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 percarbonate bleach, a non-AQA surfactant and a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant.

Background of the invention

The formulation of laundry detergents and other cleaning compositions presents enormous challenges due to the requirement for novel detergent compositions capable of removing a wide variety of soils and stains on different substrates. Thus, for effective performance of laundry detergents, hard surface cleaners, shampoos and other personal cleansing compositions, hand dishwashing detergents, and detergent compositions suitable for automatic dishwashing machines, all Reasonable selection and combination of its components is required. Generally, these detergent compositions contain one or more surfactants useful for loosening and removing various soils and stains. Looking at the various literature, it appears that detergent manufacturers have a wide choice of surfactants and surfactant blends, but the reality is that many of these ingredients are specialty chemicals and therefore not suitable for low price Items such as household laundry detergent. In fact, most of these household products, such as laundry detergents, still mainly contain a or various conventional ethoxylated nonionic and/or sulfated or sulfonated anionic surfactants.

Certain problems remain in the quick and effective removal of different soils and stains, such as body soil, fat/oil stains and certain food stains. These soils contain a mixture of hydrophobic triglycerides, fats, mixed polysaccharides, inorganic salts, and proteins, making them extremely difficult to remove. After washing, small amounts of hydrophobic dirt and residual stains usually remain on the surface of the fabric. Since hydrophobic soils are not completely washed away, continuous washing and wear will allow residual soil and stains to accumulate, and these soils and stains can also attract particulate dust, causing fabrics to turn yellow. Eventually, the fabric becomes dirty in appearance, so the user considers it impossible to wash, and discards it.

The literature shows that a variety of nitrogen-containing cationic surfactants can be used in a variety of cleaning compositions. These materials, usually in the form of amino, amido, or quaternary ammonium or imidazolinium compounds, are designed for specific applications. For example, a variety of amino and quaternary ammonium surfactants have been suggested for use in shampoo compositions and are said to impart hair cosmetic benefits. Other nitrogen-containing surfactants provide fabric softening and antistatic effects when used in some laundry detergents. However, the commercial use of these substances has been largely limited due to difficulties encountered in producing these compounds on a large scale. Another limitation is that anionic active ingredients in detergent compositions may form precipitates during ionic interactions with cationic surfactants. The aforementioned nonionic and anionic surfactants are still the main surfactants in today's laundry compositions.

It has now been found that certain bis-alkoxylated quaternary ammonium (bis AQA) compounds can be used in various detergent combinations in order to enhance cleaning performance on a variety of soils and stains, especially the commonly encountered hydrophobic soils in things. Surprisingly, it has now been found that compositions containing dual AQA surfactants and percarbonate bleach have superior cleaning and bleaching performance compared to compositions containing only one of these.

The dual AQA surfactants of the present invention are of real benefit to the formulator over known cationic surfactants. For example, the dual AQA surfactants used in the present invention can significantly enhance the performance of "everyday" fatty/oily hydrophobic soils typically encountered in cleaning. In addition, dual AQA surfactants are compatible with anionic surfactants commonly used in detergent compositions, such as alkyl sulfates and alkylbenzene sulfonates; The incompatibility of cationic surfactants has become one of the factors limiting the use of known cationic surfactants. Low levels (as low as 3 ppm in the wash) of dual AQA surfactants can produce the effects described herein. Dual AQA surfactants can be formulated over a wide pH range of 5-12. Dual AQA surfactants can be prepared as a pumpable 30% by weight solution, so they are easy to use in the manufacturing plant. Double AQA surfactants with a degree of ethoxylation of more than 5 sometimes exist in liquid form and are therefore available as 100% pure material. In addition to its beneficial performance properties, the ready availability of high concentration dual AQA surfactant solutions provides a real economical advantage in shipping costs. Unlike some cationic surfactants known in the art, dual AQA surfactants are also compatible with various fragrance ingredients.

Percarbonates, which provide peroxide bleaching action to wash liquors, are the foundational technology for new ultra-dense particle laundry detergent formulations. Peroxide bleaches are hydrophilic and are effective in decolorizing pigments (e.g., particle stains or beverage stains) and helps remove color from organic residue associated with body soil.

It is believed that the double AQA is effective in dissolving fatty/oily soils so that the hydrophilic peroxide bleach can access colored bodies (eg, entrapped pigments) in the soils, resulting in enhanced soil decolorization. Accordingly, the present invention provides a detergent composition having an excellent cleaning effect because the composition cleans hydrophobic fatty/oily soils as well as hydrophilic colored soils very effectively.

Background technique

US Patent No. 5,441,541, issued August 15, 1995 to A. Mehreteab and F. J. Loprest, relates to mixtures of anionic/cationic surfactants. UK 2,040,990 3 September 1980 to A.P.murphy, R.J.M.Smith and M.P. Brooks, relating to ethoxylated cationic surfactants in laundry detergents.

Summary of the invention

The present invention provides a composition comprising percarbonate bleach, a non-AQA surfactant and an effective amount of a bis-alkoxylated quaternary ammonium (bis-AQA) cationic surfactant having the formula, the composition can be prepared by mixing these components,

Wherein R ¹ is a linear, branched or substituted C ₈ -C ₁₈ alkyl, alkenyl, aryl, alkaryl, ether or glycidyl ether moiety, R ² is a C ₁ -C ₃ alkyl moiety , R ³ and R ⁴ can be changed independently, each selected from hydrogen, methyl and ethyl, X is an anion, and A and A' can be changed independently, each is C ₁ ~ C ₄ alkoxy, p and q They can be changed independently, and each is an integer of 1-30.

DETAILED DESCRIPTION OF THE INVENTION Percarbonate Bleach

The first essential component of the present invention is percarbonate bleach. According to the present invention, alkali metal or alkaline earth metal percarbonates, especially sodium percarbonate, are preferred percarbonates for inclusion in the compositions of the present invention. Sodium percarbonate is an addition compound having the _{formula 2Na2CO3-3H2O2} , _commercially available as a crystalline _solid . Its commercial sources include: Solvay, FMC, Tokai Denka, etc.

Preferred percarbonate bleaches contain dry particles having an average particle size of 0.5 to 1 mm, wherein: not more than 10% by weight of said particles are smaller than 0.2mm and not more than 10% by weight of said particles are larger than 1.250mm.

The content of percarbonate is 1-50% by weight of the detergent composition, preferably 1-30%, most preferably 5-20%.

Most preferably, the percarbonate is added to the coated composition to provide in-product stability.

Suitable coatings for in-product stability contain mixed salts of water soluble alkali metal sulphates and carbonates. GB-1466799, issued to Interox on March 9, 1977, already describes such coatings and their application methods. The weight ratio of the mixed salt paint to the percarbonate ranges from 1:200 to 1:4, more preferably from 1:99 to 1:9, most preferably from 1:49 to 1:19. Preferably, the mixed salt is a mixed salt of sodium sulfate and sodium carbonate having the general formula Na ₂ SO ₄ ·nNa ₂ CO ₃ , wherein n is 0.1-3, preferably n is 0.3-1.0, and most preferably n is 0.2-0.5.

Other coatings containing silicates (alone, or with borates or boric acids or other inorganics), waxes, oils, fatty soaps, may also be advantageously used in the present invention. Bis-Alkoxylated Quaternary Ammonium (Double AQA) Cationic Surfactant

The second essential component of the present invention comprises two AQA surfactants of the following structural formula in an effective amount: Wherein R ¹ is straight chain, branched or substituted C ₈ -C ₁₈ alkyl, alkenyl, alkenyl, Aryl, alkaryl, ether, glycidyl ether; ^R2 is an alkyl group containing 1 to 3 carbon atoms, preferably methyl; ^R3 and ^R4 can vary independently, each selected from hydrogen ( Preferred), methyl and ethyl, X ^- is an anion sufficient to generate electrical neutrality, such as chloride, bromide, methylsulfate, sulfate; A and A' can be changed independently, each selected from C ₁ ~C ₄ alkoxy, especially ethoxy, propoxy, butoxy and mixed groups thereof; p is 1-30, preferably 1-15, more preferably 1-8, even more preferably 1 ~4, and q is 1-30, preferably 1-15, more preferably 1-8, even more preferably 1-4. Most preferably p and q are 1 at the same time.

Bis AQA compounds wherein the substituent R ¹ is C ₈ -C ₁₂ , especially C ₈ -C ₁₀ hydrocarbyl, increase the dissolution rate of laundry detergent granules compared to longer chain species, even under cold water conditions. Therefore, for some formulators, C ₈ -C ₁₂ bis AQA surfactants are preferred. The level of dual AQA surfactants used in the preparation of finished detergent compositions is from 0.1 to 5% by weight, typically from 0.45 to 2.5% by weight. The weight ratio of double AQA to percarbonate bleach ranges from 1:100 to 5:1, more preferably from 1:60 to 2:1, most preferably from 1:20 to 1:1.

The present invention employs an "effective amount" of dual AQA surfactants in order to enhance the performance of cleaning compositions containing other optional ingredients. In the context of the present invention, an "effective amount" of a dual AQA surfactant means an amount sufficient to directionally or significantly improve the performance of the cleaning composition on at least some of the target soils and stains at a 90% confidence level. Thus, in compositions whose targets include certain food stains, formulators can use sufficient dual AQA to at least directionally improve cleaning performance on such stains. Likewise, in compositions whose targets include clay stains, the formulator can use sufficient dual AQA to at least directionally improve cleaning performance on such soils.

The dual AQA surfactants may be used in combination with other detersive surfactants at effective levels in order to achieve at least one targeted improvement in cleaning performance. In the case of fabric washing compositions, this "use level" varies not only depending on the type and severity of soils and stains, but also on the temperature of the wash water, the volume of the wash water and the type of washing machine.

For example, for a top-mounted vertical axis American automatic washing machine with 45-83 liters of water in the washing liquid, a washing cycle of 10-14 minutes, and a washing water temperature of 10-50°C, it is preferred that the washing liquid contains 2-50 ppm , preferably 5 to 25 ppm of double AQA surfactants. For high-efficiency liquid detergents, the concentration in the product of the double AQA surfactant is 0.1-3.2% by weight, preferably 0.3-1.5% by weight, based on the use ratio of 50-150ml per wash. For dense (“high density”) granular laundry detergents (density above 650 g/l), the in-product concentration of dual AQA surfactants is 0.2% to 5.0% by weight, preferably 0.5 to 2.5% by weight. For spray-dried granular detergents (that is, "loose type", with a density below 650g/l), the concentration of double AQA surfactants in the product is 0.1-3.5 based on the use ratio of 80-100 grams per wash. % by weight, preferably 0.3 to 1.5% by weight.

For example, for a front-loading horizontal axis European-style automatic washing machine with 8-15 liters of water in the washing liquid, a washing cycle of 10-60 minutes, and a washing water temperature of 30-95°C, it is preferred that the washing liquid contains 13-900 ppm, Preferred is 16-390 ppm of double AQA surfactant. For high-efficiency liquid detergents, the concentration in the product of the double AQA surfactant is 0.4-2.64% by weight, preferably 0.55-1.1% by weight, based on the use ratio of 45-270ml per wash. For dense ("high density") granular laundry detergents (density above 650 g/l), the in-product concentration of dual AQA surfactants is 0.5 to 3.5 based on a use rate of 40 to 210 grams per wash. % by weight, preferably 0.7 to 1.5% by weight. For spray-dried granular detergents (that is, "loose type", with a density below 650g/l), the concentration of double AQA surfactants in the product is 0.13-1.8 based on the use ratio of 140-400 grams per wash. % by weight, preferably 0.18 to 0.76% by weight.

For example, for a top-mounted vertical axis Japanese-style automatic washing machine with 26-52 liters of water in the washing liquid, a washing cycle of 8-15 minutes, and a washing water temperature of 5-25°C, it is preferred that the washing liquid contains 1.67-66.67ppm, 3 to 6 ppm of double AQA surfactant is preferred. For high-efficiency liquid detergents, the concentration in the product of the double AQA surfactant is 0.25-10% by weight, preferably 1.5-2% by weight, based on the use ratio of 20-30ml per wash. For dense ("high density") granular laundry detergents (density above 650 g/l), the in-product concentration of dual AQA surfactants is 0.25 to 10, based on a use rate of 18 to 35 grams per wash. % by weight, preferably 0.5 to 1.0% by weight. For spray-dried granular detergents (i.e. "loose type", density below 650g/l), the concentration of double AQA surfactant is 0.25-10% by weight based on the use rate of 30-40 grams per wash , preferably 0.5 to 1% by weight.

As can be seen from the foregoing, the amount of double AQA surfactants used in the range of machine washing can vary according to the user's habits and specific practices, and the type of washing machine. In this context, however, the heretofore unappreciated advantage of dual AQA surfactants is that when other surfactants (typically anionic, or anionic/nonionic mixtures) in the finished composition ) and when used at lower levels, it at least provides improved directional performance on various soils and stains. This is in contrast to other compositions in the art where the various cationic surfactants are used together with the anionic surfactants in stoichiometric or near stoichiometric amounts. Generally in the practice of the present invention, the weight ratio range of the double AQA surfactant to the anionic surfactant in the laundry composition is 1:70 to 1:2, preferably 1:40 to 1:6, more preferably 1:30 to 1:6, most preferably 1:15 to 1:8. In laundry compositions comprising both anionic and nonionic surfactants, the weight ratio of double AQA: mixed anionic/nonionic surfactants is in the range of 1:80 to 1:2, preferably 1:50 to 1:8 .

Various other cleaning compositions containing anionic surfactants, optionally nonionic surfactants and specialized surfactants, such as Betaine, Sultaine, Amine Oxide. These compositions include, but are not limited to, hand dishwashing products (especially liquid or gel), hard surface cleaners, shampoos, personal cleansing bars, laundry bars, and the like. Due to the minimal differences in the habits and practices of users of such compositions, inclusion of about 0.25 to 5% by weight, preferably about 0.45 to 2% by weight of the double AQA surfactant in the composition can achieve Satisfied with the effect. Also, in the case of granular and liquid laundry compositions, the weight ratio of dual AQA surfactants to other surfactants present in the composition is low, ie, substoichiometric for anionic surfactants. Preferably such cleaning compositions have the same dual AQA/surfactant ratio as just mentioned for machine laundry compositions.

Compared with other cationic surfactants known in the art, the bis-alkoxylated cationic surfactants of the present invention have sufficient solubility so that they can be combined with very low levels of nonionic surfactants containing, for example, alkyl Sulfate surfactants are used in combination in mixed surfactant systems. This is an important factor for formulators to consider when designing the types of detergent compositions commonly used in top loading washing machines, especially in North America, and under Japanese usage conditions. Typically, in such compositions, the anionic surfactant:nonionic surfactant weight ratio ranges from about 25:1 to 1:25, preferably from about 20:1 to 3:1. This is in contrast to European-type formulations where the anionic:nonionic surfactant ratio ranges from about 10:1 to 1:10, preferably from about 5:1 to 1:1.

方案2

方案3

方案4

Preferred ethoxylated cationic surfactants of the present invention are available from Akzo Nobel Chemicals Company under the trade name ETHOQUAD. Alternatively, this material can be synthesized using the following various reaction schemes (where "EO" represents a _-CH2CH2O- unit) _. plan 1

Scenario 2

Option 3

Option 4

The following is an economical reaction scheme. Option 5

The following parameters summarize alternative 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°C. The reaction pressure is 50-1000 psig. A base catalyst is used, preferably sodium hydroxide. In the reactant, the molar ratio of amine to alkyl sulfate is 2:1-1:1. The reaction is preferably carried out with C ₈ -C ₁₄ alkyl sulfate (sodium salt). The ethoxylation and quaternization steps are carried out using conventional conditions and conventional reactants.

In some cases, Reaction Scheme 5 produces products that are substantially soluble in the aqueous reaction medium, which may form gels. Although the desired product can be recovered from the gel, an alternative two-step synthesis, Scheme 6 below, may be preferred in some industrial production situations. The first step in scheme 6 is carried out in the manner in scheme 5. The second step (ethoxylation) is preferably performed with ethylene oxide and an acid, such as HCl, to form a quaternary surfactant. As shown below, chlorohydrins, i.e., chloroethanols, can be used in the reaction to give the desired bishydroxyethyl derivatives.

For Reaction Scheme 6, the following parameters summarize alternative 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°C. The reaction pressure is 50-1000 psig. A base, preferably sodium hydroxide, is used to react with the HSO ₄ ⁻ generated during the reaction, or an excess of amine can be used to react with an acid. The molar ratio of amine to alkyl sulfate is generally 10:1 to 1:1.5, preferably 5:1 to 1:1.1, most preferably 2:1 to 1:1. During the product recovery step, since the desired substituted amine is insoluble in the aqueous reaction medium, it can simply be separated as a different phase from the aqueous reaction medium. The second step of the process is carried out under conventional reaction conditions. Under standard reaction conditions, further ethoxylation reaction and quaternization reaction were carried out to obtain double AQA surfactants.

Monoethoxylation occurs by optionally carrying out Scheme 7 with ethylene oxide under standard ethoxylation conditions (but no catalyst present).

方案7

These other reaction schemes _are illustrated below, wherein "EO" represents a _-CH2CH2O- unit. During the reaction, use inorganic base, organic base or excess amine reactant to neutralize the generated HSO ₄ . Option 6

Option 7

Several of the above-mentioned reactions are further exemplified below, which is only for the convenience of the formulator, and is not meant to be limited thereto. Synthesis Method A Preparation of N,N-bis(2-hydroxyethyl)dodecylamine

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

In the manner described in Synthesis A, 1 mole of sodium lauryl sulfate was reacted with 1 mole of ethanolamine in the presence of a base. The resulting 2-hydroxyethyldodecylamine is recovered and 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% by weight sodium hydroxide solution (0.095 moles), and 72 grams of distilled water were added to the glass autoclave liner. The glass liner was sealed into a 500 ml stainless steel rocker autoclave and heated to 160-180° C. for 3-4 hours under a nitrogen pressure of 300-400 psig. The mixture was cooled to room temperature, then the liquid contents of the glass liner were poured into a 250 mL separatory funnel along with 80 mL of chloroform. Shake the funnel well for a few minutes, then allow the mixture to begin to separate. The lower chloroform layer was drained, then the chloroform was evaporated to give the product. Then, in the presence of a base catalyst, the product is reacted with 1 molar equivalent of ethylene oxide at 120-130° C. to produce the desired final product.

The disubstituted amines prepared according to the aforementioned syntheses can be further ethoxylated in a standard manner. In the present invention, the method of quaternization reaction with alkyl halides to form the double AQA surfactant is conventional.

In light of the foregoing, the following is a non-limiting description of the dual AQA surfactants useful in the present invention. It should be understood that the degree of alkoxylation for the double AQA surfactants is reported as an average value in accordance with common practice for ethoxylated nonionic surfactants. This is because ethoxylation reactions generally result in mixtures of species with different degrees of ethoxylation. Therefore, it is common practice to record the total EO value instead of an integer, such as "EO2.5", "EO3.5".

Name R ¹ R ² ApR ³ A′qR ⁴

Double AQA-1 C ₁₂ ～C ₁₄ CH ₃ EO EO (also known as coconut methyl EO2)

Double AQA-2 C ₁₂ ～C ₁₆ CH ₃ (EO) ₂ EO

Bis AQA-3 C ₁₂ ~C ₁₄ CH ₃ (EO) ₂ (EO) ₂ (also known as coconut methyl EO4)

Double AQA-4 C ₁₂ CH ₃ EO EO

Double AQA-5 C ₁₂ ~C ₁₄ CH ₃ (EO) ₂ (EO) ₃

Double AQA-6 C ₁₂ ~C ₁₄ CH ₃ (EO) ₂ (EO) ₃

Double AQA-7 C ₈ ~C ₁₈ CH ₃ (EO) ₃ (EO) ₂

Double AQA-8 C ₁₂ ~C ₁₄ CH ₃ (EO) ₄ (EO) ₄

Double AQA-9 C ₁₂ ~C ₁₄ C ₂ H ₅ (EO) ₃ (EO) ₃

Double AQA-10 C ₁₂ ~C ₁₈ C ₃ H ₇ (EO) ₃ (EO) ₄

Double AQA-11 C ₁₂ ～C ₁₈ CH ₃ (propoxy) (EO) ₃

Double AQA-12 C ₁₀ ～C ₁₈ C ₂ H ₅ (isopropoxy) ₂ (EO) ₃

Double AQA-13 C ₁₀ ~C ₁₈ CH ₃ (EO/PO) ₂ (EO) ₃

Double AQA-14 C ₈ ~C ₁₈ CH ₃ (EO) ₁₅ ^* (EO) ₁₅ ^*

Double AQA-15 C ₁₀ CH ₃ EO EO

Double AQA-16 C ₈ ~C ₁₂ CH ₃ EO EO

Double AQA-17 C ₉ ~C ₁₁ CH ₃ EO3.5, average

Double AQA-18 C ₁₂ CH ₃ EO3.5, average

Double AQA-19 C ₈ ~C ₁₄ CH ₃ (EO) ₁₀ (EO) ₁₀

Dual AQA-20 C ₁₀ C ₂ H ₅ (EO) ₂ (EO) ₃

Double AQA-21 C ₁₂ ~C ₁₄ C ₂ H ₅ (EO) ₅ (EO) ₃

Double AQA-22 C ₁₂ ～C ₁₈ C ₃ H ₇ Bu (EO) ₂

^* Optionally methyl or ethyl terminated ethoxy. Highly preferred dual AQA surfactants for use in the present invention have the formula:

Wherein R ¹ is a C ₈ -C ₁₈ hydrocarbon group and a mixed group thereof, preferably a C ₈ , C ₁₀ , C ₁₂ , C ₁₄ alkyl group and a mixed group thereof; X is a conventional anion providing charge balance, preferably chlorine. With reference to the double AQA general structure mentioned above, because in the preferred compound, R ¹ is derived from coconut (C ₁₂ ~ C ₁₄ alkyl) partial fatty acid, R ² is a methyl group, and ApR ³ and A'pR ⁴ are respectively is monoethoxy, so preferred compounds of this class are referred to herein as "coconut MeEO2" or "bis AQA-1" as listed above.

Other dual AQA surfactants useful in the present invention include compounds having the formula:

wherein R ¹ is a C ₈ -C ₁₈ hydrocarbon group, preferably a C ₈ -C ₁₄ alkyl group; p and q are independently 1-3, R ² is a C ₁ -C ₃ alkyl group, preferably a methyl group, and X is an anion, especially chloride or bromide.

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

Highly preferred dual AQA surfactants for use in formulations have the formula wherein p and/or q are integers in the range 10-15. The compounds are particularly useful in laundry handwash detergent compositions. Non-AQA detergent surfactants

In addition to the dual AQA surfactants, the compositions of the present invention may also preferably comprise non-AQA surfactants. Non-AQA surfactants can include essentially any anionic, nonionic or other cationic surfactant. anionic surfactant

Non-limiting examples of anionic surfactants generally used in the present invention at levels of 1 to 55% by weight include: conventional C ₁₁ -C ₁₈ alkylbenzene sulfonates ("LAS"); and primary ("AS" ), branched or random C ₁₀ ~ C ₂₀ alkyl sulfate; the structural formula is CH ₃ (CH ₂ ) _x (CHOSO ₃ ^- M ⁺ )CH ₃ and CH ₃ (CH ₂ ) _y (CHOSO ₃ ^- M ⁺ ) CH ₂ CH ₃ C ₁₀ ~ C ₁₈ secondary (2,3) alkyl sulfate, wherein: x and (y+1) are at least 7, preferably at least 9 integers, and M is a water-soluble cation (especially is sodium); unsaturated sulfates, such as oleyl sulfate; C ₁₂ ~ C ₁₈ α-sulfonated fatty acid esters; C ₁₀ ~ C ₁₈ sulfated polyglycosides; C ₁₀ ~ C ₁₈ alkyl alkoxy sulfates ("AE _x S", especially EO 1-7 ethoxysulfate), and C ₁₀ -C ₁₈ alkyl alkoxy carboxylates (especially EO 1-5 ethoxycarboxylate). C ₁₂ -C ₁₈ betaines and sultaines, C ₁₀ -C ₁₈ amine oxides may also be included in the overall composition. _C10 - _C20 conventional soaps may also be used. If a lot of lather is desired, branched chain _C10 - _C16 soaps can be used. Other commonly used surfactants are listed in standard textbooks. nonionic surfactant

Non-limiting examples of nonionic surfactants generally used in the present invention at levels of 1 to 55% by weight include: alkoxylated alcohols (AE's) and alkylphenols, polyhydroxy fatty acid amides (PFAA's), Alkyl polyglycosides (APG's) C ₁₀ -C ₁₈ glyceryl ethers.

More specifically, in the present invention, condensation products of aliphatic primary and secondary alcohols with 1 to 25 moles of ethylene oxide (AE) are suitable as nonionic surfactants in the present invention. The alkyl chain of the aliphatic alcohol can be straight or branched, primary or secondary, and generally contains 8 to 22 carbon atoms. Preferably per mole its alkyl group contains 8 to 20 carbon atoms, more preferably alcohols with 10 to 18 carbon atoms and 1 to 10, more preferably 2 to 7, most preferably 2 to 5 moles of ethylene oxide condensation product. Examples of such nonionic surfactants that are commercially available include: Tergitol ^™ 15-s-9 (a condensation product of a C ₁₁ -C ₁₅ linear alcohol with 9 moles of ethylene oxide) and Tergitol TM 15-s-9 supplied by UnionCarbide Corporation. ^TM 24-L-6 NMW (condensation product of C ₁₂ -C ₁₄ primary alcohols with narrow molecular weight distribution and 6 moles of ethylene oxide); Neodol ^TM 45-9 (C ₁₄ -C ₁₅ linear Alcohol and 9 moles of ethylene oxide), Neodol ^TM 23-3 (condensation product of C ₁₂ ~C ₁₃ linear alcohols and 3 moles of ethylene oxide), Neodol ^TM 45-7 (C ₁₄ ~C ₁₅ Condensation product of linear alcohol with 7 moles of ethylene oxide) and Neodol ^TM 45-5 (condensation product of C ₁₄ to C ₁₅ linear alcohol with 5 moles of ethylene oxide); Kyro ^TM supplied by Procter & Gamble Company EOB (condensation product of _C13 - _C15 alcohol with 9 moles of ethylene oxide); and Genapol LAO3O or O5O (condensation product of _C12 - _C14 alcohol with 3 or 5 moles of ethylene oxide) supplied by Hoechest. Among these AE nonionic surfactants, the preferred range of HLB is 8-11, most preferably 8-10. Condensates with propylene oxide and butylene oxide can also be used.

Another preferred nonionic surfactant useful herein is a polyhydroxy fatty acid amide having the formula:

Wherein R ¹ is H, or C _1-4 hydrocarbon group, 2-hydroxyethyl, 2-hydroxypropyl or a mixed group thereof; R ² is C _5-31 hydrocarbon group; and Z is polyhydroxyl hydrocarbon group, or its alkoxy An alkylated derivative group, the polyhydroxyl hydrocarbyl having at least 3 straight chain hydrocarbyl groups directly attached to the hydroxyl groups on the chain. Preferably R ^is methyl, ^R is a straight chain C _11-15 alkyl or C _15-17 alkyl or alkenyl chain, such as coconut alkyl or a mixture thereof, and Z is derived from a reducing sugar, such as glucose , Reductive amination reaction of fructose, maltose and lactose. Typical examples thereof include C ₁₂ -C ₁₈ and C ₁₂ -C ₁₄ N-methyl glucamides. See US5194639 and 5298636. N-alkoxy polyhydroxy fatty acid amides may also be used, see US5489393.

In the present invention, what can also be used as nonionic surfactants are: the alkyl polysaccharides disclosed in U.S. Patent 4,565,647 issued to Llenado on January 21, 1986, with hydrophobic groups containing 6 ~30 carbon atoms, preferably 10-16 carbon atoms; and polysaccharides, such as polyglycosides whose hydrophilic groups contain 1.3-10, preferably 1.3-3, most preferably 1.3-2.7 sugar units. Any reducing sugar containing 5 or 6 carbon atoms can be used, such as glucose, galactose, and the galactosyl moiety can be substituted with glucosyl (hydrophobic groups can optionally be attached to 2-, 3-, 4- Allelically, this gives glucose or galactose as opposed to glucoside or galactose). Intersaccharide linkages may be located, eg, between one position of an added sugar unit and the 2-, 3-, 4- and/or 6-position of the preceding sugar unit.

Preferred alkyl polyglycosides have the formula:

R ² O(C _n H _2n O(glycosyl) _x

Wherein: R ^is selected from alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixed groups 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 1.3-10, preferably 1.3-3, more preferably 1.3-2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alcohol or alkylpolyethoxylated alcohol is first made and then reacted with glucose, or a source of glucose, to form the glucoside (attached at the 1-position). The added glycosyl unit can then be linked between its 1-position and the 2-, 3-, 4- and/or 6-position (preferably the 2-position predominates) of the preceding glycosyl unit.

In the surfactant system of the present invention, polyethylene oxide, polypropylene oxide and polybutylene oxide condensates of alkylphenols are also suitable for use as nonionic surfactants, wherein polyethylene oxide condensates are preferred of. These compounds include: the condensation products of linear or branched alkylphenols with alkylene oxides, the alkyl group of which contains 6 to 14 carbon atoms, preferably 8 to 14 carbon atoms. In a preferred embodiment, the amount of ethylene oxide is 2 to 25 moles, preferably 3 to 15 moles of ethylene oxide per mole of alkylphenol. Commercially available such nonionic surfactants include: Igepal ^™ CO-630 supplied by GAF Corporation; and Triton ^™ X-45, X-114, X-100 and X-102 supplied by Rohm & Hass Company. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

The condensation products of the hydrophobic base obtained by the condensation reaction of propylene oxide with propylene glycol and ethylene oxide are also suitable 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, up to a polyoxyethylene content of 50% of the total weight of the condensation product, which is equivalent to Condensed with up to 40 moles of ethylene oxide. Examples of such compounds include certain of the commercially available Pluronic ^™ surfactants supplied by BASF.

In the nonionic surfactant system of the present invention, also suitable as nonionic surfactants are: the reaction product of propylene oxide and ethylenediamine and the condensation product of ethylene oxide. The hydrophobic portion of these products consists of the reaction product of ethylenediamine with excess propylene oxide, usually having a molecular weight of 2500-3000. The hydrophobic part undergoes condensation reaction with ethylene oxide, and the condensation product contains 40-80% by weight of polyoxyethylene, and its molecular weight is usually 5000-11000. Examples of such nonionic surfactants include certain Tetronic( ^TM) compounds commercially available from BASF. Other cationic surfactants

Suitable cationic surfactants are preferably water-dispersible compounds having surfactant properties which contain at least one ester linkage (ie, -COO-) and at least one electropositive group.

Other suitable cationic surfactants include: quaternary ammonium surfactants selected from mono C ₆ -C ₁₆ , preferably C ₆ -C ₁₀ N-alkyl or alkenyl ammonium surfactants, wherein the remaining N sites are Substituted by methyl, hydroxyethyl or hydroxypropyl groups. For example, US Patent Nos. 4,228,042, 4,239,660 and 4,260,529 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 is not meant to be limiting. bleach activator

Bleach activators are a preferred ingredient in the compositions herein. For bleaching compositions comprising a bleaching agent and a bleach activator, the amount of the bleach activator, if present, will generally be from 0.1 to 60%, more typically from 0.5 to 40%, of the bleaching composition.

In aqueous solution (ie, during the wash), a peroxygen bleach, such as percarbonate, is mixed with a bleach activator to allow the in situ formation of the peroxyacid corresponding to the bleach activator. Various non-limiting examples of bleach activators are disclosed in US Patent 4,915,854, issued April 10, 1990 to Mao et al., and US Patent 4,412,934. Nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TEAD) activators are commonly used, and mixtures thereof can also be used. Additionally, see US4634551 for other typical bleaches and activators which may be used in the present invention.

Highly preferred amido-derived bleach activators have the formula:

R ¹ N(R ⁵ )C(O)R ² C(O)L or R ¹ C(O)N(R ⁵ )R ² C(O)L,

Wherein ^R1 is an alkyl group containing 6-12 carbon atoms, ^R2 is an alkylene group containing 1-6 carbon atoms, ^R5 is H or an alkyl group containing 1-10 carbon atoms, Aryl, or alkaryl, and L is any suitable leaving group. By leaving group is meant any group which can be displaced from the bleach activator by nucleophilic attack of the bleach activator by the perhydrolyzed anion. A preferred leaving group is phenylsulfonate.

Preferred examples of bleach activators having the above structural formula include: (6-octanoylaminocaproyl) oxybenzenesulfonate, (6-nonanoylaminocaproyl) oxybenzenesulfonate described in U.S. Patent No. 4,634,551 , (6-decanoylaminocaproyl)oxybenzenesulfonate, and mixtures thereof, which are incorporated herein by reference.

Another bleach activator includes the benzoxazine-type activators disclosed in US Patent 4,966,723, Hodge et al., issued October 30, 1990, 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 having the formula:

Wherein R ⁶ is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing 1 to 12 carbon atoms. Highly preferred caprolactam activators include: benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecyl caprolactam, benzoyl valerolactam , octanoyl valerolactam, decanoyl valerolactam, undecyl valerolactam nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, and mixtures thereof. See US Patent 4,545,784, Sanderson, October 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam absorbed into sodium perborate, which is incorporated herein by reference. bleach catalyst

Bleach catalysts are a preferred ingredient in the compositions of the present invention. Manganese compounds can be used to catalyze the bleaching compounds, if desired. Such compounds are well known in the art and include, for example, the manganese-based compounds disclosed in US5,246,621, US5,244,594, US5,194,416, US5,114,606 and European Patent Application Publication Nos. catalyst. Preferred examples of these catalysts include: Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO ) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4 , 7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-tri Azacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (OCH ₃ ) ₃ (PF ₆ ) and its mixture. Other metal-based bleach catalysts include those disclosed in US Patent 4,430,243 and US Patent 5,114,611. The use of manganese in combination with various complex ligands for bleach enhancement is also reported in the following US patents: 4,728,455, 5,284,944, 5,246,612, 5,256,779, 5,280,117, 5,274,147, 5,153,161 and 5,227,084.

As a practical matter (and not limiting), the compositions and methods of the present invention can be adapted so as to provide active bleach catalyst species in the aqueous wash liquor on the order of at least one part per million, and preferably in the wash liquor Provide 0.1-700ppm, more preferably 1-500ppm catalyst material in.

Cobalt bleach catalysts which can be used in the present invention are known and are described, for example, by ML Tobe in "Base Hydrolysis of Transition-Metal Complex", Adv. Inog. Bionorg. Mech., (1983), 2, pages 1-94 . The most preferred cobalt catalysts useful in the present invention are: cobalt pentaaminoacetate salts having the formula [Co( _NH3 ) _5OAc ] _Ty , where "OAc" represents the acetate moiety and " _Ty " is an anion, especially is cobalt chloride pentaaminoacetate, [Co(NH ₃ ) ₅ OAc]Cl ₂ and [Co(NH ₃ ) ₅ OAc](OAc) ₂ , [Co(NH ₃ ) ₅ OAc](PF ₆ ) ₂ , [ Co(NH ₃ ) ₅ OAc](SO ₄ ), [Co(NH ₃ ) ₅ OAc](BF ₄ ) ₂ , and [Co(NH ₃ ) ₅ OAc](NO ₃ ) ₂ (“PAC” in the present invention ).

These cobalt catalysts can be prepared, for example, by known methods taught by Tobe's article and references cited therein, and references J. Chem.Ed.(1989), 66, (12), 1043-45, "The Synthesis and Characterization of Inorganic Compounds" (The Synthesis and Characterization 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 Physical Chemistry, 56, 22-25 (1952).

As a practical matter, and without limitation, the automatic dishwashing compositions and cleaning methods of the present invention can be adapted so as to provide an active bleach catalyst species equivalent to at least 0.01 ppm in the aqueous wash medium, and preferably in the wash medium. From 0.01 to 25 ppm, more preferably from 0.05 to 10 ppm, most preferably from 0.1 to 5 ppm of bleach catalyst material is provided in the liquor. In order to maintain this level in the wash liquor of the 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 bleach

The detergent compositions herein may optionally contain other bleaching agents. If present, these other bleaching agents will generally comprise from about 1 to 30%, more usually from about 5 to 20%, of the detergent compositions, especially for laundering of fabrics.

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

Another class of bleaches which may be used without limitation includes percarboxylic acid bleaches and their salts. Suitable examples of such bleaching agents include: magnesium monoperphthalate hexahydrate, magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxyperoxybutyric acid and diperoxydodecanedioic acid. Magnesium salt. U.S. Patent 4,483,781 issued November 20, 1984 to Hartman, U.S. Patent Application 740,446 filed June 3, 1985 by Burns et al., European Patent Application 0133354 published February 20, 1985 by Banks et al., and 1983 Such bleaches are disclosed in US Patent 4,412,934 issued November 1 to Chung et al. Also highly preferred bleaching agents include: 6-nonylamino-6-oxyperoxycaproic acid, described in US Patent 4,634,551, Burns et al., issued January 6,1987.

Peroxygen bleach can also be used. Suitable peroxygen bleaching compounds include: sodium pyrophosphate peroxyhydrate, urea peroxyhydrate and sodium peroxide. Perborate bleach, persulfate bleach (eg, OXONE commercially available from DuPont) can also be used.

Bleaching agents other than oxygen bleaching agents are known in the art and can be used in the present invention. A class of non-oxygen bleaches of particular interest includes photoactivated bleaches such as sulfonated zinc and/or aluminum phthalocyanines. See US Patent 4,033,718, issued July 5, 1977 to Holcombe et al. If used, detergent compositions will generally contain from about 0.025 to 1.25% by weight of such bleaching agents, especially sulfonated zinc phthalocyanines.

A mixture of bleaches can also be used. builder

To help control mineral, especially Ca2 ⁺ and/or Mg2 ⁺ hardness in the wash water, or to help remove particulate soils from surfaces, the compositions of the present invention may optionally, but preferably contain detergent builders . Builders work through a variety of mechanisms, including: forming soluble or insoluble complexes with hardening ions by ion exchange, and creating surfaces that are more conducive to the precipitation of hardening ions than the surface of the item being cleaned. Builder levels can vary widely depending on the end use and physical form of the composition. Built detergents generally contain at least 1% builder. Liquid formulations generally contain from 5 to 50%, more typically from 5 to 30%, of builder. Granular formulations generally comprise from 10 to 80%, more typically from 15 to 50%, by weight of the detergent composition, of a detergent builder. Lower or higher levels of builders are not excluded. For example, some detergent additives or high-surfactant formulations can be built without builders.

Suitable builders may be selected from: phosphates and polyphosphates, especially their sodium salts; silicates, including water-soluble and aqueous solid types, and including those with chain, layered, or three-dimensional structures salts, and amorphous solids or unstructured liquids; carbonates; bicarbonates; sesquicarbonates and carbonate minerals other than sodium carbonate or sodium sesquicarbonate; aluminosilicates; organic mono-, Di-, tri-, and tetracarboxylates, especially water-soluble non-surfactant carboxylates in the form of acid, sodium, potassium, or alkanolammonium salts, and aliphatic and aromatic oligomers or water-soluble low molecular weight carboxylates polymers and phytic acid. For pH buffering etc. these materials may be supplemented with borates or with sulfates, especially sodium sulfate and any other fillers or carriers which may contribute to the stabilization of detergents containing surfactants and/or builders. The detergent composition is important.

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

Phosphorus-containing detergent builders are generally preferred whenever regulations permit, and include, but are not limited to, alkali metal, ammonium, and alkanolammonium salts of polyphosphates, specifically tripolyphosphates, pyrophosphates, and glassy polymeric metaphosphates; and phosphonates.

Suitable silicate builders include: alkali metal silicates, especially those liquid and solid alkali metal silicates having a _SiO2 : _Na2O ratio in the range of 1.6:1 to 3.2:1, including, (Especially for automatic dishwashing purposes) solid aqueous 2-ratio (ratio 2) silicates supplied by PQ Corp under the tradename ^BRITESIL_ , such as BRITESIL _H2O ; and layered silicates, such as 3, 1987 Described in US Patent 4,664,839 issued to HP Rieck on December 12. NaSKS-6, sometimes referred to simply as "SKS-6", is a crystalline layered aluminum-free delta- _{Na2SiO 5} state silicate supplied by the Hoechst Corporation which is especially preferred in granular laundry compositions. See the preparations in DE-A-3,417,649 and DE-A-3,742,043. Other phyllosilicates of the general formula _{NaMSixO 2x+1} yH ₂ O can also be used in the present invention, wherein: M is sodium or hydrogen, n is 1.9 to 4, preferably 2, and y is 0 to 20, Preferably 0. Phyllosilicates from the company Hoechst include: NaSKS-5, NaSKS-7 and NaSKS-11 which are alpha-, beta- and gamma-phyllosilicates, respectively. Other silicates can also be used, such as magnesium silicate, which can be used in the granules as a crisping agent, as a bleach stabilizer, and as a component of suds control systems.

Also suitable for use in the present invention are synthetic crystalline ion exchange materials with a chain structure or hydrates thereof whose anhydride form composition can be represented by the general formula: xM ₂ O ySiO ₂ zM'O, wherein M is Na and /or K, M' is Ca and/or Mg, y/x is 0.5-2.0 and z/x is 0.005-1.0, as described in US 5427711 issued to Sakaguchi et al. in 1995.

Suitable carbonate builders include: the alkaline earth and alkali metal carbonates described in German Patent Application No. 2321001 published on November 15, 1973, and of course used as seeds or in synthetic detergent bars etc. There are: sodium bicarbonate, sodium carbonate, sodium sesquicarbonate, and other carbonate minerals, such as trona, or any common double salt of sodium carbonate and calcium carbonate, which has the composition 2Na ₂ CO ₃ ·Ca when anhydrous ₂ CO ₃ double salts, even calcium carbonate including calcite, aragonite and vaterite, especially the relatively high-density calcite has a high surface area.

Aluminosilicate builders are especially useful in granular detergents, but can also be added to liquids, creams or gels. Those aluminosilicates suitable for this purpose have the empirical formula: [M _z (AlO ₂ ) _z (SiO ₂ ) _v ] xH ₂ O, where z and v are integers of at least 6 and the molar ratio of z to v is between 1.0-0.5, and x is an integer of about 15-264. Aluminosilicates can be crystalline or amorphous, naturally occurring or synthetically derived. A method of preparing aluminosilicates is disclosed in US Patent 3,985,669, issued October 12, 1976 to Krummel et al. Preferred synthetic crystalline aluminosilicate ion exchange materials are commercially available under the trade names Zeolite A, Zeolite P(B), Zeolite X, and so-called Zeolite MAP (however different it may be from Zeolite P). Natural forms of aluminosilicates, including clinoptilolite, may also be used. The structural formula of ZeoliteA is: Na ₁₂ [(AlO ₂ ) ₁₂ (SiO ₂ ) ₁₂ ]·xH ₂ O, where x is 20-30, especially 27. Dehydrated zeolites (x=0-10) can also be used. Preferably, the aluminosilicate particle diameter is between 0.1 and 10 microns.

Suitable organic detergent builders include polycarboxylates, including the water-soluble nonsurfactant 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 forms. When used in salt form, alkali metals such as sodium, potassium and lithium, or alkanolammonium salts are preferred. Polycarboxylate builders include: polycarboxylate ethers such as oxydisuccinates, see U.S. Patent 3,128,287 issued April 7, 1964 to Berg and U.S. Patent 3,635,830 issued January 18, 1972 to Lamberti et al; "TMS/TDS" builders in U.S. Patent 4,633,071 issued May 5 to Bush et al; other carboxylate ethers, including cyclic and alicyclic compounds, as in U.S. Patents 3,923,679, 3,835,163, 4,158,635, 4,120,874, and 4,102,903 as described.

Other suitable builders include: hydroxy polycarboxylate ethers, copolymers of maleic anhydride and ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid, carboxylate Methoxysuccinic 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 particularly important carboxylate builders, eg, for heavy duty liquid detergents, because they can be derived from renewable sources and are biodegradable. Citrates can also be used in granular compositions, especially in combination with zeolite and/or layered silicate builders. Oxydisuccinates are also particularly useful in such compositions and mixtures.

The various alkali metal phosphates, such as sodium tripolyphosphate, sodium pyrophosphate and sodium orthophosphate, may be used where permitted, especially when formulating bars for hand washing. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (such as those in U.S. Pat. ), and has the required descaling properties.

Certain detergent surfactants or their short-chain homologues also have a builder effect. In order to have a clear guideline, when substances have surfactant efficacy, these substances are generally classified as detersive surfactants. The preferred example of the surfactant with builder function is: 3,3-dicarboxy-4-oxa-1,6-hexanedioate and related compounds thereof, disclosed in US Patent No. 4,566,984 granted to Bush on January 28, 1986 middle. Succinic acid builders include _C5 to _C20 alkyl and alkenyl succinic acids and salts thereof. Succinate builders also include: lauryl succinate, myristyl succinate, cetyl succinate, 2-dodecenyl succinate (preferred), 2-pentadecyl Carbenyl succinate. Lauryl succinate is described in European Patent Application 86200690.5/0200263, published November 5, 1986. Fatty acids such as _C12 ～ _C18 monocarboxylic acids can also be used as surfactants and/builders alone or mixed with the aforementioned builders, especially citrate and/or succinate builders, and added to the composition, Additional builder activity can be produced. Other suitable polycarboxylates are described in US Patent 4,144,226, Crutchfield et al., issued March 13, 1979, and US Patent 3,308,067, Diehl, issued March 7, 1967. See also US Patent 3,723,322 to Diehl.

Other types of inorganic builders that can be used have the structural formula: (M _x ) _i Ca _y (CO ₃ ) _z , wherein: x and i are integers between 1 and 15, y is an integer between 1 and 10, z is an integer between 2 and 25, M _i is a cation, at least one of which is water-soluble, and satisfies the equation Σ _i =1-15 (valence of x _i ×M _i )+2y=2z at the same time, so that the structural formula has a Neutral or "balanced" charge. In the present invention, these builders are referred to as "mineral builders". Water of hydration or anions other than carbonate may be added as long as the overall charge remains balanced or neutral. The charge or valency of these anions should be added to the right side of the above equation. Preferably the water soluble cations present are selected from the group consisting of hydrogen, water soluble metals, hydrogen, boron, ammonium, silicon and mixtures thereof, more preferably sodium, potassium, hydrogen, lithium, ammonium and mixtures thereof, most preferably sodium and potassium. Non-limiting examples of non-carbonate anions include: chloride, sulfate, fluoride, oxygen, hydroxide, silica, chromate, nitrate, borate, and mixtures thereof. Such builders in their simplest form are preferably selected from _Na2Ca ( _{CO3 ) 2} , _K2Ca ( _CO3 ) ₂ , _Na2Ca2 ( _CO3 ) ₃ , NaKCa( _CO3 ) ₂ , _NaKCa2 (CO ₃ ) ₃ , K ₂ Ca ₂ (CO ₃ ) ₃ and mixtures thereof. Particularly preferred builders described herein are all crystal-modified _Na2Ca ( _CO3 ) ₂ . Suitable builders are defined above and may be further illustrated by way of example and may include natural or synthetic forms of any one or mixture of the following minerals, including acaciasite, uranite, zeolite Y, bismuth carbon Calcite stone, carbon boron magnesium calcium stone, yellow carbon strontium soda stone, potassium carbonate calcium stone, cannonite, cerium soda stone, soda calcium silicate, potassium calcium nepheline, yttrium strontium carbon Y, potassium calcium calcium Stone, Fairchildite, Sulfur Potassium Calcium Stone, Carbon Boron Manganite, Monoclinic Soda Lime, Girvasite, Ilmenite, Sulfur Carbon Calmangite, Kamphaugite Y, Fluorocarbonate Bismuth Calcium Stone, Khanneshite, LepersonniteGd, Lepersonnite Cancryptite, Carbonite Y, Slightly Alkaline Cancryptite, Carbontellurite, Nicarbonite, Nicarbonite, Remondite Ce, Potassium Cancryptite, Platenite, Soda Calcium Carbonate chrysophyllite, osmanthite, soda-mayenite, molybdenite, cupolite, sulphate, and Zemkorite. Preferred mineral forms include nilmanite, sorrelite and sorrelite. enzyme

Enzymes may be included in the compositions of the present invention for a variety of purposes including: removal of protein-based, carbohydrate-based, or triglyceride-based stains from various substrates; inhibition of transfer of leaching dyes during fabric laundering; and for fabric reforming. Suitable enzymes include proteases, amylases, lipases, cellulases, peroxidases, and mixtures thereof of any suitable origin such as vegetable, animal, bacterial, fungal and yeast origin. Its preference is influenced by various factors such as: pH-activity and/or stability optima, thermostability, and stability to active detergents, builders. In this respect, bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases, and fungal cellulases.

As used herein, "detergent enzyme" means any enzyme that has cleaning, stain removal or other beneficial effects in laundry, hard surface cleaning or personal care detergent compositions. 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 well suited for automatic dishwashing are amylases and/or proteases.

In general, the amount of enzyme added to the detergent or detergent additive composition should be sufficient to produce a "cleaning effective amount". The term "cleaning effective amount" refers to: any amount capable of producing cleaning, stain-removing, soil-removing, whitening, deodorizing, or freshness-enhancing effects on substrates, such as fabrics and tableware. In practice, in current commercial formulations, the amount of active enzyme ingredient is typically up to 5 mg, more typically between 0.01 and 3 mg, per gram of detergent composition. Unless otherwise stated, the compositions of the present invention generally comprise from 0.001 to 5%, preferably from 0.01 to 1% by weight of a commercial enzyme preparation. Typically in commercial formulations, the amount of protease should be sufficient to provide 0.005 to 0.1 Anson Units (AU) of activity per gram of composition. For some detergents (e.g., for automatic dishwashing), active enzymes are increased in commercial formulations in order to substantially reduce the total amount of non-catalytically active material and thus improve spotting/filming or other end results content. Higher active ingredient levels are also welcome in highly concentrated detergent formulations.

Suitable examples of proteases are subtilisins, which are produced by certain strains of Bacillus subtilis and Bacillus licheniformis. Another suitable protease is produced by a Bacillus strain that is most active throughout the pH range of 8-12, has been developed by Novo Industries A/S of Denmark (hereinafter "Novo") and is sold under the trade name ^ESPERASE® . The preparation of this and similar enzymes is described in British Patent 1243784 to Novo. Other suitable proteases include: ALCALASE ^_ and SAVINASE ^_ from Novo, and MAXATASE ^_ from International Bio-Synthetic, Inc, The Netherlands; Protease B disclosed on January 28, 1985 and EP130756 on January 9, 1985. In addition, high pH proteases, see, Bacillus strain NCIMB 40338 described in WO 9318140A to Novo. In WO 9203529A to Novo, enzymatic detergents comprising a protease, one or more other enzymes, and a reversible protease inhibitor are described. Other preferred proteases include those of WO 9510591A to Procter & Gamble. Where desired, proteases with reduced absorption and increased hydrolysis can be obtained as described in WO 9507791 to Procter & Gamble. WO 9425583 to Novo describes a detergent trypsin-like protease recombinant suitable for the present invention.

In more detail, a particularly preferred protease called "Protease D" is a carbonyl hydrolase variant whose amino acid sequence cannot be found in nature, and which is obtained from a carbonyl hydrolase precursor by the following substitutions : Substitute the amino acid residue corresponding to the +76 position in the carbonyl hydrolase with a different amino acid, preferably also selected from (according to the 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, Mixed substitutions of multiple amino acid residues at one or more positions +217, +218, +222, +260, +265 and/or +274 are described in A. Baeck et al. entitled "Protease-containing cleaning Compositions" in U.S. Patent Application Serial No. 08/322,676, and in U.S. Patent Application Serial No. 08/322,677 to C. Ghosh et al. Both were on October 13, 1994.

Amylases of the invention which are particularly suitable (but not limited to) for automatic dishwashing purposes include: α-amylases described in GB 1,296,839 (Novo), ^RAPIDASE® sold by International Bio-Synthetics, Inc., TERMAMYL sold by Novo Corporation ^_ , and FUNGAMYL ^_ sold by Novo Corporation, wherein FUNGAMYL ^_ is particularly preferred. Methods of increasing enzyme stability, such as oxidative stability, are known. See, eg, J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. In some preferred embodiments of the present invention, amylases with improved stability, especially with improved oxidative stability, the reference point of which was introduced in 1993, can be used in detergents such as automatic dishwashing ^TERMAMYL_ of the market. These preferred amylases of the present invention are characterized as "stability-increased" amylases, characterized at least by one or more of the stability, e.g. Oxidative stability to hydrogen peroxide/tetraacetylethylenediamine in buffer solution, thermal stability at normal washing temperature such as 60°C, or alkali stability at pH 8-11 has measurable degree of improvement. Stability can be measured using any known art test. See, eg, the disclosure of WO 9402597. Amylases with increased stability are available from Novo or from Genencor International. In the present invention, a highly preferred class of amylases are all derived by site-directed mutagenesis from one or more Bacillus amylases, especially Bacillus α-amylases, regardless of whether one, two or both Whether one or more amylase strains are their close precursors. Preference is given to using amylases which have increased oxidative stability relative to the aforementioned reference amylases, in particular for bleaching, more preferably oxygen bleaching as opposed to chlorine bleaching, of detergent compositions according to the invention. Such preferred amylases include: (a) amylases according to the above incorporated Novo WO 9402597 (February 3, 1994), which can be further described by a mutant variant, wherein C Amylase or threonine, preferably replace the methionine residue at position 197 of Bacillus licheniformis α-amylase (called TERMANYL_) with threonine, or similar parental amylase variants such as Bacillus amyloliquefaciens, Bacillus subtilis or Stereoisomeric thermophilic variants of the same position; (b) Genencor International on March 13-17, 1994 by C. Mitchinson to the 207th Annual Meeting of the American Chemical Society entitled "Antioxidant α- Amylases" paper, which describes amylases with increased stability. It is mentioned in the article: Bleach can inactivate alpha-amylases in automatic dishwashing detergents, except for the stability-enhanced amylase produced by Genencor from Bacillus licheniformis NCIB8061. Methionine (Met) proved to be the most easily modifiable residue. Met was substituted one at a time at positions 8, 15, 197, 256, 304, 366, and 438, generating heterosexual variants, notably M197L and M197T, with the M197T variant being the most stably expressed variant. Its stability was determined in CASCADE ^_ and SUNLIGHT ^_ . (c) Particularly preferred for the present invention are amylase variants with additional modifications in close relatives described in WO 9510603A, commercially available under the tradename DURAMYL ^® from the patent assignee Novo Corporation. Other particularly preferred stability-enhanced amylases include the amylases described in WO 9418314 (Genencor International) and WO 9402597 (Novo). Any other oxidative stability-enhanced amylase may also be used, for example amylases obtained by site-directed mutagenesis from known chimeric, hybrid or simple mutant parent forms of available amylases. Other preferred enzyme modification treatments are also possible, see WO 9509909A (Novo).

Other amylases include: amylases described in WO 95/26397 and co-pending patent PCT/DK96/00056 filed by Novo Nordisk. The specific amylases used in the detergent composition of the present invention include alpha-amylases with the following characteristics: measured by the Phadebas_α ^- amylase activity assay, at a temperature of 25 to 55°C and a pH of 8 to 10, the The specific activity is at least 25% higher than that of ^Termamy® (see WO95/26397 pages 9-10 for assay analysis of this ^Phadebas® alpha-amylase activity). The present invention also includes: α-amylase whose amino acid sequence identity exceeds 80% with the SEQ ID table in the literature. These enzymes are preferably added to the laundry detergent composition in an amount of 0.00018% to 0.060% by weight of the total composition, more preferably 0.00024% to 0.048% by weight of the pure enzyme in the total composition.

Cellulases useful in the present invention include bacterial and fungal cellulases, which preferably have a pH between 5 and 9.5. U.S. Patent No. 4,435,307, granted to Barbesgoard et al. on March 6, 1984, discloses suitable cellulase derived from Humicola insolens, or Humicola strain DSM1800, or produced by Aeromonas genus capable of producing cellulase 212- Suitable cellulases derived from fungi, and cellulases extracted from the hepatopancreas of the marine mollusk Dolabella Auricula Solander. Suitable cellulases are also disclosed in GB-A-2,075,028, GB-A-2,095,275 and DE-OS-2,247,832. ^CAREZYME_ and ^CELLUZYME_ (Novo) are especially useful. See also WO9117243 (Novo).

Lipases suitable for use in detergents include: Pseudomonas microorganisms such as those produced by Pseudomonas stutzeri ATCC 19.154 disclosed in GB 1372034. See also Japanese Patent Application No. 5320487 published on February 24,1978. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan, under the tradename Lipase P "Amano" or "Amano-P". Other suitable commercially available lipases include: Amano-CES lipase from Chromobacterium viscosus, such as Chromobacterium viscosus variant lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; U.S. Biochemical Corp., USA, and Disoynth, The Netherlands Lipase from Chromobacterium viscosus Co.; and lipase from Pseudomonas gladioli. LIPOLASE® enzyme derived from Humicola lanuginosa and available 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, so far only lipases derived from Humicola lanuginosa and produced in the host Aspergillus graminearum have been found to be widely used as additives in fabric washing products. As mentioned above, it is available from Novo Nordisk under the trademark Lipolase ^(TM) . In order to optimize the stain removal performance of Lipolase, Novo Nordisk has obtained a large number of Lipolase variants. As described in WO 92/05249, the variant D96L of the natural Humicola lanuginosa lipase improved lard stain removal by a factor of 4.4 compared to the original lipase (corresponding enzyme dosage of 0.075-2.5 mg protein/liter ). Novo Nordisk disclosed in Research Disclosure No. 35944 on March 10, 1994: in each liter of washing solution, the amount of lipase variant (D96L) added is correspondingly 0.001-100 mg (5-500,000 LU/liter). The use of low levels of D96L variants in detergent compositions containing dual AQA surfactants in the manner disclosed in the present invention can improve the whiteness retention of fabrics, especially when D96L is used in an amount of 50-8500 LU / liter of washing solution.

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

For "solution bleaching", or preventing the transfer of dyes or pigments that have been released from the substrate during the wash to other substrates in the wash, peroxidase enzymes can be combined with an oxygen-containing source such as percarbonate, perborate, Use in combination with hydrogen peroxide, etc. Known peroxidases include: horseradish peroxidase, ligninase, haloperoxidase, such as chloro- or bromoperoxidase. Peroxidase-containing detergent compositions are disclosed in WO 89099813A (published October 19, 1989, Novo), and WO 8909813A to Novo.

WO 9307263A and WO 9307260A to Genencor International, WO 8908694A to Novo and US Patent 3,553,139, issued January 5, 1971 to McCarty et al also disclose various enzymes and their incorporation into synthetic detergent compositions. Enzymes are further described in US Patent 4,101,457, Place et al., issued July 18, 1978, and in US Patent 4,507,219, Hughes, issued March 26, 1985. US Patent 4,261,868, Hora et al., issued April 14, 1981, discloses enzymes for use in liquid detergent formulations and their incorporation into such formulations. Enzymes for use in detergents can be stabilized by various methods. Various enzyme stabilization techniques are disclosed and exemplified in US Patent 3,600,319, issued August 17, 1971 to Gedge et al., and European Patents EP 199,405 and EP 200,586, issued October 29, 1986 to Venegas. Enzyme stabilization systems are also described in US Patent No. 3,519,570 et al. WO9401532A to Novo describes Bacillus sp. AC13 capable of obtaining proteases, xylanases and cellulases. enzyme stabilization system

The enzyme-containing composition of the present invention also optionally comprises 0.001-10% by weight, preferably 0.005-8% by weight, most preferably 0.01-6% by weight of an enzyme stabilizing system. The enzyme stabilization system can be any stabilization system compatible with the wash enzyme. The stabilizing system can be provided by other active ingredients in the formulation, or it can be added separately, such as by the formulator or by the detergent enzyme manufacturer. Such a stabilizing system may comprise: calcium ion, boric acid, propylene glycol, short-chain carboxylic acid, boric acid, etc. and mixtures thereof, and may be designed according to the type and physical form of the detergent composition in order to solve different stability problems.

One way to achieve stabilization is to provide these ions to the enzyme by using a water-soluble source of calcium and/or magnesium ions in the finished composition. Calcium ions are generally more effective than magnesium ions, so it is preferred in the present invention if only one cation is used. For a typical detergent composition, especially a liquid composition, it comprises about 1 to 30, preferably about 2 to 20, more preferably about 8 to 12 millimoles of calcium ions per liter of finished detergent composition, However, it can vary depending on various factors, including the type and amount of enzyme added. Water-soluble calcium or magnesium salts are preferably used, including, for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, calcium maleate, calcium hydroxide, and calcium acetate; more generally, calcium sulfate may be used or the corresponding magnesium salts of the listed calcium salts. Of course, the calcium and/or magnesium content may be further increased, for example, in order to enhance the degreasing effect of certain surfactants.

Another way to achieve stabilization is to use borate species. See US Patent 4,537,706 to Severson. Although more generally, boric acid or other borate compounds, such as borax or orthoborate, are preferred for use in liquid detergents at a level of up to about 3% by weight, borate stabilizers, if used, are also present. It can be as high as 10% or more of the composition. Substituted boronic acids, such as phenylboronic acid, butylboronic acid, p-bromophenylboronic acid, etc., can be used in place of boric acid and, because of the use of such substituted boron derivatives, the total boron content of the detergent composition can be reduced.

Some detergent compositions, such as the stabilization system of automatic dishwashing compositions, can also contain 0 to 10% by weight, preferably 0.01% to 6% by weight, of chlorine bleach scavenger, which can be added to prevent the presence of chlorine bleach in various water sources. Chlorine bleach species attack and inactivate enzymes, especially under alkaline conditions. Although the chlorine content in water is relatively low, generally in the range of 0.5-.75ppm, however, in the process of tableware or fabric washing, the amount of chlorine in the total water that can be in contact with enzymes can reach a relatively large amount; therefore, the use of chlorine in Sometimes enzyme stability is problematic. Since percarbonate reacts with chlorine bleaching substances, the use of other chlorine stabilizers, although effective, is generally not necessary. Suitable chlorine scavenger anionic materials are known and readily available and, if used, can be salts containing ammonium cations such as sulfites, bisulfites, thiosulfites, thiosulfates, iodide etc. In addition, antioxidants such as carbamates, ascorbic acid, etc.; organic amines such as ethylenediaminetetraacetic acid (EDTA) or its alkali metal salts, monoethanolamine (MEA) and mixtures thereof may be used. In addition, special enzyme inhibition systems can be added so that different enzymes can have maximum compatibility. Other conventional scavengers such as bisulfites, nitrates, chlorides, hydrogen peroxides such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphates, condensed phosphoric acid can be used if desired Salt, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof. In general, since ingredients listed separately (eg, hydrogen peroxide species) can function as chlorine scavengers on the basis of recognized superior performance, it is not absolutely required to add chlorine scavengers unless they can be added Compounds that function to the desired extent are not present in the enzyme-containing embodiments of the invention; even then, scavengers are added for optimum effect only. Also, the formulator can employ the ordinary skill of a chemist in order to avoid the use of any enzyme scavengers or stabilizers which are substantially incompatible when formulated with other active ingredients. With regard to the use of ammonium salts, this salt can be easily mixed into the detergent composition, but it tends to absorb water and/or release ammonia during storage. Therefore, it is desirable to protect such material, if present, in granules, as described in US Patent 4,652,392 to Baginski et al. polymer detergent

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, 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.

In general, preferred SRAs contain a hydrophilic portion and a hydrophobic portion, wherein: the hydrophilic portion renders the surface of hydrophobic fibers, such as polyester and nylon, hydrophilic; and the hydrophobic portion deposits onto the hydrophobic fiber , and remains adhered to hydrophobic fibers through wash and rinse cycles, thereby becoming an anchor for the hydrophilic portion. This ensures that stains created after SRA treatment are more easily removed in subsequent wash steps.

SRA can include: various charged, such as anionic or even cationic (see US4,956,447), as well as uncharged monomer units, and its structure can be linear, branched or even star . They may include capping groups which are particularly effective in controlling molecular weight or modifying physical or surface-active properties. In order to be used in different fibers or fabrics, and in various detergent or detergent additive products, its structure and charge distribution can be tailored according to the specific situation.

Preferred SRAs include oligoesters of terephthalates; usually by a process involving at least one transesterification/oligomerization reaction in the presence of a metal catalyst, such as titanium(IV) alkoxide. preparation. Such esters can be made using addition monomers that can be incorporated into the ester structure via one, two, three, four, or more sites, without, of course, forming a highly crosslinked overall structure.

Suitable SRAs include: sulfonation products of substantially linear ester oligomers comprising an oligoester backbone of terephthaloyl and oxyalkenyloxy repeat units, and an alkene covalently attached to the backbone. Propyl-derived sulfonated terminal moieties are described, for example, in US 4,968,451, J.J. Scheibei and E.P. Gosselink, Nov. To treat allyl alcohol, (b) transesterify/oligomerize the product of (a) with dimethyl terephthalate (“DMT”) and 1,2-propanediol (“PG”) in a two-step process ”) for the reaction, and (c) reacting the product of (b) with sodium metabisulfite in water; Gosselink et al. Anion-blocked terephthalic acid 1,2 in US 4,711,730, Dec. 8, 1987 - Propylene/poly(oxyethylene) terephthalate polyesters such as poly(ethylene glycol) methyl ether, DMT, PG and poly(ethylene glycol) (“PEG”) transesterification/oligomerization; partially and fully anionically terminated oligoesters such as ethylene glycol ("EG"), PG, DMT, and 3,6 - oligomers of sodium dioxa-8-hydroxyoctanesulfonate; non-ionic endblocked block polyester oligomers such as DMT, Me endcapped PEG in US 4,702,857 of Gosselink on October 27, 1987 and EG and/or PG, or derived from mixtures of DMT, EG and/or PG, Me-terminated PEG, and sodium dimethyl-5-sulfoisophthalate; and issued October 31, 1989 to Maldonado, Gosselink et al. Anion (especially sulfaroyl) terminated terephthalates in US 4,877,896 to Al. The latter is a typical SRA that can be used in detergent and fabric conditioner products, exemplified by: an ester composition made from the monosodium salt of m-sulfobenzoic acid, PG and optionally (but preferably) DMT, further comprising Added PEG (eg, PEG 3400).

SRA also includes: simple block copolymers of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, see 25 May 1976 US 3,959,230 issued to Hays on July 8, 1975 and US 3,893,929 issued to Basadur on July 8, 1975; cellulose derivatives, such as the hydroxyether cellulose polymer METHOCEL from Dow; and C ₁ ~ C ₄ alkyl cellulose and C ₄ Hydroxyalkylcelluloses, see US 4,000,093, issued December 28, 1976 to Nico et al. Suitable SRAs characterized by poly(vinyl ester) hydrophobic moieties include poly(vinyl esters) grafted onto polyalkylene oxide backbones, such as poly(C ₁ -C ₆ vinyl esters), preferably poly(vinyl esters). (vinyl acetate) graft copolymer. See, European Patent Application 0,219,048, published April 22, 1987 by Kud et al. Commercially available examples include: SOKALAN SRA, eg SOKALAN HP-22 from BASF, Germany. Other SRAs are polyesters derived from polyethylene oxide glycol with an average molecular weight of 300-5000, the repeating units of which contain 10-15% by weight of ethylene terephthalate and 80-90% by weight of polyoxyethylene terephthalate. Ethylene ester. Commercial examples thereof include ZELCON 5126 from DuPont Corporation, and MILEASET from ICI.

Another preferred SRA is an oligomer having the empirical formula (CAP) ₂ (EG/PG) ₅ (T) ₅ (SIP) ₁ containing terephthaloyl (T), sulfoisophthaloyl Acyl (SIP), oxyethyleneoxy and oxy-1,2-propylene (EG/PG) units and are preferably capped with a capping group (CAP), preferably with a modified hydroxyethylsulfonate acid groups, such as an oligomer comprising 1 sulfoisophthaloyl unit, 5 terephthaloyl units, oxygen in a given ratio (preferably about 0.5:1 to 10:1) ethyleneoxy and oxy-1,2-propyleneoxy units, and two capping units derived from sodium 2-(2-hydroxyethoxy)-ethanesulfonate. The SRA also preferably comprises 0.5% to 20% by weight of the oligomer of a crystalline reducing stabilizer, such as anionic surfactants such as linear sodium dodecylbenzene sulfonate, or selected from xylene-, isopropyl Benzene- and toluene-sulfonates or mixtures thereof, wherein these stabilizers or modifiers are added to the synthesis reactor in the manner described in US 5,415,807, issued May 16, 1995 to Gosselink, Pan, Kellett and Hall . Monomers suitable for the above SRAs include: sodium 2-(2-hydroxyethoxy)-ethanesulfonate, DMT, sodium dimethyl-5-sulfoisophthalate, EG and PG.

Another preferred class of SRA is the oligoester, which includes: (1) comprising three main chains (a), (b) and (c), (a) being selected from dihydroxysulfonate, polyhydroxysulfonic acid At least one unit of a salt, a unit having at least a trifunctional group to form an ester linkage to produce a branched oligomer backbone, and mixed units thereof; (b) being at least one terephthaloyl unit; and (c) is at least one unsulfonated unit that is 1,2-oxyalkyleneoxy; and (2) is selected from nonionic capping units, anionic capping units (e.g. alkoxylated, preferably ethoxylated hydroxy ethanesulfonate, alkoxylated propanesulfonate, alkoxylated propanesulfonate, alkoxylated phenolsulfonate, sulfaroyl derivatives, and mixtures thereof) unit. 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) denotes a di(oxyethylene)oxy unit; (SEG) denotes a sulfoethyl ether unit derived from glycerol, and related units; (B) represents a branching unit, which has at least three functional groups 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 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 0.05～12; m is about 0.01～10; And x, y', y ", y_, z, z', q and m represent the average number of moles of the corresponding units per mole of said ester, wherein said ester The molecular weight is about 500-5000.

Preferred SEG and CAP monomers for the above esters include: sodium 2-(2,3-dihydroxypropoxy)ethanesulfonate (“SEG”), 2-{(2-(2-hydroxyethoxy)ethoxy Sodium ethyl}ethanesulfonate ("SE3") and its homologues, and mixtures thereof, and ethoxylation and sulfonation products of allyl alcohol. Preferred such SRA esters include: In the presence of a catalyst, sodium 2-{(2-(2-hydroxyethoxy)ethoxy}ethanesulfonate and/or 2-[2-{(2-(2-hydroxyethoxy)ethoxy) }Ethoxy]sodium ethanesulfonate, DMT, 2-(2,3-dihydroxypropoxy)sodium ethanesulfonate, EG and PG obtained by transesterification and oligomerization, it can be called is (CAP)2(T)5(EG/PG)1.4(SEG)2.5(B)0.13, wherein: CAP is (Na+ ^- O ₃ S[CH ₂ -CH ₂ O]3.5)-, and B is a Glyceryl units, after complete hydrolysis the EG/PG molar ratio measured by conventional gas chromatography was about 1.7:1.

Another class of SRAs includes: (I) nonionic terephthalates using diisocyanate coupling agents to link polymeric ester structures, see US 4,201,824 to Violland et al. and US 4,240,918 to Lagasse et al; SRAs with ester end groups obtained by adding trimellitic anhydride to known SRAs to convert the terminal hydroxyl groups to trimellitate esters. With the correct choice of catalyst, trimellitic anhydride can be bonded to the end group of the polymer by forming an ester bond through one of the isolated carboxyl groups, rather than opening the anhydride bond. Both nonionic and anionic SRAs can be used as starting materials as long as they contain esterifiable hydroxyl end groups. See US 4,525,524 to Tung et al. Additionally, SRAs include: (III) urethane-linked terephthalate anion-based SRAs, see US 4,201,824 to Violland et al; (IV) poly(vinyl caprolactam), and its combination with mono Corresponding copolymers such as vinylpyrrolidone and/or (dimethylaminoethyl) methacrylate, etc., including nonionic and cationic polymers, see Ruppert et al. US4,579,681; (V) except BASF's In addition to the SOKALAN class there are also graft copolymers obtained by grafting acrylic monomers onto sulfonated polyesters; these SRAs certainly have similar soil release and anti-redeposition activities to the known cellulose ethers, see Rhone -PoulencChemie. EP 279,134A in 1988; (VI) grafts of vinyl monomers, such as acrylic acid and vinyl acetate grafted onto proteins (such as casein), see EP 457,205 of BASF A (1991); (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 of Bevan et al. from Unilever NV (1974). Other useful SRAs are described in US 4,240,918, 4,787,989, 4,525,524 and 4,877,896. Sludge removal/anti-redeposition agent

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

The most preferred soil removal/anti-redeposition agent is ethoxylated tetraethylenepentylamine. Representative ethoxylated amines are also described in US Patent 4,597,898, issued July 1, 1986 to VanderMeer. Another preferred class of soil removal/antiredeposition agents are the cationic compounds disclosed in European Patent Application 111965, Oh and Grosselink, June 27,1984. Other soil removal/anti-redeposition agents that can be used include ethoxylated amine polymers, described in European Patent Application 111984, Grosselink, published June 27, 1984; zwitterionic polymers, published in July 1984 Grosselink, European Patent Application 112,592, published 4; amine oxides, described in US Patent 4,548,774, Connor, October 22, 1985. Other soil removal/anti-redeposition agents known in the art may also be used in the compositions of the present invention. See US Patent 4,891,160, issued January 2, 1990 to VanderMeer, and International Patent 95/32272, published November 30, 1995. Another class of preferred anti-redeposition agents includes carboxymethylcellulose (CMC). These substances are known in the art. polymer dispersant

In the compositions according to the invention, especially in the presence of zeolite and/or layered silicate builders, it may be preferred to use polymeric dispersants at levels from 0.1 to 7% by weight. Suitable dispersing agents include polycarboxylate polymers and polyethylene glycols, although others known in the art can also be used. It is believed, although not wishing to be bound by any theory, that when used in combination with other builders, including low molecular weight polycarboxylates, polymeric dispersants may provide a Deposition action to improve the overall performance of detergent builders.

Polycarboxylate polymers can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in the acid form. Unsaturated monomeric 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 Methylmalonic acid. In the polycarboxylate polymers of the present invention, carboxyl-free monomeric moieties such as vinyl methyl ether, styrene, ethylene, etc. may also be present as long as the moieties do not constitute more than 40% by weight.

Particularly suitable polycarboxylate polymers can be derived from acrylic acid. The acrylic acid-based polymers useful in the present invention are the water-soluble salts of polymerized acrylic acid. The average molecular weight of the acid state of the polymer is 2000-10000, more preferably 4000-7000, most preferably 4000-5000. Water-soluble salts of such acrylic acid polymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Such suitable water-soluble polymers are known materials. The use of such polyacrylates in detergent compositions has been disclosed, for example, in US Patent 3,308,067, Diehl, issued March 7,1967.

Acrylic/maleic acid based copolymers can also be used as a preferred component of the dispersing/anti-redeposition agent. These materials include the water-soluble salts of copolymers of acrylic acid and maleic acid. The average molecular weight of the acid state of the copolymer is preferably in the range of 2,000-100,000, more preferably in the range of 5,000-75,000, and most preferably in the range of 7,000-65,000. In the copolymer, the ratio of acrylic acid moieties to maleic acid moieties is generally in the range of 30:1 to 1:1, more preferably in the range of 10:1 to 2:1. Water-soluble salts of such acrylic acid/maleic acid copolymers may include, for example, alkali metal, ammonium and substituted ammonium salts. Such water-soluble acrylic acid/maleic acid copolymers are known substances and have been described in European Patent Application No. 66915 published on December 15, 1982 and in EP 193360 published on September 3, 1986, wherein EP 193360 also describes such polymers comprising hydroxypropyl acrylate. Other useful dispersants include maleic/acrylic acid/vinyl alcohol terpolymers. Such materials are also disclosed in EP 193360 and include, for example, a 45/45/10 terpolymer of maleic acid/acrylic acid/vinyl alcohol.

Another polymeric material that can be included is polyethylene glycol (PEG). PEG has dispersant properties and can be used as a soil removal-anti-redeposition agent. The molecular weight range for this use is generally from 500 to 100,000, preferably from 1,000 to 50,000, most preferably from 1,500 to 10,000.

Polyaspartic acid and polyglutamic acid dispersants can also be used, especially in combination with zeolite builders. The molecular weight (average) of the dispersant such as polyaspartic acid is preferably 10,000. brightener

In the cleaning compositions of the present invention, generally 0.01% to 1.2% by weight of any fluorescent whitening agent or other whitening agent known in the art can be added. Commercial optical brighteners useful in the present invention can be divided into several subgroups which include, but are not necessarily limited to, stilbene derivatives, pyrazolines, oxinones, carboxylic acids, methylenecyanines, dibenzothiophenes - 5,5-dioxides, azoles, 5- and 6-membered ring heterocycles, and other mixed brighteners. Examples of these brighteners are disclosed in the book "Production and Application of Optical Brighteners" by M. Zahradnik, John Wiley & Son. New York (1982).

Specific examples of optical brighteners useful in the present invention are identified in US Patent 4,790,856, issued December 13,1988 to Wixon. These brighteners include the PHORWHITE series available from Verona. Other brighteners disclosed in this reference include: Tinopal UNPA, Tinopal CBS and Tinopal 5BM from Ciba-Geigy; ArticWhite CC and Artic White CWD, 2-(4-styryl-phenyl)-2H- Naphtho[1,2-d]triazole; 4,4′-bis(1,2,3-triazol-2yl)-stilbene; 4,4′-bis(styryl)biphenyl; and amino Oxyrone. Specific examples of these brighteners include: 4-methyl-7-diethyl-aminoxanthone; 1,2-bis(benzimidazol-2-yl)-ethylene; 1,3-bis(benzimidazol-2-yl)-ethylene; phenyl-pyrazoline; 2,5-bis(benzoxazol-2-yl)thiophene; 2-styryl-naphthalene-[1,2-d]oxazole; and 2-(stilbene-4- base)-2H-naphtho[1,2-d]triazole. See also US Patent 3,646,015 issued February 29,1972 to Hamilton. dye transfer inhibitor

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 laundering. Typically, such dye transfer inhibiting agents include polyvinylpyrrolidone polymers, polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanines, peroxidases, and its mixture. If used, these inhibitors will generally comprise from 0.01 to 10%, preferably from 0.01 to 5%, most preferably from 0.05 to 2%, by weight of the composition.

More specifically, the polyamine N-oxide polymers preferred for use in the present invention comprise units of the formula RA _x -P, wherein: P is a polymerizable unit to which an NO group can be attached, or the NO group can become Part of a polymerizable unit, or the NO group can be attached to both units; A is one of the following structures: -NC(O)-, -C(O)-, -S-, -O-, -N= ; 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 NO group may be attached, or NO Groups become part of these groups. For preferred polyamine N-oxide polymers where R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

The NO group can be represented by the following general formula:

Wherein: R ₁ , R ₂ , R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or their mixed groups; x, y and z are 0 or 1; and the nitrogen atom of the NO group can be connected to on or as part of any of the foregoing groups. For the amine oxide units of N-oxide polymers, the pKa<10, preferably pKa<7, more preferably pKa<6.

Any polymer backbone can be used as 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 in which: one monomer is amine N-oxide and the other monomer is N-oxide. For amine N-oxide polymers, the ratio of amine to amine N-oxide is generally from 10:1 to 1:1,000,000. In polyamine oxide polymers, however, the number of amine oxide groups can be varied by suitable copolymerization or by suitable degrees of N-oxidation. Polyamine oxides can be obtained with almost any degree of polymerization. Usually, its average molecular weight ranges from 500 to 1,000,000, more preferably from 1,000 to 500,000, and most preferably from 5,000 to 100,000. This preferred substance may be referred to as "PVNO".

The most preferred polyamine oxide for use in the detergent compositions of the present invention is: poly(4-vinylpyridine-N-oxide) having an average molecular weight of 50,000 and a ratio of amine to amine N-oxide of 1:4.

Also preferred for use in the present invention are copolymers of N-vinylpyrrolidone and N-vinylimidazole (known as "PVPVI" species). The average molecular weight of PVPVI is preferably in the range of 5,000-1,000,000, more preferably 5,000-200,000, and most preferably 10,000-20,000. (The average molecular weight range is determined by light scattering as described in Barth et al., Chemical Analysis , Vol. 113. "Modern Method of Polymer Characterization"), which discloses The content is hereby incorporated by reference into the present invention.) For PVPVI copolymers, the molar ratio of N-vinylimidazole to N-vinylpyrrolidone is usually 1:1 to 0.2:1, more preferably 0.8:1 to 0.3 :1, most preferably 0.6:1 to 0.4:1. These copolymers can be linear or branched.

Polyvinylpyrrolidone ("PVP") having an average molecular weight of 5,000 to 400,000, preferably 5,000 to 200,000, more preferably 5,000 to 50,000 may also be used in the compositions of the present invention. PVP is known to those skilled in the detergent art; see, for example, EP-A-262897 and EP-A-256696, incorporated herein by reference. Compositions containing PVP may also comprise polyethylene glycol ("PEG") having an average molecular weight of from 500 to 100,000, preferably from 1,000 to 10,000. In the wash solution, the PEG/PVP ratio in ppm is preferably from 2:1 to 50:1, more preferably from 3:1 to 10:1.

In the detergent composition of the present invention, 0.005-5% by weight of a certain hydrophilic fluorescent whitening agent can also be optionally included, which also has the effect of inhibiting dye transfer. If used, the compositions of the present invention preferably contain from 0.01 to 1% by weight of such optical brighteners.

The hydrophilic fluorescent whitening agent that can be used in the present invention has the following structural formula:

Wherein: R ₁ is selected from aniline, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R ₂ is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N - methylamino, morpholino, chlorine and amino; and M is a salt-forming cation, such as sodium or potassium.

In the above formula, when R ₁ is anilino, R ₂ is N-2-bis-hydroxyethyl, and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4-anilino- 6-(N-2-bis-hydroxyethyl)-s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid and its disodium salt. This particular brightener is commercially available from Ciba-Geigy under the tradename Tinopal-UNPA-GX. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener for use in the detergent compositions herein.

In the above formula, when R ₁ is anilino, R ₂ is N-2-hydroxyethyl-N-2-methylamino, and M is a cation such as sodium, the whitening agent is 4,4'-bis[ (4-anilino-6-(N-2-hydroxyethyl-N-methylamino)-s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid disodium salt. This particular brightener is commercially available from Ciba-Geigy Corporation under the tradename Tinopal 5BM-GX.

In the above formula, when _R1 is anilino, _R2 is morpholino, and M is a cation such as sodium, the whitening agent is 4,4'-bis[(4-anilino-6-morpholino- s-triazin-2-yl)amino]-2,2'-stilbene disulfonic acid disodium salt. This particular brightener is commercially available from Ciba-Geigy Corporation under the tradename Tinopal AMS-GX.

The particular fluorescers selected for use in the present invention provide particularly effective dye transfer inhibiting effects when combined with the selected dye transfer inhibiting polymers described above. By mixing the selected polymer (e.g., PVNO and/or PVPVI) with the selected optical brightener (e.g., Tinopal-UNPA-GX, Tinopal 5BM-GX, and/or TinopalAMS-GX), the aqueous wash solution produces significantly better dye transfer inhibition than either of these two detergent ingredients alone. Without being bound by theory, it is believed that such brighteners are based on the following mechanism of action: due to their high affinity for fabrics in the wash liquor, they deposit relatively quickly on these fabrics. In wash liquors, the extent to which brighteners are deposited on fabrics can be defined by a parameter known as the "exhaustion coefficient". The consumption coefficient is generally defined as the ratio of the brightener a) deposited on the fabric to the initial brightener concentration b) in the wash liquor. In the present invention, brighteners with higher exhaustion coefficients are most suitable for inhibiting dye transfer.

Of course, the optional use of other conventional optical brightener compounds in the compositions of the present invention is also contemplated, but this will only provide conventional fabric "brightening" benefits, not true dye transfer inhibiting benefits. These uses are conventional and thus well known in detergent formulations. Chelating agent

The detergent compositions herein may also optionally contain one or more iron and/or manganese chelating agents. Such chelating agents may be selected from the group consisting of amino carboxylates, amino phosphonates, polyfunctionally substituted aromatic chelating agents and mixtures thereof, as defined below. Without wishing to be bound by any theory, it is believed that the beneficial effects of these materials are due in part to their unusual ability to remove iron and manganese ions from wash liquors by forming water-soluble chelates.

Amino carboxylates that can be used as chelating agents include: EDTA, N-HydroxyethylEDTA, Nitrilotriacetate, EDTA, Triethylene Ethyltetraaminehexaacetate, diethylenetriaminepentaacetate, and ethanol diglycine, their alkali metal, ammonium, and substituted ammonium salts, 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 ethylenediaminetetrakis (methylene phosphonates), ie DEQUEST. Preferably these amino phosphonates do not contain alkyl or alkenyl groups with more than 6 carbon atoms.

Multifunctional substituted aromatic chelating agents are also suitable for use in the compositions of the present invention. See US Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds in the acid state are dihydroxydisulfobenzenes, such as 1,2-dihydroxy-3,5-disulfobenzene.

The preferred biodegradable chelating agent for use in the present invention is ethylenediamine disuccinate ("EDDS"), particularly its [S,S] isomer, as described in Hartman and Perkin, Nov. 3, 1987. Described in US Patent 4,704,233.

The compositions of the present invention may also contain a water-soluble methylglycine diacetic acid (MGDA) salt (or acid), which may act as a chelating agent, or as a co-builder with water-insoluble builders such as zeolites, layered silicates, etc. use simultaneously.

If utilized, these chelating agents will generally comprise from 0.1 to 15% by weight of the detergent compositions herein. More preferably, it is 0.1 to 3.0% by weight of the composition. Foam inhibitor

Compounds for reducing or inhibiting suds formation may be added to the compositions of the present invention. Suds suppression is particularly important for front loading European style washing machines and the so-called "high concentration wash process" described in US Patents 4,489,455 and 4,489,574.

A wide variety of substances can be used as suds suppressors, and suds suppressors are well known to those skilled in the art. See, eg, Kirk Othmer Encyclopedia of Chemical Technology, Third Edition, Vol. 7, pp. 430-447 (John Wiley & Son. Inc., 1979). One particularly valuable class of suds suppressors includes fatty monocarboxylic acids and their water-soluble salts. See US Patent 2,954,347, issued December 27, 1960 to Wayne St. John. The fatty monocarboxylic acids and their water-soluble salts useful as suds suppressors generally have hydrocarbyl chains 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, and ammonium and alkanolammonium salts.

The detergent compositions herein can also contain non-surfactant suds suppressors. These include, for example, high molecular weight hydrocarbons such as paraffin, fatty acid esters (eg, fatty acid triglycerides), fatty acid esters of monovalent alcohols, aliphatic C ₁₈ -C ₄₀ ketones (eg, stearyl ketone) and the like. Other suds suppressors include: N-alkylated aminotriazines, such as tri- to hexa-alkyl melamines, or di- to tetra-alkyl diamine chlorotriazines (cyanuric chloride with two or three moles of 1 reaction products of primary or secondary amines with ~24 carbon atoms); propylene oxide; and monostearyl phosphates such as monostearyl phosphate and monostearyl dialkali metals (e.g., K, Na, and Li ) phosphates and esters. Hydrocarbons such as paraffins and chlorinated paraffins may be used in liquid form. Liquid hydrocarbons are liquid at room temperature and atmospheric pressure, their melting temperature ranges from -40°C to 50°C, and their minimum boiling point is not less than 110°C (at atmospheric pressure). It is also known that waxy hydrocarbons having a melting point preferably below 100° C. can be used. Hydrocarbon materials constitute the preferred suds suppressors for use in detergent compositions. Hydrocarbon foam suppressors are described, for example, in US Patent 4,265,779, issued May 5,1981 to Gandolfo et al. Therefore, the hydrocarbon material includes: aliphatic, alicyclic, aromatic, and heterocyclic saturated or unsaturated hydrocarbons having 12 to 70 carbon atoms. In the discussion of the suds suppressor, the term "paraffin" is used to mean that mixtures of true paraffins and cyclic hydrocarbons are also included.

Another preferred non-surfactant suds suppressor includes silicone suds suppressors. Such materials include: silicone oils such as polydimethylsiloxane, dispersions or emulsions of silicone oils or resins, and mixtures of polyorganosiloxanes with silica particles in which the polyorganosiloxane is chemisorbed or fused into the silica. Silicone suds suppressors are known in the art, for example in U.S. Patent 4,265,779 issued May 5, 1981 to Gandolfo et al. and European Patent Application No. 89307851.9 published February 7, 1990 to Starch. M.S. already described.

Other silicone suds suppressors are disclosed in US Patent 3,455,839 which relates to compositions and methods for defoaming aqueous solutions of polydimethylsiloxane liquids by adding small amounts of them.

For example, German patent application DOS 2124526 describes mixtures of siloxanes and silanized silicas. US Patent 3,933,672 to Bartolotta et al. and US Patent 4,652,392 to Baginski et al., issued March 24, 1987, disclose the use of silicone antifoam and suds control agents in granular detergent compositions.

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

(i) a polydimethylsiloxane liquid having a viscosity of about 20cs. to 1500cs. at 25°C;

(ii) per 100 parts by weight of (i), about 5 to 50 parts of siloxane resin composed of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units, wherein (CH ₃ ) ₃ SiO _1/2 The ratio of units to _SiO2 units is about 0.6:1 to 1.2:1; and

(iii) Per 100 parts by weight of (i), about 1-20 parts of solid silica gel is contained.

In preferred silicone suds suppressors for use herein, solvents for the continuous phase include: certain polyethylene glycols or polyethylene glycol-polypropylene glycol copolymers or mixtures thereof (preferred), or polypropylene glycol . The primary silicone suds suppressors are branched/crosslinked and preferably non-linear.

For example, a typical liquid laundry detergent composition for suds control may optionally comprise from about 0.001 to 1, preferably from about 0.01 to 0.7, most preferably from about 0.05 to 0.5 percent by weight of said silicone suds suppressor , comprising: (1) a non-aqueous emulsion of a primary antifoaming agent which is a mixture of (a) polyorganosiloxane, (b) resinous or forming siloxane The siloxane compound of the resin, (c) a fine particle filler, and (d) a catalyst for promoting the reaction of the mixture components (a), (b) and (c) to form a silanolate; (2) at least one non- an ionic silicone surfactant; and (3) polyethylene glycol or a polyethylene glycol-polypropylene glycol copolymer having a water solubility of greater than about 2% by weight at room temperature; and the absence of polypropylene glycol. In granular compositions, gels, etc., similar amounts can be used. Also, see U.S. Patents 4,978,471 issued to Starch on December 18, 1990 and 4,983,316 issued to Starch on January 8, 1991, U.S. Patents 5,288,431 issued to Huber et al. on January 22, 1994, and U.S. Patents 4,639,489, and US Pat. No. 4,749,740 to Aizawa et al., from column 1, line 46 to column 4, line 35.

The silicone suds suppressors of the present invention preferably comprise polyethylene glycol, or polyethylene glycol-polypropylene glycol copolymers, each having an average molecular weight of less than about 1000, preferably about 100-800. For the polyethylene glycol or polyethylene glycol-polypropylene glycol copolymer in the present invention, its 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 with an average molecular weight of less than about 1000, more preferably about 100 to 800, most preferably 200 to 400, and polyethylene glycol-polypropylene glycol copolymers, preferably PPG 200/PEG 300. The weight ratio of polyethylene glycol:polyethylene glycol-polypropylene glycol copolymer is preferably about 1:1 to 1:10, most preferably 1:3 to 1:6.

Preferred silicone suds suppressors for use herein do not include polypropylene glycol, especially 4000 molecular weight. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIL L101.

Other suds suppressors useful herein include secondary alcohols (eg, 2-alkyl alkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in US Patent 4,798,679 and EP 150,872. Secondary alcohols include C ₆ -C ₁₆ alkyl alcohols having a C ₁ -C ₁₆ chain. A preferred alcohol is 2-butyloctanol, which is available from Condea under the tradename ISOFOL 12. Mixtures of secondary alcohols are available from Enichem under the tradename ISALCHEM 123. Mixed suds suppressors generally comprise a mixture of alcohol and silicone in a weight ratio of 1:5 to 5:1.

For any detergent composition for use in automatic washing machines or dishwashing machines, the suds formed should not overflow the washing machine, or negatively affect the washing mechanism of the dishwashing machine. If used, suds suppressors are preferably used in "suds suppressing amounts". "Suds suppressing amount" means that the formulator of the composition can select an amount of suds suppressing sufficient to completely control the suds, thus resulting in a low sudsing laundry or dishwashing detergent for use in automatic washing machines or dishwashing machines.

The compositions of the present invention generally comprise 0 to 10% of a suds suppressor. When monocarboxylic fatty acids and their salts are used as suds suppressors, they can be used in amounts up to 5% by weight of the detergent composition. Preferably 0.5% to 3% of fatty monocarboxylate suds suppressors are used. Silicone suds suppressors can be used at levels up to 2.0% by weight of the detergent composition, although higher levels can also be used. The upper limit is determined according to the actual situation, and the main consideration is to minimize the cost and use a lower amount under the premise of effectively controlling the foam. Silicone suds suppressors are preferably used at 0.01% to 1%, more preferably at about 0.25% to 0.5%. These weight percentages as used herein include any silica that may be used in combination with the polyorganosiloxane, as well as any additives that may be used. The amount of monostearyl phosphate foam suppressor is generally 0.1% to 2% by weight of the composition. Hydrocarbon suds suppressors are generally used in amounts of 0.01% to 5.0% by weight of the composition, although higher levels may be used. Alcohol foam inhibitors are generally used in an amount of 0.2% to 3% by weight of the finished composition. Alkoxylated Polycarboxylates

To provide additional degreasing properties, alkoxylated polycarboxylates prepared from polyacrylates can be used in the present invention. Such materials are described in WO 91/08281 and PCT 90/01815 (page 4 ff.), which are incorporated herein by reference. Chemically, these materials comprise polyacrylates having 1 ethoxyl side chain for every 7-8 acrylate units. The structural formula of its side chain is -(CH ₂ CH ₂ O) _m (CH ₂ ) _n CH ₃ , wherein m is 2-3 and n is 6-12. The side chains are attached to the polyacrylate "backbone" via ester linkages, forming a "comb" shaped polymer structure. Its molecular weight can vary, but usually ranges from 2,000 to 50,000. Such alkoxylated polycarboxylates may comprise from 0.05 to 10% by weight of the compositions herein. fabric softener

In order to produce a fabric softening effect while fabrics are washed, various fabric softeners that act by washing are generally optionally used, particularly fine smectite clays in U.S. Patent 4,062,647 issued to Storm and Nirshl on December 13, 1977, and other softener clays known in the art in an amount of 0.5% to 10% by weight of the composition of the present invention. Clay softeners can be used in combination with amine and cationic softeners as disclosed in US Pat. No. 4,375,416 issued March 1, 1983 to Crisp et al. and US Pat. spices

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 includes a wide range of natural extracts and fragrances that contain complex blends of ingredients such as orange oil, lemon oil, rose extract, lavender, musk, patchouli, balsamic oil, sandalwood oil, pine oil, cedarwood, and more . Finished fragrances can contain very complex mixtures of these ingredients. Usually, the finished fragrance accounts for 0.01-2% by weight of the composition of the present invention, and individual fragrance components may account for 0.0001-90% by weight of the finished fragrance composition.

In Example XI below, several perfume formulations are given. Non-limiting examples of perfume ingredients useful in the present invention include: 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene , methyl ionone, γ-methyl ionone, methyl cedryl ketone, methyl dihydrojasmonate, methyl-1,6,10-trimethyl-2,5,9-cyclododeca Carbotrien-1-yl-one, 7-acetyl-1,1,3,4,4,6-hexamethyltetrahydronaphthalene, 4-acetyl-6-tert-butyl-1,1-di Methylindane, p-hydroxy-phenyl-butanone, benzophenone, methyl-β-naphthalenone, 6-acetyl-1,1,2,3,3,5-hexamethyldi Indane, 5-acetyl-3-isopropyl-1,1,2,6-tetramethylindane, 1-dodecanal, 4-(4-hydroxy-4-methylpentyl)- 3-cyclohexene-1-carboxaldehyde, 7-hydroxy-3,7-dimethyloctanal, 10-undecene-1-al, isohexenylcyclohexylcarboxaldehyde, formyltricyclodecane , Condensate of hydroxychalconal and methyl anthranilate, condensation product of hydroxychalconal and indole, condensation product of phenylacetaldehyde and indole, 2-methyl-3-(p-tert-butylbenzene base)-propionaldehyde, ethyl vanillin, piperonal, hexyl cinnamaldehyde, amyl cinnamaldehyde, 2-methyl-2-(p-isopropylphenyl)-propionaldehyde, coumarin, γ-decane Lactone, cyclopentadecanide, 16-hydroxy-9-hexadecandiolide, 1,3,4,6,7,8-hexahydro-4,6,6,7,8, 8-hexamethylcyclopenta-γ-2-benzopyran, β-naphthol methyl ether, ambroxane, dodecahydro-3a,6,6,9a-tetramethylnaphtho[ 2,1b]furan, cedrol, 5-(2,2,3-trimethylcyclopent-3-enyl)-3-methylpentan-2-ol, 2-ethyl-4-(2, 2,3-Trimethyl-3-cyclopenten-1-yl)-2-buten-1-ol, caryophyllenol, tricyclodecenyl propionate, tricyclodecenyl acetate, water Benzyl sylate, cedryl acetate, and p-(tert-butyl)cyclohexyl acetate.

Particularly preferred fragrances that maximize the odor of cellulase-containing finished products include, but are not limited to: Hexylcinnamaldehyde, 2-methyl-3-(p-tert-butylphenyl)-propanal , 7-acetyl-1,2,3,4,5,6,7,8-octahydro-1,1,6,7-tetramethylnaphthalene, benzyl salicylate, 7-acetyl-1 , 1,3,4,4,6-hexamethyltetralin, p-tert-butylcyclohexyl acetate, methyl dihydrojasmonate, β-naphthol methyl ether, methyl-β-naphthone, 2-Methyl-2-(p-isopropylphenyl)-propanal, 1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl -cyclopenta-γ-2-benzopyran, dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan, anisaldehyde, coumarin, cedrol, vanillin, Cyclo-pentadecanide, tricyclodecenyl acetate and tricyclodecenyl propionate.

Other spices include essential oils, balsams, and resins of various origins, including (but not limited to): Peru balsam, frankincense resin, benzoin, cistus resin, nutmeg, cinnamon oil, benzoin resin, coriander, and hybrid lavender. Other fragrance compounds include: phenylethyl alcohol, terpineol, linalool, linalyl acetate, geraniol, nerol, 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 useful in detergent compositions, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solvents for block compositions solid fillers etc. If high suds is desired, a suds booster such as C ₁₀ -C ₁₆ alkanolamides can generally be added to the composition in an amount of 1-10%. C ₁₀ -C ₁₄ monoethanol and diethanolamides are a typical class of these suds boosters. It is also advantageous to use such suds boosters concomitantly with the high sudsing accessory surfactants mentioned above, such as amine oxides, betaines and sultaines. If necessary, water-soluble magnesium and/or calcium salts such as MgCl ₂ , MgSO ₄ , CaCl ₂ , CaSO ₄ etc. can be added in an amount usually 0.1-2% to generate additional foam and increase degreasing performance.

The various soil release ingredients used in the compositions of the present invention can also be stabilized by absorbing the ingredients onto a porous hydrophobic substrate and then coating the substrate with a hydrophobic coating. Preferably the detersive ingredient can be premixed with the surfactant prior to adsorption onto the porous substrate. In use, the detersive ingredients are released from the substrate into the aqueous wash solution where they can perform their intended detersive function.

To illustrate this technique in more detail, porous hydrophobic silica (trade name SIPERN TD10. DeGussa) can be mixed with a proteolytic enzyme solution containing 3-5% _C13-15 ethoxylated alcohol (EO7) nonionic surfactant. By stirring, the obtained powder was dispersed in silicone oil (various silicone oils with a viscosity ranging from 500 to 12500 can be used). The resulting silicone oil dispersion is emulsified or added to a finished detergent base. In this way ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric conditioners and hydrolyzable surfactants can be "protected" for washing agents, including liquid laundry detergent compositions.

Liquid detergent compositions may contain 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 (such as 1,3-propanediol, ethylene glycol, glycerol, and 1 , 2-propanediol). The compositions of the present invention may comprise from 5 to 90%, usually from 1 to 50%, of such carriers.

In the washing process, the detergent composition of the present invention is preferably formulated with washing water having a pH value of 6.5-11, preferably 7.5-10.5. The pH value of the finished liquid dishwashing preparation is preferably from 6.8 to 9.0. Laundry products typically have a pH of 9-11. Techniques for controlling pH within the recommended range for use include the use of buffers, bases, acids, etc., which are well known to those skilled in the art. pellet production

Add the bis-alkoxylated cationic surfactant of the present invention into the blender, and then carry out conventional spray drying, which helps to remove various impurities, potential malodorous substances, and short-chain amine pollutants. If the formulator wishes to prepare premixed granules containing alkoxylated cationic surfactants for use in high density granular detergents and the like, then the basicity of the granule composition is preferably not too high. US 5366652 describes a process for the preparation of high density (above 650 g/l) granules. To eliminate the odor of unwanted amines, the granules are formulated for effective use at a pH of 9 or less. This can be achieved by adding small amounts of acidic substances, such as boric acid, citric acid, etc., or suitable pH buffering agents to the granules. In addition, predictable problems with amine malodors can also be masked using the perfume ingredients disclosed herein.

Example

The following examples illustrate the invention, but are not meant to be limited thereto or to limit its scope. All parts, percentages and ratios used herein are expressed as percent by weight unless otherwise specified.

In the following examples, the symbols for component abbreviations have the following meanings: LAS: Sodium linear C ₁₂ alkylbenzene sulfonate TAS: Sodium tallow alkyl sulfate C ₄₅ AS: C ₁₄ ~ C ₁₅ linear sodium alkyl sulfate C _xy EzS: C _1x ~C _1y branched chain alkyl sodium sulfate condensed with z moles of ethylene oxide C ₄₅ E ₇ : C _14-15 predominantly linear primary alcohol condensed with an average of 7 moles of ethylene oxide C ₂₅ E ₃ : C _12-15 branched primary alcohol condensed with an average of 3 moles of ethylene oxide C ₂₅ E ₅ : C _12-15 branched primary alcohol condensed with an average of 5 moles of ethylene oxide CoCoEO2: R ₁ N ⁺ (CH ₃ )(C ₂ H ₄ OH) ₂ , where R ₁ =C ₁₂ to C ₁₄ Soap: Sodium linear alkyl carboxylate, derived from an 80/20 mixture of tallow and coconut oil TFAA: C ₁₆ ~C ₁₈ alkyl N-methylglucamide TPKFA: C ₁₂ ~C ₁₄ topped whole fraction fatty acid STPP: anhydrous sodium tripolyphosphate zeolite A: having the structural formula Na ₁₂ (AlO ₂ SiO ₂ ) ₁₂ ·27H ₂ O hydrated aluminosilicate

Sodium with a primary particle size of 0.1 to 10 microns NaSKS-6: a crystalline layered silicate having the structural formula δ-Na ₂ Si ₂ O ₅ Citric acid: anhydrous citric acid Carbonate: anhydrous sodium carbonate, particle size 200-900 μm Bicarbonate: Anhydrous sodium bicarbonate, particle size distribution 400-1200 μm Silicate: Amorphous sodium silicate (SiO ₂ : Na ₂ O ratio = 2.0) Sodium sulfate: Anhydrous sodium sulfate citric acid Salt: Trisodium citrate dihydrate, 86.4% active, particle size distribution of

425～850μmMA/AA: 1:4 maleic acid/acrylic acid copolymer, the average molecular weight is 70000CMC: Sodium carboxymethylcellulose Protease: Proteolytic enzyme, activity 4KNP U/g, manufactured by NOVO Industries A/S

Sold under the trade name SavinaseAlcalase: proteolytic enzyme, activity 3AU/g, manufactured by NOVO Industries A/S

   Cellulase for sale: Cellulolytic enzyme, activity 1000 CEVU/g, produced by NOVO

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

Selling, trade name Termamyl 60T lipase: lipohydrolase, activity 100KLU/g, trade name LipolaseEndolase: Endoglunase enzyme, activity 3000 CEVU/g, produced by NOVO

Industries A/S sells PB4: Sodium perborate tetrahydrate, nominal formula NaBO ₂ 3H ₂ O 3H ₂ O ₂ PB1: Anhydrous sodium perborate bleach, nominal formula NaBO ₂ H ₂ O ₂ percarbonate: Sodium percarbonate with nominal molecular formula 2Na ₂ CO ₃ 3H ₂ O ₂ NOBS: Sodium salt of nonanoyloxybenzenesulfonate TAED: Tetraacetylethylenediamine DTPMP: Diethylenetriaminepenta(methylenephosphine salt), supplied by Monsanto,

The trade name is DEQUEST 2060 Photoactivator: Sulfonated zinc phthalocyanine, encapsulated with bleaching dextrin water-soluble polymer Brightener 1: 4,4′-bis(2-sulfostyrene)biphenyl disodium salt Brightener 2: 4,4′-bis(4-anilino-6-morpholino-1,3,5-triazine-2

-yl) amino) disodium stilbene-2,2′-disulfonate HEDP: 1,1-hydroxyethylene diphosphonic acid PVNO: polyvinylpyridine N-oxide PVPVI: copolymer of polyvinylpyrrolidone and vinylimidazole SRA1 : sulfobenzoyl-terminated esters with oxyethyleneoxy and terephthalmic

Formyl backbone SRA2: Diethoxylated poly(1,2-propylene terephthalate) short block poly

Compound silicone defoamer: polydimethylsiloxane foam control agent, which uses silicone-oxyethylene

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

The ratio of dosage is 10:1～100:1

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

Example I

According to the present invention, the following 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 powder STPP 24.0 - 24.0 Zeolite A - 24.0 -C ₄₅ AS 8.0 5.0 11.0MA/AA 2.0 4.0 2.0LAS 6.0 8.0 11.0TAS 1.5 - -CoCoMeEO2 ^* 1.5 1.0 2.0 Silicate 7.0 3.0 3.0CMC 0 1.0 5 1. Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DTPMP 0.4 0.4 0.2 Spray

C ₄₅ E7 2.5 2.5 2.0

C ₂₅ E3 2.5 2.5 2.0

Silicone defoamer 0.3 0.3 0.3

Spices 0.3 0.3 0.3 Dry additives

Carbonate 6.0 13.0 15.0

PB4 - 4.0 10.0

PB1 4.0 - 0

Percarbonate 18.0 18.0 21.0

TAED 3.0 3.0 -

Photoactivated Bleach 0.02 0.02 0.02

Protease 1.0 1.0 1.0

Lipase 0.4 0.4 0.4

Ayrase 0.25 0.30 0.15 sodium sulfate 3.0 3.0 5.0 (moisture & impurities) to: 100.0 100.0 100.0 density (G/L) 630 670 670

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

Example II

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

D E F Blown Powder Zeolite A 30.0 22.0 6.0 Sodium Sulfate 19.0 5.0 7.0MA/AA 3.0 3.0 6.0LAS 13.0 11.0 21.0C ₄₅ AS 8.0 7.0 7.0CoCoMeEO2 ^* 1.0 1.0 1.0 Silicate- 1.0 5.0 Soap- - 2.0 Brightener 1 0.2 0.2 0.2 Carbonate 8.0 16.0 20.0DTPMP - 0.4 0.4 Spray

C ₄₅ E7 1.0 1.0 1.0 Dry additive PVPVI/PVNO 0.5 0.5 0.5 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.1 0.1 0.1 Cellulase 0.1 0.1 0.1 NOBS - 6.1 4.5 Percarbonate 7.0 5.0 6.0 Sodium sulfate - 6.0 - Balance (moisture & impurities) to: 100 100 100

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

Example III In accordance with the present invention, the following high density detergent formulations were prepared.

G H I Blown Powder Zeolite A 15.0 15.0 15.0 Sodium Sulfate 0.0 5.0 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 2.0 Agglomerates LAS 0 2.0 1.0 TA 5 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0 Spray Fragrance 0.3 0.3 0.3C ₄₅ E7 2.0 2.0 2.0C ₂₅ E3 2.0 - - Dry Additive Citrate 5.0 - 2.0 Bicarbonate - 3.0 - Carbonate Salt 8.0 15.0 10.0 TAED 6.0 2.0 5.0 Percarbonate 13.0 7.0 10.0 Polyethylene oxide - - 0.2 (MW5000000) Smectite - - 10.0 Protease 1.0 1.0 1.0 Lipase 0.4 0.4 0.4 Amylase 0.6 0.6 0.6 Cellulase 0.6 0.6 0.6 Silicone defoamer 5.0 5.0 5.0 Dry additive sodium sulfate 0.0 3.0 0.0 Balance (moisture & impurities) to: 100.0 100.0 100.0 Density (g/l) 850 850 850

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

Example IV In accordance with the present invention, the following high density detergent formulations were prepared.

M N Blown Powder Zeolite A 2.5 2.5 Sodium Sulfate 1.0 1.0 CoCoMeEO2 ^* 1.5 1.5 Agglomerate C ₄₅ AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0MA/AA 4.0 2.0CMC 0.5 0.5DTPMP 0.4 0.4 Spray C ₂₅ E5 5.0 5.0 Fragrance 0.5 0.5 Dry Additive HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 15.0 15.0 SRA1 0.3 0.3 Protease 1.4 1.4 Lipase 0.4 0.4 Cellulase 0.6 0.6 Amylase 0.6 0.6 Siloxane Disinfectant Foaming agent 5.0 5.0 Brightening agent 1 0.2 0.2 Brightening agent 2 0.2 - Balance (moisture & impurities) to: 100 100 Density (g/l) 850 850

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

Any of the granular detergent compositions provided by the present invention can also be tabletted using known tableting methods to obtain tablet detergents.

High performance liquid detergent compositions containing a non-aqueous carrier medium particularly suitable for laundry use can be produced in the manner disclosed in detail below. In addition, this non-aqueous composition can be prepared according to the disclosure content 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 into the present invention. These compositions may contain various particulate soil removal ingredients (eg, the bleaches disclosed above) stably suspended therein. Accordingly, these non-aqueous compositions may contain a LIQUID PHASE (liquid phase) and optionally (but preferably) a SOLID PHASE (solid phase), as described in detail below and in the references cited. The AQA surfactant is incorporated into the composition in the same amount and manner as described above for other laundry detergent compositions. liquid phase

The liquid phase will generally comprise from 35 to 99% by weight of the detergent compositions herein. More preferably the liquid phase generally comprises from 50 to 95% by weight of the compositions of the invention. Most preferably the liquid phase generally comprises 45-75% by weight of the compositions of the invention. The liquid phase in the detergent compositions herein must contain relatively high concentrations of certain anionic surfactants in combination with certain non-aqueous liquid diluents. (A) Essential anionic surfactants

Anionic surfactants are an essential component of the non-aqueous liquid phase and are selected from alkali metal salts of alkylbenzenesulfonic acids, wherein the alkyl group contains 10-16 carbon atoms and may be in a linear or branched configuration. (See US Patents 2,220,099 and 2,477,383, incorporated herein by reference). Particularly preferred are sodium and potassium linear alkylbenzene sulfonates (LAS) in which the average number of carbon atoms in the alkyl group is 11-14. Sodium C ₁₁ -C ₁₄ LAS is particularly preferred.

The alkylbenzene sulfonate anionic surfactants are soluble in the non-aqueous liquid diluent which constitutes the second essential component of the non-aqueous phase. In order to form a structured liquid phase to produce suitable phase stability and acceptable rheological properties, the amount of alkylbenzenesulfonate anionic surfactant should be 30-65% by weight of the liquid phase. More preferably, in the composition of the present invention, the amount of the alkylbenzenesulfonate anionic surfactant is 35-0% by weight of the non-aqueous liquid phase. This use concentration of the anionic surfactant corresponds to an anionic surfactant concentration of 15-0%, more preferably 20-0% by weight of the composition in the total composition. (B) Non-aqueous liquid diluent

To form the liquid phase of the detergent compositions of the present invention, the above-mentioned alkylbenzenesulfonate anionic surfactants are used in combination with a non-aqueous liquid phase diluent comprising two essential 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 compositions of the present invention includes an alkoxylated fatty alcohol. This substance is itself an anionic surfactant. This substance corresponds to the general formula:

R ¹ (G _m H _2m O) _n OH

Wherein R ¹ is a C ₈ -C ₁₆ alkyl group, m is 2-4, and n is 2-12. R ¹ is preferably a primary or secondary alkyl group containing 9 to 15 carbon atoms, more preferably 10 to 14 carbon atoms. Additionally, the alkoxylated fatty alcohol is preferably an ethoxylate containing 2 to 12 ethylene oxide moieties per molecule, more preferably 3 to 10 ethylene oxide moieties per molecule.

Typically, the hydrophilic-lipophilic balance (HLB) is 3-17 for the alkoxylated fatty alcohol component of the liquid diluent. More preferably such materials have an HLB of 6-15, most preferably 8-15.

Examples of fatty alcohol alkoxylates used as an essential component of the non-aqueous liquid diluent in the composition of the present invention include those derived from alcohols having 12 to 15 carbon atoms and containing 7 moles of ethylene oxide substance. These materials are commercially available from Shell Chemical Company under the tradenames Neodol 25-7 and Neodol 23-6.5. Other useful Neodols include: Neodol 1-5, an ethoxylated fatty alcohol with 5 moles of ethylene oxide, with an average number of carbon atoms in the alkyl chain of 11; Neodol 23-9, with 9 moles of ethylene oxide ethoxylated C ₁₂ -C ₁₃ primary alcohols; and Neodol 91-10, ethoxylated C ₉ -C ₁₁ primary alcohols with 10 moles of ethylene oxide. Such alcohol ethoxylates are commercially available from Shell Chemical Company under the tradename Dobanol. Dobanol 91-5 is an ethoxylated C ₉ -C ₁₁ fatty alcohol with an average of 5 moles of ethylene oxide, while Dobanol 25-7 is an ethoxylated C ₁₂ ~ C ₁₅ fatty alcohol.

Other examples of suitable ethoxylated alcohols include: Tergitol 15-S-7 and Tergitol 15-S-9, both linear secondary alcohol ethoxylates, commercially available from Union Carbide Corporation. The former is a mixed ethoxylation reaction product of _C11 - _C15 linear secondary alkanols with 7 moles of ethylene oxide, while the latter is a similar product but reacted with 9 moles of ethylene oxide.

Other alcohol ethoxylates that can be used in the composition of the present invention are higher molecular weight nonionic surfactants, such as Neodol 45-11, which is a similar ethylene oxide condensation product of higher fatty alcohols, wherein higher fatty alcohols have 14 to 15 carbon atoms, and the number of oxirane groups per mole is 11. These products are also commercially supplied by Shell Chemical Company.

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

For the detergent compositions herein, the second essential component of the liquid diluent forms part of the liquid phase which comprises the non-aqueous low polarity organic solvent. The term "solvent" as used herein refers to the non-surface-active carrier or diluent portion of the liquid phase of the compositions 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 particulate form. Thus, the term "solvent" does not imply that the solvent is capable of actually dissolving all detergent composition components added thereto.

Non-aqueous organics useful as solvents in the present invention are low polarity liquids. For the purposes of the present invention, "low polarity" liquids have only a low, if any, tendency to dissolve sodium percarbonate. Therefore, more polar solvents such as ethanol should not be used. Suitable low polarity solvents useful in the non-aqueous liquid detergent compositions of the present invention actually include non-ortho _C4 - _C8 alkylene glycols, alkylene glycol mono-lower alkyl ethers, low molecular weight polyethylene glycols , low molecular weight methyl esters and amides.

Preferred nonaqueous low polarity solvents for use in the compositions of the present invention include non-ortho _C4 - _C8 branched or linear alkylene glycols. Such substances include hexanediol (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 - _C3 alkylene glycol mono- _C2 - _C6 alkyl ethers. 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 preferred. Such compounds are marketed under the trade names Dowanol, Carbitol, and Cellosolve.

Another preferred non-aqueous 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 includes low molecular weight methyl esters. This material has the general formula: R ¹ -C(O)-OCH ₃ , where R ¹ ranges from 1-18. Examples of suitable low molecular weight methyl esters include: methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.

Of course, the non-aqueous, low polarity organic solvents employed should be compatible with and non-reactive with other composition components, such as bleaches and/or activators used in the liquid detergent compositions of the present invention. Generally, this solvent component is used in an amount of 1 to 70% by weight of the liquid phase. The non-aqueous low-polarity organic solvent more preferably accounts for 10-60% by weight of the liquid phase, and most preferably accounts for 20-50% by weight of the liquid phase of the composition. In the liquid phase, this use concentration of the organic solvent corresponds to a solvent concentration in the total composition of 1-50%, more preferably 5-40%, most preferably 10-30% by weight of the composition. iii) Alcohol Ethoxylate to Solvent Ratio

In liquid diluents, the ratio of alcohol ethoxylate to organic solvent can be used to modify the rheology of the final detergent composition. Generally, the weight ratio of alcohol ethoxylate to organic solvent is 50:1 to 1:50. More preferably the ratio is from 3:1 to 1:3. iv) Liquid diluent concentration

While being related to the concentration of the alkylbenzene sulfonate anionic surfactant mixture, the amount of total liquid diluent in the non-aqueous liquid phase of the present invention can also be determined by the type and amount of other ingredients in the composition, and by the desired composition performance to decide. In the compositions of the present invention, the liquid diluent generally comprises from 35 to 70% of the non-aqueous liquid phase. More preferably, the liquid diluent generally comprises 50-65% of the non-aqueous liquid phase. This corresponds to a concentration of the non-aqueous liquid diluent in the total composition of 15 to 70% by weight of the composition, more preferably 20 to 50% by weight. Solid Phase

The non-aqueous detergent compositions of the present invention must also contain 1 to 65% by weight, more preferably 5 to 50% by weight, of solid phase particulate matter dispersed and suspended in the liquid phase. Generally, the size of such particles is from 0.1 to 1500 microns. More preferably such particles have a size of 5 to 200 microns.

Granular materials for use herein may comprise one or more particulate detergent composition components which are substantially insoluble in the non-aqueous liquid phase of the compositions herein. The types of particulate matter that can be used will be described in detail below. Preparation and use of the composition

The non-aqueous liquid detergent compositions of the present invention may be prepared by combining the essential and optional components thereof in any conventional order and mixing, such as stirring the resulting mixture of components, to form the phase stable compositions of the present invention . In a typical method of preparing such compositions, the essential ingredients and certain preferred optional ingredients are mixed in a particular order and under certain conditions.

In the first step of this typical preparation, a mixture of the two main components of an alkylbenzenesulfonate anionic surfactant and a non-aqueous diluent is heated to 30-100°C to form a mixture of these materials.

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

In the third step, the liquid phase mixture of these substances is cooled to 0-35°C. This cooling step can be used to form a structured surfactant-containing liquid matrix into which the particulate matter of the detergent compositions herein can be incorporated or dispersed.

In the fourth step, the particles are added, that is, the particles are mixed with the liquid phase under shear stirring conditions. When more than one particle is to be added, it is preferred to add in a certain order. For example, substantially all of the optional solid particulate surfactant having a particle size of 0.2 to 1000 microns may be added while maintaining shear agitation. After addition of all optional surfactants, substantially all of the organic builder, such as citrate and/or fatty acid, and/or alkali, is added while continuing to maintain the composition component mixture under shear stirring conditions Particles of aggressive substances such as sodium carbonate. Other solid optional ingredients are then added to the composition at this point. Agitation of the mixture is continued and, if necessary, increased to form a uniform dispersion of insoluble solid phase particles in the liquid phase.

After the addition of some or all of the foregoing solid materials to the stirred mixture, the highly preferred peroxygen bleach particles are added while maintaining the mixture, also under shear stirring conditions. Since the peroxygen bleach is added last, or after all or most of the other components, especially after the alkaline material particles, the desired stabilization of the peroxygen bleach can be achieved. If enzyme granules are added, they are preferably added last to the non-aqueous liquid base.

As a final step, after all particulates have been added, the mixture is continued to be agitated 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, a slurry of premixed particles of one or more solid components and a small amount of one or more liquid components may be added to the agitated mixture. Therefore, a premix of a small amount of alcohol alkoxylate and/or non-aqueous low-polarity solvent and organic builder particles and/or inorganic alkaline substance particles and/or bleach particles can be prepared respectively, and then mixed with slurry form into the stirred mixture of composition components. This premix slurry should be added prior to the addition of the peroxygen bleach and/or enzyme granules which themselves can be formulated as part of the premix slurry in a similar manner.

Compositions of the invention prepared in the manner described above can be used to form aqueous washes for laundry and fabric bleaching. Generally, such aqueous laundry/bleach solutions are formed by adding an effective amount of the composition to water, preferably in a conventional automatic fabric laundering washing machine. The aqueous laundry/bleach solution thus formed is then contacted, preferably under agitation, with the fabrics to be washed and bleached therein.

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

Example V

A non-limiting example of a bleach-containing non-aqueous liquid laundry detergent was prepared having the composition shown in Table I.

Table I

Component weight % range (wt%) liquid phase C ₁₂ sodium linear alkylbenzene sulfonate (LAS) 25.3 18-35C _12-14 EO5 alcohol ethoxylate 13.6 10-20 hexanediol 27.3 20-30 fragrance 0.4 0-1.0 Double AQA-1 ^* 2.0 1-3.0 Solid phase protease 0.4 0-1.0 Trisodium citrate, anhydrous 4.3 3-6 Sodium percarbonate 3.4 2-7 Sodium nonanoyloxybenzenesulfonate (NOBS) 8.0 2 -12 Sodium Carbonate 13.9 5-20 Diethyltriaminepentaacetic Acid (DTPA) 0.9 0-1.5 Whitening Agent 0.4 0-0.6 Foam Inhibitor 0.1 0-0.3 A Small Amount ----

^* CoCoMeEO2 and double AQA-1 can be replaced by double AQA surfactant 2-22 or other double AQA surfactants of the present invention.

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

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

Example VI

The hand wash detergent formulations of the present invention are prepared by mixing together the ingredients in the weight percentages given below.

A B C DLAS 15.0 12.0 15.0 12.0TFAA 1.0 2.0 1.0 2.0C ₂₅ E5 4.0 2.0 4.0 2.0AQA-9 ^* 2.0 3.0 3.0 2.0STPP 25.0 25.0 15.0 15.0MA/AA 3.0 3.0 3.0 3.0CMC 0.4 0.4 0.4 0.4DTPMP 1.0 1.6 1.6 1.6碳酸Salt 2.0 2.0 5.0 5.0 Bicarbonate - - 2.0 2.0 Silicate 7.0 7.0 7.0 7.0 Protease 1.0 - 1.0 1.0 Amylase 0.4 0.4 0.4 - Lipase 0.12 0.12 - 0.12 Photoactivated Bleach 0.3 0.3 0.3 0.3 Sulfate 2.2 2.2 2.2 2 Percarbonate 4.0 5.4 4.0 2.3NOBS 2.6 3.1 2.5 1.7SRA1 0.3 0.3 0.7 0.3 Brightener 1 0.15 0.15 0.15 0.15 Balance Impurities/Water 100.0 100.0 100.0 100.0 to 100

^* AQA-9 can be replaced by any of the AQA surfactants described herein. Preferred AQA surfactants useful in this example are those with 10-15 ethoxy groups, eg AQA-10, AQA-16.

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

New high-performance hand dishwashing compositions may contain a variety of ingredients that contribute to specific product-use properties such as degreasing power, high sudsing, mildness and skin-feel. Such ingredients for use with the dual AQA surfactants of the present invention include: amine oxide surfactants, betaine and/or sultaine 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, the preferred liquid and/or gel hand dishwashing compositions may also contain calcium ions, magnesium ions, or calcium/magnesium ion mixtures, which provide additional degreasing properties, especially in combination with the present invention. When AQA surfactants are used in combination with detergency mixtures such as amine oxides, alkyl sulfates and alkyl ethoxy sulfates. The source of magnesium or calcium or mixed Mg/Ca ions will generally comprise 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. Also, these compositions may also contain nonionic surfactants, especially polyhydroxy fatty acid amides and alkyl polyglucosides. Preference is given to C ₁₂ -C ₁₄ (coconut alkyl) species. A particularly preferred nonionic surfactant for use in hand dishwashing liquids is C ₁₂ -C ₁₄ N-methyl glucamide. Preferred amine oxides include _C12 to _C14 dimethylamine oxide. Alkyl sulfates and alkyl ethoxy sulfates are as described above. These surfactants are typically used in dishwashing liquids at levels of 3 to 50% of the finished composition. The formulation of dishwashing liquid compositions has been described in more detail in various patent publications, including US5378409, US5376310 and US5417893, which are incorporated herein by reference.

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

Automatic dishwashing detergents containing granular phosphate are further illustrated in Examples A and B below.

Example VII

Weight % Actives Ingredient A B STPP (Anhydrous) ¹ 31 26 Sodium Carbonate 22 32 Silicate (% _SiO2 ) 9 7 Surfactant (Non-ionic) 3 1.5 NaDCC Bleach ² 2 - Bis AQA-1 ^* 0.5 1.0 Sodium Percarbonate 3.2 5TAED - 1.5Savinase(AU/g) - 0.04Termamyl(Amu/g) 425 Sulfate 25 25 Fragrance/Minor to 100% to 100%

¹ sodium tripolyphosphate

² sodium dichlorocyanurate

^* Bis AQA-1 surfactant can be replaced by Bis AQA-2 to Bis AQA-22.

Various gelling agents such as CMC and clay can be used in the composition of the present invention to change its viscosity or hardness according to the needs of the formulator.

Example VIII

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

Component ratio (weight)

Dual AQA-1+Dual AQA-5 1:1

Dual AQA-1+Dual AQA-10 1:1

Dual AQA-1+Dual AQA-15 1:2

Dual AQA-1+Dual AQA-5+Dual AQA-20 1:1:1

Dual AQA-2+Dual AQA-5 3:1

Dual AQA-5+Dual AQA-15 1.5∶1

Dual AQA-1+Dual AQA-20 1:3

Mixtures of the dual AQA surfactants of the present invention with corresponding cationic surfactants containing only a single ethoxylated chain may also be used. Thus, the present invention can use, for example, ethoxylated cationic surfactants having the formula R ¹ N ⁺ CH ₃ [EO] _x [EO] _y X ^- and R ¹ N ⁺ (CH ₃ ) ₂ [EO] _z X ^- agent mixture, wherein R ¹ and X have been disclosed above, and (x+y) or z of one of the cationic surfactants is 1 to 5, preferably 1 to 2, and (x+y) of the other cationic surfactants y) or z is 3-100, preferably 10-20, most preferably 14-16. Such compositions advantageously improve soil release performance (especially from a fabric laundering perspective) over a broad range of water hardness relative to the cationic surfactants of the invention used individually. Cationic surfactants with a shorter EO (e.g., EO2) have been found to improve the cleaning performance of anionic surfactants in soft water, while cationic surfactants with a higher EO (e.g., EO15) can be used to increase anionic surfactants The hardness tolerance of the agent is improved, which improves the cleaning performance of anionic surfactants in hard water. In the field of soil removal, common sense tells us that builders optimize the performance "window" of anionic surfactants. However, it has hitherto not been possible to widen this performance window to satisfy substantially all water hardness conditions.

The laundry detergent composition of the present invention prepared using one or more of the aforementioned ingredient mixtures may optionally be compounded with any non-phosphate or phosphate builder, or a mixture thereof, usually in an amount by weight of the finished composition 5 to 70% of that.

Example IX

Mixtures of conventional non-AQA surfactants which may be used in combination with the dual AQA surfactants of any of the preceding examples are illustrated below, but are not meant to be limiting. The ratio of non-AQA surfactants in the mixture is expressed in parts by weight of the surfactant mixture. Mixture AC

Composition ratio

AS ^* /LAS 1:1

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

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

^* In the foregoing, substantially linear primary AS surfactants may be replaced by equivalent amounts of secondary AS or branched AS, oleyl sulfate, and/or mixtures thereof, including mixtures with linear primary AS described above. The "tallow-based" chain length AS is particularly useful in hot water up to boiling water conditions. "Coconut-based" AS is preferred for cooler wash temperatures.

The above alkyl sulfate/anionic surfactant mixture can be modified by adding thereto a nonionic non-AQA surfactant in a weight ratio of anionic surfactant (all) to nonionic surfactant of 25:1 ~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, as disclosed above. Mixture DF

AS ^* /AES 1:1

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

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

^* Can be replaced by secondary, branched or oil-based AS mentioned above.

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

AS/AES blends, or AS/AES/LAS blends derived therefrom, can also be used in combination with the nonionic surfactants mentioned in blends A-C, where the anionic surfactants (all) are combined with the nonionic surfactants The weight ratio is 25:1～1:5.

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

Very preferred mixtures of the foregoing non-AQA surfactants comprise from 3 to 60% by weight of the total finished laundry detergent composition. The finished composition preferably contains 0.25 to 3.5% by weight of the double AQA surfactant.

Example X

This example illustrates perfume formulations (A-C) made according to the invention which can be used for incorporation into any of the preceding examples containing double AQA detergent compositions. The various components and amounts are given below.

weight%

Fragrance ingredients A B C Hexylcinnamaldehyde 10.0 - 5.0 2-Methyl-3-(p-tert-butylphenyl)-propionaldehyde 5.0 5.0 -7-Acetyl-1,2,3,4,5,6,7 , 8-Octahydro-1,1,6,7-tetramethylnaphthalene 5.0 10.0 10.0 Benzyl salicylate 5.0 - -7-acetyl-1,1,3,4,4,6-hexamethyltetra Hydronaphthalene 10.0 5.0 10.0 p-tert-butylcyclohexyl acetate 5.0 5.0 - Methyl dihydrojasmonate - 5.0 - β-naphthol methyl ether - 0.5 - Methyl β-naphthalenone - 0.5 -2-Methyl-2 -(p-isopropylphenyl)-propionaldehyde 2.0 -1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-γ -2- - 9.5-Chrene dodecahydro-3a,6,6,9a-tetramethylnaphtho[2,1b]furan- - 0.1 anisaldehyde- - 0.5 coumarin- - 5.0 cedrol- - 0.5 Vanillin- - 5.0 Cyclo-n-pentadecanylide 3.0 - 10.0 Tricyclodecenyl acetate - - 2.0 Cistus oleoresin - - 2.0 Tricyclodecenyl propionate - - 2.0 Phenylethyl alcohol 20.0 10.0 27.9 Terpineol 10.0 5.0 - Linalool 10.0 10.0 5.0 Linalyl acetate 5.0 - 5.0 Geraniol 5.0 - - Nerol - 5.0 - Acetic acid of 2-(1,1-dimethylethyl)-cyclohexanol Esters 5.0 - - Orange Oil, cold pressed - 5.0 - Benzyl Acetate 2.0 2.0 - Orange Terpene - 10.0 - Eugenol - 1.0 - Diethyl Phthalate - 9.5 - Lemon Oil, cold pressed - - 10.0 Total 100.0 100.0 100.0

The aforementioned 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 containing the double AQA surfactants. Thus, the deposition and/or retention of the perfume or its individual components 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.