially Salts, silicates, for example, water-soluble and hydrated solid forms and chain structures, layer structures Or having a three-dimensional structure, as well as amorphous solid or unstructured liquid types, Nate, bicarbonate, sesquicarbonate and sodium carbonate, sesquichar Carbonate minerals other than sodium silicate, aluminosilicate, organic mono-, di- , Tri- and tetracarboxylates, especially in acid form, sodium salt form, potassium Water-soluble non-surfactant carboxylates in salt or alkanol ammonium salt form And oligomers or water-soluble low molecular weight polymer carboxylates, for example, It can be selected from the group consisting of aliphatic and aromatic types, and phytic acid. These can be used, for example, by borate for pH buffering purposes or by sulfates, especially sulfates. Detergent composition containing sodium acid salt and stable surfactant and / or builder May be supplemented by other fillers or carriers that may be important for product engineering .   Builder mixtures (sometimes called "builder systems") can be used and typically Are two or more conventional builders (optionally chelating agents, pH buffers or (Complemented by filler) (these latter substances are generally noted here in their amounts). I will explain separately when I put it). Relative amounts of surfactants and builders in the detergent With respect to the preferred builder system, typically the weight of surfactant to builder Formulated in a ratio of 60: 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. : 1.0.   Often preferred P-containing detergency builders where permitted by law Without limitation, tripolyphosphate, pyrophosphate, glassy polymer Polyphosphates exemplified by metaphosphates and alkalis of phosphonic acids Metal salts, ammonium salts and alkanol ammonium salts.   Suitable silicate builders include alkali metal silicates, especially SiO_Two: Na_TwoLiquids and solids with an O ratio of 1.6: 1 to 3.2: 1 (especially automatic dishwashing) For example, the solid hydrate 2 silicate commercially available as Britesyl H20, and the layer Silicates such as H.I. P. US Patent issued May 12, 1987 to Rick No. 4,664,839. NaSKS-6 (time (Abbreviated as “SKS-6”) is a crystalline layered a commercially available from Hoechst. Δ-Na without Luminium_TwoSiO_FiveForm silicate and granular laundry composition Are particularly preferred. German Patent DE-A 3,417,649 and DE -See the production method of A 3,742,043. Other layered silicates, for example, General formula NaMSi_xO_{2x + 1}・ YH_TwoO (where M is sodium or hydrogen , X is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 Are also or can be used here. Hoechst? These layered silicates include NaSK as α, β and γ layer silicate forms. S-5, NaSKS-7 and NaSKS-11. Other silicate For example, magnesium silicates may also be useful, and they may be more granular. Serves as a bleaching agent, as a stabilizer for bleach, and as a component of foam control system be able to.   No. 5,427,711 to Sakaguchi et al. On June 27, 1995. The following general formula xM in chain structure and anhydride form as taught in the specification:_TwoO ・ ySi O_TwoZM'O (where M is Na and / or K and M 'is Ca and / or Or Mg; y / x is 0.5-2.0 and z / x is 0.005-1. 0) or a synthetic crystalline ion exchange material having a composition represented by Hydrates are suitable for use herein.   Sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other cars Advantages of bonate minerals, such as trona or sodium carbonate and calcium carbonate Multiple salts, for example, composition 2Na_TwoCO_Three・ CaCO_ThreeHaving (anhydrous At some time), and calcium carbonates, such as calcite, aragonite and battera Sites, especially those with a high surface area compared to compact calcite, are May be useful for use in synthetic detergent solids, As a carbonate builder, a German patent issued on November 15, 1973 Alkaline earth metals and alkalis as disclosed in Japanese Patent Application No. 2,321,001. Limetal carbonates.   Aluminosilicate builders are particularly useful in granular detergents, Or gel. For this purpose, the empirical formula [M_z(AlO_Two)_z(SiO_Two )_v] XH_TwoO (where z and v are integers of at least 6; The ratio is in the range of 1.0 to 0.5 and x is an integer of 15 to 264) Those are suitable. Aluminosilicates can be crystalline or amorphous. And can be naturally occurring or synthetically derived. Aluminosilicate Is disclosed in U.S. Pat. No. 3,985, issued October 12, 1976 to Krumel et al. No. 669. Preferred synthetic crystalline aluminosilicate ion Exchange materials include zeolite A, zeolite P (B), zeolite X and zeolite It can be obtained as what is called zeolite MAP to any extent different from pit P. Kula Natural forms, including inotirolite, may be used. Zeolite A has the formula N a₁₂[(AlO_Two)₁₂(SiO_Two)₁₂] XH_TwoO (where x is 20-30, especially 27). Dehydrated zeolites (x = 0-10) may also be used. Preferably, the aluminosilicate has a particle size of 0.1 to 10 μm in diameter.   Suitable organic detergency builders include water-soluble non-surfactant dicarboxylates And polycarboxylate compounds, including tricarboxylates . More typically, the builder polycarboxylate comprises a plurality of carboxylate Group, Preferably it has at least three carboxylate. Carboxylate building Der can be formulated in acid, partially neutral, neutral or overbased forms. Salt form Sometimes alkali metal salts such as sodium, potassium, lithium salts, or Alkanol ammonium salts are preferred. As polycarboxylate builder Ether polycarboxylates such as oxydisuccinate (1964 Berg U.S. Pat. Nos. 3,128,287 and 1972, issued Apr. 7, 1972. See U.S. Pat. No. 3,635,830 to Lamberci et al. U.S. Pat. No. 4,663,071, issued May 5, 1987 to Bush et al. The "TMS / TDS" builder herein; and other ether carboxylates; For example, cyclic compounds and alicyclic compounds, for example, US Pat. No. 3,923,67 No. 9, No. 3,835,163, No. 4,158,635, Nos. 4,120,874 and 4,102,903. Is included.   Other suitable builders are ether hydroxy polycarboxylates, anhydrous maleic Copolymer of formic acid and ethylene or vinyl methyl ether, 1,3,5-tri Hydroxybenzene-2,4,6-trisulfonic acid, carboxymethyloxyco Various types of polyacetic acids such as succinic acid, ethylenediaminetetraacetic acid, and nitrilotriacetic acid Potassium metal salts, ammonium salts and substituted ammonium salts, and mellitic acid, Acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, Tyloxysuccinic acid, and their soluble salts.   Citric acid-based builders, such as citric acid and its soluble salts, are For availability from sources and biodegradability, e.g. in heavy duty liquid detergents An important carboxylate builder. Sight rates are especially high for zeolites and Granular compositions can also be used in combination with and / or layered silicates. Oki Sisuccinate, hydroxyiminodisuccinate, and methylglycinedia Acetate is also particularly useful in such compositions and combinations.   Where acceptable, and especially in the formulation of solids for use in hand washing operations , Sodium tripolyphosphate, sodium pyrophosphate, sodium orthophosphate Alkali metal phosphates such as can be used. Phosphonate builder, for example, Ethane-1-hydroxy-1,1-diphosphonate and other known phosphones For example, U.S. Pat. Nos. 3,159,581 and 3,213,030. Specification, 3,422,021, 3,400,148, and No. 3,422,137 can also be used and have desirable anti-scaling properties In some cases.   Certain detergent surfactants or their short-chain homologs also have a builder effect. In the sense of clearly evaluating the formulation, when they have surfactant capabilities, these Are accounted for as detergent surfactants. Preferred type for builder functionality Discloses Bush U.S. Pat. No. 4,566,984, issued Jan. 28, 1986. 3,3-dicarboxy-4-oxa-1,6-hexanediate disclosed in the detailed description And related compounds. As succinic acid builder, C_Five~ C₂₀ Alkyl and alkenyl succinic acids and their salts are mentioned. Succinay Lauryl succinate, myristyl succinate, palmi succinate Tyl, 2-dodecenyl succinate (preferred) and 2-pentadecenyl succinate are also listed. I can do it. Lauryl succinate is described in European Patent Application No. 8 published November 5, 1986. 6200690.5 / 0,200,263. fatty acid, For example, C₁₂~ C₁₈Monocarboxylic acids can also be included in the composition as surfactant / builder substances. Alone or with the builder, in particular sight rate and / or succinate building And can be formulated to provide additional builder activity. other A suitable polycarboxylate is Clutch Feel, published March 13, 1979. Et al., U.S. Pat. No. 4,144,226 and issued Mar. 7, 1967. No. 3,308,067 to Deal. Deal See also U.S. Patent No. 3,723,322.   Another class of inorganic builder substances that can be used are those of the formula (M_x)_iCa_y(CO_Three)_z( In the formula, x and i are integers of 1 to 15, y is an integer of 1 to 10, and z is 2 An integer from 〜25 to M_iAre cations, at least one of which is water-soluble Is a cation and has the formula Σ_{i = 1 ~ 15}(X_i× M_i+ 2y = 2z, the formula is neutral Or "satisfied to have a" balanced "charge). These builders Are referred to herein as "mineral builders." Other than hydration water or carbonate On may be added if the total charge is balanced or neutral. Such a shade The ionic charge or valence effect should be added to the right side of the above equation. Preferably Represents hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon, and Mixtures, more preferably sodium, potassium, hydrogen, lithium, ammonium Water-soluble cations selected from the group consisting of Lium and potassium are highly preferred. Non-limiting examples of non-carbonate anions and Chloride, sulfate, fluoride, oxygen, hydroxide, From the group consisting of iodine, chromates, nitrates, borates and mixtures thereof The choice is given. A preferred builder of this kind in its simplest form is Na_Two Ca (CO_Three)_Two, K_TwoCa (CO_Three)_Two, Na_TwoCa_Two(CO_Three)_Three, NaKCa (C O_Three)_Two, NaKCa_Two(CO_Three)_Three, K_TwoCa_Two(CO_Three)_ThreeAnd their combinations Selected from the group consisting of Particularly preferred substances for the builders described here are crystals Na of any nature modified_TwoCa (CO_Three)_TwoIt is. Suitable builders of the above kind are And further exemplified by any one of the following minerals in natural or synthetic form: Or combinations: Afghanite, Undersonite, Ashcro Fucin Y, Bayer Light, Volka Light, Berbanite, Butulite, Mosquito Nklinite, carbocellite, carletonite, davin, donateite Y, Fairchildite, Ferris Light, Flange Knight, Godfreyite, -Lussac stone, Gilbasite, Gregorianite, Jurassite, Kampha Ugaite Y, Ketonerite, Kannescheid, Reperson Knight Gd, Rio Thai G, Maker Beilite Y, Microsommite, Muroseite, Natrofair tilde Light, Niereleaite, Lemon Dite Ce, Sacrophanite, Shrekkinge Light, Shortite, Slight, Tunisite, Tuscanite, Tyrolite, Bishite Unebite, and zemkolite. Preferred mineral forms include nierreite, Fairchillite and Shortite.bleach   The compositions described herein may contain a bleach. If so, this Such bleaches typically comprise 1% to 30% of the detergent composition, especially for fabric laundering. %, More typically from 5% to 20%.   In one preferred aspect, the bleaching system comprises a source of hydrogen peroxide and a bleaching catalyst. Contains a medium. The production of organic peroxyacids depends on the combination of the bleach activator and the hydrogen peroxide source. Produced by field reactions. Preferred hydrogen peroxide sources include inorganic perhydrates Bleaching agents. In another preferred aspect, the preformed peracid is a combination Mix directly into the product. Hydrogen peroxide source and bleach activator in combination with preformed peracid Compositions containing a mixture with are also contemplated.   Preferred peroxygen bleaches are perhydrate bleaches. Perhydrate While bleach itself has some bleaching ability, good bleach is Formed as a product of the reaction between the released hydrogen peroxide and the bleach activator Present in peracids. Preformed peracids are also contemplated as preferred peroxygen bleaching species.   Examples of suitable perhydrate salts include perborates, percarbonates, perphosphates , Persulfates and persilicates. Preferred perhydrate salts are Always It is an alkali metal salt. Perhydrate salts can be combined with crystalline solids without additional protection. You may mix. However, for certain perhydrate salts, A preferred implementation of a particulate composition such as is better with perhydrate salts in a granular product. Utilize a coated form of the material that provides excellent storage stability.   Sodium perborate has the nominal formula NaBO_TwoH_TwoO_TwoMonohydrate or tetrahydrate of   NaBO_TwoH_TwoO_Two・ 3H_TwoIt can be in the form of O.   Alkali metal percarbonates, especially sodium percarbonate, are distributed in the compositions according to the invention. It is a preferred perhydrate in any case. Sodium percarbonate is 2Na_TwoCO_Three・ 3 H_TwoO_TwoIs an addition compound having the formula corresponding to and commercially available as a crystalline solid I have. Sodium percarbonate, a hydrogen peroxide addition compound, releases hydrogen peroxide when dissolved. It tends to release quite quickly, which can lead to localized high bleach concentrations. Direction may increase. Preferred percarbonate bleaches are from 500 μm to 1 μm. Dry particles having an average particle size in the range of 2,000 μm (less than 10% by weight of Less than 200 μm and less than 10% by weight of the particles are greater than 1,250 μm I).   Percarbonates most preferably provide such compositions with in-product stability. Formulated in a coating form to give. Suitable coating materials that provide in-product stability are water soluble alcohols. It consists of a mixed salt of potassium metal sulfate and carbonate. Such coatings are compatible with coating methods. In the meantime, British Patent No. 1,46 granted to Interlocks on March 9, 1977 No. 6,799, previously described. Mixed salt coating material vs. percarbonate Weight ratio of 1: 200 to 1: 4, more preferably 1:99 to 1: 9, most preferably Also preferably from 1:49 to 1:19. Preferably, the mixed salt has the general formula N a_TwoSO_Four・ N ・ Na_TwoCO_Three(In the formula, n is 0.1-3, preferably n is 0.1. 3 to 1.0, most preferably n is 0.2 to 0.5) With thorium / sodium carbonate.   Silicates (alone or with borate or boric acid or other minerals), Other coatings containing c, oils, fatty soaps can also be used to advantage within the present invention.   Bleaches that can be used without restriction include percarboxylic acid bleaches and their salts. Include. A preferred example of this type of bleach is magnesium monoperoxyphthalate. Hexahydrate, magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4 -Oxoperoxybutyric acid and diperoxidedecanedioic acid. This Such bleaching agents are disclosed in Hartman, U.S. Pat. U.S. Patent Application No. 483,781, filed June 3, 1985 by Barnes et al. No. 740,446, European Patent of Banks et al. Published on February 20, 1985. Application No. 0,133,354 and Chan, published November 1, 1983 And U.S. Pat. No. 4,412,934. Highly preferred Examples of bleaching agents include U.S. Pat. No. 4,633, issued Jan. 6, 1987 to Burns et al. 6-nonylamino-6-oxoperoxyca as described in U.S. Pat. Pronic acid is also included.   Other suitable additional bleaches include light-activated bleaches, such as zinc sulfonates Examples include phthalocyanine and / or aluminum phthalocyanine. Hol See U.S. Pat. No. 4,033,718, issued Jul. 5, 1977 to Combe et al. Teru. If used, detergent compositions will typically include such bleaches, especially sulfones. It will contain 0.025-1.25% by weight of zinc phonocyanine phthalocyanine.   Potassium peroxymonopersulfate is another inorganic perhydrate useful in the present compositions. Salt.   Mixtures of bleaches can also be used.Bleach activator   Bleaching activators are preferred when the compositions of the present invention additionally include a peroxygen bleach. Component. The bleach activator, when present, typically comprises a bleach and a bleach activator. From 0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition comprising It is.   Peroxygen bleach, perborate, and the like are preferably combined with a bleach activator, This means that in situ aqueous solutions of peroxy acids or peracids corresponding to the bleach activators Production (ie, during the cleaning process). Various non-limiting examples of activators include Mao and the like. U.S. Pat. No. 4,915,854 issued Apr. 10, 1990 and U.S. Pat. It is disclosed in U.S. Pat. No. 4,412,934. Nonanoyloxyben Zensulfonate (NOBS) and tetraacetylethylenediamine (TAE) D) Activators are typical and mixtures thereof can also be used. Other references useful here For a typical bleach and activator, see also U.S. Pat. No. 4,634,551. reference.   Highly preferred amide-derived bleach activators have 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 having 6 to 12 carbon atoms;^TwoIs alk having 1 to 6 carbon atoms Ren and R^FiveIs H or alkyl, aryl or alka having 1 to 10 carbon atoms L is a suitable leaving group) belongs to. The leaving group is a nucleophilic attack on the bleach activator by a perhydrolytic anion. Is a group that is displaced from the bleach activator as a result of A preferred leaving group is phenyl It is a sulfonate.   Preferred examples of bleach activators of the above formula include U.S. Pat. No. 4,634,551. (6-Octanamidocapu) as described in the specification (herein incorporated by reference). Loyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxy Benzenesulfonate, (6-decaneamidocaproyl) oxybenzenesulfo And mixtures thereof.   Another type of bleach activator is disclosed in Hodge et al. No. 4,966,723 (hereby incorporated by reference). Consists of a sagin type activator. Highly preferred active agents of the benzoxazine type have the formula belongs to.   Yet another class of preferred bleach activators includes acyllactam activators, especially those of the formula (Where R⁶Is H or an alkyl, aryl, alkoxy ally having 1 to 12 carbon atoms Or alkaryl group) Acylcaprolactam and acylvalerolactam. Highly preferred New lactam activators include benzoylcaprolactam and octanoylcaprol Lactam, 3,5,5-trimethylhexanoylcaprolactam, nonanodolphin Prolactam, decanoylcaprolactam, undecenoylcaprolactam, Nzoylvalerolactam, octanoylvalerolactam, decanoylvalerolactam Tom, undecenoylvalerolactam, nonanoylvalerolactam, 3,5,5 -Trimethylhexanoylvalerolactam and mixtures thereof. Acylcap containing benzoylcaprolactam adsorbed on sodium perborate US Patent issued Oct. 8, 1985 to Sanderson disclosing Lolactam See also U.S. Pat. No. 4,545,784, incorporated herein by reference.Bleaching catalyst   A bleach catalyst is an optional component of the composition of the present invention. If desired, the bleaching compound may Can be catalyzed by manganese compounds. Such compounds are well known in the art, For example, US Pat. No. 5,246,621, US Pat. No. 5,244,59 No. 4, U.S. Pat. No. 5,194,416, U.S. Pat. No. 5,114, No. 606 and European Patent Application Publication No. 549,271 A1, No. 5 49,272A1, 544,440A2 and 544,4 Mention may be made of the manganese-based catalysts disclosed in 90A1. these Preferred examples of the catalyst include Mn^IV _Two(U-O)_Three(1,4,7-trimethyl-1 , 4,7-Triazacyclononane)_Two(PF₆)_Two, Mn^III _Two(U-O)₁(U-O Ac)_Two(1,4,7-trimethyl-1,4,7-triazacyclononane)_Two− ( ClO_Four)_Two, Mn^IV _Four(U-O)₆(1,4,7-triazacyclononane)_Four(C 10_Four)_Four, Mn^IIIMn^IV _Four(U-O)₁(U-OAc)_Two(1,4,7-trimethyl 1,4,7-triazacyclononane)_Two(ClO_Four)_Three, Mn^IV(1,4,7 -Trimethyl-1,4,7-triazacyclononane)-(OCH_Three)_Three(PF₆) , And mixtures thereof. As a bleach catalyst based on other metals Are disclosed in U.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,61. No. 1 discloses the one disclosed. Manganese in combination with various complex ligands Increasing bleaching has also been reported in the following U.S. patents: No. 4,728,455, 5,284,944, 5,2 46,612, 5,256,779, 5,280,117 No. 5,274,147, No. 5,153,161, and And 5,227,084.   In practice, and without limitation, the compositions and methods of the present invention provide for active bleaching in aqueous washes. Laundry fluid that can be adjusted to provide at least about 1 part per 10 million catalyst species 0.1 ppm to 700 ppm, more preferably 1 ppm to 500 pp m.   Cobalt bleach catalysts useful herein are known and are described, for example, in M.S. L. Tobe's Base Hydrolysis of Transition Metal Complexes, "Adv. Inorg. Bioinorg. Mech., (1983) , 2, pp. 1-94. Most preferred cobalt useful here The catalyst has the formula [Co (NH_Three)_FiveOAc] T_y(Where “OAc” is the acetate part Minutes, "T_yIs an anion) with cobalt pentaamine acetate And especially cobalt pentaamine acetate chloride [Co (NH_Three)_FiveOAc] Cl_TwoAnd [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(Here "PAC").   These cobalt catalysts are prepared in known manner, for example, in the above-mentioned Tobe article and there. No. 4,810, issued Mar. 7, 1989 to Diakun et al. , 410 and J.A. Chem. Ed. (1989),66(12), 1043 -45; Synthesis and characterization of inorganic compounds; L. Jolly (Prentice-Ho 1970) pp. 461-463; Inorg. Chem.,18, 1497- 1502 (1979); Inorg. Chem.,21, 2881-2885 (1982). Inorg. Chem.,18Inorg., 2023-2025 (1979); Synthesis, 173-176 (1960); and Journal of Physical Chemistry,56, 22-25 (1952).   In practice, and without limitation, the automatic dishwashing compositions and cleaning methods of the present invention include To provide at least about 1 part / 100 million parts of active bleaching catalyst in the neutral washing medium. The bleaching catalyst species in the washing solution is preferably 0.01 ppm to 25 ppm, more preferably 0.05 ppm to 10 ppm, most preferably 0.1 ppm to 5 ppm. I will get it. In order to obtain such an amount in the washing solution of the automatic dish washing method, the present invention A typical automatic dishwashing composition comprises 0.0005 to 0.2 weight of the cleaning composition. %, More preferably 0.004 to 0.08% by weight of the bleaching catalyst, especially manganese or Will contain a cobalt catalyst.enzyme   Enzymes are protein-based stains and carbohydrate-based from substrates Removal of stains or stains based on triglycerides, escape in fabric washing The detergent composition of the present invention is used for various purposes including prevention of dye transfer and restoration of fabric. Can be combined. Suitable enzymes include any suitable source, e.g., plants, animals, cells. Proteases, amylases, lipases, cellulases of fungal, fungal and yeast origin, Peroxidase, and mixtures thereof. The preferred choice is the factor Eg, pH activity and / or stability optima, thermal stability, active detergents, building Is affected by stability against In this regard, bacterial or fungal enzymes, For example, bacterial amylase and protease, and fungal cellulase are preferred. No.   As used herein, “detergent enzymes” refers to laundry, hard surface cleaning or personal Has a cleaning, stain removal or otherwise beneficial effect in LUCARE detergent composition Means an enzyme. Preferred detergent enzymes are protease, amylase, lipase And hydrolases. The preferred enzymes for washing purposes are limited But not including proteases, cellulases, lipases and peroxidases Can be Amylases and / or proteases are highly preferred for automatic dishwashing No.   Enzymes usually provide a "cleaning effective amount" to a detergent or detergent additive composition. Mix in an amount sufficient to The term "cleaning effective amount" refers to cloth, table Cleaning, stain removal, dirt removal, whitening, deodorization, Means any amount capable of producing a freshness improving effect. Of currently marketed formulations For practical use, typical amounts are up to 5 mg of active enzyme per gram of detergent composition (weight ), More typically 0.01 mg to 3 mg. In other words, the composition is typically Contains 0.001 to 5% by weight of a commercially available enzyme preparation, preferably 0.01 to 1% by weight. Will include. Protease enzymes are usually added to such commercially available formulations with 1 g of composition. 0.005 to 0.1 Anson units (AU) per activity Present in small amounts. For certain detergents, for example, in automatic dishwashing, Minimize the total amount of non-catalytically active materials, thereby reducing spotting / filming Or to increase the active enzyme content of commercial preparations to improve other end results May be desirable. Also, higher amounts of active ingredients are desirable in highly concentrated detergent formulations. There is something new.   Suitable examples of proteases are Bacillus subtilis and B. from certain strains of licheniformis The resulting subtilisin. One suitable protease is Novo Danish ・ Developed by Industries A / S (hereinafter “Novo”) and Esperase It is obtained from a strain of Bacillus having the property. The preparation of this and similar enzymes No. 1,243,784 to Novo. Other suitable Protease as disclosed in EP 130,756A published Jan. 9, 2006 A and EP 303,761A and 1 published April 28, 1987. A protection as disclosed in EP 130,756A published January 9,985. Aase B. Baci as described in WO 9318140A to Novo See also high pH protease from llus sp. NCIMB 40338. Protease One or more other enzymes and enzyme detergents containing reversible protease inhibitors are In WO 9203529A. Other preferred protea WO 9510591A to Procter End Gambling The description is given. When desired, reduced adsorption and increased Proteases with hydrolysis are available from Procter End Gambling in WO It is available as described in 9507791. Here is the preferred detergent for recombinant Trypsin-like proteases are described in WO 9425583 to Novo. Have been.   More particularly, particularly preferred proteases (referred to as "Protease D") are A. Beck et al. Patent Application “Protease-Containing Cleaning Composition” (US Patent Application No. 08 / 322,676) and C.I. Gauche et al. Bleaching Composition Containing Enzyme "(U.S. patent application Ser. No. 08 / 322,677) Bacillus amyloliquefacie as described in In carbonyl hydrolase equivalent to position +76 according to ns subtilisin numbering At positions (preferably also +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +1 56, +166, +195, +197, +204, +206, +210, +21 6, +217, +218, +222, +260, One or more equivalent to those selected from the group consisting of +265 and / or +274 Different in place of multiple amino acid residues (in combination with above amino acid residue positions) Derived from the precursor carbonyl hydrolase by using amino acids Carbonyl hydrolase variant with an amino acid sequence not found in nature is there.   Here, suitable amylase is not limited to the purpose of automatic dish washing, but in particular, For example, α-Amirror described in GB 1,296,839 to Novo ZE, manufactured by International Bio-Synthetics, Inc. Engineering enzymes for stability, eg, oxidative stability, is known. For example, J.Bi biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-65. See page 21. In certain preferred embodiments of the composition, commercial Amylases with improved stability in any detergent, especially improved oxidative stability Can be used. These preferred amylases of the invention have minimal, oxidative stability, For example, hydrogen peroxide / tetraacetylethylenedia Oxidation stability to min, heat stability, eg at normal wash temperature such as 60 ° C Thermal stability, or alkali stability, eg, alkali stability at pH 8-11 By one or more measurable improvements (measured relative to the control point amylase) They share the characteristic of being a "stability enhancing" amylase that can be characterized. Stable Sex can be measured using any of the technical tests disclosed in the art. For example, WO See the references disclosed in U.S. Pat. No. 9,402,597. Amylase with enhanced stability Or from Genenkol International. One species of the present invention A class of highly preferred amylases include one, two or many amylase strains immediately. Bacillus amylase, especially Bacillus α- Attributes derived from one or more amylases using site-directed mutagenesis Have a share. The oxidative stability enhancing amylase as compared to the control amylase is particularly The bleaching detergent composition of the present invention, more preferably an oxygen bleaching detergent composition (What is chlorine bleaching? Separate) and preferred for use. Such preferred amylases include ( a) Termamyl using alanine or threonine, preferably threonine A mutant having a substitution of an amino acid residue, or a homologous variant of a similar parent amylase, For example, B. amyloliquefaciens, B.A. subtilis, or B. stearothermophilus Therefore, before the Novo published on February 3, 1994, as further illustrated, WO 94 Amylase according to JP-A-02597; (b) C.I. 1994 by Mitchinson March 13-17 207th American Chemical Society National ・ Genencol-in in the paper “Oxidation-resistant α-amylase” presented at the meeting Stability-enhancing amylase as described by Ternation (including Bleach in automatic dishwashing detergent inactivates α-amylase but improved Oxidation-stable amylase is described by Genencol in B.A. licheniformis NCIB806 1 was found to be produced. Methionine (Met) is the most denatured It was identified as a likely residue. Met is 8, 15, 197, 256, Substitutions at positions 304, 366 and 438 resulted in certain mutants, Of particular importance are 97L and M197T, with the M197T mutant having the most stable expression. Amylase variants with additional modifications in the immediate parent available as . Other particularly preferred oxidative stability enhancing amylases include Genencol Interchange Na WO 9418314 to Noval and WO 940259 to Novo No. 7 are mentioned. Other oxidative stability enhancing amylases The available amino acids of known chimeric, hybrid or simple mutant parent forms It can be used to derive from an enzyme by site-directed mutagenesis. Other good Preferred enzyme modifications are accessible. WO No. 9509909A to Novo See booklet. Other amylase enzymes are described in WO 95/26397. And co-pending application PCT / DK96 / 00056 by Novo Nordisk Those listed. Specific amylase for use in the detergent composition of the present invention At a temperature in the range of 25 ° C. to 55 ° C. and a pH value in the range of 8 to 10. The activity assay is described on pages 9 to 10 of WO 95/26397. ). In addition, the amino acid sequence shown in the SEQ ID list in the literature is Α-amylases that are both 80% homologous are included herein. These enzymes are good Preferably, the laundry detergent composition contains 0.00018-0.060% by weight of the total composition of pure detergent. Neat enzymes, more preferably 0.00024-0.048% pure by weight of the total composition Mix in the amount of enzyme.   Cellulases that can be used in the present invention include bacterial cellulases and fungal cellulases. (Preferably having a pH optimum of 5 to 9.5). 19 U.S. Pat. No. 4,435,307 issued March 6, 1984 to Barbeth Gode et al. The book states that Humicola insolens or Humicola strain DSM1800 or Aeromona A suitable fungal cellulase from a cellulase 212-producing fungus belonging to the genus Cellular extracts from the hepatopancreas of phosphorus molluscs (Dolabella Auricula Solander) Disclose. Suitable cellulases are also described in UK Patent No. 2.075.0. 28, UK Patent No. 2.095.275 and DE-OS No. 2. See also specification No. 43.   A lipase enzyme suitable for use in detergents is disclosed in British Patent No. 1,372,034. Pseudomonas stutzeri ATCC 19.154 or other Pseudo as disclosed in the textbook and those produced by the monas group of microorganisms. February 24, 1978 See also lipase in the published JP-A-53-20487. This lipase Amano Pharmaceutical Co., Ltd. in Nagoya, Japan Available in "Amano" or "Amano-P". Other suitable commercial lipases Examples include Amano-CES, Chromobacter viscosum, and -Chromobacter viscosum var.lipolyticu from Yo-Jozo Company m Lipase from NRRLB 3673; U.S.A. S. Biochemical Corp And Chromobacter vis from Disoint Company of the Netherlands cosum lipase, lipase from Pseudomonas gladioli. Humicola lanuginosa and commercially available from Novo, Denmark It is a preferred lipase for use herein. Stabilized against peroxidase The modified lipase and amylase variants are described in WO 9414951A to Novo It is described in the specification. WO 9205249 and RD 9435 See also 9044.   Despite the vast majority of publications on lipase enzymes, Humicola lanuginosa Only lipase derived from and produced in Aspergillus oryzae as host So far, it has found wide application as an additive for fabric cleaning products. that is , As mentioned above, from Novo Nordisk^TMAvailable at Lipo La Novo Nordisk has developed a number of variants to optimize the made. As described in WO 92/05249, native Humicola l The D96L mutant of anuginosa lipase is 4.4 times larger than wild-type lipase. Improve de-staining efficiency (enzyme 0.075-2 protein / l) . 5 mg). Published March 10, 1994 by Novo Nordisk Published Research Disclosure No. 35944 states that a lipase mutant (D96L) contains one liter of washing solution. 0.001 to 100 mg (5 to 500,000 LU / liter) of lipa per Torr It discloses that it may be added in an amount corresponding to the protease variant. The present invention D96L is used in an amount within the range of 50 LU to 8500 LU per liter of washing solution. Detergent composition containing bis-AQA surfactant with a small amount of D96L mutant Used in a fabric to provide improved whiteness maintenance benefits on fabrics. You.   A cutinase enzyme suitable for use herein is WO 8809 to Genencol. No. 367A.   Peroxidase enzymes are removed from the substrate during "solution bleaching" or washing operations. To prevent the transfer of dyes or pigments to other substrates present in the cleaning solution, In combination with an oxygen source, such as percarbonate, perborate, hydrogen peroxide, etc. Is also good. Known peroxidases include horseradish peroxidase Ligninase and haloperoxidase, such as chloroperoxy And bromoperoxidase. Peroxidase-containing detergent The composition was disclosed in Novo, WO 8999813A, published October 19, 1989. And WO 9089813 A to Novo.   The means of incorporation into a wide range of enzyme substances and synthetic detergent compositions is also WO 9307263A and WO 9307260 to National No. A, WO 89908694A to Novo, McCarty and the like U.S. Pat. No. 3,553,139 issued Jan. 5, 1971. ing. The enzyme is further disclosed in US Pat. No. 101,457 and Hughes issued March 26, 1985. No. 4,507,219. Yeast useful for liquid detergent formulations The basic substance and the method of incorporation into such formulations are described in Hora, published April 14, 1981. Et al., U.S. Pat. No. 4,261,868. Use with detergent Enzymes can be stabilized by various techniques. Enzyme stabilization technology Et al., US Pat. No. 3,600,319, issued Aug. 17, 1971; Venegas EP 199,405 published October 29, 1986 and EP No. 200,586 is disclosed and exemplified. Also, enzyme stabilization system Are described, for example, in U.S. Pat. No. 3,519,570. Protection Useful Bacillus sp. AC13 to provide ase, xylanase and cellulase No. WO9401532A to Novo.Enzyme stabilization system   The enzyme-containing composition of the present invention may optionally contain an enzyme stabilizing system of 0.001 to 10 times. %, Preferably 0.005 to 8% by weight, most preferably 0.01 to 6% by weight. May be included. An enzyme stabilization system is any stabilization system that is compatible with the detergent enzyme. You can also. Such systems may be inherently provided by other formulation active ingredients. Well or, for example, by a prescriber or detergent ready enzyme (dete rgent-ready enzyme) may be added separately by the manufacturer. Such stability For example, calcium ion, boric acid, propylene glycol, short chain cal The detergent composition can be composed of boric acid, boronic acid, and mixtures thereof, and Designed to handle different stabilization issues depending on type and physical form.   One stabilization approach is a water-soluble calcium ion source and / or a water-soluble calcium ion source. The use of a magnesium ion source in the finished composition (this is To the enzyme). Calcium ions are generally magnesium ions If it is more effective and only one cation should be used, it is preferred here. New Changes can be made depending on factors including the number, type and amount of enzymes to be combined However, typical detergent compositions, especially liquid detergent compositions, are equivalent to one liter of the finished detergent composition. About 1 to about 30 mmol, preferably about 2 to about 20 mmol, more preferably It will contain from about 8 to about 12 mmol of calcium ions. Preferably water-soluble Calcium or magnesium salts such as calcium chloride, calcium hydroxide , Calcium formate, calcium malate, calcium maleate, calcium hydroxide Calcium and calcium acetate, more generally calcium sulfate or Magnesium salts corresponding to the umium salts may also be used. Further increase in calcium And / or magnesium may, of course, be, for example, greases of certain surfactants. May be useful to promote cutting action.   Another stabilization approach is through the use of borate species. Severson US Patent No. See 4,537,706. More typically boric acid or other borate Compounds, such as borax or orthoborate, up to about 3% by weight in liquid detergent applications However, when used, borate-type stabilizers can be used in up to 10% of the composition. Or more. Substituted boric acids such as phenylboronic acid, Tamboronic acid, p-bromophenylboronic acid, etc. can be used in place of boric acid. And the reduced amount of total boron in the detergent composition is determined by the use of such substituted boron derivatives. May be possible.   Certain cleaning compositions, e.g., automatic dishwashing composition stabilizing systems, may provide many supplies. Chlorine bleach species present in water attack and inactivate enzymes, especially under alkaline conditions 0 to 10% by weight of chlorine bleach scavenger added to prevent . It may further contain from 0.01 to 6% by weight. The amount of chlorine in water may be low. It may be typically in the range of 0.5 ppm to 1.75 ppm, for example, Available chlorine in the total volume of water in contact with the enzyme during dishwashing or fabric washing is compared Enzymatic stability to chlorine during use is sometimes problematic. You. Percarbonate has the ability to react with chlorine bleach, The use of additional stabilizers may not be necessary, most commonly (improved results). Although fruit may be obtained from their use). Suitable chlorine scavenger y ON is widely known and readily available and, if used, sulfite , Bisulfite, thiosulfite, thiosulfate, iodide, etc. Both can be salts containing ammonium cations. Carbamate, a Antioxidants such as scorbate, ethylenediaminetetraacetic acid (EDTA), Organic amines such as rukari metal salts, monoethanolamine (MEA), and the like These mixtures can likewise be used. Similarly, special enzyme suppression systems require that different enzymes It can be formulated to have maximum compatibility. Bisulfate, nitrate, chlori , Sodium perborate tetrahydrate, sodium perborate monohydrate, sodium percarbonate Source of hydrogen peroxide such as sodium, phosphate, condensed phosphate, acetate , Benzoate, citrate, formate, lactate, malate, tartre Other common scavengers such as salts, salicylates and mixtures thereof can also be used if desired. You can use it. In general, the chlorine scavenger function should be separate with a better recognized function Because it can be performed by the described components (eg, a hydrogen peroxide source), As long as the compound performing is not absent from the enzyme-containing embodiment of the invention, separate chlorine There is no absolute requirement to add a scavenger. Even then, the scavenger will provide optimal results Add only for. In addition, the prescriber is primarily concerned with the Use the routine skill of chemists in avoiding the use of tolerant enzyme scavengers or stabilizers. Will do. In connection with the use of ammonium salts, such salts may be used in detergent compositions. But can adsorb water and / or release ammonia during storage Tend. Therefore, such substances, if present, are preferably particles, e.g. For example, Protected in those described in U.S. Pat. No. 4,652,392 to Bagginsky et al. I do.Polymer antifouling agent   Known polymeric antifouling agents (hereinafter “SRA” or “SRAs”) may be Can be used in the detergent composition of the present invention. If utilized, SRAs generally have a composition 0.01-10.0%, typically 0.1-5%, preferably 0.1% by weight of the product. Will account for 2 to 3.0% by weight.   Preferred SRAs are typically made of hydrophobic fibers such as polyester, nylon, etc. A hydrophilic segment for hydrophilizing the surface; And remains adhered throughout the completion of the rinse cycle, thereby providing a hydrophilic seal. And a hydrophobic segment to serve as a segment anchor. This means that S To make it easier to clean stains that occur after treatment with RA using a later cleaning method. Can be made possible.   SRA uses various charged species, such as anionic or even cationic species (US Pat. No. 4,956,447) as well as uncharged monomer units. The structure may be linear, branched or even star-shaped. Do they control molecular weight Includes capped moieties that are particularly effective in altering physical properties or surface activity May be. Structure and charge distribution for different fiber or fabric types application And it may be tailored for various detergent or detergent additive products.   Preferred SRAs include oligomeric terephthalates, typically Often, at least one air-catalyst using a metal catalyst such as a titanium (IV) alkoxide is used. Oligomer terefs produced by a process involving stele exchange / oligomerization Talates are mentioned. Such esters are, of course, fully crosslinked Ester structure through 1, 2, 3, 4 or more positions without forming a structure It may be produced using additional monomers that can be incorporated.   Suitable SRAs include, for example, J. Shabel and E.L. P. Gosselin Described in US Pat. No. 4,968,451 issued Nov. 6, 1990. Oligomers of terephthaloyl and oxyalkyleneoxy repeating units such as Consists of a steal backbone and an allylic-derived sulfonated end covalently linked to the backbone The sulfonation products of substantially linear ester oligomers (such ester Gomer ethoxylates (a) allyl alcohol and (b) the product of (a) in two steps. Dimethyl terephthalate ("DMT") in the transesterification / oligomerization process And 1,2-propylene glycol (“PG”), (c) and (b) Can be produced by reacting the product with sodium metabisulfite in water) U.S. Pat. No. 4,711,730 issued Dec. 8, 1987 to Gosselink et al. End-capped 1,2-propylene / polyoxyethylene resin Phthalate polyester, for example, poly (ethylene glycol) methyl ether , DMT, PG and esters of poly (ethylene glycol) ("PEG") Produced by exchange / oligomerization; Gosselink, Jan. 2, 1988 Partial and complete anion powders of US Pat. No. 4,721,580 issued on the 6th. End-capped oligomeric esters such as ethylene glycol ("EG"), PG, DMT and Na 3,6-dioxa-8-hydroxyoctanesulfonate Oligomers from US Pat. No. 4, issued Oct. 27, 1987 to Gosselink. 702,857, Non-ion capped block polyester oligomer Compounds such as DMT, Me-capped PEG and EG and / or P G or DMT and EG and / or PG and Me-capped PEG and dimethyl Produced from a combination with sodium 5-sulfoisophthalate; U.S. Pat. No. 4,877, issued Oct. 31, 1989 to Donado, Gosselink, et al. 896, anion (especially sulfoaroyl) end-capped terephthalates Acid esters (the latter being useful in both laundry and fabric conditioning products) RA And one example is prepared from m-sulfobenzoic acid-sodium salt, PG and DMT. Ester composition (optionally but preferably added PEG) EG3400).   As SRA, ethylene terephthalate or propylene terephthalate is used. And polyethylene oxide terephthalate or propylene oxide terephthalate A simple copolymer block with a rate (US issued May 25, 1976 to Haze Patent No. 3,959,230 and issued on July 8, 1975 to Bassada No. 3,893,929), METHOCEL from Dow. Cellulosics such as hydroxyether cellulose polymers available as) Derivative, C₁~ C_FourAlkyl cellulose and C_FourHydroxyalkyl cellulose (US Patent No. 4,000,093 issued December 28, 1976 to Nicol et al. See the specification). Poly (vinyl ester) by hydrophobic segment Suitable SRAs to be characterized include poly (vinyl esters) such as C₁ ~ C₆Graft copolymer of vinyl ester, preferably polyalkylene oxide Poly (vinyl acetate) grafted on the main chain. 198 by Kood et al. See European Patent Application No. 0219048 published on April 22, 2007. With commercially available examples For example, SOKALAN SRA, available from BASF in Germany, Curan HP-22. Other SRAs have average molecular weights of 300-5,000. Polyoxyethylene Terephthalate Derived from Polyoxyethylene Glycol Contains 10 to 15% by weight of ethylene terephthalate together with 90 to 80% by weight Polyester having repeating units. Commercial examples include Zel from DuPont ZELCON 5126 and MILEASE T from ICI .   Another preferred SRA is one sulfoisophthaloyl unit, five terephthaloyl units Oxyethylene in a specified ratio, preferably from about 0.5: 1 to about 10: 1. Oxy and oxy-1,2-propyleneoxy units, and 2- (2-hydrido) Roxyethoxy) -two endcaps derived from sodium ethanesulfonate Terephthaloyl (T), sulfoisophthalo as in oligomers containing units Yl (SIP), oxyethyleneoxy and oxy-1,2-propylene (E G / PG) units and preferably end caps (CAP), preferably modified Empirical formula with isethionate as a terminal group (CAP)_Two(EG / PG)_Five(T)_Five( SIP)₁Is an oligomer having The SRA is preferably an oligomer 0.5 to 20% by weight of a crystallinity reducing stabilizer such as linear dodecylbenzenes Anionic surfactants such as sodium sulfonate or xylene sulfonate, Mensulfonate, and selected from toluenesulfonate or mixtures thereof Members (all of these stabilizers or modifiers were issued on May 16, 1995) No. 5,415,807 to Gosselink, Bread, Kerret and Hall (Introduced into a synthesis pot as taught in the specification). Suitable for the SRA Examples of such monomers include sodium 2- (2-hydroxyethoxy) -ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG .   Still another group of preferred SRAs includes (1) (a) dihydroxysulfonate, Lihydroxysulfonates, units that are at least trifunctional (whereby A ter bond is formed to form a branched oligomer backbone), and combinations thereof. (B) at least one unit selected from the group consisting of: At least one unit, and (c) a 1,2-oxyalkyleneoxy moiety A backbone comprising at least one unsulfonated unit that is Capping units, anionic capping units, such as alkoxylated isethionates , Preferably ethoxylated isethionate, alkoxylated propane sulfonate, Alkoxylated propane disulfonate, alkoxylated phenol sulfonate, S One or more capped units selected from rufoaroyl derivatives and mixtures thereof It is an oligomer ester containing a position. Of such esters, the empirical formula ｛(CAP) x (EG / PG) y ′ (DEG) y ″ (PEG) y ′ ″ (T) z (SIP) z ′ (SEG) q (B) m｝ Wherein CAP, EG / PG, PEG, T and SIP are as defined above. , (DEG) represents di (oxyethylene) oxy unit; (SEG) represents glyce Represents units derived from sulfoethyl ether of phosphorus and related subunits; (B) is a branching unit which is at least trifunctional, whereby an ester bond is formed X is from about 1 to about 12; y ' Is about 0.5 to about 25; y "is 0 to about 12; y" "is 0 to about 10 Yes; y '+ y "+ y"' is from about 0.5 to about 25 in total; z is from about 1.5 to about Z 'is 0 to about 12; z + z' is about 1.5 to about 25 in total. Yes; q is about 0.05 to about 12; m is about 0.01 to about 10; x, y ', Y ", y"', z, z ', q and m are the corresponding amounts per mole of the ester. Represents the average number of moles of units, said ester having a molecular weight of about 500 to about 5,000. Do) Are preferred.   Preferred SEG and CAP monomers for the ester include 2- (2,3- Sodium dihydroxypropoxy) ethanesulfonate ("SEG"), 2- {2- ( Sodium 2-hydroxyethoxy) ethoxydiethanesulfonate (“SE3”) and And its homologues and their mixtures and allyl alcohol Honed products. Suitable SRA esters of this type include 2- {2- (2-hydroxyethoxy) ethoxy using the appropriate Ti (IV) catalyst Sodium ethanesulfonate and / or 2- [2- {2- (2-hydroxy [Ciethoxy) ethoxy [ethoxy] sodium ethanesulfonate, DMT, 2- Sodium (2,3-dihydroxypropoxy) ethanesulfonate, EG, and And products which transesterify and oligomerize PG and PG; (CAP) 2 (T) 5 (EG / PG) 1.4 (SEG) 2.5 (B) 0.13 (where CA P is (Na^+-O_ThreeS [CH_TwoCH_TwoO] 3.5-, and B is a unit derived from glycerin. Yes, the molar ratio of EG / PG is determined by conventional gas chromatography after complete hydrolysis. Is about 1.7: 1 as measured by   Additional types of SRAs include (I) dimers to attach the polymeric ester structure. Non-Ion Terephthalate Using Bioisocyanate Coupling Agent (Bioland And U.S. Pat. No. 4,201,824 to Lagasse et al. 240,918), (II) adding a terminal hydroxyl group to trimellitic acid ester Addition of trimellitic anhydride to the known SRA to convert to SRA with carboxylate end groups formed (with appropriate choice of catalyst, Trimellitic anhydride is more capable of isolating trimellitic anhydride than opening anhydride bonds. A bond to the end of the polymer is formed through the ester of rubonic acid. Non-ion SRA Alternatively, either the anionic SRA has a hydroxyl end group that can be esterified. As far as possible, they may be used as starting materials. U.S. Pat. No. 4,525,525 to Tang et al. No. 524); (III) based on urethane-bound terephthalate Anion SRA (see US Pat. No. 4,201,824 to Bioland et al.) (IV) including poly (vinylcaproleum) including nonionic and cationic polymers Lactam) and vinylpyrrolidone and / or dimethylaminoethyl methacrylate Related copolymers with monomers such as relates (U.S. Pat. (V) No. 681); (V) An acrylic monomer is coated on a sulfonated polyester. Graft copolymers produced by rafting (Socaran from BASF (In addition to the molds) (these SRAs have an antifouling activity similar to known cellulose ethers) And is claimed to have anti-redeposition activity. Lone-Pourenk He (VI EP 279,134A to Me) (VI) Casein Grafting of vinyl monomers such as acrylic acid and vinyl acetate onto proteins such as (See EP 457,205A to BASF (1991)); (VII ) Condensing adipic acid, caprolactam and polyethylene glycol -Polyamide SRA (particularly processing polyamide fabrics) (For Bevan et al. Issued to Unilever NV in 1974) 335,044). Other useful SRAs are described in U.S. Pat. No. 4,240,918, No. 4,787,989, No. 4,525. No. 524 and 4,877,896.Clay stain removal / anti-redeposition agent   The composition of the present invention optionally has clay soil removal and anti-redeposition properties. Water-soluble ethoxylated amines. Granular detergent set containing these compounds The composition typically contains 0.01 to 10.0% by weight of a water-soluble ethoxylated amine. I do. Liquid detergent compositions typically contain 0.01 to 5 water-soluble ethoxylated amines. %.   The most preferred antifouling / anti-redeposition agent is ethoxylated tetraethylenepentamine It is. An exemplary ethoxylated amine is Vandermeal, issued July 1, 1986. U.S. Patent No. 4,597,898. Another group prefer New clay soil removal / redeposition inhibitors are available from Oh and Go, published June 27, 1984. The cationic compounds disclosed in Serink European Patent Application No. 111,965. is there. Other clay soil removal / redeposition inhibitors that may be used include June 2, 1984 The et al. Disclosed in European Patent Application No. 111,984 to Gosselink published on the 7th. Xylated amine polymers; Gosselink's European patent application published July 4, 1984 112,592; zwitterpolymers disclosed on Oct. 22, 1985 The amine oxides disclosed in US Pat. No. 4,548,744 to Conner No. Other clay stain removers and / or anti-redeposition agents known in the art also include Available in the present composition. Vandermeal U.S. Patent issued Jan. 2, 1990 No. 4,891,160 and WO 95 / published Nov. 30, 1995. See 32272. Another class of preferred antiredeposition agents is carboxy. And cimethylcellulose (CMC) materials. These substances are known .Whitening agent   Any optical or other brightener or whitening agent known in the art may be used in the present invention. Detergent compositions can typically be incorporated in amounts of 0.01 to 1.2% by weight. In the present invention Commercially available optical brighteners, which may be used for Stilbene, pyrazoline, coumarin, cal Bonic acid, methine cyanine, dibenzothiophene-5,5-dioxide, azole Derivatives of 5- and 6-membered heterocyclic compounds, and other miscellaneous drugs. It is. Examples of such brighteners are described in "Production and Application of Fluorescent Brighteners", M.W. Zara Donic published by John Willie End Sands of New York (1982) Is disclosed. Specific examples of optical brighteners useful in the present compositions are Wixon No. 4,790,856, issued Dec. 13, 1988. It is fixed. These brighteners include PHORWHI from Verona. TE) series brighteners. Other brighteners disclosed in this document include Ciba Tinopal UNPA, Tinopal CBS and Teinopal available from Geigy And Tinopearl 5BM; Artic White CC and Arte Dick White CWD; 2- (4-styrylphenyl) -2H-naphtho [ 1,2-d] triazole; 4,4'-bis- (1,2,3-triazole-2 -Yl) -stilbene; 4,4'-bis (styryl) bisphenyl; Nocmarin is mentioned. Specific examples of these brighteners include 4-methyl-7- 1,2-bis (benzimidazol-2-yl) ethyl 1,3-diphenylpyrazoline; 2,5-bis (benzoxazole-2 -Yl) thiophene; 2-styryl-naphtho [1,2-d] oxazole; and And 2- (Stilben-4-yl) -2H-naphtho [1,2-d] triazole and the like. It is. U.S. Patent No. 3,646,015 issued to Hamilton on February 29, 1972 See also issue specification.Dye transfer inhibitor   The composition of the present invention can be used to dye one fabric to another during the cleaning process. It may also include one or more substances that are effective in inhibiting charge transfer. Generally, this Such dye transfer inhibitors include polyvinylpyrrolidone polymer, polyamine N- Oxide polymer, copolymer of N-vinylpyrrolidone and N-vinylimidazole , Manganese phthalocyanine, peroxidase, and mixtures thereof, It is. If used, these agents typically comprise from 0.01 to 10% of the composition. % By weight, preferably 0.01 to 5% by weight, more preferably 0.05 to 2% by weight. Occupy.   More specifically, preferred polyamine N-oxide polymers for use herein are And the following structural formula RA_x-P [wherein P is a polymerizable unit (to which an NO group is bonded) Or the N—O group can form part of a polymerizable unit, or the N—O group can be both A can be bonded to a unit of the formula: A is a compound having the following structure: -NC (O)-, -C (O) O -, -S-, -O-, -N =; x is 0 or 1; R is aliphatic , Ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof (To which the nitrogen of the NO group can be attached, or the NO group is a part of these groups) Is a unit). Preferred polyamine N-oxides are R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, Peridine and derivatives thereof.   The NO group has the following general structure (Where R₁, R_Two, R_ThreeIs an aliphatic, aromatic, heterocyclic or alicyclic group or X, y and z are 0 or 1; the nitrogen of the NO group is Can bind or form part of any of the above groups) Is represented by The amine oxide unit of the polyamine N-oxide has a pKa <10 , Preferably pKa <7, more preferably pKa <6.   As long as the resulting amine oxide polymer is water-soluble and has a dye transfer inhibiting property, Alternatively, any polymer backbone can be used. Examples of suitable polymer backbones include polyvinyl, Polyalkylene, polyester, polyether, polyamide, polyimide, poly Acrylates and mixtures thereof. One of these polymers is Wherein the monomeric form is an amine N-oxide and the other monomeric form is an N-oxide Random or block copolymers. Amine N-oxide polymers are Typically, the ratio of amine to amine N-oxide is from 10: 1 to 1: 1,000,000. 00. However, amine oxides present in polyamine oxide polymers The number of side groups can be varied by a suitable copolymerization or by a suitable degree of N-oxidation. . Polyamine oxides can be obtained at almost any degree of polymerization. Typical Typically, the average molecular weight is from 500 to 1,000,000, more preferably from 1,000 0 to 500,000, most preferably in the range of 5,000 to 100,000. You. This preferred type of material can be referred to as "PVNO".   The most preferred polyamine N-oxides useful in the detergent compositions of the present invention have an average Having a molecular weight of 50,000 and an amine to amine N-oxide ratio of 1: 4 (4-vinylpyridine-N-oxide).   Copolymer of N-vinylpyrrolidone and N-vinylimidazole polymer (class As "PVPVI") is also preferred for use herein. Preferably , PVPVI is more preferred in the average molecular weight range of 5,000 to 1,000,000. Ku Should be between 5,000 and 200,000, most preferably between 10,000 and 20,000 [The average molecular weight range is described in Chemical Analysis by Bath et al., Vol. Measurement by light scattering as described in “Modern Methods of Body Characterization” (disclosure disclosed). Here incorporated as reference)). PVPVI copolymers are typically N-vinyl The molar ratio of imidazole to N-vinylpyrrolidone is from 1: 1 to 0.2: 1, more preferably. Or 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1. Have. These copolymers can be either linear or branched.   The composition of the present invention has an average molecular weight of 5,000 to 400,000, preferably 5, 000 to 200,000, more preferably 5,000 to 50,000 Rivinylpyrrolidone ("PVP") may also be used. PVP is used in the detergent field. It is known to those skilled in the art. For example, EP-A-262,897 and EP-A See A 256,696 (hereby incorporated by reference). Contains PVP The composition has an average molecular weight of 500 to 100,000, preferably 1,000 to 1 Polyethylene glycol having "0000" ("PEG") can also be included. Like Alternatively, the ratio (based on ppm) of PEG to PVP supplied in the cleaning solution is 2: 1 To 50: 1, more preferably 3: 1 to 10: 1.   The detergent compositions of the present invention may optionally provide certain parenteral agents that also provide a dye transfer inhibiting effect. It may also contain 0.005 to 5% by weight of an aqueous optical brightener. If you use it, The composition will preferably contain from 0.01 to 1% by weight of such an optical brightener. .   The hydrophilic optical brightener useful in the present invention has a structural formula (Where R₁Are anilino, N-2-bis-hydroxyethyl and NH-2-H Selected from droxyethyl; R_TwoIs N-2-bis-hydroxyethyl, N-2- Selected from hydroxyethyl-N-methylamino, morpholino, chloro and amino Where M is a salt-forming cation such as sodium, potassium, etc.) It has.   In the above formula, R₁Is anilino and R_TwoIs N-2-bis-hydroxyethyl And when M is a cation such as sodium, the brightener is 4,4'-bis [(4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazine -2-yl) amino] -2,2'-stilbene disulfonic acid and disodium Salt. This particular brightener species is available from Ciba-Geigy Corporation. It is commercially available under the trade name Tinopal-UNPA-GX. Chino Pearl- UNPA-GX is a preferred hydrophilic optical brightener useful in the detergent compositions of the present invention. You.   In the above formula, R₁Is anilino and R_TwoIs N-2-hydroxyethyl-N-2- When methylamino and M is a cation such as sodium, the brightener is , 4,4'-bis [(4-anilino-6- (N-2-hydroxyethyl-N-me Tylamino) -s-triazin-2-yl) amino] -2,2'-stilbene Sulfonic acid disodium salt. This particular brightener species is Ciba-Geigy Marketed under the trade name Tinopearl 5BM-GX.   In the above formula, R₁Is anilino and R_TwoIs morpholino and M is sodium When it is a cation such as, for example, the brightener is 4,4'-bis [(4-anilino-6 -Morifolino-s-triazin-2-yl) amino] 2,2'-stilbenzis It is the sodium salt of sulfonic acid. This particular brightener species is available from Ciba Geigy Corp. Commercially available under the trade name Tinopearl AMS-GX.   The specific optical brightener species selected for use in the present invention is the specific polymer described above. Provides particularly effective dye transfer inhibition performance benefits when used in conjunction with dye transfer inhibitors . Such predetermined polymeric substances (eg, PVNO and / or PVPVI) And such predetermined optical brighteners (for example, Tinopearl-UNPA-GX, Tinopa 5BM-GX and / or Tinopearl AMS-GX) More than one of these two detergent composition components when used alone, an aqueous cleaning solution Gives significantly better dye transfer inhibition in Without being limited by theory, Such brighteners have a high affinity for fabrics in the wash liquor, It is believed that they act on these fabrics and therefore deposit relatively quickly on these fabrics. Increase The degree to which the whitening agent adheres to the fabric in the cleaning solution is called the "exhaustion coefficient". Parameters can be specified. The wear coefficient is generally determined by (a) It is as a ratio of the whitening agent substance to be deposited to the initial concentration of the whitening agent in the washing liquid (b). Relatively Brighteners having a high wastage coefficient are most preferred in the context of the present invention to suppress dye transfer. Suitable.   Of course, other conventional optical brightener type compounds may, in some cases, have true dye transfer inhibition. Used in this composition to provide benefits over normal fabric "brightening" rather than antistatic effect It will be appreciated that it is possible. Such uses are common in detergent formulations And it is well known.Chelating agent   Also, the detergent composition of the present invention may comprise one or more iron and / or manganese chelates. An agent may optionally be included. Such chelating agents are defined below. Aminocarboxylate, aminophosphonate, polyfunctionally substituted aromatic It can be selected from the group consisting of rating agents and mixtures thereof. By theory Although not intended to be limiting, the benefits of these materials are partially Extraordinary ability to remove iron and manganese ions from cleaning fluids by generating rates It is thought that.   Aminocarboxylates useful as any chelating agent include ethylene. Diamine tetraacetate, N-hydroxyethyl ethylenediamine triacete , Nitrilotriacetate, ethylenediaminetetrapropionate, Ethylenetetraamine hexaacetate, diethylenetriaminepentaacetate And ethanol diglycine, their alkali metal salts, ammonium salts, and And substituted ammonium salts and mixtures thereof.   Also, aminophosphonates allow at least a small amount of total phosphorus to be allowed in the detergent composition. Is suitable and suitable for use as a chelating agent in the compositions of the present invention. Examples of these are ethylenediaminetetrakis (methylenephos) as a quest. Honate). Preferably, these aminophosphonates are less than six. It does not contain alkyl or alkenyl groups having more carbon atoms.   Also, polyfunctionally substituted aromatic chelators are useful in the present compositions. Conner See U.S. Pat. No. 3,812,044, issued May 21, 1974. Acid form Preferred compounds of this type are 1,2-dihydroxy-3,5-disulfobenze And dihydroxydisulfobenzene.   Preferred biodegradable chelators for use herein are Hartmann and Parr. No. 4,704,233 issued to Kins on Nov. 3, 1987. Ethylenediaminedisuccinate ("EDDS") as described, especially [S, S ] Isomer.   This composition is used together with insoluble builders such as zeolites and layered silicates. Water-soluble methyl glycine diacetate (M GDA) salts (or acid forms).   If utilized, these chelating agents will generally be present in the detergent compositions of the present invention. . Will account for 1-15% by weight. More preferably, if used, clean The tonifying agent will make up from 0.1 to 3.0% by weight of such a composition.Foam suppressant   Compounds for reducing or inhibiting foam formation can be incorporated into the compositions of the present invention. . Foam suppressors are disclosed in U.S. Patent Nos. 4,489,455 and 4,489,574. So-called "high concentration cleaning method" and front charging as described in the specification May be of particular importance in European type washing machines.   Various materials may be used as foam inhibitors, and foam inhibitors are well known to those skilled in the art. is there. For example, Kirk Othmer Encyclopedia of Chemical Technology, 3rd edition, Volume 7, pages 430-447 (John Willie End Sons, Inc.) -Porated, 1979). One category of foam inhibitors of particular interest Include monocarboxylic fatty acids and their soluble salts. Wayne St U.S. Pat. No. 2,954,347 issued Sep. 27, 1960 to John reference. Monocarboxylic fatty acids and their salts used as foam inhibitors are typically Has a hydrocarbyl chain having 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. You. Suitable salts include alkali metal salts, for example, sodium salts, potassium salts, And lithium salts, and ammonium salts and alkanol ammonium salts No.   Further, the detergent composition of the present invention may contain a non-surfactant foam inhibitor. these As, for example, high molecular weight hydrocarbons, for example, paraffin, fatty acid ester ( For example, fatty acid triglyceride), fatty acid ester of monohydric alcohol, aliphatic C₁₈ ~ C₄₀Ketones (eg, stearone) and the like. Other foam inhibitors , N-alkylated aminotriazines, for example, primary or secondary having 1 to 24 carbon atoms. Trial formed as a product of 2 or 3 moles of secondary amine and cyanuric chloride From melmelamine to hexaalkylmelamine or dialkyldiamine chloride From lutriazine to tetraalkyldiamine chlorotriazine, Oxides, and monostearyl phosphates, such as monostearyl alcohol Phosphoryl esters and monostearyl dialkali metals (eg, K, Na, And Li) phosphates and phosphate esters. Paraffin, ha Hydrocarbons such as loparaffin are available in liquid form. Liquid hydrocarbons are at room temperature And liquid at atmospheric pressure and pour point -40C to 50C and minimum boiling point 110 C. (atmospheric pressure). A waxy hydrocarbon, preferably having a melting point of 1; It is known to utilize those having less than 00 ° C. Hydrocarbons, detergent composition A preferred category of foam inhibitors. Hydrocarbon foam inhibitors include, for example, Gand No. 4,265,779 issued May 5, 1981 to Rufo et al. Are listed. As the hydrocarbon, thus, an aliphatic having 12 to 70 carbon atoms, Alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons are included. This suppression The term "paraffin" used in the discussion of foaming agents refers to true paraffin and cyclic hydrocarbons. And mixtures thereof.   Another preferred category of non-surfactant suds suppressors consists of silicone suds suppressors . This category includes polyorganosiloxanes such as polydimethylsiloxane. Sun oils, dispersions or emulsions of polyorganosiloxane oils or resins; Combination of liorganosiloxane and silica particles (polyorganosiloxane is Chemisorption or fusion onto silica). Silicone foam suppressors For example, U.S. Pat. No. 4,265,779 and M.M. S. Starch February 7, 1990 It is disclosed in published European patent application 89307851.9.   Other silicone suds suppressors contain the composition and a small amount of polydimethylsiloxane fluid. U.S. Patent No. No. 3,455,839.   Mixtures of silicone and silanized silica are described, for example, in German patent application DOS No. 2 , 124, 526. Silicone in granular detergent compositions N Defoamers and defoamers are described in U.S. Pat. No. 3,933,672 to Baltrotta et al. And U.S. Patent No. 4,652, issued March 24, 1987 to Bagginski et al. No. 392.   Exemplary silicone-based suds suppressors for use herein are essentially   (I) Polydimethylsiloxane having a viscosity at 25 ° C. of about 20 cs to about 1,500 cs Loxane fluid;   (Ii) (i) from about 5 to about 50 parts per hundred parts by weight of (CH_Three)_ThreeSiO_1/2single Position vs SiO_TwoA unit ratio of about 0.6: 1 to about 1.2: 1 of (CH_Three)_ThreeSiO_1/2single And SiO_TwoA siloxane resin consisting of units; and   (Iii) (i) about 1 to about 20 parts of solid silica gel per 100 parts by weight It is a foam control agent having a foam suppressing amount consisting of   In preferred silicone suds suppressors for use herein, the continuous phase solvent is Specific polyethylene glycol or polyethylene-polypropylene glycol Copolymer or their mixture (preferred) or polypropylene glycol Become. The primary silicone suds suppressor is branched / crosslinked and preferably not linear .   To further illustrate this point, a typical liquid laundry detergent set with controlled foam The composition may optionally comprise (1) (a) a polyorganosiloxane and (b) a resinous silicone. Loxane or silicone resin-forming silicone compound and (c) finely divided filler material And (d) mixture components (a), (b) and (c) to produce silanolates. A non-aqueous emulsion of a primary antifoaming agent, which is a mixture with a catalyst to promote the reaction of ) At least one nonionic silicone surfactant; and (3) water at room temperature. Polyethylene glycol or polyethylene-polyether having a solubility of about 2% by weight or more Copolymer of polypropylene glycol (without polypropylene glycol) ) From about 0.001 to about 1% by weight, preferably about 0. 1% by weight of said silicone foam inhibitor. From 0.01 to about 0.7% by weight, most preferably from about 0.05 to about 0.5% by weight Will. Similar amounts can be used for particulate compositions, gels, and the like. December 1990 Starch U.S. Pat. No. 4,978,471, issued on Jan. 18, 1991 Jan. Starch U.S. Pat. No. 4,983,316, issued on Feb. 18, 1994. U.S. Patent No. 5,288,431 issued to Huber et al. U.S. Pat. Nos. 4,639,489 and 4,749,74 to Aizawa et al. See also column 0, column 1, column 46 to column 4, line 35.   The silicone suds suppressors of the present invention are preferably polyethylene glycol and polyester. Copolymer of ethylene glycol / polypropylene glycol (all are average (Having a molecular weight of about 1,000 or less, preferably about 100 to 800). Departure Ming's polyethylene glycol and polyethylene / polypropylene copolymers are It has a solubility in water at room temperature of about 2% by weight or more, preferably about 5% by weight or more.   Preferred solvents of the present invention have an average molecular weight of about 1,000 or less, more preferably about 1 Polyethylene glycol having from 00 to 800, most preferably from 200 to 400 And polyethylene glycol / polypropylene glycol copolymers, preferably Or PPG200 / PEG300. Polyethylene glycol vs. polyethylene The weight ratio of the copolymer of lene glycol / polypropylene glycol is about 1: 1 to 1 : 10, most preferably 1: 3 to 1: 6.   The preferred silicone foam inhibitor used herein is polypropylene glycol, especially Does not contain 4,000 molecular weight polypropylene glycol. They like Or ethylene oxide such as PLURONIC L101 and propylene It does not contain a block copolymer with an oxide.   Other foam inhibitors useful herein are secondary alcohols (e.g., 2-alkyl alk Knol) and the mixing of alcohols and silicone oils such as silicones (US Pat. Nos. 4,798,679 and 4,075,118). And EP 150,872). As a secondary alcohol Is C₁~ C₁₆C with a chain₆~ C₁₆Alkyl alcohol is mentioned. preferable Alcohol is available from Condea under the trademark ISOFOL 12 It is chill octanol. A mixture of secondary alcohols was obtained from Enikem under the trademark Isa. Available from ISALCHEM 123. The mixed suds suppressor is typically 1: 5 5: 1 by weight of a mixture of alcohol and silicone.   In the case of detergent compositions to be used in automatic washing machines or dishwashers, the foam is Should not be formed to the extent of overflowing or the washing mechanism of the dishwasher Should not be adversely affected. Foam suppressants, when utilized, are preferably "suppressed". Foam volume ". "Amount of foam control" means that the formulator of the composition Enough foam to produce a low-foaming laundry detergent or dishwashing detergent for use in jars. This means that the amount of antifoam that will be controlled in minutes can be selected.   The composition will generally comprise from 0% to 10% of a foam inhibitor. Used as foam suppressant When doing so, the monocarboxylic fatty acids and their salts are typically used in detergent compositions. Will be present in amounts up to 5% by weight. Preferably, fatty monocarboxylate 0.5% to 3% of foam control agents are utilized. Large amounts may be used, but silicone Suds suppressors are typically utilized in amounts up to 2.0% by weight of the detergent composition. this The upper limit is primarily a small amount of effectiveness to keep costs to a minimum and to effectively control foam. Realistic and practical due to concerns about Preferably, a silicone foam inhibitor 0.1. From 01% to 1%, more preferably from 0.25% to 0.5% is used. Use here These weight percent values used are silica, which may be used in combination with the polyorganosiloxane, As well as any materials that may be utilized. Monostearyl phosphate foam inhibitor Is generally utilized in an amount of 0.1 to 2% by weight of the composition. Can be used in large quantities , Hydrocarbon suds suppressors are typically utilized in amounts of 0.01% to 5.0%. A Rucol foam inhibitors are typically used at 0.2-3% by weight of the finished composition.Alkoxylated polycarboxylate   Manufactured from alkoxylated polycarboxylates, for example polyacrylates Those are useful herein to provide additional grease removal performance. like this Substances are described in WO 91/08281 and PCT 90/01815 4 See pages et seq. (Here incorporated by reference). Chemically, these substances are From polyacrylates with one ethoxy side chain for every eight acrylate units Become. The side chain has the formula-(CH_TwoCH_TwoO)_m(CH_Two)_nCH_Three(Where m is 2-3 And n is from 6 to 12). Side chains are added to the polyacrylate main chain. Stele bonds provide a "comb" polymer type structure. The molecular weight can vary, but typically Specifically, it is in the range of 2000 to 50,000. Such alkoxylated polycarbonate Ruboxylate can represent from 0.05 to 10% by weight of the composition.Fabric softener   Various through-the-wash fabric softeners, especially 197 U.S. Pat. No. 4,062,6 issued to Dec. 13, 1995 to Storm and Nilshur. No. 47, the fine smectite clay, as well as other softener clays known in the art, And, in some cases, typically provide the benefits of fabric softening concurrently with fabric cleaning. It can be used in the composition in an amount of 0.5 to 10% by weight to give. Clay softeners For example, U.S. Pat. No. 4,375,416 to Crisp et al. And Harris et al., U.S. Patent No. 4,291, issued September 22, 1981. It can be used in combination with amine and cationic softeners as disclosed in US Pat.Spice   Flavoring and flavoring ingredients useful in the compositions and methods of the present invention include various natural and Synthetic chemical components, including, but not limited to, aldehydes, ketones, and esters. Also, Various natural extracts and essences, which can consist of complex mixtures of For example, orange oil, lemon oil, rose extract, lavender, musk, patchouli, ba Lusamic essence, sandalwood oil, pine oil and cedar are included. Finished fragrance May consist of a very complex mixture of such components. The finished fragrance is Formally, it accounts for 0.01 to 2% by weight of the detergent composition of the present invention and contains individual flavor components. Can account for 0.0001% to 90% of the finished perfume composition.   Non-limiting examples of fragrance ingredients useful herein include 7-acetyl-1,2,3,4, 5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, Non-methyl, yonone gamma-methyl, methyl cedrone, dihydrojasmonate Tyl, methyl-1,6,10-trimethyl-2,5,9-cyclodecatriene- 1-yl ketone, 7-acetyl-1,1,3,4,4,6-hexamethyltetra Phosphorus, 4-acetyl-6-t-butyl-1,1-dimethylindane, p-hydro Xyphenyl-butanone, benzophenone, methyl β-naphthyl ketone, 6-a Cetyl-1,1,2,3,3,5-hexamethylindane, 5-acetyl-3- Isopropyl-1,1,2,6-tetramethylindane, 1-dodecanal, 4 -(4-hydroxy-4-methylpentyl) -3-cyclohexene-1-carbo Xylaldehyde, 7-hydroxy-3,7-dimethyloctanal, 10-un Decene-1-al, isohexenylcyclohexylcarboxaldehyde, e Lumil tricyclodecane, hydroxycitronellal and methyl anthranilate Condensate of hydroxycitronellal and indole, phenylacetate Condensation product of aldehyde and indole, 2-methyl-3- (pt-butylphenyl) ) -Propionaldehyde, ethyl vanillin, heliotropin, hexylsine Namic aldehyde, amylcinamic aldehyde, 2-methyl-2- (p- Isopropylphenyl) -propionaldehyde, coumarin, γ-decalactone , Cyclopentadecanolide, 16-hydroxy-9-hexadecenoic acid lactone , 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexameth Tylcyclopenta-γ-2-benzopyran, β-naphthol methyl ether, N Broxane, dodecahydro-3a, 6,6,9a-tetramethylnaphtho [2,1 b] Furan, cedrol, 5- (2,2,3-trimethylcyclopent-3-e Nyl) -3-methylpentan-2-ol, 2-ethyl-4- (2,2,3-to Limethyl-3-cyclopenten-1-yl) -2-buten-1-ol, cario Filen alcohol, tricyclodecenyl propionate, tricyclodecenyl acetate Benzyl salicylate, seryl acetate, and p- (t-butyl) cycloacetate Hexyl.   Particularly preferred perfume substances are those having the greatest odor in the finished product composition containing cellulase. It gives improvement. These flavors include, without limitation, hexylcinna Mic aldehyde, 2-methyl-3- (pt-butylphenyl) -propion 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, pt-butylcycloacetate Rohexyl, methyl dihydrojasmonate, β-naphthol methyl ether, Tyl-β-naphthyl ketone, 2-methyl-2- (p-isopropylphenyl)- Propionaldehyde, 1,3,4,6,7,8-hexahydro-4,6,6 7,8,8-hexamethylcyclopenta-γ-2-benzopyran, dodecahydro -3a, 6,6,9a-tetramethylnaphtho [2,1b] furan, anisalde Hyd, coumarin, cedrol, vanillin, cyclopentadecanolide, trici acetate Clodecenyl, and tricyclodecenyl propionate.   Other fragrance materials include essence oils, resinoids, and wood from various sources. Fats, for example, without limitation, Lab Dunham resin, nutmeg, cassia oil, benzoin resin, cilantro and Lavandin. Other fragrance chemicals include phenylethyl alcohol Kohl, terpineol, linalool, linalyl acetate, geraniol, nerol , 2- (1,1-dimethylethyl) -cyclohexanol acetate, benzyl acetate, and And eugenol. Carriers such as diethyl phthalate are used in finished fragrance compositions Can be used with things.Other ingredients   Various other ingredients useful in detergent compositions, such as other active ingredients, carriers, hydrogels Trops, processing aids, dyes or pigments, solvents for liquid formulations, solid charges for solid compositions Fillers and the like can be included in the composition. If high foaming is desired, C_Ten~ C₁₆Al Foaming agents such as canolamide are incorporated into the composition, typically in amounts of 1% to 10%. it can. C_Ten~ C₁₄Monoethanol and diethanolamide are typical types Examples of such foaming agents are: Such a foaming agent may be used in combination with the amine oxide, It is also advantageous to use in combination with any high foaming surfactant such as You. If desired, soluble magnesium and / or calcium salts, for example, MgCl_Two, MgSO_Four, CaCl_Two, CaSO_FourGives additional foam and grease Typically, 0.1% to 2% can be added to enhance removal performance.   Various detergent components used in the present composition may optionally include the aforementioned components in a porous hydrophobic form. By absorbing it on a body and then coating the substrate with a hydrophobic coating. Can be further stabilized. Preferably, the detergent component is bound before it is absorbed by the porous substrate. Mix with surfactant. In use, the detergent components are released from the substrate in an aqueous cleaning solution, Therefore, the intended cleaning function is performed.   In order to illustrate this technique in more detail, porous hydrophobic silica (trademark of Degussa) The sipper nut (SIPERNAT) D10] is C_{13 ~ 15}Ethoxylated alcohol (EO7 ) Mix with a proteolytic enzyme solution containing 3% to 5% of a nonionic surfactant. Typically, the enzyme / detergent solution is 2.5 times the weight of the silica. Obtained The powder obtained is mixed with a silicone oil (a variety of silicones in the range of 500 to 12,500) while stirring. Corn oil viscosity can be used). The resulting silicone oil dispersion is emulsified You Or otherwise add to the final detergent matrix. By this means, the enzyme , Bleach, bleach activator, bleach catalyst, photoactivator, dye, fluorescent agent, fabric condition Ingredients, such as detergents and hydrolyzable surfactants, can be used in detergents including liquid laundry detergent compositions. Can be "protected" for use.   Liquid detergent compositions can contain water and other solvents as carriers. methanol, Small molecules exemplified by ethanol, propanol, and isopropanol Primary or secondary alcohols are preferred. Monohydric alcohol is a surfactant Is preferred to solubilize but polyols such as 2-6 carbon atoms and Those containing 2 to 6 hydroxy groups (for example, 1,3-propanediol, Ethylene glycol, glycerin, and 1,2-propanediol) are also used it can. The composition comprises from 5% to 90% of such carriers, typically from 10% to 50%. May be contained.   The detergent composition of the present invention is preferably washed when used in aqueous cleaning operations. Formulated so that the purified water has a pH of 6.5-11, preferably 7.5-10.5 Will be. The liquid dishwashing product formulation preferably has a pH between 6.8 and 9.0. I do. Laundry products typically have a pH of 9-11. Recommended pH for use Techniques for control include the use of buffers, alkalis, acids, etc. It is known.Granule preparation   The bis-alkoxylated cationic surfactant of the present invention is added to the crutcher mix. After treatment with conventional spray drying, short-chain amines with residual (potentially Helps remove contaminants. Used by formulators, for example, in high-density granular detergents To produce mixable particles containing alkoxylated cationic surfactants for use In that case, it is preferred that the particle composition is not highly alkaline. High density (6 The preparation of the granules (> 50 g / l) is described in US Pat. No. 5,366,652. Are listed. Such particles are used to avoid the smell of impurity amines. It may be formulated to have an effective pH in use of 9 or less. This means that Adding an acidity source such as boric acid or citric acid or an appropriate pH buffer to the particles Thus it can be achieved. In another form, the expected Problems can be masked by the use of perfume ingredients as disclosed herein .                                    An example   The following examples further describe and demonstrate preferred embodiments within the scope of the present invention. Examples are , Provided solely for purposes of illustration and should not be construed as limiting the invention. The reason Are many variations possible without departing from the spirit and scope of the invention It is.   In the examples below, the abbreviated component identification has the following meaning:   LAS: Straight chain C₁₂Sodium alkylbenzene sulfonate   C45AS: C₁₄~ C_FifteenLinear sodium alkyl sulfate ethylene oxide   C25E9: C condensed with an average of 9 moles of ethylene oxide_{12 ~ 15}First branch Grade alcohol   Coco EO2: R₁・ N⁺(CH_Three) (C_TwoH_FourOH)_Two(Where R₁Is C₁₂~ C₁₄ Is)   Zeolite A: Formula having a primary particle size of 0.1 to 10 μm Na₁₂(AlO_TwoSiO_Two)₁₂・ 27H_TwoO hydrated sodium aluminosilicate   NaSKS-6: Formula δ-Na_TwoSi_TwoO_FiveCrystalline layered silicate   Carbonate: anhydrous sodium carbonate having a particle size of 200 μm to 900 μm   Silicate: Amorphous sodium silicate (SiO_Two: Na_TwoO ratio 2.0)   MA / AA: maleic acid / acrylic acid 4: 6 copolymer, average molecular weight 11, 000   Protease: Trade name Savinase by Novo Industries A / S Active 4K NPU / g proteolytic enzyme on the market   Cellulase: Sold under the trade name Carezyme by Novo Industries A / S Cellulase degrading enzyme with activity of 1000 CEVU / g sold   Amylase: Termamil 60 by Novo Industries A / S Active 60KNU / g amylolytic enzyme sold under T   Lipase: Sold by Novo Industrose A / S under the trade name Lipolase Lipolytic enzyme having an activity of 100 kLU / g   PB1: Nominal formula NaBO_Two・ H_TwoO_TwoAnhydrous sodium perborate bleach   NOBS: Nonanoyloxybenzenesulfonate in the form of its sodium salt   In the examples below, all amounts are stated as% by weight relative to the composition.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification code FI C11D 3/08 C11D 3/08 3/12 3/12 (81) Designated country EP (AT, BE, CH, DE, DK, ES , FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN , TD, TG), AP (GH, KE, LS, MW, SD, SZ, UG, ZW), UA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM , AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, HU, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD , SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW

Claims (1)

[Claims] 1. (A) a soil dispersant polymer, (b) a non-AQA surfactant, and (c) a formula Wherein R ¹ is a linear, branched or substituted C ₈ -C ₁₈ alkyl, alkenyl, aryl, alkaryl, ether or glycityl ether moiety; R ² is a C ₁ -C ₃ alkyl moiety; R ³ and R ⁴ and hydrogen can vary independently selected from methyl and ethyl, X is an anion, a and a 'are and each C ₁ -C ₄ alkoxy can change independently, p and q Can be independently varied and is an integer in the range of 1 to 30) of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant, and the weight ratio of (c) to (a) is A composition characterized by being in the range of about 1:11 to about 1:14. 2. The composition of claim 1, wherein the soil dispersant polymer is a polymeric polycarboxylate. 3. The polymer polycarboxylates can be obtained from acrylic acid / maleic acid-based copolymers having an average molecular weight in the acid form of 2,000 to 100,000, water-soluble salts of the copolymers, and mixtures thereof. The composition according to claim 2, wherein the composition is selected from the group consisting of: 4. The composition according to claim 1, further comprising a builder component. 5. The composition according to any one of claims 1 to 4, wherein the builder is selected from the group consisting of a mineral builder, an aluminosilicate, a layered silicate or a phosphate builder. 6. The composition according to any one of claims 1 to 5, wherein the composition is prepared by mixing a non-AQA surfactant and an AQA surfactant. 7. The composition according to any one of claims 1 to 6, wherein the non-AQA surfactant is an anionic surfactant. 8. The composition according to any of the preceding claims, wherein the ratio of bis-AQA to non-AQA surfactant is from 1:15 to 1: 8. 9. The bis -AQA surfactant R ¹ is C ₈ -C ₁₈ alkyl, R ² has methyl, A and A 'is an ethoxy or propoxy group, the formula p and q are each 1 to 30 integer, wherein Item 9. The composition according to any one of Items 1 to 8.