CN1259993A - Detergent compositions - Google Patents

Abstract

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

Description

Detergent composition

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 loosen and remove different types of soils and stains. The study of the existing literature appears to indicate that detergent manufacturers can choose a wide range of surfactants and surfactant combinations, but in fact many of these components are specialty chemicals which are not suitable for low unit consumer products 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 food stains can be problematic. Such soils comprise a mixture of hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous substances and are therefore notoriously difficult to remove. Further problems encountered are lime soap deposits; insoluble hard ion salts of fatty acids (e.g., Ca) resulting from degradation of triglyceride soils²⁺/Mg²⁺). After washing, low levels of hydrophobic soils, residual stains and lime soap deposits often remain on the fabric surface.Constant washing and wear coupled with limited removal of soils, stains and deposits, they build up on fabrics over multiple washes, they further entrap dirty 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 in the form of amino-, amido-or quaternary ammonium salts or imidazole compounds, which are generally designed for specific uses. For example, various amino and quaternary ammonium surfactants have been suggested for use in shampoo compositions, said to provide a cosmetic effect to the hair. Other nitrogen-containing surfactants are used in some laundry detergents to provide fabric softening and antistatic effects. However, for the most part, the commercial use of such 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 and 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 various types of soils and stains, especially hydrophobic types of soils and lime soap deposits, which are commonly encountered. The bis-AQA surfactants of the present invention provide significant benefits to formulators over previous cationic surfactants 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 a 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 easily controllable in the production facility. bis-AQA surfactants having a degree of ethoxylation above 5 are sometimes present in liquid form and can therefore be provided as 100% pure 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.

It has also been found that compositions containing a soil dispersant polymer and a bis-AQA surfactant provide additional superior cleaning and whiteness performance, particularly enhanced cleaning performance on soil/mud soils as well as soils found on socks, than products containing either component alone. Polymeric dispersants enhance overall detergency by crystal growth inhibition, peptization to release particulate soils, anti-redeposition, and soil solubilization. While not wishing to be bound by theory, it is believed that the effect of the bis-AQA/soil dispersant polymer system is a result of: (1) the action of AQA on the stained surface reduces the formation of calcium soaps and removes any calcium soaps present, thereby promoting improved polymer deposition; (2) AQA provides deep soil solubilisation whilst the polymer acts as a "grease removal carrier", stripping the AQA solubilised soil components and dispersing them into the aqueous wash liquor.

Background

US5441541 granted on 8/15/1995 to a.mehretab 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.

None of the prior art provides all of the advantages and benefits of the present invention.

Summary of The Invention

The invention provides a composition, which comprises the following components or is prepared by mixing the following components: a soil dispersant polymer, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant having the formula:

wherein R is¹Is straight-chain, branched or substituted C₈-C₁₈Alkyl, alkenyl, aryl, alkaryl, etherOr sugar alcohol 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-C₄The alkoxy groups, p and q can vary independently and are integers from 1 to 30, wherein the weight ratio of the bis-AQA to the soil dispersant polymer ranges from about 1: 11 to about 1: 14.

These and other features, objects, and advantages of the present invention will become apparent to those skilled in the art from a reading of the present disclosure.

Detailed Description

While the specification concludes with claims particularly pointing out and distinctly claiming the invention, it is believed that the present invention will be better understood from the following description.

All percentages are by weight of the total composition, unless otherwise specifically indicated. All proportions are by weight unless specifically stated otherwise. As used herein, "comprising" means that other steps and other components that do not affect the end result can be added, and the term includes the terms "consisting of … …" and "consisting essentially of … …".

All documents cited are incorporated herein by reference in their entirety. None of the documents cited allow any definition to be seen as available from the prior art of the present invention.

It has surprisingly been found that compositions containing a soil dispersant polymer and a bis-AQA surfactant in specific proportions provide additional superior cleaning and whiteness performance, particularly in soil/mud soils and in sock soils, to promote cleaning performance, over products containing either component alone. This surprising advantage is apparent when the weight ratio of bis-AQA to soil dispersant polymer is in the range of from about 1: 11 to about 1: 14, preferably from about 1: 12 to about 1: 13.

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 5% to 20%, preferably from 10% to 15%, more preferably from 13% to 14% by weight of the composition of the present invention. Preferred dispersants for use in the present invention include polymeric polycarboxylates.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, particularly 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 of the present invention, the presence of a monomeric moiety containing a non-carboxylate group such as vinylmethyl ether, styrene, ethylene, or the like, is also suitable, provided that the moiety does not constitute more than 40% by weight.

Particularly suitable polymeric polycarboxylates can be derived from acrylic acid. Such acrylic acid-based polymers that may be used in the present invention are water-soluble salts of polyacrylic acid. The average molecular weight of such polymers in 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 materials. The use of such polyacrylates in detergent compositions is disclosed in US3308067 to Diehl, granted 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 acid form is preferably 2000-100000, more preferably 5000-75000, and most preferably 7000-65000. In such copolymers, the ratio of acrylate to maleate moieties 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. Soluble acrylate/maleate copolymers of this type are known from European patent application EP66915, published 12/15 1982, and also from European patent application EP193360, published 9/3 1986, which also describes polymers of this type comprising hydroxypropyl acrylate. Other useful dispersants include maleic/acrylic/vinyl alcohol terpolymers. This material is also disclosed in EP193360 and includes, for example, the acrylic/maleic/vinyl alcohol terpolymer of 45/45/10.

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 having the formula:wherein R is¹Is a straight, branched or substituted alkyl, alkenyl, aryl, alkaryl, ether or sugar radical containing from 8 to 18 carbon atoms, preferably from 8 to 16 carbon atoms, most preferably from 8 to 14 carbon atoms, more preferably from 1 to 8, even more preferably from 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, especially 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 0.3% to 4%, preferably from 0.5% to 2%, more preferably from 0.8% to 1.2% by weight. As noted above, the weight ratio of the bis-AQA surfactant to the soil dispersant polymer is from about 1: 11 to about 1: 14, preferably from about 1: 12 to about 1: 13.

The weight ratio of bis-AQA surfactant 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 soil soils, the formulator will use sufficient bis-AQA in the composition to at least directionally improve cleaning performance against such soils.

The bis-AQA surfactants may be used in combination with other detersive surfactants in amounts effective to achieve at least a directional improvement in cleaning performance. This "amount of application" 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, U.S. type 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 aqueous wash solution preferably includes from 2ppm to 50ppm, preferably from 5ppm to 25ppm, of the bis-AQA surfactant. 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 ("compact") 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. "puffy"; 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 aqueous 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 ("compact") 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 140g to 400g per load.

For example, in a top-loading vertical axis Japanese automatic washing machine using 26 to 52 liters of water in the wash bath, with wash cycles 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 aqueous 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, calculated as 20ml to 30ml per wash load. For compact ("compact") 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, and the type of washing machine. In this context, however, one previously unrecognized advantage of bis-AQA surfactants is their ability to provide at least directionally improved cleaning performance over a range of soils and stains, even when used in relatively low amounts relative to other surfactants (typically anionic or anionic/nonionic mixtures) in the finished composition. This is different from other compositions of the prior art, where various cationic and anionic surfactants are used in 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 specific surfactants such as betaines, sultaines, amine oxides, and the like, can also be formulated in the manner of this invention using an effective amount of the bis-AQA surfactants. 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. Due to the subtle differences in the habits and experiences of 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 the bis-AQA surfactant to the other surfactants present in such compositions is low, i.e., is a sub-stoichiometric amount compared to the anionic surfactant. Preferably such cleaning compositions comprise the bis-AQA/surfactant ratios just described above for the laundry compositions for machine use.

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: conventional designs are used in top-loading automatic washing machines, particularly for detergent compositions of the type used in north america and under japanese use conditions. Generally, such compositions comprise anionic surfactant to nonionic surfactant in a weight ratio in the range of 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 anionic to nonionic surfactant in a ratio in the range of about 10: 1 to 1: 10, preferably about 5: 1 to 1: 1.

Preferred ethoxylated cationic surfactants of the present invention are available from Akzo Nobel Chemicals Company under the tradename ETHOQUAD. Alternatively, such materials may 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 summarize the optional and preferred reaction conditions of scheme 5. Step 1 of the reaction is preferably carried out in an aqueous medium. The reaction temperature is generally 140 ℃ to 200 ℃. The reaction pressure is 50-1000 lb/in². A base catalyst, preferably sodium hydroxide, may be used. The molar ratio of reactant amine to alkyl sulfate is from 2: 1 to 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 reactants.

In some cases, scheme 5 produces a product that can form a gel sufficiently soluble in the aqueous reaction medium. While the desired product can be recovered from the gel, an additional two-step synthetic route 6 below may be more desirable in certain commercial 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 100-230 ℃. The reaction pressure is 50-1000 lb/in². Alkali, preferably sodium hydroxide, may be used with the HSO produced during the reaction₄The reaction may alternatively be carried out using an excess of amine to react with the acid. 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 is simply separated from the aqueous reaction medium as a distinct phase in which it is insoluble. The second step of the process is carried out under conventional reaction conditions. Further ethoxylation and quaternization to give the bis-AQA surfactants was 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 one of an inorganic base, an organic base or an excess of amine reactant₄。

Route 6

Route 7

The following also illustrates several of the above reactions, merely for the convenience of the formulator and is not meant to limit them.

Synthesis A

Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

To a glass autoclave liner were added 19.96g of sodium dodecyl sulfate (0.06921 moles), 14.55g of diethanolamine (0.1384 moles), 7.6g of 50 wt% 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 liquid contained in the glass liner was 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.

Synthesis of B

Preparation of N, 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.

Synthesis C

Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

To a glass autoclave liner were added 19.96g of sodium lauryl sulfate (0.06921 moles), 21.37g of ethanolamine (0.3460 moles), 7.6g of 50 wt% 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 liquid contained in the glass liner was 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 absence 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 will be appreciated that the degree of alkoxylation of the bis-AQA surfactants described herein is reported as an average value, and the following are common examples of conventional ethoxylated nonionic surfactants. This is because ethoxylation generally produces mixtures of materials having different degrees of ethoxylation. Thus, the total EO values are generally reported rather than integer values, e.g., "EO 2.5", "EO 3.5".Name R¹R²ApR³A’qR⁴bis-AQA-1 (also known as coconut methyl EO2) C₁₂-C₁₄CH₃EO bis-AQA-2C₁₂-C₁₆CH₃(EO)₂EO bis-AQA-3 (coconut methyl EO4) C₁₂-C₁₄CH₃(EO)₂(EO)₂bis-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-13C₁₀C₁₈CH₃(EO/PO)₂(EO)₃bis-AQA-14C₈-C₁₈CH₃(EO)₁₅ ^*(EO)₁₅ ^*bis-AQA-15C₁₀CH₃EO bis-AQA-16C₈-C₁₂CH₃EO bis-AQA-17C₉-C₁₁CH₃Average EO3.5 bis-AQA-18C₁₂CH₃Average EO3.5 bis-AQA-19C₈-C₁₄CH₃(EO)₁₀(EO)₁₀bis-AQA-20C₁₀C₂H₅(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 radicals and mixtures thereofX is any suitable anion providing 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' pR⁴Are both monoethoxy groups, and therefore this preferred type of compound is referred to herein as "coconut methyl EO 2" or "bis-AQA-1" in the above list.

Other useful bis-AQA surfactants of the present invention include compounds of the formula:

wherein R is¹Is C₈-C₁₈Hydrocarbyl, preferably C₈-C₁₄Alkyl, independently p is 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]Those in which the units (i-Pr) or the n-propoxy units (Pr) or mixtures of EO and/or Pr and/or i-Pr units are substituted.

Highly preferred bis-AQA compounds for use in the formulated formulations are those in which p and/or q are integers in the range of 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 the present invention, typically used in amounts of 1% to 55% by weight, include: conventional C₁₁-C₁₈Alkyl benzene sulfonic acidSalts ("LAS") and branched primary ("AS") 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-soluble cation, especially sodium, unsaturated sulfates such as oleyl sulfate, C₁₂-C₁₈a-sulfonated fatty acid ester, C₁₀-C₁₈Sulfated alkylpolyglycoside, C₁₀-C₁₈Alkyl alkoxy sulfates ("AExS"; especially EO1-7 ethoxy sulfate), C₁₀-C₁₈Alkyl alkoxy carboxylates (especially EO1-5 ethoxy carboxylate). C₁₂-C₁₈Betaines and sulfobetaines, C₁₀-C₁₈Amine oxides may also be included in the overall composition. Can also be usedC₁₀-C₂₀Conventional soaps. If high foaming is desired, a branched chain C may be used₁₀-C₁₆Soap. Other conventional useful 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. Preference is given to condensation products of alcohols having an alkyl radical having from 8 to 20 carbon atoms, more preferably from 10 to 18 carbon atoms, with from 1 to 10 mol, preferably from 2 to 7 mol, most preferably from 2 to 5 mol, of ethylene oxide per mole of the alcohol. Examples of 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(C₁₃-C₁₅Condensation products of alcohols with 9 mol of ethylene oxide) 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 amides having 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 -17}Alkyl or alkenyl groups such as coconut oil alkyl or mixtures thereof, and 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 acids may also be usedAn amine; 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 of 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, and a polysaccharide (e.g., 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 the glycosyl moiety may be substituted with glucose, galactose and galactosyl moieties (the hydrophobic group optionally being attached at the 2-, 3-, 4-, etc. position, thereby 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 the glucoside (attachment at the 1 position). The additional glycosyl units can then be linked betweentheir 1-position and the 2-, 3-, 4-and/or 6-position of the preceding glycosyl unit, preferably predominantly between the 2-positions.

Polyethylene oxide, polypropylene oxide and polybutylene oxide condensation products of alkyl phenols are also suitable for use as the nonionic surfactant in the surfactant systems of the present invention, with 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 linear or branched configuration with alkylene oxides. In a preferred embodiment, the amount of ethylene oxide present per mole of alkylphenol is equal to 2 to 25 molesAnd 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. TheseSurfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkylphenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic group formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the other nonionic surfactants of the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of 1500 to 1800 and exhibits water insolubility. The addition of polyoxyethylene moieties to the hydrophobic portion tends to increase the water solubility of the overall molecule and at a polyoxyethylene content of 50% of the total weight of the condensation product, the liquid character of the product is maintained, which corresponds to condensation with up to 40 moles of ethylene oxide. Examples of this type of compound include some commercially available pluronics^TMSurfactant, sold by BASF.

Also suitable for use as thenonionic 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 that the 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^TMCompound, sold by BASF.

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 in which the remaining N positions are substituted with methyl, hydroxyethyl or hydroxypropyl groups. 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 act by a variety of mechanisms, including by ion exchange to form soluble or insoluble complexes with hardness ions and by providing a surface that is more suitable for precipitating hardness ions 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 a chain structure, a layer structure, or a three-dimensional structure, 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 tetracarboxylic acid salts, especially water-soluble, non-surfactant carboxylates in the acid, sodium, potassium, or alkanolammonium form, as well as oligomeric or water-soluble low molecular weight polymeric carboxylates, including aliphatic and aromatic types; and phytic acid. Also to be complemented are e.g. borates for pH-buffering purposes, or sulfates, especially sodium sulfate, and any other filler or carrier important for producing detergent compositions containing stable surfactants and/or builders.

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 in the range of from 0.90: 1.0 to 4.0: 1.0, more preferably in the range of from 0.95: 1.0 to 3.0: 1.0.

When permitted by legislation, phosphorus-containing detergent builders are often preferred, 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, the solid hydrated silicate having a ratio of 2 for automatic dishwashing purposes, sold by PQ company under the trade name BRIISI^_E.g. BRIIESIL H₂O; and layered silicates such as those described in US4664839 issued on 12.5.1987 to h.p. rieck. 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-3742043A preparation method. Other phyllosilicates, e.g. those of the general formula NaMSi_xO_2x+1·yH₂Layered silicates of O, in which M is sodium or hydrogen, x has a value of 1.9 to 4, preferably 2, y is 0 to 20Layered silicates available from Hoechst alsoinclude 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, 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, granted on month 6, 1995, 27.

Suitable carbonate builders include the alkali metal and alkaline earth metal carbonates as disclosed in German patent application 2321001 published on 11/15/1973, but sodium bicarbonate, sodium carbonate, sodium sesquicarbonate and other carbonate minerals such as trona, or any suitable double salt of sodium carbonate with calcium carbonate, for example having a composition of 2Na when anhydrous₂CO₃.CaCO₃And even calcium carbonates including calcite, aragonite and vaterite, particularly those of the type having a high surface area relative to dense calcite, are also 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_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 preparing aluminosilicates is disclosed in U.S. Pat. No.3,137,669 to Krummel et al, issued 10/12/1976. Preferred synthetic crystallinealuminosilicate ion exchange materials may be prepared from zeolite A, zeolite P (B),Zeolite X and so-called zeolite MAP (which differs to some extent from zeolite P) are commercially available. Natural types, including clinoptilolite, may also be used. Zeolite a has the formula:

Na₁₂[(AlO₂)₁₂(SiO₂)₁₂].xH₂o, wherein x is 20 to 30, especially 27. Dehydrated zeolites (x ═ 0 to 10) can 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, neutral 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 taught by Berg, U.S. patent No. 3128287, issued 1964, month 7, and Lamberti et al, U.S. patent No. 3635830, issued 1972, month 1, 18; "TMS/TDS" builders and other ether carboxylates, including cyclic and alicyclic compounds, as disclosed in U.S. Pat. No. 5,5,071 to Bush et al, 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; carboxymethyloxysuccinic acid; various alkali metal, ammonium and substituted ammonium salts of polyacetic acids, such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, aswell as mellitic acid, succinic acid, polymaleic acid, benzene-1, 3, 5-tricarboxylic acid, carboxymethyloxysuccinic 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, because of 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, hydroxyiminodisuccinates, and methylglycine diacetate are also particularly useful in these compositions and mixtures.

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. Examples of preferred types having a builder function are: 3, 3-dicarboxy-4-oxa-1, 6-hexanedioic acid salt and related 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, issued 11/5 in 1986. Fatty acids, e.g. C₁₂-C₁₈The monocarboxylic acids may also be used as surfactant/builder substances alone or in combination with the above-mentioned builders, in particular citrate and/or succinate buildersIncorporated into the compositions of the present invention to provide additional builder activity. Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,44226 to Crutchfield et al, granted on 3/13 1979, and U.S. Pat. No. 3308067 to Diehl, granted on 3/7 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_iThe valence of) +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. The effect of the charge or valence of such anions 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 in their simplest form of this type are selected from Na₂Ca(CO₃)₂、K₂Ca(CO₃)₂、Na₂Ca₂(CO₃)₃、NaKCa(CO₃)₂、NaKCa₂(CO₃)₃、K₂Ca₂(CO₃)₃And mixtures 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: acalcitonite, uraninite, kainite Y, cannibalite, colemanite, strontianite, monocalcite, cancrinite, kenyaite, canasite, kacrinite, strontianite Y, kalium-calcite, Ferrisurite, kakainite, monetite, monocalcite, Girvasite, ilmenite, manganite, Kamphaugite Y, procalcite fluorocarbon, Khanneshite, Lepersonnite Gd, eucrytite, bariumenite Y, eucryptite, tellurite, nycite, nycamnesite, nystovite, Remondite Ce, sacalcite, uraniniteCaldotite, silphite, dawsonite, kalsilite, sepiolite, cancrinite and Zemkorite. Preferred mineral forms include nesquehonite, kallmatite and canasite.

Bleaching agent

The compositions described herein may comprise 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 organic peroxyacid is generated by the in situ reaction of a bleach activator with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include inorganic perhydrate bleaches. In another preferred aspect, 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, the excellent bleaching power lies in the peracid formed from the reaction of the hydrogen peroxide released by the perhydrate and the bleach activator. Preformed peracids are also contemplated as preferred peroxygen 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 salt may be incorporated as a crystalline solid without additional protection. However, for certain perhydrate salts, a preferred embodiment of the particulate composition employs a coated form of the material to provide said perhydrate salt with good storage stability in the particulate product.

Sodium perborate may be of nominal formula NaBO₂H₂O₂NaBO monohydrate or tetrahydrate₂H₂O₂·3H₂In the form of O.

Alkali metal percarbonates, particularly sodium percarbonate, are preferred for inclusion in the compositions of the inventionThe perhydrate of (a). Sodium percarbonate having a structure corresponding to 2Na₂CO₃·3H₂O₂The addition compounds of (a), which are commercially available in crystalline solid form. Sodium percarbonate, i.e. a hydrogen peroxide addition compound, tends to release hydrogen peroxide quite rapidly on dissolution, which may increase the tendency to produce local high bleach concentrations. Preferred percarbonate bleaching agents comprise dry particles having an average particle size in the range of 500-1000 microns, not more than 10% by weight of the particles being less than 200 microns and not more than 10% by weight of the particles being greater than 1,250 microns.

The percarbonate is most preferably incorporated into such compositions in 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 previously been described in GB-1466799 to Interox on 3/9 of 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.Na₂CO₃Wherein 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 acid 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 U.S. patent No. US4483781 to Hartman, issued on 20/11/1984, U.S. patent application 740446 to Burns et al, issued on 3/6/1985, european patent application 0133354 to Banks et al, issued on 20/2/1985, and U.S. patent No. US4412934 to Chung et al, issued on 1/11/1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxo-peroxyhexanoic acid as described in U.S. patent No. 4,34551 to Burns et al, 6.1.7.

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

Potassium peroxymonopersulfate is another inorganic perhydrate salt useful in the compositions of the present 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. When present, the amount of bleach activator is typically from 0.1% to 60%, more typically from 0.5% to 40% of the bleaching composition comprising bleach plus bleach activator.

Peroxygen bleaches, perborates, etc. are preferably combined with bleach activators, which result in the in situ generation of a 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 alkaryl group containing from 1 to 10 carbon atoms, and L is any suitable leaving group. The leaving group being displaced from the bleach activator as a result of nucleophilic attack of the perhydrolyzed anion on the bleach activatorAny group. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators of the above formula include (6-octanoylamino-hexanoyl) oxybenzene-sulfonate, (6-nonanoylamino hexanoyl) oxybenzene-sulfonate, (6-decanoylamino-hexanoyl) oxybenzene-sulfonate, and mixtures thereof, as described in U.S. patent No. 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 having from 1 to 12 carbon atoms. Highly preferred lactam activators 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 granted on 8/10/1985Sanderson, U.S. Pat. No. 4,45784, incorporated herein by reference, discloses acyl caprolactams, including benzoyl caprolactam, which are 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 catalyzed by a manganese compound. Such compounds are well known in the art and include, for example, those described in US5246621, US5244594, US5194416, US5114606 and European patent applicationPlease disclose manganese-based catalysts disclosed in 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. The use of manganese with various complex ligands for improving bleaching is also reported 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", higher inorganic bio-inorganic mechanisms (adv.inorg. bio inorg. 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, 22-25 (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 wash aqueous 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 aqueous wash solutions for automatic dishwashing processes, 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 to achieve various cleaning purposes, including removal of protein-, carbohydrate-or triglyceride-based stains from substrates, and to avoid dye transfer by shedding during fabric washing, and for fabric restoration. 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, 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 provides a cleaning, stain removal, soil removal, whitening, deodorizing or rejuvenating benefit to 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. In other words, the compositions of the present invention 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 in an amount 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 results. 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. A 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, hereinafter referred to as "Novo" and used as ESPERASE^_And (5) selling. The preparation of this and similar enzymes is described in British patent Specification GB1243784 to Novo. It is composed ofOther 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 130756A on 9/1/1985. See also the high pH protease from bacillus NCIMB40338 described in WO9318140A to Novo. 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&A protease with reduced adsorption and increased hydrolysis can be obtained as described in WO9507791 from company G. Trypsin-like recombinant proteases suitable for detergents according to the invention are described in WO9425583 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 derived from a carbonyl hydrolase precursor, which derivative is based on Bacillus amyloliquefaciens subtilisin numbering, and which preferably also incorporate substitution of various amino acid residues at positions in the carbonyl hydrolase corresponding to +76, at positions corresponding to one or more amino acid residues selected from the group consisting of +99, +101, +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, with different amino acids, as in the A.Baeck et al patent application having U.S. patent application Ser. No. 08/322676, entitled "cleaning compositions containing proteases",Baeck et al, and c.ghosh et al, having U.S. patent application serial No. 08/322677 entitled "protease-containing bleaching composition", both of which were filed on day 10, 13 of 1994.

Amylases suitable for the present invention, particularly for, but not limited to, automatic dishwashing purposes, include, for example, the British patent Specification in Novoα -amylase described in GB 1296839;RAPIDASE from 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 (J.BiologcalChem.), 260, 11, 6.1985, 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^_The preferred amylases of the present invention have at least one measurable improvement in oxidative stability, e.g., stability to hydrogen peroxide/tetraacetylethylenediamine in a buffered solution at pH9-10, thermal stability, e.g., at a temperature of 60 ℃ at typical washing temperatures, or alkaline stability, e.g., at a pH of from 8 to 11, as determined by comparison with the reference point amylase identified above, the stability being determined using any of the experimental techniques disclosed in the prior art, see, e.g., the reference document disclosed in WO 94597Methionine residue, which is known as TERMAMYL^_Or a homologous position variant of a similar parent amylase, such as Bacillus amyloliquefaciens, Bacillus subtilis, or 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, dated 13-17, 1994, under the title "antioxidant α -amylase", wherein it is noted that bleach in automatic dishwashing detergents inactivates the α -amylase, but an amylase that improves oxidative stability has been obtained by Genencor from Bacillus licheniformis NC8061 methionine (Met) was identified as the most likely residue to be improved, Met was substituted one at a time at positions 8, 15, 197, 256, 304, 366, and 438, importantly specific mutants, particularly M197L and M197T, wherein M197T is the most stably expressed variant.Measure CASCADE^_And SUNLIGHT^_Stability; (c) particularly preferred amylases in the present invention include amylase variants having other modifications in the immediate matrix as described in WO9510603A, which may be DURAMYL from Novo of the assignee^_And (4) purchasing. Other particularly preferred oxidative stability-enhancing amylases include those described in WO9418314 to Genencor International and WO9402597 to Novo. Any other oxidative stability-enhanced amylase may be used, e.g., derived by site-directed mutagenesis from commercially available known chimeric, mixed or simple mutant parent forms of amylase. Other preferred enzyme modifications are acceptable. See WO9509909A to Novo.

Other amylases include those described in WO95/26397 and Novo Nordisk, pending application PCT/DK 96/00056. Specific amylases useful in the detergent compositions of the invention include alpha-amylases, characterized by passage through Phadebas^_a-amylase activity assay having a specific activity greater than Termamyl at 25 ℃ -55 ℃ and a pH in the range of 8-10^_At least 25% of the specific activity. (this Phadebas)^_a-Amylase Activity assay is described in WO95/26397, pages 9-10). The present invention is also included in the referenceAlpha-amylases with at least 80% homology of the amino acid sequences shown in the SED ID lists in the literature. These enzymes are preferably incorporated in the laundry detergent composition at levels 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. 4,3,6,307 issued to Barbesgord et al, 1984, discloses suitable mold cellulases from Humicola insolens or Humicola strain DSM1800 or a mold belonging to the genus Aeromonas that produces cellulase 212, and cellulases 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 WO9117243 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, lipases from Chromobacter viscosum, e.g., the variant of Chromobacter viscosumHeteropolyticum NRRLB 3673 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. Lipolase derived 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 WO9414951A to Novo. See also WO9205249 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 so far been found to be widely used as additives for fabric washing products. As mentioned above, it is available from Novo Nordisk under the trade name Lipolase^TMAnd (4) obtaining the product. To maximize the stain removal performance of Lipolase, Novo Nordisk has made many variants. As described in WO92/05249, the D96L variant of the native Humicola lanuginosa lipase increased the efficiency of lard removal by a factor of 4.4 compared to the wild-type lipase (enzymes compared in the range of 0.075-2.5mg protein per liter). It is disclosed by Novo Nordisk 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/l) 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 WO8809367A to Genencor.

Peroxidases may be used in conjunction with oxygen sources, e.g., percarbonates, perborates, hydrogen peroxide, etc., which are used to "solution bleach" or to prevent dyes or pigments dislodged from the substrate during the wash process from migrating to other substrates present in the wash solution. Known peroxidases include horseradish peroxidase, ligninase, and haloperoxidase such as chloro-or bromo-peroxidase. Detergent compositions containing peroxidase are disclosed in WO89099813A published by Novo on 10/19 of 1989 and WO8909813A by Novo.

Various enzymatic materials and methods for their incorporation into synthetic detergent compositions are also disclosed in WO9307263A and WO9307260A by Genencor International, WO8908694A by Novo, and U.S. Pat. No. 5,35 to McCarty et al, 1971. Some enzymes are also disclosed in Place et al, US4101457, issued on 7/18 1978, and in Hughes, US4507219, issued on 3/26 1985. Enzymatic materials for use in liquid detergent formulations, and methods for their incorporation into these formulations, are disclosed in US4261868 to Hora et al, issued 4/14 in 1981. Enzymes used in detergents can be stabilized by various techniques. Enzyme stabilization techniques are disclosed and exemplified in U.S. Pat. No. 4,17,1971 issued to Gedge et al, US3600319, EP199405, and European patent EP200586 to Venegas, published 10/29 1986. Enzyme stabilization systems are also described, for example, in US patent No. US 3519570. Useful bacillus AC13 producing proteases, xylanases and cellulases is described in WO9401532A by 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%, most 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, although the level may vary depending on, among other factors, the variety, type and level of enzyme species 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 species. See U.S. Pat. No. 4,310,706 to Severson. When used, borate stabilizers may be present in amounts up to 10% or more of the composition, but for use in liquid detergents, boric acid or other borate compounds such as borax or orthoborate are more typically present in amounts up to about 3% by weight. Substituted boronic 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. Although the level of chlorine in water may be very small, typically in the range of 0.5ppm to 1.75ppm, the amount of chlorine available in the total volume of water that is contacted with the enzyme, for example, in dishwashing or fabric laundering, may be relatively large; therefore, in use, there is sometimes a problem in the stability of the enzyme to chlorine. Due to the percarbonate's ability to react with chlorine bleach, it is most often not necessary to use additional anti-chlorine stabilizers, although improved results can be obtained with them. 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), it is not absolutely necessary to add a separate chlorine scavenger unless a compound having such a function to the desired degree is absent from the enzyme-containing embodiments of the present invention; even so, the chlorine scavenger is added only for best results. 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 the chemist. With respect to the use of ammonium salts, the salts may simply be mixed with the detergent composition, but they tend to absorb water and/or release 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 generated after 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 structures of which may be linear, branched or even star-shaped. They may include end-capping moieties that are particularly effective in controlling molecular weight or altering physical or surface activity. The structure and charge distribution can 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 can be added to 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 U.S. patent No. US4968451 to j.j.scheibel and e.p.gosselink, issued 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, issued 12/8/1987; some or all ofthe anion-terminated oligomeric esters of Gosselink, US patent 4721580, issued 26.1.1988, such as oligomers derived from ethylene glycol ("EG"), PG, DMT, and sodium 3, 6-dioxa-8-hydroxyoctane sulfonate; non-ionic end-capped block polyester oligomeric compounds, such as products made from DMT, (Me) -capped PEG and EG and/or PG, or from a mixture of DMT, EG and/or PG, Me-capped PEG and sodium dimethyl 5-sulfoisophthalate, in Gosselink, granted on 27.10.1987; and Maldonado, Gosselink et al, US patent 4877896, issued on 31/10/1989, the anions, particularly sulfoaroyl-terminated terephthalates, which are typically SRA's useful in both laundry and fabric conditioning products, an example being an ester composition prepared from mono-sodium meta-sulfobenzoate, PG and DMT, optionally but preferably also containing 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 US3959230 on 25.5.1976 and US3893929 on Basadur on 8.7.7.1975; cellulose derivatives such as hydroxy ether cellulose polymers available from Dow as METHOCEL; c₁-C₄Alkyl celluloses and C₄Hydroxyalkyl cellulose, see Nicol et al, U.S. Pat. No. 4,000,93, 12/28/1976. Suitable SRA's characterized by a poly (vinyl ester) hydrophobic moiety include poly (vinyl ester) graft copolymers, e.g., C₁-C₆Vinyl esters, preferably poly (vinyl acetate), which are grafted onto a polyoxyalkylene 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, derived 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)₁The oligomer of (a) contains terephthaloyl (T), Sulfoisophthaloyl (SIP), oxyethylene and oxy-1, 2-propylene (EG/PG) units and is preferably capped with a capping group (CAP), preferably a modified isethionate, such as one sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethylene and oxy-1, 2-propylene oxy units in a defined ratio, preferably about 0.5: 1 to about 10: 1, and two capping units derived from sodium 2- (2-hydroxyethoxy) -ethanesulfonate. The SRA preferably further comprises an oligomer in an amount by weightFrom 0.5% to 20% of a crystallization-reducing stabilizer, for example an anionic surfactant such as sodium dodecylbenzenesulfonate or a substance selected from the group consisting of xylene-, cumene-, and toluene sulfonates or mixtures thereof, which are added to the synthesis kettle, all as taught in US5415807 to Gosselink, Pan, Kellett and Hall, granted on 5/16 of 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 mixtures 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 di (oxyethylene) oxy units, (SEG) represents units derived from the sulfoethyl ether of glycerol and related partial units, (B) represents branching units which are at least trifunctional whereby ester bonds are formed 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; the sum z + z' 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 unit per mole of the esterThe ester has a molecular weight of 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 analogs 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 represented by (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13, where CAP is (Na)⁺-O₃S[CH₂CH₂O]3.5) -and B are units derived from glycerol, the molar ratio of EG/PG is about 1.7: 1, as determined by conventional gas chromatography after complete hydrolysis.

Another class of SRA's includes: (I) nonionic terephthalates attached to polyester structures using diisocyanate 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 adding trimellitic anhydride to known SRA's. By appropriate selection of the catalyst, the trimellitic anhydride can be bound to the end groups of the polymer by the isolated carboxylic ester of trimellitic anhydride rather than by opening of the anhydride linkage. Either nonionic or anionic SRA's may be used as starting materials, provided they have hydroxyl end groups that can be esterified, see Tung et al, U.S. Pat. Nos. 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. nos. 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, particularly for the treatment of polyamide fibers, see DE2335044 to Unilever N.V. 1974. Other useful SRA's are described in US patents US4240918, US4787989, US4525524 and US 4877896.

Soil-removing/anti-redeposition agent

The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having soil removal and anti-redeposition properties. Granular detergent compositions 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 soil-removing-antiredeposition agent is the cationic compounds disclosed in european patent application EP111965 to Oh and Gosselink, published on 27.6.4. Other 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 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 agent or other 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 these brighteners are disclosed in "The Production and Application of fluorescent whitening 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 those indicated in US patent US4790856 to Wixon, granted 12 months and 13 days 1988. These brighteners include Verona's PHORWHITE brightener family. Other whitening agents disclosed in this reference include: tinopal UNPA, Tinopal CBS and Tinopal5BM, 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- (stilben-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, manganese phthalocyanines, 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 ═ or; 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 atom of the N-O group may be attached or of which the N-O group is part. 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 combination 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 pK_a<10, preferably pK_a<7, more preferably pK_a＜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-oxidepolymers generally have an amine to amine N-oxide ratio of from 10: 1 to 1: 1000000. However, the amount of amine oxide 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" class) 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 invention may optionally also 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 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.

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.

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]-disodium salt of 2, 2' -stilbenedisulfonic acid. Such special whitening agents are commercially available from Ciba-Geigy under the trade name Tinopal5 BM-GX.

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. Whitening agents for this bead 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 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 deposit relatively quickly on these fabrics. The extent to which the brightener deposits on fabrics in the wash solution can be defined by a parameter known as the "exhaustion coefficient". The exhaustion coefficient is generally the ratio between a) the brightener material deposited on 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 migration.

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 a conventional fabric "whitening" effect, rather than a true dye transfer inhibiting effect. 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 an advantage of these materials is in part their extraordinary ability to remove iron and manganese from the wash solution by forming soluble chelates.

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 chelants in the compositions of the present invention when at least low total phosphorus levels are permitted in the detergent compositions of the present invention, including: ethylenediamine tetra (methylene phosphonate) is 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 compositionsof the present invention may also contain a water-soluble methylglycinediacetic acid (MGDA) salt (or acid form) as a chelating agent, or as a co-builder used with, for example, insoluble builders such as zeolites, layered silicates.

If used, the chelants are generally used at levels of from 0.1% to 15% by weight of the detergent composition of the present 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 european-type washing 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, e.g. paraffins, fatty acid esters (e.g. glycerol)Fatty acid triesters), fatty acid esters of monohydric alcohols, fatty acid 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 with 2 or 3 moles of a primary or secondary amine containing 1 to 24 carbon atoms, propylene oxide, and monostearyl phosphate salts, such as monostearyl alcohol phosphate esters and distearyl (e.g., K, Na, and Li) phosphate salts and phosphate esters. Hydrocarbons such as paraffins andthe halogenated paraffin may be used in liquid form. The liquid hydrocarbon should be liquid at room temperature and atmospheric pressure, and should have 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. And 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 of such suds suppressors is meant to include mixtures of true paraffins and cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors comprises silicone suds suppressors. This class includes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsifiers of polyorganosiloxane oils or resins, and mixtures of polyorganosiloxane with silica particles, where the polyorganosiloxane 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.

Typical suds suppressors based on polysiloxanes for use in the present invention are suds suppressing amounts of suds controlling agents consisting essentially of:

(i) 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 of (i) (by weight);

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 primary silicone suds suppressor is 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 antifoam agent which is a mixture of (a), (b), (c) and (d) wherein (a) is a polyorganosiloxane, (b) is a resinous polysiloxane or a polysiloxane resin-yielding polysiloxane compound, (c) is a finely divided filler and (d) is a catalyst which facilitates the reaction of mixture components (a), (b) and (c) to form silanolates; (2) at least one nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water of greater than about 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 US4983316 to Starch, granted on 8.1.1991, Huber et al, US 5288431 to 2.22.1994, and US4639489 and US4749740 to Aizawa et al, at column 1, line 46 to column 4, line 35.

The silicone suds suppressors of the present invention preferably comprise 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. The weight ratio of polyethylene glycol to polyethylene glycol-polypropylene glycol copolymer is preferably from about 1: 1 to 1: 10, and most preferably from 1: 3 to 1: 6.

The silicone suds suppressorsused in the present invention are preferably free of polypropylene glycol, especially polypropylene glycol 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. Mixed suds suppressors typically comprise a mixture of alcohol and silicone in a weight ratio of from 1: 5 to 5: 1.

For any detergent composition used in an automatic washing machine or a dishwashing machine, suds cannot reach the level of overflowing 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 for use 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 present at levels 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 of practical significance primarily due to considerations 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%. In the present invention, these weight percent values include any silica that may be used with the polyorganosiloxane as well as any optional materials that may be used. Monostearyl phosphate suds suppressors are generally used in amounts 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 materials 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 to 3 and n is 6 to 12. The side chains are linked to the polyacrylate "backbone" via ester linkages to form a polymer of the type of "comb" structure. The molecular weight may vary but is generally in the range of 2000-50000. Such alkoxylated polycarboxylates may comprise 0 weight percent of the present compositions.05％-10％。

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, can also be optionally 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 be used with amines and cationic softeners as disclosed in U.S. Pat. No. 4,416 to Crisp et al, granted 3/1 1983, and in U.S. Pat. No. 4291071 to Harris et al, granted 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, 1,2, 6-dimethylcinnamyl-1, 4- (4-hydroxycyclohexyl-1, 3, 4-cyclohexyl-methyl-cyclohexyl) 1,2, 3, 3, 4-hexahydro-1, 2, 3, 3, 4-hexadecyl-1, 2-dihydroindene, 5-1, 3-isopropyl-1, 1,2, 6-tetramethyl-1, 2, 6-1, 2, 3, 3, 3-hexahydro-methyl-1, 7-hexahydro-methyl-1, 4-pentyl-methyl-2, 7-methyl-1, 4-ethyl-2-pentyl-methyl-1, 7-dihydronaphthalene-methyl-1, 7-methyl-pentyl-methyl-pentyl-8-methyl-ethyl-1, 7-methyl-pentyl-methyl-1, 7-methyl-2-1, 7-pentyl-ethyl-methyl-ethyl-2-1, 7-pentyl-2-pentyl-ethyl-2-pentyl-ethyl-8-pentyl-1, 7-pentyl-ethyl-pentyl-8-methyl-ethyl-naphthyl-2-1, 7-ethyl-1, 7-ethyl-2-1, 7-pentyl-ethyl-2-methyl-ethyl-.

Particularly preferred perfume materials are those 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, cumic aldehyde, cumarin, tricyclodecenyl acetate, tricyclodecenyl decanoate, and tricyclodecenyl decanoate.

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 beused 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 formulations, 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 adsorbing the ingredients onto a porous hydrophobic substrate, which is then coated with a hydrophobic coating agent. Preferably, the detergent component is mixed with the surfactant prior to adsorption on the porous substrate. During use, the detergent component is released from the substrate into the aqueous washing solution and performs its intended washing function in the washing solution.

To illustrate the technique in more detail, porous hydrophobic silica (trademark SIPERNATD10, DeGussa) is mixed with a mixture containing 3% -5% of C_13-15A proteolytic enzyme solution of a nonionic surfactant of ethoxylated alcohol (EO 7). The amount of enzyme/surfactant solution is typically 2.5 times the weight of the silica. The obtained powder is dispersed in silicone by stirringAlkyl oils (various silicone oils with viscosities of 500-. Dispersing the obtained polysiloxane oilEmulsified or added to the final detergent base. By this means, enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactant components as described previously can be used in "protected form" in detergents, including in liquid laundry detergent compositions.

The liquid detergent composition 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-propanediol, ethylene glycol, glycerol, and 1, 2-propanediol) may also be used. The compositions may 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 a washing operation for aqueous use is from 6.5 to 11, preferably from 7.5 to 10.5. The liquid dishwashing product formulation preferably has a pH of 6.8 to 9.0. Laundry products typically have a pH of 9-11. Methods for controlling the pH at the recommended values are 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 mixture 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 mixable particles containing 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 may be formulated to have an effective pH9 or below pH9 in use 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

The following examples further describe and demonstrate preferred embodiments within the scope of the present invention. These examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many variations thereof are possible without departing from the spirit and scope of the invention.

In the following examples, the abbreviated component symbols have the following meanings:and (3) LAS: straight chain C₁₂Sodium alkyl benzene sulfonate C45 AS: c₁₄-C₁₅Sodium linear alkyl ethylene oxide sulfate C25E 9: c condensed with an average of 9 moles of ethylene oxide_12-15Branched primary alcohol coconut EO 2: r₁N⁺(CH₃)(C₂H₄OH)₂，R₁＝C₁₂-C₁₄Zeolite a: formula Na₁₂(AlO₂SiO₂)₁₂.27H₂Hydrated sodium aluminosilicate of O, having a primary particle size of 0.1-10

Micron NaSKS-6: of the formula delta-Na₂Si₂O₅Crystalline layered silicate carbonate of (2): anhydrous sodium carbonate silicate with particle size of 200-: amorphous sodium Silicate (SiO)₂∶Na₂O ratio 2.0) MA/AA: 4: 6 maleic acid/acrylic acid copolymer, average molecular weight 11000 protease: proteolytic enzymes sold under the trade name Savinase by NOVO Industries A/S,

active 4KNPU/g cellulase: cellulolytic enzymes sold under the trade name Carezyme by NOVO Industries A/S,

activity 1000CEVU/g amylase: starch hydrolysis sold under the trade name Termamyl 60T by NOVO Industries A/S

Enzyme, activity 60KNU/g lipase: lipolytic enzyme sold under the trade name Lipolase by NOVO Industries A/S, Activity

100KLU/gPB₁: nominal NaBO₂.H₂O₂Sodium perborate anhydrous bleach NOBS: nonanoyloxybenzenesulfonate, sodium salt form

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

Examples

I II IIILAS 22.020.222.2C 45AS 4.04.03.0 coconut oil EO21.23.02.0C25E93.03.03.0MA/AA 14.020.015.0 NaSKS-65.03.04.0 zeolite A11.07.011.0 silicate 12.012.012.0 carbonate 12.012.012.0 protease 0.60.60.6 cellulase 0.50.50.5 amylase 0.60.60.6 lipase 0.30.30.3 NOBS 2.72.72.7 PB12.62.62.6 minor component/other … … … … balance to 100 … … … …

Claims (9)

1. A composition, comprising:

(a) a soil dispersant polymer;

(b) a non-AQA surfactant; and

(c) 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 alditol 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, wherein the weight ratio of (c) to (a) is in the range of 1: 11 to 1: 14.

2. The composition of claim 1 wherein the soil dispersant polymer is a polymeric polycarboxylate.

3. The composition of claim 2 wherein the polymeric polycarboxylate is selected from the group consisting of acrylic acid/maleic acid based copolymers having an average molecular weight of 2000-100000 in acid form, water soluble salts of such copolymers and mixtures thereof.

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 and 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, p andq is each an integer of 1 to 30.