CN1225677A - Detergent composition - Google Patents

Abstract

A detergent composition comprises a non-alkoxylated quaternary ammonium (non-AQA) surfactant, a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant and a percarbonate bleaching agent.

Description

Detergent composition

Technical Field

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

Background

The formulation of laundry detergents and other cleaning compositions presents significant challenges due to the requirement for new detergent compositions capable of removing a wide variety of soils and stains on a variety of substrates. Thus, for laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents and detergent compositions suitable for automatic dishwashing machines, reasonable selection and combination of ingredients are required in order to effectively exert their effects. Generally, these detergent compositions contain one or more surfactants that can be used to loosen and remove various soils and stains. Throughout the literature, it appears that detergent manufacturers have many surfactants and surfactant mixtures available for selection, but the reality is: many of these ingredients are specialty chemicals and are therefore unsuitable for low cost items such as household laundry detergents. Indeed, most 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, and in order to formulate compositions that perform well on a wide variety of soils and stains, as well as on a wide variety of fabrics.

There remains a problem in quickly and efficiently removing various soils and stains such as body soils, fat/oil stains and certain food stains. These soils contain a mixture of hydrophobic triglycerides, fats, mixed polysaccharides, inorganic salts and proteinaceous substances and are therefore very difficult to remove. After washing, the fabric surface often still has a small amount of hydrophobic soil and residual stains left on it. Because hydrophobic soils are not completely washed away, continued washing and application results in the accumulation of residual soils and stains, which can also adsorb particulate dust, resulting in fabric yellowing. Eventually, the fabric appearance becomes messy, and therefore the user thinks it cannot be cleaned and then discarded.

The literature shows that various nitrogen-containing cationic surfactants can be used in various cleaning compositions. These materials, which are typically in the form of amino, amido, or quaternary ammonium or imidazolinium compounds, are designed for particular uses. For example, various amino and quaternary ammonium surfactants have been suggested for use in shampoo compositions and are said to produce a hair styling effect. Other nitrogen-containing surfactants can provide fabric softening and antistatic benefits when used in certain laundry detergents. However, commercial use of these materials is largely limited due to difficulties encountered in large scale production of these compounds. Another limitation is that: anionic active ingredients in detergent compositions may form precipitates upon ionic interaction with cationic surfactants. The aforementioned nonionic and anionic surfactants remain the major surfactants in laundry compositions today.

It has now been found that certain bis-alkoxylated quaternary ammonium (bis-AQA) compounds can be used in a variety of detergent compositions in order to enhance cleaning performance on a variety of soils and stains, especially the hydrophobic soils which are commonly encountered. Surprisingly, it has now been found that: compositions containing the bis-AQA surfactant and percarbonate bleach have superior cleaning and bleaching performance compared to compositions containing either alone.

The bis-AQA surfactants of the present invention are truly beneficial to formulators over known cationic surfactants. For example, the bis-AQA surfactants used herein significantly enhance the effectiveness of the "everyday" fatty/oily hydrophobic soils normally encountered in cleaning. In addition, the bis-AQA surfactants are compatible with anionic surfactants commonly used in detergent compositions, such as alkyl sulfates and alkyl benzene sulfonates; generally, it has become one of the factors limiting the use of known cationic surfactants due to its incompatibility with anionic components in detergent compositions. Low levels (as low as 3ppm in the wash) of bis-AQA surfactant can produce the effects described herein. The bis-AQA surfactants can be formulated over a wide pH range of 5-12. The bis-AQA surfactants can be prepared as pumpable 30% by weight solutions and are therefore easy to use in manufacturing plants. bis-AQA surfactants with degrees of ethoxylation above 5 are sometimes present in liquid form and can therefore be used as 100% pure materials. In addition to its beneficial use properties, the ready availability of high concentration solutions of bis-AQA surfactants provides a real economic advantage in transportation costs. Unlike some cationic surfactants known in the art, bis-AQA surfactants are also compatible with a wide variety of perfume ingredients.

Percarbonate salts which provide peroxide bleaching action to the wash liquor are the basic technology for novel ultra dense granular laundry detergent formulations. Peroxide bleach is hydrophilic, and although it is not comparable to the bleaching effect produced by peracids (e.g., formed from peroxide by interactionwith TAED), it is effective in pigment decolorization (e.g., granular or beverage stains) and helps remove the color of organic residues associated with body soils.

It is believed that bis-AQA effectively dissolves fatty/oily soils such that the hydrophilic peroxide bleach is accessible to the color bodies (e.g., entrapped pigments) in the soil, resulting in improved soil decolorization. Accordingly, the present invention provides a detergent composition having excellent cleaning effects because the composition can very effectively clean hydrophobic fatty/oily soils as well as hydrophilic colored soils.

Background

US patent US5,441,541 issued 8, 15, 1995 to a.mehretab and f.j.lopast, relates to mixtures of anionic/cationic surfactants. UK 2,040,990, granted on 3.9.1980 to a.p.murphy, r.j.m.smith and m.p.brooks, relates to ethoxylated cationic surfactants in laundry detergents.

Summary of the invention

The present invention provides a composition comprising a percarbonate bleach, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula,

wherein R is¹Is straight-chain, branched or substituted C₈～C₁₈Alkyl, alkenyl, aryl, alkaryl, ether or glycidyl ether moieties, R²Is C₁～C₃Alkyl moiety, R³And R⁴Independently variable, each selected from hydrogen, methyl and ethyl, X is an anion, and A' independently variable, each being C₁～C₄The alkoxy group, p and q may be independently changed and each is an integer of 1 to 30.

Detailed description of the invention Percarbonate bleaches

The first essential component of the present invention is percarbonate bleach. According to the invention, alkali metal or alkaline earth metal percarbonates, in particular sodium percarbonate, are preferred percarbonates for inclusion in the compositions of the invention. The sodium percarbonate is a compound of formula 2Na₂CO₃·3H₂O₂The addition compounds of (a) are commercially available in the form of crystalline solids. Commercial sources include: solvay, FMC, Tokai Denka, etc.

Preferred percarbonate bleach compositions comprise dry particles having an average particle size of from 0.5 to 1mm, wherein: no more than 10% by weight of the particles are smaller than 0.2mm, and no more than 10% by weight of the particles are larger than 1.250 mm.

The percarbonate is contained in an amount of 1 to 50 wt%, preferably 1 to 30 wt%, and most preferably 5 to 20 wt% based on the weight of the detergent composition.

Most preferably, percarbonate is added to the composition in a coated state which results in-product stability.

Suitable coatings that can impart in-product stability contain mixed salts of water-soluble alkali metal sulfates and carbonates. GB-1466799 to Interox on 9.3.1977 has already described such coatings and methods for their application. The weight ratio of the mixed salt coating to the percarbonate is 1: 200-1: 4, more preferably 1: 99-1: 9, and most preferably 1: 49-1: 19. Preferably, the mixed salt is of the formula Na₂SO₄·nNa₂CO₃A mixed salt of sodium sulfate and sodium carbonate of (1), wherein: n is 0.1 to 3, preferably 0.3 to 1.0, and most preferably 0.2 to 0.5.

Other coatings containing silicates (alone or in combination with borates or boric acid or other minerals), waxes, oils, fatty soaps may also be advantageously used in the present invention. Bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactants

The second essential component of the present invention comprises an effective amount of a bis-AQA surfactant of the formula:wherein R is¹Is a straight chain, branched or substituted C having 8 to 18 carbon atoms, preferably 8 to 16 carbon atoms, most preferably 8 to 14 carbon atoms₈～C₁₈Alkyl, alkenyl, aryl, alkaryl, ether, glycidyl ether groups; r²Is an alkyl group having 1 to 3 carbon atoms, preferably a methyl group; r³And R⁴Independently variable, each selected from hydrogen (preferred), methyl and ethyl, X^-Anions sufficient to produce charge neutrality, such as chloride, bromide, methylsulfate, sulfate; a and A' may be independently varied and are each selected from C₁～C₄Alkoxy, especially ethoxy, propoxy, butoxy and mixtures thereof; p is 1 to 30, preferably 1 to 15, more preferably 1 to 8, even more preferably 1 to 4, and q is 1 to 30, preferably 1 to 15, more preferably 1 to 8, even more preferably 1 to 4. Most preferably, p and q are both 1.

In which the substituent R is as compared with longer chain substances¹Is C₈～C₁₂In particular C₈～C₁₀Hydrocarbyl bis-AQA compounds increase the dissolution rate of the laundry detergent granule, even under cold water conditions. Thus, for some formulators, C₈～C₁₂bis-AQA surfactants are preferred. The level of bis-AQA surfactant used to prepare the finished detergent composition is from 0.1 to 5 wt%, typically from 0.45 to 2.5 wt%. The weight ratio of the bis-AQA to the percarbonate bleaching agent is 1: 100-5: 1, more preferably 1: 60-2: 1, and most preferably 1: 20-1: 1.

To enhance the performance of cleaning compositions containing other optional ingredients, an "effective amount" of the bis-AQA surfactant is used herein. In the present invention, an "effective amount" of a bis-AQA surfactant means: an amount sufficient to directionally or significantly enhance the performance of the cleaning composition on at least some target soils and stains with a 90% confidence level. Thus, formulators can use, at least directionally, sufficient bis-AQA to enhance cleaning performance on certain food stains in compositions whose targets include such stains. Also, formulators can employ bis AQA in compositions whose target includes soil stains, at least in an amount sufficient to directionally enhance cleaning performance of such soils.

To achieve at least one directional improvement in cleaning performance, the bis-AQA surfactants can be used in effective amounts in combination with other detersive surfactants. In the case of fabric washing compositions, this "usage" varies depending not only on the type and severity of the soils and stains, but also on the temperature of the wash water, the volume of wash water and the type of washing machine.

For example, for a top-loading vertical shaft American-type automatic washing machine with washing liquid of 45-83 liters of water, 10-14 minutes of a washing cycle and washing water temperature of 10-50 ℃, the following are preferred: the cleaning solution contains 2-50 ppm, preferably 5-25 ppm of bis-AQA surfactant. In the case of the high-efficiency liquid detergent, the in-product concentration of the bis-AQA surfactant is 0.1 to 3.2 wt%, preferably 0.3 to 1.5 wt%, calculated from the use ratio of 50 to 150ml per washing amount. For dense ("high density") granular laundry detergents (densities above 650g/l), the in-product concentration of the bis-AQA surfactant, calculated as 60-95 grams per wash usage, is 0.2% to 5.0% by weight, preferably 0.5 to 2.5% by weight. For spray-dried granular detergents (i.e. "loose", density below 650g/l), the in-product concentration of the bis-AQA surfactant is 0.1 to 3.5 wt%, preferably 0.3 to 1.5 wt%, calculated as 80 to 100 grams per wash usage.

For example, for a front-loading horizontal axis European style automatic washing machine with washing liquid of 8-15 liters of water, 10-60 minutes of one washing cycle and 30-95 ℃ of washing water, the following is preferable: the cleaning solution contains 13-900 ppm, preferably 16-390 ppm of bis-AQA surfactant. For the high-efficiency liquid detergent, the in-product concentration of the bis-AQA surfactant is converted into 0.4-2.64 wt%, preferably 0.55-1.1 wt% according to the use ratio of 45-270 ml per washing amount. For dense ("high density") granular laundry detergents (densities above 650g/l), the in-product concentration of the bis-AQA surfactant is 0.5 to 3.5 wt%, preferably 0.7 to 1.5 wt%, calculated as 40 to 210 grams per wash, of usage rate. For spray-dried granular detergents (i.e. "loose", density below 650g/l), the in-product concentration of the bis-AQA surfactant is 0.13 to 1.8 wt%, preferably 0.18 to 0.76 wt%, calculated as 140 to 400 grams per wash at the rate used.

For example, for a top-loading vertical axis Japanese automatic washing machine with washing water of 26-52 liters in washing liquid, 8-15 minutes in one washing cycle and 5-25 ℃ of washing water temperature, the following is preferred: the cleaning solution contains 1.67-66.67 ppm of bis-AQA surfactant, preferably 3-6 ppm. For the high-efficiency liquid detergent, the in-product concentration of the bis-AQA surfactant is converted into 0.25-10 wt%, preferably 1.5-2 wt% according to the use ratio of 20-30 ml per washing amount. For dense ("high density") granular laundry detergents (densities above 650g/l), the in-product concentration of the bis-AQA surfactant, calculated as 18-35 grams per wash at the use rate, is 0.25-10 wt%, preferably 0.5-1.0 wt%. For spray-dried granular detergents (i.e. "loose", density below 650g/l), the concentration of the bis-AQA surfactant is 0.25 to 10 wt%, preferably 0.5 to 1 wt%, calculated from a usage rate of 30 to 40 grams per wash.

From the foregoing, it can be seen that the amount of bis-AQA surfactant used in the machine wash range can vary depending upon the habits and practices of the user, as well as the type of washing machine. However, in this context, the advantages of bis-AQA surfactants not heretofore appreciated are: it is at least capable of providing improved directional performance on a wide variety of soils and stains when used at lower levels in view of the other surfactants (typically anionic surfactants, or mixtures of anionic/nonionic surfactants) in the finished composition. This is to be distinguished from other compositions in the art in which various cationic surfactants are used in stoichiometric or near stoichiometric amounts with anionic surfactants. Generally in the practice of the present invention the weight ratio of bis-AQA surfactant to anionic surfactant in the laundry composition is in the range of 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 comprising both anionic and nonionic surfactants, the weight ratio of bis-AQA to mixed anionic/nonionic surfactant is in the range 1: 80 to 1: 2, preferably 1: 50 to 1: 8.

In the manner of the present invention, various other cleaning compositions can also be formulated using an effective amount of a bis-AQA surfactant, including anionic surfactants, optionally nonionic surfactants, and specialized surfactants such as betaines, sultaines, amine oxides. These compositions include, but are not limited to, hand dishwashing products (especially liquids or gels), hard surface cleaners, shampoos, bar personal cleansing compositions, bar laundry compositions, and the like. Because of the minimal variation in the habits and practices of the users of such compositions, satisfactory results are achieved by including from about 0.25% to about 5%, preferably from about 0.45% to about 2%, by weight of the bis-AQA surfactant in the composition. Also, in the case of granular and liquid laundry compositions, the weight ratio of the bis-AQA surfactant to the other surfactants present in the composition is relatively low, i.e. not stoichiometric enough for anionic surfactants. Preferably, the cleaning compositions have the same bis-AQA/surfactant ratio as just mentioned for use in the machine laundry composition.

The bis-alkoxylated cationic surfactants of the present invention have sufficient solubility compared to other cationic surfactants known in the art so that they can be used in combination with mixed surfactant systems having very low levels of nonionic surfactant and containing, for example, alkyl sulfate surfactants. This is an important consideration for formulators in designing the class of detergent compositions commonly used in top loading washing machines, especially for use in north america, as well as under japanese use conditions. Generally, in such compositions, the weight ratio of anionic surfactant to nonionic surfactant is 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-type formulations, in which the ratio of anionic to nonionic surfactant is in the range of about 10: 1 to 1: 10, preferably about 5: 1 to 1: 1.

Preferred ethoxylated cationic surfactants of the present invention are available from Akzo Nobel Chemicals Company under the trade name ETHOQUAD. In addition, such materials may be prepared using a variety of different reaction schemes (where "EO" represents-CH)₂CH₂O-units).Scheme 1

Scheme 2

Scheme 3

Scheme 4

The following is an economical reaction scheme.Scheme 5

The following parameters summarize the optional and preferred reaction conditions for scheme 5. Reaction step 1 is preferably carried out in an aqueous medium. The reaction temperature is usually 140 to 200 ℃. The reaction pressure is 50-1000 psig. A base catalyst, preferably sodium hydroxide, is used. In the reactant, the molar ratio of the amine to the alkyl sulfate is 2: 1-1: 1. The reaction is preferably carried out with C₈～C₁₄Alkyl sulfates (sodium salts). The ethoxylation and quaternization steps are carried out using conventional conditions and conventional reactants.

In some cases, reaction scheme 5 produces a product that is substantially soluble in an aqueous reaction medium that may form a gel. Although the desired product may be recovered from the gel, in some commercial situations, the alternative two-step synthesis scheme 6 below may be more desirable. The first step in scheme 6 is performed as in scheme 5. The second step (ethoxylation) is preferably carried out with ethylene oxide and an acid, such as HCl, to form a quaternary surfactant. As shown below, a chlorohydrin, i.e., chloroethanol, may be used in the reaction to produce the desired bis-hydroxyethyl derivative.

For reaction scheme 6, the following parameters summarize the optional and preferred reaction conditions for the first step. The first step is preferably carried out in an aqueous medium. The reaction temperature is usually 100 to 230 ℃. The reaction pressure is 50-1000 psig. Use of a base, preferably sodium hydroxide, with HSO produced during the reaction₄ ^-The reaction can be carried out or an excess of amine can be used to react with the acid. The molar ratio of amine to alkyl sulfate is usually 10: 1 to 1: 1.5, preferably 5: 1 to 1: 1.1, and most preferably 2: 1 to 1: 1. In the product recovery step, the desired substituted amine can be simply separated from the aqueous reaction medium as a distinct phase, since it is insoluble in the aqueous reaction medium. The second step of the processIs carried out under conventional reaction conditions. And under standard reaction conditions, further carrying out ethoxylation reaction and quaternization reaction to obtain the bis-AQA surfactant.

Scheme 7 optionally proceeds with ethylene oxide under standard ethoxylation conditions (but in the absence of a catalyst) such that monoethoxylation occurs.

These other reaction schemes are illustrated below, where "EO" represents-CH₂CH₂An O-unit. During the reaction, the HSO formed is neutralized using an inorganic base, an organic base or an excess of amine reactant₄。Scheme 6

Scheme 7

The following further illustrates several of the above reactions, which provide some convenience to the formulator, and is not meant to be limiting.Synthesis method A Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

19.96 grams of sodium lauryl sulfate (0.06921 moles), 14.55 gramsof diethanolamine (0.1384 moles), 7.6 grams of 50 wt% sodium hydroxide solution (0.095 moles), and 72 grams of distilled water were added to the glass autoclave liner. The glass liner is sealed into a 500 ml stainless steel shake-roll autoclave and then heated to 160-180 ℃ for 3-4 hours under a nitrogen pressure of 300-400 psig. The mixture was cooled to room temperature and then the liquid contents of the glass liner were poured into a 250 ml separatory funnel along with 80 ml chloroform. The funnel was shaken well for a few minutes and the mixture was then allowed to start to separate. The lower chloroform layer was drained and then the chloroform was evaporated to give the product.Synthesis method B Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

1 mole of sodium dodecyl sulfate is reacted with 1 mole of ethanolamine in the presence of a base in the manner described in synthesis A. The resulting 2-hydroxyethyldodecylamine was recovered and then reacted with 1-chloroethanol to prepare the title compound.Synthesis method C Preparation of N, N-bis (2-hydroxyethyl) dodecylamine

19.96 grams of sodium lauryl sulfate (0.06921 moles), 21.37 grams of ethanolamine (0.3460 moles), 7.6 grams of 50 wt% sodium hydroxide solution (0.095 moles), and 72 grams of distilled water were added to the glass autoclave liner. The glass liner is sealed into a 500 ml stainless steel shake-and-roll autoclave and then heated to 160-180 ℃ for 3-4 hours under a nitrogen pressure of 300-400 psig. The mixture was cooled to room temperature and then the liquid contents of the glass liner were poured into a 250 ml separatory funnel along with 80 ml chloroform. The funnel was shaken well for a few minutes and the mixture was then allowed to start to separate. The lower chloroform layer was drained and then the chloroform was evaporated to give the product. And then reacting the product with 1 molar equivalentof ethylene oxide at 120-130 ℃ in the presence of a base catalyst to generate the required final product.

The disubstituted amines prepared according to the aforementioned syntheses may be further ethoxylated in a standard manner. In the present invention, the quaternization with alkyl halide to produce the bis-AQA surfactants is conventional.

In light of the foregoing, the following is a non-limiting detailed description of the bis-AQA surfactants useful herein. It will be appreciated that the degree of alkoxylation used in the present invention for the bis-AQA surfactants is reported as an average value, according to common practice for ethoxylated nonionic surfactants. This is because ethoxylation generally produces a mixture of materials having different degrees of ethoxylation. Thus, it is common practice to: total EO values are reported rather than integers, e.g., "EO 2.5", "EO 3.5".

Name (name) R ¹ R ² ApR ³ A′qR ⁴

bis-AQA-1C₁₂～C₁₄CH₃EO EO (also known as coconut methyl EO2)

bis-AQA-2C₁₂～C₁₆CH₃(EO)₂EO

bis-AQA-3C₁₂～C₁₄CH₃(EO)₂(EO)₂(also known as coconut methyl EO4)

bis-AQA-4C₁₂CH₃EO EO

bis-AQA-5C₁₂～C₁₄CH₃(EO)₂(EO)₃

bis-AQA-6C₁₂～C₁₄CH₃(EO)₂(EO)₃

bis-AQA-7C₈～C₁₈CH₃(EO)₃(EO)₂

bis-AQA-8C₁₂～C₁₄CH₃(EO)₄(EO)₄

bis-AQA-9C₁₂～C₁₄C₂H₅(EO)₃(EO)₃

bis-AQA-10C₁₂～C₁₈C₃H₇(EO)₃(EO)₄

bis-AQA-11C₁₂～C₁₈CH₃(propoxy) (EO)₃

bis-AQA-12C₁₀～C₁₈C₂H₅(Isopropoxy)₂(EO)₃

bis-AQA-13C₁₀～C₁₈CH₃(EO/PO)₂(EO)₃

bis-AQA-14C₈～C₁₈CH₃(EO)₁₅ ^*(EO)₁₅ ^*

bis-AQA-15C₁₀CH₃EO EO

bis-AQA-16C₈～C₁₂CH₃EO EO

bis-AQA-17C₉～C₁₁CH₃EO3.5, average

bis-AQA-18C₁₂CH₃EO3.5, average

bis-AQA-19C₈～C₁₄CH₃(EO)₁₀(EO)₁₀

bis-AQA-20C₁₀C₂H₅(EO)₂(EO)₃

bis-AQA-21C₁₂～C₁₄C₂H₅(EO)₅(EO)₃

bis-AQA-22C₁₂～C₁₈C₃H₇Bu (EO)₂

^*Optionally methyl or ethyl terminated ethoxy. Highly preferred bis-AQA surfactants for use herein have the structural formula:

wherein R is¹Is C₈～C₁₈Hydrocarbyl and mixtures thereof, preferably C₈、C₁₀、C₁₂、C₁₄Alkyl groups and mixtures thereof; x is a conventional anion providing charge balance, preferably chlorine.With reference to the general structure of the bis-AQA mentioned above, since in preferred compounds R is¹Derived from coconut (C)₁₂～C₁₄Alkyl) partial fatty acid, R²Is methyl, and ApR³And A' pR⁴Are each a monoethoxy group, so such preferred compounds are referred to herein as "coconut MeEO 2" or "bis AQA-1" as listed above.

Other bis-AQA surfactants useful herein include compounds having the following structural formula:

wherein R is¹Is C₈～C₁₈A hydrocarbon group, preferably C₈～C₁₄An alkyl group; p and q are each independently 1 to 3, R²Is C₁～C₃Alkyl, preferably methyl, and X is an anion, especially chloride or bromide.

Other compounds of the foregoing classes include; wherein ethoxy (CH)₂CH₂O) units (EO) substituted by butoxy (Bu), isopropoxy [ CH (CH)₃)CH₂O]And [ CH₂CH(CH₃)O]Those in which the units (i-Pr) or the n-propoxy units (Pr), or mixed units of EO and/or Pr and/or i-Pr units are replaced.

A highly preferred bis-AQA surfactant for use in the formulation has the formula: wherein p and/or q is an integer in the range of 10-15. The compounds are particularly useful in laundry hand wash detergent compositions.non-AQA detersive surfactants

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

Non-limiting examples of anionic surfactants useful in the present invention, typically at levels of 1 to 55 wt%, include: conventional C₁₁～C₁₈Alkyl benzene sulfonates ("LAS"); and primary site ("AS"), branched or random C₁₀～C₂₀An alkyl sulfate; structural formula is CH₃(CH₂)_x(CHOSO₃ ^-M⁺)CH₃And CH₃(CH₂)_y(CHOSO₃ ^-M⁺)CH₂CH₃C of (A)₁₀～C₁₈A secondary (2, 3) alkyl sulfate, wherein: x and (y +1) are integers of at least 7, preferably at least 9, and M is a water-soluble cation (especially sodium); unsaturated sulfates, such as oleyl sulfate; c₁₂～C₁₈α -sulfonated fatty acid ester C₁₀～C₁₈Sulfated polysaccharidesA glycoside; c₁₀～C₁₈Alkyl alkoxy sulfates (' AE)_xS', in particular EO 1-7 ethoxy sulfate), and C₁₀～C₁₈Alkyl alkoxy carboxylates (especially EO 1-5 ethoxy carboxylates). The total composition may also contain C₁₂～C₁₈Betaines and sulfobetaines, C₁₀～C₁₈Amine oxide. Also usable are C₁₀～C₂₀Conventional soaps. If a large number of foams are desired, branched chains C may be used₁₀～C₁₆And (3) soaps. Other commonly used surfactants have been listed in standard textbooks.Nonionic surfactant

Non-limiting examples of nonionic surfactants useful in the present invention, which are generally present in amounts of 1 to 55% by weight, include: alkoxylated alcohols (AE's) and alkylphenols, polyhydroxy fatty acid amides (PFAA's), alkylpolyglycosides (APG's) C₁₀～C₁₈A glycerol ether.

More specifically, in the present invention, condensation products of primary and secondary aliphatic alcohols with 1 to 25 moles of ethylene oxide (AE) are suitable as the nonionic surfactant of the present invention. The alkyl chain of the aliphatic alcohol may be straight or branched, primary or secondary, and generally contains from 8 to 22 carbon atoms. Preferably a condensation product of an alcohol having from 8 to 20 carbon atoms, more preferably from 10 to 18 carbon atoms, per mole of alkyl group and from 1 to 10, more preferably from 2 to 7, most preferably from 2 to 5 moles of ethylene oxide. Examples of such nonionic surfactants commercially available include: tergitol supplied by Union carbide Corporation^TM15-s-9(C₁₁～C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide) and Tergitol^TM24-L-6 NMW (C with narrow molecular weight distribution)₁₂～C₁₄Condensation products of primary alcohols with 6 moles of ethylene oxide); neodol supplied by Shell chemical company^TM45-9(C₁₄～C₁₅Condensation products of linear alcohols with 9 moles of ethylene oxide), Neodol^TM23-3(C₁₂～C₁₃Condensation products of linear alcohols with 3 moles of ethylene oxide), Neodol^TM45-7(C₁₄～C₁₅Condensation products of linear alcohols with 7 moles of ethylene oxide) and Neodol^TM45-5(C₁₄～C₁₅Condensation products of linear alcohols with 5 moles of ethylene oxide); by Procter&Kyro supplied by Gamble Company^TMEOB(C₁₃～C₁₅Condensation products of alcohols with 9 moles of ethylene oxide); and Genapol LAO3O or O5O (C) supplied by Hoechest₁₂～C₁₄Condensation products of alcohols with 3 or 5 moles of ethylene oxide). Among these AE nonionic surfactants, the preferred range of HLB is 8 to 11, and most preferably 8 to 10. Condensates with propylene oxide and butylene oxide may also be used.

Another preferred nonionic surfactant useful in the present invention is a polyhydroxy fatty acid amide having the structural formula:

wherein R is¹Is H, or C_1-4A hydrocarbyl group, a 2-hydroxyethyl group, a 2-hydroxypropyl group, or a mixture thereof; r²Is C_5-31A hydrocarbyl group; and Z is a polyhydroxyhydrocarbyl having at least 3 straight-chain hydrocarbyl groups of hydroxyl groups directly connected to the chain, or an alkoxylated derivative thereof. Preferably R¹Is methyl, R²Is straight chain C_11-15Alkyl or C_15-17Alkyl or alkenyl chains, such as coconut alkyl or mixtures thereof, and Z is derived from the reductive amination of a reducing sugar, such as glucose, fructose, maltose, lactose. Typical examples thereof include C₁₂-C₁₈And C₁₂-C₁₄N-methylglucamide. See US5194639 and 5298636. N-alkoxy polyhydroxyfatty acid amides may also be used, see U.S. Pat. No. 5,5489393.

In the present invention, further usable as the nonionic surfactant are: an alkylpolysaccharide having a hydrophobic group containing 6 to 30 carbon atoms, preferably 10 to 16 carbon atoms, disclosed in U.S. Pat. No. 4565647 to Llenado, No. 1/21, 1986; and polysaccharides such as polyglycosides having a hydrophilic group containing 1.3 to 10, preferably 1.3 to 3, most preferably 1.3 to 2.7 saccharide units. Any reducing sugar containing 5 or 6 carbon atoms may be used, such as glucose, galactose, and the galactosyl moiety may be substituted with glucosyl groups (the hydrophobic group may optionally be attached to the 2-, 3-, 4-etc., so that glucose or galactose as opposed to glucoside or galactoside is obtained). The intersugar linkage may be located, for example, 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 (glycosyl)_x

Wherein: r²Selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl group contains 10 to 18, preferably 12 to 14 carbon atoms; n is 2 or 3, preferably 2; t is 0-10, preferably 0; and x is 1.3 to 10, preferably 1.3 to 3, more preferably 1.3 to 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxy alcohol is first prepared and then reacted with glucose, or a source of glucose, to form the glucoside (attachment at the 1-position). The additional glycosyl units can then be attached between their 1-position and the 2-, 3-, 4-and/or 6-position (preferably predominantly the 2-position) of the preceding glycosyl unit.

In the surfactant system of the present invention, polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkyl phenols are also suitable for use as the nonionic surfactant, with the polyethylene oxide condensates being preferred. These compounds include: a condensation product of a linear or branched alkylphenol having an alkyl group containing 6 to 14 carbon atoms, preferably 8 to 14 carbon atoms, with an alkylene oxide. In a preferred embodimentThe amount of ethylene oxide is 2 to 25 moles, preferably 3 to 15 moles, of ethylene oxide per mole of alkylphenol. Such nonionic surfactants that are commercially available include: igepal supplied by GAFCorporation^TMCO-630; and by Rohm&Triton supplied by Hass Company^TMX-45, X-114, X-100 and X-102. These surfactants are commonly referred to as alkylphenol alkoxylates (e.g., alkylphenol ethoxylates).

The condensation products of ethylene oxide with a hydrophobic base obtained by the condensation reaction of propylene oxide with propylene glycol are also suitable for use as other nonionic surfactants in the present invention. The hydrophobic portion of these compounds preferably has a molecular weight of 1500 to 1800 and exhibits water insolubility. By adding a polyoxyethylene moiety to this hydrophobic moiety, the water solubility of the molecule as a whole can be increased and the liquid character of the product can still be maintained until the polyoxyethylene content is based on the total weight of the condensation product50%, which corresponds to condensation with up to 40 mol of ethylene oxide. Examples of such compounds include certain commercially available pluronics supplied by BASF^TMA surfactant.

Among the nonionic surfactant systems of the present invention, further suitable nonionic surfactants are: condensation products of ethylene oxide with the reaction product of propylene oxide and ethylene diamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and its molecular weight is usually 2500-3000. The hydrophobic part and ethylene oxide are subjected to condensation reaction, so that a condensation product contains 40-80 wt% of polyoxyethylene, and the molecular weight of the condensation product is usually 5000-11000. Examples of such nonionic surfactants include certain Tetronic surfactants commercially available from BASF^TMA compound is provided. Other cationic surfactants

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

Other suitable cationic surfactants include: selected from mono C₆～C₁₆Preferably C₆～C₁₀Quaternary ammonium surfactants of N-alkyl or alkenyl ammonium surfactants in which the remaining N sites are substituted with methyl, hydroxyethyl or hydroxypropyl groups. For example, U.S. Pat. Nos. 4228042, 4239660 and 4260529 disclose other suitable cationic ester surfactants, including choline ester surfactants.Optional detergent ingredients

The following illustrates various optional ingredients that may be used in the compositions of the present invention, but this is not meant to be limiting.Bleach activators

Bleach activators are preferred components in the compositions of the present invention. For bleaching compositions comprising a bleaching agent and a bleach activator, if present, the bleach activator is typically present in an amount of from 0.1 to 60%, more typically from 0.5 to 40% of the bleaching composition.

Peroxygen bleaching agents, such as mixtures of percarbonate salts with bleach activators, allow the in situ generation of peroxyacids corresponding to the bleach activators in aqueous solution (i.e., during the wash). Various non-limiting examples of bleach activators are disclosed in U.S. patent 4915854 to Mao et al, 4/10/1990, and U.S. patent 4412934. Nonoyloxybenzene sulfonate (NOBS) and Tetraacetylethylenediamine (TEAD) activators are conventional, and mixtures thereof may also be used. In addition, as to other typical bleaches and activators which may be used in the present invention, see US 4634551.

Highly preferred amido-derived bleach activators have the structural formula:

R¹N(R⁵)C(O)R²c (O) L or R¹C(O)N(R⁵)R²C(O)L，

Wherein R is¹Is an alkyl group having 6 to 12 carbon atoms, R²Is an alkylene group 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 a bleach activator by nucleophilic attack of a perhydrolyzed anion on the bleach activator. A preferred leaving group is phenylsulfonate.

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

Another bleach activator includes the benzoxazine-type activator disclosed in U.S. Pat. No. 4966723 to Hodge et al, 1990, 10, 30, which is incorporated herein by reference. Highly preferred benzoxazine activators are:

another preferred bleach activator includes acyl lactam activators, especially acyl caprolactams and acyl valerolactams of the formula:

wherein R is⁶Is H or contains 1 to 12 carbon atomsAlkyl, aryl, alkoxyaryl, or alkylaryl groups of the molecule. Highly preferred caprolactam activators include: benzoyl caprolactam, octanoyl caprolactam, 3, 5, 5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecanoyl valerolactam, nonanoyl valerolactam, 3, 5, 5-trimethylhexanoyl valerolactam, and mixtures thereof. See U.S. patent 4545784 to Sanderson, 10/8/1985, which discloses acyl caprolactams, including benzoyl caprolactam absorbed into sodium perborate, and is incorporated herein by reference.Bleaching catalyst

Bleach catalysts are preferred components in the compositions of the present invention. If desired, the bleaching compound can be catalyzed by a manganese compound. Such compounds are well known in the art and include: such as manganese-based catalysts disclosed in US5,246,621, US5,244,594, US5,194,416, US5,114,606 and european patent application publication nos. 549,271a1, 549272a1, 544,440a2, 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^IIIMn^IV ₄(u-O)₁(u-OAc)₂(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(ClO₄)₃、Mn^IV(1, 4, 7-trimethyl-1, 4, 7-triazacyclononane)₂(OCH₃)₃(PF₆) And mixtures thereof. Other metal-based bleach catalysts include: catalysts disclosed in U.S. Pat. No. 4,430,243 and U.S. Pat. No. 5,114,611. The use of manganese in combination with various complex ligands to enhance bleaching is also reported 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.

For practical purposes, and without limitation, the compositions and methods of the present invention can be adapted so as to provide on the order of at least one part per million of active bleach catalyst species in an aqueous wash liquor, and preferably from 0.1 to 700ppm, more preferably from 1 to 500ppm, of catalyst species in the wash liquor.

Cobalt bleach catalysts useful in the present invention are known, for example, as described in m.l. tobe in "base hydrolysises of Transition-Metal Complex", adv.inog.bionorg.mech., (1983), 2, pagesl-94. The most preferred cobalt catalysts useful in the present invention are: having the formula [ Co (NH)₃)₅OAc]T_yWherein "OAc" represents an acetate moiety and "T" represents a salt of cobalt pentaglycinate of (1)_y"is an anion, especially cobalt pentaglycinate chloride, [ Co (NH)₃)₅OAc]Cl₂And [ 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(PAC of the present invention).

These cobalt catalysts can be prepared, for example, by known methods as taught in the following documents: the article by Tobe and references cited therein, and The references J.chem.Ed. (1989), 66, (12), 1043-45, "Synthesis and characterization of Inorganic Compounds", Diakun et al, published in 1989, 3,7, (US 4,810,410), published by J.chem.Ed. (1989), 66, (12), 1043-45 "(The Synthesis and catalysis of Inorganic Compounds, W.L.Jolly (Prentice Hall, (1970), pp.461-3), Inorg.chem., 18, 1497-1502(1979), Inorg.chem., 21, 2881-2885(1982), Inorg.chem., 18, 2023-2025(1979), Inorg.Synthesis, 173-176(1960) and Journal of chemical chemistry (56, 22-25 1952).

The invention can be adapted for practical use, not to be limited theretoAutomatic dishwashing compositions and cleaning processes are disclosed which provide on the order of at least 0.01ppm of active bleachcatalyst material in the aqueous wash medium, and preferably from 0.01 to 25ppm, more preferably from 0.05 to 10ppm, most preferably from 0.1 to 5ppm of bleach catalyst material in the wash liquor. To maintain this level in the wash liquor of an automatic dishwashing process, typical automatic dishwashing compositions of the present invention comprise from 0.0005 to 0.2%, preferably from 0.004 to 0.08%, by weight of the cleaning composition, of a bleach catalyst, especially a manganese or cobalt catalyst.Other bleaching agents

The detergent compositions of the present invention may optionally comprise other bleaching agents. If present, these other bleaching agents are typically present at levels of from about 1% to about 30%, more typically from about 5% to about 20% of the detergent composition, especially for the laundering of fabrics.

The bleaching agent used in the present invention may be any bleaching agent useful in detergent compositions in fabric cleaning, hard surface cleaning or other known or to be known laundering applications. These include oxygen bleaches as well as other bleaching agents. In the present invention, perborate bleach, such as sodium perborate (e.g., mono-or tetra-hydrate), may be used.

Another class of bleaching agents that can be used without limitation includes: percarboxylic acid bleaching agents and salts thereof. Suitable examples of such bleaching agents include: magnesium monoperphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, the magnesium salt of 4-nonylamino-4-oxyperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. patent 4483781 to Hartman at 11/20 1984, U.S. patent application 740446 to Burns et al at 6/3 1985, European patent application 0133354 to Banks et al at 2/20 1985, and U.S. patent 4412934 to Chung et al at 11/1 1983. Highly preferred bleaching agents also include: 6-nonanamido-6-oxyperoxyhexanoic acid, described in U.S. Pat. No. 4634551 to Burns et al, 1, 6, 1987.

Peroxygen bleaches may also be used. Suitable peroxy bleach compounds include: sodium pyrophosphate peroxyhydrate, urea peroxyhydrate, and sodium peroxide. Perborate bleach, persulfate bleach (e.g., OXONE, commercially available from DuPont) may also be used.

Bleaching agents other than oxygen bleaching agents are known in the art and may be used in the present invention. A non-oxygen bleaching agent of particular value comprises: photoactivated bleaching agents, such as sulfonated zinc and/or aluminum phthalocyanines. See U.S. patent 4033718 issued to holcomb et al on 5.7.7.1977. If used, the detergent compositions typically comprise from about 0.025 to 1.25 wt% of such bleaching agents, especially sulfonated zinc phthalocyanines.

Mixtures of bleaching agents may also be used.Builder

To help control minerals, especially Ca, in wash water²⁺And/or Mg²⁺Or to assist in the removal of particulate soils from surfaces, the compositions of the present invention may optionally, but preferably, comprise detergency builders. Builders function by a variety of mechanisms including: form soluble or insoluble complexes with hardness-causing ions by ion exchange methods, and produce a surface that favors the precipitation of hardness-causing ions over the surface of the article being cleaned. The amount of builder used can vary widely depending on the end use and the physical form of the composition. Built detergents typically contain at least 1% builder. The liquid formulation typically contains 5-50%, more typically 5-30% builder. The granular formulation typically comprises from 10 to 80%, more typically from 15 to 50% by weight of the detergent composition of a detergency builder for the detergent. Lower or higher levels of builder are not excluded. For example, aSome detergent additives or high surfactant formulations may be free of builders.

Suitable builders may be selected from: phosphates and polyphosphates, especially their sodium salts; silicates, including water soluble and aqueous solids types, but also those having a chain, lamellar, or three-dimensional structure, as well as amorphous solids or unstructured liquids; a carbonate salt; a bicarbonate salt; sodium carbonate or sesquicarbonate and carbonate minerals other than sodium sesquicarbonate; an aluminosilicate; organic mono-, di-, tri-, and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium or alkanolammonium salts, as well as aliphatic and aromatic oligomers or water-soluble low molecular weight carboxylate polymers and phytic acid. These materials may be supplemented with borates or with sulfates, especially sodium sulfate, and any other fillers or carriers that may be important in stabilizing surfactant and/or builder containing detergent compositions for purposes of pH buffering and the like.

Builder mixtures, sometimes referred to as "builder systems", may be used, which typically comprise two or more conventional builders, optionally supplemented with chelating agents, pH buffers or fillers, although in describing the amounts of materials of the present invention, these latter materials are generally calculated separately. With respect to the relative amounts of surfactant and builder in the detergents of the invention, preferred builder systems are generally formulated at a surfactant to builder weight ratio of from 60: 1 to 1: 80. In certain preferred laundry detergents, the ratio is in the range of 0.90: 1.0 to 4.0: 1.0, preferably 0.95: 1.0 to 3.0: 1.0.

Builders for phosphorus-containing detergents are generally preferred, as permitted by regulations, and include, but are not limited to, alkalimetal, ammonium and alkanolammonium salts of polyphosphates, particularly tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates; and a phosphonate.

Suitable silicate builders include: alkali metal silicates, especially SiO thereof₂∶Na₂Those liquid and solid alkali metal silicates having an O ratio in the range of 1.6: 1 to 3.2: 1, including the solid aqueous 2-ratio (ratio 2) silicate supplied by PQ Corp (especially for automatic dishwashing purposes), under the trade name BRITE SIL^_E.g. BRITESSIL H₂O; and layered silicates, as described in us patent 4664839 issued to h.p. rieck on 3/12 1987. NaSKS-6, sometimes referred to simply as "SKS-6", is a crystalline, layered, aluminum-free, delta-Na supplied by Hoechst corporation₂SiO₅Silicate salt, which is particularly preferred in granular laundry compositions. See DE-A-3,417,649 and DE-A-3,742,043 for processes for their preparation. General formula NaMSi_xO_2x+1·yH₂Other layer of OPhyllosilicates may also be used in the present invention, where M is sodium or hydrogen, n is 1.9 to 4, preferably 2, and y is 0 to 20, preferably 0, phyllosilicates from Hoechst include α -, β -, and gamma-phyllosilicates, respectivelyNaSKS-5, NaSKS-7 and NaSKS-11. Other silicates, such as magnesium silicate, which are useful as crispening agents, as stabilizers for bleaching agents, and as components of foam control systems in granules, may also be used.

Also suitable for use in the present invention are: a synthetic crystalline ion exchange material having a chain structure, or a hydrate thereof, the composition of which in the anhydride form may be represented by the general formula: xM₂O·ySiO₂zM 'O, where M is Na and/or K, M' is Ca and/or Mg, y/x is 0.5 to 2.0 and z/x is 0.005 to 1.0, as described in US 5427711 to Sakaguchi et al 1995.

Suitable carbonate builders include: alkaline earth and alkali metal carbonates as described in the german patent application No. 2321001, published in 1973, 11/15, can of course be used as seeds or for block synthetic detergents and the like: sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals, such as trona, or any common double salt of sodium carbonate and calcium carbonate, e.g. having the composition 2Na when anhydrous₂CO₃·Ca₂CO₃Even calcium carbonates, including calcite, aragonite and vaterite, especially in the form of relatively high density calcite, have a relatively high surface area.

Aluminosilicate builders are particularly useful in granular detergents, but may also be incorporated in liquids, pastes or gels. Those aluminosilicates suitable for this purpose have the empirical formula: [ M]A_z(AlO₂)_z(SiO₂)_v]·xH₂O, wherein z and v are integers of at least 6, the molar ratio of z to v is in the range of 1.0 to 0.5, and x is an integer of about 15 to 264. The aluminosilicates may be crystalline or amorphous, naturally occurring or synthetically derived. A process for preparing aluminosilicates is disclosed in U.S. Pat. No. 5,10,12 to Krummel et al, 1976, US 3985669. Preferred synthetic crystalline aluminosilicate ion exchange materials are available under the trade name Zeolite A, Zeolite P (B), Zeolite X, and so-called Zeolite MAP (regardless of how different it is from Zeolite P). Aluminosilicates in their natural form, including clinoptilolite, may also be used. The structural formula of Zeolite A is: na (Na)₁₂[(AlO₂)₁₂(SiO₂)₁₂]·xH₂O, wherein x is 20 to 30, especially 27. Dehydrated zeolite (x is 0 to 10) may also be used. Preferably, the diameter of the aluminosilicate particles is between 0.1 and 10 microns.

Suitable organic detergent builders include: polycarboxylates, including water-soluble non-surfactant dicarboxylates and tricarboxylates. Preferred polycarboxylate builders have a plurality of carboxyl groups, preferably at least 3 carboxyl groups. Polycarboxylate builders can generally be formulated in acidic, partially neutralized, neutral or overbased form. When used in the form of a salt, alkali metals such as sodium, potassium and lithium, or an alkanolammonium salt are preferred. Polycarboxylate builders include: polycarboxylate ethers, such as oxydisuccinate, see U.S. Pat. No. 3128287 to Berg at 4.7 in 1964 and U.S. Pat. No. 3635830 to Lamberti et al at 1.18 in 1972; "TMS/TDS" builder in U.S. Pat. No. 4633071 issued to Bush et al at 5.5.1987; other carboxylate ethers, including cyclic and alicyclic compounds, are described in U.S. Pat. Nos. 3923679, 3835163, 4158635, 4120874 and 4102903.

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

Citrate builders, such as citric acid and its water-soluble salts, are carboxylate builders of particular importance, as they can be derived from renewable materials and are biodegradable, such as for use in heavy duty liquid detergents. Citrate salts may also be used in granular compositions, particularly in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and mixtures.

Various alkali metal phosphates, such as sodium tripolyphosphate, pyrophosphate and orthophosphate, may be used as permitted, especially when formulating the nuggets for hand washing. Phosphonate builders, such as ethane-1-hydroxy-1, 1-diphosphonate and other known phosphonates (such as those of U.S. Pat. Nos. 3159581, 3213030, 3422021, 3400148 and 3422137) may also be used and have desirable detergent properties.

Certain detergent surfactants or their short chain homologues also contribute to the cleaning action. To have a clear guideline, materials are generally classified as detersive surfactants when they have surfactant efficacy. Preferred examples of the surfactant having a washing-assistant function are: 3, 3-dicarboxy-4-oxa-1, 6-adipate and related compounds are disclosed in U.S. patent 4566984 to Bush at 28.1.1986. The succinic acid builder comprises C₅～C₂₀Alkyl and alkenyl succinic acids and salts thereof. The succinate builder further comprises: lauryl succinate, myristyl succinate, cetyl succinate, 2-dodecenyl succinate (preferred), 2-pentadecenyl succinate. Lauryl succinate is described in European patent application 86200690.5/0200263 published on 5.11.1986. Fatty acids such as C₁₂～C₁₈Monocarboxylic acids may also be used as surfactants and/or builders alone or in combination with the aforementioned builders, especially citrate and/or succinate builders, in the compositions to provide additional builder activity. Other suitable polycarboxylates are described in U.S. Pat. No. 4144226 to Crutchfield et al, 3/13/1979, and U.S. Pat. No. 3308067 to Diehl, 3/7/1967. See also U.S. patent 3723322 to Diehl.

Other types of inorganic builders that can be used have the formula: (M)_x)_iCa_y(CO₃)_zWherein: x and i are integers from 1 to 15, y is an integer from 1 to 10, z is an integer from 2 to 25, M_iIs a cation, at least one ofIs watersoluble and satisfies the equation ∑_i＝1-15(x_i×M_i2y ═ 2z, so that the formula has a neutral or "balancing" charge. In the present invention, these builders are referred to as "mineral builders". As long as the overall charge balance is maintained or is neutral, water of hydration or anions other than carbonate may be added. The charge or valence of these anions should be added to the right of the above equation. Preferably the water soluble cation present is selected from: hydrogen, water-soluble metals, hydrogen, boron, ammonium, silicon and mixtures thereof, more preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, most preferably sodium and potassium. Non-limiting examples of non-carbonate anions include: chlorides, sulfates, fluorides, oxygen, hydroxides, silica, chromates, nitrates, borates, and mixtures thereof. Such builders, in the simplest form, are preferably selected from Na₂Ca(CO₃)₂、K₂Ca(CO₃)₂、Na₂Ca₂(CO₃)₃、NaKCa(CO₃)₂、NaKCa₂(CO₃)₃、K₂Ca₂(CO₃)₃And mixtures thereof. Particularly preferred builders described herein are all crystal-modified Na₂Ca(CO₃)₂. Suitable builders as defined above and as further illustrated may include natural or synthetic forms of any one or mixture of the minerals acalcite, uraninite, baclolite Y, bismuthate, colemanite, strontianite, cancrinite, glauberite, canasite, cancrinite, perfunonite Y, kalanchovite, Fairchilite, pernicite, colemanite, monoclinica, Girvasite, ilmenite, canasite, canangalite, Kamphaugite Y, bicarbonite, urannesite, Lepersonneite Gd, eucryptite, barite Y, micro-alkali cancrinite, tellurite, nannesonite, remonite, Remonite, sargaseite, canasite, cancrinite, nahcolite, calcium carbonate, and sepioliteorite. Preferred mineral forms include nyctalite, kainite and canasite.Enzyme

Enzymes may be included in the compositions of the present invention and have a variety of uses, including: removing protein-based, carbohydrate-based, or triglyceride-based stains from a variety of substrates; inhibiting the transfer of the shedding dye during the fabric washing process; and for fabric reforming. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin, such as plant, animal, bacterial, fungal, and yeast origin. The preference for this is influenced by various factors such as: pH-activity and/or stability optima, thermal stability, and stability towards active detergents, builders. In this regard, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

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

Generally, the enzyme should be added in an amount sufficient to produce a "cleaning effective amount" in the detergent or detergent additive composition. The term "cleaning effective amount" means: any amount that can produce a cleaning, stain removing, soil removing, whitening, deodorizing, or freshness enhancing effect on a substrate, such as fabric, dishware. In fact, with current commercial preparations, the amount of active enzyme ingredient per gram of detergent composition is generally up to 5mg, more generally between 0.01 and 3 mg. Unless otherwise stated, the compositions of the invention generally comprise from 0.001 to 5%, preferably from 0.01 to 1% by weight of the commercial enzyme preparation. Generally in commercial preparations, the protease should be present in an amount sufficient to provide 0.005 to 0.1Anson Units (AU) of activity per gram of composition. For certain detergents (e.g., for automatic dishwashing), the level of active enzyme in commercial formulations is increased in order to greatly reduce the total amount of non-catalytically active material and thereby enhance the spotting/filming effect or other end-effect. Higher levels of active ingredient are also desirable in highly concentrated detergent formulations.

A suitable example of a protease is surfactin, which is produced by a particular strain of Bacillus subtilis and Bacillus licheniformis. Another suitable protease is produced by a strain of Bacillus, which is most active over the entire pH range 8-12, developed by Novo Industries A/S (hereinafter "Novo") of Denmark and under the trade name ESPERASE^_And (7) selling. The preparation of this and similar enzymes is described in British patent 1243784 to Novo. Other suitable proteases include: ALCALASE from Novo^_And SAVINASE^_And MAXATASE from International Bio-Synthetic, Inc, the Netherlands^_(ii) a And protease A disclosed by EP130756 on 9.1.1985, and protease B disclosed by EP303761 on 28.4.1987 and by EP130756 on 9.1.1985. In addition, high pH proteases, see, Novo, WO 9318140A describing the Bacillus strain NCIMB 40338. In WO 9203529A to Novo, enzyme-added detergents comprising a protease, one or more other enzymes, and a reversible protease inhibitor are described. Other preferred proteases include, Procter&WO 9510591A to Gamble. If necessary, it can be as the Procter&WO 9507791 to Gamble discloses proteases with reduced absorption and improved hydrolysis.WO 9425583 to Novo describes a recombinant trypsin-like protease for detergents suitable for the present invention.

In more detail, a particularly preferred protease, designated "protease D", is a variant of a carbonyl hydrolase whose amino acid sequence, not found in nature, is derived from a carbonyl hydrolase precursor by the following substitution patterns: substitution of the amino acid residue in the carbonyl hydrolase corresponding to position +76 with a different amino acid, preferably in combination with a plurality of amino acid residues at one or more positions selected from the group consisting of (according to numbering in Bacillus amyloliquefaciens subtilisin) +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, is described in U.S. patent application No. 08/322,676 entitled "cleaning compositions containing protease" of A.Baeck et al, and U.S. patent application No. 08/322,677 entitled "bleaching compositions containing protease" of C.Ghosh et al, both of which have been filed 10, 13, years.

Amylases of the present invention which are particularly suitable, but not limited to, for automatic dishwashing purposes include the α -amylase described in GB 1,296,839(Novo), RAPIDASE sold by International Bio-Synthesis, Inc^_TERMAMYL marketed by Novo Inc^_And FUNGAMYL sold by Novo corporation^_Wherein FUNGAMYL^_Is particularly preferred. Methods for improving enzyme stability, such as oxidative stability, are known. See, e.g., J.biological chem., Vol.260, No.11, 6.1985, pp.6518-6521. In certain preferred embodiments of the invention, amylases of improved stability, especially improved oxidative stability, can be used in detergents such as automatic dishwashing, the reference point for the oxidative stability measurement being TERMAMYL, marketed in 1993^_The preferred amylases of the invention are characterized as "stability-enhanced" amylases characterized at least by a measurable improvement inone or more of stability, e.g., oxidative stability to hydrogen peroxide/tetraacetylethylenediamine in a buffered solution at a pH of 9-10, thermostability at normal washing temperatures such as 60 ℃, or alkaline stability at a pH of 8-11, as measured against the reference amylase described aboveA precursor. Preferably used in relation to the above-mentioned ginsengAmylase with increased oxidative stability over amylase, in particular bleaching of the detergent composition of the invention with oxygen bleaching, more preferably oxygen bleaching other than chlorine bleaching, such preferred amylases include (a) the amylase described in WO 9402597 to Novo (2.3.1994), which has been introduced above, and which can be further specified with a mutant variant using alanine or threonine, preferably threonine, instead of the methionine residue at position 197 of the Novo-type Bacillus licheniformis α -amylase (named MANTERYL _), or a similar parent amylase variant such as the same positional variant of Bacillus amyloliquefaciens, Bacillus subtilis or Thermomyces sterolis, (b) the Amylase International from C.Mitchinson to the 207 th American chemical Association at 3.13-17.1994, which is described as an "antioxidant α -amylase" having the highest stability, wherein the amylase variant is produced by the automatic bleaching enzyme mentioned in the text: the amylase, wherein the amylase is modified at position 6757, especially modified by the enzyme from the enzymes of SCANCN-type enzymes designated as alkaline protease variants of Bacillus amyloliquefaciens, Met^_And SUNLIGHT^_To determine its stability. (c) Particularly preferred according to the invention are amylase variants with additional modifications in close relatives as described in WO 9510603A, commercially available from Novo of the patent assignee under the trade name DURAMYL^_. Other particularly preferred stability-enhanced amylases include: amylases described in WO 9418314(Genencor International) andWO 9402597 (Novo). Any other oxidative stability-enhanced amylase may also be used, e.g., an amylase obtained by site-directed mutagenesis from a known chimeric, hybrid or simple mutant parent form of the available amylase. Other preferred enzyme modification treatments may also be performed, see WO 9509909A (Novo).

Other amylases include: amylases described in WO95/26397 and in pending patent application PCT/DK96/00056 to Novo Nordisk. Features for use in detergent compositions of the inventionThe amylase includes α -amylase prepared by Phadebas^_α -amylase activity analysis method, under the conditions of 25-55 ℃ and pH 8-10, the specific activity ratio of Termamy^_Has a specific activity of at least 25% (the Phadebas)^_α -Amylase Activity assay see WO95/26397, pages 9-10.) the present invention additionally comprises α -amylases having more than 80% homology to the amino acid sequences shown in the SEQ ID tables of the literature, which enzymes are incorporated into laundry detergent compositions preferably at a level of from 0.00018% to 0.060% by weight of the total composition of pure enzyme, more preferably at a level of from 0.00024% to 0.048% by weight of the total composition.

Cellulases useful in the present invention include bacterial and fungal cellulases having a preferred pH of between 5 and 9.5. U.S. Pat. No. 4,435,307 to Barbesgord et al, 3/6, 1984, discloses a suitable cellulase derived from Humicola insolens, or the Humicola strain DSM1800, or a suitable cellulase derived from a fungus belonging to the genus Aeromonas capable of producing cellulase 212-, and a cellulase extracted from the hepatic pancreas of the marine mollusk Dolabella auricularia 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) is particularly useful. See also WO9117243 (Novo).

Suitable lipases for use in detergents include: a lipase produced by a microorganism of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154 as disclosed in GB 1372034. See also Japanese patent application 5320487, published on 24.2.1978. Such lipases are available from Amano Pharmaceutical Co.Ltd, under the trade name Lipase P "Amano" or "Amano-P", located in Nagoya, Japan. Other suitable commercially available lipases include: Amano-CES lipases from Chromobacterium viscosum, such as Chromobacterium viscosum variant Lipotium NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; chromobacterium viscosum lipase from U.S. biochemicals, and Disoynth co, the netherlands; and a lipase of Pseudomonas gladioli. LIPOLASE _ enzyme derived from humicola lanuginosa and obtainable from Novo (see also EP341947) is a preferred lipase for use in the present invention. Peroxidase-stable lipase and amylase variants are described in WO 9414951A to Novo. See also WO 9205249 and RD 94359044.

Despite numerous publications on lipases, it has hitherto only been found that lipases derived from P.gossypii and produced in the host Aspergillus oryzae can be used extensively as additives in fabric washing products. As mentioned above, it is available from Novo Nordisk under the trademark Lipolase^TM. To optimize the stain removal performance of Lipolase, Novo Nordisk has obtained a large number of Lipolase variants. As described in WO92/05249, variant D96L of the natural P.lanuginosus lipase increased the lard stain removal capacity 4.4-fold (the corresponding enzyme was used at 0.075-2.5mg protein/liter) compared to the original lipase. Novo Nordisk is disclosed in research disclosure No. 35944 on 3/10 1994: the lipase variant (D96L) is added in an amount of 0.001 to 100mg (5 to 500,000 LU/liter) per liter of washing solution. The use of low levels of the D96L variant in a bis-AQA surfactant-containing detergent composition in the manner disclosed herein improves fabric whiteness maintenance, particularly in fabric whiteness maintenanceWhen the amount of D96L is 50-8500 LU/liter washing solution.

Cutinases suitable for use in the present invention are described in WO 8809367A of Genencor.

Peroxidase enzymes may be used in combination with oxygen-containing sources, such as percarbonates, perborates, hydrogen peroxide, etc., in order to "solution bleach," or to prevent transfer of dyes or pigments that have detached from the substrate during the washing process to other substrates in the wash liquor. Known peroxidases include: horseradish peroxidase, ligninase, haloperoxidase, such as chloro-or bromoperoxidase. Detergent compositions containing peroxidase are disclosed in WO 89099813A (published in 1989 on 10/19, Novo), and WO 8909813A by Novo.

WO 9307263A and WO 9307260A to Genencor International, WO 8908694A to Novo and U.S. Pat. No. 3553139 to McCarty et al, 1/5 1971, also disclose various enzymes and their incorporation into synthetic wash combinationsThe mode in the article. Enzymes are further described in U.S. Pat. No. 4101457 to Place et al, 7/18 in 1978, and U.S. Pat. No. 4507219 to Hughes, 3/26 in 1985. U.S. patent 4261868 to Hora et al, 4/14, 1981, discloses enzymes for use in liquid detergent formulations and methods of incorporation into the formulations. Enzymes used in detergents can be stabilized by various methods. Various enzyme stabilization techniques are disclosed and exemplified in U.S. Pat. No. 3600319 to Gedge et al at 8.17.1971 and in European patents EP 199405 and EP 200586 to Venegas at 29.10.1986. Enzyme stabilization systems are also described in U.S. patent 3519570, et al. WO9401532A to Novo describes Bacillus AC13 that is capable of obtaining proteases, xylanases and cellulases.Enzyme stabilizing system

The enzyme-containing compositions of the present invention also optionally comprise 0.001 to 10 wt%, preferably 0.005 wt% to 8 wt%, most preferably 0.01 wt% to 6 wt% of an enzyme stabilizing system. The enzyme stabilizing system may be any stabilizing system compatible with the detergent enzyme. The stabilizing system may be provided by the active ingredient in other formulations, or may be added separately, such as by the formulator or by the detergent enzyme manufacturer. Such a stabilizing system may comprise: calcium ions, boric acid, propylene glycol, short chain carboxylic acids, boric acid, and the like, and mixtures thereof, and can be designed according to the type and physical form of the detergent composition in order to solve various stability problems.

One way to create stability is to use water soluble sources of calcium and/or magnesium ions in the finished composition to provide these ions to the enzyme. Calcium ions are generally more effective than magnesium ions and therefore, if only one cation is used, it is preferred in the present invention. Typical detergent compositions, especially liquid compositions, contain from about 1 to about 30, preferably from about 2 to about 20, and more preferably from about 8 to about 12 millimoles of calcium ion per liter of finished detergent composition, but may vary depending on various factors, including the type and amount of enzyme added. 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 generally, calcium sulfate or the corresponding magnesium salt of the listed calcium salts can be used. Of course, for example, to enhance the degreasing action of certain surfactants, the calcium and/or magnesium content may be further increased.

Another way to achieve stability is to use borate-type materials. See Severson, U.S. patent 4537706. The borate stabilizer, if used, maybe present in an amount up to 10% or more of the composition, although more generally, levels of up to about 3% by weight of boric acid or other borate compounds, such as borax or orthoborate, are preferred for use in liquid detergents. Boronic acids such as phenylboronic acid, butylboronic acid, p-bromophenylboronic acid and the like may be substituted for the boric acid and, because of the use of such substituted boron derivatives, the total boron content of the detergent composition may be reduced.

The stabilizing system of certain detergent compositions, such as automatic dishwashing compositions, may also contain from 0 to 10%, preferably from 0.01% to 6%, by weight of chlorine bleach scavengers, which are added to prevent chlorine bleach species present in various water sources from attacking and inactivating the enzymes, especially under alkaline conditions. Although the chlorine content in water is low, generally in the range of 0.5 to.75 ppm, the amount of chlorine that can come into contact with enzymes in the total amount of water during washing of dishes or fabrics, etc., can be relatively large; therefore, there are some problems with enzyme stability when used in chlorine. The use of other chlorine stabilizers, while effective, is generally not necessary because of the reactivity of the percarbonate with the chlorine bleach. Suitable chlorine scavenger anionic materials are known and readily available and, if used, may be salts containing ammonium cations such as sulfites, bisulfites, thiosulfites, thiosulfates, iodides, and the like. In addition, antioxidants such as carbamate, ascorbic acid, and the like; organic amines, such as ethylenediaminetetraacetic acid (EDTA) or alkali metal salts thereof, Monoethanolamine (MEA), and mixtures thereof. In addition, special enzyme inhibition systems may be added so that the different enzymes may have the greatest compatibility. If desired, other conventional scavengers may be used, such as bisulfites, nitrates, chlorides,hydroperoxides such as sodium perborate tetrahydrate, sodium perborate monohydrate andsodium percarbonate, as well as phosphates, condensed phosphates, acetates, benzoates, citrates, formates, lactates, malates, tartrates, salicylates, and the like, and mixtures thereof. In general, since each of the ingredients (e.g., hydrogen peroxide species) which have been separately listed according to their recognized preferred function allows the chlorine scavenger to function, the addition of a chlorine scavenger is not absolutely required unless a compound capable of exerting such a function to the desired degree is not present in the enzyme-containing embodiments of the present invention; even then, scavengers are only optimalThe effect is added. Also, the formulator may employ the ordinary skill of a chemist in an effort to avoid the use of any enzyme scavengers or stabilizers which are substantially incompatible when formulated with other active ingredients. With respect to the use of ammonium salts, such salts can be simply mixed with the detergent composition, but tend to absorb water and/or release ammonia during storage. It is therefore desirable to protect such materials, if present, in the granules, as described in U.S. patent 4652392 to Baginski et al.Polymeric soil release agents

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

Generally, preferred SRAs contain a hydrophilic portion and a hydrophobic portion, wherein: the hydrophilic portion can make the surface of hydrophobic fibers, such as polyester and nylon, hydrophilic; the hydrophobic portion, in turn, is deposited onto the hydrophobic fibers and remains adhered to the hydrophobic fibers through the wash and rinse cycles, thereby acting as a fixative for the hydrophilic portion. This ensures that stains produced after SRA treatment can be more easily washed away in subsequent washing steps.

The SRA may include: various charged, such as anionic or even cationic (see US4,956,447), and uncharged monomer units, and whose structure may be linear, branched or even star-shaped. They may comprise end-capping groups which are particularly effective in controlling molecular weight or in altering physical or surface-active properties. For use on different fibers or fabrics, and for various detergent or laundry additive products, the structure and charge distribution can be tailored to the specific situation.

Preferred SRAs include oligomeric esters of terephthalate; typically by a process comprising at least one transesterification/oligomerization reaction in the presence of a metal catalyst, such as a titanium (IV) alkoxide. Such esters can be made using addition monomers that can be incorporated into the ester structure via one, two, three, four, or more sites, and of course do not form a highly crosslinked overall structure.

Suitable SRAs include: sulfonation products of substantially linear ester oligomers comprising an oligoester backbone of terephthaloyl and oxyalkenoxy repeat units, and allyl-derived sulfonated terminal moieties covalently attached to the backbone, as described, for example, in US4,968,451, 1990, 11/6/J.Scheibei and E.P.Gosselink; such an ester oligomer can be prepared by the following steps: (a) ethoxylating a treated allyl alcohol, (b) reacting the product of (a) with dimethyl terephthalate ("DMT") and 1, 2-propanediol ("PG") in a two-step transesterification/oligomerization reaction, and (c) reacting the product of (b) with sodium metabisulfite in water; the anionically end-capped 1, 2-trimethylene terephthalate/poly (oxyethylene) terephthalate polyester of Gosselink etal, US4,711,730, 12/8/1987, such as may be produced by transesterification/oligomerization of poly (ethylene glycol) methyl ether, DMT, PG, and poly (ethylene glycol) ("PEG"); partially and fully anionic blocked oligoesters such as oligomers of ethylene glycol ("EG"), PG, DMT, and sodium 3, 6-dioxa-8-hydroxyoctanesulfonate in US4,721,580, 1/26 of 1988; non-ionic end-capped block polyester oligomers such as those produced from DMT, Me-capped PEG and EG and/or PG, or from a mixture of DMT, EG and/or PG, Me-capped PEG and sodium dimethyl-5-sulfoisophthalate, as in Gosselink, US4,702,857, 10/27/1987; and anion (particularly sulfoaroyl) capped terephthalates in US4,877,896 to Maldonado, Gosselink et al, 10/31/1989. The latter are typical SRAs that can be used in detergent and fabric conditioner products, examples of which are: an ester composition made from the mono-sodium salt of meta-sulfobenzoic acid, PG, and optionally (but preferably) DMT, further comprises added PEG (e.g., PEG 3400).

The SRA further comprises: simple block copolymers of ethylene terephthalate or propylene terephthalate, with polyethylene oxide or polypropylene oxide terephthalate, see U.S. Pat. No. 3,959,230 to Hays at 25.5.1976 and U.S. Pat. No. 3,893,929 to Basadur at 8.7.7.1975; cellulose derivatives such as the hydroxyether cellulose polymer METHOCEL available from Dow; and C₁～C₄Alkyl celluloses and C₄Hydroxyalkyl cellulose, see US4,000,093 issued to Nico et al on 12/28 of 1976. Suitable SRA's characterized by a poly (vinyl ester) hydrophobic moiety include poly (vinyl esters) grafted to a polyalkylene oxide backbone, such as poly (C)₁～C₆Vinyl esters), preferably graft copolymers of poly (vinyl acetate). See, European patent application 0,219,048, published by Kud et al on 22/4/1987. Commercially available examples include: SOKALAN SRA, such as SOKALAN HP-22 available from BASF corporation, Germany. Other SRAs are polyesters derived from polyoxyethylene glycols having an average molecular weight of 300 to 5000, the repeat units of which contain 10 to 15% by weight of ethylene terephthalate and 80 to 90% by weight of polyoxyethylene terephthalate. Commercial examples include ZELCON 5126 from DuPont, and milleast from ICI.

Another preferred SRA is of empirical formula (CAP)₂(EG/PG)₅(T)₅(SIP)₁Comprising terephthaloyl (T), Sulfoisophthaloyl (SIP),Oxyethylene oxy and oxy-1, 2-propylene (EG/PG) units and preferably end-capped with an end capping group (CAP), preferably with a modified hydroxy ethanesulfonate, e.g. an oligomer comprising 1 sulfoisophthaloyl unit, 5 terephthaloyl units, oxyethylene oxy and oxy-1, 2-propyleneoxy units in a given ratio, preferably about 0.5: 1 to 10: 1, and units derived from 2- (2-hydroxyethoxy) -ethanesulfonic acidTwo end-capped units of sodium. The SRA also preferably comprises from 0.5% to 20% by weight of the oligomer of a crystalline reducing stabilizer, for example an anionic surfactant such as sodium linear dodecylbenzene sulphonate, or selected from the group consisting of xylene-, cumene-and toluene-sulphonates or mixtures thereof, wherein these stabilizers or modifiers are added to the synthesis reactor in the manner described in US5,415,807 to Gosselink, Pan, Kellett and Hall, 5, 16, 1995. Suitable monomers for the above SRA include: sodium 2- (2-hydroxyethoxy) -ethanesulfonate, DMT, sodium dimethyl-5-sulfoisophthalate, EG, and PG.

Another preferred class of SRA are oligomeric esters, including: (1) comprising three main chains (a), (b) and (c), (a) being at least one unit selected from the group consisting of dihydroxysulfonate salts, polyhydroxysulfonate salts, units having at least three functional groups to form ester bonds to produce branched oligomer main chains, and mixed units thereof; (b) is at least one terephthaloyl unit; and (c) is at least one unsulfonated unit being a1, 2-oxyalkylene oxy group; and (2) one or more end-capping units selected from the group consisting of nonionic end-capping units, anionic end-capping units (e.g., alkoxylated, preferably ethoxylated isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives, and mixtures thereof). Such esters preferably have the empirical formula:

{(CAP)_x(EG/PG)_y′(DEG)_y″(PEG)_{y_}(T)_z(SIP)_z′(SEG)_q(B)_m}

wherein CAP, EG/PG, PEG, T and SIP are as defined above, (DEG) represents a di (oxyethylene) oxy unit; (SEG) represents sulfoethyl ether units derived from glycerol, and related units; (B) represents a branching unit having at least a trifunctional group to form an ester bond to produce a branched oligomer backbone; x is about 1 to 12; y' is about 0.5 to 25; y' is about 0 to about 12; y _ is about 0 to 10; y' + y "+ y _ is about 0.5 to 25 in total; z is about 1.5 to 25; z' is about 0 to 12; z + z' is about 1.5 to 25 in total; q is about 0.05 to 12; m is about 0.01 to 10; and x, y ', y _, z, z', q and m represent the average number of moles of the corresponding units per mole of the ester, wherein the ester has a molecular weight of about 500 to 5000.

Preferred SEG and CAP monomers for the above esters include: sodium 2- (2, 3-dihydroxypropoxy) ethanesulfonate ("SEG"), sodium 2- { (2- (2-hydroxyethoxy) ethoxy } ethanesulfonate ("SE 3") and its homologs, and mixtures thereof, and ethoxylation and sulfonation products of allyl alcohol preferred SRA esters of this type include sodium 2- { (2- (2-hydroxyethoxy) ethoxy } ethanesulfonate and/or 2- [2- { (2- (2-hydroxyethoxy) ethoxy } ethanesulfonate in the presence of a suitable Ti (IV) catalyst]The product obtained by transesterification and oligomerization of sodium ethanesulfonate, DMT, sodium 2- (2, 3-dihydroxypropoxy) ethanesulfonate, EG and PG, can be referred to as (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13, wherein: CAP is (Na +^-O₃S[CH₂-CH₂O]3.5) -, and B is a glyceryl unit, the EG/PG molar ratio after complete hydrolysis, as determined by conventional gas chromatography, being about 1.7: 1.

Another class of SRA includes: (I) nonionic terephthalates that use diisocyanate coupling agents to link the polymer ester structures, see U.S. Pat. No. 4,201,824 to Violland et al and U.S. Pat. No. 4,240,918 to Lagasse et al; (II) SRA having carboxylate end groups, obtained by adding trimellitic anhydride to known SRA to convert the terminal hydroxyl groups to trimellitate. With proper selection of the catalyst, trimellitic anhydride can be bonded to the terminal groups of the polymer through one of the isolated carboxyl groups, rather than through the opening of the anhydride linkage, by forming an ester linkage. Either nonionic or anionic SRAs can be used as starting materials, so long as they contain esterifiable hydroxyl end groups. See Tung et al, US4,525,524. In addition, the SRA further comprises: (III) urethane-bonded terephthalic anion-based SRA, see U.S. Pat. No. 4,4,201,824 to Violland et al; (IV) poly (vinyl caprolactam), and its corresponding copolymers with monomers such as vinyl pyrrolidone and/or (dimethylaminoethyl) methacrylate, and the like, including nonionic and cationic polymers, see Ruppert et al, US4,579,681; (V) by grafting acrylic monomers to sulfonation in addition to the SOKALAN types from BASF corporationGraft copolymers obtained on polyesters; these SRAs certainly have similar detersive and anti-redeposition activities to known cellulose ethers, see EP 279,134a from Rhone-poulenc chemie, inc 1988; (VI) grafts of vinyl monomers, such as acrylic acid and vinyl acetate, onto proteins (e.g.casein), see EP 457,205A (1991) from BASF; (VII) polyester-polyamide SRA prepared by condensation of adipic acid, caprolactam and polyethylene glycol, which is particularly suitable for the treatment of polyamide fabrics, see DE 2,335,044 (1974) by Unilever N.V. company Bevan et al. Other useful disclosures of US4,240,918, 4,787,989, 4,525,524 and 4,877,896 are describedSRA。Soil removal/anti-redeposition agent

The compositions of the present invention may also optionally contain water-soluble ethoxylated amines having clay-soil removal/anti-redeposition properties. Granular detergent compositions containing such compounds, typically contain 0.01 to 10.0 wt% of a water-soluble ethoxylated amine; the liquid detergent composition usually contains 0.01 to 5 wt%.

The most preferred clay soil removal/anti-redeposition agent is ethoxylated tetraethylenepentamine. Representative ethoxylated amines are also described in U.S. patent 4597898 to VanderMeer on 7/1 of 1986. Another preferred class of soil removal/anti-redeposition agents are cationic compounds, as disclosed in European patent application 111965 to Oh and Grosselink, 27.6.4.1984. Other soil removal/anti-redeposition agents that can be used include ethoxylated amine polymers, described in european patent application 111984 to Grosselink, published on 27.6.1984; zwitterionic polymers are described in European patent application 112592 to Grosselink, published on 7/4/1984; amine oxides are described in U.S. patent 4548774 to Connor at 22 months 10 and 1985. Other soil removal/anti-redeposition agents known in the art may also be used in the compositions of the present invention. See U.S. patent 4891160 issued to VanderMeer on 2.1.1990 and international patent 95/32272 published on 30.11.1995. Another preferred class of antiredeposition agents includes carboxymethylcellulose (CMC). Such materials are known in the art.Polymeric dispersants

In the compositions of the present invention, it may be preferred to use polymeric dispersants in amounts of from 0.1to 7% by weight, especially in the presence of zeolite and/or layered silicate builders. Suitable dispersing agents include polycarboxylate polymers and polyethylene glycols, although other dispersing agents known in the art may also be used. It is believed, without wishing to be bound by any theory, that when used in combination with other builders (including low molecular weight polycarboxylates), the polymeric dispersant may enhance the overall performance of the detergent builder by crystal growth inhibition, particulate soil release peptization and anti-redeposition.

Polycarboxylate polymers can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in the acid state. Unsaturated monomer acids that can be polymerized to form suitable polycarboxylate polymers include: acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconic acid, mesaconic acid, citraconic acid, and methylenemalonic acid. In the polycarboxylate polymers of the invention, monomeric moieties which do not contain carboxyl groups, such as vinyl methyl ether, styrene, ethylene, etc., may also be present, provided that the content of such moieties is not more than 40% by weight.

Particularly suitable polycarboxylate polymers can be derived from acrylic acid. Such acrylic acid-based polymers useful in the present invention are water-soluble salts of polymerized acrylic acid. The average molecular weight of the polymer in an acid state is 2000-10000, more preferably 4000-7000 and most preferably 4000-5000. Such water-soluble salts of acrylic polymers may include: such as alkali metal, ammonium and substituted ammonium salts. Such suitable water-soluble polymers are known. The use of such polyacrylates in detergent compositions has been disclosed, for example, in U.S. patent 3308067 to Diehl, 3,7, 1967.

Acrylic acid/maleic acid based copolymers may also be used as a preferred component of the dispersing/anti-redeposition agent. These materials include water-soluble salts of copolymers of acrylic acid and maleic acid. The copolymer preferably has an acid average molecular weight of 2000 to 100000, more preferably 5000 to 75000, and most preferably 7000 to 65000. In the copolymer, the ratio of the acrylic acid moiety to the maleic acid moiety is generally in the range of 30: 1 to 1: 1, more preferably 10: 1 to 2: 1. Water-soluble salts of such acrylic acid/maleic acid copolymers may include: such as alkali metal, ammonium and substituted ammonium salts. Such water-soluble acrylic/maleic copolymers are known and are described in European patent application No. 66915, published 12/15 1982, and EP 193360, published 9/3 1986, wherein EP 193360 also describes such polymers comprising hydroxypropyl acrylate. Other useful dispersants include maleic/acrylic/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193360 and include, for example, 45/45/10 terpolymers of maleic/acrylic/vinyl alcohol.

Another polymeric material that may be included is polyethylene glycol (PEG). PEG has dispersant properties and can be used as a soil removal-antiredeposition agent. The molecular weight range for such use is generally 500 to 100000, preferably 1000 to 50000, most preferably 1500 to 10000.

Polyaspartic and polyglutamic acid dispersants may also be used, particularly in combination with zeolite builders. The molecular weight (average) of the dispersant such as polyaspartic acid is preferably 10000.Whitening agent

Any fluorescent whitening agent or other whitening agent known in the art may be added to the detergent compositions of the present invention, typically in an amount of from 0.01% to 1.2% by weight. Commercial optical brighteners useful in the present invention can be divided into several subgroups, which include, but are not necessarily limited to, derivatives of stilbene, pyrazolines, oxonones, carboxylic acids, methines, dibenzothiophene-5, 5-dioxides, oxazoles, 5-and 6-membered ring heterocycles, and other mixed brighteners. Examples of such brighteners are disclosed in the book "production and use of fluorescent whitening agents", m.zahradnik, published by john wiley&son, new york (1982).

Specific examples of optical brighteners which can be used in the present invention are identified in U.S. patent 4790856 to Wixon, 12/13/1988. These whitening agents include, the PHORWHITE series available from Verona. Other whitening agents disclosed in this reference include: tinopal UNPA, Tinopal CBS and Tino from Ciba-Geigypal 5 BM; articwhite CC and Articwhite CWD, 2- (4-styryl-phenyl) -2H-naphtho [1, 2-d]A triazole; 4, 4' -bis (1, 2, 3-triazol-2-yl) -stilbene; 4, 4' -bis (styryl) biphenyl; and aminooxanaphthaleneoketones. Specific examples of such whitening agents include: 4-methyl-7-diethyl-aminonaph-ranolone; 1, 2-bis (benzimidazol-2-yl) -ethylene; 1, 3-diphenyl-pyrazoline; 2, 5-bis (benzoxazol-2-yl) thiophene; 2-styryl-naphthalene- [1, 2-d]Oxazole; and 2- (stilbene-4-yl) -2H-naphtho [1, 2-d]A triazole. See also U.S. patent 3646015 to Hamilton at 29/2 1972.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 laundering process. Typically, such dye transfer inhibiting agents include: polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, peroxidase, and mixtures thereof. If used, these inhibitors are generally present in an amount of 0.01 to 10%, preferably 0.01 to 5%, most preferably 0.05 to 2% by weight of the composition.

More specifically, the polyamine N-oxide polymers preferred for use in the present invention comprise polyamine N-oxide polymers having the formulA R-A_x-P, wherein: p is a polymerizable unit to which an N-O group can be attached, or the N-O group can be part of a polymerizable unit, or the N-O group can be attached to both units; a is one of the following structures: -nc (O) -, -c (O) -, -S-, -O-, -N ═ S; x is 0 or 1; and R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or any mixture thereof to which the nitrogen atom of the N-O group may be attached or which the N-O group forms part. For the preferred polyamine N-oxide polymers, where R is a heterocyclic group, such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, and derivatives thereof.

The N-O group can be represented by the following general formula:

wherein: r₁、R₂、R₃Is aliphatic and aromaticHeterocyclic or alicyclic groups or mixtures thereof; x, y and z are 0 or 1; and the nitrogen atom of the N-O group may be attached to or part of any of the foregoing groups. For the amine oxide units of the N-oxide polymer, the pKa is<10, preferably pKa<7, more preferably pKa<6.

Any polymer backbone can be used so long as the amine oxide polymer formed is water soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are: polyvinyls, polyalkenes, polyesters, polyethers, polyamides, polyimides, polyacrylics, and mixtures thereof. These polymers include random or block copolymers, wherein: one monomer is an amine N-oxide and the other monomer is an N-oxide. For amine N-oxide polymers, the ratio of amine to N-oxide amine is typically from 10: 1 to 1: 1000000. However, in the polyamine oxidized polymers, the number of amine oxide groups can be varied by suitable copolymerization or by suitable degree of N-oxidation. Polyamine oxides having almost any degree of polymerization can be obtained. Generally, the average molecular weight is in the range of 500 to 1000000, more preferably 1000 to 500000, and most preferably 5000 to 100000. Such preferred materials may be referred to as "PVNO".

Most preferred polyamine oxides for use in the cleaning compositions of the present invention are: poly (4-vinylpyridine-N-oxide) having an average molecular weight of 50000 and an amine to amine N-oxide ratio of 1: 4.

Also preferred for use in the present invention are: copolymers of N-vinylpyrrolidone and N-vinylimidazole (known as "PVPVI" classes). The average molecular weight of PVPVPVI is preferably 5000-1000000, more preferably 5000-200000, and most preferably 10000-20000. (the average molecular weight range is determined by light scattering, as in Barth et alChemical Analysis"Modern Method of polymer Characterization" ("model Method of polymer Characterization") is described in Vol.113, the disclosure of which is incorporated herein by reference. ) For PVPVI copolymer, the molar ratio of N-vinyl imidazole to N-vinyl pyrrolidone is usually 1: 1 to 0.2: 1, more preferably 0.8: 1 to 0.3: 1, and most preferably 0.6: 1 to 0.4: 11. These copolymers may be linear or branched.

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

Optionally, the detergent composition of the present invention may further comprise 0.005 to 5 wt% of a hydrophilic fluorescent whitening agent, which also has a dye transfer inhibiting effect. If used, the compositions of the present invention preferably contain 0.01 to 1% by weight of such optical brighteners.

Hydrophilic fluorescent whitening agents useful in the present invention have the following structural formula:

wherein: r₁Selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; r₂Selected from the group consisting of N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morpholino, chloro and amino; and M is a salt-forming cation, such as sodium or potassium.

In the above formula, when R₁Is anilino, R₂Is N-2-bis-hydroxyethyl and M is a cation such as sodium, the brightener is 4, 4' -bis [ (4-anilino-6- (N-2-bis-hydroxyethyl) -s-triazin-2-yl) amino]-2, 2' -stilbene disulphonic acids and their disodium salts. This particular brightener species is commercially available from Ciba-Geigy under the trade name Tinopal-UNPA-GX. Tinopal-UNPA-GX is a preferred hydrophilic optical brightener for use in the detergent compositions of the present invention.

In the above formula, when R₁Is anilino, R₂Is N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, the brightener is 4, 4' -bis [ (4-anilino-6- (N-2-hydroxyethyl-N-methylamino) -s-triazin-2-yl) amino]-2, 2' -stilbene disulphonic acid disodium salt. This specific whitening agentCommercially available from Ciba-Geigy under the trade name Tinopal 5 BM-GX.

In the above formula, when R₁Is anilino, R₂Is morpholino and M is a cation such as sodium, the brightener is 4, 4' -bis [ (4-anilino-6-morpholino-s-triazin-2-yl) amino]-2, 2' -stilbene disulphonic acid disodium salt. This particular brightener species is commercially available from Ciba-Geigy under the trade name Tinopal AMS-GX.

The particular optical brightener species selected for use in the present invention produce particularly effective dye transfer inhibition when used in combination with the selected dye transfer inhibiting polymers described above. By combining the selected polymer (e.g., PVNO and/or PVPVI) with the selected optical brightener (e.g., Tinopal-UNPA-GX, Tinopal 5BM-GX and/or Tinopal AMS-GX), a significantly better dye transfer inhibition effect can be produced in aqueous wash solutions than by using either of the two detergent components alone. While not being bound by theory, it is believed that this whitening agent is based on the following mechanism of action: they deposit faster on fabrics in the wash liquor due to their high affinity for these fabrics. The degree of deposition of the whitening agent on the fabric in the wash liquor can be defined by a parameter known as the "exhaustion coefficient". The consumption coefficient is generally defined as: the ratio of brightener a) deposited onto the fabric to the initial brightener concentration b) in the wash liquor. In the present invention, a whitening agent having a higher consumption coefficient is most suitable for inhibiting the transfer of a dye.

Of course, it is also contemplated that other conventional optical brightener compounds may optionally be used in the compositions of the present invention, but this will only produce the conventional "whitening" effect on fabrics, and not the true dye transfer inhibition effect. These uses are conventional and are therefore well known in detergent formulations.Chelating agents

The detergent compositions of the present invention may also optionally comprise one or more iron and/or manganese chelating agents.Such chelating agents may be selected from: aminocarboxylates, aminophosphonates, multifunctional substituted aromatic chelants and mixtures thereof, as hereinafter defined. While not wishing to be bound by any theory, it is believed that the beneficial effects of these materials are due in part to their ability to unusually remove iron and manganese ions from the wash liquor by forming water-soluble chelates.

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

Amino phosphonates are also suitable for use as chelating agents in the compositions of the present invention if at least low levels of phosphorus are permitted in detergent compositions and include ethylenediamine tetra (methylene phosphonate), i.e. DEQUEST. Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.

Polyfunctionally substituted aromatic chelating agents are also suitable for use in the compositions of the present invention. See U.S. patent 3812044 issued to Connor et al on 21/5/1974. Preferred such acid compounds are dihydroxydisulfobenzenes, such as 1, 2-dihydroxy-3, 5-disulfobenzene.

The biodegradable chelating agent used in the present invention is preferably ethylenediamine disuccinate ("EDDS"), particularly the [ S, S]isomer thereof, described in us patent 4704233 to Hartman and Perkin at 11/3 of 1987.

The compositions of the present invention may also contain a water-soluble methylglycine diacetic acid (MGDA) salt (or acid) which may be used as a chelating agent, or as a co-builder, withwater insoluble builders such as zeolites, layered silicates and the like.

If used, these chelating agents typically comprise 0.1 to 15 wt.% of the cleaning compositions of the present invention. More preferably 0.1 to 3.0% by weight of the composition.Foam inhibitor

Compounds for reducing or inhibiting foam formation may be added to the compositions of the present invention. The foam-inhibiting action is particularly important in front-loading euro-type washing machines and in the so-called "high-consistency washing process" described in us patent nos. 4489455 and 4489574.

A wide variety of materials are useful as suds suppressors and suds suppressors are well known to those skilled in the art. See, for example, Kirk Othmer Encyclopedia of chemical technology, third edition, volume 7, pages 430-447 (John Wiley&son. Inc., 1979). One particularly valuable suds suppressor comprises fatty monocarboxylic acids and water-soluble salts thereof. See U.S. patent 2954347 issued to Wayne st.john, 12, 27, 1960. The fatty monocarboxylic acids and their water-soluble salts used as foam inhibitors generally have a hydrocarbyl chain of 10 to 24 carbon atoms, preferably 12 to 18 carbon atoms. Suitable salts thereof include: alkali metal salts, such as sodium, potassium and lithium salts, and ammonium and alkylolammonium salts.

The detergent compositions of the present invention may also contain non-surfactant type suds suppressors. These include, for example, high molecular weight hydrocarbons such as paraffins, fatty acid esters (e.g., fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C₁₈～C₄₀Ketones (e.g., stearyl ketone), and the like. Other foam inhibitors include: n-alkylated aminotriazines, such as tri-to hexa-alkyl melamines, or di-to tetra-alkyl diamine chlorotriazines (reaction products of cyanuric chloride with two or three moles of a primary or secondary amine having from 1 to 24 carbon atoms); propylene oxide; and monostearyl phosphates such as monostearyl alcohol phosphate and monostearyl dialkali metal (e.g., K, Na and Li) phosphates and phosphates. The hydrocarbons, such as paraffins and chlorinated paraffins, may be used in liquid form. The liquid hydrocarbon is liquid at room temperature and atmospheric pressure, has a melting temperature in the range of-40 ℃ to 50 ℃, and has a lowest boiling point of not less than 110 ℃ (atmospheric pressure). It is also known to use waxy hydrocarbons having a melting point of preferably less than 100 ℃. Hydrocarbons constitute the preferred suds suppressor for use in detergent compositions. Hydrocarbon foam inhibitors are described, for example, in U.S. Pat. No. 4265779 issued to Gandolfo et al, 5.5.5.1981. Thus, the hydrocarbon material includes: aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having 12 to 70 carbon atoms. In the discussion of the foam suppressor, the term "paraffin" is used to mean that mixtures of true paraffins and cyclic hydrocarbons are also included.

Another preferred non-surfactant type foam inhibitor includes silicone foam inhibitors. Such substances include: polyorganosiloxane oils such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins, and mixtures of polyorganosiloxane with silica particles, wherein the polyorganosiloxane is chemisorbed or fused to the silica. Silicone suds suppressors are known in the art and are described, for example, in U.S. patent 4265779 issued to Gandolfo et al, 5.1981, and in european patent application No. 89307851.9, starch.m.s., published by 1990, 2.7.4.

Other silicone suds suppressors are disclosed in U.S. patent 3455839, which relates to compositions and methods for defoaming by adding small amounts of polydimethylsiloxane fluids to aqueoussolutions.

For example, German patent application DOS 2124526 describes mixtures of siloxanes with silanized silica. U.S. patent 3933672 to Bartolotta et al and 4652392 to Baginski et al, 3/24 1987, disclose the use of silicone antifoam and foam control agents in granular detergent compositions.

A typical silicone-based suds suppressor for use in the present invention is a suds suppressing amount of a suds suppressor consisting essentially of:

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

(ii) about 5 to 50 parts by weight of (CH) per 100 parts by weight of (i)₃)₃SiO_1/2Unit and SiO₂A siloxane resin of unit composition, wherein (CH)₃)₃SiO_1/2Units and SiO₂The ratio of units is about 0.6: 1 to 1.2: 1; and

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

In a preferred silicone suds suppressor for use in the present invention, the solvents for the continuous phase include: certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycols. The primary silicone foam inhibitor is branched/crosslinked and is preferably non-linear.

For example, typical liquid laundry detergent compositions for foam control may optionally comprise from about 0.001 to about 1, preferably from about 0.01 to about 0.7, and most preferably from about 0.05 to about 0.5 weight percent of said silicone foam inhibitor, including: (1) a non-aqueous emulsion of a primary antifoam agent which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or siloxane resin-forming siloxane compound, (c) a fine particle filler, and (d) a catalyst for promotingreaction of mixture components (a), (b) and (c) to form a silanolate; (2) at least one nonionic silicone surfactant; and (3) a polyethylene glycol or polyethylene-polypropylene glycol copolymer having a water solubility at room temperature of greater than about 2% by weight; without containing polypropylene glycol. In particulate compositions, gels, and the like, similar amounts can be used. See also, us 4978471 issued to Starch on 12, 18, 1990 and us 4983316 issued to Starch on 1,8, 1991, 5288431 issued to Huber et al on 1, 22, 1994, and us 4639489, and us 4749740 issued to Aizawa et al, at column 1, line 46 to column 4, line 35.

The silicone suds suppressors of the present invention preferably comprise polyethylene glycol, or a copolymer of polyethylene-polypropylene glycol, each having an average molecular weight of less than about 1000, preferably from about 100 to about 800. For the polyethylene glycol or polyethylene-polypropylene glycol copolymers of the present invention, the water solubility at room temperature is greater than about 2% by weight, preferably greater than about 5% by weight.

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

Preferred silicone suds suppressors for use herein do not include polypropylene glycol, particularly those having a molecular weight of 4000. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIL 101.

Other foam inhibitors that may be used in the present invention include: secondaryalcohols (e.g., 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the siloxanes disclosed in U.S. patent 4798679 and EP 150872. The secondary alcohol comprises a compound having C₁～C₁₆C of the chain₆～C₁₆An alkyl alcohol. The preferred alcohol is 2-butyloctanol, available from Condea under the trade name ISOFOL 12. Mixtures of secondary alcohols are available from Enichem under the trade name ISALCHEM 123. The mixed foam inhibitor generally comprises a mixture of an alcohol and a siloxane in a weight ratio of 1: 5 to 5: 1.

For any detergent composition used in an automatic washing machine or a dishwashing machine, the foam formed should not spill out of the washing machine or negatively impact the washing mechanism of the dishwashing machine. If used, the foam-inhibiting agent is preferably used in a "foam-inhibiting amount". "foam inhibiting amount" means: the formulator of the composition can select a foam suppressor amount sufficient to fully control foam, thus resulting in a low foam laundry or dishwashing detergent for use in an automatic washing machine or dishwashing machine.

The composition of the present invention generally comprises 0 to 10% of a foam inhibitor. When monocarboxylic fatty acids and salts thereof are used as suds suppressors, they may be used in amounts up to 5% by weight of the detergent composition. Preferably 0.5% to 3% of the fat monocarboxylate suds suppressor is used. The silicone suds suppressor can be used in amounts up to 2.0 wt.% of the detergent composition, although higher amounts can also be used. The upper limit ofDepending on the actual situation, the main considerations are to minimize costs and use lower amounts with effective control of the foam. Preferably, 0.01% to 1% of a silicone suds suppressor is used, more preferably about 0.25% to 0.5%. These weight percentages used in the present invention include any silica that may be used in admixture with the polyorganosiloxane, as well as any additives that may be used. The monostearyl phosphate suds suppressor is generally used in an amount of from 0.1% to 2% by weight of the composition. The hydrocarbon suds suppressor is generally used in an amount of from 0.01% to 5.0% by weight of the composition, although higher levels may also be used. The alcohol foam inhibitor is generally used in an amount of 0.2 to up to about 03% by weight.Alkoxylated polycarboxylates

To produce additional degreasing properties, alkoxylated polycarboxylates prepared from polyacrylates may be used in the present invention. Such materials are described in WO 91/08281 and PCT 90/01815 (page 4 and below), which are incorporated herein by reference. In terms of chemical structure, these materials comprise polyacrylate having 1 ethoxy side chain per 7-8 acrylate units. The structural formula of the side chain is- (CH)₂CH₂O)_m(CH₂)_nCH₃Wherein m is 2 to 3 and n is 6 to 12. The side chains are attached to the polyacrylate "backbone" via ester linkages, forming a "comb" polymer structure. The molecular weight may vary, but is generally in the range of 2000 to 50000. Such alkoxylated polycarboxylates may comprise 0.05 to 10 weight percent of the compositions of the present invention.Fabric softener

In order to produce a fabric softening effect while washing fabrics, various fabric softeners which act by washing, particularly the smectite clay of U.S. Pat. No. 4062647 issued to Storm and Nirshl on 12/13 of 1977, and other softener clays known in the art, can optionally be used in an amount of 0.5% to 10% by weight of the composition of the invention. Clay softeners may be used in combination with the amine and cationic softeners as disclosed in us 4375416 issued to Crisp et al, 3/1 1983, and in us 4291071 issued to Harris et al, 9/22 1981.Perfume

Fragrances and fragrance ingredients useful in the compositions and methods of the present invention comprise a wide variety of natural and synthetic chemicals including, but not limited to, aldehydes, ketones, esters. Also included are various natural extracts and essences, which contain complex mixtures of various ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic oil, sandalwood oil, pine oil, cedar, and the like. The finished fragrance may contain a very complex mixture of these ingredients. Typically, the finished fragrance comprises 0.01-2 wt% of the composition of the invention, and the individual perfume components may comprise 0.0001-90 wt% of the finished fragrance composition.

In the following example XI, several perfume formulations are given, non-limiting examples of perfume ingredients which can be used in the present invention include condensates of 7-acetyl-1, 2,3, 4,5, 6,7, 8-octahydro-1, 1, 6, 7-tetramethylnaphthalene, methylionone, gamma-methylionone, methylcebenzone, methyl dihydrojasmonate, methyl-1, 6, 10-trimethyl-2, 5, 9-cyclododecatrien-1-yl-ketone, 7-acetyl-1, 1, 3,4, 4, 6-hexamethyltetralin, 4-acetyl-6-tert-butyl-1, 1-dimethylindane, p-hydroxy-phenyl-butanone, benzophenone, methyl- β -naphthalenone, 6-acetyl-1, 1,2, 3, 3, 5-hexamethylindane, 5-acetyl-3-isopropyl-1, 1,2, 6-tetramethylindane, 1-dodecyl-1, 4- (4-hydroxycyclohexyl) -1, 2,3, 3, 5-hexamethyl-1, 3-isopropyl-1, 2, 6-tetramethylcumyl-decalin, 7-2, 8-dihydrocinnamyl aldehyde, 7-methyl-1, 7-hexahydro-1, 4,4, 4-dihydrocinnamyl-1, 3, 4-ethylhexahydro-1, 4,4, 4, 6-hexamethyl-1, 4, 6-dihydrocinnamyl-1, 6-dihydrocinnamyl-methyl-1, 7-dihydrocinnamyl-1, 6-dihydrocinnamyl-1, 7-methyl-1, 7-dihydrocinnamyl-methyl-1, 6-dihydrocinnamyl-methyl-dihydrocinnamyl-1, 7-hexahydro-1, 7-methyl-1, 6,6, 7-dihydrocinnamyl-methyl-dihydrocinnamyl-1, 7-dihydrocinnamyl-methyl-2, 7-methyl-dihydrocinnamyl-2, 7-dihydrocinnamyl-2,8-dihydrocinnamyl-ethyl-dihydrocinnamyl-2, 8-dihydrocinnamyl-2, 7-dihydrocinnamyl-2, 8-dihydrocinnamyl-methyl-dihydrocinnamyl-methyl-2, 8-methyl-dihydrocinnamyl-methyl-2, 8-ethyl-methyl-2, 8-methyl-ethyl-2, 8-dihydrocinn.

Particularly preferred perfumes should be capable of maximizing the odor of finished cellulase-containing products and include, but are 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 -naphthalenone, 2-methyl-2- (p-isopropylphenyl) -propionaldehyde, 1, 3,4, 6,7, 8-hexahydro-4, 6,6, 7,8, 8-hexamethyl-cyclopenta-gamma-2-benzopyran, dodecahydro-3 a, 6,6, 9 a-tetramethylnaphtho [2, 1b]furan, anisaldehyde, cumyl alcohol, cedrol, vanillin, cyclopentadecanol, tricyclodecenyl acetate, tricyclodecenyldecanoate, and tricyclodecenyldecanoate.

Other fragrances include essential oils, resinoids and resins of various origins, including (but not limited to)Not limited to): peru balsam, mastic resin, benzoin, Cistus resin, nutmeg, cinnamon oil, benzoin resin, coriander, and hybrid lavender. Other fragrance compounds include: phenethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, the acetate of 2- (1, 1-dimethylethyl) -cyclohexanol, benzyl acetate, and eugenol. In the finished fragrance composition, a carrier, such as diethyl phthalate, may also be added.Other ingredients

The compositions of the present invention may contain various other ingredients for detergent compositions including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar compositions, etc. If high foam is desired, a foam booster, such asC, is typically added to the composition in an amount of 1-10% by weight₁₀～C₁₆An alkanolamide. C₁₀～C₁₄Monoethanol and diethanolamide are typical classes of these foam boosters. It is also advantageous to use such foam boosters with the above-mentioned high foaming adjunct surfactants, such as amine oxides, betaines and sulfobetaines. If desired, water-soluble magnesium and/or calcium salts, such as MgCl, can be added in amounts of usually 0.1-2%₂、MgSO₄、CaCl₂、CaSO₄Etc., which can create additional foam and increase degreasing properties.

The various soil release components used in the compositions of the present invention may also be stabilized by adsorbing the components onto a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. Preferably the detersive ingredient can be pre-mixed with the surfactant prior to adsorption onto the porous substrate. In use, the detersive ingredient is released from the substrate into the aqueous wash liquor, thus performing its intended detersive function.

To illustrate the technique in more detail, porous hydrophobic silica (trade name SIPERNATD10.DeGussa) may be mixed with a solvent containing 3-5% C_13-15A solution of ethoxylated alcohol (EO7) nonionic surfactant in proteolytic enzyme was mixed. The obtained powder was dispersed in a silicone oil (various silicone oils having a viscosity in the range of 500 to 12500 can be used) by stirring. And emulsifying the obtained silicone oil dispersion liquid or adding the silicone oil dispersion liquid into a finished detergent matrix. In this manner, various ingredients, such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants, can be "protected" for use in detergents, including liquid laundry detergent compositions.

Liquid detergent compositions may comprise water and other solvents as carriers. Low molecular weight primary or secondary alcohols, such as methanol, ethanol, propanol and isopropanol, are suitable. Monohydric alcohols are preferred for solubilizing surfactants, 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 be used. The compositions of the present invention may contain from 5 to 90%, typically from 1 to 50% of such carriers.

In the washing process, the detergent composition is preferably prepared into washing water with the pH value of 6.5-11, preferably 7.5-10.5. The pH value of the liquid tableware washing finished product preparation is preferably 6.8-9.0. The pH value of the laundry product is usually 9-11. Techniques for controlling the pH within the recommended use range include: the use of buffers, bases, acids, etc., are well known to those skilled in the art.Particle production

The bis-alkoxylated cationic surfactant of the present invention is added to a crutcher and then subjected to conventional spray drying, which helps to remove various impurities, potential malodors, short chain amine contaminants. If the formulator wishes to prepare pre-mixed particles containing alkoxylated cationic surfactant for use in high density particulate detergents and the like, the alkalinity of the particulate composition preferably should not be too high. US 5366652 describes a process for preparing high density (above 650g/l) particles. By formulation, such particles are effective at a pH of 9 or less in order to eliminate the odor of the amine impurity. This can be achieved by adding small amounts of acidic substances, such as boric acid, citric acid, etc., or suitable pH buffers to the particles. In addition, various problems with amine malodors that are expected to be masked using the perfume ingredients disclosed herein.

Examples

The following examples are intended to illustrate the invention, but are not intended to limit it or the scope thereof. All parts, percentages and ratios used in the present invention are expressed as weight percentages unless otherwise indicated.

In the following examples, the symbols for the abbreviations for the components have the following meanings: and (3) LAS: straight chain C₁₂Sodium alkylbenzenesulfonate TAS: tallow alkyl sodium sulfate C₄₅AS： C₁₄～C₁₅Straight chain alkyl sodium sulfate C_xyEzS: c condensed with z moles of ethylene oxide_1x～C_1yBranched alkyl sodium sulfate C₄₅E₇: c condensed with an average of 7 moles of ethylene oxide_14-15Predominantly linear primary alcohols C₂₅E₃: c condensed with an average of 3 moles of ethylene oxide_12-15Branched primary alcohol C₂₅E₅: c condensed with an average of 5 moles of ethylene oxide_12-15Branched primary alcohol CoCoCoEO 2: r₁N⁺(CH₃)(C₂H₄OH)₂Wherein R is₁＝C₁₂～C₁₄Soap: sodium linear alkyl carboxylate, 80/20 mixture derived from tallow and coconut oil TFAA: c₁₆～C₁₈Alkyl N-methylglucamide TPKFA: c₁₂～C₁₄Topping whole distillationFatty acid STPP: anhydrous sodium tripolyphosphateZeolite a: having the structural formula Na₁₂(AlO₂SiO₂)₁₂·27H₂Hydrated alumino-silicates of O

Sodium, the primary particle size of which is 0.1-10 microns NaSKS-6: having the formula delta-Na₂Si₂O₅Citric acid, crystalline layered silicate of (2): anhydrous citric acid carbonate: anhydrous sodium carbonate, bicarbonate with a particle size of 200-900 μm: anhydrous sodium bicarbonate, with a particle size distribution of 400-1200 μm silicate: amorphous sodium Silicate (SiO)₂∶Na₂O ratio ═ 2.0) sodium sulfate: anhydrous sodium sulfate citrate: trisodium citrate dihydrate, 86.4% activity, particle size distribution of

425-850 mu mMA/AA: 1: 4 maleic/acrylic acid copolymer, average molecular weight 70000 CMC: sodium carboxymethylcellulose protease: proteolytic enzyme, activity 4KNP U/g, from NOVO Industries A/S

Sold under the trade name savinase alcalase: proteolytic enzyme, Activity 3 AU/g, from NOVO Industries A/S

Selling cellulase: cellulose hydrolase, activity 1000 CEVU/g, from NOVO

Sold by Industries A/S under the trade name Carezyme amylase: starch hydrolase, activity 60 KNU/g, from NOVO Industries A/S

Sold under the trade name Termamyl 60T lipase: lipolytic enzyme, activity 100 KLU/g, trade name lipolaseendosase: endoglunase enzyme, activity 3000 CEVU/g, from NOVO

Industries A/S sells PB 4: sodium perborate tetrahydrate of nominal formula NaBO₂·3H₂O·3H₂O₂PB 1: anhydrous sodium perborate bleach of nominal formula NaBO₂·H₂O₂Percarbonate salts: nominal molecular formula of 2Na₂CO₃·3H₂O₂Sodium percarbonate NOBS: sodium salt of nonanoyloxybenzene sulfonate TAED: tetraacetylethylenediamine DTPMP: diethylene triamine penta (methylene phosphonate), supplied by Monsanto,

photoactivator under the trade name DEQUEST 2060: sulfonated zinc phthalocyanine, encapsulation of brightener 1 with bleached dextrin water-soluble polymer: 4, 4' -bis (2-sulfostyryl) biphenyl disodium salt brightener 2: 4, 4' -bis (4-anilino-6-morpholino-1, 3, 5-triazine-2

-yl) amino) stilbene-2, 2' -disulphonic acid disodium HEDP: 1, 1-hydroxyethanediphosphonic acid PVNO: polyvinylpyridine N-oxide PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole SRA 1: sulfobenzoyl end-capped esters having oxyethylene oxy and p-phenylene

Formyl backbone SRA 2: diethoxylated poly (1, 2-trimethylene terephthalate) short block poly

Compound silicone antifoam agent: polydimethylsiloxane foam control agents, in which siloxane-oxyalkyene is used

Alkyl copolymer as a dispersant, the foam control agent and the dispersion

The ratio of the agent is 10: 1-100: 1

In the following examples, all contents refer to the weight percent (%) of the composition.

Example I

According to the present invention, detergent compositions are prepared wherein A and C are phosphorus-containing detergent compositions and B is a zeolite-containing detergent composition.

A B C Blown powderSTPP 24.0-24.0 zeolite A-24.0-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^*1.51.02.0 silicate 7.03.03.0 CMC 1.01.00.5 brightener 20.20.20.2 soap 1.01.01.0 DTPMP 0.40.40.2Spray mist

C₄₅E7 2.5 2.5 2.0

C₂₅E3 2.5 2.5 2.0

Silicone antifoam 0.30.30.3

Fragrance 0.30.30.3Dry additives

Carbonate 6.013.015.0

PB4 - 4.0 10.0

PB1 4.0 - 0

Percarbonate 18.018.021.0

TAED 3.0 3.0 -

Light activated bleach 0.020.020.02

Protease 1.01.01.0

Lipase 0.40.40.4

Amylase 0.250.300.15 dry blended sodium sulfate 3.03.05.0 balance (moisture&impurities) to: 100.0100.0100.0 Density (g/l) 630670670

^*The bis-AQA-1 (CoCoMeEO2) surfactant in this example can be replaced with an equivalent amount of any of the surfactants (bis-AQA-2 to bis-AQA-22) or other bis-AQA surfactants of the present invention.

Example II

According to the present invention, the following detergent formulations were prepared.

D E F Blown powderZeolite A30.022.06.0 sodium sulfate 19.05.07.0 MA/AA 3.03.06.0 LAS 13.011.021.0C₄₅AS 8.0 7.0 7.0CoCoMeEO2^*1.01.01.0 silicate-1.05.0 soap-2.0 brightener 10.20.20.2Carbonate 8.016.020.0 DTPMP-0.40.4Spray mist

C₄₅E7 1.0 1.0 1.0Dry additivesPVPVI/PVNO 0.50.50.5 protease 1.01.01.0 Lipase 0.40.40.4 Amylase 0.10.10.1 cellulase 0.10.10.1 NOBS-6.14.5 percarbonate 7.05.06.0 sodium sulfate-6.0-balance (moisture)&Impurities) to: 100100100

^*The bis-AQA-1 (CoCoMeEO2) surfactant in this example can be replaced with an equivalent amount of any of the surfactants (bis-AQA-2 to bis-AQA-22) or other bis-AQA surfactants of the present invention.

Example IIIAccording to the present invention, the following high density detergent formulations were prepared.

G H I Blown powderZeolite a 15.015.015.0 sodium sulfate 0.05.0 0.0LAS 3.0 3.0 3.0CoCoMeEO2^*1.0 1.5 1.5DTPMP 0.4 0.4 0.4CMC 0.4 0.4 0.4MA/AA 4.0 2.0 2.0AgglomeratesLAS 5.05.05.0 TAS 2.02.01.0 silicate 3.03.04.0Zeolite A8.08.08.0 carbonate 8.08.04.0Spray mistSpice 0.30.30.3C₄₅E7 2.0 2.0 2.0 C₂₅E3 2.0 - -Dry additivesCitrate 5.0-2.0 bicarbonate-3.0-carbonate 8.015.010.0 TAED 6.02.05.0 percarbonate 13.07.010.0 polyethylene oxide-0.2 (MW5000000) smectite-10.0 protease 1.01.01.0 lipase 0.40.40.4 amylase 0.60.60.6 cellulase0.60.60.6 Silicone antifoam agent 5.05.05.0Dry additivesSodium sulfate 0.03.00.0 balance (water)&Impurities) to: 100.0100.0100.0 Density (g/l) 850850850

^*The bis-AQA-1 (CoCoMeEO2) surfactant in this example can be replaced with an equivalent amount of any of the surfactants (bis-AQA-2 to bis-AQA-22) or other bis-AQA surfactants of the present invention.

Example IVAccording to the present invention, the following high density detergent formulations were prepared.

M N Blown powderZeolite A2.52.5Sodium sulfate 1.01.0 CoCoCoMeEO 2^*1.5 1.5AgglomeratesC₄₅AS 11.014.0 zeolite A15.06.0 carbonate 4.08.0 MA/AA 4.02.0 CMC 0.50.5 DTPMP 0.40.4Spray mistC₂₅E55.05.0 spice 0.50.5Dry additivesHEDP 0.50.3 SKS 613.010.0 citrate 3.01.0 TAED 5.07.0 percarbonate 15.015.0 SRA10.30.3 protease1.41.4 Lipase 0.40.4 cellulase 0.60.6 Amylase 0.60.6 Silicone antifoam 5.05.0 brightener 10.20.2 brightener (moisture content) 20.2-balance&Impurities) to: 100100 Density (g/l) 850850

^*The bis-AQA-1 (CoCoMeEO2) surfactant in this example can be replaced with an equivalent amount of any of the surfactants (bis-AQA-2 to bis-AQA-22) or other bis-AQA surfactants of the present invention.

Any of the granular detergent compositions provided herein can also be tableted using known tabletting methods to provide a tablet detergent.

Highly effective liquid detergent compositions containing a non-aqueous carrier medium, particularly suitable for laundry applications, can be produced in the manner disclosed in detail below. Additionally, such non-aqueous compositions may be prepared according to the disclosure of the following patents: us patents 4753570, 4767558, 4772413, 4889652, 4892673; GB-A-2158838, GB-A-2195125, GB-A-2195649, US4988462, US5266233, EP-A-225654(6/16/87), EP-A-510762(10/28/92), EP-A-540089(5/5/93), EP-A-540090(5/5/93), US4615820, EP-A-565017(10/13/93), EP-A-030096(6/10/81), which are hereby incorporated by reference. These compositions may comprise various particulate detersive ingredients (e.g., the bleaching agents disclosed above) stably suspended therein. Thus, these non-aqueous compositions may contain LIQUID PHASE (in LIQUID PHASE) and optionally (but preferably) SOLID PHASE (in SOLID PHASE), as will be described in more detail below and in the references cited. The AQA surfactants are added to the compositions at the levels and in the manner as described above for other laundry detergent compositions.Liquid phase

The liquid phase typically constitutes from 35 to 99% by weight of the detergent composition of the invention. More preferably, the liquid phase generally comprises the weight of the composition of the present invention50-95% of the amount. Most preferably, the liquid phase generally comprises 45 to 75% by weight of the composition of the present invention. The liquid phase in the detergent compositions of the present invention must contain a relatively high concentration of certain anionic surfactants in combination with certain nonaqueous liquid diluents. (A)Essential anionic surfactants

Anionic surfactants are essential components in the nonaqueous liquid phase and are selected from the alkali metal salts of alkyl benzene sulphonic acids in which the alkyl group contains from 10 to 16 carbon atoms and may be of a straight or branched chain configuration. (see U.S. Pat. Nos. 2220099 and 2477383, incorporated herein by reference). Particularly 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. C₁₁～C₁₄Sodium LAS is particularly preferred.

The alkylbenzene sulfonate anionic surfactant may be dissolved in a non-aqueous liquid diluent which forms the second essential component of the non-aqueous phase. To form a structured liquid phase to give suitable phase stability and acceptable rheology, the alkylbenzene sulfonate anionic surfactant should be present in an amount of 30 to 65% by weight of the liquid phase. More preferably, the alkylbenzene sulphonate anionic surfactant is present in the composition of the present invention in an amount of from 35 to 0% by weight of the nonaqueous liquid phase. The anionic surfactant is used ina concentration corresponding to 15 to 0%, more preferably 20 to 0% by weight of the total composition of anionic surfactant.(B)Non-aqueous liquid diluent

To form the liquid phase of the detergent composition of the present invention, the above alkylbenzene sulfonate anionic surfactant is used in combination with a nonaqueous liquid phase diluent containing two main components. The two components are a liquid alcohol alkoxylate and a non-aqueous low polarity organic solvent. i)Alcohol alkoxylates

A major component of the liquid diluent used to form the composition of the present invention comprises an alkoxylated fatty alcohol. This material is also an anionic surfactant in itself. The substances correspond to the general formula:

R¹(G_mH_2mO)_nOH

wherein R is¹Is C₈～C₁₆Alkyl, m is 2 to 4, and n is 2 to 12. R¹Preferably a primary or secondary alkyl group having 9 to 15 carbon atoms, more preferably 10 to 14 carbon atoms. In addition, the alkoxylated fatty alcohol is preferably an ethoxylate comprising 2 to 12 ethylene oxide moieties per molecule, more preferably 3 to 10 ethylene oxide moieties per molecule.

The alkoxylated fatty alcohol component of the liquid diluent often has a Hydrophilic Lipophilic Balance (HLB) of 3 to 17. More preferably, the HLB of such a material is 6 to 15, and most preferably 8 to 15.

Examples of fatty alcohol alkoxylates useful as an essential component of the nonaqueous liquid diluent in the compositions of the present invention include: a substance which is produced from an alcohol having 12 to 15 carbon atoms and contains 7 moles of ethylene oxide. These materials are commercially available from Shell Chemical Company under the trade names Neodol 25-7 and Neodol 23-6.5. Other useful Neodol include: neodol 1-5, ethoxylated fatty alcohol with 5 moles of ethylene oxide with an average number of carbon atoms on the alkyl chain of 11; neodol 23-9, ethoxylated C with 9 moles of ethylene oxide₁₂～C₁₃A primary alcohol; and Neodol 91-10, ethoxylated C with 10 moles of ethylene oxide₉～C₁₁A primary alcohol. Such alcohol ethoxylates are commercially available from Shell Chemical Company under the Dobanol trade name. Dobanol 91-5 is an ethoxylated C with an average of 5 moles of ethylene oxide₉～C₁₁Aliphatic alcohol, and Dobanol 25-7 is an ethoxylated C with an average of 7 moles of ethylene oxide₁₂～C₁₅A fatty alcohol.

Other examples of suitable ethoxylated alcohols include: tergitol 15-S-7 and Tergitol 15-S-9, both of which are linear secondary alcohol ethoxylates, have been commercially available from Union Carbide Corporation. The former being C with 7 moles of ethylene oxide₁₁～C₁₅Mixed ethoxylation products of linear secondary alkanols, the latter being a similar product but with 9 moles of ethylene oxideAnd reacting.

Other alcohol ethoxylates that may be used in the compositions of the present invention are higher molecular weight nonionic surfactants such as Neodol 45-11, which are similar ethylene oxide condensation products of higher aliphatic alcohols having 14 to 15 carbon atoms and 11 ethylene oxide groups per mole. These products are also commercially available from Shell Chemical Company.

In the non-aqueous compositions of the present invention, the amount of alcohol ethoxylate component used as the major portion of the liquid diluent is generally from 1 to 60% of the composition of the liquid phase. More preferably, the alcohol ethoxylate component comprises 5-40% of the liquid phase. Most preferably, the alcohol ethoxylate component is used predominantly in the range of 5 to 30% of the liquid phase of the detergent composition. In the liquid phase, the alcohol ethoxylate is used in a concentration corresponding to an alcohol ethoxylate concentration in the total composition of 1 to 60% by weight, more preferably 2 to 40% by weight, most preferably 5 to 25% by weight of the total composition. ii)Non-aqueous low-polarity organic solvent

For the detergent compositions of the present invention, the second major component of the liquid diluent, which forms part of its liquid phase, comprises a non-aqueous low-polarity organic solvent. The term "solvent" as used herein refers to the non-surface active carrier or diluent portion in the liquid phase of the composition of the present invention. While certain essential and/or optional components of the compositions of the present invention are actually dissolved in the "solvent" containing liquid phase, other components may be dispersed in the "solvent" containing liquid phase in the form of particles. Thus, the term "solvent" is not meant to require that the solvent actually dissolve all of the detergent composition components added thereto.

Non-aqueous organic materials that can be used as solvents in the present invention are low polarity liquids. For the purposes of the present invention, "low polarity" liquids have only a low tendency, if any, to dissolve sodium percarbonate. Therefore, solvents of higher polarity, such as ethanol, should not be employed. Suitable low polarity solvents for use in the nonaqueous liquid detergent compositions of the present invention include in fact non-vicinal C₄～C₈Alkylene glycols, alkylene glycol mono-lower alkyl ethers, low molecular weight polyethylene glycols, low molecular weight methyl esters and amides.

Preferred non-aqueous, low polarity solvents for use in the compositions of the present invention include non-vicinal C₄～C₈A branched or straight chain alkylene glycol. Such materials include hexylene glycol (4-methyl-2, 4-pentanediol), 1, 6-hexanediol, 1, 3-butanediol, and 1, 4-butanediol. Hexylene glycol is most preferred.

Another preferred non-aqueous, low polarity solvent for use in the compositions of the present invention includes mono-, di-, tri-, or tetra-C₂～C₃Alkylene glycol mono C₂～C₆An alkyl ether. Specific examples of such substances include: diethylene glycol monobutyl ether, tetraethylene glycol monobutyl ether, dipropylene glycol monoethyl ether, and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether and dipropylene glycol monobutyl ether are particularly preferredAnd (4) selecting. Such compounds have been marketed under the trade names Dowanol, Carbitol, and Cellosolve.

Another preferred nonaqueous, low polarity solvent for use in the compositions of the present invention includes low molecular weight polyethylene glycols (PEGs). Such materials have a molecular weight of at least 150. Most preferably, the molecular weight of PEG is 200-600.

Another preferred non-polar, non-aqueous solvent comprises a low molecular weight methyl ester. Such materials have the general formula: r¹-C(O)-OCH₃Wherein R is¹The range of (1) to (18). Examples of suitable low molecular weight methyl esters include: methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.

Of course, the nonaqueous, low-polarity organic solvent used should be compatible with, and non-reactive with, other composition components, such as the bleach and/or activator used in the liquid detergent compositions of the present invention. Generally, the solvent component is used in an amount of 1 to 70% by weight of the liquid phase. The nonaqueous low-polarity organic solvent more preferably accounts for 10-60% of the weight of the liquid phase, and most preferably accounts for 20-50% of the weight of the liquid phase of the composition. In the liquid phase, such concentrations of organic solvent used correspond to: in the total composition, the concentration of the solvent is 1 to 50% of the total weight of the composition, more preferably 5 to 40%, and most preferably 10 to 30%. iii)Alcohol ethoxylate to solvent ratio

In the dilution of liquidsIn the agent, the ratio of alcohol ethoxylate to organic solvent can be used to modify the rheological properties of the finally formed detergent composition. Generally, the weight ratio of alcohol ethoxylate to organic solvent is from 50: 1 to 1: 50. More preferably, the ratio is 3: 1 to 1: 3. iV)Concentration of liquid diluent

While the concentration of the alkylbenzene sulfonate anionic surfactant mixture is relevant, the amount of total liquid diluent in the nonaqueous liquid phase of the present invention can also be determined by the type and amount of other ingredients of the composition, and by the desired properties of the composition. In the compositions of the present invention, the liquid diluent is typically 35 to 70% of the non-aqueous liquid phase. More preferably, the liquid diluent is generally 50-65% of the nonaqueous liquid phase. This corresponds to a non-aqueous liquid diluent concentration in the total composition of 15 to 70 wt%, more preferably 20 to 50 wt% of the composition.Solid phase

The nonaqueous detergent composition of the present invention must further contain 1 to 65% by weight, more preferably 5 to 50% by weight, of solid-phase particulate matter dispersed and suspended in a liquid phase. Generally, the size of the particles is 0.1 to 1500 μm. More preferably, the size of the particles is 5 to 200 μm.

The particulate material for use in the present invention may comprise one or more components of the detergent composition in particulate form which are substantially insoluble in the non-aqueous liquid phase of the composition of the present invention. As will be described in detail below, can be usedThe particulate species used.Preparation and use of compositions

The nonaqueous liquid detergent compositions of the present invention may be prepared by: the essential and optional components thereof are combined together in any conventional order and the resulting mixture of components is mixed, e.g., stirred, to form the phase-stable composition of the present invention. In a typical process for preparing such a composition, the essential components and certain preferred optional components are mixed in a particular order and under certain conditions.

In the first step of this typical preparation process, a mixture of the alkylbenzene sulfonate anionic surfactant and the two major components of the non-aqueous diluent is heated to 30-100 ℃ to form a mixture of these materials.

In the second step, the hot mixture formed as described above is kept at 40 to 100 ℃ for 2 minutes to 20 hours under shear stirring. Vacuum conditions may optionally be applied to the mixture at this point. The second step may be used to completely dissolve the anionic surfactant in the nonaqueous liquid phase.

In the third step, the liquid phase mixture of these substances is cooled to 0 to 35 ℃. This cooling step can be used to form a structured liquid surfactant-containing matrix into which the particles of the detergent composition of the invention can be incorporated or dispersed.

In the fourth step, the particulate matter is added, i.e. the particulate matter is mixed with the liquid phase under shear stirring. When more than one particulate is to be added, it is preferred to add them in a certain order. For example, substantially all of the optional solid particulate surfactant having a particle size of from 0.2 to 1000 microns may be added while maintaining shear agitation. After all optional surfactant is added, substantially all organic builder, such as citrate and/or fatty acid, and/or particles of alkaline material such as sodium carbonate are added while continuing to maintain the composition component mixture under shear agitation. Then, at this point, additional solid optional ingredients are added to the composition. The mixture is continued to be stirred and, if necessary, the stirring can be increased to form a homogeneous dispersion of the insoluble solid-phase particles in the liquid phase.

After some or all of the foregoing solid materials are added to the agitated mixture, the highly preferred peroxygen bleach granules are added while the mixture is also maintained under shear agitation. Since the peroxygen bleach is added last, or after all or most of the other components, in particular after the alkaline substance granules, the desired stabilizing effect of the peroxygen bleach can be achieved. If added, the enzyme granulate is preferably added last to the non-aqueous liquid matrix.

As a final step, after all the particulate matter is added, the mixture is continued to be stirred for a sufficient time until a composition having the desired viscosity and phase stability is formed. Typically, this requires stirring for 1 to 30 minutes.

As a variation of the foregoing composition preparation steps, one or more solid components may be added to the agitated mixture in the form of a slurry of pre-mixed particles of a minor amount of one or more liquid components. Thus, a premix of a small amount of the alcohol alkoxylate and/or the non-aqueous, low polarity solvent with particles of theorganic builder and/or particles of the inorganic alkaline material and/or particles of the bleach may be prepared separately and then added as a slurry to the agitated mixture of the composition components. Such premix slurry should be added prior to the addition of the peroxygen bleach and/or enzyme granules, and the bleach and/or enzyme itself may be made part of the premix slurry in a similar manner.

The compositions of the present invention prepared in the manner described above are useful in forming aqueous lotions for use in laundry and fabric bleaching. In general, it is preferred that an effective amount of the composition is added to water to form such an aqueous laundry/bleach solution in a conventional automatic fabric washing machine. The aqueous laundry/bleaching solution thus formed is then contacted with the fabric to be washed and bleached therein, preferably under agitation.

The effective amount of the liquid detergent composition added to water to form an aqueous laundry/bleach solution should be sufficient to form a composition concentration in the aqueous solution of from 500 to 7000 ppm. More preferably, the detergent composition of the present invention is formed at a concentration of 800 to 3000ppm in the aqueous laundry/bleach solution.

Example V

Non-limiting examples of non-aqueous liquid bleach-containing laundry detergents were prepared having the compositions shown in Table I.

TABLE I

Components By weight% Range (wt%) Liquid phaseC₁₂Sodium Linear alkyl benzene sulfonate (LAS) 25.318-35C_12-14EO5 alcohol ethoxylate 13.610-20 hexanediol 27.320-30 fragrance0.40-1.0 bis-AQA-1^*2.0 1-3.0Solid phaseProtease 0.40-1.0 trisodium citrate, anhydrous 4.33-6 sodium percarbonate 3.42-7 sodium Nonanoyloxybenzenesulfonate (NOBS) 8.02-12 sodium carbonate 13.95-200.90-1.5 portions of diethyl triaminepentaacetic acid (DTPA) 0.40-0.6 portions of whitening agent 0.10-0.3 portions of foam inhibitor and the rest is-

^*CoCoCoMeEO 2, bis-AQA-1 can be replaced by bis-AQA surfactants 2-22 or other bis-AQA surfactants of the present invention.

The composition can be prepared by mixing bis-AQA and LAS at 54 ℃ (130 ° F), followed by mixing hexanediol and alcohol ethoxylate 1/2 hours. The mixture was then cooled to 29 ℃ (85 ° F) at which time the remaining other components were added. The resulting composition was then stirred at 29 deg.C (85 deg.F) for an additional 1/2 hours.

The resulting composition is a stable, anhydrous, high-performance liquid laundry detergent which exhibits excellent stain and soil removal performance when used in normal fabric laundering operations.

Example VI

The hand wash detergent formulations of the present invention were prepared by mixing the various components together in the weight percentages given below.

A B C DLAS 15.0 12.0 15.0 12.0TFAA 1.0 2.0 1.0 2.0C₂₅E5 4.0 2.0 4.0 2.0AQA-9^*2.03.03.02.0 STPP 25.025.015.015.0 MA/AA 3.03.03.03.0 CMC 0.40.40.40.4 DTPMP 1.01.61.61.6 carbonate 2.02.05.05.0 bicarbonate- -2.02.0 silicate 7.07.07.07.0 protease 1.0-1.01.0 Amylase 0.40.40.4-Lipase 0.120.12-0.12 light activated bleach 0.30.30.30.3Sulfate 2.22.22.22.2 percarbonate 4.05.44.02.3 NOBS 2.63.12.51.7 SRA10.30.30.70.3 brightener 10.150.150.150.15balance impurity/water 100.0100.0100.0100.0 to 100

^*AQA-9 may be replaced by any of the AQA surfactants described herein. Can be used for the treatment of diabetesPreferred AQA surfactants of the examples are those having from 10 to 15 ethoxy groups, e.g., AQA-10, AQA-16.

The foregoing examples illustrate the invention by reference to fabric washing compositions, while the following examples will illustrate other types of cleaning compositions of the invention, but are not meant to be limiting thereof.

The novel high performance dishwashing compositions may contain ingredients which impart specific product use characteristics such as grease removal, high sudsing, mildness and skin feel comfort. These ingredients, for use with the bis-AQA surfactants of the present invention, include: amine oxide surfactants, betaine and/or sulfobetaine surfactants, alkyl sulfate and alkyl ethoxy sulfate surfactants, liquid carriers (especially water, and water/propylene glycol mixtures), natural oils such as lemon oil and the like. In addition, preferred liquid and/or gel dishwashing hand compositions may also comprise: calcium, magnesium, or calcium/magnesium mixed forms which impart additional grease removal performance, particularly when used in conjunction with detersive mixtures comprising the bis-AQA surfactants of the present invention and, amine oxides, alkyl sulfates and alkyl ethoxy sulfates. The source of magnesium or calcium or mixed Mg/Ca ions is generally present in an amount of from 0.01 to 4%, preferably from 0.02 to 2% by weight of the composition. Various water-soluble sources of these ions include: for example, sulfates, chlorides, and acetates. Furthermore, these compositions may also comprise nonionic surfactants, in particular polyhydroxy fatty acid amides and alkyl polyglucosides. Preferably C₁₂～C₁₄(coconut alkyl) group. A particularly preferred nonionic surfactant fordishwashing liquids is C₁₂～C₁₄N-methyl glucamide. Preferred amine oxides include C₁₂～C₁₄Dimethyl amine oxide. The alkyl sulfates and alkyl ethoxy sulfates are as described above. These surfactants are typically used in the dishwashing liquid in an amount of 3-50% of the finished composition. Formulations of dishwashing liquid compositions have been described in more detail in various patent publications, including US5378409, US5376310 and US5417893, which are incorporated herein by reference.

The novel automatic dishwashing detergent may comprise: various 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 used in the gel state, various gelling agents known in the literature can be used.

Examples a and B below will be further illustrated with respect to automatic dishwashing detergents containing particulate phosphate.

Example VII

Weight% of active substanceComposition (A) A BSTPP (waterless)¹3126 sodium carbonate 2232 silicate (% SiO)₂) 97 surfactant (nonionic) 31.5 NaDCC bleaching agent²2-bis-AQA-1^*0.51.0 sodium percarbonate 3.25 TAED-1.5 Savinase (AU/g) -0.04 Termamyl (Amu/g) 425 sulfate25 25PerfumeSmall amount of the extract to 100-100%

¹Sodium tripolyphosphate

²Sodium dichloro cyanurate

^*The bis-AQA-1 surfactants may be replaced by bis-AQA-2 through bis-AQA-22.

Various gelling agents such as CMC, clay, etc. may be used in the compositions of the present invention to modify their viscosity or hardness, as desired by the formulator.

Example VIII

The following illustrates bis-AQA surfactant mixtures which can be substituted for any of the bis-AQA surfactants listed in the preceding examples. As noted above, these mixtures can be used to produce various performance effects and/or to provide cleaning compositions suitable for various conditions of use. Preferably the bis-AQA surfactants in the mixture have EO units which differ by at least 1.5, preferably by 2.5 to 20. The ratio in the mixture is usually in the range of 10: 1 to 1: 10. Non-limiting examples of such mixtures are as follows.

Components Ratio (weight)

bis-AQA-1 + bis-AQA-51: 1

bis-AQA-1 + bis-AQA-101: 1

bis-AQA-1 + bis-AQA-151: 2

bis-AQA-1 + bis-AQA-5 + bis-AQA-201: 1

bis-AQA-2 + bis-AQA-53: 1

bis-AQA-5 + bis-AQA-151.5: 1

bis-AQA-1 + bis-AQA-201: 3

The bis-AQA meter of the present invention may also be usedMixtures of surfactants with corresponding cationic surfactants containing only a single ethoxylated chain. Thus, the present invention may be used, for example, with the formula R¹N⁺CH₃[EO]_x[EO]_yX^-And R¹N⁺(CH₃)₂[EO]_zX^-In which R is a hydrogen atom,in which R is a hydrogen atom¹And X is as disclosed above, and wherein one cationic surfactant has an (X + y) or z of 1 to 5, preferably 1 to 2, and the other cationic surfactant has an (X + y) or z of 3 to 100, preferably 10 to 20, most preferably 14 to 16. Such compositions advantageously improve stain removal performance (especially from a fabric laundering standpoint) over a wide range of water hardness relative to the single use of the cationic surfactants of the present invention. It has been found that shorter EO cationic surfactants (e.g., EO2) improve the cleaning performance of anionic surfactants in soft water, while higher EO cationic surfactants (e.g., EO15) can be used to increase the hardness tolerance of anionic surfactants, which improves the cleaning performance of anionic surfactants in hard water. In the field of detergency, common knowledge teaches that builders can optimise the "window" of performance of anionic surfactants. However, it has not been possible to broaden the performance window to meet substantially all water hardness conditions.

The laundry detergent compositions of the present invention, prepared using one or more of the foregoing ingredient mixtures, may optionally be formulated with any non-phosphate or phosphate builder, or mixtures thereof, typically in an amount of 5-70% by weight of the finished composition.

Example IX

The following illustrates mixtures of conventional non-AQA surfactants which may be used in admixture with the bis-AQA surfactants of any of the preceding examples, but this is not meant to be limiting. The ratio of the non-AQA surfactants in the mixture is expressed in parts by weight of the surfactant mixture.Mixtures A to C

Composition (A) Specific ratio of

AS^*/LAS 1∶1

AS/LAS 10: 1 (preferably 4: 1)

AS/LAS 1: 10 (preferably 1: 4)

^*In the foregoing, the substantially linear primary AS surfactant may be replaced by equal amounts of secondary or branched AS, oleyl sulfate, and/or mixtures thereof, including mixtures with the linear primary AS described above. The "tallow-based" chain length AS is particularly useful under hot to boiling water conditions. "Coco" AS is preferably used at colder washing temperatures.

The alkyl sulphate/anionic surfactant mixture may be modified by the addition thereto of a non-ionic non-AQA surfactant, wherein the weight ratio of anionic surfactant (all) to non-ionic surfactant is from 25: 1 to 1: 5. The nonionic surfactant may comprise any conventional ethoxylated alcohol or alkylphenol, alkyl polyglycoside or polyhydroxy fatty acid amide (not preferred if LAS is present), or mixtures thereof, such as those disclosed above.Mixtures D to F

AS^*/AES 1∶1

AS/AES 10: 1 (preferably 4: 1)

AS/AES 1: 10 (preferably 1: 4)

^*Can be replaced by the secondary, branched or oleyl AS described above.

The AS/AES mixture may be modified by adding LAS thereto, wherein the weight ratio of AS/AES (all) to LAS is from 1: 10 to 10: 1.

The AS/AES mixture or the AS/AES/LAS mixture resulting therefrom may also be used in combination with the nonionic surfactants mentioned in mixtures A-C, wherein the weight ratio of anionic surfactant(s) (all) to nonionic surfactant(s) is from 25: 1 to 1: 5.

Any of the foregoing mixtures may be modified by the addition thereto of an amine oxide surfactant, wherein the amine oxidecomprises from 1 to 50% of the total surfactant mixture.

Highly preferred mixtures of the foregoing non-AQA surfactants comprise from 3 to 60% by weight of the total laundry detergent composition. The finished composition preferably comprises 0.25 to 3.5 wt% of a bis-AQA surfactant.

Example X

This example illustrates a perfume formulation (a-C) made according to the present invention which can be used in any of the preceding examples incorporated into a bis-AQA containing detergent composition. The various ingredients and contents are given below.

By weight%

Perfume ingredients A B CHexylcinnamaldehyde 10.0-5.02-methyl-3- (p-tert-butylphenyl) -propionaldehyde 5.05.0-7-acetyl-1, 2,3, 4,5, 6,7, 8-octahydro-1, 1, 6, 7-tetramethylnaphthalene 5.010.010.0 benzyl salicylate 5.0-7-acetyl-1, 1, 3,4, 4, 6-hexamethyltetralin 10.05.010.0 p-tert-butylcyclohexyl acetate 5.05.0-methyl dihydrojasmonate-5.0- β-Naphthol methyl ether-0.5-methyl β -naphthalenone-0.5-2-methyl-2- (p-isopropylphenyl) -propanal 2.0-1, 3,4, 6,7, 8-hexahydro-4, 6,6, 7,8, 8-hexamethyl-cyclopenta-gamma-2-9.5-benzopyranododecahydro-3 a, 6,6, 9 a-tetramethylnaphtho [2, 1b]m]Furan- -0.1 anisaldehyde- -0.5 coumarin- -5.0 cedrol- -0.5 vanillin- -5.0 cyclo-n-pentadecanoic acid 3.0-10.0 tricyclodecenyl acetate- -2.0 Cistus oil resin- -2.0 tricyclodecenyl propionate- -2.0 phenylethyl alcohol 20.010.027.9 terpineol10.05.0 linalool 10.010.05.0 linalyl acetate 5.0-5.0 geraniol 5.0 acetate 5.0- -Orange oil, Cold extruded-5.0 benzyl acetate 2.02.0-orange terpene-10.0-eugenol-1.0-diethyl phthalate-9.5-lemon oil, Cold extruded-10.0 Total amount 100.0100.0100.0

The foregoing perfume compositions (typically at levels up to about 2% by weight of the total detergent composition) are premixed or sprayed into the various cleaning (including bleaching) compositions disclosed herein which contain the bis-AQA surfactants. Thus, the deposition and/or retention of the perfume or individual components thereof on the surface to be cleaned (bleached) is improved.

Claims (16)

1. A composition comprising or obtained by combiningThe following components were prepared: a percarbonate bleach, one or more non-AQA detersive surfactants, and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant of the formula,

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

2. A composition according to claim 1 which is prepared by mixing the non-AQA surfactant and the bis-AQA surfactant.

3. A composition according to either of claims 1 or 2 wherein the non-AQA surfactant is an anionic surfactant.

4. A composition according to any of claims 1 to 3 wherein the ratio of bis-AQA to non-AQA surfactant is from 1: 15 to 1: 8.

5. A composition according to any of claims 1 to 4 wherein said bis-AQA surfactant has the formula wherein R is¹Is C₈～C₁₈Alkyl radical, R²Is methyl, A and A' are ethoxy or propoxy groups, and p and q are each an integer of 1 to 8.

6. A composition according to any of claims 1 to 5 wherein said bis-AQA surfactant has the formula wherein R is¹Is C₈～C₁₈Alkyl radical, R²Is methyl, A and A' are ethoxy or propoxy groups, and p and q are each an integer of 1 to 4.

7. A composition according to any of claims 1 to 6 wherein the bis-AQA cationic surfactant has the formula wherein p and/or q are integers of from 10 to 15.

8. A composition according to any of claims 1 to 7 comprising two or more bis-alkoxylated AQA surfactants, or a mixture of a bis-AQA surfactant and a mono-ethoxylated cationic surfactant.

9. A composition according to any of claims 1 to 8 comprising two or more non-AQA surfactants and a mixture of two or more bis-AQA surfactants.

10. A composition according to any one of claims 1 to 9 in the form of granules, chunks, aqueous or non-aqueous liquids, or tablets.

11. A method of removing soils and stains by contacting said soils or stains with a detergent composition according to any of claims 1 to 10, or an aqueous medium containing said detergent composition.

12. A method according to claim 11, which is useful for removing bleach-sensitive soils from fabrics.

13. A method according to any one of claims 11 or 12 which is carried out in an automatic washing machine.

14. A process according to any one of claims 11 to 13 which is carried out by hand washing.

15. 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.

16. A method according to claim 15 which is conducted using a perfume or perfume ingredient in combination with a detergent composition comprising a bis-AQA.