CN1225673A - Detergent composition - Google Patents

Abstract

The present invention relates to a detergent composition comprising a detergent builder containing aluminosilicate, a non-alkoxylated quaternary ammonium (non-AQA) surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant.

Description

Detergent composition

Technical Field

The present invention relates to detergent compositions comprising an aluminosilicate builder, a non-AQA surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant.

Background

The manufacture of laundry detergents and other cleaning compositions presents significant challenges, since today's compositions meet the need to remove a wide variety of soils and stains from a variety of substrates. Accordingly, laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and cleaning compositions suitable for use in automatic dishwashing machines all require appropriate ingredient selection and combination for more effective soil removal. Generally, the above detergent compositions contain one or more types of surfactants intended to release and remove different kinds of soils and stains. As can be seen upon review of the existing literature, a wide selection of surfactants and surfactant combinations are effective for detergent manufacturers, and as a practical matter, many of these components are specialty chemicals which are not suitable for use in low unit cost items such as home laundry detergents. In fact, many of these household products, such as laundry detergents, still contain predominantly one or more conventional ethoxylated nonionic and/or sulfated or sulfonated anionic surfactants, possibly for economic reasons as well as the need to formulate compositions suitable for washing a wide variety of soils and stains and different fabrics.

The rapid and efficient removal of different kinds of soils and stains, such as body soils, greasy/oily soils and certain food stains, remains a problem to be solved. The soil contains a mixture of hydrophobic triglycerides, lipids, complex polysaccharides, inorganic salts and proteinaceous matter, and they are very difficult to remove. After washing, small amounts of hydrophobic soils and residual stains often remain on the fabric surface.

Detergent builders used in the compositions of the invention help to control mineral hardness, especially Ca, in the wash water²⁺And/or Mg²⁺Ions, or to assist in removing particulate soils from surfaces. Builders can function by a variety of mechanisms including forming soluble or insoluble complexes with hard ions, ion exchange, and providing a surface for the precipitation of hard ions that is more substantive than the surface of the substrate. In recent years, environmental and economic requirements have driven the synthesis of builder compoundsDevelopment of (1). These builder materials are generally inorganic and insoluble/partially soluble. WhileA particular problem with the use of insoluble/partially soluble inorganic builders is that they form insoluble complexes with hard ions which can deposit on the surface of the substrate (i.e. fabric) and become entrapped on or within the surface of the substrate (i.e. fabric) as a residual layer of the consolidated mass.

Continued washing and wearing results in limited removal of soil, stains and consolidated builder material from the fabric during cleaning which ultimately ends up on the fabric, which in turn will further trap particulate soil and cause fabric yellowing. The resulting fabric may exhibit a dull appearance that is not worn and discarded by the user.

It is suggested in the literature that a variety of cationic nitrogen-containing surfactants are suitable for use in different cleaning compositions. These materials are often designated as proprietary in the typical form of amino-, amido-, or quaternary ammonium or imidazolium compounds. For example, various amino and quaternary ammonium surfactants are believed to be useful in shampoo compositions and are said to deliver hair cosmetic benefits. Other nitrogen-containing surfactants are used in certain laundry detergents to provide fabric softening and antistatic benefits. However, in most cases, commercial application of these materials is limited due to difficulties faced in large scale production of such compounds. Another limitation is that the interaction between anionic active ingredients and cationic surfactants in detergent compositions can result in potential precipitation. The above nonionic andanionic surfactants remain the primary surfactants in existing laundry compositions.

It has been found that certain bis-alkoxylated quaternary ammonium (bis-AQA) compounds can be used in different detergent compositions to enhance detergency performance on a wide variety of common soils and stains, particularly hydrophobic soils. The bis-AQA surfactants described herein provide superior performance to manufacturers over existing cationic surfactants. For example, the bis-AQA surfactants used herein significantly improve the cleaning of "daily" obligate greasy/oily hydrophobic soils. Furthermore, 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 a common limiting factor in the use of known cationic surfactants. Low levels (as low as 3ppm in the laundry detergent) of bis-AQA surfactant can produce the above benefits. Bis-AQA surfactants can be formulated over a wide pH range of 5 to 12. Bis-AQA surfactants can be made as a 30% by weight solution that can be pumped for use and are therefore easy to handle in the factory. Bis-AQA surfactants with degrees of ethoxylation above 5 may sometimes be present in liquid form and thus may provide 100% neat starting material. In addition to its ease of handling, the availability of bis-AQA surfactants as highly concentrated solutions provides a tremendous economic benefit in terms of transportation costs.

In addition, compositions containing bis-AQA surfactants and aluminosilicate builders exhibit superior cleaning and whitening performance compared to products containing only one of the foregoing. In particular, it has been found that high levels of inorganic, insoluble or partially soluble builders can be used in the compositions of the present invention without increasing the build-up of residual builder on the substrate. Insoluble inorganic builders, such as aluminosilicates, are believed to be composed of discrete units, some of which are negatively charged at their facing surfaces. Bis-AQA containing electropositive end groups can react with the above mentioned end groups to effectively dissolve the inorganic particles in the wash water by forming a hydrophilic charged surfactant bilayer around the inorganic particles, thereby releasing the residual inorganic particles of builder/soil/stain from the fabric.

Accordingly, the present invention provides a detergent composition which effectively cleans everyday and especially hydrophobic soils using a detergent composition comprising an aluminosilicate builder and a bis-AQA surfactant.

Prior Art

United states patent 5,441,541 to mehretaab and f.j.lopast (1995,8,15 days grant) relates to anionic/cationic surfactant mixtures. Murphy, r.j.m.smith and m.p.brooks in british patent 2,040990 (published 1980,9, 3) relate to ethoxylated cationic surfactants in laundry detergents.

Summary of The Invention

The present invention provides compositions formulated with or in combination with an aluminosilicate builder, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula:wherein R is¹Is straight-chain, branched-chain, substituted C₈-C₁₈Alkyl, alkenyl, aryl, alkylaryl, ether or glycidyl (glycidyl) ether group, R²Is C₁-C₃Alkyl moiety, R³And R⁴Can be independently varied and is selected from hydrogen, methyl and ethyl, X is an anion, while A and A' can be independently varied and are each C₁-C₄Alkoxy, p and q canvary independently and are integers from 1 to 30.

Detailed Description

Aluminosilicate builders

The first essential component of the compositions of the present invention is an aluminosilicate builder. Aluminosilicate builders are particularly well suited for use in granular detergents, but may also be incorporated in liquids, pastes or gels.

Suitable aluminosilicates include those having Na_z〔(AlO₂)_z(Si_O2)_y〕·xH₂Of the O unit cell formulaAn aluminosilicate zeolite, wherein z and y are integers of at least 6; the molar ratio of z to y is in the range of 1.0 to 0.5, while x is at least 5, preferably 7.5 to 276, more preferably 10 to 264. The aluminosilicate may be crystalline or amorphous, but is preferably crystalline and hydrated, containing from 10% to 28%, more preferably from 18% to 22%, of water in bonded form.

The aluminosilicate may be a natural material, but synthetic derivatives are preferred. The synthetic crystalline aluminosilicate ion exchange materials preferably employed are commercially available products designated as zeolite a, zeolite B, zeolite P (or zeolite MAP), zeolite X, zeolite HS and mixtures thereof.

Zeolite a has the following general formula:

Na₁₂〔(AlO₂)₁₂(SiO₂)₁₂〕·xH₂o wherein x is 20 to 30, preferably 27; dehydrated zeolites (x =0) may also be employed. Zeolite X has Na as the preferred aluminosilicate₈₆〔(AlO₂)₈₆(SiO₂)₁₀₆〕·276H₂The general formula of O. Zeolite MAP disclosed in european patent-B-384,070 is also a preferred aluminosilicate builder herein. Preferably the aluminosilicate has particles of 0.1 to 10 micronsin diameter.

The aluminosilicate builder is typically present in the composition in an amount of from 1% to 80% by weight, preferably from 10% to 80% by weight, more preferably from 15% to 50% or even 60% by weight.

Bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactants

Another essential component of the present invention is an effective amount of a bis-AQA surfactant of the formula:

wherein R is¹Are linear, branched or substituted alkyl, alkenyl, aryl, alkylaryl, ether, glycidyl ether groups containing from 8 to 18 carbon atoms, preferably from 8 to 16 carbon atoms, more preferably from 8 to 14 carbon atoms; r²Is an alkyl group having 1 to 3 carbon atoms, preferably methyl; r³And R⁴Can vary independently from one another and are selected from hydrogen (preferred), methyl and ethyl; x-is an anion, such as chloride, bromide, methylsulfate, sulfate, which can provide sufficient electrical neutrality. A and A' may vary independently and are selected from C₁-C₄Alkoxy, especially ethoxy, propoxy and mixtures thereof; p is 1 to 30, preferably 1 to 15, more preferably 1 to 8, further preferably 1 to 4, and q is 1 to 30, preferably 1 to 15, more preferably 1 to 8, further preferably 1 to 4. Most preferably, p and q are both 1.

Bis-AQA compounds with a hydrocarbyl substituent R, as compared to materials with longer chains¹Is C₈-C₁₂In particular C₈-C₁₀The dissolution rate of the detergent particles can be increased, especially under cold water conditions. Thus, the manufacturer may prefer to employ C₈-C₁₂bis-AQA surfactants. The level of bis-AQA surfactant in the final laundry detergent composition is in the range 0.1% to 5%, typically 0.45to 2.5% by weight. The weight ratio of bis-AQA to percarbonate bleach is between 1: 100 and 5: 1, preferably between 1: 60 and 2: 1, most preferably between 1: 20 and 1: 1.

The present invention utilizes an "effective amount" of bis-AQA surfactant to improve the performance of cleaning compositions containing other optional ingredients. By "effective amount" of bis-AQA surfactant is meant the amount required to improve the cleaning performance of the cleaning composition to at least some of the target soils and stains with 90% confidence, directionality or significance. Thus, in compositions targeting certain food stains, the bis-AQA used by the manufacturer should be sufficient to target at least the enhanced ability to clean such stains. Similarly, in compositions targeting certain clay soils, the bis-AQA employed by the manufacturer should be sufficient to target at least enhanced cleaning of such soils.

The bis-AQA surfactants may be used in combination with other detergent surfactants and in amounts effective to at least target cleaning performance. In the case of fabric washing compositions, this "usage level" can vary with the type and severity of the soils and stains, and can depend on the temperature and volume of the wash water and the type of washing machine.

For example, in a top loading, vertical axis, U.S. type automatic washing machine, the machine has a wash tank containing 45 to 83 liters of water, a wash cycle of 10 to 14 minutes, and wash water at a temperature of 10 ℃ to 50 ℃, at which time it is preferred to have 2ppm to 50ppm, more preferably 5ppm to 25ppm, of bis-AQA surfactant in the wash liquor. The in-product concentration (by weight) of bis-AQA surfactant can be converted to 0.1% to 3.2%, preferably 0.3% to 1.5%, for a high performance liquid laundry detergent, based on a usage rate of 50ml to 150ml per wash load. The in-product concentration (by weight) of bis-AQA surfactant can be converted for high density ("compact") granular laundry detergents (densities above 650g/l) to 0.2% to 5.0%, preferably 0.5% to 2.5%, based on usage of 60g to 95 g/wash load. The in-product concentration (by weight) of bis-AQA surfactant can be converted to 0.1% to 3.5%, preferably 0.3% to 1.5%, for spray-dried particles (i.e., "bulky", density less than 650g/l) based on usage of 80g to 100 g/wash load.

For example, in a front loading, horizontal axis European style automatic washer having a wash tank capable of holding 8 to 15 liters of water, a wash cycle of 10 to 60 minutes, and a wash water temperature of 30 ℃ to 95 ℃, it is preferred to have 13ppm to 900ppm, more preferably 16ppm to 390ppm of the Pmbis-AQA surfactant in the wash liquor. The in-product concentration (by weight) of bis-AQA surfactant can be converted to 0.4% to 2.64%, preferably 0.55% to 1.1%, for high performance liquid laundry detergents based on usage rates of 45ml to 270ml per wash load. For high density ("compact") granular laundry detergents (densities above 650g/l) it is possible to convert from 0.5% to 3.5%, preferably from 0.7% to 1.5% in-product concentration (by weight) of bis-AQA surfactant, based on usage from 40g to 210 g/wash load. For spray dried particles (i.e., "bulky": density less than 650g/l), this can be converted to 0.13% to 1.8%, preferably 0.18% to 0.76% in-product concentration (by weight) of bis-AQA surfactant, based on usage of 140g to 400 g/wash load.

For example, in a top loading, vertical axis Japanese style automatic washing machine, the machine can hold 26 to 52 liters of water in the wash tank, the wash cycle is 8 to 15 minutes, and the wash water temperature is 5 ℃ to 25 ℃, at which time it is preferred to have 1.67ppm to 66.67ppm, more preferably 3ppm to 6ppm of the ppmbis-AQA surfactant in the wash liquor. The in-product concentration (by weight) of bis-AQA surfactant can be converted to 0.25% to 10%, preferably 1.5% to 2%, for high performance liquid laundry detergents based on usage of 20ml to 30ml per wash load. For high density ("compact") granular laundry detergents (densities above 650g/l), the in-product concentration (by weight) of bis-AQA surfactants can be converted to 0.25% to 10%, preferably 0.5% to 1.0%, based on usage of 18g to 35 g/wash load. For spray dried particles (i.e., "bulky": density less than 650g/l), this can be converted to 0.25% to 10%, preferably 0.5% to 1%, in-product concentration (by weight) of bis-AQA surfactant, based on usage of 30g to 40 g/wash load.

As mentioned above, the amount of bis-AQA surfactant used in the machine wash situation may depend on the habit and practice of the user, the type of washing machine. In this context, however, one heretofore unrecognized advantage of bis-AQA is that even relatively low levels of bis-AQA surfactant, as compared to other surfactants (typically anionic or anionic/nonionic surfactant mixtures), can be employed in the finished composition to at least directionally improve the cleaning performance of a range of soils or stains. This is a distinction over prior compositions where other cationic surfactants were used in stoichiometric or near stoichiometric amounts with anionic surfactants. Generally, in the practice of the present invention, the bis-AQA: the weight ratio of anionic surfactant is from 1: 70 to 1: 2, preferably from 1: 40 to 1: 6, more preferably from 1: 30 to 1: 6, most preferably from 1: 15 to 1: 8. In a laundry composition containing both anionic and nonionic surfactants, bis-AQA: the weight ratio of mixed anionic/nonionic surfactant is from 1: 80 to 1: 2, preferably from 1: 50 to 1: 8.

Many other cleaning compositions containing anionic surfactants, optionally nonionic surfactants, and specialty surfactants (e.g., betaines, sultaines, amine oxides) can also be formulated in the manner of this invention with an effective amount of bis-AQA surfactant. Such compositions include (but are not limited to): hand dishwashing products (especially liquids or gels), hard surface cleaners, shampoos, personal cleansing bars, laundry bars, and the like. Since the user of such compositions will vary little between habit and practice, it is sufficient to use bis-AQA in amounts of from about 0.25% to about 5%, preferably from about 0.45% to about 2%, by weight of the composition. Also, in the case of granular and liquid laundry compositions, the weight proportion of bis-AQA relative to other surfactants in such compositions is low, i.e. in the case of anionic surfactants, below the stoichiometric amount. Preferably such cleaning compositions contain bis-AQA/surfactant ratios as described above for the machine laundry compositions.

In contrast to other known cationic surfactants, di-alkoxylated cationic surfactants have good solubility and therefore can be used with mixed surfactant systems where the nonionic surfactant is very low and may contain, for example, alkyl sulfate surfactants. This is especially a consideration for manufacturers in preparing conventional detergent composition types for top-loading automatic washing machines, especially the type used in north america as well as japan. Generally, such compositions should contain the weight ratio of anionic surfactant to nonionic surfactant 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, where the ratio is generally from about 10: 1 to 1: 10, preferably from about 5: 1 to about 1: 1.

Preferred ethoxylated cationic surfactants herein are those sold under the tradename ETHOQUAD by Akzo Nobel Chemicals company. Furthermore, these materials can be synthesized by a number of different reaction schemes (where "EO" stands for-CH)₂CH₂An O-unit),

scheme 1

Scheme 2

Scheme 3

Scheme 4

The following is an economical reaction scheme.

Scheme 5

The following parameters summarize optional and preferred reaction conditions in scheme 5. The reaction of step 1 is preferably carried out in an aqueous medium, typically at a temperature in the range of 140 ℃ to 200 ℃ and a reaction pressure of between 50 and 1000psig, and a basic catalyst, preferably sodium hydroxide, may be employed. The molar ratio of reactant amine to reactant alkyl sulfate is from 2: 1 to 1: 1. Preference is given to using C₈-C₁₄Sodium alkyl sulfate salt. The ethoxylation and quaternization steps are carried out under conventional reaction conditions and reactants.

In some cases, the product produced in scheme 5 is sufficiently soluble in the aqueous reaction medium to form a gel. The two-step synthesis of scheme 6 below may be more preferred in certain commercial circumstances if the desired product can be recovered from the gel. The first step of scheme 6 is the same as that of scheme 5. The second step (ethoxylation) is preferably carried out using ethylene oxide and an acid (e.g., hydrochloric acid) to form the quaternary ammonium surfactant. The chlorohydrin, may also be reacted to form the desired bis-hydroxyethyl derivative, as shown below.

For reaction scheme 6, the following parameters summarize the optional and preferred conditions for the first step reaction. The first reaction step is preferably carried out in an aqueous medium. Typical reaction temperatures are 100-230 ℃. The reaction pressure is 50-1000 psig. The HSO formed during synthesis can be neutralized with a base, preferably sodium hydroxide₄Or the acid can be reacted with an excess of amine. Typical molar ratios of amine to alkyl sulphate are 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 can be conveniently separated as a distinct phase from the aqueous reaction medium in which it is insoluble. The second step of the process of this scheme is carried out under conventional reaction conditions. bis-AQA can be prepared by further performing alkoxylation and quaternization under standard reaction conditions.

Scheme 7 the monoethoxylation can optionally be accomplished using ethylene oxide and under standard ethoxylation conditions without the use of a catalyst.

The following scheme lists other schemes for such reactions, where "EO" represents-CH₂CH₂An O-unit. In the reaction, either inorganic base, organic base or excess amine reactant can be used to neutralize the HSO formed₄。

Scheme 6

Scheme 7

The following further illustrates several aspects of the above reaction, but is by no means limiting and is for the convenience of the manufacturer.

Synthesis A

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

To a glass autoclave liner (liner) were added 19.96g of sodium lauryl sulfate (0.06921mol), 14.55g of diethanolamine (0.1384mol), 7.6g of 50% by weight sodium hydroxide solution (0.095mol) and 72g of distilled water. The glass liner was sealed in a 500ml stainless steel rocking autoclave and heated to 160-. The mixture was cooled to room temperature and the liquid contents of the glass liner were poured into a 250ml separatory funnel containing 80ml chloroform. The funnel was shaken well for several minutes, and then the mixture was separated. The lower chloroform layer was discharged and the chloroform was evaporated to give the product.

Synthesis of B

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

In the manner of synthesis a,1 mole of sodium dodecyl sulfate and 1 mole of ethanolamine are reacted in the presence of a base. The resulting 2-hydroxyethyldodecylamine was recovered and reacted with 1-chloroethanol to afford the title compound.

Synthesis C

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

To the glass autoclave liner were added 19.96g of sodium lauryl sulfate (0.06921mol), 21.37g of ethanolamine (0.3460mol), 7.6g of 50% by weight sodium hydroxide solution (0.095mol) and 72g of distilled water. The glass liner was sealed in a 500ml stainless steel swing autoclave and heated to 160 and 180 ℃ for 3-4 hours under a nitrogen pressure of 300 and 400 psig. The mixture was cooled to room temperature and the liquid contents of the glass liner were poured into a 250ml separatory funnel containing 80ml chloroform. The funnel was shaken well for several minutes, and then the mixture was separated. The chloroform layer was removed and the chloroform was evaporated to give the product. The product obtained is subsequently reacted with 1 molar equivalent of ethylene oxide in the absence of a base catalyst at 120-130 ℃ to give the desired end product.

The bis-substituted amines prepared by the above syntheses may be further ethoxylated in standard fashion. In this embodiment, quaternization with an alkyl halide can produce bis-AQA surfactants.

In light of the foregoing description, the following is a non-limiting detailed description of bis-AQA surfactants useful in the present invention. It will be appreciated that the degree of alkoxylation of bis-AQA as described herein is meant to be an average value, following conventional means as in common ethoxylated nonionic surfactants. This is because, in general, ethoxylation produces mixtures of materials having different degrees of ethoxylation. Therefore, it is not surprising that the total "EO" value is not an integer value (e.g., "EO 2.5" "EO 3.5").Name R¹R²ApR³A′qR⁴bis-AQA-1 C₁₂-C₁₄CH₃EO (also preferred)CocoMeEO2)bis-AQA-2 C₁₂-C₁₆CH₃(EO)₂EObis-AQA-3 C₁₂-C₁₄CH₃(EO)₂(EO)₂(Goco Methyl EO4)bis-AQA-4 C₁₂CH₃EO EObis-AQA-5 C₁₂-C₁₄CH₃(EO)₂(EO)₃bis-AQA-6 C₁₂-C₁₄CH₃(EO)₂(EO)₃bis-AQA-7 C₈-C₁₈CH₃(EO)₃(EO)₂bis-AQA-8 C₁₂-C₁₄CH₃(EO)₄(EO)₄bis-AQA-9 C₁₂-C₁₄C₂H₅(EO)₃(EO)₃bis-AQA-10 C₁₂-C₁₈C₃H₇(EO)₃(EO)₄bis-AQA-11 C₁₂-C₁₈CH₃(propoxy) (EO)₃bis-AQA-12 C₁₀-C₁₈C₂H₅(Isopropoxy)₂(EO)₃bis-AQA-13 C₁₀-C₁₈CH₃(EO/PO)₂(EO)₃bis-AQA-14 C₈-C₁₈CH₃(EO)₁₅ ^*(EO)₁₅ ^*bis-AQA-15 C₁₀CH₃EO EObis-AQA-16 C₈-C₁₂CH₃EO EObis-AQA-17 C₉-C₁₁CH₃-EO3.5 mean-bis-AQA-18C₁₂CH₃-EO3.5 mean-bis-AQA-19C₈-C₁₄CH₃(EO)₁₀(EO)₁₀bis-AQA-20 C₁₀C₂H₅(EO)₂(EO)₃bis-AQA-21 C₁₂-C₁₄C₂H₅(EO)₅(EO)₃bis-AQA-22 C₁₂-C₁₈C₃H₇Bu (EO)₂Ethoxy, optionally terminated by methyl or ethyl

Very preferred bis-AQAs of the present invention are of the formula:

wherein R is¹Is C₈-C₁₈Hydrocarbyl and mixtures thereof, preferably C₈、C₁₀、C₁₂、C₁₄Alkyl groups and mixtures thereof, and X is any conventional anion that can provide charge balance, preferably chloride. With respect to the general bis-AQA structure described above, since in preferred compounds R is¹Is prepared from coconut base (C)₁₂-C₁₄Alkyl) fatty acid, such preferred compounds are herein written as "CocoMeEO 2" or "bis-AQA-1" as listed in the above table.

Other bis-AQA surfactants useful herein include compounds of the formula:wherein R is¹Is C₈-C₁₈Hydrocarbyl, preferably C₈-C₁₄A hydrocarbyl group; p is independently 1-3 and q is independently 1-3; r²Is C₁-C₃Alkyl, preferably methyl; and, X is an anion, particularly chloride or bromide.

Other compounds of the above type include: wherein, ethoxy (CH)₂CH₂O) units (EO) substituted by butoxy (Bu), isopropoxy [ CH (CH)₃)CH₂O and [ CH]₂CH(CH₃) O]units (i-Pr) or nA mixture of propoxy units (Pr), EO and/or Pr and/or i-Pr units.

non-AQA detersive surfactants

In addition to the bis-AQA surfactant, the present compositions further preferably comprise a non-AQA surfactant. The non-AQA surfactants can include essentially any anionic, nonionic or other cationic surfactant.

Anionic surfactants

Non-limiting examples of anionic surfactants useful in the present invention are generally used in amounts of 1% to 55% by weight, including conventional C₁₁-C₁₈Alkyl benzene sulfonates ("LAS") and branched and random primary ("AS") C₁₀-C₂₀An alkyl sulfate; c₁₀-C₁₈Of secondary (2,3) alkyl sulfates of formula CH₃(CH₂)_x(CHOSO₃ ^-M⁺)CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺)CH₂CH₃Wherein x and (y +1) are integers of at least 7, preferably 9; and, M is a water-soluble anion, preferably sodium; unsaturated sulfates, such as oleyl sulfate; c₁₂-C₁₈α -sulfonated fatty acid ester, C₁₀-C₁₈Sulfated polyglycosides, C₁₀-C₁₈Alkyl alkoxy sulfates (' AE)_xS', in particular EO1-7 ethoxylated sulfate), and C₁₀-C₁₈Alkyl alkoxy carboxylates (especially ethoxy carboxylates of EO 1-5). C may also be included in the overall composition₁₂-C₁₈Betaines and sulfobetaines, C₁₀-C₁₈Amine oxide. May also adopt C₁₁-C₂₀Conventional soaps. When high foam is desired, a branched chain C may be employed₁₀-C₁₆Soap. Other common surfactants are listed in standard textbooks.

Nonionic surfactant

Non-limiting examples of suitable nonionic surfactants typically range from 1% to 55% by weight, including: alkoxylated alcohols (AE ' S) and alkylphenols, polyhydroxyfatty amides (PFAA ' S), alkylpolyglycosides (APG ' S), C10-C18 glycerol ethers.

Specifically, in the present invention, condensation products of primary and secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide (AE) are suitably used as the nonionic surfactant in the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and typically contains from 8 to 22 carbon atoms. Condensation products of alcohols whose alkyl groups contain from 8 to 20, preferably from 10 to 18, carbon atoms and from 1 to 10, preferably from 2 to 7, most preferably from 2 to 5, mol of ethylene oxide per mol of alcohol are preferred. Commercially available examples of such nonionic surfactants include: tergitol^TM15-S-9(C₁₁-C₁₅Condensation products of linear alcohols with 9 mol of ethylene oxide) andTergitol^TM24-L-6NMW(C₁₂-C₁₄narrow molecular weight distribution condensation products of primary alcohols with 6 moles of ethylene oxide), which are products of the Union Carbide Corporation; neodol^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) and Neodol^TM45-5(C₁₄-C₁₅Condensation products of linear alcohols with 5 moles of ethylene oxide), which are products of Shell Chemical Company; kyro^TMEOB(C₁₃-C₁₅Condensation product of an alcohol with 9 moles of ethylene oxide) which is The Procter&Products of the Gamble Company; and Genapol LAO3O or O5O (C)₁₂-C₁₄Condensation products of alcohols with 3 or 5 moles of ethylene oxide), sold by Hoechst. These AE nonionic surfactants preferably have HLB in the range of 8 to 11, more preferably 8 to 10. Its condensates with propylene oxide and butylene oxide may also be employed.

Other preferred nonionic surfactants useful in the present invention are polyhydroxy fatty acid amides represented by the formula:

wherein R is¹Is H or C_1-4Alkyl, 2-hydroxyethyl, 2-hydroxypropyl or mixtures thereof; r²Is C_5-31A hydrocarbyl group and Z is a polyhydroxyhydrocarbyl group or an alkoxylated derivative thereof containing at least 3 hydroxyl groups directly attached to the hydrocarbyl linear chain. Preferably R¹Is methyl, R²Is straight chain C_11-15Alkyl radical, C_15-17An alkyl or alkenyl chain (e.g., cocoalkyl) or mixtures thereof, and Z is derived from a reducing sugar (e.g., glucose, fructose, maltose, lactose) in an amination reduction reaction. Typical examples include C₁₂-C₁₈And C₁₂-C₁₄N-methylglucamine of (1). See U.S. patent nos. 5,194,639 and 5,298,636. N-alkoxy polyhydroxy fatty acid amides, see U.S. Pat. No. 5,489,393, may also be used.

Also useful as nonionic surfactants in the present invention are alkyl polysaccharides such as those disclosed by Lienado in U.S. Pat. No. 4,565,647(1986, issued 1, 21) whose hydrophobic group contains 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, and polysaccharides such as polyglycosides whose hydrophilic group contains 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms may also be used, for example glucose, galactose, and galactosyl groups may be replaced by glucosyl groups (hydrophobic groups optionally attached at the 2-,3-, 4-, etc. positions to produce glucose or galactose as opposed to glucoside or galactoside). The intersaccharide linkage may, for example, be between one position of the addition saccharide unit and the 2-,3-, 4-and/or 6-position of the preceding saccharide unit.

Preferred alkyl polyglycosides 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, the alkyl group of these groups containing from 10 to 18, preferably from 12 to 14, carbon atoms; n is 2 or 3, preferably 2; t is 0 to 10, preferably 0; and 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 formed, andthereafter, the reaction with glucose or a glucose source produces the glycoside (attached at the 1-position). The additional glycosyl units can then be attached in their 1-position predominantly in the 2-,3-, 4-and/or 6-position, preferably in the 2-position, of the preceding glycosyl unit.

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

The condensation products of ethylene oxide with a hydrophobic base synthesized by condensing propylene oxide and propylene glycol are also suitable for use as additional nonionic surfactants in the present invention. The hydrophobic portion of such compounds should preferably have a molecular weight of 1500-1800 and should behave as water-insoluble. The hydrophobic portion increases the polyoxyethylene portion which tends to improve the overall water solubility of the molecule and the liquid character of the product is maintained up to the point where the polyoxyethylene is up to 50% by weight of the total weight of the condensation product, which corresponds to up to 40 moles of ethylene oxide being condensed. Examples of such compounds include certain commercially available pluronics^TMSurfactants, sold by BASF.

Also suitable for use as the nonionic surfactant in the nonionic surfactant systems of the present invention are the condensation products of ethylene oxide with the reaction product of propylene oxide and ethylenediamine. The hydrophobic portion of these products is composed of the reaction product of ethylenediamine and excess propylene oxide, and has a molecular weight of 2500-3000. When the hydrophobic moiety is condensed with ethylene oxide, condensation proceedsThe product contains 40-80 wt% polyoxyethylene and has a molecular weight of 5,000-11,000Until now. Examples of such nonionic surfactants include certain of the commercially available Tetronic surfactants^TMA compound produced by BASF.

Additional cationic surfactants

Suitable cationic surfactants are preferably water dispersible compounds having surfactant properties, such compounds containing at least one ester linkage (-COO-) and at least one positively charged group.

Other suitable cationic surfactants include quaternary ammonium surfactants selected from C₆-C₁₆Preferably C₆-C₁₀N-alkyl or alkenyl ammonium surfactants in which the remaining positions of N may be substituted by methyl, hydroxyethyl or hydroxypropyl groups. Other suitable cationic ester surfactants, including choline ester surfactants, may be, for example, those disclosed in U.S. patent nos. 4228024, 4239660 and 4260529.

Optional detergent ingredients

Various other optional ingredients that may be used in the compositions of the present invention are described below, but are not limited thereto.

Additional builders

The compositions of the present invention may comprise additional builders. Additional builders may be present at levels of at least 1%. Liquid formulations typically contain from 5% to 50%, more usually from 5% to 35% of builder, and a portion of this may be the additional builder. The granular formulation typically contains from 10% to 80%, more usually from 15% to 50% of builder (by weight of the detergent composition), part of which may be the additional builder. Lower or higher levels of builder are not excluded.

The present invention also relates to a mixed builder system comprising two or more builders. The hybrid builder system is optionally supplemented with a chelating agent, pH-buffer or bulking agent, but these additional materials are usually calculated separately when describing the material levels. As the relative amounts of surfactant to builder in the present invention, preferred builder systems are generally formulated in a surfactant to builder weight ratio of from 60: 1 to 1: 80. Certain preferred laundry detergents have a weight ratio in the range of 0.90: 1 to 4.0: 1.0, more preferably 0.95: 1 to 3.0: 1.0.

Suitable additional builders herein may be selected from: phosphates and polyphosphates, especially sodium salts: silicates, including the class of solids that are soluble and hydrated in water, including those having a chain structure, a layer structure, or a three-dimensional structure, as well as amorphous solids or amorphous liquids: carbonates, bicarbonates, sesquicarbonates, and carbonate minerals other than sodium carbonate or sodium sesquicarbonate: organic mono-, di-, tri-and tetra-carboxylates, especially water-soluble non-surfactant carboxylic acids in the form of the acid, sodium salt, potassium salt or (alk) alkanolammonium salt; and oligomeric or water-soluble low molecular weight polymeric carboxylates,including aliphatic and aromatic species; and phytic acid. These materials may also be supplemented with borates (e.g., for use as a pH-buffering agent) or sulfates (e.g., sodium sulfate), as well as any other fillers or carriers important in the process of making stable surfactant and/or builder-containing detergent compositions.

Phosphorus (P) -containing detergency builders, under conditions permitted by regulations, are often preferred, and include (but are not limited to): alkali metal salts, ammonium salts and alkylolammonium salts of polyphosphoric acids, such as specific examples of triphosphates, pyrophosphates, glassy polymeric metaphosphates; and a phosphonate.

Suitable silicate builders include alkali metal silicates, especially those of SiO₂∶Na₂Liquids and solids having an O ratio of between 1.6: 1 and 3.2: 1, including (especially when used in automatic dishwashing): solid hydrated silicates sold by PQ Corp under the trade name BRITESIL — at a ratio of 2, such as BRITESIL H2O; and, layered silicates, such as those disclosed in U.S. Pat. No. 4,664,839,1987,5,12 to reeck. NaSKS-6, sometimes abbreviated as "SKS-6", is a crystalline, layered, aluminum-free, delta-Na sold by Hoechst₂SiO₅Silicates are formed, and this material is particularly preferred in granular laundry compositions. See DE-A-3,417,649 and DE-A-3,742,043, a method of preparation disclosed in. Other layered silicates may also be used in the present invention, or in place of others, such as those of the formula NaMSi_xO2_x+1·yH₂The layered silicates produced by Hoechst also include NaSKS-5, NaSKS-7 and NaSKS-11 in the form of α, β and gamma-layered silicates, respectively, other silicates, such as magnesium silicate salts, which can be used as crisping agents in granules, as stabilizers in bleaches and as foam control system components.

The present invention also suitably employs a crystalline synthetic ion exchange material having a chain structure or a hydrate thereof, which has a composition represented by the following general formula (in the form of an anhydrate): XM₂O·ySiO₂zM 'O, wherein M is Na and/or K and M' is Ca and/or Mg; y/x is 0.5-2.0 and z/x is 0.005-1.0, as disclosed in U.S. Pat. No. 5,71 l (1995,6,27) to Sakaguchi et al.

Suitable carbonate builders include those alkaline earth and alkali metal carbonates disclosed in German patent application 2,321,001 (published in 1973,11,15), but sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, other carbonate minerals (e.g. trona), any conventional double salt of sodium carbonate with calcium carbonate (e.g. anhydrous composition 2 Na)₂CO₃·CaCO₃Those of (a), even calcium carbonates (including calcite, aragonite and hexagonal vaterite), especially those salt forms having a larger surface area than dense calcite, may also be employed, for example, as seeds or in synthetic washing bars.

Suitable organic detergent builders include polycarboxylic acid compounds including water-soluble, non-surface active di-and tri-carboxylates. More typical polycarboxylic acid builders contain several carboxyl groups, preferably at least 3 carboxyl groups. Carboxylate builders may be formulated in acidic, partially neutral, neutral or overbased forms. When present in salt form, alkali metal salts (e.g., sodium, potassium, and lithium) or alkanolammonium salts are preferred. Polycarboxylic acid builders include polycarboxylic acid ethers such as: oxydisuccinates, see berg, U.S. patent 3,128,287,1964.4.7 and Lamberti et al 3,635,830,1972.1.18; "TMS/TDS" builder, Bush et al, U.S. Pat. No. 4,663,071,1987.5.5; and other carboxylic acid ethers, including cyclic and acyclic compounds, such as those described in U.S. patent 3,923,679; 3,835,163, respectively; 4,158,635, respectively; 4,120,874 and 4,102,903.

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

Citric acids, such as citric acid and its soluble salts, are important carboxylic acid builders in view of being renewable resources and biodegradable, such as for use in high performance liquid detergents. Citrate salts may also be used in particulate compositions, particularly in combination with zeolites and/or layered silicates. Oxydisuccinates are also suitable for use in such compositions and in hybrid applications.

Alkali metal phosphates, such as sodium tripolyphosphate, pyrophosphate and orthophosphate, may be employed where permissible, and particularly in the preparation of hand washing bars. Phosphate builders such as ethane-1-hydroxy-1, 1-diphosphate, as well as other known phosphates (such as those disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148 and 3,422,137) may also be employed and may have desirable detergency.

Certain detersive surfactants or their short chain homologs also have builder activity. For the sake of clarity, the above materials, when they have surfactant properties, are commonly referred to as detersive surfactants. Preferred types of wash-assisting functions are for example: 3, 3-dicarboxy-4-oxa-1, 6-adipate and related compounds are disclosed in Bush, U.S. Pat. No. 4,566,984, (1986,1, 28). The succinic acid builder comprises C₅-C₂₀Alkyl or alkenyl succinic acids and salts thereof. Thesuccinate builder further comprises: dodecyl succinate, tetradecyl succinate, hexadecyl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate. Dodecyl-succinate is described in european patent application 86200690/0,200,263 (published at 1986.11.5). Fatty acids (e.g. C)₁₂-C₁₈Monocarboxylic acid) may be incorporated into the composition as a surfactant/builder material alone or in combination with the above builders (preferably citrate and/or succinate builders) to provide enhanced building activityIs strong. Other suitable polycarboxylates are disclosed in U.S. Pat. No. 4,144,226(1979.3,12) to Crutchfield et al and U.S. Pat. No. 3,308,067 (disclosed in 1967.3.7) to Diehl. See also U.S. patent 3,723,322 to Dienl.

Other inorganic builder materials which may be employed have the general 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_iIs a cation, at least one is a water-soluble cation, and satisfies the equation ∑_i=1-15(x_iMultiplying by M_iValence of) +2y =2z, so that the above formula has a neutral or "balanced" charge. Such builders are referred to herein as "inorganic builders". Water of hydration and anions other than carbonate may be added to maintain overall charge balance or neutrality. The charge or valence effect of such anions is added to the right side of the above equation. Preferably containing water-soluble cations 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, and even more preferably sodium and potassium. Non-limiting examples of non-carbonate anions include anions selected from the group consisting of chloride, sulfate, fluoride, oxide, hydroxide, silica, chromate, nitrate, borate, and mixtures thereof. Such preferred builders are selected (in their simplest form) from Na₂Ca(CO₃)₂、K₂Ca(CO₃)₂、Na₂Ca₂(CO₃)₃、NaKCa(CO₃)₂、NaKCa₂(CO₃)₃、K₂Ca₂(CO₃)₃And mixtures thereof. A particularly preferred builder material herein is Na in the form of any crystalline modification₂Ca(CO₃)₂. Suitable builders, as defined above, may be further exemplified and include any of the following materials, in natural or synthetic form, or combinations thereof: afghanite, Andersonite, Ashcropin Y, Beyerite, Borcarite, Burbank, Butschlite, Cancrinite, Carbocernaite, Carletonite, Davyne, Donnanayite Y, Fairchilite, Ferrisrite, Franzite, Gaudenoronite, Gaylosite, Girvasite, Gregorysite, Jourayskite, Kamphaugite Y, Kettnerite, Khannesite, Lepersonnite GD, Littite, MckelveyiteY, Microtomite, Mroseite, Natrearchitede, Nyereite, Remonilite, Schckrodinite, Shrokingiterite, Turonite, Tyrolite, and Viofflite. Preferred inorganics include Nyererite, fairchild, and Shortite.

Bleaching agent

The detergent compositions of the present invention may optionally contain a bleaching agent. When present, bleaching agents typically comprise from 1% to 30%, more typically from 5% to 20% of the detergent composition, particularly when used in fabric laundering.

The bleaching agent used in the present invention may be any known or known bleaching agent used in detergent compositions for textile cleaning, hard surface cleaning or other cleaning purposes. They include oxygen bleaches as well as other bleaching agents. Perborate bleaches such as sodium perborate (e.g., mono-or tetrahydrate thereof) may be used in the present invention.

Another class of bleaching agents that may be employed without limitation includes percarboxylic acid bleaching agents and salts thereof. Suitable examples of such bleaching agents include: magnesium monoperphthalate hexahydrate, magnesium meta-chloroperbenzoate, 4-nonylamino-oxoperoxybutyric acid, and magnesium diperoxydodecanedioic acid. Such bleaches are disclosed in U.S. Pat. No. 4,483,781 to Hartnan (issued to 1984.11.20), U.S. patent application 740,446 to Burns et al (issued to 1985.6.3), European patent application 0,133,354 to Bank et al (disclosed in 1985.2.20), and U.S. Pat. No. 4,412,934 to Chung et al (issued to 1983.11.1). Further preferred bleaching agents also include 6-nonylamino-6-oxoperoxyhexanoic acid disclosed in U.S. Pat. No. 4,634,551 to Burns et al (issued to 1987.1.6).

Peroxygen bleaching agents may also be employed in the present invention. Suitable peroxy bleach compounds include sodium carbonate peroxyhydrate and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Persulfate bleach (e.g., OXONE, sold by DuPont) may also be employed.

Preferred percarbonate bleach compositions comprise dry particles having a particle size in the range of from 500 microns to 1,000 microns, wherein no more than 10% by weight of said particles smaller than 200 microns and no more than 10% by weight of said particles larger than 1,250 microns are present. Optionally, the percarbonate may be coated with silicate, borate or water soluble surfactants. Percarbonate can be obtained from a variety of commercial sources, for example, FMC, Solvay and Tokai Denka.

Bleaching agents other than oxygen bleaching agents are also known to those skilled in the art and may be used in the present invention. A particularly interesting class of non-oxygen bleaches includes photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyaninedyes. See U.S. Pat. No. 4,033,718 to Holcomne et al, issued to 1977,7, 5. If they are used, the detergent compositions will generally contain from 0.025% to 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanine dyes.

Mixtures of bleaching agents may also be employed.

Bleach activators

Bleach activators (bleach boosters) are preferred components of the compositions in the presence of oxygen bleach. If present, the bleach activator level will generally be between 0.1% and 60%, more typically between 0.5% and 40%, based on the bleach composition containing the bleach-plus-bleach activator.

The peroxygen bleach and the bleach activator are combined in aqueous solution (i.e., during the washing process) to form the peroxyacid of the corresponding bleach activator in situ. Various non-limiting examples of active agents are disclosed in U.S. Pat. No. 4,915,854 to Mao et al (issued to 1990.4.10) and U.S. Pat. No. 4,412,934. Nonanoyloxybenzenesulfonate (NOBS) and Tetraacetylethylenediamine (TAED) actives are representative, and mixtures thereof may also be used. Other typical bleaching agents and bleach activators useful in the present invention are also disclosed in U.S. Pat. No. 4,634,551.

More preferred amide-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 6 to 12 carbon atoms, R²Is alkenyl 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. A leaving group is any group that can be displaced from the bleach activator by nucleophilic attack on the bleach activator by a perhydrolytic anion (perhydrolysis). A preferred leaving group is benzenesulfonate.

Preferred examples of bleach activators of the above formula include (6-octanamido-hexanoyl) oxybenzenesulfonate, (6-nonanamido hexanoyl) oxybenzenesulfonate, (6-decanamido hexanoyl) oxybenzenesulfonate, and mixtures thereof, as disclosed in U.S. Pat. No. 4,634,551, which is incorporated herein by reference.

Another class of bleach activators includes benzoxazin-based activators, disclosed in U.S. patent No. 4.966,723 to Hodge et al, entitled 1990.10.3, which is incorporated herein by reference. More preferred benzoxazine-based active agents are:

yet another preferred class of bleach activators includes acyl lactam activators, particularly acyl caprolactams and acyl valerolactams, respectively, of the formula:

wherein R is⁶Is H or an alkyl, aryl, alkoxyaryl or alkylaryl group containing from 1 to 12 carbon atoms. More preferred lactam actives 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 Sanderson, U.S. Pat. No. 4,545,784 (issued to 1985.10.8, incorporated herein by reference) which discloses acyl caprolactams, including benzoyl caprolactam, absorbed in sodium perborate.

Bleaching catalyst

Bleach catalysts are optional components of the compositions of the present invention. If present, the bleaching compound may be catalysed by a manganese compound. Such compounds are known in the art and include, for example, the manganese-based catalysts disclosed in U.S. patent 5,246,621, U.S. patent 5,244,594, U.S. patent 5,194,416, U.S. patent 5,114,606, european patent application 549,271a1, 549,272a2, 544,440a2, and 544,490a 1; preferred examples of these 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^Ⅲ-Mn^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 U.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. Improvements in or relating to manganese with various complex ligandsBleaching has been described in the following U.S. patents: 4,728,455, 5,284,944, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161 and 5,227,084.

As a practical matter and not by way of limitation, the compositions of the present invention and when used can be formulated to provide active bleach catalyst materials on the order of at least 1 million in an aqueous wash liquor, and preferably catalyst materials in the wash liquor in the range of from 0.1ppm to 700ppm, more preferably from 1ppm to 500 ppm.

The use of cobalt bleach catalysts in the present invention is known and has been disclosed, for example, in "alkaline hydrolysis of transition metal complexes" of m.l. tobe, adc.inorg.bioirig.mech. (1983), pages 2, 1-94.Most preferably, the cobalt catalyst used herein is of the formula [ Co (NH)₃)₅OAc〕T_yWherein "OAc" represents an acetate moiety and "T" represents a pentaaminato cobalt acetate salt of (A)_y"is an anion, and especially pentaaminecobalt acetate, [ 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)₂And [ Co (NH)₃)₅OAc〕(NO₃)₂(referred to herein as "PAC").

These cobalt catalysts are readily prepared by known methods, for example, as exemplified in the article by Tobe and references cited therein, U.S. Pat. No. 4,810,410 to Diakun et al, issued to 1989.3.7, J.chem.Ed (1989),66(12), 1043-45; "Synthesis and characterization of inorganic Compounds", W.L. Jolly (Prentice-Hall; 1970), pp.461-3; 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).

As a practical matter, and not by way of limitation, automatic dishwashing compositions and cleaning processes can be formulated to provide on the order of at least 1 part per billion of active bleach catalyst species in the aqueous cleaning medium, and preferably to a level of from 0.01ppm to 25ppm, more preferably from 0.05ppm to 10ppm, and most preferably from 0.1ppm to 5ppm, of bleach catalyst species in the wash liquor. To achieve such levels in the wash liquor of an automatic dishwashing process, typically the automatic dishwashing composition of the present invention will contain from 0.0005% to 0.2%, preferably from 0.004% to 0.08%, by weight of the cleaning composition, of a bleach catalyst, especially amanganese or cobalt catalyst.

Enzyme

Enzymes may be included in the detergent compositions of the present invention and their action is diverse, including: removing protein, carbohydrate or triglyceride type stains from the substrate, preventing the transfer of the cast dye during fabric washing and for fabric restoration. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures of any of their suitable starting materials (e.g., plant, animal, bacterial, fungal, and yeast origin). The choice of the preferred materials can be influenced by a number of factors, for example the optimum conditions for pH-activity and/or stability, thermal stability and stabilizers for active detergents, builders. In this respect, bacterial or fungal enzymes, such as bacterial amylases and proteases, and fungal cellulases are preferred.

As used herein, "detergent enzyme" refers to any enzyme that has a cleaning, stain removal or similar benefit in laundry, hard surface cleaning or personal care detergent compositions. Preferred detergent enzymes are hydrolases including proteases, amylases and lipases. Preferred enzymes for laundry include, but are not limited to, proteases, cellulases, lipases and peroxidases. Preferred for automatic dishwashing are amylases and/or proteases.

Enzymes are typically incorporated into detergent or laundry additive compositions at levels sufficient to provide a "cleaning effective amount". The term "cleaning effective amount" means any amount that is capable of producing a cleaning, stain removal, stain release, whitening, deodorizing, or freshness-enhancing sensation on the substrate (e.g., fabric and dishware). Typical levels of enzyme for the actual commercial preparations are up to 5mg (by weight) of active enzyme per gram of detergent composition, more usually 0.01mg to 3 mg. In other words, the compositions according to the invention should generally contain from 0.001% to 5%, preferably from 0.01% to 1%, by weight of a commercially available enzyme preparation. Proteases are often included in these commercially available formulations in amounts sufficient to provide 0.005-0.1Anson Units (AU) of activity per gram of composition. For certain detergents, such as automatic dishwashing detergents, it is desirable to increase the active enzyme content of the commercial formulations in order to minimize the total amount of non-catalytically active material and thus improve the spotting/filming or other end effects. Higher active levels are also desirable for highly concentrated detergent formulations.

An example of a suitable protease is subtilisin, which is obtainable from particular strains of Bacillus subtilis and Bacillus licheniformis. A suitable protease is obtained from a strain of Bacillus, which has the highest activity in the pH range of 8-12, and which is developed and sold under the trade name ESPERASE by Novo Industries A/S (hereinafter "Novo") of Denmark. The preparation of this enzyme and its analogues is disclosed in British patent 1,243,784 to Novo. Other suitable proteases include ALCALASE-and SAVINASE-of Novo and MAXATASE-of International Bio-Synthesis, Inc., the Netherlands; and protease a disclosed in european patent application 130,756A (1985.1.9), and protease B disclosed in european patent application 303,761a (1987.4.28) and european patent application 130,756A (1985.1.9). High pH proteases from Bacillus (Bacillus sp.) NCIMB40338 are also known from WO9318140A to Novo. Enzymatic detergents containing a protease, one or more other enzymes, and a reversible protease inhibitor are disclosed in WO9203529A to Novo. Other preferred proteases include those described by Procter&Gamble in WO 9510591A. When desired, proteases with reduced absorption and increased hydrolysis may be used, as described by Procter&Gamble in WO 9507791. Recombinant tryptase-type proteases suitable for detergents according to the invention are described in WO9425583 to Novo.

More specifically, particularly preferred proteases, so-called "protease D" are carbonyl hydrolase variants having an amino acid sequence not found in nature, derived from a carbon-based hydrolase precursor and obtained by substituting a different amino acid for the amino acid residue at position +76 of the carbonyl hydrolase, and preferably also substituted at position +76 in combination with one or more other amino acid residue positions: +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, as disclosed in Bacillus amyloliquefaciens subtilisin, e.g., in U.S. patent application Ser. No. A.Baeck et al, U.S. Ser. No. 08/322,676, entitled "protease-containing cleaning composition," and in U.S. patent application Ser. No. C.Ghosh et al, U.S. Ser. No. 08/322,677, entitled "protease-containing bleaching composition" (all of the 1994.10.13 applications).

Amylases suitable for the present invention, especially for use in automatic dishwashing, include, but are not limited to, α -amylase described in British patent No. 1,296,839 to Novo, RAPIDASE, which is commercially available from International Bio-Synthesis, Inc., and TERMAMYL of Novo, which is particularly effective in improving the stability (e.g., oxidative stability) of Novo using enzyme engineering, e.g., FUNGAMYL, which is known to be more effective in improving the stability (e.g., oxidative stability) using enzyme engineering, e.g., see J.Biochem, Vol.260, No. 11, 1985,6, 6518. page 6521. in certain preferred embodiments of the compositions of the present invention, amylases having improved stability in detergents (e.g., automatic dishwashing types), especially amylases having improved oxidative stability, which are all characterized as "improved stability" starch enzymes, which are also characterized by the use of starch oxidase variants which are obtained as a starch oxidase variants which are more stable than starch oxidase variants which are obtained from starch oxidase variants which are also disclosed in the parent Bacillus amylovor-WO 5, especially preferred from starch peroxidase, preferably from starch peroxidase, WO-No. WO-No. 5, which is also disclosed in the parent Bacillus amylovor, the invention, the parent Bacillus amylovor, which is more stable, which is found to be more stable in the stability of the same as a Bacillus amyloperoxidase, improved in the stability of starch oxidase, improved by enzymatic engineering, e.g., the parent Bacillus amyloperoxidase, e.7, the parent Bacillus amyloperoxidase, e.g.g.7, the stability of Bacillus amyloperoxidase, the parent strain of the stability test, the parent strain of the invention, the stability of the invention, the.

Other amylases include those disclosed in WO95/26397 and in Novo' co-pending patent application PCT/DK96/00056 specific amylases suitable for use in the detergent compositions of the invention include α -amylase having a higher specific activity than that of Termamyl-at a temperature of 25 ℃ to 55 ℃ and at a pH of 8 to 10, as determined by the Phadebas _ α -amylase activity test (the Phadebas _ α -amylase activity test is disclosed on pages 9-10 of WO 95/26397). α -amylases having at least 80% homology to the amino acid sequences listed in the tables referenced SEQ ID can also be included in the detergent compositions of the invention.

Cellulases useful in the present invention include bacterial as well as fungal types of cellulases, preferably those having an optimum pH between 5 and 9.5. Barbesgord et al, in U.S. Pat. No. 4,435,307(1984,3,6), disclose useful fungal cellulases obtained from the insolen Humicola or Humicola strain DSM1800, or from a cellulase 212 producing fungus belonging to the genus Aeromonas (genus Aeromonas), as well as cellulases extracted from the hepatopancreas of the marine mollusk Dolabella Quricalla Solander. Suitable cellulases are also disclosed in GB-A-2.075.028, GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME-and CELLUZYME- (Novo) are particularly effective. See WO9117243 to Novo.

Suitable lipases for detergents include those produced by a Pseudomonas group microorganism (e.g.Pseudomonas stutzeri ATCC19.154) as disclosed in GB-1,372,034. See also Japanese patent application 53,20487 (published in 1978,2, 24). The lipase is commercially available from Amano Pharmaceutical Co.led. Nagoya, Japan under the trade name Lipase P "Amamo" or "Amano-P". Other suitable commercially available lipases include: Amano-CES, lipase extracted from chromobacterium viscosum (e.g., chromobacterium viscosum variant Lipolyticum NRRLB3673, from ToYoJozo co., Tagata, Japan); chromobacterium viscosum lipases from the American Biochemical company (USA) and Disoynth Co., the Netherlands, and lipases extracted from Pseudomonas gladioli. The LIPOLASE _ enzyme obtained from Humicola lanuginosa and available from Novo (see European patent application 341,947) is a preferred lipase for use in the present invention. Peroxidase-stabilized lipase and amylase variants are disclosed in WO9414951A to Novo. See WO9205249 and RD 94359044.

Despite the large number of publications on lipases, the lipases which have hitherto only been derived from Humicola lanuginosa and which have been produced with Aspergillus oryzae (Aspergillus oryzae) as host are widely used as additives in textile washing products. Lipase is commercially available from Novo Nordisk under the trade name lipolase (Lipolase. TM.). To provide Lipolase TM with optimal stain removal performance, Novo Nordisk makes many of its variants. The D96L variant of the native Humicola lanuginosa lipase, as described in WO92/05249, improved the removalof lard stains by a factor of 4.4 over the wild-type lipase (this enzyme was compared at a level of 0.075-2,5mg protein/liter). It was indicated by Novo Nordisk published research report 35944(1994,3,10 published) that the lipase variant (D96L) can be added in an amount of 0.001-100mg (5-500,000LU/L) lipase variant per L of wash. The maintenance whitening effect provided by the present invention to fabrics is due to the use of low levels of the D96L variant in detergent compositions containing bis-AQA surfactants, especially when the D96L is used in amounts of 50LU to 8500LU per liter of wash liquor.

The class of cutinases (cutinases enzymes) suitable for use in the present invention is disclosed in WO8809367 to Genencor.

Peroxidases can be used in combination with oxygen sources (e.g., percarbonate, perborate, hydrogen peroxide, etc.) for the purpose of "solution bleaching", or to prevent dyes or pigments from falling off of one substrate in the wash liquor from transferring to another substrate in the wash. Known peroxidases include horseradish peroxidase, ligninases and haloperoxidases such as chloro-or bromo-peroxidases. Detergent compositions containing peroxidase enzymes are disclosed in WO89099813A,1989.10.19 and WO8909813A to Novo.

The range of zymogens and the manner in which they are incorporated into synthetic detergents are also disclosed in WO9307263A and WO9307260A by Genencor International, WO8908694 by Novo, and U.S. Pat. No. 3,553,139(1971,1,5) by McCarty et al. Related enzymes are further disclosed in Place et al, U.S. Pat. No. 4.101,457(1978.7,18) and Hughes, U.S. Pat. No. 4,507,219 (1985.3.26). Hora et al, in U.S. Pat. No. 4,261,868(1981.4.14), describe enzyme stocks for liquid detergent formulations and their mixing in these formulations. Enzymes used in detergents can be stabilized by a variety of processes. Enzyme stabilization techniques are disclosed and exemplified in: gedge et al, U.S. Pat. Nos. 3,600,319(1971,8,17), and Venegas, EP199,405, EP200586(1986,10, 29). Enzyme stabilization systems are also described in U.S. Pat. No. 3,519,570. The bacillus species AC13, which can produce proteases, xylanases and cellulases, is disclosed 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 detergent enzymes. This system may be provided by this functionality inherent to other formulation actives, or added separately, for example by the formulator or manufacturer of the detergent ready-to-use enzyme. The stabilizing system may contain calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boronated acids, and the like, and mixtures thereof, and they are used to address stability issues depending on the type and physical form of the detergent composition.

One method of stabilization is to use water soluble sources of calcium and/or magnesium ions in the final composition to provide these ions to the enzyme. Calcium ions are generally more effective than magnesium ions and are preferably used in the case where only one cation is used. Typical detergent compositions, especially liquid detergent compositions, will 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 factors including multiplicity, type and level of enzyme used may vary. 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 commonly calcium sulfate or the magnesium salt corresponding to the exemplified calcium salt. Of course, it may also be desirable to further increase the level of calcium and/or magnesium, for example, to promote the degreasing action of certain types of surfactants.

Another method of stabilization is the use of borates. See U.S. Pat. No. 4,537,706 to Severson. When borate stabilizers are used, the borate may comprise up to 10% or more of the composition, but more usually up to 3% by weight boric acid or other borate compounds (e.g. borax or orthoborate) are preferred for liquid detergents. Substituted boronic acids, such as phenylboronic acid, butaneboronic acid, p-bromophenylboronic acid or similar compounds, may be used in place of boronic acid and the use of these substituted boron derivatives makes it possible to reduce the total boron content of the detergent composition.

Certain cleaning composition stabilizing systems, such as automatic dishwashing compositions, may further comprise from 0% to 10%, preferably from 0.01% to 6%, by weight of a chlorine bleach scavenger to prevent the attack and inactivation of enzymes by chlorine bleach species contained in many water sources, especially under alkaline conditions. Although the chlorine content of water may be small, typically in the range of 0.5ppm to 1.75ppm, the total volume of water contacted with the enzyme (e.g., during dish-and fabric-washing processes) may be quite substantial; therefore, the stability of the enzyme to chlorine occurring during use may sometimes become a problem. Due to the percarbonate's ability to react with chlorine bleaches, additional stabilizers against chlorine are most commonly not necessary, although their use can achieve improved results. Suitable chlorine scavenger anions are widely known and readily available, and, if used, may be sulfite, bisulfite, thiosulfite, thiosulfate, iodide salts containing cationic ammonium, andthe like. Antioxidants such as carbamates, ascorbates, and the like; organic amines such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof, Monoethanolamine (MEA), and mixtures thereof can also be used. Furthermore, specific enzyme inhibition systems can be incorporated, which allow for maximum 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; and phosphates, condensed phosphates, acetates, benzoates, citrates, formates, lactates, malates, tartrates, salicylates, and the like, and mixtures thereof. In general, since the function of a chlorine scavenger can be performed by components that have been listed separately for their better recognized functions (e.g., a hydrogen peroxide source), the addition of a chlorine scavenger alone is not absolutely necessary except when the compounds of the enzyme-containing examples of the present invention are unable to perform this function to the desired degree; even then, the scavenger is added only for optimum effect. In addition, formulators employ the basic skills of their chemists to avoid the use of any enzyme scavengers or stabilizers that are not substantially compatible with other active ingredients during manufacture. In the use of ammonium salts, the salts may be mixed directly with the detergent composition, but have a tendency to absorb water and/or release ammonia during storage. Thus, if present, such materials should be pre-protected within the particle, such as disclosed in U.S. Pat. No. 4,652,392 to Baginski et al.

Polymeric soil release agent

The detergent compositions of the present invention may optionally contain known polymeric soil release agents, referred to herein as "SRA" or "SRA's". If employed, the SRA should be present in the composition in an amount of 0.01% to 10.0%, conventionally 0.1% to 5%, preferably 0.2% to 3.0% by weight.

Preferred SRA types generally contain hydrophilic segments that render the surface of hydrophobic fibers (e.g., polyester and polyamide fibers) hydrophilic and hydrophobic segments that deposit on the surface of the hydrophobic fibers and adhere thereto to act as "anchors" for the hydrophilic segments throughout the wash and rinse stages. This ensures that the stains, after being subjected to the SRA treatment, are more easily washed away in a subsequent washing process.

SRA species can contain monomer units of various charges, for example, anionic or even cationic (see us patent 4,956,447) as well as uncharged, and their structure can be linear, branched or even star-like. They may contain terminal moieties that are effective in controlling molecular weight or altering physical or surfactant properties. Such structure and charge distribution can be tailored to the type of fiber or textile being used or to the variations of the detergent or detergent additive product.

Preferred SRA's include oligomeric terephthalates, which may be prepared by at least one process including transesterification/oligomerization, and often are prepared with the use of a metal catalyst (e.g., titanium (iv) alkoxide). Such esters can be prepared from addition monomers that can be incorporated into the ester structure from 1,2,3,4 or more positions, and certainly do not produce a densely crosslinked overall structure.

Suitable SRA species include the sulfonated products of substantially linear ester oligomers comprising an oligomeric ester backbone composed of terephthaloyl and oxyalkylene repeat units, and allyl-derived sulfonated end moieties covalently attached to the backbone, such as disclosed in U.S. patent nos. 4,968,451,1990,11,6 to j.j.j.scheibel and e.p.gosselink; such ester oligomers can be prepared by (a) ethoxylating allyl alcohol, (b) two-step transesterification/oligomerization of the product of (a) with dimethyl terephthalate ("DMT") and 1, 2-propanediol ("PG"), and (c) reacting the product of (b) with sodium metabisulfite in water; non-ionic end-capped 1, 2-propylene/polyoxyethylene terephthalate products, such as poly (ethylene glycol) methyl ether, DMT, PG, and poly (ethylene glycol) ("PGE") transesterification/oligomerization, disclosed in Gosselink et al, U.S. Pat. No. 4,711,730(1987,12, 8); some or all of the anionic-terminated oligoesters disclosed in U.S. Pat. No. 4,721,580(1988,1,26) to Gosselink et al, for example, oligomers derived from ethylene glycol ("EG"), PG, DMT, and sodium 3, 6-dioxa-8-hydroxyoctanesulfonate; gosselink et al, U.S. Pat. No. 4,702,857(1987,10,27), disclose non-ionic end-capped block polyester oligomeric compounds, e.g., products derived from DMT, methyl-capped PEG and EG and/or PG, or a combination of DMT, EG and/or PG, methyl-capped PEG and sodium dimethyl-5-sulfoisophthalate; and anion (particularly sulfoaroyl) -terminated terephthalates disclosed in U.S. patent 4,877,896(1989,10,31) to Maldonado, Gosselink et al, which are representative of SRA-type materials suitable for use in laundry and fabric conditioning products, such as ester compositions made from monosodium m-sulfobenzoate, PG and DMT, optionally (but preferably) also containing additional PEG (e.g., PEG 3400).

SRA species also include: simple block copolymers of ethylene terephthalate or propylene terephthalate and polyethylene oxide or polypropylene oxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays (1976,5,25) and U.S. Pat. No. 3,893,929 to Basadur (1975,6, 8); cellulose derivatives, for example, hydroxyether cellulose polymers, available from METHOCEL sold by Dow; and, C₁-C₄Alkyl celluloses and C₄Hydroxyalkyl celluloses, see Nicol et al, U.S. patent 4,000,093(1976,12, 28). Suitable SRA-based compounds characterized by a poly (vinyl ester) hydrophobe segment include: graft copolymers of poly (vinyl esters), e.g. C₁-C₆Vinyl esters, preferably poly (vinyl acetate), are grafted to the polyalkylene oxide backbone. See, e.g., european patent application 0219048 to Kud et al (published in 1987,4, 22).

Commercially available examples include compounds of the SOKALAN SRA class, such as SOKALAN HP-22, which are sold by BASF. Other SRA-type compounds are polyesters whose repeat units contain 10 to 15 weight percent ethylene terephthalate and 90 to 80 weight percent polyoxyethylene glycol-derived polyoxyethylene terephthalate having an average molecular weight of 300-5,000. Commercially available examples include ZELCON5126 sold by dpoint and milleas sold by ICI.

Another preferred SRA is of the empirical formula (CAP)₂(EG/PG)₅(T)₅(SIP)₁The oligomer of (a) which comprises terephthaloyl (T), Sulfoisophthaloyl (SIP), oxyethyleneoxy and oxo-1, 2-propylene (EG/PG) units, and preferably contains a terminal capping group (CAP) at its terminus, the preferred terminal group being a modified isethionate group, comprising 1 sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethyleneoxy and oxo-1, 2-propyleneoxy units in a defined ratio (preferably about 0.5: 1 to about 10: 1), and 2 terminal units derived from sodium 2- (2-hydroxyethoxy) -ethanesulfonate in the oligomer. The SRA further preferably contains from 0.5% to 20% (by weight of oligomer) of crystallinity-reducing stabilizerStabilizers, such as anionic surfactants, for example, in particular sodium dodecylbenzenesulfonate in linear form, or from the group of xylene-, cumene-and toluene-sulfonates or mixtures thereof, which stabilizers or modifiers are introduced into the synthesis tank, are disclosed in Gosselnk, Pan, Kellett, all of the above&U.S. patent 5,415,807 to Hall (1995, 5, 16). Suitable monomers for the above SRA include: sodium 2- (2-hydroxyethoxy) -ethanesulfonate, DMT, sodium dimethyl-5-sulfoisophthalate, EG, and PG.

Another preferred group of SRA species are oligoesters, which include: (1) a backbone comprising (a) at least one unit selected from the group consisting of dihydroxy sulfonate esters, polyhydroxy sulfonate esters, a unit having at least 3 functional groups, thereby forming ester linkages to provide a branched oligomeric backbone, and mixtures thereof, (b) at least one terephthaloyl unit; and (c) at least one unsulfonated 1, 2-oxyalkylene unit; and (2) one or several capping units selected from the group consisting of nonionic capping units, anionic capping units, such as: alkoxylated, preferably ethoxylated isethionate, alkoxylated propane-sulfonate, alkoxylated propane-disulfonate, alkoxylated phenol-sulfonate, sulfoaroyl derivatives and mixtures thereof. Preferred among such esters are those having the empirical formula:

{(CAP)_x(EG/PG)_y’(DEG)_y”(PEG)_y”’(T)_z(SIP)_2’(SEG)_q(B)_mwherein CAP, EG/PG, PEG, T and SIP are as described above, (DEG) represents a di (oxyethylene) oxy unit; (SEG) represents units derived from the sulfoethyl ether of glycerol and units of related groups; (B) represents a branching unit that is at least trifunctional, through which unit an ester bond is formed to produce a branched oligomer backbone; x is from about 1 to about 12; y' is from about 0.5 to about 25; y "is from about 0 to about 12; y' "is 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 0 to about 12; the sum of 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 ', q, and m represent the average number of moles of the corresponding units per mole of the ester, and the ester molecular weight ranges from about 500 to about 5,000.

Preferred SEG and CAP monomers in the above esters include: sodium 2- (2-, 3-dihydroxypropoxy) ethanesulfonate ("SEG"), sodium 2- {2- (2-hydroxyethyl) ethoxy } ethanesulfonate ("SE 3"), and analogs thereof, and mixtures thereof, and ethoxylation and sulfonation products of allyl alcohol. Preferred SRA esters within this class include: the product of transesterification and oligomerization of sodium 2- {2- (2-hydroxyethoxy) ethoxy } ethanesulfonate and/or sodium 2- [ 2- {2- (2-hydroxyethoxy) ethoxy } ethoxy]ethanesulfonate, DMT, sodium 2- (2, 3-dihydroxypropoxy) ethanesulfonate, EG and PG using a suitable Ti (IV) catalyst and identified as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13, where CAP is CAP(Na^+-O₃S〔CH₂CH₂O]3.5) -, and B is a unit derived from glycerol, with an EG/PG molar ratio of about 1.7: 1, as determined by conventional gas chromatography after complete hydrolysis.

Another class of SRA materials includes (I) nonionic terephthalate and polyester structures linked by diisocyanate coupling agents, see U.S. Pat. No. 4,201,824 to Violland et al and U.S. Pat. No. 4,240,918 to Lagass et al; (II) SRA compounds with carboxylate end groups, which are prepared by adding 1,2, 4-triacid phthalic anhydride to known SRA compounds to convert the terminal hydroxyl groups to 1,2, 4-triacid phenyl esters. The catalyst is suitably selected so that the 1,2, 4-tricarboxylic anhydride is linked to the polymer terminus, and such linking is achieved by ester formation of isolated carboxyl groups in the 1,2, 4-tricarboxylic anhydride rather than by opening of the anhydride linkage. Compounds of the SRA class, whether nonionic or anionic, may be used as starting materials provided that they have hydroxyl end groups in their part which may be esterified, see Tung et al, U.S. patent 4,525,524; (III) urethane linkage modified anionic terephthalate type SRA compounds, see U.S. Pat. No. 4,201,824 to Violland et al; (IV) Poly (vinylcaprolactam) and its related copolymers with monomers such as vinylpyrrolidone and/or dimethylaminoethyl methacrylate and including nonionic and cationic copolymers, see U.S. Pat. No. 4,579,681 to Ruppert et al; (V) graft copolymers other than the SOKALAN type polymers produced by BASF, said copolymers being the product of grafting acrylic monomers onto sulfonated polyesters; the SRA-like compounds are said to have soil release and anti-redeposition effects similar to known cellulose ethers; see European patent application 279,134A (1988) to Rhone-Poulenc Chemie; (VI) grafting of vinyl monomers, such as acrylic acid and vinyl acetate, onto proteins, such as casein, see BASF, European patent application publication 457,205 (1991); (VII) Compounds of the polyester-polyamide SRA class, prepared by condensation of adipic acid, caprolactam and polyethylene glycol, are particularly suitable for the treatment of polyamide fabrics, see German patent application 2,335,044(1974) to Bevan et al to Unilever N.V. Other suitable SRA-based compounds are disclosed in U.S. patents 4,240,918, 4,787,989, 4,525,524 and 4,877,896.

Clay soil removal/anti-redeposition agent

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

The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine. Examples of ethoxylated amine compounds are further disclosed in U.S. patent 4,597,898 to VanderMeer (issued to 1986.7.1). Another preferred class of clay soil removal-antiredeposition agents are the cationic compounds disclosed in European patent application 111,965 (published in 1984,6,27) by Oh&Gosselink. Yet another class of clay-soil removal/anti-redeposition agents that can be used includes: ethoxyamine polymers described in Gosselink in European patent application 111,984(1984,7, 27); zwitterionic polymers disclosed in Gosselink in European patent application 112,592(1984,7, 4); amine oxides disclosed by Connor in us patent 4,548,744 (issued 1985,10, 22). Other known clay soil removal/anti-redeposition agents may also be employed in the compositions of the present invention. See VanderMeer, U.S. Pat. No. 4,891,160 (1990, 1,2) and WO95/32272 (1995, 11, 30). Another preferred anti-redeposition agent includes carboxymethyl cellulose (CMC) based materials. Such materials are known in the art.

Polymeric dispersant

Polymeric dispersants are suitably present in the composition in an amount of from 0.1% to 7% by weight, especially in the presence of zeolite and/or layered silicate builders. Suitable polymeric dispersants include polymeric polycarboxylates and polyethylene glycols, although other known materials may also be used. While not being bound by any theory, it is believed that polymeric dispersants, when used in combination with other builders (including lower molecular weight polycarboxylates), can generally improve the performance of detergent builders by inhibiting crystal growth, peptization release of particulate soils, and anti-redeposition.

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form polycarboxylate polymers include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, methylfumaric acid, methylmaleic acid, citraconic acid, methylenemalonic acid. It is suitable that the polymeric polycarboxylate or monomer segment contains non-carboxylic acid groups (e.g. vinyl methyl ether, styrene, ethylene) provided that such segment does not exceed 40% by weight.

Particularly suitable polymeric polycarboxylates may be derived from acrylic acid. Such acrylic acid type polymers suitable for use in the present invention are water soluble salts of polymerized acrylic acid. The average molecular weight of such a polymer acid form is preferably in the range of 2,000-10,000, more preferably 4,000-7,000, and most preferably 4,000-5,000. Such water-soluble salts of acrylic acid 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 has been disclosed in U.S. patent 3,308,067 to Diehl, (issued 1967,3,7) and the like.

Acrylic acid/maleic acid copolymers may also be used as a preferred component in the dispersion/anti-redeposition agent. Such materials include: water soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of the acid form of such a copolymer is preferably in the range of 2,000-100,000, more preferably 5,000-75,000, most preferably 7,000-65,000. The ratio of acrylic acid to maleic acid segments in the copolymer should generally be in the range of from 30: 1 to 1: 1, more preferably from 10: 1 to 2; 1. water-soluble salts of such acrylic acid/maleic acid copolymers include, for example, alkali metal salts, ammonium salts, and substituted ammonium salts. Such soluble polymers are known materials and are disclosed in european patent application 66915 (published in 1982,12,15) and EP193,360 (published in 1986,9,3), which also describes polymers containing hydroxypropyl acrylate. Other suitable dispersants include maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP193,360, which includes, for example, the acrylic/maleic/vinyl alcohol terpolymer of 45/45/10.

Another class of polymeric materials that may be included are polyethylene glycols (PEG). PEG exhibits dispersant properties and can act as a clay soil-antiredeposition agent. Typical molecular weights for the above purposes are in the range of 500-100,000, preferably 1,000-50,000, more preferably 1,500-10,000.

Polyaspartate and polyglutamate dispersing agents may also be employed, especially when a zeolite builder is used in combination. The dispersant (e.g., polyaspartate) preferably has a molecular weight (average) of 10,000.

Whitening agent

Any known fluorescent brightening agents or other brightening or whitening agents can be incorporated in the detergent compositions of the present invention at typical levels of from 0.01% to 1.2% by weight. Commercially available optical brighteners suitable for use in the present invention may be divided into subclasses which include (but are not limited to): derivatives of 1, 2-stilbene, pyrazolines, coumarins, carboxylic acids, methinecyanines, dibenzothiophene-5, 5-dioxides, pyrroles, 5-and 6-membered heterocycles, and a variety of other agents. Examples of such brighteners are disclosed in "production and use of fluorescent whitening agents" by m.zabradnik (published by John Wiley&Sons, new york (1982)).

Specific examples of optical brighteners suitable for use in the compositions of the present invention are those disclosed in U.S. Pat. No. 4,790,856 to Wixon (1988,12, 13). These include the PHORWHITE series of brighteners from Verona. Other whitening agents disclosed in this reference: tinopalUNPA, Tinopal CBS and Tinopal5 BM; a commercially available product from Ciba-Geigy; articwhite CC and Articwhite CWD,2- (4-styryl-phenyl) -2H-naphtho [ 1,2-d]triazole; 4, 4' -bis- (1,2,3, -triazol-2-yl) -1, 2-stilbene; 4, 4' -bis (styryl) biphenyl; and aminocoumarins. Specific examples of such whitening agents include:4-methyl-7-diethyl-aminocoumarin; 1, 2-bis (benzimidazol-2-yl) ethylene; 1, 3-biphenyl-pyrazoline; 2, 5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphtho [ 1,2-d]oxazole; and 2- (1, 2-stilbene-4-yl) -2H-naphtho [ 1,2-d]triazole. See also Hamilton, U.S. patent No. 3,646,015, issued to 1972,2, 29.

Dye transfer inhibitors

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

More specifically, the polyamine N-oxide polymers preferably used in the present invention comprise units having the following structural formula: R-A_x-P; wherein P is a polymerized unit, which unit may be linked to an N-O group, or an N-O group may form part of the polymerized unit, or an N-O group may link two units; a is a member of the following structure: -nc (O) -, -c (O) O-, -S-, -O-, -N =; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any combination thereof, the nitrogen of the N-O group may be attached to R, or the N-O group is part of these groups. Polyamine N-oxides are preferably those wherein R is a heterocyclic group (e.g., pyridine, pyrrole, imidazole, pyrrolidine, piperidine, and derivatives thereof).

The N-O group may be represented by the following 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 it. The amine oxide units in the polyamine N-oxide have a pKa of<10, preferably a pKa of<7, more preferably a pKa of<6.

Any polymer backbone may be employed provided that the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Suitable examples of polymeric backbones are: polyethylene, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate, and mixtures thereof. These polymers include random and block copolymers, one of which is an amine N-oxide and the other of which is an N-oxide. In amine N-oxide polymers, the typical ratio of amine to amine N-oxide is from 10: 1 to 1: 1,000,000. However, the number of amine oxide groups in the polyamine oxide polymer can be varied by appropriate copolymerization, or by appropriate degree of N-oxidation. The polyamine oxides obtained can have almost any degree of polymerization. Typically, the average molecular weight is in the range of 500-; more preferably 1,000-500,000; most preferably 5,000-100,000. These preferred classes of materials may be referred to as "PONO".

Most preferably, the polyamine N-oxide used in the detergent compositions of the present invention is poly (4-vinylpyridine-N-oxide) having an average molecular weight of 50,000 and an amine to amine N-oxide ratio of 1: 4.

Copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (a class known as "PVPVI") are also preferred for use herein. Preferably, the average molecular weight of PVPVPVI is in the range of 5,000-1,000,000, more preferably 5,000-200,000, and most preferably 10,000-20,000. (the average molecular weight range is determined by light scattering and is disclosed in Barth et al, chemical analysis, vol 113, "New method of Polymer identification", which publication is incorporated herein by reference). In the PVPVI copolymer, the molar ratio of N-vinylimidazole to N-vinylpyrrolidone is 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 either linear or branched.

The compositions of the present invention may also employ polyvinylpyrrolidone ("PVP") having an average molecular weight of 5,000-400,000, preferably 5,000-200,000, and more preferably 5,000-50,000. PVP-like materials are well known to those skilled in the detergent art; see, for example, EP-A-262,897 and EP-A-256,696, which are incorporated herein by reference. Compositions containing PVP may also contain polyethylene glycol ("PEG") having an average molecular weight of 500-100,000, preferably 1,000-10,000. The PEG/PVP ratio is preferably in the range of 2: 1 to 50: 1, more preferably 3: 1 to 10: 1, in ppm released into the wash solution.

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

Hydrophilic fluorescent whitening agents useful in the compositions of the present invention are those having the following structural formula:

wherein R is₁Selected from phenylamino, N-2-di-hydroxyethyl and NH-2-hydroxyethyl; r₂Selected from the group consisting of N-2-di-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 structural formula, R₁Is phenylamino, R₂In the case of N-2-bis-hydroxyethyl and M is a cation such as sodium, the whitening agent is 4,4 '-bis (4-phenylamino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino) -2, 2' -stilbene disulfonic acid and the disodium salt. This particulate brightener material is sold under the trade name Tinopal-UNPA-GX by Giba-Geigy. Tinopal-UNPA-GX is a preferred hydrophilic fluorescent whitening agent in the detergent compositions of the present invention.

In the above structural formula, R₁Is phenylamino, R₂In the case of N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4,4 '-bis [ (4-phenylamino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino]-2, 2' -stilbenedisulfonic acid disodium salt. This particulate brightener material is sold under the trade name Tinopal5BM-GX by Giba-Geigy.

In the above formula, when R1 is phenylamino, R2 is morpholino and M is a cation such as sodium, the brightener is the sodium salt of 4,4 '-bis [ (4-phenylamino-6-morpholino-s-triazin-2-yl) amino]2, 2' -diphenylethylene disulfonic acid. This particulate brightener material is sold under the trade name Tinopal AMS-GX by Giba-Geigy.

The particular optical brighteners selected for use in the present invention exhibit a particularly effective dye transfer inhibition benefit when used in combination with the dye transfer inhibiting agents selected above. The use of selected polymeric materials (e.g., PVNO and/or PVPVI) in combination with selected optical brighteners above (e.g., Tinopal UNPA-GX, Tinopal5BM-GX and/or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous wash solutions than either of the two detergent composition components alone. While not being bound by any theory, it is believed that such brighteners do so because they have a high degree of fabric affinity in the wash liquor and therefore deposit relatively quickly on the fabric. The extent to which the brightener deposits on the fabric in the liquor can be determined by a parameter known as the "consumption coefficient". Typically the exhaustion coefficient is the ratio of a) the deposited brightener material on the fabric to b) the initial brightener concentration in the wash liquor. In the present invention, a whitening agent having a relatively high consumption coefficient is most suitable for inhibiting dye transfer.

It will, of course, be appreciated that other conventional optical brightener-type compounds may optionally be used in the compositions of the present invention to produce a conventional fabric "whitening" effect, rather than a true dye transfer inhibition. Such applications are common and well known in detergent manufacture.

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 amino carboxylates, amino phosphonates, polyfunctionally-substituted aromatic chelating agents and mixtures thereof, as will be defined hereinafter. Without being bound by any theory, it is believed that the superiority of these materials is due in part to their unique ability to remove iron and manganese from the wash liquor by forming soluble chelates.

Aminocarboxylates useful as optional chelating agents include: alkali metal, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid, ethylenediaminetetrapropionic acid, triethylenetetraminehexaacetic acid, diethylenetriaminepentaacetic acid, and hydroxyethyldiglycine, and mixtures thereof.

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present inventionif at least low levels of total phosphorus are permitted in the detergent compositions and include the ethylenediaminetetra (methyl phosphonates) known as deqlet. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.

Polyfunctionally-substituted aromatic chelating agents may also be employed in the compositions of the present invention. See U.S. Pat. No. 3,812,044 to Connor et al (1974, 5, 21). The acid form of such preferred compounds is a dihydroxydisulfobenzene compound, such as 1, 2-dihydroxy-3, 5-disulfobenzene.

Preferred biodegradable chelating agents (sequestrars) for use in the present invention are ethylenediamine disuccinate ("EDDS"), particularly the [ S, S]isomers disclosed in U.S. Pat. Nos. 4,704,233,1987,11,3 to Hartman and Perkins.

The compositions of the invention may also contain a water-soluble methylglycine diacetic acid (MGDA) salt (or acid form) which acts as a sequestrant or auxiliary builder, when used as an auxiliary builder, for example together with insoluble builders (zeolites, layered silicates etc.).

If employed, these chelants will generally comprise from 0.1% to 15% by weight of the detergent composition of the present invention. More preferably from 0.1% to 3.0% by weight of the composition.

Suds suppressor

Compounds for reducing or inhibiting foam formation may be incorporated into the compositions of the present invention. Suds suppressors are of great importance in what is known as the "high-intensity rinse" in U.S. Pat. Nos. 4,489,455 and 4,489,574, as well as in European front-loading clothes washing machines.

Many different materials can be used as suds suppressors and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer, encyclopedia of chemical technology, 3 rd edition, volume 7, 430-447(John Wiley&sons. Inc., 1979). One class of suds suppressors of particular interest includes monocarboxylic fatty acids and soluble salts thereof. See U.S. patent 2,954,347 to Wayne st.john, issued to 1960.9.27. Monocarboxylic fatty acids and their salts used as suds suppressors generally contain 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 salts and alkanolammonium salts.

The detergent compositions of the present invention may also contain a non-surfactant suds suppressor. They bagComprises the following steps: high molecular weight hydrocarbon compounds, e.g. alkanes, fatty acid esters (e.g. triglycerides), fatty acid esters of monohydric alcohols, aliphatic C₁₈-C₄₀Ketones (e.g., stearyl ketone), and the like. Other foam inhibitors include: n-alkylated aminotriazines, such as tri-or hexa-alkylmelamines or di-to tetra-alkyldiamine chlorotriazines, which are the products of cyanuric chloride and two or three moles of a primary or secondary amine containing from 1 to 24 carbon atoms; propylene oxide; and monostearyl phosphates such as monostearyl alcohol phosphate and distearyl phosphoric acid dialkali metal (e.g., K, Na and Li) salts and phosphates. The hydrocarbon compounds are, for example, paraffins and halogenated paraffins, which can be used in liquid form. The so-called liquid hydrocarbons should be liquid at room temperature and atmospheric pressure while having a pour point of-40 ℃ to 50 ℃ and a minimum boiling point of not less than 110 ℃ at atmospheric pressure. The use of waxy hydrocarbons is also well known and preferably has a melting point below 100 ℃. Such hydrocarbons constitute a preferred class of suds suppressors for detergent compositions. Hydrocarbon suds suppressors are disclosed in U.S. Pat. No. 4,265,779 to Gandolfo et al (1981, 5, 5). Thus, the hydrocarbons include aliphatic, alicyclic, aromatic and heterocyclic saturated or unsaturated hydrocarbons having 12 to 70 carbon atoms. In the suds suppressor discussion, the term "paraffinic" as used herein shall include mixtures of true paraffins as well as cyclic hydrocarbons.

Another preferred class of non-surfactant suds suppressors comprises silicone suds suppressors. Such materials include silicone oils (e.g., polydimethylsiloxanes), dispersions or emulsions or resins of silicone oils, and combinations of polyorganosiloxanes and silica particles, where the polyorganosiloxanes are chemisorbed or fused to the silica. Silicone suds suppressors are well known to those skilled in the art and are disclosed in U.S. Pat. No. 4,265,779 to Ganodolfo et al (issued to 1982,5,5) and European patent application 89307851.9 to Starch, M.S. (published at 1990.2.7).

Other silicone suds suppressors are disclosed in U.S. Pat. No. 3,455,839, which relates to compositions and methods for eliminating aqueous foam by incorporating a small amount of polydimethylsiloxane liquid therein.

Mixtures of siloxanes and silanized silicas are disclosed in German patent application 2,124,526 et al. Silicone antifoams and foam control agents in granular detergent compositions are disclosed in U.S. Pat. No. 3,933,672 to Bartolotta et al and U.S. Pat. No. 4,652,392 to Baginski et al (issued 1987,3, 24).

Typical silicone-type suds suppressors suitable for use in the present invention are suds controlling agents in a suds suppressing amount consisting essentially of:

a polydimethylsiloxane fluid having a viscosity of from about 20cs. to about 1,500cs at 25 ℃;

(ii) about 5 to about 50 parts by weight of a silicone resin consisting of SiO per 100 parts by weight of (i)₂Unit and (CH)₃)₃SiO_1/2Unit Composition of and (CH)₃)₃SiO_1/2Unit to SiO₂The ratio of units is from about 0.6: 1 to about 1.2: 1.

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

In the preferred silicone suds suppressors for use herein, the solvent used as 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 not linear.

To further illustrate this point, typical liquid laundry detergent compositions which provide foam control will optionally contain from about 0.001 to about 1, preferably from about 0.01 to about 0.7, more preferably from about 0.05 to about 0.5, weight percent of a silicone suds suppressor. It comprises (1) a non-aqueous emulsion of a primary antifoam agent which is (a) a polyorganosiloxane, (b) a resinous silicone or silicone resin-forming silicone compound, (c) a fine powder filler, and (d) a catalyst which promotes the reaction of the mixed components (a), (b) and (c) to form a silanol (silalate); (2) at least one nonionic silicone surfactant, and (3) polyethylene glycol or polyethylene-polypropylene glycol copolymer having a water solubility at room temperature of greater than about 2% by weight and no propylene glycol. Similar amounts may be employed in particulate compositions, gels, and the like. See also us patent 4,978,471 to Starch (1990, 12,18) and us patent 4,983,316 to Starch (1991, 1,8), us patent 5,288,431 to Huber et al (1994, 2,22), us patent 4,639,489 and Aizawa et al at us patent 4,749,740 (1990, 12,18) column 1, line 46 to column 4, line 35.

The silicone suds suppressors of the present invention preferably comprise polyethylene glycol andpolyethylene/polypropylene glycol copolymers, all of which have an average molecular weight of less than about 1,000, preferably in the range of 100 and 800. The solubility of the polyethylene glycol and polyethylene/polypropylene copolymer in water at room temperature should be greater than about 2% by weight, preferably greater than about 5% by weight.

Preferred solvents of the invention are polyethylene glycols, and copolymers of polyethylene glycol/polypropylene glycol, preferably PPG200/PEG300, having an average molecular weight of less than about 1,000, more preferably in the range of 100 and 800, and most preferably in the range of 200 and 400. Polyethylene glycol: the weight ratio of polyethylene/polypropylene glycol copolymer is between about 1: 1 and 1: 10, most preferably between 1: 3 and 1: 6.

Preferably, the silicone suds suppressors used herein are free of polypropylene glycol, especially free of polypropylene glycol having a molecular weight of 4,000. They are also preferably free of block copolymers of ethylene oxide and propylene oxide, such as PLURONICL 101.

Other suds suppressors useful herein include secondary alcohols (e.g., 2-alkyl alcohols) and combinations of such alcohols with silicone oilsMixtures, such as the siloxanes disclosed in U.S. Pat. Nos. 4,798,679, 4,075,118 and EP150,872. The secondary alcohol containing C₁-C₁₆Chain length C₆-C₁₆An alkanol. One preferred alcohol is 2-butyloctanol, which is commercially available from Condea under the trademark 1SOFOL 12. Mixtures of secondary alcohols are commercially available from Enichem under the trademark ISALCHEM 123. Mixed suds suppressors typically comprise an alcohol + silicone mixture in a weight ratio of from 1: 5 to 5: 1.

For any detergent composition used in an automatic laundry or dish washing machine, suds should be limited to neither overflowing from the washing machine nor adversely affecting the dish washing mechanism. The defoamer, when employed, is preferably present in a "foam-eliminating amount". By "suds-eliminating amount" is meant an amount of suds controlling agent which the manufacturer of the composition can select sufficient to control suds whereby a low sudsing laundry or dish washing detergent for use in an automatic type laundry or dish washing machine can be made.

The compositions will generally contain from 0 to 10% of suds suppressors. When used as suds suppressors, the monocarboxylic fatty acids and salts thereof are typically present in the detergent composition in an amount up to 5% by weight. The preferable dosage of the fatty monocarboxylic acid foam inhibitor is 0.5-3%. Silicone suds suppressors are typically present in the detergent composition in amounts up to 2.0% by weight, although higher amounts may also be employed. This upper limit is applicable in practice, mainly due to the cost minimization and effective control of the foam in lower amounts. The preferred amount of silicone suds suppressor is from 0.01% to 1%, more preferably from 0.25% to 0.5%. In the present invention, these weight percentages include any silica that may be used with the polyorganosiloxane, as well as any additional materials that may be used. Monostearyl phosphate suds suppressors are typically employed in the compositions in amounts ranging from 0.1% to 2% by weight. Hydrocarbon suds suppressors are generally used in amounts ranging from 0.01% to 5.0%, although higher amounts may also be employed. Alcohol suds suppressors are generally present in the final composition in amounts of from 0.2% to 3% by weight.

Alkoxylated polycarboxylates

Alkoxylated polycarboxylates, such as those prepared from polyacrylates, may provide additional grease removal performance herein. Such materials are disclosed on page 4 and below of WO91/08281 and PCT/01815 (p.4et seq.), which are incorporated herein by reference. From a chemical perspective, these materials include polyacrylates having an ethoxy side chain every 7-8 acrylate units. The side chain is as in formula- (CH)₂CH₂O)_m(CH₂)_nCH₃Wherein m is 2 to 3 and n is 6 to 12. The side chain is connected to the polyacrylate "backbone" via an ester linkage, thereby obtaining a "comb" polymer-like structure. The molecular weight may vary, but is typically in the range of 2000-50,000. Such alkoxylated polycarboxylatesThe acid salt may be present in the composition of the invention in an amount of from 0.05% to 10% by weight.

Fabric softener

Various all-through laundry fabric softeners, especially the very fine green clays disclosed in Storm and NIRsch, U.S. Pat. No. 4,062,647 (issued 1977,12,13) and other known softener clays, may optionally be present in the compositions of the present invention in typical amounts of 0.5% to 10% by weight to provide fabric softening while cleaning fabrics. Clay softeners may be used in combination with amine and cationic softeners as disclosed in Crisp et al, U.S. Pat. No. 4,375,416(1983.3.1) and Harris et al, U.S. Pat. No. 4,291,071 (1981.9.22).

Perfume

Flavor and fragrance components suitable for use in the compositions and methods of the present invention include a number of different natural and synthetic chemical components including, but not limited to, aldehydes, ketones and esters. Also comprises various natural extracts and essence containing multiple components such as sweet orange oil, lemon oil, flos Rosae Rugosae extract, lavender, Moschus, herba Pogostemonis, balsam essence, oleum Santali albi, oleum Pini, and Toonae sinensis. The finished fragrance may comprise a very complex mixture of the above-mentioned components. Finished perfumes are typically present at levels of from 0.01% to 2% by weight of the detergent composition, and individual perfume components may comprise from 0.0001% to 90% of the finished perfume composition.

Non-limiting examples of perfume components suitable for use in the present invention include 7-acetyl-1, 2,3,4,5,6,7, 8-octahydro-1, 1, 67-tetramethylnaphthalene, methylionone, G-methylionone, methylchloropsilon, methyl 1,6, 10-trimethyl-2, 5, 9-cyclododecatriene (cyclododetectrien) -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-2, 3-dihydroindene, p-hydroxy-phenyl-butanone, benzophenone, β -naphthyl ketone, 6-acetyl-1, 1,2,3,3, 5-hexamethyl-2, 3-dihydroindene, 5-acetyl-3-isopropyl-1, 3,3, 5-hexamethyl-2, 3-dihydroindene, 3-cyclohexyl-2, 3-hydroxy-phenyl-1, 3-propenyl-2, 6-dihydronaphthalene, 7-cyclohexyl-2, 3-dimethyl-2, 3-dihydroindene, p-hydroxy-phenyl-butanone, 3,3, 5-carbanilide, 2, 8-cyclohexyl-methyl-oxo-1, 3, 7-2, 8-dihydronaphthalene, 7-cyclohexyl-hexahydro-1, 7-1, 6-hexahydro-1, 7-1, 6-dihydronaphthalene-hexahydro-1, 7-1, 3, 6-dihydronaphthalene-methyl-cinnamyl-methyl-2, 6-cinnamyl-methyl-2, 3-cyclohexyl-6-methyl-cyclohexyl-oxo-2, 7-methyl-2, 7-2, 6-8-dihydronaphthalene, 7-cinnamyl-dihydronaphthalene, 7-8-dihydronaphthalene, 6-cinnamyl-dihydronaphthalene, 7-cinnamyl-methyl-8-cinnamyl-methyl-cinnamyl-8-methyl-8-2, 7-methyl-ethyl-8-pentyl-2, 7-pentyl-8-pentyl-2.

Particularly preferred perfumes are those which maximize the odor of finished cellulase-containing compositions, including, but not limited to, hexylcinnamaldehyde, 2-methyl-3- (p-tert-butylphenyl) -propionaldehyde, 7-acetyl-1, 2,3,4,5,6,7, 8-octahydro-1, 1,6, 7-tetramethylnaphthalene, benzyl salicylate, 7-acetyl-1, 1,3,4,4, 6-hexamethyltetralin, p-tert-butylcyclohexyl acetate, methyl dihydrojasmonate, β -naphthol methyl ether, methyl β -naphthyl ketone, 2-methyl-2- (p-isopropyl-phenyl) -propionaldehyde, 1,3,4,6,7, 8-hexahydro-4, 6,6,7,8, 8-hexamethylcyclopent-gamma-benzopyran, dodecahydro-3 a,6,6,9 a-tetramethylnaphtho [ 2,1b]furan, anisaldehyde, coumarin, cedryl, decylaldehyde, tricyclodecenyl acetate, and tricyclodecenyl propionate.

Other preferred materials include perfume oils, balsams and resins of different origins including (but not limited to): peru balsam, mastic resin, storax, Cistus resin, semen Myristicae, cortex Cinnamomi oil, benzoin resin, coriander resin, and Lavender. Other fragrance chemicals include phenylethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 2- (1, 1-dimethylethyl) -cyclohexanol acetate, benzyl acetate, and eugenol. Carriers such as diethyl phthalate may be employed in the finished fragrance composition.

Other Components

Many other components suitable for use in detergent compositions may also be included in the compositions of the present invention, including: other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, and the like. If high foaming is desired, a foam booster, e.g. C, may be incorporated into the composition₁₀-C₁₆Alkanolamides, and generally they are used in amounts of 1% to 10%. C₁₀-C₁₄Monoethanol and diethanol amides are typical types of such suds boosters. It may also be beneficial to use such suds boosters in combination with added high sudsing surfactants such as the amine oxides, betaines and sultaines described above. If desired, water-soluble magnesium and/or calcium salts (e.g. Mg)₂Cl、MgSO₄、CaCl₂、CaSO₄) Can be added in the conventional amount of 0.1% -2% to provide the effects of increasing foam and improving oil removal performance.

The various detersive ingredients optionally used in the compositions of the present invention may be further stabilized by absorbing these ingredients onto a porous hydrophobic substrate and subsequently coating the substrate with a hydrophobic coating. Preferably, the detergent component should be mixed with the surfactant before being absorbed into the porous matrix. In use, the detergent component is released from within the matrix into the aqueous wash liquor, where it exerts its detersive function.

To illustrate this technique more specifically, a porous hydrophobic silica (trademark SIPERNATD10, DeGussa) is mixed with a mixture containing 3% -5% C₁₃-C₁₅A proteolytic enzyme solution of ethoxylated alcohol (EO7) nonionic surfactant was mixed. Typically, the enzyme/surfactant solution is 2.5 times (2.5X) the weight of the silica. Dispersing the obtained powder into silicone oil (intermediate viscosity) under stirringVarious silicone oils in the range of 500-12,500 may be employed). The resulting silicone oil dispersion is emulsified or otherwise added to the finished detergent matrix. By this means, the above-described enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners, and hydrolytic surfactants have become "protected" components when used in detergents, including liquid laundry detergent compositions.

Liquid detergent compositions may contain water and other solvents as carriers. Low molecular weight primary or secondary alcohols are suitable, for example methanol, ethanol, propanol and isopropanol. Monohydric alcohols are preferred for solubilizing the surfactant, but polyols such as those containing 2 to 6 carbon atoms and 2 to 6 hydroxyl groups (e.g., 1, 3-propanediol, ethylene glycol, glycerol, and 1, 2-propanediol) can also be used. Such carriers may be present in the composition in an amount of from 5% to 90%, typically from 10% to 50%.

In usein water washing operations, it is preferred to formulate detergent compositions of the invention such that the wash water pH is in the range of from 6.5 to 11, preferably from 7.5 to 10.5. The liquid laundry finished formulation preferably has a pH in the range of 6.8-9.0. The laundry product is usually at a pH of 9-11. Recommended amounts of pH control techniques include the use of buffers, bases, acids, and the like, and are well known in the art.

Granulating

The bis-alkoxylated cationic surfactant of the present invention is added to the crutcher and subsequently helps to remove any residual potentially malodorous short chain amine impurities by conventional spray drying means. Where the manufacturer wishes to prepare mixed particles containing alkoxylated cations for use in high density granular detergents and the like, it is preferred that the granular composition is not overbased. A process for preparing high density (greater than 659g/l) particles is described in U.S. Pat. No. 5,366,652. Such particles can be prepared in formulations having an effective pH of 9 or less at the time of use to avoid off-taste of contaminating amines. This can also be achieved by adding a small amount of an acid source (e.g. boric acid, citric acid, etc.) or a suitable pH buffer to the particles. In another way, problems with amine malodour may be masked by the application of perfume components as described above.

In the following examples, abbreviations for the various components used in the compositions have the following meanings: alkylbenzene sulfonate anionic surfactant having an average LAS chain length of C11.5, preferably

Sodium salt AS Primary alkyl sulphate anionic surfactant having an average chain length of C14-15, preferably

Sodium salt NI C12-15 ethoxylated alcohol, average degree of ethoxylation EO9 (nonionic surface active)

Agent) SKS-6 layered silicate, available from Hechst copolymer acrylic acid/maleic acid copolymer, sodium salt zeolite 1-10 micron zeolite APEG4000 polyethylene glycol, average molecular weight 4000NOBS nonanoyloxybenzene sulfonate bleach activator PB-1 sodium perborate monohydrate protease the proteolytic detergent enzymes described above, including BIOSAM3.0 amylase amylolytic detergent enzyme SRA-1 detergent, methylcellulose, detergent whitening agent X Tinopal _ CBS-X disclosed in US patent 5,415,807 having a molecular weight of about 13000 and a degree of substitution of 1.8-1.9SRA-2, distyryldibenzenesulfonate salts; Ciba-Geigy brightener Y Tinopal UNPA-GX, cyanuric chloride/diaminostilbene; ciba-

Geigy foam control agent silicon dioxide/siloxane foam inhibitor

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

Examples a and B describe granular detergents.

Example a component% (wt.) ppm surfactant

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2^*0.473.13 builder-alkaline

SKS-6 3.29 21.94

Copolymer 7.1047.36

Zeolite 8.4056.03

PEG4000 0.19 1.27

Sodium carbonate 17.84118.99

Silicate (2.0R) 11.4076.04 bleaching agent

NOBS 4.05 27.01

PB-13.9226.15 enzyme

Protease 0.855.67

Amylase 1.208.00 others

SRA-1 0.26 1.73

SRA-2 0.26 1.73

Whitening agent X0.211.40

Whitening agent Y0.100.67

Hydrophobic silica 0.302.00

Foam control agent 0.171.13

Sodium sulfate 5.1434.28

Fragrance 0.251.67

Miscellaneous minor ingredients and moisture 3.2821.88

Adding up to: 100667.00

Dosage-20 g/30L

^*The exemplified AQA-1 (cocomeeeo 2) surfactants can be replaced by equivalent amounts of any of the surface active AQA-2 through AQA-22 or other AQA surfactants.

Example B Components% (wt.) ppm surfactant

LAS 21.47 143.20

AS 6.55 43.69

NI 3.30 22.01

CocoMeEO2^*0.47 3.13Builder-alkalinity

SKS-6 3.29 21.94

Copolymer 7.1047.36

Zeolite 8.4056.03

PEG4000 0.19 1.27

Sodium carbonate 19.04127.00

Silicate (2.0R) 11.4076.04 bleaching agent

NOBS 4.05 27.01

PB-13.9226.15 enzyme

Protease 0.855.67 other SRA-10.261.73 SRA-20.261.73 whitener X0.211.40 whitener Y0.100.67 hydrophobic silica 0.302.00 foam control agent 0.171.13 sodium sulfate 5.1434.28 fragrance 0.251.67 miscellaneous minor ingredients and moisture 3.2821.88 add up to: 100667.00

^*The exemplary bis-AQA-1(CocoMeEO2) surfactant may be replaced by the equivalent amounts of bis-AQA-2 through bis-AQA-22 surfactants or other bis-AQA surfactants.

The following describes the test procedures and measurements performed on various soils and stains using compositions within the scope of the present invention. From the test data, it can be seen that overall cleaning performance is improved for a wide variety of different soils and stains on a variety of fabrics.

Performance test method

Preparation of samples

The preparation of the sample essentially comprises the following steps:

1. formulation of premix LAS + AS

2. Formulating a premix LAS + AS + cationic surfactant

3. Formulating a non-ionic (AE) surfactant stock solution

4. Formulation of builder solution

5. Preparation of the granules

Surfactant (b):

surfactant weight^*Active wash

gms% concentration, ppm

LAS 78.85 44.50 143.20

AS 34.5531.0043.70 cationic surfactant 01.9040.003.10

AE 19.44 100.00 22.00^*(actual weight in difference to percent active) preparation procedure for the performance test product: step I, weighing and mixing the surfactants according to the following sequence: 1. weigh 78.85gms LAS; 2. 34.55gms AS3 were weighed in the same beaker 498.10mls of distilled water was added to the LAS&A mixture of AS; 4. pre-mixing LAS and AS and heating at 40 ℃ for about 30 minutes until they are completely dissolved;

step II:

1. 01.90gms of cationic surfactant was weighed into the same beaker containing LAS + AS premix solution

2. The total volume of the solution then amounts to 500 mls.

The 500ml surfactant mixture can be washed 5 times and 100ml of this stock solution can be used per wash. This 100ml solution was added to 49L of tap water to obtain the corresponding wash concentration for each surfactant.

Step III:

1. weigh 19.44gms AE separately;

2. adding 900ml of distilled water to AE;

3. the 900ml solution was available for 18 washes;

4. 50ml of the above solution was used in each wash.

Step IV:

silicate salt: 148.32gms of distilled water per 900 ml; 50ml of this solution was used for each wash;

copolymer (b): 92.88gms per 900ml of distilled water; 50ml of the solution was used for each wash;

and (3) particle: the particle compositions were weighed separately in the same beaker.

Sequence of addition to the washing machine:

with stirring, the components were added in the following order:

1. silicate (2.0R)

2. Copolymers (as described above)

3. Particulate matter

At this point, the agitation was stopped (to avoid foaming during surfactant addition)

LAS + AS + cationic solution

AE solution

Stirring for 15 seconds

Hardness: no additional hardness was added to the highest hardness value of tap water.

Loading: typically 2.4kg of the following substrate was used:

cotton shirt (1)

T-shirt of a punch (provided by the expert panel) (3)

Big T-shirt (11)

DKPE T-shirt (1)

P/C pants (2)

Cotton shorts (1)

DKPE is a double-strand woven polyester

DMO is dirty motorcycle oil

Test results I, shown below, show the performance of the compositions of the invention using a CoCoCoMeEO 2+ LAS/AS mixture, and test results II show the use of CoCoCoMeEO 10^*+ LAS/AS performance and compare with using CoCoCoMeEO 2+ LAS. In this test, wash performance was determined on different types of soils (i.e., body soils, builder sensitive soils, bleach sensitive soils, surfactant sensitive soils, and socks). The term "bis" is as described above: "EO 10" refers to two poly-EO chains having a total average number of EO units in the molecule of 10, typically (but not limited to) about 5 EO units per chain.

Experimental results I

Premixed soil test I of CocoMeEO2 cation and LAS&AS (Total anion System) test II average applied collar-0.02-0.27-0.15 Collar 0.77S 0.73S0.75 cuff-0.170.330.08 dirty-0.10.17S 0.04 body soil (average) 0.120.240.18 Clay C/D1.03S 0.7S 0.87 Clay DKPE 0.7S-0.020.34 builder sensitive soil (average) 0.870.340.61 spinach 0.330.560.45 coffee 0.210.42S 0.32 bleach sensitive soil (average) 0.270.490.38 meat sauce 0.84S 1.08S 0.96 curry powder 1.14S 1.11S 1.13 marinade oil 0.10.160.13 DMO 0.44-0.340.05 surfactant sensitive soil 0.630.50.57 (average) (including sock) 0.390.380.39 sock (before washing) 0.320.35A 0.34 sock (after washing) 0.080.64A 0.36-0.240.280.02 triangular sock (after washing) area 0.240.280.02A

Experimental results I

Premix soil test of CocoMeEO2 cationic surfactant with LAS test I test II average applied collar 0.27-0.73-0.23 Collar-0.040.150.06 cuff-0.35-0.25-0.30 dirty 0.130.51S 0.32 body soil (average) 0.00-0.08-0.04 Clay C/D0.590.79S 0.69 Clay DKPE 0.040.660.35 builder sensitive soil (average) 0.320.730.53 spinach 0.070.580.33 coffee 0.240.240.24 bleach sensitive soil (average) 0.160.410.29 meat sauce-0.1-0.08-0.09 curry powder 0.10.540.32 marinade oil-0.53-0.02-0.28 DMO-0.220.05-0.09 surfactant sensitive soil-0.190.12-0.04 (average) average (including sock before washing) 0.33-0.070.13 sock (after washing) 0.7S-0.050.33 sock (average) triangular sock (area 0.360.020.19) 0.33-0.070.13 sock (after washing)

Results of the experiment II

Precompounding soil test of CocoMeEO10 cationic surfactant and LAS + AS test II average applied Collar 0.48-0.020.23 Collar 0.020.060.04 Cuff 0.330.250.29 dirty-0.280.11-0.09 body soil (average) 0.140.100.12 Clay C/D0.75S 0.440.60 Clay DKPE 0.27-0.47-0.10 builder sensitive soil (average) 0.51-0.020.25 spinach 0.000.330.17 coffee 0.380.82S 0.60 Bleach sensitive soil (average) 0.190.580.39 meat sauce 0.050.96S 0.51 curry powder 0.420.91S 0.67 marinade 0.23-0.070.08 DMO 0.31-0.130.09 surfactant sensitive soil 0.250.420.34 (average) (including sock)0.20.260.23 sock (before washing) 0.140.230.19 sock (after washing) -0.190.48S 0.15 sock (triangular region) -0.320.25-0.04

Results of the experiment II

Pre-blend soil for CocoMeE10 cationic surfactant and LAS used Collar 0.17 Collar-0.52 Cuff 0.19 dirty-0.17 body soil (average) -0.08 Clay C/D-0.34 Clay DKPE 0.09 builder sensitive soil (average) -0.13 spinach 0.06 coffee 0.08 Bleach sensitive soil (average) 0.07 meat sauce-0.20 curry powder-0.38 marinade oil-0.33 DMO-0.33 surfactant sensitive soil-0.31 (average) average (including socks) -0.11 socks (before washing) 0.42S socks (after washing) 0.64S socks (triangular regions) 0.22S socks

Examples

In the following examples, the abbreviated components have the following meanings: LAS straight chain C₁₂Sodium alkyl benzene sulfonate TAS tallow alkyl sodium sulfate C45AS C₁₄-C₁₅Straight chain alkyl sodium sulfate C_xyE_zC of S condensed with z moles of ethylene oxide_1x-C_1yC45E7 condensation of branched alkyl sodium sulfate C45 with an average of 7 moles of ethylene oxide₁₄-C₁₅C of a predominantly linear primary alcohol C25E3 condensed with almost 3 moles of ethylene oxide₁₂-C₁₅C of condensation of the predominantly branched primary alcohol C25E5 with an average of 5 moles of ethylene oxide₁₂-C₁₅Branched primary alcohol CocoeO 2R₁N⁺(CH₃)(C₂H₄OH)₂Wherein R is₁=C₁₂-C₁₄Sodium linear alkylcarboxylate TFAA C derived from a mixture of tallow and coconut oil from 80/20₁₆-C₁₈Alkyl N-methylglucamides TPKFA with C₁₂-C₁₄Sodium aluminosilicate of topped whole fraction fatty acid STPP anhydrous sodium tripolyphosphate Zeolite A hydrate, withgeneral formula Na₁₂(AlO₂SiO₂)₁₂.27H₂O and base particle

NaSKS-6 crystalline layered silicate with a size of 0.1-10 μm and a general formula of delta-Na₂Si₂O₅Citric acid anhydrous citric acid carbonate anhydrous sodium carbonate, its particle size is 200 μm-900 μm, and its particle size distribution is 400 μm-1200 μm₂∶Na₂O; ratio 2.0) sodium sulfate Anhydrous sodium sulfate citrate trisodium citrate dihydrate with 86.4% activity, particle size distribution

Maleic acid/propylene based copolymer with MA/AA 1: 4 of 425-850 μm, proteolytic enzyme with average molecular weight of 70,000CMC carboxymethylcellulose sodium protease activity of 4KNPU/g, traded by NOVO Industries A/S

The trade name Savinase sells proteolytic enzyme with Alcalase activity of 3AU/g, NOVO Industries A/S sells fiber hydrolytic enzyme with cellulase activity of 1000CEVU/g, NOVO Industries A/S and

starch hydrolase with an amylase activity of 60KNU/g is sold under the trade name Carezyme, commercially available from NOVO Industries A/S

The lipase activity of 100KLU/g is sold under the name Termamyl 60T as a lipolytic enzyme, commercially available from NOVO Industries A/S

The product name Lipolase sells endoglucanase (endoglucase enzyme) with an endoenzyme activity of 3000CEVU/g, and the product name (endolase) NOVO Industries A/S sells PB4 sodium perborate tetrahydrate with the general formula NaBO₂.3H₂O.H₂O₂PB1 anhydrous sodium perborate bleaching agent with the general formula of NaBO₂.H₂O₂Percarbonate sodium percarbonate of the general formula 2Na₂CO₃.3H₂O₂NOBS nonanoyloxybenzenesulfonic acid sodium salt TAED tetraacetylethylenediamine DTPMP diethylenetriamine penta (methylene phosphate) under the trade name Dequest from Monsanto

2060 selling sulfonated Zinc Phthalocyanine brightener 14, 4 '-bis (2-sulfostyryl) Biphenyl disodium brightener 24, 4' -bis (4-phenylamino-6-morpholino-1, 3, 5-triazin-2-yl) amino)

Copolymer SRA1 of stilbene-2: 2' -disodium disulfonate HEDP 1, 1-hydroxyethane diphosphate PVNO polyvinylpyridine N-oxide PVPVI polyvinylpyrrolidone and vinylimidazole contains an oxyethylene and terephthaloyl backbone terminating in a sulfobenzoyl group

Ester of (A) SRA2 diethoxylated poly (1, 2-trimethylene terephthalate) short block copolymer polysiloxane polydimethylsiloxane foam control agent containing a siloxane-oxyalkylene copolymer as a dispersant the ratio of said foam control agent to said dispersant is from 10: 1 to 100: 1

The following examples are intended to illustrate the invention but not to limit the scope thereof, and all parts, percentages and ratios used herein are by weight unless otherwise indicated.

All amounts in the following examples are meant to be in% by weight of the composition.

Example 1

The following are detergent formulations of the present invention.

Blowing powder of AB C

STPP 14.0 - 24.0

Boiling A10.024.04.0

C45AS 8.0 5.0 11.0

MA/AA 2.0 4.0 2.0

LAS 6.0 8.0 11.0

TAS 1.5 - -

CocoMeEO2^*1.5 1.0 2.0

Silicate 7.03.03.0

CMC 1.0 1.0 0.5

Whitening agent 20.20.20.2

Soap 1.01.01.0

DTPMP 0.40.40.2 spray

C45E7 2.5 2.5 2.0

C25E3 2.5 2.5 2.0

Silicone antifoaming agent 0.30.30.3

Flavor 0.30.30.3 Dry additive

Carbonate 6.013.015.0

PB4 18.0 18.0 10.0

PB1 4.0 4.0 0

TAED 3.0 3.0 1.0

Light activated bleach 0.020.020.02

Protease 1.01.01.0

Lipase 0.40.40.4

Amylase 0.250.300.15 Dry blend sodium sulfate 3.03.05.0

The balance (water and various kinds: 100.0100.0100.0)

Component) Density (g/l) 630670670^*The exemplary bis-AQA-1(CocoMeEO2) surfactants may be replaced by equivalent amounts of bis-AQA-2 through bis-AQA-22 surfactants or other bis-AQA surfactants.

Example II

The following are bleach-free detergent formulations specific for washing colored laundry.

D E F blowing powder

Boiling A15.015.02.5

Sodium sulfate 0.05.01.0

LAS 2.0 2.0 -

CocoMeEO2^*1.0 1.0 1.5

DTPMP 0.4 0.5 -

CMC 0.4 0.4 -

MA/AA 4.04.0-agglomerates

C45AS - - 9.0

LAS 6.0 5.0 2.0

TAS 3.0 2.0 -

Silicate 4.04.0-

Zeolite A10.015.013.0

CMC - - 0.5

MA/AA - - 2.0

Carbonate 9.07.07.0 spray

Fragrance 0.30.30.5

C45E7 4.0 4.0 4.0

C25E32.02.02.0 Dry additives

MA/AA - - 3.0

NaSKS-6 - - 12.0

Citrate 10.0-8.0

Bicarbonate 7.03.05.0

Carbonate 8.05.07.0

PVPI/PVNO 0.5 0.5 0.5

Alcalase 0.5 0.3 0.9

Lipase 0.40.40.4

Amylase 0.60.60.6

Cellulase 0.60.60.6

Silicone antifoaming agent 5.05.05.0 Dry additive

Sodium sulfate 0.09.00.0 balance (moisture and various impurities): to: 100.0100.0100.0 Density (g/l) 700700850^*The exemplary bis-AQA-1(CocoMeEO2) surfactants may be replaced by equivalent amounts of bis-AQA-2 through bis-AQA-22 surfactants or other bis-AQA surfactants.

Example III

The following are detergent compositions of the present invention, which are prepared as follows:

g H I blowing powder

Zeolite A30.022.06.0

Sodium silicate 19.05.07.0

MA/AA 3.0 3.0 6.0

LAS 13.0 11.0 21.0

C45AS 8.0 7.0 7.0

CocoMeEO2^*1.0 1.0 1.0

Silicate-1.05.0

Soap-2.0

Whitening agent 10.20.20.2

Carbonate 8.016.020.0

DTPMP-0.40.4 spray

C45E71.01.01.0 Dry additives

PVPVI/PVNO 0.5 0.5 0.5

Protease 1.01.01.0

Lipase 0.40.40.4

Amylase 0.10.10.1

Cellulase 0.10.10.1

NOBS - 6.1 4.5

PB1 1.0 5.0 6.0

Sodium sulfate-6.0-balance (moisture and various impurities) to: 100100100

Example IV

The following are high-density and bleach-containing detergent formulations of the present invention:

j K L blowing powder

Zeolite A15.015.015.0

Sodium sulfate 0.05.00.0

LAS 3.0 3.0 3.0

CocoMeEO2^*1.0 1.5 1.5

DTPMP 0.4 0.4 0.4

CMC 0.4 0.4 0.4

MA/AA 4.02.02.0 agglomerates

LAS 5.0 5.0 5.0

TAS 2.0 2.0 1.0

Silicate 3.03.04.0

Zeolite A8.08.08.0

Carbonate 8.08.04.0 spray

Fragrance 0.30.30.3

C45E7 2.0 2.0 2.0

C25E32.0 Dry additive

Citrate 5.0-2.0

Bicarbonate-3.0-

Carbonate 8.015.010.0

TAED 6.0 2.0 5.0

PB1 13.0 7.0 10.0

MW 5,000,000 poly-0.2

Ethylene oxide

Montmorillonite clay-10.0

Protease 1.01.01.0

Lipase 0.40.40.4

Amylase 0.60.60.6

Cellulase 0.60.60.6

Silicone defoamer 5.05.05.0 drying additive

Sodium sulfate 0.03.00.0The balance (moisture and various impurities) to: 100.0100.0100.0 Density (g/l) 850850850^*The exemplary bis-AQA-1(CocoMeEO2) surfactant may be replaced by equivalent amounts of bis-AQA-2 through bis-AQA-22 surfactants or other bis-AQA surfactants.

Example V

The following are high density detergent formulations of the present invention:

m N blowing powder

Zeolite A2.52.5

Sodium sulfate 1.01.0

CocoMeEO2^*1.51.5 agglomerates

C45AS 11.0 14.0

Zeolite A15.06.0

Carbonate 4.08.0

MA/AA 4.0 2.0

CMC 0.5 0.5

DTPMP 0.40.4 spray

C25E5 5.0 5.0

Flavor 0.50.5 Dry additive

HEDP 0.5 0.3

SKS6 13.0 10.0

Citrate 3.01.0

TAED 5.0 7.0

Percarbonate 15.015.0

SRA1 0.3 0.3

Protease 1.41.4

Lipase 0.40.4

Cellulase 0.60.6

Amylase 0.60.6

Silicone antifoaming agent 5.05.0

Whitening agent 10.20.2

Whitening agent 20.2-balance (moisture and various impurities) to: 100100 Density (g/L) 850850^*The exemplary bis-AQA-1(CocoMeEO2) surfactant may be replaced by an equivalent amount of any one of bis-AQA-2 to bis-AQA-22 or other bis-AQA surfactants.

Any of the granular detergent compositions can be formed into detergent tablets by known tabletting processes.

The preparation of high performance liquid detergent compositions containing a non-aqueous carrier medium, particularly those specific for fabric laundering, can be carried out in accordance with the manner described in detail below. On the other hand, such nonaqueous compositions may be prepared according to U.S. Pat. Nos. 4,753,570, 4,767,558, 4,772,413, 4,889,652, 4,892,673, GB-A-2,158,838, GB-A-2,195,125, GB-A-2,195,649, U.S. Pat. No. 4,988,462, U.S. Pat. No. 5,266,233, EP-A-225,654(6/16/87), EP-A-510,762(10/28/92), EP-A-540,089(5/5/93), EP-A-540,090, U.S. Pat. No. 4,615,820, EP-A-565,017(10/13/93), EP-A-030,096(6/10/81), which are incorporated herein by reference. Such compositions may contain a variety of stably suspended particulate detergent components (e.g., the bleaching agents described above). These non-aqueous compositions thus comprise a liquid phase and optionally (but preferably) a solid phase, as will be described hereinafter and in the references cited therein. The amount and manner in which the AQA surfactants are incorporated into the composition has been disclosed in the preparation of the other laundry detergent compositions described above.

Liquid phase

The liquid phase will generally comprise from 35% to 99% by weight of the detergent composition of the invention. The liquid phase will preferably comprise from 50% to 95% by weight of the composition. Most preferably, the liquid phase comprises from 45% to 75% by weight of the composition of the invention. The liquid phase of the detergent of the invention will contain predominantly a relatively high concentration of certain types of anionic surfactant in combination with certain non-aqueous liquid diluents.

(A) Predominantly anionic surfactants

Anions as main components in nonaqueous liquid phasesThe ionic surfactant is selected from one of the alkali metal salts of alkylbenzene sulfonic acid, wherein the alkyl group contains 10 to 16 carbon atoms and is in a linear or branched configuration.(see U.S. Pat. Nos. 2,220,099 and 2,477,383, incorporated herein by reference). Especially preferred are sodium and potassium linear alkyl benzene sulphonic acids (LAS) in which the average number of carbon atoms in the alkyl group is from 11 to 14. Particularly preferred is C₁₁-C₁₄Sodium salt of LAS.

The alkylbenzene sulfonate anionic surfactant should be dissolved in a non-aqueous liquid diluent which forms the second major component of the non-aqueous phase. The alkylbenzene sulfonate anionic surfactant typically comprises from 30% to 65% by weight of the liquid phase in order to form a structured liquid phase which is phase stable and has suitable rheological properties. More preferably, the alkylbenzene sulfonate anionic surfactant comprises from 35% to 50% by weight of the nonaqueous liquid phase of the composition of the present invention. The use of such concentrations of anionic surfactant corresponds to anionic surfactant concentrations in the total composition of from 15% to 60% by weight of the composition, more preferably from 20% to 40% by weight.

(B) Non-aqueous liquid diluent

To form the liquid phase of the detergent composition, the above alkylbenzene sulfonate anionic surfactant is combined with a nonaqueous liquid diluent containing two main components. These two components are an alkoxylate of a liquid alcohol and a non-aqueous, low polarity organic solvent.

I) alcohol alkoxylates

One of the major components of the liquid diluent used to form the composition of the present invention comprises an alkoxylated fatty alcohol material. This material is also a nonionic surfactant in itself. The corresponding general formula is:

R¹(C_mH_2mO)_nOH

wherein R is¹Is C₈-C₁₆M is 2-4 and n is in the range of 2-12. Preferably R¹Is a primary or secondary alkyl group containing 9 to 15, more preferably 10 to 14 carbon atoms. It is also preferred that the alkoxylated fatty alcohol contains 2 to 12 ethylene oxides per molecule, more preferably per moleculeThe molecule contains 3-10 ethylene oxide groups.

The Hydrophilic Lipophilic Balance (HLB) of the alkoxylated fatty alcohol component in the liquid diluent is generally between 3 and 17. More preferably in the range of 6-15, most preferably 8-15.

Examples of alkoxylated fatty alcohols which are one of the main components of the nonaqueous liquid diluent for the compositions of the present invention include those prepared from alcohols having 12 to 15 carbon atoms and containing 7 moles of ethylene oxide. Such starting materials are commercially available under the trade names Neodol25-7 and Neodol23-6.5 from Shell Chemical Company. Other useful Neodol based products include Neodol1-5, an ethoxylated fatty alcohol having 5 moles of ethylene oxide and an average of 11 carbon atoms of alcohol; neodol23-9, a C of 9 moles ethylene oxide₁₂-C₁₃Primary alcohol ethoxylate and Neodol91-10, a C of 10 moles ethylene oxide₉-C₁₁Ethoxylates of primary alcohols. Such ethoxylated alcohols are also sold under the trade name Dobanol by shell chemical Company. Dobanol91-5 is a compound containing on averageC of 5mol ethylene oxide₉-C₁₁Alcohol ethoxylate, and Dobanol25-7 is a C having an average of 7 moles of ethylene oxide per mole of alcohol₁₂-C₁₅An alcohol ethoxylate.

Other examples of suitable ethoxylated alcohols include: tergitol15-S-7 and Tergitol15-S-9, both of which are linear secondary alcohol ethoxylates sold by Union Carbide Corporation. The former being C₁₁-C₁₅A mixed ethoxylation product of a linear secondary alkanol of (2) and 7 moles of ethylene oxide, the latter being C₁₁-C₁₅A similar product of a linear secondary alkanol and 9 moles of ethylene oxide.

Other types of alcohol alkoxylates suitable for use in the compositions of the present invention are higher molecular weight nonionic materials, e.g., Neodol45-11, which is an ethylene oxide condensation product of a similar higher aliphatic alcohol having 14 to 15 carbon atoms and an ethylene oxide number of 11 per mole. Such products are also sold by Shell Chemical Company.

The alcohol alkoxylate component, which is used primarily as part of the liquid diluent in the nonaqueous composition, is typically present in an amount of 1% to 60% of the liquid phase composition. More preferably, the alcohol alkoxylate component should constitute from 5% to 40% of the liquid phase, and most preferably the alcohol alkoxylate component should constitute from 5% to 30% of the detergent liquid phase. The use of the alcohol alkoxylate in the liquid phase at the concentrations described above corresponds to an alcohol alkoxylate concentration of 1% to 60%, more preferably 2% to 40%, most preferably 5% to 25% by weight of the total composition.

II) nonaqueous, low-polarity organic solvents

The second major component of the liquid diluent comprising the liquid phase of the detergent composition of the present invention comprises a non-aqueous low polarity organic solvent. The term "solvent" herein refers to the non-surface active carrier or diluent portion of the liquid phase of the composition. Some of the major and/or optional composition components may actually be dissolved in the "solvent" containing liquid phase while other components are dispersed in the "solvent" containing liquid phase as particulates. Thus, the term "solvent" does not mean that the solvent material must be capable of dissolving all of the detergent components added thereto.

The non-aqueous organic used as a solvent in the present invention is a low polarity liquid. For the purposes of the present invention, a "low polarity" liquid, if added, is one that has very low solvency for one of the preferred particulate materials (i.e. peroxygen bleach, sodium perborate or sodium percarbonate) used in the compositions of the present invention, and therefore relatively highly polar solvents such as ethanol cannot be used. Suitable types of low polarity solvents suitable for use in nonaqueous liquid detergent compositions include: non-vicinal C₄-C₈Alkylene glycols, alkylene glycol mono-lower alkyl ethers, low molecular weight polyethylene glycols, low molecular weight methyl esters and amides.

Preferred types of non-aqueous, low polarity solvents in the compositions of the present invention include non-vicinal C₄-C₈Linear or branched alkylene glycols of (1). Such materials include hexanediol (4-methyl-2, 4-pentanediol), 1, 6-hexanediol, 1, 3-butanediol, and 1, 4-butanediol. Most preferred is hexylene glycol.

Another class of nonaqueous, low polarity solvents preferred for use in the present invention comprises: mono-, di-, tri-or tetra-C₂-C₃Alkylene glycol mono C₂-C₆An alkyl ether. Specific examples of such compounds include: diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, (mono-) dipropylene glycol monoethyl ether and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are particularly preferred. Such compounds are sold under the trade names Dowanol, Carbitol and Cellosolve.

Another class of nonaqueous, low polarity organic solvents that are preferred for use in the compositions of the present invention are low molecular weight polyethylene glycols (PEGs). Such materials are those having a molecular weight of at least 150. Most preferably, PEG-based compounds having molecular weights in the range of 200-600 are used.

There is also a preferred class of non-polar non-aqueous solvents which include low molecular weight methyl esters. The general formula of the material is: r¹-C(O)-OCH₃Wherein R is¹In the range of 1-18. Examples of suitable low molecular weight methyl esters include methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.

The non-aqueous, low-polarity organic solvent used should be compatible and non-reactive with other composition components in the liquid detergent composition, e.g., bleach and/or active agents. The solvent component is generally used in an amount of 1% to 70% of the liquid phase. The nonaqueous, low polarity solvent is more preferably from 10% to 60% by weight of the liquid phase, most preferably from 20% to 50% by weight. Such concentrations of the organic solvent in the liquid phase correspond to concentrations in the total composition of from 1% to 50%, more preferably from 5% to 40% by weight, most preferably from 10% to 30% by weight.

Iii) ratio of alcohol alkoxylate to solvent

In the liquid diluent, the ratio of alcohol alkoxylate to organic solvent can be used to modify the rheology of the finished detergent composition. In general, the weight ratio of alcohol alkoxylate to organic solvent should be in the range of 50: 1 to 1: 50. More preferably, the ratio should be in the range of 3: 1 to 1: 3.

Iv) concentration of liquid diluent

The amount of total liquid diluent in the non-aqueous liquid phase for a given concentration of alkylbenzene sulfonate anionic surfactant mixture will depend on the type and amount of other composition components and the desired properties of the composition. Typically, the liquid diluent will comprise from 35% to 70% of the nonaqueous liquid phase of the composition. More preferably, the liquid diluent should comprise 50% to 65% of the nonaqueous liquid phase. Thus the corresponding non-aqueous liquid diluent concentration in the total composition is from 15% to 70% by weight of the composition, more preferably from 20% to 50% by weight.

Solid phase

The nonaqueous detergent compositions of the present invention also contain predominantly from 1% to 65% by weight, more preferably from 5% to 50% by weight, of a solid phase of particulate material dispersed and suspended in a liquid phase. Typically, such particulate materials should have a size of 0.1-1500 microns. More preferably such materials should have a size of 5-200 microns.

The particulate material used in the present invention may comprise one or more components of the detergent composition in particulate form which are substantially insoluble in the nonaqueous liquid phase of the composition. Suitable particulate materials are described in detail below.

Preparation and use of compositions

The nonaqueous liquid detergent compositions of the present invention can be prepared by combining the essential and optional ingredients in any convenient order, and mixing (e.g., agitating) the combination. The resulting mixture of components can form a phase stable composition. In a typical preparation process for these compositions, the major components and certain preferred optional compositions should be combined in a particular order and under particular conditions.

In the first step of this typical manufacturing process, the mixing of the alkylbenzene sulfonate anionic surfactant with the two major components of the non-aqueous diluent is formed by heating a mixture of the materials to a temperature of from 30 ℃ to 100 ℃.

In the second step, the heated mixture is held under shear agitation at 40 ℃ to 100 ℃ for 2 minutes to 20 hours. Optionally, mixing may also be performed at this point using vacuum. The second operation completely dissolves the anionic surfactant in the nonaqueous liquid phase.

In the third step, the liquid phase mixture of the above starting materials is cooled to 0 ℃ to 35 ℃. The purpose of this cooling step is to form a structured surfactant-containing liquid matrix into which particulate material of the detergent composition can be incorporated and dispersed.

The particulate material is added as a fourth step in which the particulate material is mixed with the liquid matrix under shear agitation. When more than one particulate material is added, it should preferably be added in a certain order of addition. For example, substantially all of the optional surfactant in solid particulate form may be added as particulate bodies ranging in size from 0.2 to 1,000 microns under continuous shear agitation. After all of the optional surfactant particulates are added, substantially all of the particulate organic builder (e.g., citrate and/or fatty acid) and/or alkalinity source (e.g., sodium carbonate) can be added while continuing to maintain the shear agitation of the composition component mixture. Other optional ingredients in the form of nationality may be added to the composition at this point. The mixture is continuously stirred, and if necessary, the stirring action can be enhanced to form a homogeneous dispersion of insoluble solid phase particles in the liquid phase.

After some or all of the above solid materials are added to the agitated mixture, the highly preferred particulate peroxygen bleach can be added to the composition again, again with continued shear agitation of the mixture. The desired stabilizing effect of the peroxygen bleach can only be achieved by the final addition of the peroxygen bleach or by the addition of the peroxygen bleach after the addition of all or most of the other components, in particular the alkali-derived particulates. If enzyme granulates are to be incorporated, they are preferably added finally to the non-aqueous liquid matrix.

As a final step, when all of the particulate material has been added, the mixture should be stirred for a period of time sufficient to form a composition having the desired viscosity and phase stability characteristics. Typically, a stirring time of 1 to 30 minutes is required.

As a variation on the above-described method of preparation of the composition, one or more solid components may be added to the agitated mixture in the form of a pre-mixed slurry of particles thereof with one or more minor liquid components. Thus, small amounts of alkoxylated alcohol and/or nonaqueous, low polarity solvent may be separately formed into a premix with particles of organic builder material and/or particles of inorganic alkalinity source and/or particles of bleach activator and added as a slurry to the agitated composition component mixture. The addition of the pulp premix should be carried out before the addition of the peroxygen bleach and/or the enzyme granulate, which substances themselves may also form part of the premix pulp in a similar manner.

The compositions of the present invention prepared by the above process may be used to form aqueous lotions for use in the washing and bleaching of fabrics. Typically, an effective amount of such compositions is added to water, preferably to a daily automatic fabric washing machine, to form an aqueous laundry/bleach solution. The aqueous washing/bleaching solution thus prepared is then brought into contact with the fabrics to be washed and bleached, preferably under agitation.

An effective amount of the liquid detergent composition of the present invention is added to water to form an aqueous laundry/bleaching liquor solution, said effective amount being an amount which is capable of achieving a concentration of 500-7,000ppm in the aqueous solution. More preferably, the detergent composition in the aqueous cleaning/bleaching solution is capable of up to 800-.

Example VI

Non-limiting examples of a bleach-containing non-aqueous liquid laundry detergent made from the compositions shown in Table 1.

TABLE I

Component weight% range (% wt.)

Liquid phase C₁₂Sodium Linear alkyl benzene sulfonate (LAS) 25.318-35C_12-14Alkoxylates 13.610-20 of d EO5 alcohol

Hexanediol 27.320-30

Perfume 0.40-1.0

AQA-1^*2.0 1-3.0

Solid body

Protease 0.40-1.0

Sodium citrate, anhydrous 4.33-6

Sodium perborate 3.42-7 sodium Nonanoyloxybenzenesulfonate (NOBS) 8.02-12

Zeolite 13.95-20 Diethyltriaminepentaacetic acid (DTPA) 0.90-1.5

Whitening agent 0.40-0.6

0.10-0.3 of foam inhibitor

Small amount of the residue- -

^*CocoMeEo2, bis-AQA-1 can be replaced by bis-AQA-2 through bis-AQA-22 surfactants or other bis-AQA surfactants.

The composition was prepared by mixing bis-AQA and LAS at a temperature of 54 ℃ (130 ° F), followed by mixing with hexylene glycol and alcohol alkoxylate for 0.5 hours. The mixture was cooled to 29 ℃ (85 ° F) and the remaining components were added to the mixture. The resulting composition was thereafter stirred at 29 ℃ for a further 0.5 h.

The resulting composition is a stable, anhydrous, high performance liquid laundry detergent having excellent stain removal performance during daily fabric laundering.

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

Example VII

Component weight% range (% wt.)

A BC₁₂-C₁₈Sulfate 15.7513.50 0-25

LAS 6.75- - -0-25 sodium carbonate 15.003.001-20 DTPP¹0.700.700.2-1.0 montmorillonite Clay- -10.00-20 Sokolan CP-5²0.40 1.00 0-2.5 bis-AQA-1³2.0 0.5 0.15-3.0TSPP 5.0000-10 STPP 5.0015.000-25 zeolite 1.251.250-15 sodium laurate 9.000-15 SRA-10.300.300-1.0 protease 0.120-0.6 amylase 0.12-0.6 lipase 0.010-0.6 cellulase- - -0.150-0.3

Balance of⁴

1 Diethylenetriamine penta-sodium phosphate

2 Sokolan CP-5 is a maleic acid-acrylic acid copolymer

The 3 bis-AQA-1 may be replaced by bis-AQA-2 to bis-AQA-22 surfactants or other bis-AQA surfactants.

4 balance water (2% -8%, water including hydrates), sodium sulfate, calcium carbonate and other minor components.

The above examplesdescribe fabric washing compositions according to the invention and the following examples illustrate other types of cleaning compositions according to the invention but are not intended to limit the invention thereto.

Automatic dishwashing detergents may contain: bleaching agents, such as hypochlorite sources, perborate, percarbonate or persulfate bleaches; enzymes such as proteases, lipases and amylases or mixtures thereof; rinse aids, especially nonionic surfactants; builders, including zeolites and phosphate builders; low foaming detersive surfactants, especially ethylene oxide/propylene oxide condensates. Such compositions are typically in the form of granules or gels. If a gel form is used, various gelling agents known in the literature can be used.

Example VIII

The following describes mixtures of bis-AQA surfactants which may be substituted for any of the bis-AQA surfactants described in the above examples. As noted above, such mixtures have broad spectrum of effective properties and/or are suitable cleaning compositions for use in a variety of different application conditions. Preferably the difference between the bis-AQA surfactants in the mixture is at least 1.5, more preferably 2.5 to 20 total EO units. The mixture ratio is usually in the range of 10: 1 to 1: 10. Non-limiting examples of mixtures are as follows:

composition ratio (weight)

bis-AQA-l+bis-AQA-5 1∶1

bis-AQA-1+bis-AQA-10 1∶1

bis-AQA-1+bis-AQA-15 1∶2bis-AQA-1+bis-AQA-5+bis-AQA-20 1∶1∶2

bis-AQA-2+bis-AQA-5 3∶1

bis-AQA-5+bis-AQA-15 1.5∶1

bis-AQA-1+bis-AQA-20 1∶3

Mixtures of the corresponding cationic surfactants containing only mono-ethoxylated chains with the bis-AQA surfactants herein may also be employed. Thus, for example, compounds containing the formula R¹N⁺CH₃〔EO〕_x〔EO〕_yX-and R¹N⁺(CH₃)₂〔EO〕_zX^-Mixtures of ethoxylated cationic surfactants as shown wherein R¹And X is as defined above, and wherein the (X + y) or z of one of the cationic surfactants is in the range of 1 to 5, preferably 1 to 2, while the (X + y) or z of the other cationic surfactant is between 3 and 100, preferably 10 and 20, most preferably 14 and 16. Such compositions are capable of improving cleaning performance, particularly fabric cleaning, over a wide range of water hardness, compared to the use of each cationic surfactant alone. It has now been found that short EO chain cationic surfactants (e.g. EO2) improve the cleaning performance of anionic surfactants in soft water, whereas high EO cationic surfactants improve the hardness tolerance of anionic surfactants and thus improve the cleaning performance of anionic surfactants in hard water. It is common general knowledge in the detergent art that builders can optimize the "window" of anionic surfactant performance. However, it has heretofore been impossible to extend the range to almost all water hardness conditions.

Claims (19)

1. A composition comprising an aluminosilicate builder, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula or prepared by combining the above ingredients,

wherein R is¹Is straight-chain, branched or substituted C₈-C₁₈Alkyl, alkenyl, aryl, alkylaryl, ether or glycidyl ether groups, R²Is C₁-C₃Alkyl moiety, R³And R⁴Can be independently varied and is selected from hydrogen, methyl and ethyl, X is an anion, and A' can be independently varied and are each C₁-C₄Alkoxy, p and q can vary independently and are integers from 1 to 30.

2. A composition according to claim 1 which comprises an additional builder.

3. A composition according to claim 2 wherein the adjunct builder is selected from mineral builders, layered silicate or phosphate builders.

4. A composition according to any of claims 1 to 3 prepared by combining a non-AQA surfactant and a bis-AQA surfactant.

5. A composition according to any of claims 1 to 4 wherein the non-AQA is an anionic surfactant.

6. A composition according to any of claims 1 or 5, wherein the weight ratio of bis-AQA to non-AQA surfactant is from 1: 15 to 1: 8.

7. A composition according to any of claims 1 to 6 wherein R of the bis-AQA surfactant is represented by the formula¹Is C₈-C₁₈Alkyl radical, R²Is methyl, A and A' are ethoxy or propoxy, and p and q are each an integer from 1 to 8.

8. A composition according to any of claims 1 to 7 wherein R of the bis-AQA surfactant is represented by the formula¹Is C₈-C₁₈Alkyl radical, R²Is methyl, A and A' are ethoxy or propoxy groups, and p and q are each integers from 1 to 4.

9. A composition according to any of claims 1 to 8 which comprises two or more bis-AQA surfactants, or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant.

10. A composition according to any of claims 1 to 9 comprising two or more non-AQA surfactants and a mixture of two or more bis-AQA surfactants.

11. A composition according to any one of claims 1 to 10, which is in the form of granules, bars, aqueous or non-aqueous liquids or tablets.

12. A composition according to any of claims 1 to 11 which is substantially free of a bleach component.

13. A process for removing soils and stains by contacting said soils and stains with a detergent composition, or aqueous medium containing said detergent composition, said detergent composition being a composition according to any of claims 1 to 12.

14. A method according to claim 13 which employs ethoxylated polyamines.

15. A method according to claim 13 or 14 for removing builder sensitive soil from fabric.

16. A method according to any one of claims 13 to 15, which is carried out in an automatic washing machine.

17. A process according to any one of claims 13 to 16 which is carried out as a hand wash.

18. A method for enhancing the deposition or substantive effect of a perfume or perfume ingredient on a fabric or other surface, which comprises contacting said surface with a perfume or perfume ingredient in the presence of a bis-AQA surfactant.

19. A method according to claim 18 which is conducted using a perfume or perfume ingredient in combination with a detergent composition comprising a bis-AQA.