JPH11511797A - Detergent composition - Google Patents

Abstract

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

Description

DETAILED DESCRIPTION OF THE INVENTION                                Detergent composition                                 Background art   The present invention comprises a stain remover, a non-AQA surfactant and a bis-alkoxylated quaternary. The present invention relates to a detergent composition containing an ammonium (bis-AQA) cationic surfactant. I do.                                Background of the Invention   Laundry detergent formulations and other cleaning compositions pose significant challenges. Modern compositions are required to remove various stains and stains from various substrates Because. Therefore, laundry detergents, hard surface cleaners, shampoos and other -Sonal cleaning compositions, hand dishwashing detergents, and detergent compositions suitable for automatic dishwashers All require the proper selection and combination of ingredients to work effectively. In general , Such detergent compositions loosen and remove various types of soils and stains It contains one or more surfactants that aim to do so. Looking at the literature, there are many kinds of fields Combinations of surfactants and surfactants seem to be available to detergent manufacturers In contrast, many of these ingredients are suitable for inexpensive unit cost products such as household laundry detergents. The reality is that it is a specialty chemical that does not. Most of this like laundry detergent Household products may also contain one or more conventional ethoxylated non-ionic and / or sulphated Or are still mainly blending sulfonated anionic surfactants Is a fact. This is probably due to the variety of dirt and stains and It is necessary to formulate a composition that works reasonably well for different fabrics. Would.   Different types of stains, such as dirt, greasy / greasy stains and certain food stains Rapid and efficient removal of stains and stains can be a difficult problem. These stains Mixtures of hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous materials And all of these, to varying degrees, consist of hydrophobic components, It is well known that it is difficult to do. Low levels of hydrophobic stains and residual stains Often remains on the surface of the fabric after washing. In addition to the sequence of washing and wearing, Limited removal of hydrophobic stains increases residual soil and stain buildup, Will take up more particulate dust and yellow the fabric. Ultimately, the fabric is thin It gets dirty and consumers discard it because they can't wear it.   According to the literature, various nitrogen-containing cationic surfactants are available in various cleaning compositions. And useful. Typically, an amino, amide, quaternary ammonium or These substances, in the form of imidazolinium compounds, can be used for specialized applications. Often aimed at. For example, various amino and quaternary ammonium surfactants Agents have been proposed for shampoo compositions and are said to be good for hair styling. That Other nitrogen-containing surfactants provide fabric softening and antistatic benefits Used in some laundry detergents. However, in most cases, Commercial use is limited by the obstacles encountered in large-scale production of these compounds. Have been. A further limitation is that ionic interactions with cationic surfactants The possibility of precipitation of the anionic active component of the detergent composition caused. Said above Nonionic and anionic surfactants are still present in current laundry compositions It is the main surfactant component.   Certain bis-alkoxylated quaternary ammonium (bis-AQA) compounds are generally Improves cleaning performance on the various types of stains and stains encountered, especially hydrophobic stains It has now been discovered that it can be used in a variety of detergent compositions to do so. The present invention Of the bis-AQA surfactants were previously known in the art. Provides substantial benefits to formulators over surfactants. For example, in the present invention, Bis-AQA surfactants used in the field are often associated with "daily" fatty / Greatly improves the cleaning of oily hydrophobic stains. Further, bis-AQA surfactants Commonly used in detergent compositions such as alkyl sulfates and alkyl benzene sulfonates It has an affinity for anionic surfactants. Detergent composition has anionic surfactant The incompatibility with surfactants has generally been a factor in the use of cationic surfactants to date. Was a limiting factor. Low level (3 ppm in laundry liquor) bis-AQA surfactant The agent provides the advantages described in the present invention. Bis-AQA surfactants are 5 to 1 It can be formulated over two broad pH ranges. Bis-AQA surfactant , Can be prepared as a 30% (by weight) solution over the pump, thus easily at the manufacturing plant Can handle. Bis-AQA surfactants with a degree of ethoxylation of more than 5 are sometimes liquid And thus can be provided as a 100% stock solution. In addition to beneficial handling properties Availability of bis-AQA surfactant as a highly concentrated solution means that transportation costs A substantial economic advantage.   Further, a composition containing a stain remover (SRA) and a bis-AQA surfactant is , Additionally excellent cleaning performance and whiteness for products containing either technology alone It has also been discovered that it can perform well. SRA has a natural affinity for textiles It is like. During washing, the SRA adheres to the fabric and remains on the fabric. Therefore, the dirt and stains collected by wearing are not on the fabric itself, but on the SRA Will be left. Subsequent washing operations remove the SRA from the fabric surface and Remove dirt / stain. The advantages of the bis-AQA / SRA system are (1) bis-AQA (2) Solubilization of dirt by bis-AQA is cloth (3) Removal of the newest soil by SRA, which improves the access of the SRA to the surface, The above means that the bis-AQA can further solubilize the accumulated residual soil. It is believed to be the result. Effective for soiling (including previous soiling) with this system Good removal improves wash and fabric whiteness.                                 Background art   A. Mehreteab and Lopresto (FJ Lop) U.S. Pat. No. 5,441,541 issued Aug. 15, 1995. No. relates to anionic / cationic surfactant mixtures. Murphy (AP . Murphy), Smith (RJM Smith) and Brooks (M. P. Brooks), UK 2,040,99, issued on September 3, 1980. No. 0 relates to ethoxylated cationic surfactants in laundry detergents.                                Summary of the Invention   The present invention relates to a stain remover, a non-AQA surfactant and an effective agent represented by the following formula: Of bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant Detergent compositions prepared by containing detergents or by using them in combination. Offer.   (Where R¹Is a linear, branched or substituted C₈-C₁₈Alkyl, alkenyl, ally Alkenyl, ether or glycidyl ether component;^TwoIs C₁ -C_ThreeAn alkyl component;^ThreeAnd R^FourCan vary independently, and hydrogen and Selected from chill and ethyl, X is an anion, and A and A ′ are independently variable And C₁-C_FourAlkoxy, wherein p and q are independently variable And an integer in the range of 1 to 30)                             Detailed description of the invention Stain remover   The composition of the present invention is a polymer soil, hereinafter referred to as "SRA" or "SRA @ s". Contains a remover. SRA ‘s is from 0.01% to 10.0% of the composition, typically From 0.1% to 0.5%, preferably from 0.2% to 3.0% by weight.   Preferred SRA's are typically hydrophobic, such as polyester and nylon. A hydrophilic segment that makes the surface of the hydrophilic fiber hydrophilic, and deposited on the hydrophobic fiber, After the washing and rinsing cycles, the hydrophilic segment remains attached to the fiber. And a hydrophobic segment that acts as an anchor for This is for SRA The stains that occur after the treatment by washing more easily in subsequent washing procedures Can make it possible.   SRA ‘s are available in various forms, for example, charged anions or charged cations (US Pat. No. 4,956,447) and even containing uncharged monomer units. And the structure may be linear, branched or even star. They have a molecular weight A particularly effective encapsulation component to control the physical properties or alter physical or surfactant properties May be included. Structure and charge distribution are applicable to various fiber or fabric types And may be tailored to a variety of detergent or detergent additive products.   Preferred SRA ‘s typically include titanium (IV) alkoxides such as At least one transesterification / oligomerization often involves the use of complex metal catalysts. Oligomeric terephthalates prepared by such processes. These esters, of course, do not form a tightly crosslinked Additional objects that can penetrate the ester structure via two, three, four or more positions It may be manufactured using a mask.   Suitable SRA's include, for example, JJ Scheibel. No. 4,968,451, issued Nov. 6, 1990 and Gosselink. (Gosselink). P. Terephthaloyl and Oxyalkyleneoxy repeating unit oligomer ester backbone And an allyl-derived sulfonated end component covalently linked to the Substantially linear ester oligomer sulfonated products. These The ester oligomer comprises (a) ethoxylation of allyl alcohol, (b) the product of (a) Was converted to dimethyl terephthalic acid (“DM T ") and 1,2-propylene glycol (" PG "), (c) (b) Can be prepared by reacting the product with sodium metabisulfite in water . Further, suitable SRA's include, for example, poly (ethylene glycol) methyl ether. Esters for polyester, DMT, PG and poly (ethylene glycol) ("PEG") Gosselin, such as those produced by exchange / oligomerization k) et al., U.S. Patent No. 4,711,730, issued December 8, 1987 1,2-propylene / polyoxyethylene terephthalate polyester Ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa Gosselink (Go) such as an oligomer from -8-hydroxyoctanesulfonate U.S. Pat. No. 4,721,580 issued Jan. 26, 1988 to Ssellink). Partial and full anion end-capped oligomeric esters: eg DMT, Me-encapsulated PEG and EG and / or PG, or DMT, EG and // PG, Me-encapsulated PEG and Na-dimethyl-5-sulfoisophthale 198 by Gosselink, manufactured from a combination of luic acids Non-ion-sealing block of U.S. Pat. No. 4,702,857 of Oct. 27, 7 Polyester oligomer compound; Maldonado, Gosselink ( Gosselink et al., U.S. Pat. No. 4,877, Oct. 31, 1989. No. 896, particularly sulfoaroyl-terminated terephthalates. No. The latter is an SRA® useful in both laundry and fabric preparation products. s, one example being optional but preferably, for example, PEG3 M-sulfobenzoic acid monosodium salt, P further added with PEG such as 400 An ester composition produced from G and DMT.   SRA's includes a U.S. Patent by Hays on May 25, 1976 No. 3,959,230 and Basadu on July 8, 1975. r) ethylene terephthalic acid referred to in U.S. Pat. No. 3,893,929 Or propylene terephthalic acid and polyethylene oxide or polypropylene A simple copolymer block with oxide terephthalic acid, from Dow to METHO Cellulose such as hydroxyethercellulose polymer available as CEL Derivatives; and the United States on December 28, 1976 by Nicol et al. C referred to in patent 4,000,093₁-C_FourAlkyl cellulose and C_Four Also included are hydroxyalkyl celluloses. Poly (vinyl ester) hydrophobic Suitable SRA's characterized by a polyalkylene oxide Grafted onto the backbone, eg C₁-C₆Vinyl ester, preferably Graft copolymers of poly (vinyl ester) such as poly (vinyl acetate) No. European patent issued on April 22, 1987 by Kud et al. See application 0219048. Commercially available examples include those from BASF, Germany. SOKALAN SRA ‘s, such as SOKALAN HP-22, are available. It is. Other SRA ‘s are polyoxyethylenes having an average molecular weight of 300-5,000. 90-80% by weight of polyoxyethylene tele, derived from len glycol A repeating unit containing 10-15% by weight of ethylene terephthalate with phthalate Polyester. Commercial examples include those from DuPont. ZELCON5126 and MILEASET from ICI.   Other preferred SRAs are terephthaloyl (T), sulfoisophthaloyl (S IP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG ) An empirical formula comprising a unit and preferably terminating at a capping (CAP) (CAP)_Two(EG / PG)_Five(T)_Five(SIP)₁Is an oligomer having Of a sulfoisophthaloyl unit, five terephthaloyl units, preferably Oxyethylene oxy and o in a limiting ratio of about 0.5: 1 to about 10: 1. Xy-1,2-propyleneoxy unit and 2- (2-hydroxyethoxy) ) -D Oligo containing two end-capping units derived from sodium tansulfonate Preferably, it is a modified isethionate as in the above. The SRA is preferably Is linear sodium dodecylbenzenesulfonate or xylene-, cumene-, Examples, such as members selected from toluene-sulfonates or mixtures thereof For example, 0.5% to 20% by weight of a crystal-reducing stabilizer such as an anionic surfactant. Further comprising an oligomer of All of these stabilizers or denaturing agents may be found in May 1995 Gosselink, Pan, Keret (Ke) issued on the 16th U.S. Pat. No. 5,415,807 to Illett and Hall. Introduced into a synthesis can as taught in Suitable monomers for the above SRA , Na2- (2-hydroxyethoxy) -ethanesulfonate, DMT, Na- Dimethyl 5-sulfoisophthalate, EG and PG.   Yet another group of preferred SRA's is (1) (a) dihydroxysulfonate, At least one unit selected from the group comprising rehydroxysulfonates Therefore, the ester bond is formed by being at least trifunctional, and Sesame backbone producing units and combinations thereof (b) Terephthaloyl At least one unit (c) which is a component A backbone containing at least one non-sulfonated unit that is Ion sealing unit, alkoxylated, preferably ethoxylated isethionate, Alkoxylated propane sulfonate, alkoxylated propane disulfonate, alcohol Anionic capping units such as coxylated phenol sulfonates, sulfoaroyl And one or more sealing units selected from derivatives and mixtures thereof. Sesame ester. Preferred such esters have the empirical formula Things. ｛(CAP)_x(EG / PG)_{y '}(DEG)_{y "}(PEG)_{y '''}(T)_z(SIP)_{z '} (SEG)_q(B)_m｝   (Where CAP, EG / PG, PEG, T and SIP are as defined above. (DEG) represents di (oxyethylene) oxy unit, and (SEG) represents Units derived from the sulfoethyl ether of Lyserin and related components Represents a knit, and (B) forms an ester bond by being at least trifunctional. Represents a branching unit that yields a branched oligomer backbone, where x is from about 1 to about 12, y ′ is from about 0.5 to about 25, y ″ is from 0 to about 12, and y ″ Is from 0 to about 10 and the sum of y '+ y "+ y"' is from about 0.5 to about 25; Is from about 1.5 to about 25, z 'is from 0 to about 12, and the sum of z + z' is about 1. 5 to about 25, q is about 0.05 to about 12, and m is about 0.01 to about 25. And x, y ′, y ″, y ″ ′, z, z ′, q and m are moles of the ester Represents the average number of moles of the corresponding unit per unit, wherein the ester is from about 500 to about 5, 000)   Preferred SEG and CAP monomers for the above esters include Na-2- (2-, 3-, dihydroxypropoxy) ethanesulfonate ("SEG"), Na -2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") , Its homologues and their mixtures and the ethoxylation and allyl alcohol And sulfonated products. Preferred SRA esters of this class include: Na-2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate and And / or Na-2 [2- {2- (2-hydroxyethoxy) -ethoxy} ethoxy] C] ethanesulfonate, DMT, Na-2 (2,3-dihydroxypropoxy ) Ethane sulfonate, EG and PG using suitable Ti (IV) catalyst Tell exchange and oligomerization products. This SRA ester is (CA P)_Two(T)_Five(EG / PG)_1.4(SEG)_2.5(B)_0.13Can be expressed as Where CAP is (Na^+ -O_ThreeS [CH_TwoCH_TwoO]_3.5)-And B is glycerin And the molar ratio of EG / PG is the same as that of conventional gas chromatography after hydrolysis. Ma It is about 1.7: 1 as measured by chromatography.   Additional classes of SRA's include (I) by Violland et al. No. 4,201,824 and by Lagase et al. Diisocyanate coupling agent referred to in US Pat. No. 4,240,918 Nonionic terephthalate which binds the polymer ester structure using (II) Trimeritate of terminal hydroxyl group by adding melitate to known SRA ‘s S with carboxylate end groups produced by conversion to acid esters RA ‘s. With the proper choice of catalyst, anhydrous trimellitate Rather than by ring opening of the water bond, the independent carboxylic acid of trimellitic anhydride The ester forms a bond at the end of the polymer. Non-ionic or anionic These SRA's have an output as long as they have an esterifiable hydroxyl end group. It can be used as a generating material. U.S. Pat. See 525,524. In addition, additional classes for SRA ‘s include (III) viola See U.S. Pat. No. 4,201,824 to Violland et al. Anionic terephthalate-based SRA ‘s, a variant of a urethane binding component, (IV) See U.S. Pat. No. 4,579,681 to Rupert et al. Vinylpyrrolidone and / or both nonionic and cationic polymers Or poly (vinylcap) with a monomer such as dimethylaminoethyl methacrylate Loractam) and related copolymers, (V) Rhonpuran Chemii (Rhon e-Poulenc Chemie) EP 279,134; Acrylic monomer grafted on sulfonated polyester, referenced in 1988 Added to the SOKALAN type from BASF manufactured by Flotation polymer whose SRA's are similar to known cellulose ethers Graft polymers claimed to have removal and anti-redeposition activity, ( VI) See BASF European Patent Publication No. 457,205 (1991). Vinyl monomers such as acrylic acid and vinyl acetate to proteins such as casein Graft, (VII) 1974, Unilever NV See DE 2,335,044 by Bevan et al. Adipic acid, caprolactam and polyethylene glycol for the treatment of mid fabrics And polyester polyamide SRA's prepared by the condensation of Yes Other SRA's for use in U.S. Patent Nos. 4,240,918, 4,787, No. 989, 4,525,524 and 4,877,896. I have.   Other preferred SRAs are terephthaloyl (T), sulfoisophthaloyl (S IP), oxyethyleneoxy and oxy-1,2-propylene (EG / PG ) An empirical formula comprising a unit and preferably terminating at a capping (CAP) (CAP)_Two(EG / PG)_Five(T)_Five(SIP)₁Is an oligomer having Of a sulfoisophthaloyl unit, five terephthaloyl units, preferably Oxyethylene oxy and o in a limiting ratio of about 0.5: 1 to about 10: 1. Xy-1,2-propyleneoxy unit and 2- (2-hydroxyethoxy) ) -Comprising two end-capping units derived from sodium ethanesulfonate Preferably it is a modified isethionate as in the oligomer. The SRA is good Preferably, sodium linear dodecylbenzenesulfonate or xylene, Or a member selected from toluene-sulfonate or a mixture thereof. For example, 0.5% to 20% of a crystal-reducing stabilizer such as an anionic surfactant. It further comprises a weight percent of the oligomer. These stabilizers or denaturants are all 1995 Gosselink, Pan, Kellet issued on May 16, 2011 U.S. Pat. No. 5,415,8 to Kellett and Hall. No. 07 is introduced into the synthesis can as taught. Appropriate things for the above SRA In general, Na2- (2-hydroxyethoxy) -ethanesulfonate, DMT, Na -Dimethyl 5-sulfoisophthalate, EG and PG.   Yet another group of preferred SRA's is (1) (a) dihydroxysulfonate, At least one unit selected from the group comprising rehydroxysulfonates Therefore, the ester bond is formed by being at least trifunctional, and Sesame backbone producing units and combinations thereof (b) Terephthaloyl At least one unit (c) which is a component A backbone containing at least one non-sulfonated unit that is Ion sealing unit, alkoxylated, preferably ethoxylated isethionate, Alkoxylated propane sulfonate, alkoxylated propane disulfonate, alcohol Anionic capping units such as coxylated phenol sulfonates, sulfoaroyl And one or more sealing units selected from derivatives and mixtures thereof. Sesame ester. Preferred of such esters are those of the following empirical formula ｛(C AP)_x(EG / PG)_{y '}(DEG)_{y "}(PEG)_{y '''}(T)_z(SIP)_{z '}(S EG)_q(B)_mＣ, where CAP, EG / PG, PEG, T and And SIP are defined above, and (DEG) is di (oxyethylene) oxy (SEG) is derived from sulfoethyl ether of glycerin Unit and associated component units, wherein (B) is at least trifunctional Resulting in a branched oligomer backbone, forming an ester bond. Represents a knit, x is 1 to 12, y 'is 0.5 to 25, and y "is 0 12, y ′ ″ is from 0 to 10, and y ′ + y ″ + y ″ ′ is from 0.5 to 10. 25, z is 1.5 to 25, z 'is 0 to 12, and z + z' sum Is from 1.5 to 25, q is from 0.05 to 12, and m is from 0.01 to 10 And x, y ′, y ″, y ′ ″, z, z ′, q and m are moles of the ester Represents the average number of moles of the corresponding unit, the ester being from 500 to 5,000 It has a range of molecular weights.   Preferred SEG and CAP monomers for the above esters include Na-2- (2-, 3-, dihydroxypropoxy) ethanesulfonate ("SEG"), Na -2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") , Its homologues and their mixtures and the ethoxylation and allyl alcohol And sulfonated products. Preferred SRA esters of this class include: Na-2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate and And / or Na-2 [2- {2- (2-hydroxyethoxy) -ethoxy} ethoxy] C] ethanesulfonate, DMT, Na-2 (2,3-dihydroxypropoxy ) Ethane sulfonate, EG and PG using suitable Ti (IV) catalyst Tell exchange and oligomerization products. This SRA ester is (CA P)_Two(T)_Five(EG / PG)_1.4(SEG)_2.5(B)_0.13Can be expressed as Where CAP is (Na^+ -O_ThreeS [CH_TwoCH_TwoO]_3.5)-And B is glycerin And the molar ratio of EG / PG is the same as that of conventional gas chromatography after hydrolysis. It is about 1.7: 1 as measured by matograph.   Additional classes of SRA's include (I) by Violland et al. U.S. Pat. No. 4,201,824 and rice by Lagase et al. Diisocyanate coupling agent referred to in US Pat. No. 4,240,918 Nonionic terephthalate which binds the polymer ester structure using (II) Trimeritate of terminal hydroxyl group by adding melitate to known SRA ‘s S with carboxylate end groups produced by conversion to acid esters RA ‘s. With the proper choice of catalyst, anhydrous trimellitate Rather than by ring opening of the water bond, the independent carboxylic acid of trimellitic anhydride The ester forms a bond at the end of the polymer. Non-ionic or anionic These SRA's have an output as long as they have an esterifiable hydroxyl end group. It can be used as a generating material. U.S. Pat. See 525,524. In addition, additional classes for SRA ‘s include (III) viola See U.S. Pat. No. 4,201,824 to Violland et al. Anionic terephthalate-based SRA ‘s, a variant of a urethane binding component, (IV) See U.S. Pat. No. 4,579,681 to Rupert et al. Vinylpyrrolidone and / or both nonionic and cationic polymers Or poly (vinylcap) with a monomer such as dimethylaminoethyl methacrylate Loractam) and related copolymers, (V) Rhonpuran Chemii (Rhon e-Poulenc Chemie) EP 279,134; Acrylic monomer grafted on sulfonated polyester, referenced in 1988 Added to the SOKALAN type from BASF manufactured by Flotation polymer whose SRA's are similar to known cellulose ethers Graft polymers claimed to have removal and anti-redeposition activity, ( VI) Casein-like as referred to in EP 457,205A of BASF (1991). Grafting of vinyl monomers such as acrylic acid and vinyl acetate onto various proteins, (VI I) 1974, Beleva of Unilever NV n) et al., DE 2,335,044, in particular the treatment of polyamide fabrics Of adipic acid, caprolactam and polyethylene glycol for The prepared polyester polyamide SRA's is mentioned. Other useful S RA @ s are disclosed in U.S. Pat. Nos. 4,240,918, 4,787,989, 525,524 and 4,877,896.   Other suitable soil removers include starches grafted with polycarboxylic acid groups. Materials having a base backbone are included.Bis-alkoxylated quaternary ammonium (bis-AQA) compounds   The second essential component of the present invention comprises an effective amount of a bis-AQA surfactant represented by the following formula: Contains sexual agents.   (Where R¹Has 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably Straight chain, branched or substituted alkyl, alkenyl, preferably containing 8 to 14 carbon atoms , Aryl, alkaryl, ether or glycidyl ether components. , R^TwoIs an alkyl group containing from 1 to 3 carbon atoms, preferably methyl;^ThreeAnd And R^FourCan vary independently and include hydrogen (preferred), methyl and ethyl Selected from the group^-Chloride, bromide, methyl sulfate And anions such as sulfates, where A and A 'can vary independently and Each C₁-C_FourAlkoxy, especially ethoxy, propoxy, butoxy and their Wherein p is 1 to 30, preferably 1 to 15, and more preferably Is from 1 to 8, even more preferably from 1 to 4, and q is from 1 to 30, preferably 1 to 15, more preferably 1 to 8, still more preferably 1 to 4, most preferably Also preferably, p and q are 1.)   Hydrocarbyl substituent R¹Is C₈-C₁₂, Especially C₈-C_TenBis-AQA The compound increases the dissolution rate of laundry granules, especially under cold water conditions, compared to long chain substances. You. Therefore, C₈-C₁₂Bis-AQA surfactants are preferred by some formulators Sometimes. Bis-AQA interface used to prepare a final laundry detergent composition The level of activator is 0.1% to 5%, typically 0.45% to 2.5% by weight Range. The weight ratio of bis-AQA to percarbonate bleach was 1:10. 0 to 5: 1, preferably 1:60 to 2: 1, most preferably 1:20 to 1 : 1 range.   The present invention is directed to improving the performance of cleaning compositions containing other optional components. An "effective amount" of the bis-AQA surfactant is used. Bis-AQA field in the present invention An "effective amount" of a surfactant is defined as directional or significant at a 90% confidence level. To improve the performance of the cleaning composition on at least some of the get soils and stains Means a sufficient amount. Therefore, if the target is a composition containing a specific food stain, And the formulator at least directionally improves the cleaning performance against such stains Use sufficient bis-AQA to Similarly, the composition in which the target contains clay stains In products, formulators at least directionally improve their cleaning performance against such soils. Use enough bis-AQA to improve.   Bis-AQA surfactant achieves at least directional improvement in cleaning performance May be used in combination with other detersive surfactants at levels effective for No. In the context of a fabric laundry composition, such "use level" is a measure of dirt and stains. Not only the type and intensity, but also the washing water temperature, washing water volume and washing machine type. Can be changed.   For example, a top-mounted vertical axis U using 45 to 83 liters of water in the washing bath . S. Type automatic washing machine, 10 to 14 minutes washing cycle and 10 to 50 ° C In washing water temperature, 2 ppm to 50 ppm, preferably 5 ppm to 25 pp Preferably, m of the bis-AQA surfactant is contained in the wash water. From 50ml Based on the usage rate of 150 ml / wash load, this is a heavy duty liquid wash In the case of rinses, 0.1% to 3.2%, preferably 0.3% to 1.5% -Converted to the concentration (weight) of AQA surfactant in the product. 60g to 95g / wash Based on the usage rate of the rinsing load, this is the case for high concentration (“compact”) granular laundry detergents. If (density is greater than 650 g / l), 0.2% to 5.0%, preferably Is converted to the product concentration (weight) of 0.5% to 2.5% bis-AQA surfactant Is done. Based on the usage of 80 g to 100 g / wash load, this is For dry granules (ie "fluffy", density less than 650 g / l) 0.1% to 3.5%, preferably 0.3% to 1.5% bis-AQA interface Activity It is converted to the concentration (weight) of the active agent in the product.   For example, top-loading horizontal axis Europe with 8 to 15 liters of water in the washing bath Type automatic washing machine, 10 to 60 minute washing cycle and 30 ° C to 95 ° C washing water At temperature, 13 ppm to 900 ppm, preferably 16 ppm to 390 p Preferably, pm of the bis-AQA surfactant is contained in the wash water. 45ml Based on usage rates of 270 ml / wash load, this is a heavy duty liquid 0.4% to 2.64%, preferably 0.55% to 1.1% for laundry detergent Of the bis-AQA surfactant in the product (weight). From 40g to 21 Based on the usage of 0 g / wash load, this is a high concentration (“compact”) granule wash In the case of detergents (density greater than 650 g / l), 0.5% to 3.5%, Preferably, 0.7-1.5% bis-AQA surfactant concentration in the product (weight ). Based on usage rate of 140g to 400g / wash load, this Are spray-dried granules (ie, "fluffy", having a density less than 650 g / liter) ), 0.13% to 1.8%, preferably 0.18% to 0.76% It is converted into the concentration (weight) of bis-AQA surfactant in the product.   For example, top-loading vertical axis days using 26 to 52 liters of water in the washing bath This type of automatic washing machine, 8 to 15 minute washing cycle and 5 to 25 ° C washing water temperature In 1.67 ppm to 66.67 ppm, preferably 3 ppm to 6 p Preferably, pm of the bis-AQA surfactant is contained in the wash water. 20ml Based on the usage rate of 30ml / wash load, this is a heavy duty liquid wash 0.25% to 10%, preferably 1.5% to 2% of bis-A for rinsing It is converted to the concentration (weight) of the QA surfactant in the product. 18g to 35g / washing load This is the case for high-concentration (“compact”) granular laundry detergents, based on loading, (Density greater than 650 g / l), 0.25% to 10%, preferably 0% . Converted from 5% to 1.0% bis-AQA surfactant in product concentration (weight) You. Based on the usage rate of 30 g to 40 g / wash load, this is (Ie, "fluffy", density less than 650 g / l) % To 10%, preferably 0.5% to 1% bis-AQA surfactant in the product It is converted to concentration (weight).   As can be seen from the above description, the screws used in the washing situation of the machine washing -The amount of AQA surfactant will vary depending on the user's habits and practices, and the type of washing machine. Can be. However, in this context, prior to one of the bis-AQA surfactants The advantage that was not observed was that other surfactants (generally anionic Or an anion / non-ionic mixture). To improve performance at least directionally over a range of stains and stains. It is possible. This means that various cationic surfactants can be used at the stoichiometric level. Or other groups in the art for use with or near anionic surfactants It is distinguished from adult. Generally, in the practice of the present invention, in a laundry composition The weight ratio of bis-AQA: anionic surfactant is 1:70 to 1: 2, preferably. Or 1:40 to 1: 6, preferably 1:30 to 1: 6, most preferably 1 : 15 to 1: 8. Both anionic and nonionic surfactants Bis-AQA: mixed anion / non-ionic weight ratio in the containing laundry composition Ranges from 1:80 to 1: 2, preferably from 1:50 to 1: 8.   Anionic surfactants, optional nonionic surfactants and betaines, salts And various other cleaning compositions containing special surfactants such as amine oxides, The method of the present invention may be formulated using an effective amount of a bis-AQA surfactant. it can. Such compositions include hand dishwashing products (especially in liquid or gel form), hard surface Agents, shampoos, personal wash bars and wash bars, but are not limited thereto. Not determined. The differences between the habits and practices of the users of these compositions are extremely small. From about 0.25% to about 5%, preferably from about 0.45% to about 2% by weight of bis-A Q It is sufficient to add the A surfactant into such a composition. Again, granules and As with liquid laundry compositions, the bis-AQA interface present in such compositions The weight ratio of surfactant to other surfactants is small. That is, an anionic surfactant It is smaller than the stoichiometry in the case of a sex agent. Preferably, such cleaning compositions are mechanical In the case of laundry compositions it consists of the bis-AQA / surfactant ratio just described.   In contrast to other cationic surfactants known in the art, The bis-alkoxylated cationic surfactant in the invention is a nonionic surfactant Mixed surfactant containing, for example, an alkyl sulfate surfactant It has sufficient solubility that can be used in combination with the system. This is a top-loading Automatic washing machines, especially those of the type used in North America, and the conditions of use in Japan Is intended to be used in automatic washing machines of the type used in This can be an important consideration for formulators of certain types of detergent compositions. Typically, this The resulting composition has a composition of from about 25: 1 to about 1:25, preferably from about 20: 1 to about 3: 1. Weight ratio of anionic surfactant to nonionic surfactant. this Is typically about 10: 1 to 1:10, preferably about 5: 1 to about 1: 1. It can be contrasted with a European formulation consisting of a range of anion: nonionic ratios.   Preferred ethoxylated cationic surfactants in the present invention are Akzo Novell® Chemicals Company (Akzo Nobel Chemicals Company) y) can be obtained under the trade name ETHOQUAD. Instead, these materials , Various different reaction mechanisms (where "EO" is -CH_TwoCH_TwoO-Uni (Representing a set).Mechanism 1 Mechanism 2 Mechanism 3 Mechanism 4           The economic reaction mechanism is as follows.Mechanism 5   The following parameters summarize optional and preferred reaction conditions for mechanism 5 is there. Step 1 of the reaction is preferably performed in an aqueous medium. The reaction temperature is Typically, it is in the range of 140-200 ° C. Reaction pressure is 50-1000 psi g. A basic catalyst, preferably sodium hydroxide, can be used. Anti The molar ratio of the reactants is amino: alkyl sulfate = 2: 1 to 1: 1. The reaction is good Preferably C₈-C₁₄This is performed using an alkyl sulfate sodium salt. Ethoxylation And the quaternization step is performed using conventional conditions and reactions.   In some cases, the reaction mechanism 5 is sufficient to allow a gel to form in the aqueous reaction medium. This produces a soluble product. The required product can be recovered from the gel, but will be described later An alternative two-step synthesizer 6 may be more desirable in commercial environments. You. The first step in the mechanism 6 is performed similarly to the mechanism 5. Second step (Ethoxylation) preferably results in ethylene oxide and a quaternary surfactant The reaction is performed using an acid such as HCl. As shown below, chlorohydrin, That is, chloroethanol also reacts to produce bishydroxyethyl derivatives be able to.   For the reaction mechanism 6, the following parameters are optional and related to the first step: It summarizes the preferred reaction conditions. The first step is preferably an aqueous medium Done throughout the body. Reaction temperatures are typically in the range of 100-230 ° C. Anti The reaction pressure is 50-100 psig. Base, preferably sodium hydroxide HSO formed during the reaction with_FourAnd can be reacted. Or the excess It can also be reacted with an acid using a min. Moles of amine to alkyl sulfate The ratio is typically 10: 1 to 1: 1.5, preferably 5: 1 to 1: 1.1, It is more preferably from 2: 1 to 1: 1. In the product recovery step, The converted amine is simply separated as a distinct phase from the aqueous reaction medium, which itself is insoluble. It is. The second step of the process is performed under conventional reaction conditions. Further ethoxylation and quaternization to yield bis-AQA surfactants are standard It is performed under conditioned conditions.   Mechanism 7 optionally comprises ethylene oxide under standard ethoxylation conditions but without catalyst. To achieve monoethoxylation.   The following mechanism illustrates these additional reaction mechanisms, where "EO" is -CH_TwoCH_TwoRepresents the O-unit. In this reaction, an inorganic base, an organic base or Is the HSO formed using any of the excess amine reactants_FourNeutralize.Mechanism 6 Mechanism 7   The following further describes some of the above reactions, merely for the benefit of the formulator, It is not intended to limit the reaction.Synthetic A Preparation of N, N-bis (2-hydroxyethyl) dodecylamine   19.86 g of sodium dodecyl sulfate (0.06921 mol), 14.55 g Diethanolamine (0.1348 mol), 7.6 g of 50% by weight sodium hydroxide Solution (0.095 mol) and 72 g of distilled H_TwoO for glass autoclay Add to briner. Glass liner with 500ml stainless steel swing auto Seal in a clave and place under 160-400 psig nitrogen for 3-4 hours under 160- Heat to 180 ° C. The mixture was cooled to room temperature and the liquid content of the glass liner was Pour into 250 ml separatory funnel with ml chloroform. Leave the funnel for several minutes. Shake in minutes, then allow the mixture to separate. Remove the lower chloroform layer and The product is obtained by evaporating the roform.Synthetic B Preparation of N, N-bis (2-hydroxyethyl) dodecylamine   One mole of sodium dodecyl sulfate is prepared in the manner described in Synthesis A in the presence of a base. React with 1 mol of ethanolamine. The resulting 2-hydroxyethyl dodecyl Recover amine and react with 1-chloroethanol to prepare title compound .Synthetic C Preparation of N, N-bis (2-hydroxyethyl) dodecylamine   19.86 g of sodium dodecyl sulfate (0.06921 mol), 21.37 g Ethanolamine (0.3460 mol), 7.6 g of 50% by weight sodium hydroxide Solution (0.095 mol) and 72 g of distilled H_TwoO in glass autoclave Add to liner. Glass liner with 500ml stainless steel rocking haute Seal in a rabe and 160-1 under 300-400 psig nitrogen for 3-4 hours. Heat to 80 ° C. The mixture was cooled to room temperature and the liquid content of the glass liner was Pour into a 250 ml separatory funnel with 1 liter of chloroform. Enough funnel for a few minutes The mixture is then allowed to separate. Remove the lower chloroform layer and remove The product is obtained by evaporating the form. The product is treated with a basic catalyst at 120-130 ° C. React with 1 molar equivalent of ethylene oxide in the absence.   Further ethoxylation of the bis-substituted amine prepared in the above synthesis in a standard manner can do. Quaternized with an alkyl halide, the bis-A Generating a QA surfactant is a routine procedure.   The following is the bis-AQA surfactant used in the present invention according to the above description. 5 is a non-limiting specific example of a sex agent. Bis-AQA surfactant according to the invention The degree of alkoxylation described is one-to-one with respect to conventional ethoxylated nonionic surfactants. Understand to report as an average, according to common practice. It is ethoxylated This is because the reaction generally results in a mixture of substances having different degrees of ethoxylation. Obedience Thus, all EO values are reported except as integers (eg, “EO2.5”, “EO3 . 5)) is not uncommon. ^*Ethoxy optionally terminated with methyl or ethyl   A highly preferred bis-AQA compound for use in the present invention has the formula: Is what is done.   (Where R¹Is C₈-C₁₈Hydrocarbyl and their mixed components, preferably C₈, C_Ten, C₁₂, C₁₄Alkyl and their mixed components, X, balance charge Any conventional anion to provide, preferably chloride)   With respect to the general structure of the bis-AQA surfactant described above, the preferred compound And R¹Coconut (C₁₂-C₁₄Alkyl) fraction derived from fatty acids,^TwoBut Chill, ApR^ThreeAnd A'qR^FourAre monoethoxy, A preferred type of compound is “cocoMeEO2” in the above list in the present invention. Or "Bis-AQA-I".   Other bis-AQA compounds useful in the present invention include those represented by the following formula: The compound of.   (Where R¹Is C₈-C₁₈Hydrocarbyl, preferably C₈-C₁₄Alkyl Independently, p is 1 to 3, q is 1 to 3, R¹Is C₁-C_ThreeArchi X is an anion, especially chloride or bromide. )   Other compounds of the type described above include ethoxy (CH_TwoCH_TwoO) Unit (E O) is butoxy (Bu) isopropoxy [CH (CH_Three) CH_TwoO] and [CH_Two CH (CH_ThreeO)] unit (i-Pr) or n-propoxy unit (pr) Or a mixed component of EO and / or Pr and / or i-Pr units And more substituted compounds.   Highly preferred bis-AQA compounds for use in underbuilder formulations Is an integer wherein p and / or q is an integer in the range between 10 and 15 in the above formula It is of the above formula. This compound is particularly useful in hand laundry detergent compositions.Non-AQA cleaning surfactant   In addition to the bis-AQA surfactant, the composition of the present invention preferably comprises a non-AQA It further contains a detersive surfactant. Non-AQA detersive surfactants essentially include: Any anionic, nonionic, or additional cationic surfactant may be included .Anionic surfactant   Anionic interfaces useful in the present invention, typically at a level of 1% to 55% by weight Non-limiting examples of activators include conventional C₁₁-C₁₈Alkylbenzene sulfonate ("L AS "), primary (" AS ") branched chain and random C_Ten-C₂₀Alkyl sulfate, this formula Wherein x and (y + 1) are at least 7, preferably at least 9 And M is a water-soluble cation, in particular unsaturated salts such as sodium and oleyl sulfate. Sulfate, C₁₂-C₁₈Alpha-sulfonated fatty acid ester, C_Ten-C₁₈Sulfation Polyglucoside, C_Ten-C₁₈Alkylalkoxy sulfates ("AExS"; especially EO 1-7 ethoxysulfate), and C_Ten-C₁₈Alkyl alkoxy carboxylate ( EO1-5 ethoxycarboxylate) of the formula CH_Three(CH_Two)_x(CHOSO_Three ^- M⁺) CH_ThreeAnd CH_Three(CH_Two)_y(CHOSO_Three ^-M⁺) CH_TwoCH_ThreeC_Ten-C_{1 8} Secondary (2,3) alkyl sulfates. C₁₂-C₁₈Betaine and Sur Hobetaine ("sultaine"), C_Ten-C₁₈Amine oxide is also included in the overall composition be able to. C_Ten-C₂₀May also be used. If you need high foam , Branched chain C_Ten-C₁₆Soap may be used. Other useful traditional surfactants are Listed in standard text.Nonionic surfactant   Nonionic interfaces useful in the present invention, typically at a level of 1% to 55% by weight Non-limiting examples of activators include alkoxylated alcohols (AE), alkyl phenols , Polyhydroxy fatty acid amide (PFAA), alkyl polyglycoside (ARG) And C_Ten-C₁₈Glycerol ether.   More specifically, primary and secondary aliphatic alcohols and 1-25 moles of ethylene oxide The product (AE) condensed with a resin is used as the nonionic surfactant in the present invention. Suitable for The alkyl chain of the aliphatic alcohol may be linear or branched, primary or The second can be any and generally contains from 8 to 22 carbon atoms. The preferred ones are Alkyl groups containing from 8 to 20 carbon atoms, more preferably from 10 to 18 carbon atoms. 1 to 10 moles, preferably 2 to 10 moles per mole of alcohol and alcohol 7, most preferably a condensation product with 2 to 5 ethylene oxides. This type of Examples of commercially available nonionic surfactants include Union Carbide Co. Sold by Union Carbide Corporation Tergitol (trade name) 15-S-9 (C₁₁-C_FifteenLinear alcohol and Product condensed with 9 moles of ethylene oxide) and Tergitol (trade name) 24- L-6 (C₁₂-C₁₄A condensation product of primary alcohol and 6 moles of ethylene oxide. And a narrow molecular weight distribution), Shell Chemical Company Neodol (trade name) 45-9 (C_{1 Four} -C_FifteenCondensation product of linear alcohol with 9 moles of ethylene oxide), Neodol ( Product name) 23-3 (C₁₂-C₁₃Condensation of linear alcohol with 3 moles of ethylene oxide Product), Neodol (trade name) 45-7 (C₁₄-C_FifteenLinear alcohol and 7 mol And Neodol (trade name) 45-5 (C₁₄− C_FifteenCondensation product of linear alcohol and 5 mol of ethylene oxide), Procter & Gya Sold by Promter & Gamble Company Kyro (brand name) EOB (C₁₃-C_Fifteen9 moles of alcohol and alcohol Condensation product with benzene), Genapol LA 030 or 0 sold by Hoechst 50 (C₁₂-C₁₄Alcohol and 3 or 5 moles of ethylene oxide) No. The preferred range of HLB in these AE nonionic surfactants is , 8 to 11, most preferably 8-10. Propylene oxide and butyl oxide Condensates with ren may also be used.   Another class of preferred nonionic surfactants for use in the present invention is It is a polyhydroxy fatty acid amide surfactant represented by the formula:   (Where R¹Is H, C_1-4Hydrocarbyl, 2-hydroxyethyl, 2 hydroxy Cypropyl or a mixture thereof,^TwoIs C_5-31Hydrocarbyl , Z is a straight chain hydrocarbyl chain having at least three hydroxyls directly attached to the chain Which is a polyhydroxyhydrocarbyl or an alkoxylated derivative thereof)   Preferably, R¹Is methyl and R^TwoIs linear C_11-15Alkyl, C_15-17Archi An alkenyl chain such as coconut alkyl or a mixture thereof, In the reductive amination reaction, glucose, fructose, maltose, It is derived from reducing sugars such as glucose. A typical example is C₁₂-C₁₈And C₁₂-C₁₄ N-methylglucamide is exemplified. U.S. Patent No. 5,194,639 and See U.S. Patent No. 5,298,636. N-alkoxy polyhydroxy fatty acids Amides can also be used. See U.S. Patent No. 5,489,393.   U.S. Pat. No. 4,411,211, 1986 issued to Llenado. No. 6,565,647, such as those disclosed in US Pat. Hydrophilic groups containing 0 to 16 carbon atoms and 1 such as, for example, polyglycosides . 3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7 sugars Alkyl polysaccharides having a polysaccharide hydrophilic group containing a saccharide unit are also used in the present invention. It is useful as an ionic surfactant. Any reduction containing 5 or 6 carbon atoms Sugar can also be used. For example, the glucose, galactose and galactosyl components , The glucosyl moiety can be substituted (optionally, the hydrophobic groups can be 2-, 3-, -Unlike glucoside or galactoside, Or galactose). The intersaccharide linkage is, for example, one of the additional saccharide units. Positions and 2-, 3-, 4- and / or 6-positions in the prosaccharide unit. Between.   Preferred alkyl polyglycosides are those represented by the following formula:                        R^TwoO (C_nH_2nO)_t(glycosyl)_x (Where R^TwoIs alkyl, alkylphenyl, hydroxyalkyl, hydroxy Selected from groups containing alkyl phenyl and mixtures thereof, in which alkyl The radical contains 10 to 18, preferably 12 to 14 carbon atoms and n is 2 or 3, preferably 2, t is 0 to 10, preferably 0, and x is 1.3 10, preferably 1.3 to 3, most preferably 1.3 to 2.7)   Glycosyl is preferably derived from glucose. Prepare these compounds To produce alcohol or alkylpolyethoxy alcohol first, Reacting it with glucose or a glucose source to produce glucosides (Attached at 1-position). Then the additional glycosyl unit is replaced with its own 1-position And the 2-, 3-, 4- and / or 6-position of the preglycosyl unit, preferably Can be linked predominantly to the 2-position.   Alkylphenol polyethylene, polypropylene and polybutylene oxy Sid condensates are also used as the surfactant-based nonionic surfactant of the present invention. Suitably, polyethylene oxide condensates are preferred. These compounds include linear or Represents 6 to 14 carbon atoms in any of the branched structures, preferably 8 to 14 Alkylene oxides of alkylphenols having alkyl groups containing carbon atoms And condensation products of In a preferred embodiment, the ethylene oxide is 2 To 25 moles, more preferably 3 to 15 moles of ethylene oxide mole / alkyl Phenol is present in an amount equal to moles. This type of commercially available non- The ionic surfactant includes GAF Corporation (GAF Corporation). on) sold by Igepal (trade name) CO-630 and ROHM & Tr sold by Haas Company (Rohm & Haas Company) iton (trade name) X-45, X-114, X-100 and X-102 Can be These surfactants are alkylphenol alkoxylates (eg, , Alkylphenol ethoxylate).   For the condensation of ethylene oxide with propylene oxide and propylene glycol Condensation products with hydrophobic bases formed from Suitable for use as a surfactant. The hydrophobic portion of these compounds is preferably Has a molecular weight of 1500 to 1800 and is water-insoluble. To this hydrophobic part The addition of the polyoxyethylene component tends to increase the water solubility of the molecule as a whole. And the liquid properties of the product correspond to condensation with up to 40 moles of ethylene oxide, Retained to the point where the polyoxyethylene content is 50% of the total weight of the condensation product . Examples of compounds of this type include certain commercially available products sold by BASF. Pluronic (trade name).   Ethylene oxide, resulting from the reaction of propylene oxide with ethylenediamine The product condensed with the product is also a nonionic surfactant-based nonionic surfactant according to the present invention. Suitable for use as an activator. The hydrophobic component of these products is ethylene diamine From the reaction product of propylene oxide and excess propylene oxide, generally from 2500 It has a molecular weight of 3000. The hydrophobic component contains 40% to 80% by weight of the condensed product. % Polyoxyethylene and has a molecular weight of 5,000 to 11,000 To a certain extent with ethylene oxide. This type of nonionic surfactant Examples include certain commercially available Tetronic (sold by BASF) Trade name) compounds.Additional cationic surfactant   Suitable cationic surfactants are preferably at least one ester (such as That is, a surfactant containing a -COO-) bond and at least one cationically charged group It is a water-dispersible compound having the properties of a surfactant.   Other suitable cationic surfactants include Mono C₆-C₁₆, Preferably C₆− C_TenQuaternary amines selected from N-alkyl or alkenyl ammonium surfactants Ammonium surfactants. In this case, the remaining N positions are methyl, Substituted by a roxyethyl or hydroxypropyl group. Choline ester world Other suitable cationic ester surfactants, including surfactants, include, for example, rice Nos. 4,228,042, 4,239,660 and 4,260, No. 529.Optional detergent ingredients   In the following, various optional other ingredients that may be used in the composition of the present invention are described. Although described, it is not intended to limit the ingredients.builder   Detergent builders are, for example, particularly suitable for the Ca and / or Mg mineral hardness in the wash water. Book to assist in control or to remove particulate soil from surfaces It can be optionally, but preferably, added to the composition of the invention. building Can form various soluble or insoluble complexes with hardness ions. Precipitation of hardness ions through the mechanism, by ion exchange and from the surface of the object to be cleaned By creating a surface that is convenient for Builder's Les The bell can vary greatly depending on the end use of the composition and its physical form. building Detergents typically contain at least 1% builder. Liquid formulation , Typically from 5% to 50%, more typically from 5% to 35% builder Including. Granular formulations typically comprise from 10% to 80% of the detergent composition, more typically Typically, it contains 15% to 50% by weight of the builder. However, higher than this of the builder Neither levels nor low levels are excluded. For example, certain detergent additives or high The surfactant formulation may not be builder.   Suitable builders in the present invention are phosphates and polyphosphates, especially sodium Salt; including water-soluble form and hydrated solid form, and a chain structure, a layer structure or a three-dimensional structure Having an amorphous solid form or an unstructured liquid form; carbonates , Bicarbonates, tricarbonates, and carbonates other than sodium carbonate or tricarbonate Aluminosilicates; organic mono-, di-, tri- and tetracarboxylates, especially acids Water, in the form of sodium, potassium or alkanol ammonium salts Oligomeric, including non-surfactant carboxylate, aliphatic and fragrance types Or Selecting from the group comprising water soluble low molecular weight polymer carboxylate; and phytic acid Can be. These builders are, for example, sulfates with boric acid for pH buffering purposes, In particular, a detergent composition containing sodium sulfate and a stable surfactant and / or builder Any other fillers or carriers that may be important for the engineering of the product May be supplemented by   A builder mixture sometimes called a "builder system" can be used, and these Mixtures, typically with a chelating agent, pH buffer or filler. In addition, two or more conventional builders can be blended. However, the optional supplement When the amounts of each material in the present invention are written out, they are generally counted separately. In this detergent With respect to the relative amounts of surfactant and builder, preferred builder systems are typically The formulation is formulated with a weight ratio of surfactant to builder of 60: 1 to 1:80. Certain preferred laundry detergents have the ratio from 0.90: 1.0 to 4.0: 1.0, more preferably Is preferably 0.95: 1.0 to 3.0: 1.0.   P-containing detergent builders, which are often preferred where permitted by law, include Alkaline polyphosphoric acid represented by phosphites, pyrophosphates and vitreous polymer metaphosphates Potassium metal salts, ammonium salts and alkanol ammonium salts; Honate, but not limited to.   Suitable silicate builders include PQ Corp., for example, BRITESIL H2 Sold under the brand name BRITESIL (trade name) such as O, especially automatic dishes Alkali metal silicates, including solid hydrous (2-ratio) silicates for washing purposes, especially 1.6 SiO in the range of 1: 1 to 3.2: 1_Two: Na_TwoLiquid and solid forms with O ratio And, for example, May 12, 1987 by HP Rieck. Layered silicates such as those described in U.S. Pat. Can be NaSKS-6, sometimes abbreviated as "SKS-6", is Hoechst (Ho echst), crystalline layered aluminum-free δ-Na_TwoSiO_Fiveform Form of silicon And particularly preferred in granular laundry compositions. German DE-A-3,4 17, 649 and DE-A-3,742,043. formula Wherein M is sodium or hydrogen and x is from 1.9 to 4, preferably 2 Wherein y is a number from 0 to 20, preferably 0_xO_{2x + 1} ・ YH_TwoOther layered silicates, such as those with O, are also useful in the present invention or are modified. Can be used in shape. Layered silicates from Hoechst Also, NaSKS-5, NaSKS-7 and NaSKS-7 are available as α, β and γ layered silicates. And NaSKS-11. Stabilizers for shrinkage agents and bleaching agents in granules And other silicates, such as magnesium silicate, that can act as components of foam control systems May also be useful.   U.S. Pat. No. 6,27,1995 to Sakaguchi et al. In the formula taught in US Pat. No. 5,427,711, where M is Na and / or K M ′ is Ca and / or Mg, y / x is 0.5 to 2.0, , A general formula xM in the form of an anhydride wherein z / x is from 0.005 to 1.0_TwoO ・ ySiO_TwoA synthetic crystalline ion having a chain structure and composition represented by zM'O Exchange materials or hydrates thereof are also suitable for use in the present invention.   Suitable carbonate builders include German Patent Application No. 15/15/1973. Alkaline earth metal carbonates and alkalis as disclosed in US Pat. No. 2,321,001 Metal carbonates. However, sodium bicarbonate, sodium carbonate, tricarbonate Sodium, and composition 2Na_TwoCO_Three・ CaCO_ThreeCharcoal such as those with anhydrides Sodium or calcium carbonate trona or any convenient multiple salt Large surface area compared to other carbonate materials, especially compressed calcite Even calcium carbonate containing calcite, aragonite and vaterite types Are also useful, for example, as seeds or for use in detergent bars. In some cases.   Aluminosilicate builders are particularly useful in granular detergents, It can also be added to a paste or gel. In the empirical formula, z and v are small. An integer of at least 6, wherein the molar ratio of z to v is in the range of 1.0 to 0.5; , Where x is an integer from 15 to 264 [M_Two(AlO_Two)_z(SiO_Two)_v] X H_TwoThose with O are suitable for this purpose. Aluminosilicate is crystalline, amorphous , Natural products or synthetic derivatives. The production method of aluminosilicate is U.S. Pat. No. 3,9,12 Oct. 1976 by Krummel et al. No. 85,669. Preferred synthetic crystalline aluminosilicate ion exchange materials are , Zeolite A, zeolite P (B), zeolite X and so-called zeolite M It is available as AP (different in some extent from zeolite P). Clino Natural types including pthiolite may be used. Zeolite A has the formula Na₁₂[(A 10_Two)₁₂(SiO_Two)₁₂] XH_TwoHas O, where x is 20 to 30, especially 27 It is. Dehydrated zeolites (x = 0-10) may also be used. Preferably, alumino Silicates have a particle size of 0.1-10 microns in diameter.   Suitable organic detergent builders include water-soluble non-surfactant dicarboxylates and tricarboxylic acids. A polycarboxylate compound containing a carboxylate is exemplified. More typical builders The polycarboxylate comprises a plurality of carboxylate groups, preferably at least 3 Having a carboxylate of Carboxylate builder is acid, partially neutral, neutral Or it can be formulated in overbased form. When in the form of salt, nato Alkali metal salts or alkanols such as lithium, potassium and lithium Preference is given to ammonium salts. April 7, 1964 for polycarboxylate builders U.S. Patent No. 3,128,287 to Berg, January 1972 US Patent No. 3,635,8 to Lamberti et al. Polycarboxylic acid ethers such as oxydisuccinates referred to in US Pat. U.S. Pat. No. 4,633,071 to Bush et al. "TMS / TDS" builder and U.S. Pat. No. 3,923,679, No. 835,163, No. 4,158,635, No. 4,120,874, No. 4, Others, including cyclic and alicyclic compounds, such as those described in US Pat. Of polycarboxylic acid ethers.   Other suitable builders are hydroxypolycarboxylic acid ethers, anhydrous maleic Copolymer of ethylene and vinyl or methyl ether, 1,3,5-trihydr Roxybenzene-2,4,6-trisulfonic acid, carboxymethyloxysuccinate Acids; various types of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid. Lucali metal, ammonium and substituted ammonium salts; melitic acid, succinic acid, Polymaleic acid, benzene 1,3,5-tricarboxylic acid, carboxymethyloxy Succinic acid, and their soluble salts.   Citrate salts, such as citric acid and its soluble salts, are available from renewable resources. For performance and biodegradability, for example, important for heavy duty liquid detergents It is a carboxylate builder. Citrates, especially also zeolites and / or layers It can be used in a granular composition in combination with a silicate. Oxydisuccinate Are also particularly useful in such compositions and combinations.   Where permitted, and especially for bar-shaped formulations used for hand washing Sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate Alkali metal phosphates, such as calcium, can be used. Ethane-hydroxy-1, Phosphate builders such as 1-diphosphate and, for example, US Pat. No. 9,581, No. 3,213,030, No. 3,422,021, No. 3,40 Other known phosphates, such as those of 0,148 and 3,422,137 May also be used and may have desirable anti-scaling properties.   Certain detersive surfactants or their short-chain homologs also have a builder effect. If they have a surface-active ability for the purpose of explaining a clear formulation, these Are counted as cleaning surfactants. Preferred type for builder function U.S. Pat. No. 4,566, issued to Bush on January 28, 1986. , 984,3,3-dicarboxy-4-oxa-1,6-hexane Illustrated by geoates and related compounds. Succinate builders include C_Five -C₂₀Alkyl and alkenyl succinic acids and their salts are mentioned. Ko Succinate builders include lauryl succinate, myristyl succinate, palmitic Succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate Citrates are also included. Lauryl-succinate is a European publication issued on November 5, 1986. No. 86200690.5 / 0,200,263. Fatty acids such as C₁₂-C₁₈Monocarboxylic acids can also be used alone with surfactants / builders. Builder, especially citrate and / or succinate building In addition to the above, it can be added to the composition to add builder activity. Appropriate Other polycarboxylates are available from Clutch Field on March 13, 1979 ( U.S. Pat. Nos. 4,144,226 to Crutchfield et al. U.S. Pat. No. 3,308,06 issued to Diehl on March 7, 967. No. 7. U.S. Patent No. 3,723, by Diehl See also No. 322.   Other types of inorganic builder materials that can be used are of the formula (M_x)_iCa_y( CO_Three)_zWherein x and i are integers from 1 to 15, and y is 1 From 10 to z, z is an integer from 2 to 25, and M_iIs a cation, At least one of them is water-soluble and has the formula Σi = 1-15 (x_iTo M_iAtom of + 2y = 2z is satisfied and the formula has a neutral or “balanced” charge You. In the present invention, these builders are referred to as "Minal Builders". ". Anions other than hydrated water or carbonate balance the overall charge Or as long as it is neutral. The charge or valence effect of these anions The fruit is It should be added to the right side of the above equation. Preferably, hydrogen, water-soluble metal, hydrogen, boron , Ammonium, silicon and their mixtures, more preferably sodium Containing potassium, potassium, hydrogen, lithium, ammonium and mixtures thereof Water-soluble cations are present, sodium and potassium are highly preferred No. Non-limiting examples of non-carbonate anions include chloride, sulfate, fluoride, oxygen, water Oxides, silicon dioxide, chromates, nitrates, borates and mixtures thereof And those selected from the groups containing. The simplest form of this type A good builder is Na_TwoCa (CO_Three)_Two, K_TwoCa (CO_Three)_Two, Na_TwoCa_Two(C O_Three)_Three, NaKCa (CO_Three)_Two, NaKCa_Two(CO_Three)_Three, K_TwoCa_Two(CO_Three)_Three And combinations thereof. Builder described in the present invention Particularly preferred materials with respect to Na_TwoCa (CO_Three)_Two It is. Suitable builders of the type defined above include any one of the following minerals: Or in combination with other natural or synthetic forms. Ruder includes them. That is, Afghanite and Andersonite , Ashcroftin Y, Bayerite, Volkalite, Bulbangite, Tourite, ash nepheline, carbosernate, carletonite, dabin, donnite Y, Fairchildite, Ferris Light, Flange Knight, Gaude Freud, Gerasite, Gilbasite, Gregolite, Jarlab Skye, Comefor Gaite Y, Ketter Light, Carnescheid, Lepersonite Gd, Lio Tight , McKelbait Y, Microsomit, Muroseito, Natrofeirchidite, D Relate, Lemon Dite Ce, Sacrophanite, Shorockingelite, Shi Shotite, Slight, Tunisite, Tuscanite, Tricalcite, Visne Bite and zemcolite. Preferred mineral forms include nirelate, Achillite and shortite.bleach   The composition according to the invention may contain a bleach. If present, these Bleach is typically 1% to 30% of the detergent composition, especially for fabric laundering. More typically it is present at a level of 5% to 20%.   In one preferred aspect, the bleaching system includes a hydrogen peroxide source and a bleach catalyst. The production of organic peroxyacids is based on the in situ reaction of the bleach activator with a hydrogen peroxide source. Get up. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. Deformation In a preferred aspect of the preformed peracid is added directly to the composition. Pre-generation A composition containing a mixture of a hydrogen peroxide source and a bleach activator in combination with a peracid It is.   Preferred peroxide bleaches are perhydrate bleaches. Some perfume bleach itself Although it has the bleaching power of a good bleach, the peroxides released by perhydrates Expressed in peracid formed as a product of the reaction between hydrogen and bleach activator . Preformed peracids are also considered to be preferred peroxide bleaching species.   Examples of suitable perhydrate salts include perborate, percarbonate, perphosphate, persulfate and Persilicate. Preferred perhydrate salts are usually alkali metal salts. Flood The chloride salt may be added as a crystalline solid without additional protection. But certain In the case of perhydrate salts, the preferred production of such particulate compositions is the Utilizes a coated material form that improves storage stability against salt.   Sodium perborate has the nominal formula NaBO_TwoH_TwoO_TwoMonohydrate or tetrahydrate Na BO_TwoH_TwoO_Two・ 3H_TwoIt can take the form of O.   Alkyl metal percarbonates, especially sodium percarbonate, are present in the compositions according to the invention. It is a preferred perhydrate to be added. The sodium percarbonate has the formula 2Na_TwoCO_Three ・ 3H_TwoO_TwoWhich is commercially available as a crystalline solid. Sodium percarbonate, a hydrogen peroxide compound, dissolves and A tendency to release hydrogen peroxide very quickly, which can increase the tendency for high bleach concentrations There is a direction. Preferred percarbonate bleaches are in the range of 500 to 1000 micrometers. Consisting of dry particles having an average particle size of Less than 00 micrometers and less than 10% by weight of the particles Larger than the meter.   The percarbonate is most preferably in the form of a coating that provides in-product stability. To the composition. Suitable coating materials to provide in-product stability are water-soluble A mixed salt of a alkali metal sulfate and a carbonate can be used. These coatings are Along with Roses, the license was granted to Interox on March 9, 1977. It was previously described in granted British Patent No. 1,466,799. Mixed salt coating material Is from 1: 200 to 1: 4, more preferably 1:99. To 1: 9, most preferably from 1:49 to 1:19. Preferably, The mixed salt is represented by the formula: wherein n is 0.1 to 3, preferably n is 0.3 to 1.0; Most preferably the general formula Na wherein n is from 0.2 to 0.5_TwoSO_Four. n. Na_TwoCO_Three Of sodium sulfate and sodium carbonate having the formula:   Silicates (alone or with borate, boric acid or other minerals), waxes, Oils, other coatings containing fatty soaps can also be advantageously used within the present invention. You.   Bleaching agents that can be used without limitation include percarboxylic acid bleaching agents and salts thereof. Include. Suitable examples of this class of additives include magnesium monoperoxyphthalate Rate hexahydrate; metachloroperbenzoic acid, 4-nonylamino-4-oxoperiod Magnesium salts of xylbutyric acid and diperoxide decanedioic acid; You. Such bleaches are available from Hartmann (Ha) issued November 20, 1984. rtman), U.S. Pat. No. 4,483,781, issued Jun. 3, 1985. U.S. Patent Application No. 740,446 to Burns et al. European Patent Application by Banks et al. Published February 20, 985 0,133,354 and Chu issued on November 1, 1983. ng) et al. in U.S. Pat. No. 4,412,934. Very liked A new bleach was issued to Burns et al. On January 6, 1987. 6-nonylamino-6-oxo as disclosed in U.S. Pat. No. 4,634,551. Soperoxycaproic acid is also included.   Other suitable additional bleaches include zinc sulfonate and / or aluminum Photoactive bleaching agents such as muphthalocyanines are included. Holcomb e) et al. in US Pat. No. 4,033,718 issued Jul. 5, 1977. Teru. If used, the detergent composition will typically contain from 0.025% to 1.25% by weight. , Especially zinc phthalocyanine sulfonate.   Potassium peroxymonopersulfate is another useful in the compositions of the present invention. It is an inorganic perhydrate salt.   Mixtures of bleaches can also be used.Bleach activator   Bleach activators are those in which the composition of the present invention further comprises a peroxide bleach. Therefore, it is a preferable component. If a bleach activator is present, it is typically 0.1% to 60% of the bleaching composition containing the white activator, more typically from 0.5% Present at 40% level.   Peroxide bleaches, perborates, etc., preferably correspond to the bleach activator in aqueous solution. In-situ (ie, during the cleaning process) Used in combination with a bleach activator. Various non-limiting examples of activators are described in Mao et al. U.S. Patent No. 4,915,854 and U.S. Patent issued April 10, 1990 No. 4,412,934. Nonanoyloxybenzene sulfone Acid salt (NOBS) and tetraacetylethylenediamine (TAED) activators Representative ones, and mixtures thereof can also be used. Yes in the present invention Other representative bleaching and activator applications are described in U.S. Pat. No. 4,634,5. See also No. 51.   Highly preferred amide-derived bleach activators are of the formula              R¹N (R^Five) C (O) R^TwoC (O) L or R¹C (O) N (R^Five) R^TwoC (O) L (Where R¹Is an alkyl group containing 6 to 12 carbon atoms, R^TwoHas 1 to 6 carbon atoms Including alkylene, R^FiveIs H or alkyl, aryl containing 1 to 10 carbon atoms Or alkaryl and L are any suitable leaving groups)   The leaving group is the result of a nucleophilic attack on the bleach activator by the perhydrolytic anion. And any group that is displaced from the bleach activator. Preferred leaving groups are sulf Phenyl phonate.   Preferred examples of bleach activators of the above formula include those described in U.S. Pat. No. 4,634,551. (6-Octanoic acid amide-caproyl) oxybenzenesulfone as described G, (6-nonamic acid amidocaproyl) oxybenzenesulfonate, Acid amide-caproyl) oxybenzenesulfonate and mixtures thereof And this patent is incorporated herein by reference.   Another class of bleach activators includes U.S. Pat. Benzooxy disclosed by Hodge et al. Sagin-type activators are mentioned and this patent is incorporated herein by reference.   A highly preferred activator of the benzoxazine type is of the formula:   Yet another class of preferred bleach activators includes acyllactam activators, especially And acyl valerolactams of the formula (Where R⁶Is H or an alkyl, aryl containing 1 to 12 carbon atoms or An alkoxyaryl or alkaryl group)   Highly preferred lactam activators include benzoylcaprolactam, octanoy Lcaprolactam, 3,5,5-trimethylhexanoylcaprolactam, nona Noircaprolactam, Decanoylcaprolactam, Undecenoylcaprolact Tom, benzoylvalerolactam, octanoylvalerolactam, decanoylva Reloractam, undecenoylvalerolactam, nonanoylvalerolactam, 3 , 5,5-trimethylhexanoylvalerolactam and mixtures thereof Can be Including benzoylcaprolactam adsorbed in sodium perborate Sanderson (S) on October 8, 1985, which discloses acylcaprolactam. U.S. Pat. No. 4,545,784, issued to Andersen, is incorporated herein by reference. Use and refer to this.Bleaching catalyst   A bleach catalyst is an optional component of the composition of the present invention. If necessary, add bleaching compound Catalysis can be exerted by magnesium compounds. These compounds Are known in the art and include, for example, US Pat. 6, No. 621, US Pat. No. 5,244,594, US Pat. No. 5,194,416. U.S. Pat. No. 5,114,606; European Patent Application 549,271 A1,549. , 272A1, 544, 440A2 and 544, 490A1. Nesium based catalysts are mentioned. Preferred examples of these catalysts include MnIV_Two (U-O)_Three(1,4,7-trimethyl-1,4,7-triazacyclononane)_Two (PF₆)_Two, MnIII_Two(U-O)₁(U-OAc)_Two(1,4,7-trimethyl- 1,4,7-triazacyclononane)_Two(ClO_Four)_Two, MnIV_Four(U-O)₆(1 , 4,7-Triazacyclononane)_Four(ClO_Four)_Four, MnIIIMnIV_Four(U-O)₁ (U-OAc)_Two(1,4,7-trimethyl-1,4,7-triazacyclonona N)_Two(ClO_Four)_Three, MnIV (1,4,7-trimethyl-1,4,7-triaza Cyclononane)-(OCH_Three)_Three(PF₆) And mixtures thereof. Other metal-based bleach catalysts include U.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. Enhances bleaching The use of manganese with various complex ligands has also been described in US Pat. No. 4,728, No. 455, No. 5,284,944, No. 5,246,612, No. 5,256. No. 779, No. 5,280,117, No. 5,274,147, No. 5,153. 161 and 5,227,084.   As a practical matter, and not by way of limitation, the compositions and The process comprises at least a part-per-million active bleach catalyst in aqueous laundry liquor. Species, preferably 0.1 ppm to 700 ppm, more preferably 1 ppm Can be adjusted to yield from 500 ppm of catalytic species in the wash water.   Cobalt bleach catalysts useful in the present invention are known and are described, for example, by Tove (M. L. Tobe) "Base hydrolysis of transition metal complexes"Adv. Inorg. Bio inorg. Mech. (1983), 2, pp. 1-94. The present invention The most preferred cobalt catalysts useful in the formula are those in which "OAc" is acetate [Co (NH), wherein “Ty” is an anion_Three)_FiveOAc] with Ty Cobalt pentaamine acetate, especially cobalt pentaamine acetate chloride [Co (NH_Three)_FiveOAc] Cl_Two, And [Co (NH_Three)_FiveOAc] (OAc)_Two, [ Co (NH_Three)_FiveOAc] (PF₆)_Two, [Co (NH_Three)_FiveOAc] (SO_Four), [C o (NH_Three)_FiveOAc] (BF_Four)_Two, And [Co (NH_Three)_FiveOAc] (NO_Three)_Two ("PAC" in the present invention).   These cobalt catalysts are described, for example, in Tobe's articles and references. U.S. Pat. No. 4, issued to Diakun et al. On Mar. 7, 1989. , 810, 410,J. Chem. Ed.(1989),66(12), 1043 -45; Synthesis and characterization of inorganic compounds; L. Jolly (P rentice-Hall; 1970); 461-3;Inorg. Ch em .181497-1502 (1979);Inorg. Chem.21, 2 881-2885 (1982);Inorg. Chem.18, 2023-202 5 (1979); Inorg. Synthesis, 173-176 (1960);Journal of Physical Chemistry ,56, 22-2 5 (1952).   As a practical matter, and not by way of limitation, the automatic dishwashing composition of the present invention The object and the cleaning process are at least 100 parts-per-million in aqueous cleaning media. Activated bleach catalyst species, preferably from 0.01 ppm to 25 ppm, more preferably From 0.05 ppm to 10 ppm, most preferably from 0.1 ppm to 5 ppm It can be adjusted to produce bleaching catalyst species in the wash water. Automatic dish washer pro In order to obtain such a level in the washing water of Seth, a typical automatic dish washer according to the present invention was used. The composition may comprise from 0.0005% to 0.2% of the cleaning composition, more preferably 0.0% to 0.2%. Contains from 0.4% to 0.08% by weight of bleach catalyst, especially manganese or cobalt catalyst I do.enzyme   The composition of the present invention contains an enzyme as an essential component. Enzymes are used for various purposes Can be added to the present detergent composition. Its purpose is to transfer effluent dyes in the washing of fabrics. Remove proteins, carbohydrates or triglycerides from the substrate to prevent dyeing and to restore the fabric. Removal of stains due to cerides. Suitable enzymes include plants, animals, Amylase, a protease of any suitable origin, such as bacterial, fungal and yeast origin And lipases, cellulases, peroxidases, and mixtures thereof. It is. Preferred choices include pH activity and / or stability optima, thermal stability, and And active detergents and builder stability. In this regard Such as bacterial amylase, bacterial protease and fungal cellulase. Bacterial or fungal enzymes are preferred.   The term "cleaning enzyme" as used in the present invention refers to laundry compositions, hard surface cleaning compositions Effect, stain removal effect or its effect on the product or personal care detergent composition Any enzyme having other beneficial effects is meant. Preferred cleaning enzymes are protein Hydrolytic enzymes such as ase, amylase and lipase. For washing purpose Preferred enzymes are proteases, cellulases, lipases and peroxidases But not limited to them. Very good for automatic dishwashing Is an amylase and / or a protease.   Enzymes are usually present in detergent compositions or detergents at levels sufficient to provide a "cleaning effective amount". It is added to the additive composition. The term "cleaning effective amount" refers to on a substrate such as a cloth or a dish. With cleaning effect, stain removal effect, stain removal effect, whitening effect, deodorization effect or freshness modification Any amount capable of producing a beneficial effect is meant. For current commercial products In practical terms, typical amounts are up to 5 mg, more typically 0.01 m g to 3 mg active enzyme / gram of detergent composition. In other words, in the present invention The composition will typically be from 0.001% to 5%, preferably from 0.01% to 1%. Contains% by volume commercial enzyme product. Protease enzymes are usually from 0.005 to 0. Enough to provide 1 AU (activity per gram of composition, Anson unit) At a high level in these commercial products. Specific detergents, such as in automatic dishwashing In case of minimizing the total amount of non-catalytically active substances, Increase the active enzyme content of commercial products to improve other end results It may be desirable. High activity levels, but also highly concentrated detergent formulations May be desirable.   Suitable examples of proteases are described in subtilis and B. licheniformis specific It is a subtilisin obtained from a strain. One suitable protease is Denmer Novo Industries A / S (Novo Industries A / S) (Hereinafter referred to as “Novo”) developed and sold as ESPERASE (trade name) From the strain of Bacillus having the greatest activity across the pH range of 8-12. It is. The preparation of this and similar enzymes is described in Novo, UK Patent 1,243, No. 784. Other suitable proteases include AL from Novo CALASE (trade name) and SAVINASE (trade name), and Dutch International Bio-Synthetics, Inc. online Bio-Synthetics Inc.) Product name). In addition, European Patent Publication No. 1 of January 9, 1985 Protease A disclosed in U.S. Pat. No. 30,756, European Patent on April 28, 1987 Publication No. 303,761 and European Patent Publication No. 1 of January 9, 1985. Protease B disclosed in U.S. Pat. No. 30,756. International publication by Novo Bacillus sp. Described in JP-A-9318140 SP. See also these high pH proteases. Proteases, one or more other enzymes and Enzyme detergents containing reversible protease inhibitors are described in WO 9203 by Novo. No. 529. Other preferred proteases include Proctor N International Publication No. 951 by DeGamble (Procter & Gamble) No. 0591. If necessary, reduce adsorption and hydrolyze Protease & Gamble (Procter & Gambling)  Gamble), as described in International Publication No. 9507791. Wear. The recombinant trypsin-like protease for a suitable detergent in the present invention is: It is described in WO 9425583 by Novo.   In more detail, a particularly preferred protease called "Protease D" is , A carbonyl hydrolase variant having a non-natural amino acid sequence. this U.S. Patent Application Serial No. 08/322, both filed October 13, 1994. No. 676, entitled "Protease-Containing Cleaning Composition", Baek (A. Baec) k) and US patent application Ser. No. 08 / 322,677, title of the invention. Patent for "Bleaching Composition Containing Protease Enzymes" by C. Ghosh Numbering of Bacillus amyloliquefaciens subtilisin as described in the application At the position of said carbonyl hydrolase corresponding to position +76, according to , Preferably +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +1 66, +195, +197, +204, +206, +210, +216, +21 7, including +218, +222, +260, +265, and / or +274 In combination with one or more amino acid residue positions corresponding to a position selected from the group Substitute multiple amino acid residues with different amino acids to obtain precursor Derived from rubonyl hydrolase.   The purpose of the present invention is not limited to the purpose of automatic dish washing, but is particularly suitable for the purpose. Novel amylases are described, for example, in Novo, UK Patent No. 1,296,839. Α-Amylase, International Bio-Synthetics In (International Bio-Synthetics Inc.) APIDASE (trade name) and Novo's TERMAMYL (trade name) FUNGAMYL (trade name) from Novo is particularly useful. For example, oxidation stable Enzyme engineering for improving stability, such as sex, is well known. For example, J. Biolo technical Chem., Vol. 260, no. 11, June 1985, pp6 See 518-6521. Certain preferred embodiments of the present compositions are directed to automatic dishwashing ties. Stability in detergents such as pumps, and in particular became commercially used in 1993 Oxidation stability as measured against the reference point of TERMAMYL (trade name) Improved amylase can be used. These preferred elements in the present invention are Millases are characterized, at a minimum, by one or more of the following measurable improvements: Share the characteristics of improved stability. That is, for example, to pH 9-10 Oxide against hydrogen peroxide / tetraacetylethylenediamine in buffer in solution Qualitative, e.g., thermal stability at common wash temperatures such as about 60 <0> C, e.g. Alkaline stability at a pH of from 11 to 11 Measured for amylase. Stability depends on the technical text that published the technology It can be measured using this. For example, it is disclosed in International Publication No. 9402597. See References. Stability improving amylase is available from Novo or Genenka Available from National (Genencor International) . One class of highly preferred amylases in the present invention is one, two or more. One or more Bacillus amylase strains, whether or not the amylase strain is a direct precursor Enzymes, particularly using site-directed mutagenesis from Bacillus α-amylase. Have in common. Oxidation stability improvement for the standard amylase shown above Millase is a bleaching detergent composition in the present invention, more preferably chlorine bleaching. Is preferred for use in different oxygen bleach detergent compositions. These preferred amillers In addition, (a) Novo International Publication No. 9 by Novo, Feb. 3, 1994, incorporated above. Amylase according to EP-A-402597, which in a variant is TERMAMYL (quotient B. known as "product name" position 197 of licheniformis α-amylase, or B. amyloliquefaciens, B.A. subtilis or B. kind like stearothermophilus Alanine or methionine residue located at homologous position variation of similar progenitor amylase Further examples are given by mutants substituted with threonine, preferably threonine. Amylase shown, (b) C. Mitchinson in 1994 Paper published at the 207th National Meeting of the American Chemical Society, March 13-17, 2003. Oxidizing α-amylase ”by Genenka International (Genen (Cor International) No. In the dissertation, the bleach in automatic dishwashing detergents Amylase that inactivates but has improved oxidative stability. licheniformis N It was pointed out from CIB8061 that Genenka manufactured. Methionine (Me t) was identified as a residue that was most likely to be modified. Met is at position 8, 15 , 197, 256, 304, 366 and 438 at one time, Features M197L and M197T, including M197T mutants that are expression mutants Lead to certain mutants that are important. Stability is determined by CASCADE (trade name) and SU It was measured in NLIGHT (trade name). (c) Particularly preferred in the present invention Amylases include direct species, such as those described in WO 9510603. Amylase variants having additional denaturation in DURAMYL (products Name) from the assignee Novo. Other oxidation stability improving agents which are particularly preferable Millase includes Genencor Inte International Publication No. WO 9418314 and Novo One described in International Publication No. 9402597 is exemplified. For example, get From known chimeric, hybrid and simple mutant forms of possible amylase Any other oxidative stability modifications, such as those induced by site-directed mutagenesis Good amylase can also be used. Other preferred enzyme modifications are available . By Novo See WO95050909.   Other amylases include those described in WO 95/26397. And PCT / DK96 / 000 co-pending by Novo Nordisk 56. Specific agents used in the detergent composition of the present invention Amylase was assayed using a Padebas (trade name) α-amylase activity assay. Measured temperature range from 25 ° C to 55 ° C and pH value in the range from 8 to 10 At least 25% higher than the specific activity of Termamyl (trade name) Α-amylase that is characterized by ebas (trade name) α-amylase activity assay is described in WO 95/26. 397, pages 9-10). Also included in the present invention are references At least having the amino acid sequence shown in the SEQ ID list in the literature It is an α-amylase with 80% homology. These enzymes are preferably used in whole compositions 0.00018% to 0.060% by weight of pure enzyme, more preferably the total composition From 0.00024% to 0.048% by weight of pure enzyme in laundry detergent compositions Is added.   Cellulases that can be used in the present invention preferably have a maximum between 5 and 9.5. Bacterial and fungal types with appropriate pH are included. March 6, 1984 U.S. Pat. No. 4,435,3 by Barbesgoard et al. 07 is Humicola insolens, Humicola strain DSM1800 or genusaero Appropriate fungal cellulases and fungi from cellulase 212 producing fungi belonging to monas Cellular extracted from the hepatopancreas of the western mollusc, Dolabella Auricula Solander Disclose. Suitable cellulases are described in GB 2,075,028, Also disclosed in National Patent No. 2,095,275 and DE-OS-2,247,832 Have been. CAREZYME (trade name) and CELLUZYME (trade name) (Novo) is particularly useful. See also WO 9117243 by Novo Teru.   Cellulases that can be used in the present invention preferably have a maximum between 5 and 9.5. Both bacterial and fungal types having the appropriate pH are included. March 6, 1984 U.S. Pat. No. 4,435 to Barbesgoard et al. No. 307 is from Humicola insolens or Humicola strain DSM1800. Suitable fungal cellulase or cellulase 212 belonging to genus aeromonas Extracted from the hepatopancreas of fungi and marine molluscs, Dolabella Auricula solander The disclosed cellulase is disclosed. Suitable cellulases are described in GB 2.07 5.028, UK Patent No. 2.095.275 and DE-OS-2.247 . 832 is also disclosed. CAREZYME (trade name) (Novo) is especially It is for. See also WO 9117243 by Novo.   Suitable lipases for detergent applications are disclosed in GB 1,372,034. Pseudomonas groups as shown, such as Pseudomonas stutzeri ATCC 19.154 And those produced by the microorganisms. Japanese Patent Application No. 53, February 24, 1978 See also lipase at -20487. This lipase is lipase P "Amono" Or Amano Pharmash, located in Nagoya, Japan, under the trade name "Amono-P" -Enter from Amano Pharmaceutical Co. Ltd. I can do it. Other suitable commercial lipases include Amano-CES, for example, Japan Chromobacter viscosum var. From Toyo Brewery located in Tagata, Japan. lipolyticum Lipase exChromobacter viscosum such as NRRLB3663, U.S.A. Biochemical Corp. (US Biochemical Corp.) And Chromobacter vii from Disynth Co., The Netherlands. scosum lipase; and lipase exPseudomonas gladioli. Europe Derived from Humicola lanuginosa found in State Publication No. 341,947, LIPOLASE (TM) enzyme, commercially available from It is a preferred lipase to use. Stabilized against peroxidase enzymes Lipase and amylase variants have been described by Novo in WO 941495. No. 1. WO 9205249 and RD 94359 See also 044.   Despite the large number of publications on lipase enzymes, Humicola lanuginosa Lipase derived from Aspergillus oryzae as a host Only one has heretofore been widely used as an additive for fabric laundry products. this is, Obtained from Novo Nordisk under the trade name Lipolase (trade name) as described above it can. Novo Nordis to optimize Lipolase stain removal performance Ku produced a number of variants. It is described in WO 92/052496. As noted, the native Humicola lanuginosa lipase D96L mutant is wild-type. Improves lard stain removal efficiency 4.4-fold compared to lipase (0.075 enzyme Compared in amounts ranging from 2.5 mg protein / liter). Novo Nordisk Research Publication No. published on Mar. 10, 1994 by No. 35944 is Lipa 0.001-100 mg (5-500,000 LU / Liter) Can be added in the amount corresponding to lipase mutant / washing liquid liter Is disclosed. The present invention specifically relates to D96L from 50 LU to 8500 LU. When used at a level in the range of / liter of washing liquid, the method disclosed in the present invention Low level of D96L change in detergent compositions containing bis-AQA surfactant The use of variants provides the advantage of improving the whiteness maintenance of the fabric.   Cutinase enzymes suitable for use in the present invention are internationally available from Genenka. It is described in Japanese Unexamined Patent Publication No. 8809367.   Peroxidase enzymes are removed from the substrate for "solution bleaching" or during washing. To prevent transferred dyes or pigments from migrating to other substrates present in the wash liquor. For example, it may be used in combination with an oxygen source such as percarbonate, perborate, hydrogen peroxide and the like. . Known peroxidases include horseradish peroxidase, ligninase, and Haloperoxidases such as chloro- or bromo-peroxidase include It is. The peroxidase-containing detergent composition was prepared by Novo on Oct. 19, 1989. International Publication No. 89099813 and International Publication No. 8909 by Novo. No. 813. A range of enzyme materials and their means of addition to synthetic detergent compositions include: By International (Genencor International) WO 9307263 and WO 9307260, Novo International Patent Publication No. WO 89908694 and McCarty Also disclosed in U.S. Pat. No. 3,553,139 issued Jan. 5, 1971, I have. The enzyme was purchased from Place et al. No. 4,101,457, and Hughe on March 26, 1985. s) is further disclosed in U.S. Patent No. 4,507,219. Liquid detergent distribution Useful enzyme materials for compounds and their addition to such formulations are described in US Pat. U.S. Pat. No. 4,261,868 to Hora et al. I have. Detergent enzymes can be stabilized by various techniques. Enzyme stability The conversion procedure is described in U.S. Pat. No. 3, August 17,1971 by Gedge et al. No. 6,600,319, by Venegas, Oct. 29, 1986. European Patent Publication No. 199,405 and Japanese Patent Publication No. 200,586 It is disclosed and illustrated. Enzyme stabilization systems are described, for example, in US Pat. No. 3,519, No. 570 is also disclosed. Protease, xylanase and cellulase The resulting useful Bacillus sp. AC13 is described in WO 94015 by Novo. No. 32.Enzyme stabilization system   The enzyme-containing liquid composition of the present invention is preferably used in an amount of about 0.001% to about 1%. 0%, preferably from about 0.005% to about 8%, most preferably from about 0.01% to It also contains about 6% by weight of the enzyme stabilizing system. Enzyme stabilization systems are compatible with detergent enzymes. Any stabilizing system may be used. These systems can be internalized by other compound activators Or an enzyme ready to be added to the formulator or detergent, for example. The manufacturer may add it separately. Such stabilizing systems include, for example, calcium ion , Boric acid, propylene glycol, short chain carboxylic acids, boric acid, and mixtures thereof And various safety measures depending on the type and physical form of the detergent composition. Considered to handle the stabilization problem.   One approach to stabilization is to use calcium and calcium in the final composition. And / or use a water-soluble source of such ions to provide magnesium ions to the enzyme. Is Rukoto. Calcium ions are generally more effective than magnesium ions Yes, the use of only one type of cation is preferred in the present invention. Typical The detergent composition, in particular the liquid composition, may have a concentration of from 1 to 30 per liter of the final detergent composition. From 2 to 20, more preferably from 8 to 12 mmol of calcium ions. However, it may vary depending on factors including the multiplicity, type and level of enzyme to be added. Is possible. Preferably, for example, calcium chloride, calcium hydroxide, ants Calcium acid, calcium malate, calcium maleate, calcium hydroxide And water-soluble calcium or magnesium salts, including calcium acetate You. More generally, it corresponds to calcium sulfate or the calcium salts mentioned in the examples. Magnesium salt may be used. Calcium and / or magnesium Further increases in the bell, for example, promote the lipolytic effect of certain types of surfactants Can of course be useful for   Another approach for stabilization is by using boric acid species. C See U.S. Patent No. 4,537,706 to Severson. Bo When using an acid stabilizer, the boric acid stabilizer may comprise up to 10% or more of the composition. It may be a level. However, more typically, boric acid levels up to about 3% by weight Alternatively, sodium borate or another borate compound such as orthoborate may be used as a solution. Suitable for detergent applications. Phenyl borate, butane borate or para-broborate Substituted boric acid, such as mophenyl, can be used in place of boric acid and can be used in detergent compositions. Reducing the level of total boron in the system is due to the use of these substituted boron derivatives. It may be possible.   Certain cleaning composition stabilizing systems, such as automatic dishwashing compositions, have 0-10%, Preferably, it may further comprise from 0.01% to 6% by weight of a chlorine bleach scavenger, , Chlorine-bleaching species present in many water supplies attacked enzymes, especially under alkaline conditions Added to prevent inactivation. Chlorine levels in water are representative Although it is typically in the range of 0.5 ppm to 1.75 ppm and is small, For example, the effective salt in the total volume of water that comes into contact with the enzyme during dishwashing or fabric washing Element can be relatively large and, therefore, the enzyme's safety relative to the chlorine used. Qualitative is sometimes problematic. Chlorine because percarbonate can react with chlorine bleach The use of additional stabilizers to improve the results may improve In general, it may not be important. Suitable chlorine scavenger anions are well known and easy And sulfite, hydrogen sulfite, thiosulfate, iodide It may be a salt containing an ammonium cation with a substance or the like. Carbamate, as An antioxidant such as corbate, ethylenediaminetetraacetic acid (EDTA) or Such as its alkali metal salts, monoethanolamine (MEA) and mixtures thereof Organic amines can be used as well. Similarly, special enzyme suppression systems Enzymes can be added for maximum compatibility. Bisulfite, nitric acid Salts, chlorides; sodium perborate tetrahydrate, sodium perborate monohydrate and percarbonate Hydrogen peroxide sources such as sodium acid, phosphates, condensed phosphates, acetates, benzoates, Citrate, formate, lactate, malate, tartrate, salicylate, etc. These Other conventional scavengers such as mixtures of can be used if desired. General In some cases, the function of the chlorine scavenger may be (E.g. a hydrogen peroxide source) to achieve the required function to the extent necessary. As long as the compound is present in embodiments containing the enzyme of the invention, a separate chlorine scavenger may be added. There is no absolute need to add. Even in these cases, scavengers seek optimal results It is added for protection. In addition, the formulator is completely compatible with other Chemists are advised to avoid the use of any non- Will exercise regular skills. Regarding the use of ammonium salts, these salts may be washed Can be easily mixed with the agent composition, but absorbs water and / or removes ammonia during storage. Tends to be liberated. Therefore, if such materials are present, they are preferred. More preferably, U.S. Patent No. 4,652,3, to Baginski et al. Protected in particles such as those described in No. 92.Polymer dispersant   Polymeric dispersants are particularly useful in the presence of zeolites and / or layered silicate builders. In the presence, it is advantageously available in compositions of the invention at levels of 0.1% to 7% by weight. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols. Call. However, other materials known in the art may also be used. Can be. While not intending to be limited by theory, polymeric dispersants may When used in combination with builders (including low molecular weight polycarboxylates) By suppressing crystal growth and preventing solidification and re-deposition of the removed particulate matter, overall It is believed to enhance detergent builder performance.   The polymeric polycarboxylate material is suitably unsaturated, preferably in the acid form. It can be prepared by polymerizing or copolymerizing a monomer. Suitable for polymerization Unsaturated monomeric acids that can produce high molecular weight polycarboxylates include: Crilic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconi And citric acid, mesaconic acid, citraconic acid and methylenemalonic acid. Vini Containing carboxylate radicals such as methyl ether, styrene, ethylene, etc. The presence of the high molecular weight polycarboxylate or monomer segment in the present invention. Currently, it is appropriate unless such segments constitute more than 40% by weight.   Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Wear. Such acrylic acid-based polymers useful in the present invention are polymerized acrylics. It is a water-soluble salt of luic acid. The average molecular weight of these polymers in the acid form is preferred. 2,000 to 10,000, more preferably 4,000 to 7,000, Most preferably, it is in the range of 4,000 to 5,000. Such acrylic acid po Water-soluble salts of Lima include, for example, alkali metal salts, ammonium salts and substituted anions. Monium salts can be included. This type of soluble polymer is a known material . The use of polyacrylates of this type in detergent compositions is e.g. U.S. Pat. No. 3,308,06 issued to Diehl on March 7, 2007. No. 7.   Acrylic / maleic acid based copolymers are also preferred as dispersing / redeposition inhibitors It may be used as a component. These materials include copolyacrylic acid and maleic acid. Water-soluble salts. The average molecular weight of these polymers in acid form is favorable. Preferably from 2,000 to 10,000, more preferably from 5,000 to 7,50 0, most preferably in the range of 7,000 to 65,000. Such a copoly The ratio of acrylic acid to maleic acid in the polymer is generally between 30: 1 and 1: 1. : 1, more preferably from 10: 1 to 2: 1. Such acrylic acid / The water-soluble salts of the maleic acid copolymer include, for example, alkali metal salts and ammonium salts. And substituted ammonium salts. This type of soluble acrylic acid / Maleic acid copolymer is disclosed in European Patent Application No. 669, issued December 15, 1982 No. 15, and such polymers including hydroxypropyl acrylate are also described. hand No. 193,360 issued Sep. 3, 1986. It is a known material. Other useful acid dispersants include maleic acid / acrylic acid / And vinyl alcohol terpolymers. Such materials are, for example, malein Europe, including 45/45/10 terpolymer of acid / acrylic acid / vinyl alcohol It is also disclosed in Japanese Patent Publication No. 193,360.   Another polymeric material that can be included is polyethylene glycol (PEG) is there. PEG exhibits dispersant performance and also removes clay stains and prevents redeposition. Also acts as. A typical molecular weight range for these purposes is 500 to 1 00,000, preferably 1,000 to 50,000, more preferably 1.5 It ranges from 00 to 10,000.   Polyaspartate and polyglutamate dispersants are also particularly suitable for zeolite builders. May be used in combination with-. Dispersants such as polyaspartate are preferably 10 It has a molecular weight (average) of 2,000.Clay soil removal / anti-deposition agent   The composition of the present invention comprises a water-soluble ethoxide having clay stain removal and redeposition prevention properties. A xylated amine may optionally also be included. Granule detergent composition containing these compounds Typically contains 0.01% to 10% by weight of a water-soluble ethoxylate amine. Have. Liquid detergent compositions typically contain from 0.01% to 5%.   The most preferred soil removal and redeposition inhibitor is ethoxylated tetraethylene pen. This is Tamin. Examples of ethoxylated amines can be found in Vandemee, published July 1, 1986. Further described in U.S. Pat. No. 4,597,898 to VanderMeer. Have been. Another group of preferred clay soil removal-redeposition inhibitors is 1984 June By Oh and Gosselink, published on 27th of March It is a cationic compound disclosed in state patent application 111,965. Can be used Other clay stain removal / redeposition inhibitors include, but are not limited to, those issued on June 27, 1984. As disclosed in European Patent Application 111,984 by Gosselink. Ethoxylated amine polymer, Gosselink, issued July 4, 1984 elink) disclosed in EP 112,592. And U.S. Pat. No. 4,548,744 aminooxide. Others known in the art Clay soil removal and / or redeposition inhibitors are also utilized in the compositions of the present invention. can do. VanderMeal issued on January 2, 1990 er), US Pat. No. 4,891,160 and issued Nov. 30, 1995. See WO 95/32272 at Row. Another preferred anti- redeposition agent Ips include carboxymethylcellulose (CMC) materials. these Materials are known in the art.Whitening agent   Any optical brightener known in the art, other brighteners or white The agent is typically present at a level of 0.01% to 1.2% by weight of the detergent in the present invention. It can be added to the composition. Commercial optical enhancements that may be useful in the present invention Whitening agents include stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanine, Benzothiophene-5,5-dioxide, azole, 5- and 6-membered heterocycles And other miscellaneous agents, but are not necessarily limited to Group. Examples of such brighteners are described in John Whiley & Son M.s., published by New York (1982). To Zahrdnik Published in "Production and Use of Optical Brighteners".   A specific example of an optical brightener useful in the present composition is described on December 13, 1988. Specified in U.S. Patent No. 4,790,856 issued to Wixon. It was done. These brighteners include brighteners from Verona PHORHHITE series. Other enhancements disclosed in this patent Whitening agents include Tinopa available from Ciba-Geigy. l UNPA, Tinopal CBS and Tinopal 5BM; Arti cWhite CC and Artic White CWD, 2- (4-styryl) -Phenyl) -2H-naphtho [1,2-d] triazole, 4,4-bis- ( 1,2,3-triazol-2-yl) -stilbene, 4,4′-bis (styrene Ril) bisphenyl and aminocoumarin. Identification of these brighteners Examples of 4-methyl-7-diethyl-amino-coumarin, 1,2-bis (ben (Zimidazol-2-yl) ethylene, 1,3-diphenyl-pyrazoline, 2, 5-bis (benzoxazol-2-yl) thiophene, 2-styryl-naphtho [1,2-d] oxazole and 2- (stilben-4-yl) -2H-naph [1,2-d] triazole. Hamilton See U.S. Pat. No. 3,646,015, issued Feb. 29, 1972.Transfer dye inhibitor   The composition of the present invention has a dye transfer from one fabric to another during the cleaning process. One or more materials that may be effective in suppressing the formation of the organic solvent may also be added. Generally, these Examples of the dye transfer inhibitor include polyvinylpyrrolidone polymer and polyamine N-oxide polymer. A copolymer of N-vinylpyrrolidone and N-vinylimidazole, manganese lid Russianin, peroxidase and mixtures thereof. These rolls If a dye inhibitor is used, typically from 0.01% to 10% by weight of the composition is preferred. Or 0.01% to 5%, more preferably 0.05% to 2%.   More specifically, preferred polyamine N-oxides for use in the present invention Lima comprises units having the structural formula R-Ax-P, where P is a polymerizable unit. Knitted, this unit can have an N-O group attached, or the N-O group can be polymerized Can form part of a simple unit, or the NO group can be attached to both units; A is one of NC (O)-, -C (O) O-, -S-, -O-, -N = , X is 0 or 1, and R is aliphatic, ethoxylated aliphatic, fragrance, heterocyclic, An alicyclic group or any combination thereof, to which the nitrogen of the NO group is bonded. Or the NO group is part of these groups. Preferred polyamine NO Oxides are those in which R is pyridine, pyrrole, imidazole, pyrrolidine, piperidine or And heterocyclic groups such as derivatives thereof.   The NO group can be represented by the following general structure (k). (Where R₁, R_Two, R_ThreeIs an aliphatic, fragrance, heterocyclic, alicyclic group or their X, y and z are 0 or 1 and the nitrogen of the NO group is Any of the groups can be linked or can form part of any of the groups described above. Poly The amine oxide unit of the amine N-oxide has a pKa <10, preferably pKa With Ka <7, more preferably pKa <6)   The formed amine oxide polymer is water-soluble and has dye transfer inhibiting properties Any polymer backbone can be used. The right polymer backbone Examples of polyvinyl, polyalkylene, polyester, polyether, polyamide , Polyimide, polyacrylate and mixtures thereof. These poly One monomer species is an amine N-oxide and the other monomer species is N-oxide. -Random or block copolymers which are oxides. Amine NO The oxide polymer typically has a ratio of amine to amine N-oxide of 10: 1. From 1,000,000. However, in polyamine oxide polymers The number of amine oxide groups present depends on the appropriate copolymerization or the appropriate degree of N-oxidation. Can be obtained. Polyamine oxides are obtained at almost any degree of polymerization be able to. Typically, the average molecular weight is between 500 and 1,000,000, Preferably from 1,000 to 500,000, most preferably from 5,000 to 1 It is in the range of 00,000. This preferred material grade is referred to as "PVNO". Can be.   Most preferred polyamine N-oxy useful in detergent compositions in the present invention Has an average molecular weight of 50,000 and a ratio of amine to amine N-oxide 1: 4 poly (4-vinylpyridine-N-oxide).   Copolymer of N-vinylpyrrolidone and N-vinylimidazole polymer (grade and (Referred to as "PVPVI") are also preferred for use in the present invention. Preferred Preferably, PVPVI is from 5,000 to 1,000,000, more preferably 50,000. Average from 00 to 200,000, most preferably from 10,000 to 20,000 Have a molecular weight range (average molecular weight ranges are described by Barth et al., Chemical An alysis, Vol 113, "Modern Methods of Polymer Characterization" Measured by light scattering as described in, and this disclosure is incorporated herein by reference. ). PVPVI copolymers are typically N-vinylimidazole N-vinyl The molar ratio to lupyrrolidone is from 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, most preferably 0.6: 1 to 0.4: 1. these The copolymer may be either linear or branched.   The composition of the present invention may have a molecular weight of 5,000 to 400,000, preferably 5,000. Average molecular weight of 200,000, more preferably 5,000 to 50,000. Polyvinylpyrrolidone (PVP) may also be used. PVP is used in the detergent field. It is known to the trader. For example, European Patent Publication No. 26, incorporated herein by reference. See 2,897 and EP-A-256,696. Contains PVP The composition of the present invention comprises from 500 to 100,000, preferably from 1,000 to 10, Polyethylene glycol (PEG) having an average molecular weight of 000 may also be included. . Preferably, the ratio of PEG to PVP added to the washing liquor on a ppm basis is: It is 2: 1 to 50: 1, more preferably 3: 1 to 10: 1.   The detergent composition of the present invention has a discoloration inhibiting effect of 0.005% to 5% by weight. % Of a specific type of hydrophilic optical brightener may also optionally be included. If you use The composition in the present invention preferably comprises from 0.01% to 1% by weight of such an optical Contains brightener.   Hydrophilic optical brighteners useful in the present invention are those having the following structural formula . (Where R₁Are anilino, N-2-bis-hydroxyethyl and NH-2-H Selected from droxyethyl, R_TwoIs N-2-bis-hydroxyethyl, N-2- From hydroxyethyl-N-methylamino, morpholino, chloro and amino And M is a salt-forming cation such as sodium or potassium)   In the above formula, R₁Is anilino and R_TwoIs N-2-bis-hydroxyd When chill is used and M is a cation such as sodium, the brightener is 4,4'- Bis [(4-amino-6- (N-2-bis-hydroxyethyl) -s-triazine 2-N-yl) amino] -2,2-stilbene disulfonic acid and disodium Salt. This particular brightener species is Ciba-Geigy Co. commercial under the trade name Tinopal-UNPA-GX Is sold. Tinopal-UNPA-GX is a detergent composition of the present invention. Are preferred hydrophilic optical brighteners.   In the above formula, R₁Is anilino and R_TwoIs N-2-hydroxyethyl- Whitening when N-2-methylamino and M is a cation such as sodium The agent is 4,4'-bis [(4-amino-6- (N-2-hydroxyethyl-N-meth- Tylamino) -s-triazin-2-yl) amino] 2,2′-stilbendisulfur Fonic acid and disodium salt. This particular brightener species is Ciba Geigy (C iba-Geigy Corporation) Commercially sold as BM-GX.   In the above formula, R₁Is anilino and R_TwoIs morpholino and M is na In the case of a cation such as thorium, the brightener is 4,4'-bis [(4-anilino -6-morpholino-s-triazin-2-yl) amino] -2,2'-stilbe And sodium disulfonate. This particular brightener species is Ciba Geigy (C iba-Geigy Corporation) Commercially sold as MS-GX.   The particular optical brightener species selected for use in the present invention is selected from those selected above. When used in combination with a polymeric dye transfer inhibitor, it has the advantage of particularly effective dye transfer control performance. You. Such selected polymeric materials (eg, PVNO and / or PVPVI) ) With such selected optical brighteners (eg, Tinopal UNPA-GX, T inopal 5BM-GX and / or Tinopal-AMS-GX) By using, when used alone, one of the two detergent composition components Significantly good dye transfer control in aqueous laundry liquors. Without being bound by theory, These brighteners are highly compatible with fabrics in the wash liquor, It is believed that this is due to the relatively fast deposition on the fabric. In the washing liquid The extent to which the whitening agent is deposited on the fabric depends on a parameter called the "consumption coefficient". Can be defined. The wear factor is generally calculated as follows: a) the whitening material deposited on the fabric; This is the ratio of the brightener in the solution to the initial concentration. Brighteners with relatively high wear coefficients are In the context of the invention it is most appropriate for the control of transfer dyeing.   Of course, the other conventional optical brightener species of the compound, not the true transfer inhibition effect , Optionally used in this composition to provide the traditional "whitening" benefits of fabrics It is expected that can be done. These uses are traditional and include detergents Is known to those skilled in the art.Chelating agent   The detergent composition according to the invention comprises one or more iron and / or manganese chelates An agent may optionally be included. Such chelators are aminocarboxylates , Aminophosphonates, polyfunctionally substituted perfume chelating agents and mixtures thereof And all are defined below. By the bounds of theory If not, the benefits of these materials would be partially due to the formation of soluble chelates. It is believed to be due to the excellent ability to remove iron and manganese from the rinse.   Aminocarboxylates useful as any chelating agent include ethylene dia Mintetraacetate, N-hydroxyethylethylenediaminetriacetate , Nitrilotriacetate, ethylenediaminetetrapropionate, triethyl Lentetraamine hexaacetate, diethylenetriaminepentaacetate, And their ethanol diglycine, alkali metal, ammonium, Ammonium salts and mixtures thereof.   Aminophosphates also have at least low levels of total phosphorus in the detergent composition. Where permitted, suitable for use as a chelating agent in the compositions of the present invention; Aminophosphates include ethylenediaminetetrakis as DEQUEST (Methylene phosphonate). Alkyl with more than 6 carbon atoms is also Those aminophosphonates which do not contain a alkenyl group are preferred.   Multifunctionally substituted perfume chelating agents are also useful in the compositions of the present invention. U.S. Pat. No. 3, issued to Connor et al. On May 21, 1974. See 812,044. Preferred compounds of this type in the acid form include 1 Dihydroxydisulfo such as 2,2-dihydroxy-3,5-disulfobenzene Be It is sen.   A preferred biodegradable chelating agent for use in the present invention is ethylene diamine. Disuccinate ("EDDS"), especially Hartman and No. 4,70, Nov. 3, 1987 to Perkins. [S, S] isomers as described in US Pat. No. 4,233.   The composition of the present invention may be used as a chelating agent or a zeolite or a layered sheet. As a useful co-builder with an insoluble builder, such as Methylglycine diacetate (MGDA) salt (or acid form) may also be included.   If utilized, these chelating agents generally comprise the detergent compositions of the present invention. From 0.1% to 15% by weight. More preferably, if used, clean Toning agents contain from 0.1% to 3.0% by weight of such compositions.Foaming inhibitor   Compounds for reducing or inhibiting foam formation may be added to the compositions of the present invention. it can. Foam control is disclosed in U.S. Patent Nos. 4,489,455 and 4,489,5. The so-called "high concentration cleaning process" as described in No. 74 and front charging Of particular importance in style European style washing machines.   Various materials may be used as foam inhibitors, which are known to those skilled in the art. You. For example, Kirk-Othmer Dictionary of Chemistry, Third Edition, Vol. 7, pp. 430-47 ( John Wiley & Sons, Inc., 1979). Of particular interest One class of foam inhibitors is monocarboxylic fatty acids and their soluble salts. Include. Wayne St. John on September 27, 1960 See U.S. Pat. No. 2,954,347 issued. Used as foam inhibitor Monocarboxylic fatty acids and their salts typically contain 10 to 24 carbon atoms. Having a hydrocarbyl chain of preferably 12 to 18 carbon atoms. To the appropriate salt Are alkali metal salts such as sodium, potassium and lithium salts, ammonium Salt And alkanol ammonium salts.   The detergent composition of the present invention may also contain a non-surfactant foam inhibitor. these For example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (for example, Fatty acid triglyceride), fatty acid ester of monohydric alcohol, aliphatic C₁₈-C₄₀ Ketone (eg, stearone) and the like. Other foam control agents include -To N-alkylated aminotriazines such as hexa-alkylmelamines; Is the primary or secondary cyanuric chloride containing 2 or 3 moles of 1 to 24 carbon atoms. Di-tetra-alkyldiamine chloride formed as a product with diamine Liazine; propylene oxide; monostearyl alcohol phosphate ester And monostearyl dialkali metal (eg, K, Na, and Li) phos Monostearyl phosphates such as phosphate and phosphate esters include Can be Hydrocarbons such as paraffins and haloparaffins are available in liquid form. Liquid hydrocarbons are liquids at room temperature and atmospheric pressure, and in the range of -40 ° C and 50 ° C. And a minimum boiling point (atmospheric pressure) of 110 ° C. or higher. Preferably the melting point is 10 It is also known to utilize waxy hydrocarbons below 0 ° C. Hydrocarbons, detergent composition It constitutes a preferred type of foam inhibitor for the product. For example, hydrocarbon foam inhibitors For example, the United States issued May 5, 1981 to Gandolfo et al. It is described in Japanese Patent No. 4,265,779. Thus, hydrocarbons have 12 Aliphatic, cycloaliphatic, fragrance and heterocyclic, saturated or unsaturated, having from 70 to 70 carbon atoms And saturated hydrocarbons. The "paraffin" used in this discussion of foam inhibitors The term `` quine '' is intended to include a mixture of true paraffins and cyclic hydrocarbons. Is intended.   Another preferred class of non-surfactant foam inhibitors include silicone foam inhibitors. Can be This class includes polyorganosiloxanes such as polydimethylsiloxane Oils, dispersions or emulsions of polyorganosiloxane oils or resins, and Polyorganosiloxane in which polyorganosiloxane is chemisorbed or fused onto silica Utilization of a combination of siloxane and silica particles. Silicone foam inhibitor Are known in the art, for example, Gandolfo o) et al., US Pat. No. 4,265,779, issued May 5, 1981; Issued on February 7, 1990 by Starch and Starch (MS). It is disclosed in European Patent Application No. 89307851.9.   For other silicone foam inhibitors, add a small amount of polydimethylsiloxane liquid. U.S. Pat. No. 455,839.   Mixtures of silicone and silanized silica are described, for example, in German Patent Application DOS2 , 124, 526. Silicone defoamer in granular detergent composition and And foam control agents are disclosed in Bartolotta et al., US Pat. , 933,672, issued March 24, 1987. Ki) et al. in U.S. Pat. No. 4,652,392.   Examples of silicone-based foam inhibitors used in the present invention are: Is a foaming control agent having a foaming suppression amount mainly containing     (i) about 20 cs. From about 1,500 cs. Having a viscosity of Methyl siloxane liquid.     (ii) from about 0.6: 1 to about 1.2: 1 of (CH_Three) 3SiO_1/2Unit: S iO_TwoIn the unit ratio, (CH_Three)_ThreeSiO_1/2Unit and SiO_TwoUnit and About 5 to about 50 parts by weight / 100 parts of the siloxane resin containing (i)     (iii) from about 1 to about 20 parts by weight of solid silica gel / 100 parts of (i)   In the preferred silicone foam inhibitor used in the present invention, for the continuous phase Solvent is a specific polyethylene glycol, polyethylene-polypropylene glycol Cole copolymer, their mixtures (preferred) or polypropylene bricol Consists of The primary silicone foam control agent is a branched / crosslinked one, preferably a linear is not.   To further illustrate this point, a representative liquid laundry detergent composition with controlled foaming is: About 0.001 to about 1, preferably about 0.1 to about 0.7, most preferably about 0 . From about 0.5% to about 0.5% by weight of the silicone foam inhibitor. The cone foaming inhibitor comprises (1) (a) a polyorganosiloxane and (b) a resinous silicone. A silicone compound produced by Sun or Silicon resin, and (c) a finely divided filling material, (D) Promote the reaction of mixture components (a), (b) and (c) to produce silanolate A non-aqueous emulsion of a primary antifoaming agent which is a mixture of At least one nonionic silicone surfactant, and (3) 2 Polyethylene glycol or polyethylene-polyether having a solubility of more than With a copolymer of polypropylene glycol (without using polypropylene glycol) including. Similar amounts can be used in granular compositions, gels, and the like. 1990 US Patent No. 4,983, issued to Starch on December 18, 1980. U.S. Patent No. 316, Starch issued January 8, 1991 No. 4,978,471, Huber et al., Issued Feb. 22, 1994. U.S. Pat. No. 5,288,431 to Aizawa et al. National Patent Nos. 4,639,489 and 4,749,740, column 1, line 46 See also column 4, line 35.   The silicone foam control agents in the present invention are preferably all about 1,000 Polyethylene having an average molecular weight of less than about 100, preferably between about 100 and 800 Glycol and polyethylene / polypropylene glycol copolymers. Polyethylene glycol and polyethylene / polypropylene according to the present invention The recall copolymer is present in water at room temperature in excess of about 2% by weight, preferably about 5% It has a solubility of more than%.   Preferred solvents in the present invention are less than about 1,000, more preferably 100 and less. Poly, having an average molecular weight between 800 and most preferably between 200 and 400 Ethylene glycol, and polyethylene / polypropylene glycol, preferred Is a copolymer of PPG200 / PEG300. Between about 1: 1 and 1:10 Polyethylene glycol: polyethylene, most preferably between 1: 3 and 1: 6. The weight ratio of the copolymer of propylene glycol to polypropylene glycol is preferred.   The preferred silicone foam inhibitor used in the present invention has a molecular weight of 4, especially. Contains no 000 polypropylene. They are also preferably PLURON Block copolymer of ethylenoxide and propylene oxide, such as ICL101 Does not include   Other foam inhibitors useful in the present invention are secondary alcohols (e.g., 2- Alkyl alkanols) and such alcohols and US Pat. 679,4,075,118 and EP 150.872. And mixtures with sea corn oils such as the disclosed silicones. Secondary alcohol Is C₁-C₁₆C with a chain₆-C₁₆Alkyl alcohol is mentioned. preferable The alcohol is 2-butyl octanol and has the trade name ISOFIL 12. Available from Condea. Mixtures of secondary alcohols are trade names Available as ISALCHEM from Enichem. Mixed foaming Inhibitors typically comprise alcohol and silicone in a weight ratio of 1: 5 to 5: 1. Of mixtures.   For any detergent composition used in automatic washing machines or automatic dishwashers Even the extent to which foaming overflows the washing machine or adversely affects the washing mechanism of the dishwasher Should not occur. When used, the foaming inhibitor is preferably used in the form of “foaming suppressing amount. ]. The “foaming suppression amount” allows the formulator of the composition to use an automatic washing machine or Launched sufficiently to be a low-foaming or dishwashing detergent for use in automatic dishwashers. foam This means that the amount of the foam control agent for controlling the foaming control agent can be selected.   The compositions according to the invention generally comprise from 0% to 10% of a foam control agent. Foaming When used as inhibitors, monocarboxylic fatty acids and their salts are typically Are present in amounts up to 5% by weight of the detergent composition. Preferably, 0.5 to 3% Fatty acid monocarboxylate foam inhibitors are utilized. Silicone foam inhibitor , Typically utilized in amounts up to 2.0% by weight of the detergent composition. However, it is Larger amounts may be used. This upper limit keeps costs to a minimum and effective foaming Of a practical nature primarily related to smaller effects on the control of You. Preferably 0.01% to 1% of a silicone foam inhibitor, more preferably 0% to 1%. . Use 25% to 0.5%. As used in the present invention, these weight percentages Values include any silica that may be used in conjunction with the polyorganosiloxane, Any materials that may be utilized are included. Derived from monostearyl phosphate Suds suppressors are generally utilized in amounts ranging from 0.1% to 2% by weight of the composition. Hydrocarbon foam inhibitors are typically utilized in amounts ranging from 0.01% to 5.0%. Is done. However, more levels can be used. Alcohol foam control The agent is typically used at 0.2% -3% by weight of the final composition.Alkoxylated polycarboxylate   Alkoxylated polycarboxylates, such as those prepared from polyacrylates G is useful in the present invention to add fat removal performance. These materials International Publication No. 91/08281 and PCT 90/01815 (4 pages or less) Reference) and are incorporated herein by reference. Chemically these materials Is a polymer having one ethoxy side chain per 7-8 acrylate units. Including acrylate. This side chain has the formula-(CH_TwoCH_TwoO)_m(CH_Two)_nCH_ThreeStuff Where m is 2-3 and n is 6-12. This side chain is Esterified to the relevant "backbone", resulting in a "comb" polymer structure You. The molecular weight can vary, but typically ranges from 2000 to 50,000. Such an alkoxylated polycarboxylate is used in the composition of the present invention at a concentration of 0.0 It may contain from 5% to 10% by weight.Fabric softener   Various fabric softeners during washing, especially the storm issued December 13, 1977 ( U.S. Pat. No. 4,062 to Storm) and Nirschl. No. 647, and other smectite clays known in the art. Softening clays typically have a level of 0.5% to 10% by weight in the composition. Can be used to impart the benefits of a fabric softener at the same time as fabric washing. K Ray softeners are described, for example, by Crisp et al. U.S. Pat. No. 4,375,416 and Harris, issued Sep. 22, 1981 Harris et al., US Pat. No. 4,291,071. It can be used in combination with min and cationic softeners.Fragrance   Fragrances and perfume ingredients useful in the present compositions and processes include Aldehi. Various natural and synthetic compounds including, but not limited to, Chemical components. Orange oil, lemon oil, rose extract, lavender, ja Of ko, patchouli, balsam essence, sandalwood oil, pine oil, cedar Includes a variety of natural extracts and essences that can combine complex mixtures of similar ingredients Can be Final fragrances can incorporate extremely complex mixtures of these components. Wear. The final fragrance is typically from 0.01% of the detergent composition of the present invention. 2% by weight, with the individual perfume ingredients ranging from 0.0001% to 9% of the final perfume composition. 0%.   Non-limiting examples of fragrance ingredients useful in the present invention include 7-acetyl-1,2 , 3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaph Ta Ren, Ionone Methyl, Ionone Gamma Methyl, Methyl Cedrone, Methyl Dihi Dolojasmonate, methyl 1,6,10-trimethyl-2,5,9-cyclod Decatrien-1-yl ketone, 7-acetyl-1,1,3,4,4,6-hex Samethyltetralin, 4-acetyl-6-tert-butyl-1,1-dimethyl Indane, para-hydroxy-phenyl-butanone, benzophenone, methyl -Tanaphthyl ketone, 6-acetyl-1,1,2,3,3,5-hexamethyli Ndan, 5-acetyl-3-isopropyl-1,1,2,6-tetramethylin Dan, 1-dodecanal, 4- (4-hydroxy-4-methylpentyl) -3-cy Clohexene-1-carboxaldehyde, 7-hydroxy-3,7-dimethylo Kutanal, 10-undecene-1-al, iso-hexenyl-cyclohexyl Carboxaldehyde, formyl tricyclodecane, hydroxycitronellal Product of hydroxycitronellal with methyl anthranilate, India Condensation products with phenylacetaldehyde and indole, 2-methyl-3- (para-tert-butylphenyl) -propionaldehyde , Ethyl vanillin, heliotropin, hexylcinnamaldehyde, amylcin Namaldehyde, 2-methyl-2- (para-iso-propylphenyl) -propyl Onaldehyde, coumarin, decalactone gamma, cyclopentadecanolide, 1 6-hydroxy-9-hexadecenoic acid lactone, 1,3,4,6,7,8 -Hexahydro-4,6,6,7,8,8-hexamethylcyclopenta-gamma -2-benzopyran, beta-naphthol methyl ether, ambroxane, Decahydro-3a, 6,6,9a-tetramethylnaphtho [2,1b] furan, Dorol, 5- (2,2,3-trimethylcyclopent-3-enyl) -3-me Tylpentan-2-ol, 2-ethyl-4- (2,2,3-trimethyl-3- Cyclopenten-1-yl) -2-buten-1-ol, caryophyllene alcohol , Tricyclodecenyl propionate, tricyclodecenyl acetate, Re Benzyl citrate, seryl acetate and para- (tert-butyl) cyclo Hexyl acetate is mentioned.   Particularly preferred perfume materials are most preferred in final product compositions containing cellulases. It brings great incense improvement. These flavoring agents include hexylcinnamal Dehyde, 2-methyl-3- (para-tert-butylphenyl) -propiona Aldehyde, 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1 , 1,6,7-Tetramethylnaphthalene, benzyl salicylate, 7-acetyl- 1,1,3,4,4,6-hexamethyltetralin, para-tert-butyloxy Clohexyl acetate, methyl dihydrojasmonate, beta-naphthol Methyl ether, methyl beta-naphthyl ketone, 2-methyl-2- (para So-propylphenyl) -propionaldehyde, 1,3,4,6,7,8- Xahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gamma- 2-benzopyran, dodecahydro-3a, 6,6,9a-tetramethylnaphtho [ 2,1b] furan, anisaldehyde, coumarin, cedrol, vanillin, shiku Lopentadecanolide, tricyclodecenyl acetate and tricyclodecenyl Pionates include, but are not limited to.   Other flavoring materials include essential oils, resinoids; Nam Resinoid, Stylax, Radanam Resin, Nikuzuku, Cassia Oil, Ben Various types including, but not limited to, zoin resins, cilantro and lavandin And resins from sources. Another flavoring chemical is phenylethyl alcohol. Rucol, terpineol, linalool, linalyl acetate, geraniol, nero 2- (1,1-dimethylethyl) -cyclohexanol acetate, acetate acetate And eugenol. Carrier like diethyl phthalate It can be used in the final perfume composition.Other ingredients   Various other ingredients useful in detergent compositions are incorporated into the compositions of the present invention. Can be added. They include other active ingredients, carriers, hydrotrols , Processing aids, dyes, pigments, solvents for liquid formulations, solid fillers for rod compositions, etc. Is mentioned. If high foaming is required, C_Ten-C₁₆Foaming like alkanolamide Enhancers can be included in the composition, typically at a level of 1% to 10%. C_Ten-C₁₄Monoethanol and diethanolamine are two of these foam enhancers. This is an example of a typical class. The amine oxide, betaine and Use these foam enhancers with any of the high foaming surfactants like sultein It is also advantageous to do so. If necessary, MgCl_Two, MgSO_Four, CaCl_Two, CaS O_FourWater-soluble magnesium and / or calcium salts such as %-Add at 2% level to add foam or enhance fat removal performance be able to.   The various cleaning components optionally used in the present composition are based on a porous hydrophobic substrate. Further stabilization by absorbing the components and then coating the substrate with a hydrophobic coating can do. Preferably, the cleaning components are interfacial before being absorbed by the porous substrate. Mix with activator. In use, the cleaning components are released from the substrate into the aqueous laundry liquor. Therefore, the intended cleaning function is realized.   In order to explain this method in more detail, porous hydrophobic silica (trade name: SIPER) NATD10, DeGussa) from 3% to 5% C_13-15Etoki Mixed with proteolytic enzyme containing silylated alcohol (EO7) nonionic surfactant I do. Typically, the enzyme / detergent solution is 2.5 times the weight of the silica. The obtained powder is treated with silicone oil (various silicones in the range of 500-12,500). (Oil viscosity can be used) with stirring to disperse. The obtained silicone oil Emulsify the dispersion or otherwise add to the final detergent mother liquor. By this method, Enzymes, bleach, bleach activator, bleach catalyst, photoactivator, dye, fluorescent agent, fabric Ingredients such as preparations and hydrolyzable surfactants, including liquid laundry detergent compositions Can be "protected" for use in detergents.   Liquid cleaning compositions may contain water or other solvents as a carrier. Meta Low, typified by ethanol, propanol and isopropanol A primary or secondary alcohol of molecular weight is suitable. Monohydric alcohol is a surfactant Is preferred to solubilize but 2 to 6 carbon atoms and 2 to 6 hydroxy groups Polyols such as those containing (eg, 1,3-propanediol, ethylene glycol) Recall, glycerin and 1,2 propanediol) can also be used. The composition comprises from 5% to 90%, typically 10% to 50% of such a carrier. May be included.   The detergent composition of the present invention is preferably used during aqueous washing operations, The pH of the wash water is between 6.5 and 11, preferably between 7.5 and 10.5. To be prescribed. The product formulation for liquid dishwashing is preferably pH 6.8 and 9. It is between 0. Laundry products typically have a pH of 9-11. Recommended usage level Methods for controlling pH include the use of buffers, alkalis, acids, etc. It is known to those skilled in the art.Production of granules   The bis-alkoxylated cationic surfactant of the present invention is added to the detergent mixture and After conventional spray drying, no residual potentially odorous short-chain amine contaminants Promotes removal. Formulators, for example, alkoxylated for high-density granular detergents If you want to prepare mixable particles containing a cationic surfactant, It is preferred that the child composition is not a strong alkali. High density (greater than 650 g / l) A process for preparing granules is described in US Pat. No. 5,366,652. . These particles should be used in 9 or less in use to avoid the smell of impurity amines. It may be formulated to have an effective pH. This is a small amount such as boric acid, citric acid, etc. of This can be achieved by adding an acid source or a suitable pH buffer to the particles. . In another aspect, the present invention provides for the anticipated problems associated with amine odors. As disclosed, masking can be achieved through the use of perfume ingredients.         In the following examples, the abbreviated component designations have the following meanings. LAS: Linear C₁₂Sodium alkylbenzene sulfonate TAS: Tallow alkyl sodium sulfate C45AS: C₁₄-C_FifteenSodium linear alkyl sulfate CXyEzS: C₁x-C₁y-branched sodium alkylsulfate zmol                     Condensation with lenoxide C45E7: C_14-15Echile with an average of 7 moles of dominant linear primary alcohol                     And condensation C25E3: C_12-15Ethylene oxide with an average of 3 moles of branched primary alcohol                     Condensation with Sid C25E5: C_12-15Ethylene oxide with an average of 5 moles of branched primary alcohol                     Condensation with Sid Coco EO2: R₁N⁺(CH_Three) (C_TwoH_FourOH)_Two, Where R₁= C₁₂−                     C₁₄ Soap: derived from an 80/20 mixture of tallow oil and coconut oil                     Straight alkyl carboxylate TFAA: C₁₆-C₁₈Alkyl N-methylglucamide TPKFA: C12-C14 head cut fatty acid STPP: anhydrous sodium tripolyphosphate Zeolite A: has a primary particle size in the range of 0.1 to 10 microns                     Formula Na₁₂(AlO_TwoSiO_Two)₁₂・ 27H_TwoO aluminum                     Sodium nosilicate hydrate NaSKS-6: Formula δ-Na_TwoSi_TwoO_FiveCrystalline layered silicate Citric acid: Citric anhydride Carbonate: having a particle size between 200 μm and 900 μm                     Sodium bicarbonate Bicarbonate: has a particle size between 40 μm and 1200 μm                     Anhydrous sodium bicarbonate Silicate: amorphous sodium silicate (SiO_Two: Na_TwoO; 2.0 ratio) Sodium sulfate: anhydrous sodium sulfate Citrate: an activity with a particle size between 425 μm and 850 μm                     86.4% trisodium citrate dihydrate MA / AA: 1: 4 maleic acid / acrylic acid copolymer average molecular weight 7                     0000 CMC: Sodium carboxymethylcellulose Protease: Novo Industries A / S (Novo Industries)                     tries A / S) sold under the trade name Savinase                     Active 4K NPU / g proteolytic enzyme for sale Alcalase: Novo Industries A / S (Novo Indus)                     tries A / S) sells 3 AU / g of active protein.                     White decomposition enzyme Cellulase: Novo Industries A / S (Novo Indus)                     tries A / S) sold under the trade name Carezyme                     Cellulose degradation of 1000 CEVU / g of activity sold                     enzyme Amylase: Novo Industries A / S (Novo Indus)                     tries A / S) is trade name Termamyl60T                     60KNU / g starch-degrading yeast sold for sale                     Elementary Lipase: Novo Industries A / S (Novo Industry)                     ries A / S) sold under the trade name Lipolase                     Active lipolytic enzyme with 100 kLU / g Endolase: Novo Industries A / S (Novo Indus                     tries A / S) is active 3000EVU /                     g Endoglunase enzyme PB4: Nominal formula NaBO_Two・ 3H_TwoO-H_TwoO_TwoSodium perborate                     Tetrahydrate PB1: Nominal NaBO_Two・ H_TwoO_TwoAnhydrous sodium perborate bleach Percarbonate: Nominal formula 2Na_TwoCO_Three・ 3H_TwoO_TwoSodium percarbonate NOBS: Nonanoyloxybenzene sulfate in the form of sodium salt TAED: Tetraacetylethylenediamine DTPMT: Monsanto is trade name Dequest                     Diethylenetriamine penta sold as 2060                     (Methylene phosphonate) Photoactivation: bleached dextrin                     Sulfonated zinc phthalocyanine encapsulated in soluble polymer Brightener 1: 4,4'-bis (2-sulfostyryl) biphenyl dinatto                     Lium Brightener 2: 4,4'-bis (4-amino-6-morpholino-1,3,5                     -Triazin-2-yl) amino) stilbene-2: 2 '                     -Disodium disulfonate HEDP: 1,1-hydroxyethanediphosphonic acid PVNO: polyvinyl pyridine N-oxide PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole                         SRA1: Oxyethyleneoxy and te                         Sulfobenzoyl having a phthaloyl backbone                         End-blocking ester SRA2: Diethoxylated poly (1,2 propylene terephthalate)                     Short-chain block polymer silicone antifoaming agent:                     Polydimethyene containing oxane-oxyalkylene copolymer                     Siloxane foam control agent, the dispersant of the foam control agent                     With a ratio of 10: 1 to 100: 1 The following examples are illustrative of the invention, but limit or otherwise define the scope of the invention It is not intended to do so. All parts and percentages used in the present invention Percentages and ratios are expressed as weight percentages unless otherwise specified.   In the following examples, all levels are stated as% by weight of the composition.                                   Example I   The following detergent formulations according to the invention are prepared. Here, A and C are phosphorus-containing detergents. Wherein C is a zeolite-containing detergent composition. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                   Example II   The following bleach-free detergent compositions are particularly useful in washing colored garments. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                   Example III   The following detergent formulations according to the invention are prepared. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                   Example IV   The following high density, bleach-containing detergent formulations according to the present invention are prepared. ^*The example bis-AQA-1 (coco MeEO2) surfactant has an equivalent amount of surfactant Any of bis-AQA-2 to bis-AQA-22 or other in the present invention May be replaced by a bis-AQA surfactant.                                   Example V The following high-density detergent formulations according to the invention are prepared. ^*An example bis-AQA-1 (coco MeEO2) surfactant is the surfactant bis-A Any of QA-2 to bis-AQA-22 or other bis in the present invention -It may be replaced by an equivalent amount of the AQA surfactant. Any of the granular detergent compositions provided in the present invention can be prepared by using a known tableting method. The tablet may be formed into a washed tablet. The following Examples A and B further illustrate the invention in the present invention with respect to bar soap bars. Is what you do.                                   Example VI ¹: Sodium diethylene triamine penta (phosphonate)^Two : Sokolan CP-52 is a maleic / acrylic copolymer. 3: Bis-AQA-1 is obtained from an equivalent amount of bis-AQA surfactant, bis-AQA2 Bis-AQA-22 or other bis-AQA surfactant in the present invention May be replaced.^Four : Water (2% to 8% including water of hydration), sodium sulfate, calcium carbonate And other minor components.                                   Example VII   The present invention is achieved by mixing together the components in weight percentages as indicated below. The following hand laundry detergent formulation is prepared. AQA-9^*Placement with any of the AQA surfactants described in the present invention. May be replaced. Preferred AQA surfactants for use in this example include, for example, Having 10 to 15 ethoxy groups such as AQA-10 and AQA-16 You.   The above examples are illustrative of the present invention with respect to a fabric laundry composition. It is not intended to limit the light. Also, a bis-AQA surfactant and a stain remover Combinations of hard surface cleaners, cosmetic soaps or gels, shampoos, hands and It is expected that this would be useful in formulating automatic dishwashing detergent compositions and the like.   The following examples further illustrate the invention in the present invention with respect to hand dishwashing liquids. .                                  Example VIII ^*Bis-AQA-2 to Bis-AQA-22 or other bis in the present invention -It may be replaced by an AQA surfactant.^** Cocoalkyl betaine The following examples further illustrate the invention in the present invention with respect to hard surface cleaners. You.                                   Example IX ^*Bis-AQA-2-bis-AQA-22 or other bis- in the present invention It may be replaced by an AQA surfactant. The following examples further illustrate the invention in the present invention with respect to cosmetic soaps or gels. Things.                                   Example X ^*Bis-AQA-2-bis-AQA-22 or other bis- in the present invention It may be replaced by an AQA surfactant. ** All or part of soap is C₁₂-C₁₄Alkyl sulfate or C₁₂-C₁₆ It may be replaced by a synthetic cationic surfactant such as an alkyl ethoxy sulfate.   Examples A and B below illustrate the invention with respect to an automatic dishwashing detergent containing granular phosphate. This further exemplifies the invention.                                   Example XI ¹: Sodium tripolyphosphate^Two : Sodium dichlorocyanurate^* Bis-AQA-1 surfactants are converted from bis-AQA-2 to bis-AQA-22. It may be replaced more.                                   Example XII   The following replaces the bis-AQA surfactant described in any of the above examples FIG. 1 illustrates a mixture of bis-AQA surfactants that can be used. Above As disclosed, such mixtures have a range of performance advantages, And / or used to obtain useful cleaning compositions over a variety of conditions of use be able to. Preferably, the bis-AQA surfactant in such a mixture comprises The EO units differ by at least 1.5, preferably 2.5-20. like this The ratio range (weight) for the resulting mixture is typically 10: 1-1: 10. . Non-limiting examples of such mixtures are as follows.component                                                       Ratio (weight) Bis-AQA-1 + Bis-AQA-5 1: 1 Bis-AQA-1 + Bis-AQA-10 1: 1 Bis-AQA-1 + Bis-AQA-15 1: 2 Bis-AQA-1 + Bis-AQA-5           + Bis-AQA-20 1: 1: 1 Bis-AQA-2 + Bis-AQA-5 3: 1 Bis-AQA-5 + Bis-AQA-15 1.5: 1 Bis-AQA-1 + Bis-AQA-20 1: 3   Bis-AQA surfactants according to the invention comprise a pair comprising only a single ethoxylated chain. Mixtures with the corresponding cationic surfactants can also be used. So, for example, , Where R¹And X is as disclosed above, and the cationic surfactant Has (x + y) or z in the range of 1-5, preferably 1-2, and the other has (X +) in the range of 3-100, preferably 10-20, most preferably 14-16 Formula R with y) or z¹N⁺CH_Three[EO]_x[EO]_yX^-And R¹N⁺(CH_Three)_Two [EO]_zX^-Mixture of ethoxylated cationic surfactants used in the present invention Can be Such compositions may be used individually in the present invention. Detergent performance over a wider range of water hardness than surfactants (especially for fabric washing situations) Hey ) Is advantageously improved. Shorter EO cationic surfactants (eg, EO2) In order to improve the cleaning performance of anionic surfactants in soft water, longer EO The cationic surfactant (for example, EO15) has a hardness tolerance of an anionic surfactant. Of anionic surfactants in hard water by acting to improve Improving performance has now been discovered. The traditional wisdom in cleaning technology is that builders Suggests that the performance "window" of anionic surfactants can be optimized . However, to date, this window has been expanded to cover essentially all conditions of water hardness. Incorporation was impossible to achieve.                                  Example XIII   This example was added to any of the previous examples of bis-AQA containing detergent compositions. To illustrate, the perfume formulation (AC) made according to the present invention is illustrated. Mr The various components and levels are described below.   The above-mentioned perfume composition contains the bis-AQA surfactant disclosed in the present invention. Mixed or sprayed with any of the cleaning (including bleaching) compositions (Typically, at levels up to about 2% by weight of the total detergent composition). Washed (or drifted) White) improved adhesion and / or retention of perfume or its individual components on the surface Is thus secured.

────────────────────────────────────────────────── ─── Continuation of front page    (72) Inventor Laura, Kron             Fair Fee, Ohio, USA             Ludo, Lake, Mead, Drive, 5656 (72) Inventors Kenneth, William, Willman             Fair Fee, Ohio, USA             Ludo, Williamsburg, Way, 5603 (72) Inventors Thomas, Anthony, Kryp             United States Ohio, Loveland,             Three, Chimneys, Rain, 599 (72) Inventor John, Downing, Curry             Oxford, Ohio, United States             Road, Stone, Creek, Drive, 95 (72) Inventors Sanjeef, Krishnadas, Manohar             Fair Fee, Ohio, USA             Ludo, Meadowlawn, Way, 2014 Bee (72) Inventors Ian, Martin, Dodd             Loughborough, Holywell, De             Live, 47 (72) Inventor Kevin, Lee, Cott             United States Ohio, Cincinnati,             Bentbrook, Drive, 2920 (72) Inventor Hajime Baba             2-9-22-206 Hachiman-cho, Nada Ward, Kobe City, Hyogo Prefecture (72) Inventor Rinko Katsuta             6-2-1, Minatojima-Nakamachi, Chuo-ku, Kobe City, Hyogo Prefecture             Kobe Park City, Sea 507 (72) Inventor Frank, Andrey, Kubitok             United States Ohio, Cincinnati,             Richwood, Avenue, 1103 (72) Inventor Mark, Cyan-Quen, Mao             2-23-13 Sumiyoshi Honcho, Higashinada Ward, Kobe City, Hyogo Prefecture (72) Michael, Alan, John, Moss             Stockholm, Northumberland, United Kingdom             Sfield, Painshawfield,             Road, 13 (72) Inventor Masaru Murata             6-5-A3, Yumabacho, Nishinomiya City, Hyogo Prefecture (72) Inventors Peter, Robert, Foley             United States Ohio, Cincinnati,             Lytle, Place 1, Apartment             906 (72) Inventors Layan, Keshaf, Panandadaikar             United States Ohio, West, Chi             Esther, Oregon, Pass, 6484 (72) Inventor Kakumanu, Pramod             United States Ohio, West, Chi             Esther, Kingfisher, Rain,             7986 (72) Inventors Kizar, Mohammed, Kang, Sarnaik             Higashi-Nada-ku, Koyo-cho, Kobe City, Hyogo Prefecture             ―302 (72) Inventors Christian, Arthur, Jax, Ka             Miel, Toen             Belgian Bae 9120, Haasdonk, Bae             Quitohustrato, 4

Claims (1)

[Claims] 1. A soil remover, a non-AQA surfactant, and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant represented by the following formula: , Detergent compositions. Wherein R ¹ is a linear, branched or substituted C ₈ -C ₁₈ alkyl, alkenyl, aryl, alkaryl, ether or glycidyl ether moiety, R ² is a C ₁ -C ₃ alkyl moiety, R ³ And R ⁴ can be independently varied and selected from hydrogen, methyl and ethyl, X is an anion, A and A ′ can be independently varied and are each C ₁ -C ₄ alkoxy, p and q Can vary independently and are integers ranging from 1 to 30). The composition of claim 1, wherein the soil remover is based on a sulfobenzoyl end-capped ester and a sulfonated end-capped polyethylene terephthaloyl copolymer having five sulfoisophthaloyl units. 3. 3. The composition according to any one of claims 1 or 2, prepared by mixing a non-AQA surfactant and an AQA surfactant. 4. The composition according to any one of claims 1 to 3, wherein the non-AQA surfactant is an anionic surfactant. 5. The composition according to any one of claims 1 to 4, wherein the ratio of bis-AQA to non-AQA surfactant is from 1:15 to 1: 8. 6. Wherein the bis-AQA surfactant has the formula: wherein R ¹ is C ₈ -C ₁₈ alkyl, R ² is methyl, A and A ′ are ethoxy or propoxy groups, and p and q are each 1 The composition according to any one of claims 1 to 5, wherein the composition is an integer from 1 to 8. 7. Wherein the bis-AQA surfactant has the formula: wherein R ¹ is C ₈ -C ₁₈ alkyl, R ² is methyl, A and A ′ are ethoxy or propoxy groups, and p and q are each 1 The composition according to any one of claims 1 to 6, wherein the composition is an integer from 1 to 4. 8. The composition according to any one of claims 1 to 7, wherein the bis-AQA cationic surfactant is one wherein p and / or q is an integer in the range of 10 to 15. 9. 9. The composition according to any one of claims 1 to 8, comprising two or more bis-AQA surfactants or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant. Stuff. 10. 10. The composition according to any one of the preceding claims, comprising two or more non-AQA surfactants and a mixture of two or more bis-AQA surfactants. 11. The composition according to claim 1, which is in the form of a granule, a stick, an aqueous liquid, a non-aqueous liquid or a tablet. 12. A method for removing dirt and stains by bringing dirt and stains into contact with the composition according to any one of claims 1 to 11 or an aqueous medium comprising the detergent composition. 13. 13. The method of claim 12, wherein the method removes soil, builder sensitive soil, bleach sensitive soil, or surfactant sensitive soil from the fabric. 14． 14. The method according to any one of claims 12 or 13, wherein the dish or other hard surface is cleaned. 15. The method according to any one of claims 12 to 14, which is performed by an automatic machine. 16. The method according to any one of claims 12 to 15, which is performed by hand. 17． 17. The method according to any one of claims 12 to 16, further comprising an amylase, a protease, a lipase, or a cellulase or a cellulite enzyme, or a mixture thereof. 18. 18. The method according to any one of claims 12 to 17, wherein a high level of a non-AQA surfactant is used. The method according to any one of claims 12 to 18, wherein an ethoxylated polyamine surfactant is used. 20. The method according to any one of claims 12 to 19, comprising two or more bis-AQA surfactants or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant. 21. The method according to any one of claims 12 to 20, comprising two or more bis-AQA surfactants or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant. 22. A method of improving the adhesion or persistence of a fragrance or fragrance component on a fabric or other surface comprising contacting the fragrance or fragrance component with the fabric or other surface in the presence of a bis-AQA surfactant . 23. 23. The method of claim 22, wherein the method is performed using a combination with a detergent composition comprising bis-AQA, a flavoring agent or a flavoring agent component.