CN1225115A - Detergent composition - Google Patents

Abstract

A detergent composition comprising a soil release agent a non-dual AQA surfactant and an dual-alkoxylated quaternary ammonium (dual-AQA) cationic surfactant.

Description

Detergentcomposition

Technical Field

The present invention relates to detergent compositions comprising a soil dispersant polymer, a non-AQA surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant.

Background

The formulation of laundry detergents and other cleaning compositions presents considerable challenges due to the requirement that modern compositions be capable of removing a wide variety of soils and stains from a wide variety of substrates. Accordingly, laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for use in automatic dishwashing machines all require the proper selection and combination of ingredients to achieve effective performance. Typically, such detergent compositions contain one or more types of surfactants which are used to disperse and remove different types of soils and stains. Studying the existing literature appears to suggest that detergent manufacturers may choose a wide range of surfactants and combinations of surfactants, but in fact many of these components are specialty chemicals which are not suitable for low unit cost items such as household laundry detergents. It is the case that most such household products, such as laundry detergents, still contain predominantly one or more conventional ethoxylated nonionic and/or sulfated or sulfonated anionic surfactants, presumably due to economic considerations and the need to formulate compositions that are reasonably good for a wide variety of soils and stains and a wide variety of fabric benefits.

The rapid and efficient removal of different types of soils and stains such as body soils, greasy/oily soils and certain foodstains can be problematic. Such soils comprise a mixture of hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous materials and are therefore known to be difficult to treatTo be removed. Further problems are encountered with deposits in the form of calcium soaps: insoluble hard ion salts of fatty acids (e.g., Ca) produced by triglyceride soil degradation²⁺/Mg²⁺). After washing, low levels of hydrophobic soils, residual stains and lime soap deposits often remain on the fabric surface. Continued washing and abrasion, coupled with limited removal of soils, stains and deposits, build up on fabrics over multiple washes which further entrap dirt particles leading to fabric yellowing. Finally, the fabric presents a dull appearance that consumers perceive that the fabric is not wearable and should be discarded.

Various nitrogen-containing cationic surfactants have been suggested in the literature for use in various cleaning compositions. Such materials are generally compounds in the form of amino-, amido-or quaternary ammonium salts or imidazolium salts, which are usually designed for specific uses. For example, various amino and quaternary ammonium surfactants have been suggested for use in shampoo compositions, said to provide hair cosmetic benefits to the hair. Other nitrogen-containing surfactants are used in some laundry detergents to provide fabric softening and antistatic benefits. However, for the most part, the commercial use of these materials has been limited by difficulties encountered in the large scale production of such compounds. A further limitation is the potential precipitation of anionic active components of the detergent composition with cationic surfactants due to their ionic interactions. The above mentioned nonionic and anionic surfactants remain as the major surfactant components in today's laundry compositions.

It has been found that certain bis-alkoxylated quaternary ammonium (bis-AQA) compounds can be used in various detergent compositions to enhance cleaning performance on many types of soils and stains, especially hydrophobic soils and lime soap deposits, which are commonly encountered. The bis-AQA surfactants of the present invention provide significant benefits to formulators over cationic surfactants previously known in the art. For example, the bis-AQA surfactants used herein provide significant improvements in cleaning "everyday" greasy/oily hydrophobic soils typically encountered. In addition, the bis-AQA surfactants are compatible with anionic surfactants commonly used in detergent compositions, such as alkyl sulfates and alkyl benzene sulfonates; incompatibility with anionic components of detergent compositions is often the limiting factor in the use of cationic surfactants to date. Low levels (as low as 3ppm in the aqueous wash solution) of bis-AQA surfactants can produce the benefits described herein. The bis-AQA surfactants can be formulated over a wide range of pH 5-12. The bis-AQA surfactants can be prepared as 30% by weight solutions which are pumpable and therefore easy to handle in production facilities. bis-AQA surfactants with degrees of ethoxylation above 5 are sometimes present in liquid form and thus may be provided as 100% neat materials. In addition to the beneficial treatment properties of bis-AQA, bis-AQA surfactants are available in highly concentrated solutions, which provides significant economic advantages in terms of transportation costs.

In addition, it has been found that compositions containing a soil dispersant polymer and a bis-AQA surfactant provide additional superior cleaning and whiteness performance over products containing this single technology. Polymeric dispersants enhance overall cleaning by crystal growth inhibition, peptization of particulate soil release, anti-redeposition, and solubilization of soil. It is believed that the benefits of the bis-AQA/soil dispersant polymersystem are due to: (1) AQA acts on the stained surface to minimize lime soap formation and to remove any lime soap present, thereby promoting improved polymer deposition; (2) AQA further solubilises the soil and the polymer acts as a "grease conveyor", stripping off the AQA solubilised soil components and dispersing them into the aqueous wash liquor.

Background

US5441541 issued 8/15/1995 to a.methreteab and f.j.loprept relates to mixtures of anionic/cationic surfactants. UK2040990 to a.p.murphy, r.j.m.smith and m.p.brooks, granted on 3.9.1980, relates to ethoxylated cationic surfactants in laundry detergents.

Summary of The Invention

Hair brushThere is also provided a composition comprising or prepared from in combination: a soil dispersant polymer, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula:

wherein R is¹Is straight-chain, branched or substituted C₈-C₁₈Alkyl, alkenyl, aryl, alkaryl (alkanyl), ether or glycosyl ether moiety, R²Is C₁-C₃Alkyl moiety, R³And R⁴Independently variable and selected from hydrogen, methyl and ethyl, X is an anion, A and A' independently variable and are each C₁-C₄Alkoxy, p and q can vary independently and are integers from 1 to 30.

Detailed description of the invention soil dispersant polymers

The compositions of the present invention comprise a soil dispersant polymer. The soil dispersant polymer is present in an amount of from 0.1% to 7% by weight of the composition of the present invention. During the wash process, these polymers actat the stain/wash solution interface.

Dispersants suitable for use in the present invention include polymeric polycarboxylates and polyethylene glycols, although other dispersants known in the art may be used.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, especially in the acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. In the polymeric polycarboxylates or monomeric moieties of the present invention, it is also suitable to contain non-carboxylate groups such as vinyl methyl ether, styrene, ethylene and the like, provided that the moiety does not exceed 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers that can be used in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably 2000-10000, more preferably 4000-7000 and most preferably 4000-5000. Water-soluble salts of such acrylic polymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Such soluble polymers are known. The use of such polymeric acrylates in detergent compositions is disclosed in US3308067 to Diehl, granted on 3.7.1967.

Acrylic acid/maleic acid based copolymers may also be used as preferred soil dispersant polymers. Such materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of such copolymers in the acid form is preferably 2000-100000, more preferably 5000-75000, and most preferably 7000-65000. The ratio of acrylate to maleate moieties in such copolymers is generally from 30: 1 to 1: 1, more preferably from 10: 1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers may include, for example, alkali metal salts, ammonium salts and substituted ammonium salts. Such soluble acrylate/maleate copolymers are known substances described in European patent application EP66915, published 12/15 1982, and in European patent application EP193360, published 9/3 1986, the latter also describing such polymers including hydroxypropyl acrylate. Another useful class of dispersants includes maleic/acrylic/vinyl alcohol terpolymers. This material is also disclosed in EP193160 and includes, for example, 45/45/10 acrylic acid/maleic acid/vinyl alcohol terpolymers.

Another class of polymeric dispersant materials that can be included are polyethylene glycols (PEG). PEG has the properties of a dispersant as well as the benefits of clay soil-anti-redeposition agent removal. The molecular weight range for this use is typically 500-.

Polyaspartate and polyglutamate dispersant polymers may also be used, with dispersants such as polyaspartate preferably having a molecular weight (average) of 10000.

The most preferred dispersant polymers have the following characteristics, which include: (1) a suitable low molecular weight "hydrophobic" polymeric backbone; and (2) pendant "hydrophilic" groups that provide steric stabilization. Preferred soil dispersant polymers are polyalkoxylated-polyalkylamine polymers (PPP), most preferred are ethoxylated/propoxylated polyalkylamine or polyalkylimine polymers such as ethoxylated Polyvinylamines (PEAs) or Polyethyleneimines (PEIs) as described in patent application WO 95/32272. Bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactants

The second essential component of the present invention comprises an effective amount of a bis-AQA surfactant of the formula:wherein R is¹Is a straight, branched or substituted alkyl, alkenyl, aryl, alkaryl, ether or glycosyl ether moiety containing from 8 to 18 carbon atoms, preferably from 8 to 16 carbon atoms, most preferably from 8 to 14 carbon atoms; r²Is an alkyl group having 1 to 3 carbon atoms, preferably methyl; r³And R⁴Independently variable and selected from hydrogen (preferred), methyl and ethyl, and X "is an anion sufficient to provide electrical neutrality, e.g., chlorine, bromine, methyl sulfate, sulfate. A and A' can be independently varied and are each selected from C₁-C₄Alkoxy, especially ethoxy, propoxy, butoxy and mixtures thereof; p is 1 to 30, preferably 1 to 15, more preferably 1 to 8, even more preferably 1 to 4 and q is 1 to 30, preferably-15, more preferably 1 to 8, even more preferably 1 to 4. Most preferably, both p and q are 1.

Wherein the hydrocarbyl substituent R¹Is C₈-C₁₂In particular C_8-10The bis-AQA compounds of (a) enhance the dissolution rate of laundry particles, particularly under cold water conditions, over materials having longer chain lengths. Thus, C₈-C₁₂bis-AQA surfactants may be preferred by some formulators. The level of bis-AQA surfactant used to prepare the finished laundry detergent compositions may range from 0.1% to 5%, typically from 0.45% to 2.5% by weight. The weight ratio of bis-AQA to percarbonate bleach is in the range 1: 100 to 5: 1, preferably 1: 60 to 2: 1, most preferably 1: 20 to 1: 1.

The present invention employs an "effective amount" of a bis-AQA surfactant to improve the performance of cleaning compositions containing other optional ingredients. By "effective amount" of the bis-AQA surfactants herein is meant an amount sufficient to improve the removal performance of the cleaning compositions against at least some of the target soils and stains, with a directional or significant 90% confidence level. Thus, where the target soils of the composition comprise certain food stains, the formulator will use sufficient bis-AQA in the composition to at least directionally improve cleaning performance against such stains. Also, where the target soil of the composition comprises clay soil, the formulator will use sufficient bis-AQA in the composition to at least directionally improve cleaning performance against such soil.

The bis-AQA surfactants may be combined with other detersive surfactants in an amount effective to achieve at least a directional improvement in cleaning performance. This "amount" in the fabric washing composition can vary, depending not only on the type and severity of the soils and stains, but also on the temperature of the wash water, the volume of wash water and the type of washing machine.

For example, in a top-loading vertical shaft American automatic washing machine using 45 to 83 liters of water in the wash bath, with a wash cycle of 10 to 14 minutes and wash water temperatures of 10 ℃ to 50 ℃, the bis-AQA surfactant is preferably included in the wash solution in an amount of 2ppm to 50ppm, preferably 5ppm to 25 ppm. For heavy duty liquid laundry detergents, the bis-AQA surfactants are converted to a concentration in the product of 0.1% to 3.2%, preferably 0.3% to 1.5%, by weight, based on the amount used per wash load of 50ml to 150 ml. For compact ("compacted") granular laundry detergents (densities above 650g/l), the bis-AQA surfactants are converted to concentrations in the product of 0.2% to 5.0%, preferably 0.5% to 2.5%, by weight, calculated as 60g to 95g per wash load. For spray dried granules (i.e. "bulk"; density less than 650g/l), the bis-AQA surfactant is converted to a concentration in the product of 0.1% to 3.5%, preferably 0.3% to 1.5%, by weight, calculated as 80g to 100g per load.

For example, in a front loading horizontal axis European style automatic washing machine using 8 to 15 liters of water in the wash bath, wash cycle of 10 to 60 minutes, and wash water temperature of 30 ℃ to 95 ℃, it is preferred to include 13ppm to 900ppm, preferably 16ppm to 390ppm, of the bis-AQA surfactant in the wash solution. For heavy duty liquid laundry detergents, the bis-AQA surfactants are converted to a concentration in the product of 0.4% to 2.64%, preferably 0.55% to 1.1%, by weight, calculated as 45ml to 270ml per wash load. For compact ("compacted") granular laundry detergents (densities above 650g/l), the bis-AQA surfactants are converted to concentrations in the product of 0.5% to 3.5%, preferably 0.7% to 1.5%, by weight, calculated as 40g to 210g per wash load. For spray dried granules (i.e., "fluffy"; density less than 650g/l), the bis-AQA surfactant is converted to a concentration in the product of 0.13% to 1.8%, preferably 0.18% to 0.76%, by weight, calculated as the amount used per load from 140g to 400 g.

For example, in a top-loading vertical shaft Japanese automatic washing machine using 26 to 52 liters of water in the wash bath, with a wash cycle of 8 to 15 minutes, and wash water temperatures of 5 ℃ to 25 ℃, it is preferred to include 1.67ppm to 66.67ppm, preferably 3ppm to 6ppm, of the bis-AQA surfactant in the wash solution. For heavy duty liquid laundry detergents, the bis-AQA surfactants are converted to a concentration in the product of 0.25% to 10%, preferably 1.5% to 2%, by weight, based on the amount used per wash load of 20ml to 30 ml. For compact ("compacted") granular laundry detergents (densities above 650g/l), the bis-AQA surfactants are converted to concentrations in the product of 0.25% to 10%, preferably 0.5% to 1.0%, by weight calculated as 18g to 35g per wash load. For spray dried granules (i.e., "fluffy"; density less than 650g/l), the bis-AQA surfactant is converted to a concentration in the product of 0.25% to 10%, preferably 0.5% to 1%, by weight, calculated as 30g to 40g per wash load.

From the foregoing, it can be seen that the amount of bis-AQA surfactant used in machine washing can vary, depending on the habits and experience of the user, the type of washing machine, etc. In this context, however, one heretofore unrecognized advantage of bis-AQA surfactants is that they can provide at least a directional improvement in performance over a wide variety of soils and stains, even when used in relatively low amounts relative to other surfactants (typically anionic surfactants or anionic/nonionic surfactant mixtures) in the finished composition. This is different from other compositions of the prior art, where various cationic and anionic surfactants are used in stoichiometric or near stoichiometric amounts. In general, in the practice of the present invention, the bis-AQA: the weight ratio of anionic surfactant is in the range of 1: 70 to 1: 2, preferably 1: 40 to 1: 6, more preferably 1: 30 to 1: 6, most preferably 1: 15 to 1: 8. In a laundry composition comprising anionic and nonionic surfactants, the ratio of bis-AQA: the weight ratio of mixed anionic/nonionic surfactant is in the range of 1: 80 to 1: 2, preferably 1: 50 to 1: 8.

Various other cleaning compositions comprising anionic surfactants, optionally nonionic surfactants, and specialty surfactants such as betaines, sultaines, amine oxides may also be formulated in the manner of this invention using an effective amount of a bis-AQA surfactant. Such compositions include, but are not limited to, hand dishwashing products (especially liquids or gels), hard surface cleaners, shampoos, personal wash bars, laundry bars, and the like. With minimal variation in the habits and experiences of the users of such compositions, it is desirable to include from about 0.25% to about 5%, preferably from about 0.45% to about 2%, by weight of the bis-AQA surfactant in such compositions. In addition, in the case of granular and liquid laundry compositions, the weight ratio of bis-AQA surfactant to other surfactants present in such compositions is low, i.e., sub-stoichiometric in the case of anionic surfactants. Such cleaning compositions preferably contain the AQA/surfactant ratios just described above for the machine laundry compositions.

In contrast to other cationic surfactants known in the art, the di-alkoxylated cationic surfactants of the present invention have sufficient solubility that they can be used in combination with mixed surfactant systems which have very low levels of nonionic surfactant and which contain, for example, alkyl sulfate surfactants. This may be an important consideration for the formulator of detergent compositions of the following type: are conventionally designed for use in top-loading automatic washing machines, particularly for washing machine types used in north america and detergent compositions under japanese use conditions. Generally, such compositions comprise anionic surfactant to nonionic surfactant in a weight ratio ranging from about 25: 1 to about 1: 25, preferably from about 20: 1 to about 3: 1. This is in contrast to European formulations which generally contain anions in a ratio in the range of from about 10: 1 to about 1: 10, preferably from about 5: 1 to about 1: a nonionic surfactant.

Preferred ethoxylated cationic surfactants of the present invention are available under the trade name ETHOQUAD from Akzo Nobel Chemicals. In addition, such materials can be synthesized using a number of different reaction schemes (where "EO" represents-CH)₂CH₂O-unit): route 1

Route 2

Route 3

Route 4

The economic reaction route is as follows: route 5

The following parameters outline optional and preferred reaction conditions for scheme 5. Step 1 of the reaction is preferably carried out in an aqueous medium. The reaction temperature is generally in the range of 140 ℃ to 200 ℃. The reaction pressure is 50-1000 lb/in². A base catalyst, preferably sodium hydroxide, may be used. Molar ratio of reactants amine: the alkyl sulfate is 2: 1-1: 1. Preference is given to using C for the reaction₈-C₁₄Sodium alkyl sulfate. The ethoxylation and quaternization steps are carried out using conventional conditions and reactantsAnd (4) row by row.

In some cases, scheme 5 produces a gel-forming product that is sufficiently soluble in the aqueous reaction medium. Although the desired product can be recovered from the gel, an alternative, the following two-step synthetic scheme 6 may be more desirable in certain industrial situations. The first step in route 6 is according to route 5. The second step (ethoxylation) is preferably carried out using ethylene oxide and an acid such as HCl, which results in a quaternized surfactant. As shown below, chloroethanol, i.e., chloroethanol, may also be reacted to give the desired dihydroxyethyl derivative.

For scheme 6, the following parameters summarize optional and preferred reaction conditions for the first step. The first step is preferably carried out in an aqueous medium. The reaction temperature is generally 100 ℃ to 230 ℃. The reaction pressure is 50-1000 lb/in². Alkali, preferably sodium hydroxide, may be used with the HSO produced during the reaction₄The reaction or excess amine may be used to react with the acid as well. The molar ratio of amine to alkyl sulfate is generally from 10: 1 to 1: 1.5, preferably from 5: 1 to 1: 1.1, more preferably from 2: 1 to 1: 1. In the product recovery step, the desired substituted amine, which is insoluble in the aqueous reaction medium, is simply separated from the aqueous reaction medium as a distinct phase. The second step of the process is carried out under conventional reaction conditions. The ethoxylation and quaternization to obtain the bis-AQA surfactants was further carried out under standard reaction conditions.

Route 7 can optionally be carried out using ethylene oxide under standard ethoxylation conditions, but without a catalyst, to achieve mono-ethoxylation.

These additional reaction schemes are illustrated below, where "EO" represents-CH₂CH₂An O-unit. In this reaction, the HSO produced is neutralized with an inorganic base, an organic base or an excess of amine reactant₄. Route 6

Route 7

The following further illustrates several of the above reactions, merely for the convenience of the formulator, and is not intended to limit them. Preparation of synthetic AN, N-bis (2-hydroxyethyl) dodecylamine

Addition of 19 to the glass autoclave liner96g of sodium lauryl sulfate (0.06921 mol), 14.55g of diethanolamine (0.1384 mol), 7.6g of 50% by weight sodium hydroxide solution (0.095 mol) and 72g of distilled water. The glass liner was enclosed in a 500ml stainless steel rocking autoclave at 300-²Heated to 160 ℃ and 180 ℃ under nitrogen for 3-4 hours. The mixture was cooled to room temperature and the glass-lined liquid contents were poured into a 250ml separatory funnel along with 80ml chloroform. The funnel was shaken well for a few minutes and then the mixture was allowed to separate into layers. The lower layer of chloroform was drained off and the chloroform was evaporated to give the product. Preparation of synthesis of BN, N-bis (2-hydroxyethyl) dodecylamine

1 mol of sodium dodecyl sulfate was reacted with 1 mol of ethanolamine in the presence of a base according to the procedure described for Synthesis A. The resulting 2-hydroxyethyldodecylamine was recovered and reacted with 1-chloroethanol to prepare the title compound. Preparation of synthetic CN, N-bis (2-hydroxyethyl) dodecylamine

To the glass autoclave liner was added 19.96g of sodium lauryl sulfate (0.06921 moles), 21.37g of ethanolamine (0.3460 moles), 7.6g of 50 weight percent sodium hydroxide solution (0.095 moles), and 72g of distilled water. The glass liner was enclosed in a 500ml stainless steel rocking autoclave at 300-²Heated to 160 ℃ and 180 ℃ under nitrogen for 3-4 hours. The mixture was cooled to room temperature and the glass-lined liquid contents were poured into a 250ml separatory funnel along with 80ml chloroform. The funnel was shaken well for a few minutes and then the mixture was allowed to separate into layers. The lower layer of chloroform was drained off and the chloroform was evaporated to give the product. The product is then reacted with 1 molar equivalent of ethylene oxide in the presence of a base catalyst at 120-130 ℃ to produce the desired end product.

The disubstituted amines prepared in the above synthesis may be further ethoxylated in a standard manner. Quaternization with alkyl halides is conventionally used to form the bis-AQA surfactants of the present invention.

In view of the foregoing, the following non-limiting specific description of the bis-AQA surfactants useful herein is provided. It is to be understood that the degree of alkoxylation of the bis-AQA surfactants described herein is by averageReported below are common examples of conventional ethoxylated nonionic surfactants. This is because ethoxylation generally produces mixtures of materials having different degrees of ethoxylation. Thus, total EO values are typically reported rather than integer values, e.g., "EO 2.5", "EO 3.5". Symbol R¹R²ApR³A’qR⁴bis-AQA-1 (also called C)₁₂-C₁₄CH₃EO is coconut methyl EO2) bis-AQA-2C₁₂-C₁₆CH₃(EO)₂EO bis-AQA-3 (coconut C)₁₂-C₁₄CH₃(EO)₂(EO)₂Methyl EO4) bis-AQA-4C₁₂CH₃EO bis-AQA-5C₁₂-C₁₄CH₃(EO)₂(EO)₃bis-AQA-6C₁₂-C₁₄CH₃(EO)₂(EO)₃bis-AQA-7C₈-C₁₈CH₃(EO)₃(EO)₂bis-AQA-8C₁₂-C₁₄CH₃(EO)₄(EO)₄bis-AQA-9C₁₂-C₁₄C₂H₅(EO)₃(EO)₃bis-AQA-10C₁₂-C₁₈C₃H₇(EO)₃(EO)₄bis-AQA-11C₁₂-C₁₈CH₃(propoxy) (EO)₃bis-AQA-12C₁₀-C₁₈C₂H₅(Isopropoxy)₂(EO)₃bis-AQA-13C₁₀-C₁₈CH₃(EO/PO)₂(EO)₃bis-AQA-14C₈-C₁₈CH₃(EO)₁₅ ^*(EO)₁₅ ^*bis-AQA-15C₁₀CH₃EO bis-AQA-16C₈-C₁₂CH₃EO bis-AQA-17C₉-C₁₁CH₃Average EO 3.5-bis-AQA-18C₁₂CH₃Average EO 3.5-bis-AQA-19C₈-C₁₄CH₃(EO)₁₀(EO)₁₀bis-AQA-2O C₁₀C₂H₅(EO)₂(EO)₃bis-AQA-21C₁₂-C₁₄C₂H₅(EO)₅(EO)₃bis-AQA-22C₁₂-C₁₈C₃H₇Bu (EO)₂ ^*Ethoxy, optionally capped with methyl or ethyl.

Highly preferred bis-AQA compounds for use herein have the formula:wherein R is¹Is C₈-C₁₈Hydrocarbyl and mixtures thereof, preferably C₈、C₁₀、C₁₂、C₁₄Alkyl groups and mixtures thereof, X is any convenient anion that provides charge balance, preferably chlorine. With respect to the general structure of bis-AQA described above, since in preferred compounds R¹Is prepared from coconut (C)₁₂-C₁₄Alkyl) partial fatty acid, R²Is methyl, ApR³And A' pR⁴Each is a monoethoxy group, and thus this preferred type of compound is referred to herein as "coconut methyl EO 2" or "bis-AQA-1" in the above list.

Other bis-AQA surfactants useful herein includeA compound of formula (la):wherein R is¹Is C₈-C₁₈Hydrocarbyl, preferably C₈-C₁₄Alkyl, p is independently 1-3, q is 1-3, R²Is C₁-C₃Alkyl, preferably methyl, and X is an anion, especially chlorine or bromine.

Other compounds of the above type include those in which the ethoxy group (CH)₂CH₂O) units (EO) substituted by butoxy (Bu), isopropoxy [ CH (CH)₃)CH₂O]And [ CH₂CH(CH₃O]Units (i-Pr) or n-propoxy units (Pr), or mixtures of EO and/or Pr and/or i-Pr units.

Highly preferred bis-AQA compounds for use in under-formulated formulations are those in which p and/or q are integers of from 10 to 15. The compounds are particularly useful in hand laundry detergent compositions. non-AQA detersive surfactants

In addition to the bis-AQA surfactant, the compositions of the present invention preferably also comprise a non-AQA surfactant. The non-AQA surfactants can include essentially any anionic, nonionic or otherwise cationic surfactant. Anionic surfactants

Non-limiting examples of anionic surfactants suitable for use in the present invention, typically in amounts of 1% to 55% by weight, include: conventional C₁₁-C₁₈Alkyl benzene sulfonates ("LAS") and primary ("AS"), branched and random C₁₀-C₂₀Alkyl sulfates of the formula CH₃(CH₂)_x(CHOSO₃ ^-M⁺)CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺)CH₂CH₃C of (A)₁₀-C₁₈Secondary (2,3) alkyl sulfates wherein x and (y +1) are integers of at least 7, preferably at least 9, M is a water-solubilizing cation, especially sodium, unsaturated sulfates such as oleyl sulfate, C₁₂-C₁₈α -sulfonated fatty acid ester, C₁₀-C₁₈Sulfated alkylpolyglycoside, C₁₀-C₁₈Alkyl alkoxy sulfates ('AExS'; in particularEO 1-7 ethoxy sulfate), C₁₀-C₁₈Alkyl alkoxy carboxylates (especially EO1-5 ethoxy carboxylate). C₁₂-C₁₈Betaines and sulfobetaines ("sultaines"), C₁₀-C₁₈Amine oxides may also be included in the overall composition. Also usable are C₁₀-C₂₀Conventional soaps. If high foaming is desired, a branched chain C may be used₁₀-C₁₆Soap. Other conventional suitable surfactants are listed in standard textbooks. Nonionic surfactant

Non-limiting examples of nonionic surfactants useful in the present invention, typically at levels of from 1% to 55% by weight, include alkoxylated alcohols (AE's) and alkyl phenols, polyhydroxy fatty acid amides (PFAA's), alkyl polyglycosides (APG's), C₁₀-C₁₈A glycerol ether.

More specifically, condensation products of primary and secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide (AE) are suitable for use as the nonionic surfactant of the present invention. The alkyl chain of the aliphatic alcohol can be of the linear or branched, primary or secondary type and generally contains from 8 to 22 carbon atoms. Preferred are the condensation products of alcohols having an alkyl group containing from 8 to 20 carbon atoms, more preferably from 10 to 18 carbon atoms, with from 1 to 10 moles, preferably from 2 to 7 moles, most preferably from 2 to 5 moles, of ethylene oxide per mole of the alcohol. Commercially available nonionic surfactants of this type include Tergitol^TM15-S-9(C₁₁-C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide), Tergitol^TM24-L-6 NMW(C₁₂-C₁₄Condensation products of primary alcohols with 6 moles of ethylene oxide and having a narrow molecular weight distribution), both sold by the Union Carbide Corporation; neodol sold by Shell Chemical Company^TM45-9(C₁₄-C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide), Neodol^TM23-3(C₁₂-C₁₃Condensation products of linear alcohols with 3 moles of ethylene oxide), Neodol^TM45-7(C₁₄-C₁₅Condensation products of linear alcohols with 7 moles of ethylene oxide), Neodol^TM45-5(C₁₄-C₁₅Condensation products of linear alcohols with 5 moles of ethylene oxide); kyro^TMEOB(C₁₂-C₁₅Of alcohols with 9 mol of ethylene oxideCondensation products) from The Procter&Sold by Gamble Company; and Genapol LA 030 or 050 (C) sold by Hoechst₁₂-C₁₄Condensation products of alcohols with 3 or 5 moles of ethylene oxide). The preferred HLB range for these AE nonionic surfactants is from 8 to 11, most preferably from 8 to 10. Condensates with propylene oxide and butylene oxide may also be used.

Another preferred class of nonionic surfactants suitable for use in the present invention are polyhydroxy fatty acid amide surfactants of the formula:

wherein R is¹Is H, or C_1-4Hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof, R²Is C_5-31Hydrocarbyl, Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain directly linked to at least 3 hydroxyl groups, or an alkoxylated derivative thereof. Preferably R¹Is methyl, R²Is straight chain C_11-15Alkyl or C_15-17Alkyl or alkenyl groups such as coconut alkyl or mixtures thereof, Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose in a reductive amination reaction. Typical examples include C₁₂-C₁₈And C₁₂-C₁₄N-methylglucamide. See US5,194,639 and US 5298636. N-alkoxy polyhydroxy fatty acid amides may also be used; see US 5489393.

Also suitable for use as nonionic surfactants in the present invention are alkyl polysaccharides, such as those disclosed in U.S. Pat. No. 4,565,647 issued to Llenado on 21.1.1986, having a hydrophobic group containing 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, and a polysaccharide, such as a polyglycoside, hydrophilic group containing 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms may be used, for example glucose, galactose, the glucosyl moiety may be substituted with a galactosyl moiety (the hydrophobic group is optionally attached at the 2-,3-, 4-, etc. position, thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide linkage may be, for example, between the 2-,3-, 4-and/or 6-position of the preceding saccharide unit and a position of another saccharide unit.

Preferred alkylpolyglycosides have the formula:

R²O(C_nH_2nO)_t(sugar base)_xWherein R is²Selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group contains from 10 to 18 carbon atoms, preferably from 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is 0 to 10, preferably 0; x is 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first prepared and then reacted with glucose or a source of glucose to form glucoseGlycoside (attached at position 1). The additional glycosyl units can then be linked between their 1-position and the 2-,3-, 4-and/or 6-position of the preceding glycosyl unit, preferably predominantly between the 2-positions.

The condensation products of polyethylene oxide, polypropylene oxide and polybutylene oxide of alkyl phenols are also suitable for use as the nonionic surfactant in the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols having an alkyl group containing from 6 to 14 carbon atoms, preferably from 8 to 14 carbon atoms, in a straight or branched chain configuration with alkylene oxides. In a preferred embodiment, the amount of ethylene oxide present per mole of alkylphenol is equal to 2 to 25 moles, more preferably 3 to 15 moles. Commercially available nonionic surfactants of this type include Igepal^TMCO-630, sold by GAF Corporation; and Triton^TMX-45, X-114, X-100 and X-102, all by Rohm&Sold by the Haas company. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkylphenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant of the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of 1500 to 1800 and exhibits water insolubility. Addition of polyethylene oxide moieties to the hydrophobic moiety tends to increase the water solubility of the overall molecule, and the liquid of the productThe bulk characteristics are maintained to the point that the polyoxyethylene content is 50% of the total weight of the condensation product, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of this type of compound include some of the commercially available Pluronic sold by BASF^TMA surfactant.

Also suitable for use as the nonionic surfactant in the nonionic surfactant systems of the present invention are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine with excess propylene oxide and generally has a molecular weight of 2500 to 3000. The hydrophobic part is condensed with ethylene oxide to such an extent thatthe condensation product contains from 40 to 80% by weight of polyoxyethylene and has a molecular weight of from 5000 to 11000. Examples of this type of nonionic surfactant include some of the commercially available Tetronic surfactants sold by BASF^TMA compound is provided. Additional cationic surfactants

Suitable cationic surfactants are preferably water-dispersible compounds of surfactant nature comprising at least one ester bond (i.e., -COO-) and at least one charged cationic group.

Other suitable cationic surfactants include quaternary ammonium surfactants selected from mono-C₆-C₁₆Preferably C₆-C₁₀N-alkyl or alkenyl ammonium surfactants, wherein the remainder of NThe position is substituted by methyl, hydroxyethyl or hydroxypropyl. Other suitable cationic ester surfactants, including choline ester surfactants, are disclosed, for example, in US4228042, 4239660 and 4260529. Optional detergent ingredients

The following illustrates various other optional components that may be used in the compositions of the present invention, but are not meant to be limiting thereof. Builder

Detergent builders may optionally, but preferably, be included in the compositions of the present invention, for example to assist in controlling mineral, especially Ca and/or Mg, hardness in the wash water, or to assist in the removal of particulate soils from surfaces. Builders can operate by a variety of mechanisms, including forming soluble or insoluble chelates with hardness ions, by ion exchange, and by providing a surface more suitable for hardness ion deposition than the surface of the article being laundered. Builder levels can vary widely, depending on the end use and physical form of the composition. The builder detergent will generally comprise at least 1% builder. Liquid formulations typically contain from 5% to 50%, more typically from 5% to 35% builder. The granular formulations typically comprise from 10% to 80%, more typically from 15% to 50% builder by weight of the detergent composition. Lower or higher levels of builder are not excluded. For example, certain detergent additives or high surfactant formulations may be free of builders.

Suitable builders of the present invention may be selected from phosphates and polyphosphates, especially sodium salts; silicates, including water-soluble and hydrated solid types, and including those having chain-, layer-, or three-dimensional structures, as well as amorphous-solid or unstructured liquid types; carbonate, bicarbonate, sesquicarbonate, and carbonate minerals other than sodium carbonate or sesquicarbonate; an aluminosilicate; organic mono-, di-, tri-, and tetracarboxylates in the form of acid, sodium, potassium or alkanolammonium salts, especially water-soluble, non-surfactant carboxylates, and also low-polymeric or water-soluble, low-molecular-weight polymeric carboxylates, including aliphatic and aromatic types; and phytic acid. Also to be supplemented are borate salts, e.g. for pH-buffering purposes, or sulfate salts, especially sodium sulfate, and any other fillers or carriers important for the production of stable surfactants and/or builder-containing detergent compositions.

Builder mixtures, sometimes referred to as "builder systems", may be used, typically comprising two or more conventional builders, optionally supplemented with chelating agents, pH buffers or fillers, although the latter are usually calculated separately when describing levels of materials herein. With respect to the relative amounts of surfactant and builder used in the detergents of the invention, it is preferred that the builder system is generally formulated in a weight ratio of surfactant to builder of from 60: 1 to 1: 80. Certain preferred laundry detergents have a ratio of said surfactant to builder inthe range of from 0.90: 1 to 4.0: 1.0, more preferably in the range of from 0.95: 1.0 to 3.0: 1.0.

P-containing detergent builders are often preferred when permitted by regulations, including, but not limited to, alkali metal, ammonium and alkanolammonium salts of polyphosphoric acid, exemplified by: tripolyphosphates, pyrophosphates, glassy polymeric metaphosphates and phosphonates.

Suitable silicate builders include alkali metal silicates, especially SiO₂∶Na₂Those liquid and solid silicates having an O ratio of 1.6: 1 to 3.2: 1, including, in particular, solid hydrated silicates having a ratio of 2 for automatic dishwashing purposes sold by PQ company under the trade name BRITESSIL^RFor example BRITESSIL H₂O; and layered silicates such as those described in US4664839, h.p. rieck, 5/12 1987. NaSKS-6, sometimes abbreviated as "SKS-6", is a crystalline, layered, aluminum-free, delta-Na sold by Hoechst₂SiO₅Silicates in their form, which are particularly preferred in granular laundry compositions. See DE-A-3417649 and DE-A-3742043 for a process for the preparation thereof. Other phyllosilicates, e.g. those of the general formula NaMSi_xO_2x+1·yH₂Layered silicates available from Hoechst also include NaSKS-5, NaSKS-7, and NaSKS-11, which are layered silicates in the α, β, and γ forms.

Also suitable for use in the present invention are synthetic crystalline ion exchange materials, or hydrates thereof, having a chain structure and a composition represented by the general formula: xM₂O·ySiO₂zM 'O, wherein M is Na and/or K and M' is Ca and/or Mg; y/x is 0.5-2.0 and z/x is 0.005-1.0 as taught in Sakaguchi et al US5427711, 6.1995, 27.l.

Suitable carbonate builders include the alkali and alkaline earth metal carbons disclosed in German patent application 2321001 published on 11/15/1973Acid salts, but sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonate minerals such as trona, or any suitable complex salt of sodium carbonate and calcium carbonate, for example of composition 2Na when anhydrous₂CO₃·CaCO₃And even calcium carbonates including calcite, aragonite and especially vaterite in which the relatively dense calcite has a high surface area form, are suitable, for example as seed crystals or for use in synthetic detergent bars.

Aluminosilicate builders are particularly suitable for use in granular detergents, but may also be incorporated into liquid, paste or gel preparations. Suitable for the purposes of the present invention are those having the following empirical formula: [ M]A_z(AlO₂)_z(SiO₂)_v]·xH₂O, wherein z and v are integers of at least 6, the molar ratio of z to v is in the range of 1.0 to 0.5, and x is an integer of 15 to 264. The aluminosilicates may be crystalline or amorphous, naturally occurring or synthetically derived. A process for the preparation of aluminosilicates is disclosed in U.S. Pat. No.3,3985669 to Krummel et al, 10/12/1976. Preferred synthetic crystalline aluminosilicate ion exchange materials are commercially available as zeolite a, zeolite P (b), zeolite X and so-called zeolite MAP (which differs to some extent from zeolite P). Natural types, including clinoptilolite, may also be used. Zeolite a has the formula: na (Na)₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂O, wherein x is 20 to 30, especially 27. Dehydrated zeolites (x =0-10) may also be used. Preferably, the aluminosilicate has a particle size of 0.1 to 10 microns in diameter.

Suitable organic detergent builders include polycarboxylate compounds, including water-soluble, non-surfactant di-and tri-carboxylates. More generally, the builder polycarboxylate has a plurality of carboxylate groups, preferably at least 3 carboxylate groups. Carboxylate builders can be formulated in acidic, partially neutralized, neutralized or overbased forms. When in salt form, alkali metals such as sodium, potassium and lithium or alkanolammonium salts are preferred. Polycarboxylate builders include ether polycarboxylates such as oxydisuccinate, as described in Berg, U.S. Pat. No. 4,7,1964, and U.S. Pat. No.3,3128287 to Lamberti et al, U.S. Pat. No. 1,18,1972; "TMS/TDS" builders and other ether polycarboxylates, including cyclic and alicyclic compounds, as disclosed in U.S. Pat. No. 4,510,071 to Bush et al, 5.5.1987, including cyclic and alicyclic compounds, as disclosed in U.S. Pat. Nos. 3923679; US 3835163; US 4158635; those described in US4120874 and US 4102903.

Other suitable builders are ether hydroxypolycarboxylates, copolymers of maleic anhydride with ethylene or vinyl methyl ether; 1,3, 5-trihydroxybenzene-2, 4, 6-trisulfonic acid; carboxymethoxysuccinic acid; various alkali metal, ammonium and substituted ammonium salts of polyacetic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, as well as mellitic acid, succinic acid, polymaleic acid, benzene-1, 3, 5-tricarboxylic acid, carboxymethoxysuccinic acid and soluble salts thereof.

Citrates, such as citric acid and soluble salts thereof, are important carboxylate builders, for example, for use in heavy duty liquid detergents, due to their availability from renewable resources and their biodegradability. Citrates may also be used in particulate compositions, especially in combination with zeolites and/or layered silicates. Oxydisuccinates are also particularly useful in these compositions and combinations.

Where permitted, alkali metal phosphates such as sodium tripolyphosphate, pyrophosphate and orthophosphate may be used, particularly in bar formulations for hand washing operations. Phosphonate builders, such as ethane-1-hydroxy-1, 1-diphosphonate and other well known phosphonates, such as those disclosed in US 3159581; 3213030, respectively; 3422021, respectively; 3400148 and 3422137, which have desirable anti-fouling properties.

Certain detersive surfactants or their short-chain analogs also have a builder effect. For formulations of a well-defined purpose, these materials are classified as detersive surfactants when they have surfactant power. Illustrative of preferred types having builder functionality are: 3, 3-dicarboxy-4-oxa-1, 6-hexanedioic acid salt and the corresponding compounds are disclosed in Bush, US4566984 on 28.1.1986. The succinic acid builder comprises C₅-C₂₀Alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include lauryl succinate, myristyl succinate, palmityl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate. Lauryl succinate is described in European patent application 86200690.5/0,200,263 published on 5.11.1986. Fatty acids, e.g. C₁₂-C₁₈Monocarboxylic acids may also be incorporated into the compositions of the present invention as surfactant/builder materials alone or in combination with the above-mentioned builders, especially citrate and/or succinate builders, to provide additional builder activity. Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,44226 to Crutchfield et al, 3/13 of 1979 and U.S. Pat. No. 3308067 to Diehl, 3/7 of 1967. See also U.S. Pat. No.3,3723322 to Diehl.

Other types of inorganic builder materials that can be used have the formula: (M)_x)_iCa_y(CO₃)_zWherein x and i are integers from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, M_iAre cationic, at least one of which is water soluble and satisfies the equation ∑_i-1-15(x_iMultiplying by M_iIs) +2y =2z, such that the formula has a neutral or "balanced" charge. These builders are referred to herein as "mineral builders". Hydrated water or non-carbonate anions can be added provided that the overall charge is balanced or neutral. This effect of the anionic charge or valence state should be added to the right of the above equation. Preferably, there is present a water-soluble cation selected from the group consisting of hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon and mixtures thereof, more preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, sodium and potassium being highly preferred. Non-limiting examples of non-carbonate anions include those selected from the group consisting of: chlorine, sulfate, fluorine, oxygen, hydroxide, silica, chromate, nitrate, borate and mixtures thereof. Preferred builders of this type in their simplest form are selected fromNa₂Ca(CO₃)₂、K₂Ca(CO₃)₂、Na₂Ca₂(CO₃)₃、NaKCa(CO₃)₂、NaKCa₂(CO₃)₃、K₂Ca₂(CO₃)₃And combinations thereof. Particularly preferred materials for use as builders herein are any crystal-modified Na₂Ca(CO₃)₂. Suitable builders of the above-defined type are further illustrated below, including natural or synthetic forms of any one or combination of the following minerals: acalcite, uraninite, kainite Y, cannibalite, colemanite, wainesite, strontianite, cancrinite, eucheumasite, cancrinite, strontianite Y, kalsilite, sendust (Ferrisurite), perkalite, canganite, monocalcite, girvastasite, ilmenite, manganosite, Kamphaugite Y, brushite, Khanneshite, leprosonite Gd, eucryptite, bariumenite Y, eucryptite, tellurite, nacalcite, nycamonite Ce, Remondite, savatite, uraninite, natronite, natrolite, zernite, and calcium sulfate. Preferredmineral forms include nesquehonite, kallmatite and canasite. Bleaching agent

The compositions described herein may contain a bleaching agent. When present, such bleaching agents are generally present at levels of from 1% to 30%, more usually from 5% to 20% of the detergent composition, especially for laundering fabrics.

In a preferred aspect, the bleaching system comprises a source of hydrogen peroxide and a bleach catalyst. The bleach activator reacts in situ with the source of hydrogen peroxide to produce an organic peroxyacid. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In another preferred case, the preformed peracid is incorporated directly into the composition. Compositions comprising a mixture of a hydrogen peroxide source and a bleach activator in combination with a preformed peracid are also contemplated.

Preferred peroxygen bleaching agents are perhydrate bleaches. Although the perhydrate bleach itself has some bleaching power, an excellent bleach lies in the peracid formed from the reaction between the hydrogen peroxide released by the perhydrate and the bleach activator. Preformed peracids are also contemplated as a preferred bleaching species.

Examples of suitable perhydrate salts include perborate, percarbonate, perphosphate, persulfate and persilicate salts. Preferred perhydrate salts are typically alkali metal salts. The perhydrate salts may be included in the present invention as a crystalline solid without additional protection. However, for certain perhydrate salts, a preferred example of such a particulate composition is the use of the material in a coated form which provides the perhydrate salt with better storage stability in the particulate product.

Sodium perborate may be in the form of the monohydrate, nominally NaBO₂H₂O₂Or tetrahydrateCompound NaBO₂H₂O₂.3H₂O。

Alkali metal percarbonates, particularly sodium percarbonate, are preferred perhydrates for inclusion in the compositions of the invention. The sodium percarbonate having a structure corresponding to 2Na₂CO₃.3H₂O₂The addition compound of formula (la) is obtained commercially as a crystalline solid. Sodium percarbonate is a hydrogen peroxide addition compound that tends to release hydrogen peroxide quite rapidly on dissolution, which increases the tendency to produce local high bleach concentrations. Preferred percarbonate bleach compositions comprise dry particles having an average particle size in the range of from 500 microns to 1000 microns, no more than 10% by weight of said particles being less than 200 microns and no more than 10% by weight of said particles being greater than 1,250 microns.

The percarbonate is most preferably incorporated into such compositions in a coated form which provides stability in the product. Suitable coating materials that provide stability in the product include mixed salts of water soluble alkali metal sulfates and carbonates. Such coating agents and methods have been described in GB-1466799 to Interox on 9/3/1977. The weight ratio of mixed salt coating material to percarbonate is in the range 1: 200 to 1: 4, more preferably 1: 99 to 1: 9, most preferably 1: 49 to 1: 19. Preferably the mixed salt is of the formula Na₂SO₄.n.Na₂CO₃Sulfur (2) ofSodium and sodium carbonate, where n is 0.1 to 3, preferably n is 0.3 to 1.0, most preferably n is 0.2 to 0.5.

Other coating materials containing silicates (alone or in combination with borates or boric acid or other minerals), paraffins, oils, fatty soaps are also advantageous for use in the present invention.

Bleaching agents which may be used without limitation include percarboxylic acid bleaching agents and salts thereof. Suitable examples of such bleaches include magnesium monoperoxyphthalate hexahydrate, magnesium m-chloroperbenzoate, magnesium 4-nonylamino-4-oxoperoxybutyrate and magnesium diperoxydodecanedioate. These bleaches are disclosed in Hartman, U.S. patent No. US4483781,1985, issued 11/20 1984, Burns et al, U.S. patent application No. 3/6, 740446,1985, European patent application No. 0133354, issued on 20/2, Bank et al, and in Chung et al, U.S. patent No. US4412934, issued 11/1 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxo-peroxyhexanoic acid as described in U.S. patent No. US463455l issued to Burns et al on 6.1.1987.

Other suitable additional bleaching agents include photoactivated bleaching agents such as sulfonated zinc and/or aluminum phthalocyanines. See US4033718 to holcomb et al, granted on 7/5/1977. If used, detergent compositions typically contain from 0.025% to 1.25% by weight of such bleaching agents, especially zinc phthalocyanine sulphonates.

Potassium peroxymonopersulfate is another inorganic perhydrate salt suitable for use in the compositions of the invention.

Mixtures of bleaching agents may also be used. Bleach activators

In case the composition of the present invention further comprises a peroxygen bleach, a bleach activator is a preferred component. Bleach activators, when present, are typically present at levels of from 0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition comprising the bleach plus bleach activator.

Peroxygen bleaches, perborates, etc., are preferably combined with bleach activators, which result in the in situ generation of the peroxyacid or peracid corresponding to the bleach activator in aqueous solution (i.e., during the wash). Various non-limiting examples of activators are disclosed in U.S. patent No. 4915854, and U.S. patent No. 4412934, issued to Mao et al at 4/10 1990. Nonoyloxybenzene sulfonate (NOBS) and Tetraacetylethylenediamine (TAED) activators are typical activators, and mixtures thereof may also be used. Other typical bleaching agents and activators suitable herein are further described in US 4634551.

Highly preferred amido-derived bleach activators are those of the formula:

R¹N(R⁵)C(O)R²c (O) L or R¹C(O)N(R⁵)R²C (O) L wherein R¹Is an alkyl radical having from 6 to 12 carbon atoms, R²Is alkylene having 1 to 6 carbon atoms, R⁵Is H or an alkyl, aryl, or alkylaryl group containing from 1 to 10 carbon atoms, and L is any suitable leaving group. A leaving group is any group that is displaced from the bleach activator as a result of nucleophilic attack of the perhydrolytic anion on the bleach activator. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators of the above formula include (6-octanoylaminohexanoyl) oxybenzenesulfonate, (6-nonanoylaminocaproyl) oxybenzenesulfonate, (6-decanoylaminohexanoyl) oxybenzenesulfonate, and mixtures thereof, as described in U.S. Pat. No. 4,4634551, which is incorporated herein by reference.

Another class of bleach activators includes the benzoxazines disclosed in U.S. Pat. No. 4,4966723 to Hodge et al, granted on 30.10.1990 (which is incorporated herein by reference). Highly preferred activators of the benzoxazine class are:

another class of preferred bleach activators include acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formula:

wherein R is⁶Is H or an alkyl, aryl, alkoxyaryl, or alkylaryl group containing from 1 to 12 carbon atoms. Highly preferred lactamsActivators include benzoyl caprolactam, octanoyl caprolactam, 3,5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5, 5-trimethylhexanoyl valerolactam and mixtures thereof. See also U.S. Pat. No. 4,45784 to Sanderson, issued on 8/10/1985, incorporated herein by reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed into sodium perborate. Bleaching catalyst

Bleach catalysts are optional components of the compositions of the present invention. If desired, the bleaching compound may be catalysed by a manganese compound. Such compounds are well known in the art and include, for example, manganese-based catalysts as disclosed in US patent nos. 5246621, US5244594, US5194416, US5114606 and european patent application publications EP549271a1, EP549272a1, EP544440a2 and EP544490a 1; preferred examples of such catalysts include Mn^Ⅳ ₂(u-O)₃(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(PF₆)₂,Mn^Ⅲ ₂(u-O)₁(u-OAc)₂(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(ClO₄)₂,Mn^Ⅳ ₄(u-O)₆(1,4, 7-triazacyclononane)₄(ClO₄)₄,Mn^ⅢMn^Ⅳ ₄(u-O)₁(u-OAc)₂(1,4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(ClO₄)₃,Mn^Ⅳ(1,4, 7-trimethyl-1, 4, 7-triazacyclononane) - (OCH₃)₃(PF₆) And mixtures thereof. Other metal-based bleach catalysts include those disclosed in US4430243 and US 5114611. Use the beltManganese, with various complex ligands, has also been reported for use in improving bleaching power in the following U.S. patents: US4728455, US5284944, US5246612, US5256779, US5280117, US5274147, US5153161, US 5227084.

In practice, without limitation, the compositions and methods of the present invention may be adjusted to provide at least about one per million of active bleach catalyst in an aqueous wash solution, preferably from 0.1ppm to 700ppm, more preferably from 1ppm to 500ppm, of such catalyst in an aqueous laundry solution.

Cobalt bleach catalysts for use in the present invention are known and are described, for example, in m.l. tobe, "alkaline hydrolysis of transition metal complexes", adv.inorg.bioirig.mech. (1983),2, pages 1-94. The most preferred cobalt catalyst suitable for the present invention is of the formula [ Co (NH)₃)₅OAc]T_YWherein "OAc" represents an acetate moiety and "T" represents a salt of cobalt pentamine acetate_y"is an anion, in particular cobaltpentaamineacetic acid [ Co (NH)₃)₅OAc]Cl₂(ii) a And [ Co (NH)₃)₅OAc](OAc)₂；[Co(NH₃)₅OAc](PF₆)₂；[Co(NH₃)₅OAc](SO₄)；[Co(NH₃)₅OAc](BF₄)₂(ii) a And [ Co (NH)₃)₅OAc](NO₃)₂(herein "PAC").

These cobalt catalysts are readily prepared by known methods, such as those taught in the Tobe article and references cited therein, U.S. Pat. No. 4,810,410 to Diakun et al, 3/7 in 1989; chem.ed. (1989),66(12), 1043-; synthesis and characterization of inorganic compounds, W.L. Jolly (Prentice-Hall; 1970), pp.461-463; inorganic chemistry, 18, 1497-; inorganic chemistry, 21,2881-2885 (1982); inorganic chemistry, 18,2023-2025 (1979); inorganic synthesis,173-176 (1960); and journal of physico-chemical, 56, 2225 (1952).

In practice, without limitation, the automatic dishwashing compositions and cleaning methods of the present invention can be adjusted to provide at least about one per ten million parts of active bleach catalyst in the aqueous wash medium, preferably from 0.01ppm to 25ppm, more preferably from 0.05ppm to 10ppm, and most preferably from 0.1ppm to 5ppm, of bleach catalyst in the wash solution. To achieve such amounts in the wash solution of an automatic dishwashing process, typical automatic dishwashing compositions of the present invention will contain from 0.0005% to 0.2%, more preferably from 0.004% to 0.08%, by weight of the cleaning composition, of a bleach catalyst, particularly a manganese or cobalt catalyst. Enzyme

The detergent compositions of the present invention may comprise enzymes for various purposes including removal of protein, carbohydrate or triglyceride based stains from substrates, and for avoiding dye transfer during fabric washing, and for fabric rejuvenation. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof, of any suitable origin, e.g., vegetable, animal, bacterial, fungal, and yeast origin. The preferred choice is influenced by factors such as pH-activity and/or stability optima, thermostability, and stability towards active detergents and builders, etc. In this respect, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

As used herein, "detersive enzyme" refers to any enzyme that has a washing, stain removal or other benefit in a laundry, hard surface cleaning or personal care detergent composition. Preferred detersive enzymes are hydrolases such as proteases, amylases, and lipases. Preferred enzymes for laundry use include, but are not limited to, proteases, cellulases, lipases and peroxidases. Highly preferred for automatic dishwashing are amylases and/or proteases.

Enzymes are typically incorporated in detergent or detergent additive compositions in sufficient amounts to provide an "effective cleaning amount". The term "effective cleaning amount" refers to any amount that is capable of producing a cleaning, stain removal, soil removal, whitening, deodorizing, or rejuvenating improvement effect on a substrate such as fabric, dishware. In the practice of current commercial formulations, the amount of active enzyme per gram of detergent composition is generally up to about 5mg by weight, more typically 0.01 mg to 3 mg. Unless otherwise indicated, the compositions herein generally comprise from 0.001% to 5%, preferably from 0.01% to 1%, by weight of the commercial enzyme preparation. Proteases are typically present in commercial preparations at levels sufficient to provide 0.005 to 0.1Anson Units (AU) of activity per gram of composition. For certain detergents, such as those used in automatic dishwashing, it may be desirable to increase the active enzyme content of such commercial formulations in order to minimize the total amount of catalytically-free active material, thereby improving spotting/filming or other end effects. Higher active levels are also desirable in highly concentrated detergent formulations.

Examples of suitable proteases are subtilisins, which are obtained from particular strains of Bacillus subtilis and Bacillus licheniformis. Another suitable protease is obtained from a strain of Bacillus having maximum activity in the pH range 8-12, developed by Novo industries A/S of Denmark and identified as ESPERASE^_Sold, hereinafter referred to as "Novo". The preparation of this and similar enzymes is described in British patent Specification GB1243784 to Novo. Other suitable proteases include ALCALASE from Novo^_And SAVINASE^_And MAXATASE from International Bio-Synthesis, Inc. of the Netherlands^_(ii) a And protease A as described in European patent application 130756A on 9/1/1985, and protease B as described in European patent application 303761A on 28/4/1987 and European patent application 130756 on 9/1/1985. See also WO 9318140A to NovoFrom the genus Bacillus NCIMG 40338. Enzyme-added detergents containing a protease, one or more other enzymes, and a reversible protease inhibitor are described in WO9203529A to Novo. Other preferred proteases include those described in P&Those of WO9510591A from company G. When required, e.g. at P&The proteases with reduced absorption and increased hydrolysis can be obtained as described in WO 9507791 of company G. Trypsin-like recombinant proteases suitable for detergents according to the invention are described in WO 9425583 to Novo.

In particular, particularly preferred proteases referred to as "protease D" are carbonyl hydrolase variants having an amino acid sequence not found in nature, which are obtained from a carbonyl hydrolase precursor by the following substitutions: in accordance with the numbering of Bacillus amyloliquefaciens subtilisin, at a position in the carbonyl hydrolase corresponding to +76, also preferably in combination with one or more amino acid residue positions corresponding to a position selected from the group consisting of +99, +10l, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265, and/or +274, various amino acid substitutions of various amino acid residues at those positions are described in U.S. patent application Ser. No. 08/322676, A.Baeck et al, entitled "protease-containing Wash compositions", and U.S. patent application Ser. No. 08/322677, entitled "protease-containing bleaching compositions",C.Ghosh et al, both of these patent applications were filed 10/13 of 1994.

Amylases suitable for the present invention, particularly for, but not limited to, automatic dishwashing purposes, include, for example, the α -amylase described in British patent Specification GB-1296839 to Novo, RAPIDASE, International Bio-Synthesis, Inc^_TERMAMYL OF NOVO^_. FUNGAMYL from Novo^_Is particularly useful. Enzyme engineering to improve stability, e.g. oxidative stability, is known. See, e.g., journal of biochemistry, 260, 11 th, 6 th 1985, 6518-6521. Certain preferred embodiments of the compositions of the present invention may utilize amylases of improved stability in detergents, such as automatic dishwashing type detergents, especially against TERMAMYL, used commercially in 1993^_An amylase having improved oxidative stability as measured by the reference point of (a). These preferred amylases of the invention have the characteristics of an "enhanced stability" amylase, at least characterized by one or more measurable improvements, as measured in comparison to the reference point amylase identified above: oxidative stability, e.g., stability to hydrogen peroxide/tetraacetylethylenediamine in a buffer solution at pH 9-10; thermal stability, e.g. at usual washing temperatures such as 60At a temperature of DEG C; or alkaline stability, e.g. at pH from 8 to 11. Stability can be determined using any of the experimental techniques disclosed in the prior art. See, for example, the references disclosed in WO 9402597. Stability-enhanced amylases may be obtained from Novo or from genencor international. A very preferred class of amylase enzymes of the inventionHaving in common that they are derived by site-directed mutagenesis from one or more Bacillus amylases, especially Bacillus α -amylases, whether one or not, the two or more amylase strains being direct precursors, amylases with enhanced oxidative stability compared to the reference amylase identified above are preferably used, especially in bleach detergent compositions of the invention, more preferably in oxygen bleach detergent compositions other than chlorine-based bleaching^_Or a homologous positional variant of a similar parent amylase, such as Bacillus amyloliquefaciens, Bacillus subtilis, or thermophilic bacillus stearothermophilus, (b) an enhanced stability amylase described by Genencor International, published by C.Mitchinson at the national meeting of the U.S. chemical society of U.S. No. 207, 13-17, 1994, under the title "antioxidant α -amylase", wherein it is noteworthy that bleaches in automatic dishwashing detergents inactivate α -amylase, but amylases improving oxidative stability have been obtained by Genencor from Bacillus licheniformis NC8061 methionine (Met) was identified as the most likely residue to be modified, Met was substituted one at a time at positions 8,15,197,256,304,366, and 17, to give specific 438 mutants, of particular importance M197L and M197T, wherein M197T is the most stable expressed variant^_And SUNLIGHT^_Stability; (c) particularly preferred amylases in the present invention include amylase variants having other modifications in the direct parent as described in WO 9510603A, which may be DURAMYL from Novo of the assignee^_And (4) purchasing. Other particularly preferred oxidative stability-enhancing amylases include those described in WO 9418314 to Genencor International and WO9402597 to Novo. Any other oxidative stability-enhanced amylase may be used, e.g., from a known chimeric, mixed or simple mutant parent form by site-directed mutagenesisA commercially available amylase of formula (la). Other preferred enzyme modifications are achievable. See WO 9509909A to Novo.

Other amylases include those described in WO95/26397 and Novo Nordisk, pending application PCT/DK 96/00056. Specific for use in the detergent compositions of the present inventionThe amylase includes α -amylase, and is characterized by being obtained by Phadebas^_α -Amylase Activity test assay (Phadebas, supra)^_α -Amylase Activity test is described in WO95/26397, pages 9-10). The specific activity ratio Termamyl is determined at 25 ℃ -55 ℃ and a pH in the range from 8 to 10^_Also included in the present invention are α -amylases that are at least 80% homologous to the amino acid sequence shown in the SED ID arrangement of this reference, these enzymes preferably being incorporated into laundry detergent compositions at a level of from 0.00018% to 0.060% pure enzyme, more preferably from 0.00024% to 0.048% pure enzyme by weight of the total composition.

Cellulases usable in the present invention include cellulases of the bacterial and fungal type, preferably having an optimum pH range of 5-9.5. U.S. Pat. No. 4,220,307 to Barbesgord et al, 3/6, discloses suitable cellulase enzymes for molds from Humicola insolens or Humicola strain DSMl800 or a mold belonging to the genus Aeromonas that produces cellulase 212, and cellulase enzymes extracted from the hepatopancreas of the marine mollusk Dolabella Auricula solander. Suitable cellulases are also disclosed in GB-A-2075028; GB-A-2095275 and DE-OS-2247832. CAREZYME^_And CELLUZYME^_(Novo) is particularly useful. See also WO 9117243 to Novo.

Suitable lipases which may be used in detergents include those produced by microorganisms of the Pseudomonas family, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in British patent GB-1372034. See also the lipase disclosed in Japanese patent application No. 53-20487, published 24/2/1978. Such lipases are commercially available from Amano pharmaceutical co.ltd., Nagoya, Japan under the trade name lipase P "Amano" or "Amano-P". Other suitable commercial lipases include Amano-CES fromChromobacter viscosum lipases, for example, Chromobacter viscosum var. lipolyticum NRRLB3673 from Toyo Jozo Co., Tagata, Japan; chromobacter viscosum lipases from U.S. Biochemical Corp., U.S. A., and Disoynth Co.Netherlands, and lipases from Pseudomonas gladioli (Pseudomonas gladioli). Lipolase, obtained from Humicola lanuginosa and commercially available from Novo (see also EP341947)^_The enzyme is a lipase which is preferably used herein. Peroxidase-stable lipase and amylase variants are described in WO 9414951A to Novo. See also W09205249 and RD 94359044.

Although a large number of documents disclose lipases, only lipases derived from Humicola lanuginosa (Humicola lanuginosa) and produced in Aspergillus oryzae as a host have hitherto been found to be widely used as additives for fabric washing products. As mentioned above, it may be prepared by Novo NordiskLipolase as trade name^TMAnd (4) obtaining the product. To maximize the stain removal performance of Lipolase, NovoNordisk has made many variants. The D96L variant of the native humicola lanuginosa lipase, as described in WO92/05249, exhibited a 4.4-fold increase in lard-removing potency over the wild-type lipase (enzymes compared in the range of 0.075-2.5mg protein per liter). It is disclosed by NovoNordisk in Research Disclosure No.35944 published on 3/10 of 1994 that a lipase variant (D96L) can be added in an amount corresponding to 0.001-100mg (5-500,000LU/1) of lipase variant per liter of wash solution. In the manner disclosed herein, the use of low levels of the D96L variant in detergent compositions containing bis AQA surfactants according to the present invention provides improved whiteness maintenance benefits to fabrics, particularly when D96L is used in amounts of 50LU to 8500LU per liter of wash solution.

Cutinases suitable for use in the present invention are described in WO 88809367A to Genencor.

Peroxidases may be used in conjunction with oxygen sources, e.g., percarbonate, perborate, hydrogen peroxide, and the like, which are used to "solution bleach" or prevent the transfer of dyes or pigments removed from a substrate during a wash process to other substrates present inthe wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidase such as chloro-and bromo-peroxidase. Detergent compositions containing peroxidase are disclosed in WO 89099813a by Novo at 10/19 of 1989 and WO 8909813a by Novo.

Various enzymatic materials and methods for their incorporation into synthetic detergent compositions are also disclosed in WO 9307263A and WO 9307260A of Genencor International, WO 8908694A of Novo, and U.S. Pat. No. 5 McCarty et al, 1971, US 3553139. Some enzymes are also disclosed in Place et al, US4101457, 18, 1978 and Hughes, US4507219, 26, 3, 1985. Enzyme materials for use in liquid detergent formulations, and their incorporation into these formulations, are disclosed in US4261868 to Hora et al, 4.14.1981. Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Pat. No. 8/17 1971 to Gedge et al, US patent No. 3600319,1986, European patent Nos. EP199405 and EP200586 to Venegas, No. 10/29. Enzyme stabilization systems are also described, for example, in US patent No. US 3519570. Useful bacilli AC13 to give proteases, xylanases and cellulases are described in WO 9401532A to Novo.

Enzyme stabilizing system

The enzyme-containing compositions of the present invention may also optionally contain from 0.001% to 10%, preferably from 0.005% to 8%, more preferably from 0.01% to 6%, by weight of an enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system compatible with detersive enzymes. The system may be provided by the other formulation actives themselves or added separately by, for example, the formulator or the manufacturer of the detergent ready-to-use enzyme. Such stabilizing systems may contain, for example, calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acid and mixtures thereof, and are designed to address various stabilizing problems depending on the type and physical form of the detergent composition.

One method of stabilization is to use a water soluble source of calcium and/or magnesium ions in the finished composition, which provides these ions to the enzyme. Calcium ions are generally more effective than magnesium ions, and if only one type of cation is used, calcium ions are preferred for use herein. Typical detergent compositions, especially liquid detergents, contain from about 1 to about 30, preferably from about 2 to about 20, more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, and can vary depending upon such factors as the variety, type, and level of enzyme being incorporated. Preferably, water soluble calcium or magnesium salts are used, including for example calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide and calcium acetate, more typically calcium sulfate or magnesium salts corresponding to the exemplified calcium salts may be used. It is of course useful to further increase the calcium and/or magnesium content, for example to promote the degreasing action of certain types of surfactants.

Another method of stabilization is the use of borate series. See U.S. Pat. No. 4,310,706 to Severson. When used, the borate stabilizer may be present in an amount of up to 10% or more of the composition, but for use in liquid detergents, it is more usually desirable to have a level of boric acid or other borate compound such as borax or orthoborate up to about 3% by weight. Substituted boric acids such as phenylboronic acid, butylboronic acid, p-bromophenylboronic acid and the like may be used in place of boric acid, and although such substituted boron derivatives are used, it is still possible to reduce the total boron content of the detergent composition.

The stabilizing system of certain cleaning compositions, such as automatic dishwashing compositions, may also contain from 0 to 10%, preferably from 0.01% to 6%, by weight, of chlorine bleach scavengers, which are added to avoid enzyme damage and inactivation by chlorine bleach species present in many water sources, especially under alkaline conditions. The chlorine content in water may be very small, typically in the range of 0.5ppm to 1.75ppm, whereas the available chlorine in the total volume of water in contact with the enzyme, e.g. in dishwashing or in fabric washing, may be relatively large; thus, there are times when chlorine stability to enzymes is problematic in use. Due to the ability of percarbonates to react with chlorine bleach, it is most often not necessary to use other chlorine-resistant stabilisers, although their use may give improved results. Suitable chlorine scavenger anions are well known and readily available and, if used, may be sulfites, bisulfites, thiosulfites, thiosulfates, iodides, and the like, containing ammonium cations. Antioxidants such as carbamates, ascorbic acid and the like, organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof, Monoethanolamine (MEA), and mixtures thereof may also be used. Likewise, specific enzyme inhibition systems may be incorporated to maximize compatibility of the different enzymes. Other conventional scavengers such as bisulfates, nitrates, chlorides, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphates, condensed phosphates, acetates, benzoates, citrates, formates, lactates, malates, tartrates, salicylates, and the like, and mixtures thereof, may be used if desired. In general, since the separately listed components having better established functionality may function as chlorine scavengers, (e.g., sources of hydrogen peroxide), there is no absolute need to add a chlorine scavenger alone unless a compoundhaving such a function to the desired degree is absent from the enzyme-containing embodiments of the present invention; even then, the chlorine scavenger is added only for optimum effect. In addition, the formulator will also avoid the use of any enzyme scavengers or stabilizers which are largely incompatible with the other active ingredients at the time of formulation, according to the common general knowledge of chemistry. Where the use of ammonium salts is concerned, the salts may simply be incorporated with the detergent composition, but they tend to absorb water and/or give off ammonia during storage. Thus, if such materials are present, they need to be protected in particles, as described in US4652392 to Baginski et al. Polymeric soil release agents

Known polymeric soil release agents, hereinafter referred to simply as "SRA" or "SRA's", may optionally be used in the detergent compositions of the present invention. If used, SRA's generally comprise from 0.01% to 10.0%, typically from 0.1% to 5%, preferably from 0.2% to 3.0% by weight of the composition.

Preferred SRA's typically have hydrophilic moieties that hydrophilize the surface of hydrophobic fibers, such as polyester and nylon, and hydrophobic moieties that deposit on the hydrophobic fibers and remain attached thereto throughout the wash and rinse processes, thus serving as anchors for the hydrophilic moieties. This may allow stains subsequently generated by treatment with SRA to be more easily cleaned in a subsequent washing process.

SRA's may comprise various charged, such as anionic or even cationic (see US4956447) monomer units as well as uncharged monomer units, the structure of which may be linear, branched or even star-shaped. They may include end-capping moieties that are particularly effective for controlling molecular weight or selecting physical properties or surface activity. The structure and charge distributioncan be adjusted to suit different fiber or fabric types and various detergent or laundry additive products.

Preferred SRA's include oligomeric terephthalates, which are generally prepared by a process involving at least one transesterification/oligomerization reaction, typically in the presence of a metal catalyst such as a titanium (iv) alkoxide. The esters may be prepared using other monomers that are capable of introducing the ester structure through one, two, three, four or more positions, without, of course, forming a densely crosslinked overall structure.

Suitable SRA's include sulfonated products of substantially linear ester oligomers containing an oligomeric ester backbone of terephthaloyl groups and oxyalkylene repeat units and allyl-derived sulfonated terminal moieties covalently attached to the backbone, for example as described in US patent No. 4968451 to j.j.scheibel and e.p.gosselink, 11.6.1990. The ester oligomer can be prepared by the following steps: (a) ethoxylated allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1, 2-propanediol ("PG") in a two-step transesterification/oligomerization process; and (C) reacting the product of (b) with sodium metabisulfite in water; non-ionically-terminated 1, 2-propylene/polyoxyethylene terephthalate polyesters, such as those prepared by transesterification/oligomerization of poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ("PEG"), in U.S. Pat. No. 4,4711730 to Gosselink et al, 12/8/1987; partially-and fully-anionically blocked oligomeric esters such as those derived from ethylene glycol ("EG"), PG, DMT, and sodium 3, 6-dioxa8-hydroxyoctane sulfonate, as in us patent 4721580 to Gosselink, 26.1.1988; non-ionic end-capped block polyester oligomeric compounds, such as those made from DMT, (Me) -end-capped PEG and EG and/or PG, or made from a mixture of DMT, EG and/or PG, Me-end-capped PEG and sodium dimethyl-5-sulfoisophthalate, of Gosselink, 27.10.1987; and Maldonado, Gosselink et al, U.S. Pat. No. 4,4877896, on 31/10/1989, the anions, particularly the sulfoaroyl-terminated terephthalates, which are typically SRA's useful in both laundry and fabric conditioning products, an example being an ester composition made from monosodium m-sulfobenzoate, PG and DMT, optionally but preferably also with added PEG, e.g., PEG 3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see Hays, US3959230, 5/25 1976, and Basadur, US3893929, 7/8 1975; cellulose derivatives such as hydroxy ether cellulose polymers available from Dow as METHOCEL; and C₁-C₄Alkyl celluloses and C₄A hydroxyalkyl cellulose; see 1976Nicol et al, U.S. Pat. No. 4,000,93, 12 months and 28 days. Suitable SRA's characterized by a poly (vinyl ester) hydrophobic moiety include graft copolymers of poly (vinyl esters), e.g., C₁-C₆Vinyl esters, preferably poly (vinyl acetate), which are grafted onto a polyalkylene oxide backbone. See European patent application EP0219048 to Kud et al, published 22.4.1987. Examples of commercially available materials include SOKALAN SRA's such as SOKALAN HP-22, which is commercially available from BASF corporation of Germany. Other SRA's are polyesters with repeat units comprising 10-15% by weight ethylene terephthalate and 90-80% by weight polyoxyethylene terephthalate, obtained from polyoxyethylene glycol having an average molecular weight of 300-. Examples of commercial products include ZELCON 5126 from dupont and millase from ICI.

Another preferred SRA is a compound of empirical formula (CAP)₂(EG/PG)₅(T)₅(SIP)₁An oligomer of (A) which contains terephthaloylGroup (T), Sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1, 2-propylene (EG/PG) units and preferably capped with an end group (CAP), preferably a modified isethionate, such as one sulfoisophthaloyl unit, 5 terephthaloyl units in the oligomer, an defined ratio of oxyethyleneoxy and oxy-1, 2-propyleneoxy units, preferably a ratio of about 0.5: 1 to about 10: 1, and two capping units derived from sodium 2- (2-hydroxyethoxy) -ethanesulfonate. The SRA preferably also contains from 0.5% to 20% by weight of the oligomer of a crystallinity-reducing stabilizer, for example an anionic surfactant such as sodium linear dodecylbenzene sulfonate or a material selected from the group consisting of xylene, cumene, and toluene sulfonates or mixtures thereof, which stabilizers or modifiers are added to the synthesis kettle, all as taught in US5415807 to Gosselink, Pan, Kellett and Hall, granted on 5/16 1995. Suitable monomers for the above SRA include sodium 2- (2-hydroxyethoxy) -ethylsulfonate, DMT, sodium dimethyl 5-sulfoisophthalate, EG and PG.

Another preferred SRA's are oligomeric esters containing the following moieties: (1) a scaffold comprising (a) at least one unit selected from the group consisting of: dihydroxy sulfonate esters, polyhydroxy sulfonate esters, units having at least three functionalities, thereby forming ester linkages to provide branched oligomeric backbones, and combinations thereof; (b) at least one unit which is a terephthaloyl moiety; and (c) at least one non-sulfonated unit that is a1, 2-oxyalkylene moiety; and (2) one or more end-capping units selected from the group consisting of nonionic end-capping units, anionic end-capping units such as alkoxylated, preferably ethoxylated, isethionate, alkoxylated propanesulfonate, alkoxylated propanedisulfonate, alkoxylated phenolsulfonate, sulfoaroyl derivatives and mixtures thereof. Preferred are esters having the following empirical formula:

{(CAP)_x(EG/PG)_y’(DEG)_y”(PEG)_y_(T)_z(SIP)_z’(SEG)_q(B)_mwherein CAP, EG/PG, PEG, T and SIP are as defined above, (DEG) represents a di (oxyethylene) oxy unit, (SEG) represents a unit derived from a sulfoethyl ether of glycerol and related moietiesUnits, (B) represents branched units which are at least trifunctional, thereby forming ester linkages to give a branched oligomer backbone, x is from about 1 to about 12, y ' is from about 0.5 to about 25, y "is from 0 to about 12, y _ is from 0 to about 10, the sum of y ' + y" + y _ is from about 0.5 to about 25, z is from about 1.5 to about 25, z ' is from 0 to about 12; z + z' together is from about 1.5 to about 25, q is from about 0.05 to about 12; m is from about 0.01 to about 10, and x, y ', y ", y _, z, z', q, and m represent the average number of moles of the corresponding units per mole of the ester, which has a molecular weight of from about 500 to about 5000.

Preferred SEG and CAP monomers for the above esters include sodium 2- (2-, 3-dihydroxypropoxy) ethanesulfonate ("SEG"), sodium 2- {2- (2-hydroxyethoxy) ethoxy } ethanesulfonate ("SE 3") and homologs and mixtures thereof and the products of ethoxylation and sulfonation of allyl alcohol. Preferred SRA esters of this type include sodium 2- {2- (2-hydroxyethoxy) ethoxy } ethanesulfonate and/or 2- [2- {2- (2-hydroxyethoxy) ethoxy } ethoxy]Sodium ethanesulfonate, DMT, sodium 2- (2, 3-dihydroxypropoxy) ethanesulfonate, EG, and PG, transesterification and oligomerization products using suitable Ti (IV) catalysts, which products may be designated (CAP)₂(T)₅(EG/PG)_1.4(SEG)_2.5(B)_0.13Wherein CAP is (Na)^+-O₃S[CH₂CH₂O]_3.5) And B are units derived from glycerol, the molar ratio EG/PG being about 1.7: 1, as determined by conventional gas chromatography after complete hydrolysis.

Another class of SRA's includes: nonionic terephthalates bonded to polyester structures using diisocyanurate coupling agents, see U.S. Pat. No. 4,4201824 to Violland et al and U.S. Pat. No. 4,4240918 to Lagasse et al; and (II) SRA's with carboxylate end groups prepared by converting the terminal hydroxyl groups to trimellitate esters by the addition of trimellitic anhydride to known SRA's. With proper selection of the catalyst, trimellitic anhydride forms linkages to the ends of the polymer through the isolated carboxylic acid ester of trimellitic anhydride rather than through the opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials, provided they have hydroxyl end groups which may be esterified. See Tung et al, US 4525524; (iii) anionic terephthalate-based SRA's linked to urethanes, see U.S. patent nos. 4201824 to vilolland et al; (iv) poly (vinyl caprolactam) and related copolymers with monomers such as vinyl pyrrolidone and/or dimethylaminoethyl methacrylate, including nonionic and cationic polymers, see U.S. Pat. No. 4,4579681 to Ruppert et al; (V) graft copolymers, furthermore of the SOKALAN type from BASF corporation, prepared by grafting acrylic monomers onto sulfonated polyesters; these SRAs are believed to have soil release and anti-redeposition activities similar to known cellulose ethers; see EP279134A, 1988, by ronalprenk company; (VI) grafts of vinyl monomers such as acrylic acid and vinyl acetate on proteins such as casein, see EP457205A (1991) from BASF; (VII) polyester-polyamide SRA's prepared by condensation of adipic acid, caprolactam and polyethylene glycol, especially for the treatment of polyamide fabrics, see DE2335044 to Unilever N.V. 1974. Other useful SRA's are described in US patents US4240918, US4787989, US4525524 and US 4877896.

Clay soil removal/antiredeposition agents

The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay soil removal and anti-redeposition properties. Granular detergentcompositions containing these compounds typically contain from 0.01% to 10.0% by weight of a water-soluble ethoxylated amine; liquid detergent compositions typically contain from 0.01% to 5% by weight of a water-soluble ethoxylated amine.

The most preferred soil removal and anti-redeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amines are further described in U.S. patent No. US4597898 to VanderMeer, issued on 7/1 1986. Another preferred class of clay soil removal-antiredeposition agents are the cationic compounds disclosed in European patent application EP l11965 to Oh and Gosselink, published on 27.6.4. Other clay soil removal/anti-redeposition agents that may be used in the present invention include ethoxylated amine polymers disclosed in european patent application 111984 to Gosselink, published on 27.6.4 1984; zwitterionic polymers disclosed in European patent application EP112592 to Gosselink, published on 4.7.4.1984; and Connor, US patent US4548744 issued on 10/22/1985. Other clay soil removal and/or anti-redeposition agents known in the art can also be used in the compositions of the present invention. See US4891160 by VanderMeer, granted on 2.1.1990, and WO95/32272, published on 30.11.1995. Another preferred class of antiredeposition agents includes carboxymethyl cellulose (CMC) materials. These materials are well known in the art. Whitening agent

Any fluorescent whitening or other whitening or whitening agent known in the art may generally be incorporated into the detergent compositions of the present invention at levels of from 0.01% to 1.2% by weight. Commercially available optical brighteners which may be used in the present invention may be classified into groups which include, but are not necessarily limited to, stilbene, pyrazoline, coumarin, carboxylic acid, methine cyanine, dibenzothiophene-5, 5-dioxide, pyrrole, derivatives of 5-and 6-membered heterocycles, and other heterochrome agents. Examples of such brighteners are disclosed in "the production and Application of fluorescent whitening agents (the production and Application of F1 ecological brightening agents)", M.Zahradnik, published by John Wiley&Sons, New york (1982).

Specific examples of optical brighteners used in the compositions of the present invention are the same as disclosed in U.S. patent No. US4790856 to Wixon, granted 12/13/1988. These brighteners include Verona's PHORWHITE brightener family. Other whitening agents disclosed in this reference include: tinopal UNPA, Tinopal CBS and Tinopal 5BM, commercially available from Ciba-Geigy; artic White CC and Artic White CWD,2- (4-styrylphenyl) -2H-naphtho [1,2-d]triazole; 4, 4' -bis (1,2, 3-triazol-2-yl) stilbene; 4, 4' -bis (styryl) biphenyl; and aminocoumarins. Specific examples of these whitening agents include: 4-methyl-7-diethylaminocoumarin; 1, 2-bis (benzimidazol-2-yl) ethylene; 1,3 diphenylpyrazoline; 2, 5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphtho [1,2-d]oxazole; and 2- (stilbene-4 yl) -2H-naphtho [1,2 d]triazole. See also Hamilton, US patent US3646015, issued 2, 29, 1972.

Dye transfer inhibitors

The compositions of the present invention may also include one or more materials effective to inhibit the transfer of dyes from one fabric to another during the cleaning process. Typically, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, magnesium phthalocyanine, peroxidases, and mixtures thereof. If used, these agents are generally present in an amount of from 0.01% to 10%, preferably from 0.01% to 5%, more preferably from 0.05% to 2% by weight of the composition.

More specifically, the polyamine N-oxide polymers preferred for use in the present invention comprise polyamine polymers having the following structural formula: R-A_x-a unit of P; wherein P is a polymerizable unit to which an N-O group may be attached or an N-O group may constitute a part of the polymerizable unit or an N-O group may be attached to both units; a is one of the following structures: -nc (O) -, -c (O) O-, -S-, -O-, -N =; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof to which the nitrogen of the N-O group may be attached or to which the N-O group isAnd (b) a portion. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The N-O group may be represented by the following general structure:

wherein R is₁,R₂,R₃Is an aliphatic, aromatic, heterocyclic or alicyclic group or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the N-O group may be attached to or form part of any of the foregoing groups. The amine oxide units of the polyamine N-oxide have a pKa of<10, preferably a pKa of<7, more preferably a pKa of<6.

Any polymer backbone can be used in the present invention so long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymeric backbones include vinyl polymers, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates, and mixtures thereof. These polymers include random or block copolymers where one monomer type is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers generally have an amine to amine N-oxide ratio of from 10: 1 to 1: 1000000. However, the number of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by appropriate degree of N-oxidation. Polyamine oxides can be obtained in almost any degree of polymerization. Typically, the average molecular weight ranges from 500-; more preferably 1000-; most preferably 50000-100000. Such preferred materials may be referred to as "PVNO".

The most preferred polyamine N-oxide useful in the detergent compositions of the present invention is poly (4-vinylpyridine-N-oxide) having an average molecular weight of 50000 and an amine to amine N-oxide ratio of 1: 4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (known as "PVPVI") are also preferred for use in the present invention. Preferably, PVPVI has an average molecular weight of 5000-. (the average molecular weight range is determined by light scattering methods as described in Barth et al, chemical analysis, vol 113, "modern methods of Polymer characterization", the disclosure of which is incorporated herein by reference). The PVPVI copolymers generally have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone of from 1: 1 to 0.2: 1, more preferably from 0.8: 1 to 0.3: 1, most preferably from 0.6: 1 to 0.4: 1. These copolymers may be linear or branched.

The compositions of the present invention may also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of from 5000 to 400000, preferably from 5000 to 200000, and more preferably from 5000 to 50000. PVP is known to those skilled in the detergent art; see, for example, EP-A-262897 and EP-A-256696, both of which are incorporated herein by reference. Compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of 500 to 100000, preferably 1000 to 10000. Preferably, the ratio of PEG to PVP released in ppm in the wash solution is from 2: 1 to 50: 1, more preferably from 3: 1 to 10: 1.

The detergent compositions of the present invention may also optionally contain from 0.005% to 5%by weight of certain types of hydrophilic optical brighteners which also provide dye transfer inhibition. If used, the compositions of the present invention preferably contain from 0.01% to 1% by weight of the optical brightener.

Hydrophilic fluorescent whitening agents that may be used in the present invention have the following structural formula:wherein R is₁Selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; r₂Selected from the group consisting of N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; and M is a salt-forming cation such as sodium or potassium.

When in the above formula, R₁Is anilino, R₂When N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4, 4' -bis [ (4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino]-2, 2' -stilbenedisulfonic acid and disodium salt. Such special whitening agents are commercially available from Ciba-Geigy under the trade name Tinopal-UNPA-GX. Tinopal-UNPA-GX is a preferred hydrophilic optical brightener for use in the detergent compositions of the present invention.

When in the above formula, R₁Is anilino, R₂When N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4, 4' -bis [ (4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino]-2, 2' -stilbenedisulfonic acidDisodium salt of an acid. Such special whitening agents are commercially available from Ciba-Geigy under the trade name Tinopal 5 BM-GX.

When in the above formula, R₁Is anilino, R₂Is morpholino and M is a cation such as sodium, the brightener is 4, 4' -bis [ (4 anilino-6-morpholino-s-triazin-2-yl) amino]-2, 2' -stilbene disulfonic acid sodium salt. Such special whitening agents are commercially available from Ciba-Geigy under the trade name Tinopal AMS-GX.

These particular fluorescent whitening agents selected for use in the present invention provide particularly effective dye transfer inhibition properties when used in combination with the selected polymeric dye transfer inhibiting agents described hereinabove. The use of such selected polymeric materials (e.g., PVNO and/or PVPVI) in combination with such selected optical brighteners (e.g., Tinopal UNPA-GX, Tinopal 5BM-GX, and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than is the case for detergent compositions employing these two components alone. Without wishing to be bound by theory, it is believed that such brighteners work in this manner because they have a high affinity for fabrics in the wash solution and therefore adhere relatively quickly to these fabrics. The degree to which the brightener adheres to fabric in the wash solution can be defined by a parameter known as the "exhaustion coefficient". The exhaustion coefficient is usually taken as the ratio between a) the brightener material attached to the fabric and b) the initial brightener concentration in the wash liquor. Brighteners with a relatively high exhaustion coefficient are most suitable in the context of the present invention for inhibiting dye transfer.

It will, of course, be appreciated that other conventional optical brightener type compounds may optionally be used in the compositions of the present invention to provide conventional fabric "whitening" action, rather than true dye transfer inhibition. Such applications are conventional and well known in detergent formulations. Chelating agents

The detergent compositions of the present invention may also optionally contain one or more iron and/or manganese sequestrants. Such chelating agents may be selected from the group consisting of aminocarboxylates, aminophosphonates, multifunctional substituted aromatic chelating agents, and mixtures thereof, all as defined hereinafter. Without being bound by theory, it is believed that the advantages of these materials are in part due to their superior performance in removing iron and manganese from the wash solution by forming soluble chelators.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetate, N-hydroxyethylethylenediaminetriacetate, nitrilotriacetate, ethylenediaminetetrapropionate, triethylenetetramine hexaacetate, diethylenetriaminepentaacetate and ethanoldiglycine, alkali metal, ammonium and substituted ammonium salts thereof and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the present invention when at least a low total phosphorus content is permitted in the present compositions, and include: ethylenediamine tetra (methylene phosphonate), known as DEQUEST. These amino phosphonates preferably do not contain alkyl or alkenyl groups with more than six carbon atoms.

Multifunctional substituted aromatic chelating agents may also be used in the compositions of the present invention. See Connor et al, US3812044, granted 5/21/1974. Preferably such compounds in acid form are dihydroxydisulfobenzenes such as 1, 2-dihydroxy-3, 5-disulfobenzene.

The biodegradable chelating agents preferably used in the present invention are ethylenediamine disuccinate ("EDDS"), particularly the [ S, S]isomers thereof as described in US patent No. US4704233 to Hartman and Perkins, granted on 3.11.1987.

The compositions of the present invention may also contain a water-soluble methylglycinediacetic acid (MGDA) salt (or acid form) as a chelating agent, or it may contain an effective co-builder, for example an insoluble builder such as a zeolite, a layered silicate.

These chelating agents, if used, are generally used at levels of from 0.1% to 15% by weight of the detergent composition of the invention. If a chelating agent is used, it is more preferably used in an amount of 0.1% to 3.0% by weight of the composition. Suds suppressor

Compounds that reduce or inhibit foam formation may be incorporated into the compositions of the present invention. Suds suppression is particularly important in the so-called "high-consistency washing process" as described in US4489455 and 4489574 and in the case of front-loading euro-washer machines.

Various materials may be used in the present invention as suds suppressors, which are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of chemical technology, 3 rd edition, volume 7, pages 430-447 (John Wiley&Sons, Inc., 1979). One particularly important class of suds suppressors comprises monocarboxylic fatty acids and soluble salts thereof. See US2954347 to Wayne st.john, granted 9, 27, 1960. Monocarboxylic fatty acids and their salts useful as suds suppressors generally have hydrocarbyl chains containing from 10 to 24 carbon atoms, preferably from 12 to 18 carbon atoms. Suitable salts include alkali metal salts, such as sodium, potassium, and lithium salts, and ammonium and alkanolammonium salts.

The detergent compositions of the present invention may also contain non-surfactant suds suppressors. Such suds suppressors include, for example: high molecular weight hydrocarbons such as paraffins, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monohydric alcohols, aliphatic C_18-40Ketones (e.g., stearyl ketone), and the like. Other suds suppressors include N-alkylated aminotriazines, such as tri-to hexa-alkylmelamines or di-to tetra-Alkyldiamine chlorotriazines, which are the reaction product of cyanuric chloride with2 or 3 moles of a primary or secondary amine having from 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphate salts, such as monostearyl alcohol phosphate and distearyl alkali metal (e.g., K, Na, and Li) phosphate and phosphoric acid esters. Hydrocarbons such as paraffins and halogenated paraffins may be used in liquid form. The liquid hydrocarbon is liquid at room temperature and atmospheric pressure, and has a pour point of-40 ℃ to 50 ℃ and a minimum boiling point of not less than 110 ℃ (atmospheric pressure). The use of waxy hydrocarbons is known, preferably having a melting point below 100 ℃. Such hydrocarbons are a preferred class of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Pat. No. 4,65779 to Gandolfo et al, granted on 5/1981. Thus, the hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having 12 to 70 carbon atoms. The term "paraffin" as used in the discussion relating to such suds suppressors includes mixtures of true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors comprises silicone suds suppressors. This category includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and combinations of polyorganosiloxane with silica particles, where the polysiloxane is chemisorbed or fused to the silica. Silicone suds suppressors are well known in the art, as disclosed in U.S. Pat. No. 4,65779 to Gandolfo et al, issued 5/5 1981, and in European patent application 89307851.9 to Starch, M.S., published 2/7 1990.

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3455839, which relates to compositions and methods for eliminating aqueous foam by incorporating a small amount of polydimethylsiloxane fluid into the composition.

Mixtures of polysiloxanes and silanized silicas are described, for example, in German patent application DOS 2124526. Silicone antifoam and foam control agents in granular detergent compositions are disclosed in Bartolotta et al, U.S. Pat. No.3,33672 and Baginski et al, US4652392, issued 3/24 1987.

An exemplary silicone-based suds suppressor for use in the present invention is a suds suppressing amount of a suds controlling agent consisting essentially of:

a polydimethylsiloxane fluid having a viscosity of from about 20cs. to about 1500cs. at 25 ℃;

(ii) from about 5 to about 50 parts per 100 parts by weight (i) of a polysiloxane resin Consisting of (CH)₃)₃SiO_1/2Unit and SiO₂Unit is pressed (CH)₃)₃SiO_1/2A unit: SiO 2₂Units are comprised in a ratio of about 0.6: 1 to about 1.2: 1; and

(iii) from about 1 to about 20 parts of solid silica gel per 100 parts by weight of (i);

in the preferred silicone suds suppressors for use herein, the solvent for the continuous phase is comprised of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol. The polysiloxane suds suppressor is predominantly branched/crosslinked and preferably non-linear.

To further illustrate this point, typical liquid laundry detergent compositions having controlled suds optionally contain from about 0.001% to about 1%, preferably from about 0.01% to about 0.7%, most preferably from about 0.05% to about 0.5%, by weight of said silicone suds suppressor which comprises (1) a non-aqueous emulsion of a primary suds suppressor which is a mixture of (a), (b) (c) and (d) wherein (a) is a polyorganosiloxane, (b) is a resinous silicone or silicone compound which produces a silicone resin, (c) is a finely divided filler and (d) is a catalyst which facilitates reaction of mixture components (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) a copolymer of polyethylene glycol or polyethylene polypropylene glycol having a solubility in water of more than 2% by weight at room temperature; polypropylene glycol was not present. Similar amounts can be used in particulate compositions, gels, and the like. See also US4978471 to Starch, granted on 18.12.1990, and US 5288431 to Huber et al, granted on 2.22.2. 4983316,1994 to Starch, granted on 8.1.1991, and US4639489 and US4749740 to Aizawa et al, at column 46, to column 4, line 35.

Preferred silicone suds suppressors of the present invention include polyethylene glycol and polyethylene/polypropylene glycol copolymers having an average molecular weight of less than about 1000, preferably about 100-. The solubility of the polyethylene glycol and polyethylene/polypropylene glycol copolymers of the present invention in water at room temperature is greater than about 2% by weight, preferably greater than about 5% by weight.

Preferred solvents for the present invention are polyethylene glycol having an average molecular weight of less than about 1000, more preferably about 100-800, and most preferably 200-400, and copolymers of polyethylene glycol/polypropylene glycol, preferably PPG200/PEG 300. Polyethylene glycol: the weight ratio of the polyethylene-polypropylene glycol copolymer is preferably from about 1: 1 to 1: 10, most preferably from 1: 3 to 1: 6.

The preferred silicone suds suppressors for use herein are free of polypropylene glycol, especially those having a molecular weight of 4000. It is also preferably free of block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other suds suppressors which can be used in the present invention include secondary alcohols (such as 2-alkyl alkanols) and mixtures of these alcohols with silicone oils, such as the silicones disclosed in US4798679, US4075118 and european patent EP 150872. The secondary alcohol comprises a compound having C_1-16C of the chain_6-16An alkyl alcohol. The preferred alcohol is 2-butyloctanol, which is available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available from Enichem under the trademark isachem 123. The mixed suds suppressors generally comprise a weight ratio of 1: 5-5: 1 mixture of alcohol and polysiloxane.

For any detergent composition used in an automatic washing machine or a dishwashing machine, the foam formed cannot reach the level of overflow from the washing machine or negatively impact the washing mechanism of the dishwashing machine. When a suds suppressor is used, it is preferably present in a "suds suppressing amount". By "suds suppressing amount" is meant that the formulator of the composition can select an amount of the suds controlling agent sufficient to control suds to provide a low sudsing laundry or dishwashing detergent which can be used in an automatic washing machine or a dishwashing machine.

The compositions of the present invention typically contain from 0% to 10% of suds suppressors. When monocarboxylic fatty acids and salts thereof are used as suds suppressors, they are generally used in amounts up to 5% by weight of the detergent composition. Preferably, from 0.5% to 3% of a fatty monocarboxylate suds suppressor is used. The silicone suds suppressors are generally used in amounts up to 2.0% by weight of the detergent composition, although higher levels may also be used. This upper limit is practical due to the primary concerns of keeping costs to a minimum and the effectiveness of lower amounts to effectively control foam. Preferably from 0.01% to 1% of a silicone suds suppressor is used,more preferably from 0.25% to 0.5%. These weight percent values used in the present invention include any silica that may be used in combination with the polyorganosiloxane as well as any additive materials that may be used. The monostearylphosphate suds suppressors are typically present in an amount of from 0.1% to 2% by weight of the composition. Typically, the amount is from 0.01% to 5.0%, although higher amounts of hydrocarbon suds suppressors can be used. Alcohol suds suppressors are generally used in amounts of 0.2% to 3% by weight of the final composition. Alkoxylated polycarboxylates

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, are suitable for use herein to provide additional grease removal performance. Such substances are described in WO91/08281 and PCT90/01815, page 4 and the following, which are incorporated herein by reference. Chemically, these materials include polyacrylates having an ethoxy side chain for every 7-8 acrylate units. The side chain has the formula: - (CH)₂CH₂O)_m(CH₂)_nCH₃Wherein m is 2-3 and n is 6-12. The side chain is connected with polyacrylate skeleton via ester bond to form comb structureThe polymer of (1). The molecular weight may vary but is generally in the range of 2000-50000. Such alkoxylated polycarboxylates may comprise from 0.05% to 10% by weight of the compositions herein.

Fabric softener

Various fabric softeners which undergo the entire process of laundering, particularly the fine particle smectites disclosed in U.S. patent nos. 4062647 to Storm and Nirschl, issued 12/13 of 1977, and other softener clays known in the art, may optionally be used in the compositions of the present invention to achieve fabric softening while cleaning fabrics, typically in amounts of 0.5% to 10% by weight of the composition of the present invention. Clay softeners may beused in combination with amines and cationic softeners as disclosed in U.S. Pat. No. 4,416 to Crisp et al, entitled 3/1 1983, and in U.S. Pat. No. 4291071 to Harris et al, entitled 9/22 1981.

Perfume

Fragrances and odoriferous components suitable for use in the compositions and methods of the present invention include a variety of natural and synthetic chemical components including, but not limited to, aldehydes, ketones, esters. Also included are various natural extracts and essences, which may comprise complex mixtures of some components, such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsam, sandalwood oil, pine oil, cedar oil. Finished perfumes can contain extremely complex mixtures of these components. Finished perfumes typically comprise from 0.01% to 2% by weight of the detergent compositions of the present invention, and individual perfumed components may comprise from 0.0001% to 90% by weight of the finished perfume composition.

Non-limiting examples of fragrance components suitable for use in the present invention include 7-acetyl 1,2,3,4,5,6,7, 8-octahydro-1, 1,6, 7-tetramethylnaphthalene, methylionone, gamma-methylionone, methylceberrulone, methyl dihydrojasmonate, methyl 1,6, 10-trimethyl-2, 5, 9-cyclododecatrien-1-yl ketone, 7-acetyl-1, 1,3,4,4, 6-hexamethyl 1,2,3, 4-tetrahydronaphthalene, 4-acetyl-6-tert-butyl-1, 1-dimethyl 1, 2-dihydroindene, p-hydroxy-phenyl-butanone, benzophenone, methyl β naphthyl ketone, 6-acetyl-1, 1,2,3,3, 5-hexamethyl 1, 2-dihydroindene, 5-acetyl-3-isopropyl-1, 1,2, 6-tetramethyl-1, 2-dihydroindene, 1-hexahydro-1, 4- (4-hydroxycyclohexyl-4-cyclohexyl) 1,2,3, 4-hexahydro-1, 2-hexadecyl-1, 2-dihydroindene-1, 3,3, 3-isopropyl-1, 2, 6-tetramethyl-1, 2, 6-1, 2-dihydroindene, 1,3, 3, 3-hexahydro-hexadecyl-methyl-1, 3,3, 3, 7-hexahydro-methyl-1, 7-pentyl-methyl-1, 4-pentyl-1, 7-1, 4-2-ethyl-pentyl-1, 7-2-1, 7-dihydroindene-8, 7-methyl-8, 7-dihydronaphthalene, 7-methyl-ethyl-methyl-8, 7-methyl-8, 7-oxo-methyl-2, 7-ethyl-1, 4-ethyl-1, 7-ethyl-2-methyl-1, 7-ethyl-2-ethyl-methyl-2-ethyl-2-pentyl-2-pentyl-2-ethyl-8, 7-pentyl-2-8-naphthyl-pentyl-ethyl-8, 7-naphthyl-ethyl-pentyl.

Particularly preferred perfumes are those perfume materials which provide maximum odor improvement to finished compositions containing cellulase enzymes, including, but not limited to, hexylcinnamaldehyde, 2-methyl-3- (p-tert-butylphenyl) propanal, 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-hexamethyl-1, 2,3, 4-tetrahydronaphthalene, p-tert-butylcyclohexyl acetate, methyl dihydrojasmonate, β -naphthylmethyl ether, methyl β -naphthylketone, 2-methyl-2- (p-isopropylphenyl) propanal, 1,3,4,6,7, 8-hexahydro-4, 6,7,8, 8-hexamethylcyclopenta-gamma-2-benzopyran, dodecahydro-3 a,6,6,9 a-tetramethylnaphtho [2,1b]furan, anisic acid, vanillin, cedryl alcohol, tricyclodecenyl decanoate, tricyclodecenyl propionate, and tricyclodecenyl propionate.

Other fragrances include essential oils, resinoids, and resins derived from various sources, including, but not limited to: peru balsam, mastic resin, benzoin, Cistus resin, nutmeg, Chinese cinnamon bark oil, benzoin resin, coriander oil, and lavandin. Other fragrance chemicals include phenylethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2- (1, 1-dimethylethyl) -cyclohexanol acetate, benzyl acetate, and eugenol. A carrier such as diethyl phthalate may be used in the finished fragrance composition.

Other Components

Various other ingredients useful in detergent compositions may be included in the compositions of the present invention, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, and the like.If high foam is desired, a foam booster such as C may be incorporated into the composition_10-16Alkanolamides, generally in amounts of from 1% to 10%. C_10-14Monoethanol and diethanol amides are typical examples of such suds boosters. It is also advantageous to use such suds boosters with high sudsing optional surfactants such as the amine oxides, betaines and sultaines described above. If desired, it is also possible to add, for example, MgCl₂，MgSO₄、CaCl₂、CaSO₄In order to obtain more foam and to enhance grease removal, water-soluble magnesium and/or calcium salts are generally used in amounts of 0.1% to 2%.

The various detersive ingredients used in the compositions of the present invention can also optionally be further stabilized by absorbing said ingredients onto a porous hydrophobic substrate, which is then coated with a hydrophobic coating agent. Preferably, the detergent component is mixed with a surfactant prior to absorption into the porous matrix. In use, the detergent component is released from the substrate into an aqueous detergent solution and performs its intended cleaning function in the aqueous detergent solution.

To illustrate the technique in more detail, porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) was mixed with a mixture containing 3% -5% of C_13-15Ethoxylated alcohol (EO7) non-ionic surfactant. Amount of the enzyme/surfactant solutionTypically 2.5 times the weight of the silica. The resulting powder was dispersed with stirring in a silicone oil (various silicone oils having a viscosity of 500-12500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent base. By this means, components such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photosensitizers, dyes, optical brighteners, fabric conditioners and hydrolyzable surfactants can be "protected" for use in detergents, including in liquid laundry detergent compositions.

Liquid detergent compositions may contain water and other solvents as carriers. Suitable are low molecular weight primary or secondary alcohols, such as methanol, ethanol, propanol and isopropanol. Monohydric alcohols are preferably used to solubilize the surfactant, but polyols such as alcohols containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (e.g., 1,3 propylene glycol, ethylene glycol, glycerol, and 1, 2-propylene glycol) may also be used. The compositions generally contain from 5% to 90%, typically from 10% to 50%, of such carriers.

The detergent compositions of the present invention are preferably formulated such that the pH of the wash water during use in an aqueous washing operation is from 6.5 to 11, preferably from 7.5 to 10.5. The preferred pH of the liquid dishwashing product formulation is from 6.8 to 9.0. Laundry products typically have a pH of 9-11. Methods of controlling the pH at the recommended use value include the use of buffers, bases, acids, and the like, which are familiar to those skilled in the art. Particle manufacture

The bis-alkoxylated cationic surfactant of the present invention is added to the blender and then dried by conventional spray drying to help remove any residual short chain amine contaminants that may be odorous. If the formulator wishes to prepare blendable granules containing the alkoxylated cationic surfactant for use in, for example, high density granular detergents, it is preferred that the granular composition is not overbased. A process for preparing high density (above 650g/l) granules is described in US 5366652. Such particles can be formulated to have an effective use pH of 9 or below pH9 to avoid the odor of contaminating amines. This can be achieved by adding a small amount of an acidic source, such as boric acid, citric acid, etc., or a suitable pH buffer to the particles. In another embodiment, the anticipated problems associated with amine odors can be masked by the use of a perfume component as disclosed herein.

Examples

In the following examples, the abbreviated component symbols have the following meanings: and (3) LAS: straight chain C₁₂Sodium alkylbenzenesulfonate TAS: tallow alkyl sodium sulfate C45 AS: C₁₄-C₁₅Linear alkyl sodium sulfate CxyEzS: c condensed with Z moles of ethylene oxide_1X-C_1YSodium branched alkyl sulfate C45E 7: predominantly C condensed with an average of 7 moles of ethylene oxide_14-15Linear primary alcohol C25E 3: c condensed with an average of 3 moles of ethylene oxide_12-15Branched primary alcohol C25E 5: c condensed with an average of 5 moles of ethylene oxide_12-15Branched primary alcohol coconut EO 2: R₁N⁺(CH₃)(C₂H₄OH)₂,R₁=C₁₂-C₁₄Soap: linear alkylcarboxylic acids from 80/20 tallow and coconut oil mixtures

Sodium TFAA: C₁₆-C₁₈Alkyl N-methylglucamides TPKFA: C₁₂-C₁₄Topping full-distillate fatty acids STPP: anhydrous sodium tripolyphosphate zeolite a: formula Na₁₂(AlO₂SiO₂)_12.27H₂Hydrated sodium aluminosilicate of O, primary particle

The particle size is 0.1-10 microns NaSKS-6: of the formula delta-Na₂Si₂O₅Citric acid, crystalline layered silicate of (2): anhydrous citric acid carbonate: particle size 200-900 μm anhydrous sodium carbonate bicarbonate: anhydrous sodium bicarbonate silicate with particle size distribution of 400-: amorphous sodium Silicate (SiO)₂∶Na₂O ratio =2.0) sodium sulfate: citric acid sodium sulfate anhydrideSalt: 86.4% active lemon with particle size distribution of 425 and 850 microns

Trisodium acid dihydrate PEA: polyethoxylated polyvinylamine Polymer MA/AA: 1: 4 maleic acid/acrylic acid copolymer having an average molecular weight of 70000PA 30: polyacrylic acid 480N with an average molecular weight of about 8000: 3: 7 acrylic/methacrylic acid having an average molecular weight of about 3500

Regular copolymer CMC: sodium carboxymethylcellulose protease: sold under the trade name Savinase by NOVO Industries A/S

The proteolytic enzyme Alcalase having an activity of 4 KNPU/g: having an activity of 3AU/g sold by NOVO Industries A/S

Proteolytic enzyme cellulase: sold under the name Carezyme by NOVO Industries A/S

A cellulose hydrolase amylase having an activity of 1000 CEVU/g: from NOVO Industries A/S under the trade name Termamyl 60T

A starch hydrolase lipase sold with an activity of 60 KNU/g: sold under the trade name Lipolase by NOVO Industries A/S

The activity of (a) is 100KLU/g of the lipolytic enzyme endonuclease: endoglucanase (Endoglucase) PB having an activity of 3000CEVU/g (Endoglase) sold by NOVO Industries A/S₄: nominally NaBO₂.3H₂O.H₂O₂Sodium perborate tetrahydrate PB of₁: nominally NaBO₂.H₂O₂Anhydrous sodium perborate bleach percarbonate: nominally of the formula 2Na₂CO₃·3H₂O₂Sodium percarbonate NOBS: nonanoyloxybenzene sulfonate in sodium salt form TAED: tetraacetylethylenediamine DTPMP: aEthyltriaminepenta (methylene phosphonate), commercially available from Monsanto

The name Dequest 2060 sells light-activated: sulfonated zinc phthalocyanine brightener encapsulated with a bleach-soluble dextrin polymer 1: 4,4 '-bis (2-sulfostyryl) biphenyl disodium brightener 2: 4, 4' -bis (4-phenylamino-6-morpholino-1, 3, 5-triazin-2-yl)

Amino) stilbene-2: 2' -disodium disulfonate HEDP 1, 1-hydroxyethane diphosphonic acid PVNO polyvinylpyridine N-oxide PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole SRA 1: sulfobenzoyl-terminated polymers bearing oxyethylene oxy and p-phenylene bis

Ester of acyl skeleton SRA 2: diethoxylated poly (1, 2-trimethylene terephthalate) short blocks

Polymeric polysiloxanes resist: the weight ratio of the foam control agent to the dispersing agent is

10∶1-100∶1

The following examples are intended to illustrate the invention, but not to limit or otherwise define the scope of the invention. All parts, percentages and ratios used herein are expressed in weight percent unless otherwise indicated.

In the following examples, all levels are expressed as% by weight of the composition.

Example I

The following are detergent formulations according to the invention.

aB C blown powder STPP 14.0-24.0 zeolite A10.024.04.0C 45AS 8.05.011.0 MA/AA 2.04.0-PEA 1.0-2.0 LAS 6.08.011.0 TAS 1.5- -coconut MeEO2^*1.51.02.0 silicate 7.03.03.0 CMC 1.01.00.5 brightener 20.20.20.2 soap 1.01.01.0 DTPMP 0.40.40.2 is sprayed with C45E72.52.52.0C25E32.52.52.0 polysiloxane antifoaming agent 0.30.30.3 perfume 0.30.30.3 dry additiveCarbonate 6.013.015.0 PB418.018.010.0PB14.04.00TAED 3.03.01.0 light activated bleach 0.020.020.02 protease 1.01.01.0 lipase 0.40.40.4 amylase 0.250.300.15 dry blended sodium sulfate 3.03.05.0 balance (water and minor components) to 100.0100.0100.0 density (g/l) 630670670 the bis-AQA-1 (coconut MeE02) surfactant of this example may be replaced with an equivalent amount of any of bis-AQA-2 to bis-AQA-22 surfactants or other bis-AQA surfactants herein.

Example II

The following bleach-free detergent formulations are particularly useful for washing colored garments.

D E F blown powdered zeolite A15.015.02.5 sodium sulfate 0.05.01.0 LAS 2.02.0-coconut MeEO2^*1.01.01.5 DTPMP 0.40.5-CMC 0.40.4-MA/AA 4.04.0-PEA- -4.0 agglomerates C45 AS- -9.0 LAS 6.05.02.0 TAS 3.02.0-silicate 4.04.0-Zeolite A10.015.013.0 CMC-0.5 MA/AA-2.0 carbonate 9.07.07.0 spray dried additive of spice 0.30.30.5 C45E74.04.04.0C25E32.02.02.0 MA/AA-3.0 NaSKS-6-12.0 citrate 10.0-8.0 bicarbonate 7.03.05.0 carbonate 8.05.07.0 PVPVI/PVNO 0.50.50.5 Alcalase 0.50.30.9 lipase 0.40.40.4 amylase0.60.60.6 cellulase 0.60.60.6 Silicone antifoam 5.05.05.0 Dry additive sodium sulfate 0.09.00.0 balance (water and minor ingredients) to 100.0100.0100.0 Density (g/l) 700700850 the bis-AQA-1 (coconut MeEO2) surfactant of this example can be replaced with an equivalent amount of any of bis-AQA-2 to-AQA-22 surfactants or other bis-AQA surfactants herein.

Example III

The following detergent formulations according to the invention were prepared.

Gah I blown powdered zeolite a 30.022.06.0Sodium sulfate 19.05.07.0 MA/AA 3.03.06.0 LAS 13.011.021.0C 45AS 8.07.07.0 coconut MeEO2^*1.01.01.0 silicate-1.05.0 soap- -2.0 whitener 10.20.20.2 carbonate 8.016.020.0 DTPMP-0.40.4 spray C45E71.01.01.0 dry additive PVPVI/PVNO 0.50.50.5 protease 1.01.01.0 lipase 0.40.40.4 amylase 0.10.10.1 cellulase 0.10.10.1 NOBS-6.14.5PB11.05.06.0 sodium sulphate-6.0-equilibria (water and minor components) to 100100100 the bis-AQA-1 (coconut MeEO2) surfactant of this example may be replaced by an equivalent amount of any of bis-AQA-2 to bis-AQA-22 or other bis-AQA surfactants herein.

Example IV

The following high-density and bleach-containing detergent formulations according to the invention were prepared:

j K L blown powdered zeolite a 15.015.015.0 sodium sulfate 0.05.00.0 LAS 3.03.03.0Coconut MeEO2^*1.01.51.5 DTPMP 0.40.40.4 CMC 0.40.40.4 MA/AA 4.02.02.0 agglomerate LAS 5.05.05.0 TAS 2.02.01.0 silicate 3.03.04.0 Zeolite A8.08.08.0 carbonate 8.08.04.0 spray perfume 0.30.30.3 C45E72.02.02.0C25E32.0- -Dry additive citrate 5.0-2.0 bicarbonate-3.0-carbonate 8.015.010.0 TAED 6.02.05.0 PB113.07.010.0MW5000000 polyethylene oxide- -0.2 Bentonite- -10.0 protease 1.01.01.0 Lipase 0.40.40.4 Amylase 0.60.60.6 cellulase 0.60.60.6 Silicone antifoam 5.05.05.0 Dry additive sodium sulfate 0.03.00.0 balance (Water and minor Components) to 100.0100.0100.0 Density (g/l) 850850850^*The bis-AQA-1 (coconut MeEO2) surfactant of this example was used in the same amount as bis-AQA-2Any surfactant to bis-AQA-22 or other bis-AQA surfactants herein.

Example V

The following high density detergent formulations according to the invention were prepared:

m N blown powdered zeolite A2.52.5 sodium sulfate 1.01.0 coconut MeEO2^*1.51.5 agglomerate C45AS 11.014.0 Zeolite A15.06.0 carbonate 4.08.0 MA/AA 4.02.0 CMC 0.50.5 DTPMP 0.40.4 sprayed with C25E55.05.0 spice 0.50.5 Dry additive HEDP 0.50.3 SKS 613.010.0 citrate 3.01.0 TAED 5.07.0 percarbonate15.015.0 SRA 10.30.3 protease 1.41.4 lipase 0.40.4 cellulase 0.60.6 amylase 0.60.6 polysiloxane antifoaming agent 5.05.0Whitening agent 10.20.2 whitening agent 20.2-balance (water and minor components) to 100100 density (g/l) 850850 the bis-AQA-1 (coconut MeEO2) surfactant of this example may be replaced with an equivalent amount of any of bis-AQA-2 to bis-AQA-22 surfactants or other bis-AQA surfactants herein.

Any of the granular detergent compositions provided herein can be made into tablets using known tableting processes to obtain detergent tablets.

The following examples a and B further illustrate the laundry bars of the present invention.

Example VI composition wt% range

A BC₁₂-C₁₈Sulfate 15.7513.500-25 LAS 6.75-0-25 Na₂CO₃15.00 3.00 1-20DTPP¹0.700.700.2-1.0 Bentonite-10.00-20 Sokolan CP-5²0.401.000-2.5 bis-AQA-1³2.00.50.15-3.0 TSPP 5.0000-10 STPP 5.0015.000-25 Zeolite 1.251.250-15 sodium laurate-9.000-15 SRA-10.300.300-1.0 protease-0.120-0.6 amylase 0.12-0-0.6 lipase-0.100-0.6 cellulase-0.150-0.3

The balance of⁴----------¹Diethylenetriamine penta (phosphonic acid) sodium salt²Sokolan CP-5 is a maleic acid-acrylic acid copolymer³The bis-AQA-1 may be replaced with equivalents of bis-AQA-2 to bis-AQA-22 surfactants or other bis-AQA surfactants herein.⁴The balance includes water (2% -8%, including water of hydration), sodium sulfate, calcium carbonate and other minor ingredients.

Example VII

The following hand wash detergent formulations according to the invention were prepared by mixing together the components in the weight percentages indicated below:

A B C DLAS 15.0 12.0 15.0 12.0TFAA 1.0 2.0 1.0 2.0C25E5 4.0 2.0 4.0 2.0AQA-9^*2.03.03.02.0 STPP 25.025.015.015.0 MA/AA 3.03.03.03.0 CMC 0.40.40.40.4 DTPMP 1.01.61.61.6 carbonate 2.02.05.05.0 bicarbonate- -2.02.0 silicate 7.07.07.07.0 protease 1.0-1.01.0 amylase 0.40.40.4-lipase0.120.12-0.12 photoactivated bleach 0.30.30.30.3 sulfate 2.22.22.22.2 PB14.05.44.02.3NOBS 2.63.12.51.7 SRA 10.30.30.70.3 brightener 10.150.150.150.15 balance minor component/water to 100.0100.0100.0100.0 AQA-9^*Any of the AQA surfactants described herein may be substituted. Preferred AQA surfactants for use in this embodiment are those having from 10 to 15 ethoxy groups; such as AQA-10, AQA-16.

The above examples illustrate the compositions of the present invention relating to the laundering of fabrics, while the following examples are intended to illustrate other types of cleaning compositions according to the present invention, but are not intended to be limiting thereto.

The following examples further illustrate shampoos of the invention.

EXAMPLE VIII component% (wt%) Range (wt%) bis-AQA-1^*1.50.5-3.0 ammonium lauryl sulfate 3.52.0-5.0C₁₂-C₁₄E0(3) sulfate 8.54.0-10.0 cetyl alcohol 0.450.3-1.5 PVP/VA¹4.00-6.0 Zinc pyrithione²1.00-1.5 sodium citrate 1.50-1.0 Permethrin^_30.450-1.0 polysiloxane⁴1.00-2.0 ethylene glycol distearate 3.00-4.0 water and minor components in balance^*The bis-AQA-2 to bis-AQA-22 surfactants or other bis-AQA surfactants herein may be used insteadAnd (4) replacing.¹Polyvinylpyrrolidone/vinyl acetate polymer (5/95).²According to US 4345080.³Anti-pediculosis agents available from Fairfield USA.⁴Polydimethylsiloxane, available from General Electric Company.

The following examples A and B further illustrate the present invention with respect to phosphate-containing granular automatic dishwashing detergents.

Example IX

% by weight of active substance component A BSTPP (anhydrous)¹4526 sodium carbonate-12 Zeolite 5.07.0 Silicate (SiO)₂％) 9 7Surfactant (nonionic) 31.5 NaDCC bleaching agent²2-bis-AQA-1^*0.51.0 sodium perborate 7.795 TAED-1.5 Co catalyst 0.20.2 PA 302.02.0 Savinase (Au/g) -0.04 Termamyl (Amu/g) 425 sulfate 2525 fragrance/minor component to 100%¹Sodium tripolyphosphate²Sodium dichloro cyanurate^*The bis-AQA-1 surfactants may be replaced by bis-AQA-2 to bis-AQA-22.

Example X

The following examples further illustrate the invention with respect to automatic dishwashing liquid-gels or other detergents having the benefit of increasing stain removal levels.

% by weight of active substance of component A B C DE F G citric acid 16.516.516.516.516.51010 Na₂CO₃/K₂CO₃- - -2525251515 bis-AQA-1^*0.50.70.50.50.40.60.748 ON 4444444 HEDP/SS-EDDS 220-2221.51.5 benzoyl peroxide 888881.51.5 butylated hydroxymethyl 0.050.050.050.050.050.050.05 Benzene (BHT) surfactant 2.52.51.51.51.51.51.5 boric acid-444444 sorbitol-666666 Savinase 24L- - -0.53-slurried- - -0.53Savinase 16 LMaxamyl/- -0.31-Termamyl slurried-0.31-Termamyl water-balance-the bis-AQA-1 (coconut MeEO2) surfactant of this example can be replaced with equivalents of any of bis-AQA-2 to bis-AQA-22 surfactants or other bis-AQA surfactants herein.

Various gelling agents such as CMC and clay may be used in the composition to provide varying viscosities or hardnesses according to the requirements of the formulator.

Example XI

The following illustrates bis-AQA surfactant mixtures which may be used in place of the bis-AQA surfactants listed in any of the above examples. As disclosed above, such mixtures can be used to provide various performance benefits and/or to provide cleaning compositions suitable for a wide variety of use conditions. Preferably, the bis-AQA surfactants in such mixtures differ by at least 1.5, preferably from 2.5 to 20 total EO units. The ratio of such mixtures (by weight) is generally in the range from 10: 1 to 1: 10. Non-limiting examples of such mixtures are as follows: the proportion (weight) of the components is bis-AQA-1 + bis-AQA-51: 1 bis-AQA-1 + bis-AQA-101: 1 bis-AQA-1 + bis-AQA-151: 2 bis-AQA-1 + bis-AQA-5 + bis-AQA-201: 1 bis-AQA-2 + bis-AQA-53: 1 bis-AQA-5 + bis-AQA-151.5: 1 bis-AQA-1 + bis-AQA-201: 3

It is also possible to use a mixture of the bis-AQA surfactants herein with the corresponding cationic surfactants containing only a single ethoxylated chain. Thus, for example, the invention may be used with the formula R¹N⁺CH₃[EO]_x[EO]_yX^-And R¹N⁺(CH₃)₂[EO]_zX^-In which R is a salt of a nonionic surfactant, in which R is a salt of a nonionic surfactant¹And X is as above, wherein one of the cationic surfactants has an (X + y) or z of 1 to 5, preferably 1 to 2, and the other cationic surfactant has an (X + y) or z of 3 to 100, preferably 10 to 20, most preferably 14 to 16. The composition is more than the single componentThe use of the cationic surfactants of the present invention advantageously provides improved wash performance (particularly in washing fabrics) over a wider range of water hardness. It has now been found that shorter EO cationic surfactants (e.g. EO2) improve the cleaning performance of anionic surfactants in soft water, while higher EOThe cationic surfactant (e.g., EO15) has the effect of improving the hardness resistance of anionic surfactants, thereby improving the cleaning performance of anionic surfactants in hard water. Conventional wisdom in the art of washing suggests that builders can optimize the performance "window" of anionic surfactants. However, to date, it has not been possible to extend the window to include substantially all water hardness conditions.

Example XII

This example illustrates a perfume formulation (a-C) prepared according to the present invention for incorporation into any of the above examples of bis-AQA containing detergent compositions. The various components and amounts are listed below:

(wt%) perfume component A B C hexylcinnamaldehyde 10.0-5.02-methyl-3- (p-tert-butylphenyl) propanal 5.05.0-7-acetyl-1, 2,3,4,5,6,7, 8-5.010.010.0 benzyl octahydro-1, 1,6, 7-tetramethylnaphthalenylsalicylate 5.0-7-acetyl-1, 1,3,4,4, 6-hexamethyl 10.05.010.0 yl 1,2,3, 4-tetrahydronaphthaleneacetic acid p- (tert-butyl) cyclohexyl ester 7-dihydrojasmonic acid methyl ester-5.0- β -naphthylmethyl ether-0.5-methyl β -naphthalenone-0.5-2-methyl-2- (p-isopropylphenyl) -propan-2.0-al 1,3,4,6,7, 8-hexahydro-9.5-4, 6,6,7,8, 8-hexamethylcyclopenta- γ -2-benzopyran-dodecahydro-3 a,6,6, 9-methyl-3, 6,7, 8-hexahydronaphthoic acid methyl ester-2- (p-isopropylphenyl) -propan-2.0-aldehyde 1,6, 6,6, 8, 8-hexahydrocinnamyl alcohol ester-cinnamyl alcohol acetate-2, cinnamyl alcohol ester-cinnamyl alcohol-3, 6,6, 8-hexahydro-methyl-2-cinnamyl alcohol ester-methyl-2-cinnamyl alcohol ester-ethyl-2-ethyl-2-ethyl-3, 3-ethyl-cinnamyl alcohol ester-ethyl-5-cinnamyl alcohol ester-ethyl-3, 3-ethyl-cinnamyl alcohol ester-ethyl-cinnamyl alcohol-3, 3-ethyl-5-2-ethyl-5-ethyl

The above perfume compositions are blended or sprayed (typically at levels up to about 2% by weight of the total detergent composition) into any cleaning (including bleaching) compositions containing the bis-AQA surfactants disclosed herein. Improved deposition and/or retention of the perfume or individual components thereof on the surface being cleaned (or bleached) is thus obtained.

Claims (20)

1. A composition comprising or prepared from a combination of: a soil dispersant polymer, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula:

wherein R is¹Is straight-chain, branched or substituted C₈-C₁₈Alkyl, alkenyl, aryl, alkaryl, ether or glycosyl ether moieties, R²Is C₁-C₃Alkyl moiety, R³And R⁴Independently variable and selected from hydrogen, methyl and ethyl, X is an anion, A and A' independently variable and are each C₁-C₄Alkoxy, p and q can vary independently and are integers from 1 to 30.

2. A composition according to claim 1 wherein said soil dispersant polymer is an ethoxylated polyamine.

3. A composition according to claim 1 or 2 wherein said soil dispersant polymer is a polyethoxylated polyvinylamine polymer.

4. A composition according to any of claims 1 to 3, further comprising a builder component.

5. A composition according to any of claims 1 to 4 wherein the builder is selected from inorganic builders, aluminosilicates, layered silicates or phosphate builders.

6. A composition according to any of claims 1 to 5 which is prepared by mixing the non-AQA surfactant with the AQA surfactant.

7. A composition according to any of claims 1 to 6 wherein the non-AQA surfactant is an anionic surfactant.

8. A composition according to any of claims 1 to 7 wherein the ratio of bis-AQA to non-AQA surfactant is from 1: 15 to 1: 8.

9. A composition according to any of claims 1-8, wherein said bis-AQA surfactant has the formula wherein R¹Is C₈-C₁₈Alkyl radical, R²Is methyl, A and A' are ethoxy or propoxy, and p and q are each an integer of 1 to 8.

10. A composition according to any of claims 1-9, wherein said bis-AQA surfactant has the formula wherein R¹Is C₈-C₁₈Alkyl radical, R²Is methyl, A and A' are ethoxy or propoxy, and p and q are each an integer of 1 to 4.

11. A composition according to any of claims 1 to 10 wherein the bis-AQA cationic surfactant formula wherein p and/or q is an integer from 10 to 15.

12. A composition according to any of claims 1 to 11 comprising two or more bis-AQA surfactants or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant.

13. A composition according to any of claims 1 to 12 comprising a mixture of two or more non-AQA surfactants and two or more bis-AQA surfactants.

14. A composition according to any of claims 1 to 13, which is in the form of granules, bars, aqueous liquid or non-aqueous liquid or tablets.

15. A method for removing soils and stains by contacting said soils and stains with a detergent composition according to any of claims 1 to 14 or an aqueous medium comprising said detergent composition.

16. A method according to claim 15 for removing builder sensitive soil from fabric.

17. A method according to any of claims 14-16, which is carried out in an automated machine.

18. A method according to any of claims 14 to 17, which is carried out manually.

19. A method for enhancing the deposition or substantivity of perfumes or perfume ingredients onto fabrics or other surfaces comprising contacting said surfaces with a perfume or perfume ingredient in the presence of a bis-AQA surfactant.

20. A method according to claim 19 which is conducted using a perfume or perfume ingredient in combination with a detergent composition comprising a bis-AQA.